CA2094395A1 - Surface finish compositions - Google Patents

Surface finish compositions

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Publication number
CA2094395A1
CA2094395A1 CA002094395A CA2094395A CA2094395A1 CA 2094395 A1 CA2094395 A1 CA 2094395A1 CA 002094395 A CA002094395 A CA 002094395A CA 2094395 A CA2094395 A CA 2094395A CA 2094395 A1 CA2094395 A1 CA 2094395A1
Authority
CA
Canada
Prior art keywords
composition
tetrafluoroethylene
substrate
molecular weight
fluorocarbon polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002094395A
Other languages
French (fr)
Inventor
Gary E. Huggins
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PREEMPTIVE TECHNOLOGIES Inc
Eeonyx Corp
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CA2094395A1 publication Critical patent/CA2094395A1/en
Abandoned legal-status Critical Current

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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M111/00Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
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    • C10M103/00Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/02Carbon; Graphite
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    • C10M107/00Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/38Lubricating compositions characterised by the base-material being a macromolecular compound containing halogen
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
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    • C10M2201/041Carbon; Graphite; Carbon black
    • C10M2201/0413Carbon; Graphite; Carbon black used as base material
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    • C10M2201/041Carbon; Graphite; Carbon black
    • C10M2201/042Carbon; Graphite; Carbon black halogenated, i.e. graphite fluoride
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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Materials For Medical Uses (AREA)
  • Detergent Compositions (AREA)
  • Adornments (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Thin impermeable, surface hardened, corrosion-resistant, durable, dry lubricant surface finishes are provided as well as surface finished products and methods for the production thereof. The surface finishes comprise particulate mixtures of sulfur containing metallic compounds and fluorocarbon polymers and are applied to surfaces of substrates such as metallic surfaces.

Description

WO 93/~3921 PCI/U592/1~7061 2~43~5 i !

DEBCRIPTION

81JRFACE FINIB~I COMP08ITION~3 TECHNI CAL FI ELD
This invention relates to surface finishes which impart nonabradable and nonetchable, durable dry lubricity, corrosion resistance and improved wet film ~ntrapment characteristics to a substrate and to methods 15 for applying such surface finishes to a substrate.
Although this invention is primarily directed to ~he surface finishing of metallic substrates, it should be noted that it is likewise applicable to surface finishes for application to other suitable substrate materials such as ceramic compositions. Furthermore, it should be noted that the metallic substrates employed herein may range from very hard metals having a hardness factor measured on the Rockwell C scale of greater than 40 to so~t metals having hardness values measured on the Rockwell B scale.
Accordingly, a diversity of substrate materials may be utilized in this invention provided that the material has sufficient structural integrity to withstand the high pressure impact application techniques employed herein.
A wide variety of corrosion-resistant coatings as well as methods for the application of such coatings to substrates have been disclosed heretofore. Examples thereof may be found in U.S. Patent Nos. 3,574,658;
3,754,976; 4,228,670; 4,312,900; 4,333,840; 4,415,419;
4,552,784; 4,553,417 and 4,753,094.

W O 93/0392] PC~r/US92/07061 2~9439S 2 : ~

In this regard, several of the a}~ove-noted patents disclose processes for applying coatings to the surface of work pieces by a peening or blasting procedure in which the coating material is applied to the surface by pellets or other shot material and is impacted at high pressure against the surface of the work piece in order to apply the coating on the pellets or shot to the surface of the work piece. For example, in U.S. Patent No. 3,574,658, a method is disclosed for applying a dry lubricant in the nature of a molybdenum or tungsten disulfide coating to the shot material and then applying this dry lubricant material to the surface of the work piece as a coating.
U.s. Patent No. 3,754,976 discloses a co~ting process wherein shot and powdered metal are peened against the surface oî a work piece which has previously been cleaned with a gentle stream of peening particles in the absence of the coating material. U.S. Patent No. 4,228,670 discloses a process wherein steel or glass shot is co-mingled with lubricant and blasted against a work piece in order to apply the lubricant to the work piece surface. U.S. Patent No. 4,312,900 discloses a process wherein the work pi~ce surface is initially pitted by shot blasting using abrasive materials such as glass or sand followed by buffing dry molybdenum disulfide into the pits created in the surface of the work piece by the shot blasting. U.S. Patent No. 4,552,784 discloses a further process for applying a metal powder to the surface of a work piece by a peening technique. Again, in U.S. Patent No. 4,753,094, a process is taught wherein a thin film coating of molybdenum disulfide is applied to a substrate surface by a peening action in order to adhere the molybdenum disulfide to the surface of the substrate as a coating thereon.

