HUT67837A - Surface-treating method for making of a corrosion-resistant, impermeable surface-finish, and the surface-finished product thereof - Google Patents

Description

The present invention relates to a surface treatment method for forming a corrosion-resistant impermeable layer on a substrate surface. The process of the present invention provides a substrate that exhibits a non-abrasive, non-abrasive (non-etchable), durable, dry state slip (slippery, smear), corrosion resistance, and improved wet film bonding capability. The invention also relates to a process for applying a surface treatment agent to a substrate.

The process of the present invention is carried out by preparing a fine particle mixture comprising a sulfur-containing metal compound and a hydrofluorocarbon polymer, and then spraying the material containing the resulting fine particle mixture under pressure into the substrate surface; then contacting the jet of material with the substrate surface under pressure for a suitable period of time to interact with the substrate surface to form a thin, impermeable, surface-hardened, corrosion-resistant, slippery finish under durable, dry conditions.

Although the invention is primarily directed to the surface treatment of metallic substrates, it should be noted that the solution may likewise be applicable to surface treatments carried out on other suitable substrates, such as ceramic compositions. It should also be noted that as the metallic substrate used in the present invention, metals from very hard metals having a hardness factor of more than 40 on the Rockwell C scale to soft metals may be classified as Rockwell B hardness factors.

Accordingly, the present invention may be applied to substrates of a variety of materials, provided that the substrate material has a structural strength such that it can withstand high pressures required to carry out the application process of the invention.

A wide variety of corrosion-resistant coatings, as well as the application and application of such coatings to substrates have been known; as an example we mention

574,658, 3,754,976, 4,228,670, 4,312,900, 4,333,840,

U.S. Patent Nos. 415,419, 4,522,784, 4,553,417, and 4,753,094.

The aforementioned patents disclose processes for applying coatings to the workpiece surface by applying cold working or blasting, the coating material being applied in the form of pellets or other particulate material, whereby a high pressure is applied to the workpiece surface; Thus, the coating is applied to the workpiece surface in the form of pellets or granules.

U.S. Patent 3,574,658 discloses a method for applying a dry lubricant in the form of a molybdenum or tungsten disulfide coating and a method for applying this dry lubricant in the form of a coating on a workpiece surface. United States, US 3,754,976, ···

U.S. Pat. No. 4,122,125 describes a coating process in which the granular or powdered metal is cold-worked on a workpiece surface previously cleaned with a slight radius of cold-workable particles without the coating material. U.S. Patent No. 4,228,670 discloses a method of mixing a steel or glass filler with a lubricant and applying it to the workpiece for application.

U.S. Pat. No. 4,312,900 discloses a process wherein the workpiece is first made to have a rough surface by applying granular abrasives, such as by blowing glass or sand, and then by spraying dry molybdenum disulphide into holes in the workpiece by spraying the granules. U.S. Patent 4,552,784 discloses a further process wherein metal powder is applied to the workpiece surface by cold working. U.S. Pat. No. 4,753,094 discloses a process for applying a thin film coating of molybdenum disulfide to a substrate by cold machining to provide adhesion of the molybdenum disulfide as a coating on the substrate.

In contrast, none of the methods known to date have provided a product in which all of the product's features and properties would achieve the product of the present invention; and to date no processes for the preparation of such a product have been disclosed. Intensive research and development of substrate • · «

- to extend the wear life and improve the friction properties of surfaces, such as metal surfaces, and to reduce the cost of repair and replacement of parts. These efforts have so far been relatively unsuccessful in the use of coatings, paints and lubricants (either wet or dry) known hitherto. Known methods for treating surfaces, such as metal surfaces, have raised significant problems, and the costs, difficulties of application, and the properties of the products obtained to date have been unsatisfactory.

It has now been found that the process of the present invention may modify the surfaces in such a way that multiple layers of polymer can be bonded to the surface of the treated workpiece or substrate. In this context, the term "bond" or "knit" is used to refer to any physical or chemical bond (s) that are found in products having the desired characteristics. It is believed that the result of the surface treatment according to the invention is not a coating, but that the applied surface is permanently bonded to the substrate and can only be removed therefrom by grinding the substrate surface itself. Accordingly, the surface treatment process of the present invention provides products having a more durable, long-lasting, dry-lubricated, corrosion-resistant surface finish.

