UNCLASSI FIED

AD 40W8 431

DEFENSE DOCUMENTATION CENTERFOR

SCIENTIFIC MUi)•D TECHNICAL INFORMATION

CAMERON STATION, ALEXANDRIA, VIRGINIA

UNCLASSIFIED

NOTICE: When government or other drawings, speci-fications or other data are used for any purposeother than in connection with a definitely relatedgovernment procurement operation, the U. S.Government thereby incurs no responsibility, nor anyobligation whatsoever; and the fact that the Govern-ment may have formulated, furnished, or in any waysupplied the said drawings, specifications, or otherdata is not to be regarded by implication or other-wise as in any manner licensing the holder or anyother person or corporation, or conveying any rightsor permission to manufacture, use or sell anypatented invention that may in any way be relatedthereto.

WADMD-TR-60-557 /A

X .DEVELOPMENT OF GREASE LUBRICANTS FOR HIGH___ TEMPERATURE BALL AND ROLLER BEARINGS OFC> ELECTRICAL EQUIPMENT

IulCJ

TECHNICAL REPORT NO. WADD-TR-60-557, Part IIIC-') May 1963

Directorate of Materials and ProcessesAeronautical Systems Division

Air Force Systems CommandWright-Patterson Air Force Base, Ohio

Project No. 3044, Task No. 304403

(Prepared under Contract No. AF 33(616)-7597by the American Oil Company, Research and De~velop,-ment Department, Whiting, Indiana; K. R. Bunting,R. G. Garst, F. K. Kawahara, H. M. Sellei, T. P.Traise, H. J. Liehe and R. S. Barnes, authors.)

I

(~WAD 571RPIT

&)}DEVELOPMENT OF GREASE LUBRICANTS FOR HIGHTEMPERATURE BALL AND ROLLER BEARINGS OF

ELECTRICAL EQUIPMENT)

TECHNICAL REPORT NO. WADD-TR-60-557, Part III d

P (Ijay 19 63 M

Directorate of Materials and ProcessesAeronautical Systems Division

Air Force Systems CommandWright-Patterson Air Force Base, Ohio

~Projec-t-No. 3047 ask So, 304403

(Prepared und4Contract Ne-. AF 33616-7597by the American Oil Company, Researc a ad Develop-ment Department, Whiting, IndianapNK. R. Bunting,.R. G. Garst, F. K. Kawahara, H. M. Sellei, AT P.Traise H. .. ...... ... S--Barnes-.authors.)

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LINOTICES

When Government drawings, specifications, or other data are used

for any purpose other than in connection with a definitely related Governmentprocurement operation, the United States Government thereby incurs no re-

[ sponsibility nor any obligation whatsoever; and the fact that the Governmentmay have formulated, furnished, or in any way supplied the said drawings,specifications, or other data, is not to be regarded by implication or other-wise as in any manner licensing the holder or any other person or corporation,or conveying any rights or permission to manufacture, use, or sell any pat-ented invention that may in any way be related thereto.

ASTIA release to OTS not authorized.

Qualified requesters may obtain copies of this report from theArmed Services Technical Information Agency, (ASTIA), Arlington Hall Station,Aa.lington 12, Virginia.

I___

Copies of this report should not be returned to the Aeronauti'calSystems Division unless return is required by security considerations, con-tractual obligations, or notice on a specific document.

11

1: WADD TECHNICAL REPORT 60-557

PART III

I.

DEVELOPMENT OF GREASE LUBRICANTS FOR HIGH TEMPERATUREliBALL AND ROLLER BEARINGS OF ELECTRICAL EQUIPMENT

K. R. Bunting

R. G. GarstF. K. KawaharaH. M. Sellei

U T. P. TraiseH. J. LieheR. S. Barnes

American Oil Company

V. Research and Development DepartmentWhiting, Indiana

March 1963

Directorate of Materials and ProcessesContract No. AF33(616)-7597

L Project No. 1(3-8128)

AERONAUTICAL SYSTEMS DIVISIONAir Force Systems Command

United States Air ForceT Wright-Patterson Air Force Base, Ohio

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FOREWORD

This report was prepared by the Research and Development Departmentof the American Oil Company under USAF Contract No. AF33(616)-7597. Thecontract was initiated under Project No. 3044, "Aerospace Lubricants," TaskNo. 304403, "Grease Lubricants and Grease-Like Materials." This work was"administered under the direction of the Directorate of Materials and Processes,,Deputy for Technology, Aeronautical Systems Division, with Mr. J. Christianacting as project engineer.

1.This report covers work done from 1 November 1961 to 1 January 1963.

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ABSTRACT

"The objective of this work is the development ofrease systemscapable of operating in loaded bearings over the temperatuW range of -65to 900 F4_ Current work was done on a 0 to 600 F grease system

Most of the test work was done at 600 F under 5 lb. radial and5 lb. axial load and 50 lb. radial and 25 lb. axial load. Some testswere carried out at 650 and 700 F under light load'al-ee4ý1L 4

Greases made by blending F-6-7024 Silicone Fluid and one ofseveral polyphenyl polysiloxanes and thickening with Ammeline have giventhe longest 600 F, high-load bearing tests to date. Bearing tests on aseries of these greases range from 150 to 220 hours. Ammeline is theonly thickener that gave these long bearing tests with these blends.

With other fluids and other additives in fluids ASU and modifiedASU's gave results comparable to Ammeline. While several other experi-mental silicone fluids and additives gave results comparable to ASU orAmmeline thickened F-6-7024 Silicone Fluid, none were any better excepttitanium dioxide. When titanium dioxide was used at 2 to 3% in p-phenylazoaniline modified ASU-F-6-7024 greases 600 F high-load bearing testsof 150 hours were obtained. This compound did not show any beneficialeffect in other grease systems.

All the phosphonitrilic chloride-metal halide complexes testedshowed hydrolytic instability.

This report has been reviewed and is approved.

R. L. ADAMCZAKAsst Chief, Fuels & Lubricants BranchNonmetallic Materials Laboratory[ • / Directorate of Materials & Processes

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TABLE OF CONTENTS

Page

I. INTRODUCTION ............ ........................... . I1

II. SYNTHESIS OR PROCUREMENT OF FLUIDS .......... ............... 5

a) Phosphonitrilic Chloride Polymers ....... .............. 5

b) Silicone Fluids .................. ...................... 8

c) Siloxanes ............. ......................... .. 11

III. YNTHESIS OR PROCUREMENT OF THICKENERS .... ............. .. 15

1) Modified ASU Thickeners ...... ................. ... 15

2) High Melting Organic Polymers ..... .............. .. 17

3) Surface Modified Inorganic Thickeners ............. ... 19

IV. PREPARATION AND BENCH TESTING OF EXPERIMENTAL GREASES .......... 20

V. EVALUATION OF GREASES IN HIGH TEMPERATURE BEARING TESTS ........ 24

VI. DISCUSSION .............. ............................ .. 25

VII. CONCLUSION .............. ............................ .. 29

VIII. SUGGESTIONS FOR FUTURE WORK ......... .................... .. 30

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LIST OF TABLES

Table Page

I High Temperature Bearing Tests at600 F with 5 lb. Radial, 5 lb. Axial Load .... ........... ... 31

II High Temperature Bearing Tests at650 and 700 F with 5 lb. Radial, 5 lb. Axial Load ......... ... 36

III High Temperature Bearing Tests at600 F with 50 lb. Radial, 25 lb. Axial Load ... .......... ... 43

LIST OF FIGURES

Figure Page

1 Vapor Pressure - Temperature Data onDichlorophosphinic Nitride-Zinc Chloride Complex .......... ... 66

2 Vapor Pressure - Temperature Data onDichlorophosphinic Nitride-Ferric Chloride Complex ......... ... 67

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I. INTRODUCTION

Current and future Air Force weapons systems demand lubricantscapable of performing satisfactorily at higher temperatures than thosecurrently available. At the same time, the good low-temperature per-formance of currently used lubricants should be matched to permit operat-ing at the low extreme of ground and airborne ambient temperatureconditions. Greases are desirable lubricants for use in the ball androller bearings of the electrical equipment of these weapons systems.Such greases should permit small bearings, rotating at high speeds underlight loads, to be run for appreciable lengths of time at the hightemperature without a drastic increase in power requirement. In addition,at low temperature, bearings filled with these greases should beginrotating and run without unusual power requirements.

