WO2014143937A1

WO2014143937A1 - Fiber-containing composites

Info

Publication number: WO2014143937A1
Application number: PCT/US2014/028127
Authority: WO
Inventors: Choongnyun P. Kim; John Kang
Original assignee: Liquidmetal Coatings, Llc
Priority date: 2013-03-15
Filing date: 2014-03-14
Publication date: 2014-09-18
Also published as: CN105531391A; US20160047028A1

Abstract

Provided in one embodiment is a method for producing a composition, the method comprising forming a coating material on a substrate using a first material and a second material; wherein the coating material comprises an amorphous alloy and the second material, the first material is adapted to form the amorphous alloy, the first material is at a first temperature during the forming process, and the first temperature is lower than a melting temperature of the second material.

Description

FIBER-CONTAINING COMPOSITES

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the priority benefits of U.S. provisional patent

61/791,728 filed March 15, 2013, the entire contents of which are incorporated herein by reference.

BACKGROUND

[0002] Wear resistant coatings offer many advantages that have led to widespread use in a variety of applications. Among the advantages wear resistant coatings provided for industrial tool applications were improved service lifetimes and a reduced need for frequent inspections. Despite the many advantages conventional wear resistant coatings provide, these coatings do not offer the hardness and wear resistance desired for many applications.

[0003] Accordingly, there exists a need for coating materials that provide improved properties, such as hardness and wear resistance.

SUMMARY

[0004] Provided in some embodiments is a coating material comprising an amorphous alloy and a second material, a method of making the coating material, and a method of improving the properties of a coating material comprising an amorphous alloy. The coating material provides improved properties in comparison to conventional coating materials.

[0005] One embodiment provides a method comprising forming a coating material on a substrate using a first material and a second material. The coating material may comprise an amorphous alloy and the second material, and the first material may be adapted to form the amorphous alloy. The first material may be processed at a first temperature during the forming process, and the first temperature may be lower than a melting temperature of the second material. [0006] Another embodiment provides a method comprising dispersing particles of a second material in a first coating material to form a second coating material comprising the first coating material and the second material. The second coating material may have at least one improved property compared to the first coating material.

[0007] Another embodiment provides a composition, the composition comprising a coating material, and a substrate. The coating material may be disposed over the substrate, and the coating material may comprise an amorphous alloy and particles of a second material.

[0008] It should be appreciated that all combinations of the foregoing concepts and additional concepts discussed in greater detail below (provided such concepts are not mutually inconsistent) are contemplated as being part of the inventive subject matter disclosed herein. In particular, all combinations of claimed subject matter appearing at the end of this disclosure are contemplated as being part of the inventive subject matter disclosed herein. It should also be appreciated that terminology explicitly employed herein that also may appear in any disclosure incorporated by reference should be accorded a meaning most consistent with the particular concepts disclosed herein.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The skilled artisan will understand that the drawings primarily are for illustrative purposes and are not intended to limit the scope of the inventive subject matter described herein. The drawings are not necessarily to scale; in some instances, various aspects of the inventive subject matter disclosed herein may be shown exaggerated or enlarged in the drawings to facilitate an understanding of different features. In the drawings, like reference characters generally refer to like features (e.g., functionally similar and/or structurally similar elements).

[0010] Figures 1(a)- 1(b) depict, respectively, a coating material comprising an amorphous alloy and a coating material comprising the amorphous alloy and tungsten carbide particles, in one embodiment. [0011] Figures 2(a)-2(b) depict, respectively, a coating material comprising an amorphous alloy and a coating material comprising the amorphous alloy and tungsten carbide particles, in one embodiment.

[0012] Figure 3 depicts a cross-section of a coating material disposed on a substrate according to one embodiment.

[0013] Figure 4 depicts the microstructure of a coating material according to one embodiment.

DETAILED DESCRIPTION

[0014] One embodiment is related to a method for forming a coating material comprising an amorphous alloy and a second material at a first temperature, wherein the first material may be adapted to form the amorphous alloy, and the first temperature may be lower than the melting temperature of the second material. Another embodiment is related to a method of improving a property of a coating material comprising an amorphous alloy, the method comprising dispersing particles of a second material in the coating material. Another embodiment is related to a coating material disposed on a substrate material, wherein the coating material may comprise an amorphous alloy and particles of a second material.

Amorphous Alloys

[0015] An alloy may refer to a mixture, including a solid solution, of two or more metal elements - e.g., at least 2, 3, 4, 5, or more elements. The term "element" herein may refer to an element that may be found in a Periodic Table. A metal may refer to any of alkali metals, alkaline earth metals, transition metals, post-transition metals, lanthanides, and actinides.

[0016] An amorphous alloy may refer to an alloy having an amorphous, non-crystalline atomic structure or microstructure. The amorphous structure may refer to a glassy structure with no observable long range order; in some instances, an amorphous structure may exhibit some short range order. Thus, an amorphous alloy may sometimes be referred to as a "metallic glass." An amorphous alloy may refer to an alloy of which at least about 50% is an amorphous phase - e.g., at least about 60%>, about 70%>, about 80%>, about 90%, about 95%, about 99% or more. The percentage herein may refer to volume percent or weight percent, depending on the context. The term "phase" herein may refer to a physically distinctive form of a substance, such as microstructure. For example, a solid and a liquid are different phases. Similarly, an amorphous phase is different from a crystalline phase.

