CA1338292C

CA1338292C - Elastomer ptfe composition, articles, and manufacturing methods

Info

Publication number: CA1338292C
Application number: CA000505522A
Authority: CA
Inventors: William Everett Peters
Original assignee: Alphaflex Industries Inc
Current assignee: Alphaflex Industries Inc
Priority date: 1985-12-09
Filing date: 1986-04-01
Publication date: 1996-04-30
Anticipated expiration: 2013-04-30
Also published as: KR880700691A; EP0248898A1; JPS63501726A; AU588091B2; NO873311D0; DK413487D0; WO1987003515A1; AU7022887A; EP0248898A4; NO873311L; BR8607025A; US4962136A; DK413487A

Abstract

Compositions are disclosed containing an elastomer, particulate polytetrafluoroethylene and an amount of molybdenum disulfide effective to permit their manufacture. The particulate polytetrafluoroethylene may include amounts from 25 percent by weight to 80 percent by weight, and/or include small amounts of fibrillated polytetrafluoroethylene. Also disclosed are additives for such compositions, and methods for preparing such compositions and additives using polytetrafluoroethylene and molybdenum disulfide, and improved compositions and products. Compositions and products of the invention can also be provided with the advantages of many of the unique properties of polytetrafluoro-ethylene combined with the advantageous properties of elastomers.
Among the properties of PTFE that may be realized in such compo-sitions and products are chemical inertness and stability, insolu-bility, heat resistance, electrical insulation and surface lubricity and abrasion resistance, and these properties may be incorporated into an elastic article or product.

Description

ELASTOMER PTFE COMPOSITION, ARTICLES, AND MANUFACTURING METHODS
BACKGROUND OF THE INVENTION
This invention relates to new compositions, articles comprised of new compositions and new methods of manufacture. More particularly, this invention re-lates to elastomer-polytetrafluoroethylene compositions and additives, methods of manufacture, and articles manufactured with such compositions having remarkably increased durability in their applications.
It has long been a desire to combine the prop-erties of an elastomer, such as rubber, and polytetra-fluoroethylene, referred to frequently as PTFE. Past efforts to manufacture compositions with beneficial combined properties have not been wholly successful.
In addition, the past attempts to incorporate PTFE into rubber, for example, have been generally limited to attempts and compositions containing no more than 20 percent by weight of PTFE. Such compositions have failed to provide a sufficient combined benefit from the properties of PTFE and elastomers to have great commercial importance. Higher percentages of PTFE could not be obtained because of the inability to uniformly mix the PTFE particulate matter with the elastomer com-position. It is believed the difficulty of obtaining uniform mixtures and higher percentages of PTFE were the result of PTFE's unique properties, and probably the propertles of lts surface whlch reslst wettlng. Because of these propertles, unlform mixlng and bondlng of PTFE partlculate materlal and natural and synthetlc rubbers have not been achleved ln composltlons wlth any commerclally slgnificant incorporation of PTFE.
~UMMARY OF THE INVENTION
This invention is based on the discovery of new compositions, includlng an elastomer, for example, a natural or synthetic rubber, polytetrafluoroethylene, and an amount of molybdenum disulfide effective to provide a uniform mixing of the polytetrafluoroethylene and the elastomer.
Accordlngly, the present lnvention provides a substantially uniform composition comprising:
(a) from about 2 to about 80 percent by weight polytetra-fluoroethylene;
(b) from about 1 to about 30 percent by weight molybdenum disulflde; and (c) an elastomeric material.
In one embodiment the compositlon comprises:
(a) about 25-80 percent polytetrafluoroethylene;
~b~ about 1-30 percent molybdenum dlsulflde; and (c) the balance of an elastomerlc material.
In another embodiment, the composltion comprises (a) about 2 to about 6 percent fibrillated polytetra-fluoroethylene;
(b) an effective amount of molybdenum disulfide; and (c) the balance of an elastomeric material.

1338~92 71035-12 The present lnventlon also provldes a method of lncorporatlng partlculate materlal lnto an elastomer, comprlslng:
placlng together a quantlty of elastomer and from about 2 percent to about 80 percent by welght partlculate polytetra-fluoroethylene materlal, addlng from about 1 percent to about 30 percent by welght molybdenum dlsulflde, and mechanlcally mlxlng together the elastomer, partlculate polytetrafluoroethylene materlal, and the molybdenum dlsulflde to obtaln a unlform dlsperslon of the partlculate polytetrafluoro-ethylene materlal ln the elastomer.
The present lnventlon further provldes a method of lmprovlng the physlcal propertles of elastomerlc composltlons, the lmprovement comprlslng addlng to the elastomerlc composltlon as lt ls belng mlxed polytetrafluoro-ethylene partlcles capable of flbrlllatlon and molybdenum dlsulflde partlcles and shearlng the polytetra-fluoroethylene partlcles ln the presence of the molybdenum dlsulflde partlcles ln mlxlng to flbrlllate the polytetrafluoroethylene partlcles and mlx the flbrlllated polytetrafluoroethylene and molybdenum dlsulflde partlcles unlformly wlthln the elastomerlc composltlon.
The present lnventlon yet also provldes an addltlve for elastomer composltlons, comprlslng:
partlculate polytetrafluoroethylene and partlculate molybdenum dlsulfide, sald partlculate molybdenum dlsulflde havlng an average partlcle slze substantlally smaller than the average partlcle slze of sald partlculate polytetrafluoroethylene and ln .~ ~

133%292 substantlal part adherent to sald partlculate polytetrafluoro-ethylene, whereln sald molybdenum dlsulfide comprlses at least about 0.5 parts by welght per part of partlculate polytetra-fluoroethylene.
New composltlons lncludlng about 2 percent to about 6 percent of such flbrlllated PTFE, an effectlve amount of moly-bdenum dlsulflde, and an elastomer, such as natural or butyl rubber, can provlde composltlons wlth exceptlonal durablllty and llfe wlthout loss of thelr elastic and frlctlonal characterlstlcs, wlth a total polytetrafluoroethylene content of up to about 12 percent. The lnventlon can lmprove many physlcal propertles of elastomers and can be used to extend and strengthen more expenslve elastomer.
Composltlons and products of the lnventlon can also be provlded wlth the advantages of many of the unlque propertles of polytetrafluoroethylene comblned wlth the advantageous propertles of elastomers. Among the propertles of PTFE that may be reallzed ln such composltlons and products are chemlcal lnertness and stablllty, lnsolublllty, heat reslstance, electrlcal lnæulatlon and surface lubrlclty and abraslon reslstance;

D 2b ~ . L

~ _3_ 1338~92 and these properties may be incorporated into an elastic article or product. The invention may be considered as permitting the advantages of the unique properties of elastomers to be imparted to polytetrafluoroethylene, the most advantageous of such properties being elasticity and "memory," recovery from deformation.
The invention is particularly effective in increasing the life of products that are exposed to repeated flexure through the application of compression and tensile forces. Even small amounts, i.e., 2 percent to 6 percent, of fibrillated PTFE uniformly mixed in elastomer compositions can provide unexpected increases in durability and life. In such applications, elasto-meric products particularly fail through the accumula-tive effects of heat generated within the products as a result of such recurrent forces; that is, such products frequently fatigue and fail through the heat loss repre-sented by the hysteresis of their elastic deformation.
It is believed that internally generated heat, probably the result of internal friction accompanying the flexure of the elastomeric material, effects a gradual change in the composition, particularly in its physical prop-erties, and provides a progressive failure. With com-positions of the invention, products subject to such fatigue failures can be manufactured with useful lives several times those of products manufactured with prior elastomeric compositions. Such products include auto-mobile and aircraft tires, pads for the tracks in mili-tary tanks, shock absorbers, O-rings, and the like.
Where lubricity is undesirable, such as in the manufac-ture of tires for automobiles, aircraft, and other vehicles, the total PTFE content of the composition is preferably less than about 12 percent. However, the invention also permits an elastic product having a lubricious surface and can provide particularly effec-tive O-rings, bearing-seals and the like.

