AD-A120 092 PENNWALT CORP KING OF PRUSSIA PA CENTRAL RESEARCH AN--ETC F/6 11/6SOLID LUBRICANTS FOR IMPROVED WEAR RESISTANCE,(U)

UNCLASSIFIED JUL 82 J P KING, Y ASMEROM N00014'79-C-0305'eEIEIEEIIEIIEEllEEEEllElll.EEIIEIIIEEIIIEEEEEEEEEEEEI

OFFICE OF NAVAL RESEARCHCONTRACT N00014-79-C-00

FINAL REPORTO April 1979 - 30 Spmber 1981

SOLID LUBRICANTS FOR IMPROVED WEAR RESISTANCE

James P. King and Yayesh Asmerom

PFnnbwlt CorpwntionCntrl Rhurch and Devlopmen

KingofPrusua, PA 19406

July 1982

, DTIC

S OCT 1 2 Q62

Rproduction in whole or in pert is permitted for any pwposevb ft United Stetes Government.

Approved for Public Release. Distribution unlimited.

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Solid Lubricants for Improved Wear Final ReportResistance 1 April 1979-30 Sept. 1981

6. PERFORMING ORG. REPORT NUMBER

7 AUTHOR(s) S. CONTRACT OR GRANT NUMBER(@)

James P. King and Yayesh Asmerom N00014-79-C-0305

9 PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT. PROJECT, TASKPennwalt Corporation AREA W WORK UNIT NUMBERS900 First AvenueKing of Prussia, PA 19406

11. CONTROLLING OFFICE NAME AND ADDRESS 12. REPORT DATEDepartment of the Navy July 1982Office of Naval Research 13. NUMBER OF PAGES

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IS. SUPPLEMENTARY NOTES

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19. KEY WORDS (Continue on reverse aide if necessary and Identify by block number)

Antimony thioantimonateAntiwear additivesExtreme pressure additivesMetal sulfidesOxythiomolybdates

20. ABSTRACT (Continue on reverse side It necessary and identify by block number)

Detailed studies including synthesis, characterization andevaluation of antimony thioantimonate, SbSbS4 , were carried out.

As a solid lubricant additive in various greases, this material

exhibited superior extreme pressure and antiwear properties as

demonstrated by the Four-Ball weld points and load-wear indexes

DD I JAN, 1473 EDITION OF I NOV65 IS OBSOLETE UNCLASSIFIEDSECURITY CLASSIFICATION OF THIS PAGE (When Date Enterer'

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on both AISI-52100 and AISI-440C steels. Moreover, impressive

abrasive wear resistance properties were imparted by low

concentrations of SbSbS 4 in greases deliberately contaminated

with hard abrasive particles. This additive appeared to be

compatible with all the base greases investigated including a

silicone grease in which very few additives show good response.

The lubricant properties of a number of cerium and zinc

thio- and oxythiomolybdates were also investigated. The cerium

complexes, as additives in a lithium grease, showed excellent

antiwear properties on both chrome tool and stainless steel.

However, their non-stoichiometric composition and tendency to

form hydrates caused complications during synthesis and

evaluation of properties. The zinc complexes were found to be

even more promising as antiwear additives, especially for high

temperature use on stainless steel.

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Table of Contents

Page No.

A. Objective 1

B. Introduction 1

C. Antimony Thioantimonate - SbSbS 2

1. General 2

2. Field Tests 2

3. Aircraft Arresting Cables 3

4. Toxicology 3

D. Cerium Oxythiomolybdates 3

1. General 3

2. Reaction of Ammonium Molybdate with

Hydrogen Sulfide 4

3. Reaction of Sodium Molybdate with

Sodium Sulfide 6

4. Reaction of Sodium Molybdate with

Cesium Acetate 6

5. Thermogravimetric Analysis of Cs2MoOS 3and Selected Samples of Cerium

Oxythiomolybdate Complexes 7

a. Cesium Oxythiomolybdate - Cs2MoOS 3 7

b. Cerium Oxythiomolybdate Complexes

Prepared by Different Methods 7

E.- Zinc Thio- and Oxythiomolybdates 8

1. General 8

2. Preparation of ZnMoS 4 '3H20 and ZnMoS 4 8

3. Preparation of ZnMoO2 S2 .3H2 0 and

ZnMoO 2 S2 9

4. Preparation of ZnMoOS3 "3H2 0 and ZnMoOS3 10

5. Toxicology 10

F. References 11

G. Acknowledgement 11

'A NOW

List of Tables

Page No.

Table I. Shell Four-Ball Weld Points and Load

Wear Indices of Cerium Oxythiomolyb-

date in Lithium and Aluminum Complex

Greases on Chrome Tool Steel Balls

(AISI-52100) 12

Table II. Shell Four-Ball Weld Point and LoadWear Index of Cerium Oxythiomolybdate

in Lithium Grease on Stainless Steel

Balls (AISI-440C) 13

Table III. Shell Four-Ball Wear Prevention

Characteristics of Lithium Grease

Containing Additives on Chrome Tool

Steel Balls (AISI-52100) and Stain-

less Steel Balls (AISI-440C) 14

Table IV. Effect of Concentration of

Ce2 (MoO 1.2S2 .8 )3. 6H20 in Lithium Grease

on Wear Scar Diameters 15

Table V. Lubricant Properties of Thio- and

Oxythiomolybdate Complexes 19

List of Figures

Page No.

Figure I. Wear Scar Diameter vs. Load 16

Figure II. Thermogravimetric Analysis of

Cs2MoOS 3 in Air and Nitrogen 17

Figure III. Thermogravimetric Analysis in Air of

Cerium Oxythiomolybdate Complexes

Prepared By Two Different Methods 18

Figure IV. Thermogravimetric Analysis of ZnMoO2 S2in Air 20

List of Appendixes

Appendix I. "Investigation of Extreme-Pressure and

Antiwear Properties of Antimony Thioantimonate",

ASLE Transactions, 24, 497-504 (1981)

Appendix II. "Effect of Antimony Thioantimonate in Greases

on Abrasive Wear", manuscript presented at the

Symposium on Innovation for Maintenance

Technology Improvements, NBS, April 21-23, ]981

SOLID LUBRICANTS FOR IMPROVED WEAR RESISTANCE

A. OBJECTIVE

This program was for development of superior extreme

pressure, antiwear, thermally stable lubricants and lubricant

additives for use in both conventional and corrosion resistant

metal surfaces. It was the objective of this task to extend

the useful life of Navy lubricated bearings, seals, splines,

aircraft arresting cables, and sliding metallic surfaces.

Lubricants for corrosion resistant metals are particularly

desirable because the use of these metals in corrosive

environments is often precluded by the lack of lubricants

suitable under these conditions.

B. INTRODUCTION

The approach investigated in this program was a follow-up

to an earlier study carried out at Pennwalt's laboratories with

partial support by the U. S. Navy and where a number of complex

metal chalcogenides had been examinedI- 4 for their performance

as extreme pressure and antiwear additives in greases, solid

film lubr-cants, and fluids. As extreme pressure and antiwear

additives, these complex chalcogenides had been found superior

to simple sulfides, including MoS2. One composition, arsenic

thioantimonate was a particularly outstanding solid lubricant

and, therefore, became the subject of much characterization and2evaluation. When the safety of all inorganic arsenic

compounds came under question, further development of arsenic

thioantimonate was terminated. However, under that program

other promising leads had been uncovered and which were then

selected for additional studies in a subsequent effort whose

results are summarized in this report. Of particular interest

was antimony thioantimonate (SbSbS4 ) which received special

attention in this study. Other promising materials described

r1

in this report include cerium and zinc oxythiomolybdates.

While SbSbS 4 was found to be an outstanding extreme pressure

lubricant additive with unique antiabrasive properties, the

oxythiomolybdates were noteworthy for their antiwear

characteristics and high thermal stability.

C. ANTIMONY THIOANTIMONATE - SbSbS 4

1. General

Laboratory synthesis and performance data on SbSbS4are described in detail in the attached copies of

publications (Appendix I and II). The preparative method

reported in Appendix I represents an improved reaction

route with greater simplicity, reproducibility, product

priority, and higher yield compared with the original

method. 3 Commercial production of SbSbS4 should be

possible without a major process development effqrt. A

cost estimate for the production of several million pounds

of SbSbS4 has shown that this product can be made

available at a price comparable to, and possible lower

than, that of molybdenum disulfide, MoS 2.