The ultimate objective of this contract is the development ofa grease system capable of operating in lightly-loaded ball and rollerbearings over a temperature range of -65 to 900 F. This ultimateobjective will be reached stepwise by development of grease systems forthe following temperature ranges:

0 to 600 F-40 to 700 F

0 to 800 F40 to 900 F

-65 to 900 F

The specific performance criteria these greases must meet are:

At low temperature - the temperature at which a greased 20 mmbearing has a starting torque of not more than 5,000 g. - cm. and arunning torque of not more than 500 g. cm. is defined as the lowest usabletemperature of the grease.

At high temperature - the performance characteristics of greases

are established by determining the number of continuous hours they willpermit satisfactory operation of a 20 mm bearing, under fifty radial andtwenty-five pounds axial load, rotating at 10,000 rpm, in air. A minimumof 200 hours at 600 and 700 F and 100 hours at 800 and 900 F arj requiredfor a grease to be considered satisfactory. Relubrication is not per-missible at 600 and 700 F, but it is permitted every 50 hours at 800 and900 F.

Manuscript released by the authors March 1963 for publication as a WADDTechnical Report.

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Greases are two-phase system, a solid or thickener phasedispersed in a liquid or fluid phase. In greased ball bearings, thelubrication is provided primarily by the fluid, while the thickenergives the system enough body to remain in and around the bearing andact both as reservoir of fluid and as a seal against contamination.It is this combination of properties that make grease lubrication pref-erable over the other possible methods. The advantages of greaselubrication over fluid or mist lubrication are the simplicity andweight savings gained by the elimination of pumps, reservoirs, filtersand lines and the protection against contamination. Dry film lubricantswill not permit operating bearings at as high speeds or as high loadsas greases because of the inability of the dry films to heal or reform

their films.

The low-temperature behavior of a grease is dependent primarilyon the low-temperature fluidity characteristics of the fluid and second-arily on the kind and amount and degree of dispersion of the thickener.

The high-temperature behavior of a grease is dependent on thethermal and oxidative stability and volatility of both the fluid andthe thickener, the lubricating ability of the fluid, the phase stabilityof the thickener (i.e. not undergoing a phase change in the temperaturerange of interest), and the ability of the grease not to undergo a detri-mental change in consistency as the result of exposure to high temperatureand working in the bearing.

Extensive research and development has been done to extend theuseful temperature range of greases, particularly for military aircraft

use. The first significant progress was made with the development ofhigh-melting soap thickeners and oxidation inhibitors to improve thestability of petroleum oils. These developments culminated in greasessuch as those meeting Specification MIL-G-3545, "Lubricating Grease,High Temperature," which are capable of operating over a range of 0 to300 F. Greases of this type usable at temperatures below 0 F are at-tainable, but a major improvement in low temperature performance resultsin a drastic decrease in high temperature performance because of theincreased volatility which necessarily accompanies improved low temperatureproperties in petroleum oils.

The next advances came with the use of synthetic fluids, suchas esters and silicones. These synthetic fluids have wider liquid ranges,higher viscosity indexes and lower volatility characteristics than docomparable petroleum oils and their use led to diester fluid greases such

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as those meeting Specification MIL-G-3278, "Grease, Aircraft and Instrument(For Low and High Temperature)," which have a useful temperature range of-65 to 250 F. While these greases have improved low temperature properties

Sthey are not as effective at high temperatures as the best petroleum oilgreases. This high temperature limitation is caused by the solubility ofsoap thickeners in synthetic fluids at elevated temperatures. Siliconefluid-soap thickened greases were not used extensively because of theirpoorer lubricity and lack of an appreciably wider temperature range.

Some of the synthetic fluids are stable enough to use in greasesat temperatures much higher than 250 F. This prompted a search for highertemperature thickeners. A number of inorganic thickeners, such as clays,silicas and carbon blacks, have been used as grease thickeners for manyyears and they have excellent high-temperature stability. However, it isnecessary to coat the surfaces of these inorganic thickeners with polarorganic compounds to make them oleophilic enough to serve as thickenersfor ball bearing greases. Without the proper kind and amount of surfacecoating the mechanical stability, age hardening, leakage and/or waterresistance of these greases will be unsatisfactory. The currently usedorganic coatings all. desorb or oxidize at relatively low temperatures andattempts to develop coatings which had stability at high temperatures wereunsuccessful. A number of non-soap, high-melting organic compounds, whichcould be prepared in the desired small particle-size range and whose surfaceshad the proper degree of oleophilic character, were developed as hightemperature thickeners.

Using high temperature thickeners of this type and selected esterfluids, greases have been made which meet Specification MIL-G-25760,"Grease, Aircraft, Ball and Roller Bearing, Wide Temperature Range," andwill lubricate heavily loaded bearings from -40 to 350 F. When one ofthese high-temperature thickeners is dispersed in the proper silicone fluid,greases are obtained that will lubricate lightly-loaded bearings from -65 to450 F and that meet Specification MIL-G-25013, "Grease, Ball and RollerBearing, Extreme High Temperature." Using different silicone fluids, greasesare obtained that have a useful temperature range of -100 to 400 F and meetSpecification MIL-G-27343, "Grease, Ball and Roller Bearing, for TemperaturesRanging From Minus 100 to Plus 400 F."

The upper temperature limits on these greases are primarily dueto the high-temperature instability of the fluids used. These greases canbe used at higher temperatures than those quoted as the upper limit, butthe period of satisfactory operating time is drastically reduced. Forexample, in lightly-loaded, high-speed ball bearings over 500 hours of

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satisfactory operation are obtained at 350 F with MIL-G-25760 type greasesand 450 F with MIL-G-25013 type greases. At 600 F, under similar con-ditions, operating times are less than 4 hours with MIL-G-25760 type

L• greases and about 50 hours with MIL-G-25013 type greases.

The upper temperature limit of the high temperature thickenersused in these greases has not been definitely established but the bestof them appear to be capable of serving at temperatures above 600 F, but

probably below 700 F. Thus, the development of greases for use over therange of -65 to 900 F depends on finding both fluids and thickeners thatare superior to those currently used in greases. However, for the 0 to600 F range, the problem appears to be finding a better fluid and combin-ing it with one of the superior currently available thickeners.

Under previous years' contracts, equipment was built or obtainedfor running dropping points, evaporations, roll stabilities, and loadedbearing tests or greases at temperatures up to 900 F. Most bearing tests,in the previous work, were run at 600 F under modified CRC L-35 conditions,using Pope type spindles and MRC S-17 bearings.

As discussed above, the methyl-phenyl silicone fluids were themost promising fluids known for high temperature greases at the outsetof this work. Several of these fluids with any one of several high-melting organic thickeners gave bearing tests of 50 to 60 hours, Furthertesting of silicone fluids uncovered DC-QF-6-7024 Eluid which whenthickened with one of several thickeners gave bearing tests in excessof 100 hours. Many other silicones were tested, but none gave any betterresults. With all these silicone fluids, failures were attributed tothe instability of the silicone fluids.

Other fluids and thickeners considered as potentially promisingfor use in high temperature greases were synthesized or obtained fromavailable sources and screened for thermal stability and low volatility.Thickeners were also evaluated for thickening ability over the temperaturerange.

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7"Phenoxyphenyl ethers and polyphenyls showed promise as high

temperature fluids. Bearing failures of greases made from these fluidswere interpreted as due to volatility of the fluid rather than instability.

"Phosphonitrilic chloride polymers and complexes with metalhalides exhibit fluidity over very wide temperature ranges. However, athigh temperatures they evolve hydrogen chloride upon exposure to air,are acidic, and are corrosive to metals.

High melting inorganic and organic materials have been studiedas potential thickeners for high temperature greases. Surface-treated,finely-divided inorganic solid thickeners such as silica, carbon blackand glass fibers have shown promise. Some triazine derivatives andaryl substituted ureas have also shown promise as high temperature greasethickeners.

