WO2022056059A1

WO2022056059A1 - Thermal-diffused metal on electroless metal or metal alloy having a phosphorous component

Info

Publication number: WO2022056059A1
Application number: PCT/US2021/049559
Authority: WO
Inventors: Richard Ian MACMOY
Original assignee: Macmoy Richard Ian
Priority date: 2020-09-09
Filing date: 2021-09-09
Publication date: 2022-03-17

Abstract

Disclosed are compositions, apparatuses, and methods for electroless-plating metal or metal alloy in a solution comprising phosphorous to produce a phosphorus electroless metal or metal alloy followed by thermal-diffused-coating of the phosphorus electroless metal or metal alloy with solid particles of aluminum, bismuth, zinc, silicon, chromium, cadmium, tin, carbon, or combinations thereof to produce a composition, wherein the composition may be formed, such as molded, or unformed into an apparatus, itself, or may be applied, such as sprayed, coated, brushed, or otherwise onto an apparatus, such substrate comprising a bolt or otherwise, wherein the composition optionally acts as a dry lubricant.

Description

THERMAL-DIFFUSED METAL ON ELECTROLESS METAL OR METAL ALLOY HAVING A PHOSPHOROUS COMPONENT

REFERENCE TO RELATED APPLICATION

[0001] This application is a Patent Cooperation Treaty application, which claims priority to United States provisional patent application serial number 63/075,923 filed on 9 September 2020 that is hereby incorporated by this reference in its entirety.

FIELD

[0002] This application relates to compositions, apparatuses, and methods for thermal- diffused metal coating of electroless metal and/or metal alloys, which comprise phosphorous.

BACKGROUND

[0003] In the design and manufacture of metal components, there is often a need to modify properties of the material surface against corrosion resistance, wear, and other deleterious effects. Sometimes, electroless-plating of metals are used to provide a barrier to chemical altering and wearing of metal parts.

[0004] Also, thermal-diffused zinc (“TDZ”) may coat substrates, e.g., metallic parts. Broadly, TDZ may be considered a chemical-vapor, deposition process performed by rotating retorts. In the TDZ process, ferrous metal is heated to an elevated temperature within a TDZ- retort furnace; neither gas nor vacuum is needed while zinc atoms are diffused onto/into the surface and sub-surface of the ferrous metal. The zinc content in the surface and near subsurface of the ferrous material is increased while new intermetallic zinc rich alloy layers are formed. Thus, the characteristics of the ferrous material are modified to provide a hardened outer surface surrounding an interior core.

[0005] In response to the continued demand for new goods and services, engineers and scientists are always seeking to enhance products through material selection and/or process development. One ferrous material of interest is a steel material made available under the trademark of Intermetallic (TZN) Thermal Zinc Nickel, which is used in relation to API SCT threaded tool joints and couplers.

[0006] While there are prior processes for TDZ in steel materials, there remains a need for additional developments. In furtherance of this need, the present disclosure provides a novel and non-obvious/inventive compositions, methods, and apparatuses for TDZ enhancing metals and metal alloys. SUMMARY

[0007] In one example embodiment, disclosed are methods for electroless-plating metal or metal alloy in a solution comprising phosphorous, e.g., a phosphate solution, to produce a phosphorus electroless metal or metal alloy followed by thermal-diffused-coating of the phosphorus electroless metal or metal alloy with solid particles of aluminum, bismuth, zinc, silicon, chromium, cadmium, tin, carbon, or combinations thereof to produce a composition, wherein the composition may be formed, such as molded, or unformed into an apparatus, itself, or may be applied, such as sprayed, coated, brushed, or otherwise onto an apparatus, such substrate comprising a bolt or otherwise, wherein the composition optionally acts as a dry lubricant.