2. Field Tests

Field tests with greases containing SbSbS4 are being

carried out by the Marine Corps at Camp Lejeune, NC, on

high mobility vehicles. Another series of field tests is

expected to start shortly at a Marine Corps base in

California.

Test results to date from Camp Lejeune (after about

one year of use in heavy duty vehicles) indicate that

grease with SbSbS4 as an additive is greatly superior to

the standard GAA grease used by the military.

-2-

3. Aircraft Arresting Cables

The Naval Air Engineering Center, Lakehurst, NJ, is

evaluating greases containing SbSbS4 on arresting cables

used on aircraft carriers. Major improvements including

longer cable lives and less slippery decks are sought.

This application study is spoinsored by NAEC (contract

N68335-81-C-5280); however, the ONR program provides the

necessary basic technical underpinning.

4. Toxicology

Because greases containing SbSbS 4 have advanced to

the field test stage, we have obtained acute oral and

dermal toxicity data on this compound which indicate that

it is nontoxic. All animals survived at an oral dose of 5

g/kg (rats) and a dermal dose of 2 g/kg (rabbits), were

normal clinically, and gained weight throughout this

study. Skin and eye irritation tests also indicate that

the compound is substantially benign. Arrangements have

been made with the Naval Medical Research & Development

Command for a 90-day subchronic dermal study which is

expected to be completed by early 1983.

D. CERIUM OXYTHIOMOLYBDATES

1. General

Numerous attempts to prepare cerium thiomolybdate,

Ce2 (MoS4 )3, gave products with elemental analysis

corresponding to cerium oxythiomolybdate complexes,

Ce2 (MOOxS4 .x)3*nH20, where x = 1-3. These complexes were

evaluated for lubricant properties in a lithium base

grease and found to exhibit good antiwear properties on

both chrome tool and stainless steels. These results

prompted our further study of the synthesis, character-

-3-

ization, and evaluation of cerium oxythiomolybdate

complexes. A number of reactions were carried out using

three different routes but in all cases the reaction

products were found to be non-stoichiometric. It was not

clear whether this non-stoichiometry reflected the

particular nature of complex sulfides involving cerium and

molybdenum or was due to lack of suitable reaction

conditions. The three reaction routes, the resulting

compositions, and their performance as lubricant additives

are summarized below.

2. Reaction of ammonium molybdate with hydrogen sulfide

(NH4 )6 Mo7 024"4H20 + nH2S ----> (NH4 )2moo x S4-x + by-products3 (NH4 )MOOxS4 -x + 2CeCl 3 .7H20 --;o Ce 2 (MoOxS4 -x)3 nH 20 + by-products

Analysis of the cerium complex reaction products

showed variable ratios of sulfur to cerium depending on

the particular experiment. A large supply of cerium

complex, prepared by the above reaction sequence for

detailed evaluation and characterization, approximated

Ce2 (MoO 1.2S2 .8 )3 -6H20 by elemental analysis. The material

was found to be amorphous by X-ray diffraction.

Tables I through IV summarize the performance data of

Ce(MoO 1.2S2 .8 )3.6H 20 as a lubricant additive at various

concentrations primarily in a lithium grease. For

reference purposes, the lubricating properties of greases

containing 5% MoS 2 are also listed. On chrome tool steel

52100 the weld point of the base grease containing 5%

cerium complex is comparable to that of the grease

containing MoS2 ; however, the load wear index and wear

prevention characteristics of the grease containing the

cerium complex are definitely superior (Table I). On

stainless steel 440-C the grease containing 5% cerium

-4-

complex again shows superior antiwear characteristics and

comparable extreme pressure properties to those of

molybdenum disulfide.

A lithium grease containing a mixture of 1% SbSbS4and 1% Ce2 (MoO 2S2 8 )3 -6H2 0 was also evaluated. The

objective of this experiment was to see whether such a

combination could impart both extreme pressure and

antiwear properties to the base grease at a low level of

additive concentration. The results are recorded in

Tables I, II, and III and show that this combination at a

total concentration level of 2% greatly improves the EP

and antiwear properties of base grease.

The concentration effect (0.1 to 5%) of the cerium

complex in a lithium grease on the wear prevention

characteristics is shown in Table IV. The scar diameters

on chrome tool steel are quite small and do not show much

concentration dependence as indicated by very little

change in the wear scar diameters of the greases

containing 0.5 to 5% of the cerium complex. In the case

of stainless steel, there is a definite trend of

increasing wear scar diameters with decreasing

concentration of the cerium complex.

The cerium complex was also evaluated in an aluminum

complex grease. The Shell Four-Ball weld points and load

wear indices of this grease containing 5% MoS2 and 5%

Ce2 (MoO 1.2S2 .8 )3 -6H20 are recorded in Table I. It appears

that the cerium complex shows slightly superior EP

performance to MoS 2.

-5-

I * _ ,,i ' .. .

3. Reaction of Sodium Molybdate with Sodium Sulfide

Na2MoO4*211 2 0 + 3Na 2 S ---> Na2 MOoxS 4 -x + by-products

3Na MOoxS4 x + 2CeC1 3 .7H20 0 Ce(MoO xS4 x) 3 nH 2 +

by-products

Because of difficulties encountered in controlling

the flow of hydrogen sulfide in the reaction with ammonium

molybdate, sodium molybdate was treated with sodium

sulfide to produce a solution of sodium oxythiomolybdate.

The sodium oxythiomolybdate solution was then treated with

a cerium trichloride solution at different pH ranges.

None of the product analyses correspond to the expected

cerium to molybdenum ratio. No additional work on this

reaction was carried out.

4. Reaction of Sodium Molybdate with Cesium Acetate

Na 2MoO 4*2H 20 + CsOAc 2 Cs2moos 3 + by-products3Cs 2MoOS 3 + 2CeCI 3 -7H20 -) Ce 2 (MoOS3 )3 + by-products

The synthesis of cesium oxythiomolybdate, Cs 2MoOs3

was carried out as reported in the literature5 by reaction

of cesium acetate with sodium molybdate followed by

passing hydrogen sulfide through the reaction mixture at

pH 10.

Attempts were then made to prepare Ce2 (MoOS3)3.nH20

starting from Cs2MoOS In our first attempt, an aqueous

solution of CeCl 3 -7H20 was added to an aqueous solution of

Cs2MoOS 3 in 2:3 molar ratio at room temperature. A light

brown solid was isolated (about 50% yield) whose analysis

(Ce:Mo:S = 2:2.2:5.7) did not correspond to the expected

composition, Ce*2(mos3)3.nH 20. However, its extreme

pressure and antiwear properties in a lithium grease are

superior to those of the sample obtained from ammonium

oxythiomolybdate (Figure I).

-6-

5. Thermogravimetric Analysis of Cs2MoOS 3 and Selected

Samples of Cerium Oxythiomolybdate Complexes

a. Cesium Oxythiomolybdate - Cs2MoOS3

Thermogravimetric analysis of cesium

oxythiomolybdate was carried out both in air and

nitrogen at a heating rate of 50C/minute. Tnis

product was selected for thermal study because it has

a well defined composition and, therefore, it can

provide information on the expected thermal stability-2

of complexes containing the MoOS 3 anion. As shown

in Figure II, the material is remarkably stable both

in air and nitrogen. With the exception of a slight

weight loss of about 2% at 280 0 C followed by gradual

weight gain of up to 4% around 410 0C in air, there is

no change until 600'C. Under nitrogen, there is

essentially no change in weight up to 600*C; a very

slight deflection showing less than 2% weight loss

between 300 and 5000C may be attributed to the

presence of impurities.

b. Cerium Oxythiomolybdate Complexes Prepared by

Different Methods

Two samples of cerium oxythiomolybdate complexes

prepared from ammonium oxythiomolybdate and cesium

oxythiomolybdate, respectively, were selected for

thermal study in air. The TGA curves are shown in

Figure III. The initial weight loss up to 300 0 C for

both samples may be attributed to water and this

appears to be consistent with the elemental analysis.

