US3127346A - Dry lubricant composition and a - Google Patents

Dry lubricant composition and a Download PDF

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US3127346A
US3127346A US3127346DA US3127346A US 3127346 A US3127346 A US 3127346A US 3127346D A US3127346D A US 3127346DA US 3127346 A US3127346 A US 3127346A
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film
lubricant
sns
additive
sulfide
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M7/00—Solid or semi-solid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single solid or semi-solid substances
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
    • C10M2201/066—Molybdenum sulfide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/08—Solids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

Definitions

  • a type of lubricant to which this invention is more particularly directed is a solid or dry lubricant as differentiated from liquid and/or grease type lubricants.
  • a good example of a solid lubricant and bearing material is nylon or Teflon which are employed as bearings in relatively light applications.
  • Another example of a well known solid lubricant is graphite which, in flake or powder form, is maintained between relatively moving surfaces as a lubricant material.
  • Certain inorganic compounds i.e., the sulfides, disulfides, selenides and tellurides of such metals as molybdenum, tungsten, titanium, zirconium, uranium, etc., are characterized by a laminated or plate-like crystal structure in which the metallic atoms are arranged in a single common plane while the non-metallic atoms are attached to the metallic atoms to form layers on both sides of this plane.
  • the non-metallic atoms in each of the crystals in the sandwich structure have very little attraction for each other so that these crystals will slip readily with respect to each other under the action of low shearing forces.
  • non-metallic atoms have an affinity for adjacent metal surfaces so that the crystals attached to such surfaces will exhibit very strong resistance to the action of forces normal to the direction of shear. Consequenty, these compounds have excellent lubricating properties and also have excellent anti-seizing properties. These lubricants will be hereafter referred to as lamellar metal compound lubricants.
  • M05 and W8 molybdenum disulfide
  • M08 and W5 more particularly, have more pronounced disadvantages as dry lubricants including, first, they have a high wear rate and thus wear quite rapidly with continual replenishment being necessary; second, as the lubricant wears, large amounts of the material are accumulated between moving surfaces and may in some instances cause jamming or other undesirable effects. Furthermore, these lubricants have poor load carrying ability and their use is thereby restricted to light applications.
  • this invention provides additives for the lamellar metal compound lubricants as dry lubricants which increase the load carrying ability or decrease the wear rate while not adversely alfecting the lubrication characteristics.
  • FIG. 1 is a curve representing SnS mixtures.
  • the crystals of solid lubricant should be orientated with the planes of easy cleavage along the sliding direction. Such preferred orientation occurs in the case of films of the lamellar metal compound lubricants as described.
  • M08 is one of the more widely employed and satisfactory dry lubricants of the lamellar type.
  • Coefficient Disc Metal The values in Table I and the following tables were obtained by forming a solid lubricant film on various surfaces by rubbing. After a continuous film was formed on the metal surface, the M05 which provided the film was substituted by a further steel surface in the form of a A; inch diameter hemispherical rider, and the coefiicient of friction was measured between the rider riding and the film formed on the other metal surface. Tests were made in air, at room temperature and at a relative humidity of 30-35%. Speed was about 2 feet per second. It is noticeable that on chromium, and cast iron very high loadings were possible.
  • stannic sulfide SnS
  • a molybdenum disu-lfide film on mild steel can carry a load of only a few hundred grams, but when as little as by weight of stannic sulfide is present in a film to comprise by weight 90% M08 and 10% SnS the load carrying ability may be increased many times.
  • the breaking strength of the film was not exceeded.
  • Soft surfaces, such as copper and tin, show a relatively low breaking strength even with the stannic sulfide present.
  • the crystal structure of stannic sulfide is that of an inorganic layer lattice. This is a structure which is common to a number of inorganic solid lubricants, however, an investigation of frictional behavior of stannic sulfide indicates that this material has a high coefficient of friction on a large number of metallic surfaces, and thus is a poorer solid lubricant than M08 Typical behavior of a solid form of SnS sliding on various surfaces is shown in Table II as follows:
  • SnS is basically a poorer lubricant than M08
  • a sliding pellet of mixtures of SnS and M08 indicates a much lower coefiicient of (friction than that of an SnS pellet alone as indicated in the following table:
