WO2011031912A2 - Polycrystalline compacts having material disposed in interstitial spaces therein, cutting elements and earth-boring tools including such compacts, and methods of forming such compacts - Google Patents
Polycrystalline compacts having material disposed in interstitial spaces therein, cutting elements and earth-boring tools including such compacts, and methods of forming such compacts Download PDFInfo
- Publication number
- WO2011031912A2 WO2011031912A2 PCT/US2010/048343 US2010048343W WO2011031912A2 WO 2011031912 A2 WO2011031912 A2 WO 2011031912A2 US 2010048343 W US2010048343 W US 2010048343W WO 2011031912 A2 WO2011031912 A2 WO 2011031912A2
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- WIPO (PCT)
- Prior art keywords
- grains
- particles
- polycrystalline
- hard material
- metal
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 343
- 238000000034 method Methods 0.000 title claims abstract description 81
- 238000005520 cutting process Methods 0.000 title claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 149
- 229910052751 metal Inorganic materials 0.000 claims abstract description 93
- 239000002184 metal Substances 0.000 claims abstract description 93
- 238000000576 coating method Methods 0.000 claims abstract description 74
- 239000011248 coating agent Substances 0.000 claims abstract description 64
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 30
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 150000004767 nitrides Chemical class 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 229910003460 diamond Inorganic materials 0.000 claims description 116
- 239000010432 diamond Substances 0.000 claims description 116
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 48
- 229910052799 carbon Inorganic materials 0.000 claims description 46
- 239000003054 catalyst Substances 0.000 claims description 44
- 239000003153 chemical reaction reagent Substances 0.000 claims description 26
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 3
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 19
- 239000002105 nanoparticle Substances 0.000 description 78
- 239000013078 crystal Substances 0.000 description 19
- 238000005755 formation reaction Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000002386 leaching Methods 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 229910052582 BN Inorganic materials 0.000 description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 6
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 6
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 5
- 229910003472 fullerene Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000000231 atomic layer deposition Methods 0.000 description 4
- 150000001722 carbon compounds Chemical class 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000009527 percussion Methods 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005118 spray pyrolysis Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- 229910003468 tantalcarbide Inorganic materials 0.000 description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 2
- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- YOKBFUOPNPIXQC-UHFFFAOYSA-N anti-tetramantane Chemical compound C1C(CC2C3C45)CC6C2CC52CC5CC7C2C6C13CC7C4C5 YOKBFUOPNPIXQC-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- AMFOXYRZVYMNIR-UHFFFAOYSA-N ctk0i0750 Chemical compound C12CC(C3)CC(C45)C1CC1C4CC4CC1C2C53C4 AMFOXYRZVYMNIR-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
- B24D3/04—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic
- B24D3/06—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic metallic or mixture of metals with ceramic materials, e.g. hard metals, "cermets", cements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
- B24D3/04—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic
- B24D3/06—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic metallic or mixture of metals with ceramic materials, e.g. hard metals, "cermets", cements
- B24D3/10—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic metallic or mixture of metals with ceramic materials, e.g. hard metals, "cermets", cements for porous or cellular structure, e.g. for use with diamonds as abrasives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D99/00—Subject matter not provided for in other groups of this subclass
- B24D99/005—Segments of abrasive wheels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/06—Stabilisation of hydrogen cyanide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B10/00—Drill bits
- E21B10/46—Drill bits characterised by wear resisting parts, e.g. diamond inserts
- E21B10/54—Drill bits characterised by wear resisting parts, e.g. diamond inserts the bit being of the rotary drag type, e.g. fork-type bits
- E21B10/55—Drill bits characterised by wear resisting parts, e.g. diamond inserts the bit being of the rotary drag type, e.g. fork-type bits with preformed cutting elements
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B10/00—Drill bits
- E21B10/46—Drill bits characterised by wear resisting parts, e.g. diamond inserts
- E21B10/56—Button-type inserts
- E21B10/567—Button-type inserts with preformed cutting elements mounted on a distinct support, e.g. polycrystalline inserts
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
- C04B2235/427—Diamond
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/782—Grain size distributions
- C04B2235/783—Bimodal, multi-modal or multi-fractional
Definitions
- the present invention relates generally to polycrystalline compacts, which may be used, for example, as cutting elements for earth-boring tools, and to methods of forming such polycrystalline compacts, cutting elements, and earth-boring tools.
- Earth-boring tools for forming wellbores in subterranean earth formations generally include a plurality of cutting elements secured to a body.
- fixed-cutter earth-boring rotary drill bits also referred to as "drag bits”
- drag bits include a plurality of cutting elements that are fixedly attached to a bit body of the drill bit.
- 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.
- earth-boring tools typically include a bit body to which cutting elements are attached.
- the cutting elements used in such earth-boring tools often include polycrystalline diamond compacts (often referred to as "PDC”), which act as cutting faces of a polycrystalline diamond material.
- Polycrystalline diamond material is material that includes interbonded grains or crystals of diamond material. In other words, polycrystalline diamond 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.
- Polycrystalline diamond compact cutting elements are typically formed by sintering and bonding together relatively small diamond grains 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 a layer ⁇ e.g., a compact or "table") of polycrystalline diamond material on a cutting element substrate.
- a catalyst e.g., cobalt, iron, nickel, or alloys and mixtures thereof
- HTHP high temperature/high pressure
- the cutting element substrate may comprise a cermet material ⁇ i.e., a ceramic-metal composite material) such as, for example, cobalt-cemented tungsten carbide.
- the cobalt (or other catalyst material) in the cutting element substrate may be swept into the diamond grains during sintering and serve as the catalyst material for forming the inter-granular diamond-to-diamond bonds, and the resulting diamond table, from the diamond grains.
- powdered catalyst material may be mixed with the diamond grains prior to sintering the grains together in a HTHP process.
- catalyst material may remain in interstitial spaces between the grains of diamond in the resulting polycrystalline diamond compact.
- the presence of the catalyst material in the diamond table may contribute to thermal damage in the diamond table when the cutting element is heated during use, due to friction at the contact point between the cutting element and the formation.
- Polycrystalline diamond compact cutting elements in which the catalyst material remains in the polycrystalline diamond compact are generally thermally stable up to a temperature of about seven hundred and fifty degrees Celsius (750°C), although internal stress within the cutting element may begin to develop at temperatures exceeding about three hundred and fifty degrees Celsius (350°C).
- This internal stress is at least partially due to differences in the rates of thermal expansion between the diamond table and the cutting element substrate to which it is bonded. This differential in thermal expansion rates may result in relatively large compressive and tensile stresses at the interface between the diamond table and the substrate, and may cause the diamond table to delaminate from the substrate.
- some of the diamond crystals within the polycrystalline diamond compact may react with the catalyst material causing the diamond crystals to undergo a chemical breakdown or back-conversion to another allotrope of carbon or another carbon-based material.
- the diamond crystals may graphitize at the diamond crystal boundaries, which may substantially weaken the diamond table.
- some of the diamond crystals may be converted to carbon monoxide and carbon dioxide.
- thermally stable polycrystalline diamond compacts which are also known as thermally stable products, or "TSPs" have been developed.
- TSPs thermally stable products
- Such a thermally stable polycrystalline diamond compact may be formed by leaching the catalyst material (e.g., cobalt) out from interstitial spaces between the interbonded diamond crystals in the diamond table using, for example, an acid or combination of acids (e.g., aqua regia). All of the catalyst material may be removed from the diamond table, or catalyst material may be removed from only a portion thereof.
- Thermally stable polycrystalline diamond compacts in which substantially all catalyst material has been leached out from the diamond table have been reported to be thermally stable up to temperatures of about twelve hundred degrees Celsius (1 ,200°C). It has also been reported, however, that such fully leached diamond tables are relatively more brittle and vulnerable to shear, compressive, and tensile stresses than are non-leached diamond tables. In addition, it is difficult to secure a completely leached diamond table to a supporting substrate. In an effort to provide cutting elements having polycrystalline diamond compacts that are more thermally stable relative to non-leached polycrystalline diamond compacts, but that are also relatively less brittle and vulnerable to shear,
- cutting elements have been provided that include a diamond table in which the catalyst material has been leached from a portion or portions of the diamond table. For example, it is known to leach catalyst material from the cutting face, from the side of the diamond table, or both, to a desired depth within the diamond table, but without leaching all of the catalyst material out from the diamond table.
- the present invention includes polycrystalline compacts that comprise a plurality of grains of hard material having an average grain size of about five hundred nanometers (500 nm) or less.
- the plurality of grains of hard material are interspersed and interbonded to form a polycrystalline hard material.
- the polycrystalline hard material has an interstitial material disposed in at least some interstitial spaces between the plurality of grains of hard material.
- the interstitial material comprises at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
- the present invention includes polycrystalline compacts comprising a first plurality of grains of hard material having a first average grain size and at least a second plurality of grains of hard material having a second average grains size.
- the second average grain size of the at least a second plurality of grains is at least about one hundred and fifty (150) times larger than the first average grain size of the first plurality of grains.
- the first plurality of grains and the at least a second plurality of grains are interspersed and interbonded to form a polycrystalline hard material.
- the polycrystalline hard material may further include an interstitial material disposed in at least some interstitial spaces between the first plurality of grains and the at least a second plurality of grains of the polycrystalline hard material.
- the interstitial material comprises at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
- the interbonded grains comprise a first plurality of grains having a first average grain size and at least a second plurality of grains having a second average grain size at least one hundred and fifty (150) times larger than the first average grain size of the first plurality of grains.
- the interbonded grains comprise a first plurality of grains having a first average grain size and at least a second plurality of grains having a second average grain size at least one
- polycrystalline compact may further include an interstitial material disposed in at least some interstitial spaces between the interbonded grains of the polycrystalline hard material.
- the interstitial material comprises at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
- Additional embodiments of the present invention include earth-boring drill bits that have a bit body and a plurality of cutting elements attached to the bit body.
- At least one cutting element of the plurality comprises a hard polycrystalline material that includes a first plurality of grains having a first average particle size, and at least a second plurality of grains having a second average particle size at least one hundred and fifty (150) times larger than the first average particle size of the first plurality of grains.
- the first plurality of grains and the second plurality of grains are interspersed and interbonded to form the polycrystalline hard material.
- An interstitial material may be disposed in at least some interstitial spaces between the interspersed and interbonded grains of the polycrystalline hard material.
- the interstitial material comprises at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
- Additional embodiments of the present invention include methods of making a polycrystalline compact.
- the methods include at least partially coating each nanoparticle of a plurality of nanoparticles of hard material with a coating material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
- the nanoparticles are sintered to form a polycrystalline hard material comprising a plurality of grains formed from the plurality of nanoparticles.