A number of different bearing designs and metallurgies weretested in the previous work. The MRC S-17 bearings have given the longestbearing tests.

The work reported here is a continuation and extension of thepromising developments of the previous work. Emphasis has been on syn-thesizing less volatile and more stable fluids, improving current anddeveloping new thickener systems, and evaluating greases under the higherload conditions specified by the contract.

The program was divided into four phases:

1) the synthesis or procurement of fluids.2) the synthesis or procurement of thickeners.3) the preparation and bench testing of greases made from

phase 1 and 2 materials and4) the evaluation of the performance characteristics of these greases

in high temperature bearing tests.

II. SYNThESIS OR PROCUREMENT OF FLUIDS

Most of the work on fluids concentrated on three classes ofconipounds: the phosphonitrilic chlorides, silicone fluids, andpolyphenyl siloxanes.

a) Phosphonitrilic Chloride Polymers

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L The dichloro phosphinic nitride-metal halide complexes are

liquids over extremely wide temperature ranges. However, they appearto lack hydrolytic stability, are acidic, and corrosive to metals.Several approaches were taken to overcome these deficiencies.

The preparation and properties of a number of these polymersand complexes were reported in ASD Technical Report 61-2. The zinc andferric chloride complexes appeared to be the most promising. A sampleof the zinc chloride complex was prepared in these laboratories andanother obtained from the project engineer, ASD. The sample preparedhere was fluid at room temperature and did not distill at 400 C (750 F)at 0.4 mm, The elemental analyses of the two samples appear somewhatdifferent:

(PNC1 2 )n/ZnCl 2 % UnaccountedSample % Zn % P % C1 % N For

K-108-134 15.0 7.4 58.2 5.0 14.4ASD 12.6 9.0 51.1 6.0 21.3

Both samples evolved hydrochloric acid on exposure to air. The sampleprepared here was sent to Materials Central, ASD at the request of theproject engineer. The sample obtained from ASD had a viscosity of 523 csat 100 F and 46oll at 210 F and a pour point of 25 F. A vapor pressuredetermination of this sample, using an isotensicope, was made and thedata are shown in Figure I. The thermal decomposition temperature was333 C (631 F), although some decomposition must occur as low as 250 C(482 F) because small bubbles kept appearing and growing in the fluidabove this temperature. Below 333 C, the vapor pressure fits theintegrated Clausius-Clopeyron equation:

log1 0 P ( m m) = -1503/T ('K) + 4.77

Hvap = 6.88 K cal/mole

The low latent heat of vaporization suggests it may occur by depolymerization.

Dichloro phosphinic nitride-Ferric chloride n-mer

This material is reported to have a pour point of -46 C and notto polymerize at 670 C, although some decomposition did occur during heating.A sample of this material was prepared by heating a mixture of 104 g. (1 M)of phosphorous pentachloride, 27 g. (0.5 M) of ammonium chloride, 16.2 g.

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(0.1 M) of ferric chloride in 400 ml. of 1,2,4 trichloro benzene to 152 Cfor 11 hours. The mixture was filtered and solvents removed at 65 C/0.2 mm.

7- There remained 65.5 g. of black liquid which was heated to 425 C/0.3 mm. forJI 2 hours. At 365 C/0.3 mm. about 10 g. of a yellow solid distilled over.L- After cooling, the dark liquid was filtered in a dry box and 45.5 g.

recovered. Elemental analysis of the prefiltered product was: Fe - 7.69%,P - 17.03%, Cl - 65.4%, N - 5.95%, unaccounted for 3.93%. The filteredproduct is a mobile liquid at room temperature. One drop of this fluid in3 ml. of water gave a solution with a pH of 1 in 10 seconds. A sample ofthis material solidified to a black solid when heated to 600 F for 24. hoursin with an Almen pin.

A vapor pressure determination, using an isoteniscope, gave abroken curve. The data are shown in Figure II. No meaningful latent heatof vaporization could be calculated. Apparently, depolymerization beganabout 325 C (617 F) and then some repolymerization occurred about 355 C(671 F).

Diphenyl phosphinic nitride polymer

Diphenyl phosphinic nitride polymer was prepared by the followingset of reactions:

P 2PCl + Cl2 0 • 2 PC13

PPPCI 3 + NH3 --- (02PN)x + 3HCl

A

-(P = N) ---ý trimer, tetramer, etc.

12 g. of chlorine gas was added to 37.55 g. (0.17 M) of diphenylchlorophosphine dissolved in 75 ml. of carbon tetra chloride and cooledto -15 C. This yellow solution was held overnight at -30 C and thenwarmed gradually to 25 C and stirred for two hours. The resultant di-phenyl trichlorophosphorane was recrystallized from benzene to give 36 g.of product. This compound was then dissolved in liquid ammonia at -30 Cand held overnight. The solution was then warmed to room temperature,which vaporized the excess ammonia. The resultant mixture was thenextracted with chloroform to remove trimer and tetramer. There remained8.6 g. of product which was heated for two hours at 270 C. Extraction withbenzene yielded 5.5 g. of soluble material.

7

A portion of the diphenyl phosphinic nitride n-mer was placedin a test tube with an Almen pin and heated to 600 F. After only 2 hours,

Sthe white solid changed to a charred black mass.

Bis (triphenyl silanyl) phosphinic nitride

L. This compound was prepared by dropwise addition of 7.6 g. (0.05 M)

of phosphorous oxy chloride to a mixture of 42.4 g. (0.15 M) of triphenylsilanol in 40 g. of pyridine and 50 g. of xylene. The reaction mixturewas then heated to 220 F for several hours. Maceration in hot ethanolleft 38 g. of product melting at 236-239 C (457-462 F).

A portion of this product was placed in a test tube with anAlmen pin and heated to 600 F. After several days all of the product hadvolatilized and condensed around the cooler top of the tube. The condensedmaterial was colorless and had the same melting point as the originalproduct. This product appears to be stable, if ways could be found tolower the melting point and volatility this would be a promising classof compounds.

Perfluoroalkyl phosphonitrilates

Olin-Organics Division supplied samples of three perfluoroalkylphosphonitrilates. These samples were placed in test tubes with Almenpins and heated to 600 F. The following results were obtained:

Fluid Formula % Fluid Lost After 24 hrs.

N 3 P 3 [oCH 2 (CF2 )4 H 6 97.5

N4 P4[OCH2 (CF 2 ) 6 H]8 99.0

N4F4[OCH2 (CF2 )4 H] 4 [OCH, (CF,)8 H]4 98.6

While the sample originally were colorless liquids, all that remained afterthe test were black powders.

b) Silicone Fluids

Because the best high temperature test results have been obtainedwith Dow Corning's F-6-7024 Silicone Fluid, a number of experimental siliconefluids from both General Electric and Dow Corning were screened and evaluated.

The first series of fluids were screened by thickening them witharyl substituted urea and testing the resultant grease under modified L-35

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conditions at 600 F. Data on these experimental silicone fluids and thegreases made from them were:

SFluid Viscosity Bearing Test - Hours

G.E. 189-114 690 c.s. at 100 F 190189-159 1200 c.s. " 130, 180189-150 1220 c.s. " " 134128-457 1430 c.s. 110128-458 1640 c.s. " " 91128-433 540 c.s. " " 45, 62128-467 (128-433 inhibited) 70, 96

D.C. F-6-7024, lot 6 900 c.s. at 25 C 160F-6-7024, lot 17 7180 c.s. " " 80F-6-7039 (F-6-7024, lot 6 -inhibited 152

XF-6-7042 (F-6-7024, lot 6 - 4 timesinhibitor 95, 107

XF-6-7043 (F-6-7024, lot 6-8 times

Teinhibitor) 80

The second series of fluids were screened by thickening themwith ASU and testing the resultant greases under modified L-35 conditionsat 650 F. Data obtained were:

Fluid Bearing Test - Hours

G.E. 128-534 35128-557 28128-558 27128-559 70128-565 35114-1403 74, 62

D.C. F-6-7024, lot 6 - cut #1 3F-6-7024, lot 6 - cut #2 26F-6-7024, lot 6 - residue 78F-6-7051 53F-6-7068 57

185 Of the G.E. Silicone Fluids, 189-114, 189-159, 114-1403 and

128-559 (inhibited 114-1403) appear comparable but not superior toDC F-6-7024.