[0008] In another example embodiment, disclosed are compositions comprising a phosphorus electroless metal or metal alloy having a thermal-diffused coating comprising aluminum, bismuth, zinc, silicon, chromium, cadmium, tin, carbon, or combinations thereof. [0009] In yet another example embodiment, disclosed are apparatuses, wherein the disclosed composition is applied, in any fashion known in the art, to a substrate, such as a bolt, a screw, a machined part, a threaded part, or additive part for optionally adhering or connecting, whether removably or irremovably, to another substrate. In other embodiments, the composition is an apparatus, whether formed, such as through molding, or unformed, i.e., in its natural form.

DETAILED DESCRIPTION

[0010] Below, directional terms, such as “above,” “below,” “upper,” “lower,” “front,” “back,” “top,” “bottom,” etc., are used for convenience in referring to the accompanying drawings. In general, “above,” “upper,” “upward,” “top,” and similar terms refer to a direction away the earth’s surface, and “below,” “lower,” “downward,” “bottom,” and similar terms refer to a direction toward the earth’s surface, but is meant for illustrative purposes only, and the terms are not meant to limit the disclosure.

[0011] As used herein, “substantially” is defined to mean that the particular component is largely, but not wholly, absent a particular component. In some embodiments, small or infinitesimal amounts of the component may be present, such as because of standard or nonstandard manufacturing methods, including, for example, recycling or contamination during processing.

[0012] As used herein, “about” is defined to mean ± 10%. [0013] Various specific embodiments, versions and examples are now be described, including exemplary embodiments and definitions that are adopted herein for purposes of understanding. While the following detailed description gives specific preferred embodiments, those skilled in the art will appreciate that these embodiments are exemplary only, and that the disclosure can be practiced in other ways. For purposes of determining infringement, the scope of the invention will refer to the any claims, including their equivalents, and elements or limitations that are equivalent to those that are recited.

[0014] In various embodiments, disclosed are methods comprising, consisting essentially of or consisting of: electroless-plating of electroless-plating metal or metal alloy in a solution comprising, consisting essentially of or consisting a solvent and phosphorous, e.g., a phosphorous salt, complex, or otherwise, to produce a phosphorus electroless metal or metal alloy followed by thermal-diffused coating of the phosphorus electroless metal or metal alloy with vaporized, solid particles, e.g., dust, powder, granules etc., of aluminum, bismuth, zinc, silicon, chromium, cadmium, tin, carbon, or combinations thereof to produce a composition, which is an apparatus, formed (e.g., molded) into an apparatus or in some other fashion known in the art, applied, adhered, or connected - whether removably (as is the usual case when the composition is applied, e.g., spraying, coating, brushing, etc.) or irremovably - to a substrate, e.g., bolt, screw, bearing, wrench, handle, joints, couplers, rig or car parts, computer part, circuitry, carbon fiber, polymer, plastic, ceramics, metals, metal alloys, etc. In example embodiments, zinc particles may be on the order of about 50 pm or smaller and aluminum granules may be on the order of about 3 mm or smaller. Generally, smaller, solid particles increase homogeneity of the disclosed, thermal-diffused coating onto the phosphorus electroless metal or metal alloy. In principle, dust or powders particles should be smaller than about 50 pm, and granules should be smaller than about 3 mm for the disclosed methods.

[0015] Electroless-plating and TDZ are known processes in the art, but their combination for the disclosed methods, compositions and apparatuses are not. Disclosed are methods and compositions include electroless-plating metal or metal alloy in a solution comprising phosphorous to produce a phosphorus electroless metal or metal alloy. The metal or metal alloy to be electroless-plated may comprise, consist essentially or, or consists of nickel, chromium, cobalt, copper, silver, gold, palladium, or an alloy of one of these metals or combination(s) of these metals.