- the plurality of grains are interspersed and interbonded to form the polycrystalline hard material
- Still further embodiments of the present invention include methods of making a polycrystalline compact.
- the methods include at least partially coating each particle of a first plurality of particles having a first average particle size with a coating material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
- the coated first plurality of particles are dispersed among at least a second plurality of particles having a second average particle size that is larger than the first average particle size of the first plurality of particles, and the first plurality of particles and the at least a second plurality of particles are sintered to form a polycrystalline hard material that includes a first plurality of grains formed from the first plurality of particles and a second plurality of grains formed from the second plurality of particles.
- the first plurality of grains and the second plurality of grains are interspersed and interbonded to form the polycrystalline hard material.
- the first average particle size of the first plurality of particles and the second average particle size of the second plurality of particles may be selected to cause the second plurality of grains to have a second average grain size at least about one hundred and fifty (150) times larger than a first average grain size of the first plurality of grains.
- FIG. 1 A is a partial cut-away perspective view illustrating an embodiment of a cutting element comprising a polycrystalline compact of the present invention
- FIG. IB is a simplified drawing showing how a microstructure of the polycrystalline compact of FIG. 1 A may appear under magnification, and illustrates interbonded and interspersed larger and smaller grains of hard material;
- FIG. 2 is a simplified drawing of a coated nanoparticle that may be used to form a polycrystalline compact like that of FIGS. 1A and IB in accordance with some embodiments of methods of the present invention;
- FIG. 3 is a simplified drawing of another coated nanoparticle that may be used to form a polycrystalline compact like that of FIGS. 1 A and IB in accordance with some embodiments of methods of the present invention.
- FIG. 4 is a perspective view of an embodiment of a fixed-cutter earth-boring rotary drill bit that includes a plurality of polycrystalline compacts like that shown in FIGS. 1A and IB.
- drill bit means and includes any type of bit or tool used for drilling during the formation or enlargement of a wellbore and includes, for example, rotary drill bits, percussion bits, core bits, eccentric bits, bicenter bits, reamers, mills, drag bits, roller cone bits, hybrid bits and other drilling bits and tools known in the art.
- fullerene means and includes cage-like hollow molecules comprising a plurality of carbon atoms bonded together in a polyhedral structure.
- Fullerenes may include, for example, between about twenty (20) and about one hundred (100) carbon atoms.
- C 60 is a fullerene having sixty (60) carbon atoms, and is a relatively common, commercially available fullerene.
- Other fullerenes include, for example, C 30 , C 32 , C 34 , C 38 , C4 40 , C 42 , C 44 , C 46 , C 48 , C 50 , and C 52 and C 70 .
- nanoparticle means and includes any particle having an average particle diameter of about 500 nm or less.
- carbon compound means and includes any material comprising two or more chemical elements, one of which is carbon, that together form a generally crystalline substance having a defined chemical composition. Carbon compounds do not include pure allotropes (e.g., diamond, graphite, amorphous carbon, buckminsterfuUerenes, etc.), which comprise only the element of carbon. Carbides are carbon compounds.
- 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.
- 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 material or materials used to form the polycrystalline material.
- pressure e.g., compaction
- inter-granular bond means and includes any direct atomic bond (e.g., covalent, metallic, etc.) between atoms in adjacent grains of material.
- the term "diamondoid” means and includes the carbon cage molecule known as adamantane (Ci 0 Hi 6 ), which is the smallest unit cage structure of the diamond crystal lattice, as well as variants of adamantane (e.g., molecules in which other atoms (e.g., N, O, Si, or S) are substituted for carbon atoms in the molecule) and carbon cage polymantane molecules including between two (2) and about twenty (20) adamantane cages per molecule (e.g., diamantane, triamantane, tetramantane, pentamantane, hexamantane, heptamantane, etc.).
- adamantane e.g., molecules in which other atoms (e.g., N, O, Si, or S) are substituted for carbon atoms in the molecule
- carbon cage polymantane molecules including between two (2) and about twenty (20) a
- catalyst material refers to any material that is capable of substantially catalyzing the formation of inter-granular bonds between grains of hard material during an HTHP process.
- catalyst materials for diamond include cobalt, iron, nickel, other elements from Group VIIIA of the Periodic Table of the Elements, and alloys thereof.
- non-catalytic metal refers to any metal or metal alloy that is not a catalyst material.
- hard material means and includes any material having a Knoop hardness value of about 3,000 g f /mm 2 (29,420 MPa) or more.
- Hard materials include, for example, diamond and cubic boron nitride.
- FIG. 1 A is a simplified, partially cut-away perspective view of an
- element 10 comprises a polycrystalline compact in the form of a layer of hard polycrystalline material 12, also known in the art as a polycrystalline table, that is provided on (e.g., formed on or attached to) a supporting substrate 16 with an interface 14 therebetween.
- a polycrystalline table also known in the art as a polycrystalline table
- the cutting element 10 in the embodiment depicted in FIG. 1 A is cylindrical or disc- shaped, in other embodiments, the cutting element 10 may have any desirable shape, such as a dome, cone, chisel, etc.
- the polycrystalline material 12 comprises
- the cutting element 10 may be referred to as a polycrystalline diamond compact (PDC) cutting element.
- the polycrystalline material 12 may comprise another hard material such as, for example, polycrystalline cubic boron nitride.
- FIG. IB is an enlarged view illustrating how a microstructure of the polycrystalline material 12 of the cutting element 10 may appear under
- the polycrystalline material 12 includes at least some grains of hard material that have an average grain size of about five-hundred nanometers (500 nm) or less (e.g., between about one nanometer (1 nm) and about one-hundred and fifty nanometers (150)).
- at least some grains of hard material in the microstructure of the polycrystalline material 12 may be nanoparticles.
- the grains of the polycrystalline material 12 may have a multi-modal (e.g., bi-modal, tri-modal, etc.) grain size distribution.
- the layer of hard polycrystalline material 12 includes a first plurality of grains 18 of hard material having a first average grain size, and at least a second plurality of grains 20 of hard material having a second average grain size that differs from the first average grain size of the first plurality of grains 18.
- the second plurality of grains 20 may be larger than the first plurality of grains 18.
- the average grain size of the larger grains 20 may be at least about one hundred and fifty (150) times greater than the average grain size of the smaller grains 18.
- the average grain size of the larger grains 20 may be at least about five hundred (500) times greater than the average grain size of the smaller grains 18.
- the average grain size of the larger grains 20 may be at least about seven hundred fifty (750) times greater than the average grain size of the smaller grains 18.
- the smaller grains 18 and the larger grains 20 may be interspersed and interbonded to form the layer of hard polycrystalline material 12.
- the smaller grains 18 and the larger grains 20 may be mixed together and bonded directly to one another by inter-granular diamond-to-diamond bonds 26 (represented by dashed lines in FIG. IB).
- the average grain size of grains within a microstructure may be determined by measuring grains of the microstructure under magnification.
- a scanning electron microscope (SEM), a field emission scanning electron microscope (FESEM), or a transmission electron microscope (TEM) may be used to view or image a surface of a polycrystalline material 12 (e.g., a polished and etched surface of the polycrystalline material 12).
- SEM scanning electron microscope
- FESEM field emission scanning electron microscope
- TEM transmission electron microscope
- Commercially available vision systems are often used with such microscopy systems, and these vision systems are capable of measuring the average grain size of grains within a microstructure.
- the average grain size of the smaller grains 18 may be between about one nanometer (1 nm) and about one hundred and fifty nanometers (150 nm).
- the average grain size of the larger grains 20 may be between about five microns (5 ⁇ ) and about forty microns (40 ⁇ ).
- the ratio of the average grain size of the larger grains 20 to the average grain size of the smaller grains 18 may be between about 33 : 1 and about 40,000: 1.
- the large difference in the average grain size between the smaller grains 18 and the larger grains 20 may result in smaller interstitial spaces 22 or voids
- any material present within the interstitial spaces 22 may also be more evenly distributed throughout the microstructure of the polycrystalline material 12 within the relatively smaller interstitial spaces 22 therein.
- the number of smaller grains 18 per unit volume of the polycrystalline material 12 may be higher than the number of larger grains 20 per unit volume of the polycrystalline material 12.
- the smaller grains 18 may comprise between about one-half of one percent (0.5%) and about thirty percent (30%) by volume of the polycrystalline material 12. More specifically, the smaller grains 18 may comprise between about one-half of one percent (0.5%) and about ten percent (10%) by volume of the polycrystalline material 12, or even between about one-half of one percent (0.5%) and about five percent (5%) by volume of the polycrystalline material 12.
- the remainder of the volume of the polycrystalline material 12 may be substantially comprised by the larger grains 20.
- a relatively small percentage of the remainder of the volume of the polycrystalline material 12 (e.g., less than about ten percent (10%)) may comprise interstitial spaces 22 between the smaller grains 18 and the larger grains 20, which spaces may be at least partially filled with a interstitial material 34 and a catalyst material 24, as described below.
- the interstitial spaces 22 interspersed throughout the microstructure of the polycrystalline material 12 between the smaller grains 18 and the larger grains 20 may have an interstitial material 34 disposed therein that originates from a coating (not shown in FIG. IB) disposed on the smaller grains 18 prior to fabrication of the polycrystalline material 12.
- the coating material that is originally present on the smaller grains 18 may ultimately reside in the interstitial spaces 22 after fabrication of the polycrystalline material 12.
- the interstitial material 34 may comprise at least one of a boride, a carbide, a nitride, a metal carbonate (e.g., calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, etc.), a metal bicarbonate, and a non-catalytic metal.
- the interstitial material 34 may comprise a metal carbide such as silicon carbide, titanium carbide, tungsten carbide, tantalum carbide, etc. in some embodiments.
- the interstitial material 34 may comprise a carbon nitride material or a carbon boride material.
- the polycrystalline material 12 may also include a catalyst material 24 disposed in interstitial spaces 22 between the smaller grains 18 and the larger grains 20 of the polycrystalline hard material.
- the catalyst material 24 may comprise a catalyst material 24 capable of (and used to) catalyze the formation of the inter-granular bonds 26 between the grains of the smaller grains 18 and the larger grains 20 of the polycrystalline material 12.
- the interstitial spaces 22 between the smaller grains 18 and the larger grains 20 in some or all regions of the polycrystalline material 12 may be at least substantially free of such a catalyst material 24.
- the interstitial spaces 22 may comprise voids filled with gas ⁇ e.g., air), in addition to any interstitial material 34 present therein.
- the catalyst material 24 may comprise a Group VIIIA element (e.g., iron, cobalt, or nickel) or an alloy thereof, and the catalyst material 24 may comprise between about one half of one percent (0.1%) and about ten percent (10%) by volume of the hard polycrystalline material 12.
