WO2022212588A1 - Copper-based alloy and metal matrix composite formed using same - Google Patents

Copper-based alloy and metal matrix composite formed using same Download PDF

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Publication number
WO2022212588A1
WO2022212588A1 PCT/US2022/022662 US2022022662W WO2022212588A1 WO 2022212588 A1 WO2022212588 A1 WO 2022212588A1 US 2022022662 W US2022022662 W US 2022022662W WO 2022212588 A1 WO2022212588 A1 WO 2022212588A1
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WO
WIPO (PCT)
Prior art keywords
alloy
mmc
matrix composite
copper
metal matrix
Prior art date
Application number
PCT/US2022/022662
Other languages
French (fr)
Inventor
James Nathaniel Vecchio
Andy Bell
Original Assignee
Oerlikon Metco (Us) Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oerlikon Metco (Us) Inc. filed Critical Oerlikon Metco (Us) Inc.
Priority to CA3212946A priority Critical patent/CA3212946A1/en
Priority to EP22723238.6A priority patent/EP4314366A1/en
Priority to US18/550,446 priority patent/US20240167124A1/en
Priority to CN202280024983.5A priority patent/CN117098864A/en
Priority to AU2022249075A priority patent/AU2022249075A1/en
Priority to JP2023555576A priority patent/JP2024512922A/en
Publication of WO2022212588A1 publication Critical patent/WO2022212588A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/10Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on titanium carbide
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/0425Copper-based alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/10Alloys containing non-metals
    • C22C1/1036Alloys containing non-metals starting from a melt
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C22C32/0052Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • C22C9/05Alloys based on copper with manganese as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • C22C9/06Alloys based on copper with nickel or cobalt as the next major constituent

Definitions

  • the disclosure relates generally to tungsten carbide particles, and more particularly to textured spheroidal tungsten carbides, composites formed thereof, and methods of applying the composites.
  • a metal matrix composite refers to a composite material which includes particles that are embedded within a metallic matrix.
  • a MMC generally includes a high-melting temperature metallic powder that is infiltrated with a single metal or more commonly an alloy having a lower melting temperature than the powder.
  • MMCs have various applications, including mining equipment.
  • the physical properties of MMCs can be engineered through component materials and manufacturing processes thereof.
  • an alloy in one aspect, includes: manganese (Mn) at 5.6-10.4 weight percent (wt. %); nickel (Ni) at 3.5-6.5 wt. %; tin (Sn) at 1.4-4 wt. %; and copper (Cu) exceeding 55 wt. % and up to a balance of the alloy, wherein the alloy has a solidus temperature lower than a melting temperature of Cu. In some embodiments, the alloy has a solidus temperature is lower than 1300 K.
  • the alloy forms a single phase solid solution having a face-centered cubic (FCC) crystal structure from a solidus temperature down to at least 400 K below the solidus temperature. In some embodiments, greater than 90 wt.% of the alloy is a single phase solid solution with a face-centered cubic (FCC) crystal structure at room temperature. In some embodiments, the alloy further includes up to 2 wt. % of impurities. In some embodiments, the elemental composition does not include one or more of Si, B and Zn.
  • FCC face-centered cubic
  • the techniques described herein relate to an alloy, wherein the alloy has an electrical conductivity higher than 2.5 MS/m. In some embodiments, the alloy has a thermal conductivity higher than 10 W/mK.
  • the alloy forms a matrix of a metal matrix composite (MMC) material, wherein the MMC material further includes tungsten carbide particles. In some embodiments, the alloy forms a matrix of a metal matrix composite (MMC) material, wherein the MMC material forms part of a drilling component. In some embodiments, the alloy forms a matrix of a metal matrix composite (MMC) material, wherein the MMC material has a toughness greater than 4,000 in*lbf/in 3
  • the techniques described herein relate to an alloy, wherein the alloy is part of a feedstock for forming a metal matrix composite (MMC) material, wherein the feedstock further includes tungsten carbide particles.
  • MMC metal matrix composite
  • Another aspect describes a metal matrix composite material including reinforcement particles embedded in a copper-based matrix, wherein the copper-based matrix includes greater than 55 wt. % copper (Cu) and greater than 1.4 wt. % tin (Sn).
  • the copper-based matrix includes: 1.4-2.6 wt. % tin (Sn); 5.6-10.4 wt. % manganese (Mn); and 3.5-6.5 wt. % nickel (Ni), wherein the copper- based matrix has a solidus temperature lower than Cu. In some embodiments, the solidus temperature of the copper-based matrix is lower than 1300 K.
  • the copper-based matrix forms a single phase solid solution having a face-centered cubic (FCC) crystal structure from a solidus temperature down to at least 400K below the solidus temperature. In some embodiments, greater than 90 wt.% of the copper-based matrix is a single-phase solid solution having a face-centered cubic (FCC) crystal structure at room temperature. In some embodiments, the copper-based matrix includes 2 wt. % or less of impurities.
  • FCC face-centered cubic
  • the copper-based matrix does not include one or more of Si, B and Zn. In some embodiments, the copper-based matrix has an electrical conductivity higher than 2.5 MS/m. In some embodiments, the copper-based matrix has a thermal conductivity higher than 10 W/mK.
  • the reinforcement particles include tungsten carbide particles. In some embodiments, the tungsten carbide particles include 50-70 vol.% of the metal matrix composite material. In some embodiments, the tungsten carbide particles have an average particle size of 1-200 mhi.
  • the tungsten carbide particles have a spheroidal shape having ratio, between a first length along a major axis and a second length along a minor axis, of 1.20 or lower. In some embodiments, the tungsten carbide particles have a surface that is textured to have a grain boundary area fraction greater than 5.0 %. In some embodiments, the metal matrix composite material has a transverse rupture strength exceeding 175 ksi. In some embodiments, the metal matrix composite material forms part of a drilling component.
  • FIG. 1 illustrates a scanning electron microscopy (SEM) image of a prior art metal powder with angular particles.
  • FIG. 2 illustrates an optical micrograph of a prior art metal matrix composite (MMC) prepared using angular particles.
  • MMC metal matrix composite
  • FIG. 3 illustrates an optical micrograph of a MMC prepared using spheroidal or substantially spherical particles.
  • FIG. 4 illustrates an apparatus for producing an MMC.
  • FIG. 5 illustrates an embodiment of earth-engaging tool with a drill bit.
  • FIG. 6 illustrates strength and reliability improvements of some MMC embodiments
  • FIG. 7 illustrates a scanning electron micrograph (SEM) of a conventional
  • FIGS. 8-9 illustrate scanning electron micrographs of an MMCs according to embodiments.
  • FIG. 10 illustrates a binary image of FIG. 7.
  • FIG. 11 illustrates a binary image of FIG. 8.
  • FIG. 12 illustrates a binary image of FIG. 9.
  • FIG. 13 illustrates an optical micrograph of a MMC comprising tungsten carbide particles embedded in a Cu-based matrix, according to embodiments.
  • FIG. 14 shows example samples prepared for testing MMCs having Cu- based matrix and tungsten carbide particles, according to embodiments.
  • FIG. 15. illustrates experimental results of strength testing of a MMC comprising tungsten carbide particles embedded in a Cu-based matrix, according to embodiments.
  • spheroidal or substantially spherical fused tungsten carbide particles and metal matrix composites (MMCs) formed from tungsten carbide particles can include a matrix comprising copper and/or copper alloys, along with tungsten carbide particles.
  • the tungsten carbide particles and MMCs formed therefrom can have substantially improved properties over conventional angular fused tungsten carbide particles as well as MMCs formed therefrom.
  • embodiments of the disclosure can be used to improve erosion resistance and impact resistance of resulting metal matrix composites.
  • a feedstock alloy for forming a copper-based matrix of a MMC with reinforcement particles.
  • the copper-based matrix, and the MMC integrating the copper-based matrix may both be reinforced with particles.
  • the particles may be spherical tungsten carbide particles.
  • the copper-based matrix as well as MMCs formed therefrom can have substantially improved properties over conventional matrices or MMCs formed therefrom.
  • the thermal conductivity of MMCs and components incorporating the same may be improved.
  • Spheroidal or substantially spherical fused tungsten carbide particles can be made from commercially available fused tungsten carbide powder or a mixture of tungsten, mono tungsten carbide and/or carbon.
  • spheroidal or substantially spherical fused tungsten carbide particles can have a combined carbon composition from 3.7 to 4.2 (or about 3.7 to 4.2) wt. % carbon (C), with the balance of the composition being tungsten (W).
  • the fused tungsten carbide particles can be produced by several methods. In some methods, a mixture of tungsten powder blended with mono tungsten carbide and carbon powder is melted.
  • the molten mixture of tungsten powder, mono tungsten carbide and carbon powder is then atomized by a rotation atomizing process or an ultra-high temperature melting & atomizing process.
  • a rotation atomizing process includes spinning or rotating the molten mixture such that centrifugal forces break the liquid and throw off molten metal as a spray of droplets. These droplets may then solidify as powder particles.
  • Atomization processes generally spheroidize molten tungsten carbide into spheroidal or substantially spherical fused tungsten carbide particles during the rapid solidification process due to surface tension of the molten metal.
  • spheroidal or substantially spherical fused tungsten carbide particles may be based on the modification of regular fused tungsten carbide powder.
  • Plasma spraying, electric induction or electric resistance furnace melting may be used during the spheroidization process to obtain fine spheroidal or substantially spherical fused tungsten carbide particles.
  • Sphericity can be defined by an aspect ratio of the spheroidal or substantially spherical particles.
  • the aspect ratio can be a ratio of a first length along a major axis to a second length along a minor axis of the particles, or a ratio of the longest axis length to the shortest axis length of the spheroidal or substantially spherical particles.
  • a perfect spherical particle would have an aspect ratio of exactly one.
  • angular particles have an aspect ratio of at least 1.30.
  • spherical or substantially spherical fused tungsten carbide particles can have an aspect ratio of ⁇ about 1.20, ⁇ about 1.10, about ⁇ 1.05, or a value within any range of these values.
  • the aspect ratio can represent an average value of aspect ratios of a plurality of fused tungsten carbide particles.
  • each of the particles can have an aspect ratio within a range disclosed herein.
  • the specific density of the spherical or substantially spherical fused tungsten carbide powder can be around 16.5 g/cm 3 with a micro-hardness as defined by a Vickers pyramid number (HV) ranging from 2,700-3,300 HV (or about 2,700 - about 3,300 HV) or any value there between.
  • HV Vickers pyramid number
  • the inventors have found that these high microhardness values might be attributed to, among other things, the particle shape and internal micro structure resulting from the spheroidization processes as described herein.
  • conventional mostly angular fused tungsten carbide particles exhibit a substantially inferior hardness of about 1,500-2,200 HV.
  • MMCs containing spheroidal or substantially spherical fused tungsten carbide particles are more wear resistant than those that contain a similar size and fraction of angular fused tungsten carbide particles.
  • FIG. 1 shows a scanning electron microscope (SEM) image of an angular metallic powder.
  • FIG. 2 illustrates an optical micrograph of a MMC prepared using metallographic techniques from an angular conventional fused tungsten carbide powder.
  • the MMC includes a soft phase 202, a particulate phase 204 formed from a powder similar to that shown in FIG. 1, and a particulate-to-soft phase interface 206.
  • the soft phase 202 can be formed by a matrix material that is first melted and subsequently cooled.
  • the conventional MMC includes two principal phases.
  • the soft phase 202 is formed through the liquid metal infiltration of the particulate phase 204.
  • the particulate phase 204 can include metal carbides, borides or oxides.
  • the particulate phase 204 can include tungsten carbides including: mono tungsten carbide, fused tungsten carbide or cemented tungsten carbide. Typically, the tungsten carbide particles are angular, as shown in FIG. 1. Between the soft phase 202 and the particulate phase 204 there is an interface 206. The inventors have discovered that all three phases 202, 204, and 206 can contribute to the strength and wear properties of the MMC.
  • FIG. 3 illustrates an optical micrograph of a metal matrix composite (MMC) 300 prepared using spheroidal or substantially spherical carbide particles.
  • MMC metal matrix composite
  • the MMC 300 includes spheroidal or substantially spherical fused tungsten carbide particles 302 and a soft phase 304, which are combined to form the metal matrix composite (MMC) 300.
  • the MMC 300 additionally includes a spheroidal or substantially spherical fused tungsten carbide-to-soft phase interface 306.
  • the interface 306 includes metallic or metallurgical bonds formed between the tungsten carbide particles 302 and the soft phase 304.
  • the metallurgical bonds disclosed herein may comprise diffused atoms and/or atomic interactions, and may include chemical bonds formed between atoms of the particles 302 and the atoms of the soft phase 304.
  • a metallurgical bond is more than a mere mechanical bond. Under such conditions, the component parts may be wetted to and by the metallic binding material. Wetting is the ability of a liquid to maintain contact with a solid surface resulting from intermolecular interactions when the liquid and the solid surface are brought together.
  • a powder mixture including the spheroidal or substantially spherical tungsten carbide particles is formed.
  • the MMC formed from the spheroidal or substantially spherical may be called spherical MMCs, whereas the conventional MMCs formed from angular powders may be called angular MMCs.
  • a liquid metal infiltration route can be used to form MMC.
  • Liquid metal infiltration is a process in which a compacted powder material is immersed inside a liquid metal (e.g., a binding material) or contacts the liquid metal (e.g., the binding material).
  • the liquid metal fills the pores in the compacted powder material, a process that is driven by surface energy of the compacted powder material.
  • a metallic binding material may, be any suitable brazing metal, including: copper, chromium, tin, silver, cobalt nickel, cadmium, manganese, zinc and/or cobalt or an alloy thereof.
  • the metallic binding material can be liquid cast through tungsten carbide powder and solidified to form a MMC.
  • a graphite mold assembly 412, 414 is produced that reflects a negative of the desired shape of a drill bit 500.
  • a powder 408 comprising the spheroidal or substantially spherical particles is poured and compacted in the mold assembly 412, 414.
  • a binder 406, e.g., copper or copper alloy, and steel parts 404 may be added.
  • Configured mold assembly 412, 414 is heated to melt at least the binder 406.
  • a sand component 402 which defines regions within the resulting casting that is free from MMC.
  • the binder 406 infiltrates the powder 408 and creates bonds to the steel parts 404.
  • the solidified structure contains a plurality of composites advantageously located for strength and wear considerations.
  • the binder may be copper. In some embodiments, the binder may be a copper-based alloy. In some embodiments, a quaternary material system may be used as the binder 406. In some embodiments, the binding material can be a quatemary system comprising copper (47 - 58 wt.% or about 47 - about 58), manganese (23 - 25 wt.% or about 23 - about 25 wt.%), nickel (14 - 16 wt.% or about 14 - about 16 wt.%) and zinc (7 - 9 wt.% or about 7 - about 9 wt.%).
  • the inventors have discovered that the tungsten carbide particles and MMCs formed therefrom according to some embodiments of the disclosure can be particularly useful for applying in mining equipment, such as drills. However, it should be understood that embodiments are not so limited, and the tungsten carbide particles and MMCs formed therefrom can be used in a variety of other applications in which abrasion resistant materials are employed.
  • Earth-engaging drill bits are used extensively in industries including the mining, oil and gas industries for exploration and retrieval of minerals and hydrocarbon resources.
  • Examples of earth-engaging drill bits include polycrystalline diamond compact (PDC) bits.
  • a drill bit wears when it mbs against a formation of metal or rocks in the ground or against a metal casing tube. This wear may lead to the loss of function and failure of the drill bit.
  • a cooling and lubricating drilling fluid is circulated through the drill bit using high hydraulic energies.
  • the drilling fluid may contain abrasive particles, for example sand, which when impelled by the high hydraulic energies can exacerbate wear at the face of the drill bit and elsewhere.
  • Drill bits may have a body comprising at least one of hardened and tempered steel, and a metal matrix composite (MMC).
  • a steel drill bit body may have increased ductility and may be more easily manufactured.
  • a steel drill bit body may be manufactured using casting and wrought manufacturing techniques, examples of which include but are not limited to forging or rolled bar techniques. The steel properties after heat treatment are consistent and repeatable. Fracture of steel-bodied drill bits is infrequent; however, a worn steel drill bit body may be difficult for an operator to repair.
  • Wing or blade of a drill bit that fractures.
  • Wing or blade failures are economically damaging for drill bit manufacturers.
  • the retrieval of a worn or failed drill bit from a drilled hole, for example a well or borehole, is undesirable.
  • the non-productive time required to retrieve and introduce into the drilled hole a replacement drill bit may cost millions of dollars.
  • Drill bits and other earth-engaging tools with increased wear resistance and lower rates of failure may save considerable time and money. Therefore, developing an ultra-high- strength MMC for drill bits is desirable to reduce or prevent fracture during drilling.
  • the strength of a sample of an MMC may be determined using a transverse rupture strength (TRS) test.
  • TRS transverse rupture strength
  • a load is centrally applied to the cubic or cylindrically shaped MMC sample that is supported between two points.
  • the rupture strength is the maximum weight that the MMC can support.
  • a plurality of samples may be tested to derive a mean strength and a standard deviation which may be used to describe the MMC.
