Patent Grant
10858892
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 metal-solvent 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. Interstitial regions between the bonded diamond grains are occupied by the metal-solvent catalyst.
Despite the availability of a number of different PDCs, manufacturers and users of PDCs continue to seek PDCs with improved mechanical properties.
Embodiments of the invention relate to PDCs including a PCD table in which at least one Group VIII metal thereof is alloyed with at least one alloying element to improve a thermal stability and/or a wear resistance of the PCD table. The disclosed PDCs may be used in a variety of applications, such as rotary drill bits, machining equipment, and other articles and apparatuses.
In an embodiment, a PDC is disclosed. The PDC includes a substrate and a PCD table bonded to the substrate. The PCD table includes an upper surface, at least one side surface, and an interfacial surface spaced from the upper surface and bonded to the substrate. The PCD table further includes a plurality of bonded diamond grains defining a plurality of interstitial regions; a first region extending inwardly from one or more of the upper surface or the at least one side surface; and a second region extending inwardly from the interfacial surface. The first region further includes an alloy disposed in at least a portion of the plurality of interstitial regions in the first region. The alloy includes at least one Group VIII metal and at least one metallic alloying element. For example, the at least one metallic alloying element may include phosphorous and the alloy may include at least one intermediate compound including the at least one Group VIII metal and the phosphorous, while the second region is substantially free of phosphorous and the alloy.
In an embodiment, a method of fabricating a PDC is disclosed. The method includes providing an assembly including a substrate and a PCD table bonded to the substrate. The PCD table includes an upper surface, at least one side surface, an interfacial surface bonded to the substrate, and a plurality of bonded diamond grains defining a plurality of interstitial regions. At least a portion of the plurality of interstitial regions includes at least one Group VIII metal disposed therein. The assembly includes at least one material positioned adjacent to the PCD table. For example, the at least one material may include phosphorous and/or or another at least one alloying element. The method includes subjecting the assembly to a heating process effective to at least partially melt the at least one alloying element of the at least one material and alloy the at least one Group VIII metal with the at least one alloying element to form an alloy. For example, when the at least one alloying element includes phosphorous, the alloy includes at least one intermediate compound including the at least one Group VIII metal and the phosphorous, and the PCD table including a first region extending inwardly from the upper surface and the at least one side surface that includes the at least one intermediate compound and a second region extending inwardly from the interfacial surface that is substantially free of phosphorous and the alloy.
Other embodiments include applications utilizing the disclosed PDCs in various articles and apparatuses, such as rotary drill bits, 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.
The drawings illustrate several embodiments of the invention, wherein identical reference numerals refer to identical or similar elements or features in different views or embodiments shown in the drawings.
Embodiments of the invention relate to PDCs including a PCD table in which at least one Group VIII metal thereof is alloyed with at least one alloying element to improve a thermal stability and/or a wear resistance of the PCD table. The disclosed PDCs may be used in a variety of applications, such as rotary drill bits, machining equipment, and other articles and apparatuses.
The PCD table 102 may be integrally formed with the substrate 104. For example, the PCD table 102 may be integrally formed with the substrate 104 in an HPHT process by sintering of diamond particles on the substrate 104. The PCD table 102 further includes a plurality of directly bonded-together diamond grains exhibiting diamond-to-diamond bonding (e.g., sp3 bonding) therebetween. The plurality of directly bonded-together diamond grains define a plurality of interstitial regions. For example, the diamond grains of the PCD table 102 may exhibit an average grain size of about less than 40 μm, about less than 30 μm, about 18 μm to about 30 μm, or about 18 μm to about 25 μm (e.g., about 19 μm to about 21 μm). The PCD table 102 defines the working upper surface 112, at least one side surface 114, and an optional peripherally-extending chamfer 113 that extends between the at least one side surface 114 and the working upper surface 112.
A metallic interstitial constituent is disposed in at least a portion of the interstitial regions of the PCD table 102. In an embodiment, the metallic interstitial constituent includes and/or is formed from an alloy that is chosen to exhibit a selected melting temperature or melting temperature range and/or bulk modulus that are sufficiently low so that it does not break diamond-to-diamond bonds between bonded diamond grains during heating experienced during use, such as cutting operations. For example, the alloy may exhibit a bulk modulus that is less than that of a Group VIII metal in substantially pure form. During cutting operations using the PCD table 102, the relatively deformable metallic interstitial constituent may potentially extrude out of the PCD table 102. However, before, during, and after the cutting operations, the PCD table 102 still includes the metallic interstitial constituent distributed substantially entirely throughout the PCD table 102.
According to various embodiments, the alloy includes at least one Group VIII metal including cobalt, iron, nickel, or alloys thereof and at least one alloying element (e.g., a metallic alloying element) selected from silver, gold, aluminum, antimony, boron, carbon, cerium, chromium, copper, dysprosium, erbium, iron, gallium, germanium, gadolinium, hafnium, holmium, indium, lanthanum, magnesium, manganese, molybdenum, niobium, neodymium, nickel, phosphorus, praseodymium, platinum, ruthenium, sulfur, antimony, scandium, selenium, silicon, samarium, tin, tantalum, terbium, tellurium, thorium, titanium, vanadium, tungsten, yttrium, zinc, zirconium, any combination thereof, or other constituents. The at least one alloying element or combination of alloying elements may be present with the at least one Group VIII metal in an amount of about greater than 0 to about 40 atomic %, about 5 atomic % to about 35 atomic %, about 15 atomic % to about 35 atomic %, about 20 atomic % to about 35 atomic %, about 5 atomic % to about 15 atomic %, or about 30 atomic % to about 35 atomic % of the alloy. For example, a more specific group for the at least one alloying element includes boron, copper, gallium, germanium, gadolinium, phosphorous, silicon, tin, zinc, zirconium, and combinations thereof. The at least one alloying element may be alloyed with the at least one Group VIII metal in an amount at a eutectic composition, hypo-eutectic composition, or hyper-eutectic composition for the at least one Group VIII-alloying element chemical system if the at least one Group VIII-alloying element has a eutectic composition. In some embodiments, the at least one alloying element may lower a melting temperature of the at least one Group VIII metal, a bulk modulus of the at least one Group VIII metal, a coefficient of thermal expansion of the at least one Group VIII metal, or any combination thereof.
The at least one Group VIII metal may be infiltrated from the cementing constituent of the substrate 104 (e.g., cobalt from a cobalt-cemented tungsten carbide substrate) and alloyed with the at least one alloying element provided from a source other than the substrate 104. For example, the at least one alloying element may be alloyed with the at least one Group VIII metal and mixed with the diamond particles, the at least one alloying element (e.g., in powder or granule form) may be mixed with diamond particles prior to HPHT processing, the at least one alloying element may be diffused into the at least one Group VIII metal after the at least one Group VIII metal has infiltrated between the diamond particles to form the diamond grains, or combinations thereof. In such an embodiment, a depletion region of the at least one Group VIII metal in the substrate 104 in which the concentration of the at least one Group VIII metal is less than the concentration prior to being bonded to the PCD table 102 may be present at and near the interfacial surface 106. In such an embodiment, the at least one Group VIII metal may form and/or carry tungsten and/or tungsten carbide with it during infiltration into the diamond particles being sintered that, ultimately, forms the PCD table 102.