- a Group VIIIA element e.g., iron, cobalt, or nickel
- the catalyst material 24 may comprise between about one half of one percent (0.1%) and about ten percent (10%) by volume of the hard polycrystalline material 12.
- the catalyst material 24 may comprise a carbonate material such as, for example, a carbonate of one or more of magnesium, calcium, strontium, and barium. Carbonates may also be used to catalyze the formation of polycrystalline diamond. Accordingly, the interstitial material 34 may also act as a catalyst material 24 in some embodiments of the invention.
- the layer of hard polycrystalline material 12 of the cutting element 10 may be formed using a high temperature/high pressure (HTHP) process.
- HTHP high temperature/high pressure
- the polycrystalline material 12 may be formed on a supporting substrate 16 (as shown in FIG. 1A) of cemented tungsten carbide or another suitable substrate material in a conventional HTHP process of the type described, by way of non-limiting example, in U.S. Patent No. 3,745,623 to Wentorf et al. (issued July 17, 1973), or may be formed as a freestanding polycrystalline material 12 (i.e., without the supporting substrate 16) in a similar conventional HTHP process as described, by way of non-limiting example, in U.S.
- the catalyst material 24 may be supplied from the supporting substrate 16 during an HTHP process used to form the polycrystalline material 12.
- the substrate 16 may comprise a cobalt-cemented tungsten carbide material.
- the cobalt of the cobalt-cemented tungsten carbide may serve as the catalyst material 24 during the HTHP process.
- a particulate mixture comprising larger particles of hard material, as well as coated, smaller nanoparticles of hard material (as described in detail below) may be subjected to elevated temperatures (e.g., temperatures greater than about one thousand degrees Celsius (1 ,000°C)) and elevated pressures (e.g., pressures greater than about five gigapascals (5.0 GPa)) to form inter-granular bonds 26 between the particles, thereby forming the larger grains 20 and the smaller grains 18 of the polycrystalline material 12 from the larger and smaller particles, respectively.
- elevated temperatures e.g., temperatures greater than about one thousand degrees Celsius (1 ,000°C)
- elevated pressures e.g., pressures greater than about five gigapascals (5.0 GPa)
- the particulate mixture may be subjected to a pressure greater than about six gigapascals (6.0 GPa) and a temperature greater than about one thousand five hundred degrees Celsius (1 ,500°C) in the HTHP process.
- the time at the elevated temperatures and pressures may be relatively short when compared to conventional HTHP processes to prevent the atoms of the smaller grains 18 from diffusing to, and being incorporated into, the larger grains 20.
- the particulate mixture may be subjected to a pressure greater than about six gigapascals (6.0 GPa) and a temperature greater than about one thousand and five hundred degrees Celsius (1,500°C) for less than about two minutes (2.0 min) during the HTHP process.
- the particulate mixture may be subjected to a pressure greater than about seven point seven gigapascals (7.7 GPa) and a temperature greater than about two thousand degrees Celsius (2,000°C).
- a carbonate catalyst material 24 e.g., a carbonate of one or more of magnesium, calcium, strontium, and barium
- the particulate mixture may comprise particles for forming the larger grains 20 previously described herein.
- the particulate mixture may also comprise particles of catalyst material 24.
- the particulate mixture may comprise a powder-like substance. In other embodiments, however, the particulate mixture may be carried by (e.g. , on or in) another material, such as a paper or film, which may be subjected to the HTHP process.
- the particulate mixture may also comprise smaller particles (e.g. , nanoparticles) for forming the smaller grains 18 previously described herein, which may be provided as coated nanoparticles 28 like that shown in the simplified illustration of FIG. 2.
- the coated nanoparticles 28 may comprise nanoparticles 30 of a hard material that are at least partially coated with a coating material 37 prior to being subjected to the HTHP process.
- the nanoparticles 30 may comprise, for example, diamond or diamondoid nanocrystals.
- the coating material 37 corresponds to, and may ultimately form, the interstitial material 34 previously described with reference to FIG. IB.
- the coating material 37 may comprise at least one of a boride, a carbide, a nitride, a metal carbonate (e.g., calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, etc.), a metal bicarbonate, and a non-catalytic metal.
- the coating material 37 may comprise a metal carbide such as silicon carbide, titanium carbide, tungsten carbide, tantalum carbide, etc. in some embodiments.
- the coating material 37 may comprise a carbon nitride material or a carbon boride material.
- Nitrogen and boron are elements known to diffuse readily in certain hard materials, such as diamond.
- elements of the coating material 37 may migrate to, and diffuse within, the smaller grains 18, the larger grains 20, or to both the smaller grains 18 and the larger grains 20 during an HTHP process used to form the polycrystalline material 12, without adversely affecting the physical properties of the polycrystalline material 12 in any significant manner.
- processes such as liquid sol-gel, flame spray pyrolysis, chemical vapor deposition (CVD), physical vapor deposition (PVD) (e.g., sputtering), and atomic layer deposition (ALD), may be used to provide the coating material 37 on the nanoparticles 30.
- CVD chemical vapor deposition
- PVD physical vapor deposition
- ALD atomic layer deposition
- Other techniques that may be used to provide the coating material 37 on the nanoparticles 30 include colloidal coating processes, plasma coating processes, microwave plasma coating processes, physical admixture processes, van der Waals coating processes, and electrophoretic coating processes.
- coating material 37 may be provided on the nanoparticles 30 in a fluidized bed reactor.
- nanoparticles 30 of diamond or diamondoid crystals typically comprise a relatively thin carbon-based, non-diamond outer layer or shell.
- a shell may comprise, for example, amorphous carbon, and is often referred to in the art as a "carbon onion.”
- carbon onion such a carbon-based, non-diamond outer layer or shell on the
- nanoparticles 30 may be at least partially replaced with a coating material 37 by, for example, reacting the carbon of the carbon-based, non-diamond outer layer or shell with one or more additional elements to form the coating material 37, or by removing the non-diamond outer layer or shell on the nanoparticles 30 and subsequently depositing the coating material 37 over the nanoparticles 30.
- coated nanoparticles 28 like that shown in FIG. 2 may be formed by nitriding (reacting nitrogen with) or boriding (reacting boron with) the relatively thin carbon-based, non-diamond outer layer or shell of nanoparticles 30 of diamond or diamondoid crystals to form a carbon nitride or a carbon boride coating material 37.
- coated nanoparticles 28 like that shown in FIG. 2 may be formed by depositing a non-catalytic metal over nanoparticles 30 of diamond or diamondoid crystals to form a non-catalytic metal coating material 37.
- coated nanoparticles 28 like that shown in FIG. 2 may be formed by at least partially coating the nanoparticles 30 with a reagent material capable of reacting with carbon to form the coating material 37, and reacting the reagent material with carbon atoms in or on each of the nanoparticles 30 to form the coating material 37, as described below with reference to FIG. 3.
- FIG. 3 illustrates a multi-layer coated nanoparticle 28' that includes a diamond nanoparticle 30, a non-diamond carbon shell 32 at least partially coating the diamond nanoparticle 30, and a layer of reagent material 35 at least partially coating the carbon shell 32.
- the carbon shell 32 and the reagent material 35 are depicted in FIG. 3 as completely encapsulating the nanoparticle 30, in other embodiments, they may only partially coat the nanoparticle 30.
- the diamond nanoparticle 30 may comprise a single diamond crystal or a cluster of diamond crystals.
- the reagent material 35 comprises a material capable of reacting with carbon atoms of the carbon shell 32 to form the coating material 37 (FIG. 2).
- the reagent material 35 may comprise, for example, at least one of nitrogen, a nitrogen compound, a carbonate-forming metal, a metal carbonate, a bicarbonate-forming metal, a metal bicarbonate, a carbide- forming metal, and a metal carbide.
- the carbon shell 32 may react with the reagent material 35 to form the coating material 37.
- at least a portion of the non-diamond carbon shell 32 may undergo a change in atomic structure during or prior to sintering. Carbon atoms in the non-diamond carbon shell 32 may diffuse to and enter the diamond crystal structure of the diamond nanoparticle 30 ⁇ i.e., contribute to grain growth of the diamond nanoparticle 30). Some atoms of the non-diamond carbon shell 32 may also be incorporated into the larger grains 20, or may nucleate and form additional, new smaller grains 18.
- the coated nanoparticles 28 and the diamond nanoparticles 30 may have an average particle size selected to cause the average grain size of the smaller grains 18 (formed from the diamond nanoparticles 30) to be between about one nanometer (1 nm) and about one hundred and fifty nanometers (150 nm).
- the particulate mixture used to form the polycrystalline material 12 may further comprise particles for forming the larger grains 20.
- the average particle size of these relatively larger particles may be selected to cause the average grain size of the larger grains 20 (formed from the relatively larger particles) to be between about five microns (5 ⁇ ) and about forty microns (40 ⁇ ).
- the average thickness of the carbon shell 32 and the resulting coating material 37 layer may be selected dependent upon the particular material compositions of these layers, as well as on the desired final composition and microstructure of the polycrystalline material 12.
- Multi-layer coated nanoparticles 28' like that shown in FIG. 3 may be formed by providing (e.g., depositing, growing, forming, etc.) reagent material 35 on the nanoparticles 30, which may have a naturally occurring non-diamond carbon shell 32 thereon.
- the process used to provide the reagent material 35 on the nanoparticles 30 will depend upon the particular composition of the reagent material 35 to be provided on the nanoparticles 30.
- processes such as liquid sol-gel, flame spray pyrolysis, chemical vapor deposition (CVD), physical vapor deposition (PVD) (e.g., sputtering), and atomic layer deposition (ALD), may be used to provide the reagent material 35 on the nanoparticles 30.
- CVD chemical vapor deposition
- PVD physical vapor deposition
- ALD atomic layer deposition
- Other techniques that may be used to provide the reagent material 35 on the nanoparticles 30 include colloidal coating processes, plasma coating processes, microwave plasma coating processes, physical admixture processes, van der Waals coating processes, and electrophoretic coating processes.
- the non-diamond carbon shell 32 and the reagent material 35 may be provided on the nanoparticles 30 in a fluidized bed reactor.
- the non-diamond carbon shell 32 may be formed on the nanoparticle 30 by, for example, heating the nanoparticle 30 to an elevated temperature and causing an outer region of the diamond nanoparticle 30 to decompose from diamond to a carbon-based, non-diamond material such as amorphous carbon.