[0016] The solution for the electroless-plating may be aqueous, non-aqueous (e.g., alcoholic, haloalkenyl, etc.), a molten salt (e.g., NaCl), or otherwise. In addition to the chosen solvent, the solution may further comprise, consist essentially of, or consist of a phosphorous component, such as phosphate ionic compound(s). The phosphorous component for the electroless-plating solution should contain about 8 wt.% to about 15 wt.% of the phosphorous electroless metal or metal alloy composition to be produced by the electroless-plating. In various embodiments, the phosphorous component will contain about 8 wt.%, about 9 wt.%, about 10 wt.%, about 11 wt.%, about 12 wt.%, about 13 wt.%, about 14 wt.%₄ about 15 wt.%₄ any interval in between these weight percentages. In still additional embodiments, the phosphorous component will contain about 15 wt.% to about 25 wt.%, and, without being pedantic, any interval(s) of weight percentages in between about 15 wt.% to about 25 wt.%.

[0017] Turning to the thermal-diffused coating of the phosphorus electroless metal or metal alloy, the thermal-diffused coating may comprise, consists essentially of, or consists of vaporized, solid particles (e.g., powder, dust, etc.) in a retort of aluminum, bismuth, zinc (e.g., TDZ), silicon, chromium, cadmium, tin, carbon, or combinations thereof. Additionally and alternatively, the thermal-diffused coating comprise, consists essentially of, or consists of vaporized, solid particles in a retort of one or more metals, semimetals, alloys, or combinations thereof.

[0018] For thermal-diffused coating of the phosphorus electroless metal or metal alloy, said coating may be sprayed, brushed, applied, or otherwise coated (in-line or out-of-line, such as on a manufacturing press, for instance), as known in the art and whether in the same retort container or another container or vessel in communication therewith, while the abovediscussed metals, semimetals, alloys, or combinations thereof are in a vaporized state at one or more predetermined temperatures, all of which are at temperatures below that for galvanization. The coating may be applied to any substrate, such as those discussed herein or others. As such, the disclosed thermal-diffused coating of the phosphorus electroless metal or metal alloy is a safer process in its using of cooler, heated gas(es), i.e., sherardizing, as opposed to using hotter, heated liquid(s), i.e., galvanizing. In one example embodiment, heating of the thermal-diffused-coating occurs at least at one predetermined temperature for each application onto the phosphorus electroless metal or metal alloy. In a more particularized discussion of that previous, example embodiment, the at least one predetermined temperature for one or at least two applications is about 275°C through about 450°C to form a vapor for application onto the phosphorus electroless metal or metal alloy; such a process may be used, for example, in TDZ onto electroless phosphorus-nickel or electroless phosphorous-nickel alloy. In another more particularized discussion of the previous, example embodiment, the at least one predetermined temperature for one or at least two applications is about 275°C through about 650°C to form a vapor for each of at least two applications onto the phosphorus electroless metal or metal alloy; such a process may be used, for example, in thermal-diffused coating with silicon onto electroless phosphorus-nickel or electroless phosphorous-nickel alloy. The coating, itself, occurs within a range from about 100 kPa through about 225 kPa of pressure.

[0019] Subsequent to and/or during (i.e., simultaneously for at least a portion of) the thermal-diffused coating of the phosphorus (i.e., or other semimetal) electroless metal or metal alloy, the substrate may undergo agitating, by one or more methods, such as mechanically and/or by electric current.

[0020] The compositions arising from the disclosed methods may be an apparatus, itself, such as when not formed into a specific thing, i.e., a substrate in its natural state, or when molded (whether in-line molding, injection molding, etc.) or otherwise formed into or onto a substrate, such as a bolt, screw, car part, rig part, threaded apparatus, computer part, circuitry, carbon fiber, polymer, plastic, ceramics, metals, metal alloys, etc. The composition may be or formed into a machined apparatus, attachable thereto, or an additive-manufactured apparatus. In still other example embodiments, the composition may be applied to, adhered onto, or connected with a substrate, such as any of those previously mentioned herein or any other substrate so as to take advantage of one or more desirous and unexpected benefits, some of which are discussed next.