Depending on the alloy system, in some embodiments, the alloy disposed interstitially in the PCD table 102 includes: one or more solid solution alloy phases of the at least one Group VIII metal and the at least one alloying element; one or more intermediate compound phases (e.g., one or more intermetallic compounds) between the at least one alloying element and the at least one Group VIII metal and/or other metal (e.g., tungsten); one or more binary or higher-order intermediate compound phases; one or more carbide phases between the at least one alloying element, carbon, and optionally other metal(s); the at least one alloying element in elemental form, carbon, and optionally other metals; or combinations thereof. In some embodiments, when the one or more intermediate compounds are present in the alloy, the one or more intermediate compounds are present in an amount less than about 40 weight % of the alloy, such as less than about 30 weight % less, less than about 20 weight %, less than about 15 weight %, less than about 10 weight %, about 5 weight % to about 35 weight %, about 10 weight % to about 30 weight %, about 15 weight % to about 25 weight %, about 5 weight % to about 10 weight %, about 1 weight % to about 4 weight %, or about 1 weight % to about 3 weight %, with the balance being the one or more solid solution phases and/or one or more carbide phases. In other embodiments, when the one or more intermediate compounds are present in the alloy, the one or more intermediate compounds are present in the alloy in an amount greater than about 80 weight % of the alloy, such as greater than about 90 weight %, about 90 weight % to about 100 weight %, about 90 weight % to about 95 weight %, about 90 weight % to about 97 weight %, about 92 weight % to about 95 weight %, about 97 weight % to about 99 weight %, or about 100 weight % (i.e., substantially all of the alloy). That is, in some embodiments, the alloy may be a multi-phase alloy that may include one or more solid solution alloy phases, one or more intermediate compound phases, one or more carbide phases, one or more elemental constituent (e.g., an elemental alloying element, elemental carbon, or an elemental group VIII metal) phases, or combinations thereof. The inventors currently believe that the presence of the one or more intermediate compounds may enhance the thermal stability of the PCD table 102 due to the relatively lower coefficient of thermal expansion of the one or more intermediate compounds compared to a pure Group VIII metal, such as cobalt. Additionally, in some embodiments, the inventors currently believe that the presence of the solid solution alloy of the at least one Group VIII metal may enhance the thermal stability of the PCD table 102 due to lowering of the melting temperature and/or bulk modulus of the at least one Group VIII metal. In some embodiments, the presence of the solid solution alloy of the at least one Group VIII metal and alloying element may decrease or eliminate the tendency of the at least one Group VIII metal therein to cause back-conversion of carbon atoms of the diamond grains in the PCD table 102 to graphite at high temperatures, such as those experienced under drilling conditions by a PDC cutter.
For example, when the at least one Group VIII element is cobalt and the at least one alloying element is boron, the alloy may include WC phase, CoAWBBC (e.g., Co21W2B6) phase, CoDBE (e.g., Co2B or BCo2) phase, and Co phase (e.g., substantially pure cobalt or a cobalt solid solution phase) in various amounts. According to one or more embodiments, the WC phase may be present in the alloy in an amount less than 1 weight %, or less than 3 weight %; the CoAWBBC (e.g., Co21W2B6) phase may be present in the alloy in an amount less than 1 weight %, about 2 weight % to about 5 weight %, more than 10 weight %, about 5 weight % to about 10 weight %, or more than 15 weight %, the CoDBE (e.g., Co2B or BCo2) phase may be present in the alloy in an amount greater than about 1 weight %, greater than about 2 weight %, or about 2 weight % to about 5 weight %; and the Co phase (e.g., substantially pure cobalt or a cobalt solid solution phase) may be present in the alloy in an amount less than 1 weight %, or less than 3 weight %. Any combination of the recited concentrations for the foregoing phases may be present in the alloy. In some embodiments, the maximum concentration of the Co21W2B6 may occur at an intermediate depth below the working upper surface 112 of the PCD table 102, such as about 0.010 inches to about 0.040 inches, about 0.020 inches to about 0.040 inches, or about 0.028 inches to about 0.035 inches (e.g., about 0.030 inches) below the working upper surface 112 of the PCD table. In the region of the PCD table 102 that has the maximum concentration of the Co21W2B6 phase, the diamond content of the PCD table may be less than 90 weight %, such as about 80 weight % to about 85 weight %, or about 81 weight % to about 84 weight % (e.g., about 83 weight %).
In an embodiment, when the at least one alloying element is phosphorous, the at least one Group VIII element is cobalt, and the substrate 104 is a cobalt-cemented tungsten carbide substrate, the alloy may include a WC phase, a Co2P cobalt-phosphorous intermetallic compound phase, a Co phase (e.g., substantially pure cobalt or a cobalt solid solution phase), and optionally elemental phosphorous in various amounts or no elemental phosphorous. In such an embodiment, the phosphorous may be present with the cobalt in an amount of about 30 atomic % to about 34 atomic % of the alloy and, more specifically, about 33.33 atomic % of the alloy. According to one or more embodiments, the WC phase may be present in the alloy in an amount less than 1 weight %, or less than 3 weight %; the Co2P cobalt-phosphorous intermetallic compound phase may be present in the alloy in an amount greater than 80 weight %, about 80 weight % to about 95 weight %, more than 90 weight %, about 85 weight % to about 95 weight %, or about 95 weight % to about 99 weight %; and the Co phase (e.g., substantially pure cobalt or a cobalt solid solution phase) may be present in the alloy in an amount less than 1 weight %, or less than 3 weight %. Any combination of the recited concentrations (or other concentrations disclosed herein) for the foregoing phases may be present in the alloy.
Table I below lists various different embodiments for the at least one alloying element of the alloy of the metallic interstitial constituent. For some of the at least one alloying elements, the eutectic composition with cobalt and the corresponding eutectic temperature at 1 atmosphere is also listed. As previously noted, in such alloys, in some embodiments, the at least one alloying element may be present at a eutectic composition, hypo-eutectic composition, or hyper-eutectic composition for the cobalt-alloying element chemical system.
In a more specific embodiment, the alloy includes cobalt for the at least one Group VIII metal and zinc for the at least one alloying element. For example, the alloy of cobalt and zinc may include a cobalt solid solution phase of cobalt and zinc and/or a cobalt-zinc intermetallic phase. In another embodiment, the alloy includes cobalt for the at least one Group VIII metal and zirconium for the at least one alloying element. In a further embodiment, the alloy includes cobalt for the at least one Group VIII metal and copper for the at least one alloying element. In some embodiments, the at least one alloying element is a carbide former, such as aluminum, niobium, silicon, tantalum, or titanium. In some embodiments, the at least one alloying element may be a non-carbon metallic alloying element, such as any of the metals listed in the table above. In other embodiments, the at least one alloying element may not be a carbide former or may not be a strong carbide former compared to tungsten. For example, copper and zinc are examples of the at least one alloying element that are not strong carbide formers. For example, in another embodiment, the alloy includes cobalt for the at least one Group VIII metal and boron for the at least one alloying element. In such an embodiment, the metallic interstitial constituent may include a number of different intermediate compounds, such as BCo, W2B5, B2CoW2, Co2B, WC, Co21W2B6, Co3W3C, CoB2, CoW2B2, CoWB, combinations thereof, along with some pure cobalt. It should be noted that despite the presence of boron in the alloy, the alloy may be substantially free of boron carbide in some embodiments but include tungsten carbide with the tungsten provided from the substrate 104 during the sweep through of the at least one Group VIII metal into the PCD table 102 during formation thereof.
In an embodiment, nickel is the at least one Group VIII metal and phosphorous is the at least one alloying element. In such an embodiment, a metallic interstitial constituent comprising a nickel-phosphorous alloy may include on or more of Ni3P, NiP2, or elemental phosphorus in one or more regions of the PCD table. The eutectic amount of phosphorus alloyed with nickel in Ni3P is 19 atomic % and the eutectic amount of phosphorus in NiP2 is about 47 atomic %. The eutectic temperatures of Ni3P and NiP2 are about 891° C. and about 860° C., respectively.
In an embodiment, iron is the at least one Group VIII metal and phosphorous is the at least one alloying element. In such an embodiment, a metallic interstitial constituent comprising an iron-phosphorous alloy may include on or more of Fe—Fe3P, Fe3P—Fe2P, Fe2P—FeP, or elemental iron in one or more regions of the PCD table. The eutectic amount of phosphorus alloyed with iron in Fe—Fe3P is 17 atomic %, the eutectic amount of phosphorus alloyed with iron in Fe3P—Fe2P is 24 atomic %, and the eutectic amount of phosphorus in Fe2P—FeP is about 40 atomic %. The eutectic temperatures of Fe—Fe3P, Fe3P—Fe2P, and Fe2P—FeP are about 1048° C., about 1166° C., and about 1262° C., respectively.