- the reagent material 35 may react with the
- multi-layer coated nanoparticles 28' like that of FIG. 3 may be transient in nature, such that they are not formed or stable for any significant period of time, and coated
- nanoparticles 28 like that shown in FIG. 2 may simply form as the reagent material 35 is deposited over the non-diamond carbon shell 32. In other words,
- the reagent material 35 may not react with the non-diamond carbon shell 32 to form the coating material 37 without further processing.
- multi-layer coated nanoparticles 28' like that of FIG. 3 may form upon deposition of the reagent material 35, and the multi-layer coated nanoparticles 28' may subsequently be subjected to one or more of a selected temperature, pressure, and atmosphere to cause the reagent material 35 and the non-diamond carbon shell 32 to react with one another to form the coating material 37.
- the reagent material 35 and the non-diamond carbon shell 32 may react with one another during an HTHP process used to form the polycrystalline material 12 from a particulate mixture including the multi-layer coated
- nanoparticles 28' are nanoparticles 28'.
- the coated nanoparticle 28 of FIG. 2 may comprise a nanoparticle 30 and a coating material that is not reactive with the nanoparticle 30.
- the coating material may comprise a material that will not react with the nanoparticle 30 or the non-diamond carbon shell 32, but that will thermally stabilize the coating material
- nanoparticle 30 during an HTHP process used to form a polycrystalline material 12, as discussed in further detail below.
- a particulate mixture that includes relatively smaller particles (e.g., coated particles like the coated particle 28 of FIG. 2 or multi-layer coated particles 28' like that of FIG. 3) for forming the smaller grains 18, relatively larger particles for forming the larger grains 20, and, optionally, a catalyst material 24 (for catalyzing the formation of inter-granular bonds 26 between the smaller grains 18 and the larger grains 20) may be subjected to an HTHP process to form a polycrystalline material 12. After the HTHP process, catalyst material 24 (e.g., cobalt) may be disposed in at least some of the interstitial spaces 22 between the interbonded smaller grains 18 and larger grains 20.
- relatively smaller particles e.g., coated particles like the coated particle 28 of FIG. 2 or multi-layer coated particles 28' like that of FIG. 3
- a catalyst material 24 for catalyzing the formation of inter-granular bonds 26 between the smaller grains 18 and the larger grains 20
- the coating material 37 on the smaller particles may be displaced or diffuse during the HTHP process to allow the formation of inter-granular bonds 26 between the nanoparticles 30 and the relatively larger particles of hard material.
- the coating material 37 may also be disposed in at least some of the interstitial spaces 22 between the smaller grains 18 and the larger grains 20 of the polycrystalline material 12, and, thus, may be characterized as the interstitial material 34 previously described herein with reference to FIG. IB.
- the catalyst material 24, the interstitial material 34, or both the catalyst material 24 and the interstitial material 34 may be removed from the polycrystalline material 12 after the HTHP process, as is known in the art.
- a leaching process may be used to remove the catalyst material 24 and/or the interstitial material 34 from the interstitial spaces 22 between the interbonded smaller grains 18 and larger grains 20 of the polycrystalline material 12.
- the polycrystalline material 12 may be leached using a leaching agent and process such as those described more fully in, for example, U.S. Patent No. 5,127,923 to Bunting et al. (issued July 7, 1992), and U.S. Patent No. 4,224,380 to Bovenkerk et al.
- aqua regia a mixture of concentrated nitric acid (HN0 3 ) and concentrated hydrochloric acid (HC1)
- HN0 3 concentrated nitric acid
- HC1 concentrated hydrochloric acid
- HF boiling hydrofluoric acid
- One particularly suitable leaching agent is hydrochloric acid (HC1) at a temperature of above one hundred and ten degrees Celsius (110°C), which may be provided in contact with the polycrystalline material 12 for a period of about two (2) hours to about sixty (60) hours, depending upon the size of the body comprising the polycrystalline material 12.
- the interstitial spaces 22 between the interbonded smaller grains 18 and larger grains 20 within the polycrystalline material 12 may be at least substantially free of catalyst material 24 used to catalyze formation of inter-granular bonds 26 between the grains in the polycrystalline material 12, and may be at least substantially free of interstitial material 34. Furthermore, only a portion of the polycrystalline material 12 may be subjected to the leaching process, or the entire body of the polycrystalline
- material 12 may be subjected to the leaching process.
- Embodiments of cutting elements 10 of the present invention that include a polycrystalline compact comprising polycrystalline material 12 formed as previously described herein, such as the cutting element 10 illustrated in FIG. 1 A, may be formed and secured to an earth-boring tool such as, for example, a rotary drill bit, a percussion bit, a coring bit, an eccentric bit, a reamer tool, a milling tool, etc., for use in forming wellbores in subterranean formations.
- FIG. 4 illustrates a fixed cutter type earth-boring rotary drill bit 36 that includes a plurality of cutting elements 10, each of which includes a polycrystalline compact comprising polycrystalline material 12 as previously described herein.
- the rotary drill bit 36 includes a bit body 38, and the cutting elements 10, which include polycrystalline compacts 12, are bonded to the bit body 38.
- the cutting elements 10 may be brazed (or otherwise secured) within pockets formed in the outer surface of the bit body 38.
- Polycrystalline hard materials having a relatively large difference in average grain size between a first plurality of relatively smaller grains and a second plurality of relatively larger grains may exhibit improved thermal stability, improved mechanical durability, or both improved thermal stability and improved mechanical durability relative to previously known polycrystalline hard materials.
- By surrounding the relatively larger grains with the relatively smaller grains less catalyst material may be disposed in interstitial spaces between the grains in the ultimate polycrystalline hard material, which may improve one or both of the thermal stability and the mechanical durability of the polycrystalline hard material.
- nanoparticles are relatively reactive compared to larger particles due, at least in part, to the high surface energy of the nanoparticles
- nanoparticles of a hard material used to form the relatively smaller grains of hard material in the polycrystalline hard material may be coated, as described hereinabove, to improve the stability (e.g., thermal stability) of the nanoparticles during an HTHP process used to form the polycrystalline hard material.
- Embodiment 1 A polycrystalline compact, comprising:
- a plurality of grains of hard material having an average grain size of about five hundred nanometers (500 nm) or less, the plurality of grains of hard material being interspersed and interbonded to form a polycrystalline hard material, wherein the polycrystalline hard material further comprises an interstitial material disposed in at least some interstitial spaces between the plurality of grains of hard material, the interstitial material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
- Embodiment 2 The polycrystalline compact of Embodiment 1 , wherein the plurality of grains of hard material comprises grains of diamond.
- Embodiment 3 The polycrystalline compact of Embodiment 2, wherein the interstitial material comprises at least one of carbon nitride, carbon boride, a metal carbonate, and a metal bicarbonate, and a metal carbide.
- Embodiment 4 The polycrystalline compact of Embodiment 3, further comprising a catalyst material disposed in at least some interstitial spaces between the first plurality of grains and the at least a second plurality of grains of the polycrystalline hard material.
- Embodiment 5 A polycrystalline compact, comprising:
- first plurality of grains of hard material having a first average grain size
- second plurality of grains of hard material having a second average grains size that is at least about one hundred and fifty (150) times larger than the first average grain size of the first plurality of grains, the first plurality of grains and the at least a second plurality of grains being interspersed and interbonded to form a polycrystalline hard material
- the polycrystalline hard material further comprises an interstitial material disposed in at least some interstitial spaces between the first plurality of grains and the at least a second plurality of grains of the polycrystalline hard material, the interstitial material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
- Embodiment 6 The polycrystalline compact of Embodiment 5, wherein the second average grains size of the at least a second plurality of grains is between two hundred and fifty (250) times and seven hundred and fifty (750) times larger than the first average grain size of the first plurality of grains.
- Embodiment 7 The polycrystalline compact of Embodiment 5, wherein the first average grain size is between about one nanometer (1 nm) and about one hundred and fifty nanometers (150 nm), and the second average grain size is between about five microns (5 ⁇ ) and about forty microns (40 ⁇ ).
- Embodiment 8 The polycrystalline compact of Embodiment 5, wherein the first plurality of grains comprises between about one-half of one percent (0.5%) and about thirty percent (30%) by volume of the polycrystalline hard material.
- Embodiment 9 The polycrystalline compact of Embodiment 5, wherein each of the first plurality of grains and the at least a second plurality of grains comprises grains of diamond.
- Embodiment 10 The polycrystalline compact of Embodiment 5, wherein each of the first plurality of grains and the at least a second plurality of grains comprises grains of cubic boron nitride.
- Embodiment 11 The polycrystalline compact of Embodiment 5, wherein the interstitial material comprises at least one of carbon nitride, carbon boride, a metal carbonate, a metal bicarbonate, and a metal carbide.
- Embodiment 12 The polycrystalline compact of Embodiment 5, further comprising a catalyst material disposed in at least some interstitial spaces between the first plurality of grains and the at least a second plurality of grains of the polycrystalline hard material.
- Embodiment 13 A cutting element, comprising:
- the polycrystalline compact comprising: a plurality of interspersed and interbonded grains of hard material forming a polycrystalline hard material, wherein the grains of the plurality of interspersed and interbonded grains comprise a first plurality of grains having a first average grain size and at least a second plurality of grains having a second average grain size at least one hundred and fifty (150) times larger than the first average grain size; and an interstitial material disposed in at least some interstitial spaces between the interbonded grains of the polycrystalline hard material, the interstitial material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
- Embodiment 14 The cutting element of Embodiment 13, wherein the second average grain size of the at least a second plurality of grains is between two hundred and fifty (250) times and seven hundred and fifty (750) times larger than the first average grain size of the first plurality of grains.
- Embodiment 15 The cutting element of Embodiment 13, wherein each of the first plurality of grains and the at least a second plurality of grains comprises grains of diamond.
- Embodiment 16 The cutting element of Embodiment 13, wherein each of the first plurality of grains and the at least a second plurality of grains comprises grains of cubic boron nitride.
- Embodiment 17 The polycrystalline compact of Embodiment 13, wherein the interstitial material comprises at least one of carbon nitride, carbon boride, a metal carbonate, a metal bicarbonate, and a metal carbide.
- Embodiment 18 An earth-boring drill bit, comprising:
- a plurality of cutting elements attached to the bit body, at least one cutting element of the plurality of cutting elements comprising a hard polycrystalline material including:
- a first plurality of grains having a first average grain size at least a second plurality of grains having a second average grain size at least one hundred and fifty (150) times larger than the first average grain size of the first plurality of grains, the first plurality of grains and the second plurality of grains being interspersed and interbonded with one another to form a polycrystalline hard material; and an interstitial material disposed in at least some interstitial spaces between the interspersed and interbonded grains of the polycrystalline hard material, the interstitial material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal .
