Summary of Results for PHA Glass Study: Composition and .../67531/metadc... · P.C).Box 62, CM...

. .

WSRC-TR-99-O0332

Summary of Results for PHA Glass Study: Composition andProperty Measurements

by

T. B. Edwards

Westinghouse Savannah River CompanySavannah River SiteAiken, South Carolina 29808

J. R. Harbour

R. J. Workman

DOE Contract No. DE-AC09-96SR18500

This paper was prepared in connection with work done under the above contract number with the U. S.Department of Energy. By acceptance of this paper, the publisher and/or recipient acknowledges the U. S.Government’s right to retain a nonexclusive, royalw-free license in and to any copyright covering this paper,along with the right to reproduce and to authorize others to reproduce all or part of the copyrighted paper.

WSRC-TR-99-O0332Revision O

Keywords: Coupled Operation, DWPF,Liquidus Temperature, PC(33, PCT,

Salt Disposition, Viscosity

Retention Time: Permanent

SUMMARYOFRESULTSFORPHA GLASSSTUDY:COMPOSITIONANDPROPERTYMEASUREMENTS(U)

T. B. EdwardsJ. R. HarbourR. J. Workman

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Westinghouse Savannah River CompanyL&=—q*= —~ m—wQ%---

Savannah River Technology Center g -~k”== ~

Aiken, SC 29808LE =-- A a. -—

SAVANNAH RIVER SITE

PREPARED FOR THE U.S. DEPARTMENT OF ENERGY UNDER CONTRACT NO. DE-AC09-96SR18500

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I‘l%is report was prepzwd = ~ acc~wt of work sponso~ by M agency of the United StatesGovernment. Neither the unit~ Sutes Gove~$nt nor my agency thereof, nor any of theiremployees, makes any w~~v, express or ~ph~d, or assmnes any legaI liability orresponsibility for the ace-y, completeness: or usefulness of any information, apparatus,produq or process discIo=L w ~esents that IS use wotid not tinge privately owned rights.Reference herein to any specific commercial pduc~ process, or service by trade name,trademark, manufacturer, of otherwise does not necessdy constitute or imply its tmdorsemen~recommendation, or f.avomg by the United States Government or any agency thereof. Theviews and opinions of authors expressed herein do not necessarily state or reflect those of theUnited States Government or any agency thereof.

WSRC-TR-99~00332’Revision O

DISCLAIMER

I This report has been reproduced directly from the best available copy.

Available to DOE and DOE contractors from the OiTiceof Scientific and Technical Information,P.C).Box 62, CM Ridge, TN 37831; prices available from (615) 576-8401.

Aviiilabk to the public from the National Technical Information Service, U.S. 13epu-trnent oft2cmmerce; 5285 Port Royal Road, Springfield, VA 22161.

ii

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Portions of this document may be illegiblein electronic image products. Images areproduced from the best available originaldocument.


Summary of Results for PHA Glass Study:Composition and Property Measurements (U)September 9, 1999

Document #iDDrOVdS

[2LMZd && q“/d- ‘zYT. B. Edwarhs, Author DateStatistical Consulting Section

__U!32_Date

‘7%%&&? (3. kZ2Q2L@&_ -97

R J. Workman, Autk& DateImmobilization Technology Section

IK. G. Brown, Technical Review

*

Immobilization Technology Section

R. k. *

W. L. Tamosaitis, ManagerWaste Processing Technology Section

“ +

% U* ~E. W. Holtzscheite~ Manager DateImmobilization Technology SectionAuthorized Derivative Classifier

J 7k2---J@’. Carter, Manager, HLW Process Engineering

e Signifies Satisfactory Completion of PHA Glass Study

71,7L%

Date

*K. j. Rueter, Director, Salt Disposition Engineering Date ‘Signature Signifies Satisfactory Completion of PHA Glass Study

...111

WSRC-TR-99-00332Revision O

This page intentionally left blank.

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TABLE OF CONTENTS

Summary and Conclusions .. . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .ktioduction .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Resdtsmd Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...

Target and Measured Chemical Compositions . . . . . . . . . . . . . . . . . . . . . . . ...PCT Results . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ....Viscosity at 1150 “C .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ....Liquidus Temperatue (TL) .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . ..Surface Crystallization .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Phase Separation .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..

Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .References .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . ...Appendix: Supplemental Tables and Exhibits . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . .

12445671011131517

v



vi


SUMMARYANDCONCLUSIONSThis report provides a summary of the results obtained for a limited variability study for glassescontaining Precipitate Hydrolysis Aqueous (PHA), Monosodiumtitanate (MST), and either simulatedPurex or HM sludge. Twenty glasses containing Purex sludge and three glasses containing HM sludgewere fabricated and tested. The fabricated glasses were tested for durability using the ProductConsistency Test (PCT) and characterized by measuring the melt viscosity and an approximate,bounding liquidus temperature. The current models used by Defense Waste Processing Facility(DWPF) for predicting durability, viscosity, and Iiquidus temperature were applied to all 23 glasses.The goal of this work was to identify any major problems from a glass perspective that couldpotentially preclude the use of higher levels of PHA and MST at DWPF.

The selection of Purex sludge for the majority of the glasses fabricated in this study was based on theknowledge that this sludge type has historically been the most difilcult sludge to incorporate into glass.Depleted uranium was introduced into the simulated Purex sludge to better represent the uraniumcontent (- 9 wt% oxide) of actual sludge.

One of the major concerns for this study was the effect of higher levels of PHA in the glass. The planfor this work was to vary the PHA level from 7 to 13 wt% oxide, which can be compared to theexpected/design basis of 6 to 8 wt% oxide. Another concern was the potential for higher levels oftitanium (from MST) into the glass. The current limit for Ti02 in the DWPF glass is 1 wt$%whereasthe scope of this work varied the Ti02 level fkom 1 to 2 wt%.

Frit 202 was used in this study and was the frit originally designed for coupled operations at DWPF.

As part of this study, the model predictions were made using targeted, measured, and bias-correctedmeasured compositions of the glasses. For glasses where there were no batching difflcukies, it wasdemonstrated that the results were essentially insensitive to the type of composition used in thesemodels. This provides evidence that the glasses produced were close to the targeted compositions, andthat the analytical measurements were of high quality.

Glass Durability. All 23 glasses were very durable as measured by the PCT. The values ranged from0.90 to 1.76 gLLfor boron release for the Purex glasses and from 0.45 to 0.50 @L,for boron release forthe HM glasses. For comparison, the reference Environmental Assessment (EA) glass has a boron rateof 16.7 #L.

Model Pre&ction of Durability. The PCCS durability model predicted values for boron release thatwere all within the 95% prediction limits of the model.

Homogeneity. The durability model was developed for glasses that are not phase separated(amorphous) and this is controlled through application of a homogeneity discriminator. The majorityof the glasses (17 of the 23 glasses) failed this discrimination model. The PCT results for the glassesof this study (all of which were rapidly quenched) revealed that measured durability is not a functionof predicted phase separation based upon the current homogeneity model. Further work (includingkinetic studies) is required to resolve this apparent inconsistency.

Mui&s. For ~S s~dy, the liwidus tempera~e was bounded by performing 24-hem isothe~lholds (as required) for the glass melts at 900”C, 950”C, 1000”C, and 105O”C. X-ray diffraction wasused to detect crystallization, in this case Trevorite. For the 22 wt% and 26 w&%Purex glasses, nocrystals were detected in the bulk at 900”C or at the top surface of the glasses. For the 30 WW Purexglasses, crystals were evident at temperatures higher than 900”C, but at 1000”C they were below theXRD detection limit. Given the fact that liquidus temperatures were only approximated, the 30 wt%loading of Purex may be near or at the edge of acceptability for liquidus. A small amount of surfacecrystallization (after the isothermal hold at 900”C) was evident on the glass surface near the center of


the crucible for four of the 30 wt% Purex glasses. The crystals detected were Trevorite. For HMglasses, no crystals were detected in the bulk or on the surface after 24 hours at 900”C.

Viscositv. The melt viscosities for 11 of these 23 glasses were measured and predictions reported at1150°C (nominal temperature of the glass within the DWPF melter). For the Purex containing glasses,the measured viscosities were within the DWPF range of 20 to 100 poise for the 22 wt% and 26 wt%Purex glasses. However, the 30 v&ZoPurex glasses had viscosities that were very near the lower limitof 20 poise, and consequently, may not be acceptable from an operations perspective. Although theHM sludge glass measured (lOwt% PHA) had a viscosity of -90 poise, the HM glasses at 7wt% PHAare predicted to be higher than the 100 poise limit for DWPF.

Limitations. All of the conclusions are provided based on the scope of the current work. Onelimitation of this scope, based upon schedule and budget, was the absence of any investigation ofkinetic effects. Thus, one can not rule out that amorphous phase separation occurs with centerlinecooling, for example. A second limitation was the restriction on independent variation of chemicalconstituents. In a major variability study, ranges are established for each element, and a statisticallydesigned set of glasses identified which not only covers a larger region of compositional space, butalso provides the potential for revealing trends in the properties over linear variations of elementalconcentrations. A third limitation was that only approximate measurements of the liquidustemperatures were made. A fourth limitation was that a thorough search (beyond scanning electronmicroscopy) for phase separation was not conducted. This type of investigation requires considerableefforts using transmission electron microscopy (TEM) and other high resolution techniques. Finally,although the strategy was that HM and Purex containing glasses would cover the extremes, no Blendsludge glasses were fabricated to verify this.