[0017] Amorphous alloys may contain a variety of metal elements. In some

embodiments, the amorphous alloys may comprise iron, chromium, silicon, boron, manganese, nickel, molybdenum, niobium, copper, cobalt, carbon, zirconium, titanium, beryllium, aluminum, gold, platinum, palladium, phosphorous, or combinations thereof. In some embodiments, the amorphous alloys may be zirconium-based, titanium-based, iron-based, copper-based, nickel-based, gold-based, platinum-based, palladium-based, or aluminum-based. The term "M-based" when referring to an alloy may refer to an alloy comprising at least about 30%> of the "M" element - e.g., about 40%>, about 50%>, about 60%), about 70%), about 80%>, about 90%>, about 95%, or more. The percentage herein may refer to volume percent or weight percent, depending on the context.

[0018] An amorphous alloy may be a bulk solidifying amorphous alloy. A bulk solidifying amorphous alloy, bulk metallic glass ("BMG"), or bulk amorphous alloy may refer to an amorphous alloy that may be adapted to have at least one dimension in the millimeter range. In one embodiment, this dimension may refer to the smallest dimension. Depending on the geometry, the dimension may refer to thickness, height, length, width, radius, and the like. In some embodiments, this smallest dimension may be at least about 0.5 mm - e.g., about 1 mm, about 2 mm, about 3 mm, about 4 mm, about 5 mm, about 6 mm, about 8 mm, about 10 mm, about 12 mm, or more. The magnitude of the largest dimension is not limited and may be in the millimeter range, centimeter range, or even meter range.

[0019] An amorphous alloy, including a bulk amorphous alloy, described herein may have a critical cooling rate of about 500 K/sec or less. The term "critical cooling rate" herein may refer to the cooling rate below which an amorphous structure is not energetically favorable and thus is not likely to form during a fabrication process. In some embodiments, the critical cooling rate of the amorphous alloy may be, for example, about 400 K/sec or less - e.g., about 300 K/sec or less, about 250 K/sec or less, about 200 K/sec or less.

[0020] The amorphous alloy may have a variety of chemical compositions. In one embodiment, the amorphous alloy is a Zr-based alloy, such as a Zr-Ti based alloy, such as (Zr, Ti)_a(Ni, Cu, Fe)_b(Be, Al, Si, B)_c, where each of a, b, and c is independently a number representing atomic % and a is in the range of from 30 to 75, b is in the range of from 5 to 60, and c in the range of from 0 to 50. Other incidental, inevitable minute amounts of impurities may also be present. In some embodiments, these alloys may accommodate substantial amounts of other transition metals, such as Nb, Cr, V, Co. A "substantial amount" in one embodiment may refer to about 5 atm% or more - e.g., 10 atm%, 20 atm%, 30 atm%, or more.

[0021] In one embodiment, an amorphous alloy herein may have the chemical formula (Zr, Ti)_a(Ni, Cu)_b(Be)_c, where each of a, b, and c is independently a number representing atomic % and a is in the range of from 40 to 75, b is in the range of from 5 to 50, and c in the range of from 5 to 50. Other incidental, inevitable minute amounts of impurities may also be present. In another embodiment, the alloy may have a composition (Zr, Ti)_a(Ni, Cu)_b(Be)_c, where each of a, b, and c is independently a number representing atomic % and a is in the range of from 45 to 65, b is in the range of from 7.5 to 35, and c is in the range of from 10 to 37.5 in atomic percentages.

[0022] In another embodiment, the amorphous alloy may have the chemical formula (Zr)_a(Nb, Ti)_b(Ni, Cu)_c(Al)_d, where each of a, b, c, and d is independently a number representing atomic % and a is in the range of from 45 to 65, b is in the range of from 0 to 10, c is in the range of from 20 to 40, and d is in the range of from 7.5 to 15. Other incidental, inevitable minute amounts of impurities may also be present.

[0023] In some embodiments, the amorphous alloy may be a ferrous-metal based alloy, such as (Fe, Ni, Co) based compositions. Examples of such compositions are disclosed in U.S. Pat. No. 6,325,868 and in publications (A. Inoue et. al, Appl. Phys. Lett., Volume 71, p 464 (1997)), (Shen et. al, Mater. Trans., JIM, Volume 42, p 2136 (2001)), and Japanese patent application 2000126277 (Publ. # 2001303218 A). For example, the alloy may be Fe₇₂A₁₅Ga₂PnC₆B₄, or Fe₇₂Ai₇ZrioMo₅W₂Bi₅.

[0024] In some embodiments, the amorphous alloy may be at least one of Fe-Cr-B-Mo- C alloy, Ni-Cr-Si-B-Mo-Cu-Co alloy, Fe-Cr-B-Mn-Si alloy, Fe-Cr-B-Si alloy, Fe-Cr-B- Mn-Si-Cu-Ni-Mo alloy, Fe-Cr-B-Mn-Si-Ni alloy, Fe-Cr-Si-B-Mn-Ni-WC-TiC alloy, Fe- Cr-Si-Mn-C-Nd-Ti alloy. In at least one embodiment, the amorphous alloy may be a Fe- based alloy or a Ni/Cr-based alloy.

[0025] Amorphous alloys, including bulk solidifying amorphous alloys, may have high strength and high hardness. The strength may refer to tensile or compressive strength, depending on the context. For example, Zr and Ti-based amorphous alloys may have tensile yield strengths of about 250 ksi or higher, hardness values of about 450 HV or higher, or both. In some embodiments, the tensile yield strength may be about 300 ksi or higher - e.g., at least about 400 ksi, about 500 ksi, about 600 ksi, about 800 ksi, or higher. In some embodiments, the hardness value may be at least about 500 HV - e.g., at least about 550 HV, about 600 HV, about 700 HV, about 800 HV, about 900 HV, about 1000 HV, or higher.

