SUBCOMMITTEE ON MATERIALS 101st Annual Meeting – Pittsburgh, Pennsylvania Tuesday, August 4, 2015 - 3:00 pm – 5:00 pm EST

TECHNICAL SECTION 3a - HYDRAULIC CEMENT

Mark Felag (RI) Chair and Gina Ahlstrom (FHWA) Vice Chair

Research Liaison – Bob Horwhat (PA)

AMRL SUPPORT – Brian Johnson, Maria Knake and Sonya Puterbaugh

Harmonization Task Group – Don Streeter (NY) – Co-Chair

Sergeant at Arms – Lyndi Blackburn (AL) & Special Guest – 5 Cent

I. Call to Order and Opening Remarks Chair Felag (RI) Vice Chair Ahlstrom (FHWA)

The meeting was called to order at 3:06 PM. The Chair introduced the Vice Chair, AASHTO

Liaisons, and Sergeant at Arms (Blackburn) and welcomed all attendees. The Chair thanked all of the AASHTO/AMRL staff and liaisons for their work behind the scenes.

II. Roll Call – See Pages 8 & 9 Introductions were made by all members, friends, and visitors.

III. Approval of Technical Section Mid-Year Minutes – Attachments 1 & 1a

A motion was made by Pennsylvania to approve the minutes. A second was made by Maine. The minutes were approved unopposed.

IV. Presentations Performance Engineered Mixtures – Ahlstrom – Attachment 2 A presentation was made on FHWA’s Motivation to Move towards Performance Engineered Concrete Mixtures.

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• MAP 21 legislation focused on performance, as well as desire from public agencies. • It is important for all stakeholders communicate the same message • Information, research, and MAP-21 funds are available to advance the development of a

performance based specification for paving concrete. • FHWA hopes to draft a provisional specification in the next year. • Expert Task Group (ETG) includes experts from Academia, Industry, FHWA, and DOTs.

They meet regularly to discuss the development of a specification. • First ETG meeting lead to the decision on key properties that need to be evaluated for

hardened concrete, plastic concrete, and prequalification. • Champion states have been identified as possible lead adopters. These states are

gathering data on new tests, and possibly parallel testing. • The National Concrete Consortium (NCC) will provide input on the specification. • The next steps include the “2015 Summer of Data Gathering,” report at fall NCC

meeting, refine the draft specification, and gain stakeholder support and ultimately AASHTO support. The goal is to have a draft specification for the 2016 Annual SOM meeting.

Technical Section Award of Appreciation – Paul Tennis (PCA) The chairman presented an award to Paul Tennis (PCA) for recognition of his work for TS 3a, for his work on the harmonization of cement specifications, his work on other task forces and general cement help.

L to r, Mark Felag (RI) Chair, Paul Tennis (PCA) and Gina Ahlstrom (FHWA) Vice Chair

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“Just Vote No - Confessions of a Tech Section Chair” – 5 Cent – Attachment 3 A musical guest, 5 Cent, sang a brief song entitled “Just Vote No - Confessions of a Tech Section Chair,” sang to the tune of “Let it Go” from the hit Disney Musical Frozen.

5 Cent Presenting “Just Vote No - Confessions of a Tech Section Chair”

V. Old Business A. SOM Ballot Items - None B. TS ballots - None C. Task Force Reports

i. TF 09-01 – Harmonization Task Force – Streeter (NY) /Tennis (PCA) – Attachment 4

Mr. Tennis gave a brief presentation on work completed by the task force and then discussed new changes proposed by the Task Force.

1. M 240 – Attachments 4a

• Remove Methylene Blue Index (MBI) and Total Organic Content (TOC) requirements.

2. M 85 – Attachments 4b

• Increase the provisions for LOI for mixes containing limestone (allows for production with a lower environmental footprint).

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3. M 240 – Attachments 4c • The 5% limits are questionable, especially for cement with small

amounts of ingredients like silica fume. New proposed limits factor in variation due to chemical test method, ingredient chemistry, and amount of ingredient.

4. T 105 – Attachment 4d

• Add a value for Table 1, Column 3 for the maximum difference

between averages of duplicate analyses of certified value. This will aid in qualifying rapid method of analysis.

5. M 85 – Revision for Calculating Base Cement Oxides - Geissel’s Email – Attachment 4e

• Provide a procedure on determining the base cement phase composition. Currently, the base cement composition must be reported, but the calculation is not described in the standard.

A motion was made by Wisconsin to move these proposed changes to concurrent ballot. North Carolina seconded the motion. The motion passed unopposed. The chairman recognized the members of the task group and thanked them for their efforts.

VI. New Business A. Research Proposals – Horwhat (PA)

The research liaison Horwhat (PA) has not received any research needs statements for Tech Section 3a. Amir Hannah (NCHRP) and Bob Horwat (PA) mentioned that Project 381 is seeking research panel members. Horwhat and Felag volunteered to serve on the panel.

i. Durability and Service Life of Cracked Concrete – Felag – Attachments 5 & 5a The chairman discussed a research problem statement on the Durability and Service Life of Cracked Concrete that was developed from the TRB meeting by the concrete committee chairs. North Carolina made a motion to endorse the research problem statement, and Pennsylvania made a second to the motion. The motion passed unopposed.

B. AASHTO AMRL/CCRL Issues – i. CCRL – Johnson

An AASHTO R 18 ballot will be coming out soon. Brian Johnson (AMRL) asked members to review the equipment tables in R 18 and provide comments. If you

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have comments about the AASHTO Accreditation Program, particularly how accreditation items are listed, please contact Brian. Suggestions are welcome for cement accreditation. If you have any questions about CCRL, you can contact them directly or send your comments and questions to Brian and he will put you in touch with them.

ii. Carryover Queries – Felag – Attachment 6 1. Keywords – Attachment 6a

The chairman will add keywords to TS 3a standards editorially. 2. T 107 – Attachment 6b

Changes will be made editorially. 3. T 131 – Nothing to be changed. 4. T 137 – Attachment 6c

Changes will be made editorially. 5. T 353 – Not discussed at meeting but included in Queries

Changes will be made editorially.

C. NCHRP Issues - Hanna (NCHRP) - (5 minutes) Amir Hanna gave a brief update on on-going and new research projects related to Tech Section 3a.

• On-going projects include: o 18-16 Self-Consolidating Concrete o 20-7(331) Permeability Synthesis, a draft report will be done soon.

• Not yet started: o 18-17- entrained air voids. Will be awarded soon. o 20-07(381) “Using Resistivity Measurements to Develop a Formation Factor

Specification”. There was a discussion about the needs statement. There was some confusion about the level of work detailed in the statement. 20-7 projects are short duration and low cost and Amir felt the level of effort was too great. There will be a follow-up conversation with the authors to clarify, although Amir felt it would probably not be funded.

Amir reminded members that very few problem statements are received in the area of cement and concrete, and urged members to submit anything that they might have in this area.

D. Correspondence, calls, meetings/ Presentation by Industry

i. Mid-Year Web Meeting – November 17th at 2 p.m. The mid-year meeting will be early this year as part of the changes made to accommodate the new rolling ballot system.

ii. New Harmonization Request – July 2015 – July 9th Email Awaiting Response 1. M 303 Lime for Asphalt Mixtures – ASTM C 1097 2. M 216 Lime for Soil Stabilization – ASTM C 977 – Already Done.

A harmonization request was received from ASTM for standard M303 and M216. M 216 is already harmonized. The Chair has inquired with ASTM regarding the need for

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harmonization for harmonization of M303 and C1097, but has not yet received a response. There may be some differences with the chemical requirements and with the gradations. Robin Graves will try getting the Chair more information. We will await more information from ASTM before moving on this item.

E. Proposed New Standards - None.

F. Proposed New Task Forces - None.

G. Standards Requiring Reconfirmation - Attachment 7

T 98-12 – Fineness by Turbidimeter T 137-12 – Air Content of Hydraulic Cement Mortar A ballot will be sent out in September to reconfirm T 98 and T 137.

H. SOM Ballot Items (including any ASTM changes) M 152M/M 152-15 – C 230/C 230M – 13 new is 14 – Flow Table – Attachments 8 & 8a A motion was made by New Jersey and a second by Oklahoma to send this change to concurrent letter ballot. The ballot passed unopposed. M 210M/M210 – 14 – App. For Measuring Length Change - Ballot as a Practice – Attachment 9 A motion was made to ballot M210 with a new designation as a practice and not a specification by Pennsylvania. A second was made by North Carolina. The motion passed unopposed. M 216-13 – Lime for Soil Stabilization – Ballot Title Change- Attachment 10 This change will be made editorially. T 105-14 – C 114-13 new is 15 – Chemical Analysis – Attachment 11 A motion was made to make several changes to AASHTO T105 to better align the standard with C114 by Maine, and a second was made by Wisconsin. The motion passed unopposed. T 127 -15 – ASTM C183-13 new is 15 – Sampling Hydraulic Cement – Ballot as Practice and Other Changes – Attachment 12 A motion was made to send the item to concurrent ballot by Alabama and the motion was seconded by Maine. The motion passed unopposed. T 133 -11(15) – C188-09 new is 14 - Density – Attachment 13 A motion was made to send the item to concurrent letter ballot by Pennsylvania. A second was made by Maine. The motion passed unopposed. T 162 –15 – C 305-13 new is 14 – Mechanical Mixing of Hydraulic Cement and Mortars – Attachment 14

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A motion was made to send the item to concurrent letter ballot by Oklahoma. A second was made by Alabama. The motion passed unopposed.

VII. Open Discussion VIII. Adjourn - Approximately at 4:35 p.m.

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Felag, Mark E mark.felag@dot.ri.gov RIDOT

Chair Voting

Ahlstrom, Gina gina.ahlstrom@dot.gov Federal Highway Administration

Vice Chair Voting

Puterbaugh, Sonya Rose sputerbaugh@amrl.net AMRL Liaison Non-Voting

Knake, Maria mknake@amrl.net AMRL Liaison Non-Voting

Rothblatt, Evan erothblatt@aashto.org AASHTO Liaison Non-Voting

Johnson, Brian bjohnson@amrl.net AMRL Member Non-Voting

Lenker, Steven E. slenker@amrl.net AMRL Member Non-Voting

Blackburn, Lyndi D blackburnl@dot.state.al.us Alabama DOT Member Non-Voting

Connery, James P. James.Connery@ct.gov CTDOT Member Voting

Doyle, Gregory gregory.j.doyle@dot.gov FHWA Member Non-Voting

Virmani, Paul Y. paul.virmani@dot.gov FHWA Member Non-Voting

Crawford, Gary L gary.crawford@dot.gov FHWA Member Non-Voting

Bergin, Michael J michael.bergin@dot.state.fl.us Florida DOT Member Voting

Douds, Richard rdouds@dot.ga.gov Georgia DOT Member Non-Voting

Ikehara, Brian brian.ikehara@hawaii.gov Hawaii DOT Member Voting

Mueller, Matthew W. Matthew.Mueller@illinois.gov Illinois DOT Member Voting

Kreider, Richard E. richard.kreider@ksdot.org Kansas DOT Member Voting

Abadie, Christopher David Chris.Abadie@la.gov Louisiana DOTAD Member Voting

Charoenpap, Richie richie.charoenpap@la.gov Louisiana DOTAD Member Non-Voting

Bradbury, Richard L Richard.Bradbury@maine.gov Maine DOT Member Voting

Grieco, John E. john.grieco@state.ma.us Massachusetts DOT Member Voting

Staton, John F. statonj@michigan.gov Michigan DOT Member Voting

Turgeon, Curt curt.turgeon@state.mn.us Minnesota DOT Member Voting

Williams, III, James A. jwilliams@mdot.state.ms.us Mississippi DOT Member Voting

Tedford, Darin P dtedford@dot.state.nv.us Nevada DOT Member Voting

Sheehy, Eileen eileen.sheehy@dot.nj.gov New Jersey DOT Member Voting

Streeter, Donald A. donald.streeter@dot.ny.gov New York State DOT Member Voting

Peoples, Christopher A. cpeoples@ncdot.gov North Carolina DOT Member Voting

Seward, Kenny R. kseward@odot.org Oklahoma DOT Member Voting

Horwhat, Robert D rhorwhat@pa.gov Pennsylvania DOT Member Voting

Ramirez, Timothy tramirez@pa.gov Pennsylvania DOT Member Non-Voting

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Hazlett, Darren

darren.hazlett@txdot.gov

Texas DOT

Member

Voting

Ahearn, William E.

bill.ahearn@state.vt.us Vermont AOT Member Voting

Babish, Charles A. andy.babish@vdot.virginia.gov Virginia DOT Member Voting

Williams, Kurt willikr@wsdot.wa.gov Washington State DOT Member Voting

Farley, Paul M paul.m.farley@wv.gov West Virginia DOT Member Voting

Prowell, Jan jprowell@astm.org CCRL Friend Non-Voting

Innis, Al al.innis@holcim.com Holcim (US) Inc. Friend Non-Voting

Blair, Bruce bruce.blair@lafarge.com Lafarge Friend Non-Voting

Sutter, Larry llsutter@mtu.edu Michigan Technological

University Friend Non-Voting

Lobo, Colin L clobo@nrmca.org NRMCA Friend Non-Voting

Melander, John jmelander@cement.org Portland Cement Association Friend Non-Voting

Tennis, Paul D ptennis@cement.org Portland Cement Association Friend Non-Voting

Sant, Gaurav N. gsant@ucla.edu University of California, Los

Angeles Friend Non-Voting

Hooton, Robert Douglas hooton@civ.utoronto.ca University of Toronto Friend Non-Voting

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First Name Last Name Title EmailJohn Melander John M Melander, Consultant jmmelandeMaria Knake AMRL mknake@aRon Holsinger Consultant ronald2040Brandi Mitchell Chemist brandi.mitcLyndi Blackburn ALDOT blackburnl@Robert Horwhat PENNDOT rhorwhat@Michael Benson AR State Highway And Transportation Department michael.beSteven Ingram AL DOT ingrams@dMerrill Zwanka SC DOT zwankame@Karl Zipf Del DOT karl.zipf@sMichael San Angelo State Materials Engineer michael.sanPeter Wu GA DOT pwu@dot.gMark Felag RI DOT mark.felag@Deborah Kim AASHTO dkim@aashWallace Heyen NE DOR walley.heyeChris Peoples NC DOT cpeoples@Mick Syslo NE DOR mick.syslo@Steven Krebs WI DOT steven.krebGreg Uherek AMRL guherek@aDarin Tedford NV DOT dtedford@Kurt Williams WA DOT willikr@wsColin Lobo NRMCA clobo@nrmGina Ahlstrom FHWA gina.ahlstroMacKenzie Fountain MS DOT mfountain@Allen Myers KY Transportation Cabinet allen.myersMatt Mueller matthew.mEric Carleton National Precast Concrete Association ecarleton@Paul Tennis Portland Cement Association ptennis@ceBruce Blair Lafarge bruce.blair@Steve Lenker Director AMRL CCRL slenker@amMichael Black KY Transportation Cabinet michael.blaMichael Sullivan MS DOT msullivan@Brett Trautman MO DOT brett.trautmBrian Johnson AMRL bjohnson@Mladen Gagulic VTAOT mladen.gagDarren Hazlett TX DOT darren.hazlMichael Doran TNDOT michael.doSonya Puterbaugh Laboratory Assessor sputerbaugWilliam Rogers Georgia Asphalt Pavement Association wrogers@gBen Franklin Dir Of Tech Services bfranklin@Robin Graves Vulcan Materials Company gravesr@vmAl Innis Holcim al.innis@hoRoss Metcalfe MT DOT rmetcalfe@Bill Bailey VADOT bill.bailey@Anne Holt Ontario Ministry of Transportation anne.holt@James Williams MS DOT jwilliams@

Richard Douds GADOT rdouds@doColin Franco RI DOT colin.francoRon Horner ND DOT rhorner@nMike Mance WV DOH mike.a.manEileen Sheehy NJ DOT eileen.sheeCharles Babish VADOT andy.babishJohn Staton MI DOT statonj@mRichard Bradbury MEDOT richard.braAmir Hanna TRB ahanna@naLisa Zigmund OH DOT lisa.zigmunCraig Wallace Headwaters Resources cwallace@hKenny Seward OK DOT kseward@oGarth Newman WAQTC garth.newmRobert Lutz AMRL rlutz@amrl

Phone Present Organizatio Presentatio Presentatio Presenter F Presenter L Other Prese847-942-2332 1 SOM TS 3a 8/4/2015 Default Presenter240-436-4804 1 SOM TS 3a 8/4/2015 Default Presenter301-916-2507 1 SOM TS 3a 8/4/2015 Default Presenter502-564-3160 1 SOM TS 3a 8/4/2015 Default Presenter334-206-2203 1 SOM TS 3a 8/4/2015 Default Presenter717-705-3840 1 SOM TS 3a 8/4/2015 Default Presenter501-569-2185 1 SOM TS 3a 8/4/2015 Default Presenter334-206-2335 1 SOM TS 3a 8/4/2015 Default Presenter803-737-6682 1 SOM TS 3a 8/4/2015 Default Presenter302-760-2380 1 SOM TS 3a 8/4/2015 Default Presenter907-269-6234 1 SOM TS 3a 8/4/2015 Default Presenter404-608-4840 1 SOM TS 3a 8/4/2015 Default Presenter401-641-8279 1 SOM TS 3a 8/4/2015 Default Presenter202-624-5883 1 SOM TS 3a 8/4/2015 Default Presenter402-479-4677 1 SOM TS 3a 8/4/2015 Default Presenter919-329-4000 1 SOM TS 3a 8/4/2015 Default Presenter402-479-4750 1 SOM TS 3a 8/4/2015 Default Presenter

bs@dot.wi.gov 1 SOM TS 3a 8/4/2015 Default Presenter240-436-4840 1 SOM TS 3a 8/4/2015 Default Presenter775-888-7784 1 SOM TS 3a 8/4/2015 Default Presenter360-709-5410 1 SOM TS 3a 8/4/2015 Default Presenter240-485-1160 1 SOM TS 3a 8/4/2015 Default Presenter202-366-4612 1 SOM TS 3a 8/4/2015 Default Presenter662-563-4271 1 SOM TS 3a 8/4/2015 Default Presenter502-564-3160 1 SOM TS 3a 8/4/2015 Default Presenter

mueller@illinois.gov 1 SOM TS 3a 8/4/2015 Default Presenter@precast.org 1 SOM TS 3a 8/4/2015 Default Presenter

803-493-5441 1 SOM TS 3a 8/4/2015 Default Presenter@lafarge.com 1 SOM TS 3a 8/4/2015 Default Presentermrl.net 1 SOM TS 3a 8/4/2015 Default Presenter502-564-3160 1 SOM TS 3a 8/4/2015 Default Presenter601-359-1666 1 SOM TS 3a 8/4/2015 Default Presenter573-751-1036 1 SOM TS 3a 8/4/2015 Default Presenter240-436-4820 1 SOM TS 3a 8/4/2015 Default Presenter802-828-6405 1 SOM TS 3a 8/4/2015 Default Presenter512-416-2456 1 SOM TS 3a 8/4/2015 Default Presenter615-350-4105 1 SOM TS 3a 8/4/2015 Default Presenter

gh@amrl.net 1 SOM TS 3a 8/4/2015 Default Presenter770-378-5206 1 SOM TS 3a 8/4/2015 Default Presenter

3149745095 1 SOM TS 3a 8/4/2015 Default Presentermcmail.com 1 SOM TS 3a 8/4/2015 Default Presenterolcim.com 1 SOM TS 3a 8/4/2015 Default Presenter406-444-9201 1 SOM TS 3a 8/4/2015 Default Presenter804-328-3106 1 SOM TS 3a 8/4/2015 Default Presenter416-235-3724 1 SOM TS 3a 8/4/2015 Default Presenter601-359-7007 1 SOM TS 3a 8/4/2015 Default Presenter

404-608-4805 1 SOM TS 3a 8/4/2015 Default Presenter401-222-3030 1 SOM TS 3a 8/4/2015 Default Presenter701-328-6904 1 SOM TS 3a 8/4/2015 Default Presenter304-558-9846 1 SOM TS 3a 8/4/2015 Default Presenter609-530-2307 1 SOM TS 3a 8/4/2015 Default Presenter804-328-3102 1 SOM TS 3a 8/4/2015 Default Presenter517-322-5701 1 SOM TS 3a 8/4/2015 Default Presenter207-441-2474 1 SOM TS 3a 8/4/2015 Default Presenter202-334-1432 1 SOM TS 3a 8/4/2015 Default Presenter614-275-1351 1 SOM TS 3a 8/4/2015 Default Presenter239-565-2338 1 SOM TS 3a 8/4/2015 Default Presenter405-522-4999 1 SOM TS 3a 8/4/2015 Default Presenter208-334-8039 1 SOM TS 3a 8/4/2015 Default Presenter240-436-4801 1 SOM TS 3a 8/4/2015 Default Presenter

enters

Meeting Date:

3a Executive TeamChair - Mark Felag (RI)Vice Chair - Gina Ahlstrom (FHWA)Research Liaison - Robert Horwhat (PA)Harmonization Task Group Co-Chair - Don Streeter (NY)AMRL Support - Brian Johnson, Maria Knake and Sonya PuterbaughSergeant at Arms - Lyndi Blackburn (AL)Special Guest - 5 Cent (RI)

Standard Designation

Summary of Proposed Changes TS, Full or Concurrent? Attach #

All Revise to……M 240 Remove MBI and TOC requirements Concurrent - 4a

M 85Increase provisions for LOI and IR for mixes containing limestone. Concurrent - 4b

M 240 Change ingredient requirements Concurrent - 4c

T 105

Add a value to Table 1 for the maximum different between averages of duplicate analyses of certified values; better alignment with ASTM Concurrent - 4d

M 85 Revision to Calculate Base Oxides Concurrent - 4eT 98 Reconfirmation in 2016 TST 137 Reconfirmation in 2016 TSM152 Changes to align with ASTM Concurrent - 8&8aM210 New designation as a practice Concurrent - 9T 105 Edits in 5.2 Concurrent - 11T127 Ballot as a practice, other minor changes Concurrent - 12T133 Equivalency with ASTM Concurrent - 13T162 Equivalency with ASTM Concurrent - 14

Research Liaison: Bob Horwat (PA) (see below)

TS 3a Meeting Summary

Items approved by the TS for Subcommittee Ballot:

8/4/2015 15:00

New Task Forces Formed: None

Other Action Items:

A motion was made and approved to endorse a research problem statement on Durability and Service Life of Cracked Concrete in Structures. The Chair was one of the authors of the proposal.

Changes will be made editorially to add keywords to TS 3a standards.

3a Technical Section Award of Appreciation was awarded to Paul Tennis of the PCA

5 Cent presented 'Just Vote No - Confessions of a Tech Section Chair' to the tune of 'Let it Go'

Meeting was well organized and run without any incidents due to the good work of the 3a Team!

Changes will be made editorially to T107 (Q), T131 (Q), T137 (Q), T 353 (Q) and M216 (title change)

SUBCOMMITTEE ON MATERIALS Mid-Year Web Meeting Friday, February 6, 2015

Scheduled for 1:30 pm – 3:00 pm EST (actual 1:35 pm – 2:29 pm)

Meeting Minutes

(The Powerpoint used during the meeting is Attachment aa)

I. Call to Order and Opening Remarks - Chair Intro, Thank you, Awards, Other Stuff Introduction music was by Barry Manilow. Participants enjoyed the music while others were signing in. Mark Felag (RI) called the meeting to order at 1:35 pm. Mark has been the Chair of Tech Section 3a for 24 years. There were 17 Members, 8 Proxies, 4 Friends and 5 Guests present for a total of 34 people. He thanked the participants of the committee for all their work. The chair discussed awards he was able to give out at the Annual Meeting last August. One was to Reynolds Tony as the Vice Chair for 14 years and the second was to John Melander for his work with the Harmonization Group, a monumental effort.

II. Roll Call – Attachment a – 3a Roster and Attachment b – Attendance Listing Send an email to Mark (RI) or Sonya (AMRL) if you would like to be a Member or Friend of the committee.

III. Approval of Technical Section Minutes – Annual Meeting 2014 – Attachment c There was a motion by James Williams (MS) to approve the minutes of the meeting. Don Streeter (NY) seconded. The minutes for the 2014 Annual Meeting were approved.

IV. Old Business A. SOM Ballot Items

We had 12 ballot items (concurrent) and all passed. The three negative votes on Items 53 - 55 were from Mark Felag, the Chair, as an administrative negative. This is done so edits can be coordinated with ASTM. The negatives were discussed and the Chair will withdraw them pending publication coordination. Item 51 (Concurrent ballot item to revise M85) passed with 35 affirmatives. Arkansas had a comment regarding potential issues with total chlorides when referenced to AASHTO T105. Don Streeter stated that this comment was provided to the Harmonization Task Group. The same comment was raised in ASTM as well. The Task Group is proposing to consider this as new business and Mark agreed.

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Item 52 (Concurrent ballot item to revise M85) passed with 45 affirmatives and no substantial comments. Item 53 (Concurrent ballot item to revise M240) passed with 44 affirmatives and no substantial comments. Item 54 (concurrent ballot item to revise M152) passed with 46 affirmatives and no substantial comments. Item 55 (Concurrent ballot to revise M201) passed with 46 affirmatives and no substantial comments. Item 56 (Concurrent ballot item to revise T106) passed with 46 affirmatives and no substantial comments. Item 57 (Concurrent ballot item to revise T127) passed with 46 affirmatives and no substantial comments. Item 58 (Concurrent ballot item to revise T131) passed with 46 affirmatives and no substantial comments. Item 59 (Concurrent ballot to revise T154) passed with 46 affirmatives and no substantial comments. Item 60 (Concurrent ballot item to revise T162) passed with 46 affirmatives and no substantial comments. Item 61 (Concurrent ballot item to revise T185) passed with 46 affirmatives and no substantial comments. Item 62 (Concurrent ballot item to revise T186) passed with 46 affirmatives and no substantial comments.

B. TS letter ballots – Reconfirmation – See V. New Business Section G below.

C. Task Force Reports TF 09-01 – Harmonization Plus – Streeter/Melander (See Attachment d) Don Streeter (NY) provided an update on the Harmonization Task Force efforts. The group looked at M85/C150, M240/C595, and M327/C465. John Melander (Friend) and Paul Tennis (Friend) have been instrumental in this effort. This has been a continuous effort and the group has regular conference calls. Jim Pierce is the co-chair along with Don. They are looking for new members for the Task Force so if anyone is interested please let Don know. Items 51, 52, and 53 of the AASHTO ballot all passed. The comment from Arkansas on Item 51 will be addressed as new business by the Task Force. ASTM balloted parallel chances to ASTM C150 and ASTM C595. There were three negatives for ASTM C150 which concerned including provisions for reporting of chloride content and concerns about method ASTM C114 provisions for qualifying rapid methods of test. These issues have been tabled pending a review by another ASTM committee. This does not affect the AASHTO specification. There is a proposed revision to C114 and T105 to include the chloride value. A parallel T105 change will be presented to AASHTO 3a subsequent to the mid-year meeting. There is a proposed revision to M240 and C595 regarding tolerance requirements for ingredient content. Any changes will be presented to AASHTO 3a subsequent to the mid-year meeting. The Task Force is working on several new business items including:

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• Consider revising the M 240/C595 criteria for methylene blue index and total organic carbon content based on results of research conducted by CTLGroup that was presented to TS 3a at the July 2014 meeting

• Develop criteria for use of Type IL portland-limestone cements in sulfate environments. • Evaluate revision of Option R criteria related to ASR – possible approaches include using

C1567 rather than C227 or referencing of C1778 (AASHTO PP 65) • Refinements to new Table 4 (harmonize strengths, review footnotes) • M 85/C150 topics include:

o Revision of loss on ignition and insoluble residue limits to harmonize with CSA requirements

o Consider other options for C1702 heat of hydration criteria: options include limits appropriate to modern cements and concrete; report values without limits

o Continue to monitor technical developments related to direct determination of phases

TF 07-01 – ASR – Ahlstrom (FHWA) The specifications that were developed under the FHWA ASR Development and Deployment Program and the FHWA ASR Research Program have all been balloted. 3c has these specifications. Gina and Mark recommend that the Task Force be disbanded. This does not require a vote. The chair thanked Gina for her work and disbanded the Task Force.

V. New Business A. Research Proposals – Horwhat (PA)

AASHTO research liaisons are new and were established to encourage development of problem statements. Bob Horwhat has not received any new statements. There is a problem statement being circulated through the TRB committees on the Durability and Service Life of Concrete (Bridge Decks). We may be asked to support that problem statement.

B. AMRL/CCRL Issues – Lenker/Prowell

Nothing to report.

C. NCHRP Issues – Hanna (NCHRP) NCHRP is working on FY 2016 now. There were no FY 2015 projects related to cement. There was one concrete project approved last year NCHRP 18-17 Entrained Air Void System for Durable Concrete which 3a helped in writing and approving. Amir encouraged the Tech Section to submit more problem statements. A decision on FY 2016 projects will be made the end of March. October 15 is the new deadline for submitting problem statements. No extensions will be given if the deadline is missed. NCHRP Report 749 “Methods for Evaluating Fly Ash for Use in Highway Concrete” has been published. TRB committees will be refining the problem statement on concrete bridge deck cracking. Research needs statements should be sent to Bob Horwhat (PA) who is our Tech Section research liaison and Mark. In August we will look at any statements and endorse them at the Tech Section and then they will be brought to the full SOM, prioritized, and then sent to NCHRP.

D. Correspondence, calls, meetings/ Presentation by Industry M 85 – Bogue Equations – Alaska Email An email was sent through Evan Rothblatt (AASHTO) to Mark. There are some issues that need to be looked at concerning the Bogue equation where Annex A1 may not work if you have limestone or inorganic processing agent in the cement as allowed by this specification. Mark is recommending that the Harmonization Task Force look at this issue. Don Streeter (NY) and Paul Tennis (Friend) agreed to look into the issue further and see if there are any potential ballot items.

Tech Section 3a

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M 216 – Alabama Email – Blackburn (AL) In November Lyndi Blackburn (AL) sent an email to Mark to look at some minor changes to M216 such as looking at why T219 is not referenced in M216. Lyndi agreed to draft something up and will send to Mark for the committee to review and provide comments. This could be a Tech Section ballot for official comments with potentially getting initial comments from the Committee by email. Andy Babish (VA) suggested possibly saving time by balloting the draft specification changes. Mark will consider these options further once he receives Lyndi’s proposed changes.

E. Proposed New Standards Nothing to report.

F. Proposed New Task Forces Nothing to report.

G. Standards Requiring Reconfirmation – Ballot now – M 327, T 107, T 133 and T 192 – Attachment e The ballot is out now for the reconfirmation. It closes February 13. Please look at the ballot and vote.

H. SOM Ballot Items (including any ASTM changes) This will be an annual meeting agenda item.

VI. Open Discussion The annual meeting is August 2-7, 2015 in Pittsburgh, PA. Registration is open and it is suggested that hotel reservations are made early as they can always be changed or cancelled later. 3a will meet on Tuesday, August 4 at 3:00. Mark thanked Sonya Puterbaugh (AMRL) for the work she did to prepare for the mid-year meeting. The PowerPoint slides were great. Sonya also did an excellent job with all of the edits she made to the balloted items. Mark thanked all of the people for participating in the webinar and for their work throughout the year.

VII. Adjourn – 2:29 pm

Tech Section 3a

Page 4 of 4

1/30/2015

http://materials.transportation.org/Pages/Membership.aspx 1/2

Restore to Default Order

Below is the roster for the Subcommittee on Materials. Use the dropdown menu if you would like to view membership for a specifictechnical committee. These rosters are as uptodate as AASHTO's official membership database.

The columns are sortable by clicking on the column title.

Committee Name:  SOMTechnical Section 3a

Name Email Address Agency Name Designation Member Type

Felag, Mark E mark.felag@dot.ri.gov Rhode IslandDepartment ofTransportation

Chair Voting

Ahlstrom, Gina gina.ahlstrom@dot.gov Federal HighwayAdministration

Vice Chair Voting

Johnson, Brian bjohnson@amrl.net AASHTO MaterialReference Laboratory

Liaison NonVoting

Knake, Maria mknake@amrl.net AASHTO MaterialReference Laboratory

Liaison NonVoting

Rothblatt, Evan erothblatt@aashto.org American Association ofState Highway andTransportation Officials

Liaison NonVoting

Azari, Haleh hazari@amrl.net AASHTO MaterialReference Laboratory

Member NonVoting

Lenker, Steven E. slenker@amrl.net AASHTO MaterialReference Laboratory

Member NonVoting

Puterbaugh, Sonya sputerbaugh@amrl.net AASHTO MaterialReference Laboratory

Member NonVoting

Blackburn, Lyndi D blackburnl@dot.state.al.us Alabama Department ofTransportation

Member NonVoting

Cox, Bernard coxb@dot.state.al.us Alabama Department ofTransportation

Member Voting

Connery, James P. James.Connery@ct.gov Connecticut Departmentof Transportation

Member Voting

Doyle, Gregory gregory.j.doyle@dot.gov Federal HighwayAdministration

Member NonVoting

Vanikar, Suneel N. suneel.vanikar@dot.gov Federal HighwayAdministration

Member NonVoting

Virmani, Paul Y. paul.virmani@dot.gov Federal HighwayAdministration

Member NonVoting

Crawford, Gary L gary.crawford@dot.gov Federal HighwayAdministration

Member NonVoting

Bergin, Michael J michael.bergin@dot.state.fl.us Florida Department ofTransportation

Member Voting

Douds, Richard rdouds@dot.ga.gov Georgia Department ofTransportation

Member NonVoting

Hasty, Charles Allen chasty@dot.ga.gov Georgia Department ofTransportation

Member Voting

Ikehara, Brian brian.ikehara@hawaii.gov Hawaii Department ofTransportation

Member None

Mueller, Matthew W. Matthew.Mueller@illinois.gov Illinois Department ofTransportation

Member Voting

Kreider, Richard E. richard.kreider@ksdot.org Kansas Department ofTransportation

Member Voting

Abadie, ChristopherDavid

Chris.Abadie@la.gov Louisiana Department ofTransportation andDevelopment

Member Voting

Charoenpap, Richie richie.charoenpap@la.gov Louisiana Department ofTransportation andDevelopment

Member NonVoting

Bradbury, Richard L Richard.Bradbury@maine.gov Maine Department ofTransportation

Member Voting

Grieco, John E. john.grieco@state.ma.us MassachusettsDepartment ofTransportation

Member Voting

1/30/2015

http://materials.transportation.org/Pages/Membership.aspx 2/2

Staton, John F. statonj@michigan.gov Michigan Department ofTransportation

Member Voting

Turgeon, Curt curt.turgeon@state.mn.us Minnesota Departmentof Transportation

Member Voting

Williams, III, James A. jwilliams@mdot.state.ms.us Mississippi Departmentof Transportation

Member Voting

Kaiser, Reid rkaiser@dot.state.nv.us Nevada Department ofTransportation

Member Voting

Tedford, Darin P dtedford@dot.state.nv.us Nevada Department ofTransportation

Member Voting

Sheehy, Eileen eileen.sheehy@dot.nj.gov New Jersey Departmentof Transportation

Member Voting

Streeter, Donald A. donald.streeter@dot.ny.gov New York StateDepartment ofTransportation

Member Voting

Peoples, ChristopherA.

cpeoples@ncdot.gov North CarolinaDepartment ofTransportation

Member Voting

Toney, Reynolds H. rtoney@odot.org Oklahoma Departmentof Transportation

Member Voting

Horwhat, Robert D rhorwhat@pa.gov PennsylvaniaDepartment ofTransportation

Member Voting

Ramirez, Timothy tramirez@pa.gov PennsylvaniaDepartment ofTransportation

Member NonVoting

Hazlett, Darren darren.hazlett@txdot.gov Texas Department ofTransportation

Member Voting

Ahearn, William bill.ahearn@state.vt.us Vermont Agency ofTransportation

Member Voting

Babish, Charles A. andy.babish@vdot.virginia.gov Virginia Department ofTransportation

Member Voting

Williams, Kurt willikr@wsdot.wa.gov Washington StateDepartment ofTransportation

Member Voting

Farley, Paul M paul.m.farley@wv.gov West VirginiaDepartment ofTransportation

Member Voting

Prowell, Jan jprowell@astm.org Cement and ConcreteReference Laboratory

Friend NonVoting

Innis, Al al.innis@holcim.com Holcim (US) Inc. Friend NonVoting

Blair, Bruce bruce.blair@lafarge.com Lafarge Friend NonVoting

Sutter, Larry llsutter@mtu.edu Michigan TechnologicalUniversity

Friend None

Lobo, Colin L clobo@nrmca.org NRMCA Friend NonVoting

Tennis, Paul D ptennis@cement.org Portland CementAssociation

Friend NonVoting

Melander, John jmelander@cement.org Portland CementAssociation

Friend NonVoting

Sant, Gaurav N. gsant@ucla.edu University of California,Los Angeles

Friend NonVoting

Hooton, RobertDouglas

hooton@civ.utoronto.ca University of Toronto Friend NonVoting

 © American Association of State Highway and Transportation Officials.444 N Capitol St. NW  Suite 249  Washington, DC 20001

FHWA’s Motivation to Move Towards Performance Engineered Concrete Mixtures Gina Ahlstrom Team Leader-Pavement Design and Analysis Office of Asset Management, Pavements, and Construction

Motivation

• MAP-21 legislation focuses on performance

• Desire by Public Agencies and Industry to move toward performance ▫ Optimized mixture designs (gradation, cement

content, cont.) ▫ Improved durability ▫ Sustainability

Why Now? • Desire to have FHWA, DOT’s, and Industry communicating the

same message ▫ Optimize concrete mixture designs, enhance performance, and

sustainability

• Knowledge about performance based concrete paving mixtures is available ▫ Ternary pooled fund project TPF-5(117) ▫ Work by industry and academia

• Synergy with other funded research ▫ NCHRP 20-7 on F factor ▫ TPF- 5(297) on SAM

• Funding and Mechanisms are currently available

▫ MAP 21 funds ▫ FHWA Cooperative Agreements with CP Tech and ACI

Our (Lofty) Vision • Implement the adoption of performance engineered

concrete mixtures. ▫ Accelerated evaluation of key new test methods (Champion

States summer 2015) ▫ Develop a draft AASHTO (provisional) specification (In

progress; Draft to TAC/NCC Sept 2015; Revised spring 2016)

▫ Parallel testing with States using draft specification

▫ AASHTO ballots provisional specification for performance engineered concrete mixtures

How do we get there?

Expert Task Group

Champion States-Technical Advisory

Committee

Stakeholders-NCC

Expert Task Group (ETG) • Experts from Academia, Industry, DOT’s

▫ Gina Ahlstrom, FHWA ▫ Tom Cackler, CP Tech/Woodland Consulting, Inc. ▫ Mark Felag, Rhode Island DOT ▫ Doug Hooten, University of Toronto ▫ Ken Hover, Cornell ▫ Cecil Jones, ACI/Diversified Engineering Services ▫ Steve Kosmatka, PCA ▫ Tyler Ley, Oklahoma State ▫ Colin Lobo, NRMCA ▫ Maria Masten, Minnesota DOT ▫ Mike Praul, FWHA ▫ John Staton, Michigan DOT ▫ Peter Taylor, CP Tech ▫ Mike Tholen, ACI ▫ Paul Tikalsky, Oklahoma State University ▫ Gerry Voigt, ACPA ▫ Tom Yu, FHWA

Role of ETG

• Cooperatively develop a framework and implementation plan for Performance Engineered Concrete Mixtures

• Meet periodically with the goal of implementation ▫ First meeting April 2014 ▫ Second meeting April 2015

Outcome from First ETG Meeting HARDENED CONCRETE

PLASTIC CONCRETE (Agency)

PREQUALIFICATION

Agency Contractor

1. Mechanical properties modulus abrasion 2. Freeze/thaw 3. Permeability 4. Volume change

Identity properties 1. Unit weight 2. Air properties 3. Water ratio 4. Workability placeability paveability

Evaluation All ingredients MRD Mixtures

Design Compatibility Aggregate system Mixture properties Quality Plan

Role of Champion States – Technical Advisory Committee • Champions - Lead Adopters

• Focus on implementation of the specification

• Assistance with data gathering on promising

new tests

• Consideration of performance specification/parallel testing of new specification

Role of Stakeholders-National Concrete Consortium (NCC) • Review the draft AASHTO specification

• Provide feedback and input on implementation

of the specification

• Provide feedback and input on the Quality Plan

Next Steps • “2015 Summer of Data Gathering”

• Report early results at the fall NCC meeting

• Refine draft AASHTO specification ▫ Review by TAC and NCC (fall NCC meeting)

• Stakeholder support AASHTO support

“Just Vote No - Confessions of a Tech Section Chair”

Sung to “Let it Go” - Frozen

by 5 Cent (RI) – 2015

This is the fictional story of me, a TS Chair who is looking at a very marked up specification with a lot of comments and negatives. I am tired and confused on how to handle it. I fight this struggle knowing I have the power, the power as Chair. I can use editorials and non-persuasives to essentially ignore them to make the ‘perfect spec’, which I do. - Mark Felag (RI)

The snow glows white on the mountain tonight Not a footprint to be seen A kingdom of isolation, And it looks like I'm the queen.

The tech spec white on the computer tonight Many redlines to be seen I feel alone in isolation, In so deep I can’t keep keen.

The wind is howling like this swirling storm inside Couldn't keep it in, heaven knows I tried!

The negatives sent so many that I cannot hide Couldn't keep it in, Evan knows I tried!

Don't let them in, don't let them see Be the good girl you always have to be Conceal, don't feel, don't let them know Well, now they know!

Don't let them in, don't let them see Be the good chair you always want to be Conceal, don't feel, don't let them know Well, now they know!

Let it go, let it go Can't hold it back anymore Let it go, let it go Turn away and slam the door!

Just vote no, just vote no Can't hold it back anymore Just vote no, just vote no Non persuasive, slam the door!

I don't care What they're going to say Let the storm rage on, The cold never bothered me anyway!

I don't care What they're going to say Let the No’s rage on, Negatives never bothered me anyway!

It's funny how some distance Makes everything seem small And the fears that once controlled me Can't get to me at all!

Negatives get some distance Makes all the comments seem small And the fears of it being persuasive Can't get to me at all!

It's time to see what I can do To test the limits and break through No right, no wrong, no rules for me I'm free!

It's time to see what I can do To test the limits and break through Editorial, non-persuasive. I'm free!

Let it go, let it go I am one with the wind and sky Let it go, let it go You'll never see me cry!

Just vote no, just vote no I am one with the knowing it why Just vote no, just vote no Members never see me cry!

Here I stand And here I'll stay Let the storm rage on!

Here I stand And here I'll stay Let the No’s rage on!

My power flurries through the air into the ground My soul is spiraling in frozen fractals all around And one thought crystallizes like an icy blast I'm never going back, The past is in the past!

My power is being chair, it never lets me down My brain is spiraling different symbols all around And one thought non-persuasive always will last I'm never looking back, Non-persuasives will last!

