CN118215752A

CN118215752A - Movable part with surface coating

Info

Publication number: CN118215752A
Application number: CN202280056497.1A
Authority: CN
Inventors: A·哈霍东斯; M·卡尔加; E·厄尔加尔; D·丘奇
Original assignee: Maxwell Trier Ltd
Current assignee: Maxwell Trier Ltd
Priority date: 2021-06-18
Filing date: 2022-06-20
Publication date: 2024-06-18
Also published as: CN118202092A; CN118202091A; CN118176328A

Abstract

An apparatus having a movable member with a coated surface is described. In some examples, the movable member may contact the functional fluid during movement of the movable member. The movable component comprises a coated surface having a surface coating comprising an alloy layer. The alloy layer comprises molybdenum or tungsten in combination with one or more other materials.

Description

Movable part with surface coating

Priority and related applications

The present application is related to and claims priority and benefit from U.S.63/212,515 submitted at 18 of 2021, U.S.63/223,497 submitted at 19 of 2021, 7, and U.S.63/226,649 submitted at 28 of 2021.

Technical Field

Certain configurations described herein relate to surface coatings that may be used on components intended to be moved from an initial position to another position. More particularly, certain embodiments relate to surface coatings comprising an alloy layer that may be present on a movable component.

Background

Many different articles have movable parts that withstand pressure and environment during use. These pressures and environmental exposures can shorten the life of the article.

Disclosure of Invention

Various articles and devices having coated surfaces comprising surface coatings are described. The surface coating may comprise an alloy layer that may extend the life of the article and device. The articles and devices may take many different configurations, but typically have a movable member that moves from a first or initial position to a second position that is different from the first or initial position. The exact movement of the movable member may vary, and exemplary movements include, but are not limited to, linear movements, rotational movements, reciprocating movements, and the like. The movable member may move in response to forces including hydraulic, pneumatic, gravitational, compressive, or other forces. Illustrations of various devices having movable components are discussed in detail below. Various movable components include those found in hydraulic devices, pneumatic devices, rotating devices, reciprocating devices, and other devices having components that are capable of moving (e.g., rotating, linearly moving, etc.) from one location to another.

In one aspect, an apparatus includes a movable member configured to contact a functional fluid during movement of the movable member. The functional fluid may be air, gas, oil, hydraulic fluid, or other fluid that may provide force to the movable member and cause movement or may resist the force provided by the movable member. In some constructions, the movable component includes a coated surface. For example, the movable member may contain a coated surface that contacts the functional fluid during movement, or may contain a coated surface that is exposed to the environment when the movable member is moved. In some embodiments, the coated surface comprises a surface coating comprising an alloy layer. For example, there may be an alloy comprising molybdenum and one or more combinations of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron. In other embodiments, the alloy layer may comprise molybdenum and at least one compound comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron.

In certain embodiments, the alloy layer of the movable device comprises molybdenum or tungsten and one or more elements selected from the group consisting of nickel, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron or a compound comprising one or more of nickel, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In certain examples, molybdenum or tungsten is present in the surface coating at 35% by weight or less based on the surface coating weight, or at 25% by weight or less based on the surface coating weight, or at 15% by weight or less based on the surface coating weight, or molybdenum or tungsten is present in the alloy layer at 35% by weight or less based on the alloy layer weight, or at 25% by weight or less based on the alloy layer weight, or at 15% by weight or less based on the alloy layer weight, or molybdenum or tungsten is present in the surface coating at 65% by weight or more based on the surface coating weight, or at 75% by weight or more based on the surface coating weight, or at 85% by weight or more based on the surface coating weight, or molybdenum or tungsten is present in the alloy layer at 65% by weight or less based on the alloy layer weight, or at 75% by weight or less based on the alloy layer weight, or at 85% by weight or less based on the alloy layer weight.

In some examples, the alloy layer consists essentially of nickel and molybdenum, or consists essentially of nickel, molybdenum, and one of tin, phosphorus, iron, magnesium, or boron, or consists essentially of nickel and tungsten, or consists essentially of nickel, tungsten, and one of tin, phosphorus, iron, magnesium, or boron.

In other examples, the surface roughness Ra of the coated surface is less than 1 micron and molybdenum or tungsten is present in the alloy layer at 20% or less by weight based on the weight of the surface coating, and the surface coating does not comprise a noble metal or silver or gold.

In certain embodiments, the alloy layer is an electrodeposited alloy layer or an exposed outer layer of a surface coating. In some examples, the exposed outer layer consists essentially of (i) molybdenum or tungsten and only one of nickel, cobalt, tin, phosphorus, iron, chromium, magnesium, or boron, or (ii) molybdenum or tungsten and only two of nickel, cobalt, tin, phosphorus, iron, chromium, magnesium, or boron, or (iii) molybdenum and phosphorus or both tungsten and phosphorus and at least one of nickel, cobalt, tin, chromium, tungsten, iron, magnesium, or boron.

In some examples, the alloy layer is an electrodeposited alloy layer, further comprising an intermediate layer between the substrate surface and the alloy layer, wherein the intermediate layer comprises one or more of nickel, nickel alloy, copper alloy, nickel tungsten alloy, cobalt alloy, nickel phosphorus alloy, molybdenum or tungsten, or both, and an alloy of at least one of nickel, cobalt, chromium, tin, phosphorus, iron or boron.

In other embodiments, the movable device comprises an additional layer formed on the alloy layer, wherein the additional layer comprises one or more of nickel, nickel alloy, nickel tungsten alloy, cobalt phosphorus alloy, nickel phosphorus alloy, alloys of molybdenum with at least one of nickel, cobalt, chromium, tin, phosphorus, iron, or boron, ceramics comprising compounds of tungsten, chromium, aluminum, zirconium, titanium, nickel, cobalt, molybdenum, silicon, boron, metal nitrides, metal carbides, boron, tungsten carbide, chromium oxide, aluminum oxide, zirconium oxide, titanium dioxide, nickel carbide, nickel oxide, nanocomposites, oxide composites, or combinations thereof.

In certain constructions, the alloy layer further comprises one or more particles selected from the group consisting of solid nanoparticles, polymer particles, hard particles, silica particles, silicon carbide particles, titanium dioxide particles, polytetrafluoroethylene particles, hydrophobic particles, diamond particles, particles functionalized with hydrophobic groups, solid particles, and combinations thereof. In some examples, the alloy layer is present as an exposed outer layer of the surface coating, wherein the exposed outer layer is an electrodeposited alloy layer, and wherein the electrodeposited alloy layer does not comprise a noble metal. The exposed alloy layer also contains particles, if desired.

In some embodiments, the movable member is configured to move in a linear direction, a rotational direction, or both. In some examples, the movable member is configured to move in response to a compressive force provided to the movable member. In other embodiments, the movable member is configured to move from the second position back to the first position in response to a compressive force provided to the movable member.

In other constructions, the movable member is configured to move in response to hydraulic pressure provided to the movable member. In some examples, the movable member is configured to move from the second position back to the first position in response to hydraulic force provided to the movable member.

In certain embodiments, the surface coating of the movable component is located outside of the housing of the device.

In some examples, the device is configured as a hydraulic device comprising a piston member, and wherein the piston member comprises a coated surface. In other examples, the device is configured as a pneumatic device comprising a piston member, and wherein the piston member comprises a coated surface. In some embodiments, the apparatus is configured as a work roll or a roll comprising a coated surface. In further embodiments, the apparatus is configured as a steel work roll comprising a coated surface. In certain examples, the device is configured as a shock absorber that includes a piston member, and wherein the piston member includes a coated surface.

Additional features and aspects of the movable device are described in more detail below.

Drawings

Certain aspects, embodiments, and constructions are described with reference to the accompanying drawings, wherein:

FIG. 1 is a schematic representation of an apparatus comprising a surface coating on a substrate;

FIG. 2 is a schematic representation of an apparatus comprising two layers in a coating on a substrate;

FIG. 3 is another illustration of an apparatus comprising two layers in a coating on a substrate;

FIGS. 4A and 4B are illustrations of an apparatus comprising a textured surface;

FIGS. 5A and 5B are illustrations of a device comprising two or more layers;

FIGS. 6, 7, 8 are illustrations of coatings;

FIGS. 9, 10, 11 are illustrations of non-planar surfaces;

FIG. 12 is a schematic representation of a device having multiple coatings;

FIG. 13 is a diagram of a mobile device;

FIG. 14 is an illustration of a piston member;

FIG. 15 is a diagrammatic view of a housing;

FIG. 16 is an illustration of a piston member within a housing of a movable device;

FIG. 17A is a diagram showing a rotational motion of a substrate;

FIG. 17B is another illustration showing a rotational motion of the substrate;

FIG. 18 is a diagram showing a cylindrical substrate;

FIG. 19A is a diagram showing a rotor;

FIG. 19B is a diagram showing a blade;

FIG. 19C is a diagram showing two work rolls;

FIG. 20 is a diagram showing a shock absorber;

FIG. 21 is a diagram showing a hydraulic or pneumatic device;

FIG. 22 is a photograph showing two coatings on different articles;

FIGS. 23A and 23B are photographs showing a hard chrome coating and an electroless nickel coating;

24A, 24B, 24C, 24D and 24E are photographs showing the results of salt spray tests performed on test coatings;

FIG. 25 is a graph comparing salt spray tests;

Fig. 26A, 26B, 26C, 26D and 26E are photographs showing the appearance of the coating after 5000 hours and salt spray test;

FIG. 27 is a photograph showing an image of a slit strip before and after coating;

FIGS. 28A and 28B are images of MaxShield-V1 (FIG. 28B) and MaxShield-V2 (FIG. 28A) coatings after 6% elongation;

FIG. 29 is a microscopic image of MaxShield-V1 coating;

FIG. 30 is a graphical representation of an apparatus for measuring coefficient of friction;

FIG. 31 is a diagram showing a crack;

FIGS. 32A and 32B are images of two carbon steel bars coated with MaxShield-V1 after testing (FIG. 32B) and before testing (FIG. 32A);

FIG. 33 is a microscopic image of the steel bar of FIG. 32B;

FIG. 34 is an illustration of an apparatus for abrading a coated surface by applying a (1) kg load on each abrading wheel;

FIG. 35 is a graph comparing wear indices of different coatings;

FIG. 36 is a graph showing coefficient of friction versus cycle;

FIG. 37 is a graph showing the corrosion rates of different coatings;

FIGS. 38A and 38B are enlarged images showing the plating and heat treatment coating; and

Fig. 39A, 39B, 39C, and 39D are images showing surface coating.

Those skilled in the art having the benefit of this description will appreciate that the layers and features shown in the drawings are not necessarily drawn to scale. The arrangement and size of the various layers and features in the figures are not intended to imply that any one arrangement or thickness is required unless specifically discussed with reference to the figures.

Detailed Description

Components for use in articles having movable components require protective coating techniques. While various specific illustrations of coated devices are described in more detail below, devices typically include movable components that contact a functional fluid or other material. The term "functional fluid" refers to a fluid designed to provide motive force or lubricate one or more components during movement of a piston member (e.g., to provide an oil film on a surface, or otherwise participate in movement of a piston member). In some cases, the functional fluid may also provide resistance during movement of the piston member. In some examples, the functional fluid may be used to prevent the piston member from moving from the first position to the second position. One or more surfaces of the movable member may comprise a coating, such as an alloy coating. The coating may provide wear resistance in the presence of a functional fluid during movement of the movable component or may provide wear resistance to the surface of the movable component external to the housing. The movable component typically includes an underlying substrate and a coating on one or more surfaces of the substrate. One or more other components of the device may also include a coating if desired, for example, a housing that functionally operates with the movable component may also contain a coating if desired.

In certain embodiments, the materials and methods described herein may be used to provide a coating on a surface of a movable component. The particular material or materials in the coating may vary, and many different materials, coatings, and layers are described in more detail below. Specific materials for specific devices are also described in more detail below. The exact coating thickness used may vary from device to device. For example, the coating thickness may vary depending on the application of the movable part. Typical coating thicknesses may be less than 10um to 1mm. For example, for applications that handle highly corrosive environments, the thickness may be 25-100um、25-200um、100-200um、50-150um、25-330um、100-300um、100-400um、100-500um、100-600um、100、125、150、175、200、225、250、275、300、325、350、375、400、425、450、475、500、525、550、575、600、700、725、800、825、850、875 or 900um.

In certain embodiments, the movable component may comprise one or more layers, as described below in connection with fig. 1-12. Specific articles or devices including the substrate and/or other layers are also described. The specific materials in the surface coating may vary. In some constructions, the surface coating comprises one or more metals. In some embodiments, the surface coating may comprise a metal alloy, such as an alloy comprising two or more metals. In some embodiments, the surface coating comprises a metal alloy containing only two metals or a metal and another material. In certain embodiments, the surface coating comprises a metal alloy containing only three metals or a metal and two other materials. In other embodiments, the surface coating may comprise only a single layer formed on the substrate. For example, the monolayer may be exposed to the environment to protect the underlying substrate from degradation. In some cases, the surface coating may include only a first layer formed on the substrate and a second layer formed on the first layer.

In some embodiments, the alloy layer may "consist essentially of" two or more materials. The phrase "consisting essentially of" ("consists essentially of" or "consisting essentially of") is intended to refer to particular materials and those materials that have only small amounts of impurities and do not materially affect the basic feature(s) of the construction. The term "consisting of" means only those materials and any impurities that cannot be removed by conventional purification techniques.

In certain embodiments, the alloy layers described herein may include one, two, or more group IV transition metals including scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc.

In other constructions, the alloy layers described herein can include one, two, or more group V metals including yttrium, zirconium, niobium, ruthenium, rhodium, palladium, silver, and cadmium.

In some constructions, the alloy layers described herein can include one, two, or more group VI metals including non-radioactive lanthanides (La, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb and Lu), hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, and mercury.

In other embodiments, the alloy layers described herein may comprise one, two, or more group VII metals, including non-radioactive actinides (Th, pa, U).

In some cases, the alloy layers described herein may include one or more metals from group IV metals and one or more metals from group V metals or group VI metals or group VII metals.

In other cases, the alloy layers described herein may include one or more metals from group V metals and one or more metals from group VI metals or group VII metals.

In other examples, the alloy layers described herein may include one or more metals from group VI metals and one or more metals from group VII metals.

In some embodiments, the alloy layers described herein include only two metals, one from group IV metals and the other from group V metals, group VI metals, or group VII metals.

In some embodiments, the alloy layers described herein include only two metals, one from group V metals and the other from group VI metals or group VII metals.

In other embodiments, the alloy layers described herein include only two metals, one from the group VI metals and the other from the group VII metals.

In some examples, the alloy layers described herein include only two metals, both of which are group IV metals.

In some embodiments, the alloy layers described herein include only two metals, both of which are group V metals.

In some embodiments, the alloy layers described herein include only two metals, both of which are group VI metals.

In some embodiments, the alloy layers described herein include only two metals, both of which are group VII metals.

The alloy layers described herein may also include group II species (Li, be, B, and C) or group III species (Na, mg, al, si, P and S) in addition to or in place of other metals, if desired. These materials may be present in combination with one, two, three or more metals.

In some embodiments, the alloy layers described herein comprise molybdenum and one or more additional metals, such as one or more additional metals selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In certain embodiments, the metal alloy comprises molybdenum and only one additional metal, for example only one additional metal selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In certain embodiments, the metal alloy comprises molybdenum and only two additional metals or materials, such as only two additional metals or materials selected from the group consisting of group IV metals, group V metals, group VI metals, group VII metals, group II materials, and group III materials. In some embodiments, the surface coating has a monolayer formed on the substrate, wherein the monolayer comprises molybdenum and one or more additional metals, such as one or more additional metals selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In some embodiments, the surface coating has a monolayer formed on the substrate, wherein the monolayer comprises molybdenum and only one additional metal, such as only one additional metal selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In some examples, the surface coating has a monolayer formed on the substrate, wherein the monolayer comprises molybdenum and only two metals or species, such as only two metals or species selected from the group consisting of group IV metals, group V metals, group VI metals, group VII metals, group II species, and group III species.

In some embodiments, the alloy layers described herein comprise tungsten and one or more additional metals, such as one or more additional metals selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In certain embodiments, the metal alloy comprises tungsten and only one additional metal, for example only one additional metal selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In certain embodiments, the metal alloy comprises tungsten and only two additional metals or materials, such as only two additional metals or materials selected from the group consisting of group IV metals, group V metals, group VI metals, group VII metals, group II materials, and group III materials. In some embodiments, the surface coating has a monolayer formed on the substrate, wherein the monolayer comprises tungsten and one or more additional metals, such as one or more additional metals selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In some embodiments, the surface coating has a monolayer formed on the substrate, wherein the monolayer comprises tungsten and only one additional metal, such as only one additional metal selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In some examples, the surface coating has a monolayer formed on the substrate, wherein the monolayer comprises tungsten and only two metals or species, such as only two metals or species selected from the group consisting of group IV metals, group V metals, group VI metals, group VII metals, group II species, and group III species.

In some embodiments, the alloy layers described herein comprise nickel and one or more additional metals, such as one or more additional metals selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In certain embodiments, the metal alloy comprises nickel and only one additional metal, for example only one additional metal selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In certain embodiments, the metal alloy comprises nickel and only two additional metals or materials, such as only two additional metals or materials selected from the group consisting of group IV metals, group V metals, group VI metals, group VII metals, group II materials, and group III materials. In some embodiments, the surface coating has a monolayer formed on the substrate, wherein the monolayer comprises nickel and one or more additional metals, such as one or more additional metals selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In certain embodiments, the surface coating has a monolayer formed on the substrate, wherein the monolayer comprises nickel and only one additional metal, such as only one additional metal selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In some examples, the surface coating has a monolayer formed on the substrate, wherein the monolayer comprises nickel and only two metals or species, such as only two metals or species selected from the group consisting of group IV metals, group V metals, group VI metals, group VII metals, group II species, and group III species.

In certain configurations, the alloy layer comprises (i) molybdenum and (ii) at least one element selected from the group consisting of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron or at least one compound comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In certain embodiments, the alloy does not contain a noble metal.

In certain configurations, the alloy layers described herein comprise two or more of nickel, molybdenum, copper, phosphorus, boron nitride, silicon carbide, aluminum oxide, molybdenum disulfide, carbon fibers, carbon nanotubes, particles, cobalt, tungsten, gold, platinum, silver, or alloys or combinations thereof.

In other embodiments, the alloy layers described herein comprise two or more of nickel, molybdenum, copper, phosphorus, boron nitride, silicon carbide, aluminum oxide, molybdenum disulfide, carbon fibers, carbon nanotubes, particles, cobalt, tungsten, gold, platinum, silver, or alloys or combinations thereof.

In certain embodiments, the alloy layers described herein comprise an alloy of (i) molybdenum, molybdenum oxide, or other compound of molybdenum, and (ii) a transition metal, transition metal oxide, or other compound of transition metal.

In certain embodiments, the alloy layers described herein comprise only two metals: (i) Molybdenum, molybdenum oxide or other compounds of molybdenum, and (ii) transition metals, transition metal oxides or other compounds of transition metals.

In certain embodiments, the metal alloys of the layers described herein comprise only two metals: (i) Tungsten, tungsten oxide or other compounds of tungsten, and (ii) transition metals, transition metal oxides or other compounds of transition metals.

In certain embodiments, the alloy layers described herein comprise only two metals: (i) Nickel, nickel oxide or other compound of nickel, and (ii) a transition metal, transition metal oxide or other compound of a transition metal. In some embodiments, the transition metal, transition metal oxide, or other compound of a transition metal includes scandium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, technetium, silver, cadmium, lanthanum, platinum, gold, mercury, actinium, and combinations thereof. For example, the metal alloy coating may comprise a Ni-Mo alloy, a Ni-W alloy, or have only a Ni-Mo alloy or a Ni-W alloy.

In certain embodiments, the alloy layer exhibits at least twice the corrosion resistance as compared to a chromium coating according to ASTM B117 salt spray corrosion test. In some embodiments, the metal alloy layer does not exhibit hydrogen embrittlement as measured according to ASTM F519 standard.

In embodiments where the alloy layer includes molybdenum, molybdenum oxide, or other compounds of molybdenum, these materials may be present in the metal alloy coating at 35% or less (or 25% or less) by weight based on the weight of the alloy or the weight of the surface coating. In some other cases where the alloy layer includes molybdenum, molybdenum oxide, or other compounds of molybdenum, these materials may be present in the metal alloy coating at 48% or less by weight based on the weight of the alloy layer or surface coating.

