US 12,649,963 B2Grant
Spheroidal tungsten carbide particles
Issue Date:2026-06-09
•28 Claims
•13 Drawing Sheets
Abstract
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. In one aspect, a powder blend comprises fused tungsten carbide particles. The fused tungsten carbide particles have a spheroidal or substantially spherical 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 fused tungsten carbide particles have a surface that is textured to have a grain boundary area fraction greater than 5.0%.
Metadata
Assignee
- Oerlikon Metco (US) Inc.
Inventors
- Zhongming Wang
- Andy Bell
- Zhe Zhang
- Bob Horswell
- James Nathaniel Vecchio
- Justin Lee Cheney
- Roland Facundo
Application Information
Application Number:US 17/760,483
Filing Date:2021-02-23
Priority Date:2020-02-25
Art Unit:1738
Classifications
IPC:
B22F1/05B22F1/065B22F3/00B22F5/00C01B32/949C22C29/00C22C29/08
Field of Search:
C01B 32/949C04B 2235/528C22C 29/08
Patent Drawings (13 sheets)
Description
BACKGROUND
Field
[0001] 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
[0002] 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
[0003] In one aspect, a high strength drill bit comprises a metal matrix composite (MMC) comprising fused tungsten carbide particles within a matrix, wherein the fused tungsten carbide particles have a spheroidal or substantially spherical shape and a surface that is textured to have a grain boundary area fraction of at least 5.0%.
[0004] In some embodiments, the matrix comprises copper or a copper alloy.
[0005] In some embodiments, the plurality of tungsten carbide particles have a grain boundary area fraction of at least 10.0%. In some embodiments, the plurality of tungsten carbide particles have a grain boundary area fraction of at least 12.0%. In some embodiments, the plurality of tungsten carbide particles have a grain boundary area fraction of at least 20.0%. The boundary area fraction can also have a value in a range defined by any of these values.
[0006] In some embodiments, the metal matrix composite has a Weibull modulus of 15 or greater. In some embodiments, the metal matrix composite has a Weibull modulus of 20 or greater. In some embodiments, the metal matrix composite has a Weibull modulus of 25 or greater. The Weibull modulus can also have a value in a range defined by any of these values.
[0007] In some embodiments, a linear extrapolation to a 1 in 10,000 probability of failure for the metal matrix composite equates to 80 ksi or greater. In some embodiments, a linear extrapolation to a 1 in 10,000 probability of failure for the metal matrix composite equates to 140 ksi or greater. In some embodiments, a linear extrapolation to a 1 in 10,000 probability of failure for the metal matrix composite equates to 180 ksi or greater. The linear extrapolation can also have a value in a range defined by any of these values.
[0008] In some embodiments, the metal matrix composite has a transverse rupture strength of at least 140 ksi. In some embodiments, the metal matrix composite has a transverse rupture strength of at least 450 ksi. In some embodiments, the metal matrix composite has a transverse rupture strength of at least 700 ksi. The transverse rupture strength can also have a value in a range defined by any of these values.
[0009] In some embodiments, the metal matrix composite has an erosive volume loss of 0.10 cm3 or less. In some embodiments, the metal matrix composite has an erosive volume loss of 0.08 cm3 or less. In some embodiments, the metal matrix composite has an erosive volume loss of 0.04 cm3 or less. The erosive volume loss can also have a value in a range defined by any of these values.
[0010] In another aspect, a method of forming a metal matrix composite (MMC) comprises adding into a mold fused tungsten carbide particles having a spheroidal or substantially spherical shape and a surface that is textured to have a grain boundary area fraction greater than 5.0%. The method additionally comprises adding a binder material comprising copper into the mold. The method additionally comprises melting the binder material to infiltrate the fused tungsten carbide particles. The method further comprises solidifying the molten binder material to form the MMC.
[0011] In some embodiments, the method comprises forming the MMC 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.
[0012] In some embodiments, the plurality of tungsten carbide particles have a grain boundary area fraction of at least 10.0%. In some embodiments, the plurality of tungsten carbide particles have a grain boundary area fraction of at least 12.0%. In some embodiments, the plurality of tungsten carbide particles have a grain boundary area fraction of at least 20.0%. The grain boundary fraction can also have a value in a range defined by any of these values.
[0013] In some embodiments, the metal matrix composite has a Weibull modulus of 15 or greater. In some embodiments, the metal matrix composite has a Weibull modulus of 20 or greater. In some embodiments, the metal matrix composite has a Weibull modulus of 25 or greater. The Weibull modulus can also have a value in a range defined by any of these values.
[0014] In some embodiments, a linear extrapolation to a 1 in 10,000 probability of failure for the metal matrix composite equates to 80 ksi or greater. In some embodiments, a linear extrapolation to a 1 in 10,000 probability of failure for the metal matrix composite equates to 140 ksi or greater. In some embodiments, a linear extrapolation to a 1 in 10,000 probability of failure for the metal matrix composite equates to 180 ksi or greater. The linear extrapolation can also have a value in a range defined by any of these values.
[0015] In some embodiments, the metal matrix composite has a transverse rupture strength of at least 140 ksi. In some embodiments, the metal matrix composite has a transverse rupture strength of at least 450 ksi. In some embodiments, the metal matrix composite has a transverse rupture strength of at least 700 ksi. The transverse rupture strength can also have a value in a range defined by any of these values.
[0016] In some embodiments, the metal matrix composite has an erosive volume loss of 0.10 cm3 or less. In some embodiments, the metal matrix composite has an erosive volume loss of 0.08 cm3 or less. In some embodiments, the metal matrix composite has an erosive volume loss of 0.04 cm3 or less. The erosive volume loss can also have a value in a range defined by any of these values.
[0017] In another aspect, a powder blend comprises fused tungsten carbide particles. The fused tungsten carbide particles have a spheroidal or substantially spherical 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 fused tungsten carbide particles have a surface that is textured to have a grain boundary area fraction greater than 5.0%.
[0018] In some embodiments, the textured surface is defined by having a needle-like topography, wherein a grain boundary area fraction is greater than 5.0%.
[0019] In some embodiments, the powder blend is used in infiltration casting to form a high strength MMC. In some embodiments, the powder blend is used to form a high strength MMC that has a Weibull modulus of 15 or greater. In some embodiments, the powder blend is used 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. In some embodiments, the powder blend is used to form a high strength MMC that has an erosive volume loss of 0.10 cm3 or lower. In some embodiments, the powder blend is used to form a high strength MMC that has an ASTM 611 volume loss of 1.00 cm3 or lower.
[0020] In another aspect, a metal matrix composite (MMC) comprises fused tungsten carbide particles having a spheroidal or substantially spherical shape and a surface that is textured to have a grain boundary area fraction greater than 5.0%. The MMC additionally comprises a matrix having embedded therein the fused tungsten carbide particles.
[0021] In some embodiments, the MMC is formed by infiltration of the tungsten carbide particles using a liquid metal formed of a metal or a metal alloy, e.g., copper or a copper alloy, wherein the metal matrix composite exhibits high strength.
[0022] In some embodiments, the metal matrix composite has a Weibull modulus of 15 or greater. In some embodiments, a linear extrapolation of the Weibull plot to a 1 in 10,000 probability of failure equates to an applied stress of 80 ksi or greater. In some embodiments, the metal matrix composite has an erosive volume loss of 0.10 cm3 or lower. In some embodiments, the metal matrix composite has an ASTM 611 volume loss of 1.00 cm3 or lower.
[0023] In some embodiments, the metal matrix composite has the textured tungsten particles having a D50 between 1 μm and 10 μm and the MMC has a transverse rupture strength of 360 ksi or greater. In some embodiments, the textured tungsten carbide particles have a D50 between 11 μm and 20 μm and the MMC has a transverse rupture strength of 280 ksi or greater. In some embodiments, the textured tungsten carbide particles have a D50 between 21 μm and 40 μm and the MMC has a transverse rupture strength of 230 ksi or greater. In some embodiments, the textured tungsten carbide particles have a D50 between 41 μm and 60 μm and the MMC has a transverse rupture strength of 180 ksi or greater. In some embodiments, the textured tungsten carbides have a D50 between 61 μm and 80 μm and the MMC has a transverse rupture strength of 160 ksi or greater. In some embodiments, the textured tungsten carbides have a D50 between 81 μm and 100 μm and the MMC has a transverse rupture strength of 140 ksi or greater. In some embodiments, the textured tungsten carbide particles have a D50 between 101 μm and 200 μm and the MMC has a transverse rupture strength of 100 ksi or greater. The D50 and the transverse rupture strength can have a value in a range defined by any of these values.
[0024] In some embodiments, the metal matrix composite is used to form a drill bit containing a plurality of cutting elements and contained within its construction is a metal matrix composite.
[0025] Further disclosed herein are embodiments of a drill bit formed from the disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] FIG. 1 illustrates a scanning electron microscopy (SEM) image of a prior art metal powder with angular particles.
[0027] FIG. 2 illustrates an optical micrograph of a prior art metal matrix composite (MMC) prepared using angular particles.
[0028] FIG. 3 illustrates an optimal micrograph of a MMC prepared using spheroidal or substantially spherical particles.
[0029] FIG. 4 shows a perspective view of an embodiment of earth-engaging tool with a drill bit.
[0030] FIG. 5 illustrates strength and reliability improvement of embodiments of the disclosed ultra-high-strength MMC (right) and conventional MMC (left).
[0031] FIG. 6 illustrates an SEM image of a prior art MMC.
[0032] FIGS. 7-8 illustrate an SEM image of an MMC according to the disclosure.
[0033] FIG. 9 illustrates a binary image of FIG. 6 .
[0034] FIG. 10 illustrates a binary image of FIG. 7 .
[0035] FIG. 11 illustrates a binary image of FIG. 8 .
[0036] FIG. 12 illustrates a mold geometry for liquid metal infiltration of powder to create a drill-bit body.
DETAILED DESCRIPTION
[0037] Disclosed herein are embodiments of spheroidal or substantially spherical fused tungsten carbide particles, and metal matrix composites (MMCs) formed from the tungsten carbide particles. The MMCs can include a matrix comprising copper and/or copper alloys, along with the tungsten carbide particles. The tungsten particles as well as MMCs formed therefrom according to embodiments 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 composite (MMC).
[0038] The spheroidal or substantially spherical fused tungsten carbide particles can generally be made from regular fused tungsten carbide powder or a mixture of tungsten, mono tungsten carbide and/or carbon. In some embodiments, the spheroidal or substantially spherical fused tungsten carbide particles can have a composition of combined carbon from 3.7 to 4.2 (or about 3.7 to 4.2) wt. %, with tungsten being the balance. The particles can be produced via a number of methods. In some methods, a mixture of tungsten powder blended with mono tungsten carbide and carbon powder is melted first. The molten mixture is then atomized by a rotation atomizing process or an ultra-high temperature melting & atomizing process. These processes spheroidizes molten tungsten carbide into spheroidal or substantially spherical fused tungsten carbide particles during the rapid solidification process due to surface tension. Other methods may be based on the modification of regular fused tungsten carbide powder. Plasma spraying, electric induction or electric resistance furnace melting is applied during the spheroidization process to obtain fine spheroidal or substantially spherical fused tungsten carbide particles.
[0039] As described herein, “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, or a ratio of the longest axis length to the shortest axis length, of the spheroidal or substantially spherical particles. For example, a “perfectly” spherical particle would have an aspect ratio of exactly one. On the other hand, “angular” particles, such as discussed above in the art, have an aspect ratio of at least 1.30.
[0040] In embodiments of the disclosure, spheroidal or substantially spherical fused tungsten carbide particles disclosed herein can have an aspect ratio of 1.20 (or about 1.20) or lower. In some embodiments, a spherical fused tungsten carbide can have an aspect ratio of 1.10 (or about 1.10) or lower. In some embodiments, a spherical fused tungsten carbide can have an aspect ratio of 1.05 (or about 1.05) or lower. The aspect ratio can also have a value in a range defined by any of these values. The aspect ratio as disclosed herein 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 as disclosed herein.
[0041] The spheroidal or substantially spherical fused tungsten carbide powder specific density can be around 16.5 g/cm3 with micro-hardness advantageously ranging from 2,700-3,300 HV (or about 2,700-about 3,300 HV). These properties can be attributed to, among other things, the particle shape and internal microstructure resulting from the spheroidization processes described above. In comparison, a mostly angular fused tungsten carbide exhibits a substantially inferior hardness of about 1,500-2,200 HV only. Generally, MMCs containing spheroidal or substantially spherical fused tungsten carbide particles are more wear resistant than those that contain angular fused tungsten carbide for particles having a comparable size and fraction. In the following, various microstructural distinctions between conventional angular tungsten carbide particles and MMCs formed therefrom, and spheroidal or substantially spherical tungsten carbide particles and MMCs formed therefrom according to embodiments, are described.