[0026] In one embodiment, ferrous metal based amorphous alloys, including the ferrous metal based bulk solidifying amorphous alloys, can have tensile yield strengths of about 500 ksi or higher and hardness values of about 1000 HV or higher. In some

embodiments, the tensile yield strength may be about 550 ksi or higher - e.g., at least about 600 ksi, about 700 ksi, about 800 ksi, about 900 ksi, or higher. In some

embodiments, the hardness value may be at least about 1000 HV - e.g., at least about 1100 HV, about 1200 HV, about 1400 HV, about 1500 HV, about 1600 HV, or higher.

[0027] As such, any of the aforedescribed amorphous alloys may have a desirable strength-to-weight ratio. Furthermore, amorphous alloys, particularly the Zr- or Ti- based alloys, may exhibit good corrosion resistance and environmental durability. The corrosion herein may refer to chemical corrosion, stress corrosion, or a combination thereof.

[0028] The amorphous alloys, including bulk amorphous alloys, described herein may have a high elastic strain limit of at least about 0.5%, including at least about 1%, about 1.2%, about 1.5%, about 1.6%, about 1.8%, about 2%, or more - this value is much higher than any other metal alloy known to date.

[0029] In some embodiments, the amorphous alloys, including bulk amorphous alloys, may additionally include some crystalline materials, such as crystalline alloys. The crystalline material may have the same or different chemistry from the amorphous alloy. For example, in the case wherein the crystalline alloy and the amorphous alloy have the same chemical composition, they may differ from each other only with respect to the microstructure.

[0030] In some embodiments, crystalline precipitates in amorphous alloys may have an undesirable effect on the properties of amorphous alloys, especially on the toughness and strength of these alloys, and as such it is generally preferred to minimize the volume fraction of these precipitates. However, there may be cases in which ductile crystalline phases precipitate in-situ during the processing of amorphous alloys, which may be beneficial to the properties of amorphous alloys, especially to the toughness and ductility of the alloys. One exemplary case is disclosed in C. C. Hays et. al, Physical Review Letters, Vol. 84, p 2901, 2000. In at least one embodiment herein, the crystalline precipitates may comprise a metal or an alloy, wherein the alloy may have a composition that is the same as the composition of the amorphous alloy or a composition that is different from the composition of the amorphous alloy. Such amorphous alloys comprising these beneficial crystalline precipitates may be employed in at least one embodiment described herein.

Coating Material [0031] The coating materials described herein may be disposed over a substrate. One embodiment provides a coating material that comprises an amorphous alloy and particles of a second material.

[0032] The amorphous alloy may be any of the amorphous alloys described herein. In at least one embodiment, the amorphous alloy may be a bulk amorphous alloy. In another embodiment, the amorphous alloy may not be a bulk amorphous alloy.

[0033] The coating material may further comprise a crystalline material. The crystalline material may be a crystalline alloy having the same or different chemical composition from the amorphous alloy. The crystalline material may have a melting temperature below the degradation temperature of the second material. The degradation temperature of a material herein may refer to a temperature when the material starts to exhibit changes in at least one property. For example, the degradation may be a melting temperature, glass transition temperature, crystallization temperature, or other temperatures, depending on the context and the material. In another embodiment, degradation may refer to a temperature at which the material begins to interact chemically with another material (e.g., chemical reaction).

[0034] In at least one embodiment, the crystalline material comprises crystal (or "grain") sizes in the nanometer range, micron range, millimeter range, centimeter range, or any combinations thereof. For example, the first material may comprise a nano- crystalline material. The crystalline material may comprise an alloy of the same composition as the amorphous alloy in the coating material, an alloy different from the amorphous alloy in the coating material, a metal, a non-metal, or any combinations thereof.

[0035] The second material may be a hard phase material. In one embodiment, the second material may be a ceramic or metal. In at least one embodiment, the second material may be a refractory metal - e.g., tungsten, tantalum, molybdenum, any other suitable refractory metal, or combinations thereof. In another embodiment, the second material may be a ceramic - e.g., a carbide material or boride material. The ceramic may be silicon carbide, tungsten carbide, chromium carbide, silicon boride, tungsten boride, chromium boride, or combinations thereof.

[0036] The coating material may comprise the second material in the form of particles dispersed in a matrix material comprising the amorphous alloy. The second material particles may be evenly distributed throughout the coating material. The particles may have any suitable geometry. In one embodiment, the particles may be in the shape of spheres, spheroids, cubes, cuboids, cones, platelets, needles, or rods.

[0037] In one embodiment, the second material may have a melting temperature that is higher than the melting temperature of the amorphous alloy. In another embodiment, the second material is less ductile than a matrix material comprising the amorphous alloy.

[0038] The second material may be present in the coating material as particles of any suitable size. In one embodiment, the particles may have a size of about 10 mesh to about 325 mesh - e.g., about 14 mesh to about 270 mesh, about 18 mesh to about 230 mesh, about 20 mesh to about 200 mesh, about 25 mesh to about 170 mesh, about 30 mesh to about 140 mesh, about 35 mesh to about 120 mesh, about 40 mesh to about 100 mesh, about 45 mesh to about 80 mesh, about 45 mesh to about 70 mesh, or about 50 mesh to about 60 mesh.

[0039] The substrate may be a metal or metal alloy. In one embodiment, the substrate is a steel material, an aluminum alloy, or any other suitable metal or alloy material. The substrate may be a portion of a tool or device where increased wear resistance is desired. In one embodiment, the substrate may be a portion of an industrial tool, drilling equipment, or mining equipment. In another embodiment, the substrate may be a portion of an abrasive tool or device.