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Additives in Silicone Fluids

The poor load carxying capacity of silicone fluids led to thej_ consideration of a number of additives which might improve these fluids'

performance in higher-load bearing tests. Knowledge of the effect of theseadditives on the stability of silicone fluids was desired and the shortageof bearing tester facilities dictated the use of the fluid screening testfor this purpose. A vial containing 0.3 g. of sample and an Almen pinwere placed in a test tube and heated to 600 F. The following results wereobtained:

% Remaining Observations atFluid Composition 46 hrs. 64 hrs. 64 hrs.

1. QF-6-7024, lot 6 21.8 12.3 Yellow liquidat 600 F.Solid at 70 F.

2. 1 + 4% Sulfur - 58.4 Yellow solidat 600 F.

3. 1 + 15% Lead Oxide 44 Yellow solidat 600 F.

4. 1 + 10% Phenylpydrazine - 16.8 Yellow liquidat 600 and 70 F.

5. 1 + 4% Phthalonitrile 7.4 Colorless liquidat 600 and 70 F.

6. 1 + 6% Urea 40.5 Liquid at600 and 70 F.

Additives such as sulfur and lead oxide appear to increase the

"gelation tendencies of this silicone fluid, while urea appears to holdsome promise for reducing the evaporation or fragmentation and evapora-tion tendencies.

Using a 5 g. sample of F-6-7024 Silicone Fluid instead of 0.3 g.sample gave a much slower evaporation rate:

Hours 22 44 139 226

% Remaining 97 94.8 86.8 78.3

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The odor of formaldehyde was detected during this test and a positivealdehyde test was obtained using Fuchsin reagent for aldehydes. Theseresults suggest oxygen attack on the methyl groups of the silicone

j fluid. Volatiles have been collected for NlR and molecular weightdeterminations which may shed further light on the mechanisms involved.

The lower evaporation rate of the larger sample may be due tothe smaller surface to air ratio. Similar tests with nitrogen shouldgive additional information and are planned.

c) Siloxanes

The excellent bearing test results obtained with methyl phenylsilicone fluids suggested the synthesis of a number of phenyl siloxanes.

Hexaphenyl disiloxane

29.45 g. (0.1 M) of triphenyl chlorosilane (mp. 98 C) was addeddropwise to 27.6 g. (0.1 M) of triphenyl silanol (mp. 152 C) in one moleof pyridine. After addition was complete, the mixture was heated to 100 Cfor 3 hours. The solvents were then removed and the mixture extractedwith ether. The extract was water washed until neutral and then driedand the solvent removed. Recrystallization from hexane ethanol gave aproduct with a mp. of 233-5 C. Mass spectrometry indicates this productis 99+ % pure. Elemental analysis: found - C-81.97%, H - 5.97%;calculated - C - 81.00%, H - 5.6%.

Octaphenyl trisiloxane

Redistilled dichloro diphenyl silane (0.5 M) in pyridine andbenzene was reacted with triphenyl silanol (0.1 M). The reaction mixturewas heated to 100 C for 3 hours, then cooled and stripped of solventsand extracted with ether. The ether extract was washed with water,dried, and the solvents removed. Maceration with hot ethanol gave 30 g.of a product melting at 130-140 C. Recrystallization from hexane ethanolgave 6.5 g. of a product melting at 210 C, which from its molecularweight is mostly hexaphenyl disiloxane. The mother liquor gave 8 g. ofproduct with a mp. of 140-4 C and a MW of 694 ± 21 and 8 g. of anotherproduct with a mp. of 137-144 C and a MW of 756 ± 23.

Further work on these compositions will be done.

Heptaphenyl methyl trisiloxane

0.05 M of methyl phenyl dichlorosilane was added dropwise to asolution of 0.1 M triphenyl silanol in pyridine and benzene. Working the

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Hexaphenyl dimethyl trisiloxane

The addition of 0.075 M of dimethyl dichlorosilane to 0.15 Mof triphenyl silanol in pyridine and benzene and working up in the usualmanner gave 33.5 g. of a crystalline product with a mp. of 135-7 C.

p-Phenoxyphenyl diphenyl silanol

p-Phenoxyphenyl magnesium bromide was prepared by reactingp-bromophenyl phenyl ether with magnesium in tetrahydrofuran.

This solution was then added dropwise to a solution of diphenyldichloro silane in toluene. The reaction mixture was heated from 70-80 Cfor 10 hours. After cooling, the mixture was poured into ice water andstirred vigorously. Extraction with ether-chloro benzene, water-washingand drying, and subsequent removal of the solvents at 60 C/0.2 mm. lefta product which contained only 0.29% chlorine.

Bis (phenoxyphenyl) hexaphenyl trisiloxane

p-Phenoxy phenyl diphenyl silanol was reacted with dichlorodiphenyl silane in pyridine-benzene solution. After stripping of solventsat 50 C/0.3 mm., the product was dissolved in ether and washed untilneutral. Removal of the solvents left a brown, viscous liquid that isnot tacky.

Octaphenyl cyclotetra siloxane

40 g. of diphenyl dihydroxy silane was dissolved in 300 ml.of ethanol containing 6 drops of 5% sodium hydroxide and the mixtureheated at 172 F for 4 hours. The reaction mixture was then cooled andthe product filtered off and washed first with 50 ml. of 95% ethanoland then with 100 ml. of 90% ethanol. After drying overnight theproduct weighed 34 g. and had a mp. of 202-4 C. Mass spectrometryindicates this product is 99+ % pure.

Tris (triphenyl siloxyl) phenyl silane

The addition of 0.02 M of phenyl trichloro silane in benzeneto 0..06 M of triphenyl silanol in pyridine and working up in the usual

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manner gave 21 g. of a crude product. Recrystallization from a mixtureof 60 ml. chlorobenzene, 50 ml. acetone, and 100 ml. benzene gave 4 g.of product with a mp. of 227-232 C.

Tris (undecaphenyl penta siloxyl) phenyl silane_

Tris (w chlqro octaphenphenyl tetra siloxyl) phenyl silane wasL_ prepared by beating 0.02 M octaphenyl cyclotetra siloxane and 0.007 M ofphenyl trichloro silane in 60 g. of phenyl ether to 255 C for 6 hours.This compound was added to 0.04 M of triphenyl silanol in 79 g. ofpyridine and this mixture heated to 200 F for 4 hours. Solvents wereremoved and the product taken up in ether and washed. Removal of the

ether left 79.7 g. of crude product. Washing with hexane to remove thephenyl ether left 16 g. of product with a mp. of 138-162 C. Recrystal-lization from 50 ml. benzene and 100 ml. hexane left 13 g. of productwith a mp of 141-166 C.

Polyphenyl polysiloxane

a -w 0.01 M octyl cyclotetra siloxane was reacted with 0.005 Mdiphenyl dichloro silane by heating to 240 C for several hours. 8.28 g.of triphenyl silanol in 79 g. pyridine was added and this mixture heatedand the solvents then removed. The crude product was dissolved inchlorobenzene and water washed. Stripping the solvent and maceratingthe product in ethanol left 6.7 g. of white crystals with a mp. of175-188 C. Elemental analysis - C - 72-82%, H-5.44%, Cl 0.03%.

Penta deca phenyl methyl hepta siloxane

dichloro nonaphenyl methyl penta siloxane was prepared byheating 0.02 M octylphenyl cyclotetra siloxane and 0.02 M phenyl methyldichloro silane in 40 g. of phenyl ether at 225-250 C for 7 hours,This mixture was then added to 0,08 M of triphenyl silanol in 79 g.pyridine and 79 g. benzene and the resultant mixture heated at 205 Ffor 6 hours. Removal of the solvent left 102 g. of crude product whichwas taken up in 400 ml. of ether and water washed. Removal of thesolvent left 72.5 g. of product which was hexane washed to remove thephenyl ether. This left 21.5 g. of crystalline product. Recrystalliza-tion from 50 ml. benzene and 75 ml, hexane left 19 g. of product with amp. of 110-114 C.