':

wo93/o3s2l PCT/US92/0706~
2~9;43!~

However, none of the prior disclosures have provided products demonstrating the combination of characteristics and properties which are achieved by the products of the present invention nor do they provide processes for producing such products. Indeed, the need to prolong the wear-life of substrate surfaces such as metal surfaces and to reduce the frictional properties thereof in order to reduce repair and replacement costs has been and continues to be the focus of intensive research and development efforts. Nonetheless, these efforts have achieved only relatively limited success resulting from the use of previously known coatings, paints and lubricants (both wet and dry). Each of the known techniques for treating substrates such as metal surfaces has presented significant problems and drawbacks in regard to the cost, difficulties in application, product properties achieved and the like.
Particularly, it is presently believed that the processes of the present invention achieve surface modification whereby plural polymers are bonded with the surface of the treated work piece or substrate. For purposes hereof, the term bond or bonded will apply to either physical or chemical bonds which result in products demonstrating the desired characteristics. Based on this belief, it is presently hypothesized that the surface finishes of this invention are not coatings but are permanently bonded with the substrate and can only be removed by grinding away the substrate surface itself.
~ccordingly, the surface-finishing processes of the present invention result in products with permanent finishes having a degree of long lasting, durable dry lubricity and corrosion resistance which has not been achieved heretofore.

:,.

.
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W~93/03921 PCT/U~92/070~

209 ~39~ _4_ With regard to prior processes ~or impar~ing desirable physical properties of polymers to substrate surfaces such as metal surfaces, it has been common to employ fluorocarbon polymers such as tetrafluoroethylene (TFE) sold, for example, under the tradename "Teflon" by E.I. Du Pont de Nemours & Co. (Inc.), as a coating material.
Teflon coated surfaces are known to reduce friction and adhesion but must be applied to the substrate by use of primers such as epoxy. The coated surface, accordingly, abrades under modest pressure, does not coat evenly or thinly and requires high temperatures for application.

SUMMARY OF THE INVENTION
The present invention overcomes many of the known shortcominqs of the prior art. The invention comprises preparing a particulate mixture of a sulfur containing metallic compound such as molybdenum disulfide or tungsten disulfide and a fluorocarbon polymer such as tetrafluoroethylene, preferably in a ratio of about l:l to about lO:l parts fluorocarbon polymer to sulfur containing metallic compound (on a weight percentage basis).
A pressurized stream of the particulate mixture is impacted onto the surface of a substrate at a sufficient pressure and for a sufficient period of time to cause surface modification whereby the particulate mixture interacts with the substrate. As a result of the application of such surface finishes to the surface of the substrate, it has been found that the resulting product demonstrates outstanding corrosion resistance as well as long lasting, durable dry lubricity characteristics.
Furthermore, the surface finishes have been found to provide a relatively thin, impermeable, surface hardened exterior on the surface of the substrate or work piece.

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WO 93/03921 PCI'/VS92/07061 5- ~9~395 These surface finishes have been found ~Q be sufficiently thin so that the finishes do not interfere with critical tolerances of any processed parts or components.
Accordingly, it is a general object of the present invention to provide new and improved surface finishes for application to substrates and to provide methods of applying such surface finishes to substrates.
Another object is to provide corrosion-resistant surface finishes demonstrating long lasting, durable dry lubricity characteristics as well as providin~ an impermeable, surface hardened outer surface on a substrate.
A further object is to provide methods for producing corrosion-resistant, long lasting, durable dry lubricant surface finishes on substrates.
A further object is to provide a surface finished product having a high degree of permanent dry lubricity.
Another object is to provide a metal sur~ace exhibiting long lasting, durable dry lubricity and hi~h resistance to temperature extremes.
A still further object is to provide methods for producing thin surface finishes which exhibit long lasting, durable dry lubricity; corrosion and heat resistance as well as improved thin film entrapment (or retention) properties.
Yet another object is to provide methods for relatively easy and inexpensive application of the surface finishes of this invention to substrate surfaces.
Other objects of this invention, in addition to those set ~orth above, will become apparent to one of ordinary skill in the art from the following description.