  • Tables II and III indicate the coefiicient of friction of pellets rubbing on a surface, they also are illustrative of the feature that adding SnS to M05 where SnS is a poorer lubricant than M08 does not greatly affect the coefiicient of friction of M08 alone. In addition, it was observed that the wear rate of the pellet was markedly low compared to M08 alone.
  • lubrication of 1090 steel, Table IV was increased over an application of M08 SNS film by providing a film of SnS and then superimposing a film of M08
  • the SnS should have a minimum of stannic oxide present or, alternatively, the oxide present, in any ratio of M08 and SnS should be of a small amount so as not to affect lubrication.
  • a sulfide is an effective additive to a lamellar metal compound lubricant provided that it is less thermodynamically stable than the sulfide of the surface material to which it is attached. For example, if a sulfide additive is to be employed with M08 to lubricate a steel shaft, then the additive must be thermodynamically less stable than FeS.
  • the contribution to the total frictional force may be small providing the area of such reaction film is also small.
  • the important property of the reaction film then is to prevent rapid propagation of film failure once a weak spot occurs. It is also believed that there is good adherence between the sulfide reaction film and the M lubricant. Therefore, the M05 may spread out more readily to cover the break. This reasoning is supported in that M08 showed excellent and rapid film forming on chemically sulfided surfaces.
  • Table VI sets forth numerous sulfides employed as additives to M08 as a dry lubricant. The particular technique for studying these films was the same as those employed previously. Mild steel was employed as the substrate in all instances. Tests were made in air, at room temperature, and at a relative humidity of about 30-35%. The additive concentration was standardized at 10% by weight of the pellet, and the rider in each instance was a inch diameter steel hemisphere. Compacting pellet pressure was about 26 tons per square inch for pellets in this as well as other tables.
  • Table VI are indicative, when compared to that of MoS on mild steel, that the load carrying ability of an MoS additive film is much greater than M05 without an additive.
  • the crystal structure of the additive is also a factor influencing the usefulness thereof.
  • Table VI it is noted that the black modification of I-lgS 6 is a less effective additive for M03 whereas the red modification is an outstanding additive.
  • Copper was chosen as exemplary for its good film forming properties. Additives lower the wear rate of the film considerably. Several operations on other metal surfaces, for example steel, indicate that wear rate is proportionately reduced.
  • the amount by weight of additive may vary for particular circumstances. For example, considering Wear rate, only a small percentage is necessary since a progressively higher wear rate is encountered when the amount of additive increases over that amount provid ing a minimum wear rate. Generally, a positive amount from about 0 to 50% provides a reduced wear rate from a minimum wear rate at about 2% and increasing at 50%. The wear rate at 50% additive, however, is still lower than M08 alone.
  • the wear rate of various mixtures of, for example, M05 and SnS is given in FIG. 1. Referring now to FIG. 1, it is understood that, as before mentioned, only a small amount of SnS or other additive is needed to markedly decrease the Wear rate, and additional amounts may be added to provide a wear rate which is still below that of M08 alone.
  • the wear rate factor is important because it may be decreased substantially without substantially affecting the lubrication characteristics of M08 alone. Curves for other mentioned additives are similar.
  • the dry lubricant of this invention may be applied to a given surface by means well known to those skilled in the art.
  • One preferred method is to employ the lubricant as a solid stick type of lubricant because in this form the stick may be made up without a binder which ordinarily limits the lubrication characteristics of stick lubricants.
  • Other means of application are numerous including, for example, providing a film of lubricant from a liquid mixture by spraying, dipping or otherwise coating a surface to be lubricated.
  • the shaft may be mounted in a lathe or other similar rotary apparatus and a small diameter pellet of the lubricant material, suitably attached to a holder is forced against the shaft and moves along the shaft to provide a film of desired width.
  • the force maintained between the lamellar metal compound lubricant and the surface to which the film is to be attached should be greater than the force usually contemplated in the term rubbing and in most instances is great enough to be just under the crumbling or breaking strength of the lamellar metal compound lubricant. Only a few passes 7 along the shaft are necessary, since a maximum buildup of the lubricant film is soon reached and no additional benefit is gained by further application.