[0042] FIG. 1 shows a scanning electron microscope (SEM) image of a prior art metal powder. As shown, the prior art metal powder is angular.
[0043] FIG. 2 illustrates an optical micrograph of a prior art MMC prepared using metallographic techniques. As shown, the MMC includes a soft phase 1, a particulate phase 2 formed from a powder similar to that shown in FIG. 1 , and a particulate-to-soft phase interface 3. Soft phase can be formed a matrix material that is first melted and subsequently cooled. Thus, the prior art MMC includes two principle phases. The soft phase 1 is formed through the liquid metal infiltration of the particulate phase 2.
[0044] The particulate phase 2 can include metal carbides, borides or oxides. For example, the particular phase 2 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 1 and the particulate phase 2 there is an interface 3. As described herein, the inventors have discovered that all three can contribute to the strength and wear properties of the MMC.
[0045] FIG. 3 illustrates an optical micrograph of a metal matrix composite (MMC) 20 prepared using spheroidal or substantially spherical carbide particles according to embodiments. As shown, the MMC 20 includes spheroidal or substantially spherical fused tungsten carbide particles 4 and a soft phase 5, which are combined to form the metal matrix composite (MMC) 20. The MMC 20 additionally includes a spheroidal or substantially spherical fused tungsten carbide-to-soft phase interface 6.
[0046] The interface 6 includes metallic or metallurgical bonds formed between the tungsten carbide particles 4 and the soft phase 5. It will 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 4 and the atoms of the soft phase. 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.
[0047] Before being incorporated into the MMC, a mixture including the spheroidal or substantially spherical tungsten carbide particles is in the form of a powder. The MMC formed from the spheroidal or substantially spherical particles discussed herein may be called spherical MMC, whereas the prior art MMC formed from angular powder may be called angular MMC.
[0048] In some embodiments, a liquid metal infiltration route can be used to form the MMC. For example, a metallic binding material may, for example, be generally any suitable brazing metal, including copper, chromium, tin, silver, cobalt nickel, cadmium, manganese, zinc and cobalt or an alloy thereof. The metallic binding material can be liquid cast through tungsten carbide powder and solidified to form the MMC.
[0049] Specifically, liquid metal infiltration of powder containing the components described herein is described with reference to FIG. 12 . A graphite mold assembly 32, 34 is produced that reflects a negative of the desired shape of a drill bit 10 (FIG. 4 ). A powder 30 comprising the spheroidal or substantially spherical particles is poured and compacted in the mold assembly. Subsequently, a binder 29, e.g., copper or copper alloy binder, and steel parts 24 may be added. Thus configured mold assembly is heated to melt at least the binder 29. Within the mold is a sand component 21 whose function is to define regions within the resulting casting that is free from MMC. Upon melting, the binder 29 infiltrates the powder 30 and creates bonds to the steel parts 24. Upon cooling, the solidified structure contains a plurality of composites advantageously located for strength and wear considerations.
[0050] In some embodiments, a quaternary material system may be used as the binder 29. In some embodiments, the binding material can be a quaternary system comprising copper (47-58 wt. % or about 47-about 58), manganese (23-25 wt. % or about 23-about 25), nickel (14-16 wt. % or about 14-about 16) and zinc (7-9 wt. % or about 7-about 9). This composition can provide for an advantageous combination of properties for liquid metal infiltration and the resulting mechanical properties of the MMC. However, other compositions can be used as well and the composition is not limiting.
Drill Bits
[0051] The inventors have discovered that the tungsten carbide particles and MMCs formed therefrom according to embodiments of the disclosure can be particularly useful for applying onto mining equipment, such as drills as described herein. However, it will 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.
[0052] 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.
[0053] A drill bit wears when it rubs against either of a formation or a metal casing tube. The wear may lead to the loss of function and failure of the drill bit. A cooling and lubricating drilling fluid are generally 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.
[0054] 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 favorable for manufacture. A steel drill bit body may be manufactured using casting and wrought manufacturing techniques, examples of which include but 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.
[0055] A MMC drill bit body may wear more slowly than a steel drill bit body. An MMC drill bit body known in the art, however, more frequently fractures during casting and/or processing and/or use from thermal and mechanical shock. Fracturing may cause an early removal of a drill bit from service because it may be structurally unsound or have cosmetic defects. Alternatively, the MMC drill bit body of the prior art 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.
[0056] 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.
[0057] The strength of a sample of an MMC may be determined using a transverse rupture strength (TRS) test, where a load is centrally applied to the cubic or cylindrically shaped MMC sample that is supported between two points. A plurality of samples may be tested to derive a mean strength and a standard deviation which are then taken as being representative. The reliability analysis of the TRS of MMC can provide additional information such as the failure possibility under different stress.
[0058] 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. The high-velocity drilling-mud exits nozzles with the intention of cooling the bit and evacuating the detritus. Drilling mud contains materials such as bentonite, clay and surfactants, which also contains hard and angular minerals from the rock material removal process. The contact between the PDC bits and drilling mud may also degrade the drill bits by erosion. Therefore, the MMC disclosed herein has high erosion resistance accompanied with ultrahigh strength to improve the reliability and performance of the drill bits during the drilling.
[0059] FIG. 4 shows a perspective view of an embodiment of earth-engaging tool in the form of a drill bit 10 which comprises a bit body 12 comprising an MMC 20 (FIG. 3 ) according to embodiments disclosed herein. Some, or all, of the bit body 12 may be formed from embodiments of the MMC 20. In some embodiments, a majority of the bit body 12 is formed from embodiments of the MMC 20. Further, the tool can include a nozzle port 19, e.g., for hydraulic fluid, a blade 16 that supports cutting elements, cutting elements 15, such as polycrystalline diamond compact (PDC) cutter, and junk slots 14 for carrying cuttings away in a fluid from a face of the bit.
[0060] The MMC 20 can be formed from a mixture, which comprises a plurality of mostly spheroidal or substantially spherical particles.
[0061] Structural features of the drill bit 10, will now be described, by way of example. It will 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 12 can have protrusions in the form of radially projecting and longitudinally extending wings or blades 13, which are separated by channels at the face 16 of the drill bit 10 and junk slots 14 at the sides of the drill bit 10. A plurality of cemented tungsten carbide or PDC cutters 15 are brazed within pockets on the leading faces of the blades 13 extending over the face 16 of the bit body 12. The PDC cutters 15 may be supported from behind by buttresses 17, for example, which may be integrally formed with the bit body 12.
[0062] The drill bit 10 may further include a shank 18 in the form of an API threaded connection portion for attaching the drill bit 10 to a drill string (not shown). Furthermore, a longitudinal bore (not shown) extends longitudinally through at least a portion of the bit body 12, and internal fluid passageways (not shown) provide fluid communication between the longitudinal bore and nozzles 19 provided at the face 16 of the bit body 12 and opening onto the channels leading to junk slots 14 for removing the drilling fluid and formation cuttings from the drill face.
[0063] During formation cutting, the drill bit 10 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 is attached—is pumped through the bore, the internal fluid passageways, and the nozzles 19 to the face of the bit body and PDC cutters 15. As the drill bit 10 is rotated, the PDC cutters 15 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 14 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
[0064] While the strength of a sample of an MMC may be determined using a TRS test, the failure to take a statistical approach of the TRS data may not:
-
- [0065] 1. indicate the likelihood of failure;
- [0066] 2. access the probability of failure at a given stress value; and/or
- [0067] 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.
[0068] The strength distribution in a population of samples of the MMC used in the earth-engaging and other tools may be determined using Weibull statistics, which is a probabilistic approach that enables a likelihood of failure to be established at a given applied stress. Embodiments of the disclosed MMCs may be used with an earth-engaging tool 10, for example, which are generally faithful to a Weibull distribution.
[0069] A Weibull strength distribution is described by:
[0070]
[0071] The variables in the equation are: F is the probability of failure for a sample; σ is the applied stress; σu is the lower limit stress needed to cause failure, which is often assumed to be zero; σ0 is the characteristic strength; m is the Weibull modulus, a measure of the variability of the strength of the material; V is volume of specimen.
[0072] The above equation is typically rearranged and presented on a double logarithmic plot of (1/(1−F)) versus logarithm of a and the slope used to calculate m, assuming σu is zero.
[0073] FIG. 5 shows a Weibull plot of empirical strength data for a plurality of samples of the same type of angular MMC similar to those shown in FIG. 2 , containing predominately angular particles (MMC A, left) and an MMC containing predominately spheroidal or substantially spherical particles similar to those shown in FIG. 3 (MMC B, right) according to embodiments. The MMCs illustrated in FIG. 5 are composed of textured spheroidal or substantially spherical tungsten carbide and a Cu53 copper binder. The left-hand axis values are indicative of a function of the probability of failure, the right-hand values are indicative of a percentage probability of failure, and the bottom 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 and the sample of spherical MMC follow a Weibull distribution. The slope of each line defines the respective Weibull moduli. The angular MMC has a Weibull modulus of 13.76 and the spherical MMC 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.
[0074] In some embodiments, the spherical MMC has a Weibull modulus of 15 (or about 15) or greater. In some embodiments, the spherical MMC has a Weibull modulus of 20 (or about 20) or greater. In some embodiments, the spherical MMC has a Weibull modulus of 25 (or about 25) or greater. The Weibull modulus can also have a value in range defined by any of these values.
[0075] A Weibull plot can be used to design drill bit body blade heights and widths to a predetermined failure rate, and particularly 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, it may have an unacceptable probability of failure. Alternatively, the reliability of a drill bit comprising angular MMC can be compared the reliability of another identically configured drill bit comprising spherical MMC.
[0076] Linear extrapolation to a 1 in 10,000 probability of failure equates to applied stress of about 60 ksi (kilopound per square inch) and 188 ksi for angular MMC and spherical MMC, respectively.
[0077] In some embodiments of this disclosure, the linear extrapolation to a 1 in 10,000 probability of failure for the spherical MMC equates to 80 (or about 80) ksi or greater. In some embodiments of this disclosure, the linear extrapolation to a 1 in 10,000 probability of failure for the spherical MMC equates to 100 (or about 100) ksi or greater. In some embodiments of this disclosure, the linear extrapolation to a 1 in 10,000 probability of failure for the spherical MMC equates to 120 (or about 120) ksi or greater. In some embodiments of this disclosure, the linear extrapolation to a 1 in 10,000 probability of failure for the spherical MMC equates to 140 (or about 140) ksi or greater. In some embodiments of this disclosure, the linear extrapolation to a 1 in 10,000 probability of failure for the spherical MMC equates to 160 (or about 160) ksi or greater. In some embodiments of this disclosure, the linear extrapolation to a 1 in 10,000 probability of failure for the spherical MMC equates to 180 (or about 180) ksi or greater. The linear extrapolation to a 1 in 10,000 probability of failure may have a value in a range defined by any of these values.
Microstructure
[0078] In this disclosure, the surface topography of spheroidal or substantially spherical fused tungsten particles that form a powder was examined in detail. The surface condition of the novel spheroidal or substantially spherical fused tungsten carbide has a textured surface. The inventors have discovered that this texture can increase the available surface area at the interface 6 between the soft phase 5 and the spheroidal or substantially spherical fused tungsten carbide particles 4, as shown in FIG. 3 .
[0079] FIG. 6 illustrates the surface morphology of a tungsten particle in a conventional MMC. As shown, the microstructure 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.
[0080] The strength of an MMC system can be associated with one or more of three different components: 1) the strength of the copper binder, the strength of the tungsten carbide particles, and 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 area, the alloy has more area to bond to the carbide particles, thus increasing the interfacial strength.
[0081] FIG. 7 illustrates the surface morphology of a spheroidal or substantially spherical tungsten particle in an MMC according to embodiments of this disclosure. As shown, the microstructure includes a “needle-like” topographical features (e.g., the 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.
[0082] FIG. 8 illustrates the surface morphology of a spheroidal or substantially spherical tungsten particle in an MMC according to embodiments of this disclosure. As shown, the microstructure 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.
[0083] In order 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 SEM image that can be attributed to grain boundaries is analyzed. As described herein, an area fraction of grain boundary 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 boundary can be quantified using images, e.g., high contrast or binary images such as those shown in FIGS. 9-11 . 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 boundary. 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 boundary on the surface of the tungsten carbide particles, e.g., less than 5%. On the contrary, the “needle-like” surface morphology of tungsten particles according to embodiments 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. 6 is 3.6% while the value in FIG. 7 is 14.2%. For an even better case, the area fraction of the grain boundary in FIG. 8 is as high as 20.1% showing the more uniform and finer grains overall.