~- _4_ 1338292 Thus, this invention is also based on the discovery that the form of the particulate polytetra-fluoroethylene can be of particular importance in im-proving elastomers, such as EPsyn~55 sold by Copolymer Rubber & Chemical Corporation and silicone rubber, hav-ing low tensile strengths and low moduli of elasticity, and particularly that small amounts of fibrillated PTFE, such as TEFLON~K-10 sold by E. I. du Pont de Nemours and FLUON~CD1 sold by ICI Americas, when mixed into such elastomers, can improve their tensile strength or their moduli of elasticity or both, particularly at high temperatures, both in the presence of PTFE in other forms and in the base elastomers. It has been dis-covered that fibrillated PTFE is so effective in such compositions that only a small weight percentage of about 4 percent (i.e., 2-6 percent) is necessary to achieve the substantial benefits of the component.
Such small amounts of fibrillated PTFE can even signif-icantly improve the moduli of elasticity of elastomers with high tensile strengths, such as nitrile rubber and butadiene acrylonitrile, and again this improvement in the modulus of elasticity continues at elevated temper-atures. Products where such improved compositions are important include, for example, O-rings, lip seals for hydraulic and pneumatic cylinders, seals for pumps, valves, and other such hydraulic components.
It should be understood that reference to "fibrillated PTFE" in this and my prior applications means PTFE that is fibrillated in the body of my compo-sition. Such "fibrillated PTFE" is manufactured as a coagulated dispersion polymer which may fibrillate under shear and is thus capable of fibrillation. As purchased, the fibrillated PTFE are coagulated dispersion polymer particles. FLUON CD1 manufactured by ICI Americas, ~Trade~

- 133829~

Inc., is one such fibrillated PTFE. Such PTFE is pref-erably added to the mixer and fibrillated as it is mixed with the other components of the composition.
The invention permits a combination of the physical properties of elastomers and PTFE to obtain their desirable physical properties and permits the development of new products with strikingly improved durability and performance in many applications.
It has been discovered that the presence of effective amounts of molybdenum disulfide will permit the manufacture of such compositions with significant and effective combinations of polytetrafluoroethylene and elastomers. It is believed that the molybdenum disulfide permits elastomers to wet the extensive sur-face of particulate polytetrafluoroethylene, permitting the intimate dispersion and mechanical interaction of the elastomer and PTFE in percentages of polytetrafluoro-ethylene which can be greater than 25 percent by weight of the total composition.
It has also been discovered that effective amounts of molybdenum disulfide will permit the intimate mixing of solid components with elastomers with a re-duced heat buildup and a reduced loss of elastomer scorch safety, not only with PTFE particulate matters but with other particulate matter, including granular, flaked and powdered fillers and fibrous materials such as cotto~ and rayon fibers. Compositions of this inven-tion are thus the result of a method comprising mixing together an elastomer, such as natural or synthetic rubber, particulate material, preferably including PTFE
powders capable of fibrillation, and an amount of molybdenum disulfide that is effective to uniformly incorporate the particulate material, and most particu-larly the fibrillated PTFE, in the elastomer material.
Effective amounts of molybdenum disulfide lie in the range from about 3 percent to about 30 percent by 13~829~

weight of the composition, and are determined by addition to the composition as it is being mixed. The amount of molybdenum disulfide which is effective appears to depend upon the quality and nature of the particulate material and the quantity of molybdenum disulfide. In making a composition with lower amounts of polytetrafluoroethylene, e.g., about 2-6 percent of fibrillated PTFE, the amount of molybdenum disulfide may be approximately equal to about 1.25 parts of molybdenum disulfide per part of fibrillated PTFE.
Where the particulate PTFE in the composition is not in fibrillated form, about 0.75 parts of molybdenum disulfide per part of PTFE may be used. At higher amounts of polytetrafluoroethylene, e.g., about 35-40 percent, the amount of molybdenum disulfide can be sub-stantially reduced to the range of 0.5 to 0.6 parts of molybdenum disulfide per part of PTFE.
A number of products may be molded from com-positions resulting from such a method of manufacture and cured (or vulcanized) to provide an elastic solid product with improved physical properties as a result of the quantity of particulate material such as poly-tetrafluoroethylene incorporated into the composition of the product.
One product of this invention comprises an improvement for watercraft and a method for enhancing efficient movement through water, an outer hull covering for such watercraft comprising a layer made of a compo-sition containing about 25-80 percent polytetrafluoro-ethylene, about 1-30 percent molybdenum disulfide, and the balance of an elastomeric material. In this context, all percentages in this application are given by weight of the total composition unless otherwise indicated.
In its most preferred form, this covering layer and method were prepared as a substantially 7 1338~9~

homogenous combination of about 50 percent reprocessed polytetrafluoroethylene powder, about 20 percent molyb-denum disulfide, and the balance (about 30 percent) of ethylene- propylene terpolymer as the base elastomer.
The composition was cured by standard procedures to form a layer having a preferred thickness of about one-half inch. The layer material was pressed, formed, and cut into patterned sheets which were later assembled to form a continuous, adherent covering on a metal sub-strate such as the outer hull or surface of a watercraft.
The preferred layer material provides a hard, durable, and resilient covering that requires little maintenance and provides improved sound insulation and ease of repair. It provides anti-fouling assistance and enhances speed and energy efficiency by substan-tially lowering the coefficient of friction of the outer surface and reducing drag due to water resistance to movement by the watercraft. Its uses are broad, includ-ing all types and sizes of watercraft and other struc-tures from rowboats and surfboards to sailboats, ocean liners, tankers, conventional and atomic-powered sub-marines and other military vessels and to wharfs, docks, buoys, and the like. Other uses include as sound mountings for various types of equipment and as O-ring seals, valves, fittings, and many uses in the rubber industry. The substrate or surface to which applicant's covering layer adheres can be metal, natural or syn-thetic rubber, plastic, fiberglass, concrete, wood or other material.
Related objects and advantages of the present invention will be apparent from the following more de-tailed description.