[0021] For easy visualization, the vaporized, solid particles in the retort container or other closed system for the thermal-diffused coating of the phosphorus electroless metal or metal alloy resembles a smoke-filled chamber. Movement at least towards equilibrium occurs between the vaporized, solid particles and the electroless phosphorous metal or metal alloy in a closed system so as to allow diffusion of each into one another, such that at least a portion of the phosphorous on an exterior of the phosphorus electroless metal or metal alloy is replaced and/or a portion of the phosphorous in an interior of the phosphorus electroless metal or metal alloy is replaced. At least a portion of the phosphorous or other semimetal used in the electroless-plating is left behind by the vaporizing during the coating discussed in the next paragraph. For example, an unexpected advantage of the disclosed methods is that thermal-diffused-coating penetrates the aluminum, bismuth, zinc, silicon, chromium, cadmium, tin, carbon, or combinations thereof into an interior of the phosphorus electroless metal or metal alloy so as to create a barrier on the coated substrate.

[0022] Yet another unexpected advantage is that the disclosed methods stemming from the thermal-diffused coating of a phosphorus electroless metal or metal alloy provide at least substantially anticorrosive compositions, which do not alter the underlying tensile strength or plasticity of the substrate. For example, the disclosed method of thermal-diffused coating of an electroless-plated phosphorous nickel or nickel-cobalt alloy has about or at least four times greater anticorrosiveness than without the disclosed method. Using an empirical example, the disclosed method produced 2000 salt spray hours when using nickel under Bl 17 and 2500 salt spray hours when using nickel-cobalt alloy under Bl 17, but, without the disclosed method, nickel and nickel-cobalt alloy only lasted 500-700 salt spray hours before onset of corrosion.

[0023] Still another unexpected result from the disclosed method was that hardness on an exterior of the composition is greater than that of: (i) the phosphorus electroless metal or metal alloy; and (ii) the metal or metal alloy of the phosphorus electroless metal or metal alloy. Still yet another unexpected result from the disclosed method was that the composition has a total coefficient of friction, e.g., kinetic plus static, not exceeding about 0.13 or about 0.15, which makes the composition a dry lubricant; that is, the composition, whether itself or applied to a different substrate (if considering the composition, itself, to simultaneously be its own substrate) obviates the need to apply another coating to a substate to permit torquing, sliding, or other frictional movement, which, over time, and often only after one or a very few times, removes the another coating from the substrate. For example, a screw constituting the composition or having the composition applied thereto, would not need an additional coating, such as a wet coating applied to the screw, to impart low-friction mating during threading and unthreading because the lubricity of the composition, which is a dry lubricant having a total coefficient of friction not exceeding about 0.13 or about 0.15. Total coefficients of friction are not this low for at least the disclosed phosphorous electroless metal or metal alloys without thermal-diffused coating, and, as a result, are not dry lubricants.

[0024] Another remarkably unexpected advantage of the disclosed methods, compositions and apparatuses is that that microscopic analysis has shown that thermal- diffused-coating comprises, consists essentially of, or consists of coating a substantially homogenous layer onto an exterior of the phosphorus electroless metal or metal alloy. Furthermore, this substantially homogenous layer may comprise, consist essentially of, or consist of multiple layers of the composition atop each other. [0025] Still another remarkably unexpected advantage of the disclosed methods, compositions and apparatuses is that the thermal-diffused-coating of the electroless-plating metal or metal alloy is quicker for a predetermined coating thickness onto the phosphorus electroless metal or metal alloy as compared to electroless metal or metal alloy without the phosphorous or semimetal used instead of phosphorous in the electroless-plating step of the phosphorus electroless metal or metal alloy.

[0026] Turning now to more specifics of an example embodiment, which are also true for the other disclosures herein, subsequent to electroless-plating a phosphorus nickel alloy, the dried alloy is loaded into a steel retort in order to apply a thermal-diffused coating of zinc in a retort, which is sealed shut, such as by mechanical bolting or clamping. TDZ coating with zinc dust powder, which is about from 1 pm through about 4 pm in diameter is exposed to heat at 400° to 420°C for one or more hours. The retort creates its own vapor pressure, without needing addition of an inert gas thereto, in order to transfer the zinc ions to the heated nickel alloy surface. The retort is rotated to allow the zinc dust to fold over repeatedly to result in packed dust, and thereby resulting in better ion depletion of the zinc powder and a stronger vapor pressure. Several thermal blanket medias may be used as well in the retort as a thermal regulator. Ceramics and aluminum granules are both commonly used to hold heat against parts while being processed.