  • the reliability analysis of the TRS of an MMC can provide additional information such as the failure possibilities under different stresses.
  • MMC drill bits can generally perform better in erosion than steel bits, they still may encounter rapid deceleration of particles in hydraulic fluids, resulting in the erosive removal of material.
  • high-velocity drilling-mud exits nozzles to cool the bit and evacuate detritus.
  • Drilling mud contains materials such as bentonite, clay and surfactants, which also contain hard and angular minerals from the rock material. The contact between the PDC bits and drilling mud may erode portions of the drill bits.
  • the MMC disclosed herein has high erosion resistance accompanied with ultrahigh strength to improve the reliability and performance of the drill bits during drilling.
  • FIG. 5 shows a perspective view of an embodiment of earth-engaging tool in the form of a drill bit 500 which comprises a bit body 502 comprising an MMC FIG.300.
  • the bit body 502 may be formed from embodiments of the MMC 300.
  • a majority of the bit body 502 is formed from embodiments of the MMC 300.
  • the tool can include a nozzle port 516, e.g., for hydraulic fluid, a face 510 that supports cutting element 508, such as polycrystalline diamond compact (PDC) cutters, and junk slots 506 for carrying cuttings away in a fluid from a face of the drill bit 500.
  • PDC polycrystalline diamond compact
  • the bit body 502 can have protrusions in the form of radially projecting and longitudinally extending wings or blades 504, which are separated by channels at the face 510 of the drill bit 500 and junk slots 506 at the sides of the drill bit 500.
  • a plurality of cemented tungsten carbide or PDC cutting elements 508 can be brazed within pockets on the leading faces of the blades 504 extending over the face 510 of the bit body 502.
  • the PDC cutting elements 508 may be supported from behind by buttresses 512, for example, which may be integrally formed with the bit body 502.
  • the drill bit 500 may further include a shank 514 in the form of an American Petroleum Institute (API) threaded connection portion for attaching the drill bit 500 to a drill string (not shown). Furthermore, a longitudinal bore (not shown) can extend longitudinally through at least a portion of the bit body 502, and internal fluid passageways (not shown) may provide fluid communication between the longitudinal bore and nozzles 516 provided at the face 510 of the bit body 512 and opening onto the channels leading to junk slots 506 for removing the drilling fluid and formation cuttings from the drill face.
  • API American Petroleum Institute
  • the drill bit 500 is positioned at the bottom of a hole and rotated while weight-on-bit is applied.
  • a drilling fluid for example a drilling mud delivered by the drill string to which the drill bit 500 is attached - is pumped through the bore, the internal fluid passageways, and the nozzles 516 to the face 510 of the bit body 502 and PDC cutting elements 508.
  • the PDC cutting elements 508 scrape across, and shear away, the underlying earth formation.
  • the formation cuttings mix with, and are suspended within, the drilling fluid and pass through the junk slots 506 and up through an annular space between the wall of the hole (in the form of a well or borehole, for example), and the outer surface of the drill string to the surface of the earth formation.
  • the strength of a sample of a MMC may be determined using a TRS test, but using averaging and using other statistical methods to analyze the TRS results may also be important. If the values are not thoroughly analyzed, the TRS data may not:
  • the strength distribution in a population of samples of the MMC used in earth-engaging and other tools may be determined using Weibull statistics, which is a probabilistic approach that enables a calculation of the likelihood of failure to be established at a given applied stress.
  • Embodiments of the disclosed MMCs may be used with an earth- engaging tool, e.g., a drill bit 500, for example, which generally follow a Weibull distribution.
  • F which is the probability of failure for a sample
  • s which is the applied stress
  • iF u which is the lower limit stress needed to cause failure, which is often assumed to be zero
  • s 0 which is the characteristic strength
  • m which is the Weibull modulus, a measure of the variability of the strength of the material
  • V which is the volume of specimen.
  • FIG. 6 illustrates a Weibull plot of empirical strength data for a plurality of samples of the same type of angular MMC 602 similar to those shown in FIG. 2, containing predominately angular particles and an MMC containing predominately spheroidal or substantially spherical particles 604 similar to those shown in FIG. 3.
  • the MMCs illustrated in FIG. 6 are composed of textured spheroidal or substantially spherical tungsten carbide and a Cu53 copper binder, a known copper alloy.
  • the y-axis values on the left most y-axis are indicative of a function of the probability of failure, the y-axis values on the right most y-axis are indicative of a percentage probability of failure.
  • the x-axis values are indicative of a function of the applied stress at the time of failure during a TRS test.
  • the empirical strength data for the samples of angular MMC 602 and the sample of spherical MMC 604 follow a Weibull distribution. The slope of each line defines the respective Weibull moduli.
  • the angular MMC 602 has a Weibull modulus of 13.76 and the spherical MMC 604 has a Weibull modulus of 27.94.
  • the Weibull modulus is one measure of material strength variability. For example, for a Weibull modulus of 4, there will be a 30% variation (one standard variation) in strength.
  • the spherical MMC 604 has a Weibull modulus of > 15 (or about 15), > 20 (or about 20), > 25 (or about 25) or greater, or a value in range defined by any of these values.
  • a Weibull plot can be used to design drill bit body blade heights and widths to a predetermined failure rate, and particularly help determine how thin and tall the drill bit body blades can be for the predetermined failure rate.
  • a taller and thinner blade may remove a formation faster than a shorter wider blade. However, a taller and thinner blade may have an unacceptable probability of failure.
  • the reliability of a drill bit comprising angular MMC 604 can be compared the reliability of another identically configured drill bit comprising spherical MMC 602.
  • Linear extrapolation to a 1 in 10,000 probability of failure equates to applied stress of about 60 ksi (kilopound per square inch) for an angular MMC 602 and 188 ksi for aspherical MMC 604.
  • the linear extrapolation to a 1 in 10,000 probability of failure for the spherical MMC 604 equates to 80 (or about 80) ksi or greater, 100 (or about 100) ksi or greater, 120 (or about 120) ksi or greater, 140 (or about 140) ksi or greater, 160 (or about 160) ksi or greater, 180 (or about 180) ksi or greater, or a value in a range defined by any of these values.
  • the novel spheroidal or substantially spherical fused tungsten carbide has a textured surface.
  • this texture can increase the available surface area at the interface 306 between the soft phase 304 and the spheroidal or substantially spherical fused tungsten carbide particles 302, as shown in FIG. 3.
  • the strength of an MMC system can be associated with one or more of three different components: the strength of the copper binder, the strength of the tungsten carbide particles, and/or the binding strength between the copper binder and the incorporated tungsten carbide particles.
  • the strength of the copper binder the strength of the tungsten carbide particles
  • the binding strength between the copper binder and the incorporated tungsten carbide particles can occur when the MMC undergoes high stress.
  • the alloy has more area to bond to the carbide particles, thus increasing the interfacial strength.
  • FIG. 7 illustrates the surface morphology of a tungsten particle in a conventional MMC.
  • the micro structure has soccer-ball-like topographical features of conventional fused tungsten carbide particles.
  • the surface is relatively smooth, resulting in a low surface area and relatively low interfacial strength when incorporated within a MMC.
  • FIG. 8 illustrates the surface morphology of a spheroidal or substantially spherical tungsten particle in an MMC.
  • the microstructure includes needle-like topographical features (e.g., texturing) of spheroidal or substantially spherical fused tungsten carbide.
  • the surface is mostly textured with a fine-grained structure, resulting in a high surface area and better interfacial strength when incorporated within a MMC.
  • FIG. 9 illustrates the surface morphology of a spheroidal or substantially spherical tungsten particle in an MMC.
  • the microstmcture includes dense needle-like like topographical features of spheroidal or substantially spherical fused tungsten carbide.
  • the surface is mostly textured with a finer grained structure resulting in an even higher surface area and exceptional interfacial strength when incorporated within a MMC.
  • an area fraction of grain boundaries refers to the area in an image, e.g., an optical or SEM image, of a surface of a sample, e.g., the surface of a tungsten carbide particle, that can be attributed to grain boundaries.
  • the area fraction of grain boundaries can be quantified using images, e.g., high contrast or binary images such as those shown in FIG.s 10-12.
  • the number of dark pixels as a fraction of a total number of pixels within an imaged field can correspond the area fraction of grain boundaries.
  • the inventors have discovered that the conventional soccer-ball-like surface morphology of tungsten carbide particles leads to a relatively low area fraction of grain boundaries on the surface of the tungsten carbide particles, e.g., less than 5%.
  • the needle-like surface morphology of tungsten carbide particles of spheroidal MMCs leads to a relatively high area fraction of grain boundary on the surface of the tungsten carbide particles, e.g., over 10% (or about 10%).
  • the area fraction of the grain boundary in FIG. 10, which is a binary image of the MMC of FIG. 7, which illustrates a conventional MMC is 3.6%.
  • FIG. 11 is a binary image of the MMC of FIG. 8, which illustrates a MMC made from spheroidal or substantially spherical tungsten carbides
  • FIG. 12 a binary image of FIG. 9, illustrates a MMC made from spheroidal or substantially spherical tungsten carbides in which the area fraction of grain boundaries is 20.1%.
  • a high area fraction of grain boundaries may lead to more uniform and finer grains overall.
  • the inventors have discovered that the combination of the spheroidal shape of the tungsten carbide particles, and the needle-like surface morphology of the formed MMC, may give rise to a relatively high surface area of the tungsten carbide particles, which in turn gives rise to the relatively high grain boundary area fraction.
  • the high gran boundary area fraction can be proportional to the amount of high strength interfaces formed between the tungsten carbide particles and the metal matrix. High amounts of high strength interfaces can lead to improved mechanical and tribological properties of MMCs, including high TRS values and increased erosion resistance.
  • the needle-like topography comprises needle-like structures that are elongated along surfaces of the tungsten carbide particles.
  • the needle-like structures have at least a portion length portion having a length exceeding, e.g., 0.5, 1, 2, 3, 4, 5 mhi, or a value in a range defined by any of these values, while having a width that is less than 2, 1, 0.5, 0.2, 0.1 mhi, or a value in a range defined by any of these values.
  • the needle-like structures may have a ratio of the longest length to the smallest width of the needle like structures that exceeds 2, 5, 10, 20 or a value in a range defined by any of these values.
  • the spheroidal or substantially spherical fused tungsten carbide particles have a grain boundary area fraction of 5.0% (or about 5.0%) or greater. 10.0% (or about 10.0%) or greater, 12.0% (or about 12.0%) or greater, 12.0% (or about 12.0%) or greater, 20.0% (or about 20.0%), or a value in a range defined by any of these values.
  • FIG. 10 illustrates a binary image of FIG. 7.
  • FIG. 11 shows a binary image of FIG. 8, which includes an analyzed area fraction of 14.2% and variation of 9.4% when divided into nine parts.
  • FIG. 12 shows a binary image of FIG. 9, which includes an analyzed area fraction of 20.1% and variation of 3.8% when divided into nine parts.
  • the size of the spheroidal or substantially spherical fused tungsten particle may between 1 to 200 pm.
  • the variation of the size of the spheroidal or substantially spherical fused tungsten particle can result in the change in TRS of the final infiltrated MMC.
  • Powder particle size distribution is measured and determined by MicroTrac per ASTM B822, hereby incorporated by reference in its entirety.
  • the powder particle size distribution is defined by describing values, namely:
  • an MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 1 pm and 10 pm has a TRS greater than or equal to 360 ksi (or about 360 ksi, greater than or equal to 530 ksi (or about 530 ksi), greater than or equal to 700 ksi (or about 700 ksi), or a value in a range defined by any of these values.
  • the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 11 pm and 20 pm has a TRS greater than or equal to 280 ksi (or about 280 ksi), greater than or equal to 365 ksi (or about 365 ksi), greater than or equal to 450 ksi (or about 450 ksi), or value in a range defined by any of these values.
  • the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 21 pm and 40 pm has a TRS greater than or equal to 230 ksi (or about 230 ksi), greater than or equal to 260 ksi (or about ksi), greater than or equal to 290 ksi (or about 290 ksi), or a value in a range defined by any of these values.
  • the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 41 pm and 60 pm has a TRS greater than or equal to 180 ksi, greater than or equal to 200 ksi, greater than or equal to 220 ksi, or a value in a range defined by any of these values.
  • the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 61 pm and 80 pm has a TRS greater than or equal to 160 ksi (or about 160 ksi), greater than or equal to 170 ksi (or about 170 ksi), greater than or equal to 180 ksi (or 180 ksi), or a value in a range defined by any of these values.
  • the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 81 pm and 100 pm has a TRS greater than or equal to 140 ksi (or about 140 ksi), greater than or equal to 150 ksi (or about 150 ksi), greater than or equal to 160 ksi (or about 160 ksi), or a value in a range defined by any of these values.
  • the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 101 pm and 200 pm has a TRS greater than or equal to 100 ksi (or about 100 ksi), greater than or equal to 120 ksi (or about 120 ksi), greater than or equal to 140 ksi (or about 140 ksi), or a value in a range defined by any of these values.
  • Laboratory testing enabled the abrasion and erosion resistance of angular and spherical MMCs to be measured and compared to one another.
  • An erosion test simulating real drilling condition was carried out by using a modified high-pressure abrasive waterjet cutting machine.
  • a special sample holder adjustable between 0° and 90° relative to the waterjet was designed to allow the adjustment of the impacting angle between the sample surface and slurry jet produced by the waterjet cutting machine.
  • the distance between the nozzle and the sample was selected as 1,000 mm in order to avoid cutting the sample and to enlarge the contact area between the jet and sample.
  • Garnet was used as the erodent.
  • the pressure of the waterjet was 50 ksi and the test duration was 10 min.
  • a balance with an accuracy of 1 mg was used to measure the weight of the coupon before and after the test.
  • An MMC sample produced from spherical fused tungsten carbide particles and made by liquid infiltration was tested for erosion at a 30° impact angle with volume loss of 0.022 cm 3 .
  • a reference MMC made from angular fused tungsten carbide particles was tested under the same conditions and experienced a volume loss of 0.17 cm 3 .
  • the spherical MMC has an erosive volume loss of 0.10 (or about 0.10) cm 3 or less , 0.08 (or about 0.08) cm 3 or less, 0.06 (or about 0.06) cm 3 or less, 0.04 (or about 0.04) cm 3 or less, or a value in a range defined by any of these values.
  • a standard ASTM 611 high stress abrasion test hereby incorporated by reference in its entirety, was performed on an MMC produced from spherical fused tungsten carbide particles and a reference MMC made from angular fused tungsten carbide particles
  • An MMC produced from spherical fused tungsten carbide particles under the testing conditions had volume loss of 0.51 cm 3 while a reference MMC made from angular fused tungsten carbide particles had a volume loss of 1.28 cm 3 under the same testing conditions.
  • the spherical MMC has an ASTM 611 volume loss of 1.00 (or about 1.00) cm 3 or lower, 0.80 (or about 0.80) cm 3 or lower, 0.60 (or about 0.60) cm 3 or lower, or a value in a range defined by any of these values.
  • metal matrix composite materials include reinforcement particles embedded in a matrix.
  • the physical properties of the reinforcement particles and the matrix can synergistically complement each other to form a metal matrix composite material that has a unique set of properties that are difficult to achieve with a single material.
  • an MMC that includes tungsten carbide particles embedded in a Cu-based matrix can provide a combination of high strength and high hardness, which can be difficult to achieve simultaneously in a single material.
  • MMCs are drilling technology, e.g., earth drilling technology for extracting hydrocarbon fuel.
  • Components used in drilling e.g., drill bits
  • the combination of these properties can be demanded under relatively harsh conditions for some applications.
  • the harsh conditions may include high temperature, which can result from friction caused by operation of the drill bits.
  • the performance levels of some MMCs which may be sufficient at moderate temperatures, may degrade to unacceptable performance levels at elevated temperatures.
  • MMCs that combine the various advantageous mechanical properties of MMCs based on tungsten carbide particles embedded in a Cu-based matrix, while also being designed to maintain the advantageous properties under heat-generating conditions by efficiently dissipating heat.
  • MMC made from spheroidal or substantially spherical fused tungsten carbide particles increase the thermal shock resistance of components fabricated therefrom.
  • an alloy e.g., a feedstock alloy, configured to form a matrix of an MMC having high thermal conductivity, for various applications including drilling is produced.
  • the MMCs formed using the feedstock alloy can maintain various advantageous performance criteria as described above, in in addition to significantly improving the thermal shock resistance of the MMCs.
  • the reduction of thermal shock can in turn reduce fracture failures. For drilling applications, reduction of the tendency of the drill bit body to fracture during operation can significantly improve productivity and reduce cost associated with replacement or repair thereof.
  • the feedstock alloy for forming the matrix should be compatible with and integrate well with the reinforcement particles. This is in part because, as described above, one of the processes for fabricating MMCs involves infiltration of the network of pores formed by the reinforcement particles. To serve as an effective infiltrant, the alloy for forming the matrix can have a melting temperature below that of the reinforcement particles. The alloy, when melted, should have a high fluidity to provide the surface tension and capillary force for facilitating the infiltration process. In a liquid state, the alloy should form a low contact angle with the surfaces of the reinforcement particles. Furthermore, any chemical reaction between the alloy and the reinforcement particles should be kept to a relatively low level, as such reactions can impede the infiltration process by altering the composition of the matrix relative to the feedstock alloy, as well as detrimentally affecting the performance of the resulting MMC.
