# Patent

## Title
Methods of fabricating a polycrystalline diamond body with a sintering aid/infiltrant at least saturated with non-diamond carbon and resultant products such as compacts

## Abstract

Embodiments of the invention relate to methods of fabricating a polycrystalline diamond compacts and applications for such polycrystalline diamond compacts. In an embodiment, a method of fabricating a polycrystalline diamond body includes mechanically milling non-diamond carbon and a sintering aid material for a time and aggressiveness sufficient to form a plurality of carbon-saturated sintering aid particles and sintering a plurality of diamond particles in the presence of the plurality of carbon-saturated sintering aid particles to form the polycrystalline diamond body.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. application Ser. No. 13/397,971 filed on 16 Feb. 2012, which is a continuation-in-part of U.S. application Ser. No. 13/323,138 filed on 12 Dec. 2011 (now U.S. Pat. No. 8,911,521 issued on 16 Dec. 2014), which is a continuation-in-part of U.S. application Ser. No. 12/394,356 filed on 27 Feb. 2009 (now U.S. Pat. No. 8,080,071 issued on 20 Dec. 2011), which claims the benefit of U.S. Provisional Application No. 61/068,120 filed on 3 Mar. 2008. The contents of each of the foregoing applications are incorporated herein, in their entirety, by this reference.


BACKGROUND
Wear-resistant, polycrystalline diamond compacts (“PDCs”) are utilized in a variety of mechanical applications. For example, PDCs are used in drilling tools (e.g., cutting elements, gage trimmers, etc.), machining equipment, bearing apparatuses, wire-drawing machinery, and in other mechanical apparatuses.
PDCs have found particular utility as superabrasive cutting elements in rotary drill bits, such as roller-cone drill bits and fixed-cutter drill bits. A PDC cutting element typically includes a superabrasive diamond layer commonly known as a diamond table. The diamond table is formed and bonded to a substrate using a high-pressure/high-temperature (“HPHT”) process. The PDC cutting element may be brazed directly into a preformed pocket, socket, or other receptacle formed in a bit body. The substrate may often be brazed or otherwise joined to an attachment member, such as a cylindrical backing. A rotary drill bit typically includes a number of PDC cutting elements affixed to the bit body. It is also known that a stud carrying the PDC may be used as a PDC cutting element when mounted to a bit body of a rotary drill bit by press-fitting, brazing, or otherwise securing the stud into a receptacle formed in the bit body.
Conventional PDCs are normally fabricated by placing a cemented-carbide substrate into a container with a volume of diamond particles positioned on a surface of the cemented-carbide substrate. A number of such containers may be loaded into an HPHT press. The substrate(s) and volume(s) of diamond particles are then processed under HPHT conditions in the presence of a catalyst material that causes the diamond particles to bond to one another to form a matrix of bonded diamond grains defining a polycrystalline diamond (“PCD”) table. The catalyst material is often a metal-solvent catalyst (e.g., cobalt, nickel, iron, or alloys thereof) that is used for promoting intergrowth of the diamond particles.
In one conventional approach, a constituent of the cemented-carbide substrate, such as cobalt from a cobalt-cemented tungsten carbide substrate, liquefies and sweeps from a region adjacent to the volume of diamond particles into interstitial regions between the diamond particles during the HPHT process. The cobalt acts as a catalyst to promote intergrowth between the diamond particles, which results in formation of a matrix of bonded diamond grains having diamond-to-diamond bonding therebetween, with interstitial regions between the bonded diamond grains being occupied by the solvent catalyst.
The presence of the solvent catalyst in the PCD table is believed to reduce the thermal stability of the PCD table at elevated temperatures. For example, the difference in thermal expansion coefficient between the diamond grains and the solvent catalyst is believed to lead to chipping or cracking of the PCD table during drilling or cutting operations, which consequently can degrade the mechanical properties of the PCD table or cause failure. Additionally, some of the diamond grains can undergo a chemical breakdown or back-conversion to graphite via interaction with the solvent catalyst. At high temperatures, portions of the diamond grains may transform to carbon monoxide, carbon dioxide, graphite, or combinations thereof, causing degradation of the mechanical properties of the PCD table. One conventional approach for improving the thermal stability of PDCs is to at least partially remove the solvent catalyst from the PCD table of the PDC by acid leaching.
Despite the availability of a number of different PDCs, manufacturers and users of PDCs continue to seek PDCs that exhibit improved wear resistance and thermal stability.
SUMMARY
Embodiments of the invention relate to methods of fabricating PDCs and applications for such PDCs. In an embodiment, a method of fabricating a PCD body is disclosed. The method includes mechanically milling non-diamond carbon and a sintering aid material for a time and aggressiveness sufficient to form a plurality of carbon-saturated sintering aid particles. The method further includes sintering a plurality of diamond particles in the presence of the plurality of carbon-saturated sintering aid particles to form the PCD body. The PCD body may be used as a PCD table in a PDC or in other applications.
Other embodiments include PCD elements and PDCs formed by the above-described methods, and applications utilizing such PCD bodies and PDCs in various articles and apparatuses, such as rotary drill bits, bearing apparatuses, wire-drawing dies, machining equipment, and other articles and apparatuses.
Features from any of the disclosed embodiments may be used in combination with one another, without limitation. In addition, other features and advantages of the present disclosure will become apparent to those of ordinary skill in the art through consideration of the following detailed description and the accompanying drawings.



BRIEF DESCRIPTION OF THE DRAWINGS
The drawings illustrate several embodiments of the invention, wherein identical reference numerals refer to identical elements or features in different views or embodiments shown in the drawings.
FIG. 1A is a cross-sectional view of an embodiment of a PDC precursor assembly including a mixture comprising a plurality of sintering aid particles at least saturated with carbon and a plurality of diamond particles positioned adjacent to a substrate.
FIG. 1B is a cross-sectional view of a PDC formed by HPHT processing of the PDC precursor assembly shown in FIG. 1A.
FIG. 1C is an isometric view of the PDC shown in FIG. 1B.
FIG. 1D is a cross-sectional view of the PDC shown in FIGS. 1B and 1C in which the PCD table has been leached to a selected depth according to an embodiment.
FIG. 2A is a cross-sectional view of an embodiment of a PDC precursor assembly including a mixture comprising a plurality of sintering aid particles at least saturated with carbon, a plurality of carbon-saturated sintering aid particles coated with submicron diamond particles, and a plurality of diamond particles positioned adjacent to a substrate.
FIG. 2B is a cross-sectional view of a PDC formed by HPHT processing of the PDC precursor assembly shown in FIG. 2A.
FIG. 3A is a cross-sectional view of an embodiment of a PDC precursor assembly including at least one layer of a plurality of carbon-saturated sintering aid particles disposed between at least one layer of a plurality of diamond particles and a substrate.
FIG. 3B is a cross-sectional view of a PDC formed by HPHT processing of the PDC precursor assembly shown in FIG. 3A.
FIGS. 4A-4F are cross-sectional views illustrating different stages in various embodiments of a method for fabricating a PDC and the PDC so formed.
FIGS. 5A-5F are cross-sectional views illustrating different stages in various embodiments of a method for fabricating a PDC and the PDC so formed.
FIGS. 6 and 7 are isometric and top elevation views, respectively, of an embodiment of a rotary drill bit that may employ one or more of the disclosed PDC embodiments.
FIG. 8 is an isometric cut-away view of an embodiment of a thrust-bearing apparatus that may utilize one or more of the disclosed PDC embodiments.
FIG. 9 is an isometric cut-away view of an embodiment of a radial bearing apparatus that may utilize one or more of the disclosed PDC embodiments.