[0084] The inventors have discovered that the combination of the spheroidal shape of the tungsten carbide particles, and the needle-like surface morphology thereof, gives rise to the relatively high surface area of the tungsten particle carbide particles, which in turn gives rise to the relatively high grain boundary area fraction. The high grain boundary area fraction can be proportional to the amount of high strength interfaces formed between the tungsten carbide particles and the metal matrix, and can in turn be proportional to the mechanical and tribological properties of the MMCs, including the TRS and the erosion resistance. According to embodiments, in addition, 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 μm, 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 μm, 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 that exceeds 2, 5, 10, 20 or a value in a range defined by any of these values.
[0085] 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. some embodiments of this disclosure, the spheroidal or substantially spherical fused tungsten carbide particles have a grain boundary area fraction of 10.0% (or about 10.0%) or greater. In some embodiments of this disclosure, the spheroidal or substantially spherical fused tungsten carbide particles have a grain boundary area fraction of 12.0% (or about 12.0%) or greater. In some embodiments of this disclosure, the spheroidal or substantially spherical fused tungsten carbide particle have a grain boundary area fraction of 12.0% (or about 12.0%) or greater. In some embodiments of this disclosure, the spheroidal or substantially spherical fused tungsten carbide particle have a grain boundary area fraction of 20.0% (or about 20.0%) or greater. The grain boundary area fraction can also have a value in a range defined by any of these values.
[0086] Homogeneity of the grain boundary distribution in the particle surface was also characterized. The original microstructure image was equally separated into nine 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 separated parts were calculated. The lower the value of variance, the more uniform the distribution of the grain boundary. This lower variation can provide for improved strength to the MMC. For example, the variation in FIG. 8 (3.8) is lower than that in FIG. 7 (9.4), indicating a more uniform distribution of grain boundaries in FIG. 8 .
[0087] FIG. 9 illustrates a binary image of FIG. 6 . FIG. 10 shows a binary image of FIG. 7 , which includes an analyzed area fraction of 14.2% and variation of 9.4 when divided into nine parts. FIG. 11 shows a binary image of FIG. 8 , which includes an analyzed area fraction of 20.1% and variation of 3.8 when divided into nine parts.
Physical Properties
[0088] In the present disclosure, the size of the spheroidal or substantially spherical fused tungsten particle may between 1 to 200 μm. The variation of the size of the spheroidal or substantially spherical fused tungsten particle can results in the change in TRS of the final infiltrated MMC.
[0089] The powder particle size distribution is measured and determined by MicroTrac per ASTM B822, hereby incorporated by reference in its entirety. It can be defined by describing 3 points the curve, namely:
-
- [0090] D10 or 10th percentile particle diameter (μm)
- [0091] D50 or average particle diameter (μm)
- [0092] D90 or 90th percentile particle diameter (μm)
[0093] Advantageously, the inventors have discovered that the D50 of the tungsten carbide particles can be tuned to achieve a target value of the TRS. In some embodiments, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 1 μm and 10 μm, has a TRS greater than or equal to 360 ksi (or about 360 ksi). In some embodiments of this disclosure, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 1 μm and 10 μm, has a TRS greater than or equal to 530 ksi (or about 530 ksi). In some embodiments of this disclosure, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 1 μm and 10 μm, has a TRS greater than or equal to 700 ksi (or about 700 ksi). The TRS can have a value in a range defined by any of these values.
[0094] In some embodiments, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 11 μm and 20 μm, has a TRS greater than or equal to 280 ksi (or about 280 ksi). In some embodiments of this disclosure, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 11 μm and 20 μm, has a TRS greater than or equal to 365 ksi (or about 365 ksi). In some embodiments of this disclosure, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 11 μm and 20 μm, has a TRS greater than or equal to 450 ksi (or about 450 ksi). The TRS can have a value in a range defined by any of these values.
[0095] In some embodiments, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 21 μm and 40 μm, has a TRS greater than or equal to 230 ksi (or about 230 ksi). In some embodiments of this disclosure, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 21 μm and 40 μm, has a TRS greater than or equal to 260 ksi (or about ksi). In some embodiments of this disclosure, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 21 μm and 40 μm, has a TRS greater than or equal to 290 ksi (or about 290 ksi). The TRS can have a value in a range defined by any of these values.
[0096] In one embodiment, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 41 μm and 60 μm, has a TRS greater than or equal to 180 ksi. In a preferred embodiment of this disclosure, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 41 μm and 60 μm, has a TRS greater than or equal to 200 ksi. In a still preferred embodiment of this disclosure, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 41 μm and 60 μm, has a TRS greater than or equal to 220 ksi. The TRS can have a value in a range defined by any of these values.
[0097] In some embodiments, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 61 μm and 80 μm, has a TRS greater than or equal to 160 ksi (or about 160 ksi). In some embodiments of this disclosure, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 61 μm and 80 μm, has a TRS greater than or equal to 170 ksi (or about 170 ksi). In some embodiments of this disclosure, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 61 μm and 80 μm, has a TRS greater than or equal to 180 ksi (or 180 ksi). The TRS can have a value in a range defined by any of these values.
[0098] In some embodiments, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 81 μm and 100 μm, has a TRS greater than or equal to 140 ksi (or about 140 ksi). In some embodiments of this disclosure, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 81 μm and 100 μm, has a TRS greater than or equal to 150 ksi (or about 150 ksi). In some embodiments of this disclosure, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 81 μm and 100 μm, has a TRS greater than or equal to 160 ksi (or about 160 ksi). The TRS can have a value in a range defined by any of these values.
[0099] In some embodiments, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 101 μm and 200 μm, has a TRS greater than or equal to 100 ksi (or about 100 ksi). In some embodiments of this disclosure, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 101 μm and 200 μm, has a TRS greater than or equal to 120 ksi (or about 120 ksi). In some embodiments of this disclosure, the MMC formed from spheroidal or substantially spherical fused tungsten carbide particles that have an average particle size (D50) between 101 μm and 200 μm, has a TRS greater than or equal to 140 ksi (or about 140 ksi). The TRS can have a value in a range defined by any of these values.
[0100] Laboratory testing enabled the abrasion and erosion resistance of angular and spherical MMCs to be measured and compared.
[0101] 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° was designed to allow the adjustment of the impacting angle between the sample surface and slurry jet. The stand-off distance between the nozzle and the sample was selected as 1,000 mm in order to avoid cutting of the sample and to enlarge the contact area between the jet and sample. The garnet is used as the erodent. The pressure of the waterjet was 50 ksi. The test duration was 10 min. A balance with an accuracy of 1 mg is used to measure the weight of the coupon before and after the test.
[0102] An MMC sample incorporating embodiments of the disclosed spherical fused tungsten carbide particles and made by liquid infiltration was tested for erosion at 30° impact angle with volume loss at 0.022 cm3 comparing to conventional counterpart at 0.17 cm3.
[0103] In some embodiments of this disclosure, the spherical MMC has an erosive volume loss of 0.10 (or about 0.10) cm3 or lower. In some embodiments of this disclosure, the spherical MMC has an erosive volume loss of 0.08 (or about 0.08) cm3 or less. In some embodiments of this disclosure, the spherical MMC has an erosive volume loss of 0.06 (or about 0.06) cm3 or lower. In some embodiments of this disclosure, the spherical MMC has an erosive volume loss of 0.04 (or about 0.04) cm3 or lower. The volume loss can have a value in a range defined by any of these values.
[0104] For standard ASTM 611 high stress abrasion test, hereby incorporated by reference in its entirety, a certain sample made of embodiments of the disclosed material has volume loss of 0.51 cm3 comparing to conventional MMCs of 1.28 cm3 volume loss.
[0105] 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. In some embodiments of this disclosure, the spherical MMC has an ASTM 611 volume loss of 0.80 (or about 0.80) cm3 or lower. In some embodiments of this disclosure, the spherical MMC has an ASTM 611 volume loss of 0.60 (or about 0.60) cm3 or lower. The volume loss can have a value in a range defined by any of these values.
ADDITIONAL EXAMPLES
[0106] 1. A powder blend comprising fused tungsten carbide particles, wherein the fused tungsten carbide particles comprise:
-
- [0107] 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
- [0108] a surface that is textured to have a grain boundary area fraction greater than 5.0%.
[0109] 2. The powder blend of Example 1, further comprising metallic tungsten particles.
[0110] 3. The powder blend of Examples 1 or 2, wherein the textured surface has a needle-like topography.
[0111] 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 μm.
[0112] 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.
[0113] 6. The powder blend of Example 5, wherein the matrix comprises copper or a copper alloy.
[0114] 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.
[0115] 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.
[0116] 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.
[0117] 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.
[0118] 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.
[0119] 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 μm.
[0120] 13. A metal matrix composite (MMC) material, comprising:
-
- [0121] 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
- [0122] a matrix having embedded therein the fused tungsten carbide particles.
[0123] 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.
[0124] 15. The MMC material of Examples 13 or 14, wherein the matrix comprises copper or a copper alloy.
[0125] 16. The MMC material of any one of Examples 13-15, wherein the MMC material has a Weibull modulus of 15 or greater.
[0126] 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.
[0127] 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.
[0128] 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.
[0129] 20. The MMC material of any one of Examples 13-19, wherein the fused tungsten carbide particles have a D50 between 1 μm and 10 μm and the MMC material has a transverse rupture strength of 360 ksi or greater.
[0130] 21. The MMC material of any one of Examples 13-20, wherein the fused tungsten carbide particles have a D50 between 11 μm and 20 μm and the MMC material has a transverse rupture strength of 280 ksi or greater.
[0131] 22. The MMC material of any one of Examples 13-21, wherein the fused tungsten carbide particles have a D50 between 21 μm and 40 μm and the MMC has a transverse rupture strength of 230 ksi or greater.
[0132] 23. The MMC material of any one of Examples 13-22, wherein the fused tungsten carbide particles have a D50 between 41 μm and 60 μm and the MMC has a transverse rupture strength of 180 ksi or greater.
[0133] 24. The MMC material of any one of Examples 13-23, wherein the fused tungsten carbide particles have a D50 between 61 μm and 80 μm and the MMC has a transverse rupture strength of 160 ksi or greater.
[0134] 25. The MMC material of any one of Examples 13-24, wherein the fused tungsten carbides have a D50 between 81 μm and 100 μm and the MMC has a transverse rupture strength of 140 ksi or greater.
[0135] 26. The MMC material of any one of Examples 13-25, wherein the fused tungsten carbides have a D50 between 101 μm and 200 μm and the MMC has a Transverse Rupture Strength of 100 ksi or greater.
[0136] 27. The MMC material of any one of Examples 13-26, wherein the MMC material forms part of a high strength drill bit.
[0137] 28. A method of forming a metal-matrix composite (MMC) material, the method comprising:
-
- [0138] 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%;
- [0139] adding a binder material comprising copper into the mold;
- [0140] melting the binder material to infiltrate the fused tungsten carbide particles; and
- [0141] solidifying the molten binder material to form the MMC material.
[0142] 29. The method of Example 28, wherein the fused tungsten carbide particles have the grain boundary area fraction of at least 10.0%.
[0143] 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%.
[0144] 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%.
[0145] 32. The method of any one of Examples 28-31, wherein the MMC material has a Weibull modulus of 15 or greater.
[0146] 33. The method of any one of Examples 28-32, wherein the MMC material has a Weibull modulus of 20 or greater.
[0147] 34. The method of any one of Examples 28-33, wherein the MMC material has a Weibull modulus of 25 or greater.
[0148] 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.
[0149] 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.
[0150] 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.
[0151] 38. The method of any one of Examples 28-37, wherein the MMC material has a transverse rupture strength of at least 140 ksi.
[0152] 39. The method of any one of Examples 28-38, wherein the MMC material has a transverse rupture strength of at least 450 ksi.
[0153] 40. The method of any one of Examples 28-39, wherein the MMC material has a transverse rupture strength of at least 700 ksi.
[0154] 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.
[0155] 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.
[0156] 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.
[0157] 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.
[0158] 45. A high strength drill bit comprising:
-
- [0159] 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%.
[0160] 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%.
[0161] 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%.
[0162] 49. The drill bit of any one of Examples 45-48, wherein the metal matrix composite has a Weibull modulus of 15 or greater.
[0163] 50. The drill bit of any one of Examples 45-49, wherein the metal matrix composite has a Weibull modulus of 20 or greater.
[0164] 51. The drill bit of any one of Examples 45-50, wherein the metal matrix composite has a Weibull modulus of 25 or greater.
[0165] 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.
[0166] 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.
[0167] 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.
[0168] 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.
[0169] 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.
[0170] 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.
[0171] 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.
[0172] 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.
[0173] 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.
[0174] 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.
[0175] 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.
[0176] 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.
[0177] 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.
[0178] 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.
[0179] 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.
[0180] Some embodiments have been described in connection with the accompanying drawings. The figures 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.
[0181] 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. A powder blend comprising fused tungsten carbide particles, wherein the fused tungsten carbide particles comprise:
a spheroidal shape having a ratio of a first length along a major axis to a second length along a minor axis of 1.2 or lower;
a textured external surface comprising a grain boundary area fraction greater than 5%; and
an external surface composition comprising fused tungsten carbide.