DESCRIPTION OF THE PREFERRED EMBODIMENTS
For purposes of promoting an understanding of the principles of the invention, reference will now be -8- 133 8~ 92 made to the preferred embodiments; and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended, such alterations and further modifications of such embodiments, and such further applications of the principles of the invention being contemplated as would normally occur to one skilled in the art to which the invention relates.
The invention permits the modifications of the physical properties of elastomeric materials, and particularly rubber and synthetic rubber, and in some applications, such as an outer hull covering as a result loading in the base elastomeric material at least about 25 percent polytetrafluoroethylene and an amount of molybdenum disulfide. In another sense, with high PTFE
percentages, the invention can be considered as lending the elasticity and memory of elastomeric materials to a material with polytetrafluoroethylene properties.
In a preferred form, the composition of the invention contains about 25-80 percent polytetrafluoro-ethylene, about 1-30 percent molybdenum disulfide, and the balance of an elastomeric material; a still more preferred composition range for the components of this invention is about 25-50 percent polytetrafluoroethylene, about 3-20 percent molybdenum disulfide, and the balance of elastomeric material. A preferred composition for exposure to sea water contains 50 percent polytetra-fluoroethylene, about 20 percent molybdenum disulfide, and the remaining about 30 percent of a base elastomer comprising ethylene-propylene terpolymer resin. A por-tion, preferably no more than about 4 percent, of the PTFE may be fibrillated PTFE.
Ethylene-propylene terpolymer resin is a syn-thetic rubber and is known for its versatility and re-sistance to long-term water immersion, and particularly 1338~92 g for its resistance to degradation by sea water. It is readily vulcanized, using, for example, a sulfur and peroxide curing agent and has been used in the past for such things as automotive parts, cable coatings, hoses, footwear, and other products. The specific ethylene-propylene terpolymer compound usable in such composi-`B~ tions is a NORDEL~brand marketed by E. I. du Pont de Nemours Co., Inc. Such a composition is particularly preferred for use in sea water and in such applications as outer hull coverings for watercraft. Other elas-tomers work as a base material, particularly with other applications. For example, natural rubber works as an effective base material for use in fresh water.
Polytetrafluoroethylene may be that commonly known by the federally registered trademark TEFLON which is the name for compounds marketed by E. I. du Pont de Nemours Co., Inc.; FLUON which is the name for compounds marketed by ICI Americas; and WHITCON 2 which is the name of a particulate powder marketed by ICI Americas.
Such materials are recognized for heat resistance and friction-reduction as when used, for example, on the surfaces of kitchen utensils and for other mechanical applications. Such materials are available in various forms. This more common form of particulate PTFE is manufactured by grinding or fracturing larger PTFE par-ticles into powdered particulate PTFE. A base elastomer can be, for example, loaded with a reprocessed poly-tetrafluoroethylene in the form of a cryogenically ground powder. TL-115A is a specifically usable com-pound and is a trademark designation for the compound manufactured by LNP Corp. of Malvern, Pennsylvania, and marketed by HARDWICK of 60 S. Seiberling Street, Akron, Ohio 44305. TL-115A is known for its bearing charac-teristics as an additive in thermoplastic and thermoset polymeric systems. It has an irregular particle shape ~ a~ rk -lo- 1~38292 ranging in size from about 2-45 microns, although par-ticles substantially larger in size up to at least about 75-100 microns work in applicant's invention without appreciably affecting surface texture or drag coeffi-cient; for example, in the hull coverings for watercraft.
As previously stated, the amount of polytetrafluoro-ethylene loading in a preferred composition varies from the broad range of at least about 25 percent to an amount of about 50 percent which is presently most preferred as a covering layer for use in sea water. One charac-teristic of this most preferred composition is its hard-ness of about 80-90 durometer which is beneficial not only for durability, but also for drag coefficient and sound attenuation properties.
The third component of the composition of this invention is molybdenum disulfide in the preferred ranges previously specified. The specific molybdenum disulfide is technical grade powder in the form of flat crystals which are added to the base elastomer and the polytetrafluoroethylene components to arrive at the final composition. Of course, alternate embodiments can include fillers such as conventional pigments and others; and the same are within the scope and contem-plation of applicant's invention as disclosed and claimed herein.
The method of preparing one preferred compo-sition is first to combine the various dry ingredients to arrive at a substantially homogeneous combination.
A curing agent is added, and the mixture is placed in a reaction vessel appropriate for vulcanizing resins of this type. The component is cured, i.e., vulcanized, using standard procedures by applying heat and pressure for a specified period of time. A standard 24" X 24"
O-ring press can be used to cure the compound in the shape of a flattened layer or sheet. In commercial use, the material can be calendered or otherwise pressed and cured into appropriately sized sheet stock from which modular panels can be cut or otherwise shaped.
In making such compositions with fibrillated PTFE, the fibrillated PT~E, such as ICI Americas's FLUON
CDl, or du Pont's TEFLON~k-10, is preferably added to the mixer (e.g., a Banbury~ ill) as purchased, that is, in particulate form. In mixing of the composition, this PTFE component of the composition is fibrillated uniformly in the composition; and it lends surprising durability to the composition and strengthens many elas-tomer components that are made from such compositions.
The particulate polytetrafluoroethylene and molybdenum disulfide make a highly desirable and novel additive for elastomeric compositions. In preparing such additives, particulate polytetrafluoroethylene and particulate molybdenum disulfide are placed together in a mixing apparatus, such as a rotating mixing barrel, and tumbled and intermixed together. Preferably, the particle size of the molybdenum disulfide particles is generally several times smaller than the particle size of the particulate polytetrafluoroethylene. For example, where the average particle size of the polytetrafluoro-ethylene lies in the range of 2-45 microns, the average particle size of the molybdenum disulfide will be about one-third to one-tenth that of the particulate polytetra-fluoroethylene or smaller. The particulate matter is mixed together for a sufficient time that the molybdenum disulfide particles are generally adherent to the poly-tetrafluoroethylene particles, and the mixture particles become uniformly grey-black in appearance. As an example, 150 pounds of additive material was obtained with fifteen minutes of agitation and mixing. The ad-herence of the molybdenum disulfide particles to the particulate polytetrafluoroethylene is believed to be due to an electrostatic charge differential that may be developed between the polytetrafluoroethylene particles - 1338~92 and the molybdenum disulfide particles while they are being mixed together.
In order to permit better formulation and mixing of many varied compositions and more effective use of the molybdenum disulfide, it is preferred to produce two additives: one with fibrillated polytetra-fluoroethylene and one with particulate polytetrafluoro-ethylene. In preparing the additives with fibrillated polytetrafluoroethylene, typically approximately equal parts of particulate molybdenum disulfide and fibrillated polytetrafluoroethylene are mixed together although a greater proportion of molybdenum disulfide may be used. In preparing the additives with granular polytetrafluoroethylene, lesser amounts of molybdenum disulfide may be used, typically about one-half part of molybdenum disulfide per part of granular polytetra-fluoroethylene may be used for many applications.
The use of such polytetrafluoroethylene-molyb-denum disulfide additives is preferred in making the compositions of this invention. The prior association of molybdenum disulfide particles with polytetrafluoro-ethylene particles greatly assists the uniform mixing of the particulate polytetrafluoroethylene into the elastomer, particularly where the elastomer composition will include fibrillated polytetrafluoroethylene, which is more difficult to mix into the elastomer. The molyb-denum disulfide associated with the surface of the poly-tetrafluoroethylene particles is believed to enhance the entry of the polytetrafluoroethylene particles into the elastomer and deter adherent association of the polytetrafluoroethylene particles with themselves.
In the generally preferred procedure for pre-paring elastomer compositions of this invention with elastomers such as fluorohydrocarbons, natural rubber buna N, SBR, EPDM, and the like, the elastomer composi-tion, carbon black, and other components, except curing agents, are first mixed, for example, on a Banbury mixer.
The additive with fibrillated polytetrafluoroethylene is then added on the mixer and mixing continues until the temperature of the mixture begins to rise sharply.
The additive with granular polytetrafluoroethylene, where used, is then added to the mixer; and mixing con-tinues until the temperature, rheology and appearance indicate that a uniform mixture has been achieved. The fibrillated polytetrafluoroethylene is best uniformly mixed and fibrillated in the composition by this pro-cedure, where it is added to the elastomer first on the mixer and before any curing agents are added. The mixed composition is then sheeted by running it through a mill in several passes, turning ninety degrees between each pass as commonly practiced in the art. The sheeted mixture should have a uniform corrugated surface ap-pearance and should not show shiny spots.
The sheeted mixture is then chopped for a second pass through the mixer and the addition of curing agents. After the curing agents are uniformly mixed into the elastomer polytetrafluoroethylene composition, the entire composition is milled, sheeted, and cooled in manner common to elastomer preparation and is ready to use.
Where elastomers, like silicone, with no in-tegrity in the base elastomer are formulated with this invention, mixing of the fibrillated polytetrafluoro-ethylene additive is first accomplished on a mill.
Such base elastomers are given integrity by the fibril-lated polytetrafluoroethylene and the initial mixing continues on the mill until the elastomer resembles rubber. Mixing of such elastomer compositions continues with the procedure described above, but in a mill rather than a mixer. It is possible, however, that sufficient integrity may be obtained that mixing of the elastomer composition may be accomplished on a Banbury mixer. As - 1~38292 set forth above, to avoid loss of scratch resistance, any curing agents should be added in a second mixing pass after the particulate polytetrafluoroethylene has been uniformly mixed with the elastomer.
It is also possible to mix polytetrafluoro-ethylene-molybdenum disulfide additives with base elas-tomers that are in emulsion form. The additives can be uniformly mixed with the fluid elastomer emulsion; and where fibrillated polytetrafluoroethylene particles are used, they will become fibrillated as the base elastomer is later mixed with other components.
For the purpose of promoting a better under-standing of the invention, the following examples are given of specific compositions of the invention and their methods of preparation.
Example 1 A 100 g amount of applicant's composition was compounded by combining 50 percent by weight TL-115A
polytetrafluoroethylene powder with 20 percent by weight molybdenum disulfide crystals and with 30 percent by weight NORDEL ethylene-propylene terpolymer resin in a container. The dried ingredients were thoroughly blended to arrive at a substantially homogeneous mixture, and a standard peroxide curing agent was added. The compound was placed in an O-ring press having a 24-inch square bed and was heated for ten minutes at 350 F.
The resulting vulcanized sheet material was dark grey in color, was 0.1 inch thick and tested at a hardness level of 85-90 durometer.
Example 2 A 100 g amount of applicant's composition was compounded by combining 25 percent by weight TL-115A
polytetrafluoroethylene powder with three percent by weight molybdenum disulfide and 72 percent by weight NORDEL ethylene-propylene terpolymer resin. The in-gredients were blended and cured as in Example 1.

Several ring-shaped pieces were molded from this mate-rial and were found to work effectively as O-rings in various mechanical applications.
Examples 3, 4, 5, 6, 7, 8 The effect of inclusion of the invention in ethylene propylene terpolymer elastomers, such as Copolymer Rubber & Chemical Corporation's EPsyn R 55, can be observed from the following examples and tests.
Composition samples were prepared with 100 parts of the base elastomer mixture which included 100 parts of a composition sold by Copolymer Rubber & Chemical Corporation under its registered trademark EPsyn 55 and other standard ingredients of such elastomer composi-tions. Example 3 sets forth the test of this composi-tion for comparison with the invention. In the compo-sition of Example 4, 50 parts of particulate PTFE, such as WHITCON 2 of ICI Americas, was added to the basic elastomer mixture of Example 3 with an effective amount of molybdenum disulfide. In Example 5, 100 parts of WHITCON 2 were added to the basic elastomer mixture of Example 3 with an effective amount of molybdenum disulfide. In Example 6, four parts of fibrillated PTFE, such as FLUON CDl sold by ICI Americas, was added to the basic elastomer mixture of Example 3 with an effective amount of molybdenum disulfide. In Example 7, 46 additional parts of particulate PTFE, such as WHITCON 2, were added to the mixture of Example 6 with an effective amount of molybdenum disulfide to make a total of 50 parts of PTFE in the composition. In Example 8, 96 additional parts of WHITCON 2 were added to the compo-sition of Example 6 with an effective amount of molyb-denum disulfide to provide a total of 100 parts of PTFE
in the composition. The physical properties, tensile strength, elongation, modulus, and hardness of the com-positions of Examples 3-8 are presented in the table below.