  • a feedstock alloy for forming a matrix of an MMC includes an elemental composition including copper (Cu) as a majority element.
  • Some reinforcement particles such as some tungsten carbide particles, have relatively low thermal conductivity, and the thermal conductivity of the MMC may be limited by that of a matrix having a relatively high thermal conductivity.
  • the thermal conductivity of the MMC can drop proportionally due to a corresponding reduction in the volume fraction of the matrix.
  • the reduction in thermal conductivity of the MMC with increasing reinforcement particle content can be offset by incorporating a relatively high copper content.
  • some tungsten carbide particles can have a higher thermal conductivity than the MMC.
  • a feedstock alloy for forming a matrix of an MMC includes an elemental composition including a copper (Cu) concentration exceeding 55, 60, 65, 70, 75, 80, 85 weight percent (wt. %), or a value in a range defined by any of these values.
  • Cu copper
  • the high Cu content can provide improved thermal conductivity, among other advantages.
  • elemental copper may offer one of the highest thermal conductivities, it may not offer one or more other desirable characteristics associated with the fabrication of the MMC or the resulting mechanical properties thereof.
  • the inventors have discovered a combination of alloying elements for alloying with Cu to form a feedstock alloy for forming the matrix.
  • the elemental composition of the feedstock alloy for forming the matrix includes: tin (Sn) at a concentration exceeding 1.4 wt.
  • the combined concentration of Sn, Ni and Mn is less than 20 wt.%, 30 wt. %, 40 wt. %, 45 wt. % or a value in a range defined by any of these values, according to embodiments.
  • an elemental composition of a feedstock alloy for forming a matrix of an MMC includes Sn at a concentration exceeding 1.4, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0 wt. %, or a concentration within a range defined by any of these values.
  • the elemental composition may include Sn at 1.4-4 wt. %, 1.7-2.3 wt. %, or about 2.0 wt. %.
  • the elemental composition of the feedstock alloy additionally includes Mn at a concentration exceeding 5.6, 6.4, 6.8, 7.2, 7,6, 8.0, 8.4, 8.8, 9.2, 9.6, 10.4 wt. %, or a concentration within a range defined by any of these values.
  • the elemental composition includes Mn at 5.6-10.4 wt. %, 6.8-9.2 wt. %, or about 8.0 wt. %.
  • the composition of the feedstock alloy additionally includes Ni at a concentration exceeding 3.5, 4.0, 4.3, 4.5, 4.7, 5.0, 5.3, 5.5, 5.8, 6.0, 6.5 wt. %, or a concentration in a range defined by any of these values.
  • the elemental composition includes Ni at 3.5-6.5 wt. %, 4.3-5.8 wt. %, or about 5.0 wt. %.
  • the elemental composition of the feedstock alloy may include additional elements, which may include incidental impurities, at a combined concentration less than 10 wt. %, 5 wt. %, 2 wt. %, 1 wt. % or a value in a range defined by any of these values.
  • additional elements which may include incidental impurities, at a combined concentration less than 10 wt. %, 5 wt. %, 2 wt. %, 1 wt. % or a value in a range defined by any of these values.
  • Cu may be present as a balance of the elemental composition, in addition to the additional or impurity elements.
  • the relatively high Cu concentration of the feedstock can provide high thermal and/or electrical conductivity. It will be appreciated that the high thermal conductivity can be indirectly measured by measuring the electrical conductivity of the allow.
  • the feedstock has an electrical conductivity greater than 2.0 mega Siemens (MS)/meter (m), 2.5 MS/m, 3.0 MS/m, 3.5 MS/m, or a value in a range defined by any of these values.
  • the feedstock can have thermal conductivity that can have a value related to the electrical conductivity through, e.g., Wiedemann-Franz’s law. Wiedemann-Franz’s law states that the ratio of the electronic contribution of the thermal conductivity to the electrical conductivity is proportional to the temperature.
  • the feedstock can have thermal conductivity greater than 10 W/mK, 11 W/mK, 12 W/mK, 13 W/mK, 14 W/mK, 15 W/mK, 16 W/mK or a value in a range defined by any of these values.
  • the combination of Cu, Sn, Mn and Ni forms a feedstock alloy that can provide various advantages over relatively pure elemental Cu as a source of the matrix of an MMC.
  • the advantages may include in one or more of: lower melting temperature, lower contact angle with tungsten carbide and/or lower reactivity with tungsten carbide.
  • the combination of elements can additionally provide advantages over relatively pure elemental Cu as source of the matrix of an MMC including one or more of: higher strength, higher abrasion resistance and/or higher hardness.
  • the combination of the elements in the feedstock alloy can provide further advantages over elemental Cu when the elemental composition of the feedstock does not include one or more of Si, B and/or Zn, or when present, Si, B and/or Zn is present at a combined concentration less than 10 wt. %, 5 wt. %, 2 wt. %, 1 wt. % or a value in a range defined by any of these values.
  • the feedstock alloy for forming a matrix of an MMC is a pre-formed alloy that is solidified from a liquid having the alloy composition, e.g., by melting the constituent elements at a temperature sufficient to melt each of the constituent elements.
  • Having the feedstock in the form of a preformed alloy, as opposed to a mixture of elemental powder, can provide various advantages can lower the melting temperature of the feedstock alloy, such that the MMC can be effectively formed at lower temperatures.
  • the lower feedstock melting temperature can make different chemical compositions of feedstocks compatible with existing methods for manufacturing MMCs, including those described above. Due to the temperature constraints of some existing manufacturing methods, a feedstock for forming the matrix of an MMC that has a melting temperature exceeding 1300K may be difficult to fully melt to infiltrate the reinforcement particles for manufacturing into a matrix of an MMC.
  • the feedstock including these elements to be in an alloy form that has a melting temperature lower than each of these individual elements.
  • the feedstock in the form of an alloy has a composition such that the alloy has a solidus temperature lower than a melting temperature of substantially pure Cu.
  • the solidus temperature of the alloy is lower than 1300 K, 1275K, 1250K, 1225K, 1200K, or a solidus temperature in a range defined by any of these values.
  • the feedstock alloy can be present as, or liquefied and solidified into, a single phase solid solution.
  • An alloy or matrix in the form of a single phase solid solution can provide advantages in various mechanical and thermal properties over a multi-phase alloy.
  • thermal conductivity can be enhanced due to, e.g., the suppression of phonon scattering that can occur at phase boundaries.
  • the absence of phase boundaries can also enhance the strength of the alloy by reducing boundary-originating defects such as dislocations.
  • the inventors have found that one measure of the availability of an alloy as a single phase solid solution is a temperature range below the solidus temperature within which the alloy is present, or predicted to be present under thermodynamic equilibrium conditions, as a single phase solid solution. Such temperature range may be referred to as a single phase temperature range.
  • the elemental composition of the alloy comprising Cu, Sn, Mn and Ni as disclosed herein has a single phase temperature range greater than 400K such that, from the solidus temperature down to at least 400K below the solidus temperature, the alloy forms a single phase solid solution having a face-centered cubic (FCC) crystal structure.
  • the single phase temperature range of the feedstock alloy below the solidus temperature within which the alloy is present may exceed 375K, 400K, 425K, 450K, 475K or a value in a range defined by any of these temperatures.
  • the FCC crystal structure may correspond to a base crystal structure of Cu in which Sn, Mn and Ni can be present as substitutional and/or interstitial elements.
  • the feedstock alloy has a relatively wide single phase temperature range as described herein, the feedstock alloy can be formed into a matrix that is substantially present as a single phase alloy at room temperature. In some embodiments, at room temperature, greater than 80 wt. %, 85 wt. %, 90 wt. %, 95 wt. % or a value in range defined by any of these values, of the alloy and the resulting matrix is present a single phase solid solution having a face-centered cubic (FCC) crystal structure.
  • FCC face-centered cubic
  • the feedstock alloy as described herein can be used to form a metal matrix composite (MMC) material comprising reinforcement particles embedded in a copper-based matrix.
  • MMC metal matrix composite
  • a formed copper-based matrix can have any and/or all of the physical and chemical characteristics of the feedstock alloy used to form the matrix as described, including the elemental composition.
  • the chemical composition of feedstock alloy and a matrix of a MMC material formed therefrom can be substantially the same.
  • the matrix of an MMC has an elemental composition including copper (Cu) exceeding 55 weight percent (wt. %) and tin (Sn) exceeding 1.4 wt. %.
  • the elemental composition of the matrix includes Sn at a concentration exceeding 1.4, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0 wt. %, or having a concentration within a range defined by any of these values; Mn at a concentration exceeding 5.6, 6.4, 6.8, 7.2, 7,6, 8.0, 8.4, 8.8, 9.2, 9.6, 10.4 wt.
  • Ni at a concentration exceeding 3.5, 4.0, 4.3, 4.5, 4.7, 5.0, 5.3, 5.5, 5.8, 6.0, 6.5 wt. %, or a concentration in a range defined by any of these values.
  • the matrix of the MMC can have any and/or all of the physical and chemical characteristics of the feedstock alloy, including the solidus temperature, the single phase temperature range, electrical conductivity and thermal conductivity as described above, overlapping details of which are omitted here for brevity.
  • the reinforcement particles can include tungsten carbide particles.
  • the tungsten carbide particles can have any and/or all of the characteristics of the spheroidal tungsten carbide particles described above, overlapping details of which are omitted herein for brevity.
  • the tungsten carbide particles can have a spheroidal shape having ratio of a first length along a major axis to second length along a minor axis that is 1.20 or lower.
  • the tungsten carbide particles have a surface that is textured to have a grain boundary area fraction greater than 5.0 %.
  • the tungsten carbide particles can have a D50 between 1 pm and 10 pm; between 11 pm and 20 pm; between 21 pm and 40 pm; between 41 pm and 60 pm; between 61 pm and 80 pm; between 81 pm and 100 pm; between 101 pm and 200 pm; or a value in a range defined by any of these values, where the dimension D refers to the longest lateral dimension of the reinforcement tungsten carbide particles, and D50 refers to a median value of the longest lateral dimensions of the tungsten carbide particles.
  • the reinforcement particles of MMC materials are not so limited, and in some other embodiments, the tungsten carbide particles can have a spheroidal shape having a ratio of a first length along a major axis to second length along a minor axis that is 1.20 or greater, and/or a surface that is textured to have a grain boundary area fraction lower than 5.0 %..
  • the tungsten carbide particles do not have a spheroidal shape and/or a textured surface.
  • FIG. 13 illustrates an optical micrograph of a MMC comprising tungsten carbide particles 1301 embedded in a Cu-based matrix 1302, according to embodiments. Unlike the spheroidal tungsten carbide particles of the MMC described above with respect to FIG. 3, and similar to the tungsten carbide particles of the MMC described above with respect to FIG. 2, the tungsten carbide particles 1301 of the MMC illustrated in FIG. 13 are angular particles having irregular shapes.
  • the reinforcement particles e.g., tungsten carbide particles
  • the MMC including the Cu-based matrix at greater than 40 vol. %, 50 vol. %, 60 vol. %, 70 vol. %, 80 vol. %, or a value in a range defined by any of these values, for example 50-70 vol. %.
  • a method of forming a metal-matrix composite (MMC) material comprises providing reinforcement particles 408, e.g., tungsten carbide particles, and a feedstock alloy 410 for forming a copper-based matrix in a mold assembly 412, 414, wherein the feedstock alloy 410 has an elemental composition including copper (Cu) exceeding 55 weight percent (wt. %) and tin (Sn) exceeding 1.4 wt. %.
  • reinforcement particles 408 e.g., tungsten carbide particles
  • a feedstock alloy 410 for forming a copper-based matrix in a mold assembly 412, 414, wherein the feedstock alloy 410 has an elemental composition including copper (Cu) exceeding 55 weight percent (wt. %) and tin (Sn) exceeding 1.4 wt. %.
  • the reinforcement particles 408 are disposed below the feedstock alloy 410 such that gravity pulls liquefied alloy 410 into a porous network formed by the reinforcement particles 408. Subsequently, the method further comprises melting the alloy 410, infiltrating a network of pores formed by the reinforcement particles 408 with the liquefied alloy 410, and wetting the surfaces of the reinforcement particles 408. Subsequently, the liquefied alloy 410 is solidified within the network to form the MMC material comprising the reinforcement particles 408 embedded in in the copper-based matrix.
  • the feedstock can be liquefied at temperatures substantially lower than the melting temperatures of at some of the elemental metals including Cu, Mn and Ni.
  • melting comprises heating the mold to a temperature lower than melting temperatures of one or more of Cu, Mn and Ni, or lower than 1083 °C (1356 K), 1244 °C (1517 K), 1453 °C (1726 K).
  • melting comprises heating the mold to a temperature of 1000-1200 °C.
  • fabricated MMCs can form at least a portion of a drilling component, such as a drill bit as described above, the details of which are omitted herein for brevity.
  • the MMCs according to embodiments when fabricated with tungsten carbide particles and Cu-based alloys as described above, can have TRS values greater than 175 ksi, 200 ksi, 220 ksi, 250 ksi, or a value in a range defined by any of these values.
  • the Cu-based alloys disclosed herein provide additional toughness when used as the binder component in MMCs.
  • the Cu-based alloys can have toughness levels of greater than 3,000 in*lbf/in 3 , 4,000 in*lbf/in 3 , 5,000 in*lbf/in 3 ,or a value in a range defined by any of these values.
  • FIG. 14 shows example samples that have been prepared for testing MMCs having Cu-based matrix and tungsten carbide particles as described herein.
  • cylindrical MMC samples having 0.5 mm diameter and 100 mm length were prepared using a graphite mold with appropriate dimensions, by first filling the mold with tungsten carbide particles and placing pieces of the Cu-based feedstock alloy over the tungsten carbide particles. The mold was then placed in a furnace at a temperature of 1180 °C for a period of 1 hour to melt the Cu-based alloy and infiltrate the tungsten carbide particles with the liquefied Cu-based alloy, and subsequently solidifying the alloy to form the final MMC cylindrical samples as shown.
  • the cylindrical samples were then tested using a standard 3 point bend test to measure the transverse rupture strength.
  • the illustrated samples were fabricated using spherical tungsten carbide particles with a particle size distribution (PSD) defined by upper and lower size limit of 32-75 microns (corresponding to 200 mesh and 450 mesh and a D50 of 70 microns).
  • PSD particle size distribution
  • the prepared MMC cylindrical samples as shown in FIG. 14 were demonstrated to have a TRS of 175-250 ksi.
  • the MMC sample using a Cu53 alloy had a thermal conductivity of 13.96 W/mK and the drill bit sample using the disclosed alloy had a thermal conductivity of 16.77 W/mK.
  • the MMC sample using the disclosed copper alloy had an average TRS strength of 240 ksi, above that of the Cu53 alloy, 224 ksi.
  • the comparative experimental results are illustrated in Table 1.
  • Table 1 Transverse Rupture Strength (ksi) Comparison
  • FIG. 15 shows TRS testing results of MMCs having Cu-based matrix and tungsten carbide particles as described herein.
  • a cylindrical MMC sample with a copper- based matrix comprising 2.89% tin (Sn), 7.56% manganese (Mn), 4.88% nickel (Ni), and 84.67 wt. % of Cu (X17C MMC sample), as well as a reference MMC sample made from a Cu53 alloy were manufactured by a similar process as described above in FIG. 14.
  • TRS testing was performed on both the Cu53 MMC sample as well as the X17C MMC sample.
  • the UHS+X17C sample exhibited an increase in both strength and toughness relative to the Cu53 sample. Additional Examples I
  • a powder blend comprising fused tungsten carbide particles, wherein the fused tungsten carbide particles comprise: a spheroidal shape having ratio of a first length along a major axis to second length along a minor axis that is 1.20 or lower; and a surface that is textured to have a grain boundary area fraction greater than
  • Example 2 The powder blend of Example 1, further comprising metallic tungsten particles.
  • the needle-like topography comprises needle-like structures elongated along surfaces of the tungsten carbide particles, wherein at least some of the needle-like structures have a portion having a width not exceeding 1 mhi.
  • powder blend of any one of Examples 1-4 wherein the powder blend is configured to form a metal-matrix composite (MMC) including the fused tungsten carbide particles embedded in a matrix.
  • MMC metal-matrix composite
  • Example 6 The powder blend of Example 5, wherein the matrix comprises copper or a copper alloy.
  • MMC metal-matrix composite
  • a metal matrix composite (MMC) material comprising: fused tungsten carbide particles having a spheroidal shape and a surface that is textured to have a grain boundary area fraction greater than 5.0 %; and a matrix having embedded therein the fused tungsten carbide particles.
  • Example 14 The MMC material of Example 13, wherein at least some of the fused tungsten carbide particles have a ratio of a first length along a major axis to second length along minor axis length that is 1.20 or lower.