- Embodiment 19 The earth-boring drill bit of Embodiment 18, wherein the second average grain size of the at least a second plurality of grains is between two hundred and fifty (250) times and seven hundred and fifty (750) times larger than the first average grain size of the first plurality of grains.
- Embodiment 20 The earth-boring drill bit of Embodiment 18, wherein each of the first plurality of grains and the at least a second plurality of grains comprises grains of diamond.
- Embodiment 21 The earth-boring drill bit of Embodiment 18, wherein each of the first plurality of grains and the at least a second plurality of grains comprises grains of cubic boron nitride.
- Embodiment 22 The earth-boring drill bit of Embodiment 18, wherein the interstitial material comprises at least one of carbon nitride, carbon boride, a metal carbonate, a metal bicarbonate, and a metal carbide.
- Embodiment 23 A method of forming a polycrystalline compact, comprising:
- each nanoparticle of a plurality of nanoparticles of hard material with a coating material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal; and
- Embodiment 24 The method of Embodiment 23, further comprising selecting each nanoparticle of the plurality of nanoparticles to comprise diamond.
- Embodiment 25 The method of Embodiment 24, further comprising selecting the coating material to comprise at least one of carbon nitride, carbon boride, a metal carbonate, a metal bicarbonate, and a metal carbide.
- Embodiment 26 The method of Embodiment 25, wherein at least partially coating each nanoparticle of the plurality of nanoparticles comprises:
- each nanoparticle of the plurality of nanoparticles at least partially coating each nanoparticle of the plurality of nanoparticles with a reagent material capable of reacting with carbon to form the coating material;
- Embodiment 27 A method of forming a polycrystalline compact, comprising:
- each particle of a first plurality of particles of hard material having a first average particle size with a coating material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal;
- second average particle size of the second plurality of particles to cause the second plurality of grains to have a second average grain size at least about one hundred and fifty (150) times larger than a first average grain size of the first plurality of grains.
- Embodiment 28 The method of Embodiment 27, further comprising selecting the first average particle size of the first plurality of particles and the second average particle size of the second plurality of particles to cause the second average grain size of the second plurality of grains to be between two hundred and fifty (250) times and seven hundred and fifty (750) times larger than the first average grain size of the first plurality of grains.
- Embodiment 29 The method of Embodiment 28, wherein at least partially coating each particle of the first plurality of particles of hard material with the coating material comprises at least partially coating each particle of the first plurality of particles of hard material with at least one of nitrogen, a nitrogen compound, a carbonate-forming metal, a metal carbonate, a bicarbonate-forming metal, a metal bicarbonate, a carbide- forming metal, and a metal carbide.
- Embodiment 30 The method of Embodiment 27, further comprising selecting each particle of the first plurality of particles and each particle of the at least a second plurality of particles to comprise diamond.
- Embodiment 31 The method of Embodiment 30, wherein at least partially coating each particle of the first plurality of particles of hard material with the coating material comprises:
- each particle of the first plurality of particles at least partially coating each particle of the first plurality of particles with a reagent material capable of reacting with carbon to form the coating material; and reacting the reagent material with carbon atoms in or on each particle of the first plurality of particles to form the coating material.
- Embodiment 32 The method of Embodiment 27, further comprising selecting each particle of the first plurality of particles and each particle of the at least a second plurality of particles to comprise cubic boron nitride.
- Embodiment 33 The method of Embodiment 27, wherein sintering the first plurality of particles and the at least a second plurality of particles to form the polycrystalline hard material comprises subjecting the first plurality of particles and the at least a second plurality of particles to a high temperature/high pressure (HTHP) process.
- HTHP high temperature/high pressure
- Embodiment 34 The method of Embodiment 33, wherein sintering the first plurality of particles and the at least a second plurality of particles to form the polycrystalline hard material comprises subjecting the first plurality of particles and the at least a second plurality of particles to a pressure greater than about five gigapascals (5.0 GPa) and a temperature greater than about 1,000 °C.
- sintering the first plurality of particles and the at least a second plurality of particles to form the polycrystalline hard material comprises subjecting the first plurality of particles and the at least a second plurality of particles to a pressure greater than about five gigapascals (5.0 GPa) and a temperature greater than about 1,000 °C.
- Embodiment 35 The method of Embodiment 34, wherein subjecting the first plurality of particles and the at least a second plurality of particles to a pressure greater than about five gigapascals (5.0 GPa) and a temperature greater than about 1 ,000 °C comprises subjecting the first plurality of particles and the at least a second plurality of particles to a pressure greater than about six and one half gigapascals (6.5 GPa) and a temperature greater than about 1,500 °C for less than about two minutes (2.0 min).
- 5.0 GPa gigapascals
- a temperature greater than about 1 ,000 °C comprises subjecting the first plurality of particles and the at least a second plurality of particles to a pressure greater than about six and one half gigapascals (6.5 GPa) and a temperature greater than about 1,500 °C for less than about two minutes (2.0 min).
- Embodiment 36 The method of Embodiment 27, further comprising:
- Embodiment 37 The method of Embodiment 27, further comprising forming the first plurality of grains to comprise between about one-half of one percent (0.5%) and about thirty percent (30%) by volume of the polycrystalline hard material.
- Embodiment 38 The method of Embodiment 27, further comprising catalyzing the formation of inter-granular bonds between the grains of the first plurality of grains and the second plurality of grains.
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Abstract
Polycrystalline compacts include smaller and larger hard grains that are interbonded to form a polycrystalline hard material. The larger grains may be at least about 150 times larger than the smaller grains. An interstitial material comprising one or more of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal may be disposed between the grains. The compacts may be used as cutting elements for earth-boring tools such as drill bits, and may be disposed on a substrate. Methods of making polycrystalline compacts include coating smaller hard particles with a coating material, mixing the smaller particles with larger hard particles, and sintering the mixture to form a polycrystalline hard material including interbonded smaller and larger grains. The sizes of the smaller and larger particles may be selected to cause the larger grains to be at least about 150 times larger than the smaller grains.
Description
POLYCRYSTALLINE COMPACTS HAVING MATERIAL DISPOSED IN INTERSTITIAL SPACES THEREIN, CUTTING ELEMENTS AND EARTH-BORING TOOLS INCLUDING SUCH COMPACTS, AND
METHODS OF FORMING SUCH COMPACTS
PRIORITY CLAIM
This application claims the benefit of the filing date of United States Patent Application Serial No. 12/558,184, filed September 11, 2009, for "Polycrystalline Compacts Having Material Disposed in Interstitial Spaces Therein, Cutting
Elements, and Earth-Boring Tools Including Such Compacts, and Methods of Forming Such Compacts."
TECHNICAL FIELD
The present invention relates generally to polycrystalline compacts, which may be used, for example, as cutting elements for earth-boring tools, and to methods of forming such polycrystalline compacts, cutting elements, and earth-boring tools.
BACKGROUND
Earth-boring tools for forming wellbores in subterranean earth formations generally include a plurality of cutting elements secured to a body. For example, fixed-cutter earth-boring rotary drill bits (also referred to as "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. In other words, earth-boring tools typically include a bit body to which cutting elements are attached.
The cutting elements used in such earth-boring tools often include polycrystalline diamond compacts (often referred to as "PDC"), which act as cutting faces of a polycrystalline diamond material. Polycrystalline diamond material is material that includes interbonded grains or crystals of diamond material. In other
words, polycrystalline diamond 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.
Polycrystalline diamond compact cutting elements are typically formed by sintering and bonding together relatively small diamond grains 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 a layer {e.g., a compact or "table") of polycrystalline diamond material on a cutting element substrate. These processes are often referred to as high temperature/high pressure (HTHP) processes. The cutting element substrate may comprise a cermet material {i.e., a ceramic-metal composite material) such as, for example, cobalt-cemented tungsten carbide. In such instances, the cobalt (or other catalyst material) in the cutting element substrate may be swept into the diamond grains during sintering and serve as the catalyst material for forming the inter-granular diamond-to-diamond bonds, and the resulting diamond table, from the diamond grains. In other methods, powdered catalyst material may be mixed with the diamond grains prior to sintering the grains together in a HTHP process.
Upon formation of a diamond table using a HTHP process, catalyst material may remain in interstitial spaces between the grains of diamond in the resulting polycrystalline diamond compact. The presence of the catalyst material in the diamond table may contribute to thermal damage in the diamond table when the cutting element is heated during use, due to friction at the contact point between the cutting element and the formation.
Polycrystalline diamond compact cutting elements in which the catalyst material remains in the polycrystalline diamond compact are generally thermally stable up to a temperature of about seven hundred and fifty degrees Celsius (750°C), although internal stress within the cutting element may begin to develop at temperatures exceeding about three hundred and fifty degrees Celsius (350°C). This internal stress is at least partially due to differences in the rates of thermal expansion between the diamond table and the cutting element substrate to which it is bonded. This differential in thermal expansion rates may result in relatively large
compressive and tensile stresses at the interface between the diamond table and the substrate, and may cause the diamond table to delaminate from the substrate. At temperatures of about seven hundred and fifty degrees Celsius (750°C) and above, stresses within the diamond table itself may increase significantly due to differences in the coefficients of thermal expansion of the diamond material and the catalyst material within the diamond table. For example, cobalt thermally expands significantly faster than diamond, which may cause cracks to form and propagate within the diamond table, eventually leading to deterioration of the diamond table and ineffectiveness of the cutting element.
Furthermore, at temperatures at or above about seven hundred and fifty degrees Celsius (750°C), some of the diamond crystals within the polycrystalline diamond compact may react with the catalyst material causing the diamond crystals to undergo a chemical breakdown or back-conversion to another allotrope of carbon or another carbon-based material. For example, the diamond crystals may graphitize at the diamond crystal boundaries, which may substantially weaken the diamond table. In addition, at extremely high temperatures, in addition to graphite, some of the diamond crystals may be converted to carbon monoxide and carbon dioxide.
In order to reduce the problems associated with differential rates of thermal expansion and chemical breakdown of the diamond crystals in polycrystalline diamond compact cutting elements, so-called "thermally stable" polycrystalline diamond compacts (which are also known as thermally stable products, or "TSPs") have been developed. Such a thermally stable polycrystalline diamond compact may be formed by leaching the catalyst material (e.g., cobalt) out from interstitial spaces between the interbonded diamond crystals in the diamond table using, for example, an acid or combination of acids (e.g., aqua regia). All of the catalyst material may be removed from the diamond table, or catalyst material may be removed from only a portion thereof. Thermally stable polycrystalline diamond compacts in which substantially all catalyst material has been leached out from the diamond table have been reported to be thermally stable up to temperatures of about twelve hundred degrees Celsius (1 ,200°C). It has also been reported, however, that such fully leached diamond tables are relatively more brittle and vulnerable to shear,
compressive, and tensile stresses than are non-leached diamond tables. In addition, it is difficult to secure a completely leached diamond table to a supporting substrate. In an effort to provide cutting elements having polycrystalline diamond compacts that are more thermally stable relative to non-leached polycrystalline diamond compacts, but that are also relatively less brittle and vulnerable to shear,
compressive, and tensile stresses relative to fully leached diamond tables, cutting elements have been provided that include a diamond table in which the catalyst material has been leached from a portion or portions of the diamond table. For example, it is known to leach catalyst material from the cutting face, from the side of the diamond table, or both, to a desired depth within the diamond table, but without leaching all of the catalyst material out from the diamond table.