13~8292 E~oeLE 3 4 5 6 7 8 Rheograph Properties Model 100 320F. 30 Minute Motor Min. Torque, in.-lbs.9.1 9.5 10.7 9.7 11.0 12.0 Max. Torque, in.-lbs.60.059.5 60.8 89.2 88.5 89.4 T2, minutes 3.0 3.1 3.2 3.0 2.8 2.7 Tgol minutes 17.8 14.5 13.2 19.0 16.7 16.7 Press Cure@

Tensile, psi @ RT 15' 725 1075 900 1075 1025 875 @ 300F. 15' 350 425 400 500 475 450 ~l~ngAtion, % @ RT 220 470 410 380 400 370 @ 300F. 110 160 140 110 150 150 100% Modulus, psi @ RT 475 325 325 500 475 450 @ 300F. 325 350 350 475 425 400 Hardness, Shore A @ RT 67 69 69 70 71 75 As can be determined from comparison of this data, the tensile strength at room temperature and at 300 F. of the composition of Examples 4-8 are substan-tially improved compared with the basic elastomer mixture of Example 3. Furthermore, the inclusion of only four parts of fibrillated PTFE in such compositions will provide them with tensile strength at room tempera-ture and at 300 F. which is substantially better than the basic elastomer mixture, and the improvement in tensile strengths of the compositions with fibrillated PTFE are particularly significant at elevated tempera-tures such as 300 F. In addition to the significant improvement in the tensile strengths of such elastomer mixtures, the inclusion of four parts of fibrillated PTFE in the compositions of Examples 6-8 substantially improve the modulus level elasticity of the composition, both at room temperature and at 300 F. Elongation of the compositions of Examples 4-8 is also substantially mproved .

Examples 9, 10, 11, and 12 The effect of the invention in silicone elastomer compositions is shown in a comparison of Examples 9-12 and the results of their testing.
Example 9 is a silicone rubber composition including additives. Example 10 is a composition including the silicone rubber composition of Example 9 with the addition of 100 parts of particulate polytetrafluoro-ethylene such as WHITCON 2 and an effective amount of molybdenum disulfide. Example 11 is the mixture of the silicone rubber composition of Example 9 with four parts of fibrillated PTFE, such as FLUON CD1 and an effective amount of molybdenum disulfide. Example 12 is the silicone rubber-fibrillated PTFE mixture of Example 11 with 96 additional parts of particulate PTFE
such as WHITCON 2 and an effective amount of molybdenum disulfide. The physical properties of the compositions of Examples 9-12 are presented below.

E ~ PLE 9 10 11 12 Rheograph Properties Model 100 320F. 60 Minute Motor Min. Torque, in.-lbs. 22.2 16.6 23.0 14.5 Max. Torque, in.-lbs. 57.8 45.8 38.0 29.7 T2, minutes 1.1 1.1 1.6 1.2 Tgo l minutes 4.3 4.9 4.7 4.2 Press CureQ

Tensile, psi @ RT 6' 800 475 2575 275 @ 300F. 6' 500 350 400 200 Flon~tion, % @ RT 100 110 50 20 @ 300F. 70 90 40 40 100% ~k~ , psi @ RT 800 425 --- ___ @ 300F. --- --- --- ---Hardness, Shore A @ RT 80 82 80 79 These compositions demonstrated chemical inertness, stability, heat resistance, surface lubricity, and abrasion resistance. Silicone elastomer composi-tions of this invention can be formulated having tensile strengths and tear strengths many times greater than the original elastomer. Such elastomers can provide tensile strengths and tear strengths that are two to three times greater than that of the silicone elastomer itself without loss of the chemical inertness, stability, heat resistance, and electrical insulating properties of the silicone elastomer, and with improved abrasion resistance.
Silicone compositions of the invention can provide substantially improved electrical insulation, particularly in applications such as insulation for spark plug wires. In such applications, the improved silicone elastomer of this invention surrounds in a generally concentric fashion the conductor carrying the high voltage necessary to produce a spark in the spark plugs of an automobile. The spark plug wires must operate adjacent the engine block of the automobile which now runs much better because of the emission limitation and gasoline efficiency requirements of the United States, and must insulate the high voltage conductor from the engine parts. Electrical conductivity of electrical insulating materials in most cases increases substantially with temperature, and this is generally true of electrically insulating elastomers.
Because of the higher temperatures at which automobile engines now operate, many elastomers previously used as insulation for spark plug wires are no longer reliable insulators in that application; and silicone elastomers, which are generally more expensive than the prior elastomers in use, are used because of their more reliable electrical insulating properties at higher temperatures. Silicone spark plug wire insulation is, 1338~9~
, however, subject to mechanical failure due to pulling,tearing, and abrasion because of its generally poor physical properties. With this invention, the physical properties of the silicone elastomer can be substantially improved in this application. Silicone polytetrafluoro-ethylene elastomers of this invention can double or triple the tensile strength, tear strength, and abrasion resistance of silicone elastomer spark plug wire insulation, with no significant loss in heat resistance or electrical insulating properties, and can substan-tially extend the reliability and, it is believed, the life of silicone elastomer electrical insulation.
The improved silicone elastomer compositions of this invention have extended applicability to products in which substantially more expensive elas-tomers are now used because of the unique properties of the silicone elastomer and polytetrafluoroethylene and may permit a substantial reduction in the cost of such products. In addition, the invention can provide similar improvements in other electrically insulating elastomers because of the heat resistance, chemical inertness, and electrical insulating properties of the polytetrafluoroethylene. Elastomers of this invention can provide excellent cable and wire insulation. In addition to the aforementioned properties, the invention can provide a flexible and tough cable or wire insula-tion with improved surface lubricity which will permit a cable to be pulled through conduit with greater ease and reliability. With the invention, elastomers less expensive than silicone elastomers may once again be usable for automotive spark plug wire insulation.
Examples 13, 14, 15, 16, 17, and 18 Examples 13-18 permit a comparison of the effect of the invention in nitrile rubber compositions, such as Copolymer Rubber & Chemical Corporation's COPO 1500. Example 13 is a standard nitrile rubber 13382~2 mixture including 100 parts of nitrile rubber.
Example 14 is the nitrile rubber mixture of Example 13 with 50 parts of a particulate PTFE such as WHITCON 2 and an effective amount of molybdenum disulfide.
Example 15 is the nitrile rubber mixture of Example 13 with 100 parts of particulate PTFE such as WHITCON 2 and an effective amount of molybdenum disulfide.
Example 16 is the nitrile rubber mixture of Example 13 with four parts of a fibrillated PTFE such as FLUON CDl and an effective amount of molybdenum disulfide.
Example 17 is the nitrile rubber-fibrillated PTFE
mixture of Example 16 with an additional 46 parts of particulate PTFE such as WHITCON 2 and an effective amount of molybdenum disulfide. Example 18 is the nitrile rubber-fibrillated PTFE mixture of Example 16 with an additional 96 parts of PTFE such as WHITCON 2 and an effective amount of molybdenum disulfide. The physical properties of the compositions of Examples 13-18 are compared in the table below.

E ~ PLE 13 14 15 16 17 18 Rheograph PL~e,~ies Model 100 320F. 30 Minute Motor Min. Torque, in.-lbs. 9.8 10.1 10.4 10.3 11.0 11.7 MaY. Torque, in.-lbs. 48.9 47.6 45.7 50.0 49.0 46.9 T2, minutes 3.5 3.9 4.1 3.9 3.9 3.8 Tgol minutes 11.7 12.3 13.8 13.9 14.2 16.4 Press Cure@

Tensile, psi @ RT12' 3275 2650 2050 3000 2350 1900 @ 300F. 12' 1000 675 550 850 875 575 .lon~tion, % @ RT 540 530 470 500 460 420 @ 300F. 490 380 360 330 370 330 300% Modulus, psi @ RT 1500 1275 1125 1800 1550 1350 @ 300F. 575 525 475 800 725 525 Hardness, Shore A @ RT 66 69 70 68 69 74 Comparisons of the composition properties demonstrate the increased modulus of elasticity that is obtained with the addition of only four parts of fibrillated PTFE in nitrile rubber compositions of the invention. Comparison also demonstrates the signifi-cantly improved tensile strength at such elevated temperatures as 300 F. with the incorporation of four parts of fibrillated PTFE and 50 to 100 parts of total PTFE.
Examples 19, 20, 21, 22, 23, and 24 Examples 19-24 permit a comparison of the effect of the invention in butadiene acrylonitrile elastomers. Example 19 is an elastomer mixture includ-ing 100 parts of butadiene acrylonitrile elastomer.
Example 20 is the butadiene acrylonitrile elastomer mixture of Example 19 with 50 parts of particulate PTFE
such as WHITCON 2 and an effective amount of molybdenum disulfide. Example 21 is the butadiene acrylonitrile mixture of Example 19 with 100 parts of particulate PTFE such as WHITCON 2 and an effective amount of molybdenum disulfide. Example 22 is the butadiene acrylonitrile mixture of Example 19 with four parts of fibrillated PTFE such as FLUON CD1 and an effective amount of molybdenum disulfide. Example 23 is the butadiene acrylonitrile elastomer-fibrillated PTFE
mixture of Example 22 with an additional 46 parts of particulate PTFE such as WHITCON 2 and an effective amount of molybdenum disulfide. Example 24 is butadiene acrylonitrile elastomer-fibrillated PTFE mixture of Example 22 with an additional 96 parts of particulate PTFE such as WHITCON 2 and an effective amount of molybdenum disulfide. The compositions of Examples 19-24 are compared below.