[0040] The coating material described herein may have a tensile stiffness of greater than about 50 GPa - e.g., greater than about 100 GPa, about 150 GPa, about 200 GPa, about 250 GPa, about 300 GPa, about 350 GPa, about 400 GPa, about 450 GPa, or more. In at least one embodiment, the tensile stiffness is in the range of about 100 to about 500 GPa - e.g., about 150 to about 450 GPa, about 200 to about 400 GPa or about 250 to about 350 GPa.

[0041] The coating material described herein may have a Vickers hardness of about 400 HV to about 1000 HV - e.g., about 450 HV to about 950 HV, about 500 HV to about 900 HV, about 550 HV to about 850 HV, about 600 HV to about 800 HV, or about 650 HV to about 750 HV. In at least one embodiment, the coating material has a Vickers hardness of about 500 HV. In one embodiment, the coating material exhibits a Vickers hardness of at least about 400 HV - e.g., at least about 425 HV, about 450 HV, about 475 HV, about 500 HV, about 525 HV, about 550 HV, about 575 HV, about 600 HV, about 625 HV, about 650 HV, about 675 HV, about 700 HV, about 725 HV, about 750 HV, about 775 HV, about 800 HV, about 825 HV, about 850 HV, about 875 HV, about 900 HV, about 925 HV, about 950 HV, about 975 HV, about 1000 HV, or more.

[0042] The coating materials described herein may be resistant to wear and/or corrosion. In one embodiment, the corrosion may refer to chemical corrosion, stress corrosion, or both. The wear resistance may be directly related to the hardness of the material, with wear resistance increasing as hardness increases. In at least one embodiment, the wear resistance is at least about twice as high - e.g., at least about three times as high, about four times as high, or about five times as high, as the wear resistance of a coating material that comprises the amorphous alloy in the absence of the second material.

[0043] The compositions described herein may comprise any amount of a matrix material comprising an amorphous alloy, depending on the application. For example, a composition may comprise about 10% to about 99% by volume of the matrix material - e.g., about 15% to about 95%, about 20% to about 90%, about 25% to about 80%, about 30%) to about 75%), about 35% to about 70%, or about 40% to about 60%. In at least one embodiment, the composition comprises greater than about 10% by volume of the matrix material - e.g., greater than about 15%, about 20%, about 25%, about 30%, about 40%, about 50%, about 60%, about 70%, about 75%, about 80%, about 90%, about 95%, or more of the matrix material. In at least one embodiment, the composition comprises less than about 99% by volume of the matrix material - e.g., less than about 95%, about 90%, about 85%, about 80%, about 75%, about 60%, about 50%, about 40%, about 30%, about 25%, about 15%, or less of the matrix material. The volume fraction of the matrix material in the composition may affect the mechanical properties of the material, such as tensile strength, tensile stiffness, and hardness. Depending on the application, the volume percentage of the matrix material may be the same, greater than, or smaller than that of the second material.

[0044] The compositions described herein may comprise any amount of the second material, depending on the application. For example, a composition may comprise about 1%) to about 90%) by volume of the second material - e.g., about 5% to about 85%, about 10% to about 80%, about 20% to about 75%, about 25% to about 70%, about 30% to about 65%, or about 40% to about 60%. In at least one embodiment, the composition comprises greater than about 1% by volume of the second material - e.g., greater than about 2%, about 5%, about 10%>, about 15%, about 20%, about 25%, about 30%, about 40%, about 50%, about 60%, about 70%, about 75%, about 80%, about 85%, or more of the second material. In at least one embodiment, the composition comprises less than about 90%) of the second material - e.g., less than about 85%, about 80%, about 75%, about 60%, about 50%, about 40%, about 30%, about 25%, about 15%, about 10%, about 5%, or less of the second material. The volume fraction of the second material in the composition may affect the mechanical properties of the material, such as tensile strength, tensile stiffness, and hardness. Depending on the application, the volume percentage of the second material may be the same as, greater than, or smaller than that of the matrix material containing the amorphous alloy.

[0045] The coating material may be in the form of a layer disposed over the substrate. In one embodiment, the coating material layer has a thickness of at least about 75 microns - e.g., at least about 100 microns, about 200 microns, about 300 microns, about 400 microns, about 500 microns, about 600 microns, about 700 microns, about 800 microns, about 900 microns, about 1 mm, about 5 mm, about 1 cm, or more. In at least one embodiment, the coating material layer has a thickness from about 75 microns to about 1 cm - e.g., about 100 microns to about 5 mm, about 200 microns to about 1 mm, about 300 microns to about 900 microns, about 400 microns to about 800 microns, or about 500 microns to about 700 microns.

[0046] The coating material may exhibit improved properties when compared to coating materials comprising the second material disposed in a matrix material substantially free of amorphous alloy. In one embodiment, the coating material exhibits improved second material pull-out protection. In another embodiment, the coating material exhibits improved adhesion to the substrate.

[0047] The coating material may exhibit improved properties when compared to coating materials comprising the amorphous alloy and substantially free of the second material. In one embodiment, the coating material exhibits improved hardness and wear resistance.

Method of Producing a Coating Material

[0048] Provided in some embodiments herein are methods of producing any of the compositions described above. The following description applies to at least some embodiments of the method of producing a coating material described herein.

[0049] In one embodiment, the coating material may be formed on a substrate using a first material and a second material. The coating material may comprise an amorphous alloy and the second material, and the first material may be adapted to form the amorphous alloy. During the forming process the first material may be at a first temperature, and the first temperature may be less than the melting temperature of the second material. By employing a first temperature of less than the melting temperature of the second material the second material may be incorporated in the coating material in a substantially unchanged, or unchanged, state.