DETAILED DESCRIPTION
Embodiments of the invention relate to PDCs comprising a PCD table sintered using a sintering aid material that has been at least saturated with non-diamond carbon and/or infiltrated with an infiltrant that is at least saturated with non-diamond carbon. HPHT sintering diamond particles in the presence of a sintering aid that has been at least saturated and, in some cases, supersaturated with non-diamond carbon may promote diamond growth during HPHT sintering and may result in improved thermal stability and/or wear resistance of the PCD so formed. The disclosed PDCs herein may be used in a variety of applications, such as rotary drill bits, mining tools, drill bits, bearing apparatuses, wire-drawing dies, machining equipment, and other articles and apparatuses.
FIG. 1A is a cross-sectional view of an embodiment of a PDC precursor assembly 100 for forming a PCD body from a mixture 105 comprising a plurality of sintering aid particles at least saturated with carbon (i.e., carbon-saturated sintering aid particles) and a plurality of diamond particles. Such an assembly 100 may be HPHT processed to form a PCD table 106 (FIG. 1B) integrally formed with and bonded to a substrate 102 (FIG. 1B). The plurality of sintering aid particles that are at least saturated with non-diamond carbon may sometimes be referred to herein in the different embodiments as carbon-saturated sintering aid particles and may be saturated or supersaturated with carbon at standard temperature and pressure (i.e., 0° C. and 1 atmosphere). For example, when the sintering aid particles are saturated with non-diamond carbon, they may include carbon at about the solubility limit for carbon in the particular sintering aid material at standard temperature and pressure (i.e., 0° C. and 1 atmosphere). As another example, when the sintering aid particles are supersaturated with non-diamond carbon, they may include carbon in excess of the solubility limit for carbon in the particular sintering aid material at standard temperature and pressure (i.e., 0° C. and 1 atmosphere or above). As used herein, the phrases “at least saturated with carbon,” “saturated with carbon,” and variants thereof include materials that are supersaturated with carbon and materials that are saturated with carbon. For example, the carbon supersaturated in the sintering aid material may have a concentration of about 5 atomic % to about 30 atomic %, such as about 10 atomic % to about 20 atomic %, about 20 atomic % to about 30 atomic %, or about 18 atomic % to about 25 atomic %.
According to one or more embodiments, the carbon-saturated sintering aid particles may be formed by mechanically milling sintering aid particles with a non-diamond carbon to mechanically alloy the sintering aid particles with non-diamond carbon. For example, the non-diamond carbon may be selected from amorphous carbon (e.g., lamp black carbon), graphite particles (e.g., crystalline and/or amorphous graphite), graphene, nanotubes, fullerenes, combinations of the foregoing, and the like, while the sintering aid materials from which the sintering aid particles are made may be selected from cobalt, nickel, iron, copper, aluminum, titanium, tungsten, niobium, zirconium, tantalum, boron, silicon, alloys of any of the foregoing materials, any other suitable metal and/or alloy, or combinations of any of the foregoing sintering aid materials. Some of the foregoing metal and alloys may not be carbide formers that will partially consume diamond particles during HPHT sintering, such as copper and copper alloys. Some of the foregoing metal and alloys from which the sintering aid particles may be made are common diamond catalysts (e.g., cobalt, iron, and nickel). However, other ones of the foregoing metals and alloys (e.g., aluminum, copper, titanium, tungsten, boron, silicon, and alloys) from which the sintering aid particles may be made are not typically known as solvent catalysts, but can facilitate diamond sintering when mechanically alloyed with selected amount(s) of non-diamond carbon. Accordingly, a particular sintering aid material may or may not be a diamond catalyst depending on its composition and nature.
According to various embodiments, the graphite and/or graphite particles mechanically milled with the sintering aid particles may be crystalline graphite particles, amorphous graphite particles, synthetic graphite particles, carbon-12 graphite, carbon-13 graphite, carbon-14 graphite, substantially pure polycrystalline graphite, or combinations thereof. Amorphous graphite refers to naturally occurring microcrystalline graphite. Crystalline graphite particles may be naturally occurring or synthetic. Various types of graphite particles are commercially available from Ashbury Graphite Mills of Kittanning, Pa.
In an embodiment, the non-diamond carbon (in any form such as graphite, amorphous carbon, etc.) may be made substantially of only one of carbon-12, carbon-13, or carbon-14. For example, in an embodiment, the non-diamond carbon may be made of about 99.00 weight % carbon-12 to less than about 100 weight % carbon-12, or about 99.00 weight % carbon-12 to about 99.99 weight % carbon-12, or about 99.50 weight % carbon-12 to about 99.99 weight % carbon-12, or about 99.30 weight % carbon-12 to about 99.99 weight % carbon-12, about 99.30 weight % carbon-12 to about 99.50 weight % carbon-12, or about 99.80 weight % carbon-12 to about 99.99 weight % carbon-12, with the balance being carbon-13 and/or carbon-14. In some embodiments, the carbon-13 and/or carbon-14 may be present in combination with the carbon-12 in an amount less than that may naturally occur in combination with carbon-12.
In another embodiment, the non-diamond carbon (in any form such as graphite, amorphous carbon, etc.) may be made of about 99.00 weight % carbon-13 to less than about 100 weight % carbon-13, or about 99.00 weight % carbon-13 to about 99.99 weight % carbon-13, or about 99.50 weight % carbon-13 to about 99.99 weight % carbon-13, or about 99.30 weight % carbon-13 to about 99.99 weight % carbon-13, about 99.30 weight % carbon-13 to about 99.50 weight % carbon-13, or about 99.80 weight % carbon-13 to about 99.99 weight % carbon-13, with the balance being carbon-12 and/or carbon-14. In some embodiments, the carbon-12 and/or carbon-14 may be present in combination with the carbon-13 in an amount less than that may naturally occur in combination with carbon-13.
In another embodiment, the non-diamond carbon (in any form such as graphite, amorphous carbon, etc.) may be made of about 99.00 weight % carbon-14 to less than about 100 weight % carbon-14, or about 99.00 weight % carbon-14 to about 99.99 weight % carbon-14, or about 99.50 weight % carbon-14 to about 99.99 weight % carbon-14, or about 99.30 weight % carbon-14 to about 99.99 weight % carbon-14, about 99.30 weight % carbon-14 to about 99.50 weight % carbon-14, or about 99.80 weight % carbon-14 to about 99.99 weight % carbon-14, with the balance being carbon-12 and/or carbon-13. In some embodiments, the carbon-12 and/or carbon-13 may be present in combination with the carbon-14 in an amount less than that may naturally occur in combination with carbon-14.
It should be noted that substantially all of the non-diamond carbon may be converted to diamond during HPHT processing to form PCD. However, the particular carbon isotopes may remain in the PCD in approximately the same or similar ratio as present in the non-diamond carbon combined with the sintering aid material before HPHT processing, but now in the form of diamond. For example, the carbon present in the PCD as diamond may be substantially only one of carbon-12, carbon-13, or carbon-14 (i.e., the dominant carbon isotope), with the balance of any carbon being the other one(s) of carbon-12, carbon-13, or carbon-14 in an amount less than that may naturally occur in combination with the dominant carbon isotope present in the PCD.
Mechanically alloying is a process in which a powder and/or a particulate mixture is subjected to impacts by an impacting medium that cause a multiplicity of deformations, particle weldings, and fracturing until the powder and/or particulate mixture is converted to an essentially uniform particulate product. Stamping mills, jaw crushers, and ball mills may be used to breakdown particles by impact and crushing. In earlier stages of powder preparation of brittle metals, gyratory crushers may also be used. A ball mill is a horizontal barret-shaped container containing a number of balls that are free to tumble about as the container is rotated, crushing and abrading particles that are introduced into the container. Mechanical milling of the non-diamond carbon and the sintering aid material may be achieved by such ball milling, attritor milling, horizontal ball milling, or high energy ball milling. While the foregoing milling techniques may be used for mechanical alloying, other types of mechanical milling apparatuses may be used to practice the various embodiments disclosed herein.