INTRODUCTIONOne of the Alternative Salt Disposition Flowsheets being considered would require that the DefenseWaste Processing Facility (DWPF) vitrify a coupled feed containing High Level Waste (HLW) andPrecipitate Hydrolysis Aqueous (PHA). A Technical Task Request (TTR) [1] was received by theSavannah River Technology Center (SRTC) requesting that a glass variability study be conducted toexplore the processability and product quality of the glass composition region for this alternative(Small Tank TPB Precipitation) to the In-Tank Precipitation (ITT) Process. A Task Technical andQuality Assurance (’IT&QA) plan [2] was issued by SRTC in response to the Till. The objective ofthis task was to obtain information on the feasibility of incorporating anticipated levels of PHA intoDWPF glass with and without doubling the nominal levels of monosodium titanate (MST). The studyprogressed through four phases of investigation, the detailed results of which have each been issued intechnical reports (see references [3] through [6]). The purpose of this final report is’to consolidate theresults of these four phases and provide overall conclusions.

Table 1 provides a general overview of the glass compositions that were batched, fabricated, and testedas part of this study. The glasses were selected from a set of candidate glasses that involved threesludge types: Purex, HM, and Blend; covered sludge loadings (in the glass) of 22, 26, and 30 oxideweight percent (wt%); utilized PHA loadings (in the glass) of 7, 10, and 13 oxide wt90; and includedMST concentrations (in the glass) at 1.25 and 2.5 wt%. For each composition, the remainder of theglass consisted of Frit 202. The goal of using Purex sludge as the major sludge type with only a fewglasses containing HM was realized. However, no glasses were fabricated using the Blend sludge (asludge representing the combination of HM and Purex). In all likelihood, DWPF macrobatches will beblends of tanks containing various wastekludge types.

2

Revision O

Table 1: General Compositions of the PHA GlassesGlass Sludge Sludge Frit

Phase11111122222

:33333444444

IDpha07pha08pha09pha10phal 1pha12pha13pha14pha15pha16pha17pha18phaolphso2pha03pha04phao5phao6phal lCpha12cpha17cpha18cpha20

PurexPurexPurexPurexPurexPurexPurexPurexPurexPurexPurexPurexPurexPurexPurexPurexPurexPurexPurexPurexPurexPurexHMHM

Loading26%267026%26%26%26%30%30%30%30%30%30%22%22%22%22%22%22%26%26%30%30%22%26%

PHA7%10%13%7%10’%13%7%10%13%7%10%13%7%10%13%7%10%13%10%13%10%13%10%10%

MST1.25%1.25%1.25%2.50%2.50%2.50%1.25%1.25%1.25%2.50%2.50%2.50%1.25%1.25%1.25%2.50%2.50%2.50%2.50%2.50%2.50%2.50%1.25%1.25%

20265.75%62.75%59.75%64.50%61.50%58.50%61.75%58.75%55.75%60.50%57.50%54.50%69.75%66.75%63.75%68.50%65.50%62.50%61.50%58.50%57.50%54.50%66.75%62.75%

4 pha32 HM 30% 10% 1.25% 58.75%

The primary property of interest in this study was the durability (as measured by the 7-day ProductConsistency TesL PCT [7]) of the test glasses: The PCT is the recognized standard for dete~ning thedurability of vitrified HLW, and the Environmental Assessment (EA) glass is the reference standardfor assessing acceptable durability determined using the PCT.l The measurement of durability wasconducted to the specifications of the PCT Method A of ASTM C1285 for each and every glass of thisstudy. (See the analytical plan [8] and the individual phase reports, [3] through [6], for details.)

Processing properties of interest for these glasses included viscosity at 1150”C and liquidustemperature. Methods used to complete these two types of measurements did not follow standardASTM procedures. However, viscosity was measured at SRTC using a Harrop viscometer [9] that hasyielded good results [10]. The standard ASTM procedure for measuring liquidus temperature, TL,usesa gradient furnace. Since no such capability exists at SRTC, it was beyond the scope of this study topursue this process for obtaining T~ measurements. To gain insight into this important processablilityproperty for the PHA glasses, au attempt was made to obtain an upper bound on the TL’s usingisothermal holds at 900, 950, 1000, and 105O”C and (non-quantitative) XRD evaluations (with asensitivity of - 0.7 to 1 wt% for crystalline Trevorite in the glass). The results from thesemeasurements are presented in this final report (the reports for the individual phases ([3], [4], [5], and[6]) provide greater detail).

In the report for each phase of this study, comparisons were provided between

● the measured and target compositions of the test glasses and

● the property measurements and their predictions derived from models that are used by theDefense Waste Processing Facility (DWPF) as part of its Product Composition ControlSystem (PCCS). These models relate processability and product quality (e.g., viscosity,TL, and durability) to glass composition.

These comparisons have been consolidated and provided in the sections that follow.

1 For a glass to demonstrate acceptable durability its PCT leach rate must be 2-sigma better thimthe PCT leach rateof theEA glass.


RESULTSAND DISCUSSIONThe composition and property measurements of the glasses comprising the four phases of the PHAstudy were conducted in parallel with glasses from the corresponding phases of the other ITPreplacement alternative, Crystalline Silicotitanate. This second study was designated as the CST study(references [11], [12], [13], and [14] provide the reports for the four phases of this study). Conductingthe two studies in parallel helped to ensure that the CST and PHA glasses were fabricated,characterized, and analyzed under very similar conditions. For a full description of the analytical plansor of the review of the measurement data, see the individual reports for the phases of the PHA study[3]-[6].

Target and Measured Chemical CompositionsTable A.1 in the Appendix provides the target oxide compositions for each of the PHA glassesprepared using Purex sludge. Table A.2 in the Appendix provides the target oxide compositions forthe three PHA glasses prepared using HM sludge.

4

Measurements of the compositions of the test glasses were conducted by the SRTC-Mobile Laboratory(SRTC-ML) or by the Analytical Development Section (ADS) of SRTC. Standards were includedwith the test glasses and bias-corrections were conducted for many of these measurements. Details areprovided in the individual phase reports. The target, measured, and bias-corrected compositions of theglasses tested as part of this study are provided in Table A.3 of the Appendix. In most instances, theproperty predictions were essentially insensitive to’ the way the compositions of these glasses wererepresented (i.e., whether by the targeted, measured, or bias-corrected measurements). In certaininstances discrepancies between target and measured compositions were investigated to gain insightinto the batching andlor targeting processes.

One such discrepancy found during Phase 2 (glasses pha13-phal 8) involving the components of PHAsuggested a batching error centered on the use of anhydrous sodium borate versus hydrated sodiumborate. Although the problem existed in all six Phase 2 glasses, those at the lowest levels of PHA (i.e.,phal 3 and pha16) were least affected. The other four glasses were re-batched as part of Phase 4 (i.e.,glasses pha14c, pha15c, pha17c, and phal 8c) of this study. Table A.3 contains the results for all of thePHA glasses, but the original glasses: pha14, pha15, pha17, and phal 8 are excluded from the otheranalyses presented in this summary report. For full discussion of this discrepancy see reference [4],and for a discussion of the re-batched results see reference [6]. Exhibit A. 1 in the Appendix providesplots of the compositions (target, measured, and bias corrected) of these glasses by oxide.

Another discrepancy, discovered during Phases 1 and 2, was the factor used to account for the MST

components in the final glass product. This problem revealed itself in compositions that failed to meet

the desired TiOz targets and led to a re-evaluation of MST, a source of Ti02 in the glass. A subsequentanalysis of MST revealed a larger than expected moisture content. The problem was corrected forPhase 3, and additional glasses (phal lc, pha12c, pha17c, and pha18c designated in Phase 4 with a “c”suffix, see Table 1) from the first two phases were introduced into Phase 4. The T102 levels were met .for Phases 3 and 4.

An additional comment about this exhibit and table is worth mentioning. The sum of oxides for aI1ofthese glasses fell within the interval of 95 to 105 wt%, a measure of the quality of the analyticalresults.


PCT ResultsAll of the PHA glasses, after being batched and fabricated, were subjected to the 7-day ProductConsistency Test (PCT) as an assessment of their durabilities [7]. More specifically, Method A ofPCT (ASTM C1285) was used for these measurements. Durability is the critical product qualitymetric for vitrified nuclear waste. The PCT responses (for four elements: boron, silicon, sodium, andlithium) were normalized to the units of grams-per-liter (g/L) using the measured, measured bias-corrected, and target compositions. In addition to the PHA test glasses, the Environmental Assessment(EA) glass and the ARM glass were subjected to the PCT. The individual phase reports provide thedetails of the analytical plan and resulting data supporting these tests. The results from these tests aresummarized in Table A.4 of the Appendix.