In some cases, the alloy layer may be composed of a single layer. In other constructions, two or more layers may be present in the surface coating. As described herein, the two layers may comprise the same or different materials. When the materials are the same, the materials may be present in different amounts in the two layers or may be deposited in different layers using different processes.

In some embodiments, the alloy layer may include a molybdenum alloy, such as molybdenum in combination with one or more of nickel, chromium, carbon, cobalt, tin, tungsten, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper. For example, molybdenum may be present in an amount of 35 wt% or less, and the other components may be present in an amount of 65 wt% or more. More than two components or metals may be present if desired. In other embodiments, the surface coating may comprise an alloy of molybdenum and one other metal or substance, such as a combination of molybdenum with only one of nickel, chromium, carbon, cobalt, tin, tungsten, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper. In other embodiments, the surface coating may comprise an alloy of molybdenum and two other metals, such as molybdenum in combination with only two of nickel, chromium, carbon, cobalt, tin, tungsten, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper.

In some embodiments, the alloy layer may comprise a tungsten alloy, such as tungsten in combination with one or more of nickel, molybdenum, chromium, carbon, cobalt, tin, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper. In other embodiments, the surface coating may comprise an alloy of tungsten and one other metal or substance, such as a combination of tungsten with only one of nickel, molybdenum, chromium, carbon, cobalt, tin, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper. In some embodiments, the surface coating may comprise an alloy of tungsten and two other metals, such as tungsten in combination with only two of nickel, molybdenum, chromium, carbon, cobalt, tin, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper. In some embodiments, the surface coating may comprise a tungsten alloy, such as tungsten in combination with one or more of chromium, molybdenum, carbon, cobalt, tin, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper. For example, tungsten may be present in an amount of 35 wt% or less, and the other components may be present in an amount of 65 wt% or more. More than two components or metals may be present if desired. In other embodiments, the surface coating may comprise an alloy of tungsten and one or two other metals or substances, such as tungsten in combination with only one of nickel, molybdenum, chromium, carbon, cobalt, tin, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper. In other embodiments, the surface coating may comprise an alloy of tungsten and two other metals, such as tungsten in combination with only two of nickel, molybdenum, chromium, carbon, cobalt, tin, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper.

In some embodiments, the surface coatings described herein may provide desired performance criteria including, but not limited to, specific surface roughness (Ra) as described in ISO4287 and ISO4288 standards. For example, a profilometer may be used to measure roughness. The coating thickness can also be measured using non-destructive techniques (e.g., magnetic measurement tools, XRF) or sampling and destructive techniques (e.g., cross-sectional analysis). The precise surface roughness (Ra) may vary, for example, and may be equal to or less than 1 micron or may be between 0.1 micron and 1 micron. The device may also have a desired coefficient of friction (CoF). This characteristic is generally dependent on both the surfaces rubbing against each other and the fluid located between them. The roughness of each surface, the viscosity of the fluid, and the test temperature all affect the measurement of the coefficient of friction. CoF can be measured according to, for example, the Block on ring test specified in ASTM G99-17 or ASTM G77-17. The coating or one or more layers of the coating may provide a particular hardness as tested according to ASTM E384-17. For example, the hardness of the coating may be greater than 600 vickers as measured according to ASTM E384-17. When the coating comprises multiple monolayers, the hardness of any one or more of the layers is greater than 600 vickers (measured according to ASTM E384-17). In some embodiments, the outer layer of the coating may have a vickers hardness greater than 600 as measured according to ASTM E384-17. In other embodiments where the coating has a vickers hardness of 600 or greater as measured according to ASTM E384-17, one of the layers, when present alone, may have a vickers hardness of less than 600 as measured according to ASTM E384-17.

Although the various layers and substrates are described below with reference to fig. 1-12 as having a planar surface, a planar surface is not necessary and may not be desirable in some cases. For example, the substrate (or any layer or both) may have a roughened surface or be intentionally roughened or intentionally smoothed as desired. As an example, the substrate may have a textured surface that includes a transferred texture, a partial or complete replica of which will be transferred to other objects in contact with such a surface having the transferred texture. In one embodiment, such a surface may be part of an article or device that contacts another material during use or movement. For example, a steel work roll for a cold rolling process, the surface of which has a certain transfer texture, may be transferred to a steel sheet during rolling. Another example is the steel work roll described in the previous embodiment, wherein spark roughening (EDT) is used to form the transfer texture. Another example is a work roll used in a hot rolling process. In another embodiment, the transfer texture may be part of a mold designed to transfer texture to another object. In one embodiment, the texture is transferred to the metal. In one embodiment, texture is transferred to the polymer. In one embodiment, the texture is transferred to a molten metal that solidifies later. In one embodiment, the texture is transferred to a liquid or fluid that is subsequently cured.

In another embodiment, the surface may have an adhesion roughness designed to increase the adhesion between such surface and another surface or a coating applied on top. In one embodiment, the adhesion texture is used to increase the adhesion of the substrate to the thermal spray coating. In another embodiment, the adhesion texture is used to increase the adhesion of a tungsten-containing coating on a surface. In another embodiment, the adhesive layer is used to increase the adhesion of the coating layer compared to one or a combination of nitrides, metal carbides, borides, tungsten carbide, tungsten alloys, tungsten compounds, stainless steel, ceramics, chromium carbide, chromium oxide, chromium compounds, aluminum oxide, zirconium oxide, titanium dioxide, nickel carbide, nickel oxide, nickel alloys, cobalt compounds, cobalt alloys, cobalt-phosphorus alloys, molybdenum compounds, nanocomposites, oxide composites.

In another embodiment, roughness is added to affect light reflection. In one embodiment, the surface roughness is changed to have a smaller roughness. In one embodiment, the surface roughness is changed to less than 1um. In another embodiment, the surface roughness is changed to less than 0.5um. In one embodiment, the surface after the roughness change is shiny. In another embodiment, the surface after the roughness change is exposed and requires a human touch. In another embodiment, the surface reflects less light and becomes less shiny. In one embodiment, the contact angle of water on the surface with the altered roughness is less than the original surface.

In some embodiments, the roughness may have an irregular shape or a corresponding pattern. In certain embodiments, the roughness Ra of the coated surface is less than 1um. In another embodiment, the roughness Ra of the coated surface is greater than 1um and less than 10um. In another embodiment, the roughness Ra of the coated surface is greater than 10um and less than 100um, and in another embodiment, the Ra of the surface is less than 0.7. In some embodiments, ra is less than 0.5um and greater than 0.05um. In another embodiment, ra is less than 0.5um. In another embodiment, ra is less than 0.4um. In another embodiment, ra is less than 0.3um. In another embodiment, ra is less than 0.2um. In another embodiment, ra is less than 0.1um. In another embodiment, the pattern is made using grinding, spraying, sandblasting (sand blasting, abrasive blasting, sandblasting), polishing, grinding, honing, batch finishing, tumbling finishing, vibration finishing, polishing, buffing, lapping, electrochemical etching, chemical etching, laser patterning, or other methods. In another method, the surface is textured using shot peening (SB), laser Beam Texturing (LBT), and electric discharge roughening (EDT) or Electron Beam Texturing (EBT). Spark roughening (EDT) may be used to create texture on a steel substrate. Electrodeposition techniques may be used to form the texture. Thermal spray techniques may be used to form the texture. The cross-section of the pattern may have a specific geometry, such as rectangular, triangular, star-shaped, circular, or a combination thereof. The pattern may be ridges, pillars, spirals, combinations thereof or other shapes. Ra may be greater than 100um. Cutting, milling, molding, and/or other tools may be used to create the pattern.

Certain embodiments are described in more detail below with reference to a coating or layer. The coating or layer may comprise a single material, a combination of materials, an alloy, a composite, or other materials and compositions described herein. In embodiments where the layer involves a metal alloy, the metal alloy may comprise two or more materials, for example two or more metals. In some constructions, one metal may be 79% or more by weight present in the layer, while another material may be 21% or less by weight present in the layer. For example, one of the layers described herein may comprise a molybdenum alloy, a tungsten alloy, or a nickel alloy. One material may be 79% or more by weight present in a layer, while the other material(s) may be 21% or less by weight present in a layer. When the metal alloy comprises molybdenum, the molybdenum in the layer may be 21% or less, or 79% or more by weight, and other material(s) may be present, so that the sum of the weight percentages adds up to 100 weight%. Or the other material(s) may be 79% or more by weight present in the layer and the molybdenum may be 21% or less by weight present in the layer. One or more of the layers may also comprise another metal or metal alloy. Small amounts of impurities may also be present, which add a negligible amount to the weight of the entire alloy layer or surface coating.

The exact amount of each material present may be selected to provide a layer or article having the desired performance criteria. The weight percentages may be based on the weight of the alloy layer or the entire surface coating. In some embodiments, one metal in a layer is present in the layer at 35% by weight or less, for example at 34％、33％、32％、31％、30％、29％、28％、27％、26％、25％、24％、23％、22％、21％、20％、19％、18％、17％、16％、15％、14％、13％、12％、10％、9％、8％、7％、6％、5％、4％、3％、2％、1％% by weight or less. For example, one or more of molybdenum, tungsten, or cobalt is present in the layer or coating at 35% or less by weight, e.g., at 25%, 24%, 23%, 33%, 31%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1% or less by weight. In other constructions, one or more layers may include 65% or more by weight of the metal present in a layer, e.g., 65%, 70%, 75%, 80%, 81%, 82%, 83%, 84%, 85%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or more by weight present in the layer or coating. For example, nickel may be present in the alloy layer or surface coating at 65%, 70%, 75%, 80%, 81%, 82%, 83%, 84%, 85%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or more by weight of the layer or coating. Or molybdenum may be present in the alloy layer or surface coating at 65%, 70%, 75%, 80%, 81%, 82%, 83%, 84%, 85%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or more by weight of the layer or surface coating.

In some embodiments, the alloy layers described herein may be absent any noble metal. The term "noble metal" refers to gold, silver, ruthenium, rhodium, palladium, osmium, iridium, and platinum. For example, the alloy layer (and/or the entire surface coating) may be free (without) each of gold, silver, ruthenium, rhodium, palladium, osmium, iridium, and platinum. The elimination of noble metals can reduce overall costs.

In certain embodiments, when nickel is present in the metal alloy layer, nickel may be present in the same layer without any tungsten or cobalt. For example, when the layer comprises a nickel alloy, the layer is free of tungsten or cobalt, for example 0 wt% cobalt or tungsten is present. The layer may also have 0 wt% noble metal.

In certain examples, the alloy layer may include non-metallic materials and additives as desired. For example, particles, nanoparticles, nanomaterials, or other materials comprising one or more of Polytetrafluoroethylene (PTFE), siC, siO2, diamond, graphite, graphene, boron, boride, functionalized silicon particles, fluorosilicones, siloxanes, tiO2, nanotubes, and nanostructures may be present in the metal alloy layer. Additional materials are described in more detail below.

In some examples, one of the metals of the layers described herein is nickel. For example, nickel alloys, nickel compounds, nickel composites, nickel phosphorus alloys, nickel molybdenum alloys, nickel cobalt alloys, nickel tungsten alloys, nickel cobalt phosphorus alloys, nickel tungsten phosphorus alloys, nickel alloys comprising only nickel and molybdenum, nickel alloys comprising at least nickel and transition metals, nickel alloys comprising at least two metals other than any noble metal, nickel alloys comprising at least nickel and refractory metals other than tungsten and any noble metal, nickel alloys comprising at least nickel and cobalt and any noble metal, nickel alloys comprising at least nickel and particles, nickel and nanoparticle alloys, nickel and SiO2, siC or other silicon compounds, nickel and boride, bromine nitride or other boron compounds, nickel and PTFE or other fluorine compounds, chromium carbide, chromium oxide or other chromium compounds may be present in one or more of the layers.

In certain embodiments, one of the metals of the alloy layers described herein is molybdenum. For example, molybdenum alloys, molybdenum complexes, molybdenum-tin alloys, alloys containing at least molybdenum and nickel, alloys containing at least molybdenum and tin, alloys containing at least molybdenum and cobalt, alloys containing at least molybdenum and phosphorous, alloys containing only nickel and molybdenum, alloys containing only tin and molybdenum, alloys containing only cobalt and molybdenum, alloys containing only nickel, molybdenum and phosphorous, molybdenum alloys containing at least two metals other than noble metals, molybdenum alloys containing at least molybdenum and transition metals other than noble metals, molybdenum alloys containing at least two metals (excluding substances of high interest according to european law), alloys containing molybdenum and particles, alloys containing molybdenum and soft particles, alloys containing molybdenum and nanoparticles, alloys containing molybdenum and SiO2, siC or other silicon compounds, alloys containing molybdenum and boride, bromine nitride or other boron compounds, alloys containing molybdenum and PTFE or other fluorine compounds, alloys containing molybdenum and chromium, chromium carbide, chromium oxide or other compounds may be present in one or more layers of the present.

In another embodiment, one of the metals of the alloy layers described herein is cobalt. For example, cobalt alloys, cobalt compounds, cobalt composites, cobalt phosphorus alloys, cobalt molybdenum phosphorus alloys, cobalt tungsten phosphorus alloys, cobalt alloys containing only cobalt and molybdenum, cobalt alloys containing at least cobalt and transition metals, cobalt alloys containing at least two metals other than any noble metal, cobalt alloys containing at least cobalt and refractory metals other than noble metals, cobalt alloys containing at least cobalt and refractory metals other than tungsten and any noble metal, cobalt alloys containing at least cobalt and no cobalt and any noble metal, cobalt and particle containing composites, cobalt and nanoparticle containing composites, cobalt and SiO2, siC or other silicon compounds containing composites containing cobalt and boride, bromine nitride or other boron compounds containing composites containing cobalt and PTFE or other fluorine compounds, chromium carbide, chromium oxide or other chromium compounds containing composites.

In some embodiments, one of the metals of the alloy layers described herein is tin. For example, tin alloys, tin compounds, tin composites, tin phosphorus alloys, tin molybdenum phosphorus alloys, tin tungsten phosphorus alloys, tin alloys containing only tin and molybdenum, tin alloys containing at least tin and transition metals, tin alloys containing at least two metals other than noble metals, tin alloys containing at least tin and refractory metals other than tungsten and any noble metals, tin alloys containing at least tin and no noble metals, tin alloys containing at least tin and particles, tin alloys containing tin and nanoparticles, tin alloys containing tin and SiO2, siC or other silicon compounds, tin and boron compounds, bromine nitride alloys or other boron compounds, tin alloys containing tin and PTFE or other fluorine compounds, chromium alloys containing tin, molybdenum and chromium carbides, chromium oxides or other chromium compounds.

In another embodiment, one of the metals of the alloy layers described herein is tungsten. For example, tungsten alloys, tungsten compounds, tungsten composites, tungsten phosphorus alloys, tungsten molybdenum phosphorus alloys, tungsten alloys containing only tungsten and molybdenum, tungsten alloys containing at least tungsten and transition metals, tungsten alloys containing at least two metals (excluding noble metals), tungsten alloys containing at least tungsten and refractory metals other than noble metals, tungsten alloys containing at least tungsten and excluding nickel and noble metals, composite alloys containing tungsten and particles, composite alloys containing tungsten and nanoparticles, composite alloys containing tungsten and SiO2, siC or other silicon compounds, composite alloys containing tungsten and boride, bromine nitride or other boron compounds, composite alloys containing tungsten and PTFE or other fluorine compounds, composite alloys containing tungsten, molybdenum and chromium, chromium carbide, chromium oxide or other chromium compounds.

In certain embodiments, one or more of the alloy layers described herein may be considered "hard" layers. The hard layer typically has a higher vickers hardness than the substrate and/or any underlying layers. Although not required, the hard layer is typically present as an outer layer. In some embodiments, the hard layer comprises one or more of a nitride, a metal nitride, a carbide, a metal carbide, a boride, a metal boride, tungsten carbide, a tungsten alloy, a tungsten compound, stainless steel, ceramic, chromium carbide, chromium oxide, a chromium compound, aluminum oxide, zirconium oxide, titanium dioxide, nickel carbide, nickel oxide, a nickel alloy, a cobalt compound, a cobalt alloy, a cobalt-phosphorus alloy, molybdenum, a molybdenum compound, a nanocomposite, an oxide composite, or a combination thereof.

In certain embodiments, a simplified illustration of the alloy layers of the substrate and the surface coating is shown in FIG. 1. The article or device 100 includes a substrate 105 (which is shown in cross-section in fig. 1) and a first layer 110 on a first surface 106 of the substrate 105. Although not shown, layers or coatings may also be present on the surfaces 107, 108, and 109 of the substrate 105. Layer 110 is shown in fig. 1 as a solid layer of uniform thickness that exists across surface 106 of substrate 105. Such a configuration is not necessary and different regions of layer 110 may comprise different thicknesses or even different materials. Furthermore, certain areas of the surface 106 may not include any surface coating at all. In some embodiments, substrate 105 may be or may include a metallic material including, but not limited to, steel (carbon steel, tool steel, stainless steel, etc.), copper alloy, aluminum alloy, chromium alloy, nickel alloy, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, hastelloy, inconel, nichrome, monel, other substrates comprising at least one metal, or nitrided or carburized substrates. In some embodiments, the substrate may be porous or may be non-porous. Layer 110 typically comprises one or more metals or two or more metals or three or more metals or materials. For example, layer 110 may be a metal alloy formed from two or more metals. In some embodiments, layer 110 is an alloy layer formed of only two metals or two materials. In some examples, layer 110 is the only layer present in the surface coating. In some examples, layer 110 is an outer or exposed layer such that the layer may contact surrounding fluids or other materials and protect underlying substrate 105 and any layers between layer 110 and substrate 105.

In some embodiments, one of the metals in layer 110 is nickel. In other embodiments, one of the metals in layer 110 is molybdenum. In other embodiments, one of the metals in layer 110 is tungsten. In other embodiments, one of the metals in layer 110 is cobalt. In further embodiments, one of the metals in layer 110 is molybdenum in the form of a molybdenum alloy. In other embodiments, layer 110 may comprise a nickel alloy, a molybdenum alloy, a cobalt alloy, a tungsten alloy, or a combination thereof. In other examples, layer 110 may be a nickel-molybdenum alloy. In some constructions, the layer 110 may be composed of a nickel-molybdenum alloy, with no other material present in the layer 110. In some constructions, the layer 110 can include a nickel molybdenum phosphorus alloy. In some constructions, the layer 110 may be composed of a nickel molybdenum phosphorus alloy, with no other material present in the layer 110.

In some constructions, the precise thickness of the layer 110 may vary from 1 micron to about 2mm, depending on the device in which the layer 110 is located. For example, layer 110 may have a thickness of about 5 microns to about 1mm or about 7 microns to about 900 microns. When multiple layers are present in the topcoat, each layer may have a thickness of from 1 micron to about 2mm, or the total thickness of all layers may be from about 1 micron to about 2mm.

In certain embodiments, layer 110 may also include other materials such as particles, fibers, non-metals (e.g., phosphorus, boron nitride, silicon compounds such as silicon dioxide, silicon carbide, etc.), aluminum oxide, molybdenum disulfide, carbon fibers, carbon nanotubes, cobalt, tungsten, tin, gold, platinum, silver, and combinations thereof. The particles may be soft particles, such as polymer particles, PTFE particles, fluoropolymers, and other soft particles. The particles may be hard particles such as diamond, boron nitride, silicon compounds such as silica, silicon carbide, and the like. The particles may be hydrophobic or hydrophilic. Hydrophobic particles such as PTFE particles, polytetrafluoroethylene particles, fluoropolymers, silicon-based particles, hard particles are functionalized with hydrophobicity, hydrophilicity, or both. Such as functionalized silica or silicon carbide in fluorine-containing compounds, florin molecules, silicon compounds, silicon-containing molecules, and other polymers. Other particles such as titanium dioxide and other catalysts may also be used, either functionalized or used as such.