The plurality of sintering aid particles and the non-diamond carbon are subjected to mechanical milling (e.g., attritor and/or ball milling) to such an extent that the sintering aid particles are mechanically alloyed with a selected concentration of carbon so that the sintering aid particles become at least saturated with carbon, and in some embodiments, supersaturated with carbon at standard temperature and pressure (i.e., 0° C. and 1 atmosphere) or above. For example, the mechanical milling of the plurality of sintering aid particles and the non-diamond carbon may be performed for about 100 hours to about 1100 hours, such as about 200 hours to about 500 hours or about 150 hours to about 700 hours. In some embodiments, the milling may be carried out for approximately 1000 hours to about 2200 hours.
In another embodiment, the milling may be carried out up to about 2000 hours resulting in the formation of metastable phases of Ni—C, Co—C, Cu—C, Al—C, Fe—C, Ti—C, W—C, B—C, Si—C, among others. For example, in some embodiments, the supersaturated solid solubility of carbon in copper mechanically alloyed with carbon may be as high as 28.5 atomic %. The metallographic structure of these metastable phases may be observed by scanning electron microscopy (“SEM”) and transmission electron microscopy (“TEM”). TEM observation of the effects of the milling process may reveal a structural change of the powders subjected to the ball-milling process. For example, in an embodiment, the grain size may be observed to decrease as mechanical alloy processing time is increased.
In other embodiments, identification of the phases and measurement of the lattice constants may be achieved by mechanically slicing samples of the mechanically alloyed particles for analysis by X-ray diffractometry. In an embodiment, such analysis of nickel and non-diamond carbon reveals the formation of a Ni—C supersaturated phase that may be observed with increased milling time. For example, in an embodiment, the non-diamond carbon concentration after approximately 1000 hours of mechanical alloying nickel particles with carbon may be estimated to be about 9 atomic % to about 12 atomic %.
In other embodiments, the plurality of carbon-saturated sintering aid particles or material may comprise a carbon content of greater than about 0.01 atomic %. For example, in an embodiment, the carbon concentration of the carbon-saturated sintering aid particles or material following mechanical alloying may be about 0.01 atomic % to about 35 atomic %, about 10 atomic % to about 30 atomic %, about 5 atomic % to about 25 atomic %, from about 20 atomic % to about 30 atomic %, about 10 atomic % to about 20 atomic %, about 5 atomic % to about 15 atomic %, about 1 atomic % to about 10 atomic %, about 25 atomic % to about 30 atomic %, and about 20 atomic % to about 25 atomic %. Carbon-saturated sintering aid particles or material may exhibit any of the carbon content ranges as described herein, without limitation.
Such carbon-saturated sintering aid materials present within the mixture 105, shown in FIG. 1A, are believed to promote diamond growth between diamond particles during HPHT sintering so that the diamond-to-diamond bond density and/or quality increases. The increased diamond-to-diamond bond density present in the sintered PCD table 106 (FIG. 1B) is believed to increase the wear resistance and/or thermal stability as compared to a sintered PCD table fabricated without using carbon-saturated sintering aid particles.
Referring again to FIG. 1A, the plurality of diamond particles may be mixed with the carbon-saturated sintering aid particles to form the mixture 105. In some embodiments, the carbon-saturated sintering aid particles may partially or substantially completely coat the diamond particles. The plurality of diamond particles of the mixture 105 may exhibit one or more selected sizes. The one or more selected sizes may be determined, for example, by passing the diamond particles through one or more sizing sieves or by any other method. In an embodiment, the plurality of diamond particles may include a relatively larger size and at least one relatively smaller size. As used herein, the phrases “relatively larger” and “relatively smaller” refer to particle sizes determined by any suitable method, which differ by at least a factor of two (e.g., 40 μm and 20 μm). More particularly, in various embodiments, the plurality of diamond particles may include a portion exhibiting a relatively larger size (e.g., 100 μm, 90 μm, 80 μm, 70 μm, 60 μm, 50 μm, 40 μm, 30 μm, 20 μm, 15 μm, 12 μm, 10 μm, 8 μm) and another portion exhibiting at least one relatively smaller size (e.g., 30 μm, 20 μm, 10 μm, 15 μm, 12 μm, 10 μm, 8 μm, 4 μm, 2 μm, 1 μm, 0.5 μm, less than 0.5 μm, 0.1 μm, less than 0.1 μm). In an embodiment, the plurality of diamond particles may include a portion exhibiting a relatively larger size between about 40 μm and about 15 μm and another portion exhibiting a relatively smaller size between about 12 μm and 2 μm. Of course, the plurality of diamond particles may also include three or more different sizes (e.g., one relatively larger size and two or more relatively smaller sizes) without limitation. The sintering aid particles may exhibit any of the particle sizes and distributions discussed above for the diamond particles.
It is noted that the as-sintered diamond grain size of the PCD table 106 in FIG. 1B may differ from the average particle size of the plurality of diamond particles prior to sintering due to a variety of different physical processes, such as grain growth, diamond particles fracturing, nucleation and subsequent growth of new diamond crystals, carbon provided from another carbon source, or combinations of the foregoing.
FIGS. 1B and 1C are cross-sectional and isometric views, respectively, of a PDC 120 formed by HPHT processing of the PDC precursor assembly 100 shown in FIG. 1A. The PDC 120 includes the PCD table 106 comprising a sintering aid material from the plurality of sintering aid particles that are at least saturated with carbon. The PCD table 106 includes a working upper surface 108, an interfacial surface 104, and at least one lateral surface 110 extending therebetween. Although the upper surface 108 is illustrated as being substantially planar, the upper surface 108 may have a nonplanar geometry, such as a convex or concave geometry. Furthermore, the PCD table 106 may include a chamfer 112 or other edge geometry that extends about the upper surface 106. For example, the chamfer 112 may be formed by grinding, lapping, laser machining, electro-discharge machining, or combinations of the foregoing. Additionally, other regions of the PCD table 106 may also function as a working region, such as the at least one lateral surface 110.
The substrate 102 (having any suitable geometry) of the PDC 120 is bonded to the interfacial surface 104 of the PCD table 106. Suitable materials for the substrate 102 include cemented carbides, such as titanium carbide, niobium carbide, tantalum carbide, vanadium carbide, tungsten carbide, or combinations of any of the preceding carbides cemented with iron, nickel, cobalt, or alloys thereof. In an embodiment, the substrate 102 may comprise cobalt-cemented tungsten carbide. Although the interfacial surface 104 of the substrate 102 is illustrated as being substantially planar, the interfacial surface may exhibit a selected nonplanar geometry and the back surface 104 of the PCD table 106 may exhibit a correspondingly configured geometry.