Methods known hitherto have been used to transfer the beneficial physical properties of polymers to the substrate surface, for example, metal surfaces with fluorocarbon polymers such as tetrafluoroethylene (TFE, in short: ··· ····. * ·· . * marketed, for example, under the trade name Teflon 'by EI Du Pont de Nemours & Co.). It is known to reduce the friction of Teflon-coated surfaces, but their adhesion to the substrate must be ensured by the use of primary materials such as epoxy compounds. As a result, the coating is already abraded from the coated surface under moderate pressure, the coating is uneven, thin, and requires high temperatures to be applied.

The present invention overcomes many of the drawbacks of the prior art. The present invention provides a mixture of fine particles of a sulfur-containing metal compound, such as molybdenum disulfide or tungsten disulfide, and a fluorocarbon polymer, such as tetrafluoroethylene, in which the fluorocarbon polymer is the ratio of sulfur to metal compound ranges from about 1: 1 to about 10: 1.

In the present invention, the fine particle mixture is radially pressurized with the substrate surface under pressure at a suitable pressure and for a period of time to effect surface modification by interaction of the fine particle mixture with the substrate. The application of surface treatment agents to the substrate surface results in the product so treated exhibiting excellent corrosion resistance and long-term dry lubricity. It has also been found that this surface treatment produces a relatively thin, impermeable, surface-hardened surface on the substrate or workpiece. This surface design is thin enough not to affect the critical tolerance properties of the machined parts or components.

Accordingly, the present invention relates to a new and improved surface treatment agent for substrates, and to a process for the application of surface treatment agents X to substrates.

Furthermore, the object of the present invention is to provide an impermeable and hardened outer surface of the substrate by using corrosion-resistant, long-lasting, non-slip surface treatment agents.

The invention further relates to a process for providing a corrosion-resistant, long-lasting, slippery surface on substrates in a dry state.

The invention also relates to surface-treated, durable, dry-slip products.

FIELD OF THE INVENTION The present invention relates to a process for forming metal surfaces which are durable, dry, slippery and resistant to extreme temperatures. The present invention also relates to methods for providing a long-life, dry-slip, corrosion- and heat-resistant improved film finish (or film retention).

Another object of the present invention is to provide a relatively easy and inexpensive method of applying the surface treatment agent of the invention.

It is an object of the present invention, apart from those listed above

will be apparent to one of skill in the art from the following description.

Figure 1 is a schematic diagram illustrating the process of the present invention; the method is used to form a dry slippery, corrosion-resistant substrate surface.

Figure 1 illustrates an embodiment of the process of the present invention wherein a substrate is surface treated.

In the embodiment illustrated in Figure 1, a multi-step operation is used; during this process, a substrate surface is first pre-cleaned with a solvent to remove loosely adhering surface contaminants such as hydrocarbons and other physical and chemical residues prior to further processing. This preliminary cleaning step is performed to reduce surface contamination, which may interfere with the application of the surface treatment agent to the substrate.

The solvent used in the preliminary purification is to some extent substrate specific. For example, heavily soiled, fatty substrates must be treated with Stoddard solvent to clean the substrate surface. For non-degassed substrate surfaces, such as chromium, molybdenum or stainless steel, 1,1,1-trichloroethane or an equivalent solvent may be used by ultrasonic cleaning. For degassed substrates, a Branson IS solvent is used by ultrasonic purification.

During laboratory pre-solvent solvent cleaning, a metal surface is brushed with a Stoddard solvent in a HurriSafe Special Formula Degreaser (1: 4) dilution in a HurriKleen cold washer, then the substrate is air dried. Subsequently, the material is purified using either a Branson IS cleaning solution (1:10 dilution) or a 1,1,1-trichloroethane pre-cleaner (commercially available from Brownells) using a Branson 8200 ultrasonic cleaning device (diluted 1:10 in Branson IS cleaner). Purification time at 40 ° C is about 15 minutes.

As shown in Figure 1, after completion of the solvent pre-purification step, the substrate is subjected to abrasive cleaning, surface disintegration; Thus, a sufficient and sufficient amount of disrupted area is provided on the substrate surface in order to ensure proper interaction with the applied surface treatment agent. In this abrasive (abrasion, abrasion) cleaning step, any oxidation or other impurities remaining on the substrate after the previous pre-cleaning step are removed.