  • Burnishing of the surface after application of the dry lubricant provides a marked improvement including that the burnishing action provides a much stronger bond between the lubricant and the surface, and that the film evidences long life with actual improvement in lubricating characteristics.
  • burnishing as employed is similar to the term as employed in the metal working art. Specifically, and for example, a dry lubricant film was applied to a shaft as described. Thereafter, a /8 inch diameter steel ball was pressed into the shaft just sufliciently to metal work the surface and one pass made over the dry lubricant area.
  • the shaft of a very small fan motor such as employed to maintain air circulation in freezers, having an applied burnished film of M08 has been in substantially continuous operation over a period of a year with no additional lubrication provided or necessary.
  • a preferred substrate for this burnishing method has been discovered to be chromium which is generally impervious, crack free, and maintained in a chemically clean state until just prior to the application of the lubricant film.
  • EXAMPLE I An M03 film was applied to a chromium plate as described above from pure pellets, a molykote microsize M08 A inch diameter pellet with an applied load of 2 kg. was rubbed on the plate at a speed of 100 feet per minute. Compacting pressure of the pellet was about -15 tons per square inch. A thin haze of MoS formed almost instantly followed by a slow increase as rubbing continued.
  • the film as obtained in the above example was burnished and tested by having a /8 inch diameter steel hemisphere loaded gradually from zero with 5 0100 gram increments while running on the film. This rubbing geometry imposed a severe test on the M08 film. Apparent areas of contact are quite small and in many instances, apparent pressures on the order of 50,000 p.s.i. are observed. This indicates a case of extreme pressure lubrication.
  • EXAMPLE II A film acquired in accordance with the teachings of Example I was utilized under tests as above described for a total time of 30 hours. During this run, exposure was made to water vapor in the range of partial pressures from 0 to 25 millimeter of mercury. At the termination of this test, the film was still intact with a coetficient of friction in dry nitrogen of .03.
  • the sulfide additives of this invention provide improved lubrication by way of increased load carrying ability, decreased wear rate and corresponding reduced film thickness without substantially affecting the coefiicient of friction. Therefore, the prime disadvantage of film thic. ness and high wear rate is minimized.
  • the pellets have a contact surface of about inch and were employed with 1.8 kilogram loading, unless otherwise indicated. Sliding speed was about 2 ft./sec. Copper plates were from commercial spinning grade copper sheet.
  • lamellar metal compound lubri cants refers to the general description of such lubricants as given in column 1 of this specification.
  • a method for applying a dry lubricant to a metal surface capable of forming a sulfide comprising the steps of:
  • a dry lubricant for application between juxtaposed surfaces at least one of which is a metal capable of forming a sulfide said lubricant comprising a mixture of at least one lamellar metal compound lubricant chosen from the group consisting of M08 W5 ZrS and TiS with at least one additive chosen from the group consisting of Sb S PtS, red HgS, Ag S, PbS, FeS, T i 8 Cu S, CuS, Au S, Bi S S, SnS black HgS, T1 8 Cr S CaS, BaS and CdS, provided that any additive employed must be less thermodynamically stable than the sulfide of the metal surface being lubricated and less thermodynamically stable than the lubricant material chosen.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Lubricants (AREA)
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3173045A (en) * 1960-03-23 1965-03-09 Gen Electric Electric current collection and delivery apparatus for dynamoelectric machine
US3297572A (en) * 1964-09-01 1967-01-10 Gen Electric Graphite lubricating composition of increased load carrying capacity
US3301780A (en) * 1964-05-05 1967-01-31 Gen Electric Preparation of compacted body of improved lubricating agents
US3344065A (en) * 1965-01-25 1967-09-26 Molykote Produktions G M B H Extreme pressure lubricants
US3377279A (en) * 1964-07-22 1968-04-09 Molykote Produktions G M B H Method of preparing lubricants
US3549217A (en) * 1968-11-29 1970-12-22 Nalco Chemical Co Center plate lubricating device
US3769098A (en) * 1971-05-19 1973-10-30 Kito Kk Process of manufacturing fine powders of metal halide
WO1995002657A1 (fr) * 1993-07-14 1995-01-26 Chemson Polymer-Additive Gesellschaft M.B.H. Additif de lubrifiant solide pour melanges destines a des garnitures de friction a agglomerant resinoïde
JP2022548662A (ja) * 2019-09-18 2022-11-21 ゲーカーエン ドライブライン インターナショナル ゲゼルシャフト ミト ベシュレンクテル ハフツング 硫化銅を含む等速ジョイント用グリース組成物
US11725158B2 (en) 2019-09-18 2023-08-15 Gkn Driveline International Gmbh Grease composition for constant velocity joints
US11732209B2 (en) 2019-10-30 2023-08-22 Gkn Driveline International Gmbh Grease composition