13

I

I

£ Dimerization of 5 Phenyl Ether

223 g. (0.5 M) of bis (m-phenoxy phenoxy) benzene was iodinatedwith 0.5 M iodine monochloride in acetic acid by refluxing 15 hrs. at120 C. The reaction mixture was stirred into water and extracted withether. The ether extract was washed free of acetic acid, dried and thesolvent removed to give 270.5 g. of product. The iodine content of theproduct was 19.5%, and by titration 96.1% of the iodine was aryl iodide.

0.05 M of this product in 30 ml. of tetrahydrofuran was slowlyadded to 0.1 M of magnesium in 100 ml. of tetrahydrofuran. At 150 Fafter 2 hours reaction began and continued for 4 hours. 13 g. ofanhydrous cupric chloride was added and heating continued 4 more hours.The reaction mixture was poured into ice water and the product thentaken up in ether. The ether solution was washed with ammonium hydroxide,potassium iodide and water. Solvents were removed at 65 C/0.2 mm. andleft 24.4 g. of a brown viscous liquid. Copper and potassium wereabsent and the iodine content was 1.95 %.

Bis (triphenyl silyl) glutarate

This compound was prepared by reacting 0.1 M of triphenyl silanolin 150 g. of pyridine and 0.05 M of perfluoro glutaroyl chloride in 20 ml.of benzene at 106 C for several hours. Solvents were removed underreduced pressure and the residue macerated with absolute ethanol. The16 g. of product had a mp of 230-4 C and an analysis of C-825, H - 6.2while the calculated values are C-7-.0, H - 4.28.

Siloxane - Hydroquinone n-mers.

0.1 M of hydroquinone and 0.12 M of diphenyl dichloro silanewere reacted in 79 g of pyridine by heating to 193 F for one hour. Then0.08 M of triphenyl silanol were added and the mixture heated to 223 F for3 hours. Working up the product in the usual way gave 53 g. of product.

Evaporation Testing of Siloxanes

A number of these materials were screened by placing 0.3 g.sample and an Almen pin in a vial and placing the vial in a test tube andheating the tube to 600 F for various periods of time. The data obtainedwere.

14

h% Remaining Observations

Compound after 64 hours at 64 hours

- F-6-7024 12.3 Liquid at 600 Fsolid at 70 F

Polyphenyl polysiloxane 52.4 Colorless liquid at600 F

Octylphenyl trisiloxane 57.6 Yellow liquid

Five phenyl ether 2.6 Solid

Dimerized five phenyl ether 71.41 Black liquid

Bis(triphenyl silyl) glutarate 2.1 Solid

Hydroquinone siloxane polymer 59.4 Solid tar

Bis(phenoxy phenyl)

hexaphenyl trisiloxane 65.21 Black liquid

I After 24 hours.

While the octylphenyl trisiloxane and the polyphenyl polysiloxane appearto have about the same rate of evaporation after 64 hours and even longertimes, the trisiloxane gelled at 296 hours with about 20% remaining butthe polysiloxane was still liquid at 434 hours with about 9% remaining.

The solidifying of the hydroquinone polymer was disappointing.While most of the glutarate evaporated, the volatile portion was identicalwith the starting material, suggesting a higher molecular weight productmight have promise.

III. SYNTHESIS OR PROCUREMENT OF THICKENERS

The search for improved high temperature thickeners continuedand study was concentrated on:

1) Modified ASU thickeners2) High melting organic polymers3) Surface modified inorganic thickeners

1) Modified ASU Thickeners

Loaded bearing test results with both ASU and Ammeline thickenedF-6-7024 Silicone Fluid varied from about 50 to 100 hours at 600 F. While

15

Li

most of the variation appears to be due to differences in bearings andtesters, even under the best conditions results are still a long way fromthe desired 200 hours. Further improvements were sought in fluids,thickeners and additives to reach the desired life.

A number of different isocyanates and amines were used to makearyl substituted urea thickeners, but none were any better than thosecurrently used (TODI and p-toluidine and p-chloroaniline) and most were notas good. However, the use of p-aminobenzoic acid (p-ABA) as the aminecomponent offered the opportunity to further react with the benzoic acidgroups and possibly effect further improvements. p-Bromoaniline was moreeffective than either tribromo or trichloroaniline and p-phenyl azoanilinegave excellent results, The following results illustrate this point:

Grease Thickener Acid No. Penetration Bearing Test. HI.

1. 5% p-ABA + 5% TODI 440 26.0 482. 1 + 4%° p-bromoaniline 19 300-310 853. 1 + 6% p-bromoaniline 8 fluid4. 1 + 6% p-bromoanilipe 5.5 fluid5. 1 + 13% tribromoaniline 2.8 fluid6. 1 + 8% trichloroaniline 3.7 335 607. 1 + 4% p-azoaniline 15.3 284 1218. 1 + 6% p-azoaniline 13.6 292 67-136(6 tests)9. 1 + 8% p-azoaniline 14.5 304 115

10. 1 + 10% p-azoaniline 11.4 288 79

All of the greases in this table had been heat-treated for 4 hours at 450 F.The neutralization numbers were then determined and bearing performancetests run. No difference in performance was found for greases containingfrom 0.6 to 1.1 moles of p-phenyl azoaniline per mole of p-amino-benzoicacid, however, grease containing excess p-Azo A resulted in shorter bearingtests.

Longer heat treating times tended to lower the neutralizationnumber and bearing performance life of these greases. For example, agrease containing 6% p-Azo A heat-treated for 96 hours, had an acid numberof 0.67 and a bearing life of 31 hours. Addition of 1% chlorendicanhydride to this grease raised the acid number to 14.5 and the bearingperformance to 72 hours. It is not clear whether the moderate acidityimparted by this additive or its chlorine content was responsible for theimproved bearing performance, however, 1% of this additive in the basegrease (5% p-amino benzoic acid +5% TODI) gave no improvement.

16

Replacement of TODI with 1,5 naphthalene diisocyanate or diphenylmethane 4,4'diisocyanate resulted in greases that gave inferior bearingperformance test results.

A number of other variations in processing these greases werealso tried without obtaining significant improvement in bearing performancetests. Prepolymerizing the TODI used for the base grease gave noimprovement. Elimination of solvents in base grease preparation, gavepoorer results. Isopropanol was the solvent which gave greases withthe best bearing performances. Making heavier base greases with higherthickener contents gave no improvement.

The greases tended to be thixotropic and a number of additiveswere investigated as auxiliary thickeners. Among the additives testedwere: benzoguanamine, cymel 300 (hexamethoxy methyl melamine), azo dyes,carbon black, chlorendic anhydride, benzyl alcohol, Baymal (colloidalalumina), ironphthalocyanine, iodobenzoic acid, titanium dioxide andvarious combinations of some of these. While many of these auxiliarythickeners in the 2 to 5% range improved the consistency of the greases,none improved bearing performance, except titanium dioxide, Using 2 ormore percent titanium dioxide increased the penetration to harder than200 and the bearing performance to about 150 hours at 600 F. However,when 10% titanium dioxide was added to an Ammeline thickened grease withexcellent bearing performance, the resultant grease gave a very poorbearing test.

2) High Melting Organic Polymers

The reaction product of methylene bis 4-phenyl isocyanate andtrimellitic anhydride is a "no-melt" polymer which ought to be a goodgrease thickener if it could be produced in or made into small particlesizes. However, all attempts to get this polymer into the properparticle size range failed.

The polybenzimidoles made by reacting a phenylene diamine andesters of aromatic acids reported by C. S. Marvel and co-workers, alsocould not be obtained in or micronized into the proper particle sizerange for grease thickeners. A. coordination complex formed by reactingbenzimidazole and cobaltous nitrate had a melting point above 480 C(896 F). However, this material would not form a stable grease withF-6-7024 fluid even at 50% concentration.

17

1-An azo dye formed by the reaction of 5-chloro salicylic acid

and p-phenyl azoaniline had a melting point above 480 C(896 F) and gavegood grease when 38% was milled into F-6-7024 Silicone Fluid. However,unloaded bearing performance at 600 F of this grease and similar oneswith calcium hydroxide and with calcium hydroxide and Alon C added onlylasted from 8 to 32 hours.