2. The powder blend of claim 1, further comprising metallic tungsten particles.
3. The powder blend of claim 1, wherein the textured external surface comprises a needle-like topography.
4. The powder blend of claim 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 comprise a portion having a width not exceeding 1 μm.
5. The powder blend of claim 4, wherein at least some of the needle-like structures further comprise a ratio of a longest length to a smallest width that exceeds 2.
6. The powder blend of claim 1, wherein the powder blend is configured to form a metal-matrix composite (MMC) material comprising the fused tungsten carbide particles embedded in a matrix.
7. The powder blend of claim 6, wherein the matrix comprises copper or a copper alloy.
8. The powder blend of claim 6, wherein the MMC material has a Weibull modulus of 15 or greater.
9. The powder blend of claim 6, wherein the MMC material has a linear extrapolation of a Weibull plot to a 1 in 10,000 probability of failure that equates to an applied stress of 80 ksi or greater.
10. The powder blend of claim 6, wherein the MMC material has a high-pressure abrasive waterjet erosive volume loss of 0.1 cm3 or lower.
11. The powder blend of claim 6, wherein the MMC material has an ASTM 611 volume loss of 1 cm3 or lower.
12. The powder blend of claim 1, wherein the fused tungsten carbide particles comprise an average particle size of 1-200 μm.
13. The powder blend of claim 1, wherein the fused tungsten carbide particles comprise a fused tungsten carbide internal microstructure.
14. The powder blend of claim 1, wherein the fused tungsten carbide particles comprise a fused tungsten carbide particle composition consisting essentially of fused tungsten carbide.
15. The powder blend of claim 1, wherein the fused tungsten carbide particles comprise a specific density of about 16.5 g/cm3.
16. The powder blend of claim 1, wherein the fused tungsten carbide particles comprise a micro-hardness of about 2700-3300 HV.
17. The powder blend of claim 1, wherein the fused tungsten carbide particles comprise a fused tungsten carbide particle composition comprising:
carbon: about 3.7-4.2 wt. %; and
tungsten: balance.
18. The powder blend of claim 1, wherein the fused tungsten carbide particles comprise an internal composition comprising fused tungsten carbide.
19. The powder blend of claim 18, wherein the external surface composition and the internal composition each independently comprise:
carbon: about 3.7-4.2 wt. %; and
tungsten: balance.
20. The powder blend of claim 18, wherein the external surface composition and the internal composition are substantially the same.
21. The powder blend of claim 1, wherein the fused tungsten carbide particles have at least one of:
a D50 between 1 μm and 10 μm;
a D50 between 11 μm and 20 μm;
a D50 between 21 μm and 40 μm;
a D50 between 41 μm and 60 μm;
a D50 between 61 μm and 80 μm;
a D50 between 81 μm and 100 μm; and
a D50 between 101 μm and 200 μm.
22. The powder blend of claim 1, wherein the fused tungsten carbide particles comprise a first D50 particle size distribution of 41-80 μm, and a second D50 particle size distribution of 61-200 μm.
23. A method of forming a metal-matrix composite (MMC) material, the method comprising:
adding the powder blend of claim 1 into a mold;
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.
24. The method of claim 23, wherein the fused tungsten carbide particles comprise the grain boundary area fraction of at least 10%.
25. The method of claim 23, wherein the MMC material has a Weibull modulus of 15 or greater.
26. The method of claim 23, wherein a linear extrapolation to a 1 in 10,000 probability of failure for the MMC material equates to 80 ksi or greater.
27. The method of claim 23, wherein the MMC material has a transverse rupture strength of at least 140 ksi.
28. The method of claim 23, 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.
Patent Citations (727)
| Patent | Date | Inventor | Cited By |
|---|---|---|---|
| US2043952(A) | 1936-06-01 | Ffield | Applicant |
| US2156306(A) | 1939-05-01 | Rapatz | Applicant |
| US2507195(A) | 1950-05-01 | Winearls | Applicant |
| US2608495(A) | 1952-08-01 | Barry | Applicant |
| US2873187(A) | 1959-02-01 | Dyrkaez et al. | Applicant |
| US2936229(A) | 1960-05-01 | Shepard | Applicant |
| US3024137(A) | 1962-03-01 | Witherell | Applicant |
| US3113021(A) | 1963-12-01 | Witherell | Applicant |
| US3181970(A) | 1965-05-01 | Witherell et al. | Applicant |
| US3303063(A) | 1967-02-01 | Pietryka et al. | Applicant |
| US3448241(A) | 1969-06-01 | Buckingham et al. | Applicant |
| US3554792(A) | 1971-01-01 | Johnson | Applicant |
| US3650734(A) | 1972-03-01 | Kantor et al. | Applicant |
| US3663214(A) | 1972-05-01 | Moore | Applicant |
| US3724016(A) | 1973-04-01 | Kumar et al. | Applicant |
| US3819364(A) | 1974-06-01 | Frehn | Applicant |
| US3843359(A) | 1974-10-01 | Fiene et al. | Applicant |
| US3859060(A) | 1975-01-01 | Eiselstein et al. | Applicant |
| US3942954(A) | 1976-03-01 | Frehn | Applicant |
| US3975612(A) | 1976-08-01 | Nakazaki et al. | Applicant |
| US4010309(A) | 1977-03-01 | Peterson | Applicant |
| US4017339(A) | 1977-04-01 | Okuda et al. | Applicant |
| US4042383(A) | 1977-08-01 | Petersen et al. | Applicant |
| US4066451(A) | 1978-01-01 | Rudy | Applicant |
| US4110514(A) | 1978-08-01 | Nicholson | Applicant |
| US4214145(A) | 1980-07-01 | Zvanut et al. | Applicant |
| US4235630(A) | 1980-11-01 | Babu | Applicant |
| US4240827(A) | 1980-12-01 | Aihara | Applicant |
| US4255709(A) | 1981-03-01 | Zatsepium et al. | Applicant |
| US4277108(A) | 1981-07-01 | Wallace | Applicant |
| US4285725(A) | 1981-08-01 | Gysel | Applicant |
| US4297135(A) | 1981-10-01 | Giessen et al. | Applicant |
| US4318733(A) | 1982-03-01 | Ray et al. | Applicant |
| US4362553(A) | 1982-12-01 | Ray | Applicant |
| US4365994(A) | 1982-12-01 | Ray | Applicant |
| US4415530(A) | 1983-11-01 | Hunt | Applicant |
| US4419130(A) | 1983-12-01 | Slaughter | Applicant |
| US4576653(A) | 1986-03-01 | Ray | Applicant |
| US4596282(A) | 1986-06-01 | Maddy et al. | Applicant |
| US4606977(A) | 1986-08-01 | Dickson et al. | Applicant |
| US4635701(A) | 1987-01-01 | Sare et al. | Applicant |
| US4638847(A) | 1987-01-01 | Day | Applicant |
| US4639576(A) | 1987-01-01 | Shoemaker | Applicant |
| US4666797(A) | 1987-05-01 | Newman et al. | Applicant |
| US4673550(A) | 1987-06-01 | Dallaire et al. | Applicant |
| US4762681(A) | 1988-08-01 | Tassen et al. | Applicant |
| US4783218(A) | 1988-11-01 | Kemp et al. | Applicant |
| US4803045(A) | 1989-02-01 | Ohriner et al. | Applicant |
| US4806394(A) | 1989-02-01 | Steine | Applicant |
| US4818307(A) | 1989-04-01 | Mori et al. | Applicant |
| US4822415(A) | 1989-04-01 | Dorfman et al. | Applicant |
| US4888153(A) | 1989-12-01 | Yabuki | Applicant |
| US4919728(A) | 1990-04-01 | Kohl et al. | Applicant |
| US4943488(A) | 1990-07-01 | Sung et al. | Applicant |
| US4957982(A) | 1990-09-01 | Geddes | Applicant |
| US4966626(A) | 1990-10-01 | Fujiki et al. | Applicant |
| US4981644(A) | 1991-01-01 | Chang | Applicant |
| US5094812(A) | 1992-03-01 | Dulmaine et al. | Applicant |
| US5252149(A) | 1993-10-01 | Dolman | Applicant |
| US5280726(A) | 1994-01-01 | Urbanic et al. | Applicant |
| US5306358(A) | 1994-04-01 | Lai et al. | Applicant |
| US5375759(A) | 1994-12-01 | Hiraishi et al. | Applicant |
| US5424101(A) | 1995-06-01 | Atkins | Applicant |
| US5495837(A) | 1996-03-01 | Mitsuhashi | Applicant |
| US5567251(A) | 1996-10-01 | Peker et al. | Applicant |
| US5570636(A) | 1996-11-01 | Lewis | Applicant |
| US5618451(A) | 1997-04-01 | Ni | Applicant |
| US5820939(A) | 1998-10-01 | Popoola et al. | Applicant |
| US5837326(A) | 1998-11-01 | Dallaire | Applicant |
| US5843243(A) | 1998-12-01 | Kawasaki et al. | Applicant |
| US5858558(A) | 1999-01-01 | Zhao et al. | Applicant |
| US5861605(A) | 1999-01-01 | Ogawa et al. | Applicant |
| US5907017(A) | 1999-05-01 | Ober et al. | Applicant |
| US5911949(A) | 1999-06-01 | Ninomiya et al. | Applicant |
| US5935350(A) | 1999-08-01 | Raghu et al. | Applicant |
| US5942289(A) | 1999-08-01 | Jackson | Applicant |
| US5976704(A) | 1999-11-01 | McCune | Applicant |
| US5988302(A) | 1999-11-01 | Sreshta et al. | Applicant |
| US6071324(A) | 2000-06-01 | Laul et al. | Applicant |
| US6117493(A) | 2000-09-01 | North | Applicant |
| US6171222(B1) | 2001-01-01 | Lakeland et al. | Applicant |
| US6210635(B1) | 2001-04-01 | Jackson et al. | Applicant |
| US6232000(B1) | 2001-05-01 | Singh et al. | Applicant |
| US6238843(B1) | 2001-05-01 | Ray | Applicant |
| US6306524(B1) | 2001-10-01 | Spitsberg et al. | Applicant |
| US6326582(B1) | 2001-12-01 | North | Applicant |
| US6331688(B1) | 2001-12-01 | Hallén et al. | Applicant |
| US6332936(B1) | 2001-12-01 | Hajaligo et al. | Applicant |
| US6375895(B1) | 2002-04-01 | Daemen | Applicant |
| US6398103(B2) | 2002-06-01 | Hasz et al. | Applicant |
| US6441334(B1) | 2002-08-01 | Aida et al. | Applicant |
| US6582126(B2) | 2003-06-01 | North | Applicant |
| US6608286(B2) | 2003-08-01 | Jiang | Applicant |
| US6669790(B1) | 2003-12-01 | Gundlach et al. | Applicant |
| US6689234(B2) | 2004-02-01 | Branagan | Applicant |
| US6702905(B1) | 2004-03-01 | Qiao et al. | Applicant |
| US6702906(B2) | 2004-03-01 | Ogawa et al. | Applicant |
| US6750430(B2) | 2004-06-01 | Kelly | Applicant |
| US7052561(B2) | 2006-05-01 | Lu et al. | Applicant |
| US7219727(B2) | 2007-05-01 | Slack et al. | Applicant |
| US7285151(B2) | 2007-10-01 | Sjodin et al. | Applicant |
| US7361411(B2) | 2008-04-01 | Daemen et al. | Applicant |
| US7491910(B2) | 2009-02-01 | Kapoor et al. | Applicant |
| US7507305(B2) | 2009-03-01 | Kawasaki et al. | Applicant |
