Patent Grant
11807920
Embodiments of the disclosure relate to supporting substrates for cutting elements, and to related cutting elements, structures, earth-boring tools, and methods of forming the supporting substrates and cutting elements.
Earth-boring tools for forming wellbores in subterranean earth formations may include a plurality of cutting elements secured to a body. For example, fixed-cutter earth-boring rotary drill bits (“drag bits”) include a plurality of cutting elements that are fixedly attached to a bit body of the drill bit. Similarly, roller cone earth-boring rotary drill bits may include cones that are mounted on bearing pins extending from legs of a bit body such that each cone is capable of rotating about the bearing pin on which it is mounted. A plurality of cutting elements may be mounted to each cone of the drill bit. Other earth-boring tools utilizing cutting elements include, for example, core bits, bi-center bits, eccentric bits, hybrid bits (e.g., rolling components in combination with fixed cutting elements), reamers, and casing milling tools.
The cutting elements used in such earth-boring tools often include a volume of polycrystalline diamond (“PCD”) material on a substrate. Surfaces of the polycrystalline diamond act as cutting faces of the so-called polycrystalline diamond compact (“PDC”) cutting elements. PCD material is material that includes inter-bonded grains or crystals of diamond material. In other words, PCD material includes direct, inter-granular bonds between the grains or crystals of diamond material. The terms “grain” and “crystal” are used synonymously and interchangeably herein.
PDC cutting elements are generally formed by sintering and bonding together relatively small diamond (synthetic, natural or a combination) grains, termed “grit,” under conditions of high temperature and high pressure in the presence of a catalyst (e.g., cobalt, iron, nickel, or alloys and mixtures thereof) to form one or more layers (e.g., a “compact” or “table”) of PCD material. These processes are often referred to as high temperature/high pressure (or “HTHP”) processes. The supporting substrate may comprise a cermet material (i.e., a ceramic-metal composite material) such as, for example, cobalt-cemented tungsten carbide. In some instances, the PCD material may be formed on the cutting element, for example, during the HTHP process. In such instances, catalyst material (e.g., cobalt) in the supporting substrate may be “swept” into the diamond grains during sintering and serve as a catalyst material for forming the diamond table from the diamond grains. Powdered catalyst material may also be mixed with the diamond grains prior to sintering the grains together in an HTHP process. In other methods, the diamond table may be formed separately from the supporting substrate and subsequently attached thereto.
Upon formation of the diamond table using an HTHP process, catalyst material may remain in interstitial spaces between the inter-bonded grains of the PDC. The presence of the catalyst material in the PDC may contribute to thermal damage in the PDC when the PDC cutting element is heated during use due to friction at the contact point between the cutting element and the formation. Accordingly, the catalyst material (e.g., cobalt) may be leached out of the interstitial spaces using, for example, an acid or combination of acids (e.g., aqua regia). Substantially all of the catalyst material may be removed from the PDC, or catalyst material may be removed from only a portion thereof, for example, from a cutting face of the PDC, from a side of the PDC, or both, to a desired depth. However, a fully leached PDC is relatively more brittle and vulnerable to shear, compressive, and tensile stresses than is a non-leached PDC. In addition, it is difficult to secure a completely leached PDC to a supporting substrate.
Embodiments described herein include supporting substrates for cutting elements, and related cutting elements, structures, earth-boring tools, and methods of forming the supporting substrates and the cutting elements. For example, in accordance with one embodiment described herein, a method of forming a supporting substrate for a cutting element comprises forming a precursor composition comprising discrete WC particles, a binding agent, and discrete particles comprising Co, one or more of Al, Be, Ga, Ge, Si, and Sn, and one or more of C and W. The precursor composition is subjected to a consolidation process to form a consolidated structure including WC particles dispersed in a homogenized binder comprising Co, W, C, and one or more of Al, Be, Ga, Ge, Si, and Sn.
In additional embodiments, a method of forming a cutting element comprises providing a supporting substrate comprising WC particles dispersed within a homogenized binder comprising Co, W, C, and one or more of Al, Be, Ga, Ge, Si, and Sn. A powder comprising diamond particles is deposited directly on the supporting substrate. The supporting substrate and the powder are subjected to elevated temperatures and elevated pressures to diffuse a portion of the homogenized binder of the supporting substrate into the powder and inter-bond the diamond particles. Portions of the homogenized binder within interstitial spaces between the inter-bonded diamond particles are converted into a thermally stable material comprising κ-carbide precipitates.
In further embodiments, a cutting element comprises a supporting substrate comprising WC particles dispersed in a homogenized binder comprising Co, W, C, and one or more of Al, Be, Ga, Ge, Si, and Sn. A cutting table is directly attached to an end of the supporting substrate and comprises inter-bonded diamond particles, and a thermally stable material within interstitial spaces between the inter-bonded diamond particles. The thermally stable material comprises κ-carbide precipitates.
In yet further embodiments, a structure comprises a consolidated structure and a hard material structure directly attached to the consolidated structure. The consolidated structure comprises WC particles dispersed in a homogenized binder comprising Co, W, C, and one or more of Al, Be, Ga, Ge, Si, and Sn. The hard material structure comprises inter-bonded diamond particles and a thermally stable material within interstitial spaces between the inter-bonded diamond particles. The thermally stable material comprises κ-carbide precipitates.
The following description provides specific details, such as specific shapes, specific sizes, specific material compositions, and specific processing conditions, in order to provide a thorough description of embodiments of the present disclosure. However, a person of ordinary skill in the art would understand that the embodiments of the disclosure may be practiced without necessarily employing these specific details. Embodiments of the disclosure may be practiced in conjunction with conventional fabrication techniques employed in the industry. In addition, the description provided below does not form a complete process flow for manufacturing a cutting element or earth-boring tool. Only those process acts and structures necessary to understand the embodiments of the disclosure are described in detail below. Additional acts to form a complete cutting element or a complete earth-boring tool from the structures described herein may be performed by conventional fabrication processes.
Drawings presented herein are for illustrative purposes only, and are not meant to be actual views of any particular material, component, structure, device, or system. Variations from the shapes depicted in the drawings as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein are not to be construed as being limited to the particular shapes or regions as illustrated, but include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as box-shaped may have rough and/or nonlinear features, and a region illustrated or described as round may include some rough and/or linear features. Moreover, sharp angles that are illustrated may be rounded, and vice versa. Thus, the regions illustrated in the figures are schematic in nature, and their shapes are not intended to illustrate the precise shape of a region and do not limit the scope of the present claims. The drawings are not necessarily to scale. Additionally, elements common between figures may retain the same numerical designation.
As used herein, the terms “comprising,” “including,” “having,” and grammatical equivalents thereof are inclusive or open-ended terms that do not exclude additional, unrecited elements or method steps, but also include the more restrictive terms “consisting of” and “consisting essentially of” and grammatical equivalents thereof. As used herein, the term “may” with respect to a material, structure, feature, or method act indicates that such is contemplated for use in implementation of an embodiment of the disclosure and such term is used in preference to the more restrictive term “is” so as to avoid any implication that other, compatible materials, structures, features, and methods usable in combination therewith should or must be excluded.
As used herein, spatially relative terms, such as “below,” “lower,” “bottom,” “above,” “over,” “upper,” “top,” and the like, may be used for ease of description to describe one element's or feature's relationship to another element(s) or feature(s) as illustrated in the figures. Unless otherwise specified, the spatially relative terms are intended to encompass different orientations of the materials in addition to the orientation depicted in the figures. For example, if materials in the figures are inverted, elements described as “over” or “above” or “on” or “on top of” other elements or features would then be oriented “below” or “beneath” or “under” or “on bottom of” the other elements or features. Thus, the term “over” can encompass both an orientation of above and below, depending on the context in which the term is used, which will be evident to one of ordinary skill in the art. The materials may be otherwise oriented (e.g., rotated 90 degrees, inverted, flipped) and the spatially relative descriptors used herein interpreted accordingly.
As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items.