-22- 13382~2 E ~ PLE 19 20 21 22 23 24 Rheograph P~el~ies Model 100 320F. 30 Minute Motor Min. Torque, in.-lbs. 5.1 4.0 4.8 5.1 4.9 5.4 Max. Torque, in.-lbs. 29.8 23.3 23.6 31.2 26.8 24.8 T2, minutes 5.8 6.0 6.1 4.6 4.3 4.2 Tgol minutes 9.8 10.5 9.4 9.3 8.7 7.7 Press Cure@

Tensile, psi @ RT10' 3800 2475 1825 3250 2275 1575 @ 300F. 10' 525 425 425 675 525 425 ~l~ngAtion, % @ RT 690 640 580 620 560 500 @ 300F.320 340 360 280 280 270 200% Modulus, psi @ RT 450 350 325 825 700 600 @ 300F. 300 250 225 525 400 325 Hardness, Shore A @ RT 61 65 66 66 66 70 With the butadiene acrylonitrile rubber mixture as with the nitrile rubber mixture, the incor-poration of as little as four parts of fibrillated PTFE
in the composition imparts significant improvement in the modulus of elasticity both at room temperature and at elevated temperatures such as 300 F. In addition, the incorporation of four parts of fibrillated PTFE
improves the tensile strength of such compositions at elevated temperatures such as 300 F.
Example 25 A composition was made with 100 parts of EPsyn 4506 (a trademark of Copolymer Rubber & Chemical Corporation), 45 parts of TL 115A polytetrafluoro-ethylene powder, 50 parts of technical~grade molybdenum disulfide particles, 30 parts of HiSil1r233, 1 ~rt of TEA, 12 parts of Saret 500 and 5 parts of Varo The ingredients were mixed together and cured and formed into test samples and tested in accordance with ASTM
standards.
- ~ ~ ~ -22-- ~ 13382S2 The composition demonstrated a Compound ML 1 + 4 at 212 F. of 94, and a Mooney Scorch, at 270 F., of 9.4 minutes for a 5 point rise and a minimum reading of 54. After pressing and curing at 320 F., a tensile strength of 1400 psi, an elongation of 230 percent, a 100 percent modulus of 750 psi, a 200 percent modulus of 1250 psi and a hardness Shore A of 81 were obtained at room temperature.
Example 26 A composition was made with 100 parts of EPsyn 4506 (a trademark of the Copolymer Rubber &
Chemical Corporation), 40 parts of TL-115A, 7.5 parts of TEFLON K-10, 30 parts of technical grade molybdenum disulfide, 40 parts of HiSil 233, 15 parts of Saret B 500' 9 parts of Dicup 40KE, 5 parts of FEF Block, and 1 part of TEA. The ingredients were mixed together and cured and formed into test samples and tested in accordance with ASTM standards.
The composition demonstrated a Compound ML 1 + 4 at 212 F. of 108 and a Mooney Scorch, at 270 F., of 3.8 minutes for a 5 point rise and a minimum reading of 48. After pressing and curing at 320 F., a tensile strength of 2050 psi, an elongation of 150 percent, a 100 percent modulus of 1625 psi, and a hardness Shore A of 91 were obtained at room tempera-ture.
Examples 27, 28, 29, 30, 31, 32, 33, and 34 Compositions according to the invention were made and tested with four base elastomers including Viton, an elastomer manufactured and sold by E. I.
du Pont de Nemours Company under that trademark, Nitrile, Acrylic, and EPDM elastomers. Each of the base elastomer compositions of Examples 27, 29, 31, and 33 included elastomer and carbon black, curing agents, fillers, oxidants, and the like which the manufacturer believed advisable to lend desirable physical properties ~fa~ rk to the elastomer composition after it was cured. In Examples 28, 30, 32, and 34, respectively, particulate polytetrafluoroethylene and molybdenum disulfide were added to the elastomer of Examples 27, 29, 31, and 33 in such amount that the particulate polytetrafluoro-ethylene and molybdenum disulfide formed about 30 percent of the combined weight of the elastomer, carbon B black, particulate PTFE and Me~ components (i.e., the elastomer and carbon black comprised about 70 percent by weight of the combination, excluding curing agents, filler, oxidants, etc.). Each of these compositions included about 6 percent by weight of fibrillated polytetrafluoroethylene and about 18 percent of parti-culate polytetrafluoroethylene to comprise approxi-mately 24 percent total of polytetrafluoroethylene in the composition.
The physical properties of the base elastomer compositions are compared with the physical properties of the elastomer compositions of the invention below.
Example Example Example Example Physical ACRYLIC With EPDM With Property Base Invention BaseInvention Rubber Rubber ~ensile 96n 930 177n 7~n Modulus ~ 9 0% Modulus ~ 2 1 _ onga ion ' ~ _7 __' Durome-er ,~ 8' ie C Tear 8,. 17 . 14 . 2 .' pecif c Gravity 1. 9 -.~8 . 5.~4 Compression 22/3 0 22/3~0 70/.0~ 70/ OC
Set 81.3 81.1 66.1 58.7 Tabor Abrasion 683 332 600 176 (milligrams lost) ExampleExampleExample Example _ 32 33 34_ k~ Physical NITRILE WithVITON~ With Property BaseInvention Base Invention Rubber Rubber "ensile 1~, n :57~ 160-` 2000 0% Modulus ~ C_ ~ _54 00~ Modulus 1 ~ 0 ~ _79 _longa ion :0 ~ 17 Durome er 4 8-~ie C 'ear 2 ~.: 2~3.3 1 .726~.0 pecif-c Gravity . 9 .~4 .97.02 Compression 22/~1, 22/~12 70/~92 70/ 92 Set 34.3 44.8 28.4 29.6 Tabor Abrasion 327 176 270 148 (milligrams lost) The test data indicates elastomer compositions of the invention including Viton~and Nitrile elastomers demonstrated substantial improvements in tensile strength, 50 percent modulus, 100 percent modulus, die tear resistance and abrasion resistance. Although the elastomer compositions of the invention including acrylic and EPDM elastomers did not demonstrate increase in tensile strength, they also demonstrated a substan-tial increase in their 50 percent and 100 percent moduli, almost double the die tear resistance, and at least double or triple the abrasion resistance, respec-tfully.
Such compositions can be used, for example, to make improved rotating lip seals. Rotating lip seals are subject to abrasion wear and tearing, and the substantial improvements in tear and abrasion resis-tance demonstrated with the invention will contribute a substantial improvement in the life of rotating lip seals manufactured with such elastomers with no sacri-fice in the physical characteristics of the lip seal structure and, in many cases, a significant improvement in the strength of the lip seal.
~ r~ ~ -25-Thus, elastomers usable with this invention include the polymers known generally as rubbers, in-cluding natural rubber and synthetic rubber elastomers, and other polymers capable of forming elastic solids with similar properties. More specifically, such elastomers include, in addition to natural rubber, styrene-butadiene rubber (SBR BUNA S), acrylonitrile-butadiene rubber (BUNA N), butyl rubber (IIR), ethylene-propylene rubber (EPDM), polyurethane elastomers (AU), cis-polybutadiene (BR), polychloroprene (Neoprene, CR), poly(epichlorohydrin) (CO), polyacrylate (ABR), silicone rubbers (SI), poly (fluorinated hydrocarbons) (FPM), olefin polysulfide (Thiokol, ET), poly isoprene (IR), and the like. The compositions of the invention can also include plasticizers and softeners, extenders, reclaimed rubber, inert fillers, reinforcing fillers, coloring materials, anti-oxidants, accelerators, and vulcanization actuators.
The particulate polytetrafluoroethylene used can be ground polytetrafluoroethylene, dispersion-type polytetrafluoroethylene capable of fibrillation or a blend of both ground and fibrillatable PTFE. Such PTFE
materials are sold by the following companies under their respective trademarks:
Trade Designation Manufacturer Ground PTFE: TL 115A LNP Corp.
WHITCON 2 ICI Americas Fibrillatable PTFE: FLUON CD1 ICI Americas TEFLON K-10 du Pont Compositions of the invention can include both ground and fibrillated polytetrafluoroethylene.
Fibrillated polytetrafluoroethylene improves signifi-cantly the modulus of elasticity of most elastomers and can improve the tensile strength of elastomers with low tensile strengths. Generally, with about 4 percent weight of fibrillated PTFE, about 85 percent of its rrQd~-~a~k 133829~