In order to efficiently sinter the mixture 105 of the plurality of sintering aid particles at least saturated with carbon and the plurality of diamond particles to form the PCD table 106 bonded to the substrate 102, the PDC precursor assembly 100 may be enclosed in a pressure transmitting medium, such as a refractory metal can, graphite structure, pyrophyllite, combinations thereof, or other suitable pressure transmitting structure to form a cell assembly. Examples of suitable gasket materials and cell structures for use in manufacturing PCD are disclosed in U.S. Pat. No. 6,338,754 and U.S. patent application Ser. No. 11/545,929, each of which is incorporated herein, in its entirety, by this reference. Another example of a suitable pressure transmitting material is pyrophyllite, which is commercially available from Wonderstone Ltd. of South Africa. The cell assembly, including the pressure transmitting medium, the mixture 105 of a plurality of sintering aid particles at least saturated with carbon and a plurality of diamond particles, and the substrate 102 is subjected to an HPHT process using an ultra-high pressure press at a temperature of at least about 1000° C. (e.g., about 1100° C. to about 2200° C., or about 1200° C. to about 1450° C.) and a pressure in the pressure transmitting medium of at least about 7.5 GPa (e.g., about 7.5 GPa to about 15 GPa) for a time sufficient to sinter the diamond particles together and form the PCD table 106 comprising directly bonded-together diamond grains. For example, the pressure in the pressure transmitting medium employed in the HPHT process may be at least about 8.0 GPa, at least about 9.0 GPa, at least about 10.0 GPa, at least about 11.0 GPa, at least about 12.0 GPa, or at least about 14 GPa. Further details about HPHT processing techniques that may be used to practice the embodiments disclosed herein are disclosed in U.S. Pat. No. 7,866,418, which is incorporated herein, in its entirety, by reference.
The pressure values employed in the HPHT processes disclosed herein refer to the pressure in the pressure transmitting medium at room temperature (e.g., about 25° C., or slightly above due to compressive (friction) heating) with application of pressure using an ultra-high pressure press and not the pressure applied to the exterior of the cell assembly. The actual pressure in the pressure transmitting medium at sintering temperature may be higher. The ultra-high pressure press may be calibrated at room temperature by embedding at least one calibration material that changes structure at a known pressure, such as PbTe, thallium, barium, or bismuth in the pressure transmitting medium. Further, optionally, a change in resistance may be measured across the at least one calibration material due to a phase change thereof. For example, PbTe exhibits a phase change at room temperature at about 6.0 GPa and bismuth exhibits a phase change at room temperature at about 7.7 GPa. Examples of suitable pressure calibration techniques are disclosed in G. Rousse, S. Klotz, A. M. Saitta, J. Rodriguez-Carvajal, M. I. McMahon, B. Couzinet, and M. Mezouar, “Structure of the Intermediate Phase of PbTe at High Pressure,” Physical Review B: Condensed Matter and Materials Physics, 71, 224116 (2005) and D. L. Decker, W. A. Bassett, L. Merrill, H. T. Hall, and J. D. Barnett, “High-Pressure Calibration: A Critical Review,” J. Phys. Chem. Ref. Data, 1, 3 (1972).
During the HPHT process, the carbon-saturated sintering aid particles within the mixture 105 may at least partially melt during HPHT processing to facilitate diamond growth. Due to the additional carbon from the at least partially melted carbon-saturated sintering aid material, additional diamond may be grown between the diamond particles so that the diamond-diamond bond density increases. The PCD table 106 so-formed includes directly bonded-together diamond grains exhibiting diamond-to-diamond bonding (e.g., sp3 bonding) therebetween. The plurality of bonded diamond grains defines a plurality of interstitial regions. While most of the interstitial regions include sintering aid material provided from the carbon-saturated sintering aid particles, some of the interstitial regions near the substrate 102 may include a catalyst material disposed therein infiltrated from the substrate 102, such as iron, nickel, cobalt, or alloys thereof. The catalyst material infiltrated from the substrate 102 helps metallurgically bond the PCD table 106 so formed to the substrate 102. In some embodiments, the sintering aid material within the interstitial regions of the PCD table 106 may still be at least saturated with carbon at standard temperature and pressure (i.e., 0° C. and 1 atmosphere). In other embodiments, the sintering aid material within the interstitial regions may still even remain supersaturated with carbon at standard temperature and pressure (i.e., 0° C. and 1 atmosphere). In some embodiments, the carbon-saturated sintering aid material present in the PCD table 106 may include one or more of carbon fibrules, carbon onions, C-12, C-13, graphite, other sp2-carbon phases, metal carbide phases therein characteristic of the sintering aid material being at least saturated with carbon, or combinations thereof.
In embodiments in which at least a portion of the sintering aid material in the PCD table 106 is at least saturated with carbon, the carbon-saturated sintering aid material has less of a tendency to dissolve carbon therein at elevated temperatures. Therefore, at elevated temperatures commonly experienced during drilling when the PDC 120 is employed as a cutting element of a rotary drill bit, the carbon-saturated sintering aid material in the PCD table 106 does not significantly facilitate back conversion of the diamond grains to graphite and/or another by-product. For example, it is currently believed by the inventors that absent the sintering aid material being at least saturated with carbon, carbon from the diamond grains may be dissolved in the sintering aid material and precipitated as graphite under the non-diamond stable conditions typically experienced during drilling operations.
FIG. 2A is a cross-sectional view of an embodiment of a PDC precursor assembly 200 including a mixture 202 comprising: (i) a plurality of sintering aid particles at least saturated with carbon 208, a plurality of carbon-saturated sintering aid particles coated with submicron diamond particles 210, or combinations thereof, (ii) and a plurality of diamond particles 212 positioned adjacent to a substrate 102. In this embodiment, a plurality of submicron diamond particles may be mixed with a plurality of sintering aid particles and non-diamond carbon and be subjected to any of the mechanical milling processes disclosed herein. The product from such mechanical alloying may result in the plurality of carbon-saturated sintering aid particles coated and/or embedded with submicron diamond particles 210.
The plurality of submicron diamond particles may exhibit one or more selected submicron sizes. The one or more submicron selected sizes may be determined, for example, by passing the diamond particles through one or more sizing sieves or by any other method. In an embodiment, the plurality of submicron diamond particles may include a relatively larger size and at least one relatively smaller size. As used herein, the phrases “relatively larger” and “relatively smaller” refer to particle sizes determined by any suitable method, which differ by at least a factor of two (e.g., 40 nm and 20 nm). More particularly, in various embodiments, the plurality of submicron diamond particles may include a portion exhibiting a relatively larger size (e.g., 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 200 nm, 150 nm, 120 nm, 100 nm, 80 nm) and another portion exhibiting at least one relatively smaller size (e.g., 450 nm, 400 nm, 350 nm, 300 nm, 250 nm, 200 nm, 150 nm, 100 nm, 75 nm, 60 nm, 50 nm, 40 nm, 20 nm, 10 nm, 8 nm, 2 nm, 1 nm, 0.5 nm, less than 0.5 nm, 0.1 nm, less than 0.1 nm). In an embodiment, the plurality of submicron diamond particles may include a portion exhibiting a relatively larger size between about 400 nm and about 150 nm and another portion exhibiting a relatively smaller size between about 12 nm and 2 nm. Of course, the plurality of submicron diamond particles may also include three or more different sizes (e.g., one relatively larger size and two or more relatively smaller sizes), without limitation.
FIG. 2B is a cross-sectional view of a PDC 220 formed by HPHT processing of the PDC precursor assembly 200 shown in FIG. 2A using any of the HPHT conditions disclosed herein. The PDC 220 comprises a PCD table 222 that includes a working upper surface 224 and an interfacial surface 226 bonded to the substrate 102. The PCD table 222 includes a plurality of directly bonded-together diamond grains exhibiting diamond-to-diamond bonding therebetween (e.g., sp3 bonding) defining a plurality of interstitial regions.