  • a method of forming a metal-matrix composite (MMC) material comprising: adding into a mold fused tungsten carbide particles having a spheroidal shape and a surface that is textured to have a grain boundary area fraction greater than 5.0
  • % adding a binder material comprising copper into the mold; melting the binder material to infiltrate the fused tungsten carbide particles; and solidifying the molten binder material to form the MMC material.
  • Example 29 The method of Example 28, wherein the fused tungsten carbide particles have the grain boundary area fraction of at least 10.0%.
  • a high strength drill bit comprising: a metal matrix composite comprising fused tungsten carbide particles within a matrix, wherein the fused tungsten carbide particles have a spheroidal shape and a surface that is textured to have a grain boundary area fraction of at least 5.0%.
  • Example 46 The drill bit of Example 45, wherein the fused tungsten carbide particles have a grain boundary area fraction of at least 10.0%.
  • An alloy comprising: manganese (Mn) at 5.6-10.4 weight percent (wt. %); nickel (Ni) at 3.5-6.5 wt. %; tin (Sn) at 1.4-4 wt. %; and copper (Cu) exceeding 55 wt. % and up to a balance of the alloy, wherein the alloy has a solidus temperature lower than a melting temperature of Cu.
  • Example 65 The alloy of Example 65, comprising 1.4-2.6 wt. % tin (Sn).
  • Example 67 The alloy of Example 66, wherein the solidus temperature is lower than 1300
  • Example s 66 or 67 wherein the alloy forms a single phase solid solution having a face-centered cubic (FCC) crystal structure from a solidus temperature down to at least 400 K below the solidus temperature,.
  • FCC face-centered cubic
  • a metal matrix composite material comprising reinforcement particles embedded in a copper-based matrix, wherein the copper-based matrix comprises greater than 55 wt. % copper (Cu) and greater than 1.4 wt. % tin (Sn).
  • Example 78 The metal matrix composite material of Example 78, wherein the copper- based matrix comprises:
  • Ni nickel
  • FCC face-centered cubic
  • the metal matrix composite material of any one of Examples 78-82, wherein greater than 90 wt.% of the copper-based matrix is a single-phase solid solution having a face-centered cubic (FCC) crystal structure at room temperature.
  • FCC face-centered cubic
  • Example 88 The metal matrix composite material of Example 78, wherein the reinforcement particles comprise tungsten carbide particles.
  • Example 89 The metal matrix composite material of Example 88, wherein tungsten carbide particles comprise 50-70 vol.% of the metal matrix composite material.
  • a method of forming a metal-matrix composite (MMC) material comprising: providing reinforcement particles and an alloy for forming a copper-based matrix in a mold, wherein the alloy has an elemental composition comprising:
  • Ni nickel
  • Example 95 The method of Example 95, wherein the alloy comprises 1.4-2.6 wt. % tin
  • melting the alloy comprises heating the mold to a temperature lower than melting temperatures of one or more of Cu, Mn and Ni..
  • Example 107 The method of Example 107, wherein 50-70 vol. % of the metal matrix composite material comprises tungsten carbide particles.
  • Conditional language such as “can,” “could,” “might,” or “may,” unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain embodiments include or do not include, certain features, elements, and/or steps. Thus, such conditional language is not generally intended to imply that features, elements, and/or steps are in any way required for one or more embodiments.
  • the above recited ranges can be specific ranges, and not within a particular % of the value. For example, within less than or equal to 10 wt./vol. % of, within less than or equal to 5 wt./vol. % of, within less than or equal to 1 wt./vol. % of, within less than or equal to 0.1 wt./vol. % of, and within less than or equal to 0.01 wt./vol. % of the stated amount.
  • FIG.s are drawn to scale, but such scale should not be limiting, since dimensions and proportions other than what are shown are contemplated and are within the scope of the disclosed inventions. Distances, angles, etc. are merely illustrative and do not necessarily bear an exact relationship to actual dimensions and layout of the devices illustrated. Components can be added, removed, and/or rearranged. Further, the disclosure herein of any particular feature, aspect, method, property, characteristic, quality, attribute, element, or the like in connection with various embodiments can be used in all other embodiments set forth herein. Additionally, it will be recognized that any methods described herein may be practiced using any device suitable for performing the recited steps.

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Abstract

The disclosure relates generally to copper-based alloys, and more particularly to copper-based alloys adapted for forming metal matrix composite (MMC) materials, and to methods of making the MMC materials. In one aspect, an alloy for forming a matrix of an MMC material has an elemental composition including: manganese (Mn) at 5.6-10.4 weight percent (wt. %); nickel (Ni) at 3.5-6.5 wt. %; tin (Sn) at 1.4-4 wt. %; and copper (Cu) exceeding 55 wt. % and up to a balance of the elemental composition. The alloy has a solidus temperature lower than a melting temperature of Cu.

Description

COPPER-BASED AUUOY AND METAU MATRIX COMPOSITE FORMED USING
SAME
CROSS-REFERENCE TO REUATED APPUICATION [0001] This application claims the benefit of priority to U.S. Provisional application number 63/169669, filed April 1, 2021, entitled “COPPER-BASED ALLOY AND METAL MATRIX COMPOSITE FORMED USING SAME,” the content of which is incorporated by reference herein in its entirety.
BACKGROUND
Field
[0002] The disclosure relates generally to tungsten carbide particles, and more particularly to textured spheroidal tungsten carbides, composites formed thereof, and methods of applying the composites.
Description of the Related Art
[0003] A metal matrix composite (MMC) refers to a composite material which includes particles that are embedded within a metallic matrix. A MMC generally includes a high-melting temperature metallic powder that is infiltrated with a single metal or more commonly an alloy having a lower melting temperature than the powder. MMCs have various applications, including mining equipment. The physical properties of MMCs can be engineered through component materials and manufacturing processes thereof.
SUMMARY
[0004] In one aspect, an alloy is described. In some aspects, an alloy includes: manganese (Mn) at 5.6-10.4 weight percent (wt. %); nickel (Ni) at 3.5-6.5 wt. %; tin (Sn) at 1.4-4 wt. %; and copper (Cu) exceeding 55 wt. % and up to a balance of the alloy, wherein the alloy has a solidus temperature lower than a melting temperature of Cu. In some embodiments, the alloy has a solidus temperature is lower than 1300 K.
[0005] In some embodiments, the alloy forms a single phase solid solution having a face-centered cubic (FCC) crystal structure from a solidus temperature down to at least 400 K below the solidus temperature. In some embodiments, greater than 90 wt.% of the alloy is a single phase solid solution with a face-centered cubic (FCC) crystal structure at room temperature. In some embodiments, the alloy further includes up to 2 wt. % of impurities. In some embodiments, the elemental composition does not include one or more of Si, B and Zn.
[0006] In some aspects, the techniques described herein relate to an alloy, wherein the alloy has an electrical conductivity higher than 2.5 MS/m. In some embodiments, the alloy has a thermal conductivity higher than 10 W/mK.
[0007] In some embodiments, the alloy forms a matrix of a metal matrix composite (MMC) material, wherein the MMC material further includes tungsten carbide particles. In some embodiments, the alloy forms a matrix of a metal matrix composite (MMC) material, wherein the MMC material forms part of a drilling component. In some embodiments, the alloy forms a matrix of a metal matrix composite (MMC) material, wherein the MMC material has a toughness greater than 4,000 in*lbf/in3
[0008] In some aspects, the techniques described herein relate to an alloy, wherein the alloy is part of a feedstock for forming a metal matrix composite (MMC) material, wherein the feedstock further includes tungsten carbide particles.
[0009] Another aspect describes a metal matrix composite material including reinforcement particles embedded in a copper-based matrix, wherein the copper-based matrix includes greater than 55 wt. % copper (Cu) and greater than 1.4 wt. % tin (Sn).
[0010] In some embodiments, the copper-based matrix includes: 1.4-2.6 wt. % tin (Sn); 5.6-10.4 wt. % manganese (Mn); and 3.5-6.5 wt. % nickel (Ni), wherein the copper- based matrix has a solidus temperature lower than Cu. In some embodiments, the solidus temperature of the copper-based matrix is lower than 1300 K.
[0011] In some embodiments, the copper-based matrix forms a single phase solid solution having a face-centered cubic (FCC) crystal structure from a solidus temperature down to at least 400K below the solidus temperature. In some embodiments, greater than 90 wt.% of the copper-based matrix is a single-phase solid solution having a face-centered cubic (FCC) crystal structure at room temperature. In some embodiments, the copper-based matrix includes 2 wt. % or less of impurities.
[0012] In some embodiments, the copper-based matrix does not include one or more of Si, B and Zn. In some embodiments, the copper-based matrix has an electrical conductivity higher than 2.5 MS/m. In some embodiments, the copper-based matrix has a thermal conductivity higher than 10 W/mK. In some embodiments, the reinforcement particles include tungsten carbide particles. In some embodiments, the tungsten carbide particles include 50-70 vol.% of the metal matrix composite material. In some embodiments, the tungsten carbide particles have an average particle size of 1-200 mhi.
[0013] In some embodiments, the tungsten carbide particles have a spheroidal shape having ratio, between a first length along a major axis and a second length along a minor axis, of 1.20 or lower. In some embodiments, the tungsten carbide particles have a surface that is textured to have a grain boundary area fraction greater than 5.0 %. In some embodiments, the metal matrix composite material has a transverse rupture strength exceeding 175 ksi. In some embodiments, the metal matrix composite material forms part of a drilling component.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 illustrates a scanning electron microscopy (SEM) image of a prior art metal powder with angular particles.
[0015] FIG. 2 illustrates an optical micrograph of a prior art metal matrix composite (MMC) prepared using angular particles.
[0016] FIG. 3 illustrates an optical micrograph of a MMC prepared using spheroidal or substantially spherical particles.
[0017] FIG. 4 illustrates an apparatus for producing an MMC.
[0018] FIG. 5 illustrates an embodiment of earth-engaging tool with a drill bit. [0019] FIG. 6 illustrates strength and reliability improvements of some MMC embodiments
[0020] FIG. 7 illustrates a scanning electron micrograph (SEM) of a conventional
MMC.
[0021] FIGS. 8-9 illustrate scanning electron micrographs of an MMCs according to embodiments.
[0022] FIG. 10 illustrates a binary image of FIG. 7.
[0023] FIG. 11 illustrates a binary image of FIG. 8.
[0024] FIG. 12 illustrates a binary image of FIG. 9. [0025] FIG. 13 illustrates an optical micrograph of a MMC comprising tungsten carbide particles embedded in a Cu-based matrix, according to embodiments.
[0026] FIG. 14 shows example samples prepared for testing MMCs having Cu- based matrix and tungsten carbide particles, according to embodiments.
[0027] FIG. 15. illustrates experimental results of strength testing of a MMC comprising tungsten carbide particles embedded in a Cu-based matrix, according to embodiments.
DETAILED DESCRIPTION
[0028] Disclosed herein are embodiments of spheroidal or substantially spherical fused tungsten carbide particles and metal matrix composites (MMCs) formed from tungsten carbide particles. The MMCs can include a matrix comprising copper and/or copper alloys, along with tungsten carbide particles. In some embodiments, the tungsten carbide particles and MMCs formed therefrom can have substantially improved properties over conventional angular fused tungsten carbide particles as well as MMCs formed therefrom. In particular, embodiments of the disclosure can be used to improve erosion resistance and impact resistance of resulting metal matrix composites.
[0029] Also disclosed herein are embodiments of a feedstock alloy for forming a copper-based matrix of a MMC with reinforcement particles. The copper-based matrix, and the MMC integrating the copper-based matrix may both be reinforced with particles. In some embodiments, the particles may be spherical tungsten carbide particles. In some embodiments, the copper-based matrix as well as MMCs formed therefrom can have substantially improved properties over conventional matrices or MMCs formed therefrom. In some embodiments, the thermal conductivity of MMCs and components incorporating the same may be improved.
[0030] Spheroidal or substantially spherical fused tungsten carbide particles can be made from commercially available fused tungsten carbide powder or a mixture of tungsten, mono tungsten carbide and/or carbon. In some embodiments, spheroidal or substantially spherical fused tungsten carbide particles can have a combined carbon composition from 3.7 to 4.2 (or about 3.7 to 4.2) wt. % carbon (C), with the balance of the composition being tungsten (W). The fused tungsten carbide particles can be produced by several methods. In some methods, a mixture of tungsten powder blended with mono tungsten carbide and carbon powder is melted. The molten mixture of tungsten powder, mono tungsten carbide and carbon powder is then atomized by a rotation atomizing process or an ultra-high temperature melting & atomizing process. A rotation atomizing process includes spinning or rotating the molten mixture such that centrifugal forces break the liquid and throw off molten metal as a spray of droplets. These droplets may then solidify as powder particles. Atomization processes generally spheroidize molten tungsten carbide into spheroidal or substantially spherical fused tungsten carbide particles during the rapid solidification process due to surface tension of the molten metal.
[0031] Other methods for the production of a spheroidal or substantially spherical fused tungsten carbide particles may be based on the modification of regular fused tungsten carbide powder. Plasma spraying, electric induction or electric resistance furnace melting may be used during the spheroidization process to obtain fine spheroidal or substantially spherical fused tungsten carbide particles.
[0032] Sphericity can be defined by an aspect ratio of the spheroidal or substantially spherical particles. The aspect ratio can be a ratio of a first length along a major axis to a second length along a minor axis of the particles, or a ratio of the longest axis length to the shortest axis length of the spheroidal or substantially spherical particles. For example, a perfect spherical particle would have an aspect ratio of exactly one. On the other hand, angular particles have an aspect ratio of at least 1.30.
[0033] In some embodiments, spherical or substantially spherical fused tungsten carbide particles can have an aspect ratio of < about 1.20, < about 1.10, about < 1.05, or a value within any range of these values. In some embodiments the aspect ratio can represent an average value of aspect ratios of a plurality of fused tungsten carbide particles. In some embodiments, each of the particles can have an aspect ratio within a range disclosed herein.
[0034] The specific density of the spherical or substantially spherical fused tungsten carbide powder can be around 16.5 g/cm3 with a micro-hardness as defined by a Vickers pyramid number (HV) ranging from 2,700-3,300 HV (or about 2,700 - about 3,300 HV) or any value there between. Without being limited by theory, the inventors have found that these high microhardness values might be attributed to, among other things, the particle shape and internal micro structure resulting from the spheroidization processes as described herein. In comparison, conventional mostly angular fused tungsten carbide particles exhibit a substantially inferior hardness of about 1,500-2,200 HV. The inventors have discovered that MMCs containing spheroidal or substantially spherical fused tungsten carbide particles are more wear resistant than those that contain a similar size and fraction of angular fused tungsten carbide particles.
[0035] FIG. 1 shows a scanning electron microscope (SEM) image of an angular metallic powder.
[0036] FIG. 2 illustrates an optical micrograph of a MMC prepared using metallographic techniques from an angular conventional fused tungsten carbide powder. The MMC includes a soft phase 202, a particulate phase 204 formed from a powder similar to that shown in FIG. 1, and a particulate-to-soft phase interface 206. The soft phase 202 can be formed by a matrix material that is first melted and subsequently cooled. Thus, the conventional MMC includes two principal phases. The soft phase 202 is formed through the liquid metal infiltration of the particulate phase 204.
[0037] The particulate phase 204 can include metal carbides, borides or oxides. For example, the particulate phase 204 can include tungsten carbides including: mono tungsten carbide, fused tungsten carbide or cemented tungsten carbide. Typically, the tungsten carbide particles are angular, as shown in FIG. 1. Between the soft phase 202 and the particulate phase 204 there is an interface 206. The inventors have discovered that all three phases 202, 204, and 206 can contribute to the strength and wear properties of the MMC.
[0038] FIG. 3 illustrates an optical micrograph of a metal matrix composite (MMC) 300 prepared using spheroidal or substantially spherical carbide particles. As shown, the MMC 300 includes spheroidal or substantially spherical fused tungsten carbide particles 302 and a soft phase 304, which are combined to form the metal matrix composite (MMC) 300. The MMC 300 additionally includes a spheroidal or substantially spherical fused tungsten carbide-to-soft phase interface 306.
[0039] The interface 306 includes metallic or metallurgical bonds formed between the tungsten carbide particles 302 and the soft phase 304. It should be appreciated that the metallurgical bonds disclosed herein may comprise diffused atoms and/or atomic interactions, and may include chemical bonds formed between atoms of the particles 302 and the atoms of the soft phase 304. A metallurgical bond is more than a mere mechanical bond. Under such conditions, the component parts may be wetted to and by the metallic binding material. Wetting is the ability of a liquid to maintain contact with a solid surface resulting from intermolecular interactions when the liquid and the solid surface are brought together.
[0040] Before being incorporated into the MMC, a powder mixture including the spheroidal or substantially spherical tungsten carbide particles is formed. The MMC formed from the spheroidal or substantially spherical may be called spherical MMCs, whereas the conventional MMCs formed from angular powders may be called angular MMCs.