Permansa Red 10363, l(2-chloro-4-nitrophenyl azo)-2-naphthol,a high melting dye from Sherwin-Williams gave a No. 2 grade grease when40% was milled into F-6-7024 fluid. However, these greases became fluidafter 4 hours heat treating at 450 F.

Calcium fluoride thickened F-6-7024 Silicone Fluid at concentra-tions of 40 to 60%. However, all these greases became fluid after 4 hoursheat treating at 450 F.

A sample of purified asbestos, C-9-12M-500 ES, was receivedfrom ASD. 4.5% in F-6-7024 Silicone Fluid was adequate to make aNo. 2 grade grease, but the bearing performance of this grease was onlyfair.

Our testing of inhibited silicone fluids has never shown anyadvantage for the inhibited fluid over the uninhibited. It was suggestedthat this may be due to the inhibitor coating out on the thickener.A sample of dry, preformed ASU thickener was sent to Dow-Corning andcoated with inhibitor and returned to us, This sample, DC(X2-8-3062),was used to thicken F-6-7024 Silicone Fluid and the bearing performancetest was so poor that nothing further was done with this thickener.

TL 126 Teflon from Liquid Nitrogen Processing and DC 410 gumfrom Dow Corning both gave greases that had poor bearing performancetests.

Because Ammeline is such a satisfactory thickener, severals-triazine compounds were prepared and evaluated.

18

L Compound Structural Formula M.P.

Methylene Bis-2,4diamino-s-triazine - -CH? 410 C(770 F)

1,3 Bis- [2 4 diamino-6- N

S-triazinyl) propane XH CH2 340C(642 F)

L NH2

C1

Tri-2,4,6-P-chlorophenyl- 7 A

S-triazine 330-335 C(626-635 F)

C 1

The first two compounds were effective thickeners for F-6-7024 fluid, while

the third was not. However, greases made with the first two compounds weremechanically unstable after they had been heated to 600 F.

3) Surface Modified Inorganic Thickeners

Alizarin-diamine and its calcium complex were deposited overseveral finely divided inorganic solids but greases made from these thickenersfailed to show promise. The solids coated were Cabosil HS-5, Baragel 24

and Battery Fluff Carbon. The bearing performance of greases made fromthese thickeners were all disappointingly low.

19

1.

Vi

The surface of specially dried Cabosil HS-5 was treated withseveral reagents and the products are still undergoing evaluation. The

surface was physically coated with methyl red, (CH3 ) 2 N - - OH,

and the resultant solid milled into F-6-7024 Silicone Fluid. At 9.25% aj grease of 241 penetration was obtained. In static testing this greasewas unchanged after 100 hours at 600 F, but it gave a relatively shortbearing performance test.

The silica surface was chemically reacted with diphenyl dichlorosilane, toluene 2,4 diisocyanate, benzene phosphonic dichloride, andtitanium tetrachloride and phenol. Only the product from diphenyl di-chlorosilane has been partially evaluated. Dispersing this reactionproduct in F-6-7024 Silicone Fluid resulted in a thixatropic grease, butthe addition of pentane 1,5 diol resulted in a grease that was heat andmechanically stable. After 10 days at 600 F in a static test this greaseappears unchanged.

IV. PREPARATION AND BENCH TESTINGOF EXPERIMENTAL GREASES

Experimental thickeners were evaluated by milling them intoF-6-7024 Silicone Fluid and testing the resultant grease.

Experimental fluids were evaluated by thickening with ASU orAmmeline thickener and testing the resultant grease. Whenever feasible,the experimental fluid was used as the only fluid component; however, becauseof the high melting points of the polyphenyl siloxanes, they were generallyblended with F-6-7024 fluid.

Experimental additives, to improve oxidation stability orextreme pressure properties, were added to base greases by warming the.grease to 150-200 F adding the desired amount of additive and millingthe resultant mixture.

The development of meaningful high temperature grease benchtests remains a major problem. A number of bench tests have been in-vestigated. None correlate well with bearing test results, but a feware able to pick out greases that will not run an appreciable time inthe bearing performance test. Because of the time, expense and largeback-log of greases to be bearing performance tested, efforts continueto be put on finding more meaningful bench tests.

20

I After preparation of the greases they are heat-treated at450 F for 4 hours and remilled. Those greases that become very softare eliminated from further consideration. Those greases that becomeharder, have more fluid milled into them until they are back to thedesired 300 penetration range and they are then heat-treated for anadditional 4 hours. Further hardening after this additional heattreating, is considered cause for elimination of the material.

Those greases that survive heat-treating were then evaluatedin high temperature bearing performance tests. Screening was done inthe modified L-35 test, under 5 pounds radial and 5 pounds thrust load.The more promising greases were then tested in bearing tests employing50 pounds radial and 25 pounds thrust load.

Roll stability tests at 600 F were run on several greases.Greases thickened with regular ASU and p-Azo Aniline modified p-aminobenzoic acid ASU thickeners gave soft, non-uniform greases after 4 hoursin this test. Based on these roll stability tests these greases wouldbe considered unsatisfactory for use at 600 F, but these greases performedquite well in bearing performance tests at 600 F.

Among the factors that can cause failure of a grease in thebearing performance test are high leakage, high evaporation and drasticchanges in consistency. Bench tests designed to determine these propertiesof greases were run on a number of greases. One version of this test wasa "whirled disk," in which a 20-mesh stainless steel screen, 31 mm. indiameter was coated with a 2.5 x 24 mm. disk of grease and then the screenwas impaled on a glass rod. The test specimen was then placed in a testtube housed in a 600 F aluminum block. After the test grease reached600 F, the disk was rotated at 7500 rpm for one minute. Glass thickenedgrease and a Teflon TFE-Baymal thickened grease showed very poor adhesionin this test, although both of these greases gave very respectable bearingperformance test results. A grease, thickened with Phosphatherm RN andTeflon FEP 120, adhered to the disk extremely well, but could not even bestarted in the bearing performance test because of its extremely hightorque requirements.

In another version of this test the stainless steel screen isheated to 600 F in either an oven or an aluminum block and the greasesevaporation and leakage tendencies studied. When the screens wereheated in an oven, they were placed on watch glasses and when they wereheated in a block they were placed in test tubes. The following datawere obtained:

21

Oven Heated.

L Sample % Evaporated in Comments

1 Day

F-6-7024, lot 6 30

Dry ASU 69, 61 Residue chlorine contentnil.

LG-0677, B-417 42 No leakage.

ASU-Arochlor 1254 9 No leakage.

10% Glass Fiber- 55 Remaining greaseF-6-7024, lot 6 still soft.

ASU-5 0 ether 53 Residue was brittle

(MLO-59-692) flakes.

ASU-Silphenylene 60 Residue rubbery.

Ammeline-F-6-7024, 31 Residue soft,lot 6 greaselike.

Block Heated

LG-0677, B-565 20 Residue black and101 crusted - chlorine

content nil - noleakage.

LG-0677 + 5% PAN 25 Residue black and hard.PAN on glass wool.

LG-0677 + 5% PAN 172 " " "+ 1% excise amine reactants

LG-0677 + 5% PAN 26+ 1% MHS

LG-0677 + 5% 20 Residue black andTFE Item 6 crusted with some

yellowish particles.TL-126 Teflon- 33 High oil leakage

F-6-7024, lot 6 + 3% PAN residue hard.

40% Permansa Red + 60% All grease hadF-7024, lot 6 leaked out.

1 2 days - 15%, 5 days - 40%.

2 2 days - 29%, 5 days - 44%.

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Although these tests were run for screening purposes only, itwas hoped that some conclution might be drawn with bearing performanceresults. Disappointingly, the ASU thickened greases containing excessamine appeared poorer in this test than did the regular ASU greases,which is just the opposite of the results in the bearing performancetest. Repeatability was not very good, but trends were consistent.The disappearance of chlorine from the residue of ASU greases in thistest substantiates results obtained on residues of greases from bearingperformance tests. While this test may be useful in screening out verypoor greases, it can not be used to detect which of several good greasesis the best.