Depending on the HPHT processing technique used to form the PDC 100, the alloy disposed in the interstitial regions of the PCD table 102 may exhibit a composition and/or concentration that is substantially uniform throughout the PCD table 102. This may occur when the at least one alloying element is provided by mixing the at least one alloying element in powder or granular form with diamond particles prior to HPHT processing. In other embodiments, the composition and/or concentration of the alloy disposed in the interstitial regions of the PCD table 102 may be non-uniform and exhibit a gradient (e.g., a substantially continuous gradient) in which the concentration of the at least one alloying element decreases with distance away from the working upper surface 112 of the PCD table 102 toward the substrate 104. This may occur when the at least one alloying element is provided by placing a powder, disc, film, etc. including the at least one alloying element therein adjacent to one or more outside surfaces (e.g., corresponding to the at least a portion of a side surface 114 and/or upper surface 112) of the mass of diamond particles prior to HPHT processing. In such an embodiment, if present at all, the alloy may exhibit a decreasing concentration of any intermediate compounds with distance away from the working upper surface 112 and/or side surface 114 of the PCD table 102.
The depth to which the at least one alloying element is present in the PCD table 102 may depend upon one or more of the following: the temperature of the HPHT process, the pressure of the HPHT process, the type of the at least one alloying element used in the HPHT process, the technique used to introduce the at least one alloying element to the PCD table 102, or the amount of the at least one alloying element used in the manufacture of the PCD table 102 (e.g., thickness of the layer or concentration of the at least one alloying element). For example, the depth to which the at least one alloying element is present in the alloy of the PCD table 102 as measured from the upper surface 112 or at least one side surface 114 may be at least 20 μm, at least about 250 μm, about 400 μm to about 700 μm, or about 600 μm to about 800 μm. Any of the embodiments of a first region described herein may exhibit one or more of any of the infiltration depths described herein.
In some embodiments, when the at least one alloying element is capable of diffusing into the PCD table 102 and alloying with at least one Group VIII metal, the inventors currently believe that the depth of diffusion of the at least one alloying element should be sufficient so that the alloy forms at a depth of at least about 250 μm as measured from the upper surface 112 and/or side surface 114. Such diffusion may improve thermal stability, catalytic stability, wear resistance, or combinations thereof relative to a PCD table that does not contain appreciable amounts of the at least one alloying element. Referring to
In an embodiment, when the at least one alloying element is phosphorus and at least one Group VIII metal is cobalt, the inventors currently believe that a depth of phosphorous diffusion (e.g., a presence of Co2P) of at least about 250 μm as measured from the upper surface 112 improves thermal stability and/or wear resistance relative to a PCD table that does not contain appreciable amounts of phosphorous. Referring again to
It should be noted that when the at least one alloying element is mixed with the diamond particles used to form the PCD table (either in a powder form and/or pre-alloyed with the Group VIII metal in powder form), the alloy may be substantially homogenous and the concentration of the at least one alloying element may be substantially uniform throughout the PCD table 102. For example, in an embodiment when phosphorus is the at least one alloying element, the alloy may include almost entirely Co2P when the at least one Group VIII metal is cobalt, the alloy may include almost entirely Fe3P and/or Fe2P when the at least one Group VIII metal is iron, or the alloy may include almost entirely Ni3P and/or Ni5P2 when the at least one Group VIII metal is nickel.
The alloy of the PCD table 102 may be selected from a number of different alloys exhibiting a melting temperature of about 1400° C. or less and/or a bulk modulus at 20° C. of about 150 GPa or less. As used herein, melting temperature refers to the lowest temperature at which melting of a material begins at standard pressure conditions (i.e., 100 kPa). For example, depending upon the composition of the alloy, the alloy may melt over a temperature range such as occurs when the alloy has a hypereutectic composition or a hypoeutectic composition where melting begins at the solidus temperature and is substantially complete at the liquidus temperature. In other cases, the alloy may have a single melting temperature as occurs in a substantially pure metal or a eutectic alloy.
In one or more embodiments, the alloy exhibits a coefficient of thermal expansion of about 3×10−6 per ° C. to about 20×10−6 per ° C., a melting temperature of about 180° C. to about 1300° C., and a bulk modulus at 20° C. of about 30 GPa to about 150 GPa; a coefficient of thermal expansion of about 15×10−6 per ° C. to about 20×10−6 per ° C., a melting temperature of about 180° C. to about 1100° C., and a bulk modulus at 20° C. of about 50 GPa to about 130 GPa; a coefficient of thermal expansion of about 15×10−6 per ° C. to about 20×10−6 per ° C., a melting temperature of about 950° C. to about 1100° C. (e.g., 1090° C.), and a bulk modulus at 20° C. of about 120 GPa to about 140 GPa (e.g., about 130 GPa); or a coefficient of thermal expansion of about 15×10−6 per ° C. to about 20×10−6 per ° C., a melting temperature of about 180° C. to about 300° C. (e.g., about 250° C.), and a bulk modulus at 20° C. of about 45 GPa to about 55 GPa (e.g., about 50 GPa). For example, the alloy may exhibit a melting temperature of less than about 1200° C. (e.g., less than about 1100° C.) and a bulk modulus at 20° C. of less than about 140 GPa (e.g., less than about 130 GPa). For example, the alloy may exhibit a melting temperature of less than about 1200° C. (e.g., less than 1100° C.), and a bulk modulus at 20° C. of less than about 130 GPa.
When the HPHT sintering pressure is greater than about 7.5 GPa cell pressure, optionally in combination with the average diamond grain size being less than about 30 μm, any portion of the PCD table 102 (prior to being leached) defined collectively by the bonded diamond grains and the alloy may exhibit a coercivity of about 115 Oe or more and the alloy content in the PCD table 102 may be less than about 7.5% by weight as indicated by a specific magnetic saturation of about 15 G·cm3/g or less. In another embodiment, the coercivity may be about 115 Oe to about 250 Oe and the specific magnetic saturation of the PCD table 102 (prior to being leached) may be greater than 0 G·cm3/g to about 15 G·cm3/g. In another embodiment, the coercivity may be about 115 Oe to about 175 Oe and the specific magnetic saturation of the PCD may be about 5 G·cm3/g to about 15 G·cm3/g. In yet another embodiment, the coercivity of the PCD table (prior to being leached) may be about 155 Oe to about 175 Oe and the specific magnetic saturation of the first region 115 may be about 10 G·cm3/g to about 15 G·cm3/g. The specific permeability (i.e., the ratio of specific magnetic saturation to coercivity) of the PCD table 102 may be about 0.10 G·cm3/g·Oe or less, such as about 0.060 G·cm3/g·Oe to about 0.090 G·cm3/g·Oe. In some embodiments, the average grain size of the bonded diamond grains may be less than about 30 μm and the alloy content in the PCD table 102 (prior to being leached) may be less than about 7.5% by weight (e.g., about 1% to about 6% by weight, about 3% to about 6% by weight, or about 1% to about 3% by weight). Additionally, details about magnetic properties that the PCD table 102 may exhibit are disclosed in U.S. Pat. No. 7,866,418, the disclosure of which is incorporated herein, in its entirety, by this reference.