In other constructions, the layer 110 may comprise a nickel-molybdenum alloy, a nickel-molybdenum alloy having less than 35 weight percent molybdenum, a nickel-molybdenum-phosphorus alloy having less than 35 weight percent molybdenum, a refractory metal-nickel ductile alloy, a nickel-molybdenum ductile alloy, a refractory metal-nickel brittle alloy, a nickel-molybdenum ductile alloy, a transition metal-molybdenum brittle alloy, a transition metal-molybdenum ductile alloy, a nickel-molybdenum alloy having a hardness of less than 1100 and greater than 500 vickers hardness, a nickel-molybdenum alloy having a surface roughness Ra of less than 1 micron, a nickel-molybdenum alloy having uniform and non-uniform particle sizes, a nickel-molybdenum alloy having an average particle size of less than 2 microns, a conformal nickel-molybdenum alloy, an alloy of nickel, molybdenum and phosphorus, an alloy of cobalt and molybdenum and phosphorus, nickel, alloys of molybdenum and tungsten, alloys of nickel with materials having a lower magnetic property than nickel, alloys of molybdenum with materials having a lower hardness than molybdenum, conformal alloys of refractory metals and nickel, nickel-molybdenum ductile alloys, nickel-tungsten brittle alloys, nickel-cobalt ductile alloys, nickel-cobalt brittle alloys, alloys of nickel with materials having a higher temperature than nickel, nickel-molybdenum alloys containing a third element including, but not limited to, refractory metals, noble metals, hard particles, soft particles, hydrophobic particles, hydrophilic particles, catalysts, materials having a higher conductivity than nickel, materials having a higher conductivity than molybdenum, materials having a lower hardness than nickel, materials having a higher hardness than nickel and a lower hardness than molybdenum, or other compounds such as phosphorus, boron nitride, silicon carbide, silicon oxide, aluminum oxide, molybdenum disulfide, hard particles having a hardness HV of greater than 750 vickers, and/or hard particles having a particle size of less than 1 micron, nickel-molybdenum alloys containing a third element including, but not limited to refractory metals, noble metals, hard particles, A material more conductive than nickel, a material more conductive than molybdenum, a material softer than nickel, or other compounds such as phosphorus, boron nitride, silicon carbide, silicon oxide, aluminum oxide, molybdenum disulfide, hard particles with a hardness HV greater than 750 vickers, and/or hard particles with a particle size less than 1 micron.

In some cases, layer 110 on substrate 105 may comprise nickel tungsten or nickel tungsten alloy, wherein it comprises a third element including, but not limited to, refractory metals, noble metals, hard particles or other compounds, such as phosphorus, boron nitride, silicon carbide, alumina, molybdenum disulfide, hard particles with hardness HV >750, hard particles with particle sizes less than 500nm, highly conductive particles, carbon nanotubes, and/or carbon nanoparticles. Combinations of these materials may also be present in layer 110 on substrate 105.

In some embodiments, a simplified illustration of another apparatus is shown in fig. 2. In this illustration, the article or device 200 includes an intermediate layer 210 between the layer 110 and the underlying substrate 105. In some examples, the intermediate layer 210 may improve adhesion, may improve corrosion, may lighten the coating, or any combination thereof. For example, nickel alloys, copper alloys, nickel compounds, nickel composites, nickel phosphorus alloys, nickel molybdenum phosphorus alloys, nickel cobalt alloys, nickel tungsten alloys, nickel cobalt phosphorus alloys, copper, nickel tungsten phosphorus alloys, copper alloy, copper composite, tin alloy, tin composite, cobalt alloy, cobalt composite, cobalt molybdenum alloy, cobalt tungsten alloy, cobalt molybdenum phosphorus alloy, cobalt tungsten phosphorus alloy, molybdenum alloy, molybdenum composite, nickel alloy containing at least two metals other than noble metals, molybdenum alloy containing at least two metals other than noble metals, cobalt molybdenum alloy, cobalt tungsten alloy, cobalt molybdenum phosphorus alloy, molybdenum alloy, nickel alloy, and molybdenum alloy, and nickel alloy a molybdenum alloy comprising at least molybdenum and a transition metal, a molybdenum alloy comprising at least molybdenum and a transition metal not including a noble metal, a metallic tungsten alloy, a nickel alloy comprising at least nickel and a refractory metal (excluding a noble metal), a molybdenum tin alloy, a tungsten composite or other material may be present as layer 210 between layer 110 and substrate 105, to improve adhesion between layer 110 and layer 210. Such layers may be less than 10um, 9um, 8um, 7um, 2um, 1um, 0.75um, 0.5um, or 0.25um thick. As noted herein, in some cases, layer 210 may be a strike layer, such as a nickel layer, that is added to substrate 105 to improve adhesion between substrate 105 and layer 110.

In some constructions, the layer 210 may act as a brightening agent to increase the overall glossy appearance of the article or device 200. The bright or semi-bright layer generally reflects a higher percentage of light than layer 110. For example, the number of the cells to be processed, nickel, nickel alloy, copper alloy, nickel compound, nickel composite, nickel phosphorus alloy, nickel molybdenum phosphorus alloy, nickel cobalt alloy, nickel tungsten alloy, nickel cobalt phosphorus alloy, copper, nickel tungsten phosphorus alloy copper alloy, copper composite, tin alloy, tin composite, cobalt alloy, cobalt composite, cobalt molybdenum alloy, cobalt tungsten alloy, cobalt molybdenum phosphorus alloy, cobalt tungsten phosphorus alloy, molybdenum alloy, molybdenum composite, nickel alloy containing at least two metals other than noble metals, nickel alloy a molybdenum alloy comprising at least two metals other than noble metals, a molybdenum alloy comprising at least molybdenum and a transition metal not including noble metals, a metallic tungsten alloy, a nickel alloy comprising at least nickel and a transition metal, a nickel alloy comprising at least nickel and a refractory metal other than noble metals, a tungsten alloy, a tungsten composite or other material may be present as layer 210 between layer 110 and substrate 105, to lighten the overall coating appearance.

In other constructions, the layer 210 may function to increase the corrosion resistance of the article or device 200. For example, the number of the cells to be processed, nickel, nickel alloy, copper alloy, nickel compound, nickel composite, nickel phosphorus alloy, nickel molybdenum phosphorus alloy, nickel cobalt alloy, nickel tungsten alloy, nickel cobalt phosphorus alloy, copper, nickel tungsten phosphorus alloy copper alloy, copper composite, tin alloy, tin composite, cobalt alloy, cobalt composite, cobalt molybdenum alloy, cobalt tungsten alloy, cobalt molybdenum phosphorus alloy, cobalt tungsten phosphorus alloy, molybdenum alloy, molybdenum composite, molybdenum tin alloy, alloy containing at least molybdenum and nickel, alloy containing at least molybdenum and tin, alloy containing at least molybdenum and cobalt, composite containing molybdenum and soft particles, composite containing molybdenum and nanoparticles, composite containing molybdenum and hard particles a nickel alloy containing at least two metals other than noble metals, a molybdenum alloy containing at least molybdenum and a transition metal other than noble metals, a tungsten alloy, a nickel alloy containing at least nickel and a transition metal, a nickel alloy containing at least nickel and a refractory metal other than noble metals, a nickel alloy containing at least nickel and a refractory metal other than tungsten and noble metals, a tungsten alloy, a tungsten composite, a tungsten alloy other than an alloy containing both nickel and tungsten, chromium, a chromium compound, or other materials may be used as layer 210, is present between the layer 110 and the substrate 105 to increase corrosion resistance.

In some embodiments, the substrate 105 used with the intermediate layer 210 may be or may comprise a metallic material, including but not limited to steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum alloy, chromium alloy, nickel alloy, molybdenum molybdenum alloy, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, hastelloy, inconel, nichrome, monel, or combinations thereof. In some embodiments, the substrate may be porous or may be non-porous. In certain embodiments, layer 210 may comprise one or more materials selected from the group consisting of group II materials, group III materials, group IV metals, group V metals, group VI metals, and group VII metals. In some examples, layer 210 does not contain any noble metals. In other cases, layer 210 includes only a single metal, but may include other nonmetallic species.

In certain embodiments, layer 110 used with intermediate layer 210 generally comprises one or more metals or two or more metals. For example, layer 110 used with intermediate layer 210 may comprise any of those substances and constructions described with reference to fig. 1. For example, layer 110 used with layer 210 is a metal alloy formed from two or more metals. In some embodiments, one of the metals in layer 110 used with intermediate layer 210 is nickel. In other embodiments, one of the metals in layer 110 used with intermediate layer 210 is molybdenum. In further embodiments, one of the metals in layer 110 used with intermediate layer 210 is tungsten. In further embodiments, one of the metals in layer 110 used with intermediate layer 210 is cobalt. In further embodiments, one of the metals in layer 110 used with intermediate layer 210 is chromium. In some embodiments, layer 110 used with layer 210 may include only two metals or two substances or three metals or three substances. For example, layer 110 used with layer 210 may include only nickel and molybdenum or only nickel, molybdenum and phosphorus or only nickel and tungsten or only nickel and cobalt or only nickel, phosphorus and iron or only nickel and phosphorus.

In other embodiments, the layer 110 used with the intermediate layer 210 may comprise a nickel alloy, a molybdenum alloy, a tungsten alloy, a cobalt alloy, a chromium alloy, or a combination thereof. In other examples, layer 110 used with intermediate layer 210 may be nickel, nickel-molybdenum alloy, nickel-cobalt alloy, nickel-tungsten alloy, nickel-phosphorus alloy, cobalt-molybdenum alloy, cobalt-tungsten alloy, cobalt-phosphorus alloy, nickel-molybdenum-phosphorus alloy, cobalt-tungsten-phosphorus alloy, chromium alloy, molybdenum-tin alloy, chromium compound. In some constructions, the layer 110 used with the intermediate layer 210 may be composed of a nickel-molybdenum alloy, and no other material is present in the layer 110. In other constructions, the layer 110 used with the intermediate layer 210 may be composed of a nickel molybdenum phosphorus alloy, and no other material is present in the layer 110. In other constructions, the layer 110 used with the intermediate layer 210 may be composed of a cobalt molybdenum alloy, and no other material is present in the layer 110. In other constructions, the layer 110 used with the intermediate layer 210 may be composed of cobalt molybdenum phosphorus alloy, and no other material is present in the layer 110. In other constructions, the layer 110 used with the intermediate layer 210 may be composed of a nickel alloy that includes at least two metals in addition to the noble metal. In other constructions, the layer 110 used with the intermediate layer 210 may be composed of a molybdenum alloy that includes at least two metals in addition to the noble metal. In other constructions, the layer 110 used with the intermediate layer 210 may be composed of a molybdenum alloy that includes at least molybdenum and a transition metal. In other constructions, the layer 110 used with the intermediate layer 210 may be composed of a molybdenum alloy that includes at least molybdenum and a transition metal other than a noble metal. The exact thickness of layer 110 used with intermediate layer 210 may vary from 1 micron to about 2mm, depending on the article in which layer 110 is present. For example, the thickness of layer 110 may be about 10 microns to about 200 microns. Similarly, the thickness of the intermediate layer 210 may vary from 0.1 microns to about 2mm, for example from about 1 micron to about 20 microns. The thickness of layer 210 may be less than the thickness of layer 110 or greater than the thickness of layer 110.

In another configuration, two or more layers may be present on an underlying substrate. Referring to fig. 3, an article or device 300 is shown that includes a first layer 110 and a second layer 320 on a substrate 105. The order of the layers 110, 320 may be reversed so that the layer 320 is closer to the substrate 105 if desired. The layers 110, 320 may comprise the same or different materials, or may comprise similar materials deposited in different ways or under different conditions. For example, the layers 110, 320 in fig. 3 may independently be any of those materials described herein, e.g., any of those materials described with reference to the layers of fig. 1 or 2. In some constructions, both layers 110, 320 may be alloy layers. For example, each of the layers 110, 320 may include one or more of nickel, copper, molybdenum, cobalt, or tungsten. These layers may be formed in a similar or different manner. For example, layer 110 may be electrodeposited under alkaline conditions, and layer 220 may be electrodeposited under acidic conditions. As another example, layers 110, 320 may each independently comprise nickel, copper, molybdenum, cobalt, or tungsten, but layer 110 may be electrodeposited under alkaline conditions, while layer 220 may be deposited using physical vapor deposition techniques, chemical vapor deposition techniques, atomic layer deposition, thermal spray techniques, or other methods. The layers 110, 320 may comprise metals other than copper, such as nickel, molybdenum, cobalt, tungsten, tin, or the like, or non-metals or both. Different conditions may provide different overall structures in layers 110, 320, even though similar materials may be present. In some constructions, layer 110 may improve the adhesion of layer 320. In other constructions, the layer 110 may "highlight" the surface of the device 300, so that the device 300 has a more shiny overall appearance.

In some embodiments, the substrate 105 used with the layers 110, 320 may be or may comprise a metallic material, including but not limited to steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum alloy, chromium alloy, nickel alloy, molybdenum molybdenum alloy, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, hastelloy, inconel, nichrome, monel, or combinations thereof. In some embodiments, the substrate 105 may be porous or non-porous. Layers 110, 320 typically each comprise one or more metals or two or more metals. For example, the layers 110, 320 may be a metal alloy formed from two or more metals. In some embodiments, one of the metals in the layers 110, 320 is nickel. In other embodiments, one of the metals in the layers 110, 320 is molybdenum. In further embodiments, one of the metals in the layers 110, 320 is cobalt. In further embodiments, one of the metals in the layers 110, 320 is tungsten. The layers 110, 320 need not have the same metal, and it is desirable that the metals in the layers 110, 320 be different. In other embodiments, the layers 110, 320 may independently comprise a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, the layers 110, 320 may independently be nickel-molybdenum, nickel-molybdenum-phosphorus, tungsten, nickel-tungsten, or the like. In some constructions, one or both of the layers 110, 320 may be composed of a nickel-molybdenum alloy, and no other material is present in each layer. In other constructions, one of the layers 110, 320 may be composed of a nickel molybdenum phosphorus alloy, and no other material is present in each layer. In some constructions, both layers 110, 320 may be composed of nickel molybdenum phosphorus alloy, and no other material is present in each layer. In other constructions, one or both of the layers 110, 320 may be composed of a nickel alloy including at least nickel and a transition metal. In other constructions, one or both of the layers 110, 320 may be composed of a nickel alloy including at least nickel and a transition metal other than a noble metal. In other constructions, one or both of the layers 110, 320 may be composed of a molybdenum alloy including at least molybdenum and a transition metal. In other constructions, one or both of the layers 110, 320 may be composed of a molybdenum alloy including at least molybdenum and a transition metal other than a noble metal. The exact thickness of the layers 110, 320 may vary between 0.1 microns to about 2mm, depending on the device in which the coating is present, and the thicknesses of the layers 110, 320 need not be the same. Layer 110 may be thicker than layer 320 or may be thinner than layer 320.

In some constructions, an intermediate layer may be present between the first layer 110 and the second layer 320. The intermediate layer may comprise any of those materials described herein, for example, with reference to layer 210. Or when the coating includes a first layer 110 and a second layer 120, an intermediate layer may be present between the substrate 105 and the layer 110. In some embodiments, layer 320 may have a higher hardness than layer 110. For example, the hardness of layer 320 may be greater than 750 vickers. In certain embodiments, layer 320 comprises one or more of a nitride, a metal nitride, a carbide, a metal carbide, a boride, a metal boride, tungsten carbide, a tungsten alloy, a tungsten compound, stainless steel, a ceramic, chromium carbide, chromium oxide, a chromium compound, aluminum oxide, zirconium oxide, titanium dioxide, nickel carbide, nickel oxide, a nickel alloy, a cobalt compound, a cobalt alloy, a cobalt-phosphorus alloy, molybdenum, a molybdenum compound, a nanocomposite, an oxide composite, or a combination thereof.

In other embodiments, the surface of the substrate or surfaces of the substrate may be treated including transfer surfaces (e.g., carburized, nitrided, carbonitrided, induction hardened, age hardened, precipitation hardened, gas nitrided, normalized, low temperature treated, annealed, spray pinned, or by chemical, thermal, or physical or a combination thereof), modified surfaces, i.e., coated or treated with one or more other layers. Referring to fig. 4A, an article or apparatus 400 is shown that includes a transfer surface or treated surface 410 on a substrate 105. The article or device 400 further includes a layer 110 on the treated surface 410. Layer 110 may be any of those materials described herein with reference to layer 110 in fig. 1-3, 5A, 5B, and 12. If desired and as shown in FIG. 4B, a layer 420 may be present between the treated surface 410 of the device 450 and the layer 110. The thickness of layer/treated surface 410 may vary, for example, from about 0.1 microns to about 50 millimeters. The treated surface 410 may be harder than the underlying substrate 105 if desired. For example, the treated surface 410 may have a surface hardness of 50-70 HRC. When the treated surface/layer 410 is a transfer surface, the substrate may be, but is not limited to, steel (mild steel, stainless steel, nitrided steel, steel alloys, low alloy steel, etc.) or other metal-based materials. The exact results of the treatment may vary, and may generally be treated to enhance adhesion, change surface roughness, increase wear resistance, increase internal stress, decrease internal stress, change hardness, change lubricity, or for other reasons. Layer 110 may be used to protect device 450 from corrosion, wear, heat, and other effects. In some cases, the treated surface 410 can negatively reduce the resistance of the device 450 to corrosion, wear, a combination of corrosion and wear, heat, a combination of heat and wear, a combination of corrosion and heat, or other conditions, and the layer 110 can be used to improve performance as desired.

In some embodiments, the substrate 105 of fig. 4A and 4B may be or may comprise a metallic material, including but not limited to steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum alloy, chromium alloy, nickel alloy, molybdenum molybdenum alloy, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, hastelloy, inconel, nichrome, monel, or combinations thereof. In some embodiments, the substrate 105 may be porous or may be non-porous. The layer 110 in fig. 4A and 4B generally comprises one or more metals or two or more metals, as described herein in connection with fig. 1-3, 5A, 5B, and 12. For example, the layer 110 in fig. 4A and 4B may be a metal alloy formed of two or more metals. In some embodiments, one of the metals in layer 110 in fig. 4A and 4B is nickel. In other embodiments, one of the metals in layer 110 in fig. 4A and 4B is molybdenum. In further embodiments, one of the metals in layer 110 in fig. 4A and 4B is cobalt. In further embodiments, one of the metals in layer 110 in fig. 4A and 4B is tungsten. In further embodiments, one of the metals in layer 110 in fig. 4A and 4B is tin. In further embodiments, one of the metals in layer 110 in fig. 4A and 4B is chromium. In other embodiments, the layer 110 in fig. 4A and 4B may comprise a nickel alloy, a molybdenum alloy, or a combination thereof. In other embodiments, the layer 110 in fig. 4A and 4B may comprise a molybdenum alloy of at least two metals (optionally free of noble metals), a molybdenum alloy comprising at least molybdenum and a transition metal other than a noble metal. In other embodiments, layer 110 in fig. 4A and 4B may comprise a nickel alloy comprising at least two metals (without precious metals), a nickel alloy comprising at least nickel and a refractory metal other than a precious metal. In other examples, layer 110 in fig. 4A and 4B may be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In some constructions, the layer 110 in fig. 4A and 4B may be composed of a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy, and no other material is present in the layer 110. In other constructions, the layer 110 may include any of those materials and combinations of materials described with reference to fig. 1, 2, or 3.

In certain embodiments, the precise thickness of layer 110 in fig. 4A and 4B may vary from 1 micron to about 2mm, depending on the article or device in which layer 110 is located, e.g., the thickness may vary from about 5 microns to about 200 microns.

In some embodiments, the intermediate layer 420 may improve adhesion between the layer 110 and the layer/surface 410 when present as shown in fig. 4B. For example, copper, nickel, or other materials may be present as a thin layer, such as 1 micron thick or less, between layer 110 and layer/surface 410. Although not shown, there may be two or more layers between layer/surface 410 and layer 110.

In some embodiments, one or more layers may be present on top of the alloy layer 110. For example, a metal layer, a metal alloy layer, a particle or composite layer, or other material layer may be present on top of layer 110. Referring to fig. 5A, an article or device 500 is shown in which a layer 510 is present on top of layer 110. If desired, an additional layer 560 may be present between layer 510 and layer 110, as shown in FIG. 5B. The exact materials present in the layers 510, 560 may vary depending on the end use of the device 500.