As used herein, the term “configured” refers to a size, shape, material composition, material distribution, orientation, and arrangement of one or more of at least one structure and at least one apparatus facilitating operation of one or more of the structure and the apparatus in a predetermined way.
As used herein, the term “substantially” in reference to a given parameter, property, or condition means and includes to a degree that one of ordinary skill in the art would understand that the given parameter, property, or condition is met with a degree of variance, such as within acceptable manufacturing tolerances. By way of example, depending on the particular parameter, property, or condition that is substantially met, the parameter, property, or condition may be at least 90.0% met, at least 95.0% met, at least 99.0% met, at least 99.9% met, or even 100.0% met.
As used herein, the term “about” in reference to a given parameter is inclusive of the stated value and has the meaning dictated by the context (e.g., it includes the degree of error associated with measurement of the given parameter).
As used herein, the terms “earth-boring tool” and “earth-boring drill bit” mean and include any type of bit or tool used for drilling during the formation or enlargement of a wellbore in a subterranean formation and include, for example, fixed-cutter bits, roller cone bits, percussion bits, core bits, eccentric bits, bi-center bits, reamers, mills, drag bits, hybrid bits (e.g., rolling components in combination with fixed cutting elements), and other drilling bits and tools known in the art.
As used herein, the term “polycrystalline compact” means and includes any structure comprising a polycrystalline material formed by a process that involves application of pressure (e.g., compaction) to the precursor composition or materials used to form the polycrystalline material. In turn, as used herein, the term “polycrystalline material” means and includes any material comprising a plurality of grains or crystals of the material that are bonded directly together by inter-granular bonds. The crystal structures of the individual grains of the material may be randomly oriented in space within the polycrystalline material.
As used herein, the term “inter-granular bond” means and includes any direct atomic bond (e.g., covalent, metallic, etc.) between atoms in adjacent grains of hard material.
As used herein, the term “hard material” means and includes any material having a Knoop hardness value of greater than or equal to about 3,000 Kgf/mm2 (29,420 MPa). Non-limiting examples of hard materials include diamond (e.g., natural diamond, synthetic diamond, or combinations thereof), and cubic boron nitride.
As used herein, the term “catalytic cobalt” means and includes the catalytic crystalline form of cobalt (Co). In turn, the “catalytic crystalline form” of Co refers to disordered face-centered-cubic (FCC) gamma (γ) phase (FCC (γ)) Co. FCC (γ) Co exhibits a “disordered” configuration when Co atoms of the FCC lattice are substituted with other (e.g., replacement) atoms at irregular positions. In contrast, FCC (γ) Co exhibits an “ordered” configuration when Co atoms of the FCC lattice are substituted with other atoms at regular positions. Detection of whether FCC (γ) Co exhibits a disordered configuration or an ordered configuration can be demonstrated using X-ray diffraction techniques or in detection of magnetic phases.
Referring to
The preliminary powder may include any amounts of Co, one or more of Al, Ga, Sn, Be, Ge, and Si, and one or more of C and W able to facilitate the formation of a consolidated structure formed of and including WC particles and a homogenized binder including desired amounts of Co, W, C, and one or more of Al, Ga, Sn, Be, Ge, and Si (as well as individual element(s) of the additive(s), if any) through the consolidation process 104. Accordingly, amounts of Co, one or more of Al, Ga, Sn, Be, Ge, and Si, and one or more of C and W in the preliminary powder (e.g., as effectuated by the formulations and relative amounts of the discrete alloy particles and/or the discrete elemental particles thereof) may be selected at least partially based on amounts of W and C in the WC powder (e.g., as effectuated by the formulations and relative amounts of the discrete WC particles thereof) and amounts of the additive(s) (if any) facilitating the formation of the homogenized binder of the consolidated structure. In turn, as described in further detail below, a material composition of the homogenized binder (including the relative amounts of Co, W, C, one or more of Al, Ga, Sn, Be, Ge, and Si, and any other element(s) therein) may be selected at least partially based on desired melting properties of the homogenized binder, on desired catalytic properties of the homogenized binder for the formation of a compact structure (e.g., a cutting table, such as a PDC table) including inter-bonded diamond particles, and on desired stability properties (e.g., thermal stability properties, mechanical stability properties) of the compact structure effectuated by the formation of a thermally stable material from portions of the homogenized binder remaining within interstitial spaces between the inter-bonded diamond particles following the formation thereof. As described in further detail below, the thermally stable material of the subsequently-formed compact structure includes an E21-type phase carbide (κ-carbide) precipitate that is both thermally stable and mechanically stable. A standard enthalpy of formation of the κ-carbide precipitate is less than zero (indicating that the κ-carbide precipitate is thermally stable), and an eigenvalue from a Young's modulus calculation for the κ-carbide precipitate is positive (indicating that the κ-carbide precipitate is mechanically stable). It was unexpectedly discovered that Al, Ga, Sn, Be, Ge, and Si, individually or in combination, facilitate the formation of κ-carbide precipitates that are both thermally and mechanically stable, whereas other metalloids (boron (B), arsenic (As), antimony (Sb), bismuth (Bi), tellurium (Te)) and nonmetals (e.g., phosphorus (P), selenium (Se)) of Groups IIIA through VIA of the Periodic Table of Elements do not.
In some embodiments, the preliminary powder includes from about one (1) weight percent (wt %) of one or more of Al, Ga, Sn, Be, Ge, and Si to about 15.0 wt % of one or more of Al, Ga, Sn, Be, Ge, and Si; from about 83 wt % Co to about to 98.75 wt % Co, and from about 0.25 wt % C to about 2.0 wt % C. As a non-limiting example, the preliminary powder may include from about one (1) weight percent (wt %) Al to about 15.0 wt % Al, from about 83 wt % Co to about to 98.75 wt % Co, and from about 0.25 wt % C to about 2.0 wt % C. Relatively higher concentrations of Al in the preliminary powder may, for example, enhance thermal stability properties of a compact structure (e.g., a cutting table, such as a PDC table) formed using a homogenized binder (e.g., a homogenized Co—Al—C—W alloy binder) subsequently formed from the precursor composition, but may also increase and/or widen the melting temperature range of the homogenized binder relative to homogenized binders having relatively lower Al concentrations. Relatively higher concentrations of Co in the preliminary powder may, for example, enhance the catalytic properties (e.g., carbon solubility and liquid phase transport) of the subsequently formed homogenized binder for the formation of inter-bonded diamond particles, but may also decrease the thermal stability of the compact structure formed using the homogenized binder due to back-conversion of the inter-bonded diamond particles to other forms or phases of carbon facilitated by excess (e.g., unreacted) catalytic Co present within the compact structure during use and operation thereof. Relatively higher concentrations of C in the preliminary powder may, for example, enhance thermal stability properties of the compact structure formed by the homogenized binder through the formation of carbide precipitates. Elevated C level may modify (e.g., suppress) the melting characteristics of the homogenized binder by modifying the melting and solidification paths toward monovariant and invariant reaction lines. As another non-limiting example, the preliminary powder may include from about one (1) weight percent (wt %) to about 15.0 wt % of one of Ga, Sn, Be, Ge, and Si; from about 83 wt % Co to about to 98.75 wt % Co; and from about 0.25 wt % C to about 2.0 wt % C. As a further non-limiting example, the preliminary powder may include from about one (1) weight percent (wt %) to about 15.0 wt % of two or more (e.g., two, three, four, five, six) of Al, Ga, Sn, Be, Ge, and Si; from about 83 wt % Co to about to 98.75 wt % Co; and from about 0.25 wt % C to about 2.0 wt % C. If the preliminary powder includes two or more of Al, Ga, Sn, Be, Ge, and Si, the preliminary powder may include substantially the same weight percentage of each of the two or more of Al, Ga, Sn, Be, Ge, and Si; or may include a different weight percentage of at least one of the two or more of Al, Ga, Sn, Be, Ge, and Si than at least one other of the two or more of Al, Ga, Sn, Be, Ge, and Si.