Let it go, let it go And I'll rise like the break of dawn Let it go, let it go That perfect girl is gone!

Just vote no, just vote no And I'll rise like the break of dawn Just vote no, just vote no That perfect spec is done!

Here I stand In the light of day Let the storm rage on, The cold never bothered me anyway!

Here I stand In the tech meeting Let the No’s rage on, Negatives never bothered me anyway!

AASHTO TS3a Joint AASHTO-ASTM Harmonization Task Group Report

August 2015 Annual Meeting

Background: The Joint AASHTO-ASTM Harmonization Task Group was established in 2003 with the mission of evaluating differences between AASHTO M85 and ASTM C150 portland cement standards and developing recommendations for resolving those differences. That was accomplished with the 2009 editions. Subsequently the scope of the task group was broadened to include harmonizing the provisions of AASHTO M240 and ASTM C595 blended cement standards in addition to maintaining consistent requirements in AASHTO M85 and ASTM C150. The current mission statement reads: “To evaluate existing provisions of AASHTO and ASTM hydraulic cement standards and to develop recommendations for improvements to these standards, such that they better meet the collective needs of AASHTO members and ASTM user, general interest, and producer members.” Task Group members are:

Name Organization Representing Jim Pierce, Cochairman Bureau of Reclamation (Ret) ASTM Don Streeter, Cochairman New York DOT AASHTO Mike Bergin (Bouzid Choubane) Florida DOT AASHTO Doug Hooton University of Toronto ASTM Al Innis Holcim (US) ASTM Colin Lobo NRMCA ASTM Andy Naranjo TXDOT AASHTO (John Melander) (Consultant) (ASTM) Paul Tennis PCA ASTM Toy Poole CTLGroup ASTM James Krstulovich Illinois DOT AASHTO Adam Browne Mississippi DOT AASHTO Justin Morris Louisiana DOT AASHTO Larry Sutter Michigan Tech Academia As reported at the TS3a mid-year meeting the JAAHTG completed 3 ballot items (items 51, 52, and 53) from 2014 that are included in the 2015 publication. These items include:

#51 - M 85 proposal to include reporting of chloride content #52 - M 85 proposal on heat of hydration #53 - M 240 proposal to clarify “slag”

3 parallel items were balloted in ASTM C01 and all items passed.

1

Current Activities: The JAAHTG continues to work on a number of proposed changes to cement and blended cement specifications, primarily to address comments made by AASHTO and ASTM members when reviewing previous ballot items. The task group will develop five (5) ballot items with rationales for revisions to AASHTO M85 and M 240 and requests support for submitting these items to concurrent TS3a and SOM letter ballot this fall. Parallel changes to ASTM C150 and C595 are presently being considered by ASTM letter ballot

Item #1

Subject: MBI and TOC Provisions for Limestone for Use in AASHTO M 240 Rationale: AASHTO M 240 and ASTM C595 adopted requirements in 2012 that define portland-limestone cements as blended cements with between 5% and 15% limestone content. Current requirements for limestone used as an ingredient in blended cements include methylene blue index (MBI) limits (1.2 g/100 g maximum) and total organic carbon (TOC) content limits (0.5 % maximum). There is a lack of correlation between limestone MBI values or TOC contents and freeze-thaw performance of concretes made with portland-limestone cements, it is recommended that those criteria be removed from AASHTO M 240 and ASTM C595. The net effect of these requirements is to eliminate the use of some limestone deposits in Type IL cement that can provide specified properties and desired concrete performance.

Item #2 Subject: Proposal to Change LOI and IR Limits in AASHTO M 85 Rationale: In 2009, AASHTO M 85 was modified to permit use of up to 5% limestone as an ingredient in portland cements, in order to improve their environmental characteristics. Under the current standard, portland cements that include limestone as an ingredient are commonly constrained to about 2.5% to 3% limestone because of the LOI and IR limits. Over the past several years, manufacturers and users of M 85 portland cement have developed significant experience with limestone as a cement ingredient and it is proposed to increase the loss on ignition and insoluble residue limits in M 85 to accommodate producing cements with limestone contents closer to 5%, which will result in additional environmental benefits.

Item #3 Subject: Proposal to change requirements for ingredient tolerance in M 240 Rationale: A comment on the 2012 AASHTO Subcommittee on Materials ballot on M 240 questioned whether the current 5% tolerance on ingredients for blended cement ingredients was appropriate, particularly for ingredients used in small percentages. An example was given of a Type IP cement made with a silica fume content of 4%. The ±5% (by mass of finished cement) limit currently in C595 and M 240 means that the cement could contain between 0% and 9% silica fume and still be considered the same product, even though cements with 9% or 0% silica fume might be expected to have significantly different performance characteristics. This proposal would add limits for variation in ingredient quantity with a 99% probability of compliance. The values proposed are consistent with current production technology and includes variation due to chemical test methods used to determine the amount of ingredient, variation of ingredient chemistry, and variation in amount of the ingredient. The approach is consistent with tolerance provisions for ingredients in ASTM C1697.

2

Item #4

Subject: Revision to AASHTO T 105-14 Rationale: This ballot is to add a chloride value for Table 1, 3rd column in AASHTO T 105 for maximum difference between average of duplicates and certified value. The value proposed is 0.005. The value for difference between duplicates (column 2) currently is 0.003. ASTM adopted this proposed change to C114 earlier this year.

Item #5

Subject: Revision to AASHTO M85, for calculating base cement oxides Rationale: This ballot is in response to a request to include additional information in ASTM C150 and AASHTO M 85 on a procedure for calculating base cement oxides where the oxide analyses of the finished cement, the limestone, and inorganic processing addition, percent limestone, and percent inorganic processing addition are known. Future Business: A number of issues and recommendations have come about based on comments made by AASHTO and ASTM members when reviewing previous ballot items. Additionally, new issues have been raised asking for clarification of the standards that may require revisions. Future issues already being considered by the JAAHTG include:

AASHTO M 240 and ASTM C595

◦ Modification of LS criteria ◦ Sulfate resistance ◦ Revision of Option R criteria ◦ Refinements to new Table 4

AASHTO M 85 and ASTM C150 ◦ LOI and Insoluble Residue Limits ◦ C1702 Heat of hydration criteria ◦ Direct determination of phases

3

Standard Specification for

Blended Hydraulic Cement

AASHTO Designation: M 240M/M 240-15 ASTM Designation: C595/C595M-15 Subject: MBI and TOC Provisions for Limestone for Use in AASHTO M 240 Rationale: AASHTO M 240 and ASTM C595 adopted requirements in 2012 that define portland-limestone cements as blended cements with between 5% and 15% limestone content. This cement type is relatively new to the US, but represents an established technology in Europe and other parts of the world, with performance similar to Type I cements, but with reduced environmental impact. Current requirements for limestone used as an ingredient in blended cements include methylene blue index (MBI) limits (1.2 g/100 g maximum) and total organic carbon (TOC) content limits (0.5 % maximum).

Research from the early 1990s (Sprung and Siebel 1991) appeared to justify the MBI and TOC limits on the basis of concrete freeze-thaw testing of concrete made with cements incorporating a range of limestone compositions. However, this research was performed on concretes that would not meet US recommendations for freeze-thaw durable concrete (test mixtures were not air entrained and had a high water:cement ratio—0.60). Furthermore, this original data indicates that about 50% of the limestone not meeting the MBI or TOC limits performed well in the severe freeze-thaw test used. US cement producers have further noted that MBI or TOC requirements preclude some limestone deposits that have been successfully used in ASTM C1157 cements and in masonry cement formulations. Given that specification criteria should provide an acceptable level of confidence for producers and users that limestone does not compromise concrete durability, limits similar to those in CSA A3001 and EN 197-1 were included in proposals to define PLC in AASHTO M 240 and ASTM C595 that were adopted in 2012. However, since specifications should also avoid disqualifying limestone that performs well in service, research was initiated to determine if the freeze-thaw relationship was meaningful. LIMESTONE REQUIREMENTS For limestone used in amounts of greater than 5%, M 240 and C595 both identify three characteristics for limestone to be used as an ingredient in cement: 1) a minimum CaCO3 content of 70% by mass; 2) a maximum methylene blue index of 1.2 g/100 g; and 3) a maximum total organic carbon content of 0.2% or 0.5% by mass. The requirements reportedly are to ensure concrete freeze-thaw durability (Sprung and Siebel 1991). Methylene Blue Index The methylene blue index (MBI) is a chemical characterization technique, traditionally used to identify clay minerals in concrete aggregates. Test procedures for determining MBI of limestone used in portland-limestone cements are provided in annexes to M 240 and C595. The MBI

procedure determines the amount of methylene blue dye absorbed by a limestone sample ground to a fineness of about 500 m2/kg (Blaine). Bensted (1985) provides a comparison of results on various materials using the MBI procedure. The dye is preferentially adsorbed by clay minerals and thus the index provides an indication of the clay content of the limestone, although not a direct measure, as different clays adsorb the dye at different rates. However, Sprung and Siebel (1991) point out that the clay minerals in the limestone in their study were, similar and predominantly illitic. Referring to Bensted (1985), they note that montmorillonitic clays adsorb about 8 times as much dye (as illitic clays) and kaolinitic clays adsorb about half as much. However, they also indicate a correlation between the MBI of limestone used in cements in their study and several properties: BET specific surface area, the water demand of a limestone powder, and the water required to achieve a standard consistency for a limestone paste. In addition the MBI was related to the impact of limestone in cement on concrete frost resistance (see below). Total Organic Carbon The total organic carbon content, as the name implies, is a measure of the amount organic carbon compounds present in the limestone. These arise naturally from soils and sediments in limestone quarries or during formation of limestone in geologic processes. The TOC is determined either by subtracting the inorganic carbon content from the total carbon content, or by determining the carbon content on a sample that has had the inorganic carbon content removed by acidification. Detailed methodology is provided in annexes to M 240 and C595.

Organic carbon compounds in aggregates used in concrete are known to affect setting time and strength development, and it has been presumed that similar effects may occur if they are present in limestone used in cement: a limit of 0.5% by mass has been included in M 240 and C595. The organic carbon content may also influence the performance of admixtures, as does unburnt carbon in fly ash, and thus it may impact frost performance by reducing the air-entrainment ability of certain admixtures. Impact of Limestone Composition on Freeze-Thaw Resistance (Basis for Limestone Requirements) Although MBI and TOC contents of limestone may influence other characteristics of cements in concrete, research from the early 1990s (Sprung and Siebel 1991) on frost resistance of PLC concretes appears to have been used by European standards bodies to justify CaO content, MBI and TOC limits. In their study, limestone from 33 European sources were analyzed for a range of characteristics and then tested in pastes, mortars and concretes. The CaCO3 content ranged from 58% to 98%, the MBI ranged from 0.07% to 2.53%, and the TOC ranged from 0.04% to 0.37%. Some concretes made with cements with limestone outside of one or more of the EN197-1 limits (MBI, TOC, CaCO3) performed poorly in standardized freeze-thaw testing. The testing protocol subjected 10-cm concrete cubes, with a water:cement ratio of 0.60, without entrained air, to 100 freeze-thaw cycles between -15°C and 20°C, 1 cycle per day. These concretes would not meet building code requirements for freeze-thaw durability (ACI 318-14). Data provided in Fig. 1 is reproduced from Siebel and Sprung (1991). The concretes were made using cements with 15% limestone, ground to a fineness of about 550 m2/kg Blaine.

The data indicate that these limits should be considered conservative in classifying limestone for use in cement. Almost all limestone that meets the prescriptive limits also meets performance criteria (10% in Figure 1). However, in each case a number of limestone (50% or

2

more) that fail one or more of the prescriptive limits perform well in the German performance test. Other factors are apparently impacting the concrete freeze/thaw performance. There appears to be only limited research on these criteria since the early 1990s.

The two sets of EN197-1 TOC limits of 0.2% (-LL) or 0.5% (-L) are apparently a compromise between limits advocated based on German tests and experience using limestone deposits in other European countries. ASTM and AASHTO members reviewed CSA and EN197-1 limestone quality limits based on the history of their use in Europe, and adopted the less restrictive 0.5% TOC limit.

(a)

(b)

Figure 1. Freeze-thaw performance of non-air-entrained concretes made using cements with multiple limestone sources with a range of (a) MBI values, and (b) TOC contents. Vertical axis is weight loss after 100 freeze-thaw cycles. Horizontal line at 10% is the maximum limit selected for classifying acceptable concrete performance. Heavy blue lines are limits in EN197 (Note: EN197-1 has limits on TOC of 0.2% for -LL and 0.5% for –L). Source: Siebel and Sprung (1991). Recent Research Results Seven limestone samples, chosen to provide a wide range of methylene blue index (MBI) values and total organic carbon (TOC) contents, were investigated (Feng and Clark 2014) for the effects

3

of these characteristics on portland-limestone cement (PLC) performance. Results of testing indicated that all of the limestone samples met the AASHTO M 240/ASTM C595 CaCO3 content requirement (minimum 70% by mass) for limestone used in PLC; three of the samples exceeded the M 240/C595 MBI limit, while one of the limestone samples exceeded the M 240/C595 TOC limit. The seven limestone were ground to have a mean particle size of approximately 5 μm, and then blended with portland cements (from the same plants providing the limestone samples) to produce PLCs with a total of 15% limestone by mass. These seven PLCs were then tested to determine compliance with AASHTO M 240/ASTM C595 and, along with relative air-entraining agent dosage (AEAD) and relative water demand (WD) tests. Results (Feng and Clark, 2014) show all seven PLCs meet the standard physical requirements of AASHTO M 240/ASTM C595 for Type IL cement. All seven PLC cements meet the chemical requirements of M 240/C595 for Type IL cement. Three samples (69b, 52 and 25) exceeded the default limit for SO3 content, but were below the supplemental ASTM C1038 expansion limit. Mortar Testing Testing for relative air-entraining agent dosage (AEAD) and relative water demand (WD) were based on tests of mortars made with PLC and companion portland cements without limestone. The amount of air-entraining agent require to achieve 18% air was determined (as the interpolated dosage for two mortars, one with 15% to 18% air and one with 18% to 21% air). The relative water demand was determined as the relative quantity of water needed for a PLC-mortar to produce a similar (within 5 units) flow to that of its companion portland cement. The AEAD and WD results on mortars showed that PLCs required higher air entraining agent dosage (13% to 44% higher) than their control cements, while their water demands were similar to the control cements. However, the air-entraining agent dosages for all cements were within the range recommended by the manufacturer (16 ml/100 kg and 260 ml/100 kg cement).

Table 1. Mortar testing of Air Entraining Agent Dosage and Water Demand (Feng and Clark 2014) ID 2 35 69b 52 25 56 12

Control mix

242

242

242

242

242

242

242 water used, ml flow, % 111 126 115 95 108 102 104

15% PLC cement

244

240

240

240

244

256

246 water used, ml flow, % 109 124 114 96 107 103 104

Relative water requirement, % 101 99 99 99 101 106 102

Concrete Testing Concrete mixtures were made with the seven PLCs and their companion portland cements. The water content was 0.45 (water reducer used to achieve target slump, 3 in. to 4 in.), and the target air content was 6%. The concrete testing did not show PLC mixes require higher AEA dosages, however there was a wide variation in the dosage levels of water reducer needed. The water

AEA dosage to reach 18% air, ml/100kg cement Control mix

97

62

76

78

66

82

84 Test mix 123 70 110 105 86 108 118

Relative AEA dosage 1.27 1.13 1.44 1.34 1.30 1.31 1.40

4

reducer and air-entraining agent dosages of the concrete mixes with 15% PLC are varied and mostly dependent on their control base cement mixes. No significant difference between the PLC mixes and control mixes was observed for concrete fresh properties. ASTM C666 freeze-thaw testing results revealed all seven concrete mixtures with PLCs are freeze-thaw durable with relative dynamic moduli above 90% after about 300 cycles (as were all concretes made with their companion portland cements). The freeze-thaw resistances of concrete made with PLCs are equivalent to those made with their control base cements. The authors conclude, based on this test program, that concrete freeze-thaw resistance does not show a direct relationship with MBI and TOC content. Table 2: Freeze-Thaw Test Results and Air Content Parameters (Feng and Clark 2014)

As there is a lack of correlation between limestone MBI values or TOC contents and freeze-thaw performance of concretes made with portland-limestone cements, it is recommended that those criteria be removed from AASHTO M 240 and ASTM C595. The net effect of these requirements is to eliminate the use of some limestone deposits in Type IL cement that can provide specified properties and desired concrete performance. This proposal has been developed by the Joint AASHTO-ASTM Harmonization Task Group and a similar proposal is being considered by ASTM C01.10 for C595.

REFERENCES Bensted, J., “Application of the Methylene Blue Test to Cement Raw Materials,” Journal of Chemical Technology

and Biotechnology, Vol. 35, Iss. 4, 1985, pages 181 to 184. Feng, X., and Clark, B., Portland-Limestone Blended Cement: Effects of Limestone Characteristics, SN3241,

Portland Cement Association, Skokie, Illinois, USA, 2014, 62 pages. http://members.cement.org/EBiz55/ProductCatalog/Product.aspx?ID=2216.

Schneider, M.; Puntke, S.; Schneider, C.; and Müller, C., “Use and Reactivity of Cement Main Constituents in Germany,” Proceedings of the 11th International Congress on the Chemistry of Cement (ICCC): Cement’s Contribution to the Development in the 21st Century. Editors: Dr. G. Grieve and G. Owens, 11 - 16 May 2003, Durban, South Africa, 11 pages.

Freeze - Thaw and Hardened Air #2 OPC #2 IL #35 OPC #35 IL #52 OPC #52 IL Durability Factor, % (ASTM C666) 94 95 95 95 94 94Length Change, % (ASTM C666) 0.02 0.01 0.01 0.01 0.02 0.02Mass Change, % (ASTM C666) -0.99 -1.42 -0.26 -0.44 -0.50 -0.54

Air Content, % (ASTM C457) 5.1 5.3 4.7 4.5 2.7 4.7Spacing Factor, mm (inches) (ASTM C457) 0.229

(0.009)0.152

(0.006)0.203

(0.008)0.203

(0.008)0.381

(0.015)0.254

(0.010)

Freeze - Thaw and Hardened Air Durability Factor, % (ASTM C666)Length Change, % (ASTM C666)Mass Change, % (ASTM C666)

Air Content, % (ASTM C457)Spacing Factor, mm (inches) (ASTM C457)

#69b OPC #69b IL #56 OPC #56 IL #12 OPC #12 IL #25 OPC #25 IL 95 95 92 95 94 93 92 94

0.01 0.02 0.02 0.01 0.01 0.01 0.02 0.01 -1.03 -1.40 -0.99 -1.04 -0.66 -1.26 -1.01 -0.85

4.5 7.0 3.8 5.2 4.3 5.1 4.7 4.8 0.229

(0.009)0.152

(0.006)0.178

(0.007)0.203

(0.008)0.152

(0.006)0.152

(0.006)0.203

(0.008)0.178

(0.007)

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Siebel, E., and Sprung, S., “Einfluβ des Kalksteins im Portlandkalstein zement auf die Dauerhaftigkeit von Beton,” (“Influence of the Limestone in Portland-Limestone Cement on the Durability of Concrete,”) [in German], Beton, 1991, pages 171 to 191.

Sprung, S. and Siebel, E., “Assessment of the Suitability of Limestone for Producing Portland Limestone Cement (PKZ),” Zement-Kalk-Gips, No. 1, 1991, pages 1 to 11. [In German. English text translation: No. 3, 1991, pages 43 to 48.]

DETAILED Changes:

This ballot item is based on AASHTO M 240-15. Proposed additions are underlined and proposed deletions are shown in strikethrough font. Only changes so indicated are being balloted. Other text is provided for information only. Where necessary, tables, figures, notes, footnotes, and section numbers will be renumbered editorially.

2.4 CSA Standard: CSA A3004-D2, Determination of Total Organic Carbon in Limestone

8.2 Limestone— Limestone for use in the manufacture of portland-limestone cement, or a ternary blended cement in which limestone is an ingredient, shall have a calcium carbonate content of at least 70 percent by mass. Such limestone shall meet the requirements of Table 2 for methylene blue index and total organic carbon content. The calcium carbonate content of limestone shall be determined by multiplying the CaO content of the limestone determined by Test Methods in T 105 by a factor of 1.785.

Table 2—Requirements for Limestone for Use in Blended Cements

Applicable Test Method

CaCO3 content, min, % by mass T 105 70 a Methylene blue index, max, g/100 g See Annex A2 1.2 Total organic carbon, max, % by mass See Annex A3 0.5

a The calcium carbonate content of limestone shall be determined by multiplying the CaO content of the limestone determined by Test Methods in T 105 by a factor of 1.785.

11.1.15 Activity Index with Portland Cement—Test in accordance with Annex A1.

11.1.16 Sulfate Resistance—See ASTM C1012/C1012M.

11.1.17 Methylene Blue Index of Limestone—Annex A2.

11.1.18 Total Organic Carbon Content of Limestone—Annex A3.

11.1.1917 Loss-on-Ignition of Pozzolan—ASTM C311.

Delete Annexes A2, A3, and Appendix X1 in their entirety:

A2. Methylene Blue Index Test for Limestone A3. Total Organic Carbon Content of Limestone X1. Test of Conformity in Relation to a Specified MB Value

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Standard Specification for

Portland Cement

AASHTO Designation: M 85-15 ASTM Designation: C150/C150M-15 Subject: Proposal to Change LOI and IR Limits in AASHTO M 85 Rationale: In 2009, AASHTO M 85 was modified to permit use of up to 5% limestone as an ingredient in portland cements, in order to improve their environmental characteristics. This change was among several modifications to ASTM C150 and AASHTO M 85 that resulted in the harmonization of the provisions of these standard specifications for portland cement. To minimize the changes to M 85 (and C150), and permit users to gain experience and confidence with the use of cements with limestone, no changes to other physical and chemical requirements in M 85 were proposed, although it was recognized that the existing loss on ignition and insoluble residue requirements would often limit limestone content to a significantly lower value than 5%. Under the current standard, portland cements that include limestone as an ingredient are commonly constrained to about 2.5% to 3% limestone because of the LOI and IR limits. Over the past several years, manufacturers and users of M 85 portland cement have developed significant experience with limestone as a cement ingredient and it is proposed to increase the loss on ignition and insoluble residue limits in M 85 to accommodate producing cements with limestone contents closer to 5%, which will result in additional environmental benefits. Current maximum limits in AASHTO M 85 for loss on ignition and insoluble residue are 3.0% by mass and 0.75% by mass, respectively (except for Type IV). These values have been in place for decades, and are somewhat arbitrary. For general use (Type GU) and high early strength portland cements (Type HE) with up to 5% limestone, the Canadian standard, CSA A3001, limits LOI to a maximum of 3.5%, and IR to a maximum of 1.5%. The European Standard EN197 permits an LOI of 5% and an insoluble residue of 5% for CEM I portland cement. Calcium carbonate is roughly 44% by mass CO2, which means almost half of its weight is contributed to a loss on ignition (LOI) measurement; a cement with 5% limestone could contribute about 2.2% to the current 3.0% maximum LOI. Water chemically bound in gypsum also contributes to LOI (about 21% by mass). A cement with an SO3 content of 3.0% may indicate about 6.4% gypsum, which would contribute 1.3% to the LOI of the cement, for a total of 3.5%. If a cement requires 3.5% SO3 for optimal performance, an LOI limit of more than 3.8% would be needed to permit 5% limestone. Table 1 provides estimates of LOI for cements based on gypsum and limestone contents. (These examples exclude any LOI contribution from adsorbed water or CO2 from the atmosphere, labeled as “Clinker” LOI in the table.) Current LOI requirements limit the amount of limestone that can be added to portland cements to typically about 3%. Raising the LOI to a maximum of 3.5% would permit cements to be

1

manufactured closer to the 5% maximum limestone content, while permitting sulfate optimization, allowing a slight improvement in environmental characteristics. Limestone can also raise the insoluble residue content in the cement. Increasing the insoluble residue (IR) limit to 1.5% would generally permit up to 5% limestone to be used in portland cements. Idealized estimates of IR contents are more difficult because the range of IR values for cement ingredients varies more widely. However, Table 2 provides some example calculations for limestones from several cement plants. This ballot proposes to change the LOI limit to a maximum of 3.5% by mass for cements that contain limestone, while retaining the current LOI limits for cements without limestone. The IR limit is proposed to be raised to a maximum of 1.5% by mass for all M 95 portland cements. This proposal has been developed by the Joint AASHTO-ASTM Harmonization Task Group and a similar proposal will be considered by ASTM C01.10 on Cement for C150. Table 1. Idealized Loss on Ignition (LOI) Estimates

“Clinker” LOI

SO3 content

Equivalent gypsum

LOI from gypsum

Limestone content

LOI from limestone

Cement LOI

0 3.00 6.5 1.3 3.5 1.5 2.9 0 3.25 7.0 1.5 3.5 1.5 3.0 0 3.50 7.5 1.6 3.5 1.5 3.1 0 3.75 8.1 1.7 3.5 1.5 3.2 0 3.00 6.5 1.3 4.0 1.8 3.1 0 3.25 7.0 1.5 4.0 1.8 3.2 0 3.50 7.5 1.6 4.0 1.8 3.3 0 3.75 8.1 1.7 4.0 1.8 3.4 0 3.00 6.5 1.3 4.5 2.0 3.3 0 3.25 7.0 1.5 4.5 2.0 3.4 0 3.50 7.5 1.6 4.5 2.0 3.6 0 3.75 8.1 1.7 4.5 2.0 3.7 0 3.00 6.5 1.3 5.0 2.2 3.5 0 3.25 7.0 1.5 5.0 2.2 3.7 0 3.50 7.5 1.6 5.0 2.2 3.8 0 3.75 8.1 1.7 5.0 2.2 3.9

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Table 2. Estimates of Cement Insoluble Residue for Various Limestones*

IR

Limestone content

3% 4% 5%

Limestone 1 14.1 0.72 0.87 1.01

Limestone 2 5.4 0.46 0.52 0.57

Limestone 3 4.0 0.42 0.46 0.50

Limestone 4 17.1 0.81 0.98 1.16

Limestone 5 1.7 0.35 0.37 0.38

*Assumes base cement IR of 0.30%

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Detailed changes: This ballot item is based on AASHTO M 85-15. Proposed additions are underlined and proposed deletions are shown in strikethrough font. Only changes so indicated are being balloted. Other text is provided only to provide context for the proposed changes.

Table 1—Standard Chemical Requirementsa

Cement Type Applicable

Test Method I and IA

II and IIA

II(MH) and

II(MH)A III and IIIA IV V

Aluminum oxide (Al2O3), max, % T 105 — 6.0 6.0 — — — Ferric oxide (Fe2O3), max, % T 105 — 6.0 c 6.0b, c — 6.5 — Magnesium oxide (MgO), max, % T 105 6.0 6.0 6.0 6.0 6.0 6.0 Sulfur trioxide (SO3),d max, % T 105 When (C3A) e is 8% or less 3.0 3.0 3.0 3.5 2.3 2.3 When (C3A) e is more than 8% 3.5 f f 4.5 f f

Loss on ignition, max, % T 105 3.0 3.0 3.0 3.0 2.5 3.0 When limestone is not an ingredient 3.0 3.0 3.0 3.0 2.5 3.0 When limestone is an ingredient 3.5 3.5 3.5 3.5 3.5 3.5 Insoluble residue, max, % T 105 0.75 1.5 0.75 1.5 0.75 1.5 0.75 1.5 0.75 1.5 0.75 1.5 Tricalcium silicate (C3S), e max, % See Annex A1 — — — — 35b — Dicalcium silicate (C2S), e min, % See Annex A1 — — — — 40b — Tricalcium aluminate (C3A), e max, % See Annex A1 — 8 8 15 7b 5c Sum of C3S + 4.75C3A, max, % g — — 100b, h — — — Tetracalcium aluminoferrite plus twice the tricalcium aluminate (C4AF + 2(C3A)), or solid solution (C4AF + C2F), as applicable, max, %

See Annex A1 — — — — — 25c

a See Note 2. b Does not apply when the heat of hydration limit in Table 4 is specified. c Does not apply when the sulfate resistance limit in Table 4 is specified. d It is permissible to exceed the values in the table for SO3 content, provided it has been demonstrated by ASTM C1038/C1038M that the cement with the

increased SO3 will not develop expansion exceeding 0.020 percent at 14 days. When the manufacturer supplies cement under this provision, supporting data shall be supplied to the purchaser. See Note 6.

e See Annex A1 for calculation. f Not applicable. g See Note 5. h In addition, 3-day heat of hydration testing by ASTM C1702 shall be conducted at least once every 6 months. Such testing shall not be used for acceptance or

rejection of the cement, but results shall be reported for informational purposes.

APPENDIX

(Nonmandatory Information)

X1. MANUFACTURER’S CERTIFICATION (MILL TEST REPORT)

4

ABC Portland Cement Company Qualitytown, NJ

Plant: Example Cement Type: II(MH) Date: March 9, 2002 Production Period: March 2, 2002–March 8, 2002

STANDARD REQUIREMENTS M 85, Tables 1 and 3

CHEMICAL PHYSICAL Item Spec. Limit Test Result Item Spec. Limit Test Result SiO2 (%) a 20.6 Air content of mortar (volume %) 12 max 8 Al2O3 (%) 6.0 max 4.4 Fineness (m2/kg)

(Air permeability) 260 min 430 max 377

Fe2O3 (%) 6.0 max 3.3 CaO (%) a 62.9 Autoclave expansion (%) 0.80 max 0.04 MgO (%) 6.0 max 2.2 Compressive strength (MPa) Min: SO3 (%) 3.0 max 3.2 1 day a Loss on ignition (%) 3.0 3.5 max 2.7 3 days 7.0 23.4 Na2O (%) a 0.19 7 days 12.0 29.8 K2O (%) a 0.50 28 days a Insoluble residue (%) 0.75 1.5 max 0.27 Time of setting (minutes) CO2 (%) a 1.5 (Vicat) Limestone (%) 5.0 max 3.5 Initial Not less than

45 124

CaCO3 in limestone (%)

70 min 98 Not more than 375

Inorganic processing addition (ground, granulated blast-furnace slag)

5.0 max 3.0

Potential phase compositions (%)b

Heat of hydration (kJ/kg) ASTM C1702 3 days

c

245 C3S a 59

C2S a 11 ASTM C1038 mortar bar expansion (%)

d 0.010e

C3A 8 max 5 C4AF a 10 C4AF + 2(C3A) a 20 C3S + 4.75 C3A, (%) 100 max 83 a Not applicable. b Adjusted per Annex A1.6. c Test result represents most recent value and is provided for information only. d Required only if percent SO3 exceeds the limit in Table 1, in which case expansion shall not exceed 0.020 percent at 14 days. e Test result for this production period not available. Most recent test result provided.

OPTIONAL REQUIREMENTS

M 85, Tables 2 and 4 CHEMICAL PHYSICAL

Item Spec. Limit Test Result Item Spec. Limit Test Result Equivalent alkalies (%) f 0.52 False set (%) 50 min 82 Chloride (%) f 0.02 Compressive strength (MPa) f Limit not specified by purchaser. Test result provided for information only. 28 days 28.0 min 39.7e We certify that the above-described cement, at the time of shipment, meets the chemical and physical requirements of

M 85-xx or (other) ____________________ specification.

Signature: Title:

Figure X1.1—Example Mill Test Report

5

Standard Specification for

Blended Hydraulic Cement

AASHTO Designation: M 240/M 240M-15 ASTM Designation: C 595/C 595M-15 Subject: Proposal to change requirements for ingredient tolerance in M 240 Rationale: A comment on the 2012 AASHTO Subcommittee on Materials ballot on M 240 questioned whether the current 5% tolerance on ingredients for blended cement ingredients was appropriate, particularly for ingredients used in small percentages. An example was given of a Type IP cement made with a silica fume content of 4%. The ±5% (by mass of finished cement) limit currently in C595 and M 240 means that the cement could contain between 0% and 9% silica fume and still be considered the same product, even though cements with 9% or 0% silica fume might be expected to have significantly different performance characteristics. This proposal responds to the concern expressed and would add limits for variation in ingredient quantity with a 99% probability of compliance. The values proposed are consistent with current production technology and includes variation due to chemical test methods used to determine the amount of ingredient, variation of ingredient chemistry, and variation in amount of the ingredient. The approach is consistent with tolerance provisions for ingredients in ASTM C1697. This ballot item has been developed by AASHTO SOM Technical Section 3a Task Force 09-1 (Joint AASHTO-ASTM Harmonization Task Group) and parallel changes to ASTM C595 have been considered and approved by ASTM, pending results of the AASHTO SOM ballot. Detailed changes:

1. Replace text in Section 15.3 as shown. 2. Add Table 6 and Note 12.

This ballot item is based on AASHTO M 240-15. The specific changes proposed on the current ballot item include deletions shown in strikethrough font and additions shown as underlined. Only changes so indicated are under ballot—additional text is provided for context.

15. CERTIFICATION

15.1. At the request of the purchaser, the manufacturer shall state in writing the source, amount, and composition of the essential constituents used in manufacture of the finished cement and the composition of the blended cement purchased.

15.2. At the request of the purchaser, the manufacturer shall state in writing the nature, amount, and identity of any processing, functional, or air-entraining addition used; and also, if requested, shall supply test data showing compliance of any such processing addition with the provisions of M 327, of any such functional addition with the provisions of ASTM C 688, and of any such air-entraining addition with the provisions of ASTM C 226.

15.3. At the request of the purchaser, the manufacturer shall also state in writing that the amounts of pozzolan, slag, or limestone a constituent in the finished cement will not vary more than the percentages listed in Table 6 with a 99% probability of compliance, 5.0 mass % of the finished cement from lot to lot between lots or within a lot (See Note 12).

Table 6. Permitted Variation in Mass Percentage of Constituent

Constituent

Maximum variation in amount from target,

% by mass of blended cement

Silica fume, metakaolin, limestone ± 2.5 All other constituents ± 5.0

Note 12—To satisfy the 99% probability of compliance, the manufacturing process must be capable of producing a cement such that the standard deviation of the determined mass percentage of silica fume, metakaolin, or limestone in the cement is less than 1%. For all other ingredients, the standard deviations of their determined mass percentages have to be less than 1.9%. The variation in determined mass percentage includes that due to the amount and chemistry of the constituent, as well as that due to variation in verification testing. As an example, Type IP(5) made with silica fume indicates a blended hydraulic cement determined to contain between 2.5% and 7.5% silica fume by mass. A Type IP(20) cement made with fly ash indicates a blended cement determined to contain between 15% and 25% fly ash by mass.

15.4. Upon request of the purchaser in the contract or order, a manufacturer’s certification shall be furnished indicating that the material was tested during production or transfer in accordance with this specification, that it complies with this specification, and a report of the test results shall be furnished at the time of shipment (to include both amount retained on the 45-µm (No. 325) sieve and specific surface by the air permeability method).

Ballot: Revision to AASHTO T 105-14

Rationale: This ballot is to add a chloride value for Table 1, 3rd column in AASHTO T 105 for maximum difference between average of duplicates and certified value. The value proposed is 0.005. The value for difference between duplicates (column 2) currently is 0.003. ASTM adopted this proposed change to C114 earlier this year.

Currently there is no value listed in Table 1 of T 105 for difference between average of duplicates and certified value in Column 3 for analysis of chloride content. The value of 0.005 is proposed, based on the average of CCRL standard deviations from the Proficiency Sample Series data sets CCRL 157 through CCRL 194. The range of values for chloride in these samples was 0.040. Additionally, the NIST standards used as an XRF pressed powder calibration set yielded an RMS value of 0.00152. The data from CCRL and XRF calibration is shown below.

CCRL # average std dev CCRL # average stdev 193 0.012 0.004 194 0.017 0.005 191 0.021 0.006 192 0.04 0.014 189 0.012 0.004 190 0.001 0.003 187 0.006 0.003 188 0.007 0.004 185 0.009 0.003 186 0.006 0.003 183 0.013 0.005 184 0.026 0.008 181 0.014 0.005 182 0.005 0.003 179 0.014 0.005 180 0.005 0.003 177 0.006 0.004 178 0.016 0.006 175 0.027 0.010 176 0.017 0.006 173 0.029 0.010 174 0.005 0.003 171 0.007 0.004 172 0.008 0.003 169 0.005 0.003 170 0.002 0.004 167 0.001 0.004 168 0.006 0.004 165 0.015 0.005 166 0.012 0.004 163 0.006 0.003 164 0.006 0.003 161 0.023 0.008 162 0.013 0.005 159 0.001 0.003 160 0.007 0.003 157 0.008 0.005 158 0.007 0.003 average 0.0121 0.0049 0.0109 0.0046 stdev 0.0081 0.0022 0.0096 0.0027 Max 0.041 Min 0.001 Range 0.040

Figure 1. Calibration curve for x-ray fluorescence (XRF) intensity for chloride contents of portland cements. Specific Changes under Ballot: This ballot is based on T 105-14. The specific changes proposed on the current ballot item include deletions shown in strikethrough font and additions shown as underlined. Only changes so indicated are under ballot—additional text is provided for context.

Table 1—Maximum Permissible Variation in Resultsa

(Column 1) Analyte

(Column 2) Maximum Difference between Duplicatesb

(Column 3) Maximum Difference

of the Average of Duplicates from CRM Certificate Valuesb ,c ,d

SiO2 (silicon dioxide) 0.16 ±0.20 Al2O3 (aluminum oxide) 0.20 ±0.20 Fe2O3 (ferric oxide) 0.10 ±0.10 CaO (calcium oxide) 0.20 ±0.30 MgO (magnesium oxide) 0.16 ±0.20 SO3 (sulfur trioxide) 0.10 ±0.10 LOI (loss on ignition) 0.10 ±0.10 Na2O (sodium oxide) 0.03 ±0.05 K2O (potassium oxide) 0.03 ±0.05 TiO2 (titanium dioxide) 0.02 ±0.03 P2O5 (phosphorus pentoxide) 0.03 ±0.03 ZnO (zinc oxide) 0.03 ±0.03 Mn2O3 (manganic oxide) 0.03 ±0.03 S (sulfide sulfur) 0.01 e

Cl (chloride) 0.003 ±0.005

IR (insoluble residue) 0.10 e

Cx (free calcium oxide) 0.20 e

CO2 (carbon dioxide) 0.12 e, f Alksol (water-soluble alkali)g 0.75/ w g e

Chlsol (chloroform-soluble organic substances) 0.004 e

a When all seven Certified Reference Material (CRM) cements are required, as for demonstrating performance of rapid test methods, at least six of the seven shall be within the prescribed limits, and the seventh shall differ by no more than twice that value. When more than seven CRMs are used, as for demonstrating the performance of rapid test methods, at least 77 percent shall be within the prescribed limits, and the remainder no more than twice the value. When a lesser number of CRM cements are required, all of the values shall be within the prescribed limits.

b Where no value appears in Column 3, CRM certificate values do not exist. In such cases, only the requirement for differences between duplicates shall apply.

c Interelement corrections may be used for any oxide standardization provided improved accuracy can be demonstrated when correction is applied to all seven CRM cements.

d Where a CRM certificate value includes a subscript number, that subscript number shall be treated as a valid significant figure. e Not applicable. No certificate value given. f Demonstrate performance by analysis, in duplicate, of at least one portland cement. Prepare three standards, each in duplicate:

Standard A shall be selected portland cement, Standard B shall be Standard A containing 2.00 percent Certified CaCO3 (e.g., NIST 915a), Standard C shall be Standard A containing 5.00 percent Certified CaCO3. Weigh and prepare two separate specimens of each standard. Assign the CO 2 content of Standard A as the average of the two values determined, provided they agree within the required limit of Column 2. Assign CO2 values to Standards B and C as follows: Multiply the Certified CaCO3 value (Y) for CO2 (from the certificate value) by the mass fraction of Certified CaCO3 added to that standard (percentage added divided by 100); multiply the value determined for Standard A by the mass fraction of Standard A in each of the other standards (i.e., 0.98 and 0.95 for Standards B and C, respectively); add the two values for Standards A and B, respectively; call these values B and C.

Example: B = 0.98A + 0.02Y. C = 0.95A + 0.05Y. where for Certified CaCO3, if Y= 39.9 percent B = 0.98A + 0.80 percent by mass. C = 0.95A + 2.00 percent by mass. Maximum difference between the duplicate CO2 values for Standards B and C, respectively, shall be 0.17 and 0.24 percent by mass.

Averages of the duplicate values for Standards B and C shall differ from their assigned values (B and C) by no more than 10 percent of those respective assigned values.

g w = mass, in grams, of samples used for the test.

Standard Specification for

Portland Cement

AASHTO Designation: M 85-15 ASTM Designation: C150/C150M-15

Subject: Revision to AASHTO M 85 - Additional Information for Calculating Base Cement Oxides for Portland Cements Containing Limestone

Rationale: This ballot is in response to a request to include additional information in AASHTO M 85 and ASTM C150 on a procedure for calculating base cement oxides where the oxide analyses of the finished cement, the limestone, and inorganic processing addition, percent limestone, and percent inorganic processing addition are known. For cements containing limestone, inorganic processing additions, or a combination of limestone and inorganic processing additions, base cement oxides can be used to calculate base cement potential phase composition, and these values are adjusted for use of limestone or inorganic processing additions in accordance with Annex A1.2. As background, the current provisions for adjusting potential phase composition calculations for use of limestone and inorganic processing addition were first introduced into AASHTO M 85 and ASTM C150 in the 2009 harmonized editions of these standards. These changes included:

• New Section 5.1.4 provisions for use of inorganic processing additions • Revisions to Annex A1.2 potential phase composition equations and inclusion of new Note A1.2,

an example for adjusting potential phase composition of base cement for limestone and inorganic processing addition content

• Revisions of Appendix X1.1 to provide example reporting of inorganic processing addition content and adjusted potential phase composition of finished cement

• New Appendix X1.2 on Additional Data to provide analysis of inorganic processing additions and base cement potential phase composition.

Changes proposed by this ballot would: • Revise section 5.1.3 to include requirements to report amount of limestone and oxide analysis of

limestone similar to existing provisions of 5.1.4 for inorganic processing additions. • Remove the phrase “(or range)” from 5.1.4 so that a single value is reported and potentially used

in determining the phase composition of cement. • Include new Note A2 to provide an example method to determine base cement oxide analysis

where the oxide analysis of the finished cement, the limestone, and inorganic processing addition, percent limestone, and percent inorganic processing addition are known. Renumber subsequent existing Annex notes.

• Revise Appendix X1.1 such that example mill test report values are consistent with reported analysis of finished cement, limestone, inorganic processing addition, and provisions of Annex A1.2 for determining base cement potential phase composition using the method outlined in Note A2 for determining base cement oxides.

• Revise Appendix X1.2 to add example reporting of limestone oxide analysis under additional information and revise base cement potential phase values to be consistent with example finished

1

cement oxide analysis, limestone oxide analysis, inorganic processing additions oxide analysis. The method to determine the base cement phase composition proposed in the new Note A2 is not required, and is permitted by current provisions of M 85. This proposal would provide additional information on this calculation. This proposal has been developed by the Joint AASHTO-ASTM Harmonization Task Group and a similar proposal is being considered by ASTM Subcommittee C01.10 for C150. This ballot item is based on AASHTO M 85-15. Only additions to text shown in underline and deletions shown in strikethru font are being balloted. Other text is included for information only. Where necessary, tables, figures, notes, footnotes, and section numbers will be renumbered editorially.