In some embodiments, the substrate 105 of fig. 5A and 5B may be or may comprise a metallic material, including but not limited to steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum alloy, chromium alloy, nickel alloy, molybdenum molybdenum alloy, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, hastelloy, inconel, nichrome, monel, or combinations thereof. In some embodiments, the substrate 105 may be porous or may be non-porous. The layer 110 in fig. 5A and 5B typically comprises one or more metals or two or more metals, as described in connection with fig. 1-4B and 12. For example, the layer 110 in fig. 5A and 5B may be a metal alloy formed of two or more metals. In some embodiments, one of the metals in layer 110 in fig. 5A and 5B is nickel. In other embodiments, one of the metals in layer 110 in fig. 5A and 5B is molybdenum. In further embodiments, one of the metals in layer 110 in fig. 5A and 5B is tungsten. In further embodiments, one of the metals in layer 110 in fig. 5A and 5B is cobalt. In further embodiments, one of the metals in layer 110 in fig. 5A and 5B is chromium. In other embodiments, the layer 110 in fig. 5A and 5B may comprise a nickel alloy, a molybdenum alloy, a cobalt alloy, a tungsten alloy, or a combination thereof. In other examples, the layer 110 in fig. 5A and 5B may be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In some constructions, the layer 110 in fig. 5A and 5B may be composed of a nickel-molybdenum alloy, a nickel-molybdenum-phosphorus alloy, and no other material is present in the layer 110. In other examples, layer 110 in fig. 5A and 5B may comprise a nickel molybdenum phosphorus alloy. In other constructions, the layer 110 in fig. 5A and 5B may be comprised of nickel-cobalt alloy, nickel-tungsten alloy, nickel-phosphorus alloy, cobalt-molybdenum alloy, cobalt-tungsten alloy, cobalt-phosphorus alloy, nickel-molybdenum-phosphorus alloy, cobalt-tungsten-phosphorus alloy, chromium alloy, molybdenum-tin alloy, chromium compound in the layer 110. In other constructions, the layer 110 in fig. 5A and 5B may be composed of a molybdenum alloy comprising at least two metals (optionally free of precious metals), a molybdenum alloy comprising at least molybdenum and a transition metal other than a precious metal, a molybdenum alloy comprising at least molybdenum and a transition metal and phosphorus, a molybdenum alloy comprising at least molybdenum and a transition metal and tin, a molybdenum alloy composite comprising some particles and nanoparticles. In other constructions, the layer 110 in fig. 5A and 5B may be composed of a nickel alloy containing at least two metals (without precious metals), a nickel alloy containing at least nickel and refractory metals other than precious metals. The exact thickness of layer 110 in fig. 5A and 5B may vary from 0.1 microns to about 2mm, depending on the article in which layer 110 is present. In certain embodiments, the layers 510, 560 may each independently be a nickel layer, a nickel molybdenum layer, a metal alloy, tin, chromium, or a combination of these materials. In certain embodiments, layer 510 may comprise a nitride, a metal carbide, a boride, tungsten carbide, a tungsten alloy, a tungsten compound, stainless steel, a ceramic, chromium carbide, chromium oxide, a chromium compound, aluminum oxide, zirconium oxide, titanium dioxide, nickel carbide, nickel oxide, a nickel alloy, a cobalt compound, a cobalt alloy, a cobalt-phosphorus alloy, molybdenum, a molybdenum compound, a nanocomposite, an oxide composite, or a combination thereof. In some embodiments, layer 510 may protect layer 110 from abrasion. In another embodiment, the layer 110 may protect the substrate 105 from corrosion. In another embodiment, layer 110 may protect layer 510 from delamination, chipping, or abrasion; in another embodiment, layer 110 may increase the adhesion of layer 510 to substrate 105. In another embodiment, layer 110 may increase brightness, for example, by reflecting more light.

In other constructions, the article or device may include an outer metal layer and at least one underlying alloy layer. Referring to fig. 6, a plurality of layers is shown, including layer 110, layer 610, and layer 620. The substrate is purposely omitted from fig. 6-8 to simplify the drawing. The substrate is typically adjacent to layer 110, but it may be adjacent to another layer if desired. Layer 110 in fig. 6 generally comprises one or more metals or two or more metals or other materials as described herein with reference to fig. 1-5B and 12. For example, layer 110 in fig. 6 may be a metal alloy formed from two or more metals. In some embodiments, one of the metals in layer 110 in fig. 6 is nickel. In other embodiments, one of the metals in layer 110 in fig. 6 is molybdenum. In other embodiments, layer 110 in fig. 6 may comprise a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, layer 110 in fig. 6 may be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In some constructions, the layer 110 in fig. 6 may be composed of a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy, and no other material is present in the layer 110. The exact thickness of layer 110 in fig. 6 may vary from 1 micron to about 2mm, for example from about 5 microns to about 200 microns, depending on the device in which layer 110 is located.

In certain embodiments, layer 610 in fig. 6 generally comprises one or more metals or metal alloys, such as nickel, copper, molybdenum, nickel-molybdenum alloy, nickel-molybdenum-phosphorus alloy, or combinations thereof. The thickness of layer 610 may generally be greater than or less than the thickness of layer 110. For example, the thickness of layer 610 may vary between about 0.1 microns to about 1 micron. In some embodiments, the metal in layer 610 may be present in the form of an alloy with another metal. Layer 620 typically also comprises one or more metals such as nickel, copper, molybdenum, nickel molybdenum phosphorus, or combinations thereof. The metal of layer 620 may exist in either alloyed or unalloyed form and may exist at a thickness that is higher or lower than the thickness of layer 610. For example, layer 620 may have a thickness of about 0.1 microns to about 0.5 microns. In some embodiments, layer 620 may increase wear resistance, may increase electrical conductivity, may provide a brighter surface, and the like. In some constructions, the layers 610, 620 may comprise the same material, but these materials may be present in different amounts. For example, each of the layers 610, 620 may be a nickel-molybdenum alloy, but the amount of molybdenum in the layer 610 is different than the amount of molybdenum in the layer 620.

In certain embodiments, the layer 110 described herein with reference to fig. 1-6 may be present between two incompatible materials to allow the incompatible materials to be present in a coating or device. The term "incompatible" generally refers to materials that do not readily adhere or adhere to one another or have physical properties that render them unsuitable for use together. By including a metal alloy in layer 110, certain coatings may be included in devices having copper substrates. For example, an alloy layer of Ni-Mo or Ni-Mo-P may be present between the copper substrate and another metal layer. In certain embodiments, by including layer 110 between the metal layer (or metal alloy layer) and the substrate, the overall wear resistance of the outer metal layer may also be increased.

In certain embodiments, one or more of the layers shown in fig. 1-6 may comprise tin (Sn). For example, tin may provide some corrosion resistance. Referring to fig. 7, a plurality of layers is shown, including layer 110, layer 710, and layer 720. A substrate (not shown) is typically adjacent layer 110, but it may be adjacent layer 72 if desired. Layer 110 in fig. 7 generally comprises one or more metals or two or more metals or other materials as described herein with reference to fig. 1-6 and 12. For example, layer 110 in fig. 7 may be a metal alloy formed from two or more metals. In some embodiments, one of the metals in layer 110 in fig. 7 is nickel. In other embodiments, one of the metals in layer 110 in fig. 7 is molybdenum. In other embodiments, layer 110 in fig. 7 may comprise a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, layer 110 in fig. 7 may be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In some constructions, the layer 110 in fig. 7 may be composed of a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy, and no other material is present in the layer 110. The exact thickness of layer 110 in fig. 7 may vary from 1 micron to about 2mm, for example from about 5 microns to about 200 microns, depending on the device in which layer 110 is located.

In certain embodiments, layer 710 in fig. 7 generally comprises one or more metals or metal alloys, or combinations thereof. The thickness of layer 710 may be thicker or thinner than the thickness of layer 110. For example, the thickness of layer 710 may vary between about 0.1 microns to about 1 micron. In some embodiments, the metal in layer 710 may be present in the form of an alloy with another material (e.g., another metal). Layer 720 may comprise, for example, tin or a tin alloy, etc. The exact thickness of layer 720 may vary and may be thicker or thinner than the thickness of layer 710. For example, layer 720 may be present at a thickness greater than 5 microns, such as 10-300 microns or 10-100 microns. In some embodiments, layer 720 may be present to help keep the surface clean, may increase wear resistance, may increase electrical conductivity, may provide a brighter surface, may resist hydraulic fluids, and the like. In some constructions, the layers 710, 720 can comprise the same material, but these materials can be present in different amounts. For example, each of the layers 710, 720 may be a tin alloy, but the amount of tin in the layer 710 is different from the amount of tin in the layer 720.

In some embodiments, the tin or tin alloy layer may be present directly on the metal or metal alloy layer, as shown in fig. 8. A plurality of layers is shown, including layers 110 and 720. There are no layers between layer 110 and layer 720. A substrate (not shown) is typically attached to layer 110. Layer 110 in fig. 8 generally comprises one or more metals or two or more metals or other materials as described herein with reference to fig. 1, 2, and 3. For example, layer 110 in fig. 8 may be a metal alloy formed from two or more metals. In some embodiments, one of the metals in layer 110 in fig. 8 is nickel. In other embodiments, one of the metals in layer 110 in fig. 8 is molybdenum. In other embodiments, the layer 110 in fig. 8 may comprise a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, layer 110 in fig. 8 may be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In some constructions, the layer 110 in fig. 8 may be composed of a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy, and no other material is present in the layer 110. The exact thickness of layer 110 in fig. 8 may vary from 1 micron to about 2mm, for example, from 5 microns to 200 microns, depending on the article or device in which layer 110 is present, with typical thicknesses in the range of 10 microns or less or 5 microns or less. Layer 720 may comprise, for example, tin or a tin alloy, etc. The exact thickness of layer 720 may vary and is generally thicker than layer 710. For example, layer 720 may be present at a thickness greater than 5 microns, such as 10-500 microns or 10-200 microns. In some embodiments, layer 720 may be present to help keep the surface clean, may increase wear resistance, may increase conductivity, may provide a brighter surface, and the like.

In certain embodiments, the tin layer described with reference to fig. 7 and 8 may be replaced with a chromium layer. For example, chromium may be used to increase hardness and may also be used in decorative layers to improve the appearance of an article or device. One or both of the layers 710, 720 may be a chromium layer or a layer comprising chromium.

Referring to fig. 9, a diagram is shown that includes a substrate 905 and a first layer 912. For purposes of illustration, the surface of the substrate is shown as rough, and layer 912 generally conforms to the various peaks and valleys on the surface. The thickness of layer 912 may be the same or may be different in different regions. In some embodiments, the substrate 905 may be or may comprise a metallic material, including but not limited to steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum alloy, chromium alloy, nickel alloy, molybdenum molybdenum alloy, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, hastelloy, inconel, nichrome, monel, or combinations thereof. In some embodiments, the substrate 905 may be porous or may be non-porous. For example, coating 912 may be a metal alloy formed of two or more metals as described with reference to fig. 1-8 and 12 or other materials as described herein. In some embodiments, one of the metals in coating 912 is nickel. In other embodiments, one of the metals in coating 912 is molybdenum. In other examples, the coating 912 may be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In some constructions, the coating 912 may be composed of a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy, and no other material is present in the coating 912. The exact thickness of the coating 912 may vary from 1 micron to about 2mm, for example from about 5 microns to about 200 microns, depending on the article or device in which the coating 912 is located. While the exact function of layer 912 may be different, as discussed further below, the roughened surfaces of layer 912 and substrate 905 may provide a texture that makes the surfaces less prone to scatter light or display a fingerprint.

In some embodiments, one or more layers may be present between the substrate 905 and the layer 912. For example, one or more intermediate layers may be present between the substrate 905 and the layer 912. In some cases, the intermediate layer(s) may improve adhesion between the layer 912 and the substrate 905. For example, copper, nickel, or other materials may be present as a thin layer, such as 1 micron thick or less, between the coating 912 and the substrate 905. In certain constructions, the intermediate layer(s) may act as a brightening agent to increase the overall glossy appearance of the article surface or device surface. In other constructions, the intermediate layer(s) may function to increase the corrosion resistance of the coating. In some embodiments, the substrate 905 used with the intermediate layer may be or may comprise a metallic material including, but not limited to, steel (carbon steel, tool steel, stainless steel, etc.), copper alloy, aluminum alloy, chromium alloy, nickel alloy, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, plastic, polymer, or combinations thereof. The coating 912 used with the intermediate layer(s) typically comprises one or more metals or two or more metals. For example, the coating 912 used with the intermediate layer(s) may be a metal alloy formed of two or more metals as described with reference to fig. 1-8 and 12 or other materials as described herein. In some embodiments, one of the metals in the coating 912 used with the intermediate layer(s) is nickel. In other embodiments, one of the metals in the coating 912 used with the intermediate layer(s) is molybdenum. In other embodiments, the coating 912 used with the intermediate layer(s) may comprise a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, the coating 912 used with the intermediate layer(s) may be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In some constructions, the coating 912 used with the intermediate layer(s) may be composed of a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy, and no other material is present in the coating 912. The exact thickness of the coating 912 used with the intermediate layer(s) may vary from 1 micron to about 2 millimeters, for example from about 5 microns to about 200 microns, depending on the article or device in which the coating 912 is present.

In some embodiments, it may be desirable to have a roughened surface layer. Referring to fig. 10, an article or device comprising a substrate 105 and a roughened surface layer 1012 is shown. The roughened surface layer 1012 may comprise any of those materials described in connection with the layer 110. In this illustration, the substrate 105 is generally smooth and the layer 1012 may undergo a post-deposition step to roughen the surface layer 1012. The thickness of layer 1012 is different in different regions. In some embodiments, the substrate 105 shown in fig. 10 may be or may comprise a metallic material, including but not limited to steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum alloy, chromium alloy, nickel alloy, molybdenum molybdenum alloy, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, hastelloy, inconel, nichrome, monel, or combinations thereof. In some embodiments, the substrate 105 may be porous or may be non-porous. The coating 1012 generally comprises one or more metals as described with reference to fig. 1-8 and 12 or two or more metals or other materials as described herein. For example, coating 1012 may be a metal alloy formed from two or more metals. In some embodiments, one of the metals in coating 1012 is nickel. In other embodiments, one of the metals in coating 1012 is molybdenum. In other embodiments, the coating 1012 may comprise a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, the coating 1012 may be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In some constructions, the coating 1012 may be composed of a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy, and no other material is present in the coating 1012. The exact thickness of the coating 1012 can vary from 0.1 microns to about 2mm, for example from about 5 microns to about 200 microns, depending on the article or device in which the coating 1012 is located. Although the exact function of layer 1012 may vary, layer 1012 may provide a texture that makes the surface less prone to scattering light or displaying a fingerprint, as discussed further below.

In some embodiments, one or more layers may be present between the substrate 105 and the layer 1012. For example, one or more intermediate layers may be present between the substrate 105 and the layer 1012. In some cases, the intermediate layer(s) may improve adhesion between layer 1012 and substrate 105. For example, copper, nickel, or other materials may be present as a thin layer, such as 1 micron thick or less, between the coating 1012 and the substrate 105. In certain constructions, the intermediate layer(s) may act as a brightening agent to increase the overall glossy appearance of the article surface or device surface. In other constructions, the intermediate layer(s) may function to increase the corrosion resistance of the article or device. In some embodiments, the substrate 105 used with the intermediate layer may be or may comprise a metallic material, including but not limited to steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum alloy, chromium alloy, nickel alloy, molybdenum molybdenum alloy, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, hastelloy, inconel, nichrome, monel, or combinations thereof. In some embodiments, the substrate 105 may be porous or may be non-porous. The coating 1012 used with the intermediate layer(s) generally comprises one or more metals as described with reference to fig. 1-8 and 12 or two or more metals or other materials as described herein. For example, the coating 1012 used with the intermediate layer(s) is a metal alloy formed from two or more metals. In some embodiments, one of the metals in the coating 1012 used with the intermediate layer(s) is nickel. In other embodiments, one of the metals in the coating 1012 used with the intermediate layer(s) is molybdenum. In other embodiments, the coating 1012 used with the intermediate layer(s) may include a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, the coating 1012 used with the intermediate layer(s) may be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In some constructions, the coating 1012 used with the intermediate layer(s) may be composed of a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy, and no other material is present in the coating 1012. The exact thickness of the coating 1012 used with the intermediate layer(s) may vary from 1 micron to about 2mm, for example from about 10 microns to about 200 microns, depending on the article or device in which the layer 1012 is located.

In certain embodiments, a surface coating may be applied to the roughened surface to provide an overall smooth surface. An illustration is shown in fig. 11, where a roughened substrate 905 includes a layer 1110 that fills the peaks and valleys and provides a generally smoother outer surface. The surface layer 1110 may comprise any of those materials described in connection with layer 110 in fig. 1-8 and 12 or other materials as described herein. In this illustration, the substrate 905 may have undergone a roughening treatment and the layer 1110 may have undergone a post-deposition step, such as a shot peening or other step, to smooth the surface layer 1110 if the surface layer 1110 is not smooth after deposition. The thickness of layer 1110 varies in different regions to fill peaks and valleys. In some embodiments, the substrate 905 may be or may comprise a metallic material, including but not limited to steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum alloy, chromium alloy, nickel alloy, molybdenum molybdenum alloy, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, hastelloy, inconel, nichrome, monel, or combinations thereof. In some embodiments, the substrate 905 may be porous or may be non-porous. The coating 1110 generally comprises one or more metals or two or more metals as described herein in connection with the layer 110. For example, the coating 1110 may be a metal alloy formed from two or more metals. In some embodiments, one of the metals in the coating 1110 is nickel. In other embodiments, one of the metals in the coating 1110 is molybdenum. In other embodiments, the coating 1110 may comprise a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, the coating 1110 may be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In some constructions, the coating 1110 may be composed of a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy, and no other material is present in the coating 1110. The exact thickness of the coating 1110 can vary from 1 micron to about 2mm, for example from about 5 microns to about 200 microns, depending on the article or device in which the coating 1110 is located. Although the exact function of layer 1110 may vary, as discussed further below, layer 1110 may provide a smoother or more shinier surface, which is more aesthetically pleasing.

In some embodiments, one or more layers may be present between the substrate 905 and the layer 1110. For example, one or more intervening layers may be present between the substrate 905 and the layer 1110. In some cases, the intermediate layer(s) may improve adhesion between the layer 1110 and the substrate 905. For example, copper, nickel, or other materials may be present as a thin layer, such as 1 micron thick or less, between the coating 1110 and the substrate 905. In certain constructions, the intermediate layer(s) may act as a brightening agent to increase the overall glossy appearance of the article surface or device surface. In other constructions, the intermediate layer(s) may function to increase the corrosion resistance of the coating. In some embodiments, the substrate 105 used with the intermediate layer may be or may comprise a metallic material, including but not limited to steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum alloy, chromium alloy, nickel alloy, molybdenum molybdenum alloy, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, hastelloy, inconel, nichrome, monel, or combinations thereof. In some embodiments, the substrate 105 may be porous or may be non-porous. The coating 1110 used with the intermediate layer(s) typically comprises one or more metals or two or more metals. For example, the coating 1110 used with the intermediate layer(s) may be a metal alloy formed of two or more metals as described with reference to fig. 1-8 and 12 or other materials as described herein. In some embodiments, one of the metals in the coating 1110 used with the intermediate layer(s) is nickel. In other embodiments, one of the metals in the coating 1110 used with the intermediate layer(s) is molybdenum. In other embodiments, the coating 1110 used with the intermediate layer(s) may comprise a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, the coating 1110 used with the intermediate layer(s) may be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In some constructions, the coating 1110 used with the intermediate layer(s) may be composed of a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy, and no other material is present in the coating 1012. The exact thickness of the coating 1110 used with the intermediate layer(s) may vary from 0.1 microns to about 2mm, for example from about 5 microns to about 200 microns, depending on the article or device in which the layer 1110 is located.

In certain embodiments, a device or article described herein may include a substrate coated with a first layer, a second layer, and a third layer on a surface of the substrate. Referring to fig. 12, an article or device 1200 includes a substrate 105, a first layer 110, a second layer 320, and a third layer 1230. Each of the layers 110, 320, and 1230 may comprise any of those materials described in connection with the layers 110, 320 above. In some embodiments, layer 1230 may be a polymer coating or a metal or non-metal based coating. Layer 110 is typically a metal alloy layer comprising two or more metals as described in connection with layer 110 of fig. 1-8 or other materials as described herein.

In certain constructions, the articles and devices described herein can comprise a substrate having a coated surface, wherein the coated surface comprises a surface coating. The surface coating may comprise two or more layers. For example, an alloy layer as described in connection with layer 110 may be located on a surface of substrate 105, and a second layer may be located on alloy layer 110. In some examples, the alloy layer may include molybdenum as described herein, such as molybdenum in combination with one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. The second layer on the alloy layer may comprise a ceramic or an alloy or some harder material than the underlying molybdenum-containing layer. In other cases, depending on the intended use of the article or device, the molybdenum-containing alloy layer may be harder than the second layer. In some embodiments, the second layer may include one or more of tungsten, chromium, aluminum, zirconium, titanium, nickel, cobalt, molybdenum, silicon, boron, or combinations thereof. (ceramics include metal nitrides, metal carbides, borides, tungsten carbide, tungsten alloys, tungsten compounds, stainless steel, ceramics, chromium carbide, chromium oxide, chromium compounds, aluminum oxide, zirconium oxide (zirconia, zirconia oxide), titanium dioxide, nickel carbide, nickel oxide, nickel alloys, cobalt compounds, cobalt alloys, cobalt-phosphorus alloys, molybdenum compounds, nanocomposites, oxide composites, or combinations thereof.