[0050] The first temperature may depend on the amorphous alloy contained in the coating material. The composition of the amorphous alloy may affect the T_g, crystallization temperature (T_x), and the melting temperature (T_m). The T_g may be lower than T_x, and T_x may be lower than T_m in at least one embodiment. [0051] In one embodiment the first temperature is higher than or equal to the T_g of the amorphous alloy. This embodiment includes temperatures in the range of about 100°C to about 1500 °C - e.g., about 100°C to about 1000°C, about 100°C to about 900°C, about 100°C to about 800°C, or about 100°C to about 700°C. In at least one embodiment the first temperature is at least about 100°C - e.g., at least about 150°C, about 200°C, about 250°C, about 300°C, about 350°C, about 400°C, about 450°C, about 500°C, about 550°C, about 600°C, about 650°C, about 700°C, or higher. In at least one embodiment, the first temperature is higher than the T_g of the amorphous alloy. For example, the first temperature in at least one embodiment is at least about 0.5°C higher than the T_g of the amorphous alloy - e.g., at least about 1°C , 2°C, about 3°C, about 4°C, about 5°C, about 10°C, about 15°C, about 20°C, or higher, than T_g.

[0052] The T_g of the amorphous alloy may be in the range of about 100°C for gold based amorphous alloys, up to about 700°C for iron or refractory based amorphous alloys. For zirconium and titanium based amorphous alloy systems the T_g may be in the range of about 300°C to about 450°C. Depending on the composition of the amorphous alloy, T_g may vary.

[0053] In one embodiment, the first temperature is higher than or equal to the T_g of the amorphous alloy, and lower than the degradation temperature of the second material. The degradation temperature of the second material may be the temperature at which the second material begins to react (e.g., chemically react) with the first material, or in one embodiment may be the melting temperature of the second material. In at least one embodiment, utilizing a first temperature lower than the degradation temperature of the second material may prevent or reduce chemical reactions between the first and second materials.

[0054] In another embodiment, the first temperature is higher than or equal to the T_g of the amorphous alloy, and lower than the T_x of the amorphous alloy. This embodiment provides at least the advantage of minimizing formation of a crystalline material while allowing the amorphous metal to flow in a viscous manner during the forming process. [0055] The T_x of the amorphous alloy may be in the range of about 120 °C for gold based amorphous alloys, up to about 750°C or 800°C for iron or refractory based amorphous alloys. For zirconium and titanium based amorphous alloy systems the T_x may be in the range of about 350°C to about 500°C. Depending on the composition of the amorphous alloy, T_x may vary.

[0056] In one embodiment the first temperature is higher than or equal to the T_x of the amorphous alloy, and lower than the T_mof the amorphous alloy. In this embodiment it may be important to cool the amorphous alloy at a rate sufficient to form an alloy that is at least partially amorphous. For example, the rate may be at or greater than the critical cooling rate of the amorphous alloy. In one embodiment, the cooling rate is sufficient to produce an alloy consisting at least essentially of an amorphous alloy. The cooling rate may be achieved by employing compressed gas or air blowing, a water bath, a liquid solution bath, a heat sink, a chilling device, or combinations thereof. Active cooling processes may not be needed if a bulk solidifying amorphous alloy is utilized in this embodiment. The first temperature in at least one embodiment is at least about 1°C higher than the T_x of the amorphous alloy - e.g., at least about 5°C, about 10°C, about 15°C, about 20°C, about 25°C, about 30°C, about 35°C, or higher.

[0057] The T_m of the amorphous alloy may be in the range of about 200°C for gold based amorphous alloys, up to about 1500°C for iron or refractory based amorphous alloys. For zirconium and titanium based amorphous alloy systems the T_m may be in the range of about 650°C to about 900°C. Depending on the composition, T_m may vary.

[0058] In one embodiment the first temperature is higher than or equal to the T_m of the amorphous alloy. In this embodiment it may be important to cool the amorphous alloy at a rate sufficient to form an alloy that is at least partially amorphous. In one embodiment, the process is sufficiently fast to avoid crystallization. Such a phenomenon may be captured by having a cooling rate sufficiently fast to bypass the crystallization curve of a time -temperature transformation (TTT) diagram of the alloy. In one embodiment, the cooling rate is sufficient to produce an alloy consisting at least essentially of an amorphous alloy. The cooling rate may be achieved by employing compressed gas or air blowing, a water bath, a liquid solution bath, a heat sink or a chilling device. Active cooling processes may not be needed if a bulk solidifying amorphous alloy is utilized in this embodiment. The first temperature in at least one embodiment is at least about 1°C higher than the T_m of the amorphous alloy - e.g., at least about 5°C, about 10°C, about 15°C, about 20°C, about 25°C, about 30°C, about 35°C, or higher.

[0059] In another embodiment, the first temperature is maintained for the minimum amount of time needed for the forming of coating material to occur. Longer times may also be employed. In at least one embodiment, minimizing the time in which the first and/or second materials are at or above the first temperature may prevent or reduce chemical reactions between the first and second materials. Further, such an approach may further prevent the degradation of the second material. The first temperature may be maintained for a time that will ensure no (or substantially no) crystalline materials are formed in the amorphous alloy material. For example, the first temperature may be maintained for a time that will not intersect with the crystallization curve on the relevant Time-Temperature Transformation diagram.

[0060] The first material may comprise an amorphous alloy. In one embodiment, the first material consists at least essentially of an amorphous alloy. In another embodiment, the first material is substantially free of an amorphous alloy.