In some embodiments, the material composition of the preliminary powder is selected relative to the material composition of WC powder and any additive(s) to minimize amounts of catalytic Co within interstitial spaces of a compact structure (e.g., a cutting table, such as a PDC table) to be formed using a homogenized binder subsequently formed from the precursor composition. For example, the preliminary powder may include amounts of one or more of Al, Ga, Sn, Be, Ge, and Si, and amounts of one or more of C and W which, in combination with other elements from the WC powder and the additive(s) (if any), facilitate the formation of a homogenized binder (e.g., a homogenized alloy binder including Co, C, W, and one or more of Al, Ga, Sn, Be, Ge, and Si) including a sufficient amount of Co to facilitate the formation of a compact structure including inter-bonded diamond particles without having any catalytic Co remain within interstitial spaces of the compact structure following the formation thereof. The material composition of the preliminary powder may, for example, be selected to facilitate the complete (e.g., 100 percent) reaction of catalytic Co resulting from the infiltration of the homogenized binder into a volume of hard material (e.g., a volume of diamond powder). The amounts of Co, one or more of Al, Ga, Sn, Be, Ge, and Si, and one or more of C and W in the preliminary powder may also be selected to permit a melting temperature range of the subsequently-formed homogenized binder to be within a temperature range suitable for thermally treating (e.g., sintering) the volume of hard material to form the compact structure. In some embodiments, the preliminary powder includes about 86 wt % Co; about 13 wt % of one or more of Al, Ga, Sn, Be, Ge, and Si; and about 0.9 wt % C. In additional embodiments, the preliminary powder includes about 86 wt % Co; about 13 wt % of two or more (e.g., two, three, four, five, six) of Al, Ga, Sn, Be, Ge, and Si; and about 0.9 wt % C.
In additional embodiments, the material composition of the preliminary powder is selected relative to the material compositions of the WC powder and any additive(s) to facilitate the subsequent formation of a homogenized binder having a relatively lower melting temperature range and/or relatively narrower melting temperature range than a homogenized binder formulated to minimize the amounts of catalytic Co remaining within interstitial spaces of a compact structure to be formed using the homogenized binder. The material composition of the preliminary powder may facilitate the partial reaction (e.g., less than 100 percent, such as less than or equal to 90 percent, less than or equal to 80 percent, or less than or equal to 70 percent) of catalytic Co resulting from the infiltration of the homogenized binder into a volume of hard material (e.g., a volume of diamond powder). Accordingly, the compact structure may include catalytic Co within interstitial spaces thereof. However, the inter-bonded diamond particles of the compact structure may be at least partially protected from the catalytic Co by one or more other materials (e.g., intermetallic compound precipitates, carbide precipitates, etc.), as described in further detail below. In some embodiments, the preliminary powder includes about 89 wt % Co; about 9.2 wt % of one or more of Al, Ga, Sn, Be, Ge, and Si; and about 0.8 wt % C.
In some embodiments, at least some (e.g., all) of the discrete particles of the preliminary powder comprise discrete alloy particles individually formed of and including an alloy of Co, one or more of Al, Ga, Sn, Be, Ge, and Si, and one or more of C and W. For example, at least some (e.g., all) of the discrete particles of the preliminary powder may comprise discrete Co—Al—C alloy particles individually formed of and including an alloy of Co, Al, and C, and/or at least some (e.g., all) of the discrete particles of the preliminary powder may comprise discrete Co—Al—W alloy particles individually formed of and including an alloy of Co, Al, and W. As another example, the discrete particles of the preliminary powder may comprise one or more of discrete Co—Al—Ga—C alloy particles, discrete Co—Al—Ga—W alloy particles, discrete Co—Al—Sn—C alloy particles, discrete Co—Al—Sn—W alloy particles, discrete Co—Al—Be—C alloy particles, discrete Co—Al—Be—W alloy particles, discrete Co—Al—Ge—C alloy particles, discrete Co—Al—Ge—W alloy particles, discrete Co—Al—Si—C alloy particles, discrete Co—Al—Si—W alloy particles, discrete Co—Ga—C alloy particles, discrete Co—Ga—W alloy particles, discrete Co—Ga—Sn—C alloy particles, discrete Co—Ga—Sn—W alloy particles, discrete Co—Ga—Be—C alloy particles, discrete Co—Ga—Be—W alloy particles, discrete Co—Ga—Ge—C alloy particles, discrete Co—Ga—Ge—W alloy particles, discrete Co—Ga—Si—C alloy particles, discrete Co—Ga—Si—W alloy particles, discrete Co—Sn—C alloy particles, discrete Co—Sn—W alloy particles, discrete Co—Sn—Be—C alloy particles, discrete Co—Sn—Be—W alloy particles, discrete Co—Sn—Ge—C alloy particles, discrete Co—Sn—Ge—W alloy particles, discrete Co—Sn—Si—C alloy particles, discrete Co—Sn—Si—W alloy particles, discrete Co—Be—C alloy particles, discrete Co—Be—W alloy particles, discrete Co—Be—Ge—C alloy particles, discrete Co—Be—Ge—W alloy particles, discrete Co—Be—Si—C alloy particles, discrete Co—Be—Si—W alloy particles, discrete Co—Ge—C alloy particles, discrete Co—Ge—W alloy particles, discrete Co—Ge—Si—C alloy particles, discrete Co—Ge—Si—W alloy particles, discrete Co—Si—C alloy particles, and discrete Co—Si—W alloy particles. Each of the discrete alloy particles may include substantially the same components (e.g., Co, one or more of Al, Ga, Sn, Be, Ge, and Si, and one or more of C and W) and component ratios of as each other of the discrete alloy particles, or one or more of the discrete alloy particles may include different components and/or different component ratios than one or more other of the preliminary alloy particles, so long as the preliminary powder as a whole includes desired and predetermined ratios of Co, one or more of Al, Ga, Sn, Be, Ge, and Si, and one or more of C and W. In some embodiments, the preliminary powder is formed of and includes discrete alloy particles having substantially the same amounts of Co, C, and one or more of Al, Ga, Sn, Be, Ge, and Si as one another. In additional embodiments, the preliminary powder is formed of and includes discrete alloy particles having different amounts of two or more of Co, C, and one or more of Al, Ga, Sn, Be, Ge, and Si than one another. In further embodiments, the preliminary powder is formed of and includes discrete Co—Al—W alloy particles having substantially the same amounts of Co, W, and one or more of Al, Ga, Sn, Be, Ge, and Si as one another. In yet further embodiments, the preliminary powder is formed of and includes discrete alloy particles having different amounts of two or more of Co, W, and one or more of Al, Ga, Sn, Be, Ge, and Si than one another. In still further embodiments, the preliminary powder is formed of and includes first discrete alloy particles including Co, C, and one or more of Al, Ga, Sn, Be, Ge, and Si; and second discrete particles including Co, W, and one or more of Al, Ga, Sn, Be, Ge, and Si. The first discrete alloy particles may have substantially the same or different amounts of Co, C, and one or more of Al, Ga, Sn, Be, Ge, and Si as one another; and the second discrete alloy particles may have substantially the same or different amounts of Co, W, and one or more of Al, Ga, Sn, Be, Ge, and Si as one another.
If included in the preliminary powder, the discrete alloy particles may be formed by conventional processes (e.g., ball milling processes, attritor milling processes, cryomilling processes, jet milling processes, powder atomization processes, etc.), which are not described herein. As a non-limiting example, an initial powder formed of and including particles of Co, one or more of Al, Ga, Sn, Be, Ge, and Si, and one or more of C (e.g., lamp black, graphite, etc.) and W, alloys thereof, and/or combinations thereof may be provided into an attritor mill containing mixing structures (e.g., mixing spheres, mixing bars, etc.), and may then be subjected to a mechanical alloying process until the discrete alloy particles are formed. During the mechanical alloying process collisions between the mixing structures and the initial powder may cause particles of different materials (e.g., Co particles; one or more of Al particles, Ga particles, Sn particles, Be particles, Ge particles, and Si particles; one or more of graphite particles and W particles; alloy particles; combinations thereof; etc.) to fracture and/or be welded or smeared together. Relatively larger particles may fracture during the mechanical welding process and relatively smaller particles may weld together, eventually forming discrete alloy particles each individually comprising a substantially homogeneous mixture of the constituents of the initial powder in substantially the same proportions of the initial powder. As another non-limiting example, an alloy material may be formed by conventional melting and mixing processes, and then the alloy material may be formed into the discrete alloy particles by one or more conventional atomization processes.