ASD expressed interest in obtaining low temperature data onLG-0677 (ASU thickened F-6-7024 Silicone Fluid). Previous reportsindicated this grease is extremely brittle at -65 F. Torque and ap-parent viscosity tests were run which indicated that a temperature ofabout +15 F is the lowest temperature at which this grease can satisfythe contract specified requirements.

Apparent viscosity determinations were made on this grease at20 and 32 F at a shear rate of 20 reciprocal seconds. The data obtainedwere:

Temperature Apparent Viscosity Poisesat 20-1 sec.

32 5,60020 14,000

Torque determinations were made by the ASTM D 1478-57 Tprocedure. These data showed:

Temperature Torque, g - cm.Starting After 10 min. Running

15 10,300 8,10010 24,500 17,700

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V. EVALUATION OF GREASES IN HIGHTEMPERATURE BEARING TESTS

A total of 347 high temperature bearing tests were run with204 bearings at 10,000 rpm during this reporting period. Sixty-five

tests were run at 600 F under modified L-35 conditions. The compositionof the greases and results of their tests are shown in Table I. Sixty-two tests were run at 650 or 700 F under modified L-35 conditions,The results of these tests are shown in Table II. Two hundred andtwenty tests were run at 600 F with 50 pounds radial and 25 pounds axialload. The results of these tests are shown in Table III.

Because of the large back-log of greases for bearing testing,the lightly loaded testers were used as a screening test to selectgreases to run under higher loads. As work progressed and better per-forming greases were developed, these screening runs began to run over200 hours. As a means of accelerating these screening tests the tempera-ture was raised to 650 F in many tests and to 700 F in a few tests. Itwas realized that no correlation has been established between runningtimes at 600 F and 650 F, but for ASU greases it was found that 650 Ftests lasted approximately 0.3 to 0.4 as long as 600 F tests. A typical

600 F test on an ASU thickened F-6-7024 Silicone Fluid containing phenylalpha naphthylamine is about 200 hours and at 650 F the average of17 tests on this type of grease was 65 hours. There are real dangersin accelerating tests by raising the temperature. Changes in compositionor consistency can occur or the stability temperature of one or morecomponent may be exceeded which would make any comparison between resultsat two temperatures very misleading. The correlation found for one greasesystem certainly may not hold for a different system. However, becausethe ultimate goal is for systems suitable for much higher temperaturesand the pressing need for a screening test, data at higher temperatureswere considered worthwhile to obtain.

oth A method was developed for measuring belt tension, as a partof the program to eliminate as many bearing performance test variablesas possible. All of the high-temperature, high speed bearing testers

use the weight of the motor, partly counterbalanced, to apply tensionto the drive belt. Tension was measured and adjusted to fifteen poundswith a spring scale and a dial indicator. The dial indicator was mountedagainst the motor pulley to detect movement; the spring scale was connectedto the center of the motor pulley to pull in the direction of the testspindle. Gradually increasing tension was applied to the scale. The scalereading was taken just as the motor and pulley started to move. Thismethod was adopted as routine for use with all bearing testers.

24

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About mid-year, a series of low bearing performance test resultscaused concern. Careful rechecking of conditions, procedures and testerdimensions failed to suggest any cause for these low results. A group ofninety-eight MRC S-17 bearings and two New Departure X-14047 bearings wereanalyzed by Bearing Inspection, Inc. on their Model BA-20-2 ElectronicBearing Analyzer. The bearings were also measured for bore, OoD., width andeccentricity. All of the bearings met ABEC Class 3 inspections. Both ofthe X-14047 bearings were smooth and quiet on the dynamic analyzer. Ofthe 98 MRC S-17 bearings, 67 were rated good on relative noise and vibra-tion, 19 were marginal and 14 were rated rejected. Most of the rejectswere due to inner race faults.

As these bearings were used for performance testing, an attemptwas made to correlate bearing performance with dynamic analysis rating.However, no detectable pattern could be found. Long and short tests wereobtained with each class of rated bearings.

An experimental bearing from the Marlin-Rockwell Corporationwith a MoZS cage, failed after 18 hours with an ASU-F-6-7024 grease. Cagebreakage was found after the test.

A special packing and start-up technique was developed for usewith the dry, fibrous greases resulting when high percentages of polyphenylpolysiloxanes were tested. Quite short tests were obtained when severalof these materials were tested in the usual way. However, much longertests were obtained when the grease was packed firmly into one side of thebearing; the bearing turned over and four drops of F-6-7024 fluid wasdistributed over the bearing and this side firmly packed with grease.The test unit was then assembled and heated to 500 F, and the bearingrotated 12 times by hand before the high speed test was started.

VI. DISCUSSION

The development of longer-lived, 600 F greases continues to dependprimarily on finding more satisfactory fluids. While better bearings,thickeners and additives are also important and desirable the most dramaticincreases in bearing performance result when more stable, less volatilefluids are used. The phenyl siloxanes fluid systems offer real promiseof meeting the requirements for a 600 F. grease.

25

L

At the beginning of this reporting period ASU or Ammeline thickenedF-6-7024 Silicone Fluid were the most satisfactory greases that had beendeveloped. At 600 F under light load the best of these greases run satis-factorily for about 200 hours. Increasing to 50 pounds radial and 25 poundsaxial load reduces the performance life of these greases to about 80-120hours.

A number of other thickener systems were tested and none werefound to give better results than ASU or Ammelineo Most of them were notnearly as good. However, the search for better and higher temperaturethickeners must continue because both ASU and Ammeline will not be stable

enough for use at 700 F. Also, there is always the hope that a really goodthickener will give better performance at 600 F also.

The best bearing test results were obtained with MRC S-17bearings. Twenty-five tests were run under higher load conditions withNew Departure X-14047 bearings. In general, there is some indication thatthe X-14047 bearings may be less sensitive to E.P. additives in some formula-tions than the MRC S-17 bearings. However, only one test was greater than90 hours and six were in the 75 to 85-hour range. On the average, this isnot as long test lives as obtained with the S-17 bearings. Two tests wererun with Barden BJH-204 bearings. Both tests were shorter than thoseobtained on the same grease on S-17 or X-14047 bearings. These results onthe different bearings is in line with results obtained in previous years atlower loads.

A large number of additives were tested in varying percentagesin a number of grease formulations but only a few were found to be effective.

In previous work it was found that methyl hydrogen silicone addedto ASU-F-6-7024 grease gave the best bearing performance tests obtainable.Further testing this reporting period gave variable results, due possiblyto variations from lot to lot of MHS. It was most effective in extendingtest times under high load conditions at 600 F. The optimum amount appearedto be between 1 and 2%:

Batch of MHS % in Grease Bearing Test Hours

1043, lot 301 1 106"2 95

"4 41043, lot 302 1 58, 56

The effect of MHS as a load carrying additive is quite limited and falls farshort of the goal of 200 hours.

26

An excess of amine in ASU-F-6-7024 greases show a definiteimprovement in loaded and unloaded bearing tests. The amines may beeither e:-cess amine reactants or phenyl alpha naphtha amine in the rangeof 1%. For example, 1% PANA raises these greases'high-load test performancefrom about fifty hours to about ninety hours.

Unfortunately combining both MHS and PANA in the same grease,results in shorter tests than those obtained on the grease without anyadditives.

Titanium dioxide used as an auxiliary thickener to overcome thethixotropy cf p-phenyl Azo aniline modified ASU grease gave greases withexcellent bearing performance tests when enough TiO? was used to result ina very hard grease, i.e. penetration less than 200. Tests of 150 hourswere obtained with gi&ases of this type containing 3% TiO2 . Lesser orgreater amounts of TiOz resulted in shorter tests and use of a number ofother auxiliary thickeners in this grease system showed no improvementin bearing test performance. Also, use of TiO. with ASU or Ammelineresulted in no improvement in bearing performance.