[0041] In some embodiments, a liquid metal infiltration route can be used to form MMC. Liquid metal infiltration is a process in which a compacted powder material is immersed inside a liquid metal (e.g., a binding material) or contacts the liquid metal (e.g., the binding material). The liquid metal fills the pores in the compacted powder material, a process that is driven by surface energy of the compacted powder material. For example, a metallic binding material may, be any suitable brazing metal, including: copper, chromium, tin, silver, cobalt nickel, cadmium, manganese, zinc and/or cobalt or an alloy thereof. The metallic binding material can be liquid cast through tungsten carbide powder and solidified to form a MMC.
[0042] Specifically, liquid metal infiltration of a powder containing the components is described with reference to FIG. 4. A graphite mold assembly 412, 414 is produced that reflects a negative of the desired shape of a drill bit 500. A powder 408 comprising the spheroidal or substantially spherical particles is poured and compacted in the mold assembly 412, 414. Subsequently, a binder 406, e.g., copper or copper alloy, and steel parts 404 may be added. Configured mold assembly 412, 414 is heated to melt at least the binder 406. Within the mold 412, 414 is a sand component 402 which defines regions within the resulting casting that is free from MMC. Upon melting, the binder 406 infiltrates the powder 408 and creates bonds to the steel parts 404. Upon cooling, the solidified structure contains a plurality of composites advantageously located for strength and wear considerations.
[0043] In some embodiments, the binder may be copper. In some embodiments, the binder may be a copper-based alloy. In some embodiments, a quaternary material system may be used as the binder 406. In some embodiments, the binding material can be a quatemary system comprising copper (47 - 58 wt.% or about 47 - about 58), manganese (23 - 25 wt.% or about 23 - about 25 wt.%), nickel (14 - 16 wt.% or about 14 - about 16 wt.%) and zinc (7 - 9 wt.% or about 7 - about 9 wt.%).
Drill Bits
[0044] The inventors have discovered that the tungsten carbide particles and MMCs formed therefrom according to some embodiments of the disclosure can be particularly useful for applying in mining equipment, such as drills. However, it should be understood that embodiments are not so limited, and the tungsten carbide particles and MMCs formed therefrom can be used in a variety of other applications in which abrasion resistant materials are employed.
[0045] Earth-engaging drill bits are used extensively in industries including the mining, oil and gas industries for exploration and retrieval of minerals and hydrocarbon resources. Examples of earth-engaging drill bits include polycrystalline diamond compact (PDC) bits.
[0046] A drill bit wears when it mbs against a formation of metal or rocks in the ground or against a metal casing tube. This wear may lead to the loss of function and failure of the drill bit. During drilling, a cooling and lubricating drilling fluid is circulated through the drill bit using high hydraulic energies. The drilling fluid may contain abrasive particles, for example sand, which when impelled by the high hydraulic energies can exacerbate wear at the face of the drill bit and elsewhere.
[0047] Drill bits may have a body comprising at least one of hardened and tempered steel, and a metal matrix composite (MMC). A steel drill bit body may have increased ductility and may be more easily manufactured. A steel drill bit body may be manufactured using casting and wrought manufacturing techniques, examples of which include but are not limited to forging or rolled bar techniques. The steel properties after heat treatment are consistent and repeatable. Fracture of steel-bodied drill bits is infrequent; however, a worn steel drill bit body may be difficult for an operator to repair.
[0048] A MMC drill bit body may wear more slowly than a steel drill bit body. Conventional MMC drill bit bodies, however, more frequently fracture during casting and/or processing and/or use from thermal and mechanical shock. Fracturing may cause an drill bit to be removed from service early due to cosmetic or structural defects within the bit. Alternatively, conventional MMC drill bit bodies may fail catastrophically with the loss of part of the cutting structure, which may result in sub-optimal drilling performance and early retrieval of the drill bit.
[0049] In many cases, it is a wing or blade of a drill bit that fractures. Wing or blade failures are economically damaging for drill bit manufacturers. The retrieval of a worn or failed drill bit from a drilled hole, for example a well or borehole, is undesirable. The non-productive time required to retrieve and introduce into the drilled hole a replacement drill bit may cost millions of dollars. Drill bits and other earth-engaging tools with increased wear resistance and lower rates of failure may save considerable time and money. Therefore, developing an ultra-high- strength MMC for drill bits is desirable to reduce or prevent fracture during drilling.
[0050] The strength of a sample of an MMC may be determined using a transverse rupture strength (TRS) test. In a TRS test, a load is centrally applied to the cubic or cylindrically shaped MMC sample that is supported between two points. The rupture strength is the maximum weight that the MMC can support. A plurality of samples may be tested to derive a mean strength and a standard deviation which may be used to describe the MMC. The reliability analysis of the TRS of an MMC can provide additional information such as the failure possibilities under different stresses.
[0051] While MMC drill bits can generally perform better in erosion than steel bits, they still may encounter rapid deceleration of particles in hydraulic fluids, resulting in the erosive removal of material. During drilling, high-velocity drilling-mud exits nozzles to cool the bit and evacuate detritus. Drilling mud contains materials such as bentonite, clay and surfactants, which also contain hard and angular minerals from the rock material. The contact between the PDC bits and drilling mud may erode portions of the drill bits. The MMC disclosed herein has high erosion resistance accompanied with ultrahigh strength to improve the reliability and performance of the drill bits during drilling.
[0052] FIG. 5 shows a perspective view of an embodiment of earth-engaging tool in the form of a drill bit 500 which comprises a bit body 502 comprising an MMC FIG.300. Some, or all, of the bit body 502 may be formed from embodiments of the MMC 300. In some embodiments, a majority of the bit body 502 is formed from embodiments of the MMC 300. Further, the tool can include a nozzle port 516, e.g., for hydraulic fluid, a face 510 that supports cutting element 508, such as polycrystalline diamond compact (PDC) cutters, and junk slots 506 for carrying cuttings away in a fluid from a face of the drill bit 500.
[0053] It should be appreciated, however, that other embodiments of a tool may have some or none of the described structural features, or may have other structural features. The bit body 502 can have protrusions in the form of radially projecting and longitudinally extending wings or blades 504, which are separated by channels at the face 510 of the drill bit 500 and junk slots 506 at the sides of the drill bit 500. A plurality of cemented tungsten carbide or PDC cutting elements 508 can be brazed within pockets on the leading faces of the blades 504 extending over the face 510 of the bit body 502. The PDC cutting elements 508 may be supported from behind by buttresses 512, for example, which may be integrally formed with the bit body 502.
[0054] The drill bit 500 may further include a shank 514 in the form of an American Petroleum Institute (API) threaded connection portion for attaching the drill bit 500 to a drill string (not shown). Furthermore, a longitudinal bore (not shown) can extend longitudinally through at least a portion of the bit body 502, and internal fluid passageways (not shown) may provide fluid communication between the longitudinal bore and nozzles 516 provided at the face 510 of the bit body 512 and opening onto the channels leading to junk slots 506 for removing the drilling fluid and formation cuttings from the drill face.
[0055] During formation cutting, the drill bit 500 is positioned at the bottom of a hole and rotated while weight-on-bit is applied. A drilling fluid - for example a drilling mud delivered by the drill string to which the drill bit 500 is attached - is pumped through the bore, the internal fluid passageways, and the nozzles 516 to the face 510 of the bit body 502 and PDC cutting elements 508. As the drill bit 508 is rotated, the PDC cutting elements 508 scrape across, and shear away, the underlying earth formation. The formation cuttings mix with, and are suspended within, the drilling fluid and pass through the junk slots 506 and up through an annular space between the wall of the hole (in the form of a well or borehole, for example), and the outer surface of the drill string to the surface of the earth formation.
Physical Properties [0056] The strength of a sample of a MMC may be determined using a TRS test, but using averaging and using other statistical methods to analyze the TRS results may also be important. If the values are not thoroughly analyzed, the TRS data may not:
1. indicate the likelihood of failure;
2. access the probability of failure at a given stress value; and/or
3. allow measurement of changes or improvements to powder compositions and the MMCs made with the powders, in particular the relationship between stress and reliability.
[0057] The strength distribution in a population of samples of the MMC used in earth-engaging and other tools may be determined using Weibull statistics, which is a probabilistic approach that enables a calculation of the likelihood of failure to be established at a given applied stress. Embodiments of the disclosed MMCs may be used with an earth- engaging tool, e.g., a drill bit 500, for example, which generally follow a Weibull distribution.
[0058] A Weibull strength distribution is described by the function:
Figure imgf000013_0001
[0059] The variables in the equation are: F , which is the probability of failure for a sample; s, which is the applied stress; iFu, which is the lower limit stress needed to cause failure, which is often assumed to be zero; s0, which is the characteristic strength; m, which is the Weibull modulus, a measure of the variability of the strength of the material; and V, which is the volume of specimen.
[0060] The above equation is typically rearranged and presented on a double logarithmic plot of (1/(1- F )) versus logarithm of s and the slope used to calculate m, assuming s, is zero.
[0061] FIG. 6 illustrates a Weibull plot of empirical strength data for a plurality of samples of the same type of angular MMC 602 similar to those shown in FIG. 2, containing predominately angular particles and an MMC containing predominately spheroidal or substantially spherical particles 604 similar to those shown in FIG. 3. The MMCs illustrated in FIG. 6 are composed of textured spheroidal or substantially spherical tungsten carbide and a Cu53 copper binder, a known copper alloy. The y-axis values on the left most y-axis are indicative of a function of the probability of failure, the y-axis values on the right most y-axis are indicative of a percentage probability of failure. The x-axis values are indicative of a function of the applied stress at the time of failure during a TRS test. The empirical strength data for the samples of angular MMC 602 and the sample of spherical MMC 604 follow a Weibull distribution. The slope of each line defines the respective Weibull moduli. The angular MMC 602 has a Weibull modulus of 13.76 and the spherical MMC 604 has a Weibull modulus of 27.94. The Weibull modulus is one measure of material strength variability. For example, for a Weibull modulus of 4, there will be a 30% variation (one standard variation) in strength.
[0062] In some embodiments, the spherical MMC 604 has a Weibull modulus of > 15 (or about 15), > 20 (or about 20), > 25 (or about 25) or greater, or a value in range defined by any of these values.
[0063] A Weibull plot can be used to design drill bit body blade heights and widths to a predetermined failure rate, and particularly help determine how thin and tall the drill bit body blades can be for the predetermined failure rate. A taller and thinner blade may remove a formation faster than a shorter wider blade. However, a taller and thinner blade may have an unacceptable probability of failure. Alternatively, the reliability of a drill bit comprising angular MMC 604 can be compared the reliability of another identically configured drill bit comprising spherical MMC 602.
[0064] Linear extrapolation to a 1 in 10,000 probability of failure equates to applied stress of about 60 ksi (kilopound per square inch) for an angular MMC 602 and 188 ksi for aspherical MMC 604. In some embodiments, the linear extrapolation to a 1 in 10,000 probability of failure for the spherical MMC 604 equates to 80 (or about 80) ksi or greater, 100 (or about 100) ksi or greater, 120 (or about 120) ksi or greater, 140 (or about 140) ksi or greater, 160 (or about 160) ksi or greater, 180 (or about 180) ksi or greater, or a value in a range defined by any of these values.
Micro structure
[0065] The inventors have discovered that the novel spheroidal or substantially spherical fused tungsten carbide has a textured surface. The inventors have further discovered that this texture can increase the available surface area at the interface 306 between the soft phase 304 and the spheroidal or substantially spherical fused tungsten carbide particles 302, as shown in FIG. 3.
[0066] The strength of an MMC system can be associated with one or more of three different components: the strength of the copper binder, the strength of the tungsten carbide particles, and/or the binding strength between the copper binder and the incorporated tungsten carbide particles. Thus, if the tungsten carbide particles and copper do not bond well, a failure can occur when the MMC undergoes high stress. By having carbide particles with larger surface areas, the alloy has more area to bond to the carbide particles, thus increasing the interfacial strength.
[0067] FIG. 7 illustrates the surface morphology of a tungsten particle in a conventional MMC. As shown, the micro structure has soccer-ball-like topographical features of conventional fused tungsten carbide particles. The surface is relatively smooth, resulting in a low surface area and relatively low interfacial strength when incorporated within a MMC.
[0068] FIG. 8 illustrates the surface morphology of a spheroidal or substantially spherical tungsten particle in an MMC. The microstructure includes needle-like topographical features (e.g., texturing) of spheroidal or substantially spherical fused tungsten carbide. The surface is mostly textured with a fine-grained structure, resulting in a high surface area and better interfacial strength when incorporated within a MMC.
[0069] FIG. 9 illustrates the surface morphology of a spheroidal or substantially spherical tungsten particle in an MMC. The microstmcture includes dense needle-like like topographical features of spheroidal or substantially spherical fused tungsten carbide. The surface is mostly textured with a finer grained structure resulting in an even higher surface area and exceptional interfacial strength when incorporated within a MMC.
[0070] To quantify the spheroidal or substantially spherical fused tungsten carbide particles by their surface features, the fraction of a surface area in a fixed view field of an optical or scanning electron microscope (SEM) image that can be attributed to grain boundaries is analyzed. An area fraction of grain boundaries refers to the area in an image, e.g., an optical or SEM image, of a surface of a sample, e.g., the surface of a tungsten carbide particle, that can be attributed to grain boundaries. The area fraction of grain boundaries can be quantified using images, e.g., high contrast or binary images such as those shown in FIG.s 10-12. For example, the number of dark pixels as a fraction of a total number of pixels within an imaged field can correspond the area fraction of grain boundaries. The inventors have discovered that the conventional soccer-ball-like surface morphology of tungsten carbide particles leads to a relatively low area fraction of grain boundaries on the surface of the tungsten carbide particles, e.g., less than 5%. The needle-like surface morphology of tungsten carbide particles of spheroidal MMCs leads to a relatively high area fraction of grain boundary on the surface of the tungsten carbide particles, e.g., over 10% (or about 10%). For example, the area fraction of the grain boundary in FIG. 10, which is a binary image of the MMC of FIG. 7, which illustrates a conventional MMC, is 3.6%. In contrast, the area fraction of the grain boundary in FIG. 11, which is a binary image of the MMC of FIG. 8, which illustrates a MMC made from spheroidal or substantially spherical tungsten carbides, is 14.2%. FIG. 12, a binary image of FIG. 9, illustrates a MMC made from spheroidal or substantially spherical tungsten carbides in which the area fraction of grain boundaries is 20.1%. A high area fraction of grain boundaries may lead to more uniform and finer grains overall.
[0071] The inventors have discovered that the combination of the spheroidal shape of the tungsten carbide particles, and the needle-like surface morphology of the formed MMC, may give rise to a relatively high surface area of the tungsten carbide particles, which in turn gives rise to the relatively high grain boundary area fraction. The high gran boundary area fraction can be proportional to the amount of high strength interfaces formed between the tungsten carbide particles and the metal matrix. High amounts of high strength interfaces can lead to improved mechanical and tribological properties of MMCs, including high TRS values and increased erosion resistance.
[0072] The needle-like topography comprises needle-like structures that are elongated along surfaces of the tungsten carbide particles. The needle-like structures have at least a portion length portion having a length exceeding, e.g., 0.5, 1, 2, 3, 4, 5 mhi, or a value in a range defined by any of these values, while having a width that is less than 2, 1, 0.5, 0.2, 0.1 mhi, or a value in a range defined by any of these values. The needle-like structures may have a ratio of the longest length to the smallest width of the needle like structures that exceeds 2, 5, 10, 20 or a value in a range defined by any of these values. [0073] In some embodiments of this disclosure, the spheroidal or substantially spherical fused tungsten carbide particles have a grain boundary area fraction of 5.0% (or about 5.0%) or greater. 10.0% (or about 10.0%) or greater, 12.0% (or about 12.0%) or greater, 12.0% (or about 12.0%) or greater, 20.0% (or about 20.0%), or a value in a range defined by any of these values.
[0074] Homogeneity of the grain boundary distribution in the particle surface was also characterized. Each micro structural image of FIGS. 10-12 were separated into nine equal parts. The grain boundary area fraction in each separated part was measured individually. Then the variation of the grain boundary area fraction for the nine equal parts was calculated. The lower the value of variance, the more uniform the distribution of the grain boundaries. This lower variation can provide for improved strength of the MMC. For example, the variation in FIG. 10 was measured to be 3.8%, which is lower than the value measured in FIG. 11, which was 9.4%, indicating a more uniform distribution of grain boundaries in FIG. 11 relative to FIG. 10.
[0075] FIG. 10 illustrates a binary image of FIG. 7. FIG. 11 shows a binary image of FIG. 8, which includes an analyzed area fraction of 14.2% and variation of 9.4% when divided into nine parts. FIG. 12 shows a binary image of FIG. 9, which includes an analyzed area fraction of 20.1% and variation of 3.8% when divided into nine parts.
Physical Properties
[0076] In some embodiments, the size of the spheroidal or substantially spherical fused tungsten particle may between 1 to 200 pm. The variation of the size of the spheroidal or substantially spherical fused tungsten particle can result in the change in TRS of the final infiltrated MMC.