The interstitial regions of the PCD table 222 may include a sintering aid material disposed therein provided from the plurality of sintering aid particles 208 that were at least saturated with carbon and/or a sintering aid material provided from the plurality of carbon-saturated sintering aid particles coated with submicron diamond particles 210 present in the mixture 202 of the PDC precursor assembly 200 in FIG. 2A. Catalyst material from the substrate 102 may also infiltrate into the mixture 202 during HPHT processing (e.g., cobalt from a cobalt-cemented tungsten carbide substrate) to occupy some of the interstitial regions adjacent to the substrate 102, which helps metallurgically bond the PCD table 222 to the substrate 102. In some embodiments, the sintering aid material within the interstitial regions of the PCD table 222 may be at least saturated or even supersaturated with carbon at standard temperature and pressure (i.e., 0° C. and 1 atmosphere). For example, the sintering aid material located in the interstitial regions of the PCD table 106 may be at least saturated with carbon and, in some embodiments, supersaturated with carbon for temperature and pressure conditions typically experienced during subterranean drilling operations. In some embodiments, the carbon-saturated sintering aid material may include one or more of carbon fibrules, carbon onions, carbon-12, carbon-13, graphite, other sp2-carbon phases, metal carbide phases therein characteristic of the sintering aid material being at least saturated with carbon, or combinations thereof. It is believed that the presence of the carbon-saturated sintering aid material may provide the ability to offer more carbon during sintering and promote extra diamond-to-diamond bonding growth resulting in an increase of the diamond-to-diamond bond density and/or quality.
In another embodiment, the mixture 202 may be formed into a green body and positioned adjacent to the substrate 102, and subjected to HPHT processing to form the PDC 220. A green body may assist with manufacturing and handling of the mixture 202 because a suitable sacrificial binder (e.g., a wax or polymer binder) is added to the mixture 202 that binds the particles together.
FIG. 3A is a cross-sectional view of an embodiment of a PDC precursor assembly 300 including at least one layer of a plurality of carbon-saturated sintering aid particles 304 positioned between at least one layer of a plurality of diamond particles 302 and a substrate 102. The plurality of carbon-saturated sintering aid particles within the region 304 may be fabricated employing any of the mechanical alloying processes disclosed herein in conjunction with any of the sintering aid materials discussed herein. Similarly, the plurality of diamond particles may exhibit any of the size distributions previously discussed. In another embodiment, the at least one layer of the plurality of diamond particles 302 may be disposed between the substrate 102 and the at least one layer of the plurality of carbon-saturated sintering aid particles 304.
FIG. 3B is a cross-sectional view of a PDC 320 formed by HPHT processing of the PDC precursor assembly 300 shown in FIG. 3A using any of the HPHT conditions disclosed herein. The PDC 320 comprises a PCD table 322 that includes an upper surface 324 and an interfacial surface 326 bonded to the substrate 102. The PCD table 322 includes a plurality of directly bonded-together diamond grains exhibiting diamond-to-diamond bonding therebetween (e.g., sp3 bonding) defining a plurality of interstitial regions.
During HPHT processing, the sintering aid material from the layer 304 at least partially melts and infiltrates into the plurality of diamond particles of the layer 302 to facilitate formation of the PCD table 322 from the diamond particles and promotes diamond growth. As with other embodiments, the sintering aid material located in the interstitial regions of the PCD table 322 may be provided from the plurality of carbon-saturated sintering aid particles that are at least saturated with carbon. For example, after HPHT processing, the sintering aid material may still be at least saturated or even still supersaturated. Catalyst material from the substrate 102 may also infiltrate into the diamond particles during HPHT processing (e.g., cobalt from a cobalt-cemented tungsten carbide substrate) to occupy some of the interstitial regions (e.g., adjacent to the substrate 102), which may help metallurgically bond the PCD table 322 to the substrate 102.
FIGS. 4A-4F are cross-sectional views illustrating a method of fabricating a PDC according to an embodiment that comprises forming a PCD table from a plurality of sintering aid particles at least saturated with carbon and a plurality of diamond particles in a first HPHT process followed by at least partially leaching the so-formed PCD table. A PDC is subsequently formed by bonding the at least partially leached PCD table to a substrate in a second HPHT process.
FIG. 4A illustrates a PDC precursor assembly 400 including a mixture 402 comprising a plurality of carbon-saturated sintering aid particles mixed with a plurality of diamond particles assembled with a substrate 102. The plurality of carbon-saturated sintering aid particles may be fabricated employing any of the mechanical alloying processes and any of the sintering aid materials discussed herein. Similarly, the plurality of diamond particles may be of any of the size distributions previously discussed.
Referring to FIG. 4B, a PDC 410 is formed by the HPHT processing of the PDC precursor assembly 400 shown in FIG. 4A using any of the HPHT conditions disclosed herein. The PDC 410 comprises a PCD table 412 that includes an upper surface 414, an optional chamfer 418, and an interfacial surface 416 bonded to the substrate 102. The PCD table 412 includes a plurality of directly bonded-together diamond grains exhibiting diamond-to-diamond bonding therebetween (e.g., sp3 bonding) defining a plurality of interstitial regions.
During HPHT processing, the sintering aid material from the plurality of carbon-saturated sintering aid particles facilitate formation of the PCD table 412 from the plurality of diamond particles and promotes diamond growth as previously discussed. As with other embodiments, the sintering aid material located in the interstitial regions of the PCD table 412 so formed may be provided from the plurality of carbon-saturated sintering aid particles. For example, the sintering aid material may still be at least saturated or even still supersaturated after HPHT processing. Catalyst material from the substrate 102 may also infiltrate into the mixture 402 during HPHT processing (e.g., cobalt from a cobalt-cemented tungsten carbide substrate) to occupy some of the interstitial regions adjacent to the substrate 102, which helps metallurgically bond the PCD table 412 to the substrate 102.
The PCD table 412, shown in FIG. 4B, may be separated from the substrate 102 using a grinding process, wire-electrical-discharge machining (“wire EDM”), combinations thereof, or another suitable material-removal process. FIG. 4C shows the separated PCD table 422. The separated PCD table 422 may be leached by immersion in an acid, such as aqua-regia, nitric acid, hydrofluoric acid, or subjected to another suitable process to remove at least a portion of the catalyst material and carbon-saturated sintering aid material from the interstitial regions of the separated PCD table 422 and form an at least partially leached PCD table 432 as shown in FIG. 4D. For example, the separated PCD table 422 may be immersed in the acid for about 2 to about 7 days (e.g., about 3, 5, or 7 days) or for a few weeks (e.g., about 4 weeks) depending on the process employed. In other embodiments, the PCD table 412 may not be formed on the substrate 102, thereby eliminating the need for removal of the substrate 102.
Referring to FIG. 4E, a PDC precursor assembly 440 may be formed by positioning an additional substrate 102 adjacent to the at least partially leached PCD table 432. The at least partially leached PCD table 432 includes a working surface 434 and an opposing interfacial surface 436 positioned adjacent to the substrate 102. The at least partially leached PCD table 432 also includes a plurality of interstitial regions that were previously occupied by the sintering aid and/or catalyst material. These previously occupied interstitial regions form a network of at least partially interconnected pores that extend between the working surface 434 and interfacial surface 436. The assembly 440 may be subject to HPHT processing for a time sufficient to bond the at least partially leached PCD table 432 to the substrate 102 and form a PDC 450 as shown in FIG. 4F.