In some embodiments in which the at least one Group VIII metal is cobalt and the PCD table 102 is unleached, the PDC 100 may exhibit a thermal stability characterized by a distance that it may cut in a mill test (as described in more detail below) prior to failure of at least about 155 inches, such as 155 inches to about 300 inches, 160 inches to about 170 inches, about 170 inches to about 220 inches, about 190 inches to about 240 inches, about 220 inches to about 260 inches, or about 250 inches to about 290 inches. The thermal stability of a PDC may be evaluated in a mill test in which the PDC is used to cut a Barre granite workpiece without any coolant (i.e., dry cutting of the Bane granite workpiece in air). The test parameters used for the mill test may be a back rake angle for the PDC of about 20°, an in-feed for the PDC of about 50.8 cm/min, a width of cut for the PDC of about 7.62 cm (i.e., two PDC cutters mounted to a fly cutter assembly), a depth of cut for the PDC of about 0.762 mm, a rotary speed on the workpiece of about 3000 RPM, an indexing across the workpiece (e.g., in the Y direction) of about 7.62 cm, about 20 seconds between cutting passes, and the size of the Bane granite workpiece may be approximately 30.48 cm wide by 30.48 cm high by 73.66 cm long. The PDC may be held in a cutting tool holder, with the substrate of the PDC tested thermally insulated on its back side via an alumina disc and along its circumference by a plurality of zirconia pins. Failure is considered when the PDC can no longer cut the workpiece.
Referring specifically to the cross-sectional view of
The leached region 122 has been leached to deplete the metallic interstitial constituent therefrom that previously occupied the interstitial regions between the bonded diamond grains of the leached region 122. The leaching may be performed in a suitable acid (e.g., aqua regia, nitric acid, hydrofluoric acid, or combinations thereof) so that the leached region 122 is substantially free of the metallic interstitial constituent. As a result of the metallic interstitial constituent (e.g., a Group VIII metal-alloying metal alloy such as a cobalt-phosphorus alloy) being depleted from the leached region 122, the leached region 122 may be relatively more thermally stable than the underlying region 115.
Generally, a selected leach depth 123 may be greater than 250 μm. For example, the selected leach depth 123 for the leached second region 122 may be about 300 μm to about 425 μm, about 250 μm to about 400 μm, about 350 μm to about 400 μm, about 350 μm to about 375 μm, about 375 μm to about 400 μm, or about 500 μm to about 650 μm. The selected leach depth 123 may be measured inwardly from at least one of the upper surface 112, the chamfer 113, or the at least one side surface 114. Any of the embodiments of PDCs described herein may include a leached region extending any of the leach depths described above. Any of the leached regions described herein may include at least a portion of any of the first regions described herein. For example, any of the embodiments described with respect to
The diamond particles 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). 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 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 assembly 300 may be placed in a pressure transmitting medium, such as a refractory metal can embedded in pyrophyllite or other pressure transmitting medium, and subjected to a first stage HPHT process. For example, the first stage HPHT process may be performed using an ultra-high pressure press to create temperature and pressure conditions at which diamond is stable. The temperature of the first stage HPHT process may be at least about 1000° C. (e.g., about 1200° C. to about 1600° C.) and the pressure of the HPHT process may be at least 4.0 GPa (e.g., about 5.0 GPa to about 12 GPa or about 7.5 GPa to about 11 GPa) for a time sufficient to sinter the diamond particles to form a PCD table. For example, the pressure of the first stage HPHT process may be about 7.5 GPa to about 10 GPa and the temperature of the HPHT process may be about 1150° C. to about 1450° C. (e.g., about 1200° C. to about 1400° C.). The foregoing pressure values employed in the HPHT process refer to the cell pressure in the pressure transmitting medium that transfers the pressure from the ultra-high pressure press to the assembly.
In an embodiment, during the first stage HPHT process, the at least one Group VIII metal from the substrate 104 or another source (e.g., metal-solvent catalyst mixed with the diamond particles) liquefies and infiltrates into the mass of diamond particles 302 and sinters the diamond particles together to form a PCD table having diamond grains exhibiting diamond-to-diamond bonding (e.g., sp3 bonding) therebetween with the at least one Group VIII metal disposed in the interstitial regions between the diamond grains. In an embodiment, the at least one alloying element from the at least one material 304 does not melt during the first stage HPHT process (e.g., sintering conditions) and/or is enclosed within a protective enclosure or behind a protective partition made from a material that does not melt during the first stage HPHT process regardless of the melting temperature of the at least one material 304. Thus, in such an embodiment, the at least one alloying element and/or protective partition or enclosure has a melting temperature or range thereof greater than the at least one Group VIII metal (e.g., cobalt) that is used. Suitable materials for the protective partition or enclosure include, but are not limited to, silicon, iridium, zirconium, molybdenum, tungsten, tungsten carbide, niobium, tantalum, titanium, another refractory material, or alloys of one or more of the foregoing. In an embodiment, if the substrate 104 is a cobalt-cemented tungsten carbide substrate, cobalt from the substrate 104 may be liquefied and infiltrate the mass of diamond particles 302 to catalyze formation of the PCD table, and the cobalt may subsequently be cooled to below its melting point or range. Then, the temperature of a second stage heating process (e.g., alloying conditions) may be increased (e.g., about 1850° C. to about 1900° C.) to diffuse the at least one alloying element into the at least one Group VIII metal (e.g., while the at least one Group VIII metal is liquefied). In an embodiment, the protective partition or enclosure may be melted or at least softened to promote diffusion of the at least one alloying element therein (e.g., boron, phosphorous, silicon, etc.) into the at least one Group VIII metal.
In an embodiment where the at least one alloying element includes phosphorus, at atmospheric pressure, white phosphorous melts at around 44.2° C., violet phosphorous melts at around 589.5° C., black phosphorous melts at around 610° C., and red phosphorous melts at around 621° C. Red phosphorous is amorphous, and black phosphorous may be formed by heating white or red phosphorous at high pressure. Amorphous red phosphorous tends to remain amorphous after exposure to about 5.2 GPa. The inventors currently believe that red phosphorous changes to orthorhombic crystal structure after HPHT processing, which is the typical crystal structure for black phosphorous. The inventors also currently believe that amorphous red phosphorous changes to orthorhombic black phosphorous before reaction with cobalt to form Co2P. Therefore, it may be desirable to use a protective partition or enclosure to promote diffusion of an alloying element having a melting point below that of the Group VIII metal, such as phosphorus, into the at least one Group VIII metal in the sintered polycrystalline diamond mass.
After sintering the diamond particles to form the PCD table in the first stage HPHT process, in a second stage heating process (e.g., a second stage HPHT process or other heating process), the temperature is increased from ambient or from the temperature employed in the first stage HPHT process (e.g., sintering conditions), while still maintaining application of the same, less, or higher cell pressure to maintain diamond-stable conditions. The temperature of the second stage heating process (e.g., alloying conditions) may be chosen to partially or completely diffuse and/or melt the at least one alloying element and/or protective enclosure of the at least one material 304 into the at least one Group VIII metal, which then alloys with at least some of the at least one Group VIII metal interstitially disposed in the PCD table and forms the final PCD table 102 having the alloy disposed interstitially between at least some of the diamond grains. Optionally, the temperature of the second stage heating process may be controlled so that the at least one Group VIII metal is still liquid or partially liquid so that the alloying with the at least one alloying element occurs in the liquid phase, which may speed diffusion of the at least one alloying element into the at least one Group VIII metal. However, in some embodiments, diffusion may occur via solid state and/or liquid diffusion, without limitation.
In an embodiment, after the first stage HPHT process, the pressure transmitting medium, (e.g., refractory metal can embedded in pyrophyllite or other pressure transmitting medium) may be removed from around the sintered PCD table and/or PDC including such a sintered PCD table. Subsequently, the sintered PCD table and/or PDC may be reloaded into another pressure transmitting medium having the at least one alloying element therein or may be sealed in a container configured to prevent oxidizing conditions from reaching the at least one alloying element (e.g., phosphorus) therein. In an embodiment, after removing the pressure transmitting medium from around the sintered PCD table and/or PDC, the sintered PCD and/or PDC may be placed in contact with the at least one alloying element in and may be heated according to the second stage heating process. In such an embodiment, an inert environment may be provided, while heating (e.g., a partial vacuum environment, argon gas, or N2 gas) to avoid oxidizing the at least one alloying element.