As seen in Table A.4, the durabilities for the PHA glasses are much better than those of EA samples.Figure 1 provides an opportunity for a closer look at these results using measured and bias-correctedcompositions. Figure 1 is a plot of the DWPF model that relates the common logarithm of thenormalized PCT (in this case for B) to a linear function of a free energy of hydration term (AGP,kcal/100g glass) derived from the glass (measured and bias-corrected) compositions [15]. Predictionlimits (at 95% confidence) for an individual (new) PCT result are also plotted around this linear fit.The PCT results for EA (shown as a diamond), ARM (shown as a “z”), and the PHA glasses (eachshown as an “x”) are presented on this plot. Note that the PHA results reveal acceptable andpredictable PCTS. Figure 2 provides a plot of the boron results based upon target compositions, whichshows a similar pattern of behavior. Exhibit A2 in the Appendix provides similar plots of the PHAdurability measurements versus the DWPF durability models for B, Si, Na, and Li. The behaviors seenin the plots for Si, Na, and Li are similar to that demonstrated by the B results: acceptable andpredictable durabilities.

Figure 1. Figure 2.Log NL(B)(g/L)By de] Gp Log NL(B)(g/L)Bydel Gp

(Using PHA Measured& Bias-corrected (Using target impositions for the PHA glasses% llA s-A ARM wfmw.mw= m-mnnncitinns) #L.17A ntd ARM m=fe-nre rnmnn.aitinnc)

c1

1:\. EA

\

.0-

EId-16-U .14-13.,2.,,.,0.9 .8 .7 .6 .S

——1

3F?zf;

4-

EI7.16.15.14.13.12-11.10.9 -# .7 4

5


Viscosity at 1150°CViscosity measurements were made on several of these PHA glasses at SRTC using a Harrop, high-temperature viscometer [9]. The viscosity (in Poise) of each of these glasses at 1150°C was estimatedfrom a Fulcher equation fitted to a set of viscosity measurements taken over an appropriate range oftemperatures. The functional form of the (three-parameter) Fulcher equation (expressed in Poise) usedto fit these data is given by equation (l):

lnfi=A+(T~C)(1)

where A, B, and C represent the parameters of the model that were determined from the availablemeasurements (represented by ‘?l, expressed in Poise) at various temperatures (represented by T). The

fitted model was then used to predict the viscosity of the given glass at 1150°C.

Although no definitive error analysis has been completed on the use of the Harrop viscometer, SRTChas conducted several sets of viscosity measurements using this viscorneter with good results [10].Viscosity measurements were not conducted for all of these PHA glasses. Table 2 provides the resultsthat were obtained as part of this study.

rable 2: Viscosity Results (in Poise) By Glass ID for the PHA Glasseviscosity Predicted Predicted Predicted

Glass IDphaOlpha02pha03phao4phao5phao6phao7pha08phao9pha10phal 1phallcpha12pha12cpha13pha14cpha15cpha16pha17cpha18cpha20pha26pha32

(P0i5ej

@ 1150 “c43.9

Not measured33.1

Not measuredNot measuredNot measured

52.639.531.850.937.7

Not hkasmed

29.227.6

Not MeasuredNot hklsurd

22,8Not M=SUII%

Not MeasuredNot MeasuredNot MeasmedNot Measured

89.7

(measuredcomposition)

57.756.039.471.845.839.065.753.342.767.559.445.642.132.742.431.422.039.432.721.796.798.490.4

(lias-comeeted (targetcomposition) composition)

57.7 70.260.8 53.142.6 39.177.3 67.450.1 50.642.1 36.966.1 58.054.1 42.744.0 30.568.2 55.360.7 40.451.2 40.443.4 28.536.7 28.545.4 46.7NIA 33.3NIA 23.042.1 44.237.1 31.324.8 21.3105.8 102.0106.3 97.099.5 91.9

Figure 3 provides a plot of the measured viscosities versus the viscosities predcted from the DWPFmodel using target, measured, and bias-corrected compositions. A 45-de~ee (diagonal) line is alsoshown to provide a point of reference.

6


I?iJ re 3: Viscosity Measurements versus Property Predic

110]

1/+●

40 ● *+ *

‘$+30 *

++

203040506070 80901001

Viscosity PredicilOn

+— y-axis: Viscosity (measured) - Poise

‘Diagonal

ms

For the Purex glasses, the measured viscosities were within the DWPF range of 20 to 100 poise for the22 wt% and 26 wt% Purex loadings. For these glasses, the measured viscosities ranged from 28 to 53poise, values that are much lower than current operations. The measured viscosity of glass pha12c isonly 28 poise and is approaching the lower limit for viscosity. The results show, as expeeted, that theviscosity values decrease as the PHA concentration in the glass is increased.

For the 30 wt% Purex glasses at high PHA loadings, the measured viscosities were very near the lowerlimit of 20 poise and, consequently, may not be acceptable fi-oman operations perspective. Althoughthe HM sludge glass (pha32) had a measured viscosity of -90 poise at 10 wt% PHA, the HM glasses at7 WMO PHA are predicted to be - 120 poise, a value that is significantly higher than the 100 poiseupper limit for DWPF.

There are several interesting trends observed in these data. Whether one uses the target, measured, orbias-corrected measured compositions to predict viscosities using the current model, the predictedviscosities are almost always higher than the viscosities determined born measurements for the glassesbatched using Purex sludge. This possible overprediction also occurs for the glasses made using HMsludge.

Liquidus Temperature (T~)The standard ASTM procedure for measuring liquidus temperature uses a gradient furnace. Theequipment for determining liquidus temperature by this method is being installed and tested withbSRTC in a clean laboratory. Due to the presence of depleted uranium in the glass samples (as well asthe early stage of equipment setup), this method for liquidus determination was not available at SRTCfor these analyses. A decision was therefore made to perform isothermal holds using reasonablequantities of the glass to bound the liquidus temperature.

7


XRD was selected as the method of detection for crystal formation in the glasses after an isothermalhold. It is estimated that the sensitivity of XRD (non-quantitative) is -0.7 to 1 wt% for a crystallinephase (in this case, Trevorite [16]). Therefore, for this type of measurement, absence of detection of acrystalline phase was evidence that the Iiquidus temperature is less than the temperature of thatisothermal hold. On the other hand, detection of Trevorite (or any other primary crystalline phase)indicates that the Iiquidus temperature is higher than the temperature of the isothermal hold. Thebounds on the Iiquidus temperatures for these PHA glasses, estimated to the detection capabilities ofXRD, are given in Table 3. The model predictions for TL based upon target, measured, and bias-corrected compositions are also provided in this table.

Fable 3: Liquidus Temperature (“C)By Glass ID for ‘tie CST Glasse!Estimated TL. Predicted Predicted Predicted

Glass IDphaOlpha02pha03phao4phao5phao6phao7pha08phao9phalophallphal lCpha12pha12cpha13pha14cpha15cpha16pha17cpha18cpha20pha26pha32

By BoundingProcedure

c900°cC900”c<900”C<900”C<900”CC900”cC900”cC900”C<900”C<900”C<900”C<900”C<900”C<900”C<900°c

<1OOO”C<1OIXPC<900”C<1OOO”C<950”Caoo”cC900”cC900”c

(measuredcomposition)

954.6957.1966.5923.1967.5968.5966.8973.2%9.2953.7957.0987.3973.1997.51040.71059.81073.91039.71050.91073.8916.2928.3959.2

(biis-corrected (targetcomposition) composition)

950.8 949.3949.4 956.1958.4 963.6917.3 952.0959.0 959.1960.3 966.9973.2 949.3980.0 956.1975.2 963.6959.3 952.0962.7 959.1977.5 1001.5979.2 966.9987.1 1012.21033.4 1032.9NIA 1045.4NIA 1059.3

1032.7 1037.91037.6 1051.01059.2 1065.7910.2 906.3922.3 935.6950.8 970.7

Figure 4 provides a comparison between the TL predictions of Table 12 and the correspondingbounding measurements. A 45-degree (diagonal) line is also shown to provide a point of reference.

Revision O

Figure 4: T~ Measurements versus Property Predictions

1075

1025

975

925

875%& 975 1025 I&s

Liquidus Temp.ratwe PmJkiton

+— y-axix TL (bounded)-“C‘Diagonal

—

For the 22 wt% and 26 wt% Purex glasses, no crystals were detected in the bulk of the glasses at900°C. For the 30 wt% Purex glasses; crystals were evident at temperatures higher than 900:C, but at1000”C they were below the XRD detection limit. Given the fact that Iiquidus temperatures were onlyapproximated, the 30 wt% loading of Purex may be near or at the edge of acceptability for liquidus.For HM glasses, no crystals were detected in the bulk after 24 hours at 900°C. Thus, theseapproximate bounding measurements of liquidus temperature suggest that the liquidus constraint(-1025°C [17]) can be met for these Purex and HM glasses.


Surface CrystallizationFor Iiquidus measurements, crystal formation only in the interior or bulk glass region is considered.Therefore; samples submitted for XRD analysis were bulk samples. However, crystals can format theinterface of the glass and the crucible and/or the glass and air. For completeness, the detection of thesesurface crystals on the top of the glass is provided in Table 4 as a function of temperature.