5. INGREDIENTS 1

5.1. The cement covered by this specification shall contain no ingredients except as follows: 2

5.1.1. Portland Cement Clinker. 3

5.1.2. Water or Calcium Sulfate or Both—The amounts shall be such that the limits shown in Table 1 for sulfur 4 trioxide and loss on ignition shall not be exceeded. 5

5.1.3. Limestone—The amount shall be not more than 5.0 percent by mass such that the chemical and physical 6 requirements of this standard are met (see Note 3). The limestone, defined in ASTM C51, shall be naturally 7 occurring and consist of at least 70 percent by mass of one or more of the mineral forms of calcium 8 carbonate. If limestone is used, the manufacturer shall report the amount used, expressed as a percentage of 9 cement mass, along with the oxide composition of the limestone. 10 Note 3—The standard permits up to 5 percent by mass of the final cement product to be naturally 11 occurring, finely ground limestone, but does not require that limestone be added to the cement. Cement 12 without ground limestone can be specified in the contract or order. 13

5.1.4. Inorganic Processing Additions—The amount shall not be more than 5.0 percent by mass of cement. Not 14 more than one inorganic processing addition shall be used at a time. For amounts greater than 1.0 percent, 15 they shall have been shown to meet the requirements of M 327 for inorganic processing additions in the 16 amount used or greater. If an inorganic processing addition is used, the manufacturer shall report the amount 17 (or range) used, expressed as a percentage of cement mass, along with the oxide composition of the 18 processing addition (see Note 4). 19 Note 4—These requirements are based on data and recommendations by Taylor.i 20

21

ANNEX 22

(Mandatory Information) 23

A1. CALCULATION OF POTENTIAL CEMENT PHASE COMPOSITION 24

A1.1. All values calculated as described in this annex shall be rounded according to ASTM E29. When evaluating 25 conformance to a specification, round values to the same number of places as the corresponding table entry 26

2

before making comparisons. The expressing of chemical limitations by means of calculated assumed phases 27 does not necessarily mean that the oxides are actually or entirely present as such phases. 28

A1.2. When expressing phases, C = CaO, S = SiO2, A = Al2O3, F = Fe2O3. For example, C3A = 3CaO·Al2O3. 29 Titanium dioxide and phosphorus pentoxide (TiO2 and P2O5) shall not be included with the Al2O3 content. 30 See Note A1. 31 Note A1—When comparing oxide analyses and calculated phases from different sources or from different 32 historic times, be aware that they may not have been reported on exactly the same basis. Chemical data 33 obtained by Reference and Alternate Test Methods of T 105 (wet chemistry) may include titania and 34 phosphorous as alumina unless proper correction has been made (see T 105), while data obtained by rapid 35 instrumental methods usually do not. This can result in small differences in the calculated phases. Such 36 differences are usually within the precision of the analytical methods, even when the methods are properly 37 qualified under the requirements of T 105. 38

A1.3. When the ratio of percentages of aluminum oxide to ferric oxide is 0.64 or more, the percentages of 39 tricalcium silicate, dicalcium silicate, tricalcium aluminate, and tetracalcium aluminoferrite shall be 40 calculated from the chemical analysis as follows: 41

(A1.1) 42

43 (A1.2) 44

45 (A1.3) 46

47 (A1.4) 48

A1.3.1. When the alumina-ferric oxide ratio is less than 0.64, a calcium aluminoferrite solid solution (expressed as 49 ss(C4AF + C2F)) is formed. No tricalcium aluminate will be present in cements 50 of this composition. Dicalcium silicate shall be calculated as in Equation A1.2. Contents of this solid 51 solution and of tricalcium silicate shall be calculated by the following formulas: 52

(A1.5) 53 54

(A1.6) 55

A1.4. If no limestone or inorganic processing additions are used in the cement, or in the absence of information on 56 limestone or inorganic processing additions used in the cement, phases shall be calculated using procedures 57 in Equations A1.1 to A1.6 without adjustment. 58

A1.5. In the absence of information on limestone or inorganic processing additions content, results shall note that 59 no adjustment has been made for possible use of limestone or inorganic processing additions. 60

A1.6. When inorganic processing additions, limestone, or both are used with the base cement (portland cement 61 clinker and any added calcium sulfate), the contents of C3S, C2S, C3A, and C4AF, shall be adjusted as 62 follows: 63

A1.6.1. The percentage of C3S, C2S, C3A, and C4AF in the base cement (See Note A2) shall be determined based on 64 chemical analyses using methods in T 105 and using Equations A1.1 to A1.6 as appropriate. The contents of 65

( ) ( )( ) ( )( )

3 2

2 3 2 3

3

tricalcium silicate (C S) 4.071 % CaO 7.600 % SiO

6.718 % Al O 1.430 % Fe O

2.852 % SO

= × − × −

× − × −

×

2 2 3dicalcium silicate (C S) (2.867 % SiO ) (0.7544 % C S)= × − ×

3 2 3 2 3tricalcium aluminate (C A) (2.650 % Al O ) (1.692 % Fe O )= × − ×

4 2 3tetracalcium aluminoferrite (C AF) 3.043 % Fe O= ×

4 2 2 3 2 3ss(C AF C F) (2.100 % Al O ) (1.702 % Fe O )+ = × + ×

3 2

2 3 2 3

3

tricalcium silicate (C S) (4.071 % CaO) (7.600 % SiO ) (4.479 % Al O ) (2.859 % Fe O ) (2.852 % SO )

= × − × −× − × −×

3

each of these phases shall be adjusted to account for the use of limestone or inorganic processing additions 66 as follows: 67

(A1.7) 68

where: 69 Xb = the percentage by mass of C3S, C2S, C3A, or C4AF in the base cement (portland cement clinker 70

and any calcium sulfate); 71 L = the percentage by mass of limestone; 72 P = the percentage by mass of inorganic processing addition; and 73 Xf = the percentage by mass of C3S, C2S, C3A, or C4AF in the finished cement. 74

75 The adjusted values for the finished cement shall be reported on the manufacturer’s report. 76

77 Note A2— Where the oxide analysis of the finished cement, the limestone, and inorganic processing 78 addition, are known along with the mass percentage of limestone (L) and mass percentage of inorganic 79 processing addition (P), one method of determining the base cement oxide composition is to use the 80 following equation: 81 Ob = 100 × (Of - (L/100 × Ol) - (P/100 × Op))/(100 - L - P) 82 where: 83 Ob = the base cement oxide content (% by mass of base cement) 84 Of = the finished cement oxide content (% by mass of finished cement) 85 Ol = the limestone oxide content (% by mass of limestone) 86 Op = the inorganic processing addition oxide content (% by mass of inorganic processing addition). 87 The base cement phase composition can be determined using these values of oxide analyses in equations 88 A1.1 to A1.6. Eq. A1.7 is used to calculate the adjusted phase composition. 89

90 91

Note A23—For example, where the cement includes 3.5 percent limestone and 3.0 percent of an inorganic 92 processing addition and the base cement has 60 percent C3S, 15 percent C2S, 7 percent C3A, and 10 percent 93 C4AF, the adjusted phase composition is: 94

95 96

97 98

99 100

101 102

A1.6.2. Only the percentages of C3S, C2S, C3A, and C4AF shall be adjusted by the procedure in Section A1.6.1. 103

A2. LIMESTONE CONTENT OF PORTLAND CEMENT 104

(100 )100f b

L PX X − −= ×

360 (100 3.5 3.0)C S 56%

100f× − −

= =

215 (100 3.5 3.0)C S 14%

100f× − −

= =

37 (100 3.5 3.0)C A 7%

100f× − −

= =

410 (100 3.5 3.0)C AF 9%

100f× − −

= =

4

A2.1. When limestone is used, the limestone content in portland cement shall be derived from the determination of 105 CO2 in the finished cement. Analysis of CO2 shall be based on methods described in T 105. The percent 106 limestone in the cement is calculated from the CO2 analysis based on the CO2 content of the limestone used. 107 The limestone content of the cement is calculated as follows: 108

109

(A2.1) 110

111 Note A34—For example, where the determined CO2 content in the finished cement equals 1.5 percent and 112 the CO2 content of the limestone equals 43 percent (CaCO3 in limestone equals 98 percent), then: 113

114

A2.2. This specification requires that the limestone to be used must contain a minimum of 70 percent CaCO3. The 115 manufacturer shall include the CaCO3 content of the limestone on the manufacturer’s report. Calculate the 116 CaCO3 content of the limestone as follows: % CaCO3 = 2.274 × % CO2. 117 Note A45—For verification of limestone content of cement, the purchaser must analyze for CO2 content 118 and make a correction for the content of CaCO3 in the limestone in order for the data to be comparable to 119 the manufacturer’s report. 120

A2.3. Portland cements that do not contain limestone can contain baseline levels of CO2 inherent in manufacture, 121 for example, due to carbonation. This baseline CO2 content is included as part of any calculated limestone 122 content. 123

124

APPENDIX 125

(Nonmandatory Information) 126

X1. MANUFACTURER’S CERTIFICATION (MILL TEST REPORT) 127

X1.1. To provide uniformity for reporting the results of tests performed on cements under this specification, as 128 required by Section 15 of M 85, Manufacturer’s Certification, an example Mill Test Report is shown in 129 Figure X1.1. 130

X1.2. The identity information given should unambiguously identify the cement production represented by the 131 Mill Test Report and may vary, depending on the manufacturer’s designation and purchaser’s requirements. 132

X1.3. The Manufacturer’s Certification statement may vary, depending on the manufacturer’s procurement order 133 or legal requirements, but should certify that the cement shipped is represented by the certificate and that the 134 cement conforms to applicable requirements of the specification at the time it was tested (or retested) or 135 shipped. 136

X1.4. The sample Mill Test Report has been developed to reflect the chemical and physical requirements of this 137 specification and recommends reporting all analyses and tests normally performed on cements meeting 138 M 85. Purchaser reporting requirements should govern if different from normal reporting by the 139 manufacturer or from those recommended here. 140

X1.5. Cements may be shipped prior to later-age test data being available. In such cases, the test value may be left 141 blank. Alternatively, the manufacturer can generally provide estimates based on historical production data. 142 The report should indicate if such estimates are provided. 143

2

2

% CO in the cement100 % limestone in cement

% CO in the limestone× =

1.5 100 3.5% limestone content in cement43

× =

5

X1.6. In reporting limits from the tables in M 85 on the Mill Test Report, only those limits specifically applicable 144 should be listed. In some cases, M 85 table limits are superseded by other provisions. 145

X1.7. When limestone or inorganic processing additions or both are used in the cement, additional data are 146 reported by the manufacturer. An example additional data report is shown in Figure X1.2. 147

148 149

6

ABC Portland Cement Company Qualitytown, NJ

Plant: Example Cement Type: II(MH) Date: March 9, 2002 Production Period: March 2, 2002–March 8, 2002

STANDARD REQUIREMENTS M 85, Tables 1 and 3

CHEMICAL PHYSICAL Item Spec. Limit Test Result Item Spec. Limit Test Result SiO2 (%) a 20.6 Air content of mortar (volume %) 12 max 8 Al2O3 (%) 6.0 max 4.4 Fineness (m2/kg)

(Air permeability) 260 min 430 max 377

Fe2O3 (%) 6.0 max 3.3 CaO (%) a 62.9 Autoclave expansion (%) 0.80 max 0.04 MgO (%) 6.0 max 2.2 Compressive strength (MPa) Min: SO3 (%) 3.0 max 3.2 1 day a Loss on ignition (%) 3.0 max 2.7 3 days 7.0 23.4 Na2O (%) a 0.19 7 days 12.0 29.8 K2O (%) a 0.50 28 days a Insoluble residue (%) 0.75 max 0.27 Time of setting (minutes) CO2 (%) a 1.51.2 (Vicat) Limestone (%) 5.0 max 3.5 Initial Not less than

45 124

CaCO3 in limestone (%)

70 min 9879 Not more than 375

Inorganic processing addition (ground, granulated blast-furnace slag)

5.0 max 3.0

Potential phase compositions (%)b

Heat of hydration (kJ/kg) ASTM C1702 3 days

c

245 C3S a 59

C2S a 1110 ASTM C1038 mortar bar expansion (%)

d 0.010e

C3A 8 max 5 C4AF a 10 C4AF + 2(C3A) a 20 C3S + 4.75 C3A, (%) 100 max 83 a Not applicable. b Adjusted per Annex A1.6. c Test result represents most recent value and is provided for information only. d Required only if percent SO3 exceeds the limit in Table 1, in which case expansion shall not exceed 0.020 percent at 14 days. e Test result for this production period not available. Most recent test result provided.

OPTIONAL REQUIREMENTS

M 85, Tables 2 and 4 CHEMICAL PHYSICAL

Item Spec. Limit Test Result Item Spec. Limit Test Result Equivalent alkalies (%) f 0.52 False set (%) 50 min 82 Chloride (%) f 0.02 Compressive strength (MPa) f Limit not specified by purchaser. Test result provided for information only. 28 days 28.0 min 39.7e We certify that the above-described cement, at the time of shipment, meets the chemical and physical requirements of

M 85-xx or (other) ____________________ specification.

Signature: Title:

150 Figure X1.1—Example Mill Test Report 151

7

ABC Portland Cement Company Qualitytown, NJ

Plant: Example Cement Type: II(MH) Date: March 9, 2002

Production Period: March 2, 2002–March 8, 2002

Additional Data

152 Limestone Inorganic Processing Addition Data

Type ---- Ground, Granulated Blast-Furnace Slag

Amount (%) 3.5 3.0

SiO2 (%) 12.9 33.1 Al2O3 (%) 3.0 10.9 Fe2O3 (%) 1.0 1.1 CaO (%) 43.5 44.4 SO3 (%) 0.6 0.2

Base Cement Phase Composition

C3S (%) 63

C2S (%) 1211

C3A (%) 5

C4AF (%) 11

153 We certify that the above-described data represents the materials used in the cement manufactured during the

production period indicated.

Signature: Title:

154 Figure X1.2—Example Additional Data Report 155

8

AASHTO STANDING COMMITTEE ON RESEARCH AMERICAN ASSOCIATION OF STATE HIGHWAY AND TRANSPORTATION

OFFICIALS

I. PROBLEM NUMBER

To be assigned by NCHRP

II. PROBLEM TITLE

Durability and Service Life of Cracked Concrete in Structures

(Development of a Recommended Practice)

III. RESEARCH PROBLEM STATEMENT

Concrete is the second most used commodity in the world. It is well documented that the majority of concrete durability problems in transportation infrastructure are caused by the ingress of water and salts (e.g., corrosion of reinforcing steel, freezing and thawing damage, etc.). Many improvements have been implemented in specifying longer lasting less-permeable concrete. Cracking in concrete is especially problematic as it provides a direct pathway for external fluids to enter into it and subsequently cause damage. Bridge engineers need to know what remaining service life is available, especially in concrete decks, when prioritizing the bridge preservation program. Research is also needed to determine what to do or not do with cracked structures, and how to maintain and repair them to maximize service life and minimize life-cycle cost. Improvements in the lifespan of concrete will lead to tremendous economic savings over the life-cycle of structures, and a reduced environmental impact from concrete reconstruction. This work will provide the practitioner with a recommended practice on how corrosion, freeze-thaw and other deterioration mechanisms in concrete are influenced by cracking, and therefore provide information necessary to more effectively perform preventative maintenance on the concrete.

IV. LITERATURE SEARCH SUMMARY

The TRB E-Circular 107 on Control of Cracking in Concrete notes that laboratory studies have shown that crack width has a significant influence on corrosion, but also notes “there are controversial findings about the impact of crack width on corrosion rate...” Unfortunately, almost all previous research and testing has focused on the penetrability of the concrete matrix or corrosion damage (NCHRP Report 558), and has neglected the impact of cracking. For example, in the case of concrete bridge decks, quantifying how cracks affect reinforced concrete’s durability and service life will have tremendous benefits for bridge life-cycle management and preventative maintenance. Although significant advancements have been made to identify the

1

causes of and reduce early-age cracking in concrete, many existing structures are cracked, and early-age cracking is even observed in many newly constructed bridge decks. Nationally, it is estimated that 62% of bridge decks crack prematurely, and the annual corrosion damage for structural concrete is $8.3 billion.

V. RESEARCH OBJECTIVE

Although attempts can be made to minimize cracking, it is unrealistic to expect that concrete will not crack. Laboratory and field research is needed to quantify how these cracks impact the moisture and salt penetrability and hence the durability of concrete. This research is needed to improve the prediction of the impact of cracks on the durability of concrete and the subsequent impact on predictive service life models. This will focus on steel reinforced structures but exclude jointed plain concrete pavements. It should consider test methods that can be used to evaluate the durability of cracked concrete and the characteristics of cracks in field placed concrete. The research must consider concrete infrastructure applications in different exposure conditions, and address the evaluation of potential service life models with regard to their ability to characterize durability performance, ease of implementation in current software, and other relevant factors, and the approach for validating the proposed enhancements for a range of materials and environments. Also needed are enhancements to existing service life modeling software. The outcome of the research will be an AASHTO recommended practice that owners can use to determine the best options for various cracking under different environmental conditions, potentially for use in asset management. VI. ESTIMATE OF PROBLEM FUNDING AND RESEARCH PERIOD

$650,000 and 3 years

VII. URGENCY, PAYOFF POTENTIAL, AND IMPLEMENTATION

The outcomes of this research will be to develop a scientifically based recommended practice procedure that enables crack width, severity and environmental conditions to be considered appropriately when estimating service life and life cycle cost of cracked concrete structures. It is estimated that initiating best practices for preventative maintenance could save up to 25% or $2 billion annually.

VIII. PERSON(S) DEVELOPING THE PROBLEM

TRB Concrete Section Committees with input from AASHTO Subcommittees on Materials, Bridges and Structures, Construction, and Maintenance.

IX. PROBLEM MONITOR

To be determined.

X. DATE AND SUBMITTED BY

2

Revision of August 6, 2015

Endorsed by the TRB Concrete Committees, the FHWA Concrete Team, AASHTO Subcommittee on Construction, and AASHTO Subcommittee on Materials Technical Sections 3a – Cement, 3b – Plastic Concrete Properties and 3c – Hardened Concrete Properties.

Tyson D. Rupnow, Ph.D, P.E. Associate Director, Research Louisiana Transportation Research Center 4101 Gourrier Avenue Baton Rouge, LA 70808 Office: 225-767-9124 Fax: 225-767-9108 Email: Tyson.Rupnow@la.gov

Mark E. Felag, P.E. Managing Engineer Rhode Island Department of Transportation Two Capitol Hill – Room 022 Providence, RI 02903 Office: 401-222-2524 x-4130 Fax: 401-222-3489 Email: mark.felag@dot.ri.gov

3

NCHRP Project 20-05

Synthesis Topic 47-01

Control of Cracking in Concrete Bridges

Tentative Scope Despite many advances in bridge design, concrete technology, and corrosion-resistant reinforcement, cracking of concrete continues to be a concern for bridge owners; particularly for bridges exposed to severe environments. The presence of cracks provides a direct path for water and chlorides to penetrate the concrete and reach the reinforcement. This in turn, can lead to freeze-thaw damage to the concrete or corrosion of the reinforcement. However, there appears to be little or no correlation between crack width, corrosion, and service life. The AASHTO LRFD Bridge Design Specifications provides requirements for minimum amounts of reinforcement and maximum spacing of reinforcement to control crack widths. In some cases, these requirements are based on in-depth research, while others are based on experience. Nevertheless, bridge owners find the need to supplement the AASHTO provisions with their own requirements. The control of cracking for aesthetic, durability, and structural reasons becomes increasingly important as service life goals are extended and higher strength concrete, higher strength reinforcement, and different types of reinforcement are used in bridge construction. The overall goal of the synthesis is to provide a compilation of methods used to control cracking in concrete bridges and the influence of cracking on long-term durability. Specifically, the synthesis will address the following types of cracking:

• Flexural cracks in nonprestressed members • Shrinkage cracks in nonprestressed concrete bridge decks • Splitting cracks in pretensioned anchorage zones • Vertical cracks in pretensioned beams prior to transfer of the prestressing force • Reflective cracking in cast-in-place partial-depth decks and overlays

The synthesis will include information related to the use of steel reinforcement with specified yield strengths from 60 to 100 ksi, corrosion-resistant steel reinforcement, and fiber-reinforced polymer reinforcement. The selection of concrete constituent materials and construction methods to reduce the potential for shrinkage cracking will be addressed. Finally, the synthesis will address remedial measures that may be taken after cracks occur. The synthesis will be beneficial to bridge owners and designers and the AASHTO Subcommittee on Bridges and Structures in their Grand Challenges to extend bridge service life and advance the AASHTO specifications. Information Sources:

1. AASHTO LRFD Bridge Design Specifications, Seventh Edition, American Association of State Highway and Transportation Officials, Washington, DC, 2014.

2. Darwin, D., “Low-Cracking High-Performance Concrete Bridge Decks,” Concrete Bridge Views, Issue No. 78, September/October 2014, available at http://www.concretebridgeviews.com.

3. Frosch, R. J., “Fundamentals of Crack Control in Reinforced Concrete,” Concrete Bridge Views, Issue No. 77, July/August 2014, available at http://www.concretebridgeviews.com.

4. Lwin, M. M. and Russell, H. G., “Reducing Cracks in Concrete Bridge Decks,” HPC Bridge Views, Issue No. 45, Fall 2006, p. 1, available at http://www.concretebridgeviews.com.

5. ACI Committee 224, “Control of Cracking in Concrete Structures (ACI 224R),” American Concrete Institute, Farmington Hills, MI, 45 pp.

TRB Staff Jon Williams Phone: 202-334l-3245 Email: jwilliams@nas.edu Meeting Dates First Panel: Teleconference with Consultant: Second Panel:

Carryover Queries and FYIs for TS 3a

Std./Page Section/Figure

Number Query

all — Many of the queries below are “catch-ups.” As you prepare your tech section ballots, please ensure that standards include the following:

• Updates to referenced documents, both listed and text citations.

• References (uncited background info), if any.

• A complete, up-to-date list of keywords, which are essential for online searchability.

• Annex titles.

MEF Response: OK

Please provide keywords for the standards listed below:

Part 1: M 152M/M 152, M 303.

Part 2: T 132, T 162, T 218, T 219, T 232, T 353.

MEF Response: Could this be done by one of our Technical Writers? This would add consistency to not only 3a standards but others as well.

T 107-1 2.2 ASTM E29 is listed in referenced documents but it is not cited in the text. If it should be cited, please indicate where. Otherwise, please mark it for deletion.

MEF Response: I have corrected on a draft.

T 131-8 on Annexes The annexes had been wrongly numbered as A1, A2, etc. instead of A, B, etc. This has been corrected. Please check that all callouts of other sections, figures, tables, and notes are correctly updated.

MEF Response: They are still A1, A2, etc. Is this correct?

T 137-1 2.2 ASTM C91/C91M is listed in referenced documents but it is not cited in the text. If it should be cited, please indicate where. Otherwise, please mark it for deletion.

MEF Response: I have corrected a draft.

T 353-1 2.2

The following ASTM standards are listed as referenced documents but are not cited: C115/C115M, C204, and C430.

1. Which standards, if any, should be cited in the text and where?

2. Which standards, if any, should be listed in a separate references section?

MEF Response: Is this T137 or another standard? The standards listed are NOT referenced in T137.

AASHTO Subcommittee on Materials

Technical Section 3a – Hydraulic Cement

Ballot for Keywords

M 152 – Flow Table for Use in Tests of Hydraulic Cement - Hydraulic Cement, Portland Cement, Flow.

M 303 – Lime for Asphalt Mixtures - Lime, Hydrated Lime, Lime for Asphalt.

T 132 – Tensile Strength of Hydraulic Cement Mortars – Hydraulic Cement, Strength, Tensile Strength.

T 162 - Mechanical Mixing of Hydraulic Cement Pastes and Mortars of Plastic Consistency – Hydraulic Cement, Pastes, Plastic Consistency, Mixing.

T 218 – Sampling Hydrated Lime – Lime, Sampling, Hydrated Lime.

T 219 - Testing Lime for Chemical Constituents and Particle Sizes – Lime, Testing, Chemical Testing.

T 232 - Determination of Lime Content in Lime-Treated Soils by Titration – Lime, Titration, Testing.

T 353 - Particle Size Analysis of Hydraulic Cement and Related Materials by Light Scattering – Portland Cement, Hydraulic Cement, Testing, Particle Size, Light Scattering.

Standard Method of Test for

Autoclave Expansion of Hydraulic Cement

AASHTO Designation: T 107M/T 107-11 (2015) ASTM Designation: C151/C151M-09

1. SCOPE

1.1. This test method covers determination of the autoclave expansion of hydraulic cement by means of a test on a neat cement specimen.

1.2. The values stated in either SI units or inch-pound units are to be regarded separately as standard. The values stated in each system may not be exact equivalents; therefore, each system shall be used independently of the other. Combining values from the two systems may result in non-conformance with the standard.

1.3. This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific precaution statements, see the section on Safety Precautions.

2. REFERENCED DOCUMENTS

2.1. AASHTO Standards: M 201, Mixing Rooms, Moist Cabinets, Moist Rooms, and Water Storage Tanks Used in the

Testing of Hydraulic Cements and Concretes M 210M/M 210, Use of Apparatus for the Determination of Length Change of Hardened

Cement Paste, Mortar, and Concrete T 129, Amount of Water Required for Normal Consistency of Hydraulic Cement Paste T 162, Mechanical Mixing of Hydraulic Cement Pastes and Mortars of Plastic Consistency

2.2. ASTM Standards: C856, Standard Practice for Petrographic Examination of Hardened Concrete C1005, Standard Specification for Reference Masses and Devices for Determining Mass and

Volume for Use in the Physical Testing of Hydraulic Cements C1157/C1157M, Standard Performance Specification for Hydraulic Cement E29, Standard Practice for Using Significant Digits in Test Data to Determine Conformance

with Specifications

3. SIGNIFICANCE AND USE

3.1. The autoclave expansion test provides an index of potential delayed expansion caused by the hydration of CaO or MgO or both, when present in hydraulic cement.1

Standard Method of Test for

Air Content of Hydraulic Cement Mortar

AASHTO Designation: T 137-12 ASTM Designation: C185-08

1. SCOPE

1.1. This test method covers the determination of the air content of hydraulic cement mortar under the conditions hereinafter specified.

1.2. The values stated in SI units are to be regarded as the standard.

1.3. Values in SI shall be obtained by measurement in SI units or by appropriate conversion, using the Rules for Conversion and Rounding in IEEE/ASTM SI10, of measurements made in other units.

1.4. This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Warning—Fresh hydraulic cementitious mixtures are caustic and may cause chemical burns to skin and tissue upon prolonged exposure.

2. REFERENCED DOCUMENTS

2.1. AASHTO Standards: M 85, Portland Cement M 152M/M 152, Flow Table for Use in Tests of Hydraulic Cement M 240M/M 240, Blended Hydraulic Cement T 106M/T 106, Compressive Strength of Hydraulic Cement Mortar (Using 50-mm or 2-in.

Cube Specimens) T 127, Sampling and Amount of Testing of Hydraulic Cement T 162, Mechanical Mixing of Hydraulic Cement Pastes and Mortars of Plastic Consistency

2.2. ASTM Standards: C91/C91M, Standard Specification for Masonry Cement C778, Standard Specification for Standard Sand C1005, Standard Specification for Reference Masses and Devices for Determining Mass and

Volume for Use in the Physical Testing of Hydraulic Cements E438, Standard Specification for Glasses in Laboratory Apparatus E694, Standard Specification for Laboratory Glass Volumetric Apparatus

2.3. IEEE/ASTM Standard: SI10, American National Standard for Metric Practice

TECHNICAL SECTION 3A, HYDRAULIC CEMENTS POZZOLANIC MATERIALSSTANDARDS STATUS AS OF July 1, 2015

SAMPLING HYDRAULIC CEMENT

T127-15* C 183-13 ASTM C 183-15YES -PRAC

SRP

AUTOCLAVE EXPANSION OF PORTLAND CEMENT

T 107M/T 107-11(2015)

C 187-11e1 ASTM C 187- 11e1 NONORMAL CONSISTENCY OF

HYDRAULIC T 129-14

COM. STRENGTH OF HYDRAULIC CEMENT OF

MORTAR CUBEST 106M/T 106 - 15 C 109/C109M-13

ASTM C 109/C109M-13

NO

C 151/C151M-09ASTM C

151/C151M-09NO

BLENDED HYDRAULIC CEMENTS

M 240M/M 240-15*

C 595/C 595M-15ASTM C

595/C595M-15NO

LIME FOR SOIL STAB. M 216-13

NONE NO

C150/C150M-15

C230/C230M-13ASTM C

230/C230M-14

ASTM C 150/C150M-15

NO

C977-10 ASTM C 977-10YES - TITLE

MEF

TIME OF SETTING OF HYDRAULIC CEMENT BY

VICAT NEEDLET 131-15 C 191-13 ASTM C 191-13 NO

FINENESS OF PC BY THE TURBIDIMETER

T 98-12* C 115-10e1 ASTM C 115-10e1 NO

CHEMICAL ANALYSIS HYDRAULIC CEMENT

LIME FOR ASPHALT MIXTURES

M 303-89 (2014) NONE

PROCESSING ADDITIONS M 327-11(2015) ASTM C 465-10 ASTM C 465-10 NO

T 105-14* C 114-13 ASTM C 114-15 YES SRP

APP. FOR MEAS. LENGTH CHANGE OF PASTE,

MORTAR, CONCRETE

C490/C 490M-11e1

ASTM C 490/C 490M -11e1

YES - PRAC

MEF

MOIST CAB, ROOMS, ETC. USED IN TESTING CEM. &

CONCRETE

FLOW TABLE FOR USE IN TESTING HYD. C.

PORTLAND CEMENT

RESTITLE AASHTO # ASTM # LATEST ASTM ACTION

M 152M/M 152 -15

M 85-15

M 201-15

M210M/M 210-14

SRP

C511-13 ASTM C 511-13

YES

NO

ATTACH

10 & 11

12

13

4 & 14

15

TECHNICAL SECTION 3A, HYDRAULIC CEMENTS POZZOLANIC MATERIALSSTANDARDS STATUS AS OF July 1, 2015

T 218-86 (2013) NONE NONE NOSAMPLING HYDRATED

LIME

T 192-11(2015) C 430-08 ASTM C 430-08 NOFINENESS OF HYDRAULIC CEMENT BY THE NO. 325

SIEVE

* SOME DIFFERENCES BETWEEN THE TWO STANDARDS

DET. OF LIME CONTENT BY TITRATION

NONONENONET 232-90 (2013)

T 219-87 (2013) NONE NONE NOTESTING LIME FOR CHEM.

CON. AND PART. SIZES

PARTICLE SIZE BY LIGHT SCATTERING

NONONENONET 353-14

ASTM C 451-13 NOEARLY STIFFENING OF PORTLAND CEMENT

(PASTE METHOD)

T 185-15 C 359-13 ASTM C 359 – 13 NOEARLY STIFFENING OF PORTLAND CEMENT (MORTAR METHOD)

T 186-15* C 451-13

T 162-15 C305-13 ASTM C 305-14 YES SRPMECHANICAL MIXING OF

HYDRAULIC CEMENT PASTES AND MORTARS

T 154-15 C 266-13 ASTM C 266-13 NOTIME OF SETTING OF

HYDRAULIC CEMENT BY GILLMORE NEEDLES

T 153-13 C 204-11e1 ASTM C 204-11e1 NOFINENESS OF P.C. BY AIR

PERM. APPARATUS

AIR CONTENT OF HYDRAULIC CEMENT

MORTART 137-12 C 185-08 ASTM C 185-08 NO

DENSITY OF HYDRAULIC CEMENT

T 133-11 (2015) C 188-09 14 ASTM C 188-14 YES MEF

TENSILE STRENGTH OF HYDRAULIC CEMENT

MORTARSNONE NONET 132-87 (2013) NO

TITLE AASHTO # ASTM # LATEST ASTM ACTION RES ATTACH

16

17

Standard Specification for

Flow Table for Use in Tests of Hydraulic Cement

AASHTO Designation: M 152M/M 152-15161 ASTM Designation: C230/C230M-1314

1. SCOPE

1.1. This specification covers requirements for the flow table and accessory apparatus (see Note 1) used in making flow tests for consistency of mortars in tests of hydraulic cement such as, but not limited to, ASTM C1437. Note 1—To help clarify the design of the flow table and accessory apparatus, see the drawing in Figure 1 (SI units) or Figure 2 (U.S. Customary units). This drawing is for informational purposes only.

1.2. The values stated in either SI units or inch-pound units shall be regarded separately as standard. The values stated in each system may not be exact equivalents; therefore, each system must be used independently of the other. Combining values from the two systems may result in nonconformance with the standard. It is permissible to use an inch-pound caliper and mold with an SI flow table or an SI caliper and mold with an inch-pound flow table. It is not permissible to mix an SI mold with an inch-pound caliper or an inch-pound mold with an SI caliper.

1.3. This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

2. REFERENCED DOCUMENTS

2.1. ASTM Standards: C1437, Standard Test Method for Flow of Hydraulic Cement Mortar Manual of Cement Testing, Annual Book of ASTM Standards, Volume 04.01

3. FLOW TABLE AND FRAME

3.1. The flow table apparatus shall consist of an integrally cast rigid iron frame and a circular rigid tabletop 255.0 ± 2.5 mm [10 ± 0.1 in.] in diameter, with a shaft attached perpendicular to the tabletop by means of a screw thread. The tabletop and shaft with contact shoulder shall be mounted on a frame in such a manner that it can be raised and dropped vertically through the specified height of 12.7 ± 0.13 mm [0.500 ± 0.005 in.] for new tables and 12.7 ± 0.38 mm [0.500 ± 0.015 in.] for tables in use, by means of a rotated cam. The tabletop shall have a fine machined plane surface, free of blowholes and surface defects. The top shall be scribed with eight equidistant lines 68 mm [25/8 in.] long, extending from the outside circumference toward the center of the table. Each line shall end with a scribed arc, 6 mm [1/4 in.] long, whose center point is the center of the table top with a radius of 59.5 mm [23/8 in.]. The scribe lines shall be made with a 60-degree tool to a depth of 0.25 mm [0.01 in.]. The tabletop shall be of cast brass or bronze

having a Rockwell hardness number not less than 25 HRB with an edge thickness of 7.5 mm [0.3 in.] and shall have six integral radial stiffening ribs. The tabletop and attached shaft shall have a mass of 4.08 ± 0.05 kg [9 ± 0.1 lb], and the mass shall be symmetrical around the center of the shaft.

3.2. The cam and vertical shaft shall be of medium carbon machinery steel, hardened where indicated in Figure 1 (SI units) or Figure 2 (U.S. Customary units) on the end of the shaft contacting the cam and the tip of the cam contacting the shaft. The shaft shall be straight, and the difference between the diameter of the shaft and the diameter of the bore of the frame shall be not less than 0.05 mm [0.002 in.] and not more than 0.08 mm [0.003 in.] for new tables and shall be maintained at 0.05 to 0.25 mm [0.002 to 0.010 in.] for tables in use. The end of the shaft shall not fall upon the cam at the end of the drop, but shall make contact with the cam not less than 120 degrees from the point of drop. The face of the cam shall be a smooth spiraled curve of uniformly increasing radius from 13 to 32 mm [1/2 to 11/4 in.] in 360 degrees, and there shall be no appreciable jar as the shaft comes into contact with the cam. The cam shall be so located, and the contact faces of the cam and shaft shall be such that the table does not rotate more than one revolution in 25 drops. The surfaces of the frame and of the table that come into contact at the end of the drop shall be maintained smooth, plane, and horizontal and parallel with the upper surface of the table and shall make continuous contact over a full 360 degrees.

3.3. The supporting frame of the flow table shall be integrally cast of fine-grained, high-grade cast iron. The frame casting shall have three integral stiffening ribs extending the full height of the frame and located 120 degrees apart. The top of the frame shall be chilled to a depth of approximately 6.0 mm [1/4 in.], and the face shall be ground and lapped square with the bore to give 360 degrees contact with the shaft shoulder. The underside of the base of the frame shall be ground to secure complete contact with the steel plate beneath.

3.4. The flow table shall be driven by a motor (see Note 2) connected to the camshaft through an enclosed worm gear speed reducer and flexible coupling. The speed of the camshaft shall be approximately 100 rpm. The motor drive mechanism shall not be fastened or mounted on the table base plate or frame. Note 2—A 40 W (1/20 hp) motor has been found adequate.

3.5. The performance of a flow table shall be considered satisfactory if, in calibration verification tests, the table gives a flow value that does not differ by more than five percentage points from flow values obtained with suitable calibration materials.2 (See Note 3.) Perform the verification at least every 2 ½ years. Note 3—Some causes of and solutions to unsatisfactory performance of the flow table may be found in the section on flow tables in the ASTM Manual of Cement Testing.

4. FLOW TABLE MOUNTING

4.1. The flow table frame shall be tightly bolted to a cast iron or steel plate at least 25 mm [1 in.] thick and 250 mm [10 in.] square. The top surface of this plate shall be machined to a smooth plane surface. The plate shall be anchored to the top of a concrete pedestal by four 13-mm [1/2-in.] bolts that pass through the plate and are imbedded at least 150 mm [6 in.] in the pedestal. The pedestal shall be cast inverted on the base plate. A positive contact between the base plate and the pedestal shall be obtained at all points. No nuts or other such leveling devices shall be used between the plate and the pedestal. Leveling shall be effected by suitable means under the base of the pedestal.

4.2. The pedestal shall be 250 to 275 mm [10 to 11 in.] square at the top, and 375 to 400 mm [15 to 16 in.] square at the bottom, 625 to 750 mm [25 to 30 in.] in height, and shall be of monolithic construction cast from concrete having a density of at least 2240 kg/m3 [140 lb/ft3]. A stable gasket cork padding, 13 mm [1/2 in.] thick and the same size as the pedestal bottom or four pieces of padding 13 mm [1/2 in.] thick and approximately 100 mm [4 in.] square, shall be inserted under the pedestal of the four corners, respectively. The flow table shall be checked frequently for levelness of the tabletop, stability of the pedestal and tightness of bolts and nuts in the table base and the pedestal table. (A torque of 27 N·m [20 lb·ft] is recommended when tightening those fastenings.)

4.3. The tabletop, after the frame has been mounted on the pedestal, shall be level along two diameters at right angles to each other in both the raised and lowered positions.

5. FLOW TABLE LUBRICATION

5.1. The vertical shaft of the table shall be kept clean and shall be lightly lubricated (see Note 4) with a light oil (SAE-10). Oil shall not be present between the contact faces of the tabletop and the supporting frame. Oil on the cam face will lessen wear and promote smoothness of operation. The table should be raised and permitted to drop a dozen or more times just prior to use if it has not been operated for some time. Note 4—It has been demonstrated that an absence of lubrication on the table shaft will significantly reduce the flow reading.

6. MOLD AND CALIPER

6.1. The conical mold for casting the flow specimen shall be of cast bronze or brass., constructed as shown in Figure 1 or Figure 2. The Rockwell hardness number of the metal shall be not less than 25 HRB. The height of the mold shall be 50.0 ± 0.5 mm [2.00 ± 0.02 in.]. The diameter of the top opening shall be 70.0 ± 0.5 mm [2.75 ± 0.02 in.] for new molds and 70.0 + 1.3 and –0.5 mm [2.75 + 0.05 and –0.02 in.] for molds in use. The diameter of the bottom opening shall be 100.0 ± 0.5 mm [4.00 ± 0.02 in.] for new molds and 100.0 + 1.3 and –0.5 mm [4.00 + 0.05 and –0.02 in.] for molds in use. The surfaces of the base and top shall be parallel and at right angles to the vertical axis of the cone. The mold shall have a minimum wall thickness of 5 mm [0.2 in.]. The outside of the top edge of the mold shall be shaped so as to provide an integral collar for convenient lifting of the mold. All surfaces shall be machined to a smooth finish. A circular shield approximately 255 mm [10 in.] in diameter, with a center opening approximately 100 mm [4 in.] in diameter, made of nonabsorbing material not attacked by the cement, shall be used with the flow mold to prevent mortar from spilling on the tabletop.

6.2. A caliper consisting of one fixed jaw and one jaw movable along a permanent scale shall be provided for measuring the diameter of the mortar after it has been spread by the operation of the

TS-3a M 152M/M 152-6 AASHTO

table. The scale shall be machine divided into 40 increments with 4.0 mm [0.16 in.] between divisions with major division lines every five divisions and the increment number every ten divisions (see Note 5). The construction and accuracy of the instrument caliper shall be such that the distance between the jaws shall be 100 ± 0.25 mm [4 ± 0.01 in.] when the indicator is set at zero. Note 5—The caliper is graduated to indicate one fourth of the actual flow percentage, so that the readings of four measurements on the caliper may be added to give the flow value without the necessity of calculating the average of four individual measurements of the total flow.

1 This method agrees with ASTM C230/C230M-14.ASTM C230/C230M-13. 2 Such material may be obtained from the Cement and Concrete Reference Laboratory at the National Institute of Standards and Technology, Washington, DC 20234.

TS-3a M 152M/M 152-6 AASHTO

Standard Specification Practice for

Use of Apparatus for the Determination of Length Change of Hardened Cement Paste, Mortar, and Concrete

AASHTO Designation: M 210M/M 210-14 ASTM Designation: C490/C490M-11ε1

1. SCOPE

1.1. This standard practice covers the requirements for the apparatus and equipment used to prepare specimens for the determination of length change in hardened cement paste, mortar, and concrete; the apparatus and equipment used for the determination of these length changes; and the procedures for its use.

1.2. Methods for the preparation and curing of test specimens, conditions of testing and curing, and detailed procedures for calculating and reporting test results are contained in applicable test methods.

1.3. The values stated in either SI units or inch-pound units are to be regarded separately as the standard. The values stated in each system may not be exact equivalents; therefore, each system shall be used independently of the other. Combining values from the two systems may result in nonconformance with the standard.

2. REFERENCED DOCUMENTS

2.1. AASHTO Standard: M 201, Mixing Rooms, Moist Cabinets, Moist Rooms, and Water Storage Tanks Used in the

Testing of Hydraulic Cements and Concretes

2.2. ASTM Standard: C1005, Standard Specification for Reference Masses and Devices for Determining Mass and

Volume for Use in the Physical Testing of Hydraulic Cements

3. TERMINOLOGY

3.1. length change—an increase or decrease in the linear dimension of a test specimen, measured along the longitudinal axis, due to causes other than applied load.