Before or after alloying, the PDC may be subjected to finishing processing to, for example, chamfer the PCD table, form a desired outer diameter or other lateral dimension (e.g., centerless grinding, form a desired geometry (e.g., wave pattern, zig-zag pattern, or any single feature in the upper surface, planarize the upper surface thereof, or combinations thereof. The temperature of the second stage heating process may be about 1500° C. to about 1900° C., and the temperature of the first stage HPHT process may be about 1350° C. to about 1450° C. After and/or during cooling from the second stage heating process, the PCD table 102 bonds to the substrate 104. As discussed above, the alloying of the at least one Group VIII metal with the at least one alloying element may lower a melting temperature of the at least one Group VIII metal and and/or may lower at least one of a bulk modulus or coefficient of thermal expansion of the at least one Group VIII metal.
For example, in an embodiment, the at least one material 304 may comprise boron particles, such as boron particles mixed with aluminum oxide particles. In another embodiment, the at least one material 304 may comprise copper or a copper alloy in powder or foil form. In such embodiments, the pressure of the second stage heating process may be about 5.5 GPa to about 6.5 GPa cell pressure and the temperature of the second stage heating process may be about 1550° C. to about 1650° C. (e.g., 1600° C.), which is maintained for about 1 minutes to about 35 minutes (e.g., about 2 minutes to about 35 minutes, about 2 minutes to about 5 minutes, about 10 to about 15 minutes, about 5 to about 10 minutes, or about 25 to about 35 minutes).
In an embodiment, a second stage heating process may not be needed. Particularly, alloying may be possible in a single HPHT process. In an example, when the at least one alloying element is copper or a copper alloy, the copper or copper alloy may not always infiltrate the un-sintered diamond particles under certain conditions. For example, after the at least one Group VIII metal has infiltrated (or as it infiltrates the diamond powder) and at least begins to sinter the diamond particles, copper may be able and/or begin to alloy with the at least one Group VIII metal. Such a process may allow materials that would not typically infiltrate diamond powder to do so during or after infiltration by a catalyst.
Alloying may be possible by merely heating (e.g., in a partial vacuum or in an inert gas environment such as argon, helium, nitrogen, carbon dioxide, any other inert gas, or combinations thereof) the at least one alloying element positioned adjacent to a previously sintered PCD table to a temperature above the melting point of the at least one alloying element and the at least one group VIII metal (which may be disposed in the sintered PCD table or in a substrate adjacent thereto. In such an embodiment, the at least one alloying element may react with the at least one Group VIII metal to at least partially alloy therewith. In an embodiment the at least one alloying element may be subjected to a temperature above the melting point of the at least one alloying element yet below the melting temperature of the at least one group VIII metal. The second stage heating process may include a pressure of about 2 GPa or less, such as about 0.0 GPa to about 2 GPa, about 0.5 GPa to about 1.5 GPa, about 1 GPa or less, about 0.5 GPa or less, at about atmospheric pressure, or under vacuum of less than about 10−2 torr, such as about 10−3 torr to about 10−9 torr, about 10−2 torr to about 10−5 torr, about 10−5 torr to about 10−9 torr, or less than about 10−9 torr. As used herein pressure includes negative pressure such as vacuum or partial vacuum pressures. For example, in an embodiment, the second stage heating process may be carried out using a pressure of about 10−9 torr to about 2 GPa, such as about 10−5 torr to about 1 GPa. In such an embodiment, the at least one alloying element may react with the at least one Group VIII metal to at least partially alloy therewith. For example, the PCD table may be disposed into the at least one alloying element to a depth, as measured from the upper surface, of about 0.005 inches or more, such as about 0.01 inches to about 0.1 inches, about 0.02 inches to about 0.06 inches, about 0.04 inches, or less than about 0.01 inches. In order to provide contact, the PCD table may at least partially contact a powder including the at least one alloying element, or may at least partially contact a solid body (e.g., pellet or green state part) having a selected surface configuration (e.g., matching).
At least one material 304′ of any of the at least one alloying elements (or mixtures or combinations thereof) disclosed herein may be positioned adjacent to an outer surface of the PCD table 102′, such as adjacent to one or more of the upper surface 112′, side surface 114′, or chamfer 113′ of the PCD table 102′ to form the precursor PDC assembly 310. For example, the at least one material 304′ may be positioned on at least 50% of a surface area of the upper surface 112′, all of the surface area of the chamfer 113′, and/or at least part of the surface area (e.g., more or less than 50%) of the side surface 114′. For example, the at least one material 304′ may be in the form of particles of the alloying element(s), a thin disc of the alloying element(s), a green body of particles of the alloying element(s), an alloy of at least one Group VIII metal and the at least alloying element (e.g., a Co—P alloy) in any of the preceding forms, or combinations thereof. Although the PCD table 102′ is illustrated as being chamfered with a chamfer 113′ extending between the upper surface 112′ and at least one side surface 114′, in some embodiments, the PCD table 102′ may not have a chamfer. As the PCD table 102′ is already formed, any of the at least one alloying elements disclosed herein may be used, regardless of its melting temperature. The precursor PDC assembly 310 may be subjected to an HPHT process using the same or similar HPHT conditions as the second stage heating process discussed above or even lower temperatures for certain low-melting at least one alloying elements, such as bismuth. For example, the temperature may be about 800° C. or less, such as about 400° C. to about 800° C., about 200° C. to about 500° C., about 100° C. to about 400° C., about 500° C. to about 800° C., or about 600° C. to about 700° C., about 600° C., or about 650° C., for such embodiments. During the second stage heating process, the at least one alloying element partially or completely melts and/or diffuses to alloy with the at least one Group VIII metal of the PCD table 102′ which may or may not be liquid or partially liquid depending on the temperature and pressure. The at least one alloying element may alloy with the at least one Group VIII metal substantially through the entire PDC table or to a depth therein as measured from the outer surface of the PCD table (e.g., having a uniform concentration or a concentration that varies).
In some embodiments, the pressure employed in the second stage heating process may be below that of the first stage HPHT process or pressure typically used in HPHT processes which is typically above about 2 GPa. In some embodiments, such second stage heating may take place without additional pressure applied to the assembly, such as only at ambient pressure or under vacuum, so long as the elevated temperature is sufficient to melt the at least one alloying element. In an embodiment, when the at least one material 304″ includes phosphorus, the PCD table 102′ may be infiltrated by heating the phosphorus to about 44.1° C. or more (e.g., about 610° C. depending on the form of phosphorus). Such second stage heating may take place in a vacuum furnace or other non-reactive conditions (e.g., Ar or N2 gas atmosphere), which may prevent oxidation (e.g., ignition or burning) of the phosphorus at elevated temperatures. The duration of the second stage heating can be 10 minutes or more, such as about 5 minutes to 24 hours, about 1 hour to about 18 hours, about 2 hours to about 12 hours, about 3 hours to about 9 hours, about 6 hours, about 6 hours to about 18 hours, about 12 hours, or less than about 24 hours. In some embodiments, the furnace temperature may be returned to a lower temperature (e.g., ambient) prior to exposing the PCDs to the ambient environment, such that oxidation reactions therewith are limited.
In an embodiment, the pressure and/or temperature of the second stage heating process may be chosen at least partially based on the specific alloying element used in order to promote diffusion and/or alloying of the at least one alloying element into the PCD table 102′ to a selected depth measured from the upper surface 112′, such as at least 250 μm, at least about 250 μm, about 400 μm to about 700 μm, about 600 μm to about 800 μm, or greater than 1000 μm. For example, in an embodiment, the at least one material 304′ may comprise boron or phosphorous particles. In another embodiment, the at least one material 304′ may comprise copper or a copper alloy in powder or foil form. In such embodiments, the pressure of the second stage heating process may be about 5.5 GPa to about 6.5 GPa cell pressure and the temperature of the second stage heating process may be about 1550° C. to about 1650° C. (e.g., 1600° C.), which is maintained for about 2 minutes to about 35 minutes (e.g., about 10 to about 15 minutes, about 5 to about 10 minutes, or about 25 to about 35 minutes).