Table 4. Surface Crystals for the PHA Glasses as a Function of Temperature----after the 24 hour heat treatment----

1150”C 1Ooo”c 950°c 900”CphaOl No test No test No test Nonepha02 No test No test No test Nonephao3 No test No test No test Nonephao4 No test No test No test Nonephaos No test No test No test Nonephao6 No test No test No test Nonephao7 No test No test No test Nonepha08 No test No test No test Nonephao9 No test No test No test Nonepha10 No test No test No test Nonephal 1 No test No test No test Nonephallc No test No test No test Nonepha12 No test No test No test Nonepha12c No test No test No test Nonepha13 none none none nonepha14c No test none none crystatspha15c No test none No test Crystatspha16 none none none nonepha17c No test none none Crystatspha18c No test No test No test Clystatspha20 No test No test No test Nonepha26 No test No test No test Nonepha32 No test No test No test None

The crystals observed were located on the top glass surface at the center of the crucible. The chemicalcomposition of the surface crystals was determined by EDS and is consistent with the Trevorite(NiFe20,J crystal structure, Trevorite has also been observed during previous studies on these types ofsystems. The chemical composition indicates that other cations are substituted into the crystalstructure in small amounts and these include Ti, Cr, and Mn.

10


Phase SeparationThe formation of separate amorphous phases in glass is referred to as amorphous phase separation orinhomogeneity. Crystal formation, as determined by liquidus temperature measurements, on the otherhand may indicate a “separation of phases,” but reflects crystalline particles within the glass matrix.Amorphous phase separation is to be avoided since the models currently used to predict durability donot apply for glasses predicted to be phase separated. The property acceptance region, or PAR, limitfor the homogeneity constraint in the Product Composition Control System (PCCS) is nominally avalue of211 [17]. The limit for the measurement acceptance region, or MAR, for this property will beeven higher. In order to pass this constraint, the predicted homogeneity based upon the measuredcomposition must be greater than the MAR value. The homogeneity values calculated using thetarg~ted and measured-chemical compositions are all well below- the PAR value.provided in Table 5.

Table 5: Homogeneity Property Predictions

I IHomogeneity Property Prediction

based on(Acceptability Requires aVatue>211)

Target Measmed Bias-CorrectedGlass ID Composition Composition CompositionphaOl 200.1 204.2 199.9pha02 199.8 199.1 196.9pha03 199.4 198.6 196.6phao4 198.4 195.7 193.9pha05 198.0 193.3 191.3pha06 197.7 198.7 1%.6pha07 207.9 197.1 201.3pha08 207.5 202.9 207.2pha09 207.2 198.3 202.4pha10 206.1 196.3 200.4phal 1 205.8 200.5 204.7phal lC 205.8 203.7 200.5pha12 205.4 202.0 206.1phalk 205.4 205.2 202.0pha13 215.6 215.7 217.5pha14c 215.3 214.5 NJApha15c 214.9 212.6 N/Apha16 213.9 221.7 223.0pha17c 213.5 211.1 207.1pha18c 213.2 218.9 214.8pha20 201.1 199.2 197.4

P- 209.1 206.0 203.5pha32 217.1 208.8 206.6

These value; are

Figure 5 provides a plot of the (common logarithm of the) normalized PCT response versus thehomogeneity prediction based upon targe~ measured, and bias-comected compositions. A vertical lineon the x-axis at211 represents the PAR value for the homogeneity property constraint. The horizontalline at - 1.23 represents the common logarithm of the normalized PCT response of EA glass. Thereference response for EA is 16.7 @.

11


;ure 5: Homogeneity Predictions versus Loglo(Normalized PCT Respor

1.0

I

.

4

.o.5~190 195 200 205 210 215 220

HomogeneityPrediction. . .

The PCT responses of the PHA glasses made using Purex cover the a wide range of homogeneitypredictions ad their PCT response all fall within ‘the interval of 0.90 g/L to l~76g/L. Tie PCTresponses for the three PHA glasses made using HM sludge fall within the interval of 0.45 ~ to 0.50

m.

The homogeneity constraint was developed for glasses that do contain PHA. Therefore, thepredictability of phase separation by this model should be applicable. It turns out that 17 of the 23PHA glasses failed to meet this homogeneity constraint. A significant search for phase separation inthese glasses was beyond the scope of work for”this task. Therefore, it is unclear whether phaseseparation has occurred, or would occur upon center-line cooling, in these glasses. On the other hand,all of the PCT results are acceptable and predictable and the results shown in Figure 5 suggest nodependence of durability on the homogeneity value for these glasses.

Further work (including kinetic studies) would be required to resolve this apparent inconsistency.

12


CONCLUSIONSThis report provides a summary of the results obtained for a limited variability study for glassescontaining PHA, MST, and either simulated Purex or HM sludge. Twenty glasses containing Purexsludge and three glasses containing HM sludge were fabricated and tested. The fabricated glasses weretested for durability using the PCT and characterized by measuring the melt viscosity and anapproximate, bounding liquidus temperature. The current models used by DWPF for predictingdurability, viscosity, and Iiquidus temperature were applied to all 23 glasses. The goal of this workwas to identify any major problems from a glass perspective that could potentially preclude the use ofhigher levels of PHA and MST at DWPF.

The selection of Purex sludge for the majority of the glasses fabricated in this study was based on theknowledge that this sludge type has historically been the most difficult sludge to incorporate into glass.Depleted uranium was introduced into the simulated Purex sludge to better represent the uraniumcontent (- 9 wt% oxide) of actual sludge.

One of the major concerns for this study was the effect of higher levels of PHA in the glass. The planfor this work was to vary the PHA level from 7 to 13 W% oxide, which can be compared to theexpected/design basis of 6 to 8 wt~o oxide. Another concern was the potential for higher levels oftitanium (from MST) into the glass. The current limit for Ti02 in the DWPF glass is 1 wt~o whereasthe scope of this work varied the Ti02 level from 1 to 2 wt%.

Frit 202 was used in this study and was the frit originally designed for coupled operations at DWPF.

As part of this study, the model predictions were made using targeted, measured, and bias-comectedmeasured compositions of the glasses. For glasses where there were no batching difficulties, it wasdemonstrated that the results were essentially insensitive to the type of composition used in thesemodels. This provides evidence that the glasses produced were close to the targeted compositions, andthat the analytical measurements were of high quality.

Glass Durability. All 23 glasses were very durable as measured by the PCT. The values ranged flom0.90 to 1.76@ for boron release for the Purex glasses and from 0.45 to 0.50 g/L for boron release forthe HM glasses. For comparison, the reference Environmental Assessment (EA) glass has a boron rateof 16.7 #L.

Model Prediction of Durability. The PCCS durability model prcdcted values for boron release thatwere all within the 95% prediction limits of the model.

Homogeneity. The durability model was developed for glasses that are not phase separated(amorphous) and this is controlled through application of a homogeneity discriminator. The majorityof the glasses (17 of the 23 glasses) failed this discrimination model. The PCT results for the glassesof this study (all of which were rapidly quenched) revealed that measured durability is not a functionof predicted phase separation based upon the current homogeneity model. Further work (includingkinetic studies) is required to resolve this apparent inconsistency.

Li@dus. For ~IS study, the Muidus temperaturewas bounded W performing24-hour isothermalholds (as required) for the glass melts at 900”C, 950”C, 1000”C, and 105O”C. X-ray diffraction wasused to detect crystallization, in this case Trevorite. For the 22 wt%oand 26 wt$ZoPurex glasses, nocrystals were detected in the bulk at 900”C or at the top surface of the glasses. For the 30 wt% Purexgla&es, crystals were evident at temperatures higher than 900”C, but at 1000”C they were below theXRD detection limit. Given the fact that liquidus temperatures were only approximated, the 30 wt%loadlng of Purex may be near or at the edge of acceptability for liquidus. A small amount of surfacecrystallization (after the isothermal hold at 900”C) was evident on the glass surface near the center ofthe crucible for four of the 30 wt% Purex glasses. The crystals detected were Trevorite. For HMglasses, no crystals were detected in the bulk or on the surface after 24 hours at 900”C.”

13


Viscositv. Themelt viscosities for 11 of these 23glasses were measnred andpredictions reported atl1500C(nomind temperatme of theglass witiintie DWPFmelter). Forthel%rex containing glasses,themeasured viscosities were within the DWPFrangeof2Oto 100poise forthe22wt% and26wt%Purex glasses. However, the 30 wt% Purex glasses had viscosities that were very near the lower limitof 20 poise, and consequently, may not be acceptable from an operations perspective. Although theHM sludge glass measured (lOwt% PHA) had a viscosity of -90 poise, the HM glasses at 7wt% PHAare predicted to be higher than the 100 poise limit for DWPF.

Lhnitations. All of the conclusions are provided based on the scope of the current work. Onelimitation of this scope, based upon schedule and budget, was the absence of any investigation ofkinetic effects. Thus, one can not rule out that amorphous phase separation occurs with centerlinecooling, for example. A second limitation was the restriction on independent variation of chemicalconstituents. In a major variability study, ranges are established for each element, and a statisticallydesigned set of glasses identified which not only covers a larger region of compositional space, butalso provides the potential for revealing trends in the properties over linear variations of elementalconcentrations. A third limitation was that only approximate measurements of the liquidustemperatures were made. A fourth limitation was that a thorough search (beyond scanning electronmicroscopy) for phase separation was not conducted. This type of investigation requires considerableefforts using transmission electron microscopy (TEM) and other high-resolution techniques. Finally,although the strategy was that HM and Purex containing glasses would cover the extremes, no Blendsludge glasses were fabricated to verify this.

14


ReferenCeS[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]

[10]

[11]

[12]

[13]

[14]

[15]

[16]

[17]

Elder, H. H., “Technical Task Requesh DWPF Waste Qualification – DWPF CoupledOperation Chemistry,” HLW-SDT-lTR-99-07 .0, February 2,1999.