[0027] Once the part, e.g., substrate, has emerged from the retort, the zinc powder is removed, and the excess dust is removed with an ultrasonic bath or with a centripetal polisher, and a vibratory material may be used to polish down the surface for desired finish. No other cleaning process is required. Notably, this is an additional, unexpected benefit because the disclosed methods and compositions do not require surface treatments before ultimate use. That is, the disclosed methods produce compositions that are apparatuses or are applied to apparatuses that exclude surface treatment since the total coefficient of friction and corrosiveness are so low.

[0028] The disclosed methods applied to substrates differ greatly from what is known in the art by not incorporating the substrate in any way. In fact, the employed electroless- plating of metal or metal alloy prevents the substrate from forming carbides by suffocating it, and replacing the alpha layer with two beta layers onto which the thermal-diffused coating builds at least twice as quickly as the normal speed of sherardizing when all variables are constant. In addition, the disclosed methods, as compared to not thermal-diffused coating a phosphorus electroless metal or metal alloy, removes more brittleness as it changes the amorphous structure, removes porosity, and increases hardness of the substrate to which the disclosed method is applied.

[0029] The disclosed method, such as a thermal-diffused coating onto an electroless- plated Ni-Co-P, but also as to at least the other electroless-plated phosphorous metal or metal alloys disclosed herein, allows the following: 1) produce thicker deposits with less shoplevel plating expertise; 2) introduce a significant amount of phosphorus into the deposit, which may have a major influence on the physical properties coated electro-plated metal or metal alloy, such as increased anticorrosiveness, increased hardness, maintained ductility, reduced plasticity, etc.; 3) produce a deposit, which is at least substantially uniform in thickness at every location across a coated part of the substrate with the composition; (4) produce a deposit that protects against thermal expansion and acts as thermal insulation to the substrate’s tensile properties and hardness; 5) produce a rich metal oxide outer layer, which provides a constituent built-in dry lubricant with a total coefficient of friction not exceeding about 0.15 or about 0.13 after multiple uses; and 6) removes the possibility of hydrogen stress cracking and internal hydrogen processes.

[0030] A sodium hypophosphate-reduced bath may be used, such as the one disclosed here:

1) Fill a clean polypropylene tank half full with deionized water. The tank material must be able to withstand 82.2°C. Stainless tanks may be used if they are anodically protected.

2) Add enough nickel sulfamate to yield a concentration of 4 grams nickel (as metal) per liter.

3) Add enough cobalt chloride to yield a concentration of 6 grams per liter.

4) Add enough sodium hypophosphite to yield a concentration of 40 grams per liter.

5) Fill tank to operating level with deionized water. Mix well.

6) Raise bath to operating temperature about 82.2°C. Teflon heaters may be preferable.

7) Add a suitable wetting agent, such as sodium laurel sulfate, to lower the surface tension from about 3.5 through about 4.0 Pa.

8) Filter bath using 10 pm polypropylene spun filters.

[0031] The plating rate of this bath should be between 15 to 22 pm per hour. SEM studies show that using the foregoing methodology results in a thermal-diffused coating onto a metal or metal alloy that is uniform, equiaxed, and substantially free of defects. And when using electroless-plated Ni-Co-P, EDS/EDAX studies show that the nickel and cobalt composition ranged from about 40 wt.% through about 70 wt.%.

[0032] Steps for thermal diffusion of a gas, such as vaporized zinc for the thermal- diffused coating, but also as to vaporizing other metals, semimetals, or alloys thereof, may follow the example disclosure here:

1) Fill a stainless-steel retort, such as one with a diameter of 91 centimeters in internal diameter 183 centimeters in length.