This abrasive cleaning / disintegration step may be carried out in a blow-down chamber by the pre-cleaning process described in U.S. Patent 4,753,094, which is incorporated herein by reference. In this step, the specific parameters of the treatment process must be selected depending on the substrate material and its intended use. Accordingly, for example, pressure, velocity, temperature, application angle, application time, and other similar process parameters may be varied depending upon the purpose of the final treatment of the substrate; For example, slippage in the dry state, enhancement of abrasion resistance, reduction of adhesion, variation of operating temperature range and / or increased corrosion resistance.

With respect to the substrate-applied materials used in this abrasive cleaning / disintegration step, it has been found that non-ferrous softer types and alloys (e.g., aluminum, copper, lead, magnesium, zinc, beryllium, gold, tin, bronze, brass) glass beads, nylon, plastic or aluminum particles are preferably used to blow off the surface of the substrate. For harder metals other than iron, such as nickel, as well as ferrous metals and alloys (e.g., iron, molybdenum, chromium, tungsten, vanadium, steel grades and stainless steel), alumina, silica carbide particles, glass beads, sand particles , steel particles can be used to cold-clean the substrate surface. In this regard, it has been found that less aggressive media (e.g., glass beads) may be used where the property to be developed is to eliminate surface adhesion; however, the use of a more aggressive excipient, such as alumina or silicon carbide, is desirable when a surface treatment agent is desired to provide a finished product with higher wear resistance or improved dry lubricity.

For the abrasive cleaning step, it is believed that for pressures that can be applied to the inflation process, hard and very hard substrates, such as chromium and molybdenum steels and tungsten carbides, may be pressurized to about 1700 kPa; lower pressures up to about 140 kPa can be used for other applications. As used herein, the term application pressure refers to the pressure applied when the substrate is 5 cm from the nozzle of the dispensing device.

The temperature range used in the abrasive (abrasion, abrasion) cleaning step is freely variable and is not critical to the quality of the surface treatment. However, it has been found that a temperature range of from room temperature to about 50 ° C is advantageous in carrying out this purification step.

In our laboratory, abrasive cleaning / disintegration procedures were carried out on substrates using alumina (Brownells product, extremely finely divided) in a Techni Blast 36 Model purifier (trade name: Surfgard) at 1643 liters per minute at 5000 kPa. The purification unit was equipped with a 4.8 mm ceramic nozzle nozzle. Substrates that are cleaned and abraded by glass beads (U.S. Sieve Size-Brownells # 270) are aspirated with a Trinco Direct Pressure Cabinet Model 36X0 / PC equipped with a 6.3mm inside diameter nozzle; the substrate under a pressure of 410-820 kPa (preferably about 550-690 kPa) at a distance of about 5 cm to 30 cm (preferably 15-20 cm) at an angle of about 20 ° to 90 ° (preferably about 30 ° to 60 ° C). °) until a uniformly abraded surface is obtained and all surface contamination is removed.

In the third step shown in Figure 1, the substrate is cleaned with dry, pressurized air to remove any residual cleaning / abrasive agents, thereby avoiding the possibility of reverse dirt when using different agents.

After completion of the first, second and third pre-cleaning steps, the substrate is in a state suitable for machining according to the present invention.

In the present invention, a fine particle mixture comprising a sulfur-containing metal compound and a hydrofluorocarbon polymer is directed under pressure to a surface of a substrate at a suitable pressure for a period of time; Thus, the fine-grained mixture is interacted with the substrate to form a surprisingly thin, impermeable, hard, corrosion-resistant, long lasting, slippery surface on the substrate.

In practice, the substrate surface to be treated is a preferred metal surface. However, as noted above, the substrate may be any metal, metal alloy, or ceramic composition of suitable iron type or non-iron type.

In order to facilitate collision with the surface of the substrate and the cold working of the substrate, it has been found to be appropriate to apply a cold working medium having a suitable particle size, which is sprayed onto the previously abraded surface of the substrate. Another function of the cold working medium, apart from forming a finishing material carrier, is to harden the surface of the substrate by the cold working process. In the present invention, the cold working medium is selected on the basis of its compatibility with the substrate and its affinity for the fine particle surface treatment agent.