In additional embodiments, at least some (e.g., all) of the discrete particles of the preliminary powder comprise discrete elemental particles, such as one or more of discrete elemental Co particles, discrete elemental Al particles, discrete elemental Ga particles, discrete elemental Sn particles, discrete elemental Be particles, discrete elemental Ge particles, discrete elemental Si particles, discrete C particles (e.g., discrete graphite particles, discrete graphene particles, discrete fullerene particles, discrete carbon nanofibers, discrete carbon nanotubes, etc.), and discrete elemental W particles. The preliminary powder may include any amounts of the discrete elemental Co particles, the discrete elemental Al particles, the discrete elemental Ga particles, the discrete elemental Sn particles, the discrete elemental Be particles, the discrete elemental Ge particles, the discrete elemental Si particles, the discrete C particles, and the discrete elemental W particles permitting the preliminary powder as a whole to include desired and predetermined ratios of Co, C, W, and one or more of Al, Ga, Sn, Be, Ge, and Si. If included in the preliminary powder, the discrete elemental particles (e.g., discrete elemental Co particles, discrete elemental Al particles, discrete elemental Ga particles, discrete elemental Sn particles, discrete elemental Be particles, discrete elemental Ge particles, discrete elemental Si particles, discrete C particles, discrete elemental W particles) may be formed by conventional processes (e.g., conventional milling processes), which are not described herein.
The preliminary powder may include discrete alloy particles (e.g., discrete alloy particles individually including Co, one or more of Al, Ga, Sn, Be, Ge, and Si, and one or more of C and W) but may be substantially free of discrete elemental particles (e.g., discrete elemental Co particles, discrete elemental Al particles, discrete elemental Ga particles, discrete elemental Sn particles, discrete elemental Be particles, discrete elemental Ge particles, discrete elemental Si particles, discrete C particles, and discrete elemental W particles); may include discrete elemental particles (e.g., discrete elemental Co particles; one or more of discrete elemental Al particles, discrete elemental Ga particles, discrete elemental Sn particles, discrete elemental Be particles, discrete elemental Ge particles, and discrete elemental Si particles; and one or more of discrete C particles and discrete elemental W particles) but may be substantially free of discrete alloy particles (e.g., discrete alloy particles individually including Co, one or more of Al, Ga, Sn, Be, Ge, and Si, and one or more of C and W); or may include a combination of discrete alloy particles (e.g., discrete alloy particles individually including Co, one or more of Al, Ga, Sn, Be, Ge, and Si, and one or more of C and W) and discrete elemental particles (e.g., one or more of discrete elemental Co particles, discrete elemental Al particles, discrete elemental Ga particles, discrete elemental Sn particles, discrete elemental Be particles, discrete elemental Ge particles, discrete elemental Si particles, discrete C particles, and discrete elemental W particles). In some embodiments, the preliminary powder only includes discrete alloy particles. In additional embodiments, the preliminary powder only includes discrete elemental particles. In further embodiments, the preliminary powder includes a combination of discrete alloy particles and discrete elemental particles.
Each of the discrete particles (e.g., discrete alloy particles and/or discrete elemental particles) of the preliminary powder may individually exhibit a desired particle size, such as a particle size less than or equal to about 1000 micrometers (μm). The discrete particles may comprise, for example, one or more of discrete micro-sized composite particles and discrete nano-sized composite particles. As used herein, the term “micro-sized” means and includes a particle size with a range of from about one (1) μm to about 1000 μm, such as from about 1 μm to about 500 μm, from about 1 μm to about 100 μm, or from about 1 μm to about 50 μm. As used herein, the term “nano-sized” means and includes a particle size of less than 1 μm, such as less than or equal to about 500 nanometers (nm), or less than or equal to about 250 nm. In addition, each of the discrete particles may individually exhibit a desired shape, such as one or more of a spherical shape, a hexahedral shape, an ellipsoidal shape, a cylindrical shape, a conical shape, or an irregular shape.
The discrete particles (e.g., discrete alloy particles and/or discrete elemental particles) of the preliminary powder may be monodisperse, wherein each of the discrete particles exhibits substantially the same size and substantially the same shape, or may be polydisperse, wherein at least one of the discrete particles exhibits one or more of a different particle size and a different shape than at least one other of the discrete particles. In some embodiments, the discrete particles of the preliminary powder have a multi-modal (e.g., bi-modal, tri-modal, etc.) particle (e.g., grain) size distribution. For example, the preliminary powder may include a combination of relatively larger, discrete particles and relatively smaller, discrete particles. The multi-modal particle size distribution of the preliminary powder may, for example, provide the precursor composition with desirable particle packing characteristics for the subsequent formation of a consolidated structure (e.g., supporting substrate) therefrom, as described in further detail below. In additional embodiments, the preliminary powder has a mono-modal particle size distribution. For example, all of the discrete particles of the preliminary powder may exhibit substantially the same particle size.
The WC particles of the WC powder may include stoichiometric quantities or near stoichiometric quantities of W and C. Relative amounts of W and C in the discrete WC particles may be selected at least partially based on amounts and material compositions of the discrete particles of the preliminary powder, the discrete WC particles, and the additive(s) (if any) facilitating the formation of a consolidated structure (e.g., supporting substrate) formed of and including WC particles and a homogenized binder including desirable and predetermined amounts of Co, W, C, and one or more of Al, Ga, Sn, Be, Ge, and Si (as well as individual elements of additive(s), if any) through the consolidation process 104. In some embodiments, each of the discrete WC particles of the WC powder includes stoichiometric amounts of W and C. In additional embodiments, one or more of the discrete WC particles of the WC powder includes an excess amount of C than that stoichiometrically required to form WC. In further embodiments, one or more of the discrete WC particles of the WC powder includes an excess amount of W than that stoichiometrically required to form WC.
Each of the discrete WC particles of the WC powder may individually exhibit a desired particle size, such as a particle size less than or equal to about 1,000 μm. The discrete WC particles may comprise, for example, one or more of discrete micro-sized WC particles and discrete nano-sized WC particles. In addition, each of the discrete WC particles may individually exhibit a desired shape, such as one or more of a spherical shape, a hexahedral shape, an ellipsoidal shape, a cylindrical shape, a conical shape, or an irregular shape.
The discrete WC particles of the WC powder may be monodisperse, wherein each of the discrete WC particles exhibits substantially the same size and shape, or may be polydisperse, wherein at least one of the discrete WC particles exhibits one or more of a different particle size and a different shape than at least one other of the discrete WC particles. In some embodiments, the WC powder has a multi-modal (e.g., bi-modal, tri-modal, etc.) particle (e.g., grain) size distribution. For example, the WC powder may include a combination of relatively larger, discrete WC particles and relatively smaller, discrete WC particles. In additional embodiments, the WC powder has a mono-modal particle size distribution. For example, all of the discrete WC particles of the WC powder may exhibit substantially the same particle size.
The WC powder, including the discrete WC particles thereof, may be formed by conventional processes, which are not described herein.
The binding agent may comprise any material permitting the precursor composition to retain a desired shape during subsequent processing, and which may be removed (e.g., volatilized off) during the subsequent processing. By way of non-limiting example, the binding agent may comprise an organic compound, such as a wax (e.g., a paraffin wax). In some embodiments, the binding agent of the precursor composition is a paraffin wax.