| US7553382(B2) | 2009-06-01 | Branagan et al. | Applicant |
| US7569286(B2) | 2009-08-01 | Daemen et al. | Applicant |
| US7754152(B2) | 2010-07-01 | Riebel et al. | Applicant |
| US7776451(B2) | 2010-08-01 | Jiang et al. | Applicant |
| US7935198(B2) | 2011-05-01 | Branagan et al. | Applicant |
| US8070894(B2) | 2011-12-01 | Branagan | Applicant |
| US8097095(B2) | 2012-01-01 | Branagan | Applicant |
| US8153935(B2) | 2012-04-01 | Jang et al. | Applicant |
| US8187529(B2) | 2012-05-01 | Powell | Applicant |
| US8187725(B2) | 2012-05-01 | Kiser et al. | Applicant |
| US8268453(B2) | 2012-09-01 | Dallaire | Applicant |
| US8474541(B2) | 2013-07-01 | Branagan et al. | Applicant |
| US8562759(B2) | 2013-10-01 | Cheney et al. | Applicant |
| US8562760(B2) | 2013-10-01 | Cheney et al. | Applicant |
| US8640941(B2) | 2014-02-01 | Cheney | Applicant |
| US8647449(B2) | 2014-02-01 | Cheney et al. | Applicant |
| US8658934(B2) | 2014-02-01 | Branagan et al. | Applicant |
| US8662143(B1) | 2014-03-01 | Foster | Applicant |
| US8669491(B2) | 2014-03-01 | Menon et al. | Applicant |
| US8702835(B2) | 2014-04-01 | Yu et al. | Applicant |
| US8703046(B2) | 2014-04-01 | Hanejko et al. | Applicant |
| US8704134(B2) | 2014-04-01 | Branagan et al. | Applicant |
| US8777090(B2) | 2014-07-01 | Miller et al. | Applicant |
| US8801872(B2) | 2014-08-01 | Wright et al. | Applicant |
| US8808471(B2) | 2014-08-01 | Wright et al. | Applicant |
| US8858675(B2) | 2014-10-01 | Larsson | Applicant |
| US8870997(B2) | 2014-10-01 | Klekovkin et al. | Applicant |
| US8901022(B2) | 2014-12-01 | Francy et al. | Applicant |
| US8911662(B2) | 2014-12-01 | Larsson | Applicant |
| US8920938(B2) | 2014-12-01 | Hesse et al. | Applicant |
| US8961869(B2) | 2015-02-01 | Kapoor et al. | Applicant |
| US8973806(B2) | 2015-03-01 | Cheney | Applicant |
| US8992659(B2) | 2015-03-01 | Larsson et al. | Applicant |
| US9051635(B2) | 2015-06-01 | Jou | Applicant |
| US9095932(B2) | 2015-08-01 | Miller et al. | Applicant |
| US9145598(B2) | 2015-09-01 | Oshchepkov | Applicant |
| US9174293(B2) | 2015-11-01 | Meyer | Applicant |
| US9193011(B2) | 2015-11-01 | Mars et al. | Applicant |
| US9233419(B2) | 2016-01-01 | Gries | Applicant |
| US9255309(B2) | 2016-02-01 | Aimone | Applicant |
| US9309585(B2) | 2016-04-01 | Cheney et al. | Applicant |
| US9314848(B2) | 2016-04-01 | Larsson | Applicant |
| US9340855(B2) | 2016-05-01 | Schade et al. | Applicant |
| US9394591(B2) | 2016-07-01 | Deodeshmukh et al. | Applicant |
| US9399907(B2) | 2016-07-01 | Mo et al. | Applicant |
| US9469890(B2) | 2016-10-01 | Bengtsson | Applicant |
| US9540711(B2) | 2017-01-01 | Fifield | Applicant |
| US9580773(B2) | 2017-02-01 | Aimone et al. | Applicant |
| US9631262(B2) | 2017-04-01 | Wright et al. | Applicant |
| US9724786(B2) | 2017-08-01 | Postle et al. | Applicant |
| US9725793(B2) | 2017-08-01 | Aimone et al. | Applicant |
| US9738959(B2) | 2017-08-01 | Cheney et al. | Applicant |
| US9745648(B2) | 2017-08-01 | Olserius et al. | Applicant |
| US9802387(B2) | 2017-10-01 | Cheney | Applicant |
| US9815148(B2) | 2017-11-01 | Postle | Applicant |
| US9816164(B2) | 2017-11-01 | Larsson et al. | Applicant |
| US9821372(B2) | 2017-11-01 | Gries | Applicant |
| US9834829(B1) | 2017-12-01 | Aimone et al. | Applicant |
| US9845520(B2) | 2017-12-01 | Wright et al. | Applicant |
| US9856546(B2) | 2018-01-01 | Fischer et al. | Applicant |
| US9869132(B2) | 2018-01-01 | Wyble et al. | Applicant |
| US9879333(B2) | 2018-01-01 | Gerk et al. | Applicant |
| US9908816(B2) | 2018-03-01 | Champion et al. | Applicant |
| US9914987(B2) | 2018-03-01 | Snyder et al. | Applicant |
| US9919358(B2) | 2018-03-01 | Gries | Applicant |
| US9951413(B2) | 2018-04-01 | Billieres | Applicant |
| US9957590(B2) | 2018-05-01 | Mars et al. | Applicant |
| US9957592(B2) | 2018-05-01 | Aimone et al. | Applicant |
| US9970091(B2) | 2018-05-01 | Crook et al. | Applicant |
| US9994935(B2) | 2018-06-01 | Wolverton et al. | Applicant |
| US10100388(B2) | 2018-10-01 | Cheney | Applicant |
| US10105796(B2) | 2018-10-01 | Eibl | Applicant |
| US10125412(B2) | 2018-11-01 | Kaner et al. | Applicant |
| US10173290(B2) | 2019-01-01 | Cheney | Applicant |
| US10252919(B2) | 2019-04-01 | Billieres et al. | Applicant |
| US10329647(B2) | 2019-06-01 | Cheney | Applicant |
| USRE47529(E) | 2019-07-01 | Johnson | Applicant |
| US10351921(B2) | 2019-07-01 | Snyder et al. | Applicant |
| US10351922(B2) | 2019-07-01 | Snyder et al. | Applicant |
| US10351938(B2) | 2019-07-01 | Schade et al. | Applicant |
| US10358699(B2) | 2019-07-01 | Srivastava et al. | Applicant |
| US10358701(B2) | 2019-07-01 | Reed et al. | Applicant |
| US10370740(B2) | 2019-08-01 | Reed et al. | Applicant |
| US10384313(B2) | 2019-08-01 | Persson | Applicant |
| US10400314(B2) | 2019-09-01 | Aimone et al. | Applicant |
| US10458006(B2) | 2019-10-01 | Bengtsson | Applicant |
| US10465267(B2) | 2019-11-01 | Cheney | Applicant |
| US10465268(B2) | 2019-11-01 | Bergman | Applicant |
| US10465269(B2) | 2019-11-01 | Cheney | Applicant |
| US10471503(B2) | 2019-11-01 | Wright et al. | Applicant |
| US10513758(B2) | 2019-12-01 | Mars | Applicant |
| US10519529(B2) | 2019-12-01 | Wright et al. | Applicant |
| US10550460(B2) | 2020-02-01 | Nilsson et al. | Applicant |
| US10577680(B2) | 2020-03-01 | Srivastava et al. | Applicant |
| US10597757(B2) | 2020-03-01 | Gong et al. | Applicant |
| US10702918(B2) | 2020-07-01 | Hu | Applicant |
| US10702924(B2) | 2020-07-01 | Szabo et al. | Applicant |
| US10711329(B2) | 2020-07-01 | Wright et al. | Applicant |
| US10731236(B2) | 2020-08-01 | Kaner et al. | Applicant |
| US10745782(B2) | 2020-08-01 | Wolverton et al. | Applicant |
| US10851444(B2) | 2020-12-01 | Vecchio et al. | Applicant |
| US10851565(B1) | 2020-12-01 | Krueger | Applicant |
| US10872682(B2) | 2020-12-01 | Reed et al. | Applicant |
| US10934608(B2) | 2021-03-01 | Gu | Applicant |
| US10941473(B2) | 2021-03-01 | Snyder | Applicant |
| US10954588(B2) | 2021-03-01 | Cheney | Applicant |
| US11001912(B2) | 2021-05-01 | Aimone et al. | Applicant |
| US11033998(B2) | 2021-06-01 | Kavanaugh et al. | Applicant |
| US11085102(B2) | 2021-08-01 | Cheney | Applicant |
| US11111912(B2) | 2021-09-01 | Cheney | Applicant |
| US11114226(B2) | 2021-09-01 | Jayaraman et al. | Applicant |
| US11118247(B2) | 2021-09-01 | Gong et al. | Applicant |
| US11124429(B2) | 2021-09-01 | Gore et al. | Applicant |
| US11130205(B2) | 2021-09-01 | Cheney | Applicant |
| US11174538(B2) | 2021-11-01 | Kaner et al. | Applicant |
| US11261506(B2) | 2022-03-01 | Xu et al. | Applicant |
| US11279996(B2) | 2022-03-01 | Cheney et al. | Applicant |
| US11325189(B2) | 2022-05-01 | Imano et al. | Applicant |
| US11326239(B2) | 2022-05-01 | Cao et al. | Applicant |
| US11353957(B2) | 2022-06-01 | Border et al. | Applicant |
| US11359268(B2) | 2022-06-01 | Cao et al. | Applicant |
| US11370198(B2) | 2022-06-01 | Maroli et al. | Applicant |
| US11389872(B2) | 2022-07-01 | Stawovy et al. | Applicant |
| US2001/0019781(A1) | 2001-09-01 | Hasz | Applicant |
| US2002/0054972(A1) | 2002-05-01 | Charpentier et al. | Applicant |
| US2002/0060907(A1) | 2002-05-01 | Saccomanno | Applicant |
| US2002/0098298(A1) | 2002-07-01 | Bolton et al. | Applicant |
| US2002/0148533(A1) | 2002-10-01 | Kim et al. | Applicant |
| US2002/0159914(A1) | 2002-10-01 | Yeh | Applicant |
| US2003/0000339(A1) | 2003-01-01 | Findeisen | Applicant |
| US2003/0013171(A1) | 2003-01-01 | Yang et al. | Applicant |
| US2004/0001966(A1) | 2004-01-01 | Subramanian | Applicant |
| US2004/0062677(A1) | 2004-04-01 | Chabenat et al. | Applicant |
| US2004/0079742(A1) | 2004-04-01 | Kelly | Applicant |
| US2004/0115086(A1) | 2004-06-01 | Chabenat et al. | Applicant |
| US2004/0206726(A1) | 2004-10-01 | Daemen et al. | Applicant |
| US2005/0047952(A1) | 2005-03-01 | Coleman | Applicant |
| US2005/0109431(A1) | 2005-05-01 | Kernan et al. | Applicant |
| US2005/0139294(A1) | 2005-06-01 | Kim et al. | Applicant |
| US2005/0164016(A1) | 2005-07-01 | Branagan et al. | Applicant |
| US2006/0063020(A1) | 2006-03-01 | Barbezat | Applicant |
| US2006/0093752(A1) | 2006-05-01 | Darolia et al. | Applicant |
| US2006/0163217(A1) | 2006-07-01 | Jiang | Applicant |
| US2006/0191606(A1) | 2006-08-01 | Ogawa et al. | Applicant |
| US2006/0260583(A1) | 2006-11-01 | Abi-Akar et al. | Applicant |
| US2007/0026159(A1) | 2007-02-01 | Deem | Applicant |
| US2007/0029295(A1) | 2007-02-01 | Branagan | Applicant |
| US2007/0090167(A1) | 2007-04-01 | Arjakine et al. | Applicant |
| US2007/0125458(A1) | 2007-06-01 | Kawasaki et al. | Applicant |
| US2007/0187369(A1) | 2007-08-01 | Menon et al. | Applicant |
| US2007/0219053(A1) | 2007-09-01 | Barufka et al. | Applicant |
| US2007/0253856(A1) | 2007-11-01 | Vecchio et al. | Applicant |
| US2007/0284018(A1) | 2007-12-01 | Hamano et al. | Applicant |
| US2008/0001115(A1) | 2008-01-01 | Qiao et al. | Applicant |
| US2008/0031769(A1) | 2008-02-01 | Yeh | Applicant |
| US2008/0083391(A1) | 2008-04-01 | Sawada | Applicant |
| US2008/0149397(A1) | 2008-06-01 | Overstreet | Applicant |
| US2008/0199684(A1) | 2008-08-01 | Apte et al. | Applicant |
| US2008/0241580(A1) | 2008-10-01 | Kiser et al. | Applicant |
| US2008/0241584(A1) | 2008-10-01 | Daemen et al. | Applicant |
| US2008/0246523(A1) | 2008-10-01 | Murakamo et al. | Applicant |
| US2008/0253918(A1) | 2008-10-01 | Liang | Applicant |
| US2009/0017328(A1) | 2009-01-01 | Katoh et al. | Applicant |
| US2009/0075057(A1) | 2009-03-01 | Kulkarni | Applicant |
| US2009/0075101(A1) | 2009-03-01 | Kulkarni et al. | Applicant |
| US2009/0123765(A1) | 2009-05-01 | Branagan | Applicant |
| US2009/0154183(A1) | 2009-06-01 | Nagai et al. | Applicant |