It has been found that the particle size and hardness of the cold working medium influence the application of the surface treatment agent to the cleaned, scratched substrate surface. In this regard, it has been found that a particle size of SAE from S70 to about S780 (preferably from about S70 to S230, most preferably about S170) is suitable for the process of the invention. In particular, it has been found that for softer metal substrates (e.g., metal substrates having a grade 40 or less on the Rockwell B scale or Rockwell C scale) a larger particle size (such as about SAE 170 or greater) is preferred effect. It has also been observed that for harder metals (which are on the Rockwell C scale at or above 40), such a large particle size (i.e., SAE S170 or larger) is likewise advantageous in providing a favorable surface layer. However, it is noted that in some cases a smaller particle size medium may be used to avoid surface irregularities.

Suitable cold working fluids include: steel, stainless steel, aluminum, plastic granules, which are sufficiently resistant to impact on the substrate surface.

In the present invention, a finely divided mixture of solid lubricants is generally used as a surface treatment composition; which are formulated for the desired dry slip and / or corrosion resistance and / or non-stick properties and are suitable for the purpose of the end product. Examples of solid lubricants that can be used in the finely divided mixture of the present invention include fluorocarbon polymers and carrier or binder polymers.

As the fluorocarbon polymer, for example, a finely divided fluorocarbon resin homogenate or mixture in which the carbon chain is fully fluorinated, such as tetrafluoroethylene homopolime (TFE), hexafluoropropylene (HFP), perfluoroalkoxyvinyl ether (e.g. PVE); and TFE and HFP copolymers and TFE and PVE copolymers. Polymers which are not fully fluorinated, for example: ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), ethylene chlorotrifluoroethylene (ECTFE), can also be used as fluorocarbon polymers; and copolymers of ethylene and PFE, such as E. I. Du Pont de Nemors & Co.

Copolymers of PFE, such as those sold under the tradename Tefzel by E. I. Du Pont de Nemors & Co. The molecular weight of the fluorocarbon polymers that can be used can vary within a relatively wide range, although polymers having a molecular weight of from about 800 to about 2000, in particular from about 1000 to about 1800, are preferred. It is further noted that mixtures of hydrofluorocarbon polymers of different molecular weights, for example mixtures of tetrafluoroethylenes with a molecular weight of 1100 to 1300, are advantageously used.

To sum up the above: fluorocarbon polymers are alkylated with the aim of transferring their properties to the substrate; they are selected on the basis of their affinity for the substrate, depending on the cold working medium used and / or other solid lubricants. Polymers of hydrofluorocarbons which are impermeable to water and solids, ultraviolet radiation and gases, and do not react chemically, can be used in the process of the invention. These polymers are very heat stable and resistant to higher surface temperatures, i.e., about 204-260 ° C, due to the high strength of the C-F and C-C bonds in the compounds and the nonpolar nature of the resulting linear polymer. Such resins have low friction coefficients, low dielectric constants and high scattering coefficients, high linear flexibility and high fire resistance.

• ·

Another solid lubricant component of the fine particle mixture used in the process of the invention is a sulfur-containing metal compound that plays the role of a carrier or binding molecule. The metal sulfides suitable for the purposes of the present invention have an anti-friction and dry lubricity, high temperature resistance, and / or high affinity for metals which may act as substrates; in addition, they are resistant to the cold working fluids used in the present invention and exhibit high affinity for fluorocarbon polymers as a component of the surface treatment mixture.

Suitable sulfur containing metal compounds useful in the present invention include sulfides of molybdenum, tungsten, lead, tin, copper, calcium, titanium, zinc, chromium, iron, antimony, bismuth, silver, cadmium and alloys and mixtures of these metals.

Molybdenum disulfide is preferably used as the sulfur-containing metal compound in the fine-grained mixture. Molybdenum disulphide has a high affinity for steel and other base metals, and has the ability to increase surface hardness, corrosion resistance, and heat resistance and dryness, as well as high affinity for those hydrocarbon polymer microcrystalline powders. which are advantageously used in the present invention. Molybdenum disulfide has been found to play a dual role; on the one hand, the lubricant contains an additive and, on the other hand, forms a carrier or binding molecule with the fluorocarbon polymer * · · · · · · · · · · · · · · · · · ·

The amount of fluorocarbon polymer added to the particulate mixture is determined by the amount of polymer required to saturate the carrier or binding molecule, such as molybdenum disulfide. The total amount of fine-grained mixture that is to be applied to the substrate by cold working for surface treatment is determined by the amount of material required to ensure complete coating with the cold working medium during the blasting operation.