The additive(s), if present, may comprise any material(s) formulated to impart a consolidated structure (e.g., supporting substrate) subsequently formed from the precursor composition with one or more desirable material properties (e.g., fracture toughness, strength, hardness, hardenability, wear resistance, coefficient of thermal expansions, thermal conductivity, corrosion resistance, oxidation resistance, ferromagnetism, etc.), and/or that impart a homogenized binder of the subsequently formed consolidated structure with a material composition facilitating the formation of a compact structure (e.g., a cutting table, such as a PDC table) having desired properties (e.g., wear resistance, impact resistance, thermal stability, etc.) using the consolidated structure. By way of non-limiting example, the additive(s) may comprise one or more elements of one or more of Group IIIA (e.g., boron (B), aluminum (Al)); Group IVA (e.g., carbon (C)); Group IVB (e.g., titanium (Ti), zirconium (Zr), hafnium (Hf)); Group VB (e.g., vanadium (V), niobium (Nb), tantalum (Ta)); Group VIB (e.g., chromium (Cr), molybdenum (Mo), tungsten (W)); Group VIIB (e.g., manganese (Mn), rhenium (Re)); Group VIIIB (e.g., iron (Fe), ruthenium (Ru), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni)); Group IB (e.g., copper (Cu), Silver (Ag), gold (Au)); and Group IIB (e.g., zinc (Zn), cadmium (Cd)) of the Periodic Table of Elements. In some embodiments, the additive(s) comprise discrete particles each individually including one or more of B, Al, C, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Cu, Ag, Au, Zn, and Cd.
Amounts of the preliminary powder, the WC powder, the binding agent, and the additive(s) (if any) employed to form the precursor composition may be selected at least partially based on the configurations (e.g., material compositions, sizes, shapes) of the preliminary powder, the WC powder, and the additive(s) (if any) facilitating the formation of a consolidated structure formed of and including WC particles and a homogenized binder including desired and predetermined amounts of Co, W, C, and one or more of Al, Ga, Sn, Be, Ge, and Si (as well as individual element(s) of the additive(s), if any) through the consolidation process 104. As a non-limiting example, the precursor composition may comprise from about 5 wt % to about 20 wt % of the preliminary powder, from about 80 wt % to about 95 wt % of the WC powder, from about 0 wt % to about 5 wt % of the additive(s), and a remainder of the binding agent (e.g., paraffin wax). If the preliminary powder only includes discrete alloy particles, the precursor composition may, for example, include from about 5 wt % to about 20 wt % discrete alloy particles, from about 80 wt % to about 95 wt % discrete WC particles, from about 0 wt % to about 5 wt % additive(s), and a remainder of a binding agent. Co included in the discrete alloy particles may constitute from about 4 wt % to about 18 wt % of the precursor composition; and one or more of Al, Ga, Sn, Be, Ge, and Si included in the discrete alloy particles may constitute from about 0.05 wt % to about 4 wt % (e.g., from about 0.25 wt % to about 3.5 wt %) of the precursor composition. If the preliminary powder only includes discrete elemental Co particles; discrete C particles; and one or more of discrete elemental Al particles, discrete elemental Ga particles, discrete elemental Sn particles, discrete elemental Be particles, discrete elemental Ge particles, and discrete elemental Si particles, the precursor composition may, for example, include from about 4 wt % to about 18 wt % discrete elemental Co particles; from about 0.013 wt % to about 0.3 wt % discrete C particles; from about 0.05 wt % to about 4 wt % (e.g., from about 0.25 wt % to about 3.5 wt %) of the one or more of the discrete elemental Al particles, the discrete elemental Ga particles, the discrete elemental Sn particles, the discrete elemental Be particles, the discrete elemental Ge particles, and the discrete elemental Si particles; from about 80 wt % to about 95 wt % discrete WC particles; from about 0 wt % to about 5 wt % additive(s); and a remainder of a binding agent. In some embodiments, the precursor composition comprises about 12 wt % alloy particles individually comprising Co, C, and one or more of Al, Ga, Sn, Be, Ge, and Si; and about 88 wt % discrete WC particles. In additional embodiments, the precursor composition comprises about 10.3 wt % discrete elemental Co particles, about 0.1 wt % discrete C particles, about 88 wt % discrete WC particles, and about 1.6 wt % of one or more of discrete elemental Al particles, discrete elemental Ga particles, discrete elemental Sn particles, discrete elemental Be particles, discrete elemental Ge particles, and discrete elemental Si particles. In further embodiments, the precursor composition comprises about 10.7 wt % discrete elemental Co particles, about 0.1 wt % discrete C particles, about 88 wt % discrete WC particles, and about 1.2 wt % of one or more of discrete elemental Al particles, discrete elemental Ga particles, discrete elemental Sn particles, discrete elemental Be particles, discrete elemental Ge particles, and discrete elemental Si particles.
The precursor composition may be formed by mixing the preliminary powder, the WC powder, the binding agent, the additive(s) (if any), and at least one fluid material (e.g., acetone, heptane, etc.) formulated to dissolve and disperse the binding agent using one or more conventional processes (e.g., conventional milling processes, such as ball milling processes, attritor milling processes, cryomilling processes, jet milling processes, etc.) to form a mixture thereof. The preliminary powder, the WC powder, the binding agent, the additive(s) (if any), and the fluid material may be combined in any order. In some embodiments, the preliminary powder and the WC powder are combined (e.g., using a first milling process), and then the binding agent and fluid material are combined with the resulting mixture (e.g., using a second milling process). During the mixing process, collisions between different particles (e.g., the discrete particles of the preliminary powder, the discrete WC particles of the WC powder, the additive particles (if any), etc.) may cause at least some of the different particles to fracture and/or become welded or smeared together. For example, during the mixing process at least some materials (e.g., elements, alloys) of the discrete particles of the preliminary powder may be transferred to surfaces of the WC particles of the WC powder to form composite particles comprising WC coated with an alloy comprising Co, one or more of Al, Ga, Sn, Be, Ge, and Si, and one or more of C and W. Thereafter, the fluid material may be removed (e.g., evaporated), leaving the binding agent on and around any remaining discrete particles of the preliminary powder, any remaining discrete WC particles of the WC powder, any composite particles (e.g., particles comprising WC coated with an alloy comprising Co, one or more of Al, Ga, Sn, Be, Ge, and Si, and one or more of C and W), any remaining additive particles, and any other particles comprising constituents of the discrete particles of the preliminary powder, the discrete WC particles of the WC powder, and the additive(s).
With continued reference to
The consolidated structure (e.g., supporting substrate) may be formed to exhibit any desired dimensions and any desired shape. The dimensions and shape of the consolidated structure may at least partially depend upon desired dimensions and desired shapes of a compact structure (e.g., a cutting table, such as a PDC table) to subsequently be formed on and/or attached to the consolidated structure, as described in further detail below. In some embodiments, the consolidated structure is formed to exhibit a cylindrical column shape. In additional embodiments, the consolidated structure is formed to exhibit a different shape, such as a dome shape, a conical shape, a frusto-conical shape, a rectangular column shape, a pyramidal shape, a frusto-pyramidal shape, a fin shape, a pillar shape, a stud shape, or an irregular shape. Accordingly, the consolidated structure may be formed to exhibit any desired lateral cross-sectional shape including, but not limited to, a circular shape, a semicircular shape, an ovular shape, a tetragonal shape (e.g., square, rectangular, trapezium, trapezoidal, parallelogram, etc.), a triangular shape, an elliptical shape, or an irregular shape.
The consolidation process 104 may include forming the precursor composition into green structure having a shape generally corresponding to the shape of the consolidated structure, subjecting the green structure to at least one densification process (e.g., a sintering process, a hot isostatic pressing (HIP) process, a sintered-HIP process, a hot pressing process, etc.) to form a consolidated structure including WC particles dispersed within an at least partially (e.g., substantially) homogenized binder, and, optionally, subjecting the consolidated structure to at least one supplemental homogenization process to further homogenize the at least partially homogenized binder. As used herein, the term “green” means unsintered. Accordingly, as used herein, a “green structure” means and includes an unsintered structure comprising a plurality of particles, which may be held together by interactions between one or more materials of the plurality of particles and/or another material (e.g., a binder).