| US2009/0252636(A1) | 2009-10-01 | Christopherson, Jr. et al. | Applicant |
| US2009/0258250(A1) | 2009-10-01 | Daemen et al. | Applicant |
| US2009/0285715(A1) | 2009-11-01 | Arjakine et al. | Applicant |
| US2010/0009089(A1) | 2010-01-01 | Junod et al. | Applicant |
| US2010/0028706(A1) | 2010-02-01 | Hornschu et al. | Applicant |
| US2010/0044348(A1) | 2010-02-01 | Buchmann | Applicant |
| US2010/0047622(A1) | 2010-02-01 | Fischer et al. | Applicant |
| US2010/0055495(A1) | 2010-03-01 | Sjodin | Applicant |
| US2010/0101780(A1) | 2010-04-01 | Ballew et al. | Applicant |
| US2010/0132408(A1) | 2010-06-01 | Billieres | Applicant |
| US2010/0136361(A1) | 2010-06-01 | Osuki et al. | Applicant |
| US2010/0155236(A1) | 2010-06-01 | Lee et al. | Applicant |
| US2010/0159136(A1) | 2010-06-01 | Lee et al. | Applicant |
| US2010/0166594(A1) | 2010-07-01 | Hirata et al. | Applicant |
| US2010/0189588(A1) | 2010-07-01 | Kawatsu et al. | Applicant |
| US2010/0192476(A1) | 2010-08-01 | Theisen et al. | Applicant |
| US2010/0258217(A1) | 2010-10-01 | Kuehmann | Applicant |
| US2011/0004069(A1) | 2011-01-01 | Ochs et al. | Applicant |
| US2011/0031222(A1) | 2011-02-01 | Branagan et al. | Applicant |
| US2011/0048587(A1) | 2011-03-01 | Vecchio et al. | Applicant |
| US2011/0064963(A1) | 2011-03-01 | Cheney et al. | Applicant |
| US2011/0139761(A1) | 2011-06-01 | Sugahara et al. | Applicant |
| US2011/0142713(A1) | 2011-06-01 | Kawasaki et al. | Applicant |
| US2011/0162612(A1) | 2011-07-01 | Qiao et al. | Applicant |
| US2011/0171485(A1) | 2011-07-01 | Kawamoto et al. | Applicant |
| US2011/0220415(A1) | 2011-09-01 | Jin et al. | Applicant |
| US2012/0055899(A1) | 2012-03-01 | Parmaningsih | Applicant |
| US2012/0055903(A1) | 2012-03-01 | Izutani et al. | Applicant |
| US2012/0100390(A1) | 2012-04-01 | Kuroda | Applicant |
| US2012/0103456(A1) | 2012-05-01 | Smith et al. | Applicant |
| US2012/0156020(A1) | 2012-06-01 | Kottilingam et al. | Applicant |
| US2012/0160363(A1) | 2012-06-01 | Jin et al. | Applicant |
| US2012/0258273(A1) | 2012-10-01 | Churchill et al. | Applicant |
| US2012/0288400(A1) | 2012-11-01 | Hirata et al. | Applicant |
| US2013/0039800(A1) | 2013-02-01 | Dolman | Applicant |
| US2013/0094900(A1) | 2013-04-01 | Folkmann et al. | Applicant |
| US2013/0108502(A1) | 2013-05-01 | Bei | Applicant |
| US2013/0167965(A1) | 2013-07-01 | Cheney et al. | Applicant |
| US2013/0171367(A1) | 2013-07-01 | Kusinski et al. | Applicant |
| US2013/0174612(A1) | 2013-07-01 | Linnot et al. | Applicant |
| US2013/0216722(A1) | 2013-08-01 | Kusinski et al. | Applicant |
| US2013/0220523(A1) | 2013-08-01 | Cheney | Applicant |
| US2013/0224516(A1) | 2013-08-01 | Kusinski et al. | Applicant |
| US2013/0260177(A1) | 2013-10-01 | Wallin et al. | Applicant |
| US2013/0266798(A1) | 2013-10-01 | Cheney | Applicant |
| US2013/0266820(A1) | 2013-10-01 | Kusinski et al. | Applicant |
| US2013/0294962(A1) | 2013-11-01 | Wallin et al. | Applicant |
| US2014/0024509(A1) | 2014-01-01 | Gerschefske | Applicant |
| US2014/0044587(A1) | 2014-02-01 | Crook et al. | Applicant |
| US2014/0044617(A1) | 2014-02-01 | Dreisinger | Applicant |
| US2014/0060707(A1) | 2014-03-01 | Wright et al. | Applicant |
| US2014/0066851(A1) | 2014-03-01 | Cheney, II | Applicant |
| US2014/0116575(A1) | 2014-05-01 | Cheney et al. | Applicant |
| US2014/0131338(A1) | 2014-05-01 | Postle | Applicant |
| US2014/0190594(A1) | 2014-07-01 | Branagan et al. | Applicant |
| US2014/0219859(A1) | 2014-08-01 | Cheney | Applicant |
| US2014/0234154(A1) | 2014-08-01 | Cheney et al. | Applicant |
| US2014/0248509(A1) | 2014-09-01 | Cheney et al. | Applicant |
| US2014/0263248(A1) | 2014-09-01 | Postle | Applicant |
| US2014/0272388(A1) | 2014-09-01 | Knight et al. | Applicant |
| US2014/0295194(A1) | 2014-10-01 | Yoshitaka et al. | Applicant |
| US2014/0322064(A1) | 2014-10-01 | Gerk et al. | Applicant |
| US2014/0356223(A1) | 2014-12-01 | Nilsson et al. | Applicant |
| US2015/0004337(A1) | 2015-01-01 | Zimmermann et al. | Applicant |
| US2015/0075681(A1) | 2015-03-01 | Wright et al. | Applicant |
| US2015/0086413(A1) | 2015-03-01 | Wolverton et al. | Applicant |
| US2015/0106035(A1) | 2015-04-01 | Vecchio et al. | Applicant |
| US2015/0114525(A1) | 2015-04-01 | Valls Anglés | Applicant |
| US2015/0118098(A1) | 2015-04-01 | Valls | Applicant |
| US2015/0122552(A1) | 2015-05-01 | Wang et al. | Applicant |
| US2015/0152994(A1) | 2015-06-01 | Bondil et al. | Applicant |
| US2015/0252631(A1) | 2015-09-01 | Miller | Applicant |
| US2015/0275341(A1) | 2015-10-01 | Cheney | Applicant |
| US2015/0284817(A1) | 2015-10-01 | Snyder et al. | Applicant |
| US2015/0284829(A1) | 2015-10-01 | Cheney | Applicant |
| US2015/0307968(A1) | 2015-10-01 | Mars et al. | Applicant |
| US2015/0328680(A1) | 2015-11-01 | Tuffile | Applicant |
| US2015/0367454(A1) | 2015-12-01 | Cheney | Applicant |
| US2016/0001368(A1) | 2016-01-01 | Gries et al. | Applicant |
| US2016/0002752(A1) | 2016-01-01 | Srivastava et al. | Applicant |
| US2016/0002764(A1) | 2016-01-01 | Gries et al. | Applicant |
| US2016/0017463(A1) | 2016-01-01 | Cheney | Applicant |
| US2016/0024628(A1) | 2016-01-01 | Cheney | Applicant |
| US2016/0040262(A1) | 2016-02-01 | Snyder et al. | Applicant |
| US2016/0083830(A1) | 2016-03-01 | Cheney | Applicant |
| US2016/0114392(A1) | 2016-04-01 | Berg et al. | Applicant |
| US2016/0138144(A1) | 2016-05-01 | Olsérius | Applicant |
| US2016/0144463(A1) | 2016-05-01 | Hellsten et al. | Applicant |
| US2016/0195216(A1) | 2016-07-01 | Bondil et al. | Applicant |
| US2016/0201169(A1) | 2016-07-01 | Vecchio | Applicant |
| US2016/0201170(A1) | 2016-07-01 | Vecchio | Applicant |
| US2016/0215374(A1) | 2016-07-01 | Schade et al. | Applicant |
| US2016/0222490(A1) | 2016-08-01 | Wright et al. | Applicant |
| US2016/0243616(A1) | 2016-08-01 | Gries | Applicant |
| US2016/0258044(A1) | 2016-09-01 | Litström et al. | Applicant |
| US2016/0271736(A1) | 2016-09-01 | Han et al. | Applicant |
| US2016/0289001(A1) | 2016-10-01 | Shibata et al. | Applicant |
| US2016/0289798(A1) | 2016-10-01 | Deodeshmukh et al. | Applicant |
| US2016/0289799(A1) | 2016-10-01 | Crook et al. | Applicant |
| US2016/0289803(A1) | 2016-10-01 | Cheney | Applicant |
| US2016/0329139(A1) | 2016-11-01 | Jayaraman | Applicant |
| US2016/0376686(A1) | 2016-12-01 | Jou | Applicant |
| US2017/0009324(A1) | 2017-01-01 | Crook et al. | Applicant |
| US2017/0014865(A1) | 2017-01-01 | Kusinski et al. | Applicant |
| US2017/0022588(A1) | 2017-01-01 | Tang et al. | Applicant |
| US2017/0044646(A1) | 2017-02-01 | Gong et al. | Applicant |
| US2017/0044647(A1) | 2017-02-01 | Olsen | Examiner |
| US2017/0145547(A1) | 2017-05-01 | Saal et al. | Applicant |
| US2017/0253950(A1) | 2017-09-01 | Shinohara | Applicant |
| US2017/0275740(A1) | 2017-09-01 | Bergman | Applicant |
| US2018/0016664(A1) | 2018-01-01 | Hu | Applicant |
| US2018/0021894(A1) | 2018-01-01 | Persoon et al. | Applicant |
| US2018/0066343(A1) | 2018-03-01 | Bengtsson | Applicant |
| US2018/0066345(A1) | 2018-03-01 | Cheney et al. | Applicant |
| US2018/0094343(A1) | 2018-04-01 | Gerk et al. | Applicant |
| US2018/0099877(A1) | 2018-04-01 | Chang et al. | Applicant |
| US2018/0135143(A1) | 2018-05-01 | Snyder et al. | Applicant |
| US2018/0195156(A1) | 2018-07-01 | Reed et al. | Applicant |
| US2018/0216212(A1) | 2018-08-01 | Reed et al. | Applicant |
| US2018/0230016(A1) | 2018-08-01 | Kaner et al. | Applicant |
| US2018/0230578(A1) | 2018-08-01 | Srivastava et al. | Applicant |
| US2018/0245190(A1) | 2018-08-01 | Snyder et al. | Applicant |
| US2018/0265949(A1) | 2018-09-01 | Wolverton et al. | Applicant |
| US2018/0272423(A1) | 2018-09-01 | Hu | Applicant |
| US2019/0017154(A1) | 2019-01-01 | Kaner et al. | Applicant |
| US2019/0024217(A1) | 2019-01-01 | Yolton | Applicant |
| US2019/0055860(A1) | 2019-02-01 | Jones | Applicant |
| US2019/0071318(A1) | 2019-03-01 | Kaner et al. | Applicant |
| US2019/0084039(A1) | 2019-03-01 | Hu | Applicant |
| US2019/0128072(A1) | 2019-05-01 | Griffo | Examiner |
| US2019/0135646(A1) | 2019-05-01 | Turner et al. | Applicant |
| US2019/0177820(A1) | 2019-06-01 | Larsson | Applicant |
| US2019/0234151(A1) | 2019-08-01 | Olsen et al. | Applicant |
| US2019/0300374(A1) | 2019-10-01 | Shevchenko et al. | Applicant |
| US2019/0309399(A1) | 2019-10-01 | Badwe | Applicant |
| US2019/0323107(A1) | 2019-10-01 | Srivastava et al. | Applicant |
| US2019/0368014(A1) | 2019-12-01 | Liimatainen | Applicant |
| US2019/0376165(A1) | 2019-12-01 | Wen | Applicant |
| US2020/0001367(A1) | 2020-01-01 | Duffy et al. | Applicant |
| US2020/0005975(A1) | 2020-01-01 | Jayaraman et al. | Applicant |
| US2020/0048743(A1) | 2020-02-01 | Gong et al. | Applicant |
| US2020/0063238(A1) | 2020-02-01 | Yolton | Applicant |
| US2020/0063239(A1) | 2020-02-01 | Xu et al. | Applicant |
| US2020/0078860(A1) | 2020-03-01 | Wright et al. | Applicant |
| US2020/0149141(A1) | 2020-05-01 | Wu et al. | Applicant |
| US2020/0172998(A1) | 2020-06-01 | Crudden et al. | Applicant |
| US2020/0189918(A1) | 2020-06-01 | Saeuberlich et al. | Applicant |
| US2020/0223007(A1) | 2020-07-01 | Keegan et al. | Applicant |
| US2020/0308679(A1) | 2020-10-01 | Nymann | Applicant |
| US2020/0316718(A1) | 2020-10-01 | Smathers | Applicant |
| US2020/0325561(A1) | 2020-10-01 | Kaner | Applicant |
| US2020/0370149(A1) | 2020-11-01 | Gong | Applicant |
| US2020/0385845(A1) | 2020-12-01 | Gong | Applicant |
| US2021/0040585(A1) | 2021-02-01 | Alabort | Applicant |
| US2021/0046543(A1) | 2021-02-01 | Larsson | Applicant |
| US2021/0062305(A1) | 2021-03-01 | Fang | Applicant |
| US2021/0164081(A1) | 2021-06-01 | Eibl | Applicant |
| US2021/0180157(A1) | 2021-06-01 | Bracci | Applicant |