Harbour, J. R. and T. B. Edwmds, “Technical Task and QA Plan: DWPF Coupled OperationChemistry-PHA Glass Testing,” WSRC-RP-99-O0218, Revision 1, April 23,1999.

Edwards, T. B., J. R. Harbour, R. J. Workman, “Composition and Property Measurement forPHA Phase 1 Glasses (U),” WSRC-TR-99-O0262, August 4, 1999.

Edwards, T. B., J. R. Harbour, R. J. Workman, “Composition and Property Measurement forPHA Phase 2 Glasses (U),” WSRC-TR-99-O0290, August 18, 1999.

Edwards, T. B., J. R. Harbour, R. J. Workman, “Composition and Property Measurement forPHA Phase 3 Glasses (u): WSRC-TR-99-O0292, August 18, 1999.

Edwards, T. B., J. R. Harbour, R. J. Workman, “Composition and Property Measurement forCST Phase 4 Glasses (U),” WSRC-TR-99-O0294, August 18,1999.

ASTM C1285-97, “Standard Test Methods for Determining Chemical Durability of NuclearWaste Glasses: The Product Consistency Test (PCT),” 1997.

Harbour, J. R. and T. B. Edwards, “Analytical Study Plan-CST: DWPF Waste Qualification-CST in Glass,” WSRC-RP-99-O0316, Revision O,April 14,1999.

Schumacher, R. F. and D. K. Peeler, “Establishment of Harrop, High-TemperatureViscometer,” WSRC-RP-98-O0737, Revision O,September 1998.

Schumacher, R. F., R. J. Workman, J. R. Harbour, and T. B. Edwards, “Measurements ofDWPF Glass Viscosity – Interim Report,” WSRC-RP-99-O0350, Revision O,May 5, 1999.

Edwards, T. B., J. R. Harbour, R. J. Workman, “Composition and Property Measurement forCST Phase 1 Glasses (U),” WSRC-TR-99-O0245, July 27,1999.

Edwards, T. B., J. R. Harbour, R. J. Workman, “Composition and Property Measurement forCST Phase 2 Glasses (U),” WSRC-TR-99-O0289, August 18, 1999.

Edwards, T. B., J. R. Harbour, R. J. Workman, “Composition and Property Measurement forCST Phase 3 Glasses (U): WSRC-TR-99-O0291, August 18, 1999.

Edwards, T. B., J. R. Harbour, R. J. Workman, “Composition and Property Measurement forCST Phase 4 Glasses (U)Y WSRC-TR-99-O0293, August 18, 1999.

Jantzen, C. M., J. B. Pickett, K. G. Brown, T. B. Edwards, and D. C. Beam, “Process/ProductModels for the Defense Waste Processing Facility (DWPF): Part I. Predicting GlassDurability from Composition Using a ~ermodynamic Hydration Energy Reaction mdel(THERMO) (u):’ WSRC-TR-93-672, Rev. 1, September 28,1995.

Cicero, C. A., S. L. Marra, and M. K. Andrews, “Phase Stability Determinations of DWPFWaste Glasses (U),” WSRC-TR-93-227, Revision O, 1993.

Brown, K. G. and R. L. Pestles, “SME Acceptability Determination for DWPF ProcessControl (U),” WSRC-TR-95-0364, Revision 3, February 21,1996.

15


Appendix:

Supplemental Tables and Exhibits

17


Table Al: Target Oxide Compositions (in weight percents, wt~o ‘s) of the CST G1assesPurex GlassNudge MST CST Frit ID AlzOJ B203 BaO CaO CrzOq CUO Fe203 K20 L120 MgO MnO NazO

22 1.250 3 73.750 cstol 2.556 8.223 0.084 0.841 0.106 0.047 9.843 0.092 4.750 0.067 1.727 8.84822 1.250 6 70.750 cst02 2.539 7.889 0.084 0.841 0.106 0.047 9.843 0.092 4.556 0.067 1.727 8.76022 1.250 9 67.750 cs03 2.521 7.554 “0.084 0.841 0.106 0.047 9.843 0.092 4.363 0.067 1.727 8.67222 2.500 3 72.500 CSto4 2.549 8.084 0.084 0.841 0.106 0.047 9.843 0.092 4.669 0.067 1.727 8.90022 2.500 6 69.500 cst05 2.531 7.749 0.084 0.841 0.106 0.047 9.843 0.092 4.476 0.067 1.727 8.81222 2.500 9 66.500 cst06 2.514 7.415 0.084 0.841 0.106 0.047 9.843 0.092 4.283 0.067 1.727 8.72526 1.250 3 69.750 cs@7 2.918 7.777 0.099 0.994 0.125 0.056 11.633 0.109 4.492 0.079 2.041 9.02226 1.250 6 66.750 cst08 2.901 7.443 0.099 0.994 0.125 0.056 11.633 0.109 4.299 0.079 2.041 8.93426 1.250 9 63.750 CSt@ 2.883 7.108 0.099 0.994 0.125 0.056 11.633 0.109 4.106 0.079 2.041 8.84626 2.500 3 68.500 cst10 2.911 7.638 0.099 0.994 0.125 0.056 11.633 0.109 4.411 0.079 2.041 9.07426 2.500 6 65.500 cstl 1 2.893 7.303 0.099 0.994 0.125 0.056 11.633 0.109 4.218 0.079 2.041 8.98626 2.500 9 62.500 cst12 2.876 6.969 0.099 0.994 0.125 0.056 11.633 0.109 4.025 0.079 2.041 8.89830 1.250 3 65.750 cst13 3.281 7.331 0.114 1.146 0.144 0.064 13.423 0.126 4.234 0.091 2.355 9.19530 1.250 6 62.750 cst14 3.263 6.997 0.114 1.146 0.144 0.064 13.423 0.126 4.041 0.091 2.355 9.10730 1.250 9 59.750 cst15 3.245 6.662 0.114 1.146 0.144 0.064 13.423 0.126 3.848 0.091 2.355 9.01930 2.500 3 64.500 cst16 3.273 7.192 0.114 1.146 0.144 0.064 13.423 0.126 4.154 0.091 2.355 9.24730 2.500 6 61.500 cst17 3.255 6.857 0.114 1.146 0.144 0.064 13.423 0.126 3.961 0.091 2.355 9.15930 2.500 9 58.500 cst18 3.238 6.523 0.114 1.146 0.144 0.064 13.423 0.126 3.767 0.091 2.355 9.071

Purex GlassNudge MST CST lWt ID N&Os NiO ‘ P205 Pbo S@ TI02 U305 ZnO Zr02 F Ct- (so,)-

22 1.250 3 73.750 CSO1 0.660 0.930 0.030 0.096 55.760 2.149 2.003 0.086 0.619 0.032 0.240 0.17322 1.250 6 70.750 cst02 1.320 0.930 0.030 0.096 54.144 3.199 2.003 0.086 1.129 0.032 0.240 0.17322 1.250 9 67.750 cst03 1.980 0.930 0.030 0.0% 52.528 4.249 2.003 0.086 1.639 0.032 0.240 0.17322 2.500 3 72.500 cst04 0.660 0.930 0.030 0.0% 54.837 3.247 2.003 0.086 0.619 0.032 0.240 0.17322 2.500 6 69.500 cst05 1.320 0.930 0.030 0.0% 53.221 4.297 2.003 0.086 1.129 0.032 0.240 0.17322 2.500 9 66.500 cst06 1.980 0.930 0.030 0.0% 51.604 5.347 2.003 0.086 1.639 0.032 0.240 0.17326 1.250 3 69.750 cst07 0.660 1.099 0.036 0.114 52.928 2.149 2.367 0.102 0.639 0.038 0.283 0.20526 1.250 6 66.750 cst08 1.320 1.099 0.036 0.114 51.311 3.199 2.367 0.102 1.149 0.038 0.283 0.20526 1.250 9 63.750 cst09 1.980 1.099 0.036 0.114 49.695 4.249 2.367 0.102 1.659 0.038 0.283 0.20526 2.500 3 68.500 cst10 0.660 1.099 0.036 0.114 52.004 3.247 2.367 0.102 0.639 0.038 0.283 0.20526 2.500 6 65.500 cstl 1 1.320 1.099 0.036 0.114 50.388 4.297 2.367 0.102 1.149 0.038 0.283 0.20526 2.500 9 62.500 cst12 1.980 1.099 0.036 0.114 48.771 5.347 2.367 0.102 1.659 0.038 0.283 0.20530 1.250 3 65.750 cst13 0.660 1.268 0.041 0.132 50.095 2.149 2.731 0.118 0.659 0.043 0.327 0.23630 1.250 6 62.750 cst14 1.320 1.268 0.041 0.132 48.479 3.199 2.731 0.118 1.169 0.043 0.327 0.23630 1.250 9 59.750 cst15 1.980 1.268 0.041 0.132 46.862 4.249 2.731 0.118 1.679 0.043 0.327 0.23630 2.500 3 64.500 cst16 0.660 1.268 0.041 0.132 49.172 3.247 2.731 0.118 0.659 0.043 0.327 0.23630 2.500 6 61.500 cst17 1.320 1.268 0.041 0.132 47.555 4.297 2.731 0.118 1.169 0.043 0.327 0.23630 2.500 9 58.500 cstl 8 1.980 1.268 0.041 0.132 45.939 5.347 2.731 0.118 1.679 0.043 0.327 0.236