[0061] The first material may comprise any material suitable to form an amorphous alloy as a result of the forming process. In one embodiment, the first material may comprise iron, chromium, silicon, boron, manganese, nickel, molybdenum, niobium, copper, cobalt, carbon, zirconium, titanium, beryllium, aluminum, gold, platinum, palladium, phosphorous, or combinations thereof. In another embodiment, the first material may comprise a crystalline material.

[0062] The second material may be a hard phase material. In one embodiment, the second material may be a ceramic, metal, or both. In at least one embodiment, the second material may be a refractory metal - e.g., tungsten, tantalum, molybdenum, any other suitable refractory metal, or combinations thereof. In another embodiment, the second material may be a ceramic - e.g., a carbide or boride. The ceramic may be silicon carbide, tungsten carbide, chromium carbide, silicon boride, tungsten boride, chromium boride, or combinations thereof.

[0063] The second material may be in the form of particles with a size of about 10 mesh to about 325 mesh - e.g., about 14 mesh to about 270 mesh, about 18 mesh to about 230 mesh, about 20 mesh to about 200 mesh, about 25 mesh to about 170 mesh, about 30 mesh to about 140 mesh, about 35 mesh to about 120 mesh, about 40 mesh to about 100 mesh, about 45 mesh to about 80 mesh, about 45 mesh to about 70 mesh, or about 50 mesh to about 60 mesh. The particles may have any suitable geometry. In one embodiment, the particles may be in the shape of spheres, spheroids, cubes, cuboids, cones, platelets, needles, or rods.

[0064] The forming process may employ a feedstock material that comprises the first material, the second material, or both. In at least one embodiment, the first material and second material may be part of the same feedstock material. In another embodiment, the first material and second material may be combined to form the feedstock material. The feedstock material may be in any form suitable for use in the forming process - e.g., a powder or a wire. In one embodiment, the feedstock material may further comprise any suitable carrier material.

[0065] The forming process may be any process that produces a coating material comprising an amorphous alloy and the second material disposed on the substrate. In one embodiment, the forming process may be a thermal spray process. The thermal spray process may be at least one of Twin- Wire Arc Spraying (TWAS), High Velocity Oxygen Fuel (HVOF) spraying, High Velocity Air Fuel (HVAF) spraying, and plasma spraying. In another embodiment, the forming process may be a welding process. The welding process may be at least one of Metal Inert Gas (MIG) welding and Tungsten Inert Gas (TIG) welding. In another embodiment, the forming process may be a laser cladding process.

[0066] The production of the coating material may include a heating step. In one embodiment, at least one of the first material and the second material may be heated before or during the forming process. In one embodiment, the first material is heated to the first temperature before the forming process.

[0067] The forming process may produce a layer of the coating material disposed on the substrate. The coating material layer has a thickness of at least about 75 microns - e.g., at least about 100 microns, about 200 microns, about 300 microns, about 400 microns, about 500 microns, about 600 microns, about 700 microns, about 800 microns, about 900 microns, about 1 mm, about 5 mm, about 1 cm, or more. In at least one embodiment, the coating material layer has a thickness from about 75 microns to about 1 cm - e.g., about 100 microns to about 5 mm, about 200 microns to about 1 mm, about 300 microns to about 900 microns, about 400 microns to about 800 microns, or about 500 microns to about 700 microns.

[0068] The forming process may be conducted in air, an ambient atmosphere, a controlled gas atmosphere, an inert gas atmosphere, a pressurized atmosphere, or a vacuum.

[0069] Provided in one embodiment is a method of improving a property of a first coating material comprising an amorphous alloy disposed on a substrate. The method may include dispersing particles of the second material in the first coating material to form a second coating material.

[0070] The second coating material may have at least one improved property compared to the first material. The improved property herein may refer to corrosion resistance, wear resistance, tensile strength, tensile stiffness, Vickers hardness, toughness, or any combination thereof.

[0071] A property is considered to be improved when in comparison to another material the property is more desirable for any given application. For example, in the case of tensile strength, improvement may refer to an increase in magnitude.

NON-LIMITING WORKING EXAMPLES

[0072] The following non-limiting examples were produced and analyzed. Example 1

[0073] A coating material including amorphous alloy A, as a matrix, and tungsten carbide (WC) particles was formed over an aluminum alloy substrate by a HVOF thermal spraying process. The amorphous alloy A had the composition 25-27 wt% Cr, 2.0-2.2 wt% B, 16-18 wt% Mo, 2.0-2.5 wt% C, and the balance Fe, and was formed from a first material with the same composition. The first material was fully amorphous, and the matrix material was also fully amorphous. The coating material was formed from a feedstock including a powder of the first material mixed with the WC particles. The WC particles had a size of 325/15 mesh. The coating material included 20 vol% of the WC particles, and the coating material formed a layer on the substrate with a thickness of 15- 30 mil. The hardness and Young's modulus of the coating material were higher than the hardness and Young's modulus of the amorphous alloy A.

[0074] As shown in Figure 1(a), X-ray Diffraction (XRD) analysis indicated that the amorphous alloy A was fully amorphous, and contained no crystalline material. The XRD analysis of the coating material indicated that both the amorphous alloy A and the WC particles were present, as shown in Figure 1(a).

[0075] A cross-section of the coating material 100 disposed over the substrate 200 is shown in Figure 3. The coating material 100 includes both an amorphous matrix, the dark phase, and WC particles, the bright phase. In a microscopic image of the coating material, as shown in Figure 4, both the amorphous matrix 220 and the WC particles 210 were observed. The WC particles were evenly distributed throughout the amorphous matrix.