The HPHT process bonds the at least partially leached PCD table 432 to the substrate 102 and may cause a metallic infiltrant from the substrate 102 or another source to infiltrate into the interstitial regions of the at least partially leached PCD table 432. The HPHT temperature may be sufficient to melt at least one constituent of the substrate 102 (e.g., cobalt, nickel, iron, alloys thereof, or another constituent) that infiltrates the at least partially leached PCD table 432. The PDC 450 so-formed includes a PCD table 452 in which the interstitial regions thereof are at least partially filled with the metallic infiltrant. It is noted that the PDC 450 may exhibit other geometries than the geometry illustrated in FIG. 4F. For example, the PDC 450 may exhibit a non-cylindrical geometry. For example, the PCD table 452 may be chamfered, as illustrated, after HPHT processing. Optionally, the PDC table 452 may be leached to at least partially remove the metallic infiltrant.
FIGS. 5A-5F are cross-sectional views illustrating a method of fabricating a PDC according to an embodiment that comprises forming a PCD table from a plurality of sintering aid particles at least saturated with carbon and a plurality of diamond particles in a first HPHT process and at least partially leaching the so-formed PCD table. The at least partially leached PCD table is then cleaned to remove at least some of the leaching by-products therein. A PDC is subsequently formed by positioning a plurality of carbon-saturated sintering aid particles between the at least partially leached PCD table and a substrate and bonding in a second HPHT process.
FIG. 5A illustrates an assembly 500 including a mixture 502 comprising a plurality of carbon-saturated sintering aid particles and a plurality of diamond particles. The plurality of carbon-saturated sintering aid particles found in the mixture 502 may be fabricated using any of the sintering aid materials and mechanical alloying methods disclosed herein. Similarly, the plurality of diamond particles within the mixture 502 may exhibit of any of the size distributions disclosed herein. The mixture 502 including the plurality of carbon-saturated sintering aid particles and the plurality of diamond particles may be subjected to HPHT processing to form the PCD table 512 shown in FIG. 5B using any of the HPHT conditions disclosed herein. The PCD table 512 comprises a working surface 514 and an interfacial surface 518. The PCD table 512 further includes a plurality of directly bonded-together diamond grains exhibiting diamond-to-diamond bonding therebetween (e.g., sp3 bonding) defining a plurality of interstitial regions.
During HPHT processing, the sintering aid material from the plurality of carbon-saturated sintering aid particles facilitates formation of the PCD table 512 from the plurality of diamond particles and promotes diamond growth as previously discussed. As with other embodiments, the sintering aid material located in the interstitial regions of the PCD table 512 so formed may be provided from the plurality of carbon-saturated sintering aid particles. For example, the sintering aid material may still be at least saturated or even still supersaturated after HPHT processing.
As shown in FIG. 5C, the as-sintered the PCD table 512 may be subject to leaching using any of the methods previously described to remove at least a portion of the sintering aid material from the interstitial regions of the PCD table 512 and form an at least partially leached PCD table 522 as shown in FIG. 5C.
As a result of the leaching process used to remove at least a portion of the sintering aid material, the at least partially leached PCD table 522 shown in FIGS. 5B and 5C may include leaching by-products. For example, leaching agents used to remove, for example, cobalt from the interstitial regions may leave one or more types of residual salts, one or more types of oxides, combinations of the foregoing, or another leaching by-product within at least some of the interstitial regions of the at least partially leached PCD table 522. For example, depending upon the chemistry of the leaching solution, the leaching by-products may comprise a salt of nitric acid, hydrochloric acid, phosphoric acid, acetic acid, or mixtures of the foregoing. For example, the salt may be cobalt nitrate or cobalt chloride. The leaching by-products may also comprise a metal oxide (e.g., an oxide of tungsten, cobalt or other metal) and/or another type of metal present in the sintering aid of the at least partially leached PCD table 522 prior to leaching. It is currently believed that such leaching by-products may block, obstruct, or otherwise inhibit infiltration of the at least partially leached PCD table 522 with metallic infiltrant when the at least partially leached PCD table 522 is attempted to be bonded to a substrate.
Referring to FIG. 5D, at least some of the leaching by-products may be removed from the at least partially leached PCD table 522. For example, as shown in FIG. 5D, at least some of the leaching by-products may be removed by subjecting the at least partially leached PCD table 522 to a thermal-cleaning process. In such a thermal-cleaning process, the at least partially leached PCD table 522 may be heated under partial vacuum (e.g., at a pressure less than ambient atmospheric pressure) to a temperature sufficient to sublimate at least some of the leaching by-products present in the at least partially leached PCD table 522, but below a temperature at which the diamond grains of the at least partially leached PCD table 522 may significantly degrade. For example, the at least partially leached PCD table 522 may be heated in a vacuum furnace at a temperature between at least about 600° C. and less than about 700° C. for about 0.5 hours to about 2.0 hours or more. In an embodiment, the at least partially leached PCD table 522 may be heated in a vacuum furnace at a temperature of about 650° C. for about 1 hour to about 1.5 hours.
In another embodiment, at least some of the leaching by-products may be removed from the at least partially leached PCD table 522 using a chemical cleaning process. For example, the at least partially leached PCD table 522 may be immersed in hydrofluoric acid. The concentration of the hydrofluoric acid and the immersion time of the at least partially leached PCD table 522 in the hydrofluoric acid may be selected so that at least some of the leaching by-products and, in some embodiments, substantially all of the leaching by-products may be removed from the at least partially leached PCD table 522.
In an embodiment of a chemical cleaning process, at least some of the leaching by-products may be removed using an ultrasonic cleaning process. For example, the at least partially leached PCD table 522 of FIG. 5C may be immersed in a selected solvent and ultrasonic energy applied to the selected solvent for a selected period of time to effect removal of at least some of the leaching by-products and, in some embodiments, substantially all of the leaching by-products may be removed from the at least partially leached PCD table 522. The selected solvent may be an aqueous solution (e.g., hydrofluoric acid) or an organic solvent.
Additional details about suitable cleaning techniques for removing the leaching by-products are disclosed in U.S. Pat. No. 7,845,438. U.S. Pat. No. 7,845,438 is incorporated herein, in its entirety, by this reference.
In another embodiment, following removal of at least some of the leaching by-products, the interfacial surface 526 of the at least partially leached PCD table 522 may be bonded to a substrate in an HPHT bonding process to form a PDC in the same manner as the at least partially leached PCD table 432 was bonded to form the PDC 450 shown in FIGS. 4E and 4F. During the HPHT bonding process, the at least partially leached PCD table 522 may be infiltrated only with the metallic infiltrant from the substrate, such as cobalt from a cobalt-cemented carbide substrate.