benefits can be obtained. It is believed that the more extended and complex surface of the fibrillated PTFE
may provide additional mechanical entanglement and engagement with the elastomer. The improved tensile strength and modulus can be obtained in many cases with only a modest increase in the hardness and a modest reduction in the elasticity.
Fibrillated PTFE is the result of its manu-facture from polymer emulsions and in its fibrous form, in the compositions of this invention can resemble small twisted and deformed webs of entangled fibers.
FLUON CDl is preferred over TEFLON K-10 because it seems to disperse more readily in the elastomer. Where it is desirable to maintain flexibility of the elastomer compositions of this invention, the fibrillated poly-tetrafluoroethylene desirably fibrillates to provide a high ratio between fiber length and fiber diameter. It has been found that FLUON CD1 fibrillates with a greater length to diameter ratio and is preferable in such elastomers where flexibility is a desirable characteristic.
Particulate PTFE is generally finely ground and is the result of fracturing. It is believed that the performance of ground particulate PTFE in composi-tions of this invention may be improved if it is etched with sodium in processing. The improvement believed to be available with such treatments are improved mechani-cal interaction of the elastomer and particulate PTFE
in compositions and products of the invention, and possibly improved tensile strength and modulus of elasticity. Ground PTFE can, however, effectively contribute the physical properties of polytetrafluoro-ethylene in products that do not require good tensile strength and modulus. The outer hull covering, for example, does not require these properties.

Where tensile properties are important, small amounts of fibrillated PTFE are desirably included to improve the tensile strength and modulus of most elastic products made with compositions of this inven-tion. Products of the invention with increased tensile strength and modulus of elasticity generally have greater abrasion resistance, lower flexural hysteresis, or heat build-up in use, and increased durability where subjected to mechanical flexing and abrasion. The interaction of the fibrillated PTFE and the ground PTFE
within the elastomer is not understood; but it is as if the PTFE component of such compositions yields readily when the rubber is exposed to tensile and compressive forces up to a point, and then contributes to the tensile strength and modulus of the composition as a result of the mechanical engagement of the PTFE with the elastomer in the matrix when stretched and contri-butes to the hardness as the PTFE component comes to bear the load when compressed.
The procedure for determining the quantity of PTFE needed in many applications is first to determine the total quantity of PTFE that is desirable to achieve the PTFE properties of the composition that are desired, such as lubricity and abrasion resistance, solvent resistance and chemical inertness, heat resistance and the like. The modulus of elasticity of the composition can generally be improved without substantial deterioration of other properties by using, as a portion of the PTFE component, fibrillatable PTFE
such as FLUON CD1 and TEFLON K 10.
In compositions, where lubricity is disadvan-tageous, such as the treads of vehicle tires and military tank pads, quantities of fibrillated PTFE on the order of only about 4 percent by weight within the composition can achieve 85 percent of the improvement - - 13~8292 possible with the fibrillated PTFE. In tire composi-tions, for example, about 2 percent of fibrillated PTFE
in natural rubber with up to no more than 10 percent ground PTFE can provide substantially increased life to vehicle tires without loss of their tractability. With elastomers having less strength such as butyl rubber up to about 6 percent of fibrillated PTFE with no more than 6 percent ground PTFE can provide increased life and durability. It is generally desirable to keep the quantity of fibrillated PTFE in such compositions as low as possible consistent with obtaining the needed properties. Fibrillatable PTFE is more difficult to mix with elastomers and generates more heat as it is mixed with the elastomers. The increased heat generated in mixing the components of a composition and fibril-lating the PTFE component, for example, in a Banbury mixer tends to partially cure the elastomer during mixing and reduces the scorch resistance of the re-sulting composition on molding. Scorch resistance is a measure of the ability of an elastomeric composition to be uniformly curable and to resist a preferential curing at the surfaces of a mold into which heat is transferred. Such preferential curing generally increases the resistance of the cured portion of the product to heat transfer and inhibits uniform curing of the product interior without over heating adjacent the product surface. In this regard, FLUON CDl seems to be preferable to TEFLON K-10; but both work well in the resulting composition. In addition, particulate PTFE
having an average particle size of less than 40 microns is more readily dispersed.
The molybdenum disulfide used may be that sold, for example, by ICI Americas as technical grade molybdenum disulfide. While the effective amount of molybdenum disulfide may vary from composition to composition, the amount needed to effect uniform _30_ 1338292 dispersion of particulate matter such as PTFE into theelastomer may be easily determined by adding the molybdenum disulfide and the polytetrafluoroethylene to the elastomer in the Banbury mixer until the PTFE
becomes uniformly mixed with the elastomer. The molybdenum disulfide can be incorporated into composi-tions of this invention in many cases with only a minor effect on most of their physical properties.
In addition to permitting the uniform disper-sion of significant amounts of particulate material and especially PTFE in elastomeric materials, the molybdenum disulfide can function as a significant filler for the elastomer and can be used to contribute lubricity to the surface properties of a resulting elastic product.
Furthermore, the molybdenum disulfide will reduce the heat buildup and partial curing of the elastomer during mixing of the composition and increase its scorch resistance.
Compositions of this invention and their advantages are believed to be derived in part from a matrix-like structure including an intimate mechanical interengagement of elastomer with particulate PTFE, and, where fibrillated PTFE is incorporated, in web-like structures of fibrillated PTFE within the matrix. The molybdenum disulfide is also uniformly dispersed in the elastomer matrix.
Where elastic products of such compositions are subject to surface abrasion, for example, in applications such as lip seals for hydraulic and air pump shaft seals, vane pump seals, valve seals, and the like, the elastomer at the surface may be abraded; but the surface exposed to abrasion can then become predom-inantly PTFE which is lubricious and highly abrasion resistant. To the extent PTFE is abraded from such elastic products by the roughness of opposed surfaces, such as the inner steel surfaces of hydraulic and -31- 13~829~
compressed air cylinders, pumps, valves, etc., the transfer of PTFE to the opposing surfaces tends to fill the roughness, improve the seal, and reduce the friction between the moving parts, with the elasticity of the composition continuing to maintain an effective seal.
One application of the invention is to water-craft which are required to move through the water as fast as possible or with the greatest efficiency possible, and more particularly to an improved outer hull covering for such watercraft which provides, among other advantages, reduced drag caused by water resis-tance to such movements. In connection with the movement of any object underneath or across the surface of the water, there is a continuous force exerted against such movement which is measurable and is composed of several factors, one of which is friction.
This resistance to movement through water is commonly termed "drag". With any "watercraft," which term is used in this application to mean any craft or other structure that can carry people or cargo underneath or over the surface of water, drag is a major concern because it is a significant factor in determining the maximum speed at which movement is possible as well as the efficiency of such movement in terms of cost, energy expended and the like.
In an effort to minimize drag and maximize our ability to efficiently move through water, much research has been done and continues to be done both in private industry and in civilian and military branches of government. This research involves not only varia-tions in the design, weight and other characteristics of the watercraft themselves, but also work with paints and other coatings, solutions, and various methods at-tempting to decrease this water resistance to movement and thereby increase the efficiency of water travel.

1~38292 Examples of such ongoing work are shown, for example, in U.S. Patents Nos. 3,230,919; 3,575,123;

3,990,381; 4,073,983; 4,088,622; 4,088,623; 4,241,682;
and French Patent No. 2,050,794.
Other problems with the watercraft besides drag are encountered which impair efficiency and inconvenience or endanger travelers or cargo on board such craft. One example is fouling, which refers to the buildup of foreign matter including grass or marine organisms such as algae, barnacles, and various shells which become attached to the underwater portion of the hull or other structure. A second problem is that sound travels readily through metal hulls of watercraft creating not only a nuisance, i.e., noise, but possibly a dangerous situation as with submarines and other military vessels.
In addition to the examples of the patents above, applicant is generally aware that research has been conducted at military and civilian facilities for many years in an effort to find an effective solution to efficient movement through water by watercraft, having lessened drag and eliminating problems such as fouling, sound transfer, repeated maintenance, and difficulties of repair and others.
Compositions, such as those in Example 1, can be prepared in the form of flattened layers or sheets and used as panels. These panels can correspond to patterns taken from the outer hull or surface of the watercraft, such that the sheet material is later assembled and adhered to a particular hull design or shape, much as a jigsaw puzzle. The possible thickness of applicant's covering layer is limited only by con-sideration such as cost, added weight, and the like.
Applicant's preferred thickness range is about 0.1-0.5 inch, with about 0.1 inch being most preferred.