The two samples show different modes of decomposition

with increasing temperatures. The complex prepared

from Cs2moos3 shows weight gain from 400 to 6000 C

whereas the complex prepared from ammonium

-7-14

oxythiomolybdate shows a slight weight gain between

350 and 380°C, followed by a weight loss of about 8%

from 380 to 4500 C. Both complexes appear to be

stable up to 400 0C in air after dehydration.

E. ZINC THIO- AND OXYTHIOMOLYBDATES

1. General

Synthesis and characterization of three stoichiometric

zinc thio- and oxythiomolybdates - ZnMoS 4 -3H20, ZnMoOS 3* 3H20,

and ZnMoO*2S23H 20 - and their corresponding anhydrous

compositions, was more successful. The compositions showed

considerable promise as antiwear additives especially for

high temperature use on stainless steel. For example,

ZnMoO2 S2 was found to be much superior to MoS as an extreme2 2 2pressure and antiwear additive in lithium grease and was

stable in air up to 400'C (750°F).

The following sections describe the synthetic pro-

cedures for these compositions. Table V lists the

performance data of both hydrated and anhydrous zinc

complexes. The thermogravimetric analysis of ZnMoO 2S2 in

air is shown in Figure IV.

2. Preparation of ZnMoS4 *3H2 0 and ZnMoS4

ZnCl 2 + (NH4 )2MoS4 inH 2 *3H 20+ 2NH Cl

ZnMoS4 3H 0 350°C/2hrs.. ZnMoS4 + 3H2 04"2 in N 4

A sample of 5.0 g (NH4 )2MoS4 (prepared as described6in the literature ) was dissolved in 100 ml distilled

water. The resulting solution was slowly added with an

aqueous solution of ZnCl2 (2.6 g in 20 ml distilled

water). A black solid formed immediately. The reaction

-8-

. . .. . . . . . - al-l - -.. .. II |1Z

" "1 ' W tIll I-a-

mixture was then stirred for two hours at room temperature

and filtered. The solid product was washed with acetone

and dried at 110 0C for four hours (5.3 g or 75% yield).

X-ray diffraction indicated that this material was

amorphous.

Calculated for ZnMoS 43H 20: Zn, 19.0; Mo, 27.9; S, 37.3

Found: Zn, 19.6; Mo, 28.6; S, 37.9

The anhydrous material was prepared as indicated above.

3. Preparation of ZnMoO 2 S2*3H20 and ZnMoO2 S2

Znl+MOS in HO0 22 20 +N4CZnCI2 + (NH4 )2mo 2 S2 20> ZnMoO 2S 2*3H 0 + 2NH C

ZnMoS *3H 50C2--> ZnMoO2S + 3H204 2 in N 2 2S2 2

An aqueous solution of ZnCl 2 (5.38 g in 50 ml

distilled water) was slowly added to a solution of

(NH4 )2Mo0o2S2 (9.0 g in 100 ml distilled water; the

compound was prepared as described in the literature

resulting in slightly exothermic reaction. A dark brown

solid formed immediately. The reaction mixture was

stirred for one hour at room temperature and then

filtered. The black solid was washed with distilled water

and dried at 110 0C for three hours (6.6 g or 66% yield).

X-ray diffraction indicated that this solid was amorphous.

Calculated for ZnMoO2 S2 .3H20: Zn, 21.0; Mo, 30.8; S, 20.6

Found: Zn, 23.9; Mo, 29.8; S, 23.4

The anhydrous material was prepared as indicated above.

-9-

4. Preparation of ZnMoOS 3*3H 20 and ZnMoOS 3

Cs2 moos3 + ZnCl 2 in H20>ZnMoOS3 .3H20 + 2CsCl

3in N2 ZnMoOS 3 + 3H20

A solution of 15.4 g Cs2 (MoOS3) (prepared as

described in the literature 5 ) in 100 ml distilled water

was treated with a ZnCl 2 solution (4.4 g in 30 ml

distilled water). The reaction mixture was reflexed for

1.5 hrs. A brown solid deposited. The solid product was

isolated by filtration, washed twice with distilled water

and dried at 105°C for three hours (10.2 g). X-ray

diffraction indicated that this solid was amorphous.

Calculated for Zn(MoOS3 ).3H 20: Zn, 20.0; Mo, 29.3; S, 29.3

Found: Zn, 23.4; Mo, 30.1; S, 29.2

The anhydrous material was prepared as indicated above.

5. Toxicology

Some toxicology tests were carried out on ZnMoO 2S2 *3H 20

with favorable results, as follows:

Skin irritation test: Non irritating

Eye irritation test: Mildly irritating without washout

Acute dermal LD50 (rabbits) >2g/kg

-10-

F. REFERENCES

1. M. J. Devine, J. P. Cerini, W. H. Chappell, and J. R.

Soulen, "New Sulfide Addition Agents for Lubricant

Materials," ASLE Trans., 11, pp 283-289 (1968).

2. S. M. Niazy, W. H. Chappell, and J. R. Soulen, "EP and

Anti-Wear Properties of Greases Containing a Complex

Sulfide Additive," NLGI Spokesman, 35 (12), pp 420-6

(1972).

3. W. H. Chappell, G. H. Dahl, and J. R. Soulen, "Solid

Lubricant Materials," Final Report on Contract No.

N00156-70-C-1132, 1971.

4. W. H. Chappell, J. P. King, and J. R. Soulen, "Additive

for Wear Resistance," Presented at the American Society

for Metals Conference, Cleveland, Ohio, October 1976.

5. V. A. Muller, E. Dicmann, and U. Heidborn, Zeit. fur

Anorg. und Allgem. Chem., Band 371, pp 136-148 (1969).

6. G. Kniss, Ann. Chem., 225, 29 (1884).

7. F. W. Moore and M. L. Larson, Inorg. Chem. 6, pp 998-1003

(1976).

G. ACKNOWLEDGEMENT

We would like to acknowledge the many scientific

contributions of Mr. M. J. Devine who has provided support of

the highest professional level at the request of ONR and

especially for his attention to requirements of the U. S.

Marine Corps for amphibious and desert operations.

-11-

Table I. Shell Four-Ball Weld Points and Load Wear Indices1

of Cerium Oxythiomolybdate2 in Lithium and Aluminum

Complex Greases on Chrome Tool Steel Balls (AISI-52100)

Scar DiameterWeld Point Before Weld Load Wear

Grease Composition kg mm (kg) Index

Lithium Grease 140 2.64(126) 18.3

Lithium Grease + 5% MoS 2 250 2.90(224) 30.4

Lithium Grease + 5% Cerium 250 2.02(200) 41.4Complex

Lithium Grease + 1% SbSbS4 400 1.61(315) 59.5

+ 1% CeriumComplex

Aluminum Complex Grease (ACG) 100 2.10(70) 11.8

ACG + 5% MoS2 190 2.24(160) 35.5

ACG + 5% Cerium Complex 200 2.10(160) 40.2

1. ASTM-D-2596

2. Ce2 (MO 1.2S2 .8)3 "6H20

-12-

Table II. Shell Four-Ball Weld Point and Load Wear Index1

of Cerium Oxythiomolybdate2 in Lithium Grease

on Stainless Steel Balls (AISI-440C)

Weld Point Load WearGrease Composition kg Index

Lithium Grease 80 3.5

Lithium Grease + 5% MoS 2 100 6.1

Lithium Grease + 5% Cerium Complex 100 10.4

Lithium Grease + 1% SbSbS4 and

1% Cerium Complex 140 11.8

1. ASTM-D-2596

2. Ce2 (MoO1.2S2 .8 )3 -6H20

-13-

Table III. Shell Four-Ball Wear Prevention Characteristics1 of

Lithium Grease Containing Additives on Chrome Tool

Steel Balls (AISI-52100) and Stainless Steel Balls

(AISI-440C)

Wear Scar Wear ScarDiameter on Diameter on52100 Balls 440-C Balls

Grease Composition mm mm

Lithium Grease 0.70 3.96

Lithium Grease + 5% MoS 2 0.65 2.34

Lithium Grease + 5% Cerium Complex 2 0.40 1.38

Lithium Grease + 1% SbSbS 4 and

1% Cerium Complex 2 0.43 0.84

1. ASTM-D-2266 - 1200 rpm, 1671F, 40 kg for one hour

2. Ce 2 (MOO 1 . 2 S 2 . 8 ) 3 •6H 2 0

-i4-

Ii

Table IV. Effect of Concentration of Ce2(MoOI.2S2.8) 3 -6H20 in

Lithium Grease on Wear Scar Diameters1

Wear Scar Wear ScarDiameter on Diameter on52100 Steel S.S. 440C

Balls BallsGrease Composition mm mm

Lithium Grease 0.70 3.96

Lithium Grease + 0.1% Cerium Complex 0.59 2.64

Lithium Grease + 0.5% Cerium Complex 0.39 2.47

Lithium Grease + 1% Cerium Complex 0.40 2.26

Lithium Grease + 3% Cerium Complex 0.40 1.84

Lithium Grease + 5% Cerium Complex 0.41 1.38

1. ASTM-D-2266 - 1200 rpm, 167 0F, 40 kg for one hour

-15-

Figure I. Wear Scar Diameter vs. Load(52100 Steel Balls; 250C, 1800 rpm, 10 sec.)