4. SIGNIFICANCE AND USE

4.1. This practice is intended to provide standard requirements for apparatus common to many test methods used in connection with cement and concrete and standardized procedures for its use. The detailed requirements as to materials, mixtures, specimens, conditioning of specimens, number of

TS-3a M 210M/M 210-1 AASHTO

Standard Specification for

Quicklime and Hydrated Lime for Soil Stabilization

AASHTO Designation: M 216-13 ASTM Designation: C977-10

American Association of State Highway and Transportation Officials 444 North Capitol Street N.W., Suite 249 Washington, D.C. 20001

Standard Specification for

Quicklime and Hydrated Lime for Soil Stabilization

AASHTO Designation: M 216-13 ASTM Designation: C977-10

1. SCOPE

1.1. This specification pertains to quicklime and hydrated lime, either high calcium, dolomitic, or magnesian lime, for use in stabilization of soils. (See Notes 1 and 2.) Note 1—Quicklime and hydrated lime act upon clay soils and may render such soils suitable for highway construction and other load-bearing applications. In most cases, lime causes finely divided clay particles to agglomerate into coarser particles, which improves load-bearing properties, and subsequently the lime-treated soil hardens by chemical reaction. Note 2—No attempt is made to present requirements for by-product lime, commercial lime slurry, etc. Specification requirements for these materials could be better determined on a local basis.

1.2. This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

2. REFERENCED DOCUMENTS

2.1. ASTM Standards: C25, Standard Test Methods for Chemical Analysis of Limestone, Quicklime, and Hydrated

Lime C50/C50M, Standard Practice for Sampling, Sample Preparation, Packaging, and Marking of

Lime and Limestone Products C51, Standard Terminology Relating to Lime and Limestone (as used by the Industry) C110, Standard Test Methods for Physical Testing of Quicklime, Hydrated Lime, and

Limestone D6276, Standard Test Method for Using pH to Estimate the Soil-Lime Proportion

Requirement for Soil Stabilization

3. CHEMICAL COMPOSITION

3.1. Unless otherwise specified, for definitions of terms used in this specification, refer to Definitions of Terms, ASTM C51.

3.2. Quicklime and hydrated lime for soil stabilization shall conform to the following chemical composition: Calcium and magnesium oxides (on a nonvolatile basis, minimum percent) 90.0 Carbon dioxide (taken at point of manufacture, maximum percent) 5.0

TS-3a M 216-1 AASHTO

Free moisture (taken at point of manufacture, maximum percent) 2.0

4. PHYSICAL PROPERTIES

4.1. Hydrated lime shall have not more than 3 percent retained on a No. 30 (0.590-mm) sieve and not more than 25 percent retained on a No. 200 (0.075-mm) sieve.

4.2. Quicklime:

4.2.1. Particle Size of Quicklime—Quicklime shall all pass a 1.0-in. (25.4-mm) sieve.

4.2.2. Quicklime for soil stabilization shall have a temperature rise of a minimum of 30°C in 20 min.

4.2.3. Residue of Quicklime—Quicklime for soil stabilization shall have not more than 10 percent residue.

5. FIELD APPLICATIONS

5.1. When quicklime is used, ensure that thorough mixing of the lime and soil is accomplished and all lime pebbles have been hydrated with additional water and distributed uniformly throughout the soil. There shall be no lime pebbles present before the compaction operation starts. Check by turning soil with a spade at representative intervals and inspect for visible lime pebbles. Care should be exercised on initial dry applications to minimize environmental dusting.

5.2. For hydrated lime, additional water shall be added to the lime-soil mixture to facilitate mixing and uniform distribution of the hydrated lime in the soil layer. There shall be no lime clumps present before the compaction operation starts. Check by turning soil with a spade at representative intervals and inspecting for visible lime clumps. Care should be exercised on initial dry applications to minimize environmental dusting.1

6. TEST METHOD

6.1. The chemical analysis of quicklime and hydrated lime shall be conducted in accordance with ASTM C25. (See Appendix X1.)

6.2. The particle size of hydrated lime shall be determined in accordance with the sieve analysis of hydrated lime in accordance with ASTM C110.

6.3. The quicklime temperature rise and residue should be determined in accordance with the Slaking Rate of Quicklime in ASTM C110.

6.4. Appendix X1 contains a nonmandatory test to approximate the lime-soil proportion for stabilization. A more detailed version of this test appears in ASTM D6276.

7. SAMPLING, INSPECTION, PACKAGING, AND MARKING

7.1. The sampling, inspection, rejection, retesting, packaging, and marking shall be done in accordance with ASTM C50/C50M.

TS-3a M 216-2 AASHTO

8. KEYWORDS

8.1. Highway construction; hydrated lime; lime-treated soils; load-bearing; quicklime; soil stabilization.

APPENDIX

(Nonmandatory Information)

X1. METHOD FOR DETERMINING STABILIZATION ABILITY OF LIME

X1.1. This test method usually provides a lime-soil proportion for stabilization. It gives an indication whether the soil in question can be stabilized. For most stabilization work, the results of this test should be verified by performance tests in a soil laboratory.

X1.2. Air dry a sufficient quantity of the soil to be tested and screen through a No. 40 (425-µm) sieve. Store in a closed container to maintain uniform moisture. Determine the mass, to the nearest 0.1 g, of a series of 20-g samples of soil and place in separate 150-mL containers with watertight lids.

X1.3. In the case of quicklime, rapidly crush the lime to pass a No. 6 (3.35-mm) sieve.

X1.4. Determine the mass, to the nearest 0.01 g, of a series of quantities of lime equivalent to 2, 3, 4, 5, and 6 percent of the soil sample.

X1.5. Add the lime quantity to the soil sample, mark the container with the appropriate percentage, and mix the dry contents thoroughly.

X1.6. Add the 100 mL of 70°F carbon dioxide–free distilled water or, if possible, 70°F actual water to be used on the job to each container of soil and lime. Seal with a screw-cap lid, and mix the three components by shaking the bottles. Shake each bottle for 30 s every 10 min for 1 h. After 1 h, shake vigorously and transfer part of the slurry into a beaker. Measure the pH with a low-sodium error glass electrode (previously standardized to pH 12.45 with an agitated calcium hydroxide slurry). Record the pH reading for each mixture.

X1.7. If the pH readings are 12.40 or higher, the lowest percentage that gives a pH of 12.40 is the percent required to stabilize the soil. If the pH readings do not go beyond a pH of 12.30 and 2 percentages give this reading, the lowest percent to give a pH of 12.30 is the percent required to stabilize the soil. If the highest pH reading is a pH of 12.30 and only the highest percentage lime used gives a pH of 12.30, additional testing is required using higher percentages of lime.

1 Further information on soil stabilization construction technique is available from National Lime Association Bulletin No. 326, 200 North Glebe Road, Arlington, VA, 22203. This information can be accessed online at www.lime.org.

TS-3a M 216-3 AASHTO

Standard Method of Test for

Chemical Analysis of Hydraulic Cement

AASHTO Designation: T 105-141T105-14161

ASTM Designation: C114-13C114-15

American Association of State Highway and Transportation Officials 444 North Capitol Street N.W., Suite 249 Washington, D.C. 20001

Formatted: Superscript

Standard Method of Test for

Chemical Analysis of Hydraulic Cement

AASHTO Designation: T 105-15161 ASTM Designation: C114-1315

1. SCOPE

1.1. These test methods cover the chemical analyses of hydraulic cements. Any test methods of demonstrated acceptable precision and bias may be used for analysis of hydraulic cements, including analyses for referee and certification purposes, as explained in Section 4. Specific chemical test methods are provided for ease of reference for those desiring to use them. They are grouped as Reference Test Methods and Alternate Test Methods. The reference test methods are long accepted classical chemical test methods, which provide a reasonably well-integrated basic scheme of analysis for hydraulic cements. The alternative test methods generally provide individual determination of specific analytes and may be used alone or as alternates and determinations within the basic scheme at the option of the analyst and as indicated in the individual method. The individual analyst must demonstrate achievement of acceptable precision and bias, as explained in Section 4, when these methods are used.

1.2. Contents: Section Subject 2 Referenced Documents 3 Terminology 4 Description of Referee Analyses 4.1 Referee Analyses 5 Qualification for Different Analyses 5.1 Certified Reference Materials 5.2 Requirements for Qualification Testing 5.3 Alternative Analyses 5.4 Performance Requirements for Rapid Test Methods 6 General 6.1 Interferences and Limitations 6.2 Apparatus and Materials 6.3 Reagents 6.4 Sample Preparation 6.5 General Procedures 6.6 Recommended Order for Reporting Analyses Reference Test Methods 7 Insoluble Residue 8 Silicon Dioxide 8.1 Selection of Test Method 8.2 Silicon Dioxide in Portland Cements and Cements with Low Insoluble Residue 8.3 Silicon Dioxide in Cements with Insoluble Residue Greater Than 1 Percent

TS-3a T 105-1 AASHTO

Section Reference Test Methods (continued) 9 Ammonium Hydroxide Group 10 Ferric Oxide 11 Phosphorus Pentoxide 12 Titanium Dioxide 13 Zinc Oxide 14 Aluminum Oxide 15 Calcium Oxide 16 Magnesium Oxide 17 Sulfur 17.1 Sulfur Trioxide 17.2 Sulfide 18 Loss on Ignition 18.1 Portland Cement 18.2 Portland Blast-Furnace Slag Cement and Slag Cement 19 Sodium and Potassium Oxides 19.1 Total Alkalies 19.2 Water-Soluble Alkalies 20 Manganic Oxide 21 Chloride 22 Chloroform-Soluble Organic Substances Alternative Test Methods 23 Calcium Oxide 24 Carbon Dioxide 25 Magnesium Oxide 26 Loss on Ignition 26.1 Portland Blast-Furnace Slag Cement and Slag Cement 27 Titanium Dioxide 28 Phosphorus Pentoxide 29 Manganic Oxide 30 Free Calcium Oxide Appendixes TitleAppendixes Appendix X1 Example of Determination of Equivalence Point for the Chloride Determination Appendix X2 CO2 Determinations in Hydraulic Cements

1.3. The values stated in SI units are to be regarded as the standard.

1.4. This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to consult and establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. See Sections 8.3.2.1 and 16.4.1 for specific caution statements.

TS-3a T 105-2 AASHTO

2. REFERENCED DOCUMENTS

2.1. ASTM Standards: C25, Standard Test Methods for Chemical Analysis of Limestone, Quicklime, and Hydrated

Lime D1193, Standard Specification for Reagent Water E29, Standard Practice for Using Significant Digits in Test Data to Determine Conformance

with Specifications E275, Standard Practice for Describing and Measuring Performance of Ultraviolet and Visible

Spectrophotometers E350, Standard Test Methods for Chemical Analysis of Carbon Steel, Low-Alloy Steel,

Silicon Electrical Steel, Ingot Iron, and Wrought Iron E617, Standard Specification for Laboratory Weights and Precision Mass Standards E832, Standard Specification for Laboratory Filter Papers

3. TERMINOLOGY

3.1. Definition:

3.1.1. analyte, n—A substance of interest when performing a quantitative analysis.

3.1.1.1. Discussion—For the purposes of this test method, analytes are considered to be those items listed in Column 1 of Table 1.

4. DESCRIPTION OF REFEREE ANALYSES

4.1. Referee Analyses—When conformance to chemical specification requirements is questioned, perform referee analyses as described in Section 4.1.1. The reference test methods that follow in Sections 7 through 22, or other test methods qualified according to Section 5.4, Performance Requirements for Rapid Test Methods, are required for referee analysis. A cement shall not be rejected for failure to conform to chemical requirements unless all determinations of constituents involved and all necessary separations prior to the determination of any one constituent are made entirely by these methods. When reporting the results of referee analyses, specify which test methods were used.

4.1.1. Referee analyses shall be made in duplicate and on different days. If the two results do not agree within the permissible variation given in Table 1, the determination shall be repeated until two or three results agree within the permissible variation. When two or three results do agree within the permissible variation, their average shall be accepted as the correct value. When an average of either two or three results can be calculated, the calculation shall be based on the three results. For the purpose of comparing analyses and calculating the average of acceptable results, the percentages shall be calculated to the nearest 0.01 (or 0.001 in the case of chloroform-soluble organic substances), although some of the average values are reported to 0.1 as indicated in the test methods. When a blank determination (see Note 1) is specified, one shall be made with each individual analysis or with each group of two or more samples analyzed on the same day for a given analyte. Note 1—A blank determination is a procedure that follows all steps of analysis, but in the absence of a sample. It is used for detection and compensation of systematic bias.

TS-3a T 105-3 AASHTO

Table 1—Maximum Permissible Variation in Resultsa

(Column 1) Analyte

(Column 2) Maximum Difference between Duplicatesb

(Column 3) Maximum Difference

of the Average of Duplicates from CRM Certificate Valuesb ,c ,d

SiO2 (silicon dioxide) 0.16 ±0.20 Al2O3 (aluminum oxide) 0.20 ±0.20 Fe2O3 (ferric oxide) 0.10 ±0.10 CaO (calcium oxide) 0.20 ±0.30 MgO (magnesium oxide) 0.16 ±0.20 SO3 (sulfur trioxide) 0.10 ±0.10 LOI (loss on ignition) 0.10 ±0.10 Na2O (sodium oxide) 0.03 ±0.05 K2O (potassium oxide) 0.03 ±0.05 TiO2 (titanium dioxide) 0.02 ±0.03 P2O5 (phosphorus pentoxide) 0.03 ±0.03 ZnO (zinc oxide) 0.03 ±0.03 Mn2O3 (manganic oxide) 0.03 ±0.03 S (sulfide sulfur) 0.01 e

Cl (chloride) 0.003 ±0.005e

IR (insoluble residue) 0.10 e

Cx (free calcium oxide) 0.20 e

CO2 (carbon dioxide) 0.12 e, f Alksol (water-soluble alkali)g 0.75/ w g e

Chlsol (chloroform-soluble organic substances) 0.004 e

a When all seven Certified Reference Material (CRM) cements are required, as for demonstrating performance of rapid test methods, at least six of the seven shall be within the prescribed limits, and the seventh shall differ by no more than twice that value. When more than seven CRMs are used, as for demonstrating the performance of rapid test methods, at least 77 percent shall be within the prescribed limits, and the remainder no more than twice the value. When a lesser number of CRM cements are required, all of the values shall be within the prescribed limits.

b Where no value appears in Column 3, CRM certificate values do not exist. In such cases, only the requirement for differences between duplicates shall apply.

c Interelement corrections may be used for any oxide standardization provided improved accuracy can be demonstrated when correction is applied to all seven CRM cements.

d Where a CRM certificate value includes a subscript number, that subscript number shall be treated as a valid significant figure. e Not applicable. No certificate value given. f Demonstrate performance by analysis, in duplicate, of at least one portland cement. Prepare three standards, each in duplicate:

Standard A shall be selected portland cement, Standard B shall be Standard A containing 2.00 percent Certified CaCO3 (e.g., NIST 915a), Standard C shall be Standard A containing 5.00 percent Certified CaCO3. Weigh and prepare two separate specimens of each standard. Assign the CO 2 content of Standard A as the average of the two values determined, provided they agree within the required limit of Column 2. Assign CO2 values to Standards B and C as follows: Multiply the Certified CaCO3 value (Y) for CO2 (from the certificate value) by the mass fraction of Certified CaCO3 added to that standard (percentage added divided by 100); multiply the value determined for Standard A by the mass fraction of Standard A in each of the other standards (i.e., 0.98 and 0.95 for Standards B and C, respectively); add the two values for Standards A and B, respectively; call these values B and C.

Example: B = 0.98A + 0.02Y. C = 0.95A + 0.05Y. where for Certified CaCO3, if Y= 39.9 percent B = 0.98A + 0.80 percent by mass. C = 0.95A + 2.00 percent by mass. Maximum difference between the duplicate CO2 values for Standards B and C, respectively, shall be 0.17 and 0.24 percent by mass.

Averages of the duplicate values for Standards B and C shall differ from their assigned values (B and C) by no more than 10 percent of those respective assigned values.

g w = mass, in grams, of samples used for the test.

TS-3a T 105-4 AASHTO

5. QUALIFICATION FOR DIFFERENT ANALYSES

5.1. Certified Reference Materials—A Certified Reference Material (CRM) must be used in the qualification of test methods and analysts. Acceptable reference cements are National Institute of Standards and Technology (NIST) CRMs or other reference cements traceable to the NIST CRMs. The reference cement must have an assigned value for the analyte being determined. Traceability consists of documentary evidence that the assigned values of the reference cement are compatible with the certified values of NIST CRMs. To demonstrate traceability for a given analyte, perform a referee analysis (as defined in Section 4.1) on the proposed reference cement, using an NIST CRM for demonstration of precision and accuracy. The reference cement is acceptable if its assigned value agrees with the average referee value within the limits given in Column 3 of Table 1. If the reference cement, as supplied, has no documented guarantee of homogeneity, establish its homogeneity by analyzing at least six randomly selected samples. No result shall deviate from the assigned value by more than the limits given in Column 2 of Table 1. An acceptable reference cement must be accompanied by a document showing the data produced in demonstrating traceability and homogeneity.

5.2. Requirements for Qualification Testing—Qualified test methods are required whenever testing is performed for the following reasons: (1) for Referee analyses; (2) for analyses intended for use as a basis for acceptance or rejection of a cement; or, (3) for manufacturer’s certification. When Reference Methods are used, qualification testing of the analyst is required as described in 5.2.1. When Rapid Methods are used, qualification testing of both the analyst and the test method are required as described in 5.2.1 and 5.4. Such demonstration may be made concurrently with analysis of the cement being tested. The requirements for qualification of a test method and analyst are summarized in Table 2.Referee analyses or analyses intended for use as a basis for acceptance or rejection of a cement or for manufacturer’s certification shall be made only after demonstration of precise and accurate analyses by the test methods in use by meeting the requirements of Section 5.2.1, except when demonstrated under Section 5.4, Performance Requirements for Rapid Test Methods. Such demonstration may be made concurrently with analysis of the cement being tested and must have been made within the preceding 2 years. The requirements for verification of equipment and personnel are summarized in Table 2. The demonstration is required only for those constituents being used as a basis for acceptance, rejection, or certification of a cement, but may be made for any constituent of cement for which a standard exists.

Table 2—Minimum Number of CRMs Required for Qualification of Chemical Testing

Equipment Qualification Operator Qualificationc

Method Type Referencea Otherb

None 7 1 1

a Reference methods are those outlined in Sections 7 through 22. b These may be any test method as described in Section 5.3, Alternative Analyses, or any instrumental or rapid test method,

which must be qualified in accordance with Section 5.4, Performance Requirements for Rapid Test Methods. c Each analyst performing acceptance or reference analyses must be qualified in accordance with Section 5.2.15.4, Performance

Requirements for Rapid Test Methods, at a frequency of 2 years. If qualification of the instrument is completed by a single analyst, the analyst has demonstrated individual qualifications per Section 5.2.15.4.

5.2.1. Initial qualification of the analyst shall be demonstrated by analysis of each constituent of concern in at least one CRM cement in duplicate, no matter what test method is used (Note 2)e.g., gravimetric or instrumental). Duplicate samples shall be run on different days. The same test methods to be used for analysis of cement being tested shall be used for analysis of the CRM cement. If the duplicate results do not agree within the permissible variation given in Table 1, the determinations shall be repeated, following identification and correction of problems or errors, until a set of duplicate results do agree within the permissible variation. Requalification of the analyst is required every two years. Note 2—When qualifying a Rapid Method with seven CRMs in accordance with 5.4.2, the analyst Formatted: Font: Bold

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performing the qualification of the test method may simultaneously qualify for the requirement of 5.2.1.

5.2.2. The average of the results of acceptable duplicate determinations for each constituent may differ from the CRM assigned value by no more than the value shown in Column 3 of Table 1 after necessary corrections for minor analytes are made.

5.2.3. Qualification data demonstrating that the same operator or analyst making the acceptance determination obtained precise and accurate results with CRM cements as per Section 5.4 shall be made available on request to all parties concerned when there is a question of acceptance of a cement. If the CRM used is not an NIST cement, the traceability documentation of the CRM used shall also be made available on request.

5.3. Alternative Analyses—The alternative test methods provide, in some cases, procedures that are shorter or more convenient to use for routine determination of certain constituents than are the reference test methods (see Note 23). Longer, more complex procedures, in some instances, have been retained as alternative test methods to permit comparison of results by different procedures or for use when unusual materials are being examined, where unusual interferences may be suspected, or when unusual preparation for analysis is required. Test results from alternative test methods may be used as a basis for acceptance or rejection when it is clear that a cement does or does not meet the specification requirement. Any change in test method procedures from those procedures listed in Sections 7 through 30 requires method qualification in accordance with Section 5.4, Performance Requirements for Rapid Test Methods. Note 23—It is not intended that the use of reference test methods be confined to referee analysis. A reference test method may be used in preference to an alternative test method when so desired. A reference test method must be used where an alternative test method is not provided.

5.3.1. Duplicate analyses and blank determinations are not required when using the alternative test methods. If, however, a blank determination is desired for an alternative test method, one may be used, and it need not have been obtained concurrently with the analysis. The final results, when corrected for blank values, should, in either case, be so designated.

5.4. Performance Requirements for Rapid Test Methods2, 3:

5.4.1. Definition and Scope—Where analytical data obtained in accordance with this test method are required, any test method may be used that meets the requirements of Section 5.4.2, Qualification of a Test Method. A test method is considered to consist of the specific procedures, reagents, supplies, equipment, instrument, etc.and so forth, selected and used in a consistent manner by a specific laboratory. See Note 3 4 for examples of procedures. Note 42—Examples of test methods used successfully by their authors for analysis of hydraulic cement are given in the list of references. Included are test methods using atomic absorption X-ray spectrometry and spectrophotometry-EDTA.

5.4.1.1. If more than one instrument, even though substantially identical, is used in a specific laboratory for the same analyses, use of each instrument shall constitute a separate test method and each must be qualified separately.

5.4.2. Qualification of a Test Method—Prior to use for analysis of hydraulic cement, each test method (see Section 5.4.1) must be qualified individually for such analysis. Qualification data, or if applicable, requalification data, shall be made available pursuant to the Manufacturer’s Certification section of the appropriate hydraulic cement specification.

5.4.2.1. Using the test method chosen, make single determinations for each analyte under consideration on at least seven CRM samples. Requirements for a CRM are listed in Section 5.1, Certified Reference Materials. Complete two rounds of tests on different days repeating all steps of sample

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preparations. Calculate the differences between values and averages of the values from the two rounds of tests.

5.4.2.2. When seven CRMs are used in the qualification procedure, at least six of the seven differences between duplicates obtained of any single analyte shall not exceed the limits shown in Column 2 of Table 1 and the remaining differences by no more than twice that value. When more than seven CRMs are used, the values for at least 77 percent of the samples shall be within the prescribed limits, while the values for the remainder shall differ by no more than twice that value.

5.4.2.3. For each analyte and each CRM, the average obtained shall be compared to the certified concentrations. Where a certificate value includes a subscript number, that subscript shall be assumed to be a significant number. When seven CRMs are used in the qualification procedure, at least six of the seven averages for each analyte shall not differ from the certified concentrations by more than the value shown in Column 3 of Table 1, and the remaining average by more than twice that value. When more than seven CRMs are used in the qualification procedure, at least 77 percent of the averages for each analyte shall not differ from the certified concentrations by more than the value shown in Column 3 of Table 1, and the remaining average(s) by more than twice that value.

5.4.2.4. The standardization, if needed, used for qualification and analysis of each constituent shall be determined by valid curve-fitting procedures. A point-to-point, sawtooth curve that is artificially made to fit a set of data points does not constitute a valid curve-fitting procedure. A complex polynomial drawn through the points is similarly not valid. For the same reason, empirical interelement corrections may be used only if ≤(N – 3)/2 is employed, where N is the number of different standards used. The qualification testing shall be conducted with specimens newly prepared from scratch, including all the preparation stages applicable for analysis of an unknown sample, and employing the reagents currently in use for unknown analyses.

5.4.3. Partial Results—Test methods that provide acceptable results for some analytes but not for others may be used only for those analytes for which acceptable results are obtained.

5.4.4. Report of Results—When performing chemical analysis and reporting results for Manufacturer’s Certification, the type of method (Reference or Rapid) and the test method used, along with any supporting qualification testing, shall be available on request.

5.4.5. Rejection of Material—See Section 4.1, Referee Analyses, and Section 5.3, Alternative Analyses.

5.4.6. Requalification of a Test Method:

5.4.6.1. Requalification of a test method shall be required upon receipt of substantial evidence that the test method may not be providing data in accordance with Table 1 for one or more constituents. Such requalification may be limited to those constituents indicated to be in error and shall be carried out prior to further use of the method for analysis of those constituents.

5.4.6.2. Substantial evidence that a test method may not be providing data in accordance with Table 1 shall be considered to have been received when a laboratory is informed that analysis of the same material by Reference Test Methods run in accordance with Section 4.1.1, the final average of a Cement and Concrete Reference Laboratory (CCRL) sample, a certificate value of an NIST CRM, the assigned value of an alternate CRM, or an accepted value of a known secondary standard differs from the value obtained by the test method in question by more than twice the value shown in Column 2 of Table 1 for one or more constituents. When indirect test methods are involved, as when a value is obtained by difference, corrections shall be made for minor constituents to put analyses on a comparable basis prior to determining the differences. For any constituents affected, a test method also shall be requalified after any substantial repair or replacement of one or more critical analytes of an instrument essential to the test method.

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5.4.6.3. If an instrument or piece of equipment is replaced, even if by one of identical make or model, or is significantly modified, a previously qualified test method using such new or modified instrument or equipment shall be considered a new method and must be qualified in accordance with Section 5.4.2.

5.4.7. Precision and Bias—Different analytical test methods are subject to individual limits of precision and bias. It is the responsibility of the user to demonstrate that the test methods used at least meet the limits of precision and bias shown in Table 1.

6. GENERAL

6.1. Interferences and Limitations:

6.1.1. These test methods were developed primarily for the analysis of portland cements. However, except for limitations noted in the procedure for specific constituents, the reference test methods provide for accurate analyses of other hydraulic cements that are completely decomposed by hydrochloric acid, or where a preliminary sodium carbonate fusion is made to ensure complete solubility. Some of the alternative test methods may not always provide accurate results because of interferences from elements that are not removed during the procedure. Note 5—Instrumental analyses can usually detect only the element sought. Therefore, to avoid controversy, the actual procedure used for the elemental analyses shoud be noted when actual differences with reference procedures can exist. For example, P2O5 and TiO2 are included with Al2O3 in the usual wet test method and sulide sulfur is included in most instrumental procedures with SO3.

6.1.2. When using a test method that determines total sulfur, such as most instrumental test methods, sulfide sulfur will be determined with sulfate and included as such. In most hydraulic cements, the difference resulting from such inclusion will be insignificant, less than 0.05 weight percent. In some cases, notably slags and slag-containing cements but sometimes other cements as well, significant levels of sulfide may be present. In such cases, especially if there is a question of meeting or not meeting a specification limit or when the most accurate results are desired, analytical test methods shall be chosen so that sulfate and sulfide can be reported separately.

6.1.2.6.1.2.1. Where desired, when using instrumental test methods for sulfate determination, if sulfide has been determined separately, correct the total sulfur results (expressed as an oxide) in accordance with the following calculation: SO3 = Stotal – (2.5S-) (1) where: SO3 = sulfur trioxide excluding sulfur, Stotal = toal sulfur in the sample, expressed as the oxide, from instrumental results, 2.5 = molecular ratio of SO3/S- to express sulfur as SO3, and S- = sulfur dioxide present.

6.2. Apparatus and Materials:

6.2.1. Balance—The analytical balance used in the chemical determinations shall conform to the following requirements:

6.2.1.1. The balance shall be capable of reproducing results within 0.0002 g, with an accuracy of ±0.0002 g. Direct-reading balances shall have a sensitivity not exceeding 0.0001 g (see Note 46). Conventional two-pan balances shall have a maximum sensibility reciprocal of 0.0003 g. Any rapid weighing device that may be provided, such as a chain, damped motion, or heavy riders, shall not increase the basic inaccuracy by more than 0.0001 g at any reading and with any load within the rated capacity of the balance.

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Note 46—The sensitivity of a direct-reading balance is the weight required to change the reading one graduation. The sensibility reciprocal for a conventional balance is defined as the change in weight required on either pan to change the position of equilibrium one division on the pointer scale at capacity or at any lesser load.

6.2.2. Weights—Weights used for analysis shall conform to Types I or II, Grades S or O, Classes 1, 2, or 3, as described in ASTM E617. They shall be checked at least once a year, or when questioned, and adjusted at least to within allowable tolerances for Class 3 weights (see Note 57). For this purpose, each laboratory shall also maintain, or have available for use, a reference set of standard weights from 50 g to 10 mg, which shall conform at least to Class 3 requirements and be calibrated at intervals not exceeding 5 years by the NIST. After initial calibration, recalibration by the NIST may be waived, provided it can be shown by documented data obtained within the time interval specified that a weight comparison between summations of smaller weights and a single larger weight nominally equal to that summation establishes that the allowable tolerances have not been exceeded. All new sets of weights purchased shall have the weights of 1 g and larger made of stainless steel or other corrosion-resisting alloy not requiring protective coating, and shall meet the density requirements for Grades S or O. Note 57—The scientific supply houses do not presently list weights as meeting ASTM E617. They list weights as meeting NIST or International Organization of Legal Metrology (OIML) standards. The situation with regard to weights is in a state of flux because of the trend toward internationalization. Hopefully, this will soon be resolved. NIST Classes S and S-1 and OIML Class F1 weights meet the requirements of this standard.

6.2.3. Glassware and Laboratory Containers—Standard volumetric flasks, burets, and pipets should be of precision grade or better. Standard-taper, interchangeable, ground-glass joints are recommended for all volumetric glassware and distilling apparatus, when available. Wherever applicable, the use of special types of glassware (e.g., colored glass for the protection of solutions against light, alkali-resistant glass, and high-silica glass having exceptional resistance to thermal shock) is recommended. Polyethylene containers are recommended for all aqueous solutions of alkalies and for standard solutions where the presence of dissolved silica or alkali from the glass would be objectionable. Such containers shall be made of high-density polyethylene having a wall thickness of at least 1 mm.

6.2.4. Desiccators—Desiccators shall be provided with a good desiccant such as magnesium perchlorate, activated alumina, or sulfuric acid. Anhydrous calcium sulfate may also be used, provided it has been treated with a color-change indicator to show when it has lost its effectiveness. Calcium chloride is not a satisfactory desiccant for this type of analysis.

6.2.5. Filter Paper—Filter paper shall conform to the requirements of ASTM E832, Type II, Quantitative. When coarse-textured paper is required, Class E paper shall be used; when medium-textured paper is required, Class F paper shall be used; and when retentive paper is required, Class G paper shall be used.

6.2.6. Crucibles:

6.2.6.1. Platinum Crucibles—For ordinary chemical analysis, platinum crucibles should preferably be made of pure unalloyed platinum and be of 15- to 30 -mL capacity. Where alloyed platinum is used for greater stiffness or to obviate sticking of crucible and lid, the alloyed platinum shall not decrease in weight by more than 0.2 mg when heated at 1200°C for 1 h.

6.2.6.2. Porcelain Crucibles—Should be glazed inside and out, except for the outside bottom and rim, and be of 5–10 mL capacity.

6.2.7. Muffle Furnace—The muffle furnace shall be capable of operation at the temperatures required and shall have an indicating pyrometer accurate within ±25°C, as corrected, if necessary, by

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calibration. More than one furnace may be used, provided each is used within its proper operating temperature range.

6.3. Reagents:

6.3.1. Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, where such specifications are available.4 Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening the accuracy of the determination.

6.3.2. Unless otherwise indicated, references to water shall mean water conforming to the numerical limits for Type II reagent water described in ASTM D1193.

6.3.3. Concentration of Reagents:

6.3.3.1. Prepackaged Reagents—Commercial prepackaged standard solutions or diluted prepackaged concentrations of a reagent may be used whenever that reagent is called for in the procedures, provided the purity and concentrations are as specified. Verify purity and concentration of such reagents by suitable tests.

6.3.3.2. Concentrated Acids and Ammonium Hydroxide—When acids and ammonium hydroxide are specified by name or chemical formula only, it shall be understood that concentrated reagents of the following specific gravities or concentrations by weight are intended:

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Acetic acid (HC2H3O2) 99.5 percent Hydrochloric acid (HCl) sp gr 1.19 Hydrofluoric acid (HF) 48 percent Nitric acid (HNO3) sp gr 1.42 Phosphoric acid (H3PO4) 85 percent Sulfuric acid (H2SO4) sp gr 1.84 Ammonium hydroxide (NH4OH) sp gr 0.90

6.3.3.3. The desired specific gravities or concentrations of all other concentrated acids shall be stated whenever they are specified.

6.3.4. Diluted Acids and Ammonium Hydroxide—Concentrations of diluted acids and ammonium hydroxide, except when standardized, are specified as a ratio stating the number of volumes of the concentrated reagent to be added to a given number of volumes of water (e.g., HCl (1+99) means 1 volume of concentrated HCl (sp gr 1.19) added to 99 volumes of water).

6.3.5. Standard Solutions—Concentrations of standard solutions shall be expressed as normalities (N) or as equivalents in grams per milliliter of the analyte to be determined (e.g., 0.1 N Na2S2O3 solution or K2Cr2O7 (1 mL = 0.004 g Fe2O3)). The average of at least three determinations shall be used for all standardizations. When a material is used as a primary standard, reference has generally been made to the standard furnished by NIST. However, when primary standard grade materials are otherwise available, they may be used, or the purity of a salt may be determined by suitable tests.

6.3.6. Nonstandardized Solutions—Concentrations of nonstandardized solutions prepared by dissolving a given weight of the solid reagent in a solvent shall be specified in grams of the reagent per liter of solution, and it shall be understood that water is the solvent unless otherwise specified (e.g., NaOH solution (10 g/L) means 10 g of NaOH dissolved in water and diluted with water to 1 L). Other nonstandardized solutions may be specified by name only, and the concentration of such solutions will be governed by the instructions for their preparation.

6.3.7. Indicator Solutions:

6.3.7.1. Methyl Red—Prepare the solution on the basis of 2 g of methyl red/L of 95 percent ethyl alcohol.

6.3.7.2. Phenolphthalein—Prepare the solution on the basis of 1 g of phenolphthalein/L of 95 percent ethyl alcohol.

6.4. Sample Preparation:

6.4.1. Before testing, pass representative portions of each sample through a No. 20 (850-μm) sieve or any other sieve having approximately 20 openings per 1 in. to mix the sample, break up lumps, and remove foreign materials. Discard the foreign materials and hardened lumps that do not break up on sieving or brushing.

6.4.2. By means of a sample splitter or by quartering, the representative sample shall be reduced to a laboratory sample of at least 50 g. Where larger quantities are required for additional determinations such as water-soluble alkali, chloride, and duplicate testing, and so forth, prepare a sample of at least 100 g.

6.4.3. Pass the laboratory sample through a No. 100 (150-μm) sieve. Further grind the sieve residue so that it also passes the No. 100 sieve. Homogenize the entire sample by again passing it through the sieve.

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6.4.4. Transfer the sample to a clean, dry, glass container with an airtight lid, and further mix the sample thoroughly.

6.4.5. Expedite the above procedure so that the sample is exposed to the atmosphere for a minimum time.

6.5. General Procedures:

6.5.1. Weighing—The calculations included in the individual test methods assume that the exact weight specified has been used. Accurately weighed samples, that are approximately but not exactly equal to the weight specified, may be used provided appropriate corrections are made in the calculations. Unless otherwise stated, weights of all samples and residues should be recorded to the nearest 0.0001 g.

6.5.2. Tared or Weighed Crucibles—The tare weight of crucibles shall be determined by preheating the empty crucible to constant weight at the same temperature and under the same conditions as shall be used for the final ignition of a residue and cooling in a desiccator for the same period of time used for the crucible containing the residue.

6.5.3. Constancy of Weight of Ignited Residues—To definitely establish the constancy of weight of an ignited residue for referee purposes, the residue shall be ignited at the specified temperature and for the specified time, cooled to room temperature in a desiccator, and weighed. The residue shall then be reheated for at least 30 min, cooled to room temperature in a desiccator, and reweighed. If the two weights do not differ by more than 0.2 mg, constant weight is considered to have been attained. If the difference in weights is greater than 0.2 mg, additional ignition periods are required until two consecutive weights agree within the specified limits. For ignition loss, each reheating period shall be 5 min.

6.5.4. Volatilization of Platinum—The possibility of volatilization of platinum or alloying constituents from the crucibles must be considered. On reheating, if the crucible and residue lose the same weight (within 0.2 mg) as the crucible containing the blank, constant weight can be assumed. Crucibles of the same size, composition, and history shall be used for both the sample and the blank.

6.5.5. Calculation—In all operations on a set of observed values such as manual multiplication or division, retain the equivalent of at least two more places of figures than in the single observed values. For example, if observed values are read or determined to the nearest 0.1 mg, carry numbers to the nearest 0.001 mg in calculation. When using electronic calculators or computers for calculations, perform no rounding, except in the final reported value.

6.5.6. Rounding Figures—Rounding of figures to the number of significant places required in the report should be done after calculations are completed to keep the final results substantially free of calculation errors. The rounding procedure should follow the principle outlined in ASTM E29.5 In assessing analyst and method qualification in accordance with Section 5, the individual duplicate results, the difference between them, the average of duplicates on CRMs, and the difference of this average from the certificate value shall be left unrounded for comparison with the required limits. (See Note 68.) Round results for reporting as shown in Table 3. Note 68—The rounding procedure referred to in Section 6.5.6, in effect, drops all digits beyond the number of places to be retained if the next figure is less than 5. If it is more than 5 or equal to 5 and subsequent places contain a digit other than 0, then the last retained digit is increased by one. When the next digit is equal to 5 and all other subsequent digits are 0, the last digit to be retained is unchanged when it is even and increased by one when it is odd. For example, 3.96 (50) remains 3.96, but 3.95 (50) becomes 3.96.

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6.6. Recommended Order for Reporting Analyses—The following order is recommended for reporting the results of chemical analysis of hydraulic cement: SiO2 (silicon dioxide) Al2O3 (aluminum oxide) Fe2O3 (ferric oxide) CaO (calcium oxide) MgO (magnesium oxide) SO3 (sulfur trioxide) Na2O (sodium oxide) K2O (potassium oxide) TiO2 (titanium dioxide) P2O5 (phosphorus pentoxide) ZnO (zinc oxide) Mn2O3 (manganic oxide) Insoluble residue Free calcium oxide CO2 (carbon dioxide) Water-soluble alkali Chloroform-soluble organic substances

Table 3—Rounding of Reported Results

Analyte Decimal Places SiO2 (silicon dioxide) 1 Al2O3 (aluminum oxide) 1 Fe2O3 (ferric oxide) 2 CaO (calcium oxide) 1 MgO (magnesium oxide) 1 SO3 (sulfur trioxide) 2 LOI (loss on ignition) 1 Na2O (sodium oxide) 2 K2O (potassium oxide) 2 SrO (strontium oxide) 2 TiO2 (titanium dioxide) 2 P2O5 (phosphorous pentoxide) 2 ZnO (zinc oxide) 2 Mn2O3 (manganic oxide) 3 S (sulfide sulfur) 2 Cl (chloride) 3 IR (insoluble residue) 2 Cx (free calcium oxide) 1 CO2 (carbon dioxide) 1 Alksol (water-soluble alkali) 2 Chlsol (chloroform-soluble organic substances) 3

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REFERENCE TEST METHODS

7. INSOLUBLE RESIDUE (REFERENCE TEST METHOD)

7.1. Summary of Test Method:

7.1.1. In this test method, insoluble residue of a cement is determined by digestion of the sample in hydrochloric acid followed, after filtration, by further digestion in sodium hydroxide. The resulting residue is ignited and weighed (see Note 79). Note 79—This test method, or any other test method designed for the estimation of an acid-insoluble substance in any type of cement, is empirical because the amount obtained depends on the reagents and the time and temperature of digestion. If the amount is large, there may be a little variation in duplicate determinations. The procedure should be followed closely to reduce the variation to a minimum.

7.1.2. When this test method is used on blended cement, the decomposition in acid is considered to be complete when the portland cement clinker is decomposed completely. An ammonium nitrate solution is used in the final washing to prevent finely ground insoluble material from passing through the filter paper.

7.2. Reagents:

7.2.1. Ammonium Nitrate Solution (20 g NH4NO3/L).

7.2.2. Sodium Hydroxide Solution (10 g NaOH/L).

7.3. Procedure:

7.3.1. To 1 g of the sample (see Note 810), add 25 mL of cold water. Disperse the cement in the water and while swirling the mixture, quickly add 5 mL of HCl. If necessary, warm the solution gently and grind the material with the flattened end of a glass rod for a few minutes until it is evident that decomposition of the cement is complete (see Note 911). Dilute the solution to 50 mL with hot water (nearly boiling) and heat the covered mixture rapidly to near boiling by means of a high-temperature hot plate. Then digest the covered mixture for 15 min at a temperature just below boiling (see Note 1012). Filter the solution through a medium-textured paper into a 400-mL beaker; wash the beaker, paper, and residue thoroughly with hot water; and reserve the filtrate for the sulfur trioxide determination, if desired (see Note 1113). Transfer the filter paper and contents to the original beaker, add 100 mL of hot (near boiling) NaOH solution (10 g/L), and digest at a temperature just below boiling for 15 min. During the digestion, occasionally stir the mixture and macerate the filter paper. Acidify the solution with HCl using methyl red as the indicator and add an excess of 4 or 5 drops of HCl. Filter through medium-textured paper and wash the residue at least 14 times with hot NH4NO3 solution (20 g/L), making sure to wash the entire filter paper and contents during each washing. Ignite the residue in a weighed platinum crucible at 900 to 1000°C, cool in a desiccator, and weigh. Note 108—If sulfur trioxide is to be determined by turbidimetry, it is permissible to determine the insoluble residue on a 0.5-g sample. In this event, the percentage of insoluble residue should be calculated to the nearest 0.01 by multiplying the weight of residue obtained by 200. However, the cement should not be rejected for failure to meet the insoluble residue requirement unless a 1-g sample has been used. Note 911—If a sample of portland cement contains an appreciable amount of manganic oxide, there may be brown compounds of manganese that dissolve slowly in cold diluted HCl but rapidly in hot HCl in the specified strength. In all cases, dilute the solution as soon as decomposition is complete.

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Note 1210—To keep the solutions closer to the boiling temperature, it is recommended that these digestions be carried out on an electric hot plate rather than in a steam bath. Note 1311—Continue with the sulfur trioxide determination (see Sections 17.1.2.1 through 17.1.3) by diluting to 250 mL or 200 mL, as required by the appropriate section.

7.3.2. Blank—Make a blank determination, following the same procedure and using the same amounts of reagents, and correct the results obtained in the analysis accordingly.

7.4. Calculation—Calculate the percentage of the insoluble residue to the nearest 0.01 by multiplying the weight in grams of the residue (corrected for the blank) by 100.

8. SILICON DIOXIDE (REFERENCE TEST METHOD)

8.1. Selection of Test Method—For cements other than portland and for which the insoluble residue is unknown, determine the insoluble residue in accordance with Section 7 of these test methods. For portland cements and other cements having an insoluble residue less than 1 percent, proceed in accordance with Section 8.2. For cements having an insoluble residue greater than 1 percent, proceed in accordance with Section 8.3.