In an embodiment, the at least one material 304′ may include phosphorus in any form (e.g., powder, foil, or disc form). In such an embodiment, the pressure of the second stage heating process may be about 5.2 GPa to about 6.5 GPa and the temperature of the second stage heating process may be about 1380° C. to about 1900° C., and the temperature of the first stage HPHT process may be about 1350° C. to about 1450° C. For example, in an embodiment, the pressure of the second stage heating process may be about 5.2 GPa to about 6.5 GPa (e.g., 5 GPa to about 5.5 GPa) and the temperature of the second stage heating process may be about 1000° C. to about 1500° C. (e.g., 1380° C. to about 1500, or about 1400° C.), and the pressure of the first stage HPHT process may be about 7.5 GPa to about 8.5 GPa and the temperature of the first stage HPHT process may be about 1370° C. to about 1430° C. (e.g., about 1400° C.). For example, the pressure of the second stage heating process may be lower than that of the first stage HPHT process, which may help prevent damage to the PCD table 102′ during the second stage heating process. In an embodiment, no additional pressure over the first HPHT process may be used during the second heating process and the temperature may be at least about 40° C., such as about 44° C. to about 800° C., about 400° C. to about 700° C., about 100° C. to about 500° C., about 1000° C. to about 2000° C., or about 800° C. to about 1500° C.
Processing the precursor PDC assembly 310 may result in forming the PCD table 102 having the configuration shown in
Although the PCD table 102′ is illustrated in
In some embodiments, the at least one material 304′ of the at least one alloying element may be non-homogenous. For example, the at least one material 304′ may include a layer of a first alloying element having a first melting temperature encased/enclosed in a layer of a second alloying element having a second melting temperature greater than the first melting temperature. For example, the first one of the at least one alloying element may be silicon or a silicon alloy and the second one of the at least one alloying element may be zirconium or a zirconium alloy. During the melting of the at least one material 304′ (e.g., during the second stage heating process), once the second alloying element is completely melted and alloys the at least one Group VIII metal, the first alloying element may escape and further alloy the at least one Group VIII metal of the PCD table. In other embodiments, the first alloying element may diffuse through the layer of the second alloying element via solid state or liquid diffusion to alloy the at least one Group VIII metal.
Referring to
Referring to
Referring to
Referring to
Referring to
In an embodiment, the at least one material 304′ may be distributed in a greater amount or thickness near or adjacent to one or more portions of PCD table 102′ and a lesser amount or thickness at another portion of PCD table 102′. Referring to
Referring to
In some embodiments, the body of at least one material 304′ may be disposed on less than about 50% of the surface area of one or more of the upper surface 112′ and/or side surface 114′ of the PCD table 102′, such as about 10% to about 50%, about 20% to about 40%, about 30% to about 50%, or about 33% of the surface area of the upper surface 112′ and/or side surface 114′ of the PCD table 102′. In some embodiments, the body of at least one material 304′ may be disposed on 50% or more of the surface area of one or more of the upper surface 112′ and/or side surface 114′ of the PCD table 102′, such as about 50% to about 100%, about 60% to about 90%, about 75% to about 100%, or about 80% of the surface area of the upper surface 112′ and/or the side surface 114′ of the PCD table 102′. The body of the at least one material 304′ may have a substantially uniform or a non-uniform thickness.
Referring to
In certain drilling operations, only a portion of a PDC may perform the cutting during drilling. In some embodiments, the at least one alloying element may be diffused into only the portion of the PCD table that function as a cutting region (e.g., an outer half, outer third, generally annular region, etc.). In some embodiments, the body of at least one material 304′ may be disposed on 50% or less of the surface area of the upper surface 112′ of the PCD table 102′. Referring to
In some embodiments, a body of at least one material 304′ may be disposed on 50% or less of the surface area of the upper surface 112′ and/or the side surface 114′ of the PCD table 102′. For example, the first region 308′ may include a first portion extending substantially parallel to at least a portion of the side surface 114′ and a second portion extending substantially parallel to at least a portion of the upper surface 112′. Referring to
In an embodiment, the thickness of the first region 308′ may be dependent upon the thickness of the at least one material 304′ disposed on or adjacent to the PCD table 102′. For example, the first region 308 or 308′ may extend (e.g., from the upper surface 112′ or the side surface 114′) a distance or depth of at least about at least about 250 μm, about 250 μm to about 500 μm, about 400 μm to about 700 μm, or about 600 μm to about 800 μm. In an embodiment, the first region 308′ may include a first portion having a substantially uniform first depth (e.g., thickness) and a second portion having a substantially uniform second depth. The depths of the first portion and the second portion may be substantially equal to or different than each other.
In some embodiments, one or more discrete, non-intersecting regions having the at least one alloying element therein may be formed in a PCD table 102′. For example, the one or more regions may be linear, circular, generally annular, amorphous, rectangular, or exhibit any other suitable geometric configuration. The one or more discrete, non-intersecting regions may form a pattern, be regularly spaced, or be irregularly spaced. Referring to
Still further geometric configurations for the first region are considered herein. For example, a plurality of rows (e.g., parallel rows) or discrete dots (e.g., checkerboard pattern) of the at least one material may be disposed on one or more surfaces of the PCD table 102′ to provide a resulting plurality of rows or discrete dot regions in the PCD table having the at least one alloying element therein.
In some embodiments (not shown), different alloying elements may be disposed in different portions of the same PCD table. For example, in an embodiment, a cell assembly may include a first at least one alloying element (e.g., boron) adjacent to the upper surface of the PCD table in a central region, such as depicted in
In an embodiment, a cell assembly or PCD table may include portion or region having a first alloying element substantially configured according to any of the embodiments herein. The cell assembly or PCD table may also include at least second a portion or region having the second, different alloying element substantially in a configuration according to any of the embodiments herein. Subjecting the cell assembly to a high-pressure/high-temperature process may include forming one or more different alloys corresponding to the different alloying elements. The resulting PCD table may include at least first and second regions having differing alloying elements or alloys therein, such as a different intermediate compounds having different crystal structures and/or compositions. The resulting PCD table may include at least first and second regions partially overlapping and having differing alloying elements or alloys therein, such as a different intermediate compounds. Referring to
It should be noted that in other embodiments, the at least one alloying element may be mixed with the diamond particles in powder form prior to sintering the diamond particles. For example, at least one alloying element powder having an average particle size of about 1 μm to about 20 μm, such as about 1 μm to about 7 μm may be mixed with the diamond particles in addition to or as an alternative to employing the at least one material 304 and 304′.
As noted above, the at least one material may be disposed adjacent to or mixed within diamond particles prior to or contemporaneous with formation of the PCD table.
The assembly 400 may include a substrate 104, which may be identical or similar to any substrate 104 described herein (e.g., with respect to any of composition, shape, and/or interfacial surface 106). The mass of diamond particles 402 may be positioned on the interfacial surface 106 of the substrate 104. The at least one material 404 includes any of the alloying elements disclosed herein (e.g., at least one alloying element that lowers a temperature at which melting of at least one Group VIII metal begins). For example, the at least one material 404 may be in the form of particles of the alloying element(s), a thin disc of the alloying element(s), a green body of particles of the alloying elements(s), at least one material of the alloying element(s), or combinations thereof. In some embodiments, the at least one alloying element may even comprise carbon in the form of at least one of graphite, graphene, fullerenes, or other sp2-carbon-containing particles. In an embodiment, the at least one material 404 may include phosphorus such as in the form of particles of phosphorous, a thin disc of phosphorous, a green body of particles of phosphorous, a mixture or alloy of the Group VIII metal and phosphorous in disc or powder form, or combinations thereof. The phosphorous may be any form phosphorous disclosed herein.