In other constructions, the articles or devices described herein may include a material that provides a layer of lubricating alloy. For example, the substrate may include a coated surface having a smooth alloy layer. In some embodiments, an alloy layer may be formed on the substrate and may include molybdenum or other materials as indicated in connection with layer 110 in the figures. The weight percent of molybdenum or other metals may be 35 wt% or less. The surface roughness Ra of the lubricating alloy layer may be less than 1 micron. In some cases, the alloy layer may also include one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In some embodiments, the surface coating may comprise two or more layers. For example, the base layer may be present with an alloy layer formed or added to the base layer. The base layer may be an intermediate layer between the substrate and the alloy layer, or may be a separate layer that is self-supporting and that is not present on any substrate. In some examples, the base layer may comprise one or more of a nickel layer, a copper layer, a nickel phosphorus layer, a nickel molybdenum layer, or other materials. The coating on the base layer may comprise one or more of molybdenum, nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In some cases, the alloy layer may be an exposed outer layer or may be free of precious metals. Particles may also be present in one or more of the layers, if desired. Exemplary particles are described herein.

In certain embodiments, a surface coating comprising two or more layers comprising the same material may be present on an article described herein. Or one of the layers may be a separate layer that is self-supporting and not present on any substrate. For example, a first alloy layer comprising nickel and molybdenum may be present in combination with a second alloy layer comprising nickel and molybdenum. The amount of material in the different layers may be different, or the different layers may have different additives, such as different particles or other materials. In some cases, one of the layers may be rougher than the other by varying the amount of material in the one layer. For example, the weight percent of molybdenum in the second alloy layer may be less than 30 weight percent and the roughness of the entire surface coating may be less than 1umRa. Each of the two layers may independently comprise one or more of molybdenum, nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In some cases, one of the alloy layers may be free of precious metals. In other cases, each alloy layer is free of precious metals. Particles may also be present in one or more of the alloy layers, if desired. Exemplary particles are described herein.

In certain embodiments, the article may comprise a surface coating having an alloy layer described herein and a chromium layer on top of the alloy layer. The alloy layer may include molybdenum and one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. The chromium layer may be an alloy comprising another metal or material. In some examples, the chromium layer is free of precious metals. In other cases, each of the alloy layer and the chromium layer does not contain a noble metal.

In other constructions, the surface coating may include a nickel molybdenum phosphorus (Ni-Mo-P) alloy layer. In some cases, one or more other materials may be present in the nickel molybdenum phosphorus alloy layer. For example, one or more of tungsten, cobalt, chromium, tin, iron, magnesium, or boron may be present. Particles may also be present if desired. The Ni-Mo-P alloy layer may contain less than 35 wt% molybdenum in the alloy layer or the surface coating layer.

In certain examples, the coatings described herein can be applied to a substrate using suitable methods including, but not limited to, vacuum deposition, physical Vapor Deposition (PVD), chemical Vapor Deposition (CVD), plasma deposition, brush coating, spin coating, spray coating, electrodeposition/electroplating, electroless deposition/plating, high Velocity Oxygen Fuel (HVOF) coating, thermal spraying, or other suitable methods.

In some examples, vacuum deposition may be used to deposit one or more layers of the coating. In certain embodiments, vacuum deposition typically deposits a layer of material on an atomic or molecular basis on the surface of the substrate. Vacuum deposition processes can be used to deposit one or more materials having a thickness ranging from one or more atoms to a few millimeters.

In certain embodiments, physical Vapor Deposition (PVD), a type of vacuum deposition, may be used to deposit one or more coatings described herein. PVD typically uses material vapors to produce a thin coating on a substrate. The coatings described herein may be, for example, sputtered onto the surface of the substrate or applied to the surface of the substrate using vapor phase PVD. In other embodiments, chemical Vapor Deposition (CVD) may be used to produce one or more coatings on a substrate. CVD generally involves exposing the substrate to one or more materials that react and/or decompose on the substrate surface to provide the desired coating on the substrate. In other constructions, plasma Deposition (PD), such as plasma enhanced chemical vapor deposition or plasma assisted chemical vapor deposition, may be used to provide a coating on a substrate. PD generally involves generating a plasma discharge from a reactive gas containing the material to be deposited and/or subjecting the deposited material to ions in the plasma gas to modify the coating. In other examples, atomic Layer Deposition (ALD) may be used to provide a coating on a surface. In ALD, the substrate surface is repeatedly exposed to a precursor that can react with the material surface to form a coating.

In other examples, one or more of the coatings described herein may be deposited into the surface of the substrate using brush coating, spin coating, spray coating, dip coating, electrodeposition (e.g., electroplating, cathodic electrodeposition, anodic electrodeposition, etc.), electroless plating, electrophoretic coating, electrophoretic deposition, or other techniques. When an electrical current is used to deposit a coating on a substrate, the current may be continuous, pulsed, or a combination of continuous and pulsed currents may be used. Some electrodeposition techniques are described in more detail below.

In some constructions, electrodeposition may be used to apply one or more layers of the coating. Generally, electrodeposition uses a voltage applied to a substrate placed in a bath to form a coating on a charged substrate. For example, the applied voltage may be used to reduce the ionic species present in the bath to deposit the ionic species in solid form onto the surface (or all surfaces) of the substrate. As noted in more detail below, ionic species may be deposited to provide a metal coating, a metal alloy coating, or a combination thereof. Depending on the exact ion species used and the electrodeposition conditions and techniques, the resulting properties of the formed electrodeposited coating may be selected or adjusted to provide the desired result.

In certain embodiments using electrodeposition, the ionic species may be dissolved or solvated in an aqueous solution or water. The aqueous solution may contain suitable dissolved salts, inorganic substances or organic substances to facilitate electrodeposition of the coating(s) on the substrate. In other embodiments using electrodeposition, the liquid used in the electrodeposition bath may be generally non-aqueous, e.g., include more than 50% by volume of non-aqueous materials, and may contain hydrocarbons, alcohols, liquefied gases, amines, aromatics, and other non-aqueous materials.

Generally, electrodeposition baths contain substances to be deposited as a coating on a substrate. For example, when nickel is deposited onto a substrate, the bath may contain ionic nickel or solvated nickel. When molybdenum is deposited into the substrate, the bath may contain ionic molybdenum or solvated molybdenum. When the alloy is to be deposited on a substrate, the bath may contain more than a single species, for example, the bath may contain ionic nickel and ionic molybdenum, which are co-electrodeposited to form a nickel-molybdenum alloy as a coating on the substrate. The exact form of the substance added to the bath to provide the ionic or solvated species may vary. For example, the substance may be added to the bath in the form of a metal halide, metal fluoride, metal chloride, metal carbonate, metal hydroxide, metal acetate, metal sulfate, metal nitrate, metal nitrite, metal chromate, metal dichromate, metal permanganate, metal platinate, metal cobalt nitrite, metal hexachloroplatinate, metal citrate, metal ammonium salt, metal cyanide, metal oxide, metal phosphate, metal sodium dihydrogen phosphate, metal disodium hydrogen phosphate, metal sodium salt, metal potassium salt, metal sulfamate, metal nitrite, and combinations thereof. In some examples, a single material comprising two metal species to be deposited may be dissolved in an electrodeposition bath, e.g., a metal alloy salt may be dissolved in a suitable solution prior to electrodeposition. The particular materials used in the electrodeposition bath depend on the particular alloy layer to be deposited. Exemplary materials include, but are not limited to, nickel sulfate, nickel sulfamate, nickel chloride, sodium tungstate, tungsten chloride, sodium molybdate, ammonium molybdate, cobalt sulfate, cobalt chloride, chromium sulfate, chromium chloride, chromic acid, stannous sulfate, sodium stannate, hypophosphites, sulfuric acid, nickel carbonate, nickel hydroxide, potassium carbonate, ammonium hydroxide, hydrochloric acid, or other materials.

In certain embodiments, the precise amount or concentration of the substance to be electrodeposited onto the substrate may vary. For example, the concentration of the substance may vary from about 1 gram/liter to about 400 grams/liter. If desired, additional material may be added to the bath to increase the amount of material available for electrodeposition when the ionic species are depleted by forming a coating on the substrate. In some cases, the concentration of the substance to be deposited may be maintained at a substantially constant level during electrodeposition by continuously adding material to the bath.

In certain embodiments, the pH of the electrodeposition bath may vary depending on the particular ionic species present in the bath. For example, the pH may vary between 1 and about 13, but in some cases the pH may be less than 1, or even less than 0, or greater than 13 or even greater than 14. When the metal species is deposited as a metal alloy onto the substrate, the pH may range from 4 to about 12 in some cases. However, it should be appreciated that the pH may vary depending on the particular voltage and electrodeposition conditions selected for use. Some pH adjusting and buffering agents may be added to the bath. Examples of pH adjusting agents include, but are not limited to, boric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide, glycine, sodium acetate, buffered saline, cacodylate buffer, citrate buffer, phosphate-citrate buffer, barbital buffer, TRIS buffer, glycine-NaOH buffer, and any combination thereof.

In certain embodiments, alloy plating may use complexing agents. For example, the primary role of complexing agents in alloy deposition is to complex different metal ions. Thus, without the proper complexing agent, simultaneous deposition of nickel and molybdenum and formation of alloys does not occur. Examples of complexing agents include, but are not limited to, phosphates, phosphonates, polycarboxylates, zeolites, citrates, ammonium hydroxides, ammonium salts, citric acid, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, aminopolycarboxylates, nitrilotriacetic acid, IDS (N- (1, 2-dicarboxyethyl) -D, L-aspartic acid (iminodisuccinic acid), DS (polyaspartic acid), EDDS (N, N '-ethylenediamine disuccinic acid), GLDA (N, N-bis (carboxymethyl) -L-glutamic acid) and MGDA (methylglycine diacetic acid), hexamine cobalt (III) chloride, ethylene glycol-bis (β -aminoethyl ether) -N, N' -tetraacetic acid (EGTA), ferrocene, cyclodextrins, cholic acid, polymers, and any combination thereof.

In some examples, suitable voltages may be applied to the cathode and anode of the electrodeposition bath to facilitate formation of the layer(s) described herein on the substrate. In some embodiments, a Direct Current (DC) voltage may be used. In other examples, alternating Current (AC), optionally in combination with current pulses, may be used to electrodeposit the layer. For example, alternating voltage waveforms may be used for alternating current deposition, typically sine waves, square waves, triangular waves, etc. High voltage and current densities can be used to facilitate electron tunneling through an oxide-based layer that can be formed on a substrate. In addition, the base layer may be electrically conductive in the cathode direction, which facilitates deposition of the species and avoids reoxidation thereof during half-cycles of the oxidant.

In certain embodiments, exemplary current density ranges that may be used for electrodeposition include, but are not limited to, 1mA/cm ² DC to about 600mA/cm ² DC, more specifically about 1mA/cm ² DC to about 300mA/cm ² DC. In some examples, the current density may vary from 5mA/cm ² DC to about 300mA/cm ² DC, from 20mA/cm ² DC to about 100mA/cm ² DC, from 100mA/cm ² DC to about 400mA/cm ² DC, or any value falling within these exemplary ranges. The exact time for which the current is applied may vary from about 10 seconds to several days, more specifically about 40 seconds to about 2 hours. Instead of a direct current, a pulsed current may be applied if desired.

In some examples, the electrodeposition may use a pulsed current or a pulsed reverse current during the electrodeposition of the alloy layer. In Pulsed Electrodeposition (PED), the potential or current rapidly alternates between two different values. This produces a series of pulses of equal amplitude, duration and polarity, with zero current spacing. Each pulse consists of an on Time (TON) during which the potential and/or current is applied and an off Time (TOFF) during which zero current is applied. By adjusting the pulse amplitude and width, the composition and thickness of the deposited film can be controlled at the atomic level. They facilitate initiation of the grain nuclei and greatly increase the number of grains per unit area, thereby forming a deposit of finer grains having better properties than conventional coatings.

In examples where the coating comprises two or more layers, the first and second layers of the coating may be applied using the same or different electrodeposition baths. For example, the first layer may be applied using a first aqueous solution in an electrodeposition bath. After applying the voltage for a time sufficient to deposit the first layer, the voltage may be reduced to zero, the first solution may be removed from the bath, and a second aqueous solution comprising a different material may be added to the bath. The voltage may then be reapplied to electrodeposit the second layer. In other cases, two separate baths may be used, for example a roll-to-roll (heel) process may be used, where a first bath is used to electrodeposit a first layer and a second, different bath is used to deposit a second layer.

In some cases, individual articles may be joined such that they may be sequentially exposed to individual electrodeposition baths, for example in a roll-to-roll process. For example, the articles may be connected to a common conductive substrate (e.g., a strip). In some embodiments, each electrodeposition bath may be associated with a separate anode, and the interconnected separate articles may be commonly connected to the cathode.

While the particular materials used in the electroplating process may vary, exemplary materials include cations of one or more of the following metals: nickel, molybdenum, copper, aluminum, cobalt, tungsten, gold, platinum, palladium, silver, or combinations thereof. The exact anionic forms of these metals may vary and include chloride, acetate, sulfate, nitrate, nitrite, chromate, dichromate, permanganate, platinate, cobalt nitrite, hexachloroplatinate, citrate, cyanide, oxide, phosphate, sodium dihydrogen phosphate, sodium phosphate, and combinations thereof.

In other cases, the electrodeposition process may be designed to apply an alloy layer comprising molybdenum and one or more of the group consisting of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron or at least one compound comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In some embodiments, the resulting alloy layer may be free of precious metals.

In some embodiments, there may be no intervening layer or layers between the coating 110 and the substrate 105. For example, the coating 110 may be deposited directly onto the substrate surface 105 without any intervening layers therebetween. In other cases, an intermediate layer may be present between the coating 110 and the surface 106 of the substrate 105. The intermediate layer may be formed using the same method as the coating layer 110 is formed or a different method from the coating layer 110 is formed. In some embodiments, the intermediate layer may include copper, copper alloys, nickel alloys, nickel-phosphorus alloys containing hard particles or other compounds such as phosphorus, boron nitride, silicon carbide, aluminum oxide, molybdenum disulfide, hard particles with hardness HV >1000, hard particles with a size less than 500nm, highly conductive particles, carbon nanotubes, and/or carbon nanoparticles. In other cases, the intermediate layer may comprise a nickel alloy that is less magnetic than nickel alone. In some cases, the intermediate layer may be significantly smaller than the coating 110 and may serve to enhance the adhesion of the coating 110 to the substrate 105. For example, the thickness of the intermediate layer may be 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, or 10% thinner than the thickness of the coating 110. In some embodiments, the layer between the substrate and the alloy layer may be a "nickel strike (NICKEL STRIKE)" layer known in the electroplating art.

In some embodiments, a soluble anode may be used to provide one or more of the coating materials. The soluble anode may be dissolved in an electrodeposition bath to provide a substance to be deposited. In some embodiments, the soluble anode may take the form of a disk, rod, sphere, strip of material, or other form. The soluble anode may be present in a carrier or basket connected to a power source.

In some embodiments, one or more of the coatings described herein may be deposited using an anodic oxidation process. Anodic oxidation typically uses a substrate as the anode of the electrolytic cell. Anodic oxidation can alter the microscopic texture of the surface and the metal coating formed near the surface. For example, thick coatings are typically porous and may be sealed to enhance corrosion resistance. Anodic oxidation can produce a harder, more corrosion resistant surface. In some examples, one of the coatings of the articles described herein may be produced using an anodic oxidation process, and the other coating may be produced using a non-anodic oxidation process. In other cases, each coating in the article may be produced using an anodic oxidation process. The specific materials and process conditions used for the anodization may vary. Typically, an anodized layer is grown on the surface of a substrate by applying a direct current through an electrolyte solution containing the material to be deposited. The material to be deposited may include magnesium, niobium, tantalum, zinc, nickel, molybdenum, copper, aluminum, cobalt, tungsten, gold, platinum, palladium, silver, or alloys or combinations thereof. Anodic oxidation is typically performed under acidic conditions and may comprise chromic acid, sulfuric acid, phosphoric acid, organic acids, or other acids.

In certain embodiments, the coatings described herein may be applied in the presence of other additives or agents. For example, wetting agents, leveling agents, whitening agents, defoamers, and/or emulsifiers may be present in an aqueous solution comprising the material to be deposited onto the substrate surface. Exemplary additives and agents include, but are not limited to, thiourea, domiphen bromide, acetone, ethanol, cadmium ions, chloride ions, stearic acid, ethylenediamine Dihydrochloride (EDA), saccharin, cetyltrimethylammonium bromide (CTAB), sodium Lauryl Sulfate (SLS), saccharin, naphthalene sulfonic acid, benzenesulfonic acid, coumarin, ethyl vanillin, ammonia, ethylenediamine, polyethylene glycol (PEG), bis (3-sulfopropyl) disulfide (SPS), jernus Green B (JGB), azo phenyl surfactants (AZTAB), the polyoxyethylene family of surfactants, sodium citrate, perfluoroalkyl sulfate, additive K, calcium chloride, ammonium chloride, potassium chloride, boric acid, myristic acid, choline chloride, citric acid, any redox active surfactants, any electrically conductive ionic liquid, polyethylene glycol ether, polyethylene glycol alcohol, sulfonated oleic acid derivatives, sulfate forms of primary alcohols, alkyl sulfonates, alkyl sulfates, aralkyl sulfonates, sulfates, perfluoroalkyl sulfonates, acid alkyl and aralkyl phosphates, alkyl polyethylene glycol ethers, alkyl polyethylene glycol phosphates or salts thereof, N-containing and optionally substituted and/or quaternized polymers, such as polyethylenimine and derivatives thereof, polyglycine, poly (allylamine), polyaniline (sulfonation), polyvinylpyrrolidone, gelatin, polyvinylpyridine, polyvinylimidazole, polyurea, polyacrylamide, poly (melamine-co-formaldehyde), polyalkanolamines, polyaminoamides and derivatives thereof, polyalkanolamines and derivatives thereof, polyethylenimine and derivatives thereof, quaternized polyethylenimine, poly (allylamine), polyaniline, polyurea, polyacrylamide, poly (melamine-co-formaldehyde), hydroxy-ethyl ethylenediamine triacetic acid, 2-butyne-1, 4-diol, one or more of 2,2 '-azobis (2-methylpropanenitrile), perfluorinated amino acids, glucose, cetyl methyl ammonium bromide, 1-cetyl pyridinium chloride, d-mannitol, glycine, rochell salt, N' -diphenyl benzidine, glycolic acid, tetramethyl ammonium hydroxide, reaction products of amines with epichlorohydrin, reaction products of amines, epichlorohydrin and polyalkylene oxides, reaction products of amines with polyepoxides, polyvinylpyridine, polyvinylimidazole, polyvinylpyrrolidone or copolymers thereof, aniline black, pentamethyl para-rosaniline, one or more of oils, long chain alcohols or diols, polyethylene glycols, polyethylene oxides such as Tritons, alkyl phosphates, metal soaps, special silicone defoamers, commercially available perfluoroalkyl modified hydrocarbon defoamers, perfluoroalkyl substituted silicones, perfluoroalkyl phosphonates, cationic, perfluorinated phosphate, cationic phosphates, nonionic reagents; chelating agents such as citrate, acetate, gluconate, and ethylenediamine tetraacetic acid (EDTA) or any combination thereof.

In embodiments using electroless plating, the metal coating may be produced on the substrate by autocatalytic chemical reduction of the metal cations in the bath. In contrast to electrodeposition/electroplating, no external current is applied to the substrate in electroless plating. Although not wishing to be bound by any particular configuration or example, electroless plating may provide a more uniform layer of material on a substrate as compared to electroplating. In addition, electroless plating can be used to add a coating to a non-conductive substrate.