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209~395 -6-BRIEF DESCRIPTION OF THE DRAWING
Fig. l is a schematic flow diagram illustrating the method of the present invention employed to apply a dry lubricating, corrosion-resistant finish to the surface of a substrate.

DETAILED DESCRIPTION
The drawing is a schematic flow diagram showing an embodiment of the methods of the present invention for applying surface finishes to a substrate.
In the embodiment of this invention depicted in Fig.
l, a multistep process is illustrated wherein a substrate surface is first subjected to an optional solvent precleaning step in order to remove any loose surface contamination such as hydrocarbons and other physical and chemical debris from the substrate prior to further processing. This precleaning step is employed in order to reduce contamination which may be encountered and which may thereby interfere with the blast application of the surface finish onto the substrate.
The appropriate solvent to be used for this precleaning is somewhat ubstrate specific. For example, very dirty, greasy substrates wilI require a Stoddard solvent to be employed to clean the substrate surface.
For substrate surfaces which are non-degassing, such as chrome/molybdenum or stainless steel, l,l,l trichloroethane or equivalent solvent may be employed in an ultrasonic cleaning procedure. For degassing substrates, a Branson IS solvent is employed in an ultrasonic cleaning procedure.
In a specific solvent precleaning process employed in the laboratory, a metallic substrate was brush scrubbed in Stoddard solvent with Hurri-Safe Special Formula Degreaser : . '..; '. ' ::
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at a 1:4 dilution in a Hurri-Kleen cold part washing machine and the substrate was then air dried. Thereafter, the material was cleaned in either Branson IS Formulated Cleaning Solution, l:lo dilution or 1,1,1 trich1Droethane precleaner (sold by Brownells) utilizing an indlrect method in a Branson 8200 Ultrasonic Cleaner filled with Branson IS Formulated Cleaning Solution, 1:10 dilution.
Cleaning time was about 15 minutes at 40 C.
As illustrated in ~he drawing, after comple~ion of the solvent precleaning step, the substrate is then subjected to an abrasive cleaning/sur~ace disruption step ~o create a sufficient and appropriate amount of disrupted surface area on the surface of the substrate in order to interact with the sur~ace finish material to be applied thereafter. In this abrasive cleaning step, any oxidation or contamination from the substrate material which was not removed in the precleaning step i5 removed.
This abrasive cleaning/surface disruption step may be performed in a blast cabinet environment in accordance with the procedures disclosed for precleaning in U.S.
Patent No. 4,753,094 (the disclosure of which is incorporated herein by reference). The specific parameters of treatment within this step of the process are subject to choice, depending on the substrate material and its intended end use. For example, the delivery pressure/velocity, temperature, angle of delivery, duration of blasting and like parameters o~ the process are subject to choice and will vary depending on whether final treatment of the substrate is intended to increase dry lubricity, wear resistance, quick release ~i.e., non-sticking effect), operakive temperature range and/or corrosion resistance.