DISCLOSURE
In some embodiments, the present invention includes polycrystalline compacts that comprise a plurality of grains of hard material having an average grain size of about five hundred nanometers (500 nm) or less. The plurality of grains of hard material are interspersed and interbonded to form a polycrystalline hard material. The polycrystalline hard material has an interstitial material disposed in at least some interstitial spaces between the plurality of grains of hard material. The interstitial material comprises at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
In additional embodiments, the present invention includes polycrystalline compacts comprising a first plurality of grains of hard material having a first average grain size and at least a second plurality of grains of hard material having a second average grains size. The second average grain size of the at least a second plurality of grains is at least about one hundred and fifty (150) times larger than the first average grain size of the first plurality of grains. The first plurality of grains and the at least a second plurality of grains are interspersed and interbonded to form a polycrystalline hard material. The polycrystalline hard material may further include an interstitial material disposed in at least some interstitial spaces between the first plurality of grains and the at least a second plurality of grains of the polycrystalline
hard material. The interstitial material comprises at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
Further embodiments of the present invention include cutting elements comprising a polycrystalline compact on a substrate. The polycrystalline compact comprises a plurality of interspersed and interbonded grains of hard material that form a polycrystalline hard material. The interbonded grains comprise a first plurality of grains having a first average grain size and at least a second plurality of grains having a second average grain size at least one hundred and fifty (150) times larger than the first average grain size of the first plurality of grains. The
polycrystalline compact may further include an interstitial material disposed in at least some interstitial spaces between the interbonded grains of the polycrystalline hard material. The interstitial material comprises at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
Additional embodiments of the present invention include earth-boring drill bits that have a bit body and a plurality of cutting elements attached to the bit body. At least one cutting element of the plurality comprises a hard polycrystalline material that includes a first plurality of grains having a first average particle size, and at least a second plurality of grains having a second average particle size at least one hundred and fifty (150) times larger than the first average particle size of the first plurality of grains. The first plurality of grains and the second plurality of grains are interspersed and interbonded to form the polycrystalline hard material. An interstitial material may be disposed in at least some interstitial spaces between the interspersed and interbonded grains of the polycrystalline hard material. The interstitial material comprises at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
Additional embodiments of the present invention include methods of making a polycrystalline compact. The methods include at least partially coating each nanoparticle of a plurality of nanoparticles of hard material with a coating material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal. The nanoparticles are sintered to form a polycrystalline hard material comprising a plurality of grains formed from the
plurality of nanoparticles. The plurality of grains are interspersed and interbonded to form the polycrystalline hard material
Still further embodiments of the present invention include methods of making a polycrystalline compact. The methods include at least partially coating each particle of a first plurality of particles having a first average particle size with a coating material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal. The coated first plurality of particles are dispersed among at least a second plurality of particles having a second average particle size that is larger than the first average particle size of the first plurality of particles, and the first plurality of particles and the at least a second plurality of particles are sintered to form a polycrystalline hard material that includes a first plurality of grains formed from the first plurality of particles and a second plurality of grains formed from the second plurality of particles. The first plurality of grains and the second plurality of grains are interspersed and interbonded to form the polycrystalline hard material. The first average particle size of the first plurality of particles and the second average particle size of the second plurality of particles may be selected to cause the second plurality of grains to have a second average grain size at least about one hundred and fifty (150) times larger than a first average grain size of the first plurality of grains.
BRIEF DESCRIPTION OF THE DRAWINGS
While the specification concludes with claims particularly pointing out and distinctly claiming what are regarded as embodiments of the present invention, various features and advantages of embodiments of the invention may be more readily ascertained from the following description of some embodiments of the invention when read in conjunction with the accompanying drawings, in which:
FIG. 1 A is a partial cut-away perspective view illustrating an embodiment of a cutting element comprising a polycrystalline compact of the present invention;
FIG. IB is a simplified drawing showing how a microstructure of the polycrystalline compact of FIG. 1 A may appear under magnification, and illustrates interbonded and interspersed larger and smaller grains of hard material;
FIG. 2 is a simplified drawing of a coated nanoparticle that may be used to form a polycrystalline compact like that of FIGS. 1A and IB in accordance with some embodiments of methods of the present invention;
FIG. 3 is a simplified drawing of another coated nanoparticle that may be used to form a polycrystalline compact like that of FIGS. 1 A and IB in accordance with some embodiments of methods of the present invention; and
FIG. 4 is a perspective view of an embodiment of a fixed-cutter earth-boring rotary drill bit that includes a plurality of polycrystalline compacts like that shown in FIGS. 1A and IB.
MODE(S) FOR CARRYING OUT THE INVENTION The illustrations presented herein are not actual views of any particular polycrystalline compact, microstructure of a polycrystalline compact, particle, cutting element, or drill bit, and are not drawn to scale, but are merely idealized representations employed to describe the present invention. Additionally, elements common between figures may retain the same numerical designation.
As used herein, the term "drill bit" means and includes any type of bit or tool used for drilling during the formation or enlargement of a wellbore and includes, for example, rotary drill bits, percussion bits, core bits, eccentric bits, bicenter bits, reamers, mills, drag bits, roller cone bits, hybrid bits and other drilling bits and tools known in the art.
As used herein, the term "fullerene" means and includes cage-like hollow molecules comprising a plurality of carbon atoms bonded together in a polyhedral structure. Fullerenes may include, for example, between about twenty (20) and about one hundred (100) carbon atoms. For example, C60 is a fullerene having sixty (60) carbon atoms, and is a relatively common, commercially available fullerene. Other fullerenes include, for example, C30, C32, C34, C38, C440, C42, C44, C46, C48, C50, and C52 and C70.
As used herein, the term "nanoparticle" means and includes any particle having an average particle diameter of about 500 nm or less.
As used herein, the term "carbon compound" means and includes any material comprising two or more chemical elements, one of which is carbon, that together form a generally crystalline substance having a defined chemical composition. Carbon compounds do not include pure allotropes (e.g., diamond, graphite, amorphous carbon, buckminsterfuUerenes, etc.), which comprise only the element of carbon. Carbides are carbon compounds.
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 "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 material or materials used to form 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 material.
As used herein, the term "diamondoid" means and includes the carbon cage molecule known as adamantane (Ci0Hi6), which is the smallest unit cage structure of the diamond crystal lattice, as well as variants of adamantane (e.g., molecules in which other atoms (e.g., N, O, Si, or S) are substituted for carbon atoms in the molecule) and carbon cage polymantane molecules including between two (2) and about twenty (20) adamantane cages per molecule (e.g., diamantane, triamantane, tetramantane, pentamantane, hexamantane, heptamantane, etc.).
As used herein, the term "catalyst material" refers to any material that is capable of substantially catalyzing the formation of inter-granular bonds between grains of hard material during an HTHP process. For example, catalyst materials for diamond include cobalt, iron, nickel, other elements from Group VIIIA of the Periodic Table of the Elements, and alloys thereof.
As used herein, the term "non-catalytic metal" refers to any metal or metal alloy that is not a catalyst material.
As used herein, the term "hard material" means and includes any material having a Knoop hardness value of about 3,000 gf/mm2 (29,420 MPa) or more. Hard materials include, for example, diamond and cubic boron nitride.
FIG. 1 A is a simplified, partially cut-away perspective view of an
embodiment of a cutting element 10 of the present invention. The cutting
element 10 comprises a polycrystalline compact in the form of a layer of hard polycrystalline material 12, also known in the art as a polycrystalline table, that is provided on (e.g., formed on or attached to) a supporting substrate 16 with an interface 14 therebetween. Though the cutting element 10 in the embodiment depicted in FIG. 1 A is cylindrical or disc- shaped, in other embodiments, the cutting element 10 may have any desirable shape, such as a dome, cone, chisel, etc.
In some embodiments, the polycrystalline material 12 comprises
polycrystalline diamond. In such embodiments, the cutting element 10 may be referred to as a polycrystalline diamond compact (PDC) cutting element. In other embodiments, the polycrystalline material 12 may comprise another hard material such as, for example, polycrystalline cubic boron nitride.
FIG. IB is an enlarged view illustrating how a microstructure of the polycrystalline material 12 of the cutting element 10 may appear under
magnification. As discussed in further detail below, the polycrystalline material 12 includes at least some grains of hard material that have an average grain size of about five-hundred nanometers (500 nm) or less (e.g., between about one nanometer (1 nm) and about one-hundred and fifty nanometers (150)). Thus, at least some grains of hard material in the microstructure of the polycrystalline material 12 may be nanoparticles.
As shown in FIG. IB, the grains of the polycrystalline material 12 may have a multi-modal (e.g., bi-modal, tri-modal, etc.) grain size distribution. In other words, the layer of hard polycrystalline material 12 includes a first plurality of grains 18 of hard material having a first average grain size, and at least a second plurality of
grains 20 of hard material having a second average grain size that differs from the first average grain size of the first plurality of grains 18.
For example, the second plurality of grains 20 may be larger than the first plurality of grains 18. For example, the average grain size of the larger grains 20 may be at least about one hundred and fifty (150) times greater than the average grain size of the smaller grains 18. In additional embodiments, the average grain size of the larger grains 20 may be at least about five hundred (500) times greater than the average grain size of the smaller grains 18. In yet further embodiments, the average grain size of the larger grains 20 may be at least about seven hundred fifty (750) times greater than the average grain size of the smaller grains 18. The smaller grains 18 and the larger grains 20 may be interspersed and interbonded to form the layer of hard polycrystalline material 12. In other words, in embodiments in which the polycrystalline material 12 comprises polycrystalline diamond, the smaller grains 18 and the larger grains 20 may be mixed together and bonded directly to one another by inter-granular diamond-to-diamond bonds 26 (represented by dashed lines in FIG. IB).
As known in the art, the average grain size of grains within a microstructure may be determined by measuring grains of the microstructure under magnification. For example, a scanning electron microscope (SEM), a field emission scanning electron microscope (FESEM), or a transmission electron microscope (TEM) may be used to view or image a surface of a polycrystalline material 12 (e.g., a polished and etched surface of the polycrystalline material 12). Commercially available vision systems are often used with such microscopy systems, and these vision systems are capable of measuring the average grain size of grains within a microstructure.