The at least one material 404 may be disposed on the diamond particles 402 in any configuration disclosed above for the at least one material 304. The at least one material 404 may be positioned on at least a portion of the side surface 414 of the mass of diamond particles 402. For example, as shown, the at least one material 404 may be in the form of a generally annular body of particles, a foil, or a layer disposed about the side surface 414.
As previously discussed, the substrate 104 may include a metal-solvent catalyst as a cementing constituent comprising at least one Group VIII metal, such as cobalt, iron, nickel, or alloys thereof. For example, the substrate 104 may comprise a cobalt-cemented tungsten carbide substrate in which cobalt is the at least one Group VIII metal that serves as the cementing constituent.
The assembly 400 may be placed in a pressure transmitting medium, such as a refractory metal can embedded in pyrophyllite or other pressure transmitting medium, and subjected to a first stage HPHT process. For example, the first stage HPHT process may include any of those first stage HPHT process conditions discussed herein, such as, at a temperature of at least about 1000° C. (e.g., about 1200° C. to about 1600° C.) and the pressure of at least 4.0 GPa (e.g., about 5.0 GPa to about 12 GPa or about 7.5 GPa to about 11 GPa) for a time sufficient to sinter the diamond particles to form a PCD table.
In an embodiment, during the first stage HPHT process, the at least one Group VIII metal from the substrate 104 or another source (e.g., metal-solvent catalyst mixed with the diamond particles) liquefies and infiltrates into the mass of diamond particles 402 and sinters the diamond particles together to form a PCD table having diamond grains exhibiting diamond-to-diamond bonding (e.g., sp3 bonding) therebetween with the at least one Group VIII metal disposed in the interstitial regions between the diamond grains. In an embodiment, the at least one alloying element from the at least one material 404 does not melt during the first stage HPHT process (e.g., sintering conditions) and/or is enclosed within a protective enclosure or behind a protective partition (e.g., metal film, foil, material layer, etc.) made from a material that does not infiltrate the diamond particles during the first stage HPHT process regardless of the melting temperature of the at least one material 404. Thus, in this embodiment, the at least one alloying element and/or protective partition or enclosure has a melting temperature or range greater than the at least one Group VIII metal (e.g., cobalt) that is used. Suitable materials for the protective partition or enclosure may include any of those disclosed above with respect to a protective partition or enclosure. In an embodiment, if the substrate 104 is a cobalt-cemented tungsten carbide substrate, cobalt from the substrate 104 may be liquefied and infiltrate the mass of diamond particles 402 to catalyze formation of the PCD table, and the cobalt may subsequently be cooled to below its melting point or range. Then, the temperature of the second stage heating process (e.g., alloying conditions) may be increased (e.g., to about 1850 to about 1900° C.) to diffuse the at least one alloying element into the at least one Group VIII metal (e.g., while the at least one Group VIII metal is liquefied). The second stage heating process may include any of those second stage heating process conditions discussed herein (e.g., pressure and/or temperature). In an embodiment, the protective partition or enclosure may be melted or at least softened to promote diffusion of the at least one alloying element therein (e.g., boron, phosphorous, silicon, etc.) into the at least one Group VIII metal during the second stage heating process. During the second stage heating process, the at least one alloying element may alloy with the at least one Group VIII metal substantially through the entire PDC table or to a depth therein as measured from the outer surface of the PCD table.
In an embodiment, the pressure and/or temperature of the second stage heating process may be chosen responsive to the specific alloying element used in order to promote diffusion and/or alloying of the at least one alloying element into the PCD table 102′ to a selected depth measured from the upper surface 412′ and/or side surface 414′, such as at least 250 μm, at least about 250 μm, about 400 μm to about 700 μm, about 600 μm to about 800 μm, or greater than 1000 μm.
Referring to
It should be noted that in embodiments, the at least one alloying element may be mixed with the diamond particles in powder form prior to sintering the diamond particles. For example, at least one alloying element powder having an average particle size of about 1 μm to about 20 μm, such as about 1 μm to about 7 μm may be mixed with the diamond particles in addition to or as an alternative to employing the at least one material 304, 304′, or 404,
In some embodiments, subsequent to PCD table formation and diffusion of the at least one alloying element therein, the PCD table may be leached. In another embodiment, the PCD table (e.g., bonded to a substrate) may be formed, leached, and then alloyed with at least one alloying element. For example, any of the PCD tables 102, 102′, 302′, or 402′ may be leached to remove at least a portion of the at least one alloying element and/or at least one Group VIII metal therefrom, such as the metallic interstitial constituent. Leaching may remove the at least one alloying element, at least one Group VIII metal, the alloy, or combinations thereof from the interstitial regions of the PCD table to a depth or distance from the upper surface 412′ or the side surface 414′. The resulting leached region 422 may exhibit a leach depth 423 of about 250 μm or more from the upper surface 412′ or side surface 414′ of the PCD table 402′, encompassing one or more of the first or second regions, 408 or 417. Generally, a maximum leach depth may be greater than 250 μm. For example, the leach depth 423 for the leached region 422 may be about 300 μm to about 425 μm, about 250 μm to about 400 μm, about 350 μm to about 400 μm, about 350 μm to about 375 μm, about 375 μm to about 400 μm, about 500 μm to about 650 μm, about 600 μm to about 800 μm, about 800 μm to about 1000 μm, or greater than 1000 μm.
Referring specifically to the cross-sectional view of
The leached region 422 has been leached to substantially deplete the metallic interstitial constituent therefrom that previously occupied the interstitial regions between the bonded diamond grains of the leached region 422. The leaching may be performed in a suitable acid (e.g., aqua regia, nitric acid, hydrofluoric acid, or combinations thereof) so that the leached region 422 is substantially free of the catalyst and/or metallic interstitial constituent. As a result of the metallic interstitial constituent (e.g., a Group VIII metal-alloying metal alloy such as a cobalt-phosphorus alloy) being at least partially depleted from the leached region 422, the leached region 422 is relatively more thermally stable than the underlying second region 417. The leaching process may be carried out for a selected time, with a selected acid (e.g., type of acid and/or concentration of acid), or by selective immersion in the acid to produce a desired leach depth 423, as measured from one or more of the upper surface 412″ or the side surface 414″). Additionally, different configurations of leached regions 422 may be made using masking and/or selective immersion techniques as disclosed in U.S. patent application Ser. Nos. 12/555,715 and 13/751,405 which are incorporated herein, in their entirety, by this reference.
Referring to
The leached region 422 may encompass at least a portion of the depth of the former first region 408 from which the at least one alloying element and/or at least one Group VIII material are removed during leaching. For example, the leached region 422 may extend into the PCD table 402″ more than about 10% of the depth (as measured from one or more of the upper surface 412″ or the side surface 414″) that the first region 408 extends to, such as about 20% to about 80%, about 25% to about 75%, about 30% to about 60%, about 50%, or less than about 80% of the depth that the first region 408 extends to. In an embodiment, the first region 408 may extend about 800 μm into the PCD table 402″ and the leached region 422 may extend about 500 μm into the PCD table 402″. In an embodiment, the first region 408 may extend about 800 μm into the PCD table 402″ and the leached region 422 may extend about 400 μm into the PCD table 402″. In an embodiment, the first region 408 may extend about 850 μm into the PCD table 402″ and the leached region 422 may extend about 250 μm into the PCD table 402″.
Referring to
Referring to
Referring to
A method of fabricating a PDC may include an act of providing an assembly and an act of subjecting the assembly to a heating condition (e.g., higher than ambient temperature) effective to alloy an alloying element therein. The heating condition may include a higher than ambient temperature condition effective to at least partially alloy the alloying element. The assembly may be configured identical or similarly to any assembly disclosed herein. In an embodiment, the assembly may include a substrate and a PCD table bonded to the substrate. The PCD table may include an upper surface, at least one side surface, an interfacial surface bonded to the substrate, and a plurality of bonded diamond grains defining a plurality of interstitial regions. At least a portion of the plurality of interstitial regions may include at least one Group VIII metal disposed therein. The assembly may include at least one material positioned adjacent to the PCD table. For example, the at least one material may include phosphorous. In an embodiment, the assembly may include at least another material adjacent to the PCD table, such as the at least another material may differ from the at least one material (e.g., alloying material) in one or more of composition or concentration. The at least another material may include any of those materials disclosed above for the at least one alloying element.