Referring to FIG. 5E, an assembly 540 may be formed by positioning an at least carbon-saturated infiltrant particle layer 544 between the substrate 102 and the at least partially leached and cleaned PCD table 522. However, in other embodiments, the at least partially leached and cleaned PCD table 522 may be positioned between the substrate 102 and the at least carbon-saturated infiltrant particle layer 544. For example, the at least carbon-saturated infiltrant particle layer 544 includes carbon-saturated particles made from any of the foregoing sintering aid particles that have been at least saturated with carbon. For example, the carbon-saturated particles may be unbounded or in the form of a green body. However, depending upon the infiltration conditions, composition, nature of the carbon-saturated particles, or combinations thereof, the carbon-saturated particles may or may not function as a catalyst. The at least partially leached PCD table 522 also includes a plurality of interstitial regions that were previously occupied by a sintering aid material provided from the carbon-saturated sintering aid particles within mixture 502 (shown in FIG. 5A) and form a network of at least partially interconnected pores that extend between the working surface 524 and interfacial surface 526. The assembly 540 may be subject to HPHT processing for a time sufficient to infiltrate and bond the at least partially leached and cleaned PCD table 522 to the substrate 102 and form a PDC 550 as shown in FIG. 5F. The HPHT process bonds the at least partially leached PCD table 522 to the substrate 102 and may cause a metallic infiltrant from the substrate 102 and a carbon-saturated infiltrant from the carbon-saturated infiltrant particles to infiltrate the interstitial regions of the at least partially leached PCD table 522. The PDC 550 so-formed includes a PCD table 552 in which the interstitial regions thereof are at least partially filled with the infiltrant. At least some of the interstitial regions are occupied by infiltrant provided from the carbon-saturated infiltrant particles of the layer 544, while interstitial regions at or near the substrate 102 may be occupied by the metallic infiltrant from the substrate 102. The infiltrant provided from the carbon-saturated infiltrant particles of the layer 544 may still be at least saturated or even still supersaturated with carbon after HPHT processing. It is currently believed that when the infiltrant remains at least supersaturated after HPHT processing/infiltrant, the thermal stability of the PCD table 552 may be enhanced because back conversion of the diamond grains to graphite or other reaction product is reduced.
In some embodiments, the at least partially leached PCD table 522 may be fabricated in a conventional manner. The conventionally fabricated at least partially leached PCD table may then be attached to the substrate 102 as shown and described in FIGS. 5E and 5F.
In any of the PDC embodiments disclosed herein, the PCD table may be subjected to a leaching process (e.g., an acid leaching process) to at least partially remove the sintering aid material disposed in the interstitial regions of the PCD table to a selected depth from one or more of the upper working surface, the chamfer (if present), or the at least one lateral surface. For example, according to an embodiment, FIG. 1D is a cross-sectional view of the PDC 120 in which the PCD table 110 has been leached to a selected depth “d” to form a leached region 122, with the unaffected underlying PCD table 106 labeled as region 124. For example, the selected depth “d” may be greater than about 50 μm, such as about 50 μm to about 800 μm, about 200 μm to about 800 μm, about 400 μm to about 800 μm, or about 250 μm to about 500 μm.
FIG. 6 is an isometric view and FIG. 7 is a top elevation view of a rotary drill bit 600 according to an embodiment. The rotary drill bit 600 includes at least one PDC fabricating according to any of the previously described PDC embodiments. The rotary drill bit 600 comprises a bit body 602 that includes radially and longitudinally extending blades 604 with leading faces 606, and a threaded pin connection 608 for connecting the bit body 602 to a drilling string. The bit body 602 defines a leading end structure configured for drilling into a subterranean formation by rotation about a longitudinal axis 610 and application of weight-on-bit. At least one PDC cutting element, manufactured and configured according to any of the previously described PDC embodiments (e.g., the PDC 120, 220, 320, 450, or 550), may be affixed to rotary drill bit 600 by, for example, brazing, mechanical affixing, or another suitable technique. With reference to FIG. 7, each of a plurality of PDCs 612 is secured to the blades 604. For example, each PDC 612 may include a PCD table 614 bonded to a substrate 616. More generally, the PDCs 612 may comprise any PDC disclosed herein, without limitation. In addition, if desired, in an embodiment, a number of the PDCs 612 may be conventional in construction. Also, circumferentially adjacent blades 604 define so-called junk slots 618 therebetween, as known in the art. Additionally, the rotary drill bit 600 includes a plurality of nozzle cavities 620 for communicating drilling fluid from the interior of the rotary drill bit 600 to the PDCs 612.
FIGS. 6 and 7 merely depict one embodiment of a rotary drill bit that employs at least one cutting element comprising a PDC fabricated and structured in accordance with the disclosed embodiments, without limitation. The rotary drill bit 600 is used to represent any number of earth-boring tools or drilling tools, including, for example, core bits, roller-cone bits, fixed-cutter bits, eccentric bits, bicenter bits, reamers, reamer wings, mining rotary drill bits, or any other downhole tool including PDCs, without limitation. For example, the PDCs disclosed herein may be employed in roof bolt drill bits disclosed in U.S. Application Publication No. 2011/0284294 filed on 9 Mar. 2009, which is incorporated herein, in its entirety, by this reference.
The PDCs disclosed herein may also be utilized in applications other than rotary drill bits. For example, the disclosed PDC embodiments may be used in thrust-bearing assemblies, radial bearing assemblies, wire-drawing dies, artificial joints, machining elements, and heat sinks.
FIG. 8 is an isometric cut-away view of a thrust-bearing apparatus 800 according to an embodiment, which may utilize any of the disclosed PDC embodiments as bearing elements. The thrust-bearing apparatus 800 includes respective thrust-bearing assemblies 802. Each thrust-bearing assembly 802 includes an annular support ring 804 that may be fabricated from a material, such as carbon steel, stainless steel, or another suitable material. Each support ring 804 includes a plurality of recesses (not labeled) that receives a corresponding bearing element 806. Each bearing element 806 may be mounted to a corresponding support ring 804 within a corresponding recess by brazing, press-fitting, using fasteners, or another suitable mounting technique. One or more, or all of bearing elements 806 may be configured according to any of the disclosed PDC embodiments. For example, each bearing element 806 may include a substrate 808 and a PCD table 814, with the PCD table 814 including a bearing surface 812.
In use, the bearing surfaces 812 of one of the thrust-bearing assemblies 802 bears against the opposing bearing surfaces 812 of the other one of the bearing assemblies 802. For example, one of the thrust-bearing assemblies 802 may be operably coupled to a shaft to rotate therewith and may be termed a “rotor.” The other one of the thrust-bearing assemblies 802 may be held stationary and may be termed a “stator.”
FIG. 9 is an isometric cut-away view of a radial bearing apparatus 900 according to an embodiment, which may utilize any of the disclosed PDC embodiments as bearing elements. The radial bearing apparatus 900 includes an inner race 902 positioned generally within an outer race 904. The outer race 904 includes a plurality of bearing elements 910 affixed thereto that have respective bearing surfaces 912. The inner race 902 also includes a plurality of bearing elements 906 affixed thereto that have respective bearing surfaces 908. One or more, or all of the bearing elements 906 and 910 may be configured according to any of the PDC embodiments disclosed herein. The inner race 902 is positioned generally within the outer race 904, with the inner race 902 and outer race 904 configured so that the bearing surfaces 908 and 912 may at least partially contact one another and move relative to each other as the inner race 902 and outer race 904 rotate relative to each other during use.
Although the various embodiments of methods disclosed herein are directed to employing carbon-saturated sintering aid materials to facilitate forming PCD materials and structures, in other embodiments, the carbon-saturated sintering aid materials may be replaced with any of the sintering aid materials disclosed herein that are at least saturated with hexagonal boron nitride via mechanical milling a sintering aid material and hexagonal boron nitride. Cubic boron nitride particles may be sintered in the presence of the sintering aid material at least saturated with hexagonal boron nitride to form polycrystalline cubic boron nitride.
While various aspects and embodiments have been disclosed herein, other aspects and embodiments are contemplated. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting. Additionally, the words “including,” “having,” and variants thereof (e.g., “includes” and “has”) as used herein, including the claims, are open ended and shall have the same meaning as the word “comprising” and variants thereof (e.g., “comprise” and “comprises”).