By way of example and not limitation, in embodiments in which the average grain size of the smaller grains 18 is between about one nanometer (1 nm) and about one hundred and fifty nanometers (150 nm), the average grain size of the larger grains 20 may be between about five microns (5 μιη) and about forty microns (40 μηι). Thus, in some embodiments, the ratio of the average grain size of the larger grains 20 to the average grain size of the smaller grains 18 may be between about 33 : 1 and about 40,000: 1.
The large difference in the average grain size between the smaller grains 18 and the larger grains 20 may result in smaller interstitial spaces 22 or voids
(represented as shaded areas in FIG. I B) within the microstructure of the
polycrystalline material 12 (relative to conventional polycrystalline materials), and the total volume of the interstitial spaces 22 or voids may be more evenly distributed throughout the microstructure of the polycrystalline material 12. As a result, any material present within the interstitial spaces 22 (e.g. , a carbon compound or a catalyst material, as described below) may also be more evenly distributed throughout the microstructure of the polycrystalline material 12 within the relatively smaller interstitial spaces 22 therein.
In some embodiments, the number of smaller grains 18 per unit volume of the polycrystalline material 12 may be higher than the number of larger grains 20 per unit volume of the polycrystalline material 12.
The smaller grains 18 may comprise between about one-half of one percent (0.5%) and about thirty percent (30%) by volume of the polycrystalline material 12. More specifically, the smaller grains 18 may comprise between about one-half of one percent (0.5%) and about ten percent (10%) by volume of the polycrystalline material 12, or even between about one-half of one percent (0.5%) and about five percent (5%) by volume of the polycrystalline material 12. The remainder of the volume of the polycrystalline material 12 may be substantially comprised by the larger grains 20. A relatively small percentage of the remainder of the volume of the polycrystalline material 12 (e.g., less than about ten percent (10%)) may comprise interstitial spaces 22 between the smaller grains 18 and the larger grains 20, which spaces may be at least partially filled with a interstitial material 34 and a catalyst material 24, as described below.
The interstitial spaces 22 interspersed throughout the microstructure of the polycrystalline material 12 between the smaller grains 18 and the larger grains 20 may have an interstitial material 34 disposed therein that originates from a coating (not shown in FIG. IB) disposed on the smaller grains 18 prior to fabrication of the polycrystalline material 12. The coating material that is originally present on the smaller grains 18 may ultimately reside in the interstitial spaces 22 after fabrication
of the polycrystalline material 12. The interstitial material 34 may comprise at least one of a boride, a carbide, a nitride, a metal carbonate (e.g., calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, etc.), a metal bicarbonate, and a non-catalytic metal. For example, the interstitial material 34 may comprise a metal carbide such as silicon carbide, titanium carbide, tungsten carbide, tantalum carbide, etc. in some embodiments. In additional embodiments, the interstitial material 34 may comprise a carbon nitride material or a carbon boride material.
In some embodiments, the polycrystalline material 12 may also include a catalyst material 24 disposed in interstitial spaces 22 between the smaller grains 18 and the larger grains 20 of the polycrystalline hard material. The catalyst material 24 may comprise a catalyst material 24 capable of (and used to) catalyze the formation of the inter-granular bonds 26 between the grains of the smaller grains 18 and the larger grains 20 of the polycrystalline material 12. In other embodiments, however, the interstitial spaces 22 between the smaller grains 18 and the larger grains 20 in some or all regions of the polycrystalline material 12 may be at least substantially free of such a catalyst material 24. In such embodiments, the interstitial spaces 22 may comprise voids filled with gas {e.g., air), in addition to any interstitial material 34 present therein.
In embodiments in which the polycrystalline material 12 comprises polycrystalline diamond, the catalyst material 24 may comprise a Group VIIIA element (e.g., iron, cobalt, or nickel) or an alloy thereof, and the catalyst material 24 may comprise between about one half of one percent (0.1%) and about ten percent (10%) by volume of the hard polycrystalline material 12. In additional
embodiments, the catalyst material 24 may comprise a carbonate material such as, for example, a carbonate of one or more of magnesium, calcium, strontium, and barium. Carbonates may also be used to catalyze the formation of polycrystalline diamond. Accordingly, the interstitial material 34 may also act as a catalyst material 24 in some embodiments of the invention.
The layer of hard polycrystalline material 12 of the cutting element 10 may be formed using a high temperature/high pressure (HTHP) process. Such processes,
and systems for carrying out such processes, are generally known in the art. In some embodiments, the polycrystalline material 12 may be formed on a supporting substrate 16 (as shown in FIG. 1A) of cemented tungsten carbide or another suitable substrate material in a conventional HTHP process of the type described, by way of non-limiting example, in U.S. Patent No. 3,745,623 to Wentorf et al. (issued July 17, 1973), or may be formed as a freestanding polycrystalline material 12 (i.e., without the supporting substrate 16) in a similar conventional HTHP process as described, by way of non-limiting example, in U.S. Patent No. 5,127,923 Bunting et al. (issued July 7, 1992). In some embodiments, the catalyst material 24 may be supplied from the supporting substrate 16 during an HTHP process used to form the polycrystalline material 12. For example, the substrate 16 may comprise a cobalt-cemented tungsten carbide material. The cobalt of the cobalt-cemented tungsten carbide may serve as the catalyst material 24 during the HTHP process.
To form the polycrystalline material 12 in an HTHP process, a particulate mixture comprising larger particles of hard material, as well as coated, smaller nanoparticles of hard material (as described in detail below) may be subjected to elevated temperatures (e.g., temperatures greater than about one thousand degrees Celsius (1 ,000°C)) and elevated pressures (e.g., pressures greater than about five gigapascals (5.0 GPa)) to form inter-granular bonds 26 between the particles, thereby forming the larger grains 20 and the smaller grains 18 of the polycrystalline material 12 from the larger and smaller particles, respectively. In some
embodiments, the particulate mixture may be subjected to a pressure greater than about six gigapascals (6.0 GPa) and a temperature greater than about one thousand five hundred degrees Celsius (1 ,500°C) in the HTHP process.
The time at the elevated temperatures and pressures may be relatively short when compared to conventional HTHP processes to prevent the atoms of the smaller grains 18 from diffusing to, and being incorporated into, the larger grains 20. For example, in some embodiments, the particulate mixture may be subjected to a pressure greater than about six gigapascals (6.0 GPa) and a temperature greater than about one thousand and five hundred degrees Celsius (1,500°C) for less than about two minutes (2.0 min) during the HTHP process.
In embodiments in which a carbonate catalyst material 24 (e.g., a carbonate of one or more of magnesium, calcium, strontium, and barium) is used to catalyze the formation of polycrystalline diamond, the particulate mixture may be subjected to a pressure greater than about seven point seven gigapascals (7.7 GPa) and a temperature greater than about two thousand degrees Celsius (2,000°C).
The particulate mixture may comprise particles for forming the larger grains 20 previously described herein. The particulate mixture may also comprise particles of catalyst material 24. In some embodiments, the particulate mixture may comprise a powder-like substance. In other embodiments, however, the particulate mixture may be carried by (e.g. , on or in) another material, such as a paper or film, which may be subjected to the HTHP process.
The particulate mixture may also comprise smaller particles (e.g. , nanoparticles) for forming the smaller grains 18 previously described herein, which may be provided as coated nanoparticles 28 like that shown in the simplified illustration of FIG. 2. The coated nanoparticles 28 may comprise nanoparticles 30 of a hard material that are at least partially coated with a coating material 37 prior to being subjected to the HTHP process. In embodiments in which the polycrystalline material 12 includes polycrystalline diamond, the nanoparticles 30 may comprise, for example, diamond or diamondoid nanocrystals.
As previously mentioned, the coating material 37 corresponds to, and may ultimately form, the interstitial material 34 previously described with reference to FIG. IB. Thus, the coating material 37 may comprise at least one of a boride, a carbide, a nitride, a metal carbonate (e.g., calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, etc.), a metal bicarbonate, and a non-catalytic metal. For example, the coating material 37 may comprise a metal carbide such as silicon carbide, titanium carbide, tungsten carbide, tantalum carbide, etc. in some embodiments. In additional embodiments, the coating material 37 may comprise a carbon nitride material or a carbon boride material. Nitrogen and boron are elements known to diffuse readily in certain hard materials, such as diamond. Thus in some embodiments, elements of the coating material 37 may migrate to, and diffuse within, the smaller grains 18, the larger grains 20, or to both the smaller grains 18
and the larger grains 20 during an HTHP process used to form the polycrystalline material 12, without adversely affecting the physical properties of the polycrystalline material 12 in any significant manner.
By way of example and not limitation, processes such as liquid sol-gel, flame spray pyrolysis, chemical vapor deposition (CVD), physical vapor deposition (PVD) (e.g., sputtering), and atomic layer deposition (ALD), may be used to provide the coating material 37 on the nanoparticles 30. Other techniques that may be used to provide the coating material 37 on the nanoparticles 30 include colloidal coating processes, plasma coating processes, microwave plasma coating processes, physical admixture processes, van der Waals coating processes, and electrophoretic coating processes. In some embodiments, coating material 37 may be provided on the nanoparticles 30 in a fluidized bed reactor.
As known in the art, nanoparticles 30 of diamond or diamondoid crystals typically comprise a relatively thin carbon-based, non-diamond outer layer or shell. Such a shell may comprise, for example, amorphous carbon, and is often referred to in the art as a "carbon onion." In accordance with some embodiments of the present invention, such a carbon-based, non-diamond outer layer or shell on the
nanoparticles 30 may be at least partially replaced with a coating material 37 by, for example, reacting the carbon of the carbon-based, non-diamond outer layer or shell with one or more additional elements to form the coating material 37, or by removing the non-diamond outer layer or shell on the nanoparticles 30 and subsequently depositing the coating material 37 over the nanoparticles 30.
In some embodiments, coated nanoparticles 28 like that shown in FIG. 2 may be formed by nitriding (reacting nitrogen with) or boriding (reacting boron with) the relatively thin carbon-based, non-diamond outer layer or shell of nanoparticles 30 of diamond or diamondoid crystals to form a carbon nitride or a carbon boride coating material 37.
In further embodiments, coated nanoparticles 28 like that shown in FIG. 2 may be formed by depositing a non-catalytic metal over nanoparticles 30 of diamond or diamondoid crystals to form a non-catalytic metal coating material 37.