[0077] Powder particle size distribution is measured and determined by MicroTrac per ASTM B822, hereby incorporated by reference in its entirety. The powder particle size distribution is defined by describing values, namely:
- D10 or 10th percentile particle diameter (pm)
- D50 or average particle diameter (pm)
- D90 or 90th percentile particle diameter (pm) [0078] The inventors have discovered that the D50 of tungsten carbide particles can be tuned to achieve a target TRS value. In some embodiments, an MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 1 pm and 10 pm, has a TRS greater than or equal to 360 ksi (or about 360 ksi, greater than or equal to 530 ksi (or about 530 ksi), greater than or equal to 700 ksi (or about 700 ksi), or a value in a range defined by any of these values.
[0079] In some embodiments, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 11 pm and 20 pm, has a TRS greater than or equal to 280 ksi (or about 280 ksi), greater than or equal to 365 ksi (or about 365 ksi), greater than or equal to 450 ksi (or about 450 ksi), or value in a range defined by any of these values.
[0080] In some embodiments, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 21 pm and 40 pm, has a TRS greater than or equal to 230 ksi (or about 230 ksi), greater than or equal to 260 ksi (or about ksi), greater than or equal to 290 ksi (or about 290 ksi), or a value in a range defined by any of these values.
[0081] In one embodiment, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 41 pm and 60 pm, has a TRS greater than or equal to 180 ksi, greater than or equal to 200 ksi, greater than or equal to 220 ksi, or a value in a range defined by any of these values.
[0082] In some embodiments, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 61 pm and 80 pm, has a TRS greater than or equal to 160 ksi (or about 160 ksi), greater than or equal to 170 ksi (or about 170 ksi), greater than or equal to 180 ksi (or 180 ksi), or a value in a range defined by any of these values.
[0083] In some embodiments, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 81 pm and 100 pm, has a TRS greater than or equal to 140 ksi (or about 140 ksi), greater than or equal to 150 ksi (or about 150 ksi), greater than or equal to 160 ksi (or about 160 ksi), or a value in a range defined by any of these values. [0084] In some embodiments, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 101 pm and 200 pm, has a TRS greater than or equal to 100 ksi (or about 100 ksi), greater than or equal to 120 ksi (or about 120 ksi), greater than or equal to 140 ksi (or about 140 ksi), or a value in a range defined by any of these values.
[0085] Laboratory testing enabled the abrasion and erosion resistance of angular and spherical MMCs to be measured and compared to one another.
[0086] An erosion test simulating real drilling condition was carried out by using a modified high-pressure abrasive waterjet cutting machine. A special sample holder adjustable between 0° and 90° relative to the waterjet was designed to allow the adjustment of the impacting angle between the sample surface and slurry jet produced by the waterjet cutting machine. The distance between the nozzle and the sample was selected as 1,000 mm in order to avoid cutting the sample and to enlarge the contact area between the jet and sample. Garnet was used as the erodent. The pressure of the waterjet was 50 ksi and the test duration was 10 min. A balance with an accuracy of 1 mg was used to measure the weight of the coupon before and after the test.
[0087] An MMC sample produced from spherical fused tungsten carbide particles and made by liquid infiltration was tested for erosion at a 30° impact angle with volume loss of 0.022 cm3. A reference MMC made from angular fused tungsten carbide particles was tested under the same conditions and experienced a volume loss of 0.17 cm3.
[0088] In some embodiments, the spherical MMC has an erosive volume loss of 0.10 (or about 0.10) cm3 or less , 0.08 (or about 0.08) cm3 or less, 0.06 (or about 0.06) cm3 or less, 0.04 (or about 0.04) cm3 or less, or a value in a range defined by any of these values.
[0089] A standard ASTM 611 high stress abrasion test, hereby incorporated by reference in its entirety, was performed on an MMC produced from spherical fused tungsten carbide particles and a reference MMC made from angular fused tungsten carbide particles An MMC produced from spherical fused tungsten carbide particles under the testing conditions had volume loss of 0.51 cm3 while a reference MMC made from angular fused tungsten carbide particles had a volume loss of 1.28 cm3 under the same testing conditions. [0090] In some embodiments of this disclosure, the spherical MMC has an ASTM 611 volume loss of 1.00 (or about 1.00) cm3 or lower, 0.80 (or about 0.80) cm3 or lower, 0.60 (or about 0.60) cm3 or lower, or a value in a range defined by any of these values.
High Thermal Conductivity and Low Melting Temperature Feedstock Alloy, Metal Matrix Formed from the Feedstock Alloy, and MMC formed using the Feedstock Alloy
[0091] As described above, metal matrix composite materials (MMCs) include reinforcement particles embedded in a matrix. The physical properties of the reinforcement particles and the matrix can synergistically complement each other to form a metal matrix composite material that has a unique set of properties that are difficult to achieve with a single material. For example, as described above, an MMC that includes tungsten carbide particles embedded in a Cu-based matrix can provide a combination of high strength and high hardness, which can be difficult to achieve simultaneously in a single material.
[0092] As described above, one technology area that can benefit from MMCs is drilling technology, e.g., earth drilling technology for extracting hydrocarbon fuel. Components used in drilling, e.g., drill bits, should exhibit superior strength, hardness and wear resistance. In addition, the combination of these properties can be demanded under relatively harsh conditions for some applications. The harsh conditions may include high temperature, which can result from friction caused by operation of the drill bits. The performance levels of some MMCs, which may be sufficient at moderate temperatures, may degrade to unacceptable performance levels at elevated temperatures. Thus, there is a need for MMCs that combine the various advantageous mechanical properties of MMCs based on tungsten carbide particles embedded in a Cu-based matrix, while also being designed to maintain the advantageous properties under heat-generating conditions by efficiently dissipating heat.
[0093] Accordingly, MMC made from spheroidal or substantially spherical fused tungsten carbide particles increase the thermal shock resistance of components fabricated therefrom. In some embodiments, an alloy, e.g., a feedstock alloy, configured to form a matrix of an MMC having high thermal conductivity, for various applications including drilling is produced. The MMCs formed using the feedstock alloy can maintain various advantageous performance criteria as described above, in in addition to significantly improving the thermal shock resistance of the MMCs. The reduction of thermal shock can in turn reduce fracture failures. For drilling applications, reduction of the tendency of the drill bit body to fracture during operation can significantly improve productivity and reduce cost associated with replacement or repair thereof.
[0094] It should be appreciated that, in addition to having high thermal conductivity, to serve as a synergistic matrix of an MMC, the feedstock alloy for forming the matrix should be compatible with and integrate well with the reinforcement particles. This is in part because, as described above, one of the processes for fabricating MMCs involves infiltration of the network of pores formed by the reinforcement particles. To serve as an effective infiltrant, the alloy for forming the matrix can have a melting temperature below that of the reinforcement particles. The alloy, when melted, should have a high fluidity to provide the surface tension and capillary force for facilitating the infiltration process. In a liquid state, the alloy should form a low contact angle with the surfaces of the reinforcement particles. Furthermore, any chemical reaction between the alloy and the reinforcement particles should be kept to a relatively low level, as such reactions can impede the infiltration process by altering the composition of the matrix relative to the feedstock alloy, as well as detrimentally affecting the performance of the resulting MMC.
[0095] To address these and other needs, a feedstock alloy for forming a matrix of an MMC includes an elemental composition including copper (Cu) as a majority element. Some reinforcement particles, such as some tungsten carbide particles, have relatively low thermal conductivity, and the thermal conductivity of the MMC may be limited by that of a matrix having a relatively high thermal conductivity. Furthermore, in the context of drill bits, as tungsten carbide content is increased the thermal conductivity of the MMC can drop proportionally due to a corresponding reduction in the volume fraction of the matrix. The reduction in thermal conductivity of the MMC with increasing reinforcement particle content can be offset by incorporating a relatively high copper content. However, some tungsten carbide particles can have a higher thermal conductivity than the MMC. Regardless, unlike some relatively isolated reinforcement particles, because the matrix can form an interconnected network through which heat can transfer, and/or because the matrix constitutes a substantial thermal mass faction of the resulting MMC, higher thermal conductivity of the matrix is nevertheless desirable. [0096] According to various embodiments, a feedstock alloy for forming a matrix of an MMC includes an elemental composition including a copper (Cu) concentration exceeding 55, 60, 65, 70, 75, 80, 85 weight percent (wt. %), or a value in a range defined by any of these values. The high Cu content can provide improved thermal conductivity, among other advantages.
[0097] While elemental copper may offer one of the highest thermal conductivities, it may not offer one or more other desirable characteristics associated with the fabrication of the MMC or the resulting mechanical properties thereof. To improve various mechanical properties of the matrix including strength, hardness and abrasion resistance of the matrix of the MMC, which in turn improves the corresponding mechanical properties of the resulting MMC, as well as improving infiltration characteristics described above for forming the matrix in liquid state, the inventors have discovered a combination of alloying elements for alloying with Cu to form a feedstock alloy for forming the matrix. According to various embodiments, in addition to the relatively high Cu content described above, the elemental composition of the feedstock alloy for forming the matrix includes: tin (Sn) at a concentration exceeding 1.4 wt. %, nickel (Ni) at a concentration exceeding 3.5 wt. %, and manganese (Mn) at a concentration exceeding 5.6 wt. %. To maintain the high Cu content described above, the combined concentration of Sn, Ni and Mn is less than 20 wt.%, 30 wt. %, 40 wt. %, 45 wt. % or a value in a range defined by any of these values, according to embodiments.
[0098] In some embodiments, an elemental composition of a feedstock alloy for forming a matrix of an MMC includes Sn at a concentration exceeding 1.4, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0 wt. %, or a concentration within a range defined by any of these values. In some embodiments, the elemental composition may include Sn at 1.4-4 wt. %, 1.7-2.3 wt. %, or about 2.0 wt. %. In some embodiments, the elemental composition of the feedstock alloy additionally includes Mn at a concentration exceeding 5.6, 6.4, 6.8, 7.2, 7,6, 8.0, 8.4, 8.8, 9.2, 9.6, 10.4 wt. %, or a concentration within a range defined by any of these values. In some embodiments, the elemental composition includes Mn at 5.6-10.4 wt. %, 6.8-9.2 wt. %, or about 8.0 wt. %. In some embodiments, the composition of the feedstock alloy additionally includes Ni at a concentration exceeding 3.5, 4.0, 4.3, 4.5, 4.7, 5.0, 5.3, 5.5, 5.8, 6.0, 6.5 wt. %, or a concentration in a range defined by any of these values. In some embodiments, the elemental composition includes Ni at 3.5-6.5 wt. %, 4.3-5.8 wt. %, or about 5.0 wt. %.
[0099] In some embodiments, the elemental composition of the feedstock alloy may include additional elements, which may include incidental impurities, at a combined concentration less than 10 wt. %, 5 wt. %, 2 wt. %, 1 wt. % or a value in a range defined by any of these values. In some embodiments, Cu may be present as a balance of the elemental composition, in addition to the additional or impurity elements.
[0100] Advantageously, the relatively high Cu concentration of the feedstock can provide high thermal and/or electrical conductivity. It will be appreciated that the high thermal conductivity can be indirectly measured by measuring the electrical conductivity of the allow. In some embodiments, the feedstock has an electrical conductivity greater than 2.0 mega Siemens (MS)/meter (m), 2.5 MS/m, 3.0 MS/m, 3.5 MS/m, or a value in a range defined by any of these values. Without being bound to any theory, the feedstock can have thermal conductivity that can have a value related to the electrical conductivity through, e.g., Wiedemann-Franz’s law. Wiedemann-Franz’s law states that the ratio of the electronic contribution of the thermal conductivity to the electrical conductivity is proportional to the temperature. According to embodiments, the feedstock can have thermal conductivity greater than 10 W/mK, 11 W/mK, 12 W/mK, 13 W/mK, 14 W/mK, 15 W/mK, 16 W/mK or a value in a range defined by any of these values.
[0101] When present in the disclosed amounts, the combination of Cu, Sn, Mn and Ni forms a feedstock alloy that can provide various advantages over relatively pure elemental Cu as a source of the matrix of an MMC. The advantages may include in one or more of: lower melting temperature, lower contact angle with tungsten carbide and/or lower reactivity with tungsten carbide. The combination of elements can additionally provide advantages over relatively pure elemental Cu as source of the matrix of an MMC including one or more of: higher strength, higher abrasion resistance and/or higher hardness.
[0102] In some embodiments, the combination of the elements in the feedstock alloy can provide further advantages over elemental Cu when the elemental composition of the feedstock does not include one or more of Si, B and/or Zn, or when present, Si, B and/or Zn is present at a combined concentration less than 10 wt. %, 5 wt. %, 2 wt. %, 1 wt. % or a value in a range defined by any of these values. [0103] In various embodiments, the feedstock alloy for forming a matrix of an MMC is a pre-formed alloy that is solidified from a liquid having the alloy composition, e.g., by melting the constituent elements at a temperature sufficient to melt each of the constituent elements. Having the feedstock in the form of a preformed alloy, as opposed to a mixture of elemental powder, can provide various advantages can lower the melting temperature of the feedstock alloy, such that the MMC can be effectively formed at lower temperatures. The lower feedstock melting temperature can make different chemical compositions of feedstocks compatible with existing methods for manufacturing MMCs, including those described above. Due to the temperature constraints of some existing manufacturing methods, a feedstock for forming the matrix of an MMC that has a melting temperature exceeding 1300K may be difficult to fully melt to infiltrate the reinforcement particles for manufacturing into a matrix of an MMC. Thus, based on the melting temperatures of Cu, Mn and Ni, which are 1083 °C (1356 K), 1244 °C (1517 K), 1453 °C (1726 K), respectively, the inventors have found it advantageous for the feedstock including these elements to be in an alloy form that has a melting temperature lower than each of these individual elements. Thus, according to embodiments, the feedstock in the form of an alloy has a composition such that the alloy has a solidus temperature lower than a melting temperature of substantially pure Cu. In some embodiments, the solidus temperature of the alloy is lower than 1300 K, 1275K, 1250K, 1225K, 1200K, or a solidus temperature in a range defined by any of these values.
[0104] In some embodiments, the feedstock alloy can be present as, or liquefied and solidified into, a single phase solid solution. An alloy or matrix in the form of a single phase solid solution can provide advantages in various mechanical and thermal properties over a multi-phase alloy. Without being bound to any theory, when present as a single phase solid solution, thermal conductivity can be enhanced due to, e.g., the suppression of phonon scattering that can occur at phase boundaries. The absence of phase boundaries can also enhance the strength of the alloy by reducing boundary-originating defects such as dislocations.
[0105] The inventors have found that one measure of the availability of an alloy as a single phase solid solution is a temperature range below the solidus temperature within which the alloy is present, or predicted to be present under thermodynamic equilibrium conditions, as a single phase solid solution. Such temperature range may be referred to as a single phase temperature range. In some embodiments, the elemental composition of the alloy comprising Cu, Sn, Mn and Ni as disclosed herein has a single phase temperature range greater than 400K such that, from the solidus temperature down to at least 400K below the solidus temperature, the alloy forms a single phase solid solution having a face-centered cubic (FCC) crystal structure. In some embodiments, the single phase temperature range of the feedstock alloy below the solidus temperature within which the alloy is present may exceed 375K, 400K, 425K, 450K, 475K or a value in a range defined by any of these temperatures.
[0106] The FCC crystal structure may correspond to a base crystal structure of Cu in which Sn, Mn and Ni can be present as substitutional and/or interstitial elements. When the feedstock alloy has a relatively wide single phase temperature range as described herein, the feedstock alloy can be formed into a matrix that is substantially present as a single phase alloy at room temperature. In some embodiments, , at room temperature, greater than 80 wt. %, 85 wt. %, 90 wt. %, 95 wt. % or a value in range defined by any of these values, of the alloy and the resulting matrix is present a single phase solid solution having a face-centered cubic (FCC) crystal structure.
[0107] The feedstock alloy as described herein can be used to form a metal matrix composite (MMC) material comprising reinforcement particles embedded in a copper-based matrix. A formed copper-based matrix can have any and/or all of the physical and chemical characteristics of the feedstock alloy used to form the matrix as described, including the elemental composition. In some embodiments, the chemical composition of feedstock alloy and a matrix of a MMC material formed therefrom can be substantially the same. For example, in some embodiments, the matrix of an MMC has an elemental composition including copper (Cu) exceeding 55 weight percent (wt. %) and tin (Sn) exceeding 1.4 wt. %. Similar to the feedstock alloy, the elemental composition of the matrix includes Sn at a concentration exceeding 1.4, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0 wt. %, or having a concentration within a range defined by any of these values; Mn at a concentration exceeding 5.6, 6.4, 6.8, 7.2, 7,6, 8.0, 8.4, 8.8, 9.2, 9.6, 10.4 wt. %, or a concentration within a range defined by any of these values; and Ni at a concentration exceeding 3.5, 4.0, 4.3, 4.5, 4.7, 5.0, 5.3, 5.5, 5.8, 6.0, 6.5 wt. %, or a concentration in a range defined by any of these values.
[0108] Similarly, the matrix of the MMC can have any and/or all of the physical and chemical characteristics of the feedstock alloy, including the solidus temperature, the single phase temperature range, electrical conductivity and thermal conductivity as described above, overlapping details of which are omitted here for brevity.