The process of the present invention was performed in a laboratory practice using a Techni Blast Model 36 SURFGARD Peen Plating Cold Processor at a rate of 1980 liters per minute at a pressure of 500 kPa with a 4.8 mm gun spray gun; in doing so, the fine-grained mixture was blown from a blow chamber to the surface of the substrate. The chamber contains 500 ml of molybdenum disulfide (superfine grade from Climax Molybdenum Co.) and 500 ml of tetrafluoroethylene (Teflon Fluoroadditive Type MP1100, Lot BMAB40D002, Du Pont) of about 1100 molecular weight, 500 ml of about 1300 molecular weight tetraluor-ethyl Fluoroadditive Type MP1300, Lot-68-86, Du Pont) and 100 kg S70 Steel Fill (Techni Blast) were placed. The supply chamber temperature was maintained at about 50 ° C while maintaining an outlet pressure of 560 kPa in the cold-processing nozzle. The fine-grained mixture was sprayed with the cold working medium at an angle of 45 °, at a distance of about 15-20 cm, until a smooth, non-greasy surface was obtained.

until a smooth, gap-free surface is obtained.

The process according to the invention is illustrated in Figure 1 below.

Figure 1

After completion of the fourth step of Figure 1, wherein the surface treatment agent is applied to the substrate according to the process of the present invention, the resulting

(this is the fifth step shown in Figure 1). In this process step, the substrates obtained by surface treatment according to the invention are cleaned with dry, pressurized air to remove any residual material from the surface treatment, then washed with a cleaning solution and, if desired, preserved with an oil compatible with the intended use of the product.

In a preferred embodiment of the present invention, the surface treatment is carried out on a 5 x 5 cm square surface of a 6.5 mm thick chromium molybdenum steel sample. The hardness of the chromium molybdenum steel sample, measured on a Rockwell C scale, 53. In the process, the steel sample was pre-cleaned with a suitable solvent and then subjected to an abrasive cleaning / abrasion step in a chamber where aluminum oxide particles were contacted; the operation was carried out at a pressure of 410 kPa, at an angle of about 45 °, at room temperature.

Subsequently, the sample was placed in a supply chamber and a Techni Blast Mdel 37 SURFGARD Peen Piating cold machining device equipped with a ceramic nozzle was applied to blow the fine-grained mixture onto the surface of the steel sample. The fine particle mixture was prepared by mixing 620 g of tetrafluoroethylene (Teflon Fluoroadditive Type MP1500J, Lot 999999) with a molecular weight of about 1500, in a container with 45 kg of SAE S170 steel granules, and then adding 430 g of tetrafluoroethylene in the same container. added. In another tank ··· ··· · ····· · · · · · · · · · · · · ·

- 20,860 g of molybdenum disulfide (superfine grade, Lot 510DS, Climax Molybenum Co.) were mixed with 45 kg of SAE S170 steel grain.

The contents of the two vessels were then combined with stirring, and an additional 680 g of tetrafluoroethylene (MP1500J) was added. The resulting mixture contained 1730 g of tetrafluoroethylene, approximately 850 g of molybdenum disulphide and about 90 kg of SAE S170 steel grain. In this mixture, the weight ratio of tetrafluoroethylene to molybdenum disulfide is about 2: 1.

The supply chamber temperature is maintained at about 50 ° C, and the pressure at the nozzle of the cold working machine is adjusted to 550 kPa. The cold working medium containing the fine-grained mixture was applied to the pre-cleaned, scratched sample surface at an angle of about 45 °, from a distance of about 10 cm, for about 15 seconds, to create a smooth, non-void surface on the chromium molybdenum steel sample.

Following the infusion treatment, the sample was subjected to a post-treatment purification step by treating the sample with a Stoddard solvent in a Hurri-Kleen Station. This step was followed by purification of the resulting product in a 1000 mL beaker; the reaction was performed with 1,1,1-trichloroethylene; the resulting purified surface treatment product was then air dried prior to evaluation.