- 13382~2 -The preferred method of attachment is to adhere the covering layer to the outer surface of the craft by an adhesive such as, for example, those com-monly used for bonding natural rubber and synthetic elastomers to metal and various other substrates. The bonding agent used with applicant's preferred ethylene-propylene terpolymer base material was a CA-40 brand bonding agent marketed by the 3M Company, which satis-fies government specification MIL A 46050C TYPE 1 CLASS 1 for military use, and is known to bond ethylene-propylene polymers to metal substrates and themselves.
Other adhesives and methods of attachment, of course, can be substituted with this or other base elastomers and are within the scope and contemplation of appli-cant's invention.
The preferred covering layer was attached directly to the metal substrate being covered such as the hull or other surface of a craft. An alternate embodiment is to use the covering layer to form the outer layer of a laminate structure. The object of such a laminate can be to achieve improved properties such as adhesion, specific gravity, durability or impact tolerance, heat insulation, sound attenuation or absorption, and others. Differences in construction such as, for example, a honeycomb inner layer can also be used if desired for a specific application.
The invention permits the compounding of compositions having improved properties in many other applications. For a simple example, if the object were to make a bumper to cushion the automobile door when it slams and to keep it from rattling when it is closed, the bumper must be hard enough to stay in its slot when the door is slammed; it must be soft enough to cushion the door, yet must have a sufficient modulus of elasti-city to keep the door from rattling when it is closed;
it must preferably last for the life of the car which can be expected to be on the order of five to ten years; and it must be inexpensive.
The first step in deciding upon the composi-tion of such a rubber product would be to decide upon the physical properties, such as hardness, permanent set, resilience, tensile strength, and the like. One of the advantages of compositions of the invention is their greater tolerance to aging. The method of manufacture of the product must also be considered.
Since such bumpers can have a simple shape, such as a polyhedron, it may be manufactured in simple molds from an extruded preparation of mixed composition cut into short blanks with a size sufficient to fill the mold under pressure. Thus, the composition may be extruded in the form of a uniform strip and should have good extruding characteristics. A quick cure is desirable for it is more economical than an extended cure; but it is desirable to avoid scorching and to obtain a com-position that will not partially cure if it is not immediately molded. In addition, such bumpers will generally be rather thick; so the mixed rubber should be cured slowly enough that the outside does not cure long before the inside. Generally, determining a composition for any application requires trial and error and several mixes are formulated for testing in such applications.
Examples 35 and 36 Using the invention for such bumpers may, for example, lead to a composition including reclaimed tire rubber in 200 parts by weight, particulate PTFE in 50 to 100 parts by weight, an effective amount of molyb-denum disulfide, and 10 parts by weight of antioxidants, sulfur, accelerator and fillers. Another formulation of the invention usable in such application may include 100 parts by weight oil extended, styrene-butadiene rubber, 50 to 100 parts by weight particulate PTFE, an -effective amount of molybdenum disulfide, and 10 parts by weight antioxidant, sulfur, accelerators, and other fillers. With this invention, the resulting automobile door bumpers will have a substantially reduced tendency to squeak because of their surface lubricity.
Other products of applicant's invention may include:
Example 37 A composition for use in the tread and sidewalls of an automobile tire comprising an elastomer selected from a group including a styrene butadiene rubber, natural rubber and the like in the range of about 88 weight percent to about 98 weight percent, fibrillated PTFE in the range of about 1 weight percent to about 4 weight percent, an effective amount of molybdenum disulfide, and one or more additives selected from a group comprising plasticizers and softeners, extenders, reclaimed rubber, inert fillers, carbon black, antioxidants, and accelerators and activators.
Additional amounts of particulate granular PTFE in the range of 6 to 10 percent m~nay be added along with B corresponding amounts of Me~. For roadgraders and off-highway vehicles and machinery, higher percentages of ground PTFE may be incorporated into the tread composltlon.
Example 38 A composition for the seal of an hydraulic cylinder comprising neoprene in a range of about 50 weight percent to about 75 weight percent, a blend of particulate PTFE and fibrillated PTFE in the range of about 25 weight percent to about 50 weight percent, said fibrillated PTFE being present in an amount equal to about 4 weight percent of the total composition, an effective amount of molybdenum disulfide, the neoprene component containing one or more fillers selected from a group comprising plasticizers and softeners, inert fillers, carbon black, antioxidants, and accelerators or activators in an amount from about 5 percent to about 30 percent.
Example 39 A composition for a tank pad for a military tank comprising a styrene-butadiene copolymer elastomer, a blend of particulate PTFE and fibrillated PTFE in a range of about 2 weight percent to about 6 weight percent, an effective amount of molybdenum disulfide, and one or more curing agents selected for processibility.
Products of applicant's invention, for example, include spark plug wire and wire and cable insulation formed from the cured composition of Examples 11 and 12, an improved automobile tire includ-ing a bead, a casing, and a tread and sidewall with a cured composition of Example 15, and O-ring seal formed from the cured composition of Example 2, a lip seal for an hydraulic cylinder formed from the cured composition of Example 16, and a tank pad for a military tank molded from the cured composition of Example 39.
These products each provide improved life and durability in their applications that is several times that obtainable with compositions known prior to the invention.
Using the invention, other compositions, including elastomers and polytetrafluoroethylene may be compounded to provide the products above or any of the following products: windshield wiper blades, combina-tion bearing-seals for a rotating shaft, pump seals, valve seals, static body seals (e.g., door seals) for automobiles, and other such dynamic seals where lubricity, corrosion and abrasion resistance can be desirable. Products made with compositions of this invention may be manufactured by the manufacturing techniques and processes in common use in industry.
Such products may be either extruded or molded by transfer, injection and compression molding and the like or both.
Other specific products, compositions, methods and other embodiments may be devised without departing from the spirit and scope of the invention as set forth in the following claims.

Claims

1. A substantially uniform composition comprising:
(a) from about 2 percent to about 80 percent by weight poly-tetrafluoroethylene;
(b) from about 1 percent to about 30 percent by weight molybdenum disulfide; and (c) an elastomeric material.

2. A composition according to claim 1 comprising:
(a) about 25-80 percent polytetrafluoroethylene;
(b) about 1-30 percent molybdenum disulfide; and (c) the balance of an elastomeric material.

3. The composition of claim 2 which is a substantially homogeneous combination of said components.

4. The composition of claim 3 in the form of a cured layer having a thickness of about 0.01-0.5 inch.

5. The composition of claim 3 in which said polytetra-fluoroethylene is a reprocessed powder.

6. A composition according to claim 1 comprising:
(a) about 25-50 percent polytetrafluoroethylene powder;
(b) about 3-20 percent molybdenum disulfide; and (c) the balance of an elastomeric material.

7. The composition of claim 6 in which said elastomeric material is an ethylene-propylene terpolymer.

8. The composition of claim 7 in the form of a layer of vulcanized sheet material.

9. The composition of claim 8 in which said layer has a thickness of about 0.01-0.5 inch.

10. The layer of claim 9 in which said layer is attached to a watercraft by use of an adhesive.

11. The composition of claim 6 in which said reprocessed polytetrafluoroethylene powder has a particle size of from about 2 microns to about 100 microns.

12. The composition of claim 8 in which said layer has a hardness of about 80-90 durometer.

13. A composition according to claim 1 containing:
(a) about 50 percent polytetrafluoroethylene;
(b) about 20 percent molybdenum disulfide; and (c) about 30 percent ethylene-propylene terpolymer.

14. A method for reducing drag on movement of a watercraft through water, comprising the step of applying an outer hull covering to the watercraft comprised of a layer made of a substantially uniform composition according to claim 1 containing (a) about 25-80 percent polytetrafluoroethylene;
(b) about 1-30 percent molybdenum disulfide; and (c) the balance of an elastomeric material.

15. The method of claim 14 in which said watercraft is a submarine.

16. A composition according to claim 1 resulting from a method comprising:
mixing together an elastomer, particulate polytetra-fluoroethylene in an amount in a range from about 25 percent by weight of the total composition to about 80 percent by weight of the total composition and an amount of molybdenum disulfide that is effective to uniformly incorporate the particulate polytetra-fluoroethylene in the elastomer.

17. The composition resulting from the further steps of molding and curing the composition of claim 16.

18. The composition of claim 16 wherein the particulate polytetrafluoroethylene lies in the range of 25 percent by weight to 50 percent by weight and the amount of molybdenum disulfide lies in a range of from about 0.5 parts per part of particulate polytetrafluoroethylene to about 1.0 parts per part of polytetra-fluoroethylene.