I. Lithium Grease

II. Lithium Grease + 5% Ce2 (MOOxS4 _x ) 3 nH 20 preparedfrom amimonium oxythiomolybdate

III. Lithium Grease + 5% Ce 2 (MOOxS4_x)3 .nH20 preparedfrom cerium oxythiomolybdate

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-W LA Ln LA -4

04 a -4 N.- * l en M0 .1 q

4--)

- -X

C00

0000

C00

40

C 4

.-4 4

E CD

>1

00

4

a) CDCD Q

0D

-200

APPENDIX I til% 2,.

Investigation of Extreme-Pressure and AntiwearProperties of Antimony Thioantimonate

iiIlits d t'tiltl 111 ' I ttI Ils lIt IN lis litd NVlii ANi Prpaa in ofA tMEonyTiattnt

Is (111.11 111(1 itl t it Il I stlii 1111 t .11 ' I tlv.1 l ict:l'ii.it s ll '1li/ iItt)I~ illlialn 11lId Ast~~litt .ullll

att thee sillwSL] toriato Conernc i Sn racico

Ca ...na Augus (el-2t, -,fil. cShlhS oc (2K-,, + ~idt 1(1) / 'd i anl so i il (111 ll l Il il.\ f al497lz l a s i

* ~%Is I' KIN~i. \,i M iiIf 1 siil %

H ic .111ItIIIIS iristiltide (It 9 7 .poii -Il Imitl ht*1 I~ Characterization of Antimony Thloantinionate

ltit IT) III- -k1 itt1i ii ii ii ii t 111111 lei i t, It I'1 i

Selection of Base Greases ill alll andii is .iiti hti. i \ii I itit 411mii X fi(I i

I ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~~~.l it \tit-it iit iii illsii iiii it ill -ipis I'u uiuiit W t - t- i p lil shid ii It- li t lt it., it, .1i

I , It I I .I( il I i .u li s-ilt lig ai tIll I iiitpvt Its1 (i-1 1Rec s ul t ! n (-Iscussion ik m sI 111 cl1iiI t si ii Llt.it-tt ks(( (I Ais suitv leitii it [I(- l miii i it L b can Prp rte of (b bS on Chom Toolth-11,1( 'hl1.1111L m itl~l 11i.h -.111F liii iuiit tut I It it (I (.i~ II( hat Steellalu bAIl(SI-C-52100I IlW i-

i t.N' h\N 1)1\ 1 2261.i , lt.10 S ) IS , h 'lu l l t o III ,(I ( I 'lp ~ il1C1

Ii tiiil S,-IHilii 1-iiit iiiit lillitI,- Alsg i Ti 2111 2- I10 tincIII1 Ow Rtiis 1iiiiitli '1i11us ssllis I ultilli-4 Its(. Ill(sii c hg'lm l.IT

itit-~(Lo hoiit iii~l~l iiss(I Ill -.ititil~l 111 Flttti sit)

I luuic t-i ciic pct t Ii NI F) 1 112.- t II l[ t1 1, \ l c I it',It d ilF l Il ~il c

it1 it~ \i isIt l I hI 1111j I'll ti liii 111 is s11iit1i 1ii w I Fit. Iii li itt1c i,1 itu -

I ( tu '. f usI t'sit I il Ni ti Nc- % %ct- ihmi Nit 01 (~g lh cmo rtiz t-trd anyt s 27 ( :0 In. thair le

\,I A5111-2III an kSI I lii siN AI'usi ( l Isi't- iISI o l i

till It. p o llll -it' \\ c .iim5it1 F4)l \iiiI (I s s t \t p (,I t' ct lilt (lc~iI %Nitt 1 I' s et ( I t~,(r

m d a t i c k It i I t Il i ti-ist ic %,itA I I i2tiitlit,96.tit

lk~k al . 1,11t~l'l l(,%%(If.(Ict-11111 d I Ilc'I- R suls a d D scu sio

dc lii tt ii lii il k lilt ii lililt liii. ! cam . %% c!it list I d-jIcti7 "

ti Ii 4111 1 I~t 1,x 1x lit I - 1 til I t~ (i 2 Im c ,, ~ s b

tiit a I cI~ ctii, ilt i i l tIIa I t tI Iit%,it I ii i I i it siitll t li tu tt itt li tiitu ic: I t. I,

it ,it i lt, I, \I) 4.tilitlt [11 I titi i tlllit lili Lu rctn Prp rte oI Ib bS on MStainless-icIcItI~Il Sb ll

1% L-il ,-i- l p~u t-i ill ittl i t I lit \tee AISI440

I cjw \ " 11 t.11 -1 I ' . '1 1 it lii t i s 4 111 1 1 .11. iti I ~i l .1 i is Fl -\t tl ltllt ~ i\il ilit ~ ~ ~ ~ ~ ~ ut 11 5til (lit 1lltxi'icd i Fi

___ __ __ ca w s. 1it id I Ili it 'ilI I . w\ ti .IIIL .1h [ " p lAIlt

"b' s f) p - l i t\\(iIt t -Iu t-] i I NuI~cd ()If Iit I- It Ilk I-W l

at Ic w tW I I T lI l.tts 1tt '7 8h21) i II(oIII Ilc

1.1ls il -2111 t (I 21 Mits w l~ mlid I IM2 iaink-

,I lix IIIK d I I C i I lithi Itt abt 3i 1~ tilt 777

caI I[ \lll (1 , ititluI Ilil I filli4ilis t. i c-i h llt2 II itI

A Isl 2 1111 f If,- c I Ii 111lii ill i x 'l il v t 1, 1 1 it 1 "I

i Il illg S lb il 1111 l's till I I lit 'I I (, ).1 1( L ha

gi ~ ~ ~ ~ IiII I(I ' Itc t. 1,Iifti, [I.'11i 212l tli htIci .i) Fg - ersa ilte I load AS-C-2 te al;2T

I M- \D Y %N 11,14 ANN11- KIM

I he %%cal Ili V\ efilloff ( li'llm lei isli( s of '?-pvl ( vill sbsbs'I \tit I ,III I I I'll R-11 xi I \% I- \it PKI % I \ I I( Is. III title(. i"Icam N-11111mill, ( 1,1\ and Iltllllllltllli ( olliplu\111: k' it I KI, I it '1*"(Iq (.K[ \' I I ( (:\ I 'k IMNIt. \[)ill

-d oll a Shull hall-BallRi \f 1 "(11 A -,2111, 1 \\ I N Im sNAISi (.-14 glvascs- %Vlc dull-Illillit["lei using AISI '110C tIaIIIIvsN swell halls. file mm (If-anielcr" I'll the litilluill givast, and flic 11111mill gicaw (Oll-

Wt \R S( \it \\I \K S( \It

DwItIlRA)\ I )Ix\aIiRo\ than ((of flit- sallic baw gicam (ollfallolig 5-fict(em slishs''It " to titilling .71-pel I vI it MOS , \% t-I v 100 and 3011 pet ( ent lal getISI -52 1 (it) A ISi -4-101L.I if ta( 1. 1 he 1% val %( .11 dialliclel of I lic III hillill

tillill I (IIIIJO gl ease ( (it)-1,11111lig : -)-pm ent SbSbS, ()if AIM-44M ball,I ItIIIIIIII (.1ca" I 1 71) 3,96

( .1 t-.i,( "', 0 63 (I.Ts "its OIII\ sliglltl\ 1,11 get 111,111 flic \%(-,If N( al oblamcd lot IIIv

I'llilluill Glca'c 116') 2.3-1 sattiegicacon kills M,7,4 %so.63 mm). hij -.-Mos 111 .1 slit( t Ilic gi case. the \%(-,it',III( "Ilk. (,I caw 1 99

Sdu mv (,1 2 11 slat dialliclul \\,k% Im gul than Ili-it lot lift- hasc smease (2.701

Mw' 2.1 1 % s 2.27 itim ). I It m v% (-I . I lit- [)I cs,,rt, t- ot ',-jwt ent Sbslis.