## Claims

1. A polycrystalline diamond compact, comprising:
a substrate; and
a polycrystalline diamond table bonded to the substrate, the polycrystalline diamond table including a plurality of diamond grains having diamond-to-diamond bonding therebetween, the polycrystalline diamond table formed by a method including:
mechanically milling non-diamond carbon and a sintering aid material for a time and an aggressiveness sufficient to form a plurality of the carbon-saturated sintering aid particles; and
sintering the plurality of diamond particles in the presence of a plurality of carbon-saturated sintering aid particles to form a polycrystalline diamond table, the carbon-saturated sintering aid particles catalyzing formation of diamond-to-diamond bonding between the plurality of diamond particles to form the polycrystalline diamond table.

2. The polycrystalline diamond compact of claim 1 wherein mechanically milling non-diamond carbon and a sintering aid material for a time and aggressiveness sufficient to form a plurality of carbon-saturated sintering aid particles includes ball milling, attritor milling, horizontal ball milling, or high-energy ball milling the non-diamond carbon and the sintering aid material.

3. The polycrystalline diamond compact of claim 1 wherein the time is less than about 2200 hours.

4. The polycrystalline diamond compact of claim 1 wherein the time is about 100 hours to about 1100 hours.

5. The polycrystalline diamond compact of claim 1 wherein the time is about 150 hours to about 700 hours.

6. The polycrystalline diamond compact of claim 1 wherein the plurality of sintering aid particles includes at least one member selected from the group consisting of cobalt, nickel, iron, copper, aluminum, titanium, tungsten, niobium, zirconium, tantalum, silicon, and boron.

7. The polycrystalline diamond compact of claim 1 wherein the plurality of sintering aid particles includes at least one member selected from the group consisting of copper, aluminum, and tungsten.

8. The polycrystalline diamond compact of claim 1 wherein the plurality of carbon-saturated sintering aid particles exhibit a carbon content of greater than about 0.01 atomic %.

9. The polycrystalline diamond compact of claim 1 wherein the plurality of carbon-saturated sintering aid particles exhibit a carbon content of about 10 atomic % to about 30 atomic %.

10. The polycrystalline diamond compact of claim 9 wherein the plurality of carbon-saturated sintering aid particles exhibit a carbon content of about 5 atomic % to about 25 atomic %.

11. The polycrystalline diamond compact of claim 9 wherein the plurality of carbon-saturated sintering aid particles exhibit a carbon content of about 1 atomic % to about 10 atomic %.

12. The polycrystalline diamond compact of claim 9 wherein the plurality of carbon-saturated sintering aid particles exhibit a carbon content of about 25 atomic % to about 30 atomic %.

13. The polycrystalline diamond compact of claim 1 wherein the non-diamond carbon includes at least one member selected from the group consisting of lamp black, graphite, carbon-12 graphite, carbon-13 graphite, carbon-14 graphite, carbon nanotubes, graphene, amorphous carbon, amorphous carbon-12, amorphous carbon-13, amorphous carbon-14, carbon-12, carbon-13, carbon-14, and fullerenes.

14. The polycrystalline diamond compact of claim 1 wherein the method further includes:
prior to the act of sintering, assembling the plurality of carbon-saturated sintering aid particles between the plurality of diamond particles and a substrate to form an assembly; and
wherein sintering a plurality of diamond particles in the presence of the plurality of carbon-saturated sintering aid particles to form a polycrystalline diamond table includes subjecting the assembly to a high-pressure/high-temperature process effective to infiltrate the plurality of diamond particles with a carbon-saturated infiltrant from the plurality of carbon-saturated sintering aid particles to sinter the plurality of diamond particles and form the polycrystalline diamond table that bonds to the substrate.

15. The polycrystalline diamond compact of claim 14 wherein the method further includes:
removing the polycrystalline diamond table from the substrate;
leaching the polycrystalline diamond table to at least partially remove sintering aid material, provided from the carbon-saturated infiltrant, from the polycrystalline diamond table to form an at least partially leached polycrystalline diamond table; and
bonding the at least partially leached polycrystalline diamond table to an additional substrate to form an additional polycrystalline diamond compact.

16. A polycrystalline diamond compact, comprising:
a substrate; and
a polycrystalline diamond table bonded to the substrate, the polycrystalline diamond table including a plurality of diamond grains having diamond-to-diamond bonding therebetween, the polycrystalline diamond table formed by a method including:
mechanically milling non-diamond carbon and a sintering aid material for a time sufficient to form a plurality of carbon-saturated sintering aid particles;
mixing the plurality of carbon-saturated sintering aid particles and a plurality of diamond particles to form a mixture; and
subjecting the mixture to a high-pressure/high-temperature process effective to sinter the plurality of diamond particles to form the polycrystalline diamond body.

17. The polycrystalline diamond compact of claim 16 wherein the time is about 150 hours to about 700 hours.

18. The polycrystalline diamond compact of claim 16 wherein the plurality of sintering aid particles includes at least one member selected from the group consisting of cobalt, nickel, iron, copper, aluminum, titanium, tungsten, niobium, zirconium, tantalum, silicon, and boron.

19. The polycrystalline diamond compact of claim 16 wherein the non-diamond carbon includes at least one member selected from the group consisting of lamp black, graphite, carbon-12 graphite, carbon-13 graphite, carbon-14 graphite, carbon nanotubes, graphene, amorphous carbon, amorphous carbon-12, amorphous carbon-13, amorphous carbon-14, carbon-12, carbon-13, carbon-14, and fullerenes.

20. A polycrystalline diamond compact, comprising:
a substrate;
a polycrystalline diamond table bonded to the substrate, the polycrystalline diamond table including a plurality of diamond grains having diamond-to-diamond bonding therebetween, the polycrystalline diamond table formed by a method including:
mechanically milling non-diamond carbon with a sintering aid material for a time sufficient to form a plurality of carbon-saturated sintering aid particles;
sintering a plurality of diamond particles in the presence of the plurality of carbon-saturated sintering aid particles to form a polycrystalline diamond table, wherein the carbon-saturated sintering aid particles catalyzes formation of diamond-to-diamond bonding between the plurality of diamond particles used to form the polycrystalline diamond table;
at least partially leaching a sintering aid material from the polycrystalline diamond table to form an at least partially leached polycrystalline diamond table;
forming an assembly including the at least partially leached polycrystalline diamond table positioned at least proximate to a substrate; and
subjecting the assembly to a high-pressure/high-temperature process effective to infiltrate the at least partially leached polycrystalline diamond table with an infiltrant and bond the infiltrated polycrystalline diamond table to the substrate.