We have found that the product thus obtained has a non-abrasive, non-abrasive surface that is durable, corrosion-resistant, and resistant to dry conditions. between slippery; these properties and the film coating properties under wet conditions are outstanding.

By the method described above, surface treatment may be carried out on a substrate; the product thus obtained has not yet been known, has significant advantages. The surface-treated product exhibits persistent slippery properties under dry conditions and is extremely resistant to extreme temperatures; in addition, the resulting layer forms a natural barrier to normal oxidation and corrosion since it is chemically inert.

In addition, the surface of the substrate formed by the treatment has a very high durability and is extremely thin; only about 0.5 microns in thickness, as opposed to prior art coatings, which can be several microns thick: for example, standard industrial electrolytic nickel coatings have a thickness of about 9 microns when immersed in nickel solution for 45 minutes at 90.5 ° C. In addition, the surface treatment of the present invention can be carried out relatively easily and cheaply, even at relatively low temperatures, to effect desired surface modifications.

The products of the present invention can be used for a variety of purposes in a variety of industries, particularly those used at metal-to-metal friction sites or subject to corrosion of their metal surfaces. The present invention can be used, for example, in the automotive industry, fuel management systems, steering systems, accelerators, ball bearings, rollers and other anti-friction components, as well as in consumer products such as razor blades, turbines, bearings, and a variety of related, other types of area.

Although the present invention has been described in a preferred embodiment by way of a specific example, it should be understood that this disclosure is by way of example only and without limitation. Many details can be changed in the process, the materials used and the steps of the operation, which obviously do not go beyond the spirit and scope of the invention. The scope of the invention is defined by the following claims.

Claims (38)