A number of different silicone fluids and variations ofF-6-7024 Silicone Fluid were tested without uncovering a significantlybetter fluid. A number of experimental silicone fluids from GeneralElectric and Dow Corning were made into ASU greases and tested. Most gaveshorter bearing tests than F-6-7024, but several from G.E. appeared aboutequal in performance. These fluids were numbered 189-114, 118-159, 189-150,114-1403 and 128-559. Because they did not offer significantly betterperformance they were not studied too extensively. Various viscositygrades, distillation fractions and inhibited samples of F-6-7024 were madeinto ASU greases and bearing tested. Higher viscosity grades and the lowerboiling fractions of F-6-7024 gave greases with poouer bearing performancesthan regular F-6-7024. Use of small amounts of inhibitor in F-6-7024resulted in ASU grease that gave bearing tests comparable to uninhibitedF-6-7024, while the use of large amounts of inhibitor gave greases withsignificantly poorer bearing tests. These poorer results were not due tothe inhibitor interfering with the thickener reaction- because similarpoor results were obtained when the preformed thickener was treated withthe inhibitor and then this modified thickener used to make a grease withF-6-7024 Silicone Fluid.

27

The evaporation and thermal screening tests seem to indicatedefinite limitations to the best of the present grease systems fortemperatures of 600 F and higher. Primarily this is a problem of the

* fluid rather than the thickener. The two classes of fluids which havebeen used with the most success, the polyphenyl ethers and high phenylcontent methyl phenyl silicones, both show high evaporation losses atthese elevated temperatures. There are also indications of oxidationin these tests with F-6-7024. The odor of formaldehyde and positiveFuchsin tests for aldehydes were noted and the fluid tended to darken.pi Presumably, this oxidation is on the methyl groups.

The polyphenyl polysiloxanes showed low volatility and good

thermal and oxidation stability in these screening tests, which suggeststhey are a promising class of materials for high temperature greases.Unfortunately, they have rather high melting points and as a result they

were tested in greases blended with F-6-7024 Silicone Fluid. Even when

using 60% F-6-7024 and 40% polyphenyl polysiloxane the resultant greaseswere so hard it was necessary to preheat the bearing to 500 F to obtaina good bearing test.

ASU, p-phenyl azoaniline modified ASU, and silica thickened

blends of F-6-7024 and polyphenyl polysiloxane fluids gave bearing testresults comparable to the best results obtained with straight F-6-7024fluid. However, Ammeline thickened blends gave significantly betterbearing tests, several of these tests running in excess of 200 hours at 600 F

under high load conditions. The following bearing test results were ob-tained at 600 F, under 50 pounds radial load and 25 pounds axial load,at 10,000 rpm, and using a full pack of grease made by thickening thefluid with 35% Ammeline:

Grease Test Bearing Test,Fluid Penetration No. Hours

F-6-7024 296 744 120724 113

40% •6 Si20

60% F-6-7024 100 781 133739 148

40% 8 S 02 - 725 21660% F-6-7 24

40% 016 Si706 732 17160% F-6-7024

40% 08 Si404 192 754 179

60% F-6-7024 777 164779 169

40% ý7 CH3Si3O2 170 774 20260% F-6-7024 747 168

40% 015 CH3Si 7O6 751 16460% F-6-7024

28

D

While these results are sketchy they indicate a very promising advance inbearing test life. Obviously, other compounds and concentrations need tobe explored to optimize these results.

Even more promising results were obtained when small percentageof bis(triphenyl silyl) perfluoro glutarate were added to Ammeline thickenedF-6-7024 Silicone Fluid greases. The following results were obtained at600 F, under 50 pounds radial and 25 pounds axial load, at 10,000 rpm andusing a full pack of grease:

% Additive in Grease Test Bearing TestAmmeline Thickened F-6-7024 Penetration No. Hours

f774 120

0 296 724 1131.5 300 775 150

3.0 311 763 183770 208

5.0 300 778 165

10 311 771 133

These results are comparable to those obtained with the polyphenyl poly-siloxanes, but at much lower percentages. This lower percentage enablesthe grease to maintain its low temperature properties. Bearing tests onthese greases were started in the usual way at room temperature.

The chemical analysis of the bis(triphenyl silyl) perfluoroglutarate does not correspond to the calculated composition. This raisesthe question as to just what compound this is. Preliminary results in-dicate it may be hexaphenyl disiloxane with some small amount of fluorineimpurity. This composition needs to be investigated further to followup this promising lead.

VII. CONCLUSION

Greases made by blending F-6-7024 Silicone Fluid and one ofseveral polyphenyl polysiloxanes and thickening with Ammeline have giventhe longest 600 F, high-load bearing tests to date. Bearing test resultson a series of these greases range from 150 to 220 hours. Furtherexploitation of this approach offers hope of meeting the desired 200 hoursat 600 F.

29

1

A number of experimental silicone fluids and variations ofF-6-7024 Silicone Fluid were tested and none were better than F-6-7024Silicone Fluid itself.

L' Ammeline thickener is the only thickener that gave theexceptionally high bearing tests with blends of F-6-7024 Silicone Fluidand polyphenyl polysiloxanes. With other additives in F-6-7024 SiliconeFluid ASU and p-phenyl azoaniline modified ASU were equally as good asAmmeline. For use at 700 F new thickeners will have to be developed.

Among the many additives investigated, only titanium dioxide,used as an auxiliary thickener in p-phenyl azoaniline modified ASU-F-6-7024grease gave significantly better performance.

All of the phosphonitrilic chloride-metal halide complexesstudies were hydrolytically unstable.

VIII. SUGGESTIONS FOR FUTURE WORK

The promising initial results obtained with the polyphenylpolysiloxanes should be followed up and optimized. This should enablemeeting the requirements for a 600 F grease.

To develop greases for 700 F, new thickeners will have to bedeveloped. Triazine systems and silicas appear the most promisingcandidates. New or improved fluids will also be required. More stablephosphonitrilic chlorides and the polyphenyl polysiloxanes appearattractive approaches.

30

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61

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64

0* U).r4 L4 (14.) p. $4.

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65

1(LGURE I

VIAPOR PRESSURE OF (PNCI2),,/Zn C12

1 00C

900 t

8, 001

1700

600

400

IN300I~I

20- - ------ -- -

-- -----

666

FIGURE 2

1000 VAPOR PRESSURE OF (PNCI2)n/FeCI 3

400

300

500

400

300

200

ua 60~50

40

.4P

uj67Ia

.1

1. LubricantsAeronautical Systems Division# Dir/Materiels and (Lubrication & bear-• Processes. Nonmetallic Materials Lab, Wright- ings)

Patterson AFB. Ohio. 2. GreasesRpt Nr WAM-TR-60-557, Part III. Progress report, 3. AdditivesMay 63, 67p. inol illus., tables. I. AFSO Project 3044

Unclassified Report Task 304403The objective of this work is the development of II. Contract AF 33(616)-

grease'systems capable of operating in loaded bear- 7597ings over the temperature range of -65 to 900 F. III. American Oil Co.Current work done on a 0 to 600 F grease system. Whiting. IndianaMost of the test work was done at 600 F under 5 lb. IV. K. R. Bunting, et al.radial and 5 lb. axias load and 50 lb. radial and V. Not aval fr OTS25 lb. axial load. Some tests were carried out at VI. In ASTIA collection650 and 700 F under light load also. Greases madeby blending F-6-7024 Silicone Fluid and one ofseveral polyphenyl polysiloxanes and thickeningwith Ammeline have given the longest 600 F, high-load bearing tests to date. Bearing tests on a

over)

series of these greases range fran 150 to 220 hours.Ameline is the only thickener that gave these longbearing tests with these blends. With other fluids1 and other additive, in fluids ASU and modifiedASU's gave results comparable to Ammeline. Whileseveral other experimental silicone fluids andadditives gave results comparable to ASU or Amre-! ine thickened F-6-7024 Silicone Fluid, none werein better except titanium dioxide. When titanium

dioxide was used at 2 to 3% in p-phenyl azoanilin•modified tSU-F-6-7024 greases 600 F high-load bear-ing tests of 150 hours were obtained. This compounddid not show any beneficial effect in other grease

Ii, systems. All the phosphonitrilic chloride-metalhalide complexes tested showed hydrolytic in-stability.

*1 \

I'

L!