The precursor composition may be formed into the green structure through conventional processes, which are not described in detail herein. For example, the precursor composition may be provided into a cavity of a container (e.g., canister, cup, etc.) having a shape complementary to a desired shape (e.g., a cylindrical column shape) of the consolidated structure, and then the precursor composition may be subjected to at least one pressing process (e.g., a cold pressing process, such as a process wherein the precursor composition is subjected to compressive pressure without substantially heating the precursor composition) to form the green structure. The pressing process may, for example, subject the precursor composition within the cavity of the container to a pressure greater than or equal to about 10 tons per square inch (tons/in2), such as within a range of from about 10 tons/into about 30 tons/in2.
Following the formation of the green structure, the binding agent may be removed from the green structure. For example, the green structure may be dewaxed by way of vacuum or flowing hydrogen at an elevated temperature. The resulting (e.g., dewaxed) structure may then be subjected to a partial sintering (e.g., pre-sintering) process to form a brown structure having sufficient strength for the handling thereof.
Following the formation of the brown structure, the brown structure may be subjected to a densification process (e.g., a sintering process, a hot isostatic pressing (HIP) process, a sintered-HIP process, a hot pressing process, etc.) that applies sufficient heat and sufficient pressure to the brown structure to form the consolidated structure including the WC particles dispersed in the at least partially homogenized binder. By way of non-limiting example, the brown structure may be wrapped in a sealing material (e.g., graphite foil), and may then be placed in a container made of a high temperature, self-sealing material. The container may be filled with a suitable pressure transmission medium (e.g., glass particles, ceramic particles, graphite particles, salt particles, metal particles, etc.), and the wrapped brown structure may be provided within the pressure transmission medium. The container, along with the wrapped brown structure and pressure transmission medium therein, may then be heated to a consolidation temperature facilitating the formation of the homogenized binder (e.g., the homogenized alloy binder including Co, W, C, and one or more of Al, Ga, Sn, Be, Ge, and Si) under isostatic (e.g., uniform) pressure applied by a press (e.g., a mechanical press, a hydraulic press, etc.) to at least partially (e.g., substantially) consolidate the brown structure and form the consolidated structure. The consolidation temperature may be a temperature greater than the solidus temperature of at least the discrete particles (e.g., discrete alloy particles and/or discrete elemental particles) of the preliminary powder used to form the brown structure (e.g., a temperature greater than or equal to the liquidus temperature of the discrete particles, a temperature between the solidus temperature and the liquidus temperature of the discrete particles, etc.), and the applied pressure may be greater than or equal to about 10 megapascals (A/Pa) (e.g., greater than or equal to about 50 MPa, greater than or equal to about 100 MPa, greater than or equal to about 250 MPa, greater than or equal to about 500 MPa, greater than or equal to about 750 MPa, greater than or equal to about 1.0 gigapascals (GPa), etc.). During the densification process, one or more elements of the WC particles and/or additive(s) (if any) present in the brown structure may diffuse into and homogeneously intermix with a molten alloy of Co, C, and one or more of Al, Ga, Sn, Be, Ge, and Si to form the at least partially homogenized binder (e.g., the homogenized alloy binder including Co, W, C, and one or more of Al, Ga, Sn, Be, Ge, and Si) of the consolidated structure.
As previously mentioned, following formation, the consolidated structure may be subjected to a supplemental homogenization process to further homogenize the at least partially homogenized binder thereof. If performed, the supplemental homogenization process may heat the consolidated structure to one or more temperatures above the liquidus temperature of the at least partially homogenized binder thereof for a sufficient period of time to reduce (e.g., substantially eliminate) macrosegregation within the at least partially homogenized binder and provide the resulting further homogenized binder with a single (e.g., only one) melting temperature. In some embodiments, such as in embodiments wherein the preliminary powder employed to form the consolidated structure comprises discrete elemental particles (e.g., discrete elemental Co particles, discrete elemental Al particles, discrete elemental Ga particles, discrete elemental Sn particles, discrete elemental Be particles, discrete elemental Ge particles, discrete elemental Si particles, discrete C particles, discrete elemental W particles) the at least partially homogenized binder of the consolidated structure may have multiple (e.g., at least two) melting temperatures following the densification process due to one or more regions of the at least partially homogenized binder exhibiting different material composition(s) than one or more other regions of the at least partially homogenized binder. Such different regions may, for example, form as a result of efficacy margins in source powder mixing and cold consolidation. In such embodiments, the supplemental homogenization process may substantially melt and homogenize the at least partially homogenized binder to remove the regions exhibiting different material composition(s) and provide the further homogenized binder with only one melting point. Providing the homogenized binder of the consolidated structure with only one melting point may be advantageous for the subsequent formation of a cutting table using the consolidated structure, as described in further detail below. In additional embodiments, such as in embodiments wherein the at least partially homogenized binder of the consolidated structure is already substantially homogeneous (e.g., does not include regions exhibiting different material composition(s) than other regions thereof) following the densification process, the supplemental homogenization process may be omitted.
Consolidated structures (e.g., supporting substrates) formed in accordance with embodiments of the disclosure may be used to form cutting elements according to embodiments of the disclosure. For example,
Referring to
The diamond powder 202 may be formed of and include discrete diamond particles (e.g., discrete natural diamond particles, discrete synthetic diamond particles, combinations thereof, etc.). The discrete diamond particles may individually exhibit a desired grain size. The discrete diamond particles may comprise, for example, one or more of micro-sized diamond particles and nano-sized diamond particles. In addition, each of the discrete diamond particles may individually exhibit a desired shape, such as at least one of a spherical shape, a hexahedral shape, an ellipsoidal shape, a cylindrical shape, a conical shape, or an irregular shape. In some embodiments, each of the discrete diamond particles of the diamond powder 202 exhibits a substantially spherical shape. The discrete diamond particles may be monodisperse, wherein each of the discrete diamond particles exhibits substantially the same material composition, size, and shape, or may be polydisperse, wherein at least one of the discrete diamond particles exhibits one or more of a different material composition, a different particle size, and a different shape than at least one other of the discrete diamond particles. The diamond powder 202 may be formed by conventional processes, which are not described herein.
The supporting substrate 204 comprises a consolidated structure formed in accordance with the methods previously described herein with reference to
Referring next to
During the HTHP processing, the homogenized binder of the supporting substrate 204 melts and a portion thereof is swept (e.g., mass transported, diffused) into the diamond powder 202 (
Since the diamond powder 202 (
In addition, providing the diamond powder 202 (
During the HTHP processing, the homogenized binder (e.g., homogenized alloy binder comprising Co, W, C, and one or more of Al, Ga, Sn, Be, Ge, and Si) of the supporting substrate 204 diffuses into the diamond powder 202 (
As previously mentioned, the HTHP processing heats the diamond powder 202 and the supporting substrate 204 to at least one temperature greater than the solidus temperature (e.g., to at least the liquidus temperature) of the homogenized binder of the supporting substrate 204. The temperature(s) (e.g., sintering temperature(s)) employed during the HTHP processing to form the cutting table 212 at least partially depend on the pressure(s) employed during the HTHP processing, and on the material composition of the homogenized binder of the supporting substrate 204. As described in further detail below, employing pressure(s) above atmospheric pressure (1 atm) during the HTHP processing may affect (e.g., shift) metastability lines (e.g., phase boundaries) of the liquid (L)+diamond (D)+metal carbide (MC) phase field, which may influence (e.g., compel the increase of) the temperature(s) employed to form the cutting table 212. In addition, as also described in further detail below, the material composition of the homogenized binder of the supporting substrate 204 may affect (e.g., increase, decrease) the melting temperature(s) of the homogenized binder, and may also affect (e.g., shift) the metastability lines of the L+D+MC+E21-type phase carbide (κ-carbide) phase field, which may also impact (e.g., compel the increase of) the temperature(s) employed to form the cutting table 212.