0,61) ill dic same NIII(ont. 141casc Ic"Illit'd III 100-pel(vill Ml-

6" p] ( J\ c 11 le I I I O\ t I I I ic base 141 ca sc I Scc %\ ca I da I'l I I I 1 .1 flit- 3it G I o'S4 table 'S [I,[,, file (ompalall\c %\(-,If (,I[ diallicit-1% oI both

\Iktlllllltltll I mllplc\ 1 .1, j" o W) 2 27 AIS]-)2J00 mid AISI- t IM .balls obtamcd lot life sallic basegleast., Illidel diticit-m load, I It(- (1111clemes III p(.1 fol -

(I W, Illailtv Mos 'ifid Shsbs' III diffc1cill V'Ica'c (,itIna)? thlonle am) 'Idmh," wc] Me (11111c ob\iolls I he Iv-

11 h 2 5'1 stilts ill I 'till(. S also III(II( mc that Ow lose 01 MoS off %laill-\1 1) lcs-stcel hall" is quilt. limited. I lic good pet b )I Illant c of

Sbshl" (it] o. aI polls Alm , .111d 11) a N if wl % of gi v'lw II'IN beclitilt if t 1111 l it liv, v pci 1,111% 1 Indef 111,1411 load (olldilions. Ill (little LITMCI'lill. 11 is IIIICIMSIIIII , lo

Illam applitallon" (It(- il't. ot I% tolitailling 5-pelkellt SI)Sh", giwN '111,111cl \\cat mal tit-limiledb\ 'v\eIc\\v'II plOhIcIIIN. I liviublvalilig plopcille" itIlletels Oil AISI-440C balls millet .1 gnt-1)of lotil diltvivill gfc'lw ("lli'mmig .7)-pri(cm SbSbS' him. applied load and it higliel \%eld point 111,111 [lit- sallic gicaw\\till \ls'l-I PC balk In asliell (Olitaillint ) S

p , -pel ( clit Mo, on ( lit ollic-lool sicul.lotil-Ball 1 1' Ic'tcl. Fol tollipalisoll. ille lubri(illing prop-criles of dic sallit. L"Iv'Isc% (olilaitillig .7)-pel(vill mollb(le-milli di"Illide ha\c alst been dviclillilled ()If AISI-440C CONCLUSIONAl )-pt-Itunt of SI)Sl)", ill loill greases, the\ vld polnt tit stallile"N-'Icel hall, slitmed illiplokefficills of Allfilylom I limit lit illiollaw ill(olpolated Into diffelvillJ00 11) )()1) pi'livill mcl ille Nallic glcaws tolitailling 5- to\% ( om Cliff ill loll impal 1, out -pc](clit moklmicooll. disillildc. it-Still, I]c st and ing ext rellie-pres"ll re III opert ics bot 11 on (Ill ollic I ooIgl\ (-it Ill I fill(- 7 1 lic "( al diallictel \s load glaphs 01(m (I and stainless steels. At loovel. load". tile \%cal ple\elillollill I-Ig 1 .11111 -) Indii'lit. 111,11 illc gleaNt." (olitailling SbSbS' (Ill tool s(ecl ill \aliotl gle'lNe, ilic (ollip.1-v\hIbIt vvcIlcill lesponst. 10 "I'lillics" steel. slalliless sleel table to IlloINIACIIIIIII disillfide: IIIc \\cal pIc\( Il-

ls dillit till to lillwlitatc. and Itivic mc Net\ (cl% ilddili\es Illill tioll charm lei isti( s of iffilillioln thioamilliollaft, of) si'linles,

all illip'It t good lespollse 14) -,111( one I') cast." steel ill dit'lerclit greascs sIIoAvd (olisidcl able illipt m cillcill

1)\ lilt, it-Niih, obtained oil tilt- silimne grease (ontaming 5- Mel 111"MACIIIIIII dislilfide. In gellelill. illifinlom Illio.ol-pvI(vIII MOS (scv I-it". .7)). It is sigilifitaill Illill file cmVellit- filliollille Nllo%\C(f emellew rcspollsic l(mald both lood .111dplessult. plopcific" (it ill(- sill(olle givast. I onlaimlig )-pel - stainless siccIs Ill a %aricl\ of git"'es, indilding .1 "Illmlictent SI)SI)S, If(- glealk itilplowd met Illos, of the base grease %%itil Olidi Nen ft.%% solid Illbri(allis Ill. (ollipanb1c.gIc'Isc alid the hast. gleast. (olitailling 5-pencill Mos__ Antilliom Illioamilliollate is .1 candidate solid-IIII)i I( ill( ad-

I \111 [ -1 1 ()1 1.111111 \1 "RI \,,I Co\ 1 \[\[\(. 1111tilki\ 1Cov I'\IR\lIov'ot SbSbS' \\I) MOS'o-' (AIko\Iv-foOi SlM AISI-52100

(,Rl- \sl CoMPONI I lo\ W1 I it Vol \ I (kg) Lom-N'ti m km\

Villomill (,Ica'i- 1 10 1 S.3

itillittill (.1caw WY; Sbsbs' 200 2.-,.SI lillitlin .1 caw + I slisibs, 400 43AII f1hillm ot 1,; M, "'. 126 17.61,1111111fil GI t 1,(- 3" "hSh", 620 -)7.()

lihillill (,Icaw - 3" Mos. 162 2 1 _161 c.1w 4 "" ShShS, 76o 9S. I

.1,; \146. 250 31). 1

A \ I~s lm,)I I5 lit [I) li31Rt\ III lII I( ,

P mi t a i mh i h\ I \1 1) 2 17 1II:'~,I

DI yp p"hii I \'h I MI 1) "66) F il 3 1, 17

W t ii S l m \S M ) '12

P'L p i Itl(1,) n\ V Isml 1 743 :44

udp li kg ]I'l 76o2 I

, I I t ) 22u66i' 0 70 11,63 it

!,,,k~id, Iliit. 121111 tpin .44 167 1-

11),~' .1 \SI N )3 3W311 2 0I

2-l It a 2 121- I pa P"

\S -100i s \5I I

I (.\f i- ' F \1I ttlik i s .) - Rl \,I,

( In) %S1 .\])II 2M\15-\ 4 R I \)1I'

-. \tluuttum ( Ict mnjC t :wl I~

Ii oic I 233 C

1.11M. Cram" 1. -11 s ti i H-lca )'i MI i~

Sib(~iit (.tcdw GI cs ShShS, -144o5

l.,tliiuiita\ (.Icdsc 4 5 NnS 144 4I

AIII-I(IIIi'.nv (4C4W I4tw

I\IiII 17 t I (X I .m I m. 4 k 01-1 R I5I[ S (tV\ I (R :) \\\+SbS, 2%44 MOS.