2) Add enough zinc powder, approximately half a liter of powder per load. The zinc powder may be at least 90% Zn metal and 10% ZnO, wherein the crystalline structure should appear, and product size preferably does not exceed 50 pm in diameter.

3) Add the substrate, once dried from the Ni-Co-P process, directly into the retort with the zinc powder.

4) Add lid, which is air-tight sealable, and close.

5) Rotate at rate of one full rotation per 30 sec. This should be sufficient, but slower or fasters rates are acceptable as well.

6) Heating the furnace to a temperature between 290° and 400°C for zinc, but other temperatures below galvanization may be necessary for other metals, semimetals, or alloys thereof, such as silicon, wherein the upper limit is adequate from about 600°C through about 650°C.

7) Building up of the zinc oxide on the nickel alloy surface should be about 11 pm per hour at 380°C, such as when using ASTM A1059-19.

[0033] Below are further example embodiments of the disclosed compositions, apparatuses, and methods, which are mostly written in claim- like format:

1. A composition comprising a phosphorus electroless metal or metal alloy having a thermal-diffused coating comprising aluminum, bismuth, zinc, silicon, chromium, cadmium, tin, carbon, or combinations thereof.

2. The composition of claim 1, wherein a phosphorous content is about 8 wt.% to about 15 wt.% of the phosphorus electroless metal or metal alloy.

3. The composition of claim 1, wherein the phosphorus electroless metal or metal alloy is a phosphorus electroless nickel or nickel alloy.

4. The composition of claim 1, wherein the phosphorus electroless metal or metal alloy is a phosphorus electroless chromium or chromium alloy. 5. The composition of claim 1, wherein the phosphorus electroless metal or metal alloy is a phosphorus electroless cobalt or cobalt alloy.

6. The composition of claim 1, wherein the phosphorus electroless metal or metal alloy is a phosphorus electroless copper or copper alloy.

7. The composition of claim 1, wherein the phosphorus electroless metal or metal alloy is a phosphorus electroless silver or silver alloy.

8. The composition of claim 1, wherein the phosphorus electroless metal or metal alloy is a phosphorus electroless gold or gold alloy.

9. The composition of claim 1, wherein the phosphorus electroless metal or metal alloy is a phosphorus electroless palladium or palladium alloy.

10. The composition of claim 1, wherein the composition is a dry lubricant for application to a surface of a threaded apparatus or machined part, whereby iterations of torquing are possible without a thin-film coating and/or sealer applied to the threaded apparatus or machined part.

11. The composition of claim 1, wherein the composition is at least substantially anticorrosive.

12. The composition of claim 1, wherein hardness on an exterior of the composition is greater than that of: (i) the phosphorus electroless metal or metal alloy; and (ii) the metal or metal alloy of the phosphorus electroless metal or metal alloy.

13. The composition of claim 1, wherein the composition has a total coefficient of friction, wherein this is the sum of the static and kinetic coefficients of friction, not exceeding about 0.15.

14. The composition of claim 1, wherein the composition is a threaded apparatus.

15. The composition of claim 1, wherein the composition is a machined apparatus or attachable thereto, wherein machined means deductive, i.e., take away portion(s).

16. The composition of claim 1, wherein the composition is an additive-manufactured apparatus, wherein additive-manufactured means make parts, e.g., such as printed, whereby additive is opposite of deductive.

17. The composition of claim 1, wherein the composition is applied to a substrate.

18. The composition of claim 1, wherein the composition is formed into a substrate.

19. A method comprising: electroless-plating metal or metal alloy in a solution comprising phosphorous to produce a phosphorus electroless metal or metal alloy; a thermal- diffused-coating of the phosphorus electroless metal or metal alloy with solid particles of aluminum, bismuth, zinc, silicon, chromium, cadmium, tin, carbon, or combinations thereof to produce a composition.