| US2021/0180162(A1) | 2021-06-01 | Vecchio | Applicant |
| US2021/0180170(A1) | 2021-06-01 | Pike | Applicant |
| US2021/0197524(A1) | 2021-07-01 | Maroli et al. | Applicant |
| US2021/0222275(A1) | 2021-07-01 | Saboo et al. | Applicant |
| US2021/0246537(A1) | 2021-08-01 | Maroli et al. | Applicant |
| US2021/0254202(A1) | 2021-08-01 | Gong et al. | Applicant |
| US2021/0262050(A1) | 2021-08-01 | Oshchepkov et al. | Applicant |
| US2021/0286079(A1) | 2021-09-01 | Vecchio | Applicant |
| US2021/0310106(A1) | 2021-10-01 | Wei et al. | Applicant |
| US2021/0324498(A1) | 2021-10-01 | Hericher et al. | Applicant |
| US2021/0332465(A1) | 2021-10-01 | Behera et al. | Applicant |
| US2021/0387920(A1) | 2021-12-01 | Bouttes et al. | Applicant |
| US2021/0402475(A1) | 2021-12-01 | Taneike et al. | Applicant |
| US2022/0025492(A1) | 2022-01-01 | Schade et al. | Applicant |
| US2022/0041449(A1) | 2022-02-01 | Larsson et al. | Applicant |
| US2022/0081745(A1) | 2022-03-01 | Komai et al. | Applicant |
| US2022/0165463(A1) | 2022-05-01 | Vidarsson et al. | Applicant |
| US2022/0219231(A1) | 2022-07-01 | Eibl | Applicant |
| US2022/0220583(A1) | 2022-07-01 | Ota et al. | Applicant |
| US2022/0220584(A1) | 2022-07-01 | Wang et al. | Applicant |
| US2022/0404035(A1) | 2022-12-01 | Gattei | Applicant |
| CN86102537 | 1987-09-01 | Applicant | |
| CN1033292 | 1989-06-01 | Applicant | |
| CN1225629(C) | 2005-11-01 | Applicant | |
| CN101016603 | 2007-08-01 | Applicant | |
| CN101148747 | 2008-03-01 | Applicant | |
| CN101948994 | 2011-01-01 | Applicant | |
| CN101994076 | 2011-03-01 | Applicant | |
| CN102233490(A) | 2011-11-01 | Applicant | |
| CN102286702 | 2011-12-01 | Applicant | |
| CN102357750(A) | 2012-02-01 | Applicant | |
| CN102936724 | 2013-02-01 | Applicant | |
| CN103628017 | 2014-03-01 | Applicant | |
| CN103785967 | 2014-05-01 | Applicant | |
| CN104093510 | 2014-10-01 | Applicant | |
| CN104625473 | 2015-05-01 | Applicant | |
| CN104694840 | 2015-06-01 | Applicant | |
| CN104805391 | 2015-07-01 | Applicant | |
| CN105057913 | 2015-11-01 | Applicant | |
| CN105483539 | 2016-04-01 | Applicant | |
| CN106119838 | 2016-11-01 | Applicant | |
| CN108607983 | 2018-10-01 | Applicant | |
| DE2754437 | 1979-07-01 | Applicant | |
| DE3320513 | 1983-12-01 | Applicant | |
| DE4202828 | 1993-08-01 | Applicant | |
| DE4411296 | 1995-07-01 | Applicant | |
| DE10320397(A1) | 2004-12-01 | Applicant | |
| DE10329912 | 2005-06-01 | Applicant | |
| EP346293 | 1989-12-01 | Applicant | |
| EP365884 | 1990-05-01 | Applicant | |
| EP774528 | 1997-05-01 | Applicant | |
| EP740591 | 1999-03-01 | Applicant | |
| EP1077268 | 2001-02-01 | Applicant | |
| EP939139 | 2001-10-01 | Applicant | |
| EP1270755 | 2003-01-01 | Applicant | |
| EP1279748 | 2003-01-01 | Applicant | |
| EP1279749 | 2003-01-01 | Applicant | |
| EP1120472 | 2003-07-01 | Applicant | |
| EP1477579 | 2004-11-01 | Applicant | |
| EP1361288 | 2006-09-01 | Applicant | |
| EP1721999 | 2006-11-01 | Applicant | |
| EP1857204 | 2007-11-01 | Applicant | |
| EP1694876 | 2008-01-01 | Applicant | |
| EP1953252 | 2008-08-01 | Applicant | |
| EP2050533 | 2009-04-01 | Applicant | |
| EP2305415 | 2011-04-01 | Applicant | |
| EP2388345 | 2011-11-01 | Applicant | |
| EP2628825 | 2013-08-01 | Applicant | |
| EP2639323 | 2013-09-01 | Applicant | |
| EP2660342 | 2013-11-01 | Applicant | |
| EP2072627 | 2014-04-01 | Applicant | |
| EP2730355 | 2014-05-01 | Applicant | |
| EP2743361 | 2014-06-01 | Applicant | |
| EP2104753 | 2014-07-01 | Applicant | |
| EP2777869 | 2014-09-01 | Applicant | |
| EP2778247 | 2014-09-01 | Applicant | |
| EP2873747 | 2015-05-01 | Applicant | |
| EP2563942 | 2015-10-01 | Applicant | |
| EP2064359 | 2016-04-01 | Applicant | |
| EP3034211 | 2016-06-01 | Applicant | |
| EP2235225 | 2016-10-01 | Applicant | |
| EP3093858 | 2016-11-01 | Applicant | |
| EP2659014 | 2017-04-01 | Applicant | |
| EP3156155 | 2017-04-01 | Applicant | |
| EP2147445 | 2017-05-01 | Applicant | |
| EP2252419 | 2017-06-01 | Applicant | |
| EP2265559 | 2017-06-01 | Applicant | |
| EP2329507 | 2017-06-01 | Applicant | |
| EP2285996 | 2017-08-01 | Applicant | |
| EP3211108 | 2017-08-01 | Applicant | |
| EP1700319 | 2017-10-01 | Applicant | |
| EP2207907 | 2017-12-01 | Applicant | |
| EP2788136 | 2018-01-01 | Applicant | |
| EP2414554(B1) | 2018-02-01 | Applicant | |
| EP3145660 | 2018-04-01 | Applicant | |
| EP2432908(B1) | 2018-05-01 | Applicant | |
| EP2181199 | 2018-08-01 | Applicant | |
| EP2477784 | 2018-08-01 | Applicant | |
| EP2695171 | 2018-08-01 | Applicant | |
| EP3354758 | 2018-08-01 | Applicant | |
| EP1799380 | 2018-09-01 | Applicant | |
| EP3034637(B1) | 2018-10-01 | Applicant | |
| EP3266892 | 2018-10-01 | Applicant | |
| EP3444452 | 2019-02-01 | Applicant | |
| EP2265739 | 2019-06-01 | Applicant | |
| EP3259095 | 2019-06-01 | Applicant | |
| EP1844172 | 2019-07-01 | Applicant | |
| EP3517642 | 2019-07-01 | Applicant | |
| EP3115472 | 2019-10-01 | Applicant | |
| EP3552740 | 2019-10-01 | Applicant | |
| EP2155921 | 2019-11-01 | Applicant | |
| EP3350354 | 2020-02-01 | Applicant | |
| EP3611280 | 2020-02-01 | Applicant | |
| EP3354764 | 2020-03-01 | Applicant | |
| EP3149216 | 2020-04-01 | Applicant | |
| EP2403966(B1) | 2020-05-01 | Applicant | |
| EP3362210 | 2020-05-01 | Applicant | |
| EP3134558 | 2020-07-01 | Applicant | |
| EP3514253(B1) | 2020-10-01 | Applicant | |
| EP3333275 | 2020-11-01 | Applicant | |
| EP3653736 | 2020-12-01 | Applicant | |
| EP3411169 | 2021-01-01 | Applicant | |
| EP3590642(B1) | 2021-01-01 | Examiner | |
| EP1848836(B1) | 2021-04-01 | Applicant | |
| EP3822007 | 2021-05-01 | Applicant | |
| EP2671669 | 2021-06-01 | Applicant | |
| EP3925771 | 2021-12-01 | Applicant | |
| EP3926064 | 2021-12-01 | Applicant | |
| EP3991879 | 2022-05-01 | Applicant | |
| EP3995234 | 2022-05-01 | Applicant | |
| FR1398732 | 1965-05-01 | Applicant | |
| FR2055735 | 1971-04-01 | Applicant | |
| FR2218797 | 1974-09-01 | Applicant | |
| GB465999 | 1937-05-01 | Applicant | |
| GB956740 | 1964-04-01 | Applicant | |
| GB1073621 | 1967-06-01 | Applicant | |
| GB2153846(A) | 1985-08-01 | Applicant | |
| GB2273109 | 1994-06-01 | Applicant | |
| GB2546809 | 2018-05-01 | Applicant | |
| GB2579580 | 2020-07-01 | Applicant | |
| GB2567492 | 2020-09-01 | Applicant | |
| GB2584654 | 2020-12-01 | Applicant | |
| GB2584905 | 2020-12-01 | Applicant | |
| INMUMNP-2003-00842 | 2005-04-01 | Applicant | |
| JP43-019745 | 1968-08-01 | Applicant | |
| JP45-026214 | 1970-10-01 | Applicant | |
| JP47-1685 | 1972-01-01 | Applicant | |
| JP49-056839 | 1974-06-01 | Applicant | |
| JP58-132393 | 1983-08-01 | Applicant | |
| JP59-16951 | 1984-01-01 | Applicant | |
| JP59-16952 | 1984-01-01 | Applicant | |
| JP59-150692 | 1984-08-01 | Applicant | |
| JP60-133996 | 1985-07-01 | Applicant | |
| JP6031897(B1) | 1985-07-01 | Applicant | |
| JP61-283489 | 1986-12-01 | Applicant | |
| JP63-026205 | 1988-02-01 | Applicant | |
| JP63-42357 | 1988-02-01 | Applicant | |
| JP63-65056 | 1988-03-01 | Applicant | |
| JP63-089643 | 1988-04-01 | Applicant | |
| JP63-213628 | 1988-09-01 | Applicant | |
| JP3-133593 | 1991-06-01 | Applicant | |
| JP3-248799 | 1991-11-01 | Applicant | |
| JP4-237592 | 1992-08-01 | Applicant | |
| JP4-246142 | 1992-09-01 | Applicant | |
| JP4-358046 | 1992-12-01 | Applicant | |
| JP7-179997 | 1995-07-01 | Applicant | |
| JP7-268524 | 1995-10-01 | Applicant | |
| JP8-134570 | 1996-05-01 | Applicant | |
| JP9-95755 | 1997-04-01 | Applicant | |
| JP9-108887 | 1997-04-01 | Applicant | |
| JP2001-066130 | 2001-03-01 | Applicant | |
| JP2001-303233 | 2001-10-01 | Applicant | |
| JP2002-241919 | 2002-08-01 | Applicant | |
| JP2003-205352 | 2003-07-01 | Applicant | |
| JP2004-149924 | 2004-05-01 | Applicant | |
| JP2005-042152 | 2005-02-01 | Applicant | |
| JP2005-290406 | 2005-10-01 | Applicant | |
| JP2007-154284 | 2007-06-01 | Applicant | |
| JP2008-261329 | 2008-10-01 | Applicant | |
| JP2010-138440 | 2010-06-01 | Applicant | |
| JP2010-138491 | 2010-06-01 | Applicant | |
| JP2012-000616 | 2012-01-01 | Applicant | |
| JP2014-047388 | 2014-03-01 | Applicant | |
| JP2015-083715 | 2015-04-01 | Applicant | |
| JP2015-526596 | 2015-09-01 | Applicant | |
| KR10-0935816(B1) | 2010-01-01 | Applicant | |
| SU1706398 | 1992-01-01 | Applicant | |
| TW200806801(A) | 2008-02-01 | Applicant | |
| WO84/000385 | 1984-02-01 | Applicant | |
| WO84/004760 | 1984-12-01 | Applicant | |
| WO95/004628 | 1995-02-01 | Applicant | |
| WO3/018856 | 2003-03-01 | Applicant | |
| WO6/080978 | 2006-08-01 | Applicant | |
| WO6/086350 | 2006-08-01 | Applicant | |
| WO7/120194 | 2007-10-01 | Applicant | |
| WO8/042330 | 2008-04-01 | Applicant | |
| WO8/060226 | 2008-05-01 | Applicant | |
| WO8/082353 | 2008-07-01 | Applicant | |
| WO8/105788 | 2008-09-01 | Applicant | |
| WO8/153499 | 2008-12-01 | Applicant | |
| WO9/085000 | 2009-07-01 | Applicant | |
| WO10/044740 | 2010-04-01 | Applicant | |
| WO10/046224 | 2010-04-01 | Applicant | |
| WO10/074634 | 2010-07-01 | Applicant | |
| WO10/134886 | 2010-11-01 | Applicant | |
| WO11/005403 | 2011-01-01 | Applicant | |
| WO11/021751 | 2011-02-01 | Applicant | |
| WO11/071054 | 2011-06-01 | Applicant | |
| WO11/084213 | 2011-07-01 | Applicant | |
| WO11/091479 | 2011-08-01 | Applicant | |
| WO11/152774 | 2011-12-01 | Applicant | |
| WO11/158706 | 2011-12-01 | Applicant | |
| WO12/021186 | 2012-02-01 | Applicant | |
| WO12/022874 | 2012-02-01 | Applicant | |
| WO12/112844 | 2012-08-01 | Applicant | |
| WO12/162226 | 2012-11-01 | Applicant | |
| WO13/049056 | 2013-04-01 | Applicant | |
| WO13/055652 | 2013-04-01 | Applicant | |
| WO13/060839 | 2013-05-01 | Applicant | |
| WO13/102650 | 2013-07-01 | Applicant | |
| WO13/126134 | 2013-08-01 | Applicant | |