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1254275B (de) * 1962-08-22 1967-11-16 Robert Tedden Schmierfette
DE1261975B (de) * 1962-08-29 1968-02-29 Robert Tedden Schmiermittel

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2156803A (en) * 1934-05-03 1939-05-02 Cooper Products Inc Lubricant
US2367946A (en) * 1942-12-15 1945-01-23 Westinghouse Electric & Mfg Co Process of producing metallic disulphides, tellurides, and selenides
US2420886A (en) * 1942-12-03 1947-05-20 Westinghouse Electric Corp Application of solid lubricant coatings to surfaces
US2421543A (en) * 1945-01-19 1947-06-03 Union Oil Co Lubricant
US2609342A (en) * 1949-12-03 1952-09-02 Socony Vacuum Oil Co Inc Lubricant
US2622993A (en) * 1949-08-03 1952-12-23 Deering Milliken Res Trust Process of lubricating metal surface and article resulting therefrom
GB794982A (en) * 1954-11-26 1958-05-14 Birmingham Small Arms Co Ltd Improvements in or relating to solid lubricants

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2156803A (en) * 1934-05-03 1939-05-02 Cooper Products Inc Lubricant
US2420886A (en) * 1942-12-03 1947-05-20 Westinghouse Electric Corp Application of solid lubricant coatings to surfaces
US2367946A (en) * 1942-12-15 1945-01-23 Westinghouse Electric & Mfg Co Process of producing metallic disulphides, tellurides, and selenides
US2421543A (en) * 1945-01-19 1947-06-03 Union Oil Co Lubricant
US2622993A (en) * 1949-08-03 1952-12-23 Deering Milliken Res Trust Process of lubricating metal surface and article resulting therefrom
US2609342A (en) * 1949-12-03 1952-09-02 Socony Vacuum Oil Co Inc Lubricant
GB794982A (en) * 1954-11-26 1958-05-14 Birmingham Small Arms Co Ltd Improvements in or relating to solid lubricants

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3173045A (en) * 1960-03-23 1965-03-09 Gen Electric Electric current collection and delivery apparatus for dynamoelectric machine
US3301780A (en) * 1964-05-05 1967-01-31 Gen Electric Preparation of compacted body of improved lubricating agents
US3377279A (en) * 1964-07-22 1968-04-09 Molykote Produktions G M B H Method of preparing lubricants
US3297572A (en) * 1964-09-01 1967-01-10 Gen Electric Graphite lubricating composition of increased load carrying capacity
US3344065A (en) * 1965-01-25 1967-09-26 Molykote Produktions G M B H Extreme pressure lubricants
US3549217A (en) * 1968-11-29 1970-12-22 Nalco Chemical Co Center plate lubricating device
US3769098A (en) * 1971-05-19 1973-10-30 Kito Kk Process of manufacturing fine powders of metal halide
WO1995002657A1 (fr) * 1993-07-14 1995-01-26 Chemson Polymer-Additive Gesellschaft M.B.H. Additif de lubrifiant solide pour melanges destines a des garnitures de friction a agglomerant resinoïde
JP2022548662A (ja) * 2019-09-18 2022-11-21 ゲーカーエン ドライブライン インターナショナル ゲゼルシャフト ミト ベシュレンクテル ハフツング 硫化銅を含む等速ジョイント用グリース組成物
US11725158B2 (en) 2019-09-18 2023-08-15 Gkn Driveline International Gmbh Grease composition for constant velocity joints
US11732209B2 (en) 2019-10-30 2023-08-22 Gkn Driveline International Gmbh Grease composition

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