[0109] According to various embodiments, the reinforcement particles can include tungsten carbide particles. The tungsten carbide particles can have any and/or all of the characteristics of the spheroidal tungsten carbide particles described above, overlapping details of which are omitted herein for brevity. For example, in some embodiments, the tungsten carbide particles can have a spheroidal shape having ratio of a first length along a major axis to second length along a minor axis that is 1.20 or lower. In some embodiments, the tungsten carbide particles have a surface that is textured to have a grain boundary area fraction greater than 5.0 %. In some embodiments, the tungsten carbide particles can have a D50 between 1 pm and 10 pm; between 11 pm and 20 pm; between 21 pm and 40 pm; between 41 pm and 60 pm; between 61 pm and 80 pm; between 81 pm and 100 pm; between 101 pm and 200 pm; or a value in a range defined by any of these values, where the dimension D refers to the longest lateral dimension of the reinforcement tungsten carbide particles, and D50 refers to a median value of the longest lateral dimensions of the tungsten carbide particles.
[0110] However, the reinforcement particles of MMC materials according to embodiments are not so limited, and in some other embodiments, the tungsten carbide particles can have a spheroidal shape having a ratio of a first length along a major axis to second length along a minor axis that is 1.20 or greater, and/or a surface that is textured to have a grain boundary area fraction lower than 5.0 %..
[0111] In some embodiments, the tungsten carbide particles do not have a spheroidal shape and/or a textured surface. FIG. 13 illustrates an optical micrograph of a MMC comprising tungsten carbide particles 1301 embedded in a Cu-based matrix 1302, according to embodiments. Unlike the spheroidal tungsten carbide particles of the MMC described above with respect to FIG. 3, and similar to the tungsten carbide particles of the MMC described above with respect to FIG. 2, the tungsten carbide particles 1301 of the MMC illustrated in FIG. 13 are angular particles having irregular shapes.
[0112] According various embodiments, the reinforcement particles, e.g., tungsten carbide particles, are present in the MMC including the Cu-based matrix at greater than 40 vol. %, 50 vol. %, 60 vol. %, 70 vol. %, 80 vol. %, or a value in a range defined by any of these values, for example 50-70 vol. %.
[0113] The MMCs according to embodiments can be fabricated using a method similar to that described above with respect to FIG. 4, overlapping details of which are omitted herein for brevity. For example, referring back to FIG. 4, a method of forming a metal-matrix composite (MMC) material comprises providing reinforcement particles 408, e.g., tungsten carbide particles, and a feedstock alloy 410 for forming a copper-based matrix in a mold assembly 412, 414, wherein the feedstock alloy 410 has an elemental composition including copper (Cu) exceeding 55 weight percent (wt. %) and tin (Sn) exceeding 1.4 wt. %. The reinforcement particles 408 are disposed below the feedstock alloy 410 such that gravity pulls liquefied alloy 410 into a porous network formed by the reinforcement particles 408. Subsequently, the method further comprises melting the alloy 410, infiltrating a network of pores formed by the reinforcement particles 408 with the liquefied alloy 410, and wetting the surfaces of the reinforcement particles 408. Subsequently, the liquefied alloy 410 is solidified within the network to form the MMC material comprising the reinforcement particles 408 embedded in in the copper-based matrix.
[0114] As described above, because the feedstock is in the form of an alloy 410, the feedstock can be liquefied at temperatures substantially lower than the melting temperatures of at some of the elemental metals including Cu, Mn and Ni. According to embodiments, melting comprises heating the mold to a temperature lower than melting temperatures of one or more of Cu, Mn and Ni, or lower than 1083 °C (1356 K), 1244 °C (1517 K), 1453 °C (1726 K). For example, melting comprises heating the mold to a temperature of 1000-1200 °C. Thus fabricated MMCs can form at least a portion of a drilling component, such as a drill bit as described above, the details of which are omitted herein for brevity.
[0115] As described above, one mechanical property that is a measure of strength of an MMC is the transverse rupture strength (TRS), the measurement details of which are not repeated herein for brevity. The MMCs according to embodiments, when fabricated with tungsten carbide particles and Cu-based alloys as described above, can have TRS values greater than 175 ksi, 200 ksi, 220 ksi, 250 ksi, or a value in a range defined by any of these values.
[0116] The Cu-based alloys disclosed herein provide additional toughness when used as the binder component in MMCs. The Cu-based alloys can have toughness levels of greater than 3,000 in*lbf/in3, 4,000 in*lbf/in3 , 5,000 in*lbf/in3,or a value in a range defined by any of these values.
[0117] FIG. 14 shows example samples that have been prepared for testing MMCs having Cu-based matrix and tungsten carbide particles as described herein. For measuring the TRS of MMCs according to embodiments, cylindrical MMC samples having 0.5 mm diameter and 100 mm length were prepared using a graphite mold with appropriate dimensions, by first filling the mold with tungsten carbide particles and placing pieces of the Cu-based feedstock alloy over the tungsten carbide particles. The mold was then placed in a furnace at a temperature of 1180 °C for a period of 1 hour to melt the Cu-based alloy and infiltrate the tungsten carbide particles with the liquefied Cu-based alloy, and subsequently solidifying the alloy to form the final MMC cylindrical samples as shown. The cylindrical samples were then tested using a standard 3 point bend test to measure the transverse rupture strength. The illustrated samples were fabricated using spherical tungsten carbide particles with a particle size distribution (PSD) defined by upper and lower size limit of 32-75 microns (corresponding to 200 mesh and 450 mesh and a D50 of 70 microns). The prepared MMC cylindrical samples as shown in FIG. 14 were demonstrated to have a TRS of 175-250 ksi.
[0118] Cylindrical MMC samples made from a Cu53 alloy and a chemistry according to an embodiment above, e.g. a disclosed Cu alloy, were manufactured by a similar process as described above. The MMC sample using a Cu53 alloy had a thermal conductivity of 13.96 W/mK and the drill bit sample using the disclosed alloy had a thermal conductivity of 16.77 W/mK. The MMC sample using the disclosed copper alloy had an average TRS strength of 240 ksi, above that of the Cu53 alloy, 224 ksi. The comparative experimental results are illustrated in Table 1. The elastic modulus of the disclosed copper alloy, 320 GPa, was lower than for the Cu53 alloy, 340 GPa. Table 1: Transverse Rupture Strength (ksi) Comparison
Figure imgf000029_0001
[0119] The TRS testing revealed that the disclosed Copper alloy also exhibits improved toughness in the MMC sample in comparison to Cu53 manufactured MMCs. The Cu53 MMC sample shows a toughness of 2,965 in*lbf/in3, whereas the disclosed Copper alloys shows a toughness of 5,511 in* lbf/in3.
Table 2: Toughness (in*lbf7in3) Comparison
Figure imgf000029_0002
[0120] FIG. 15 shows TRS testing results of MMCs having Cu-based matrix and tungsten carbide particles as described herein. A cylindrical MMC sample with a copper- based matrix comprising 2.89% tin (Sn), 7.56% manganese (Mn), 4.88% nickel (Ni), and 84.67 wt. % of Cu (X17C MMC sample), as well as a reference MMC sample made from a Cu53 alloy were manufactured by a similar process as described above in FIG. 14. Referring to FIG. 15, TRS testing was performed on both the Cu53 MMC sample as well as the X17C MMC sample. The UHS+X17C sample exhibited an increase in both strength and toughness relative to the Cu53 sample. Additional Examples I
1. A powder blend comprising fused tungsten carbide particles, wherein the fused tungsten carbide particles comprise: a spheroidal shape having ratio of a first length along a major axis to second length along a minor axis that is 1.20 or lower; and a surface that is textured to have a grain boundary area fraction greater than
5.0 %.
2. The powder blend of Example 1, further comprising metallic tungsten particles.
3. The powder blend of Examples 1 or 2, wherein the textured surface has a needle-like topography.
4. The powder blend of any one of Examples 1-3, wherein the needle-like topography comprises needle-like structures elongated along surfaces of the tungsten carbide particles, wherein at least some of the needle-like structures have a portion having a width not exceeding 1 mhi.
5. The powder blend of any one of Examples 1-4, wherein the powder blend is configured to form a metal-matrix composite (MMC) including the fused tungsten carbide particles embedded in a matrix.
6. The powder blend of Example 5, wherein the matrix comprises copper or a copper alloy.
7. The powder blend of any one of Examples 1-6, wherein the powder blend is configured to form a high strength MMC that has a Weibull modulus of 15 or greater.
8. The powder blend of any one of Examples 1-7, wherein the powder blend is configured to form a high strength MMC that has a linear extrapolation of the Weibull plot to a 1 in 10,000 probability of failure that equates to an applied stress of 80 ksi or greater.
9. The powder blend of any one of Examples 1-8, wherein the powder blend is used to form a high strength MMC that has an erosive volume loss of 0.10 cm3 or lower.
10. The powder blend of any one of Examples 1-9, wherein the powder blend is configured to form a high strength MMC that has an ASTM 611 volume loss of 1.00 cm3 or lower. 11. The powder blend of any one of Examples 1-10, wherein the powder blend is configured to form a portion of a high strength drill bit including a metal-matrix composite (MMC) including the fused tungsten carbide particles and a copper or copper alloy matrix.
12. The powder blend of any one of Examples 1-11, wherein the fused tungsten carbide particles have an average particle size of 1-200 mhi.
13. A metal matrix composite (MMC) material, comprising: fused tungsten carbide particles having a spheroidal shape and a surface that is textured to have a grain boundary area fraction greater than 5.0 %; and a matrix having embedded therein the fused tungsten carbide particles.
14. The MMC material of Example 13, wherein at least some of the fused tungsten carbide particles have a ratio of a first length along a major axis to second length along minor axis length that is 1.20 or lower.
15. The MMC material of Examples 13 or 14, wherein the matrix comprises copper or a copper alloy.
16. The MMC material of any one of Examples 13-15, wherein the MMC material has a Weibull modulus of 15 or greater.
17. The MMC material of any one of Examples 13-16, wherein the MMC material has a linear extrapolation of the Weibull plot to a 1 in 10,000 probability of failure that equates to an applied stress of 80 ksi or greater.
18. The MMC material of any one of Examples 13-17, wherein the MMC material has an erosive volume loss of 0.10 cm3 or lower.
19. The MMC material of any one of Examples 13-18, wherein the MMC material has an ASTM 611 volume loss of 1.00 cm3 or lower.
20. The MMC material of any one of Examples 13-19, wherein the fused tungsten carbide particles have a D50 between 1 pm and 10 pm and the MMC material has a transverse rupture strength of 360 ksi or greater.
21. The MMC material of any one of Examples 13-20, wherein the fused tungsten carbide particles have a D50 between 11 pm and 20 pm and the MMC material has a transverse rupture strength of 280 ksi or greater. 22. The MMC material of any one of Examples 13-21, wherein the fused tungsten carbide particles have a D50 between 21 pm and 40 pm and the MMC has a transverse rupture strength of 230 ksi or greater.
23. The MMC material of any one of Examples 13-22, wherein the fused tungsten carbide particles have a D50 between 41 pm and 60 pm and the MMC has a transverse rupture strength of 180 ksi or greater.
24. The MMC material of any one of Examples 13-23, wherein the fused tungsten carbide particles have a D50 between 61 pm and 80 pm and the MMC has a transverse rupture strength of 160 ksi or greater.
25. The MMC material of any one of Examples 13-24, wherein the fused tungsten carbides have a D50 between 81 pm and 100 pm and the MMC has a transverse rupture strength of 140 ksi or greater.
26. The MMC material of any one of Examples 13-25, wherein the fused tungsten carbides have a D50 between 101 pm and 200 pm and the MMC has a Transverse Rupture Strength of 100 ksi or greater.
27. The MMC material of any one of Examples 13-26, wherein the MMC material forms part of a high strength drill bit.
28. A method of forming a metal-matrix composite (MMC) material, the method comprising: adding into a mold fused tungsten carbide particles having a spheroidal shape and a surface that is textured to have a grain boundary area fraction greater than 5.0
%; adding a binder material comprising copper into the mold; melting the binder material to infiltrate the fused tungsten carbide particles; and solidifying the molten binder material to form the MMC material.
29. The method of Example 28, wherein the fused tungsten carbide particles have the grain boundary area fraction of at least 10.0%.
30. The method of Examples 28 or 29, wherein the fused tungsten carbide particles have the grain boundary area fraction of at least 12.0%. 31. The method of any one of Examples 28-30, wherein the fused tungsten carbide particles have the grain boundary area fraction of at least 20.0%.
32. The method of any one of Examples 28-31, wherein the MMC material has a Weibull modulus of 15 or greater.
33. The method of any one of Examples 28-32, wherein the MMC material has a Weibull modulus of 20 or greater.
34. The method of any one of Examples 28-33, wherein the MMC material has a Weibull modulus of 25 or greater.
35. The method of any one of Examples 28-34, wherein a linear extrapolation to a 1 in 10,000 probability of failure for the MMC material equates to 80 ksi or greater.
36. The method of any one of Examples 28-35, wherein a linear extrapolation to a 1 in 10,000 probability of failure for the MMC material equates to 140 ksi or greater.
37. The method of any one of Examples 28-36, wherein a linear extrapolation to a 1 in 10,000 probability of failure for the MMC material equates to 180 ksi or greater.
38. The method of any one of Examples 28-37, wherein the MMC material has a transverse rupture strength of at least 140 ksi.
39. The method of any one of Examples 28-38, wherein the MMC material has a transverse rupture strength of at least 450 ksi.
40. The method of any one of Examples 28-39, wherein the MMC material has a transverse rupture strength of at least 700 ksi.
41. The method of any one of Examples 28-40, wherein the MMC material has an erosive volume loss of 0.10 cm3 or less.
42. The method of any one of Examples 28-41, wherein the MMC material has an erosive volume loss of 0.08 cm3 or less.
43. The method of any one of Examples 28-42, wherein the MMC material has an erosive volume loss of 0.04 cm3 or less.
44. The method of any one of Examples 28-43, wherein the method comprises forming the MMC material as part of a high strength drill bit, wherein the method further comprises adding steel components into the mold, and wherein melting the binder material comprises at least partially encompassing the steel component.
45. A high strength drill bit comprising: a metal matrix composite comprising fused tungsten carbide particles within a matrix, wherein the fused tungsten carbide particles have a spheroidal shape and a surface that is textured to have a grain boundary area fraction of at least 5.0%.
46. The drill bit of Example 45, wherein the fused tungsten carbide particles have a grain boundary area fraction of at least 10.0%.
47. The drill bit of Examples 45 or 46, wherein the fused tungsten carbide particles have a grain boundary area fraction of at least 12.0%.
48. The drill bit of any one of Examples 45-47, wherein the fused tungsten carbide particles have a grain boundary area fraction of at least 20.0%.
49. The drill bit of any one of Examples 45-48, wherein the metal matrix composite has a Weibull modulus of 15 or greater.
50. The drill bit of any one of Examples 45-49, wherein the metal matrix composite has a Weibull modulus of 20 or greater.
51. The drill bit of any one of Examples 45-50, wherein the metal matrix composite has a Weibull modulus of 25 or greater.
52. The drill bit of any one of Examples 45-51, wherein a linear extrapolation to a 1 in 10,000 probability of failure for the metal matrix composite equates to 80 ksi or greater.
53. The drill bit of any one of Examples 45-52, wherein a linear extrapolation to a 1 in 10,000 probability of failure for the metal matrix composite equates to 140 ksi or greater.
54. The drill bit of any one of Examples 45-53, wherein a linear extrapolation to a 1 in 10,000 probability of failure for the metal matrix composite equates to 180 ksi or greater.
55. The drill bit of any one of Examples 45-54, wherein the metal matrix composite has a transverse rupture strength of at least 140 ksi.
56. The drill bit of any one of Examples 45-55, wherein the metal matrix composite has a transverse rupture strength of at least 450 ksi.
57. The drill bit of any one of Examples 45-56, wherein the metal matrix composite has a transverse rupture strength of at least 700 ksi.
58. The drill bit of any one of Examples 45-57, wherein the metal matrix composite has an erosive volume loss of 0.10 cm3 or less.
59. The drill bit of any one of Examples 45-58, wherein the metal matrix composite has an erosive volume loss of 0.08 cm3 or less. 60. The drill bit of any one of Examples 45-59, wherein the metal matrix composite has an erosive volume loss of 0.04 cm3 or less.
61. The powder blend of any one of Examples 1-12, wherein the powder blend is configured to form a metal-matrix composite (MMC) including the fused tungsten carbide particles embedded in a matrix formed of the alloy of Examples 1-12 of the Additional Examples II.
62. The MMC material of any one of Examples 13-27, wherein the matrix is formed of the alloy of Examples 65-76 of the Additional Examples II.
63. The method of any one of Examples 28-44, wherein the MMC comprises a matrix formed of the alloy of Examples 65-76 of the Additional Examples II.
64. The drill bit of any one of Examples 45-60, wherein the metal matrix composite comprises a matrix formed of the alloy of Examples 65-77 of the Additional Examples II.