18

Table A.2: Target ComposilGlass JD pha20 pha26 pha32Sludge 22 26 30MST 1.25 1.25 1.25PHA 10 10 10

Frit 202 66.75 62.75 58.75Al@3 6.046 7.048 8.051B,O, 8.803 8.488 8.174B;OCaOCr203CuoFe203K20Li20MgOMnONazO

0.045 0.053 0.0610.496 0.562 0.6280.073 0.086 0.0990.761 0.764 0.7676.363 7.507 8.6524.723 4.736 4.7494.579 4.305 4.0301.463 1.409 1.3551.955 2.311 2.6677.776 7.980 8.183


ms of PHA Phase 4 HM GlassesGlass ID pha20 vha26 Lrl-k+zSludge -22 -26 -30MST 1.25 1.25 1.25PHA 10 10 10

Frit 202 66.75 62.75 58.75NiO 0.336 0.397 0.458P205PbOSi02TiOzU30SZnoZrQ

F-cl-

(so.J-

0.0320.053

54.0861.1270.6770.0140.1190.0370.124

0.127

0.0380.063

51.6561.1250.8000.0160.1410.0440.1470.150

0.044

0.07349.2261.1230.9230.0190.1630.0510.1690.173

19

Table A.3: Targ ~ Measured and Bias-Corrected CommsitionsPh33eeI -pha07

A1z03B*O3CaO

Cr103CuoFez03K20Li20MgOM330Na20NloSiOzT102U,@zro2

Sum of Oxides

A1203B203Cao

Cr203Cuo

FezOSK20LizOMgOMnONazONloSlozTlo~U30SZr03

Sum of Oxides

A1203B203CaO

Cr203CuoFez@KZOLlzoMgOMnONazONlo!X02Ti02U30Szro2

$um of Oxides

MeasuredTarzet Measured Bias-cor.2.9617.6601.0920.1250.57611.6853.3654.5101.3812.0418.1161.099

50.7661.1262.3670.129

2.6507.6881.1190.1210.49210.3083.0844.2361.3821.8638.0710.86650.2740.6912.6330.128

2.7587.4031.0510.129051410.8553.0714.4681,4171.9387.9100.90251.0400.6892.6330.137

98.939 95.647 96.958Phase I -phaIO

MeasuredTarget Measured Bms-cor.2.894 2.636 2.7437.561 7.985 7.6931.090 1.109 1.0430.125 0.113 0.1210.576 0.501 0.52311.684 9.701 10.2053.365 3.123 3.1114.425 4.295 4.5331.356 1.337 1.3702.041 1.853 1,9288.191 8.341 8.1781.099 0.838 0.873

49.816 51.343 52.1802.224 1.369 1.3652.367 2.409 2.4090.129 0.126 0.13498.943 97.171 98.504

Phase2 -pha13Measured

Target Measured Bias-cor.3.263 3.246 3.7257.345 7.492 7.4981.239 1.357 1.1960.144 0.152 0.1490.585 0.573 0.57513.472 13.615 13.2363.380 3.470 3.6944.236 4.214 4.1711.314 1.284 1.5702.355 2.272 2.3598.363 8.342 8.6731.268 1.142 1.089

47.849 46.844 47.6191.125 0.738 0.7362.731 2.792 2.7920.149 0.182 0.19498.818 97.792 99.353

PhaseI -phu08Measured

Tart?et Measured Bias-cor.2.8~3 2.7118.488 8.7661.088 1.1290.125 0.1130.800 0.69311.683 10.6264.745 4.3524.305 4.0801.322 1.3312.041 1.8758.264 8.3911.099 0.861

48.486 50.0061.125 0.6982.367 2.1610.129 0.126

2.8228.4351.0600.1200.72511.2014.3354.3041.3651.9508.2220.89750.7780.6972.1610.134

98.950 97.963 99.250PhaseI -phall

MeasuredTarget Measured Bias-cor.2.876 2.664 2.7738.390 8.967 8.6461.086 1.102 1.0360.125 0.117 0.1240.800 0.676 0.70711.682 9.879 10.4034.745 4.255 4.2394.219 4.091 4.3151.297 1.285 1.3172.041 1.840 1.9148.339 8.432 8.2661.099 0.861 0.898

47.536 51.236 52.1132.223 1.337 1.3342.367 2.462 2.4620.129 0.122 0.13098.954 99.415 100.764



45.569 45.191 45.9161.123 0.742 0.7402.731 2.921 2.9210.149 0.171 0.18298.826 100.131 101.702


n wt %) for the CST G1asses,-Phase 1- pha09

MeasuredTarget Measured Bias-cor.2.865 2.707 2.8179.317 9.410 9.0681.083 1.099 1.0320.125 0.113 0.1211.023 0.761 0.795

11.681 9.951 10.4756.125 5.294 5.2734.099 4.037 4.2591.262 1.272 1.3042.041 1.905 1.9818.412 8.374 8.2061.099 0.857 0.893

46.206 48.081 48.9401.124 0.707 0.7052.367 2.565 2.5650.129 0.132 0.14098.958 97.306 98.618

Ph4we1 -pha12Measured

Target Measured Bh.s-cor.2.858 2.626 2.7339.219 9.724 9.3751.081 1.114 1.0470.125 0.111 0.1191.023 0.818 0.855

11.680 10.344 10.8806.125 5.514 5.4914.013 3.929 4.1451.237 1.230 1.2612.041 1.837 1.9108.487 8.543 8.3731.099 0.849 0.885

45,256 48.669 49.5022.222 1.350 1.3462.367 2.456 2.4560.129 0.122 0.129

98.962 99.327 100.600Phaee2 -pha15

MeasuredTarget Measured Bias-cor.3.227 3.116 3.5769.003 11.647 11.6571.230 1.371 1.2040.144 0.153 0.1501.031 0.959 0.962

13.467 14.684 14.275.6.140 4.607 4.9053.824 3.766 3.7271.195 1.145 1.4012.355 2.156 2.2398.659 9.959 10.3541.268 1.134 1.081

43.289 41.318 42.0111.122 0.721 0.7192.731 1.988 1.9880.149 0.183 0.19598.834 98.990 100.526

20


Table A.3: Target, Measured, and Bias-Corrected Compositions (in wt%) for the CST Glasses

AIz~Bz03Cao

CrzGCuoFeQKzOLi20MgOMnoNazONiOSi@T1o~U30SZro,

Sum of Oxides

AI*03Bz@CaO

Crz03CuoFezOsK20L120MgOMnONazON1Osio*Tlo~U308ZrQ

;nm of Oxides

Alz03B203CaO

Cr203CuoFM%K20L120MgoMnoNaZONioSi02TIO*U308Zroa

;umof Oxides



46.899 47.632 48.3742.223 1.460 1.4562.731 2.919 2.9190.149 0.179 0.19098.820 101.263 102.724

Phase3- phaOl*Measured

Rtrget Measured Bk+.s-cor.2.540 2.868 2.8567.974 9.171 9.1470.945 1.041 1.0030.106 0.178 0.1700.568 0.580 0.5789.899 9.970 9.5503.350 2.973 3.0954.785 4.751 4.6611.448 1.464 1.4531.727 2.065 2.0567.s69 8.873 8.6920.930 0.949 0.90253.684 52.702 51.8311.128 1.164 1.1152.(X73 1.542 1.5420.109 O.lal 0.10199.065 99.093 98.689


hrget Measured Bias-cor.2.532 2.517 2.5077’.876 8.901 8.8750.943 0.953 0.9320.106 0.137 0.1310.563 0.565 0.5639.898 8.351 8.0003.350 3.099 3.2264.699 4.936 4.8431.423 1.475 1.4641.727 1.794 1.7867.944 8.401 8.2300.930 0.828 0.78752.734 55.094 55.4712.226 2.373 2.2802.003 1.081 1.0810.109 0.135 0.08699.068 100.714 100.334

(continued)

Phase2 -pha17Meas.