'ththh4 S il'. (.n'.n 141- IIIB tI AI[44 02 -4

.\Ininumntmn~Si I Filli (.ni- I't \InS I44 :

.3 SCS3, . ill SI& .... ...... .3 S. t

'1 -4

Fig -Scr dameer v lod. ISI440- stinlss-teelbals, 5~C Fig5-Sar iamter s lad.AIS-440C sainessstee bals,+5+

1800rm. 18 180rpm l~s

I 3111 3.\I31133l' 8111 13131'311 33 31R1.ll-.33 'I8l,, ~iI,'. 3\(1k,\3 ~1\1811\l'.-8111l1~i'I 1 3333I 31 1 I\\~ i 3 13. I . II 31R-7-I Jil I I 33

I ~ ~ \1' \ K11. I~ [l " l l 33.i. I It 1 I I i i I , i 11 j~iS \\ 3 11,k1 m3 is3 11 I I ~ I I \ , 1 1I3 \33, 11 3

-kt__ \'l \\I)___ -' 1\3 I ') I I li 11 3 '.1 1,'' I'll, 12- 411-11

Ill 2 011 1 7 2 H 28 31

1.3 li ~gi V 8hl~8 '2133 I 'o I 10 1 74 23 IS IItill Il .3.) 1 1 3', 11 26 7:S 22 2.1 33(1

873 2 2.5 1111 -S

1113 I 18 1.51 72 1 21 .2 333

3 31131\ -,233 2131 I .333 337'o ' 9 1.1 .4 333131

1113', ', I2' 064 2.0 1 2 33 1 1 .7 .l: .2 \ i 111 ,

(1 -if 1818 I .4 \ ~

Il 1 27 .136 1.601 1318s 2.603 333131I.,313 ..... I \10l ' ,2 1 11

ACKNOWLEDGMENTS %ol 'lltli kil.P,11%l .Ipllll

IlIi[, 33333s Ilii Ibicil Noippoil tucl 13\ llc ( )Il(( ii3 f N.t'.Il REFERENCESRescal3t3 I I lit ' ,itttlti N mc g3ituc lfIli c i t liiit.33(c anditI I Ili, mv.3 \. I cIim P~3 h3' y 3 1 113333 ' . .... 1 3 1,3, I 3

Imisest igai(til (of [((I r(.'le- esite and1( Atttivt'at Iltiieties oif Atillijiis I fliigiatilrgri, 503

'gillgit, Agigi i g, III Ig 'm Ii .[,I I, .tti %tltit' mk- - lg,ni If I. tp i 13~ ~ ~ t ~ )gg , i , t .t i 1, i,

283( -2$I) ( 146S Ittidli linai H ttp i mi iigt N. \ ii iigij *'.7ii l 3 '7l,2) ~ s \1 . ~ ,l V\ It f i ';" I slltlll I R H ' an At n l\ii-Se% t l (lililit-l1 \% If , Kimr P in. 'Nu.- I, I r t Ri .stj(, R(

gg i t.t4 ' .ih 11iilig at I .rlttdc Sujlfide .Addlgit'. 'n/,G]jlttiI P~ml'g 'g i r.0 'If ig \ il ".ni. Si, - I 'gigi\,1. witttttgg i t,. ........i 35 , 2'.p , 121 1 t'ii 11,72 k \,g land. ( h w, I lIl- P470),

DISCUSSION DISCUSSION

JOSEPH P. CERINI M. B. PETERSON (Member, ASLE)C.C.L. Company Incorporated Wear SciencesPhiladelphia, Pennsylvania 19140 Arnold, Maryland 21012

he lirait '.s shld t he (onintient.ed hit (13in g alt ex ci - Hir authoi rs 1i1t- presee Sli . \tISnel et intetrest in g resultslent piec.e ii work ill thle field ot comiplex itetal t. laI(oget- t(Ct ning .1 new% IltIlii.ilit tdldiltI e 'Antliliots sulfid~e."ides. This is to h~e expietted .61sine lhe lts ase Iteeti doing Ilii hell IMint OluILS10ISt is that it I'. Iloin I eite- thIali \JOS. -extetits woi)k inth iis fietld lot il% in\ears.- it is picu-twlai Is in, Ifl-it it itileases tile "seld load to ext teinel high saluesinteresting to note thle testilts with Stainless steel and sili(o t. evenl \%iih ditth allt-to-lola i~t. t tals Stit isasS'.aiiiless steel.greases Since each 1, ill it's ttss %% a%, has ilitheteitl bh tiing Site dwi atilihots hase- tiseil stanaiil Icl t' de iies. [theprohlettis. tlts tuttle t.o less Speak i I lietils is. I hlit c r. hitss%

ilt' thIe il[h Ig ilt 01t ill at Ilt's t0ftttetlpliilg rtltlttiilg eset. a.tcles geiit'aI (questions \, Ili( Ii (il it) lti'tlsvails\ tests \% ilt atlitlgti tIhit it Itontat~te to ds(ctaitt its saloie

tiSed inii geasers. ILn ci I Ilea .i I ts It omtt~ijit I tlei I ic-stilts ss itllo nttallth sil itciest( h a'. ii-hgeil1/s 1. it-phieuis.

DISCUSSION 2. Do tltt.' atitois % Ittentit .(1)3 t tl t oitiiisti % itth MotS2-?

A. A. CONTE, JR. (Member, ASLE) o les iiii htibt sot iithe Sate I\ lies ofi~ tttitgi i ~t alt'litU.S. Naval Air Developm~ent Center t ilslt If't. (ta ilt. la 1Iii ti. v I ie ais oef ilt- twoiWarminster, Pennsylvania 18974(111iiltls(Ir

The Potentital of t tomplex ia~lc igen ides s uci as S)Sh)S, 3. Wouild tle altlll i-Spe lcu~lat e oil thle itiechan istis ofats iltproved sol 3itd Itt liia nit materials t'sptialIN It- ha id -t lithicat hiti %sithI thItis u ipolt ittd Is it at tis she.arIohrt Hate mnetails hias been %%-ell documiiented. [atttits i-el - stren'igth miatetial. or is there somic Sultur reactioncrenccs atid (/11)1 andi t Iis pa per- ssithI its %weth ofiu dati a ssi it I gives thle Itighi sseltd hIoadNs?1-113ittue Ito' demons.' triiI~ ate tilt s po tetiial.

A protpert~itut(niiit to comiplex Iiahoigettidt.s is that1tie% at-callit rphouts silid s. -I his 1tglt.' tt is iit(-(tlt tad it ii i AUTHORS' CLOSUREto what has beeti general Is (il side.red toi le at tieessa 1 hut lIn t-ejpl to I poitt raised 1\ bhi M essrs. (Coit I atnd11o1 sufti~tiiu requiiremntt of at good ol id iiht~ ii.I ittittt.'i Pttterson (-(itcetiitttg tile pIoss;ihlt. lithr--i(lil tItethaiim ntat las-er-lattt.e structure. Wiould the attlti is t. ile il ( tltiielit ailitillism tliitiant iniulitae-ttie fact that t his alioiphous()in this oihsers at ionit is thlerec amis esidei ce t hat I lit.' t I han- sulftide is soeecftist'as a Ihiritaitsiii iigit ti ts. Woirkilt. mate an ion is rwall pi esent , that is. Sh intitle + 5 o xi- is itt pitrogiress hi th il attle N at ionial Pitt eaui iii St antdardsandi~

d~at io n %title and lie SI) (at ii itt tilie +3 oxidlatioin Stite. o(it ~ l oliai oietgit illilaset htIltis it pi ssihle that at to- pret ipit at iit too k Ilia(- e il It [it-li sul- atel itttt oi itileii Il iti5etigae .1iIee tlt'~ htmsItt 1 wits int ercalate([ ilt o tlie st rt ttIt e (it Sh.SIh, lIn responitse to ile qutest i tis raised hs \NI' r te 'sil it e-

Il i e pr epiar atio o (outlilex (Ita 1togen h es S11 itc as ga rli ig t itpa ri~o oIii f resul ts ofi i ga tit d isttIltides atndII't'NloS.t . tlie resutanit pcoi ilist-i1 tetlh sia mixtilt. ot l'eS, Mois, with1 atitllnottS lilioatit itinltate-thie reasont that sscand Most, ht ill all1 ittittiates- tItixed ti tleC (lte. ti I ii-pi.'- lseVh iritin- lt o oi ttes i-ttcn(ilit at io n. Pi sitalis miixin~g FeS,, atntd Nit S.2. t st.sr lit' swetld po its otfhes tile li ase greatse t liia iliitg all

woldh ilot iri iside thle satniibenfit- fill re.sults. F inail Is. how 155 igatlm dt isit I ide [li t.- twei t determtined and t lie t es.!ts arereproducible are these results from hatch-tt.-hatch prepa- gis en inl lahle 1)1. A stutd\ using antititiis tltioant ittitnlerations and what is the anticipated coist tof ShShS., relative ast s- it %1hiia ii Itas het . Ii underitakent hi I he N atitonal B'it-11i NIOS2; eu i ldus