8.2. Silicon Dioxide in Portland Cements and Cements with Low Insoluble Residue:

8.2.1. Summary of Test Method—In this test method, silicon dioxide (SiO2) is determined gravimetrically. Ammonium chloride is added, and the solution is not evaporated to dryness. This test method was developed primarily for hydraulic cements that are almost completely decomposed by hydrochloric acid, and should not be used for hydraulic cements that contain large amounts of acid-insoluble material and require a preliminary sodium carbonate fusion. For such cements, or if prescribed in the standard specification for the cement being analyzed, the more lengthy procedure in Section 8.3 shall be used.

8.2.2. Reagent—Ammonium chloride (NH4Cl).

8.2.3. Procedure:

8.2.3.1. Mix thoroughly 0.5 g of the sample and about 0.5 g of NH4Cl in a 50-mL beaker, cover the beaker with a watch glass, and add cautiously 5 mL of HCl, allowing the acid to run down the lip of the covered beaker. After the chemical action has subsided, lift the cover, add 1 or 2 drops of HNO3, stir the mixture with a glass rod, replace the cover, and set the beaker on a steam bath for 30 min (see Note 1412). During this time of digestion, stir the contents occasionally and break up any remaining lumps to facilitate the complete decomposition of the cement. Fit a medium-textured filter paper to a funnel, transfer the jellylike mass of silicic acid to the filter as completely as possible without dilution, and allow the solution to drain through. Scrub the beaker with a policeman, and rinse the beaker and policeman with hot HCl (1+99). Wash the filter two or three times with hot HCl (1+99) and then with 10 or 12 small portions of hot water, allowing each portion to drain through completely. Reserve the filtrate and washings for the determination of the ammonium hydroxide group (see Note 1513). Note 1412—A hot plate may be used instead of a steam bath if the heat is so regulated as to approximate that of a steam bath. Under conditions where water boils at a lower temperature than at sea level, such as at higher elevations, 30 min may not be sufficient to recover all of the silica. In such cases, increase the time of digestion as necessary to get complete recovery of the silica. In no case should this time exceed 60 min. Note 1513—Determine the ammonium hydroxide group in accordance with the procedure described in Sections 9.1 through 9.3.

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8.2.3.2. Transfer the filter paper and residue to a weighed platinum crucible, dry, and ignite, at first slowly until the carbon of the paper is completely consumed without inflaming, and finally at 1100 to 1200°C for 1 h. Cool in a desiccator and weigh. Reignite to constant weight. Treat the SiO2 thus obtained, which will contain small amounts of impurities, in the crucible with 1 or 2 mL of water, 2 drops of H2SO4 (1+1), and about 10 mL of HF, and evaporate cautiously to dryness. Finally, heat the small residue at 1050 to 1100°C for 5 min, cool in a desiccator, and weigh. The difference between this weight and the weight previously obtained represents the weight of SiO2. Consider the weighed residue remaining after the volatilization of SiO2 as combined aluminum and ferric oxides, and add it to the result obtained in the determination of the ammonium hydroxide group.

8.2.3.3. If the HF residue exceeds 0.0020 g, the silica determination shall be repeated, steps should be taken to ensure complete decomposition of the sample before a silica separation is attempted and the balance of the analysis (ammonium hydroxide group, CaO, and MgO) determined on the new silica filtrate, provided the new silica determination has an HF residue of 0.0020 g or less, except as provided in Sections 8.2.3.4 and 8.2.3.5.

8.2.3.4. If two or three repeated determinations of a sample of portland cement consistently show HF residues higher than 0.0020 g, this is evidence that contamination has occurred in sampling or the cement has not been burned properly during manufacture. In such a case, do not fuse the large HF residue with pyrosulfate for subsequent addition to the filtrate from the silica separation. Instead, report the value obtained for the HF residue. Do not ignite the ammonium hydroxide group in the crucible containing this abnormally large HF residue.

8.2.3.5. In the analysis of cements other than portland, it may not always be possible to obtain HF residues under 0.0020 g. In such cases, add 0.5 g of sodium or potassium pyrosulfate (Na2S2O7 or K2S2O7) to the crucible and heat below red heat until the small residue of impurities is dissolved in the melt (see Note 14). Cool, dissolve the fused mass in water, and add it to the filtrate and washings reserved for the determination of the ammonium hydroxide group. Note 1614—A supply of nonspattering pyrosulfate may be prepared by heating some pyrosulfate in a platinum vessel below red heat until the foaming and spattering cease, cooling, and crushing the fused mass.

8.2.3.6. Blank—Make a blank determination, following the same procedure and using the same amounts of reagents, and correct the results obtained in the analysis accordingly.

8.2.4. Calculation—Calculate the percentage of SiO2 by multiplying the mass in grams of SiO2 by 200 (100 divided by the mass (see Section 8.2.3.1) or equivalent mass (see Section 8.3.2.1) of the sample used (0.5 g)). Round in accordance with Table 3.

8.3. Silicon Dioxide in Cements with Insoluble Residue Greater Than 1 Percent:

8.3.1. Summary of Test Method—This test method is based on the sodium carbonate fusion followed by double evaporation to dryness of the hydrochloric acid solution of the fusion product to convert silicon dioxide (SiO2) to the insoluble form. The solution is filtered, and the insoluble siliceous residue is ignited and weighed. Silicon dioxide is volatilized by hydrofluoric acid, and the loss of weight is reported as pure SiO2.

8.3.2. Procedure:

8.3.2.1. Weigh a quantity of the ignited sample equivalent to 0.5 g of the as-received sample calculated as follows: W = [(0.5(100.00 – I )]/100 (1)(2)

TS-3a T 105-16 AASHTO

where: W = weight of ignited sample, g, and I = loss of ignition, percent.

The ignited material from the loss on ignition determination may be used for the sample. Thoroughly mix the sample with 4 to 6 g of Na2CO3 by grinding in an agate mortar. Place a thin layer of Na2CO3 on the bottom of a platinum crucible of 20- to 30-mL capacity, add the cement-Na2CO3 mixture, and cover the mixture with a thin layer of Na2CO3. Place the covered crucible over a moderately low flame, increase the flame gradually to a maximum (approximately 1100°C), and maintain this temperature until the mass is quiescent (about 45 min). Remove the burner, lay aside the cover of the crucible, grasp the crucible with tongs, and slowly rotate the crucible so that the molten contents spread over the sides and solidify as a thin shell on the interior. Set the crucible and cover aside to cool. Rinse off the outside of the crucible and place the crucible on its side in a 300-mL casserole about one-third full of water. Warm the casserole and stir until the cake in the crucible disintegrates and can be removed easily. By means of a glass rod, lift the crucible out of the liquid, rinsing it thoroughly with water. Rinse the cover and crucible with HCl (1+3), and then add the rinse to the casserole. Very slowly and cautiously add 20 mL of HCl (sp gr 1.19) to the covered casserole. Remove the cover and rinse. If any gritty particles are present, the fusion is incomplete and the test must be repeated, using a new sample. Warning—Subsequent steps of the test method must be followed exactly for accurate results.

8.3.2.2. Evaporate the solution to dryness on a steam bath (until it no longer appears gelatinous). Without heating the residue any further, treat it with 5 to 10 mL of HCl, wait at least 2 min, and then add an equal amount of water. Cover the dish and digest for 10 min on the steam bath or a hot plate. Dilute the solution with an equal volume of hot water, immediately filter through medium-textured paper and wash the separated SiO2 thoroughly with hot HCl (1+99), then with hot water. Reserve the residue.

8.3.2.3. Again evaporate the filtrate to dryness, and bake the residue in an oven for 1 h at 105 to 110°C. Cool, add 10 to 15 mL of HCl (1+1), and digest on the steam bath or hot plate for 10 min. Dilute with an equal volume of water, filter immediately on a fresh filter paper, and wash the small SiO2 residue thoroughly as described in Section 8.3.2.2. Stir the filtrate and washings, and reserve for the determination of the ammonium hydroxide group in accordance with Sections 9.1 through 9.3.

8.3.2.4. Continue the determination of silicon dioxide in accordance with Section 8.2.3.2.

9. AMMONIUM HYDROXIDE GROUP (REFERENCE TEST METHOD)

9.1. Summary of Test Method—In this test method, aluminum, iron, titanium, and phosphorus are precipitated from the filtrate, after SiO2 removal, by means of ammonium hydroxide. With care, little if any manganese will be precipitated. The precipitate is ignited and weighed as the oxides.

9.2. Procedure:

9.2.1. To the filtrate reserved in accordance with Section 8.2.3.1 (see Note 1517), which should have a volume of about 200 mL, add HCl if necessary to ensure a total of 10 to 15 mL of the acid. Add a few drops of methyl red indicator and heat to boiling. Then treat with NH4OH (1+1) (see Note 1618) dropwise until the color of the solution becomes distinctly yellow, and add one drop in excess (see Note 1917). Heat the solution containing the precipitate to boiling and boil for 50 to 60 s. In the event difficulty from bumping is experienced while boiling the ammoniacal solution, a digestion period of 10 min on a steam bath, or on a hot plate having the approximate temperature of a steam bath, may be substituted for the 50- to 60-s boiling period. Allow the precipitate to settle (not more than 5 min) and filter using medium-textured paper (see Note 2018). Wash, with

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hot ammonium nitrate (NH4NO3, 20 g/L) (see Note 2119), twice for a small precipitate to about four times for a large one. Note 1715—If a platinum evaporating dish has been used for the dehydration of SiO2, iron may have been partially reduced. At this stage, add about 3 mL of saturated bromine water to the filtrate and boil the filtrate to eliminate the excess bromine before adding the methyl red indicator. If difficulty from bumping is experienced during the boiling, the following alternate techniques may be helpful: (1) a piece of filter paper, approximately 1 cm2 in area, positioned where the bottom and side of the beaker merge and held down by the end of a stirring rod may solve the difficulty, and (2) use of 400-mL beakers supported inside a cast aluminum cup has also been found effective. Note 1816—The NH4OH used to precipitate the hydroxides must be free of contamination with carbon dioxide (CO2). Note 1917—It usually takes 1 drop of NH4OH (1+1) to change the color of the solution from red to orange and another drop to change the color from orange to yellow. If desired, the addition of the indicator may be delayed until ferric hydroxide (Fe(OH)3) is precipitated without aluminum hydroxide (Al(OH)3) being completely precipitated. In such a case, the color changes may be better observed. However, if the content of Fe2O3 is unusually great, it may be necessary to occasionally let the precipitate settle slightly so that the color of the supernatant liquid can be observed. If the color fades during the precipitation, add more of the indicator. Observation of the color where a drop of the indicator strikes the solution may be an aid in the control of the acidity. The boiling should not be prolonged as the color may reverse and the precipitate may be difficult to retain on the filter. The solution should be distinctly yellow when it is ready to filter. If it is not, restore the yellow color with more NH4OH (1+1) or repeat the precipitation. Note 2018—To avoid drying of the precipitate with resultant slow filtration, channeling, or poor washing, the filter paper should be kept nearly full during the filtration and should be washed without delay. Note 2119—Two drops of methyl red indicator solution should be added to the NH4NO3 solution in the wash bottle, followed by NH4OH (1+1) added dropwise until the color just changes to yellow. If the color reverts to red at any time due to heating, it should be brought back to yellow by the addition of a drop of NH4OH (1+1).

9.2.2. Set aside the filtrate, and transfer the precipitate and filter paper to the same beaker in which the first precipitation was effected. Dissolve the precipitate with hot HCl (1+2). Stir to thoroughly macerate the paper, and then dilute the solution to about 100 mL. Reprecipitate the hydroxides as described in Section 9.2.1. If difficulty from bumping is experienced while boiling the acid solution containing the filter paper, it may be obviated by diluting the hot 1+2 solution of the mixed oxides with 100 mL of boiling water and thus eliminate the need for boiling. Filter the solution and wash the precipitate with about four 10-mL portions of hot NH4NO3 solution (20 g/L) (see Note 19). Combine the filtrate and washings with the filtrate set aside, and reserve for the determination of CaO in accordance with Section 15.3.1.

9.2.3. Place the precipitate in a weighed platinum crucible, heat slowly until the papers are charred, and finally ignite to constant weight at 1050 to 1100°C, taking care to prevent reduction, and weigh as the ammonium hydroxide group.

9.2.4. Blank—Make a blank determination, following the same procedure and using the same amounts of reagents, and correct the results obtained in the analysis accordingly.

9.3. Calculation—Calculate the percentage of ammonium hydroxide group by multiplying the weight in grams of ammonium hydroxide group by 200 (100 divided by the weight of sample used (0.5 g)).

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10. FERRIC OXIDE (REFERENCE TEST METHOD)

10.1. Summary of Test Method—In this test method, the Fe2O3 content of the cement is determined on a separate portion of the cement by reducing the iron to the ferrous state with stannous chloride (SnCl 2) and titrating with a standard solution of potassium dichromate (K2Cr2O7). This determination is not affected by any titanium or vanadium that may be present in the cement.

10.2. Reagents:

10.2.1. Barium Diphenylamine Sulfonate Indicator Solution—Dissolve 0.3 g of barium diphenylamine sulfonate in 100 mL of water.

10.2.2. Potassium Dichromate, Standard Solution (1 mL = 0.004 g Fe2O3)—Pulverize and dry primary standard potassium dichromate (K2Cr2O7) reagent, the current lot of NIST 136, at 180 to 200°C to constant weight. Weigh accurately an amount of dried reagent equal to 2.45700 g times the number of liters of solution to be prepared. Dissolve in water and dilute to exactly the required volume in a single volumetric flask of the proper size. This solution is a primary standard and requires no further standardization. Note 2220—Where large quantities of standard solution are required, it may be desirable for certain laboratories to use commercially produced primary standard potassium dichromate for most determinations. Such a material may be used provided that the first solution made from the container is checked as follows: Using a standard solution of NIST 136, prepared as described in Section 10.2.2, analyze, in duplicate, samples of an NIST CRM cement, by the procedure given in Section 10.3.1. Repeat using a similar solution prepared from the commercial primary standard dichromate. The average percentages of Fe2O3 found by each method should not differ by more than 0.06 percent.

10.2.3. Stannous Chloride Solution—Dissolve 5 g of stannous chloride (SnCl2 · 2H2O) in 10 mL of HCl and dilute to 100 mL. Add scraps of iron-free granulated tin and boil until the solution is clear. Keep the solution in a closed dropping bottle containing metallic tin.

10.3. Procedure—For cements other than portland and for which the insoluble residue is unknown, determine the insoluble residue in accordance with the appropriate sections of these test methods. When insoluble residue is known, proceed in accordance with Section 10.3.1 or Section 10.3.2 as is appropriate for the cement being analyzed.

10.3.1. For portland cements and cements having insoluble residue lower than 1 percent, weigh 1 g of the sample into a 500-mL Phillips beaker or other suitable container. Add 40 mL of cold water and, while the beaker is being swirled, add 10 mL of HCl. If necessary, heat the solution and grind the cement with the flattened end of a glass rod until it is evident that the cement is completely decomposed. Continue the analysis in accordance with Section 10.3.3.

10.3.2. For cements with insoluble residue greater than 1 percent, weigh a 0.500 g sample, blend with 1 g LiBO2 using a mortar and pestle, and transfer to a previously fired 8-mL carbon crucible that has 0.1 g LiBO2 sprinkled in the bottom (see Note 2123). Cover with 0.1 g LiBO2 that was used to chemically wash the mortar and pestle (see Note 2224). Place the uncovered crucible in a furnace set at 1100°C for 15 min. Remove the crucible from the furnace and check for complete fusion (see Note 2325). If the fusion is incomplete, return the crucible to the furnace for another 30 min. Again, check for complete fusion. If the fusion is still incomplete, discard the sample and repeat the fusion procedure using 0.250 g sample or a smaller quantity with the same amount of LiBO2. When the fusion is complete, gently swirl the melt and pour into a 150-mL glass beaker containing 10 mL concentrated HCl and 50 mL water. Stir continuously until the fusion product is dissolved, usually 10 min or less (see Note 24). If a stirring bar is used, remove and rinse the bar. Continue the analysis in accordance with Section 10.3.3.

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Note 2321—The firing loosens the carbon on the surface, reducing the possibility of the fusion product sticking to the crucible. Note 2422—A chemical wash is a dry rinse of the equipment in which the blending was done so that any sample adhering to this equipment will be loosened and transferred to the crucible. Note 2325—When fusion is incomplete, the sample may not be completely melted, or there may be particles on top of the bead. Usually, if the bead forms a small smooth spherical ball when taken from the furnace and before it is swirled, the sample is completely fused. Note 2426—There are usually some carbon particles that are in suspension, undissolved in the solution, but they will not interfere with the completion of the analysis.

10.3.3. Heat the solution to boiling and treat it with the SnCl2 solution, added dropwise while stirring and boiling, until the solution is decolorized. Add 1 drop in excess and cool the solution to room temperature by placing the beaker in a pan of cool water. After cooling and without delay, rinse the inside of the vessel with water, and add all at once 10 mL of a cool, saturated mercuric chloride (HgCl2) solution. Stir the solution vigorously for 1 min by swirling the beaker and add 10 mL of H3PO4 (1+1) and 2 drops of barium diphenylamine sulfonate indicator. Add sufficient water so that the volume after titration will be between 75 and 100 mL. Titrate with the standard K2Cr2O7 solution. The end point shall be taken as the point at which a single drop causes an intense purple coloration that remains unchanged on further addition of standard K2Cr2O7 solution.

10.3.4. Blank—Make a blank determination following the same procedure and using the same amounts of reagents. Record the volume of K2Cr2O7 solution required to establish the end point as described in Section 10.3.3. Because some iron must be present to obtain the normal end point, if no definite purple color is obtained after the addition of 4 drops of the standard K2Cr2O7 solution, record the blank as zero.

10.4. Calculation:

10.4.1. Calculate the percentage of Fe2O3 as follows: Fe2O3, % = E ( V – B ) × 100/W (2)(3) where: E = Fe2O3 equivalent of the K2Cr2O7 solution, g/mL; V = milliliters of K2Cr2O7 solution required by the sample determination; B = milliliters of K2Cr2O7 solution required by the blank determination; and W = mass of sample within 0.1 mg.

Round in accordance with Table 3.

11. PHOSPHORUS PENTOXIDE (REFERENCE TEST METHOD)

11.1. Summary of Test Method—This colorimetric test method is applicable to the determination of P2O5 in portland cement. Under the conditions of the test, no constituent normally present in portland cement will interfere.

11.2. Apparatus:

11.2.1. Spectrophotometer (see Note 25):

11.2.1.1. The instrument shall be equipped to measure absorbance of solutions at a spectral wavelength of 725 nm.

11.2.1.2. Wavelength measurements shall be repeatable within ±1 nm or less.

TS-3a T 105-20 AASHTO

11.2.1.3. In the absorbance range from 0.1 to 1.0, the absorbance measurements shall be repeatable within ±1 percent or less.

11.2.1.4. To establish that the spectrophotometer will permit a satisfactory degree of accuracy, qualify the instrument in accordance with Section 5.4.2 using the procedure in Sections 11.4.1 through 11.4.9. Note 2725—For the measurement of the performance of the spectrophotometer, refer to ASTM E275.

11.3. Reagents:

11.3.1. Ammonium Molybdate Solution—Into a 1-L volumetric flask introduce 500.0 mL of 10.6 N H2SO4 (see Section 11.3.7). Dissolve 25.0 g of ammonium molybdate ((NH4)6Mo7O24 · 4H2O) in about 250 mL of warm water and transfer to the flask containing the H2SO4, while swirling the flask. Cool, dilute to 1 L with water, and store in a plastic bottle.

11.3.2. Ascorbic Acid Powder—For ease in dissolving, the finest mesh available should be used.

11.3.3. Hydrochloric Acid, Standard (6.5 ± 0.1 N)—Dilute 540 mL of concentrated HCl (sp gr 1.19) to 1 L with water. Standardize against standard NaOH solution (see Section 11.3.6) using phenolphthalein as indicator. Determine the exact normality and adjust to 6.5 ± 0.1 N by dilution with water. Restandardize to ensure the proper normality has been achieved.

11.3.4. Phosphate, Standard Solution A—Dissolve 0.1917 g of oven-dried potassium dihydrogen phosphate (KH2PO4) in water and dilute to 1 L in a volumetric flask.

11.3.5. Phosphate, Standard Solution B—Dilute 50.0 mL of phosphate solution A to 500 mL with water.

11.3.6. Sodium Hydroxide, Standard Solution (1 N)—Dissolve 40.0 g of sodium hydroxide (NaOH) in water, add 10 mL of a freshly filtered saturated solution of barium hydroxide (Ba(OH)2), and dilute to 1 L with water that has been recently boiled and cooled. Shake the solution from time to time during a several-hour period, and filter into a plastic bottle. Keep the bottle tightly closed to protect the solution from CO2 in the air. Standardize against acid potassium phthalate or benzoic acid acidimetric standards furnished by NIST (Standard Samples No. 84f and 350) using the test methods in the certificates accompanying the standard samples. Determine the exact normality of the solution.

11.3.7. Sulfuric Acid, Standard (10.6 ± 0.1 N)—To a 1-L volumetric flask cooled in water, add about 600 mL of water and then, slowly, with caution, add 300 mL of concentrated H2SO4 (sp gr 1.84). After cooling to room temperature, dilute to 1 L with water. Standardize against the standard NaOH solution (see Section 11.3.6) using phenolphthalein as indicator. Determine the normality and adjust to 10.6 ± 0.1 N by dilution with water. Restandardize to ensure the proper normality has been achieved.

11.4. Procedure:

11.4.1. Prepare a series of phosphate solutions to cover the range from 0 to 0.5 percent P2O5. Prepare each solution by adding a suitable volume of standard phosphate solution B and 25.0 mL of the 6.5 N hydrochloric acid to a 250-mL volumetric flask (see Note 2826). Dilute to the mark with water. Note 2628—One milliliter of standard phosphate solution B/250 mL of solution is equivalent to 0.004 percent P2O5 for a 0.25-g cement sample. Aliquots of 0, 12.5, 25, 50, 75, 100, and 125 mL are equivalent to P2O5 contents in the sample of 0, 0.05, 0.10, 0.20, 0.30, 0.40, and 0.50 percent.

11.4.2. Prepare a blank by adding 25.0 mL of the standard HCl to a 250-mL volumetric flask and diluting to 250 mL with water.

TS-3a T 105-21 AASHTO

11.4.3. Develop colors in the series of phosphate solutions and in the blank, in accordance with Sections 11.4.6 through 11.4.8.

11.4.4. Plot the net absorbance (absorbance of standard minus that of the blank) values obtained as ordinates and the corresponding P2O5 concentrations as abscissas. Draw a smooth curve through the points. Note 2927—A suitable paper for plotting the calibration curve is a 10-by-15-in. (254-by-381-mm) linear cross-section paper having 20 by 20 divisions to the inch (25.4 mm). The percentage of P2O5 can then be plotted on the long dimension using five divisions equal to 0.01 percent P2O5. A scale of one division equal to 0.005 absorbance units is suitable as the ordinate (short dimension of the paper). Scales other than this may be used, but under no circumstances should a scale division less than 0.05 in. (1.3 mm) be used for 0.005 units of absorbance or for 0.005 percent P2O5. A separate calibration curve should be made for each spectrophotometer used, and the calibration curve checked against standard phosphate solution whenever a new batch of ammonium molybdate reagent is used.

11.4.5. Transfer 0.250 g of the sample to a 250-mL beaker and moisten with 10 mL of cold water to prevent lumping. Add 25.0 mL of the standard HCl and digest with the aid of gentle heat and agitation until solution is complete. Filter into a 250-mL volumetric flask, and wash the paper and the separated silica thoroughly with hot water. Allow the solution to cool, and then dilute with water to 250 mL.

11.4.6. Transfer a 50.0-mL aliquot (see Note 30 28) of the sample solution to a 250-mL beaker, and add 5.0 mL of ammonium molybdate solution and 0.1 g of ascorbic acid powder. Mix the contents of the beaker by swirling until the ascorbic acid has dissolved completely. Heat the solution to vigorous boiling. and then boil, uncovered, for 1.5 ± 0.5 min. Cool to room temperature and transfer to a 50-mL volumetric flask. Rinse the beaker with one small portion of water and add the rinse water to the flask. Dilute to 50 mL with water. Note 3028—The range of the test can be extended by taking a smaller aliquot of the sample solution. In such instances, the decrease in the aliquot volume must be made up by the blank solution (see Section 11.4.5) to maintain the proper acidity of the final solution. Thus, if a 25-mL aliquot of the sample solution is taken (instead of the usual 50 mL), a 25-mL aliquot of the blank solution should be added before proceeding with the test. The result of the test must then be calculated accordingly.

11.4.7. Measure the absorbance of the solution against water as the reference at 725.0 nm.

11.4.8. Develop on a 50.0-mL aliquot of the blank solution prepared in Section 11.4.2 in the same manner as was used in Section 11.4.6 for the sample solution. Measure the absorbance in accordance with Section 11.4.7 and subtract this absorbance value from that obtained for the sample solution in Section 11.4.6 to obtain the net absorbance for the sample solution.

11.4.9. Using the net absorbance value found in Section 11.4.8, record the percentage of P2O5 in the cement sample as indicated by the calibration curve. Report the percentage of P2O5 rounded in accordance with Table 3.

12. TITANIUM DIOXIDE (REFEREE TEST METHOD)

12.1. Summary of Test Method—In this test method, titanium dioxide (TiO2) in portland cement is determined colorimetrically using Tiron reagent. Under the conditions of the test, iron is the only constituent of portland cement causing a very slight interference equivalent to 0.01 percent for each 1 percent of Fe2O3 present in the sample.

12.2. Apparatus:

TS-3a T 105-22 AASHTO

12.2.1. Spectrophotometer (see Note 29):

12.2.1.1. The instrument shall be equipped to measure absorbance of solutions at a spectral wavelength of 410 nm.

12.2.1.2. Wavelength measurements shall be repeatable within ±1 nm or less.

12.2.1.3. In the absorbance range from 0.1 to 1.0, the absorbance measurements shall be repeatable within ±1 percent or less.

12.2.1.4. To establish that the spectrophotometer will permit a satisfactory degree of accuracy, qualify the instrument in accordance with Section 5.4.2 using the procedure in Sections 12.4.1 through 12.4.6 of this test method. Note 3129—For the measurement of the performance of the spectrophotometer, refer to ASTM E275.

12.3. Reagents:

12.3.1. Buffer (pH 4.7)—68 g of NaC2H3O2 · 3H2O (sodium acetate trihydrate), plus 380 mL of water, plus 100 mL of 5.0 N CH3COOH (acetic acid).

12.3.2. Ethylenedinitrilo Tetraacetic Acid Disodium Salt, Dihydrate (0.2 M EDTA)—Dissolve 37.5 g of EDTA in 350 mL of warm water and filter. Add 0.25 g of FeCl3 · 6H2O (ferric chloride hexahydrate) and dilute to 500 mL.

12.3.3. Hydrochloric Acid (1+6).

12.3.4. Hydrochloric Acid, Standard (6.5 N)—Dilute 540 mL of concentrated HCl (sp gr 1.19) to 1 L with water.

12.3.5. Ammonium Hydroxide (NH4OH, 1+1).

12.3.6. Potassium Pyrosulfate (K2S2O7).

12.3.7. Titanium Dioxide, Stock Solution A—Fuse slowly in a platinum crucible over a very small flame 0.0314 g of NIST SRM 154b (TiO2 = 99.74 percent) or its replacements with about 2 or 3 g of K2S2O7. Allow to cool, and place the crucible in a beaker containing 125 mL of H2SO4 (1+1). Heat and stir until the melt is completely dissolved. Cool, transfer to a 250-mL volumetric flask, and dilute the solution to volume.

12.3.7.1. Titanium Dioxide, Dilute Standard Solution B (1 mL = 0.0125 mg TiO2)—Pipet 50 mL of stock TiO2 solution into a 500-mL volumetric flask, and dilute to volume. One milliliter of this solution is equal to 0.0125 mg of TiO2, which is equivalent to 0.05 percent TiO2 when used as outlined in Sections 12.4.4 through 12.4.6.

12.3.8. Sulfuric acid (1+1).

12.3.9. Tiron (disodium-1,2-dihydroxybenzene-3,5 disulfonate).

12.4. Procedure:

12.4.1. Prepare a series of TiO2 solutions to cover the range from 0 to 1.0 percent TiO2. Prepare each solution in a 50-mL volumetric flask (see Note 3230).

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Note 3230—One milliliter of dilute TiO2 standard solution B per 50 mL (see Section 12.3.7.1) is equivalent to 0.05 percent TiO2 for a 0.2500-g cement sample. Aliquots of 0, 5, 10, 15, and 20 mL of dilute TiO2 standard solution are equivalent to TiO2 contents in the sample of 0, 0.25, 0.50, 0.75, and 1.0 percent. Dilute each to 25 mL with water.

12.4.2. Develop color in accordance with Section 12.4.4 starting with second sentence. Measure absorbance in accordance with Section 12.4.5.

12.4.3. Plot absorbance values obtained as ordinates and the corresponding TiO2 concentrations as abscissas. Draw a smooth curve through the points. Note 3331—A suitable paper for plotting the calibration curve is a linear cross-section paper having 10 by 10 divisions to 1 cm. A scale division equivalent to 0.002 absorbance and 0.002 percent TiO2 should be used. A separate calibration curve should be made for each spectrophotometer used.

12.4.4. Transfer a 25.0-mL aliquot of the sample solution prepared in Section 11.4.5 into a 50-mL volumetric flask (see Note 3432). Add 5 mL Tiron and 5 mL EDTA, mix, and then add NH4OH (1+1) dropwise, mixing thoroughly after each drop, until the color changes through yellow to green, blue, or ruby red. Then, just restore the yellow color with HCl (1+6) added dropwise and mixing after each drop. Add 5 mL buffer, dilute to volume and mix. Note 3432—The range of the test can be extended by taking a smaller aliquot. The results of the test must then be calculated accordingly.

12.4.5. Measure the absorbance of the solution against water as the reference at 410 nm.

12.4.6. Using the absorbance value determined in Section 12.4.5, record the percentage of TiO2 in the cement sample as indicated by the calibration curve. Correct for the iron present in the sample to obtain the true TiO2 as follows: True TiO2 = measured percent TiO2 − (0.01 × percent Fe2O3). Report the percent of TiO2 rounded in accordance with Table 3.

13. ZINC OXIDE (REFERENCE TEST METHOD)6

13.1. Any test method may be used that meets the requirements of Section 5.4 and Table 1.

13.2. Report the result rounded in accordance with Table 3.

14. ALUMINUM OXIDE (REFERENCE TEST METHOD) Note 3533—In the reference test method, Al2O3 is calculated from the ammonium hydroxide group by subtracting the separately determined constituents that usually are present in significant amounts in the ammonium hydroxide precipitate. These are Fe2O3, TiO2, and P2O5. Most instrumental test methods for Al2O3 analysis give Al2O3 alone if standardized and calibrated properly.

14.1. Calculation:

14.1.1. Calculate the percentage of Al2O3 by deducting the percentage of the sum of the Fe2O3, TiO2, and P2O5 from the percentage of ammonium hydroxide group, using unrounded values of all four quantities. All determinations shall be by referee test methods described in the appropriate sections herein. Report the Al2O3 rounded in accordance with Table 3. For nonreferee analyses, the percentages of Fe2O3, TiO2, and P2O5 can be determined by any procedure for which qualification has been shown.

TS-3a T 105-24 AASHTO

15. CALCIUM OXIDE (REFERENCE TEST METHOD)

15.1. Summary of Test Method:

15.1.1. In this test method, manganese is removed from the filtrate after the determination of SiO2 and the ammonium hydroxide group. Calcium is then precipitated as the oxalate. After filtering, the oxalate is redissolved and titrated with potassium permanganate (KMnO4). (See Note 3634.) Note 3634—For referee analysis or for the most accurate determinations, removal of manganese in accordance with Section 15.3.2 must be made. For less accurate determinations, and when only insignificant amounts of manganese oxides are believed present, Section 15.3.2 may be omitted.

15.1.2. Strontium, usually present in portland cement as a minor constituent, is precipitated with calcium as the oxalate and is subsequently titrated and calculated as CaO. If the SrO content is known and correction of CaO for SrO is desired as, for example, for research purposes or to compare results with CRM certificate values, the CaO obtained by this method may be corrected for SrO. In determining conformance of a cement to specifications, the correction of CaO for SrO should not be made.

15.2. Reagents:

15.2.1. Ammonium Oxalate Solution (50 g/L).

15.2.2. Potassium Permanganate, Standard Solution (0.18 N)—Prepare a solution of potassium permanganate (KMnO4) containing 5.69 g/L. Let this solution stand at room temperature for at least 1 week, or boil and cool to room temperature. Siphon off the clear solution without disturbing the sediment on the bottom of the bottle, and then filter the siphoned solution through a bed of glass wool in a funnel or through a suitable sintered glass filter. Do not filter through materials containing organic matter. Store in a dark bottle, preferably one that has been painted black on the outside. Standardize the solution against 0.7000 to 0.8000 g of primary standard sodium oxalate, according to the directions furnished with the sodium oxalate, and record the temperature at which the standardization was made (see Note 3735). Note 3735—Because of the instability of the KMnO4 solution, it is recommended that it be restandardized at least bimonthly.

15.2.2.1. Calculate the CaO equivalent of the solution as follows: 1 mL of 1 N KMnO4 solution is equivalent to 0.06701 g of pure sodium oxalate.

44

weight of sodium oxalate fraction of its puritynormality of KMnOmL of KMnO solution 0.06701

×=

× (3)(4)

1 mL of 1 N KMnO4 solution is equivalent to 0.02804 g of CaO.

4normality of KMnO solution 0.02804 1000.5

F × ×=

where: F = CaO equivalent of the KMnO4 solution in percent CaO/mL based on a 0.5-g sample

of cement.

TS-3a T 105-25 AASHTO

15.3. Procedure:

15.3.1. Acidify the combined filtrates obtained in the precipitations of the ammonium hydroxide group (see Section 9.2.2). Neutralize with HCl to the methyl red end point, make just acid, and add 6 drops of HCl in excess.

15.3.2. Removal of Manganese—Evaporate to a volume of about 100 mL. Add 40 mL of saturated bromine water to the hot solution and immediately add NH4OH until the solution is distinctly alkaline. Addition of 10 mL of NH4OH is generally sufficient. A piece of filter paper, about 1 cm2

in area, placed in the heel of the beaker and held down by the end of a stirring rod aids in preventing bumping and initiating precipitation of hydrated manganese oxides (MnO). Boil the solution for 5 min or more, making sure that the solution is distinctly alkaline at all times. Allow the precipitate to settle, filter using medium-textured paper, and wash with hot water. If a precipitate does not appear immediately, allow a settling period of up to 1 h before filtration. Discard any manganese dioxide that may have been precipitated. Acidify the filtrate with HCl using litmus paper as an indicator, and boil until all the bromine is expelled (see Note 3836). Note 3836—Potassium iodide starch paper may be used to indicate the complete volatilization of the excess bromine. Expose a strip of moistened paper to the fumes from the boiling solution. The paper should remain colorless. If it turns blue bromine is still present.

15.3.3. Add 5 mL of HCl, dilute to 200 mL, and add a few drops of methyl red indicator and 30 mL of warm ammonium oxalate solution (50 g/L) (see Note 3937). Heat the solution to 70 to 80°C, and add NH4OH (1+1) dropwise while stirring until the color changes from red to yellow (see Note 4038). Allow the solution to stand without further heating for 60 ± 5 min (no longer), with occasional stirring during the first 30 min. Note 3937—If the ammonium oxalate solution is not perfectly clear, it should be filtered before use. Note 4038—This neutralization must be made slowly; otherwise, precipitated calcium oxalate may have a tendency to run through the filter paper. When a number of these determinations are being made simultaneously, the following technique will assist in ensuring slow neutralization. Add 2 or 3 drops of NH4OH to the first beaker while stirring, then 2 or 3 drops to the second, and so on, returning to the first beaker to add 2 or 3 more drops, etc., until the indicator color has changed in each beaker.

15.3.4. Filter, using retentive paper, and wash the precipitate eight to ten times with hot water, the total amount of water used in rinsing the beaker and washing not to exceed 75 mL. During this washing, water from the wash bottle should be directed around the inside of the filter paper to wash the precipitate down, and then a jet of water should be gently directed toward the center of the paper to agitate and thoroughly wash the precipitate. Acidify the filtrate with HCl and reserve for the determination of MgO.

15.3.5. Place the beaker in which the precipitation was made under the funnel, pierce the apex of the filter paper with the stirring rod, place the rod in the beaker, and wash the precipitate into the beaker by using a jet of hot water. Drop about 10 drops of H2SO4 (1+1) around the top edge of the filter paper. Wash the paper five more times with hot water. Dilute to 200 mL, and add 10 mL of H2SO4 (1+1). Heat the solution to a temperature just below boiling, and titrate it immediately with the 0.18 N KMnO4 solution (see Note 4139). Continue the titration slowly until the pink color persists for at least 10 s. Add the filter paper that contained the original precipitate and macerate it. If the pink color disappears, continue the titration until it again persists for at least 10 s. Note 4139—The temperature of the 0.18 N KMnO4 solution at time of use should not vary from its standardization temperature by more than 10°F (5.5°C). Larger deviations could cause serious error in the determination of CaO.

TS-3a T 105-26 AASHTO

15.3.6. Blank—Make a blank determination, following the same procedure and using the same amounts of reagents (see Note 4240), and record the milliliters of KMnO4 solution required to establish the end point. Note 4240—When the amount of calcium oxalate is very small, its oxidation by KMnO4 is slow to start. Before the titration, add a little MnSO4 to the solution to catalyze the reaction.

15.4. Calculation:

15.4.1. Calculate the percentage of CaO as follows: CaO, % = E (V – B) (4)(5) where: E = CaO equivalent of the KMnO4 solution in percent CaO/mL based on a 0.5-g sample, V = milliliters of KMnO4 solution required by the sample, and B = milliliters of KMnO4 solution required by the blank.

Report the result rounded in accordance with Table 3.

15.4.2. If desired, calculate the percentage of CaO corrected for SrO as follows: CaOc, % = CaOi, % – 0.54 SrO, % (5)(6) where: CaOc = CaO corrected for SrO, CaOi = initial CaO as determined in Section 15.4.1, and

0.54 = 56.08103.62

= molecular weight ratio CaOSrO

.

16. MAGNESIUM OXIDE (REFERENCE TEST METHOD)

16.1. Summary of Test Method—In this test method, magnesium is precipitated as magnesium ammonium phosphate from the filtrate after removal of calcium. The precipitate is ignited and weighed as magnesium pyrophosphate (Mg2P2O7). The MgO equivalent is then calculated.

16.2. Reagent—Ammonium phosphate, dibasic (100 g/L) (NH4)2HPO4.

16.3. Procedure:

16.3.1. Acidify the filtrate from the determination of CaO (see Section 15.3.4) with HCl and evaporate by boiling to about 250 mL. Cool the solution to room temperature, add 10 mL of ammonium phosphate, dibasic, (NH4)2HPO4 (100 g/L), and 30 mL of NH4OH. Stir the solution vigorously during the addition of NH4OH, and then for 10 to 15 min longer. Let the solution stand for at least 8 h in a cool atmosphere and filter. Wash the residue five or six times with NH4OH (1+20) and ignite in a weighed platinum or porcelain crucible, at first slowly until the filter paper is charred and then burn off (see Section 16.4.1), and finally at 1100°C for 30 to 45 min. Weigh the residue as magnesium pyrophosphate (Mg2P2 O7).

16.3.2. Blank—Make a blank determination following the same procedure and using the same amounts of reagents, and correct the results obtained in the analysis accordingly.

16.4. Calculation:

16.4.1. Calculate the percentage of MgO to the nearest 0.1 as follows: MgO, % = W × 72.4 (6)(7)

TS-3a T 105-27 AASHTO

where: W = grams of Mg2P2O7, and 72.4 = molecular ratio of 2MgO to Mg2P2O7 (0.362) divided by the weight of the

sample used (0.5 g) and multiplied by 100.

Report the result rounded in accordance with Table 3. Warning—Extreme caution should be exercised during this ignition. Reduction of the phosphate precipitate can result if carbon is in contact with it at high temperatures. There is also danger of occluding carbon in the precipitate if ignition is too rapid.

17. SULFUR Note 4341—When an instrumental test method is used for sulfur or when comparing results of classical wet and instrumental test methods, consult Section 6.1.2 of these test methods.

17.1. Sulfur Trioxide (Reference Test Method):

17.1.1. Summary of Test Method—In this test method, sulfate is precipitated from an acid solution of the cement with barium chloride (BaCl2). The precipitate is ignited and weighed as barium sulfate (BaSO4), and the SO3 equivalent is calculated.

17.1.2. Procedure:

17.1.2.1. To 1 g of the sample, add 25 mL of cold water, and, while the mixture is stirred vigorously, add 5 mL of HCl (see Note 4244). If necessary, heat the solution and grind the material with the flattened end of a glass rod until it is evident that decomposition of the cement is complete (see Note 4345). Dilute the solution to 50 mL and digest for 15 min at a temperature just below boiling. Filter through a medium-textured paper and wash the residue thoroughly with hot water. Dilute the filtrate to 250 mL and heat to boiling. Add slowly, dropwise, 10 mL of hot BaCl2 (100 g/L) and continue the boiling until the precipitate is well formed. Digest the solution for 12 to 24 h at a temperature just below boiling (see Note 4446). Take care to keep the volume of solution between 225 and 260 mL and add water for this purpose, if necessary. Filter through a retentive paper, wash the precipitate thoroughly with hot water, place the paper and contents in a weighed platinum crucible, and slowly char and consume the paper without inflaming. Ignite at 800 to 900°C, cool in a desiccator, and weigh. Note 423—The acid filtrate obtained in the determination of the insoluble residue (see Section 7.3.1) may be used for the determination of SO3 instead of using a separate sample. Note 4543—A brown residue due to compounds of manganese may be disregarded (see Note 9). Note 4644—If a rapid determination is desired, immediately after adding the BaCl2, place the beaker with the solution in an ultrasonic bath for 5 min, and then continue the determination starting with “Filter through a retentive paper. . . ”. Qualify the method in accordance with the Performance Requirements for Rapid Test Methods.

17.1.2.2. Blank—Make a blank determination following the same procedure and using the same amounts of reagents, and correct the results obtained in the analysis accordingly.

17.1.3. Calculation—Calculate the percentage of SO3 to the nearest 0.01 as follows: SO3, % = W × 34.3 (7)(8) where: W = grams of BaSO4, and 34.3 = molecular ratio of SO3 to BaSO4 (0.343) multiplied by 100.

TS-3a T 105-28 AASHTO

Report the result rounded in accordance with Table 3.