20. The method of claim 19, further comprising heating the thermal-diffused-coating to at least one predetermined temperature for each application onto the phosphorus electroless metal or metal alloy.

21. The method of claim 20, wherein the at least one predetermined temperature for each application is about 275°C through about 450°C to form a vapor for application onto the phosphorus electroless metal or metal alloy.

22. The method of claim 20, wherein the at least one predetermined temperature for each application is about 275°C through about 650°C to form a vapor for application onto the phosphorus electroless metal or metal alloy.

23. The method of claim 19, wherein applying the method to a substrate does not alter tensile strength and/or plasticity of the substrate, wherein the substrate comprises a bolt, a screw, a machined part, a threaded part, or additive part for optionally adhering or connecting, whether removably or irremovably, to another substrate.

24. The method of claim 19, wherein the thermal-diffused-coating comprises vaporizing the solid particles.

25. The method of claim 19, wherein the thermal-diffused-coating comprises coating a substantially homogenous layer onto an exterior of the phosphorus electroless metal or metal alloy.

26. The method of claim 25, wherein the substantially homogenous layer comprises multiple layers.

27. The method of claim 19, wherein the thermal-diffused-coating of the electroless-plating metal or metal alloy is quicker for a predetermined coating thickness onto the phosphorus electroless metal or metal alloy as compared to electroless metal or metal alloy without the phosphorous.

28. The method of claim 19, wherein the thermal-diffused-coating of the electroless-plating metal or metal alloy is quicker for a predetermined coating thickness onto the phosphorus electroless metal or metal alloy as compared to electroless metal or metal alloy without a semimetal.

29. The method of claim 19, wherein a phosphorous content is about 8 wt.% to about 15 wt.% of the phosphorus electroless metal or metal alloy. 30. The method of claim 19, wherein the thermal-diffused-coating penetrates the aluminum, bismuth, zinc, silicon, chromium, cadmium, tin, carbon, or combinations thereof into an interior of the phosphorus electroless metal or metal alloy.

31. The method of claim 19, wherein the thermal-diffused-coating comprises replacing at least a portion of the phosphorous on an exterior of the phosphorus electroless metal or metal alloy.

32. The method of claim 19, wherein the thermal-diffused-coating comprises replacing at least a portion of the phosphorous in an interior of the phosphorus electroless metal or metal alloy.

33. The method of claim 19, wherein the solid particles are one or more metals, semimetals, or alloys thereof.

34. The method of claim 19, wherein the solution is an aqueous solution.

35. The method of claim 19, wherein the solution is a molten salt solution.

36. The method of claim 19, wherein the solution is an alcoholic solution.

37. The method of claim 19, further comprising agitating, during the thermal-diffused- coating, of a substrate undergoing the method.

38. The method of claim 37, wherein the agitating is mechanically agitating.

39. The method of claim 37, wherein the agitating is electrically agitating.

40. The method of claim 37, wherein the agitating is mechanically and electrically agitating.

41. The method of claim 19, wherein the thermal-diffused coating is coating (e.g., applied inline or out-of-line on a manufacturing press, brushed, sprayed, etc.) onto a substrate.

42. The method of claim 19, further comprising applying the method to a substrate, whether the substrate is the composition, itself, or a different object, such as bolt, screw, bearing, wrench, handle, joint, coupler, rig or car part, computer part, circuitry, carbon fiber, polymer, plastic, ceramic, metal, metal alloy, or otherwise.

43. The method of claim 19, further comprising forming, e.g., naturally forming, molding (whether in-line, injection, or otherwise), extruding, etc., a substrate, in conjunction with or as a consequence of utilizing the method.

[0034] While the foregoing is directed to example embodiments of the disclosed invention, other and further embodiments may be devised without departing from the basic scope thereof, wherein the scope of the disclosed apparatuses, compositions and methods are determined by one or more claims.

Claims

CLAIMS What is claimed is:

1. A composition comprising a phosphorus electroless metal or metal alloy having a thermal- diffused coating comprising aluminum, bismuth, zinc, silicon, chromium, cadmium, tin, carbon, or combinations thereof.