In an embodiment, providing an assembly may include positioning at least one material adjacent to at least a portion of one or more of the upper surface or the at least one side surface. In an embodiment, the layer of least one material may be positioned adjacent to more than about 50% of the surface area of one or more of the upper surface or the at least one side surface.
The method may further include an act of subjecting the assembly to a heating condition (e.g., high-temperature condition, second stage heating condition, or higher than ambient temperature condition) effective to at least partially alloy the at least one Group VIII metal with the alloying element (e.g., phosphorous) to form an alloy. The alloy may exhibit a bulk modulus that is less than that of the at least one Group VIII alone. For example, suitable temperature process conditions may include any of the second stage heating conditions disclosed herein. Subjecting the assembly to the heating condition may include subjecting the assembly to high pressures, ambient pressure, or reduced pressure (e.g., vacuum), similar or identical to any of the foregoing pressure/temperature conditions disclosed herein including any HPHT process conditions disclosed herein.
The alloy so formed may include at least one intermediate compound of the at least one Group VIII metal and the phosphorous. The resulting PCD table may include a first region extending inwardly from the upper surface and the at least one side surface that includes the at least one intermediate compound therein and a second region extending inwardly from the interfacial surface that is substantially free of phosphorous. In an embodiment when another material is disposed in the assembly, subjecting the assembly to a heating condition (e.g., high-temperature process conditions, a higher than ambient temperature condition, or HPHT process conditions) may include forming another alloy including at least another intermediate compound comprising the at least another material and the group VIII metal. In some embodiments, the one or more portions of the PDC may be further processed to a final dimension after alloying the at least one material therein.
The method may further include an act of leaching at least a portion of the PCD table. Leaching can be carried out prior to forming the alloy. Leaching may be carried out after forming the alloy. Leaching can be carried out to depth from one or more surfaces of the PCD table. For example, the PCD table may be leached to a depth of at least about 50 μm, such as 50 μm to about the full thickness of the PCD table, about 100 μm to about 500 μm, or at least about 250 μm from one or more of the upper surface or at least one side surface. In an embodiment, leaching may be carried out after forming the alloy. In such embodiments, leaching may remove at least some of the alloy.
In some embodiments, the one or more portions of the PDC may be further processed (e.g., ground, lased, lapped, etc.) to a final dimension after alloying the at least one material therein. However, such processing can remove at least a portion of the PCD table containing the beneficial alloy.
The pre-shaped shaping medium 532 may include at least one layer/region or a plurality of layers/regions of at least one material 534 (e.g., alloying element) on a surface of the pre-shaped shaping medium 532 positioned adjacent to diamond powder in the assembly 530. The layer(s)/region(s) of at least one material 534 may be adhered or coated onto the pre-shaped shaping medium 532. The layer(s)/region(s) of at least one material 534 may be applied to the pre-shaped shaping medium 532 by one or more of pressing, painting, dip-coating, adhesive, impregnation, sputtering, or spraying. For example, a suitable binder may be applied to the pre-shaped shaping medium 532 followed by applying the at least one material 534 in powder form, which bonds to the pre-shaped shaping medium 532 via the binder. This application/binding process may be repeated multiple times until a desired number of layer(s)/regions of the powdered at least one material 534/alloying material is formed on the pre-shaped shaping medium 532. Optionally, the pre-shaped shaping medium 532 may be heated to vaporize and remove the binder from the pre-shaped shaping medium 532 (e.g., prior to incorporating the pre-shaped shaping medium 532 into the assembly 530). The thickness of each layer or the multiple layer(s)/regions of the at least one material 534 may be substantially uniform and at least about 10 nm thick, such as about 10 nm to about 100 μm, about 100 nm to about 300 μm, or at least about 1 μm thick. The layer(s)/region of at least one material 534 may include any of the alloying elements disclosed herein, such as boron and/or phosphorus.
The assembly 530 may further include one or more layers or regions of diamond powder 536 that abuts the layer(s) of at least one material 534 and underlying pre-shaped shaping medium 532, filling in or at least partially taking on the shape of the pre-shaped shaping medium 532. The diamond powder in the layer of diamond powder 536 may be similar or identical to any diamond powder disclosed herein, including but not limited to diamond particle size distributions, diamond particle sizes, or catalyst content. The assembly 530 may include a substrate 538 positioned adjacent to (e.g., below) the diamond powder 536. The substrate 538 may be similar or identical to any substrate disclosed herein. The assembly 530 may be placed in a refractory metal container 540 which may be placed in a pressure transmitting medium for HPHT processing.
The method 500 includes an act 520 of subjecting the assembly 530 to HPHT conditions effective to sinter the diamond particles together and alloy the at least one material (e.g., alloying element) with another material (e.g., Group VIII catalyst) that is mixed with the diamond powder and/or infiltrated into the diamond powder during HPHT processing. For example, the at least one material may alloy with the at least Group VIII metal that is infiltrated into the diamond powder from the substrate (e.g., boron and/or phosphorous alloying with cobalt provided from a cobalt-cemented tungsten carbide substrate). The HPHT conditions may include any of the HPHT conditions disclosed herein.
The resulting PDC 550 may include a PCD table 552 bonded to the substrate 538. The PCD table 552 may exhibit a surface geometry that is complementary to the pre-shaped shaping medium 532. For example, the PCD table 552 may exhibit a surface geometry having a chamfer 553 substantially matching the chamfer 533 of the pre-shaped shaping medium 532. Accordingly, the PCD table 552 may not need to be further processed to form a chamfer therein. The PCD table 552 may include one or more regions therein. For example, the PCD table 552 may include a first region 554 extending inward from one or more outer surfaces (e.g., the upper surface, chamfer, or lateral surface) of the PCD table 552. The first region 554 may exhibit a thickness or composition identical or similar to any thickness or composition of any first region disclosed herein. For example, the first region 554 may include at least one alloy therein formed from the at least one Group VIII metal and the at least one material 534 (e.g., alloying element). The at least one alloy may be composed similarly or identical to any alloy disclosed herein. The PCD table 552 may include a second region 556 extending inward from the interface with the substrate 538. The second region 556 may exhibit a thickness or composition identical or similar to any thickness or composition of a second region disclosed herein.
In some embodiments, the outer dimensions of the PDC may be finished to size after HPHT processing. The PDC may be processed (e.g., on a centerless grinder) to remove peripheral portions thereof. However, it may remain desirable to leave one or more portions of the PCD table (e.g., cutting surface including one or more of the upper surface, lateral surface, or chamfer) in substantially the as-sintered condition or a condition requiring only minimal processing. As shown in
The PDCs disclosed herein (e.g., PDC 100 of
Thus, the embodiments of PDCs disclosed herein may be used in any apparatus or structure in which at least one conventional PDC is typically used. In one embodiment, a rotor and a stator, assembled to form a thrust-bearing apparatus, may each include one or more PDCs (e.g., PDC 100 of
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, shall be opened ended and have the same meaning as the word “comprising” and variants thereof (e.g., “comprise” and “comprises”).
This application is a divisional of U.S. application Ser. No. 14/677,875 filed on 2 Apr. 2015, which is a continuation-in-part of U.S. application Ser. No. 14/086,283 filed on 21 Nov. 2013 (now U.S. Pat. No. 9,765,572) and a continuation-in-part of U.S. application Ser. No. 14/304,631 filed on 13 Jun. 2014 (now U.S. Pat. No. 9,945,186). The disclosure of each of the foregoing applications is incorporated, in its entirety, by this reference.
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| Number | Date | Country | |
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| Parent | 14677875 | Apr 2015 | US |
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| Number | Date | Country | |
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| Parent | 14086283 | Nov 2013 | US |
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