Example 2

[0076] A coating material including a matrix material B, and tungsten carbide (WC) particles was formed over an aluminum alloy substrate by a HVOF thermal spraying process. The matrix material B had the composition 43-46 wt% Cr, 1.75-2.25 wt% Si, 5.6-6.2 wt% B, and the balance Fe, and was formed from a first material with the same chemical composition. The first material was almost fully crystalline, and the matrix material B formed therefrom included both an amorphous alloy and crystalline phases. The coating material was formed from a feedstock including a powder of the first material mixed with the WC particles. The WC particles had a size of 325/15 mesh. The coating material included 30 vol% of the WC particles, and the coating material formed a layer on the substrate with a thickness of 15-30 mil. The hardness and Young's modulus of the coating material were higher than the hardness and Young's modulus of the matrix material B.

[0077] As shown in Figure 2(a), XRD analysis indicated that the matrix material B was partially amorphous, and contained both amorphous and crystalline phases. The XRD analysis of the coating material indicated that both the matrix material B and the WC particles were present, as shown in Figure 2(b).

Table 1: Micro-Hardness test summary of Examples 1 and 2.

Conclusion

[0078] All literature and similar material cited in this application, including, but not limited to, patents, patent applications, articles, books, treatises, and web pages, regardless of the format of such literature and similar materials, are expressly

incorporated by reference in their entirety. In the event that one or more of the incorporated literature and similar materials differs from or contradicts this application, including but not limited to defined terms, term usage, described techniques, or the like, this application controls. [0079] While the present teachings have been described in conjunction with various embodiments and examples, it is not intended that the present teachings be limited to such embodiments or examples. On the contrary, the present teachings encompass various alternatives, modifications, and equivalents, as will be appreciated by those of skill in the art.

[0080] While various inventive embodiments have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and/or structures for performing the function and/or obtaining the results and/or one or more of the advantages described herein, and each of such variations and/or

modifications is deemed to be within the scope of the inventive embodiments described herein. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and/or configurations will depend upon the specific application or applications for which the inventive teachings is/are used. Those skilled in the art will recognize many equivalents to the specific inventive embodiments described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, inventive embodiments may be practiced otherwise than as specifically described and claimed. Inventive embodiments of the present disclosure are directed to each individual feature, system, article, material, kit, and/or method described herein. In addition, any combination of two or more such features, systems, articles, materials, kits, and/or methods, if such features, systems, articles, materials, kits, and/or methods are not mutually inconsistent, is included within the inventive scope of the present disclosure.

[0081] Also, the technology described herein may be embodied as a method, of which at least one example has been provided. The acts performed as part of the method may be ordered in any suitable way. Accordingly, embodiments may be constructed in which acts are performed in an order different than illustrated, which may include performing some acts simultaneously, even though shown as sequential acts in illustrative embodiments. [0082] All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and/or ordinary meanings of the defined terms.

[0083] The indefinite articles "a" and "an," as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean "at least one." Any ranges cited herein are inclusive.

[0084] The terms "substantially" and "about" used throughout this Specification are used to describe and account for small fluctuations. For example, they can refer to less than or equal to ±5%, such as less than or equal to ±2%, such as less than or equal to ±1%, such as less than or equal to ±0.5%, such as less than or equal to ±0.2%, such as less than or equal to ±0.1 %, such as less than or equal to ±0.05%.

[0085] The phrase "and/or," as used herein in the specification and in the claims, should be understood to mean "either or both" of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with "and/or" should be construed in the same fashion, i.e., "one or more" of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the "and/or" clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to "A and/or B", when used in conjunction with open-ended language such as "comprising" can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.

[0086] As used herein in the specification and in the claims, "or" should be understood to have the same meaning as "and/or" as defined above. For example, when separating items in a list, "or" or "and/or" shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as "only one of or "exactly one of," or, when used in the claims, "consisting of," will refer to the inclusion of exactly one element of a number or list of elements. In general, the term "or" as used herein shall only be interpreted as indicating exclusive alternatives (i.e. "one or the other but not both") when preceded by terms of exclusivity, such as "either," "one of," "only one of," or "exactly one of." "Consisting essentially of," when used in the claims, shall have its ordinary meaning as used in the field of patent law.

[0087] As used herein in the specification and in the claims, the phrase "at least one," in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase "at least one" refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, "at least one of A and B" (or, equivalently, "at least one of A or B," or, equivalently "at least one of A and/or B") can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.

[0088] In the claims, as well as in the specification above, all transitional phrases such as "comprising," "including," "carrying," "having," "containing," "involving," "holding," "composed of," and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases "consisting of and "consisting essentially of shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03. [0089] The claims should not be read as limited to the described order or elements unless stated to that effect. It should be understood that various changes in form and detail may be made by one of ordinary skill in the art without departing from the spirit and scope of the appended claims. All embodiments that come within the spirit and scope of the following claims and equivalents thereto are claimed.

Claims

WHAT IS CLAIMED:

1. A method comprising: forming a coating material on a substrate using a first material and a second material, wherein the coating material comprises an amorphous alloy and the second material, the first material is adapted to form the amorphous alloy, the first material is at a first temperature during the forming process, and the first temperature is lower than a melting temperature of the second material.

2. The method of claim 1, wherein the first material comprises an amorphous alloy.

3. The method of claim 1, wherein the first material consists essentially of an amorphous alloy.

4. The method of claim 1, wherein the first material consists of an amorphous alloy.

5. The method of claim 1, wherein the first material is substantially free of amorphous alloy.

6. The method of claim 1, wherein the coating material comprises a composite material comprising the second material dispersed in a matrix material, and the matrix material comprises the amorphous alloy that is formed from the first material.