4. The composition of claim 1, wherein the phosphorus electroless metal or metal alloy is a phosphorus electroless chromium or chromium alloy.

5. The composition of claim 1, wherein the phosphorus electroless metal or metal alloy is a phosphorus electroless cobalt or cobalt alloy.

13. The composition of claim 1, wherein the composition has a total coefficient of friction not exceeding about 0.15.

14. The composition of claim 1, wherein the composition is a threaded apparatus. The composition of claim 1, wherein the composition is a machined apparatus or attachable thereto. The composition of claim 1, wherein the composition is an additive-manufactured apparatus. The composition of claim 1, wherein the composition is applied to a substrate. The composition of claim 1, wherein the composition is formed into a substrate. A method comprising: electroless-plating metal or metal alloy in a solution comprising phosphorous to produce a phosphorus electroless metal or metal alloy; and thermal-diffused-coating of the phosphorus electroless metal or metal alloy with solid particles of aluminum, bismuth, zinc, silicon, chromium, cadmium, tin, carbon, or combinations thereof to produce a composition. The method of claim 19, further comprising heating the thermal-diffused-coating to at least one predetermined temperature for each application onto the phosphorus electroless metal or metal alloy. The method of claim 20, wherein the at least one predetermined temperature for each application is about 275°C through about 450°C to form a vapor for application onto the phosphorus electroless metal or metal alloy. The method of claim 20, wherein the at least one predetermined temperature for each application is about 275°C through about 650°C to form a vapor for application onto the phosphorus electroless metal or metal alloy. The method of claim 19, wherein applying the method to a substrate does not alter tensile strength or plasticity of the substrate. The method of claim 19, wherein the thermal-diffused-coating comprises vaporizing the solid particles. The method of claim 19, wherein the thermal-diffused-coating comprises coating a substantially homogenous layer onto an exterior of the phosphorus electroless metal or metal alloy. The method of claim 25, wherein the substantially homogenous layer comprises multiple layers. The method of claim 19, wherein the thermal-diffused-coating of the electroless-plating metal or metal alloy is quicker for a predetermined coating thickness onto the phosphorus electroless metal or metal alloy as compared to electroless metal or metal alloy without the phosphorous. The method of claim 19, wherein the thermal-diffused-coating of the electroless-plating metal or metal alloy is quicker for a predetermined coating thickness onto the phosphorus electroless metal or metal alloy as compared to electroless metal or metal alloy without a semimetal. The method of claim 19, wherein a phosphorous content is about 8 wt.% to about 15 wt.% of the phosphorus electroless metal or metal alloy. The method of claim 19, wherein the thermal-diffused-coating penetrates the aluminum, bismuth, zinc, silicon, chromium, cadmium, tin, carbon, or combinations thereof into an interior of the phosphorus electroless metal or metal alloy. The method of claim 19, wherein the thermal-diffused-coating comprises replacing at least a portion of the phosphorous on an exterior of the phosphorus electroless metal or metal alloy. The method of claim 19, wherein the thermal-diffused-coating comprises replacing at least a portion of the phosphorous in an interior of the phosphorus electroless metal or metal alloy. The method of claim 19, wherein the solid particles are one or more metals, semimetals, or alloys thereof. The method of claim 19, wherein the solution is an aqueous solution. The method of claim 19, wherein the solution is a molten salt solution. The method of claim 19, wherein the solution is an alcoholic solution. The method of claim 19, further comprising agitating, during the thermal-diffused-coating, of a substrate undergoing the method. The method of claim 37, wherein the agitating is mechanically agitating. The method of claim 37, wherein the agitating is electrically agitating. The method of claim 37, wherein the agitating is mechanically and electrically agitating. The method of claim 19, wherein the thermal-diffused coating is coating onto a substrate. The method of claim 19, further comprising applying the method to a substrate. The method of claim 19, further comprising forming a substrate.

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