| WO13/152306 | 2013-10-01 | Applicant | |
| WO13/167580 | 2013-11-01 | Applicant | |
| WO13/167628 | 2013-11-01 | Applicant | |
| WO13/185174 | 2013-12-01 | Applicant | |
| WO14/001544 | 2014-01-01 | Applicant | |
| WO14/023646 | 2014-02-01 | Applicant | |
| WO14/070006 | 2014-05-01 | Applicant | |
| WO14/081491 | 2014-05-01 | Applicant | |
| WO14/083544 | 2014-06-01 | Applicant | |
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| WO14/114715 | 2014-07-01 | Applicant | |
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| WO14/197088 | 2014-12-01 | Applicant | |
| WO14/201239 | 2014-12-01 | Applicant | |
| WO14/202488 | 2014-12-01 | Applicant | |
| WO15/028358 | 2015-03-01 | Applicant | |
| WO15/049309 | 2015-04-01 | Applicant | |
| WO15/075122 | 2015-05-01 | Applicant | |
| WO15/183955 | 2015-12-01 | Applicant | |
| WO16/003520 | 2016-01-01 | Applicant | |
| WO16/010599 | 2016-01-01 | Applicant | |
| WO16/041977 | 2016-03-01 | Applicant | |
| WO16/099390 | 2016-06-01 | Applicant | |
| WO16/124532 | 2016-08-01 | Applicant | |
| WO16/131702 | 2016-08-01 | Applicant | |
| WO17/041006 | 2017-03-01 | Applicant | |
| WO17/046517 | 2017-03-01 | Applicant | |
| WO17/059026 | 2017-04-01 | Applicant | |
| WO17/063923 | 2017-04-01 | Applicant | |
| WO17/091743 | 2017-06-01 | Applicant | |
| WO17/132286 | 2017-08-01 | Applicant | |
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| WO18/015547 | 2018-01-01 | Applicant | |
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| WO18/138270 | 2018-08-01 | Applicant | |
| WO18/145032 | 2018-08-01 | Applicant | |
| WO18/232618 | 2018-12-01 | Applicant | |
| WO-2018232619(A1) | 2018-12-01 | Examiner | |
| WO19/021015 | 2019-01-01 | Applicant | |
| WO19/043219 | 2019-03-01 | Applicant | |
| WO19/047587 | 2019-03-01 | Applicant | |
| WO19/108596 | 2019-06-01 | Applicant | |
| WO19/125637 | 2019-06-01 | Applicant | |
| WO19/145196 | 2019-08-01 | Applicant | |
| WO19/166749 | 2019-09-01 | Applicant | |
| WO19/194869 | 2019-10-01 | Applicant | |
| WO19/197376 | 2019-10-01 | Applicant | |
| WO19/215450 | 2019-11-01 | Applicant | |
| WO20/007652 | 2020-01-01 | Applicant | |
| WO20/043718 | 2020-03-01 | Applicant | |
| WO20/053518 | 2020-03-01 | Applicant | |
| WO20/065296 | 2020-04-01 | Applicant | |
| WO20/065297 | 2020-04-01 | Applicant | |
| WO20/074241 | 2020-04-01 | Applicant | |
| WO20/115478 | 2020-06-01 | Applicant | |
| WO20/120563 | 2020-06-01 | Applicant | |
| WO20/201437 | 2020-10-01 | Applicant | |
| WO20/201438 | 2020-10-01 | Applicant | |
| WO21/089851 | 2021-05-01 | Applicant | |
| WO21/217512 | 2021-11-01 | Applicant | |
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| WO21/231285 | 2021-11-01 | Applicant | |
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| WO22/113466 | 2022-06-01 | Applicant | |
| WO22/149539 | 2022-07-01 | Applicant |
Non-Patent Literature (40)
- Al-Aqeeli et al.: “Formation of an amorphous phase and its crystallization in the immiscible Nb—Zr system by mechanical alloying.” Journal of Applied Physics 114, 153512, 2013.Applicant
- Audouard, et al., Mar. 26-31, 2000, Corrosion Performance and Field Experience With Super Duplex and Super Austenitic Stainless Steels in FGD Systems, Corrosion 2000, 8 pp.Applicant
- Azo Materials, “Stainless Steel—Grade 420,” Oct. 23, 2001, <https://www.azom.com/article.aspx?ArticleID=972>, accessed Aug. 15, 2017.Applicant
- Branagan, et al.: Developing extreme hardness (>15GPa) in iron based nanocomosites, Composites Part A: Applied Science and Manufacturing, Elsevier Science Publishers B.V., Amsterdam, NL, vol. 33, No. 6, Jun. 1, 2002, pp. 855-859.Applicant
- Chen et al.: “Characterization of Microstructure and Mechanical Properties of High Chromium Cast Irons Using SEM and Nanoindentation,” JMEPEG 2015 (published online Oct. 30, 2014), vol. 24(1), pp. 98-105.Applicant
- Cheney, et al.: “Development of quaternary Fe-based bulk metallic glasses,” Materials Science and Engineering, vol. 492, No. 1-2, Sep. 25, 2008, pp. 230-235.Applicant
- Cheney: Modeling the Glass Forming Ability of Metals. A Dissertation submitted in partial satisfaction of the Requirements for the degree of Doctor of Philosophy. University of California, San Diego. Dec. 2007.Applicant
- C—Mo Phase Diagram [online], [retrieved on Jan. 27, 2015]. Retrieved from the Internet: <URL:http://factsage.cn/fact/documentation/SGTE/C-Mo.jpg.Applicant
- C—Nb Phase Diagram [online], [retrieved on Jan. 27, 2015]. Retrieved from the Internet: <URL:http://www.crct.polymtl.ca/fact/documentation/BINARY/C-Nb.jpg.Applicant
- Conversion Chart of Vickers Hardness (HV) to Rockwell C (HCR).Applicant
- Cr—C Phase Diagram [online], [retrieved on Jan. 27, 2015]. Retrieved from the Internet: http://www.azom.com/work/3ud2quvLOU9g4VBMjVEh_files/image002.gif.Applicant
- Crucible Industries LLC, Jun. 3, 2010, Crucible CPM S90V® data sheet, retrieved from the internet Mar. 14, 2019, https://www.crucible.com/PDFs/DataSheets2010/dsS90v1%202010.pdf, 2 pp.Applicant
- Davis, Jr, ed. Dec. 1994, Stainless steels. ASM International, Materials Park, OH, p. 447.Applicant
- Fujiki et al., 1988, The sintering phenomena and heat-treated properties of carbides and borides precipitated p/m alloys made of H.S.S. powder, Japan Society of Powder and Powder Metallurgy, 35(3):119-123.Applicant
- Gorni, Oct. 9, 2003, Austenite transformation temperatures: ferrite start and finish, in Steel Forming and Heath Treating Handbook, pp. 26-43.Applicant
- Iron-Carbon (Fe—C) Phase diagram [online], [retrieved on Jan. 27, 2015]. Retrieved from the internet: <URL:http://www.calphad.com/iron-carbon.html>.Applicant
- Khalifa, et al.: “Effect of Mo—Fe substitution on glass forming ability, thermal stability, and hardness of Fe—C—B—Mo—Cr—W bulk amorphous allows,” Materials Science and Engineering, vol. 490, No. 1-2, Aug. 25, 2008, pp. 221-228.Applicant
- Kumashiro et al., May 31, 1980, The vickers micro-hardness of nonstoichiometric niobium carbide and vanadium carbide single crystals up to 1500c, Journal of Materials Science, 15(5):1321-1324.Applicant
- Kushner et al., 1992, Thermal Spray Coatings, in Blau (ed) ASM Handbook, vol. 18, Friction, Lubrication, and Wear Technolgoy, pp. 829-833.Applicant
- Kutsova, Nov. 9, 2015, The Influence of alloying elements on structure formation, phase composition and properties of chromium-manganese iron in the cast state, Metallurgical and Mining Industry, 1084.Applicant
- Li et al., Feb. 28, 2000, Temperature dependence of the hardness of single-phase cementite films prepared by an electron-shower PVD method, Journal of the Japan Institute of Metals and Materials, 64(2):134-140.Applicant
- Liu et al., Jan. 14, 2000, Measurement of austenite-to-ferrite transformation temperature after multi-pass deformation of steels, Materials Science and Engineering A, 194(1):L15-L18.Applicant
- Miracle, D.B.: The efficient cluster packing model—An atomic structural model for metallic glasses, Acta Materialia vol. 54, Issue 16, Sep. 2006, pp. 4317-4336.Applicant
- Miyoshi et al., Apr. 25, 1965, High temperature hardness of Wc, Tic, TaC, NbC and their mixed carbides, Journal of the Japan Society of Powder and Powder Metalurgy, 12(2):78-84.Applicant
- Ohmura, Dec. 2003, Evaluation of temper softening behavior of Fe—C binary martensitic steels by nanoindentation, Scripta Materialia, 49(12):1157-1162.Applicant
- Senkov et al., Jun. 23, 2010, Refractory high-entropy alloys, Intermetallics, 18:1758-1765.Applicant
- Teng: “Processing, Microstructures, and Properties of Aluminide-Strengthened Ferritic Steels,” The University of Tennessee, Knoxville, Dec. 2011.Applicant
- Tillack, et al.: “Selection of Nickel, Nickel-Copper, Nickel-Cromium, and Nickel-Chromium-Iron Allows”. ASM Handbook, Welding, Brazing and Soldering, vol. 6,Dec. 1, 1993 (Dec. 1, 1993) pp. 586-592, XP008097120, p. 589.Applicant
- Tucker , 2013, Introduction to Thermal Spray Technology, ASM Handbook, vol. 5A, pp. 3-9.Applicant
- Wang et al., Jul. 2014, Effect of molybdenum, manganese and tungsten contents on the corrosion behavior and hardness of iron-based metallic glasses, Materials and Corrosion, 65(7):733-741.Applicant
- Wank et al., 2007, Behavior of thermally sprayed wear protective coatings exposed to different abrasive wear conditions in comparison to hard chromium platings, 7 pp.Applicant
- Wayne, 1985, Iron-rich low-coast superalloys, PhD dissertation, University of Connecticut, 184 pp.Applicant
- Wikipedia, Refractory metals, https://en/wikipedia.org/wiki/Refractory_metals.Applicant
- Yamamoto et al., 2014, Influence of Mo and W on high temperature hardness of M7C3 carbide in high chromium white cast iron, Materials Transactions, 55(4):684-689.Applicant
- Yano et al., Apr. 2011, Modification of NIAI intermetallic coatings processed by PTA with chromium carbides, ASTM International Journal, 8(4):190-204.Applicant
- Yoo et al., Jun. 2006, The effect of boron on the wear behavior of iron-based hardfacing alloys for nuclear power plants valves, Journal of Nuclear Materials, 352:90-96.Applicant
- Zhu et al., 2017, Microstructure and sliding wear performance of Cr7C3-(Ni,Cr)3(Al,Cr) coating deposited from Cr7C3 in situ formed atomized powder, J. Therm Spray Tech, 26:254-264.Applicant
- International Search Report and Written Opinion re PCT Application No. PCT/US2021/019170, mailed May 27, 2021.Applicant
- Titanium-Boron (TiB) Phase Diagram [online], [retrieved on Jan. 27, 2015]. Retrieved from the internet: <URL:http://www.calphad.com/titaniumboron.html>.Applicant
- Gunther et al., 2018, Influence of processing conditions on the degradation kinetics of fused tungsten carbides in hardfacing, International Journal of Refractory Metals & Hard Materials, 70:224-231.Applicant