In some embodiments using electroless plating, the substrate itself may act as a catalyst to reduce ionic metals and form a metal coating on the surface of the substrate. When it is desired to produce a metal alloy coating, the substrate can be used to reduce two or more different ionic metals using a complexing agent to form a metal alloy comprising the two different metals. In some examples, the substrate itself may not act as a catalyst, but a catalytic species may be added to the substrate to promote the formation of a metal coating on the substrate. Exemplary catalytic species that may be added to the substrate include, but are not limited to, palladium, gold, silver, titanium, copper, tin, niobium, and any combination thereof.

While the specific materials used in the electroless plating process may vary, exemplary materials include one or more of the following metal cations: magnesium, niobium, tantalum, zinc, nickel, molybdenum, copper, aluminum, cobalt, tungsten, gold, platinum, palladium, silver, or alloys or combinations thereof. For example, any one or more of these cations may be added to the aqueous solution as a suitable salt. Exemplary suitable salts include, but are not limited to, metal halides, metal fluorides, metal chlorides, metal carbonates, metal hydroxides, metal acetates, metal sulfates, metal nitrates, metal nitrites, metal chromates, metal dichromates, metal permanganates, metal platinates, metal cobalt nitrite, metal hexachloroplatinates, metal citrates, metal cyanides, metal oxides, metal phosphates, metal sodium dihydrogen phosphate, metal disodium hydrogen phosphate, metal sodium phosphate, and combinations thereof.

In certain embodiments, the substrates described herein may undergo a pre-coating treatment step to prepare the substrate for receiving the coating. These treatment steps may include, for example, cleaning, electrical cleaning (anode or cathode), polishing, electropolishing, preplating, heat treatment, abrasion treatment, and chemical treatment. For example, the substrate may be cleaned with an acid, base, water, salt solution, organic solvent, or other liquid or gas. The substrate may be polished using water, an acid or base (e.g., sulfuric acid, phosphoric acid, etc.), or other substances optionally in the presence of an electric current. The substrate may be exposed to one or more gases prior to application of the coating to facilitate removal of oxygen or other gases from the substrate surface. The substrate may be cleaned or exposed to an oil or hydrocarbon fluid to remove any aqueous solution or substance from the surface prior to application of the coating. The substrate may be heated or dried in an oven to remove any liquid from the surface prior to application of the coating. Other steps of treating the substrate prior to applying the coating may also be used.

In some embodiments, the coatings described herein may be sealed. Although the specific conditions and materials of the seal coating may vary, the seal may reduce the porosity and increase the hardness of the coating. In some embodiments, the sealing may be performed by subjecting the coating to steam, organic additives, metals, metal salts, metal alloys, metal alloy salts, or other materials. Sealing may be performed at a temperature higher than room temperature, for example, 30 ℃, 50 ℃, 90 ℃ or more; the sealing may be performed at room temperature or below, for example 20 ℃ or below. In some examples, the substrate and coating may be heated to remove any hydrogen or other gases in the coating. For example, the substrate and coating may be baked within 1-2 hours after coating to remove hydrogen from the article.

One of ordinary skill in the art will recognize that a combination of post-deposition treatment methods may be used. For example, the coating may be sealed and then polished to reduce surface roughness.

In some constructions, the substrate that will receive the coating may be cleaned. The substrate may then be rinsed. The substrate may then be acid treated. The acid treated substrate is then rinsed. The rinsed substrate is then added to the plating bath. The electroplated substrate may optionally be rinsed. The substrate with the coated surface may then be post-plated. Each step will be discussed in more detail below. An optional strike step may be performed between the acid treatment step and the electroplating step, if desired, to provide a nickel layer (or layer of another material) on the surface of the substrate.

In some embodiments, the cleaning step may be performed in the presence or absence of an electrical current. Cleaning is typically performed in the presence of one or more salts and/or a cleaning agent or surfactant, and may be performed at an acidic pH or an alkaline pH. Cleaning is typically performed to remove any oil, hydrocarbon or other material on the surface of the substrate.

After cleaning the substrate, the substrate is rinsed to remove any cleaning agent. The washing is usually carried out in distilled water, but it is also possible to use one or more buffer salts or at an acidic or basic pH. The flushing may be performed one or more times. The substrate is typically kept wet between the various steps to minimize the formation of oxides on the surface. A water repellency test may be performed to verify that the surface is clean and/or free of any oil.

After rinsing, the substrate may be immersed in an acid bath to activate the surface for electrodeposition, such as pickling the surface. The particular acid used is not critical. The pH of the acidic treatment may be 0-7 or even less than 0, if desired. The time the substrate remains in the acid bath may vary, for example, from 10 seconds to about 10 minutes. The acidic solution may be stirred or pumped onto the substrate surface, if desired, or the substrate may be moved within the acid tank during the pickling process.

After the pickling process, the surface may be rinsed to remove any acid. Rinsing may be performed by immersing the pickled substrate in a rinse bath, by flowing a rinse agent across the surface, or both. Multiple or single flushes may be performed as desired.

After pickling, the substrate may optionally be bumped. Without wishing to be limited by either configuration, the strike is to apply a thin layer of material to a substrate that is generally inert or less reactive with the material to be deposited. Examples of inert substrates include, but are not limited to, stainless steel, titanium, certain metal alloys, and other materials. During the strike, electrodeposition is used to apply a thin layer of material, for example up to a few microns in thickness.

The rinsed, acid-washed substrate or rinsed substrate with strike layer may then be subjected to an electrodeposition process as described above to apply a layer of material to the substrate surface. As described herein, electrodeposition may be performed using AC or DC voltages and various waveforms. The exact current density used may be varied to favor or disfavor a particular amount of the element in the final formed coating. For example, when the alloy layer comprises two metals, the current density may be selected such that one metal is present in a higher amount than the other metal in the resulting alloy layer. The pH of the electrodeposition bath may also vary depending on the particular species intended to be present in the surface coating. For example, an acidic bath (ph=3-5.5), a neutral pH bath or an alkaline pH bath (pH 9-12) may be used depending on the materials present in the electrodeposition bath and anode. The exact temperature used during the electrodeposition process may vary from room temperature (about 25 ℃) to about 85 ℃. Ideally, the temperature is below 100 ℃, so that the water in the electrodeposition bath does not evaporate to a significant extent. The electrodeposition bath may contain the material to be deposited and optionally reagents including brighteners, levelers, particles, etc. as described herein.

In some embodiments, the electrodeposition bath may include a brightening agent. A variety of organic compounds are used as brighteners to provide a bright, flat and malleable nickel coating. Brighteners can generally be divided into two categories. Class I or primary brighteners include compounds such as aromatic or unsaturated aliphatic sulfonic acids, sulfonamides, sulfonimides, and sulfonimides. The class I brighteners can be used at relatively high concentrations and produce an opaque or cloudy deposit on the metal substrate. The decomposition of the class I brighteners during electroplating can result in the incorporation of sulfur into the deposit, thereby reducing the tensile stress of the deposit. The use of a class II or secondary brightener in combination with a class I brightener results in a completely bright and flat coating. Class II brighteners are generally unsaturated organic compounds. A wide variety of organic compounds containing unsaturated functionalities such as alcohols, diols, triols, aldehydes, alkenyl, alkynyl, nitrile, pyridyl, and the like can be used as class II brighteners. Typically, the class II brighteners are derived from acetylenic or vinyl alcohols, ethoxylated acetylenic alcohols, coumarins, and pyridyl compounds. Mixtures of such unsaturated compounds can be combined with mixtures of class I brighteners to achieve maximum brightness or ductility for a given leveling rate. A variety of amine compounds may also be used as brighteners or levelers. Acyclic amines can be used as class II brighteners. Propargylamine may be used in combination with acetylenic compounds to improve leveling and low current density coverage.

In certain embodiments, the final amount of metal present in the alloy layer may vary. For example, in one electrodeposition process where two metals are present in the surface coating, one of the metals, such as molybdenum, may be present at up to about 35 wt.% based on the weight of the surface coating. In other embodiments, one of the metals, such as molybdenum, may be present at up to about 20 wt% based on the surface coating weight. In some embodiments, one of the metals, such as molybdenum, may be present at up to about 16 wt% based on the surface coating weight. In some embodiments, one of the metals, such as molybdenum, may be present at up to about 10 wt% based on the surface coating weight. In some embodiments, one of the metals, such as molybdenum, may be present at up to about 6 wt% based on the surface coating weight.

In some constructions, the substrate with the surface coating may then be rinsed or the substrate may undergo another deposition process to apply a second layer to the formed first layer. The second deposition process may be, for example, vacuum deposition, physical Vapor Deposition (PVD), chemical Vapor Deposition (CVD), plasma deposition, brush coating, spin coating, spray coating, electrodeposition/electroplating, electroless deposition/plating, high Velocity Oxygen Fuel (HVOF) coating, thermal spray coating, or other suitable method. In some cases, a second layer may be applied on top of the formed first layer using a second electrodeposition step. For example, the second layer may be an electrodeposited layer comprising one, two, three or more metals or other materials. If desired, additional layers may be formed on the second layer using electrodeposition or any of the other processes mentioned herein.

In other constructions, the material layer may be deposited on the cleaned or acid-washed substrate prior to forming the layer using an electrodeposition process. For example, one or more layers may be first formed on the substrate using vacuum deposition, physical Vapor Deposition (PVD), chemical Vapor Deposition (CVD), plasma deposition, brush coating, spin coating, spray coating, electrodeposition/electroplating, chemical deposition/electroless plating, high Velocity Oxygen Fuel (HVOF) coating, thermal spray coating, or other suitable method. The second layer may be formed on the first layer using an electrodeposition process as described herein. If desired, the first formed layer may be activated by an acid wash process prior to electrodepositing the second layer on the first layer.

Where a monolayer is formed on a substrate by electrodeposition, the substrate with the coated surface may then undergo one or more post-treatment steps including, for example, rinsing, polishing, buffing, heating, annealing, consolidation, etching, or other steps that either clean the coated surface or alter the physical or chemical properties of the coated surface. If desired, an acidic or basic solution may be used to remove some portion of the coating, depending on the materials present in the coating.

In certain embodiments, a method of producing an alloy layer on a substrate includes forming a coated surface on a substrate by electrodepositing an alloy layer on a surface of the substrate. The electrodeposited alloy layer comprises (i) molybdenum and (ii) at least one element selected from the group consisting of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron or at least one compound comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In some examples, the method includes, prior to electrodepositing the alloy layer, cleaning the substrate, rinsing the cleaned substrate, activating a surface of the cleaned substrate to provide an activated substrate, rinsing the activated substrate, and electrodepositing the alloy layer on the activated substrate. In some embodiments, the method includes subjecting the electrodeposited alloy layer to a post-deposition treatment process. In further embodiments, the post-deposition treatment process is selected from the group consisting of rinsing, polishing, buffing, heating, annealing, and consolidating. In some examples, the method includes providing an additional layer on the electrodeposited alloy layer. In other examples, the additional layer is provided using one of vacuum deposition, physical vapor deposition, chemical vapor deposition, plasma deposition, brush coating, spin coating, spray coating, electrodeposition/electroplating, chemical deposition/electroless plating, high velocity oxygen fuel coating, thermal spray coating.

In some constructions, an intermediate material layer may be provided between the substrate and the electrodeposited alloy layer prior to the electrodeposited alloy layer. In some examples, the intermediate layer is provided using one of vacuum deposition, physical vapor deposition, chemical vapor deposition, plasma deposition, brush coating, spin coating, spray coating, electrodeposition/electroplating, chemical deposition/electroless plating, high velocity oxygen fuel coating, thermal spray coating. In certain embodiments, electrodeposition uses a soluble anode or uses an insoluble anode. In some cases, the soluble anode comprises nickel or another metal.

In some constructions, the substrate to be coated may be cleaned. The substrate may then be rinsed. The substrate may then be acid treated. The acid treated substrate is then rinsed. The rinsed substrate is then added to the plating bath. The electroplated substrate may optionally be rinsed. The substrate with the coated surface may then be post-plated. Each step will be discussed in more detail below. An optional strike step may be performed between the acid treatment step and the electroplating step, if desired, to provide a nickel layer (or layer of another material) on the surface of the substrate.

In some embodiments, the electrodeposition bath may include a brightening agent. A variety of organic compounds are used as brighteners to provide a bright, flat and malleable nickel coating. Brighteners can generally be divided into two categories. Class I or primary brighteners include compounds such as aromatic or unsaturated aliphatic sulfonic acids, sulfonamides, sulfonimides, and sulfonimides. The class I brighteners can be used at relatively high concentrations and produce an opaque or cloudy deposit on the metal substrate. The decomposition of the class I brighteners during electroplating can result in the incorporation of sulfur into the deposit, thereby reducing the tensile stress of the deposit. The use of a class II or secondary brightener in combination with a class I brightener results in a completely bright and flat coating. Class II brighteners are generally unsaturated organic compounds. A wide variety of organic compounds containing unsaturated functionalities such as alcohols, diols, triols, aldehydes, alkenyl, alkynyl, nitrile, pyridyl, and the like can be used as class II brighteners. Typically, the class II brighteners are derived from acetylenic or vinyl alcohols, ethoxylated acetylenic alcohols, coumarins, and pyridyl compounds. Mixtures of such unsaturated compounds can be combined with mixtures of class I brighteners to achieve maximum brightness or ductility for a given leveling rate. A variety of amine compounds may also be used as brighteners or levelers. Acyclic amines can be used as class II brighteners. Propargyl amines may be used in combination with alkynyl compounds to improve leveling and low current density coverage.

In some embodiments, the movable member may take many different forms, including a linearly moving member, a rotationally moving member, or a member that may be otherwise moved from a first or initial position to a second position different from the first position. The component can be moved back to the original position if desired. The movable part typically comprises a coated surface, wherein the coated surface comprises a surface coating comprising an alloy layer. For example, the alloy layer contains molybdenum or tungsten. The alloy layer may further comprise one or more elements selected from nickel, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron or one or more compounds comprising nickel, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In other examples, the surface coating of the movable component is located outside of the housing of the device.

In certain embodiments, molybdenum or tungsten is present in the surface coating at 35% by weight or less based on the surface coating weight, or at 25% by weight or less based on the surface coating weight, or at 15% by weight or less based on the surface coating weight, or molybdenum or tungsten is present in the alloy layer at 35% by weight or less based on the alloy layer weight, or at 25% by weight or less based on the alloy layer weight, or at 15% by weight or less based on the alloy layer weight, or molybdenum or tungsten is present in the surface coating at 65% by weight or more based on the surface coating weight, or at 75% by weight or more based on the surface coating weight, or at 85% by weight or more based on the surface coating weight, or molybdenum or tungsten is present in the alloy layer at 65% by weight or less based on the alloy layer weight, or at 75% by weight or less based on the alloy layer weight, or at 85% by weight or less based on the alloy layer weight.

In some examples, the alloy layer of the movable component consists essentially of nickel and molybdenum, or consists essentially of nickel, molybdenum, and one of tin, phosphorus, iron, magnesium, or boron, or consists essentially of nickel and tungsten, or consists essentially of nickel, tungsten, and one of tin, phosphorus, iron, magnesium, or boron.

In certain examples, the coated surface has a surface roughness Ra of less than 1 micron and molybdenum or tungsten is present in the alloy layer at 20% or less by weight based on the weight of the surface coating and the surface coating is free of precious metals.

In some embodiments, the alloy layer is an electrodeposited alloy layer or an exposed outer layer of a surface coating. In other embodiments, the exposed outer layer consists essentially of (i) molybdenum or tungsten and only one of nickel, cobalt, tin, phosphorus, iron, chromium, magnesium, or boron, or (ii) molybdenum or tungsten and only two of nickel, cobalt, tin, phosphorus, iron, chromium, magnesium, or boron, or (iii) molybdenum and phosphorus or both tungsten and phosphorus and at least one of nickel, cobalt, tin, chromium, tungsten, iron magnesium, or boron.

In further configurations, the alloy layer is an electrodeposited alloy layer, further comprising an intermediate layer between the substrate surface and the alloy layer, wherein the intermediate layer comprises one or more of nickel, nickel alloy, copper alloy, nickel tungsten alloy, cobalt alloy, nickel phosphorus alloy, molybdenum or tungsten or both, and an alloy of at least one of nickel, cobalt, chromium, tin, phosphorus, iron or boron.

In some constructions, the movable component comprises an additional layer formed on the alloy layer, wherein the additional layer comprises one or more of nickel, nickel alloy, nickel tungsten alloy, cobalt phosphorus alloy, nickel phosphorus alloy, molybdenum, and alloys of at least one of nickel, cobalt, chromium, tin, phosphorus, iron, or boron, ceramics comprising tungsten, chromium, aluminum, zirconium, titanium, nickel, cobalt, molybdenum, silicon, boron compounds, metal nitrides, metal carbides, boron, tungsten carbide, chromium oxide, aluminum oxide, zirconium oxide, titanium dioxide, nickel carbide, nickel oxide, nanocomposites, oxide composites, or combinations thereof. The alloy layer further comprises, if desired, one or more particles selected from the group consisting of solid nanoparticles, polymer particles, hard particles, silica particles, silicon carbide particles, titanium dioxide particles, polytetrafluoroethylene particles, hydrophobic particles, diamond particles, particles functionalized with hydrophobic groups, solid particles, and combinations thereof.

In some examples, the alloy layer is present as an exposed outer layer of the surface coating, wherein the exposed outer layer is an electrodeposited alloy layer, and wherein the electrodeposited alloy layer does not comprise a noble metal. In other examples, the exposed alloy layer further comprises particles.

In some embodiments, the movable member is configured to move in one or more of a linear direction or a rotational direction. In some cases, the movable member is configured to move in response to a compressive force provided to the movable member. In other cases, the movable member is configured to move from the second position back to the first position in response to a compressive force provided to the movable member. In other embodiments, the movable member is configured to move in response to hydraulic pressure provided to the movable member. In some examples, the movable member is configured to move from the second position back to the first position in response to hydraulic pressure provided to the movable member.

In certain constructions, the device is configured as a hydraulic device comprising a piston member, and wherein the piston member comprises a coated surface. In other examples, the device is configured as a pneumatic device comprising a piston member, and wherein the piston member comprises a coated surface. In some embodiments, the apparatus is configured as a work roll (e.g., a steel work roll) or a roll comprising a coated surface. In some embodiments, the device is configured as a shock absorber comprising a piston member, and wherein the piston member comprises a coated surface. The specific configuration of the movable member is described in more detail below. While the exact operating environment may vary, in some embodiments, the movable component may be operated at or subjected to high temperatures, including, for example, greater than 100 ℃, greater than 200 ℃, greater than 500 ℃, greater than 700 ℃, or greater than 1000 ℃.

In some embodiments, a generalized illustration of a reciprocating or linear motion device is shown in FIG. 13. In one configuration, the shuttle 1300 includes a first movable member 1310 that functions in cooperation with a fixed member 1320. For example, first movable member 1310 may be moved into fixed member 1320 or around fixed member 1320 during use. In other configurations, as discussed in more detail below, the movable component may be located within a housing or other device and may move back and forth during operation of the device. In some constructions, movable member 1310, fixed member 1320, or both may include one or more of the coatings described with reference to fig. 1-12. For example, at least one of movable member 1310 and fixed member 1320 includes a coated surface. The coated surface may comprise an alloy layer. For example, the alloy layer comprises (i) molybdenum and (ii) at least one element selected from the group consisting of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron or at least one compound comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron; such alloy layers may be present alone or in combination with one or more other layers. In other cases, the alloy layer comprises (i) tungsten and (ii) at least one element of the group consisting of nickel, molybdenum, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron or at least one compound comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron, such alloy layer may be present alone or in combination with one or more other layers.

In other embodiments, the moveable components described herein may be configured as or may include a piston having a coated surface on at least one surface. The coated surface may be present on the surface contacting the functional fluid or on the outer surface of the piston. Referring to fig. 14, a piston 1400 is shown that includes a body or piston member 1410 and a surface coating 1420 on an outer surface of the piston member 1410. For example, the coating 1420 on the piston member 1410 may be any one or more of these coatings or layers described and illustrated in connection with fig. 1-12, e.g., the surface coating on the piston member 1410 may comprise an alloy layer comprising molybdenum or tungsten and at least one element selected from the group consisting of nickel, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron, or at least one compound comprising one or more of nickel, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron.

In some examples, a housing of a device comprising a movable component may include one or more coatings on a surface. For example and referring to fig. 15, a housing 1500 is shown that includes a coating 1510 on an inner surface of the housing 1500. For example, the coating 1510 on the housing 1500 may be any one or more of those coatings or layers described and illustrated in connection with fig. 1-12. The coating 1510 may be present on substantially all of the interior surface of the housing 1500, or may be present only on selected interior surfaces of the housing 1500. Furthermore, if desired, different coatings may be present on different interior surface areas of the housing 1500. Or the coatings on different interior surfaces of the housing 1500 may be the same, e.g., have the same composition, but may be present at different thicknesses at different interior surface areas. In some examples, the coating 1510 may also be present on the outer surface of the housing 1500 or on both the inner and outer surfaces of the housing.