19. The composition of claim 16 wherein the polytetra-fluoroethylene includes both fibrillated and non-fibrillated particulate material.

20. A method of producing a composition according to claim 1 comprising:
mixing together an elastomer and a particulate poly-tetrafluoroethylene with an amount of molybdenum disulfide to effect uniform mixing of the polytetrafluoroethylene in the elastomer; and curing the mixture to obtain an elastic solid with physical characteristics of both the elastomer and polytetrafluoroethylene.

21. The method of claim 20 wherein the particulate poly-tetrafluoroethylene includes about 4 percent by weight fibrillated polytetrafluoroethylene and about an equal amount of molybdenum disulfide.

22. A method of incorporating particulate material into an elastomer, comprising:
placing together a quantity of elastomer and from about 2 percent to about 80 percent by weight particulate polytetra-fluoroethylene material, adding from about 1 percent to about 30 percent by weight molybdenum disulfide, and mechanically mixing together the elastomer, particulate polytetrafluoroethylene material, and the molybdenum disulfide to obtain a uniform dispersion of the particulate polytetrafluoro-ethylene material in the elastomer.

23. The method of claim 22 wherein the quantity of partic-ulate polytetrafluoroethylene matter is in excess of 25 percent by weight.

24. The method of claim 23 wherein the elastomer is sensi-tive to and cured by exposure to heat and the amount of molybdenum disulfide is sufficient to preclude significant partial curing of the elastomer.

25. The method of claim 22 wherein the particulate poly-tetrafluoroethylene is capable of fibrillation and is fibrillated as it is mixed in the elastomer.

26. In a method of improving the physical properties of elastomeric compositions, the improvement comprising adding to the elastomeric composition as it is being mixed polytetrafluoro-ethylene particles capable of fibrillation and molybdenum disulfide particles and shearing the polytetra-fluoroethylene particles in the presence of the molybdenum disulfide particles in mixing to fibrillate the polytetrafluoroethylene particles and mix the fibrillated polytetrafluoroethylene and molybdenum disulfide particles uniformly within the elastomeric composition.

27. The method of claim 26 wherein the quantity of fibril-lated polytetrafluoroethylene added is up to about 6 percent by weight of the total composition.

28. A composition according to claim 1, comprising:
a solid matrix of cured elastomeric material, partic-ulate polytetrafluoroethylene and molybdenum disulfide in which at least a portion of said particulate polytetrafluoroethylene comprises fibrillated polytetrafluoroethylene in the range of about 2 percent to about 6 percent by weight that is uniformly dispersed in the elastomer matrix with particulate molybdenum disulfide.

29. The composition of claim 28 wherein the polytetra-fluoroethylene particles comprise from at least 25 percent to about 80 percent by weight of the total composition.

30. The composition of claim 28 in the form of an O-ring.

31. The composition of claim 28 in the form of a hydraulic seal.

32. The composition of claim 28 in the form of a bearing.

33. The composition of claim 28 wherein the total amount of particulate polytetrafluoroethylene including nonfibrillated polytetrafluoroethylene is less than about 12 percent.

34. The composition of claim 33 in the form of an automobile tread and sidewall.

35. The composition of claim 33 in the form of a pad of the track of a military tank.

36. The composition of claim 28 wherein the polytetrafluoro-ethylene particles comprise about 25 percent by weight to about 50 percent by weight of the total composition.

37. The composition of claim 2 incorporated into an O-ring.

38. The composition of claim 2 incorporated into a lip seal for a piston-cylinder combination.

39. The composition of claim 2 incorporated into a windshield wiper blade.

40. The composition of claim 2 incorporated into seals for moving parts.

41. The composition of claim 2 incorporated into a combin-ation bearing and seal for a rotating shaft.

42. The composition of claim 2 incorporated into a pump seal.

43. The composition of claim 2 incorporated into a valve seal.

44. The composition of claim 2 incorporated into a seal for a vehicle door.

45. The composition of claim 2 incorporated into a hose.

46. The composition of claim 2 incorporated into sound mountings.

47. A composition according to claim 1, comprising:
(a) about 2 to about 6 percent fibrillated polytetra-fluoroethylene;
(b) an effective amount of molybdenum disulfide; and (c) the balance of an elastomeric material.

48. The composition of claim 47 incorporated into a tire for a vehicle.

49. The composition of claim 47 wherein the composition is incorporated into the tread and sidewall of an automobile tire.

50. The composition of claim 47 in the form of a pad of a military tank.

51. A composition according to claim 1, comprising:
a fluorohydrocarbon elastomer;
particulate polytetrafluoroethylene in an amount effective to substantially improve the physical properties of the fluorohydrocarbon elastomer; and an amount of molybdenum disulfide effective to uniformly incorporate the particulate polytetrafluoroethylene in such elastomer.

52. The composition of claim 51 wherein said particulate polytetrafluoroethylene comprises a small amount of fibrillated polytetrafluoroethylene.

53. A composition according to claim 1, comprising:
a silicone rubber;
particulate polytetrafluoroethylene in an amount effective to substantially improve the physical properties of the silicone rubber; and an amount of molybdenum disulfide effective to uniformly incorporate the particulate polytetrafluoroethylene in said silicone rubber.

54. The composition of claim 53 wherein the particulate polytetrafluoroethylene comprises a small amount of fibrillated polytetrafluoroethylene.

55. The composition of claim 53 in the form of insulation for automotive spark plug wires.

56. A composition according to claim 1, comprising an elastomer selected from a group comprising natural rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, butyl rubber, ethylene propylene rubber, polyurethane elastomer, cis-polybutadiene, polychloroprene, poly(epichlorohydrin), polyacrylate, silicone rubber, poly(fluorinated hydrocarbons), olefin polysulfide, poly isoprene;
particulate polytetrafluoroethylene in an amount effective to improve the physical properties of said elastomer;
and an amount of molybdenum disulfide effective to uniformly incorporate the particulate polytetrafluoroethylene in said elastomer.

57. The composition of claim 56 wherein the particulate polytetrafluoroethylene is fibrillated polytetrafluoroethylene.

58. The composition of claim 56 wherein the particulate polytetrafluoroethylene comprises from about 25 percent to about 80 percent by weight of the total composition.

59. The composition of claim 58 in the form of insulation around an electrical conductor.

60. An additive for elastomer compositions, comprising:
particulate polytetrafluoroethylene and particulate molybdenum disulfide, said particulate molybdenum disulfide having an average particle size substantially smaller than the average particle size of said particulate polytetrafluoroethylene and in substantial part adherent to said particulate polytetrafluoro-ethylene, wherein said molybdenum disulfide comprises at least about 0.5 parts by weight per part of particulate polytetra-fluoroethylene.

61. The additive of claim 60 wherein the average particle size of said molybdenum disulfide is less than about one-third the average particle size of said particulate polytetrafluoroethylene and said polytetrafluoroethylene has an average particle size in the range of from about 2 to about 45 microns.

62. The additive of claim 60 wherein the particulate polytetrafluoroethylene is fibrillatable and the particulate molybdenum disulfide is present in the additive in an amount at least about equal in weight to the weight of the fibrillatable polytetrafluoroethylene.

63. An additive for elastomers produced by placing together particulate polytetrafluoroethylene and particulate molybdenum disulfide, said particulate molybdenum disulfide having a substantially smaller particle size than said particulate polytetrafluoroethylene and comprising at least a substantial percentage by weight of the total weight of the additive and at least about 0.5 parts by weight per part of particulate polytetra-fluoroethylene, and producing relative movement and contact between said particulate polytetrafluoroethylene and said particulate molybdenum disulfide to produce particulate polytetrafluoroethylene with adherent particles of molybdenum disulfide.

64. The additive of claim 63 wherein said particulate poly-tetrafluoroethylene and particulate molybdenum disulfide are tumbled together in a tumble mixer.

65. A method of producing an elastomer composition according to claim 1, comprising placing together particulate polytetrafluoroethylene and particulate molybdenum disulfide, said particulate molybdenum disulfide having a substantially smaller particle size than said particulate polytetrafluoroethylene and comprising at least a substantial percentage by weight of the total weight of the additive;
producing relative movement and contact between said particulate polytetrafluoroethylene and said particulate moly-bdenum disulfide to produce particulate polytetrafluoroethylene with adherent particles of molybdenum disulfide;

mixing together an elastomer and an amount of said particulate polytetrafluoroethylene and molybdenum disulfide that is effective to uniformly mix the polytetrafluoroethylene in the elastomer and to improve the physical properties of the elastomer;
and curing the mixture to obtain an elastomer composition with improved physical properties.