NI. r oit - u caise. all inIterest in g quiest itl re tgard inig at pitssilile situ.irc ot atitinit~ tis Ioalillittitate \NIli(l hInias\ t'stlt

REFERENCES trot elemeittal sitlfl illt.'il-aliicd inito ShtS3 lattii-e, Ill-

Pgttsligh. P'A 1 7,21 -\rrg i'7,7 pititlls liliit \-tasil iiilttlightli tttei it uis lii mi c dittti -

504 JAMES P. KIN; AND Y'AYIESH ASMEROM

TABLE DI-Wk.LD POINis o LI tiUM (;REAS- CON I AININsGVARIOS ADDI IIVES

Wt. Pot IN, kg

Lithium Grease 140

Lithium Grease+ 5% MoS2 250

Lithium Grease

+ 5%DibenzylDisulfide 180

Lithium Grea,;e+ 5C/%

DiphenlDisulfide 160

Lithium Grease+ 517

Ni(WI r

Disulfide 126"Lithium Grease

+ 1

SbSbISt 40)Lithium Grease

+ 5,SbSbS4 760

Dioctsl disulfiais a liquid at roomn temperature and the grease strtuoturewas destroyed upon addition ot 5' duwtvl disullide Ihis may explain thaiits weld point is h,er than the bjase grease

ent from those of the hosts because of expansion of lattices. mance results has been obtained from different batches of

Since antimsony hioantimonate is alnorphotus, formation of antimtov thioantimonate. kn estimate cost of antiniotlx

an intercalation structure in this case is doubtful. thioantimonate will be aailable upon completion of our

(;ood reprodoncibility on elemental analysis and pertor- ctirrenst scale-up studv.

,,r-.*4 -'* .. i

APPENDIX II

LF'F CT O1' ANTIiMONY fIIOANTIMONATE IN GRELASLSON' AWibASiVL WLA<

J. P. KingPennwalt Corporation

King o1 Prussia, PA 19406

Yayesh AsmeromPennwalt Corporation

King of Prussia, PA 19406

M. J. DevipeGeneral Technology

Havertown, PA 19086

Abstract: There is a crucial need for effective lubricantaa(ditives that are capable of preventing damage that mayoccur due to contamination of lubricating systems by abra-sive particles. This is an essential requirement forlubricants used in equipment and military vehicles that areoperated in sandy environments. The effect of antimonythioantimonate (SbSbS4 ) in three base greases-YMIL-G-10924,:4IL-G-24139, and MIL-G-81322-was investigated. The pres-ence of SbSbS 4 in these greases provided considerable im-p)Jovumcnts in weld point, load wear index, and wear prevun-Lion properties with two different alloys. Moreover,Lmipre.sivc wear resistance properties were imparted by lowconcentrations of SbSbS 4 in these greases deliberately con-Laminated with hard abrasive particles. The combination ofoutstanding EP and antiwear characteristics and anti-abra-swo-n properties of antimony thioantimonate makes this11l=L-ia1l L1 aLtractive candidate as a grease additive. Ex-tensive field testing of greases containing this material

ri , .. coimnended.

Key words: Solid lubricant additive; antimony thioanti-1,on1IAto; abrasive wear; extreme pressure and antiwear prop-

j INTRODUCT IONiAbratsive wear is well recognized as the primary cause ofsurf:ace damage for military vehicles and equipment as welJa:; inciusr.al machinery.1 This form of wear is encounteredwllk _orf_ign maerials, e.g., sand, grit or other hard

------------------------------------------------------------------------Manuscript nrcsented at the Symposium on Innovation forIa it t[all,' T;,.inoluY [.np Verfov lSents, sponsored by the

IIiret'ui oi Stidr 1 11(1n Naval Ail. v;tt~Gaithersburj, MD., April 21-23, 1981.

kLI .. . . . . , .

t I .. bcctw' uiLtrdincd il Lie lubricant. gourccu of'Such ihard pirticles include airborne contaminants enterinj1L,1. ayi;tWi durinj uquipment assembly or repair, finelydivided wear products front system components, fine debrisrusulLing rnom oxidation or corrosion, and operation insandy environments. Accordingly, a critical property of alubricant material or additive is its ability to prevent orliniiimizu component wear in the presence of hard abrasiveparticles.

Antimony thioantimonate (SbSbS4 ), when incorporated into anumber of selected greases as a solid additive at low con-centration, imparts outstanding extreme pressure propertieson both chrome tool and stainless steels. 2 An initialevaluation of SbSbS4 in several military greases was con-ducted with the objective of selecting one or more of thesegreases to be formulated with SbSbS 4 for field evaluationinvolving sandy environment. To investigate additive re-sponse in the presence of abrasives, a grit material havingprecise composition and known particle size was incorpor-ated into those greases with and without the presence ofSbSbS 4. The extreme pressure and antiwear characteristicsof these greases with and without SbSbS4 and MoS 2 as addi-tives were determined and compared.

PREPARATION OF ANTIMONY THIOANTIMONATE (SbSbS4 )

Antimony thioantimonate was prepared by the modified pro-cedures as described in Progress Report No. 7. A largesupply of this material was synthesized in preparation forthe coming field evaluation.

GREASES

Three fully formulated greases meeting the following mili-tary specifications were used as base materials:

MIL-G-10924 - Grease, Automotive and Artillery (GAA)MIL-G-24139 - Grease, Multipurpose Quiet ServiceMIL-G-81322 - Grease, Aircraft General Purpose Wide

Temperature Range

IO'1' MATrIAL

The grit material used in abrasive study was supplied bythe A/C Division of General Motors Corporation, Flint,Michigan. It has an average particle size of 60-80 p andthe following composition:

IG 8

,e 2U 3A 1(, 16Wt

Cau 30

Nha ,, 5 %6

iikjition LOSS 2-3%

'EST i~Yi U, L iSb

Po CX ICfI l Ile

The abrasive wear study was carried out on a Falex machineusiilj AISI-C-3135 steel pins (Rb87-9 1) and AISI-C-1137 V-blocks (Rc20-24). The testing speed, temperature, and loadwcur 290 rpm, 77*F, and 100 ibs, respectively. The follow-ing procedures were employed.

i. Test specimens (pin and V-blocks) were cleaned withxylenu followed by acetone and then air dried.

2. Test pin was inserted in pinholder.

3. Grooves of V-blocks were filled with grease sample u ,dstruck flush.

4i. V-blocks were set in their sockets.

Jaw loading assembly was mounted on lever arms.

;aw load was brought to a gauge load of 100 lbs (manualLurning of ratchet wheel).

7. Drive motor was started and test run to 30 seconds, orLo fI±luru if prior to 30 seconds. 1ailure was indi-cated by rupture of pin or rapid torque increases above0 in-lb and excessive noise.

Ti:;t tn was cleaned with xylene and acetone beforerukin5 visual observation.

'n t.= :-trei pressure and antiwear properties of the greuss. determined on Shel] Four-Ball EP and Wear Testers.

,,L:st-s consist of steel phurical specimens slidilluj. ,tLit UeCIL other. Weld points and load wear indices wuruiLkieidined in a series of runs (10 sec., 1800 rpm at 770r,')uaiuuctud at various loads, and scar diameters were meas-

'nai after each run in accordance with ASTM-D-2596. Wear

I i''l i c) iii it-L( I L: LiC:. Wule deLc-iIinud by IiesUrLiitj-C-,i Uik-Le L- oL ttLL spUcnimUns after each run Lt spct±-* .' 'm , I d),16, teLtperditure ind duration (ASTM-D-2266)I£-) *L11U,;,--jciO~hr tool : tul AiSI-C-52100 and stainless

.:tw< i , .;i -. ,iOC-we.r used.