- 23 Patent claims CLAIMS 1. A method of treating a surface to form a corrosion-resistant impermeable layer on a surface of a substrate, comprising: forming a fine particulate mixture containing a sulfur-containing metal compound and a hydrofluorocarbon polymer, and applying the resulting fine-grain mixture to a substrate ; and contacting the material jet with the substrate surface under pressure for a suitable period of time to interact with the substrate surface to form a thin, impermeable, surface-hardened, corrosion-resistant, slippery surface under durable, dry conditions. 2. A process according to claim 1, wherein the substrate is a metal. The process of claim 1, wherein the substrate is a ceramic composition. 4. The method of claim 1, wherein the fine-grained mixture is bonded to the surface of the substrate upon impact of the fines with the surface. 5. The process of claim 1 wherein the sulfur-containing metal compound is molybdenum sulfide. A process according to claim 1 wherein The sulfur-containing metal compound used herein is sulfide of tungsten, lead, tin, copper, calcium, titanium, zinc, chromium, iron, antimony, bismuth, silver, cadmium, or an alloy of these metals, or mixtures thereof. The process according to claim 1, wherein the fluorocarbon polymer is tetrafluoroethylene. The method of claim 7, wherein Hence, tetrafluoroethylene having a molecular weight of about 800-2000 is used. The method of claim 1, wherein Hence, the fluorocarbon polymer used is tetralourethylene of various molecular weights, such as about 1,100 molecular weight tetrafluoroethylene and about 1,300 molecular weight tetrafluoroethylene. The method of claim 1, wherein Hence, as a fluorocarbon polymer, hafafluoropropylene, perfluoroalkoxyvinyl ether, copolymers of tetrafluoroethylene and hexafluoropropylene, copolymers of tetrafluoroethylene and perfluoroalkoxyvinyl ether, ethylene tetrafluoroethylene, ethylene, polyvinylidene fluoride, ethyl chlorotrifluoroethylene, copolymers of ethylene and tetrafluoroethylene, or mixtures thereof. The method of claim 1, wherein Therefore, the material radius is about 140 kPa and about · · * * · «4 ··· - applied at a pressure of 25,830 kPa. The process according to claim 1, wherein the material jet is steel grain, stainless steel grain, aluminum grain, plastic grain, or mixtures thereof as a cold working medium. 13. The method of claim 1, wherein the substrate surface is subjected to a preliminary cleaning (pre-cleaning) prior to impacting the material beam with the surface. The method of claim 13, wherein the preliminary cleaning is performed by abrasive cleaning and abrasion of the surface. 15. The method of claim 1, wherein the material beam is subjected to a cleaning and preservative treatment after impacting the material beam with the substrate surface. / - · 16. A process for treating a surface on a metal substrate, comprising the step of forming a fine mixture of molybdenum disulfide and a fluorocarbon polymer; applying the fine particle mixture to the surface of the metal substrate mixed with a cold working medium; and combining the cold working medium and the fine particulate mixture with the substrate surface to provide an impermeable, surface-hardened, corrosion-resistant, durable, dry-slip finish on the substrate surface. 17. The method of claim 16, wherein The use of tetrafluoroethylene as the fluorocarbon polymer. 18. The method of claim 17, wherein the surface of the metal substrate is chemically bonded to the surface of the metal substrate upon contacting the combination of the cold working fluid and the fine particle mixture. 19. The process of claim 17 wherein the tetrafluoroethylene has a molecular weight of about 800 to about 2000. 20. The process of claim 16 wherein the fluorocarbon polymer is selected from the group consisting of tetrafluoroethylene of various molecular weights, such as tetrafluoroethylene of about 1100 molecular weight and tetrafluoroethylene of about 1300 molecular weight. 21. The method of claim 16, wherein Hence, the surface of the metal substrate is pre-cleaned prior to impacting the material with the surface. The method of claim 21, wherein the preliminary cleaning is accomplished by abrasive cleaning and surface disintegration. The method of claim 16, wherein Hence, after contacting the beam of material with the surface of the substrate, the substrate is subjected to a cleaning and preservative treatment. 24. A surface treated product characterized by r M k 4 that a substrate having a surface treated with a sulfur-containing metal compound and a fine-grained mixture of fluorocarbon polymer is impermeable to the surface of the substrate. , surface-hardened, corrosion-resistant, durable, dry-lubricated. 25. The product of claim 1, wherein z It is noted that it contains a metal as a substrate. 26. The product of claim 1, wherein z It is claimed that it contains a ceramic composition as a substrate. 27th 24th The product of claim 1, a It is noted that the fine-grained mixture is chemically bonded to the substrate surface. The product of claim 24, a Hence, it contains molybdenum disulfide as a sulfur-containing metal compound. 29. The product of claim 24, wherein the sulfide (s) of tungsten, lead, tin, copper, calcium, titanium, zinc, chromium, iron, antimony, bismuth, silver, cadmium or an alloy of these metals , or mixtures thereof. 30. The product of claim 24, wherein the fluorocarbon polymer is tetrafluoride contains ethylene. 31. The product of claim 30, wherein: -281 e w h e r t e r t h e includes tetrafluoroethylene having a molecular weight of about 800-200. 32. The product of claim 24, wherein the fluorocarbon polymer comprises a mixture of tetrafluoroethylene of various molecular weights, such as a tetrafluoroethylene having a molecular weight of about 1100 and a tetrafluoroethylene having a molecular weight of about 1300. 33. The product of claim 24 wherein the fluorocarbon polymer is hexafluoropropylene, perfluoroalkoxyvinyl ether, copolymers of tetrafluoroethylene and hexafluoropropylene, tetrafluoroethylene and perfluoroalkoxyvinyl. ether copolymers, ethylene tetrafluoroethylene, polyvinylidene fluoride, ethyl chlorotrifluoroethylene, copolymers of ethylene and tetrafluoroethylene, or mixtures thereof. 34. A surface-treated product comprising a surface having a surface metal substrate and, after treatment with a molybdenum disulphide and a fine particle mixture of a hydrofluorocarbon polymer, having an impermeable, surface-hardened, corrosion-resistant, durable, dry lubricant layer on the surface of the substrate. The product of claim 34, wherein the layer comprises tetrafluoroethylene as the fluorocarbon polymer. 36. The product of claim 35, wherein the fine-grained mixture is a metal substrate. «···· ·· ··· ··· - chemically bonded to 29 surfaces. 37. The product of claim 35, wherein the layer comprises tetrafluoroethylene having a molecular weight of about 800 to about 2000. 38. The product of claim 36, wherein the layer comprises a mixture of tetrafluoroethylene of various molecular weights, such as tetrafluoroethylene of about 1100 molecular weight and tetrafluoroethylene of about 1300 molecular weight, as the fluorocarbon polymer.