In certain configurations, the movable components and housing of the movable devices described herein may include coatings, which may be the same or may be different. Referring to fig. 16, a movable apparatus 1600 is shown that includes a piston member 1610 and a housing 1605. Piston member 1610 includes a coating 1611 and housing 1605 includes a coating 1606. The coatings 1606, 1611 may be the same or may be different. For example, the coatings 1606, 1611 can independently be any one or more of those coatings or layers described and illustrated in connection with fig. 1-12. Or the coatings 1606, 1611 may be the same, e.g., have the same composition, but may be present at different thicknesses or have different amounts of material in each coating.

In certain embodiments, the movable components described herein may be designed to rotate. Referring to fig. 17A and 17B, during use of the rotation device, the substrate may rotate about an axis. The axis may be a longitudinal axis LA or a transverse axis TA. Referring to fig. 17A, a cylindrical base 1710 is shown having a longitudinal axis LA and a transverse axis TA. The substrate need not be cylindrical, but may take other forms, including planar, curved, and other shapes. The cylindrical shape is shown in fig. 17A and 17B for illustration. As shown in fig. 17B, the base 1710 may be rotated circumferentially about the longitudinal axis LA. For example, the base 1710 may rotate clockwise as indicated by arrow 1712 about the longitudinal axis LA or may rotate counterclockwise as indicated by arrow 1714. As the substrate rotates about the transverse axis TA, it may end rotate or rotate in some way other than circumferential rotation.

In certain embodiments, a base 1810 of a rotating device is shown in fig. 18. Substrate 1810 includes a coated surface having a surface coating 1820 as described herein. The surface coating 1820 may include any of those layers described with reference to fig. 1-12. For example, the surface coating 1820 may comprise an alloy layer comprising (i) molybdenum and (ii) at least one element selected from the group consisting of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron or at least one compound comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In other cases, the surface coating 1420 may comprise an alloy layer comprising (i) tungsten and (ii) at least one element selected from the group consisting of nickel, molybdenum, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron, or at least one compound comprising one or more of nickel, molybdenum, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron.

In some embodiments, the substrate may be configured as a rotor as shown in fig. 19 A5. The rotor 1900 generally includes a shaft 1910 and one or more gears or couplings 1922, 1524 that may be coupled to other components. For example, the coupler 1924 may be coupled to a motor, engine, or other component to cause rotation of the shaft 1910. The coupler 1922 may be coupled to another component to rotate the component. One or more surfaces of the rotor 1900 may include any of those layers described with reference to fig. 1-12. For example, the surface coating on the rotor may comprise an alloy layer comprising (i) molybdenum and (ii) at least one element selected from the group consisting of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron or at least one compound comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In other cases, the surface coating on the rotor may comprise an alloy layer comprising (i) tungsten and (ii) at least one element selected from the group consisting of nickel, molybdenum, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron or at least one compound comprising one or more of nickel, molybdenum, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron.

In another configuration, the base may be configured as one or more rotatable blades. An illustration of a blade 1950 is shown in fig. 19B. One or more surfaces of blade 1950 may include any of those layers described with reference to fig. 1-12. For example, the surface coating on the blade may comprise an alloy layer comprising (i) molybdenum and (ii) at least one element selected from the group consisting of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron or at least one compound comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In other cases, the surface coating on the blade may comprise an alloy layer comprising (i) tungsten and (ii) at least one element selected from the group consisting of nickel, molybdenum, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron or at least one compound comprising one or more of nickel, molybdenum, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron.

In some examples, the substrate may be configured as a metal work roll or rolls. For example, work rolls are often used to process steel sheets. Referring to fig. 19C, metal work rolls 1970, 1980 are shown. The two work rolls 1970, 1980 may be arranged with a specific gap between them. The surface coatings 1975, 1985 on each of the work rolls 1970, 1980, respectively, may be the same or may be different. In addition, each surface coating on the work rolls 1970, 1980 may be a single layer or multiple layers. For example, the coating on each of the work rolls 1970, 1980 may be independently any of those materials, layers, coatings, etc. shown and described in connection with fig. 1-12. For example, each of the work rolls 1970, 1980 may comprise a metal alloy layer that may have the same or different composition. As shown in fig. 19C, as a piece of metal (e.g., steel) passes between the rollers 1970, 1980, the thickness of the metal decreases. For example, the thickness of the steel at point 1972 is greater than the thickness of the steel at point 1974. The exact rolling process that the work rolls 1970, 1980 exist may vary, and exemplary rolling processes include, but are not limited to roll bending, roll forming, flat rolling, ring rolling, forming rolling, controlled rolling, forging rolling, or other rolling processes. Although not shown in fig. 19C, the rollers 1970, 1980 may rotate in the same rotational direction or opposite rotational directions depending on the particular rolling process used. In typical use, one of the rolls 1970, 1980 rotates clockwise and the other of the rolls 1970, 1980 rotates counterclockwise to pull the steel between the two rolls 1970, 1980 during the metal forming operation. The specific metal plates that can be machined can vary, and exemplary metal plates include, but are not limited to, steel plates, copper plates, and plates comprising metals and metal alloys.

In other embodiments, the movable component may be present in a hydraulic device or a pneumatic device. A generalized diagram of a hydraulic device configured as a hydraulic cylinder is shown in fig. 21. The hydraulic cylinder 2100 includes a piston member or rod 2110 that moves into and out of a housing 2105. Seals 2115 are present on the ends of the housing 2105 and serve to retain the hydraulic fluid 2102 within the housing 2105. A seal is present at the end 2111 of the piston rod 2110. The housing 2105 includes a retract port 2106 and an extend port 2107. By introducing hydraulic fluid to the extension port 2107, fluid pressure may be applied to the surface 2113 at the end 2111 of the piston rod 2110. This serves to extend the piston rod 2110 and move it out of the housing 2105. To retract the piston rod 2105, fluid pressure may be applied to the surface 2113 to move the rod 2110 inwardly. Depending on the particular pressure used, the piston rod 2110 may move in and out of the housing 2105 as needed to provide force on the components connected to the cylinder 1300 or to cushion the force received by the piston 2110. In some constructions, the ports 2106, 2107 are typically coupled to a hydraulic pump (not shown) and a hydraulic fluid reservoir to pump hydraulic fluid into and/or out of the housing 2105 of the cylinder 2100. In some cases, the exposed surface of the rod 2110 may include a surface coating as described with reference to fig. 1-12. In other examples, the surface of the piston rod 2110 that contacts the hydraulic fluid may include a surface coating as described with reference to fig. 1-12. The inner and/or outer surfaces of the housing 2105 may also include a surface coating as described with reference to fig. 1-12. The pneumatic device may have a similar arrangement as the cylinder of fig. 21, but the ports 2106, 2017 are often omitted and the hydraulic fluid is replaced with a gas or a combination of gas and hydraulic fluid. In some embodiments, the outer surface of the rod 2110 may include a surface coating as described herein. For example, the surface coating comprises an alloy layer comprising (i) molybdenum and (ii) at least one element selected from the group consisting of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron or at least one compound comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. Or the surface coating of the rod 2110 may comprise an alloy layer comprising (i) tungsten and (ii) at least one element selected from the group consisting of nickel, molybdenum, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron or at least one compound comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron.

Similarly, in a hydraulic device configured as a shock absorber, ports 2106, 2107 are often omitted and the system sealed. A diagram of the shock absorber is shown in fig. 20. The shock absorber of fig. 20 is a dual tube shock absorber, but a single tube shock absorber may also include a coated surface as described herein. Referring to fig. 20, shock absorber 2000 is shown to include various components. Shock absorber 2000 includes a tube or cylinder 2002, a first end 2006, and a second end 2008 that together define a housing 2004. A working piston 2010 is movably mounted within the housing 2004 for movement between a first end 2006 and a second end 2008, for example, between a first position and a second position of the cylinder 2002. The working piston 2010 divides the housing 2004 into a first chamber 2012 and a second chamber 2014. The working piston 2010 is connected to a working rod 2016 that extends outside of the cylinder 2002. The end 2018 of the working rod 2016 generally includes a fastener 2020 that is adapted to be coupled to a moving part (not shown). In this configuration, the working piston 2010 includes a plurality of passages 2021A through which fluid passes to connect the chambers 2012 and 2014. One or more compression discs 2022 are positioned on one side of the working piston 2010 in alignment with the compression passages 2021A and restrict the flow of hydraulic fluid as the working piston 2010 moves inwardly toward the first end 2006. One or more rebound discs 2024 are positioned on the other side of the working piston 2010 in alignment with rebound passages (not shown) restricting hydraulic fluid flow as the working piston 2010 moves outwardly toward the second end 2008. Compression and rebound discs 2022, 2024 are placed on each side of the piston to provide the necessary resistance to the hydraulic fluid as the working piston 2010 moves to achieve a damping effect on the motion. These discs consist of one or more discs that cover the inlets of the rebound and compression channels to limit and/or prevent hydraulic fluid flow through the channels in one direction (compression) or the other (rebound). In a preferred configuration, the compression passages are located along the outer circumference of the working piston 2010, while the rebound passages are located near the central axis 2099 of the working piston 2010 and around its central axis 2099.

The floating piston 2030 separates and seals hydraulic fluid from the air chamber 2001. The gas within the gas chamber 2001 is compressible and provides a buffer to compensate for the movement of the lever 2016 into and out of the chamber 2014 by increasing or decreasing the volume of the chambers 2012, 2014. When the working rod 2016 enters the cylinder 2002, the volume of the working rod 2016 must be compensated because the cylinder 2002 does not expand and the volume of fluid does not decrease or can not be compressed. As the workstring 2016 enters the cavity 2014, the floating piston 2030 is pushed toward the end 2006 to increase the volume of the cavities 2012 and 2014, compressing the gas within the gas cavity 2001 and decreasing the volume of the gas cavity 2001. Similarly, as the working rod 2016 exits the lumen 2014, the volume of the lumen 2001 increases to compensate for the volume of the retracted working rod 2016. A blocking member 2032 (e.g., a PSD feature) is mounted to the floating piston 2030 by a spring 2034, holding the blocking member 2032 at a particular point X along the stroke of the working piston 2010. This position may be any percentage of the stroke of the working piston 2010, depending on the length of the spring 2034. The blocking member 2032 is an annular member that moves within the housing 2004. A large passage 2036 in the middle of the blocking member 2032 allows a nut and washer to hold the working piston 2010 to the rod 2016 therethrough without blocking hydraulic fluid flowing through the passage 2036. Rebound disc 2024 is centrally located leaving the inlet to compression passage 2021A open for hydraulic fluid to flow into passage 2021A during the first portion of the working compression stroke of piston 2010. Any one or more of the surfaces of the component shown in fig. 20 may include a surface coating as described with reference to fig. 1-12. In some embodiments, the outer surface of the stem 2016 may include a surface coating as described herein. For example, the surface coating comprises an alloy layer comprising (i) molybdenum and (ii) at least one element selected from the group consisting of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron or at least one compound comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. Or the surface coating layer comprises an alloy layer comprising (i) tungsten and (ii) at least one element selected from the group consisting of nickel, molybdenum, cobalt, chromium, tin, phosphorus, iron, magnesium and boron or at least one compound comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium or boron.

The particular movable components illustrated in fig. 13-21 are not intended to limit the types of movable components that may include the surface coatings described herein. Instead, any device having a movable part may comprise a surface coating as described in connection with fig. 1 to 12.

Certain specific examples are described to facilitate a better understanding of the techniques described herein.

Example 1

Several tests were performed on a coating layer comprising a molybdenum-nickel alloy (hereinafter referred to as MaxShield) on the surface of a test substrate (steel substrate). To better understand the effect of thickness and heat on MaxShield properties, three different versions of MaxShield coatings were tested. MaxShield-V1 has a thickness of between 20 and 30. Mu.m. In addition, maxShield-V1 was baked at 190℃for 23 hours (V1-BR) and heat-treated at 400℃for 2 hours (V1-HT) for plating tests. MaxShield-V2 has a thickness of between 70 and 90. Mu.m. MaxShield-V2 is manufactured by adopting a heat treatment process to improve the hardness and the wear resistance. MaxShield-V3 is similar to MaxShield-V2 but has not been heat treated.

MaxShield key process factors were also compared with EHCs (hard chrome plating). The EHC process is not efficient because the current density is 500ASF and the deposition rate is approximately 0.7mil/hr. While the deposition rate is doubled for MaxShield and the current is reduced by a factor of about 14, the higher deposition rate makes the MaxShield process more efficient than the EHC process.

Example 2

The original appearance of the coating is close to that of a typical nickel coating. Fig. 22 shows a hydraulic lever coated with MaxShield and compares it with a hydraulic lever coated with an EHC. MaxShield and the EHC are both ground and polished after plating. By some preliminary detection we can activate the black version of the coating. The coating may be further polished and machined to change appearance. It has conformality and can be applied to rough surfaces.

Example 3

MaxShield the most common thickness range is 1 micron to 75 microns. Coatings with a thickness exceeding 0.5mm can also be created. The coating thickness may be less than one micron and may be greater than 1.5mm if desired. The coating thickness is mainly controlled by the deposition time.

Example 4

Corrosion was detected using a detection laboratory (NADCAP certified detection facility, warranting detection service). The test is a standard corrosion test, also known as a salt spray test. In this test, the coated samples were exposed to a 5% sodium chloride mist simulating marine corrosion. The test was performed by the test laboratory according to ASTM B117-19. In this test, the corrosion performance of EHC coatings and electroless nickel coatings was compared to that of our coatings by exposure to salt fog for 5000 hours. The warranty detection service determines the corrosion rating of the different samples according to ASTM D610 corrosion rating. The standard implies a scale range between 0 and 10, where 10 corresponds to the best corrosion resistance and 0 corresponds to the worst corrosion resistance. The detection laboratory also performed salt spray tests on three MaxShield-V1 coating samples. The test was also performed on two samples of MaxShield-V2 and MaxShield-V3 coatings. We also provided EHC and electroless nickel coatings as controls to the laboratory. The warranty inspection service scored a MaxShield-V1 coating and was inspected in a salt spray chamber.

Results for the first 1000 hours. Fig. 23A and 23B show carbon steel samples coated with EHC and electroless nickel coatings having corrosion ratings of 4 and 0, respectively, after 1000 hours of exposure to salt spray. Both samples were produced by separate electroplating plants. According to ASTM D610, the corrosion rate of electroless nickel after 1000 hours is 0, indicating that more than 50% of the surface area forms rust. In addition, the corrosion rate of the EHC coating was 4, indicating that 3% to 10% of the surface area was corroded after 1000 hours. Images of all five MaxShield coatings after 1000 hours of exposure to salt spray are shown in fig. 24A-24E. Of which four samples had a corrosion rating of 9, while one of Maxshield-V1 samples had a corrosion rating of 10 after 1000 hours. A corrosion rate of 9 indicates less than 0.03% surface area formation of rust according to ASTM D610 standard. The Maxshield-V1 sample, grade 10, was completely rust free for the first 1000 hours.

Fig. 25 compares the salt spray test results of our coating with EHC coating. As shown, the corrosion level of EHC coatings suddenly drops to 4 after 400 hours of exposure to salt spray, while our coatings remain above 9 after 1000 hours of exposure.

For the scored MaxShield-V1 coating, a corrosion rating of 9 was obtained in the region remote from the scored area. The creep test rating of the scored area of this sample was 8 according to ASTM D1654. Preliminary testing of scored surfaces showed that if MaxShield were scratched and the underlying steel surface exposed at the scratched location, no significant risk of accelerated corrosion would be expected.

Corrosion test results after 1000 hours: salt spray corrosion tests were continued on MaxShield samples after 1000 hours. The grades of the samples at different times of the salt spray test and their appearance after 5000 hours are shown in fig. 26A-26E. As shown in Table 1, the grade of Maxshield-V2 and MaxShield-V3 was maintained at 9 until 4000 hours of the salt spray test.

TABLE 1-photographs of samples after 4000 hours of salt spray test of different MaxShield coatings up to a rating of 4000 hours

The corrosion ratings of the three samples MaxShield-V1 were 7, 9 and 8, respectively. The thickness of MaxShield-V1 is thinner than Maxshield-V2 and MaxShield-V3. For thinner coatings, corrosive media are more likely to reach the steel substrate from pinholes and defects in the coating and cause corrosion. This may be why Maxshield-V2 and MaxShield-V3 perform better than MaxShield-V1 when exposed to corrosive media for prolonged periods of time. As shown in the images in fig. 26A-26E, maxShield produced green rust, which can be easily distinguished from rust.

Example 5

Detection laboratory: NADCAP certification of test facilities, and ensuring detection service. The process comprises the following steps: three sets of samples were subjected to this test. Each set includes four grooved bars with MaxShield coating. The image of one of these groove strips before and after the coating is applied is shown in fig. 27. The test laboratory carried out a 200 hour continuous load test on the bars according to ASTM F519-18, with a load of 75% of the breaking strength. Results: all four groove bars MaxShield-V1 and MaxShield-V2 passed the test without any breakage. These results indicate that MaxShield-V1 and MaxShield-V2 coatings do not cause hydrogen induced cracking and are resistant to hydrogen embrittlement. It is worth mentioning that MaxShield-V3 is a thickened version of MaxShield-V1, providing more hydrogen embrittlement protection. Thus, since MaxShield-V1 has passed the test, maxShield-V3 is also expected to pass the test.

Example 6

Detection laboratory: a2LA certification and detection laboratory, anamet, inc. Procedure: ductility of MaxShield-V1 and MaxShield-V2 coatings was determined by the test laboratory according to ASTM E8-21 (metallic materials tensile test). In this test, a uniaxial tensile test was performed on the coated T bone sample until the coating flaked off and the lower surface could be seen in a 50-fold microimage.

Results: tests have shown that MaxShield-V1 and MaxShield-V2 coatings can extend to over 6% without flaking or cracking. Ductility values greater than 6% are significantly higher than those of the EHC coating (less than 0.1%) (1). The ductility is also higher than that of electroless nickel (between 1% and 1.5%) (2). Based on these results, it can be concluded that MaxShield coatings are much better shaped than EHC and electroless nickel coatings. Fig. 28A and 28B show images of MaxShield-V1 (fig. 16B) and MaxShield-V2 (fig. 28A) coatings after 6% elongation. A microscopic image of MaxShield-V1 coating is shown in FIG. 29. As shown in fig. 28A-29, the coating exhibited a ductility of at least 6% without any cracking or blistering.

Example 7

Detection laboratory: EP laboratories are listed Qmed as independent detection laboratories dedicated to nano-and micro-scale mechanical detection. The process comprises the following steps: the coefficients of friction of MaxShield-V2 and MaxShield-V3 coatings were measured by the EP laboratory according to ASTM G99-17. As shown in fig. 30, the test involved applying a force of 20N to the surface of the lubricant coating rotated 200 revolutions per minute by a hard ball made of 440C stainless steel. One of the main characteristics of an EHC is its low coefficient of friction or its slippery characteristics in a lubricated environment. In this test, the coefficient of friction of the EHC was also measured and compared to MaxShield coatings.

Results: the results of the coefficient of friction measurements for the EHC, maxshield-V2, and MaxShield-V3 coatings are shown in Table 2. As shown in this table, both versions MaxShield have a slightly lower coefficient of friction than the EHC coating. From these results, we expect MaxShield coatings to have nearly similar properties under lubricating wear conditions. It is worth mentioning that MaxShield-V1 may have a low performance in severe wear environments, which is why it is not detected here.

TABLE 2 Pin-on-disk detection results

Coating surface	Coefficient of friction
		EHC	0.106±0.003
MaxShield-V2	0.103±0.001
		MaxShield-V3	0.091±0.002

Example 8

Detection laboratory: iso certified independent laboratory, EPI materials detection group. The process comprises the following steps: the surface of the coating was subjected to a hydrogen sulfide cracking test according to NACE TM-0284. The coated surface of carbon steel was introduced into an acidic environment for 96 hours during which time H ₂ S gas and nitrogen purge gas were introduced. The surface of the coating was metallurgically polished to highlight cracks caused by H ₂ S gas. As shown in fig. 31, cracks were detected and reported as specified by the standard. Two samples of MaxShield-V1 were tested.