,_;ULT'" L ND DISCUL;SION

iArasive Wear Study

brasive weir tests were conducted with the Falex machineLou the thiee base greases (bIL-G-10924, MIL-G-24139, andbif.-G-8139J2), the three base greases with 5% MoS 2 , thethree base greases with 5' SbSbS 4 , and same modified,ireases containing abrasive particles. The results for the,1brasive wear resistance imparted by 5% concentration ofSbSbS 4 in MIL-G-10924 and MIL-G-24139 greases are presentedin Figure i. It can be observed that severe wear and su.-face damage occur with either MIL-G-10924 or MIL-G-24139(both containing 5% grit); however, SbSbS 4 virtually elim-inates such wear and surface damage. Wear effects werealso noted with MIL-G-81322 in the presence of abrasiveparticles, although the base grease is originally formu-lated to provide some degree of protection from surfacedamage in sliding contact. The presence of SbSbS4 furtherimproved Lnc antiwear properties of this grease. The pre-:;iicu of 'ioS- in all the three base greases also providesL(A JiC uree oL surfacu protection; however, by visual ob-servation the results are not as evident in all cases asthose obtained with SbSbS 4 .

xLrume Pressure and Antiwear Properties

,"; indicated earlier, all three base greases studied hadLeeji fully formulated at the source in order to meet thumilitary specifications, i.e., they contained additives.Our primary interest was to improve abrasive wear resist-ance of these greases by incorporation of SbSbS 4 ; however,!iw reme [,russ;uru and antiwear properties were also ob-taine in order to determine whether these performanceproperties were further improved by the presence of SbSbS 4.

Wu found that the weld points and load wear indices of MIL-C-10924 could be considerably improved by the presence of1 to 5' SbSbS 4 . At 52 concentration of MoS 2 no increase inwe.Ld point of this grease was observed; however, its loadweor index was somewhat higher than the base grease. In-deed, the LP properties of the base grease containing 1%SbSbSl were found to be superior to those of the same base(Jrease containing 52 MoS 2 . The antiwear characteristics of

wx-

k_"I~ Tik . id *o.. t d -1 (LO Wealr inldcx of thebj~~ ~;uddicon.~i.l~rlowur thar, that of the

Tlh. wea: rev~~o

~~ui tr 1 ,L-u tz coIontuf i i iiai 1ere~ ei~i~t~. ~L)I~u~i~ U u~ Le ijrt; asu on bc'th ci~roiae

Ltool I nCit1 li iIL! ss sriu e i s T'-(-- zxperimlential data are re-2rLC., 10 ub: ii anls. '_ j'apiial piresentatiorn is shown in

Pi~jurue 3.

! ecau-c oL I Lnt3p! Iy of MZL-G-81322 crease avail-aible to us at this -imeo, load wear indices were not deter-

.Lilu. ~:~weld ;uolnta o-f ,IIL-G-8l322 containin'g 1 and 3'CSbSbS4 snowt-d 25 and l00'- improvements over the base grease,

resecevul. Wth .~MOS2) a weld poiLnt increase of 56'%%as objserved. The base grease, as originally formulated,.showedi iyjoo wear prevention.r charac teris tics on chrome tools3tcel. 'No siLgnificant improvement of wear prevention char-ac Lt-, iic OILu both choetool and stainless steels wasuLc:1 idVud by incorp~oraitic-n of MoS- i)or SbSbS4 into the basegruso.Thu r.usults Lirfe listed in Table III.

Kyj'CLU 10h

zliTe abras~vt! wear resistance of both MIL-G-10924 andMiL-G-2-i139 greases was dramatically improved by in-

U 'oUr ua ILion1 of -low con~centrations of SbSbS4 .

If he extreme pressure and antiwear properties of three:i5 1 rsus-NTL-G-O9Z 4,MIL-G-24 139, and MIL-G-81322

_wcre cireatlv enhance-' by using SbSbS 4 as a solidtdL ULVk. AL I luw,_r cuncentration this additive out-

ioerformed MoS In all cases.

'Ii'( L Lmoriv ,ho.IV.IUJt sho wed good response- to bothLJ'il( Lool:icu AiS i-C-52 100 and stainless isteel.' iSI-Li40C in all three base greases investigated.

1 1, i it lIl Iii II~); 10 t11i Lh 172( bo '.e 4Jii'ases _u.0US not.) adverseliy affect other propertie., such as

r, f . -UlL. w±LIi SL3bS 4 LAs Uxtreme pressuru ahu anti-tc i iLu LutAiLiai for SiJl~~ftL~)AL

.JaC11fl ui: iiL pruvumunt 3S for lubricating greases,,i~.lhcti-ly LhCUI CuiL ,iIL-G-10924 (GAA) iIjipruv~iIUfl-LtLmin j ursued by the U. S. Army Mobility EquipmentIU-*-,'A.L'cii iiid Lbtv- l1utLunL Cuimmiu nd (DIDME-GL), lort sui-voir, Va.

AC KNOWLhDCYE NT

This work was supported by the Office of Naval Research.Tue guidance and encouragement provided by Commander HaroldP. M1artin is greatly appreciated.

iE .L R

Tiblc I. Weld Points, Load Wear Indices, and Wear

Scar Diameters of MIL-G-10924 Grease

Containing Additives

1 Wear Scar2

Grease Composition Weld Point, LWI Diameter,kg mm

MIL-G-10924 Grease (GAA) 160 29.3 0.62

+ 1% SbSbS 4 250 39.4 0.59

+ 5% SbSbS 4 315 56.7 0.59

+ 5% MoS2 160 38.4 0.57

1. ASTM-D-2596 - AISI 52100 Steel2. ASTM-D-2266 - 1200 rpm, 40 kg, 167 0 F for one

hour on AISI 52100 steel

- S..

C~) c .'z2 a) N4.-T 4.) 0

(1) C.'-4 E L)Q) 'U LI)4J' %T -4 I Lii H

I)U~ ) 0

(1) r-4 N4

0

U) a)aQ

N4 -H _ _ _ _ _ _ _ _(d 4-1E EC.) -H No 0

'U C, 4 Lii Li % Lii uVN CD 00

Cl r4 Cd 0D C ) -

Ci) -H Lii V)

'-4r- Cd (1 C

'U 41) Q) (1)

HO0 U)-

t a) 0 Hu-,I C%4o) 04 0r 00 0-

N 04

U) a) 0. . i I I 00Q0)' 0 4JJ 04 0 I: 00N

4 I 'U r-2 r:4 I I (N04r L I oUO C)

0 0) CfD U) U) Un

'U- 0) (/ U) C

Cd4 r.4 (J 4-4 r-41)0

A2 ONNN nr-r U0.U)

O U-4 n U C4r -(w 4~~ ~~~~.) () ( n 2 -i ~ 1 Il pt% 44

N H4u 3

4J0

$-i C-I r4 H

U)tn

4-)

0(1

w 43C) - 4 k -

H1 a l V

C)4 -1 4)

E- - 4

04 0

r. 0 ~

-1 U C) CD0 C))C

P4 a) OD O

(1) I -H*-4 4)raV

00

0H uuhf0

4 4 $ NU0 0- M 0n

-'- U0 00)0 00

Rj Ia)-

'd&4

areas of severewear

areas of lightpolishing

f Ia' b

Figure 1. Effect of SbSbS4 on Abrasive Wear

The outstanding wear resistance properties imparted by SbSbS 4 to greasescontaining grit particles (primarily SiO 2 60-80 V) are illustrated by theseFalex pins

a - grease MIL-G-24139 with 5% gritb - " it and 5% SbSbS 4

a' - " MIL-G-10924 itb' = " " and 5% SbSbS4

3.0 -

1 3 4

2.0 - A.

21.5 4i- -1.0 -

0.5 - 1

0.4 -

0.3 - . MIL-G-10924 (GAA)

2. GAA + 5% MoS2

0.2 -3. GAA + % SbSbS 44. GAA + 5% SbSbS 4

20 30 40 50 100 200 300 400 500Load, kg

Figure 2. Wear Scar Diameter vs. Load; AISI-C-52100 Steel

Balls; 25*C, 1800 rpm, 10s

/ _

1 . MI--094(M........ 0 . .... . .. . ."' " :: '"" ;' -rt 2. GM +; -) 5% MoS2 & "' . , " :

3.0 - 2 3

2.0-

1.5 -

1.0

U

0.5

1. AMI (MIL-G-24139)

2. AMI + 5% MoS2

3. AMI + 1% SbSbS 4

II I ,, I I I I20 30 50 100 200 300 400

Load, kg

Figure 3. Wear Scar Diameter vs. Load; AISI-C-52100 Steel

Balls; 25*C, 1800 rpm, 10s

iI

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