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W093/0392] PCT/US92/070~1 1 2~9 439~ -8-In regard to the blast materials to be used for this abrasive cleaning/surface disruption step, it has been found that for softer, nonferrous metals and alloys, (e.g., aluminum, copper, ~ead, magnesium, zinc, beryllium, gold, tin, bronze, brass, etc.); glass beads, nylon or plastic particles or aluminum shot may be employed for blast cleaning the surface of the substrate. For harder, nonferrous metals (e.g., nickel) and for ferrous metals and alloys, (e.g., iron, molybdenum, chromium, tungsten, vanadium, steels and stainless steel) aluminum oxide particles, silicon carbide particles, glass beads, sand particles, steel shot and the like may be used to provide the peening action in cleansing the surface of the substrate. In this regard, it has bean found that less aggressive media (e.g., glass beads) may be used for applications where a characteristic such as quic~ release or non-sticking is desired, while more aggressive media such as aluminum oxide or silicon carbide are preferred for use in applications where end product characteristics such as increased wear resistance or dry lubricity are desired.
In regard to the delivery pressures to be employed for performing this abrasive cleaning step, it is believed that pressures up to 250 psi may be employed for hard and very hard substrates such as chrome/molybdenum steels and tungsten carbides, whereas lower delivery pressures of as low as about 20 psi may be used in other applications. As employed herein, the term "delivery pressure" is defined as the blast pressure applied to a substrate at a distance of two inches from the nozzle of the delivery device.
The temperature range to be employed in performing this abrasive cleaning step appears to be a matter of selection and not to be determinative of the quality of .. . ~ . . . .................. .
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W O 93/03921 ~c~r/US92/07~61 2~3439~
the surface treatment achieved. However, it has been found that temperatures ranging between ambient temperatures and about 50~ C are suitable for this cleaning step.
In specific abrasive cleaning/surface disruption processes employed in the laboratory, substrates which were to be cleaned/disrupted with aluminum oxide (extra fine grade-Brownells) utilized a Techni Blast Model 36 Cleaning Machine, sold under the trademark "SURFGARD" at 58 cubic feet per minute at 100 pounds pressure. This cleaning machine was equipped with a 3/16 inch blast gun with a ceramic nozzle. Alternatively, substrates which were to be cleaned/disrupted with glass beads (#270 U.SO
Sieve Size-Brownells) were blasted utilizing a Trinco Direct Pressure Cabinet Nodel 36X30tPC equipped with a 1/4 inch nozzle I.D. and the substrate was blasted at 60-120 psi tpreferably ahout 80-100 psi) at a distance of between about 2 inches and 12 inches (preferably about 6-8 inches) at an angle of about 20 - ~0 (preferably about 30 -60) until a uniformly disrupted surface was obtained and all surface contamination was removed.
In step three illustrated in the drawing, the substrate is air cleaned with dry, compressed air to remove any residual cleaning/disrupting media thereby avoiding any possible cross-contamination with different media.
once the preliminary cleaning steps one, two and three are completed, the substrate is then in condition to be processed in accordance with the present invention.
In accordance with the present invention, a pressurized stream of a particulate mixture of a sulfur containing metallic compound and a fluorocarbon pol~mer is directed in a pressurized stream to impact against the :. : ,.. . .
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surface of a substrate at a sufficient pressure and for a suf~icient~ period of time to cause the particulate mixture to interact with the substrate and to provide a surprisingly thin, impermeable, surface hardened, corrosion-resistant, durable, dry lubricant finish on the surface of the substrate.
In practice, the substrate surface to be treated is preferably a metallic surface. However, as previously noted herein, the substrate may be any suitable ferrous or lo nonferrous metal or alloy of a metal or a ceramic composition.
In order to expedite the impacting or peening of the particulate matter against the surface of the substrate, it has been found that suitable peening media having suitable shot sizes should be employed for purposes of conveying the mixture to the previously disrupted surface of the substrate. Another purpose of the peening media in addition to providing a carrier for the surface finish particula~e material is to surface harden the subs~rate through the peening process. A suitable peening medium for purposes of use in the present process is chosen as a function of its compatibility with the substrate and its affinity for the particulate surface finish material which it is carrying.
In addition, the siæe and hardness of thP peening media have been found to influence the effective transfer of the surface finish material to the cleansed, disrupted substrate surface. In this regard, we have found that shot sizes ranging from SAE Size No. S70 to about S780 (preferably about Size No. S70 and S230; most preferably about Size S170) may suitably be employed in the processes of this invention. In particular, we have found that with softer metal substrates (such as those on the Rockwell B