With returned reference to
In addition to κ-carbide precipitates, the thermally stable material of the cutting table 212 may include one or more intermetallic compound phase precipitates. As a non-limiting example, the thermally stable material may include one or more FCC L12 phase (e.g., gamma prime (γ′) phase) precipitates, such as one or more of Co3(Al,W) precipitates, Co3(Al,Ga,W) precipitates, Co3(Al,Sn,W) precipitates, Co3(Al,Be,W) precipitates, Co3(Al,Ge,W) precipitates, Co3(Al,Si,W) precipitates, Co3(Ga,W) precipitates, Co3(Ga,Sn,W) precipitates, Co3(Ga,Be,W) precipitates, Co3(Ga,Ge,W) precipitates, Co3(Ga,Si,W) precipitates, Co3(Sn,W) precipitates, Co3(Sn,Be,W) precipitates, Co3(Sn,Ge,W) precipitates, Co3(Sn,Si,W) precipitates, Co3(Be,W) precipitates, Co3(Be,Ge,W) precipitates, Co3(Be,Si,W) precipitates, Co3(Ge,W) precipitates, Co3(Ge,Si,W) precipitates, Co3(Si,W) precipitates, (Co,X)3(Y,Z,W) precipitates, and (Co,X)3(Y,W,Z) precipitates; wherein X comprises Co or at least one element (e.g., Ni, Fe) that is able to occupy a site of Co in (Co,X)3(Y,W,Z), Y comprises Al, Ga, Sn, Be, Ge, or Si, and Z comprises at least one element different than Y that is able to occupy a site of Y or W in (Co,X)3(Y,W,Z). As another non-limiting example, the thermally stable material may include one or more FCC DO22 phase precipitates, such as one or more of Al3W precipitates, (Al,Ga)3W precipitates, (Al,Sn)3W precipitates, (Al,Be)3W precipitates, (Al,Ge)3W precipitates, (Al,Si)3W precipitates, Ga3W precipitates, (Ga,Sn)3W precipitates, (Ga,Be)3W precipitates, (Ga,Ge)3W precipitates, (Ga,Si)3W precipitates, Sn3W precipitates, (Sn,Be)3W precipitates, (Sn,Ge)3W precipitates, (Sn,Si)3W precipitates, Be3W precipitates, (Be,Ge)3W precipitates, (Be,Si)3W precipitates, Ge3W precipitates, (Ge,Si)3W precipitates, and Si3W precipitates. As an additional non-limiting example, the thermally stable material may include one or more D85 phase precipitates, such as Co7W6 precipitates. As a further non-limiting example, the thermally stable material may include one or more DO19 phase precipitates, such as Co3W precipitates. In some embodiments, the thermally stable material of the cutting table 212 is formed of and includes κ-carbide precipitates and FCC L12 phase precipitates.
The thermally stable material of the cutting table 212 may also include other precipitates formed of and including elements (e.g., Co, Al, W, C, X, Z) of the homogenized binder of the supporting substrate 204. By way of non-limiting example, the thermally stable material may include, beta (β) phase precipitates, such as CoAl; FCC L10 phase (e.g., gamma (γ) phase) precipitates; and/or other carbide precipitates, such as WC precipitates and/or MxC precipitates, where x>2 and M=Co,W.
The types and amounts of precipitates (e.g., κ-carbide precipitates, intermetallic compound phase precipitates, other precipitates) present in the thermally stable material of the cutting table 212 at least partially depends on the material composition (including component ratios) of the homogenized binder of the supporting substrate 204, and on the processing conditions (e.g., HTHP processing conditions, such as pressure(s) and temperature(s)) employed to form the cutting table 212 using the homogenized binder of the supporting substrate 204. By way of non-limiting example, under the conditions (e.g., homogenized binder compositions, pressures, temperatures) promoting the partition of W to FCC L12 phase precipitates (e.g., Co3(Al,W) precipitates, Co3(Al,Ga,W) precipitates, Co3(Al,Sn,W) precipitates, Co3(Al,Be,W) precipitates, Co3(Al,Ge,W) precipitates, Co3(Al,Si,W) precipitates, Co3(Ga,W) precipitates, Co3(Ga,Sn,W) precipitates, Co3(Ga,Be,W) precipitates, Co3(Ga,Ge,W) precipitates, Co3(Ga,Si,W) precipitates, Co3(Sn,W) precipitates, Co3(Sn,Be,W) precipitates, Co3(Sn,Ge,W) precipitates, Co3(Sn,Si,W) precipitates, Co3(Be,W) precipitates, Co3(Be,Ge,W) precipitates, Co3(Be,Si,W) precipitates, Co3(Ge,W) precipitates, Co3(Ge,Si,W) precipitates, Co3(Si,W) precipitates, (Co,X)3(Y,Z,W) precipitates, and (Co,X)3(Y,W,Z) precipitates), the formation of WC precipitates and/or MxC precipitates (where x>2 and M=Co,W) may be promoted, and the formation of κ-carbide precipitates may be suppressed.
The material composition of the homogenized binder present within interstitial spaces of the cutting table 212 following the formation of inter-bonded diamond particles thereof, including the types and amounts of elements included in the homogenized binder, may affect the properties of the thermally stable material formed within the interstitial spaces of the cutting table 212 as the homogenized binder ages. W partitioning of the homogenized binder may promote solid solution strengthening of the catalytic Co phase if local portioning occurs away from formed k-carbide, may locally stabilize the FCC L12 phase precipitates of the thermally stable material in the absence of κ-carbide precipitates, and may arrest lattice dislocation between the FCC L12 phase precipitates, the κ-carbide precipitates, and the γ phase matrix (if any) of the thermally stable material. Al of the homogenized binder may facilitate FCC ordering in the form of FCC L12 phase precipitates and κ-carbide precipitates, and may improve the high-temperature strength of the thermally stable material. C of the homogenized binder may facilitate the formation of the κ-carbide precipitates, may promote favorable melting characteristics of the homogenized binder, and may also increase the high-temperature strength of the thermally stable material. In addition, various other elements that may, optionally, be included in the homogenized binder may also enhance one or more properties of the thermally stable material formed therefrom.
Optionally, following formation, the cutting table 212 may be subjected to at least one solution treatment process to modify the material composition of the thermally stable material thereof. The solution treatment process may, for example, decompose κ-carbide precipitates of the thermally stable material into to one or more other precipitates, such as FCC L12 phase precipitates. By way of non-limiting example, if the homogenized binder of the supporting substrate 204 includes from about 66 wt % Co to about 90 wt % Co, from about 5 wt % Al to about 15 wt % Al, from about 0.1 wt % C to about 0.2 wt % C, and from about 5 wt % W to about 30 wt % W, and effectuates the formation of a thermally stable material including κ-carbide precipitates (e.g., Co3AlC1-x precipitates, where 0≤x≤0.5) in the cutting table 212, the cutting table 212 may optionally be subjected to a solution treatment process that heats the thermally stable material to a temperature within a range of from about 1300° C. to about 1500° C. at a pressure above the Berman-Simon line, such as a pressure greater than or equal to about 45 kbar, to decompose the κ-carbide precipitates and form FCC L12 phase precipitates. If employed, the cutting table 212 may be subjected to a single (e.g., only one) solution treatment process at a single temperature within the range of from about 1300° C. to about 1500° C. under pressure above the Berman-Simon line, or may be subjected to multiple (e.g., more than one) solution treatment processes at a multiple temperatures within the range of from about 1300° C. to about 1500° C. under pressure above the Berman-Simon line. Multiple solution treatment processes at different temperatures may, for example, facilitate the formation of precipitates (e.g., FCC L12 phase precipitates) having different grain sizes than one another. Relatively larger precipitate sizes may enhance high-temperature properties (e.g., creep rupture properties) of the thermally stable material, and relatively smaller precipitate sizes may enhance room-temperature properties of the thermally stable material.