Target Meas. Bias-cor.3.238 3.146 3.6108.075 9.512 9.5201.233 1.374 1.2030.144 0.149 0.1460.808 0.741 0.74413.469 13.834 13.4494.759 4.547 4.8413.945 3.981 3.9401.230 1.176 1.4382.355 2.344 2.4348.586 9.104 9.4651.268 1.154 1.101

44.619 44.669 45.3832.221 1.449 1.4452.731 2.487 2.4870.149 0.169 0.18098.830 99.910 101.457

Phase3- pha02*Measured

Target Measured Biae-cor.2.522 2.718 2.7078.803 8.523 8.4970.941 1.009 0.9870.106 0.169 0.1610.791 0,680 0.6779.897 9.859 9.4454.730 3.663 3.8134.579 4.679 4.5911.389 1.387 1.3761.727 1.999 1.9908.017 8.249 8,0810.930 0.924 0.87851.404 51.174 51.5571.127 1.170 1.1242.003 1.659 1.6590.109 0.153 0.09799.075 98.088 97.713

Phase3 -plu305Measured

l%rget Measured Bias-cor.2.514 2.508 2.4978.705 7.974 7.9530.939 0.920 0.9000.106 0.150 0.1430.791 0.722 0.7199.896 9.975 9.5554.730 4.309 4.4854.493 4.596 4.5091.364 1.386 1.3751.727 1.629 1.6218.092 8.054 7.8890.930 0.846 0.80450.454 48.402 48.8342.225 2.296 2.2062.003 2.869 2.8690.109 0.153 0.09699.078 96.861 96.532


Target Measured Bms-cor.3.220 3.0578.904 11.8801.228 1.4420.144 0.1491.031 0.96013.466 14.3396.139 4.8953.739 3.8251.170 1.1552.355 2.1258.734 10.0491.268 1.101

42.339 42.6402.220 1.4602.731 3.0910.149 0.206

3.50811.8901.2470.1450.96313.9405.2093.7861.4122.20610.4471.050

43.3501.4563.0910.221

98.837 102.451 103.997Phase3- pha03

MeasuretTarget Measured Biae-cor.2.504 2.542 25319.632 9.368 9.3410.936 0.941 0.9210.106 0.172 0.1641.014 1.009 1.0049.894 9.995 9.5756.110 5.606 5.8364.373 4.458 4.3741.329 1.358 1.3471.727 1.699 1.6918.165 8.181 8.0140.930 0.851 0.80949.124 48.797 49.1671.125 1.168 1.1232.003 2.760 2.7600.109 0.223 0.13599.081 99.201 98.865

Phase3 -pha06Measurei

Target Measured Bias-eOr.2.4% 2.602 25919.534 9.196 9.1730.934 0.972 0.9510.106 0.153 0.1461.014 0.953 0.9499.893 10.019 9.5986.110 5.757 5.9944.288 4.353 4.2711.304 1.316 1.3051.727 1.789 1.7808.240 8.270 8.1010.930 0.874 0.83148.174 48.432 48.7932224 2.309 2.2192.003 2.441 2.4410.109 0.16Q 0.10199.086 99.670 99.318

21


Table A.3: Target, Measured and Bias-Corrected Compositions (in wt %) for the CST Glasses1-”.=----=!

Ph43se4-phallc Phase 4-pha12c Phase4 -pha17cMekured Mess. Measure{

Target Measured Bias-cor. Target Meae. Bias-cor. Target Measured Bias-cor.A120s 2.876 2.783 2.784 2.858 2.705 2.707 3.238 3.065 3.06B203 8.390 8.420 8.429 9.219, 9.283 9.297 8.075 7.763 7.77CaO 1.086 1.118 0.966 1.081 1.159 0.999 1.233 1.270 1.09

C2-Z03 0.125 0.156 0.156 0.125 0.146 0.146 0.144 0.182 0.18Cuo 0.800 0.754 0.749 1.023 0.991 0.985 0.808 0.773 0.76Fez@ 11.682 11.171 10.672 11.680 11.348 10.842 13.469 13.470 12.86K*O 4.745 4.109 4.307 6.125 5.397 5.661 4.759 4.510 4.73L120 4.219 4.403 4.245 4.013 4.280 4.126 3.945 4.024 3.87MgO 1.297 1.295 1.270 1.237 1.248 1.224 1.230 1.091 1.07Mno 2.041 2.067 2.052 2.041 1,984 1.969 2.355 2.659 2.63NaZO 8.339 8.310 8.094 8.487 8.510 8.289 8.586 8.208 7.99NiO 1.099 0.971 0.932 1.099 0.980 0.940 1.268 1.200 1.15sio2 47.536 48.730 49.149 45.256 46.927 47.333 44.619 44.409 44.79TiOz 2.223 2.219 2.140 2.222 2.222 2.143 2.221 2.291 2.21(U,os 2.367 2.101 2.101 2.367 2.328 2.328 2.731 2.111 2.11Zr02 0.129 0.173 0.139 0.129 0.155 0.125 0.149 0.181 0.14

hm of Oxides 98.954 98.854 98.262 98.%2 99.737 99.187 98.830 97.280 96.55Phase4 -phu18c Phase4-pha20 Phase4-pho26

Measured Measured MeasuretTarget Measured Bias-cOr. Target Measured Biae-cor. Target Measured Bias-cor.

A1202 3.220 3.458 3.460 6.046 5.457 5.461 7.048 6.453 6:45Bz03 8.904 8.998 9.007 8.803 8.684 8.693 8.488 8.365 8.37CaO 1.228 1.361 1.179 0.4%

Crz030.553 0.472 0.562 0.660 0.53

0.144 0.180 0.180 0.073 0.113 0.113 0.086 0.120 o.12~Cuo 1.031 1.081 1.074 0.761 0.706 0.702 0.764 0.691 0.68Fe203 13.466 13.985 13.361 6.363 6.983 6.671 7.507 7.348 7.02(K,O 6.139 5.399 5.662 4.723 4.388 4.601 4.736 4.445 4.66L120 3.739 3.907 3.767 4.579 4.585 4.420 4.305 4.391 4.23:MgO 1.170 1.202 1.180 1.463 1.202 1.179 1.409 1.286 1.26MnO 2.355 2.617 2.598 1.955 2.024 2.009 2.311 2.320 2.30NaZO 8.734 9.046 8.810 7.776 7.509 7.314 7.980 7.952 7.74:NiO 1.268 1.207 1.158 0.336 0.341 0.327 0.397 0.377 0.36Si(& 42.339 42.936 43.322 54.086 53.279 53.711 51.656 52.378 52.54:T102 2.220 2.319 2.237 1.127 1.146 1.105 1.125 1.173 1.13U30S 2.731 2.274 2.274 0.677 0.763 0.763 0.800 0.954 0.95,Zroz 0.149 0.181 0.146 0.119 0.155 0.124 0.141 0.171 0..13

;um of Oxides 98.837 100.226 99.490 99.383 97.959 97.738 99.315 99.102 98.81,Phase4 -pha32 Phase4-pha14c Phase4 -ph4315c

MeasuredTarget Measured Bias-cor. Target Measured Target Measured

A1,03 8.051 7.112 7.117 3.245 3.293 3.227 3.322B103 8.174 7.996 8.004 8,174 7.729 9.003 8.515Cao 0.628 0.697 0.597 1.234 1.393 1.230 1.351

Crz03 0.099 0.126 0.127 0.144 0.154 0.144 0.157Cuo 0.767 0.790 0.786 0.808 0.813 1.031 1.022Fe103 8.652 8.286 7.916 13.470 13.760 13.467 13.621&o 4.749 4.356 4.567 4.760 4,487 6.140 5.389Llzo 4.030 4.080 3.933 4.030 3.979 3.824 3.797MgO 1.355 1.104 1.083 1.255 1.271 1.195 1.215MnO 2.667 2.738 2.717 2.355 2.483 2.355 2.500NazO 8.183 8.030 7.821 8.511 8.457 8.659 8.694Nlo 0.458 0.439 0.421 1.268 1.195 1.268 1.186Sloz 49.226 49.049 49.453 45.569 44.149 43.289 41.745Ti02 1.121 1.157 1.116 1.123 1.139 1.122 1.135u30g 0.923 0.923 0.923 2.731 2.460 2.731 2.611ZrQ 0.163 0.205 0.165 0.149 0.215 0.149 0.196

km of Oaides 99.246 97.165 96.822 98.826 97.052 98.834 96.530

22


Table A.4: Normalized PCTS for the CST Glasses

Glass IDEAEAEA

ARMARMARMphaolphaolphaolphao2pbao2phao2phao3phao3phao3phao4Dhao4

pha05pha05phaosphao6phao6phao6pha07pha07pha07pha08pha08pha08phao9pha09phao9pha10phalopha10phal 1phal 1phal 1phallcphallcphallcpha12pha12pha12pha12cpha12cpha12cpha13pha13pha13pha14cpha14cpha15c

CompositionPhase 1Phase 2

Phases 3-4Phase 1Phase 2

Phases 3-4measured

measuredbctarget

measmedbctarget

measured

measured bctarget

measured bctarget

measuredmeasured bc

target‘measured

measuredbctarget

measuredmeasured bc

targetmeasured

measuredbctarget

measuredmeasured bc

targetmeasured

measuredbctarget

measuredmeasuredbc

targetmeasmed

measuredbetarget

measuredmeasuredbc

target, measuredmeasuredbc

targetmeasured

measuredbctarget

measmedtarget

measuredpha15c target

log NL log NL log NL log NL[B @)]1.248511.272611.28207

-0.22197-0.27166-0.290850.168020.169160.228760.104000.105320.089%0.245240.246500.233170.187160.188430.240290.112430.113570.074340.195140.1%230.17947-0.02381-0.0Q742-0.022250.009570.026320.02358

0.102450.09068-0.04560-0.02942-0.021880.037050.052900.065960.006580.00+5120.008150.174820.190690.197980.177370.176720.180390.002240.001880.010870.063170.038850.24023

[Si@)J0.619510.613530.63353-0.50764-0.55545-0.54854-0.17747-0.17023-0.18548-0.22546-0.22870-0.22741-0.15256-0.15584-0.15546-0.13764-0.14060-0.11862-0.20595-0.20981-0.22399-0.17575-0.17897-0.17343-0.26919-0.27576-o.n343-0.25541-0.26206-0.24200-0.23318-0.24088-0.21591-0.27228-0.27930-0.25917-0.26094-0.26830-0.22838-0.27729-0.28101-0.26651-0.20543-0.21280-0.17386-0.19919-0.20293-0.18344-0.29231-0.29945-0.30154-0.25322-0.26697-0.19416