17.2. Sulfide (Reference Test Method):

17.2.1. Summary of Test Method—In this test method, sulfide sulfur is determined by evolution as hydrogen sulfide (H2S) from an acid solution of the cement into a solution of ammoniacal zinc sulfate (ZnSO4) or cadmium chloride (CdCl2). The sulfide sulfur is then titrated with a standard solution of potassium iodate (KIO3). Sulfites, thiosulfates, and other compounds intermediate between sulfides and sulfates are assumed to be absent. If such compounds are present, they may cause an error in the determination.

17.2.2. Apparatus:

17.2.2.1. Gas-Generating Flask—Connect a dry 500-mL boiling flask with a long-stem separatory funnel and a small connecting bulb by means of a rubber stopper. Bend the stem of the funnel so that it will not interfere with the connecting bulb, adjust the stem so that the lower end is close to the bottom of the flask, and connect the opening of the funnel with a source of compressed air. Connect the bulb with an L-shaped glass tube and a straight glass tube about 200 mm in length. Insert the straight glass tube in a tall-form, 400-mL beaker. A three-neck distilling flask with a long glass tubing in the middle opening, placed between the source of compressed air and the funnel, is a convenient aid in the regulation of the airflow. Rubber used in the apparatus shall be pure gum grade, low in sulfur, and shall be cleaned with warm HCl.

17.2.3. Reagents:

17.2.3.1. Ammoniacal Cadmium Chloride Solution—Dissolve 15 g of cadmium chloride (CdCl2 · 2H2O) in 150 mL of water and 350 mL of NH4OH. Filter the solution after allowing it to stand at least 24 h.

17.2.3.2. Ammoniacal Zinc Sulfate Solution—Dissolve 50 g of zinc sulfate (ZnSO4 · 7H2O) in 150 mL of water and 350 mL of NH4OH. Filter the solution after allowing it to stand at least 24 h.

17.2.3.3. Potassium Iodate, Standard Solution (0.03 N)—Prepare a solution of potassium iodate (KIO3) and potassium iodide (KI) as follows: Dry KIO3 at 180°C to constant weight. Weigh 1.0701 g of the KIO3 and 12 g of KI. Dissolve and dilute to 1 L in a volumetric flask. This is a primary standard and requires no standardization (see Note 4745). One milliliter of this solution is equivalent to 0.0004809 g of sulfur. Note 4745—The solution is very stable but may not maintain its titer indefinitely. Whenever such a solution is more than 1 year old, it should be discarded or its concentration checked by standardization.

17.2.3.4. Stannous Chloride Solution—To 10 g of stannous chloride (SnCl2 · 2H2O) in a small flask, add 7 mL of HCl (1+1), warm the mixture gently until the salt is dissolved, cool the solution, and add 95 mL of water. This solution should be prepared as needed because the salt tends to hydrolyze.

17.2.3.5. Starch Solution—To 100 mL of boiling water, add a cool suspension of 1 g of soluble starch in 5 mL of water and cool. Add a cool solution of 1 g of sodium hydroxide (NaOH) in 10 mL of water, and then add 3 g of potassium iodide (KI) and mix thoroughly.

17.2.4. Procedure:

17.2.4.1. Place 15 mL of the ammoniacal ZnSO4 or CdCl2 solution (see Note 4846) and 285 mL of water in a beaker. Put 5 g of the sample (see Note 4947) and 10 mL of water in the flask, and shake the flask gently to wet and disperse the cement completely. This step and the addition of SnCl2 should be performed rapidly to prevent the setting of the cement. Connect the flask with the funnel and bulb. Add 25 mL of the SnCl2 solution through the funnel and shake the flask. Add 100 mL of

TS-3a T 105-29 AASHTO

HCl (1+3) through the funnel and shake the flask. During these shakings, keep the funnel closed and the delivery tube in the ammoniacal ZnSO4 or CdCl2 solution. Connect the funnel with the source of compressed air, open the funnel, start a slow stream of air, and heat the flask and contents slowly to boiling. Continue the boiling gently for 5 or 6 min. Cut off the heat, and continue the passage of air for 3 or 4 min. Disconnect the delivery tube and leave it in the solution for use as a stirrer. Cool the solution to 20 to 30°C (see Note 5048), add 2 mL of the starch solution and 40 mL of HCl (1+1), and titrate immediately with the 0.03 N KIO3 solution until a persistent blue color is obtained (see Note 5149). Note 4846—In general, the ZnSO4 is preferable to the CdCl2 solution because ZnSO4 is more soluble in NH2OH than is CdCl2. The CdCl2 solution may be used when there is doubt as to the presence of a trace of sulfide sulfur because the yellow cadmium sulfide (CdS) facilitates the detection of a trace. Note 4947—If the content of sulfur exceeds 0.20 or 0.25 percent, a smaller sample should be used so that the titration with the KIO3 solution will not exceed 25 mL. Note 5048—The cooling is important because the end point is indistinct in a warm solution. Note 5149—If the content of sulfur is appreciable but not approximately known in advance, the result may be low due to the loss of H2S during a slow titration. In such a case, the determination should be repeated with the titration carried out more rapidly.

17.2.4.2. Make a blank determination, following the same procedure and using the same amounts of reagents. Record the volume of KIO3 solution necessary to establish the end point, as described in Section 17.2.4.1.

17.2.5. Calculation—Calculate the percentage of sulfide sulfur (see Section 17.2.1) as follows: sulfide, % = E(V – B) × 20 (8)(9) where: E = sulfide equivalent of the KIO3 solution, g/mL; V = milliliters of KIO3 solution required by the sample; B = milliliters of KIO3 solution required by the blank; and 20 = 100 divided by the weight of sample used (5 g).

Report the result rounded in accordance with Table 3.

18. LOSS ON IGNITION (REFERENCE TEST METHOD)

18.1. Portland Cement:

18.1.1. Summary of Test Method—In this test method, the cement is ignited in a muffle furnace at a controlled temperature. The loss is assumed to represent the total moisture and CO2 in the cement. This procedure is not suitable for the determination of the loss on ignition of portland blast-furnace slag cement and of slag cement. A test method suitable for such cements is described in Sections 18.2.1 through 18.2.3.

18.1.2. Procedure—Weigh 1 g of the sample in a tared platinum or porcelain crucible. Cover and ignite the crucible and its contents to constant weight in a muffle furnace at a temperature of 950 ± 50°C. Allow a minimum of 15 min for the initial heating period and at least 5 min for all subsequent periods.

18.1.3. Calculation—Calculate the percentage of loss on ignition to the nearest 0.1 by multiplying the loss of weight in grams by 100. Report the result rounded in accordance with Table 3.

18.2. Portland Blast-Furnace Slag Cement and Slag Cement:

TS-3a T 105-30 AASHTO

18.2.1. Summary of Test Method—Because it is desired that the reported loss on ignition represent moisture and CO2, this test method provides a correction for the gain in weight due to oxidation of sulfides usually present in portland blast-furnace slag cement and slag cement by determining the increase in SO3 content during ignition. An optional test method providing for a correction based on the decrease in sulfide sulfur during ignition is given in Sections 26.1.1 through 26.1.3.

18.2.2. Procedure:

18.2.2.1. Weigh 1 g of cement into a tared platinum or porcelain crucible and ignite in a muffle furnace at a temperature of 950 ± 50°C for 15 min. Cool to room temperature in a desiccator and weigh. Without checking for constant weight, carefully transfer the ignited material to a 400-mL beaker. Break up any lumps in the ignited cement with the flattened end of a glass rod.

18.2.2.2. Determine the SO3 content by the test method given in Sections 17.1.2 through 17.1.3 (see Note 5250). Also determine the SO3 content of a portion of the same cement that has not been ignited using the same procedure. Note 5250—Some of the acid used for dissolving the sample may first be warmed in the platinum crucible to dissolve any adhering material.

18.2.3. Calculation—Calculate the percentage loss of weight occurring during ignition, and add 0.8 times the difference between the percentages of SO3 in the ignited sample and the original cement (see Note 5351). Report the corrected percentage, rounded in accordance with Table 3, as loss on ignition. Note 5351—If a gain in weight is obtained during ignition, subtract the percentage gain from the correction for SO3.

19. SODIUM AND POTASSIUM OXIDES (REFERENCE TEST METHOD)

19.1. Total Alkalies:

19.1.1. Summary of Test Method—This test method7 covers the determination of sodium oxide (Na2O)

and potassium oxide (K2O) by flame photometry or atomic absorption (see Note 5452). Note 5452—This test method is suitable for hydraulic cements that are completely decomposed by hydrochloric acid and should not be used for determination of total alkalies in hydraulic cements that contain large amounts of acid-insoluble material, for example, pozzolan cements. It may be used to determine acid-soluble alkalies for such cements. An alternate test method of sample dissolution for such cements is in preparation.

19.1.2. Apparatus:

19.1.2.1. Instrument—Any type of flame photometer or atomic absorption unit may be used, provided it can be demonstrated that the required degree of accuracy and precision is as indicated in Section 19.1.3 (see Notes 5553 and 5654). Note 5553—After such accuracy is established for a specific instrument, further tests of instrument accuracy are not required, except when it must be demonstrated that the instrument gives results within the prescribed degree of accuracy by a single series of tests using the designated standard samples. Note 5654—For normal laboratory testing, it is recommended that the accuracy of the instrument be routinely checked by the use of either an NIST cement or cement of known alkali content.

19.1.2.2. The instrument shall consist at least of an atomizer and burner, suitable pressure-regulating devices and gages for fuel and oxidant gas, an optical system capable of preventing excessive

TS-3a T 105-31 AASHTO

interference from wavelengths of light other than that being measured, and a photosensitive indicating device.

19.1.3. Initial Qualification of Instrument—Qualify the instrument in accordance with Section 5.4.2 to establish that an instrument provides the desired degree of precision and accuracy.

19.1.4. Reagents and Materials:

19.1.4.1. Laboratory Containers—All glassware shall be made of borosilicate glass, and all polyethylene shall comply with the requirements of Section 6.2.3.

19.1.4.2. Calcium Carbonate—The calcium carbonate (CaCO3) used in the preparation of the calcium chloride stock solution (see Section 19.1.5.1) shall contain not more than 0.020 percent total alkalies as sulfate. Note 5755—Materials sold as a primary standard or ACS “low alkali” grade normally meet this requirement. However, the purchaser should assure himself that the actual material used conforms with this requirement.

19.1.4.3. Potassium Chloride (KCl).

19.1.4.4. Sodium Chloride (NaCl).

19.1.4.5. Commercially available solutions may be used in place of those specified in Section 19.1.5.

19.1.5. Preparation of Solutions:

19.1.5.1. Calcium Chloride Stock Solution—Add 300 mL of water to 112.5 g of CaCO3 in a 1500-mL beaker. While stirring, slowly add 500 mL of HCl. Cool the solution to room temperature, filter into a 1-L volumetric flask, dilute to 1 L, and mix thoroughly. This solution contains the equivalent of 63,000 ppm (6.30 percent) CaO.

19.1.5.2. Sodium-Potassium Chloride Stock Solution—Dissolve 1.8858 g of sodium chloride (NaCl) and 1.583 g of potassium chloride (KCl) (both dried at 105 to 110°C for several hours prior to weighing) in water. Dilute to 1 L in a volumetric flask and mix thoroughly. This solution contains the equivalent of 1000 ppm (0.10 percent) each of Na2O and K2O. Separate solutions of Na2O and of K2O may be used, provided that the same concentration solutions are used for calibration for cement analysis as were used for the calibration when qualifying the instrument in accordance with Section 19.1.3.

19.1.5.3. Standard Solutions—Prepare the standard solutions prescribed for the instrument and method used. Measure the required volume of NaCl-KCl stock solutions in calibrated pipets or burets. The calcium chloride stock solutions, if needed, may be measured in appropriate graduated cylinders. If the instrument being used requires an internal standard, measure the internal standard solution with a pipet or buret. Place each solution in a volumetric flask, dilute to the indicated volume, and mix thoroughly.

19.1.5.4. If more dilute solutions are required by the method in use, pipet the required aliquot to the proper sized volumetric flask, add any necessary internal standard, dilute to the mark, and mix thoroughly.

19.1.6. Calibration of Apparatus (see Note 56): Note 5856—No attempt is made in this section to describe in detail the steps for putting the instrument into operation because this will vary considerably with different instruments. The manufacturer’s instructions should be consulted for special techniques or precautions to be employed in the operation, maintenance, or cleaning of the apparatus.

TS-3a T 105-32 AASHTO

19.1.6.1. Turn on the instrument and allow it to warm up in accordance with the manufacturer’s instructions. (A minimum of 30 min is required for most instruments.) Adjust the fuel and oxidant gas pressures as required by the instrument being used. Light and adjust the burner for optimum operation. Make any other adjustments that may be necessary to establish the proper operating conditions for the instrument.

19.1.7. Procedure:

19.1.7.1. Solution of the Cement—Prepare the solution of the cement in accordance with the procedure specified by the instrument manufacturer. If no procedure is specified, or if desired, proceed as specified in Section 19.1.7.1.1 or Section 19.1.7.1.2(1-3) (see Note 5957). Note 5957—The presence of SiO2 in solution affects the accuracy of some flame photometers. In cases where an instrument fails to provide results within the prescribed degree of accuracy outlined in Sections 5.4.2.1 through 5.4.3, tests should be made on solutions from which the SiO2 has been removed. For this removal, proceed as in Section 19.1.7.2.

19.1.7.1.1. (1)Place 1.000 ± 0.001 g of the cement in a 150-mL beaker and disperse with 20 mL of water using a swirling motion of the beaker. While still swirling, add 5.0 mL of HCl all at once. Dilute immediately to 50 mL with water. Break up any lumps of cement remaining undispersed with a flat-end stirring rod. Digest on a steam bath or hot plate for 15 min, and then filter through a medium-textured filter paper into a 100-mL volumetric flask. Wash beaker and paper thoroughly with hot water, cool contents of the flask to room temperature, dilute to 100 mL, and mix the solution thoroughly. Continue as given in Section 19.1.7.2.

19.1.7.1.2. (2)Place 1.000 ± 0.001 g of cement into a platinum evaporating dish and disperse with 10 mL of water using a swirling motion. While still swirling, add 5.0 mL of HCl all at once. Break up any lumps with a flat-end stirring rod and evaporate to dryness on a steam bath. Make certain that the gelatinous appearance is no longer evident. Treat the residue with 2.5 mL of HCl and about 20 mL of water. Digest on a steam bath for 5 to 10 min and filter immediately through a 9-cm medium-textured filter paper into a 100-mL volumetric flask. Wash thoroughly with repeated small amounts of hot water until the total volume of solution is 80 to 95 mL. Cool to room temperature, dilute to the mark, and mix thoroughly.

(3)When it has been demonstrated that the removal of SiO2 is necessary to obtain the required accuracy described in Sections 5.4.2.1 through 5.4.3 for a specific flame photometer, SiO2 must always be removed when making analyses that are used as the basis for rejection of a cement for failure to comply with specifications or where specification compliance may be in question. When there is no question as to specification compliance, analyses may be made by such instruments without SiO2 removal, provided the deviations from certificate values obtained by the tests prescribed in Sections 5.4.2.1 through 5.4.3 are not more than twice the indicated limits.

19.1.7.2. If the test method in use requires more dilute solutions, an internal standard, or both, carry out the same dilutions as in Section 19.1.5.4, as needed. The standard and the sample solutions to be analyzed must be prepared in the same way and to the same dilution as the solutions of standard cements analyzed for the qualification of the instrument.

19.1.7.3. Procedure for Na2O—Warm up and adjust the instrument for the determination of Na2O as described in Section 19.1.6.1. Immediately following the adjustment and without changing any instrumental settings, atomize the cement solution and note the scale reading (see Note 6058). Select the standard solutions that immediately bracket the cement solution in Na2O content and observe their readings. Their values should agree with the values previously established during calibration of the apparatus. If not, recalibrate the apparatus for that constituent. Finally, alternate the use of the unknown solution and the bracketing standard solutions until readings of the unknown agree within one division on the transmission or meter scale, or within 0.01 weight percent for instruments with digital readout, and readings for the standards similarly agree with the calibration values. Record the average of the last two readings obtained for the unknown solution.

Formatted: Normal, Indent: Left: 0",Hanging: 1"

Formatted: Indent: First line: 0.5"

TS-3a T 105-33 AASHTO

Note 6058—The order in determining Na2O or K2O is optional. In all cases, however, the determination should immediately follow the adjustment of the instrument for that particular constituent.

19.1.7.4. If the reading exceeds the scale maximum, either transfer a 50-mL aliquot of the solution prepared in Section 19.1.7.1 to a 100-mL volumetric flask or, if desired, prepare a new solution by using 0.500 g of cement and 2.5 mL of HCl (instead of 5.0 mL) in the initial addition of acid. In the event silica has to be removed from the 0.5-g sample of cement, treat the dehydrated material with 1.25 mL of HCl and about 20 mL of water, then digest, filter, and wash. In either case, add 5.0 mL of calcium chloride stock solution (see Section 19.1.5.1) before diluting to mark with water. Dilute to the mark. Proceed as in Section 19.1.5.4 if more dilute solutions are required by the test method in use. Determine the alkali content of this solution as described in (see Section 19.1.7.3) and multiply by a factor of 2 the percentage of alkali oxide.

19.1.7.5. Procedure for K2O—Repeat the procedure described in Section 19.1.7.3, except that the instrument shall be adjusted for the determination of K2O. For instruments that read both Na2O and K2O simultaneously, determine K2O at the same time as determining Na2O.

19.1.8. Calculation and Report—From the recorded averages for Na2O and K2O in the unknown sample, report each oxide rounded in accordance with Table 3.

19.2. Water-Soluble Alkalies (see Note 6159): Note 6159—The determination of water-soluble alkali should not be considered as a substitute for the determination of total alkali according to Sections 19.1.2.1 to 19.1.8. Moreover, it is not to be assumed that in this method all water-soluble alkali in the cement will be dissolved. Strict adherence to the procedure described is essential where there is a specified limit on the content of water-soluble alkali or where several lots of cement are compared on the basis of water-soluble alkali.

19.2.1. Procedure:

19.2.1.1. Weigh 25.0 g of sample into a 500-mL Erlenmeyer flask and add 250 mL of water. Stopper the flask with a rubber stopper and shake continuously for 10 min at room temperature. Filter through a Büchner funnel that contains a well-seated retentive, dry filter paper, into a 500-mL filtering flask, using a weak vacuum. Do not wash.

19.2.1.2. Transfer a 50-mL aliquot (see Note 6260) of the filtrate to a 100-mL volumetric flask and acidify with 0.5 mL of concentrated HCl (sp gr 1.19). Add 9.0 mL of stock CaCl2 solution (63,000 ppm CaO), described in Section 19.1.5.1, to the 100-mL flask, and dilute the solution to 100 mL. If the test method in use requires more dilute solutions, an internal standard, or both, carry out the same dilutions as in Section 19.1.5.4, as needed. Determine the Na2O and K2O contents of this solution as described in Sections 19.1.7.3 and 19.1.7.5. Record the parts per million of each alkali in the solution in the 100-mL flask. Note 6260—The aliquot of the filtrate taken for the analysis should be based on the expected water-soluble alkali content. If the expected level of either K2O or Na2O is more than 0.08 weight percent of cement, or if the water-soluble alkali level is unknown, a 50-mL aliquot as given in Section 19.2.1.2 should be used to make up the initial test solution. If either the Na2O or K2O exceeds 0.16 percent, place a 50-mL aliquot of the solution from Section 19.2.1.2 in a 100-mL volumetric flask, add 5 mL of CaCl2 stock solution, and dilute to 100 mL. When the level of either K2O or Na2O is less than 0.08 percent, take a 100-mL aliquot from the original filtrate (obtained by Section 19.2.1.1), add 1 mL of HCl, and evaporate on a hot plate in a 250-mL beaker to about 70 mL. Add 8 mL of stock CaCl2 solution and transfer the sample to a 100-mL volumetric flask, rinsing the beaker with a small portion of distilled water. Cool the solution to room temperature and dilute to 100 mL.

TS-3a T 105-34 AASHTO

19.2.2. Calculations—Calculate the percentage of the water-soluble alkali, expressed as Na2O, as follows: Total water-soluble alkali, as Na2O = A + E (9)(10) A = B/(V × 10) C = D/(V × 10) E = C × 0.658 where: A = percentage of water-soluble sodium oxide (Na2O), B = parts per million of Na2O in the solution in the 100-mL flask, V = milliliters of original filtrate in the 100-mL flask, C = percent of water-soluble potassium oxide (K2O), D = parts per million of K2O in the 100-mL flask, E = percentage Na2O equivalent to K2O determined, and 0.658 = molecular ratio of Na2O to K2O.

Report the result rounded in accordance with Table 3.

20. MANGANIC OXIDE (REFERENCE TEST METHOD)

20.1. Summary of Method—In this procedure, manganic oxide is determined volumetrically by titration with sodium arsenite solution after oxidizing the manganese in the cement with sodium metabismuthate (NaBiO3).

20.2. Reagents:

20.2.1. Sodium Arsenite, Standard Solution (1 mL = 0.0003 g Mn2O3)—Dissolve in 100 mL of water 3.0 g of sodium carbonate (Na2CO3) and then 0.90 g of arsenic trioxide (As2O3), heating the mixture until the solution is as complete as possible. If the solution is not clear or contains a residue, filter the solution. Cool it to room temperature, transfer to a volumetric flask, and dilute to 1 L.

20.2.1.1. Dissolve 0.58 g of potassium permanganate (KMnO4) in 1 L of water and standardize it against about 0.03 g of sodium oxalate (Na2C2O4) oxidimetric standard furnished by NIST (Standard Sample No. 40 or its replacement) according to the directions furnished with the sodium oxalate. Put 30.0 mL of the KMnO4 solution in a 250-mL Erlenmeyer flask. Add 60 mL of HNO3 (1+4) and 10 mL of sodium nitrite (NaNO2, 50 g/L) to the flask. Boil the solution until the HNO2 is completely expelled. Cool the solution, add NaBiO3, and finish by titrating with the standard sodium arsenite (NaAsO2) solution, as described in Section 20.3.2. Calculate the manganic oxide (Mn2O3) equivalent of the NaAsO2 solution, g/mL, as follows: E = (A × 7.08) / BC (10)(11) where: E = Mn2O3 equivalent of the NaAsO2 solution, g/mL; A = grams of Na2C2O4 used; B = milliliters of KMnO4 solution required by the Na2C2O4; C = milliliters of NaAsO2 solution required by 30.0 mL of KMnO4 solution; and 7.08 = molecular ratio of Mn2O3 to 5 Na2C2O4(0.236) multiplied by 30.0 (milliliters of

KMnO4 solution).

20.2.2. Sodium Metabismuthate (NaBiO3).

TS-3a T 105-35 AASHTO

20.2.3. Sodium Nitrite Solution (50 g NaNO2/L).

20.3. Procedure:

20.3.1. Weigh 1.0 to 3.0 g of the sample (see Note 6361) into a 250-mL beaker and treat it with 5 to 10 mL of water, and then with 60 to 75 mL of HNO3 (1+4). Boil the mixture until the solution is as complete as possible. Add 10 mL of NaNO2 solution (50 g/L) to the solution and boil it until the nitrous acid is completely expelled (see Note 6462), taking care not to allow the volume of the solution to become so small as to cause the precipitation of gelatinous SiO2. There may be some separated SiO2, which may be ignored, but if there is still a red or brown residue, use more NaNO2 solution (50 g/L) to effect a complete decomposition, and then boil again to expel the nitrous acid. Filter the solution through a medium-textured paper into a 250-mL Erlenmeyer flask and wash the filter paper with water. Note 6361—The amount of cement taken for analysis depends on the content of manganese, varying from 1 g for about 1 percent of Mn2O3 to 3 g for 0.25 percent or less of Mn2O3. Note 6462—When NaNO2 is added, the expulsion of HNO2 by boiling must be complete. If any HNO2 remains in the solution, it will react with the added NaBiO3 and decrease its oxidizing value. If there is any manganese in the cement, the first small quantity of NaBiO3 should bring out a purple color.

20.3.2. The solution should have a volume of 100 to 125 mL. Cool it to room temperature. To the solution, add a total of 0.5 g of NaBiO3 in small quantities while shaking intermittently. After the addition is completed, shake the solution occasionally for 5 min and then add to it 50 mL of cool HNO3 (1+33), which has been previously boiled to expel nitrous acid. Filter the solution through a pad of ignited asbestos in a Gooch crucible or a carbon or fritted-glass filter with the aid of suction. Wash the residue four times with the cool HNO3 (1+33). Titrate the filtrate immediately with the standard solution of NaAsO2. The end point is reached when a yellow color is obtained free of brown or purple tints and does not change upon further addition of NaAsO2 solution.

20.3.3. Blank—Make a blank determination, following the same procedure and using the same amounts of reagents, and correct the results obtained in the analysis accordingly.

20.4. Calculate the percentage of Mn2O3 to the nearest 0.01 as follows: Mn2O3, % = (EV/S) × 100 (11)(12) where: E = Mn2O3 equivalent of the NaAsO2 solution, g/mL; V = milliliters of NaAsO2 solution required by the sample; and S = grams of sample used.

Report the result rounded in accordance with Table 3.

21. CHLORIDE (REFERENCE TEST METHOD)

21.1. Summary of Test Method—In this test method, acid-soluble chloride content of cement is determined by the potentiometric titration of chloride with silver nitrate (see Note 6563). The procedure is also applicable to clinker and portland cement raw mix. Under the conditions of the test, no constituent normally present in these materials will interfere (see Note 6664). Note 6563—In most cases, acid-soluble chloride content of a portland cement is total chloride content. Note 6664—Species that form insoluble silver salts or stable silver complexes in acid solution interfere with potentiometric measurements. Thus, iodides and bromides interfere, but fluorides

TS-3a T 105-36 AASHTO

will not. Sulfide salts in concentrations typical of these materials should not interfere because they are decomposed by acid treatment.

21.2. Apparatus:

21.2.1. Chloride, Silver/Sulfide Ion Selective Electrode—Or a silver billet electrode coated with silver chloride (see Note 65), with an appropriate reference electrode.

21.2.2. Potentiometer—With millivolt scale readable to 1 mV or better. A digital readout is preferred but not required.

21.2.3. Buret—Class A, 10-mL capacity with 0.05-mL divisions. A buret of the potentiometric type, having a displaced delivery tip, is convenient but not required. Note 6765—Suitable electrodes are available from Orion, Beckman Instruments, and Leeds and Northrup. Carefully following the manufacturer’s instructions, add filling solution to the electrodes. The silver billet electrodes must be coated electrolytically with a thin, even layer of silver chloride. To coat the electrode, dip the clean silver billet of the electrode into a saturated solution of potassium chloride (about 40 g/L) in water, and pass an electric current through the electrode from a 1.5- to 6-V dry cell with the silver billet electrode connected to the positive terminal of the battery. A carbon rod from an all-dry cell or other suitable electrode is connected to the negative terminal and immersed in the solution to complete the electrical circuit. When the silver chloride coating wears off, it is necessary to rejuvenate the electrode by repeating the above procedure. All of the old silver chloride should first be removed from the silver billet by rubbing it gently with fine emery paper, followed by water rinsing of the billet.

21.3. Reagents:

21.3.1. Sodium Chloride (NaCl)—Primary standard grade.

21.3.2. Silver Nitrate (AgNO3)—Reagent grade.

21.3.3. Potassium Chloride (KCl)—Reagent grade (required for silver billet electrode only).

21.3.4. Reagent Water—Conforming to the requirements of ASTM D1193 for Type III reagent water.

21.4. Preparation of Solutions:

21.4.1. Sodium Chloride, Standard Solution (0.05 N NaCl)—Dry sodium chloride (NaCl) at 105 to 110°C to a constant mass. Weigh 2.9222 g of dried reagent. Dissolve in water and dilute to exactly 1 L in a volumetric flask and mix thoroughly. This solution is the standard and requires no further standardization.

21.4.2. Silver Nitrate, Standard Solution (0.05 N AgNO3)—Dissolve 8.4938 g of silver nitrate (AgNO3) in water. Dilute to 1 L in a volumetric flask and mix thoroughly. Standardize against 5.00 mL of standard 0.05 N sodium chloride solution diluted to 150 mL with water following the titration test method given in Section 21.5.4 beginning with the second sentence. The exact normality shall be calculated from the average of three determinations as follows: N = 0.25/V (12)(13) where: N = normality of AgNO3 solution; 0.25 = milliequivalents NaCl (5.0 mL × 0.05 N); and V = volume of AgNO3 solution, mL.

TS-3a T 105-37 AASHTO

Commercially available standard solutions may be used provided the normality is checked according to the standardization procedure.

21.4.3. Methyl Orange Indicator—Prepare a solution containing 2 g of methyl orange per liter of 95 percent ethyl alcohol.

21.5. Procedure:

21.5.1. Weigh a 5.0-g sample of the cement into a 250-mL beaker (see Note 6866). Disperse the sample with 75 mL of water. Without delay slowly add 25 mL of dilute (1+1) nitric acid, breaking up any lumps with a glass rod. If the smell of hydrogen sulfide is strongly evident at this point, add 3 mL of hydrogen peroxide (30 percent solution) (see Note 6967). Add three drops of methyl orange indicator and stir. Cover the beaker with a watch glass and allow to stand for 60 to 120 s. If a yellow to yellow-orange color appears on top of the settled solids, the solution is not sufficiently acidic. Add additional dilute nitric acid (1+1) dropwise while stirring until a faint pink or red color persists. Then add 10 drops in excess. Heat the covered beaker rapidly to boiling. Do not allow to boil for more than a few seconds. Remove from the hot plate (see Note 7068). Note 6866—Use a 5-g sample for cement and other materials having an expected chloride content of less than about 0.15 percent Cl. Use proportionally smaller samples for materials with higher chloride concentrations. Use cement and other powdered materials as is without grinding. Coarse samples require grinding to pass a No. 20 mesh sieve. If a sample is too fine, excessive silica gel may form during digestion with nitric acid, thereby slowing subsequent filtration. Note 6967—Slags and slag cements contain sulfide sulfur in concentrations that can interfere with the determination. Note 7068—It is important to keep the beaker covered during heating and digestion to prevent the loss of chloride by volatilization. Excessive amounts of acid should not be used because this results in early removal of the silver chloride coating from the silver billet electrode. A slurry that is only slightly acidic is sufficient.

21.5.2. Wash a 9-cm coarse-textured filter paper with four 25-mL increments of water using suction filtering provided by a 250-mL or 500-mL Büchner funnel and filtration flask. Discard the washings and rinse the flask once with a small portion of water. Reassemble the suction apparatus and filter the sample solution. Rinse the beaker and the filter paper twice with small portions of water. Transfer the filtrate from the flask to a 250-mL beaker and rinse the flask once with water. The original beaker may be used (see Note 7169). Cool the filtrate to room temperature. The volume should not exceed 175 mL. Note 7169—It is not necessary to clean all the slurry residue from the sides of the beaker nor is it necessary that the filter remove all of the fine material. The titration may take place in a solution containing a small amount of solid matter.

21.5.3. For instruments equipped with dial readout, it is necessary to establish an approximate “equivalence point” by immersing the electrodes in a beaker of water and adjusting the instrument to read about 20 mV lower than midscale. Record the approximate millivoltmeter reading. Remove the beaker and wipe the electrodes with absorbent paper.

21.5.4. To the cooled sample (see Note 7270) beaker from Section 21.5.2, carefully pipet 2.00 mL of standard 0.05 N NaCl solution. Place the beaker on a magnetic stirrer and add a TFE-fluorocarbon-coated magnetic stirring bar. Immerse the electrodes into the solution, taking care that the stirring bar does not strike the electrodes, and begin stirring gently. Place the delivery tip of the 10-mL buret, filled to the mark with standard 0.05 N silver nitrate solution, in (preferably) or above the solution (see Note 7371). Note 7270—It is advisable to maintain constant temperature during measurement because the solubility relationship of silver chloride varies markedly with temperature at low concentrations.

TS-3a T 105-38 AASHTO

Note 7371—If the tip of the buret is out of the solution, any adhering droplet should be rinsed onto the beaker with a few milliliters of water following each titration increment.

21.5.5. Gradually titrate and record the amount of standard 0.05 N silver nitrate solution required to bring the millivoltmeter reading to –60.0 mV of the equivalence point determined in the water.

21.5.6. Continue the titration with 0.20-mL increments. Record the buret reading and the corresponding millivoltmeter reading in Columns 1 and 2 of a four-column recording form like that shown in Appendix X1. Allow sufficient time between each addition for the electrodes to reach equilibrium with the sample solution. Experience has shown that acceptable readings are obtained when the minimum scale reading does not change within a 5-s period (usually within 120 s).

21.5.7. As the equivalence point is approached, the equal additions of AgNO3 solution will cause larger and larger changes in the millivoltmeter readings. Past the equivalence point, the change per increment will again decrease. Continue to titrate until three readings past the approximate equivalence point have been recorded.

21.5.8. Calculate the difference in millivolt readings between successive additions of titrant and enter the values in Column 3 of the recording form. Calculate the difference between consecutive values in Column 3 and enter the results in Column 4. The equivalence point of the titration will be within the maximum ∆mV interval recorded in Column 3. The precise equivalence point can be interpolated from the data listed in Column 4, as shown in Appendix X1.

21.5.9. Blank—Make a blank determination using 75 mL of water in place of the sample, following the same procedure starting with the third sentence of Section 21.5.1 without delay. Correct the results obtained in the analysis accordingly (see Note 72) by subtracting the blank.

21.6. Calculations—Calculate the percent chloride to the nearest 0.001 percent as follows:

1 23.545( – ) – 0.10Cl, %

V V NW

= (13)(14)

where: V1 = milliliters of 0.05 N AgNO3 solution used for sample titration (equivalence point); V2 = milliliters of 0.05 N AgNO3 solution used for blank titration (equivalence point); N = exact normality of 0.05 N AgNO3 solution; and W = weight of sample, g.

Report the result rounded in accordance with Table 3. Note 7472—For nonreferee analysis, the blank may be omitted.

22. CHLOROFORM-SOLUBLE ORGANIC SUBSTANCES (REFERENCE TEST METHOD)

22.1. Summary of Test Method—This test method was specially designed for the determination of Vinsol resin and tallow in portland cement, although mineral oil, common rosin, calcium stearate, and other fatty acid compounds, and probably some other substances, if present, will be included in the determination. Extreme care is necessary during the entire procedure. The test method may be applied to types of cement other than portland cement, although if the cement contains a large amount of acid-insoluble matter, the emulsions may separate slowly, and less vigorous shaking, more chloroform, and more washing may be necessary.

22.2. Reagents:

TS-3a T 105-39 AASHTO

22.3. Chloroform—If the blank determination as described in Section 22.3.5 exceeds 0.0015 g, the chloroform should be distilled before use. Chloroform recovered in the procedure may be slightly acid but can be reused for the portions to be shaken with the aqueous acid solution of the sample in the 1-L funnel. Chloroform used for washing the filter and transferring the extract should be fresh or distilled from fresh chloroform.

22.3.1. Stannous Chloride (SnCl2).

22.4. Procedure:

22.4.1. Place 40 g of cement in a 1-L Squibb separatory funnel (see Note 7573) and mix it with 520 mL of water added in two approximately equal portions. Shake vigorously immediately after the addition of the first portion to effect complete dispersion. Then add the second portion and shake again. At once add rapidly 185 mL of HCl in which 10 g of SnCl2 (see Note 7674) has been dissolved, and then rapidly insert the stopper in the funnel, invert, and shake with a swirling motion for a few seconds to loosen and disperse all the cement, taking care to avoid the development of great internal pressure due to unnecessarily violent shaking. Release internal pressure immediately by opening and closing the stopcock. Repeat the shaking and release the pressure until the decomposition of the cement is complete. If necessary, break up persistent lumps with a long glass rod. Cool to room temperature rapidly by allowing tap water to run on the flask. Note 7573—The use of grease to lubricate the stopcocks and glass stoppers of the separatory funnels should be avoided. Wetting the stopcocks with water before using will assist in their easy operation. Note 7674—The purpose of the SnCl2 is to prevent the oxidation of sulfide sulfur to elemental sulfur, which is soluble in chloroform.

22.4.2. Add 75 mL of chloroform to the solution, stopper the funnel, shake it vigorously for 5 min, and allow the water and chloroform to stand 15 min to separate. Draw off the lower chloroform layer into a 125-mL Squibb separatory funnel, including the scum (see Note 7775) and a few milliliters of the aqueous layer, making sure all the scum is transferred. Keep the amount of the aqueous layer transferred to an absolute minimum because excessive water in the 125-mL funnel may result in incomplete extraction of the scum and may cause an emulsion that does not separate readily. Shake the funnel vigorously to ensure the complete extraction of the scum. Allow the chloroform to separate and draw it into a 250-mL Squibb separatory funnel that contains 50 mL of water and a few drops of HCl, making sure to keep the scum behind in the 125-mL funnel. Shake the 250-mL funnel and draw the chloroform into another 250-mL funnel that contains 50 mL of water and a few drops of HCl. Shake this funnel as in the case of the first 250-mL funnel. When the chloroform separates, draw it into a standard-taper flat-bottom boiling flask (see Note 7876), taking care not to allow any water to enter the flask. Note 7775—There is usually a dark-colored scum at the liquid interface. It may contain chloroform-soluble organic substance after shaking in the funnel, where the proportion of water to chloroform is great. It may be concentrated and confined to a small volume by gently twirling the funnel after the scum has been drawn into the narrower part of the funnel. Note 7876—The liquid is later distilled. No cork or rubber stoppers should be used. A 250- or 300-mL soil analysis flask, fitted with a condenser tube by means of a ground joint, is satisfactory. The tube may be bent near the neck, and the remaining part fitted with a water-cooling jacket. Chloroform thus recovered may be reused as described in Section 22.2.1.

22.4.3. Add 25 mL of chloroform to the solution in the original 1-L separatory funnel and carry out the operations as described in Section 22.3.2, retaining the original wash water in the 250-mL funnels. Repeat, using another 25-mL portion of chloroform.

22.4.4. Distill the combined chloroform extracts in the boiling flask until their volume is reduced to 10 to 15 mL. Filter the remaining liquid into a weighed 100-mL glass beaker or platinum dish (see Note 7977) through a small medium-textured filter paper that has been washed with fresh

TS-3a T 105-40 AASHTO

chloroform. Rinse the flask and wash the paper with several small portions of fresh chloroform. Evaporate the extracts at a low temperature (not over 63°C) to dryness (see Note 8078) and heat it in an oven at 57 to 63°C for 3 min. Pass dry air into the vessel for 15 s, cool, and determine the mass. Repeat the heating and mass determinations until two successive mass determinations do not differ by more than 0.0010 g. The higher of the last two mass determinations shall be taken as the true mass. Note 7977—A platinum dish is preferable because it quickly attains the temperature of the balance. If a glass beaker is used, it should be allowed to stand in the case of the balance for at least 20 min before determining the mass. Note 8078—Care should be taken in drying the extract because many of the chloroform-soluble organic substances are somewhat volatile when heated for a long time at even moderate temperatures. With protection from the accumulation of dust, the solution may be evaporated at room temperature overnight. When a quick evaporation is desired, the solution may be evaporated on a hot plate at low heat under a stream of dry air through a glass tube (about 10 mm in inside diameter) until it is about 3 mm in depth. Then remove the vessel from the hot plate and continue a slow stream of dry air until the residue appears dry. Then continue with a more rapid stream of dry air for 5 min at room temperature before placing the vessel in the oven at 57 to 63°C. After each 3-min heating period in the oven, pass dry air into the vessel for about 15 s before determining the mass. The air may be dried by passing it through a cheap desiccant such as calcium chloride or sulfuric acid, followed by a desiccant of high efficiency such as magnesium perchlorate or anhydrous calcium sulfate, with care taken to avoid the carrying of dust from the desiccant by the air. Instead of using compressed air, which is often contaminated with oil, dirt, and moisture, one can place the chloroform solution under a bell glass and induce a stream of air through the desiccants by means of an aspirator or vacuum pump. When Vinsol resin is known to be the only substance present, the residue is more stable and may be heated at 100 to 105°C, instead of 57 to 63°C, to expel all possible traces of chloroform.

22.4.5. Blank—Make a blank determination. Ignite a 40-g sample of the cement at 950 to 1000°C for 1 h (see Note 8179) and regrind. Treat this ignited sample by the same procedure using the same reagents as in the analysis, and correct the results accordingly. Note 8179—Care should be taken to completely burn off the organic substance. A 100-mL flat platinum dish, in which the sample is well spread out, and a muffle furnace are advised for this purpose. If such a furnace is not available, a large high-temperature burner of the Meker type may be used. Thorough stirring of the sample should be done frequently—every 5 min when a burner is used.

22.5. Calculation—Calculate the percentage of chloroform-soluble organic substances to the nearest 0.001 by multiplying the mass in grams of residue (see Note 8280) by 2.5 (100 divided by the mass of the sample used (40 g)). Report the result rounded in accordance with Table 3. Note 8280—If the organic substance in the cement is tallow, the residue is the fatty acids resulting from the hydrolysis of the tallow in the hot acid solution, and its mass should be multiplied by 1.05 to give the mass of the original glycerides in the tallow. If the original substance is calcium stearate, the residue is stearic acid, and its mass multiplied by 1.07 gives the mass of calcium stearate.

ALTERNATIVE TEST METHODS

23. CALCIUM OXIDE (ALTERNATIVE TEST METHOD)

23.1. Summary of Test Method:

TS-3a T 105-41 AASHTO

23.1.1. This test method covers the gravimetric determination of CaO after removal of SiO2 and the ammonium hydroxide groups and double precipitation of calcium as the oxalate. The precipitate is converted to CaO by ignition, and the mass is determined.

23.1.2. Strontium, usually present in portland cement as a minor constituent, is precipitated with calcium as the oxalate and is subsequently calculated as CaO. If the SrO content is known and correction of CaO for SrO is desired, as, for example, for research purposes or to compare results with CRM certificate values, the CaO obtained by this test method may be corrected by subtracting percent SrO. In determining conformance of a cement to specifications, the correction of CaO for SrO should not be made.

23.2. Procedure (see Note 81):

23.2.1. Acidify the combined filtrates obtained in the determination of the ammonium hydroxide group (see Sections 9.1 through 9.3) and, if necessary, evaporate to a volume of about 200 mL. Add 5 mL of HCl, a few drops of methyl red indicator solution, and 30 mL of warm ammonium oxalate solution (50 g/L) (see Note 3937). Heat the solution to 70 to 80°C and add NH4OH (1+1) dropwise while stirring until the color changes from red to yellow (see Note 4038). Allow the solution to stand without further heating for 1 h (not longer), with occasional stirring during the first 30 min. Filter using a retentive paper and wash moderately with cold ammonium oxalate solution (1 g/L). Reserve the filtrate and washings. Note 8381—When analyses are being made for determining conformity to specifications and there is a possibility that sufficient manganese will be present to cause the percentage of magnesium determined by alternate test methods to exceed the specification limit, manganese may be removed as directed in Section 15.3.2 before CaO is determined by this alternative test method.