7. The method of claim 1, wherein the second material comprises a refractory metal, a ceramic material, or both.

8. The method of claim 1, wherein the second material comprises tungsten, tantalum, molybdenum, tungsten carbide, silicon carbide, chromium carbide, tungsten boride, silicon boride, chromium boride, or combinations thereof.

9. The method of claim 1, wherein the second material comprises particles.

10. The method of claim 1, wherein the second material comprises particles with a size of about 10 mesh to about 325 mesh.

11. The method of claim 1 , wherein the coating material comprises the second material in a substantially unchanged state.

12. The method of claim 1, wherein the substrate comprises at least one of a metal and a metal alloy.

13. The method of claim 1, wherein the first material and second material are parts of a feedstock material employed to form the coating material in the forming.

14. The method of claim 1, further comprising forming a feedstock material comprising the first material and the second material, the feedstock material employed to form the coating material in the forming.

15. The method of claim 1, wherein the forming further comprises using a carrier material.

16. The method of claim 1, further comprising heating at least one of the first material and the second material before or during the forming.

17. The method of claim 1, wherein the forming comprises at least one of a thermal spray process, welding process, and laser cladding process.

18. The method of claim 1 , wherein the first temperature is higher than a T_g of the amorphous alloy.

19. The method of claim 1, wherein the first temperature is less than a T_m of the amorphous alloy.

20. The method of claim 1, wherein the first temperature is less than a T_x of the amorphous alloy.

21. The method of claim 1 , wherein the first temperature is greater than or equal to a T_m of the amorphous alloy.

22. The method of claim 1, wherein the coating comprises at least 10 vol% of a matrix material, which comprises the amorphous alloy formed from the first material.

23. The method of claim 1, wherein the coating comprises at least 1 vol% of the second material.

24. The method of claim 1, wherein the first material comprises a bulk amorphous alloy.

25. The method of claim 1, wherein the first material comprises iron, chromium, silicon, boron, manganese, nickel, molybdenum, niobium, copper, cobalt, carbon, zirconium, titanium, beryllium, aluminum, gold, platinum, palladium, phosphorous, or combinations thereof.

26. The method of claim 1, wherein the first material comprises at least one of Fe-Cr- B-Mo-C alloy, Ni-Cr-Si-B-Mo-Cu-Co alloy, Fe-Cr-B-Mn-Si alloy, Fe-Cr-B-Si alloy, Fe- Cr-B-Mn-Si-Cu-Ni-Mo alloy, Fe-Cr-B-Mn-Si-Ni alloy, Fe-Cr-Si-B-Mn-Ni-WC-TiC alloy, or Fe-Cr-Si-Mn-C-Nd-Ti alloy.

27. The method of claim 1, wherein the first material comprises a crystalline material.

28. The method of claim 1, further comprising forming the coating material as a layer on the substrate, the layer having a thickness of at least 75 microns.

29. The method of claim 1, wherein at least one of the first and second materials is in the form of a wire or a powder.

30. A coating material produced by the method of claim 1.

31. A method comprising : dispersing particles of a second material in a first coating material to form a second coating material comprising the first coating material and the second material; wherein the second coating material has at least one improved property compared to the first coating material.

32. The method of claim 31 , wherein the second material comprises a refractory metal, a ceramic material, or both.

33. The method of claim 31 , wherein the second material comprises tungsten, tantalum, molybdenum, tungsten carbide, silicon carbide, chromium carbide, tungsten boride, silicon boride, chromium boride, or combinations thereof.

34. The method of claim 31 , wherein the improved property is at least one of hardness and wear resistance.

35. A compo sition comprising : a coating material, and a substrate, wherein the coating material is disposed over the substrate, and the coating material comprises an amorphous alloy and particles of a second material.

36. The composition of claim 35, wherein the second material comprises a refractory metal, a ceramic material, or both.

37. The composition of claim 35, wherein the coating material comprises a composite material comprising the second material dispersed in a matrix material, and the matrix material comprises the amorphous alloy.

38. The composition of claim 35, wherein the coating material has a thickness of at least about 75 microns.

39. The composition of claim 35, wherein the coating material comprises at least 10 vol% of a matrix material comprising the amorphous alloy.

40. The composition of claim 35, wherein the coating material comprises at least 1 vol% of the second material.

41. The composition of claim 35, wherein the coating material has a hardness of at least about 400 HV.

42. The composition of claim 35, wherein the coating material has a wear resistance greater than at least one of a different coating material comprising the amorphous alloy in the absence of the second material and a different coating material comprising the second material in the absence of the amorphous alloy.

44. The composition of claim 35, wherein the substrate comprises a portion of an industrial tool, a drill, mining equipment, or an abrasive tool.

45. The composition of claim 35, wherein the coating material is an abrasive coating material.

46. The composition of claim 35, wherein the amorphous alloy comprises iron, chromium, silicon, boron, manganese, nickel, molybdenum, niobium, copper, cobalt, carbon, zirconium, titanium, beryllium, aluminum, gold, platinum, palladium, phosphorous, or combinations thereof.

47. The composition of claim 35, wherein the amorphous alloy comprises at least one of Fe-Cr-B-Mo-C alloy, Ni-Cr-Si-B-Mo-Cu-Co alloy, Fe-Cr-B-Mn-Si alloy, Fe-Cr-B-Si alloy, Fe-Cr-B-Mn-Si-Cu-Ni-Mo alloy, Fe-Cr-B-Mn-Si-Ni alloy, Fe-Cr-Si-B-Mn-Ni- WC-TiC alloy, or Fe-Cr-Si-Mn-C-Nd-Ti alloy.