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scale or on the Rockwell C scale ratings of 40 and below), use of larger size shot (such as about SAE Size No. 170 and above) is preferred in order to achieve maximum surface finish coverage~ Also, we have found that with harder metals (Rockwell C scale ratings of 40 and above), such large shot (i.e., SAE No. S170 and above) is likewise preferred for purposes of achieving continuous surface coverage. However, it is to be noted that smaller size shot may also be employed in certain applications to avoid ~o surface asperities.
Examples of suitable peening media which may be used herein are steel shot, stainless steel shot, aluminum shot, plastic shot and the like having sufficient structural integrity to withstand impact on the substrate surface.
In general, the surface finish composition of this invention is a particulate mixture of solid lubricants formulated to provide dry lubrication and/or corrosion resistance and/or non-stick properties desired for purposes of the end use of the product. Suitable solid lubricants for use in the particulate mixtures of the present invention include fluorocarbon polymers and carrier or binder polymers.
Exemplary of suitable fluorocarbon polymers are homogenates or mixtures of finely-divided fluorocarbon resins having fully fluorinated carbon backbones such as tetrafluoroethylene homopolymer (TFE), hexafluoropropylene (HFP), perfluoroalkoxyvinyl ether (PPVE), copolymers of TFE and HFP, copolymers of TFE and PPVE. Other suitable fluorocarbon polymers are fluoropolymer resins which are not fully fluorinated such as ethylenetetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF~, ethylene-chlorotrifluoroethylene (ECTFE), copolymers of ethylene .
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and TFE such as products sold under the trademark "Tefzel"
by E.I. Du Pont de Nemours ~ Co. (Inc.). The molecular weight of the fluorocarbon polymers to be u~ed herein may vary over a relatively wide range although molecular weights of from abou~ 800 to about 2000 are preferred and, particularly about 1000-1800. Furthermore, it should be noted that mixtures of fluorocarbon polymers of varying molecular weights may be advantageously employed herein as, for example, mixtures of tetrafluoroethylenes having molecular weights of 1100 and 1300.
In summary, the fluorocarbon polymers are chosen ~or their ability to impart their individual characteristics to the substrate and for their affinity to the substrate, the peening media employed, and/or the other solid lubricant material chosen. Furthermore, suitable fluorocarbon polymers for use herein are impermeable and chemically unreactive to water and other solids, W
radiation and gases. The polymers are highly thermally stable and will withstand high upper surface temperatures (i.e., about 204 C - 260 C) as a result of their high C-F and C-C bond strengths and the resulting non-polar nature of the linear polymer. These resins have a low coefficient of friction and a low dielectric constant and dissipation factor. They exhibit a high degree of linear flexibility and are flame resistant.
The other solid lubricant component of the particulate mixture employed herein is a sulfur containing metallic compound which acts as a carrier or binder molecule herein. Suitable metal sulfides for purposes of the present invention possess anti-friction/dry lubrication capabilities, can withstand increased operating temperatures and/or demonstrate high affinity towards metals such as those employed as the substrates herein or ., : .: . , :
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the peening media utilized herein as well as demonstrating high affinity toward the fluorocarbon polymers selected as part of the surface treatment mixture.
Representative of suitable sulfur containing metallic compounds for use herein are sulfides of molybdenum, tungsten, lead, tin, copper, calcium, titanium, zinc, chromium, iron, antimony, bismuth, silver, cadmium and `
alloys and mixkures thereof.
In a preferred form, molybdenum disulfide is employed as the sulfur containin~ metal compound in the particulate mixtures employed. Molybdenum disulfide has a high affinity to steel and other base metals and has the ability to increase surface hardness, corrosion resistance, elevated temperature strength and dry lubricity. It also has a high affinity to fluorocarbon micropowders which may be employed advantageously herein.
Thus, it has been found that use o* molybdenum disulfide herein provides the dual function of a dry lubricant additive as well as a carrier/binder molecule for the fluorocarbon polymer to promote coating of the peening media.
In general, the amount of fluorocarbon polymer to be incorporated in the particulate mixture to provide the requisite surface finish is determined by the amount of such polymer required to saturate the carrier or binder molecule such as molybdenum disulfide. The total amount of the particulate mixture to be employed for applying the surface finish to the substrate via a peening action in a blast cabinet is determined by the amount of material required to keep the peening medium completely coatPd during the blasting operation in the cabinet.
In a laboratory example of the practice of the present invention, a Techni Blast Model 36 SURFG~RD Peen Plating - . . :, ,, , ~. ;
- .. . .. .