The thermally stable material may at least partially (e.g., substantially) coat (e.g., cover) surfaces of the inter-bonded diamond particles of the cutting table 212. The thermally stable material may be formed directly on the surfaces of the inter-bonded diamond particles of the cutting table 212, and may at least partially impede (e.g., substantially prevent) back-conversion of the inter-bonded diamond particles to other forms or phases of carbon (e.g., graphitic carbon, amorphous carbon, etc.). In some embodiments, substantially all of the catalytic Co adjacent the inter-bonded diamond particles of the cutting table 212 is partitioned (e.g., incorporated) into κ-carbide precipitates (e.g., Co3AlC1-x precipitates, Co3(Al,Ga)C1-x precipitates, Co3(Al,Sn)C1-x precipitates, Co3(Al,Be)C1-x precipitates, Co3(Al,Ge)C1-x precipitates, Co3(Al,Si)C1-x precipitates, Co3GaC1-x precipitates, Co3(Ga,Sn)C1-x precipitates, Co3(Ga,Be)C1-x precipitates, Co3(Ga,Ge)C1-x precipitates, Co3(Ga,Si)C1-x precipitates, Co3SnC1-x precipitates, Co3(Sn,Be)C1-x precipitates, Co3(Sn,Ge)C1-x precipitates, Co3SnSiC1-x precipitates, Co3BeC1-x precipitates, Co3(Be,Ge)C1-x precipitates, Co3(Be,Si)C1-x precipitates, Co3GeC1-x precipitates, Co3(Ge,Si)C1-x precipitates, Co3SiC1-x precipitates, wherein 0≤x≤0.5) and/or other precipitates (e.g., FCC L12 phase precipitates; FCC DO22 phase precipitates; D85 phase precipitates; DO19 phase precipitates; β phase precipitates; FCC L10 phase precipitates; WC precipitates; MxC precipitates, where x>2 and M=Co,W). Accordingly, the Co of the thermally stable material may not catalyze reactions that decompose the inter-bonded diamond particles during normal use and operation of the cutting table 212. In additional embodiments, some amount of unreacted Co may be present within the thermally stable material. However, the grain sizes and distributions of the κ-carbide precipitates and/or other precipitates may be controlled to limit the exposure of the inter-bonded diamond particles of the cutting table 212 to such catalytic Co.
The cutting table 212 may exhibit enhanced abrasion resistance and thermal stability up to a melting temperature or theoretical diamond stability temperature, at or near atmospheric conditions, whichever is lower, of the thermally stable material. For example, if the melting temperature of the thermally stable material is about 1,200° C., the cutting table 212 may be thermally and physically stable at temperatures within a range from about 1,000° C. to about 1,100° C., which corresponds to the theoretical limit of diamond stability under or near atmospheric conditions (assuming no oxidation occurs). The thermally stable material within interstitial spaces between the inter-bonded diamond particles of the cutting table 212 may be thermodynamically stable at ambient pressure and temperatures, as well as at temperatures and pressures experienced, for example, during downhole drilling. The thermally stable material may render the cutting table 212 thermally stable without having to remove (e.g., leach) material from the interstitial spaces of the cutting table 212.
The cutting table 302 and the supporting substrate 304 may each individually exhibit a generally cylindrical column shape, and the interface 306 between the supporting substrate 304 and cutting table 302 may be substantially planar. A ratio of a height of the cutting element 300 to an outer diameter of the cutting element 300 may be within a range of from about 0.1 to about 50, and a height (e.g., thickness) of the cutting table 302 may be within a range of from about 0.3 millimeters (mm) to about 5 mm. Surfaces (e.g., the lateral side surface 308, the cutting face 310) of the cutting table 302 adjacent the cutting edge 312 may each be substantially planar, or one or more of the surfaces of the cutting table 302 adjacent the cutting edge 312 may be at least partially non-planar. Each of the surfaces of the cutting table 302 may be polished, or one or more of the surfaces of the cutting table 302 may be at least partially non-polished (e.g., lapped, but not polished). In addition, the cutting edge 312 of the cutting table 302 may be at least partially (e.g., substantially) chamfered (e.g., beveled), may be at least partially (e.g., substantially) radiused (e.g., arcuate), may be partially chamfered and partially radiused, or may be non-chamfered and non-radiused. As shown in
While
The methods of the disclosure may also be employed to form structures other than cutting elements. Namely, the methods of the disclosure may be used whenever it is desired to form a structure or device including a table of hard material, such as diamond table (e.g., PDC table). The methods of disclosure may, for example, be employed to form various other structures associated with (e.g., employed in) downhole operations, such as bearing structures (e.g., bearing pads, bearing discs, bearing blocks, bearing sleeves), wear structures (e.g., wear pads, wear discs, wear blocks), block structures, die structures (e.g., tool die structures, wire die structures), and/or other structures. By way of non-limiting example,
Embodiments of cutting elements (e.g., the cutting elements 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500 illustrated in
The following examples serve to explain some embodiments of the present disclosure in more detail. The examples are not to be construed as being exhaustive or exclusive as to the scope of the disclosure.
The stabilities (e.g., thermal stabilities, and mechanical stabilities) of different κ-carbide precipitates were evaluated using Vienna Ab-initio computer simulation package (VASP) methodologies. The analysis evaluated enthalpy of formation and eigenvalue from Young's modulus calculation for the different κ-carbide precipitates. Table 1 below summarizes the results of the analysis. As shown in Table 1, κ-carbide precipitates including Al, Be, Ga, Ge, Sn, and Si (e.g., Co3AlC, Co3BeC, Co3GaC, Co3GeC, Co3SnC, Co3SiC) each had an enthalpy of formation that was less than zero (indicating that the κ-carbide precipitate is thermally stable) and an eigenvalue from a Young's modulus calculation that was positive (indicating that the κ-carbide precipitate is mechanically stable), indicating that the κ-carbide precipitates are stable and suitable for inclusion in a thermally stable material of a hard material structure (e.g., cutting table) for use in an earth-boring tool. In contrast, κ-carbide precipitates including Bi, Te, Sb, Se, As, B, and P (e.g., Co3BiC, Co3TeC, Co3SbC, Co3SeC, Co3AsC, Co3BC, Co3PC) individually had one or more of an enthalpy of formation that was greater than zero (indicating that the κ-carbide precipitate is not thermally stable) and an eigenvalue from a Young's modulus calculation that was negative (indicating that the κ-carbide precipitate is not mechanically stable), indicating that the κ-carbide precipitates are not stable and are not necessarily suitable for inclusion in a thermally stable material of a hard material structure (e.g., cutting table) for use in an earth-boring tool.
Enthalpy of formation values of different quadruple element κ-carbide precipitates were studied using VASP methodology. The κ-carbide precipitates each had as an atomic ratio of Co, to one of Al, Sn, Si, Ga, and Be, to a different one of Si, Sn, Ga, Ge, Be, and Sn, to C of 6:1:1:2. The enthalpy of formation values were compared with the average enthalpy of formation values of corresponding triple element κ-carbide precipitates (i.e., a first κ-carbide precipitate including the one of Al, Sn, Si, Ga, and Be; and a second κ-carbide precipitate including the different one of Si, Sn, Ga, Ge, Be, and Sn). Table 2 below summarizes the results of the analysis. As shown in Table 2, the enthalpy of formation values for the quadruple element κ-carbide precipitates were more negative than the average enthalpy of formation values of the corresponding triple element κ-carbide precipitates. The results indicate that when all four elements are present in the system with 6:1:1:2 ratio, it is more energy favorable to form quadruple element κ-carbide precipitates than two separate triple element κ-carbide precipitates. For Co3Sn0.5Si0.5C, Co3Sn0.5Be0.5C, Co3Sn0.5Ge0.5C, Co3Si0.5Ga0.5C, Co3Si0.5Be0.5C, Co3Si0.5Ge0.5C, and Co3Be0.5Ge0.5C, the enthalpy of formation values thereof was lower than either of the corresponding triple element κ-carbide precipitates.
While the disclosure is susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and have been described in detail herein. However, the disclosure is not intended to be limited to the particular forms disclosed. Rather, the disclosure is to cover all modifications, equivalents, and alternatives falling within the scope of the disclosure as defined by the following appended claims and their legal equivalents.
This application is a divisional of U.S. patent application Ser. No. 15/842,530, filed Dec. 14, 2017, now U.S. Pat. No. 11,396,688, issued Jul. 26, 2022, which is continuation-in-part of U.S. patent application Ser. No. 15/594,174, filed May 12, 2017, now U.S. Pat. No. 11,292,750, issued Apr. 5, 2022, the disclosure of each of which is hereby incorporated herein in its entirety by this reference.
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| 20220275486 A1 | Sep 2022 | US |
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