Results: visual and stereoscopic inspection and subsequent inverted microscopy showed our coating to be free of cracking, as reported by the third party inspection center. FIGS. 32A and 32B show images of two carbon steel bars coated with MaxShield-V1 after testing (FIG. 32B) and before testing (FIG. 32A). As shown in the microscopic image of FIG. 33, the surface covered with MaxShield-V1 coating was free of hydrogen-induced bubbles or cracks. It is worth mentioning that MaxShield-V2 and MaxShield-V3 are less susceptible to hydrogen sulfide cracking due to their greater thickness than MaxShield-V1. This is why the present test is performed only on MaxShield-V1.

Microhardness test

Detection laboratory: previous microhardness tests were performed by A2LA certified test laboratory Anamet inc, maxterial inc. The process comprises the following steps: the test was performed according to ASTM E384-17. Anamet results previously obtained: the test was performed on four coated carbon steel samples. The samples and their detection results are described below: sample 1 was coated with MaxShield-V3. The vickers hardness of this sample was 660. Sample 2 was coated with MaxShield-V3. The vickers hardness of this sample was 605. Sample 3 was coated with MaxShield-V2. The average vickers hardness of this sample was 750. Sample 4 was also coated with MaxShield-V2. The average vickers hardness of this sample was 822.

These results show the effect of heat treatment on increasing the hardness of MaxShield-V2 coatings. A number of internal hardness tests have been performed on 50 mu mMaxShield coatings. These results confirm that the vickers hardness of the plating MaxShield is in the range of 630 to 670. The microhardness values obtained in this test are compared with those of several other hard coatings obtained from the literature in table 3. As shown in Table 3, all of our coatings had a higher microhardness than electroless nickel coatings. In addition, the MaxShield-V2 coating has a slightly better Vickers hardness than the heat treated electroless nickel coating. It is worth mentioning that electroless nickel is a wear resistant coating, which is known as one of the alternatives for EHC coatings. The hardness of MaxShield-V2 coatings is also comparable to EHC coatings. Furthermore, maxShield has a hardness much higher than the 241 hardness (3) of Hastelloy-B2.

High temperature performance and comparison with EHC: a point is also emphasized in table 3, namely that the hardness of the EHC coating decreases at high temperatures (4). The normal bake-release process (190 c) lasts 23 hours and the EHC hardness decreases from 800-1000 to a value between 700-750. Furthermore, as demonstrated by the cross-sectional images discussed in example 11, heat disrupts the integrity of the EHC coating by creating large macrocracks in its structure. Thus, the coating is expected to lose its corrosion protection at higher temperatures. Thus, regardless of environmental regulations and the need to eliminate EHC coatings, the coatings are not capable of functioning at high operating temperatures.

In contrast, the hardness of MaxShield-V2 coatings is expected to increase at high temperatures. In practical applications and in many cases, the coating may be exposed to high temperatures. For example, if the sample is ground or used in a high friction or high temperature environment, the hardness of MaxShield in these environments is expected to increase, unlike chromium.

TABLE 3 calculated Vickers hardness for different wear resistant coatings

Material	Microhardness (Vickers hardness)
		MaxShield-V3 (electroplating MaxShield)	630-670
MaxShield-V2 (Heat treatment MaxShield)	750–822
		Electroless Ni plating (2)	480-500
Electroless Ni-plating heat treatment (400-1 hr) (2)	700-800
		EHC-electroplating (2)	800–1000
EHC-baking-eliminating (190-23 hr) (4)	700–750
		EHC-heat treatment (400-2 hr), our internal results	700–775

Example 9 Taber abrasion test

Detection place: maxterial Inc. the procedure: the standard Taber abrasion test was performed by I company according to ASTM D4060-19. In this test, the surface of the coating was abraded using an abrasion machine shown in fig. 34 by applying a load of 1kg on each abrasion wheel.

Results: the Taber abrasion index is the milligrams weight loss per 1000 cycles. We have recently examined a modified version of MaxShield. A plating sample (MaxShield-V1) and a sample (MaxShield-V2) after heat treatment at 400℃for 2 hours were prepared and examined. The TWI results of MaxShield samples are shown in FIG. 35. The figure also shows the TWI values for the as-plated, heat treated EHC and electroless nickel coatings. At least three different samples were tested for each coating, and the results for electroless nickel and EHC coatings were consistent with those in the literature (2). These results show that the average TWI of the coating and heat treatment MaxShield are 6 and 5, respectively, very close to the results obtained for the EHC. The TWI of heat treated MaxShield is even better than the 6TWI of heat treated EHCs.

It is worth mentioning that, given the great challenges facing EHC coatings in terms of environmental regulations, electroless nickel coatings are considered by the industry as one of their viable alternatives. As shown, a plated version of our coating (MaxShield-V3) with an average TWI of 6 would be expected to exhibit better wear performance than a plated electroless nickel with an average TWI of 15. Our heat treated version of coating (MaxShield-V2) also exhibited better wear performance than heat treated electroless nickel with an average TWI of 7. As previously mentioned, the wear properties of EHC coatings may decrease after being heated. The average TWI of the heat treated EHC was 6, which is higher than the average TWI5 of the MaxShield-V2 coating.

Example 10 on-ring Block detection

Detection place: falex company process: the test was performed by Falex corporation, which is one of the industry precursors to performing the test, according to ASTMG-77-17. In this test, the test block was loaded with 30 pounds on a test ring, which was rotated 500,000 revolutions at 197 rpm. The mass scar volume is calculated from the mass scar width and the ring scar volume is calculated from the ring weight loss. Further, the coefficient of friction (CoF) value is continuously measured during the detection. The test was performed on a ring sample coated with MaxShield a minimum thickness of 0.006 inches. The ring is made of 4620 steel. The coating thickness was 0.003 "to 0.005" with a surface finish of 4 to 8 microinches by grinding and polishing. In this test, the block was uncoated PH13-8Mo steel. The detection of chrome plated rings is in progress and the results will be provided very quickly.

Results: the results of the detection are summarized in table 4. As shown in the table, the CoF of MaxShield in this test was 0.045. The MaxShield CoF was more than three times lower than the 0.146CoF reported in the chromium literature in this test (5). Fig. 36 shows the CoF versus cycle number. As shown, coF remains nearly constant during the detection process. This result means that MaxShield coatings do not create any gouging (gouging) problems.

TABLE 4 detection results of the block on ring

Block material	PH13-8 molybdenum steel	PH13-8 molybdenum steel
			Ring material	Chromium coated 4620 steel	4635 Steel coated MaxShield
Average CoF	0.146(5)	0.045
			Wear rate of average block (μg/1000 cycles)	Will be provided after the detection is completed	1.4
Wear rate of average ring (μg/1000 cycles)	Will be provided after the detection is completed	44

Example 11. Corrosion detection in corrosive acidic environments.

Detection place: maxterial Inc. the procedure: this is an internal test by our company. In this test, a coated carbon steel sample was immersed in concentrated aqueous hydrochloric acid (32% hcl) for 24 hours. The weight loss of the coating after 24 hours exposure to concentrated HCl solution was used to calculate the corrosion rate. It is worth mentioning that 32% HCl is a very strong acid and the pH is negative.

Results: FIG. 37 compares the corrosion rates of the modified MaxShield-V1 coating with existing nickel coatings, monel, inconel, and hastelloy. The rates of these coatings reported in fig. 37 are the average of corrosion tests obtained for at least three different samples. As shown, maxShield-V1 coatings have much lower corrosion rates (less than 13 mils per year, sometimes as low as 1.5 mils per year) than existing nickel coatings (80 mils per year) (6). FIG. 37 also shows a corrosion resistant bulk material,B2 and/>The corrosion rate for concentrated HCl solution was based on the values (7) (8) published in the literature. Interestingly, with/>(15 Milli-inches per year) and/>(39 Mils per year) our coatings showed lower corrosion rates. /(I)And/>Is a superalloy, which is known for its extremely strong corrosion resistance in the HCl environment. The EHC coating dissolves in concentrated HCl for less than 10 minutes and its corrosion rate is outside this number range.

EXAMPLE 12 morphology

Detection place: maxterial Inc. the procedure: the test was performed in Maxterial with the aim of studying the cross section of MaxShield, testing the thickness and assessing the effect of heat treatment on the coating structure. All metallographic work was done by Maxterial using our internal facilities. The chrome plating plant provided us with EHC samples having a thickness of about 100 μm. The cross-sections of the coated and heat treated EHC and MaxShield-V1 samples are shown in FIGS. 38A and 38B, respectively. The heat treatment has been carried out at 400℃for 2 hours. The cross-sectional analysis was performed on MaxShield-V1, a modification of 2021. As shown, the as-plated EHC has microcracks throughout the cross-section, while the as-plated MaxShield has fewer and fewer cracks. EHC cracks appear after heat treatment. As shown in fig. 38A, some cracks grow from the substrate all the way to the surface. The presence of such macrocracks in the coating structure can significantly reduce the corrosion resistance of the coating. On the other side, the cross section of MaxShield remained unchanged after heating, and no signs of crack development were observed in MaxShield. The decrease in mechanical properties of an EHC at high temperatures may be related to such crack growth and growth mechanisms that occur in EHCs upon thermal exposure. The results of the Tabor abrasion and Vickers hardness tests that have been previously reported in this report show this reduction.

Example 13 thermal Effect and adhesion bending detection

Detection place: maxterial Inc. the procedure: we performed an adhesion bend test on heat treated MaxShield samples. It is worth mentioning that the adhesion bending test according to ASTM B571-18 is always an important component of our evaluation. The reason is that if the coating does not provide strong adhesion, it does not provide wear and corrosion protection.

In this test, one side of a 1008 Carbon Steel (CS) strip with an exposed area of 3cm by 5cm was coated with MaxShield. The coated sample was then placed in an oven and heated in air at 700 c for 1 hour. The samples were tested for adhesion bending according to ASTM B571-18. The steps and results of the detection are shown in fig. 39A-39D. In this test, a piece of tape was applied to the coated surface. The air bubbles in the area under the tape have been removed, thus we ensure a firm adhesion between the coating and the tape. The taped sample is then bent to 180 degrees and the tape is removed from the coated surface. If the coating delaminates from the surface and transfers to the tape, the test fails.

Results: the tape was clean. No delamination of the coating was observed. The coating passed the adhesion bend test. After heating, the uncoated areas of the CS were covered with rust. Prior to the bend test, we covered these uncoated areas with tape to avoid loose rust particles from transferring to the coated surface.

EXAMPLE 14 formability

The process comprises the following steps: we performed a number of 180 degree bend tests on MaxShield V a 1 and always received favorable results. Carbon steel plates were coated with MaxShield a thick. The coated sheet is subjected to a forming process to manufacture a part. In these processes, the coating must be bent and shaped.

Results: after molding the coating remained intact and no flaking or defects were observed. It is worth mentioning that EHCs and thermal spray coatings are highly likely to flake off in these situations.

EXAMPLE 15 processing

We performed various processing operations on our samples. For example, we sometimes drill holes into the coated parts to prepare test samples, sometimes we polish the coating to make it shiny, or we grind them to adjust the thickness. We have never encountered any problem during these processes. Our data indicate MaxShield that processing can be performed without any adhesion failure. On the other hand, it is well known that chromium processing presents problems due to chipping and flaking problems. The reason for this is believed to be that Maxshield is more ductile than the EHC. Furthermore MaxShield adheres well to most substrates.

Example 16 overview of Process factors

MaxShield are typically produced by typical electroplating processes. The process includes appropriate cleaning and activation of the substrate after electrodeposition. Some process factors of MaxShield include: energy source: maxShield uses a direct current power supply; deposition rate: maxShield (1.5 mil/hr) is twice as fast as the deposition rate of the EHC (0.7 mil/hr). The deposition rate MaxShield will vary depending on a number of factors such as current density; electroplating efficiency: maxShield has a plating efficiency (80-90%) much higher than that of the EHC (10-35%). It should be noted that in most cases, the plating efficiency of the EHC is lower than 20%; electroplating process temperature: maxShield electroplating temperatures are within industry normal ranges (140-170F)

Example 17 safety and environmental compliance

Detection place: 2021 detection according to REACH and RoHS

Results: maxShield successfully passed both tests. MaxShield the chemicals used to coat and make MaxShield (called LeanX) do not contain high-value substances of interest (SVHC). In particular, maxShield and LeanX are free of chromium, cadmium, cyanide, lead and fluorine compounds, such as PFOS and PFAS.

Reference to the literature

1.Physical Properties of Electrodeposited Chromium.U.S.Department of Commerce,National Bureau of Standards.s.l.:Journal of Research of the National Bureau of Standards,1948.

2.Tech Metals.THE ENGINEERING PROPERTIES OF ELECTROLESS NICKEL COATINGS.Dayton:Tech Metals,1983.

3.AZO Materials.Super Alloy HASTELLOY(r)B-2Alloy(UNS N10665).[Online]https://www.azom.com/article.aspxArticleID＝7680.

4.Prado,R.Electrodeposition of Nanocrystalline Cobalt Phosphorous Coatings as aHard Chrome Alternative.Jacksonville.s.l.:NavAir,2014.

5.Prado,R.A.,et al.Electrodeposited Nanocrystalline Co-P Alloy Coatings as a Hard Chrome Alternative.s.l.:ESTCP Project WP-200936,2015.

6.Nickel Development Institute.Resistance of Nickel and High Nickel Alloys to Corrosion by Hydrochloric Acid,Hydrogen Chloride,and Chlorine.

7.Osborne,P.E.,Icenhour,A.S.and Cul,G.D.Del.Corrosion Test Results for Inconel 600vs Inconel－Stainless UG Bellows.Oak Ridge,Tennessee:OAK RIDGE NATIONAL LABORATORY,2002.

8.Corrosion Materials.Hastelloy B2 Datasheet.[Online]https://www.corrosionmaterials.com/documents/dataSheet/alloyB2DataSheet.pdf.

9.Residual Stresses and Strength of Hard Chromium Coatings.Pfeiffer,W.,et al.s.l.:Materials Science Forum,2011,Vol.681.

10.Toll Bridge Program Oversight Committee,California Transportation Commision.Report on the A354 Grade BD High-Strength Steel Rods on the New East Span of the SanFrancisco-Oakland Bay Bridge With Findings and Decisions.2013.

11.Nickel Development Institute.Resistance of Nickel and High Nickel Alloys to Corrosion by Hydrochloric Acid,Hydrogen Chloride and Chlorine.[Online]https://www.nickelinstitute.org/～/media/Files/TechnicalLiterature/ResistanceofNickelandHigh_NickelAlloystoCorrosionbyHydrochloricAcid_HydrogenChlorideandChlorine_279_.ashx.

12.Corrosion Materials.Alloy B2 Data Sheet.[Online]http://www.corrosionmaterials.com/documents/dataSheet/alloyB2DataSheet.pdf.

Claims

1. An apparatus comprising a movable member configured to contact a functional fluid during movement of the movable member, the movable member further comprising a coated surface, wherein the coated surface comprises a surface coating comprising an alloy layer, and wherein the alloy layer comprises molybdenum or tungsten.

2. The device of claim 1, wherein the alloy layer comprises molybdenum or tungsten and one or more elements selected from the group consisting of nickel, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron or one or more compounds comprising nickel, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron.

3. The device of claim 1, wherein molybdenum or tungsten is present in the surface coating at 35% by weight or less based on the weight of the surface coating, or at 25% by weight or less based on the weight of the surface coating, or at 15% by weight or less based on the weight of the surface coating.

4. The device of claim 1, wherein molybdenum or tungsten is present in the alloy layer at 35% by weight or less based on the weight of the alloy layer, or at 25% by weight or less based on the weight of the alloy layer, or at 15% by weight or less based on the weight of the alloy layer.

5. The device of claim 1, wherein molybdenum or tungsten is present in the surface coating at 65% by weight or more based on the weight of the surface coating, or at 75% by weight or more based on the weight of the surface coating, or at 85% by weight or more based on the weight of the surface coating.

6. The device of claim 1, wherein molybdenum or tungsten is present in the alloy layer at 65% by weight or less based on the weight of the alloy layer, or at 75% by weight or less based on the weight of the alloy layer, or at 85% by weight or less based on the weight of the alloy layer.

7. The device of claim 1, wherein the alloy layer consists essentially of nickel and molybdenum, or consists essentially of nickel, molybdenum, and one of tin, phosphorus, iron, magnesium, boron, or consists essentially of nickel and tungsten, or consists essentially of nickel, tungsten, and one of tin, phosphorus, iron, magnesium, or boron.

8. The apparatus of claim 7, wherein the coated surface has a surface roughness Ra of less than 1 micron and the molybdenum or tungsten is present in the alloy layer at 20% or less by weight based on the surface coating weight and the surface coating is free of precious metals.

9. The device of claim 1, wherein the alloy layer is an electrodeposited alloy layer or an exposed outer layer of the surface coating.

10. The device of claim 1, wherein the exposed outer layer consists essentially of (i) molybdenum or tungsten and only one of nickel, cobalt, tin, phosphorus, iron, chromium, magnesium, or boron, or (ii) molybdenum or tungsten and only two of nickel, cobalt, tin, phosphorus, iron, chromium, magnesium, or boron, or (iii) molybdenum and phosphorus or both tungsten and phosphorus and at least one of nickel, cobalt, tin, chromium, tungsten, iron, magnesium, or boron.

11. The device of claim 1, wherein the alloy layer is an electrodeposited alloy layer and further comprising an intermediate layer between the surface of the substrate and the alloy layer, wherein the intermediate layer comprises one or more of nickel, nickel alloy, copper alloy, nickel tungsten alloy, cobalt alloy, nickel phosphorus alloy, molybdenum or tungsten or both, and an alloy of at least one of nickel, cobalt, chromium, tin, phosphorus, iron or boron.

12. The apparatus of claim 1, wherein the coated surface comprises an additional layer formed on the alloy layer, wherein the additional layer comprises one or more of nickel, nickel alloy, nickel tungsten alloy, cobalt phosphorus alloy, nickel phosphorus alloy, alloys of molybdenum with at least one of nickel, cobalt, chromium, tin, phosphorus, iron, or boron, a ceramic, the ceramic comprises a compound of tungsten, chromium, aluminum, zirconium, titanium, nickel, cobalt, molybdenum, silicon, boron, a metal nitride, metal carbide, boron, tungsten carbide, chromium oxide, aluminum oxide, zirconium oxide, titanium dioxide, nickel carbide, nickel oxide, a nanocomposite, an oxide composite, or a combination thereof.

13. The device of claim 1, wherein the alloy layer further comprises one or more particles selected from the group consisting of: solid nanoparticles, polymer particles, hard particles, silica particles, silicon carbide particles, titanium dioxide particles, polytetrafluoroethylene particles, hydrophobic particles, diamond particles, particles functionalized with hydrophobic groups, solid particles, and combinations thereof.

14. The device of claim 1, wherein the alloy layer is present as an exposed outer layer of the surface coating, wherein the exposed outer layer is an electrodeposited alloy layer, and wherein the electrodeposited alloy layer does not comprise a noble metal.

15. The device of claim 14, wherein the alloy layer further comprises particles.

16. The device of claim 1, wherein the movable member is configured to move in a linear direction.

17. The device of claim 1, wherein the movable member is configured to move in a rotational direction.

18. The device of claim 1, wherein the movable member is configured to move in response to a compressive force provided to the movable member.

19. The apparatus of claim 18, wherein the movable member is configured to move from the second position back to the first position in response to a compressive force provided to the movable member.

20. The apparatus of claim 1, wherein the movable member is configured to move in response to hydraulic pressure provided to the movable member.

21. The apparatus of claim 20, wherein the movable member is configured to move from the second position back to the first position in response to hydraulic pressure provided to the movable member.

22. The device of claim 1, wherein the surface coating of the movable component is located outside of a housing of the device.

23. The device of claim 1, wherein the device is configured as a hydraulic device comprising a piston member, and wherein the piston member comprises a coated surface.

24. The device of claim 1, wherein the device is configured as a pneumatic device comprising a piston member, and wherein the piston member comprises the coated surface.

25. The apparatus of claim 1, wherein the apparatus is configured as a work roll comprising the coated surface.

26. The apparatus of claim 1, wherein the apparatus is configured as a steel work roll comprising the coated surface.

27. The apparatus of claim 1, wherein the apparatus is configured as a roller comprising the coated surface.

28. The device of claim 1, wherein the device is configured as a shock absorber comprising a piston member, and wherein the piston member comprises the coated surface.