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WO93/03921 PCT/U~92/070~1 209 43~5 -14-Machine, 70 cubic feet per minute at lO0 pounds pressure, 3/16 inch Suction Blast Gun with Ceramic Nozzle was employed for directing the particulate mixture against the surface of a substrate in a blast cabinet. The cabinet was loaded with 500 ml. (by volume) molybdenum disulfide (Super Fine Grada, Lot #510DS, Climax Molybdenum Co.); 500 ml. (by volume) tetrafluoroethylene having a molecular wei~ht of about llO0 (Teflon Fluoroadditive Type MPllO0, Lot #BMAB40D002, Du Pont); 500 ml~ (by volume) tetrafluoroethylene having a molecular weight of about 1300 (Teflon Fluoroadditive Type MP1300, Lot #68-86, Du Pont) and 200 pounds of S70 steel shot (Techni Blast~.
The blast cabinet temperature was maintained at a~out 50 C and the delivery pressure at the nozzle of the peen plating machine was 80 psi. The particulate mixture with the peening medium was blasted at a 45 angle at a distance of about 6-8 inches until a uniform, void-free surface treatment had been achieved.
After completion of step four in the drawing wherein the finish surface is applied to the substrate in accordance with the method of the present invention, it has been found that the resulting product may advantageously be subjected to a post-treatment cleaning and preservation step (step ~ive in the drawing). In this step of the process, the substrates having the inventive surface finish applied therein are cleaned with dry, compressed air to remove any residual surface treatment particles. Thereafter, the substrate is washed with a cleaning solution and preserved with an oil that is compatible with the end use of the material, if so desired.
In a preferred embodiment of the preæent invention, a surface finish is produced in the surface of a two inch by two inch square, l/4 inch thick chrome/molybdenum steel ~; , , W O 93/03921 PC~r/US92/07061 , ~ . ;.
-15- 2~94393 sample. The hardness of the chrome/molybdenum steel sample was 53 as measured on the Rockwell C scale. In the process, after subjecting the steel sample to appropriate solvent precleaning, the sample was subjected to an abrasive cleaning/surface disruption step in a cabinet wherein aluminum oxide shot was impacted onto the steel surface at 60 psi at an angle of about 45 under ambient temperature conditions.
Thereafter, the sample was introduced into a blast cabinet and a Techni Blast Model 36 SURFGARD Peen Plating Machine having a 3/16 inch Suction Blast Gun with ceramic Nozzle was employed to direct a particulate mixture against the surface of this sample. The particulate mixture was prepared by mixing 22 ouncas (by weight) tetrafluoroethylene having a molecular weight of about 1500 ~Teflon Fluoroadditive Type MP1500J, Lot ~999999) in a container with 100 lbs. of SAE No. S170 steel shot.
Then, an additional 14.5 ounces (by weight) of tetrafluoroethylene (MP1500J) was admixed with the steel shot in the same container. In a separate container, 30 ounces (by weight) of molybdenum disulfide ~Super Fine Grade, Lot #510DS, Climax Molybdenum Co.) was mixed with 100 lbs. of SAE No. S170 steel shot.
The contents of the two containers were then mixed together and an additional 24.3 ounces (by weight) of tetrafluoroethylene (MP1500J) was added to the mixture.
The combined mixture contained 60.8 ounces (by weight) tetrafluoroethylene, approximately 30 ounces (by weight) molybdenum disulfide and about 200 lbs. SAE No. S170 steel shot. The resulting combined mixture contained a ratio by weight of tetrafluoroethylene to molybdanum disulfide of about 2:1.

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WO 93/03921 Pcl/u~ t,-j, 2~9 433~ -16-The blast cabinet temperature was maintained at about 500 C and the delivery pressure at the nozzle of the peen plating machine was 80 psi. The steel shot peening medium having the particulate mixture intimately coatsd on the suxface of the shot was blasted onto the precleaned, disrupted surface of the sample at an angle of about 4~
at a distance of about 4 inches for a period of about 15 seeonds to form a uniform, void-free surface on the surface of the chrome/molybdenum steel sample.
Subsequent to the bla~t treatment, the sample was subjected to a post-treatment cleaning step by subjecting the sample to Stoddard solvent in a Hurri-Kleen Station.
This cleaning step was followed by subsequent cleaning of the resulting product in 1,1,1 - trichloroethylene in a 15 lO00 ml. beaker and the resulting cleaned surface finish product was subjected to air drying before evaluation~
The resulting product was found to have a nonabradable, nonetchable surface which was durable,, corrosion resistant and demonstrated dry lubricity and 20 exceptional wet film entrapment characteristics~
Thus, a method has been described herein for producing a surface finish on a substrate in a manner such that the resulting product exhibits a wide range of benefits otherwise unavailable. The surface finished product 25 demonstrates permanent dry lubricity and is highly resistant to temperature extremes. Furthermore, the r surface finished product provides a natural barrier to normal oxidation and corrosion since it is chemically inert. In addition, the finish in the treated substrate 30 surface exhibits exceptional durability and is extremely thin, being measured as low as about 0.5 micron thickness as opposed to prior art coatings wherein the coat is measured in mils such as the industry standard electroless .