[N;(g/L)J1.156921.171311.18838

-0.22580-0.26983-0.273960.110930.119880.163080.062520.071450.074910.198010.206970.198860.152470.161400.176760.043950.052940.041900.157010.165980.15859-0.06227-0.05351-0.064680.005840.014670.012480.077890.086720.07595-0.05734-0.04879-0.049470.032300.040940.03710-0.006430.00504-0.007930.143310.152030.146170.154900.166370.15610-0.00987-0.02678-0.010990.032460.02%70.17513

[Li-&L)]0.999691.020461.04022-0.16767-0.20863-0.216520.136080.144390.132990.082700.090950.092080.209290.217550.217650.178570.186830.199940.061080.069380.070920.172560.180820.179090.00931-0.01391-0.017930.050320.027060.026970.113180.089930.106530.00946-0.01400-0.003490.082960.059740.069530.002400.018310.020950.177690.154480.168500.152610.168510.180+51-0.01053-0.00603-0.012800.038020.032520.18018

B (g/Q17.7218.7319.150.600.530.511.471,481.691.271.271.231.761.761.711.541.541.741.301.301.191.571.571.510.950.980.951.021.061.061.221.271.230.900.930.951.091.131.161.021.011.021.501.551.581.501.501.511.011.001.031.161.091.74

Si Q/L)4.164.114.300.310.280.280.660.680.650.600.590.590.700.700.700.730.720.760.620.620.600.670.660.670.540.530.530.560.550.570.580.570.610.530.530.550.550.540.590.530.520.540.620.610.670.630.630.660.510.500.500.560,540.64

Na (@J14.3514.8415.430.590.540.531.291.321.461.151.181.191.581.611.581.421.451.501.111.131.101.441.471.440.870.880.861.011.031.031.201.221.190.880.890.891.081.101.090.991.010.981.391.421.401.431.471.430.980.940.981.081.071.50

Li (g/Q9.9910.4810.970.680.620.611.371.391.361.211.231.241.621.651.651.511.541.581.151.171.181.491.521.511.020.970.961.121.061.061.301.231.281.020.970.991.21-1.151.171.011.041.051.511.431.471.421.471.520.980.990.971.091.081.51

0.21601 -0.20994 0.17687 0.17711 1.64 0.62 1.50 1.50

23


Table A.4: Normalized PCTS for the CST Glasses(continued)

log NL log NL log NL log NLGlass ID Composition [B (W] [Si W)] [Na (#Q] [Li (#L)] B (#L) Si (gIL) Na (W Li (g/L)

r)ha16 measured 0.02870 -0.28244 0.00482 0.01993 1.07 0.52 1.01 1.05~ha16 measured bc 0.02834 -0.28916 -0.01207 0.02446 1.07 0.51 0.97 1.06pha16 target 0.10080 -0.27571 0.02577 0.02890 1.26 0.53 1.06 1.07pha17c measured 0.08084 -0.26107 0.07914 0.06536 1.20 0.55 1.20 1.16pha17c measuredbc 0.08047 -0.26483 0.09060 0.08127 1.20 0.54 1.23 1.21pha17c target 0.06374 -0.26312 0.05958 0.07393 1.16 0.55 1.15 1.19pha18c measured 0.24209 -0.19310 0.19460 0.20194 1.75 0.64 1.57 1.59pha18c measuredbc 0.24166 -0.19699 0.20606 0.21784 1.74 0.64 1.61 1.65pha18c target 0.24667 -0.18702 0.20982 0.22103 1.76 0.65 1.62 1,66pha20 measured -0.30200 -0.52025 -0.27890 -0.24396 0.50 0.30 0.53 0.57pha20 measured bc -0.30245 -0.52376 -0.26743 -0.22806 0.50 0.30 0.54 0.59pha20 target -0.30793 -0.52678 -0.29405 -0.24342 0.49 0.30 0.51 0.57pha26 measured -0.33060 -0.54519 -0.31561 -0.26829 0.47 0.28 0.48 0.54pha26 measuredbc -0.33098 -0.54660 -0.30414 -0.25238 0.47 0.28 0.50 0.56pha26 target -0.33691 -0.53916 -0.31714 -0.25972 0.46 0.29 0.48 0.55pha32 measured -0.33341 -0.53492 -0.30177 -0.25942 0.46 0.29 050 0.55pha32 measured bc -0.33383 -0.53848 -0.29031 -0.24352 0.46 0.29 0.51 0.57pha32 target -0.34298 -0.53649 -0.30997 -0.25411 0.45 0.29 0.49 0.56

24


Exhibit Al: Comparisons of Measured Versus Target Compositions

25

%

6C4

x Q

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‘;K_-----”-

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“.”.---’

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(Continued)

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00


Efilbit Al: Comparisons of Measured Versus Target Compositions

(Continued)

IJ.(L

‘ -#--.:---:-”””””””>-’ 8“ Xi

@\\\\

— Target (w%) x Measured (w%) E Measured Bias-Corrected (wW

39


0.25

0.20

0.15

0.10

0.05

0.00


(Continued)

Zr02

xx

❑x

Mx x x x

x

x

xx

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H ❑

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Exhibit A.2: Durability Predictions Versus Measurements

Log NL(B) (g/L) By del Gp

-o

-16 -15 -14 -13 -12 -11 -10 -9 -8 -7 -6 -5

del Gp

— Linear Fit I

PCTS normalized and del GPdetermined from measured and meaured bias-corrected compositions.

42


Exhibit A.2: Durability Predictions Versus Measurements(continued)

I.OQNTJSi) (sdLl Bv de] GII0:

O.t

0.:

0.4

0.3

0.2

0.1

$-0.0

.=

g 4“’

3 -0.2

-0.3

-0.4

-0.5

-0.6

-0.7

-0.8-16 -15 -14 -13 -12 -11 -lo -9 -8 -7 -6 -5

del C@

— Linear Fit

PCTS normalized and del Gp determined from measured and meaured bias-corrected compositions.

43


Exhibit A.2: Durability PrMlctions Versus Measurements(continued)

Log NL (Na) (E/IL)BY del GP

-16 -15 -14 -13 -12 -11 -lo -9 -8 -7 -6

del Gp

— Linear Fit I

PCTS normalized and del GPdetermined from measured and meaured bias-corrected compositions.

44



log[NL(Li) @L] By del Gp

-0

-16 -15 -14 -13 -12 -11 -lo -9 -8 -7 -6 -5

delGp

PCTS normalized

I — Linear Fit 1

and del Gp determined from measured and meaured bias-corrected compositions.

45



LOQNUB) {Q/L) Bv del ~D

1

-0

-16 -15 -14 -13 -12 -11 -10 -9 -8 -7 -6 -5

delOp

[— Lkear Fit

I

PCTS normalized and del GPdetermined from target compositions.

46


Exhibit A.2 Durabdity Predictions Versus Measurements(continued)

de]Gp

Log NL(Si) Q/L) By del Gp

5

I — Linear Fit I


47


ExMbit A.2: Durability Predictions Versus Measurements(continued)

T.rmNT. (Na) (dT.\ Rv rk+lCn

1.2

1.0

0.8

0.6

0.4

0.2

-0.0

-0.2

-0.4

-0.6-16 -15 -14 -13 -12 -11 -lo “-9 -8 -7 -6 -5

de] (3p

I — Linear Fit 1


48


Exldbit A.2: Durability Predictions Versus Measurements(continued)

log[NL(Li) @L] By del Gp

1

-o\

\\x\ \-15 -14 -13 -12 -11 -lo -9 -8

del Gp

-7

I — Linear Fit


49


Distribution

J. L.N. E.D. F.c. s.K. G.J. T.J. J.A. D.D. A.R. E.T. B.H. H.S. D.J. R.E. W.R. A.C. M.R. T.W. DD. P.L, F.

T. J.s. L.D. B.J. P.J. E.J. F.L. M.D. K.S. F.J. A.K. J.P. L.R. F.M. E.T. K.P. c.W. L.R. C.D. D.W. R.R. J.TIM

Barnes, 704-3NBibler, 773-ABickford, 773-43ABoley, 703-HBrown, 704-lTCarter, 704-3NConnelly, 773-41ACozzi, 77-43ACrowley, 773-43AEdwards, 704-25SEdwards, 773-42AElder, 704-SFiti 773-AHarbour, 773-43AHoltzscheiter, 773-AJacobs, 704-3NJantzen, 773-AJones, 704-3NKerley, 704-SLambert, 704-lTLandon, 704-lTLex, 703-HMarra, 704-25SMoore-Shedrow, 773-AMorin, 703-HOcchipinti, 704-27SOrtaldo, 704-SPapouchado, 773-APeeler, 773-43APiccolo, 704-3NPike, 704-3NRueter, 704-3NRutland, 704-196NSchumacher, 773-43ASmith, 773-43ASnyder, 704-lTSuggs, 704-196NTamosaitis, 773-ATuck5eld, 773-43AWalker, 773-AWilmarth, 773-42AWorkman, 773-A(4 copies), 70343A

Summary of Results for PHA Glass Study: Composition and .../67531/metadc... · P.C).Box 62, CM...

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