Additional Examples
Figure imgf000035_0001
65. An alloy comprising: manganese (Mn) at 5.6-10.4 weight percent (wt. %); nickel (Ni) at 3.5-6.5 wt. %; tin (Sn) at 1.4-4 wt. %; and copper (Cu) exceeding 55 wt. % and up to a balance of the alloy, wherein the alloy has a solidus temperature lower than a melting temperature of Cu.
66. The alloy of Example 65, comprising 1.4-2.6 wt. % tin (Sn).
67. The alloy of Example 66, wherein the solidus temperature is lower than 1300
K.
68. The alloy of Example s 66 or 67, wherein the alloy forms a single phase solid solution having a face-centered cubic (FCC) crystal structure from a solidus temperature down to at least 400 K below the solidus temperature,.
69. The alloy of any one of Examples 65-68, wherein greater than 90 wt.% of the alloy is a single phase solid solution with a face-centered cubic (FCC) crystal structure at room temperature. 70. The alloy of any one of Examples 65-68, wherein the alloy further comprises up to 2 wt. % of impurities.
71. The alloy of any one of Examples 65-70, wherein the elemental composition does not include one or more of Si, B and Zn.
72. The alloy of any one of Examples 65-71, wherein the alloy has an electrical conductivity higher than 2.5 MS/m.
73. The alloy of any one of Examples 65-72, wherein the alloy has a thermal conductivity higher than 10 W/mK.
74. The alloy of any one of Examples 65-73, wherein the alloy forms a matrix of a metal matrix composite (MMC) material, wherein the MMC material further comprises tungsten carbide particles.
75. The alloy of any one of Examples 65-74, wherein the alloy forms a matrix of a metal matrix composite (MMC) material, wherein the MMC material forms part of a drilling component.
76. The alloy of any one of Examples 65-75, wherein the alloy forms a matrix of a metal matrix composite (MMC) material, wherein the MMC material has a toughness greater than 4,000 in*lbf.in3.
77. The alloy of any one of Examples 65-76, wherein the alloy is part of a feedstock for forming a metal matrix composite (MMC) material, wherein the feedstock further comprises tungsten carbide particles.
78. A metal matrix composite material comprising reinforcement particles embedded in a copper-based matrix, wherein the copper-based matrix comprises greater than 55 wt. % copper (Cu) and greater than 1.4 wt. % tin (Sn).
79. The metal matrix composite material of Example 78, wherein the copper- based matrix comprises:
1.4-4 wt. % tin (Sn);
5.6-10.4 wt. % manganese (Mn); and
3.5-6.5 wt. % nickel (Ni), wherein the copper-based matrix has a solidus temperature lower than Cu.
80. The metal matrix composite material of Claim 79, wherein the copper-based matrix comprises 1.4-2.6 wt. % tin (Sn). 81. The metal matrix composite material of any one of Examples 78-80, wherein the solidus temperature of the copper-based matrix is lower than 1300 K.
82. The metal matrix composite material of any one of Examples 78-80, wherein the copper-based matrix forms a single phase solid solution having a face-centered cubic (FCC) crystal structure from a solidus temperature down to at least 400K below the solidus temperature.
83. The metal matrix composite material of any one of Examples 78-82, wherein greater than 90 wt.% of the copper-based matrix is a single-phase solid solution having a face-centered cubic (FCC) crystal structure at room temperature.
84. The metal matrix composite material of any one of Examples 78-83, wherein the copper-based matrix comprises 2 wt. % or less of impurities.
85. The metal matrix composite material of any one of Examples 78-84, wherein the copper-based matrix does not include one or more of Si, B and Zn.
86. The metal matrix composite material of any one of Examples 78-85, wherein the copper-based matrix has an electrical conductivity higher than 2.5 MS/m.
87. The metal matrix composite material of any one of Examples 78-86, wherein the copper-based matrix has a thermal conductivity higher than 10 W/mK.
88. The metal matrix composite material of Example 78, wherein the reinforcement particles comprise tungsten carbide particles.
89. The metal matrix composite material of Example 88, wherein tungsten carbide particles comprise 50-70 vol.% of the metal matrix composite material.
90. The metal matrix composite material of Examples 88 or 89 wherein the tungsten carbide particles have an average particle size of 1-200 mhi
91. The metal matrix composite material of any one of Examples 88-90, wherein the tungsten carbide particles have a spheroidal shape having ratio, between a first length along a major axis and a second length along a minor axis, of 1.20 or lower.
92. The metal matrix composite material of any one of Examples 78-91, wherein the tungsten carbide particles have a surface that is textured to have a grain boundary area fraction greater than 5.0 %.
93. The metal matrix composite material of any one of Examples 78-92, wherein the metal matrix composite material has a transverse rupture strength exceeding 175 ksi. 94. The metal matrix composite material of any one of Examples 78-93, wherein the metal matrix composite material forms part of a drilling component.
95. A method of forming a metal-matrix composite (MMC) material, the method comprising: providing reinforcement particles and an alloy for forming a copper-based matrix in a mold, wherein the alloy has an elemental composition comprising:
> 55 wt. % copper (Cu), and
> 1.4 wt. %; tin (Sn); melting at least the alloy; and solidifying the alloy to form the metal matrix composite material, wherein the reinforcement particles are embedded in the copper-based matrix.
96. The method of Example 95, wherein the alloy comprises:
1.4-4 wt. % tin (Sn);
5.6-10.4 wt. % manganese (Mn); and
3.5-6.5 wt. % nickel (Ni), wherein the alloy has a solidus temperature lower than a melting temperature of Cu.
97. The method of Example 95, wherein the alloy comprises 1.4-2.6 wt. % tin
(Sn).
98. The method of any one of Examples 95-97, wherein melting the alloy comprises heating the mold to a temperature lower than melting temperatures of one or more of Cu, Mn and Ni..
99. The method of any one of Examples 95-98, wherein melting the alloy comprises heating the mold to 1000-1200 °C.
100. The method of any one of Examples 95-99, further comprising infiltrating a porous network formed by the reinforcement particles and wetting the surfaces of the reinforcement particles with the melted alloy prior to solidifying the liquefied alloy.
101. The method of any one of Examples 95-100, wherein providing the reinforcement particles and an alloy comprises disposing the reinforcement particles below the alloy such that gravity pulls melted alloy into a porous network formed by the reinforcement particles. 102. The method of any one of Examples 95-101, wherein solidifying the alloy comprises cooling the molten alloy to room temperature, and wherein greater than 90 wt.% of the copper based matrix solidifies into a single phase solid solution having a face-centered cubic (FCC) crystal structure.
103. The method of any one of Examples 95-102, wherein the alloy comprises 2 wt. % or less impurities, and the balance of the alloy is copper.
104. The method of any one of Examples 95-103, wherein the alloy is free of one or more of Si, B and Zn.
105. The method of any one of Examples 95-104, wherein the copper based matrix has an electrical conductivity higher than 2.5 MS/m.
106. The method of any one of Examples 95-106, wherein the copper-based matrix has a thermal conductivity higher than 10 W/mK.
107. The method of any one of Examples 95-107, wherein the reinforcement particles comprise tungsten carbide particles.
108. The method of Example 107, wherein 50-70 vol. % of the metal matrix composite material comprises tungsten carbide particles.
109. The method of Examples 107 or 108, wherein the tungsten carbide particles have an average particle size of 1-200 mhi.
110. The method of any one of Examples 107-109, wherein the tungsten carbide particles have a spheroidal shape having a ratio between a first length along a major axis of the particles and a second length along a minor axis of the particles, of 1.20 or lower.
111. The method of any one of Examples 107-110, wherein the tungsten carbide particles have a surface that is textured to have a grain boundary area fraction greater than 5.0 %.
112. The method of any one of Examples 95-111, wherein the metal matrix composite material has a transverse rupture strength greater than 175 ksi.
113. The method of any one of Examples 95-112, further comprising forming the metal matrix composite material into a drilling component.
114. The alloy of Examples 65-77, wherein the alloy is included as part of a feedstock for forming a metal matrix composite (MMC) material, wherein the feedstock further comprises the powder blend according to Examples 1-12 of the Additional Examples
I.
115. The MMC material of Examples 78-94, wherein the reinforcement particles comprise the powder blend according to Examples 1-12 of the Additional Examples I.
116. The method of Examples 95-113, wherein the reinforcement particles comprise the powder blend according to Examples 1-12 of the Additional Examples I.
[0121] From the foregoing description, it will be appreciated that inventive products and approaches for alloys are disclosed. While several components, techniques and aspects have been described with a certain degree of particularity, it is manifest that many changes can be made in the specific designs, constructions and methodology herein above described without departing from the spirit and scope of this disclosure.
[0122] Certain features that are described in this disclosure in the context of separate implementations can also be implemented in combination in a single implementation. Conversely, various features that are described in the context of a single implementation can also be implemented in multiple implementations separately or in any suitable subcombination. Moreover, although features may be described above as acting in certain combinations, one or more features from a claimed combination can, in some cases, be excised from the combination, and the combination may be claimed as any subcombination or variation of any subcombination.
[0123] Moreover, while methods may be depicted in the drawings or described in the specification in a particular order, such methods need not be performed in the particular order shown or in sequential order, and that all methods need not be performed, to achieve desirable results. Other methods that are not depicted or described can be incorporated in the example methods and processes. For example, one or more additional methods can be performed before, after, simultaneously, or between any of the described methods. Further, the methods may be rearranged or reordered in other implementations. Also, the separation of various system components in the implementations described above should not be understood as requiring such separation in all implementations, and it should be understood that the described components and systems can generally be integrated together in a single product or packaged into multiple products. Additionally, other implementations are within the scope of this disclosure.
[0124] Conditional language, such as “can,” “could,” “might,” or “may,” unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain embodiments include or do not include, certain features, elements, and/or steps. Thus, such conditional language is not generally intended to imply that features, elements, and/or steps are in any way required for one or more embodiments.
[0125] Conjunctive language such as the phrase “at least one of X, Y, and Z,” unless specifically stated otherwise, is otherwise understood with the context as used in general to convey that an item, term, etc. may be either X, Y, or Z. Thus, such conjunctive language is not generally intended to imply that certain embodiments require the presence of at least one of X, at least one of Y, and at least one of Z.
[0126] Language of degree used herein, such as the terms “approximately,” “about,” “generally,” and “substantially” as used herein represent a value, amount, or characteristic close to the stated value, amount, or characteristic that still performs a desired function or achieves a desired result. For example, the terms “approximately”, “about”, “generally,” and “substantially” may refer to an amount that is within less than or equal to 10% of, within less than or equal to 5% of, within less than or equal to 1% of, within less than or equal to 0.1% of, and within less than or equal to 0.01% of the stated amount. If the stated amount is 0 (e.g., none, having no), the above recited ranges can be specific ranges, and not within a particular % of the value. For example, within less than or equal to 10 wt./vol. % of, within less than or equal to 5 wt./vol. % of, within less than or equal to 1 wt./vol. % of, within less than or equal to 0.1 wt./vol. % of, and within less than or equal to 0.01 wt./vol. % of the stated amount.
[0127] Some embodiments have been described in connection with the accompanying drawings. The FIG.s are drawn to scale, but such scale should not be limiting, since dimensions and proportions other than what are shown are contemplated and are within the scope of the disclosed inventions. Distances, angles, etc. are merely illustrative and do not necessarily bear an exact relationship to actual dimensions and layout of the devices illustrated. Components can be added, removed, and/or rearranged. Further, the disclosure herein of any particular feature, aspect, method, property, characteristic, quality, attribute, element, or the like in connection with various embodiments can be used in all other embodiments set forth herein. Additionally, it will be recognized that any methods described herein may be practiced using any device suitable for performing the recited steps.
[0128] While a number of embodiments and variations thereof have been described in detail, other modifications and methods of using the same will be apparent to those of skill in the art. Accordingly, it should be understood that various applications, modifications, materials, and substitutions can be made of equivalents without departing from the unique and inventive disclosure herein or the scope of the claims.

Claims

WHAT IS CLAIMED IS:
1. An alloy comprising: manganese (Mn) at 5.6-10.4 weight percent (wt. %); nickel (Ni) at 3.5-6.5 wt. %; tin (Sn) at 1.4-4 wt. %; and copper (Cu) exceeding 55 wt. % and up to a balance of the alloy, wherein the alloy has a solidus temperature lower than a melting temperature of Cu.
2. The alloy of Claim 1, wherein the alloy comprises tin (Sn) at 1.4-2.6 wt. %.
3. The alloy of Claim 1, wherein the solidus temperature is lower than 1300 K.
4. The alloy of Claim 1, wherein the alloy forms a single phase solid solution having a face-centered cubic (FCC) crystal structure from a solidus temperature down to at least 400 K below the solidus temperature,.
5. The alloy of Claim 1, wherein greater than 90 wt.% of the alloy is a single phase solid solution with a face-centered cubic (FCC) crystal structure at room temperature.
6. The alloy of Claim 1, wherein the alloy further comprises up to 2 wt. % of impurities.
7. The alloy of Claim 1, wherein the elemental composition does not include one or more of Si, B and Zn.
8. The alloy of any one of Claims 1-7, wherein the alloy has an electrical conductivity higher than 2.5 MS/m.
9. The alloy of any one of Claims 1-7, wherein the alloy has a thermal conductivity higher than 10 W/mK.
10. The alloy of any one of Claims 1-7, wherein the alloy forms a matrix of a metal matrix composite (MMC) material, wherein the MMC material further comprises tungsten carbide particles.
11. The alloy of any one of Claims 1-7, wherein the alloy forms a matrix of a metal matrix composite (MMC) material, wherein the MMC material forms part of a drilling component.
12. The alloy of any one of Claims 1-7, wherein the alloy forms a matrix of a metal matrix composite (MMC) material, wherein the MMC material has a toughness greater than 4,000 in*lbf.in3.
13. The alloy of any one of Claims 1-7, wherein the alloy is part of a feedstock for forming a metal matrix composite (MMC) material, wherein the feedstock further comprises tungsten carbide particles.
14. A metal matrix composite material comprising reinforcement particles embedded in a copper-based matrix, wherein the copper-based matrix comprises greater than 55 wt. % copper (Cu) and greater than 1.4 wt. % tin (Sn).
15. The metal matrix composite material of Claim 14, wherein the copper-based matrix comprises:
1.4-4 wt. % tin (Sn);
5.6-10.4 wt. % manganese (Mn); and
3.5-6.5 wt. % nickel (Ni), wherein the copper-based matrix has a solidus temperature lower than Cu.
16. The metal matrix composite material of Claim 15, wherein the copper-based matrix comprises 1.4-2.6 wt. % tin (Sn).
17. The metal matrix composite material of Claim 14, wherein the solidus temperature of the copper-based matrix is lower than 1300 K.
18. The metal matrix composite material of Claim 14, wherein the copper-based matrix forms a single phase solid solution having a face-centered cubic (FCC) crystal structure from a solidus temperature down to at least 400K below the solidus temperature.
19. The metal matrix composite material of Claim 14, wherein greater than 90 wt.% of the copper-based matrix is a single-phase solid solution having a face-centered cubic (FCC) crystal structure at room temperature.
20. The metal matrix composite material of Claim 14, wherein the copper-based matrix comprises 2 wt. % or less of impurities.
21. The metal matrix composite material of Claim 14, wherein the copper-based matrix does not include one or more of Si, B and Zn.
22. The metal matrix composite material of any one of Claims 14-21, wherein the copper-based matrix has an electrical conductivity higher than 2.5 MS/m.
23. The metal matrix composite material of any one of Claims 14-21, wherein the copper-based matrix has a thermal conductivity higher than 10 W/mK.
24. The metal matrix composite material of any one of Claims 14-21, wherein the reinforcement particles comprise tungsten carbide particles.
25. The metal matrix composite material of Claim 24, wherein tungsten carbide particles comprise 50-70 vol.% of the metal matrix composite material.
26. The metal matrix composite material of Claim 24, wherein the tungsten carbide particles have an average particle size of 1-200 mhi
27. The metal matrix composite material of Claim 24, wherein the tungsten carbide particles have a spheroidal shape having ratio, between a first length along a major axis and a second length along a minor axis, of 1.20 or lower.
28. The metal matrix composite material of Claim 24, wherein the tungsten carbide particles have a surface that is textured to have a grain boundary area fraction greater than 5.0 %.
29. The metal matrix composite material of any one of Claims 14-21, wherein the metal matrix composite material has a transverse rupture strength exceeding 175 ksi.
30. The metal matrix composite material of any one of Claims 14-21, wherein the metal matrix composite material forms part of a drilling component.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63213628A (en) * 1987-03-02 1988-09-06 Nippon Mining Co Ltd Copper alloy for fuse
EP1077268A1 (en) * 1999-08-12 2001-02-21 Smith International, Inc. Composition for binder material
US20190234151A1 (en) * 2016-08-02 2019-08-01 Halliburton Energy Services, Inc. Tools having a structural metal-matrix composite portion

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63213628A (en) * 1987-03-02 1988-09-06 Nippon Mining Co Ltd Copper alloy for fuse
EP1077268A1 (en) * 1999-08-12 2001-02-21 Smith International, Inc. Composition for binder material
US20190234151A1 (en) * 2016-08-02 2019-08-01 Halliburton Energy Services, Inc. Tools having a structural metal-matrix composite portion

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