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~093/03921 PCT/U~g2/~

17 2~9~39~

nickel coatings which have a thickness of 3/8 mil when submerged in nickel plating solution for 45 minutes at 90.50 C. Still further, the surface finishes of the present invention are applied relatively easily even at relatively low temperatures and inexpensively in order to provide the desired surface modification herein.
The products produced in accordance with this invention have a multiplicity of uses in a variety of industries and in products containing metal on metal friction points or which are subject to metal surface corrosion. Exemplary of the scope of the utilization of the present invention are applications within the automotive industry, fuel handling systems, power tools and e~uipmen~, fasteners, ball bearings, rollers and other anti-friction components, consumer products including cookware, houseware and razor blades, turbines! gears and other intermeshing machinery as well as a variety of other potential uses.
Although the invention has been described in its preferred form with a certain degree of particularity, it is to be understood that the present disclosure has been made by way of example only. Numerous changes in the details and operational steps of the methods and in the materials utilized therein will be apparent without departing from the spirit and scope of the invention, as deined in the appended claims.

., .

.

. . .. :, . . :: :

Claims (13)

We Claim:
1. A surface finish composition for application to a substrate by peening to provide an impermeable, surface hardened, corrosion-resistant, durable, dry lubricant finished product comprising a particulate mixture of a sulfur containing metallic compound and a fluorocarbon polymer.
2. The composition of claim 1 wherein said particulate mixture chemically bonds with said substrate.
3. The composition of claim 1 wherein said sulfur containing metallic compound is molybdenum disulfide.
4. The composition of claim 1 wherein said sulfur containing metallic compound is selected from the group consisting of sulfides of tungsten, lead, tin, copper, calcium, titanium, zinc, chromium, iron, antimony, bismuth, silver, cadmium and alloys and mixtures thereof.
5. The composition of claim 1 wherein said fluorocarbon polymer is tetrafluoroethylene.
6. The composition of claim 5 wherein said tetrafluoroethylene has a molecular weight of about 800-2000.
7. The composition of claim 1 wherein said fluorocarbon polymer is a mixture of different molecular weight tetrafluoroethylenes including a tetrafluoroethylene having a molecular weight of about 1100 and a tetrafluoroethylene having a molecular weight of about 1300.
8. The composition of claim 1 wherein said fluorocarbon polymer is selected from the group consisting of hexafluoropropylene, perfluoroalkoxyvinyl ether, copolymers of tetrafluoroethylene and hexafluoropropylene, copolymers of tetrafluoroethylene and perfluoroalkoxyvinyl ether, ethylenetetrafluoroethylene, polyvinylidene fluoride, ethyl-chlorotrifluoroethylene, copolymers of ethylene and tetrafluoroethylene and mixtures thereof.
9. A surface finish composition for application to a metal substrate by peening to provide an impermeable, surface hardened, corrosion-resistant, durable, dry lubricant finished product comprising a particulate mixture of molybdenum disulfide and a fluorocarbon polymer.
10. The composition of claim 9 wherein said fluorocarbon polymer is tetrafluoroethylene.
11. The composition of claim 10 wherein said particulate mixture is chemically bonded with said surface of said metal substrate.
12. The composition of claim 10 wherein said tetrafluoroethylene has a molecular weight of about 800-2000.
13. The composition of claim 11 wherein said fluorocarbon polymer is a mixture of different molecular weight tetrafluoroethylenes including a tetrafluoroethylene having a molecular weight of about 1100 and a tetrafluoroethylene having a molecular weight of about 1300.
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CZ81693A3 (en) 1994-02-16
SK45093A3 (en) 1993-09-09
NO931446D0 (en) 1993-04-20
PL298944A1 (en) 1994-01-10
CA2094396A1 (en) 1993-02-27
FI931869A0 (en) 1993-04-26
EP0558724A1 (en) 1993-09-08
NO931445L (en) 1993-04-20
WO1993003921A1 (en) 1993-03-04
MX9204930A (en) 1993-11-01
CN1073213A (en) 1993-06-16
ZA926454B (en) 1993-11-26
FI931869A (en) 1993-04-26
BR9205401A (en) 1994-03-08
HU9301210D0 (en) 1993-09-28
AU2552592A (en) 1993-03-16
JPH06501052A (en) 1994-01-27
AU2515392A (en) 1993-03-16
FI931868A (en) 1993-04-26
HUT67837A (en) 1995-05-29
IL102952A0 (en) 1993-01-31

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