23.2.2. Transfer the precipitate and filter paper to the beaker in which the precipitation was made. Dissolve the oxalate in 50 mL of hot HCl (1+4) and macerate the filter paper. Dilute to 200 mL with water, add a few drops of methyl red indicator and 20 mL of ammonium oxalate solution, heat the solution nearly to boiling, and precipitate calcium oxalate again by neutralizing the acid solution with NH4OH, as described in Section 15.3.1. Allow the solution to stand 1 to 2 h (standing for 2 h at this point does no harm), filter, and wash as before. Combine the filtrate with that already obtained and reserve for the determination of MgO (see Section 16.3.1).

23.2.3. Dry the precipitate in a tared covered platinum crucible. Char the paper without inflaming; burn the carbon at as low a temperature as possible; and, finally, heat with the crucible tightly covered in an electric furnace or over a blast lamp at a temperature of 1100 to 1200°C. Cool in a desiccator and determine the mass as CaO. Repeat the ignition to constant mass.

23.2.4. Blank—Make a blank determination, following the same procedure and using the same amounts of reagents, and correct the results obtained in the analysis accordingly.

23.3. Calculation:

23.3.1. Calculate the percentage of CaO to the nearest 0.1 by multiplying the mass in grams of CaO by 200 (100 divided by the mass of sample used (0.5 g)).

23.3.2. Correct the percent CaO for SrO, if desired, by subtracting the percent SrO.

24. CARBON DIOXIDE (REFERENCE TEST METHOD)

24.1. Any test method may be used, provided that acceptable performance has been demonstrated in accordance with Section 24.2. See Appendix X2 for guidance on methods.

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24.2. Demonstrate performance by analysis, in duplicate, of at least one portland cement. Prepare three standards, each in duplicate: Standard A shall be the selected portland cement; Standard B shall be Standard A containing 2.00 percent Certified CaCO3 (e.g., NIST 915a); Standard C shall be Standard A containing 5.00 percent Certified CaCO3. Prepare duplicate specimens of each standard. Assign the CO2 content of Standard A as the average of the two values determined, provided they agree within the required limit of Table 1, Column 2. Assign CO2 values to Standards B and C as follows: Multiply the Certified CaCO3 value (Y) for CO2 (from the certificate value) by the mass fraction of Certified CaCO3 added to that standard (percentage added divided by 100); multiply the value determined for Standard A by the mass fraction of Standard A in each of the other standards (i.e., 0.98 and 0.95 for Standards B and C, respectively); add the two values for Standard A and for Standard B, respectively; call these values B and C. Example:

B = 0.98A + 0.02Y C = 0.95A + 0.05Y

where for Certified CaCO3, if Y = 44.01 percent, then

B = 0.98A + 0.88 percent by mass C = 0.95A + 2.20 percent by mass

The difference between the duplicate CO2 values for Standards B and C, respectively, shall not exceed 0.17 and 0.24 percent by mass. The difference between the average of the duplicate values for Standards B and C and their assigned values (B and C) shall not exceed 0.13 and 0.26 percent by mass, respectively.

24.3. Report the results rounded in accordance with Table 3.

25. MAGNESIUM OXIDE (ALTERNATIVE TEST METHOD)

25.1. Summary of Test Method—This alternative test method is a volumetric procedure suitable for use when the determination of silicon dioxide (SiO2), aluminum oxide (Al2O3), ferric oxide (Fe2O3), and calcium oxide (CaO) are omitted.

25.2. Rapid Volumetric Test Method (Titration of Magnesium Oxyquinolate):

25.3. Reagents:

25.3.1. Ammonium Nitrate Solution (20 g NH4NO3/L).

25.3.2. Ammonium Oxalate Solution (50 g/L).

25.3.3. Hydroxyquinoline Solution—Dissolve 25 g of 8-hydroxyquinoline in 60 mL of acetic acid. When the solution is complete, dilute to 2 L with cold water. One milliliter of this solution is equivalent to 0.0016 g of MgO.

25.3.4. Potassium Bromate-Potassium Bromide, Standard Solution (0.2 normal)—Dissolve 20 g of potassium bromide (KBr) and 5.57 g of potassium bromate (KBrO3) in 200 mL of water and dilute to 1 L. Obtain the ratio of the strength of this solution to that of the 0.1 N Na2S2O3 solution (see Section 23.2.6) as follows: To 200 mL of water in a 500-mL Erlenmeyer flask, add 25.0 mL of the 0.2 N KBrO3-KBr solution, measured from a pipet or buret. Add 20 mL of HCl, stir, and add immediately 10 mL of potassium iodide (KI) (250 g/L). Mix well and titrate at once with the Na2S2O3 solution until nearly colorless. Add 2 mL of starch solution and titrate to the

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disappearance of the blue color. Calculate the ratio in strength of the KBrO3-KBr solution to the Na2S2O3 solution by dividing the volume of Na2S2O3 solution by the volume of KBrO3-KBr solution used in the titration.

25.3.5. Potassium Iodide Solution (250 g KI/L).

25.3.6. Sodium Thiosulfate, Standard Solution (0.1 N)—Dissolve 25 g of sodium thiosulfate (Na2S2O3·5H2O) in 200 mL of water, add 0.1 g of sodium carbonate (Na2CO3), and dilute to 1 L. Let stand at least 7 days. Standardize this solution directly against primary standard potassium dichromate (K2Cr2O7). One milliliter of 0.10 N Na2S2O3 solution is equivalent to 0.000504 g of MgO.

25.3.7. Starch Solution—To 500 mL of boiling water, add a cold suspension of 5 g of soluble starch in 25 mL of water, cool to room temperature, add a cool solution of 5 g of sodium hydroxide (NaOH) in 50 mL of water, add 15 g of KI, and mix thoroughly.

25.4. Procedure:

25.4.1. Disperse 0.5 g (see Note 8482) of the sample of cement in a 400-mL beaker with 10 mL of water, using a swirling motion. While still swirling, add 10 mL of HCl all at once. Dilute immediately to 100 mL. Heat gently and grind any coarse particles with the flattened end of a glass rod until decomposition is complete, add two or three drops of HNO3 and heat to boiling (see Note 8583). Note 8482—If SiO2, ammonium hydroxide group, and CaO are separated and determined in accordance with the appropriate sections for either the reference or alternative test methods, the remaining filtrate may be used for the determination of MgO as described in Section 25.4.1, starting with the third from the last sentence of Section 25.4.2, “Add 5 mL of HCl…”. Note 8583—In the case of cements containing blast-furnace slag or a significant quantity of sulfide sulfur, add 12 drops of HNO3 and boil for 20 min to oxidize iron and remove sulfide.

25.4.2. Add three drops of methyl red indicator to the solution, and then add NH4OH until the solution is distinctly yellow. Heat this solution to boiling and boil for 50 to 60 s. In the event difficulty from bumping is experienced while boiling the ammoniacal solution, a digestion period of 10 min on a steam bath, or a hot plate having the approximate temperature of a steam bath, may be substituted for the 50- to 60-s boiling period. Remove from the burner, steam bath, or hot plate and allow to stand until the precipitate has settled. Using medium-textured paper, filter the solution without delay, wash the precipitate twice with hot NH4NO3 (20 g/L), and reserve the filtrate. Transfer the precipitate with the filter paper to the beaker and dissolve in 10 mL of HCl (1+1). Macerate the filter paper. Dilute to about 100 mL and heat to boiling. Reprecipitate, filter, and wash the hydroxides as above. Combine this filtrate and washings with those from the first precipitation taking care that the volume does not exceed 300 mL (see Note 8684). Add 5 mL of HCl, a few drops of methyl red indicator solution, and 30 mL of warm ammonium oxalate solution (50 g/L). Heat the solution to 70 to 80°C and add NH4OH (1+1) dropwise, while stirring, until the color changes from red to yellow (see Note 4038). Allow the solution to stand without further heating for 15 min on a steam bath. Note 8684—In the case of cements containing blast-furnace slag, or which are believed to contain a significant quantity of manganese, acidify with HCl, evaporate to about 100 mL, and remove the manganese, using the procedure described in Section 15.3.1.

25.4.3. Add 10 to 25 mL of the 8-hydroxyquinoline reagent (see Note 8785) and then 4 mL of the NH4OH/100 mL solution. Stir the solution on a mechanical stirring machine for 15 min and set aside until the precipitate has settled (see Note 8886). Filter the solution using medium-textured paper and wash the precipitate with hot NH4OH (1+40). Dissolve the precipitate in 50 to 75 mL of hot HCl (1+9) in a 500-mL Erlenmeyer flask. Dilute the resulting solution to 200 mL and add 15 mL of HCl. Cool the solution to 25°C and add 10 to 35 mL of the 0.2 N KBrO3-KBr solution (see Note 8987) from a pipet or buret. Stir the solution and allow to stand for about 30 s to ensure

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complete bromination. Add 10 mL of KI (250 g/L). Stir the resulting solution well and then titrate with the 0.1 N Na2S2O3 solution until the color of the iodine becomes faintly yellow. At this point, add 2 mL of the starch solution and titrate the solution to the disappearance of the blue color. Note 8785—An excess of the 8-hydroxyquinoline reagent is needed to avoid a low result for MgO, but too great an excess will yield high results. The following guide should be used to determine the amount of reagent added:

Appropriate Content of MgO, %

Appropriate Amount of Reagent Required,

mL 0 to 1.5 10 1.5 to 3.0 15 3.0 to 4.5 20 4.5 to 6.0 25

Note 8886—The precipitate should be filtered within an hour. Prolonged standing may cause high results.

Note 8987—The amount of the standard KBrO3-KBr solution used should be as follows:

Appropriate Content of MgO, %

Amount of Standard KBrO3-KBr Solution,

mL 0 to 1 10 1 to 2 15 2 to 3 20 3 to 4 25 4 to 5 30 5 to 6 35

25.4.4. Blank—Make a blank determination following the same procedure and using the same amounts of reagents, and correct the results obtained in the analysis accordingly.

25.5. Calculation—Calculate the percentage of MgO to the nearest 0.1 as follows (see Note 9088):

( )1 2MgO, % 200E V R V= − × (14)(15)

where: E = MgO equivalent of the Na2S2O3 solution, g/mL; V1 = milliliters of KBrO3-KBr solution used; R = ratio in strength of the KBrO3-KBr solution to the Na2S2O3; V2 = milliliters of Na2S2O3 solution used; and 200 = 100 divided by the mass of sample used (0.5 g).

Report the result rounded in accordance with Table 3. Note 9088—V1R represents the volume of Na2S2O3 solution equivalent to the volume of KBrO3-KBr solution used. V2 represents the amount of Na2S2O3 required by the excess KBrO3-KBr that is not reduced by magnesium oxyquinolate.

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26. LOSS ON IGNITION (ALTERNATIVE TEST METHOD)

26.1. Portland Blast-Furnace Slag Cement and Slag Cement (Alternative Test Method):

26.1.1. Summary of Test Method—This test method covers a correction for the gain in weight due to oxidation of sulfides usually present in such cement by determining the decrease in the sulfide sulfur content during ignition. It gives essentially the same result as the reference test method (see Sections 18.2.1 through 18.2.3) that provides for applying a correction based on the increase in SO3 content.

26.1.2. Procedure:

26.1.2.1. Weigh 1 g of cement in a tared platinum crucible, cover, and ignite in a muffle furnace at a temperature of 950 ± 50°C for 15 min. Cool to room temperature in a desiccator and weigh. After weighing carefully, transfer the ignited material to a 500-mL boiling flask. Break up any lumps in the ignited cement with the flattened end of a glass rod.

26.1.2.2. Determine the sulfide sulfur content of the ignited sample using the procedure described in Sections 17.2.1 through 17.2.5. Using the same procedure, also determine the sulfide sulfur content of a portion of the cement that has not been ignited.

26.1.3. Calculation—Calculate the percentage loss of weight (see Note 9189) occurring during ignition (see Section 26.1.2.1), and add twice the difference between the percentages of sulfide sulfur in the original sample and ignited sample as determined in Section 26.1.2.2. Report this value as the loss on ignition, rounded in accordance with Table 3. Note 9189—If a gain of weight is obtained during the ignition, subtract the percentage of gain from the correction for sulfide oxidation.

27. TITANIUM DIOXIDE (ALTERNATIVE TEST METHOD)

27.1. Summary of Test Method—In this test method, titanium dioxide (TiO2) is determined colorimetrically by comparing the color intensity of the peroxidized solution of the titanium in the sample with the color intensity of a peroxidized standard solution of titanic sulfate.

27.2. Interferences—Interfering elements in the peroxide method for TiO2 are vanadium, molybdenum, and chromium. In very small quantities, the interference of the last two is negligible. However, vanadium in very small quantities causes interference and, because some cements contain this element, the Na2CO3 fusion (see Section 27.5.4) and extraction with water are necessary.

27.3. Apparatus:

27.3.1. Colorimeter—The apparatus shall consist of a colorimeter of the Kennicott or Duboscq type, or other colorimeter or spectrophotometer designed to measure light transmittancy and suitable for measurements at wavelengths between 400 and 450 nm.

27.4. Reagents:

27.4.1. Ammonium Chloride (NH4Cl).

27.4.2. Ammonium Nitrate (20 g NH4NO3/L).

27.4.3. Ferrous Sulfate Solution (1 mL = 0.005 g Fe2O3)—Dissolve 17.4 g of ferrous sulfate (FeSO4 · 7H2O) in water containing 50 mL of H2SO4 and dilute to 1 L. One milliliter is equivalent to 1 percent of Fe2O3 in 0.5 g of sample.

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27.4.4. Hydrogen Peroxide (30 percent)—Concentrated hydrogen peroxide (H2O2).

27.4.5. Sodium Carbonate (20 g Na2CO3/L).

27.4.6. Sodium or Potassium Pyrosulfate (Na2S2O7 or K2S2O7).

27.4.7. Titanic Sulfate, Standard Solution (1 mL = 0.0002 g TiO2)—Use standard TiO2 furnished by NIST (Standard Sample No. 154 or its replacements). Dry for 2 h at 105 to 110°C. Transfer a weighed amount, from 0.20 to 0.21 g of the TiO2, to a 125-mL Phillips beaker. Add 5 g of ammonium sulfate ((NH4)2SO4) and 10 mL of H2SO4 to the beaker, and insert a short-stem glass funnel in the mouth of the beaker. Heat the mixture cautiously to incipient boiling while rotating the flask over a free flame. Continue the heating until the complete solution has been effected and no unattacked material remains on the wall of the flask (see Note 9290). Cool and rapidly pour the solution into 200 mL of cold water while stirring vigorously. Rinse the flask and funnel with H2SO4 (1+19), stir, and let the solution and washings stand for at least 24 h. Filter into a 1-L volumetric flask, wash the filter thoroughly with H2SO4 (1+19), dilute to the mark with H2SO4 (1+19), and mix. Note 9290—There may be a small residue, but it should not contain more than a trace of TiO2 if the operations have been properly performed.

27.4.8. Calculate the TiO2 equivalent of the titanic sulfate solution, g/mL, as follows: E = AB/1000 (15)(16) where: E = TiO2 equivalent of the Ti(SO4)2 solution, g/mL; A = grams of standard TiO2 used (corrected for loss on drying); B = percentage of TiO2 in the standard TiO2 as certified by the NIST, divided by 100;

and 1000 = number of milliliters in the volumetric flask.

27.5. Procedure:

27.5.1. Mix thoroughly 0.5 g of the sample of cement and about 0.5 g of NH4Cl in a 50-mL beaker, cover the beaker with a watch glass, and add cautiously 5 mL of HCl, allowing the acid to run down the lip of the covered beaker. After the chemical action has subsided, lift the cover, stir the mixture with a glass rod, replace the cover, and set the beaker on a steam bath for 30 min (see Note 9391). During this time of digestion, stir the contents occasionally and break up any remaining lumps to facilitate the complete decomposition of the cement. Fit a medium-textured filter paper to a funnel and transfer the precipitate to the filter. Scrub the beaker with a rubber policeman, and rinse the beaker and policeman. Wash the filter two or three times with hot HCl (1+99), and then with 10 or 12 small portions of hot water, allowing each portion to drain through completely. Note 9391—A hot plate may be used instead of a steam bath if the heat is so regulated as to approximate that of a steam bath.

27.5.2. Transfer the filter and residue to a platinum crucible (see Note 9492), dry, and ignite slowly until the carbon of the paper is completely consumed without inflaming. Treat the SiO2 thus obtained with 0.5 to 1 mL of water, about 10 mL of HF, and 1 drop of H2SO4, and evaporate cautiously to dryness (see Note 9593). Note 9492—When it is desired to shorten the procedure for purposes other than referee analysis, usually with little sacrifice of accuracy, the procedure given in Section 27.5.2 may be omitted. Note 9593—When a determination of SiO2 is desired in addition to one of TiO2, the SiO2 may be obtained and treated with HF, as directed in Sections 8.2.3.1 through 8.2.4.

27.5.3. Heat the filtrate to boiling and add NH4OH until the solution becomes distinctly alkaline, as indicated by an ammoniacal odor. Add a small amount of filter paper pulp to the solution and boil

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for 50 to 60 s. Allow the precipitate to settle, filter through a medium-textured paper, and wash twice with hot NH4NO3 solution (20 g/L). Place the precipitate in the platinum crucible in which the SiO2 has been treated with HF and ignite slowly until the carbon of the paper is consumed. Note 9694—When a determination of ammonium hydroxide group is desired in addition to one of TiO2, the precipitation and ignition may be made as described in Sections 9.2.1 through 9.2.4. However, the crucible must contain the residue from the treatment of the SiO2 with HF unless circumstances permit its omission, as indicated in Note 9593.

27.5.4. Add 5 g of Na2CO3 to the crucible and fuse for 10 to 15 min (see Section 27.2). Cool, separate the melt from the crucible, and transfer to a small beaker. Wash the crucible with hot water, using a policeman. Digest the melt and washings until the melt is completely disintegrated, and then filter through a 9-cm medium-textured filter paper and wash a few times with Na2CO3 (20 g/L). Discard the filtrate. Place the precipitate in the platinum crucible and ignite slowly until the carbon of the paper is consumed.

27.5.5. Add 3 g of Na2S2O7 or K2S2O7 to the crucible and heat below red heat until the residue is dissolved in the melt (see Note 9795). Cool and dissolve the fused mass in water containing 2.5 mL of H2SO4. If necessary, reduce the volume of the solution (see Note 9896), filter into a 100-mL volumetric flask through a 7-cm medium-textured filter paper, and wash with hot water. Add 5 mL of H3PO4, and cool the solution to room temperature. Add H2O2 (1.0 mL of 30 percent strength or its equivalent) (see Note 9997), dilute to the mark with water, and mix thoroughly. Note 9795—Start the heating with caution because pyrosulfates (also known as fused bisulfates) as received often foam and spatter in the beginning due to an excess of H2SO4. Avoid an unnecessarily high temperature or unnecessarily prolonged heating because fused pyrosulfates may attack platinum. A supply of nonspattering pyrosulfates may be prepared by heating some pyrosulfate in a platinum vessel to eliminate the excess H2SO4 and crushing the cool fused mass. Note 9896—If the solution is evaporated to too small a volume and allowed to cool, there may be a precipitate of sulfates difficult to redissolve. In case of overevaporation, do not permit the contents to cool, but add hot water and digest on a steam bath or hot plate until the precipitate is redissolved, with the possible exception of a small amount of SiO2. Note 9997—Hydrogen peroxide deteriorates on standing. Its strength may be determined by adding a measured volume of the solution to 200 mL of cold water and 10 mL of H2SO4 (1+1) and titrating with a standard solution of potassium permanganate (KMnO4) prepared in accordance with Section 15.2.2. If the standard solution contains 0.0056357 g of KMnO4/mL, 49.5 mL of it will be required by 0.50 mL of H2O2 (30 percent).

27.5.6. Prepare from the standard Ti(SO4)2 solution a suitable reference standard solution or a series of reference standard solutions in 100-mL volumetric flasks, depending upon the type of colorimeter to be used. To each solution, add 3 g of Na2S2O7 or K2S2O7 dissolved in water, an amount of FeSO4 solution equivalent to the Fe2O3 content in 0.5 g of the cement under test, 2.5 mL of H2SO4, and 5 mL of H3PO4 (see Note 10098). When the solution is at room temperature, add H2O2 (1.0 mL of 30 percent strength or its equivalent), dilute to the mark with water, and mix thoroughly (see Note 10199). Note 10098—The color imparted to the solution by Fe2(SO4)2 is partly offset by the bleaching effect of H2SO4, H3PO4, and alkali salts on ferric and peritanic ions. The directions should be followed closely for the highest degree of precision. However, when it is desired to shorten this procedure for purposes other than referee analysis, the addition of pyrosulfate, FeSO4 solution, and H3PO4 to the color comparison solutions may be omitted, provided the Fe2O3 of the sample cement is less than 5 percent. This usually leads to little sacrifice to accuracy. Note 10199—The color develops rapidly and is stable for a sufficient period of time, but if the peroxidized solution is allowed to stand a long time, bubbles of oxygen may appear and interfere with color comparison. When the contents of a tube are first mixed, there may be fine bubbles that should be allowed to clear up before the comparison is made. Comparison between the standard and unknown solution should be made not less than 30 min after the addition of H2O2.

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27.5.7. Compare the color, light transmittancy, or absorbance of the unknown solution with the reference standard solution. The technique of comparing colored solutions or measuring transmittancy or absorbance depends on the type of apparatus (see Sections 27.5.8 through 27.5.10) and should be in accordance with standard practice appropriate to the particular type used or with instructions supplied by the manufacturer of the equipment. If the peroxidized solution of cement is compared with a single standard peroxidized solution, bear in mind that a single peroxidized solution cannot be used for the whole range in TiO2 content that may be encountered. The difference in volume or depth for the two liquids should not exceed 50 percent of the smaller value. All solutions should contain the prescribed concentrations of H2SO4, H3PO4, Fe2(SO4)3, and persulfate, except under the circumstances indicated in Note 99.

27.5.8. Colorimeter of the Kennicott Type—By means of a plunger in a reservoir of standard peroxidized solution, adjust the amount of solution through which light passes until it gives the same color intensity as the peroxidized solution of the sample.

27.5.9. Colorimeter of the Duboscq Type—Lower or raise the plungers in the cups until the two solutions give the same color intensity when viewed vertically. The color matching may be done either visually or photoelectrically.

27.5.10. Colorimeter Designed to Measure Light Transmittancy—The measurement should be made between 400 to 450 nm and may be made either visually or photoelectrically. In most colorimeters of this type, the instrument is calibrated with standard solutions, and a calibration curve showing the relation of light transmittancy or absorbance to TiO2 content is prepared in advance of the analysis of the sample for TiO2.

27.5.11. Blank—Make a blank determination, following the same procedure and using the same amounts of reagent, and correct the results obtained in the analysis accordingly.

27.6. Calculation—Calculate the percentage of TiO2, rounded in accordance with Table 3. When a colorimeter designed to measure light transmittancy is used, read the percentage of TiO2 from a calibration curve showing the relation of light intensity to TiO2 content. When the peroxidized solution of the sample is compared with a single reference standard solution, calculate the percentage of TiO2 as follows (see Note 100):

27.6.1. For Colorimeters of the Kennicott Type: TiO2, % = (100 VE/S ) × (D/C) (16)(17)

27.6.2. For Colorimeters of the Duboscq Type: TiO2, % = (100 VE/S ) × (F/G) (17)(18) where: V = milliliters of standard Ti(SO4)2 solution in the peroxidized standard solution; E = TiO2 equivalent of the standard Ti(SO4)2 solution, g/mL; S = grams of sample used; D = volume of peroxidized reference standard solution that matches the peroxidized solution

of the sample, mL; C = total volume of the peroxidized reference standard solution, mL; F = depth of peroxidized reference standard solution through which light passes; and G = depth of peroxidized solution of the sample through which light passes

. Note 102 100—The difference between D and C or between F and G should not exceed 50 percent of the smaller value.

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28. PHOSPHORUS PENTOXIDE (ALTERNATIVE TEST METHOD)

28.1. Summary of Test Method—In this test method, phosphorus is determined volumetrically by precipitation of the phosphorus as ammonium phosphomolybdate and titration with NaOH and H2SO4.

28.2. Reagents:

28.2.1. Ammonium Molybdate Solution—Prepare the solution in accordance with Section 11.3.1.

28.2.2. Ammonium Nitrate (NH4NO3).

28.2.3. Potassium Nitrate Solution (10 g/L)—Dissolve 10 g of potassium nitrate (KNO3) in water freshly boiled to expel CO2 and cooled, and dilute to 1 L.

28.2.4. Sodium Hydroxide, Standard Solution (0.3 N)—Dissolve 12 g of sodium hydroxide (NaOH) in 1 L of water that has been freshly boiled to expel CO2 and cooled. Add 10 mL of a freshly filtered, saturated solution of barium hydroxide (Ba(OH)2). Shake the solution frequently for several hours, and filter it. Protect it from contamination by CO2 in the air. Standardize the solution against standard acid potassium phthalate (Standard Sample No. 84) or benzoic acid (Standard Sample No. 39) furnished by NIST, according to the directions furnished with the standard. Calculate the phosphorus pentoxide (P2O5) equivalent (see Note 103) of the solution, g/mL, as follows: E = N × 0.003086 (18)(19) where: E = P2O5 equivalent of the NaOH solution, g/mL; N = normality of the NaOH solution; and 0.003086 = P2O5 equivalent of 1 N NaOH solution, g/mL.

Note 103 101—The value of the solution is based on the assumption that the phosphorus in cement is precipitated as ammonium phosphomolybdate (2(NH4)3PO4 · 12MoO3) and that the precipitate reacts with the NaOH solution thus:

2(NH4)3 PO4 × 12MoO3 + 46NaOH = 2(NH4)2HPO4 + (NH4)2MoO4 + 23Na2 MoO4 + 22H2O (19)(20)

The number 0.003086 is obtained by dividing the molecular weight of P2O5 (141.96) by 46 (for 46 NaOH in the equation) and by 1000 (number of milliliters in 1 L). Because the actual composition of the precipitate is influenced by the conditions under which the precipitation is made, it is essential that all the details of the procedure are followed closely as prescribed.

28.2.5. Sodium Nitrite (50 g NaNO2/L).

28.2.6. Sulfuric Acid, Standard Solution (0.15 N)—Dilute 4.0 mL of H2SO4 to 1 L with water that has been freshly boiled and cooled. Standardize against the standard NaOH solution. Determine the ratio in strength of the standard H2SO4 solution to the standard NaOH solution by dividing the volume of NaOH solution by the volume of H2SO4 solution used in the titration.

28.3. Procedure:

28.3.1. Weigh 1 to 3 g of the sample (see Note 104102) and 10 g of NH4NO3 into a 150-mL beaker. Mix the contents, add 10 mL of HNO3, and stir quickly, using the flattened end of a glass rod to crush

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lumps of cement until the cement is completely decomposed and the thick gel of silica (SiO2) is broken up. Cover the beaker with a watch glass, place it on a water bath or a hot plate at approximately 100°C for 15 to 20 min, and stir the contents occasionally during the heating. Add 20 mL of hot water to the beaker and stir the contents. If the cement contains an appreciable amount of manganese, as shown by the presence of a red or brown residue, add a few milliliters of NaNO2 (50 g/L) to dissolve this residue. Boil the contents of the beaker until all nitrous fumes are completely expelled. This procedure should not take more than 5 min, and water should be added to replace any lost by evaporation. Filter, using medium-textured paper, into a 400-mL beaker under suction and with a platinum cone to support the filter paper. Wash the residue of SiO2 with hot water until the volume of filtrate and washings is about 150 mL. Note 104 102—The amounts of sample and reagents used depend on the content of phosphorus in the cement. The minimum requirements are sufficient if the cement contains 0.5 percent P2O5 or more. The maximum amounts are required if the content of P2O5 is 0.1 percent or less.

28.3.2. Heat the solution to 69 to 71°C, remove it from the heat source, and immediately add 50 to 100 mL of the ammonium molybdate solution. Stir the solution vigorously for 5 min, wash down the sides of the beaker with cool KNO3 solution (10 g/L), cover the beaker with a watch glass, and allow to stand 2 h. Using suction, filter the precipitate (see Note 105103), decanting the solution with as little disturbance to the precipitate as possible. Stir the precipitate in the beaker with a stream of the cool KNO3 solution, decant the liquid, and then wash the precipitate onto the filter. Scrub the stirring rod and beaker with a policeman, and wash the contents onto the filter. Wash and precipitate until it is acid-free (see Note 106104), allowing each portion of wash solution to be sucked completely through before adding the next. Note 105103—The filter may be a small medium-textured filter paper supported by a platinum cone, or a small Hirsch funnel may be used with filter paper cut to fit and a thin mat of paper pulp or acid-washed asbestos pulp. The filtration should be carried out with care to avoid any loss of the precipitate. The filter should fit well, and the suction should be started before filtration and maintained until the end of the washing. Note 106104—About ten washings are usually required. Test the tenth washing with one drop of neutral phenolphthalein indicator and half a drop of the standard NaOH solution. If a definite pink color lasts at least 5 min, the precipitate is considered to be acid-free; otherwise, continue the washing.

28.3.3. Transfer the filter and precipitate to the beaker in which the precipitation took place, using small damp pieces of paper to wipe out the funnel and pick up portions of the precipitate that may remain on it. Add 20 mL of cool CO2-free water to the beaker, and break up the filter by stirring rapidly with the policeman that was used to scrub the beaker. Add an excess of the 0.3 N NaOH solution; stir the contents until all trace of yellow has disappeared; wash down the policeman and sides of the beaker with 50 mL of cool, CO2-free water; and add 2 drops of neutral phenolphthalein indicator solution. Treat the solution with a measured quantity of the 0.15 N H2SO4 solution, sufficient to destroy completely the pink color. Complete the titration with the NaOH solution until there is a definite faint pink color that lasts at least 5 min.

28.3.4. Blank—Make a blank determination, following the same procedure and using the same amounts of reagents, and correct the results obtained in the analysis accordingly.

28.4. Calculation—Calculate the percentage of P2O5 to the nearest 0.01 as follows: P2O5, % = [E(V1 – V2R)/S] × 100 (20)(21)

where: E = P2O5 equivalent of the NaOH solution, g/mL; V1 = milliliters of NaOH solution used; V2 = milliliters of H2SO4 solution used;

TS-3a T 105-51 AASHTO

R = ratio in strength of the H2SO4 solution to the NaOH solution; and S = grams of sample used.

Report the result rounded in accordance with Table 3.

29. MANGANIC OXIDE (ALTERNATIVE TEST METHOD)

29.1. Summary of Test Method—In this test method, manganic oxide is determined volumetrically by titration with potassium permanganate solution.

29.2. Reagents:

29.2.1. Potassium Permanganate, Standard Solution (0.18 N)—Prepare a solution of potassium permanganate (KMnO4) and standardize as described in Section 15.2.2, except that the manganic oxide (Mn2O3) equivalent of the solution is calculated instead of the calcium oxide (CaO) equivalent. Calculate the Mn2O3 equivalent of the solution as follows:

( )0.3534 /E B A= × (21)(22)

where: E = Mn2O3 equivalent of the KMnO4 solution, g/mL; B = grams of Na2C2O4 used; A = milliliters of KMnO4 solution required by the Na2C2O4; and 0.3534 = mole ratio of 3 Mn2O3 to 10 Na2C2O4.

29.2.2. Zinc Oxide (ZnO)—Powder.

29.3. Procedure:

29.3.1. Place 2 g of the sample in a 250-mL beaker and add about 50 mL of water to the cement. Stir the mixture until it is in suspension, and then add about 15 mL of HCl. Heat the mixture gently until the solution is as complete as possible. Add 5 mL of HNO3 and 50 mL of water to the solution and boil it until most of the chlorine has been expelled. If necessary, add hot water to maintain the solution at a volume of about 100 mL. Stop the boiling and add ZnO powder to the solution until the acid is neutralized. Add an excess of 3 to 5 g of ZnO powder to the solution and boil it for a few minutes.

29.3.2. Without filtering, and while keeping the solution hot (90 to 100°C) by intermittent or continuous heating, titrate the solution with the 0.18 N KMnO4 solution until a drop of it gives a permanent pink color (see Note 107105). When the end point is approached, add the standard solution dropwise. After each drop, stir the solution, allow the precipitate to settle a little, and observe the color of the stratum of the solution by looking through the side of the beaker. Note 107105—In the case of a cement in which the approximate content of Mn2O3 is unknown, a preliminary determination may be made with rapid titration, 0.5 to 1 mL of the standard solution being added at a time, and without an attempt to keep the solution close to the boiling point.

29.3.3. Blank—Make a blank determination, following the same procedure and using the same amounts of reagents, and correct the results obtained in the analysis accordingly.

29.4. Calculation—Calculate the percentage of Mn2O3 to the nearest 0.01 as follows:

2 3Mn O , % 50EV= × (22)(23)

TS-3a T 105-52 AASHTO

where: E = Mn2O3 equivalent of the KMnO4 solution, g/mL; V = milliliters of KMnO4 solution used; and 50 = 100 divided by the mass of sample used (2 g).

Report the result rounded in accordance with Table 3.

30. FREE CALCIUM OXIDE (ALTERNATIVE TEST METHOD)

30.1. Summary of Test Methods—These are rapid test methods for the determination of free calcium oxide in fresh clinker. When applied to cement or aged clinker, the possibility of the presence of calcium hydroxide should be kept in mind because these methods do not distinguish between free CaO and free Ca(OH)2. Two test methods are provided. Alternate Test Method A is a modified Franke procedure in which uncombined lime is titrated with dilute perchloric acid after solution in an ethylacetoacetate-isobutyl alcohol solvent. Alternate Test Method B is an ammonium acetate titration of the alcohol-glycerin solution of uncombined lime with Sr(NO3)2 as an accelerator.

30.2. Modified Franke Test Method (Alternative Method A):

30.2.1. Apparatus:

30.2.1.1. Refluxing Assembly—Consisting of a flat-bottom, short-neck Erlenmeyer flask with 250-mL capacity. The water-cooled refluxing condenser should have a minimum length of 300 mm. The flask and reflux condenser shall be connected with standard tapered ground glass joints. The reflux condenser shall be fitted with an absorption tube containing a desiccant, such as indicating silica gel and a material for the removal of CO2 such as Ascarite. The absorption tube shall be inserted with a rubber stopper in the upper end of the reflux column.

30.2.1.2. Buret—Having a 10-mL capacity and graduated in units not more than 0.05 mL.

30.2.1.3. Vacuum Filtration Assembly—Consisting of a Gooch crucible size No. 3, 25-mL capacity in which is placed a suitable filter paper (21-mm size), a Walter crucible holder, a 500-mL vacuum flask, and vacuum source. The crucible is half filled with compressed filter pulp.

30.2.1.4. Glass Boiling Beads.

30.2.2. Solutions Required:

30.2.2.1. Ethyl Acetoacetate-Isobutyl Alcohol Solvent—Three parts by volume of ethyl acetoacetate and 20 parts by volume of isobutyl alcohol.

30.2.2.2. Thymol Blue Indicator—Dissolve 0.1 g of thymol blue indicator powder in 100 mL of isobutyl alcohol.

30.2.2.3. Perchloric Acid, Standard Solution (0.2 N)—Dilute 22 mL of 70 to 72 percent perchloric acid to 1 L with isobutyl alcohol. Standardize this solution as follows: Ignite 0.1000 g of primary standard calcium carbonate in a platinum crucible at 900 to 1000°C. Cool the crucible and contents in a desiccator, and determine the mass to the nearest 0.0001 g to constant mass. Perform the mass determinations quickly to prevent absorption of water and CO2. Immediately transfer the CaO without grinding to a clean, dry Erlenmeyer flask and again determine the mass of the empty crucible to the nearest 0.0001 g to determine the amount of CaO added. Then follow procedure beginning with “Add 70 mL of the ethyl acetoacetate isobutyl alcohol . . .” in Section 30.2.3.1.

TS-3a T 105-53 AASHTO

Calculate the CaO equivalents of the standard perchloric acid solution in grams per milliliter by dividing the mass of CaO used by the volume of perchloric acid required for the titration.

30.2.3. Procedure:

30.2.3.1. Transfer 1.0000 g of ground sample (see Note 108106) into a clean, dry 250-mL Erlenmeyer flask. Add four to five glass boiling beads. Add 70 mL of prepared ethyl acetoacetate-isobutyl alcohol solvent. Agitate the flask to disperse the sample. Note 108106—Thorough grinding of the sample is essential for proper exposure of the free lime grains that often are occluded in crystals of tricalcium silicate in the cement. However, exposure of the sample to the air must be kept at a minimum to prevent carbonation of the free lime. Caution—In particular, direct breathing into the sample must be avoided. The sample should be sufficiently fine to easily pass a No. 200 (75-µm) sieve, but actual sieving is not recommended. If the sample is not to be immediately tested, it must be kept in an airtight container to avoid unnecessary exposure to the atmosphere.

30.2.3.2. Attach the flask to a reflux condenser and bring the material to a boil. Reflux for 15 min.

30.2.3.3. Remove flask from condenser, stopper, and cool rapidly to room temperature.

30.2.3.4. Filter the sample and solution using the vacuum assembly. Wash the flask and residue with small increments (10 to 15 mL) of isobutyl alcohol until a total of 50 mL has been used for the wash solution.

30.2.3.5. Add 12 drops of the thymol blue indicator to the filtrate and immediately titrate with 0.2 N perchloride acid to the first distinct color change.

30.2.4. Calculations—Calculate the percent free calcium oxide to the nearest 0.1 percent as follows:

100free CaO, % ×=

EVW

(23)(24)

where: E = CaO equivalent of the perchloric acid, g/mL; V = milliliters of perchloric acid solution required by sample; and W = mass of the sample, g.

Report the result rounded in accordance with Table 3.

30.3. Rapid Sr(NO3)2 Test Method (Alternative Test Method B):

30.3.1. Reagents:

30.3.1.1. Ammonium Acetate, Standard Solution (1 mL = 5 mg CaO)—Prepare a standard solution of ammonium acetate (NH4C2H3O2) by dissolving 16 g of desiccated ammonium acetate in 1 L of ethanol in a dry, clean, stoppered bottle. Standardize this solution by the same procedure as described in Section 30.3.2.1, except use the following in place of the sample: Ignite to constant mass approximately 0.1 g of calcium carbonate (CaCO3) in a platinum crucible at 900 to 1000°C, cool the contents in a desiccator, and determine the mass to the nearest 0.1 mg. Perform the mass determinations quickly to prevent absorption of water and CO2. Immediately transfer the CaO without grinding to a 250-mL boiling flask (containing glycerin-ethanol solvent and Sr(NO3)2), and again determine the mass of the empty crucible to determine the mass of CaO to the nearest 0.1 mg. Continue as described in Sections 30.3.2.1 and 30.3.2.2. Calculate the CaO equivalent of the ammonium acetate in grams per milliliter by dividing the mass of CaO used by the volume of solution required.

TS-3a T 105-54 AASHTO

30.3.1.2. Phenolphthalein Indicator—Dissolve 1.0 g of phenolphthalein in 100 mL of ethanol (Formula 2B) (see Note 109107). Note 109107—Ethanol denatured in accordance with Formula 2B (99.5 percent ethanol and 0.5 percent benzol) is preferred but may be replaced by isopropyl alcohol, A.R.

30.3.1.3. Glycerin-Ethanol Solvent (1+2)—Mix one volume of glycerin with two volumes of ethanol (Formula 2B). To each liter of this solution, add 2.0 mL of phenolphthalein indicator solution.

30.3.1.4. Strontium Nitrate (Sr(NO3)2)—Reagent grade.

30.3.2. Procedure:

30.3.2.1. Transfer 60 mL of the glycerin-ethanol solvent into a clean, dry, 250-mL standard-taper flat-bottom boiling flask. Add 2 g of anhydrous strontium nitrate (Sr(NO3)2), and adjust the solvent to slightly alkaline with a dropwise addition of a freshly prepared dilute solution of NaOH in ethanol until a faint pink color is formed. Weigh 1.000 g of the finely ground sample (see Note 107) into the flask, add encapsulated stirring bar, and immediately attach a water-cooled condenser (with a standard 24/40 glass joint). Boil the solution in the flask on a magnetic stirrer hot plate for 20 min with mild stirring.

30.3.2.2. Remove the condenser and filter the contents of the flask on a small polypropylene Büchner funnel under vacuum, using a 250-mL filtering flask with side tube. Bring the filtrate to a boil and immediately titrate with standard ammonium acetate solution to a colorless end point.

30.3.3. Calculation—Calculate the percent free CaO to the nearest 0.1 percent as follows: free CaO, % 100= ×EV (24)

where: E = CaO equivalent of the ammonium acetate solution, g/mL; and V = milliliters of ammonium acetate solution required by the sample.

Report the result rounded in accordance with Table 3.

31. KEYWORDS

31.1. Chemical analysis; compositional analysis; hydraulic cements.

32. REFERENCES

32.1. Bean, B. L. Improvements in the Rapid Analysis of Portland Cement by Atomic Absorption Spectrophotometry. Report No. FHWA RD-73-4. Department of Transportation, Federal Highway Administration, March 1973. (Order copies from National Technical Information Service, Springfield, VA 22151, by Order No. PB-220-549.)

32.2. Bean, B. L. and T. H. Arni. A New Rapid Test Method for Cement Analysis (Atomic Absorption Spectrophotometry), Report No. FHWA RD-72-41. Department of Transportation, Federal Highway Administration, September 1972. (Order copies from National Technical Information Service, Springfield, VA 22151, by Order No. PB-243-622.)

32.3. Crow, R. F. and J. D. Connolly. Atomic Absorption Analysis of Portland Cement and Raw Mix Using Lithium Metaborate Fusion. In Journal of Testing and Evaluation, Vol. 1, No. 5, September 1973, pp. 382–393.

TS-3a T 105-55 AASHTO

32.4. Jugovic, Z. T. Applications of Spectrophotometric and EDTA Methods for Rapid Analysis of Cement and Raw Materials. In Analytical Techniques for Hydraulic Cement and Concrete, ASTM STP 395. ASTM, 1966, pp. 65–93.

32.5. Moore, C. W. Suggested Method for Spectrochemical Analysis of Portland Cement by Fusion with Lithium Tetraborite Using an X-Ray Spectrometer. E-2 SM 10–26 in Test Methods for Emission Spectrochemical Analysis. ASTM, 1971.

APPENDIXES

(Nonmandatory Information)

X1. EXAMPLE OF DETERMINATION OF EQUIVALENCE POINT FOR THE CHLORIDE DETERMINATION

(Column 1) AgNO3, mL

(Column 2) Potential, mV

(Column 3) ΔmV a

(Column 4) Δ2mV b

1.60 125.3 5.8

1.80 119.5 1.4 7.2

2.00 112.3 1.3 8.5

2.20 103.8 1.3 9.8

2.40 94.0 0.6 9.2

2.60 84.8 2.3 6.9

2.80 77.9 0.8 6.1

3.00 71.8 1.3 4.8

3.20 67.0 The equivalence point is in the maximum ∆mV interval (Column 3), and thus between 2.20 and 2.40 mL. The exact equivalence point in this 0.20 increment is calculated from the ∆2mV (Column 4) data as follows:

E = 2.20 + ( 1.3 / (1.3 + 0.6 )) × 0.20 = 2.337 mL. Round to 2.34. a Differences between successive readings in Column 2. b Differences between successive readings in Column 3 “second differentials.”

X2. CO2 DETERMINATIONS IN HYDRAULIC CEMENTS

X2.1. Scope:

X2.1.1. This appendix contains information about methods for determination of carbon dioxide (CO2) in hydraulic cement. The methods listed received a favorable evaluation by ASTM Task Group C01.23.04.

TS-3a T 105-56 AASHTO

X2.1.2. Section X2.2 lists the analytical methods that received a favorable evaluation, briefly describes each method, suggests analytical techniques or cautions that may be useful, and indicates limitations to some of the methods.

X2.1.3. The methods listed in Sections X2.2.1, X2.2.4, X2.2.5, and X2.2.6 determine total carbon calculated as CO2. For that reason, they are not appropriate for determination of carbon dioxide in fly ash, limestones containing carbon in the form of graphite or kerogen, in other carbon-bearing materials, or in blended cements produced from these materials.

X2.1.4. The methods listed in Sections X2.2.2 and X2.2.3 can determine actual CO2 directly rather than by calculation from total carbon. They are suggested for analysis of blended cement and blended cement ingredients that are likely to contain noncarbonate carbon.

X2.1.5. The split loss on ignition method in Section X2.2.1 can give misleading results when used with materials containing CaOH2 (calcium hydroxide). This can occur with aged cement, cement made from aged clinker, or high free lime clinker, in addition to cements with a lime or hydrated lime ingredient.

X2.2. Analytical Methods:

X2.2.1. Split Loss on Ignition—This procedure is comparable to the analytical method described in ASTM C114, Section 17.1.1, with the following modifications: 1. A crucible of known mass and containing a sample of known mass is initially heated at 550°C

for 2 h. 2. After being cooled to room temperature in a desiccator, and its mass determined, the crucible

with sample is then heated at 950°C for 2 h. 3. Finally, the crucible with sample is cooled and its mass is determined as per step No. 2. 4. The difference in residue masses after the respective heat treatments is assumed to be

carbon dioxide. TGA results indicated that Ca(OH)2 can lose a significant portion of its mass above 500°C. Thus, the Split on Loss of Ignition procedure should not be used when situations described in Section X2.1.5 exist.

X2.2.2. Thermogravimetric Analysis (TGA)—This method involves the determination of sample mass loss at various temperatures. The heating of a sample through a temperature range allows for mass loss differentiation based on mineral form (e.g., CaCO3, MgCO3, CaOH2). Specific operational information is provided by the equipment manufacturers. If free carbon is present, an inert atmosphere (e.g., nitrogen) should be used for sample analysis.

X2.2.3. ASTM C25, Section 22—“Standard Test Methods for Chemical Analysis of Limestone, Quicklime, and Hydrated Lime.” This method involves decomposition of the sample with HCl. The liberated CO2 is then passed through a series of scrubbers to remove water and sulfides. The CO2 is absorbed with special Sodium Hydroxide Absorbent (Ascarite). The gain in mass of the absorption tube is determined and calculated as percent CO2. Calcium carbonate, for instance, can be calculated by multiplying the determined CO2 content by a conversion factor (e.g., CO2 × 2.2742 = CaCO3).

X2.2.4. X-Ray Fluorescence Spectroscopy—In this method, the sample is ground to a fine particle size, pressed into a flat pellet, and irradiated with the chosen instrument. Carbon content is determined by comparing the collected carbon emissions to calibration standards.

X2.2.5. Combustion by Induction Furnace/IR—This method involves volatilization by induction furnace and detection by infrared absorption. Suitable calibration standards (e.g., calcium carbonate and synthetic carbon) are available from some instrument manufacturers. NIST cement SRMs with

TS-3a T 105-57 AASHTO

known additions of NIST argillaceous limestone (or other suitable standards) should also be considered to check instrument calibration.

X2.2.6. ASTM E350—This method, “Total Carbon by the Combustion Gravimetric” from “Test Methods for Chemical Analysis of Carbon Steel, Low-Alloy Steel, Silicon Electrical Steel, Ingot Iron, and Wrought Iron,” is suitable for the determination of carbon in concentrations from 0.05 to 1.80 percent (as carbon dioxide 0.18 to 6.60 percent). The test method involves burning the sample in a stream of oxygen; the carbon dioxide in the evolved gases is then collected in a suitable absorbent and its mass determined. Time of analysis is less than 10 min.

X2.3. Cooperative Test Results:

X2.3.1. Tables X2.1 and X2.2 list results from two series of cooperative tests using several of the analytical methods evaluated by the Task Force Group. In all, five of the six methods receiving favorable ratings were included. The sixth method, ASTM C25, was specifically not tested in these cooperative series but was rated favorably because of long history of use with related materials.

X2.3.2. Table X2.1 includes results of single determinations using three of the different analytical methods. The methods used were Split Loss on Ignition, ASTM E350, and Combustion by Induction Furnace with Infrared Detection.

X2.3.3. Table X2.2 includes results based on the average of three determinations. Results from four of the different analytical methods are included. Methods used were Split Loss on Ignition, X-Ray Fluorescence Analysis, Induction Furnace with Infrared Detection, and Thermo-Gravimetric Analysis. ASTM E350 was not used in this series of tests.

Table X2.1—Cooperative Test Series No. 1 Single Determinations

Carbon Dioxide

Unknowna

Determinations Base

Cementb

Added CO2, %

Determinedc

Added CO2, % Knownd

Split LOI 2.40 0.45 1.97 2.00 2.52 0.56 1.99 2.41 0.36 2.07 2.39 0.32 2.09 2.41 0.36 2.07 2.28 0.27 2.02 ASTM E350 2.00 0.02 1.98 2.00 0.02 1.98 Induction Furnace/IR 2.46 0.40 2.07 2.53 0.48 2.08 2.38 0.40 2.00 2.42 0.48 1.97 2.02 Average Standard Deviation 0.05

a The Unknown was prepared by blending/grinding a mixture of 5.00 percent NIST SRM 1C Argillaceous Limestone and 95.00 percent CCRL Portland Cement Reference Sample No. 85. According to the Certificate of Analysis, SRM 1C had a loss on ignition of 39.9 percent. For the purpose of the cooperative test series, the loss on ignition was assumed to be CO2 only.

b The Base Cement was CCRL Portland Cement Reference Sample No. 85. c The Determined Percent Added CO2 was obtained by subtracting the Base Cement Percent CO2 from the Unknown Percent CO2. d The addition of 5.00 percent NIST SRM 1C (with a loss on ignition value of 39.9 percent) would provide 2.00 percent Added CO2. (Again, it was

assumed that the SRM 1C loss on ignition was only carbon dioxide.)

TS-3a T 105-58 AASHTO

Table X2.2—Cooperative Test Series No. 2 Average from Three Determinations

Carbon Dioxide

Unknowna

Determinations Base

Cementb

Added CO2, %

Determinedc

Added CO2, % Knownd

Split LOI 2.00 0.41 1.59 1.60 1.65 0.32 1.33 2.02 0.46 1.56 1.91 0.35 1.56 2.10 0.43 1.67 1.91 0.41 1.50 1.98 0.46 1.52 XRFA 1.68e 0.00e 1.68e Induction Furnace/IR 2.23 0.28 1.95 1.96 0.28 1.68 1.95 0.40 1.55 TGA 1.77 0.20 1.57 1.87 0.25 1.62 1.60 Average Standard Deviation 0.14

a The Unknown was prepared by blending/grinding a mixture of 4.00 percent NIST SRM 1C Argillaceous Limestone and 96.00 percent CCRL Portland Cement Reference Sample No. 85. According to the Certificate of Analysis, the SRM 1C had a loss on ignition of 39.9 percent. For the purpose of the cooperative test series, the loss on ignition was assumed to be CO2 only.

b The Base Cement was CCRL Portland Cement Reference Sample No. 85. c The Determined Percent Added CO2 was obtained by subtracting the Base Cement Percent CO2 from the Unknown Percent CO2. d The addition of 4.00 percent NIST SRM 1C (with a loss on ignition value of 39.9 percent) would provide 1.60 Added CO2. (Again, it was assumed that the

SRM 1C loss on ignition was only carbon dioxide.) e The XRF instrument was calibrated using standards composed of the Base Cement (i.e., CCRL No. 85) and NIST SRM 1C. It was assumed that

the Base Cement contained 0 percent CO2.

1 Similar to ASTM C114-13C114-15, except for terminology related to mass and weights. 2 Gebhardt, R. F. Rapid Methods for Chemical Analysis of Hydraulic Cement. ASTM STP 985, 1988. 3 Barger, G. S. A Fusion Method for the X-Ray Fluorescence Analysis of Portland Cements, Clinker and Raw Materials Utilizing Cerium (IV) Oxide in Lithium Borate Fluxes. In Proceedings of the Thirty-Fourth Annual Conference on Applications of X-Ray Analysis, Denver, CO, Volume 29, August 5, 1985, pp. 581–585. 4 ACS Committee on Analytical Reagents. Reagent Chemicals: Specifications and Procedures, 10th Edition. American Chemical Society, Washington, DC, August 2005. For suggestions on the testing of reagents not listed by the American Chemical Society, see Reagent Chemicals and Standards, by Joseph Rosin, D. Van Nostrand Co., Inc., New York, NY, and the United States Pharmacopeia, U.S. Pharmacopeia Convention, Inc., Rockville, MD. 5 See also the ASTM Manual on Presentation of Data and Control Charts Analysis, STP 15D, 1976. 6 The 1988 revision of these test methods deleted the colorimetric method for determination of ZnO using the extraction with CCl4. 7 The 1963 revision of these test methods deleted the classical (J. L. Smith) gravimetric method for the determination of Na2O and K2O in cements. The 1983 revision of these test methods deleted the details of the flame photometric procedure for the determination of Na2O and K2O.

TS-3a T 105-59 AASHTO

Standard Practice Method of Test for

Sampling and Amount of Testing of Hydraulic Cement

AASHTO Designation: T 127M/T 127-1516 ASTM Designation: C183-13C183/C183M-15

1. SCOPE

1.1. This practice covers procedures for sampling and for the amount of testing of hydraulic cement after it has been manufactured and is ready to be offered for sale.

1.2. The values stated in either SI units or inch-pound units are to be regarded separately as the standard. The inch-pound units in parentheses are for information purposes only. standard. The values stated in each system may not be the exact equivalents; therefore, each system shall be used independently of the other. Combining values from the two systems may result in non-conformance with the standard. Values in SI units [or in-pound units] shall be obtained by measurement in SI units [or inch-pound units] or by appropriate conversion, using the Rules for Conversion and Rounding given in ASTM Standard IEEE/ASTM SI 10. Values are stated in only SI units when inch-pound units are not used in practice.

1.2.1. A ton as used in this practice is 907 kg (2000 lb).

1.2.2. Values in SI units shall be obtained by measurement in SI units or by appropriate conversion, using the rules for conversion and rounding given in standard IEEE/ASTM SI10, of measurements made in other units.

1.3. The text of this standard references notes and footnotes which provide explanatory material. These notes and footnotes (excluding those in tables and figures) shall not be considered requirements of the standard.

1.3.1.4. This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

2. REFERENCED DOCUMENTS

2.1. AASHTO Standards: M 85, Portland Cement M 240M/M 240, Blended Hydraulic Cement T 98M/T 98, Fineness of Portland Cement by the Turbidimeter T 105, Chemical Analysis of Hydraulic Cement T 106M/T 106, Compressive Strength of Hydraulic Cement Mortar (Using 50-mm or 2-in.

Cube Specimens) T 107M/T 107, Autoclave Expansion of Hydraulic Cement T 131, Time of Setting of Hydraulic Cement by Vicat Needle

T 137, Air Content of Hydraulic Cement Mortar T 153, Fineness of Hydraulic Cement by Air Permeability Apparatus T 154, Time of Setting of Hydraulic Cement Paste by Gillmore Needles T 160, Length Change of Hardened Hydraulic Cement Mortar and Concrete T 186, Early Stiffening of Hydraulic Cement (Paste Method)

TS-3a T 127-1 AASHTO

2.2. ASTM Standards: C10/C10M, Specification for Natural Cement C91/C91M, Standard Specification for Masonry Cement C157/C157M, Standard Test Method for Length Change of Hardened Hydraulic-Cement

Mortar and Concrete C186, Standard Test Method for Heat of Hydration of Hydraulic Cement C227, Standard Test Method for Potential Alkali Reactivity of Cement-Aggregate

Combinations (Mortar-Bar Method) C265, Standard Test Method for Water-Extractable Sulfate in Hydrated Hydraulic Cement

Mortar C452/C452M, Standard Test Method for Potential Expansion of Portland-Cement Mortars

Exposed to Sulfate C806, Test Method for Restrained Expansion of Expansive Cement Mortar C807, Test Method for Time of Setting of Hydraulic Cement Mortar by Modificed Vicat

Needle C563, Standard Test Method for Approximation of Optimum SO3 in Hydraulic Cement Using

Compressive Strength C845/C845M, Standard Specification for Expansive Hydraulic Cement C1012/C1012M, Standard Test Method for Length Change of Hydraulic-Cement Mortars

Exposed to a Sulfate Solution C1038/C1038M, Test Method for Expansion of Hydraulic Cement Mortar Bars Stored in

Water C1157/C1157M, Standard Performance Specification for Hydraulic Cement C1328/C1328M, Standard Specification for Plastic (Stucco) Cement C1329/C1329M, Standard Specification for Mortar Cement C1357, Test Methods for Evaluation Masonry Bond Strength C1506 Test Method for Water Retention of Hydraulic Cement-Based Mortars and Plasters E11, Specification for Woven Wire Test Sieve Cloth and Test Sieves

2.3. ACI Standard: ACI 225.1R, Guide to the Selection and Use of Hydraulic Cements

2.4. IEEE/ASTM Standard: SI10, American National Standard for Metric Practice

3. TERMINOLOGY

3.1. Definitions of Terms Specific to This Standard:

3.1.1. lot (of cement)—specific quantity of cement offered for inspection at any one time. A lot may be one or more storage bins filled consecutively. A lot may also be the contents of one or more transport units representing cement drawn from the same storage bin.

3.1.2. reduced testing rate—test program that provides for the testing of only two samples from any given lot of samples obtained and prepared for testing at the normal rate as described herein. The program uses probability factors and is so designed that when results from the two samples fulfill the requirements of the program, it may be said with 95 percent confidence that fewer than 5 percent of the samples would be outside the specification limits.

TS-3a T 127-2 AASHTO

3.1.2.3.1.3. ton, n—907 kg [2000 lb] (as used in this practice)

4. SIGNIFICANCE AND USE

4.1. The sampling procedures described are intended for use in the procurement of samples of hydraulic cement after it has been manufactured and is ready to be offered for sale. They are not intended as sampling procedures for quality control purposes during manufacturing. The testing procedures outlined cover the amount of testing to be done and provide guidance for reporting on conformance or nonconformance of cements with requirements of purchase specifications.

4.2. This practice is referenced as the procedure for sampling natural cement (ASTM C10/C10M) masonry cement (ASTM C91/C91M), portland cement (M 85), blended hydraulic cement (M 240M/M 240), expansive hydraulic cement (ASTM C845/C845M), plastic (stucco) cement (ASTM C1328), mortar cement (ASTM C1329), and hydraulic cement (ASTM C1157/C1157M) based on a performance specification.

4.3. Most building codes and construction specifications require that hydraulic cement to be used in the work meet the applicable requirements of the relevant purchase specifications, such as Specifications M 85, M 240M/M 240, ASTM C91/C91M, ASTM C845/C845M, ASTM C1157/C1157M, ASTM C1328, and ASTM C1329. If the code or specification requires sampling of the manufactured cement, the provisions given in Section 4.4 are applicable. Not much cement is sold on the basis of such sampling and testing. A useful discussion of sampling and testing cement is contained in ACI 225.1R.

4.4. The procedures covered in this practice should be done by or for purchasers of hydraulic cement who are using a code or specification that requires sampling and testing to determine if the samples conform to the relevant acceptance specifications. The testing is done using specified methods to determine whether the samples yield test results that conform to the specification, and the tests serve as a basis for acceptance or rejection of the lot of material sampled.

4.5. It is neither intended nor required that all cements be tested using all the test methods referenced in Section 2.

5. KINDS AND SIZE OF SAMPLES AND BY WHOM TAKEN

5.1. A cement sample secured from a conveyor, bulk storage, or a bulk shipment in one operation shall be termed a “grab sample.” A sample obtained during a 10-min interval using an automatic sampling device that continuously samples a cement stream may also be considered a grab sample. Grab samples taken at prescribed intervals over a period of time may be combined to form a “composite sample” representative of the cement produced during that period of time.

5.2. All samples, whether grab or composite, shall have a mass of at least 5 kg [(10 lb]).

5.3. The purchaser may designate a representative to supervise the sampling, packing, and shipping of samples when it is so specified in the purchase contract.

5.4. Package the samples in moisture-proof, airtight containers numbered consecutively in the order in which the samples are taken (see Note 1). The purchase contract shall state who will pay for the costs of sampling, packaging, shipping, and testing the samples. Note 1—Polyvinyl chloride sample containers, upon occasion, have been found to affect the air-entraining potential of a cement sample. The same problem might be experienced with containers made from other plastics.

TS-3a T 127-3 AASHTO

6. TESTING-TIME REQUIREMENTS FOR THE COMPLETION OF TESTS

6.1. When tests of hydraulic cement are made at a laboratory other than that of the cement manufacturer, the cement sampling schedule, sample transportation time, and sample testing schedule must be coordinated among the purchaser, manufacturer, and testing laboratory so that the tests results will be available when required.

6.2. The manufacturer of the cement shall make the cement available to be sampled for testing early enough before the time the test results are needed so that at least the applicable time intervals listed in Section 6.3 exist.

6.3. When this has been done, the testing laboratory shall provide test results not later than the indicated number of days after sampling:

Tests Time Interval,

Days T 106M/T 106 (1-day results), T 98M/T 98, T 105, T 107M/T 107, T 131, T 137, T 153, T 154, T 186; ASTM C265, C563 8

T 106M/ T 106 (3-day results) 10 T 106M/T 106 (7-day results); ASTM C186 14 ASTM C227, C452/C452M, and C1012/C1012M (14-day results) 21 T 106M/T 106 (28-day results); ASTM C186 35 T 160 (34-day results); ASTM C157/C157M 41 ASTM C227 (56-day results) 63 ASTM C227 (91-day results) 98

7. SAMPLING

7.1. The cement may be sampled by any of the applicable methods described in this section.

7.1.1. From the Conveyor Delivering to Bulk Storage—Take one grab sample, having a mass of at least 5 kg (10 lb), at approximately 6-h intervals.

7.1.2. Transfer Sampling—Sample cement in storage while the cement is being transferred from one bin to another. Take one grab sample from the transfer stream for each 360 Mg [(400 tons]) of cement, or fraction thereof, but take no less than two grab samples and combine them to produce a composite sample.

7.1.3. Other Sampling Methods—When neither of the above sampling methods is applicable, samples may, when authorized by the purchaser, be taken by one of the following methods:

7.1.3.1. From Bulk Storage at Points of Discharge—Withdraw cement from the discharge openings in a steady stream until sampling is completed. If a high circular silo is being sampled, take all samples from one opening. If the quantity of the cement in the bin exceeds 1100 mg (1200 tons) when low rectangular bins are being sampled, discharge openings employed in the sampling shall be such that for no opening shall the number of samples represent more than one-half the contents of the bin or more than 1800 mg (2000 tons). When sampling bulk storage at points of discharge, while the cement is flowing through the openings, take samples at such intervals so that at least two grab samples shall be secured for each 360 mg (400 tons) in the bin or silo.

7.1.3.2. From Bulk Storage and Bulk Shipment by Means of a Slotted Tube Sampler—When the depth of the cement to be sampled does not exceed 2.1 m (7 ft), obtain samples using a slotted tube sampler similar to that shown in Figure 1.When desired, use a tube sampler designed for cohesive

TS-3a T 127-4 AASHTO

and semi-cohesive powders and designed for the depth of the cement to be sampled. An exampled of just one type is shown in Figure 1. It shall be between 1.5 and 1.8 m (5 and 6 ft) long and approximately 35 mm (13/8 in.) in outside diameter, and consist of two polished brass telescopic tubes with registering slots that are opened or closed by rotation of the inner tube, the outer tube being provided with a sharp point to facilitate penetration. Take samples from well- distributed points and various depths of the cement so that the samples taken will represent the cement involved.

Figure 1—Example ofSlotted Tube Sampler for Bulk Cement

7.1.3.3. From Packaged Cement by Means of Tube Sampler—Insert the sampler, shown in Figure 2, diagonally into the valve of the bag and place the thumb over the air hole. Then withdraw the sampler.Sample package cement using a tube sampler designed for cohesive and semi-cohesive powders and able to sample packaged cement from the valve of the cement bag. An example of just one type is shown in Figure 1. Take one sample from a bag in each 4.5 mg [(5 tons]) or fraction thereof.

Figure 2—Tube Sampler for Packaged Cement

7.1.3.4. From Bulk Shipment of Car or Truck: 1. Single Shipment—If only one car or truck is being loaded and the loading is continuous and

all from the same source, take a 5-kg [(10-lb]) sample. If not continuous or unknown, combine five or more portions from different points in the load to form the test sample.

2. Multiple Shipments—When the shipment consists of several cars or trucks loaded from the same source and on the same day, sample the shipment at the rate of one sample for each 90 mg [(100 tons]) of cement or fraction thereof, but take not less than two samples. Consider cement represented by such samples as a lot, and test the samples in accordance with the procedure outlined in Section 9.

TS-3a T 127-5 AASHTO

7.2. Protection of Samples—As samples are taken, place them directly in moisture-proof airtight containers to avoid moisture absorption and aeration of the sample. If the samples are placed in cans, fill the can completely and immediately seal. Use moisture-proof, multiple-wall paper bags or plastic bags if they are strong enough to avoid breakage, and if they can be sealed immediately after filling in such a manner as to eliminate excess air in the sample and avoid moisture absorption and aeration of the sample. Samples shall be treated as described in Section 8.

8. PREPARATION OF SAMPLE

8.1. Before testing, pass each sample through an 850-µm (No. 20) sieve, or any other sieve having approximately the same size openings, to mix the sample, break up lumps, and remove foreign material. Discard Do not include the foreign materials and hardened lumps that do not break up on sieving or brushing.brushing in the sample to be tested. Store the cement in airtight moisture-proof containers to prevent aeration or absorption of moisture prior to test.

9. AMOUNT OF TESTING

9.1. General—When required, the purchaser shall specify the amount of testing for heat of hydration (ASTM C186), alkali reactivity (ASTM C227), and sulfate resistance (ASTM C1012/C1012M). Make all other tests on individual grab or composite samples chosen as specified herein under Section 9.4, Selection of Samples for Testing. Do only those tests required by the applicable specification.the following specification specific requirements:

9.1.1. Heat of Hhydration of Hydraulic Cement (Test Method ASTM C186) for optional limits specified in Specifications M 85, M 240 C150/C150M, C595/C595M and ASTM C1157/C1157M;

9.1.2. Alkali rReactivity (ASTM Test Method C227) for optional limits specified in Specifications M 240C595/C595M and C1157/C1157M;

9.1.3. Sulfate Rresistance (ASTM Test Method C1012/C1012M) for optional limits specified in Specifications M 240C595/C595M and ASTM C1157/C1157M;

9.1.4. Potential Expansion of Portland-Cement Mortars Exposed to Sulfate (Test Method ASTM C452/C452M) for optional limits specified in M 85Specification C150/C150M;

9.1.5. Expansion of Hydraulic Cement Mortar Bars Stored in Water (Test Method ASTM C1028/C1038M) for limits specified in Specifications C150/C150M and C595/C595M,M 85, M 240 and ASTM C1157/C1157M;

9.1.6. Early Stiffening of Hydraulic Cement (Paste Method) (T 186est Method C451) for optional limits specified in Specification C150/C150MM 85 and ASTM C1157/C1157M;

9.1.7. Fineness of Hydraulic Cement by the 45-µm (No. 325 Sieve) (T 192est Method C430) for limits specified in Specifications ASTM C91/C91M, ASTM C1328/C1328M, and ASTM C1157/C1157M;

9.1.8. Water Retention of Hydraulic Cement-Based Mortars and Plasters (Test Method ASTM C1506) for limits specified in Specification ASTM C91/C91M, ASTM C1328/C1328M, and ASTM C1329/C1329M;

9.1.9. Evaluating Masonry Bond Strength (Test Method ASTM C1357) for limits specified in Specification ASTM C1329/C1329M;

Formatted: Heading 3, Tab stops: Not at 2.88"

TS-3a T 127-6 AASHTO

9.1.10. Restrained Expansion of Expansive Cement Mortar Test (Test MethodASTM C1357) for limits specified in Specification ASTM C1329/C1329M;

9.1.11. Time of Setting of Hydraulic Cement Mortar by Modified Vicat Needle (Test MethodASTM C807) for limits specified in SpecificationASTM C845/C845M;

9.1.9.1.12. Make all other test on individual grab or composite samples chosen as specified herein under Selection of Samples for Testing. Do only those tests required by the applicable specification.

9.2. Normal Testing—Determine the number of samples to be tested in accordance with Table 1. The normal testing rate shall be used under the following conditions:

9.2.1. Before the quality history has been established,

9.2.2. When no samples from a particular mill have been tested within a year,

9.2.3. When the quality history is based entirely on data more than 2 years old, and

9.2.4. When it is deemed necessary to recalculate the critical limit because of indicated lack of control as shown by the control chart of the range.

Table 1—Number of Samples for Test

Lot Size—Number of Samples

Number of Tests

Normal Rate Reduced Rate

2 2 2 3 3 2 4 to 10 4 2 11 to 20 6 2 Over 20 8 2

Note 2—Random grab samples taken at inappropriate times, such as immediately following the repair or adjustment of manufacturing equipment, or from inappropriate places, such as from the top surface of the material in a car, will not suitably reflect the properties of a cement, and therefore should not be used as the basis for acceptance or rejection of a lot of cement.

9.3. Reduced Testing—After the quality history has been established, test at the reduced testing rate. If the results of these tests are within the critical range, make additional tests (total equal to the number of tests at the normal rate as shown in Table 1). Note 3—When the quality history indicates that the results for a given requirement will probably be within the critical range, and substantial delay in completion of the tests would result from making additional tests (e.g., compressive strength), it may be desirable to make the tests at the normal rate rather than the reduced testing rate.

9.4. Selection of Samples for Testing—Take samples to be tested from each lot by some random method. The following method is suggested: Place a group of consecutively numbered markers equal to the number of samples in a container and mix, and then draw one marker at a time from the container until the number drawn is equal to the number of samples to be tested at the normal rate. If the testing is to be done at the reduced rate, mix the drawn markers and draw two to select the numbers of the samples to be tested.

9.5. Establishing a Quality History and Control Chart:

TS-3a T 127-7 AASHTO

9.5.1. Quality History—The quality history shall represent cement from the same source as the cement to be tested, and shall be based on data not more than 2 years old. There shall be available test results for not less than 40 test samples representing not less than seven lots of cement. The test samples shall conform to the applicable provisions of this practice. A pair shall be two test samples from the same lot, in numerical sequence. Several pairs from the same lot may be used where available. The number of paired samples representing a large lot may be reduced as follows: From the consecutively numbered group of tested samples representing the entire lot, select a subgroup by some random method. List the numbers identifying the subgroup in numerical sequence, and pair in the order of listing. Compute the range (difference between the test results of a pair) for each pair of test results. Total the ranges and divide their sum by the total number of ranges used to obtain the average range, .r Compute the average range, r , for each included physical and chemical property limited by specification requirements.

9.5.2. Critical Limit—Calculate the critical limit, C, for each included physical and chemical property limited by a specification requirement. First, multiply the average range, r , by the probability factor, 2.49; this will yield a number that for convenience is called d. If the requirement has a maximum specification limit, obtain C by subtracting d from the specification limit and, if a minimum, add d to the specification limit. Maintain quality history charts. (See Note 4.) Note 4—Improved estimates of the range r , and consequently of C, will result if the test results are not rounded. For example, the test result of 21.78 percent for SiO2 is preferred to the rounded value of 21.8 percent. For the fineness, the calculated value of 3243 is preferred to the rounded value of 3240.

9.5.3. Control Chart of the Range—Maintain a control chart of the range to indicate when the critical limit needs to be recomputed. Multiply the average range, r , as obtained in Section 9.5.2, by the probability factor 3.267 to obtain the upper control limit for the range between each consecutive pair of test results. The horizontal scale of the chart will be successive groups of two, and the vertical scale will be the range. Where the range chart indicates lack of control (points beyond the upper control limit), the critical limit, C, may need to be recalculated. Consider the occurrence of two consecutive points beyond the upper control limit for the range, or the occurrence of three points beyond the upper control limit in any series of five consecutive points cause to recalculate the critical limit. Where it becomes necessary to recalculate the critical limit, discontinue reduced testing until a new quality history has been established. (See Note 5.) Note 5—Examples of the calculation of r , d, and quality history and control charts are shown in Table 2 and Figures 3 and 4. The specification limits used in these examples are hypothetical.

TS-3a T 127-8 AASHTO

Table 2—Test Data, Type I Low-Alkali Cement

Lot No.

Sample No.

Alkalies, %

Range, %

7-Day Strength (Average of Three Specimens) Range

MPa (psi) MPa (psi) 88 1 0.58 35.5 (5150)

13 0.61 0.03 37.0 (5358) 1.44 (208) 17 0.57 32.2 (4675) 21 0.55 0.02 33.1 (4800) 0.86 (125)

91 1 0.55 32.0 (4633) 5 0.55 0.00 33.9 (4917) 1.95 (283) 13 0.57 34.3 (4975) 21 0.54 0.03 35.2 (5108) 0.92 (133)

98 5 0.55 33.8 (4896) 13 0.56 0.01 34.2 (4957) 0.42 (61) 17 0.56 35.4 (5133) 21 0.56 0.00 36.3 (5267) 0.92 (133)

106 5 0.42 35.6 (5158) 13 0.45 0.03 34.1 (4950) 1.44 (208) 17 0.47 33.3 (4832) 21 0.39 0.08 32.6 (4728) 0.72 (104)

107 4 0.47 34.1 (4938) 8 0.46 0.01 34.8 (5042) 0.72 (104) 12 0.40 32.3 (4683) 20 0.41 0.01 33.7 (4892) 1.44 (208)

111 4 0.45 36.1 (5233) 8 0.44 0.01 36.9 (5350) 0.80 (117) 12 0.41 35.6 (5163) 20 0.40 0.01 36.2 (5246) 0.57 (83)

112 3 0.45 36.8 (5333) 7 0.48 0.03 34.2 (4958) 2.59 (375) 15 0.48 34.5 (4996) 19 0.49 0.01 35.3 (5113) 0.80 (117)

113 2 0.49 34.0 (4937) 15 0.46 0.03 33.1 (4803) 0.92 (133) 20 0.47 34.4 (4994) 24 0.49 0.02 34.0 (4925) 0.48 (69)

120 1 0.46 32.5 (4717) 6 0.46 0.00 33.2 (4814) 0.67 (98) 11 0.46 32.2 (4675) 21 0.46 0.00 33.2 (4808) 0.92 (133)

123 6 0.46 36.6 (5304) 11 0.45 0.01 36.3 (5267) 0.26 (38) 21 0.44 35.3 (5117) 26 0.44 0.00 35.8 (5196) 0.55 (79)

Total 40 0.34 19.39 2811 Calculation of Critical Limit and Control Limit

Alkalies Strength,

MPa Strength,

psi Specification limit 0.60 30.0 4350 r 0.017 0.969 141

d = 2.49 r 0.042 2.413 350 Critical limit (0.60 – 0.042) (30 + 2.4) (4350 + 350) 0.558 32.4 4700 3.267 r 0.0555 3.17 459 Control limit 0.056 3.2 459

TS-3a T 127-9 AASHTO

Figure 3—Quality History Chart

Figure 4—Control Chart for RangeQuality History Chart

9.5.4. When the hydraulic cement sampled is to conform to M 85, and the manufacturer has chosen the optimized cement SO3 option as described in M 85, Table 1, footnote d, the critical limit described in Section 9.5.2 using the specification limit for SO3 is not applicable. Sections 9.5.2 and 9.5.3 dealing with the calculation of critical limit are not required for SO3 in this case.

151146137132130129126123120113112111107106989188

0.30

0.40

0.50

0.60

ALKALIES

25

30

35

404500

4000

3500

3000

Lot Number

Alk

alie

s, %

Stre

ngth

, MP

a

Stre

ngth

, psi

Spec. Limit: 0.60 %Critical Limit: 0.558 %

7-Day Strength

Critical Limit 32.4 MPa

Spec. Limit 30 MPa

Control Limit: 0.056 %

1511461371321301291261231201131121111071069891880

200

400

600

ALKALIES

0.00

0.02

0.04

0.06

0.08

Alk

alie

s, %

7-Day Strength

0

1

2

3

4

5

Control Limit: 3.2 MPa

Stre

ngth

Ran

ge, M

Pa

Lot Number

Stre

ngth

Ran

ge, p

si

TS-3a T 127-10 AASHTO

9.5.5. When the hydraulic cement sampled is to conform to M 240M/M 240, and the manufacturer has chosen the optimized cement SO3 content option as described in M 240M/M 240, Table 1, footnote a, the critical limit described in Section 9.5.2 using the specification limit for SO3 is not applicable. Sections 9.5.2 and 9.5.3 dealing with the calculation of critical limit are not required for SO3 in this case.

9.6. Reporting for Normal Testing—When the testing is done at the normal testing rate, report the cement as complying with the specification if it meets the specification requirements, and report it as failing to meet the specification requirements if it does not meet each of the requirements as specified.

9.7. Reporting for Reduced Testing—When the testing is done at the reduced testing rate, report the cement as complying with the specification if the average of the test results is further from the specified limit than the critical limit. If the average of the results for one or more requirements is between the critical limit and the specification limit, test additional samples (total equal to the number of tests at the normal rate) for that requirement, and if on completion of the additional tests all of the results meet the specified requirements, report the cement as complying with the specification. Report the cement as failing to meet the specification requirements if any test result does not conform to the respective requirements.

9.8. When a cement is reported as failing to meet the specification requirements, state in the report which requirement the cement failed and the applicable limit.

10. NONCOMPLIANCE AND RETEST

10.1. If any test result fails to meet the specification requirement, the lot of cement shall not be reported as not complying with the specification unless noncompliance is confirmed by retest as described in Section 10.2.

10.2. A retest is considered to be an additional test of a certain property that is made when the initial test of that property produces a result not complying with the specification requirements. A retest may consist of either a single determination or a set of replicate determinations.

10.3. Retests shall be conducted in accordance with the provisions, if given, of the applicable specification. If no provisions are given, the following procedure shall be used:

10.3.1. Make the retest on a portion of the same sample as was used for the initial test. Use referee methods whenever they are provided for determination of the property requiring retest and, in such case, use only the results obtained by referee methods. The retest shall consist of the same number of determinations required for the initial test, or, if a within-laboratory precision statement is given that is based on a specified number of replicates (i.e., duplicate or triplicate determinations), the number of replicates used as the basis of such precision statement. If two or more determinations are required, the value reported shall be the average of all results that are within the limits of precision of the method at the 95 percent confidence level, as stated in the applicable specification or as generally recognized.

11. KEYWORDS

11.1. Hydraulic cement; sampling; testing.

TS-3a T 127-11 AASHTO

Standard Method of Test for

Density of Hydraulic Cement

AASHTO Designation: T 133-11 (2015) 16 ASTM Designation: C188-0914

1. SCOPE

1.1. This method covers determination of the density of hydraulic cement. Its particular usefulness is in connection with the design and control of concrete mixtures.

1.2. The density of hydraulic cement is defined as the mass of a unit volume of the solids.

1.3. The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.

1.3. 1.4 Warning - Fresh hydraulic cementitious mixtures are caustic and may cause chemical burns to skin and tissue upon prolonged exposure.

1.4. This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

2. REFERENCED DOCUMENTS

2.1. AASHTO Standard: T 105, Chemical Analysis of Hydraulic Cement

2.2. ASTM Standard: C670, Standard Practice for Preparing Precision and Bias Statements for Test Methods for

Construction Materials

3. TERMINOLOGY 3.1 Definitions - For definitions of terms used in this test method, refer to ASTM C125.

4. SIGNIFICANCE AND USE 4.1 This test method provides a procedure for the determination of density of hydraulic cement samples using non-instumental techniques.

Formatted: Normal

Formatted: Normal, Indent: Left: 1"

Formatted: Normal, Indent: Left: 1"

Formatted: Normal

3.5. APPARATUS

3.1.5.1. Le Chatelier Flask—the standard flask—Is circular in cross section with shape and dimensions conforming essentially to Figure 1 (see Note 1). The requirements in regard to tolerance, inscription and length, spacing, and uniformity of graduation will be rigidly observed. There shall be a space of at least 10 mm between the highest graduation mark and the lowest point of grinding for the glass stopper. Note 1—The design is intended to ensure complete drainage of the flask when emptied and stability of standing on a level surface as well as accuracy and precision of reading.

Notes: 1. All dimensions shown in millimeters unless otherwise noted.

2. Variations of a few millimeters in such dimensions as total height of flask, diameter of base, etc., are to be expected and will not be considered sufficient cause for rejection. The dimensions of the flask shown in Figure 1 apply only to new flasks and not to flasks in use which meet the other requirements of this test method.

Figure 1—Le Chatelier Flask for Density Test

3.1.1.5.1.1. The material of construction shall be best quality glass, transparent and free of striae. The glass shall be chemically resistant and shall have small thermal hysteresis. The flasks shall be thoroughly annealed before being graduated. They shall be of sufficient thickness to ensure reasonable resistance to breakage.

3.1.2.5.1.2. The neck shall be graduated from 0 to 1 mL and from 18 to 24 mL in 0.1-mL graduations. The error of any indicated capacity shall not be greater than 0.05 mL.

3.1.3.5.1.3. Each flask shall bear a permanent identification number and the stopper, if not interchangeably ground, shall bear the same number. Interchangeable ground-glass parts shall be marked on both members with the standard-taper symbol, $ , followed by the size designation. The standard

TS-3a T 133-1 AASHTO

temperature shall be indicated, and the unit of capacity shall be shown by the letters “mL” placed above the highest graduation mark.

3.2.5.2. Kerosene, free of water, or naphtha, having a density greater than 0.7391 mL at 23 ± 2°C shall be used in the density determination.

3.3.5.3. The use of alternative equipment or methods for determining density is permitted, provided that a single operator can obtain results within ±0.03 Mg/m3 g/cm3 of the results obtained using the flask method.

4.6. PROCEDURE

4.1.6.1. Determine the density of cement on the material as received, unless otherwise specified. If the density determination on a loss-free sample is required, first ignite the sample as described in the test for loss on ignition in Section 1816.1 of T 105.

4.2.6.2. Fill the flask (see Note 2) with either of the liquids specified in Section 3.2 to a point on the stem between zero and the 1-mL mark. Dry the inside of the flask above the level of the liquid, if necessary, after pouring. Record the first reading after the flask has been immersed in the water bath (see Note 3) in accordance with Section 4.4. Note 2—It is advisable to use a rubber pad on the table top when filling or rolling the flask. Note 3—Before the cement has been added to the flask, a loose-fitting, lead-ring weight around the stem of the flask will be helpful in holding the flask in an upright position in the water bath, or the flask may be held in the water bath by a buret clamp.

4.3.6.3. Introduce a quantity of cement, weighed to the nearest 0.05 g (about 64 g for portland cement) in small increments at the same temperature as the liquid (see Note 2). Take care to avoid splashing and make sure the cement does not adhere to the inside of the flask above the liquid. A vibrating apparatus may be used to accelerate the introduction of the cement into the flask and prevent the cement from sticking to the neck. After all the cement has been introduced, place the stopper in the flask and roll the flask in an inclined position (see Note 2), or gently whirl it in a horizontal circle to free the entrapped air from the cement until no further air bubbles rise to the surface of the liquid. If a proper amount of cement has been added, the level of the liquid will be in its final position at some point of the upper series of graduations. Take the final reading after the flask has been immersed in the water bath in accordance with Section 4.4.

4.4.6.4. Immerse the flask in a constant-temperature water bath for sufficient periods of time to avoid flask-temperature variations greater than 0.2°C between the initial and final readings.

5.7. CALCULATION

5.1.7.1. The difference between the first and final readings represents the volume of liquid displaced by the mass of cement used in the test.

7.2. Calculate the cement density, p, as follows (see Notes 4 to 6): P = M/V Where:

5.2. p(Mg/m3) = p(g/cm3) = mass of cement, g/displaced volume, cm3 density of cement, g/cm3, M = mass of cement, g, and

Formatted: Normal, Indent: Left: 1"

Formatted: Normal

TS-3a T 133-2 AASHTO

V = displaced volume of liquid, cm3

Note 4—The displaced volume in milliliters is numerically equal to the displaced volume in cubic centimeters. Note 5—Density in megagrams per cubic meter (Mg/m3) is numerically equal to grams per cubic centimeter (g/cm3). Calculate the cement density, p, to three decimal places and round to the nearest 0.01 Mg/mg/cm3. Note 6—In connection with proportioning and control of concrete mixtures, density may be more usefully expressed as specific gravity, the latter being a dimensionless number. Calculate the specific gravity as follows: Sp gr = cement density/water density at 4°C where the density of water (at 4°C the density of water is 1 mg/m3(1 g/cm3)).

6.8. PRECISION AND BIAS

6.1.8.1. The single-operator standard deviation for portland cements has been found to be 0.012.1 Therefore, the results of two properly conducted tests by the same operator on the same material should not differ by more than 0.03.1

6.2.8.2. The multilaboratory standard deviation for portland cements has been found to be 0.037.1

Therefore, the results of two properly conducted tests from two different laboratories on samples of the same cement should not differ by more than 0.10.1

6.3.8.3. Because there is no accepted reference material suitable for determining any bias that may be associated with T 133, no statement on bias is being made.

7.9. KEYWORDS

7.1.9.1. Density; hydraulic cement; specific gravity.

1 These numbers represent 1s and d2s limits described in ASTM C670.

TS-3a T 133-3 AASHTO

Standard Method of Test for

Mechanical Mixing of Hydraulic Cement Pastes and Mortars of Plastic Consistency

AASHTO Designation: T 162-1516 ASTM Designation: C305-13C305-14 (Chair Comment – Please disregard section number. 1.1 should be 4.5 and 1.2 should be 4.6.)

1.1. Supplementary Apparatus—The balances, weights, glass graduates, and other supplementary apparatus used in measuring and preparing the mortar materials prior to mixing shall conform to the respective requirements for such apparatus as specified in the method for the particular test for which the mortar is being prepared.

1.1.1.2. Mechanical mixing apparatus shall be inspected and checked for conformance to the requirements of this practice at least every 2 ½ years.

2. TEMPERATURE AND HUMIDITY

2.1. The temperature and humidity of the room and the temperature of the mixing water shall be maintained as described in M 201, Section 4, Requirements for Cement Mixing Rooms.

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