In additional embodiments, coated nanoparticles 28 like that shown in FIG. 2 may be formed by at least partially coating the nanoparticles 30 with a reagent material capable of reacting with carbon to form the coating material 37, and reacting the reagent material with carbon atoms in or on each of the nanoparticles 30 to form the coating material 37, as described below with reference to FIG. 3.
FIG. 3 illustrates a multi-layer coated nanoparticle 28' that includes a diamond nanoparticle 30, a non-diamond carbon shell 32 at least partially coating the diamond nanoparticle 30, and a layer of reagent material 35 at least partially coating the carbon shell 32. Thus, although the carbon shell 32 and the reagent material 35 are depicted in FIG. 3 as completely encapsulating the nanoparticle 30, in other embodiments, they may only partially coat the nanoparticle 30. The diamond nanoparticle 30 may comprise a single diamond crystal or a cluster of diamond crystals.
As previously mentioned, the reagent material 35 comprises a material capable of reacting with carbon atoms of the carbon shell 32 to form the coating material 37 (FIG. 2). By way of example and not limitation, the reagent material 35 may comprise, for example, at least one of nitrogen, a nitrogen compound, a carbonate-forming metal, a metal carbonate, a bicarbonate-forming metal, a metal bicarbonate, a carbide- forming metal, and a metal carbide.
The carbon shell 32 may react with the reagent material 35 to form the coating material 37. In some embodiments, at least a portion of the non-diamond carbon shell 32 may undergo a change in atomic structure during or prior to sintering. Carbon atoms in the non-diamond carbon shell 32 may diffuse to and enter the diamond crystal structure of the diamond nanoparticle 30 {i.e., contribute to grain growth of the diamond nanoparticle 30). Some atoms of the non-diamond carbon shell 32 may also be incorporated into the larger grains 20, or may nucleate and form additional, new smaller grains 18.
The coated nanoparticles 28 and the diamond nanoparticles 30 may have an average particle size selected to cause the average grain size of the smaller grains 18 (formed from the diamond nanoparticles 30) to be between about one nanometer (1 nm) and about one hundred and fifty nanometers (150 nm). Furthermore, as
previously mentioned, the particulate mixture used to form the polycrystalline material 12 may further comprise particles for forming the larger grains 20. The average particle size of these relatively larger particles may be selected to cause the average grain size of the larger grains 20 (formed from the relatively larger particles) to be between about five microns (5 μπι) and about forty microns (40 μιη). The average thickness of the carbon shell 32 and the resulting coating material 37 layer may be selected dependent upon the particular material compositions of these layers, as well as on the desired final composition and microstructure of the polycrystalline material 12.
Multi-layer coated nanoparticles 28' like that shown in FIG. 3 may be formed by providing (e.g., depositing, growing, forming, etc.) reagent material 35 on the nanoparticles 30, which may have a naturally occurring non-diamond carbon shell 32 thereon. The process used to provide the reagent material 35 on the nanoparticles 30 will depend upon the particular composition of the reagent material 35 to be provided on the nanoparticles 30. By way of example and not limitation, processes such as liquid sol-gel, flame spray pyrolysis, chemical vapor deposition (CVD), physical vapor deposition (PVD) (e.g., sputtering), and atomic layer deposition (ALD), may be used to provide the reagent material 35 on the nanoparticles 30. Other techniques that may be used to provide the reagent material 35 on the nanoparticles 30 include colloidal coating processes, plasma coating processes, microwave plasma coating processes, physical admixture processes, van der Waals coating processes, and electrophoretic coating processes. In some embodiments, the non-diamond carbon shell 32 and the reagent material 35 may be provided on the nanoparticles 30 in a fluidized bed reactor.
If the nanoparticle 30 does not have a naturally occurring non-diamond carbon shell 32 thereon, the non-diamond carbon shell 32 may be formed on the nanoparticle 30 by, for example, heating the nanoparticle 30 to an elevated temperature and causing an outer region of the diamond nanoparticle 30 to decompose from diamond to a carbon-based, non-diamond material such as amorphous carbon.
In some embodiments, the reagent material 35 may react with the
non-diamond carbon shell 32 to form the coating material 37 as the reagent material 35 is deposited on the carbon shell 32 without any need for further processing to initiate the reaction therebetween. In such embodiments, multi-layer coated nanoparticles 28' like that of FIG. 3 may be transient in nature, such that they are not formed or stable for any significant period of time, and coated
nanoparticles 28 like that shown in FIG. 2 may simply form as the reagent material 35 is deposited over the non-diamond carbon shell 32. In other
embodiments, however, the reagent material 35 may not react with the non-diamond carbon shell 32 to form the coating material 37 without further processing. In other words, multi-layer coated nanoparticles 28' like that of FIG. 3 may form upon deposition of the reagent material 35, and the multi-layer coated nanoparticles 28' may subsequently be subjected to one or more of a selected temperature, pressure, and atmosphere to cause the reagent material 35 and the non-diamond carbon shell 32 to react with one another to form the coating material 37. Furthermore, in some embodiments, the reagent material 35 and the non-diamond carbon shell 32 may react with one another during an HTHP process used to form the polycrystalline material 12 from a particulate mixture including the multi-layer coated
nanoparticles 28'.
In additional embodiments, the coated nanoparticle 28 of FIG. 2 may comprise a nanoparticle 30 and a coating material that is not reactive with the nanoparticle 30. For example, in embodiments in which the nanoparticle 30 comprises diamond and has an outer non-diamond carbon shell 32 (FIG. 3), the coating material may comprise a material that will not react with the nanoparticle 30 or the non-diamond carbon shell 32, but that will thermally stabilize the
nanoparticle 30 during an HTHP process used to form a polycrystalline material 12, as discussed in further detail below.
As previously mentioned, a particulate mixture that includes relatively smaller particles (e.g., coated particles like the coated particle 28 of FIG. 2 or multi-layer coated particles 28' like that of FIG. 3) for forming the smaller grains 18, relatively larger particles for forming the larger grains 20, and, optionally, a catalyst
material 24 (for catalyzing the formation of inter-granular bonds 26 between the smaller grains 18 and the larger grains 20) may be subjected to an HTHP process to form a polycrystalline material 12. After the HTHP process, catalyst material 24 (e.g., cobalt) may be disposed in at least some of the interstitial spaces 22 between the interbonded smaller grains 18 and larger grains 20. During the HTHP process, at least some of the coating material 37 on the smaller particles may be displaced or diffuse during the HTHP process to allow the formation of inter-granular bonds 26 between the nanoparticles 30 and the relatively larger particles of hard material. After the HTHP process, the coating material 37 may also be disposed in at least some of the interstitial spaces 22 between the smaller grains 18 and the larger grains 20 of the polycrystalline material 12, and, thus, may be characterized as the interstitial material 34 previously described herein with reference to FIG. IB.
Optionally, the catalyst material 24, the interstitial material 34, or both the catalyst material 24 and the interstitial material 34 may be removed from the polycrystalline material 12 after the HTHP process, as is known in the art. For example, a leaching process may be used to remove the catalyst material 24 and/or the interstitial material 34 from the interstitial spaces 22 between the interbonded smaller grains 18 and larger grains 20 of the polycrystalline material 12. By way of example and not limitation, the polycrystalline material 12 may be leached using a leaching agent and process such as those described more fully in, for example, U.S. Patent No. 5,127,923 to Bunting et al. (issued July 7, 1992), and U.S. Patent No. 4,224,380 to Bovenkerk et al. (issued September 23, 1980). Specifically, aqua regia (a mixture of concentrated nitric acid (HN03) and concentrated hydrochloric acid (HC1)) may be used to at least substantially remove catalyst material 24 and/or interstitial material 34 from the interstitial spaces 22. It is also known to use boiling hydrochloric acid (HC1) and boiling hydrofluoric acid (HF) as leaching agents. One particularly suitable leaching agent is hydrochloric acid (HC1) at a temperature of above one hundred and ten degrees Celsius (110°C), which may be provided in contact with the polycrystalline material 12 for a period of about two (2) hours to about sixty (60) hours, depending upon the size of the body comprising the polycrystalline material 12. After leaching the polycrystalline material 12, the
interstitial spaces 22 between the interbonded smaller grains 18 and larger grains 20 within the polycrystalline material 12 may be at least substantially free of catalyst material 24 used to catalyze formation of inter-granular bonds 26 between the grains in the polycrystalline material 12, and may be at least substantially free of interstitial material 34. Furthermore, only a portion of the polycrystalline material 12 may be subjected to the leaching process, or the entire body of the polycrystalline
material 12 may be subjected to the leaching process.
Embodiments of cutting elements 10 of the present invention that include a polycrystalline compact comprising polycrystalline material 12 formed as previously described herein, such as the cutting element 10 illustrated in FIG. 1 A, may be formed and secured to an earth-boring tool such as, for example, a rotary drill bit, a percussion bit, a coring bit, an eccentric bit, a reamer tool, a milling tool, etc., for use in forming wellbores in subterranean formations. As a non-limiting example, FIG. 4 illustrates a fixed cutter type earth-boring rotary drill bit 36 that includes a plurality of cutting elements 10, each of which includes a polycrystalline compact comprising polycrystalline material 12 as previously described herein. The rotary drill bit 36 includes a bit body 38, and the cutting elements 10, which include polycrystalline compacts 12, are bonded to the bit body 38. The cutting elements 10 may be brazed (or otherwise secured) within pockets formed in the outer surface of the bit body 38.
Polycrystalline hard materials having a relatively large difference in average grain size between a first plurality of relatively smaller grains and a second plurality of relatively larger grains, as described hereinabove, may exhibit improved thermal stability, improved mechanical durability, or both improved thermal stability and improved mechanical durability relative to previously known polycrystalline hard materials. By surrounding the relatively larger grains with the relatively smaller grains, less catalyst material may be disposed in interstitial spaces between the grains in the ultimate polycrystalline hard material, which may improve one or both of the thermal stability and the mechanical durability of the polycrystalline hard material. Furthermore, as nanoparticles are relatively reactive compared to larger particles due, at least in part, to the high surface energy of the nanoparticles, nanoparticles of a hard material used to form the relatively smaller grains of hard material in the
polycrystalline hard material may be coated, as described hereinabove, to improve the stability (e.g., thermal stability) of the nanoparticles during an HTHP process used to form the polycrystalline hard material.
Additional non-limiting embodiments of the invention are described below. Embodiment 1 : A polycrystalline compact, comprising:
a plurality of grains of hard material having an average grain size of about five hundred nanometers (500 nm) or less, the plurality of grains of hard material being interspersed and interbonded to form a polycrystalline hard material, wherein the polycrystalline hard material further comprises an interstitial material disposed in at least some interstitial spaces between the plurality of grains of hard material, the interstitial material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
Embodiment 2: The polycrystalline compact of Embodiment 1 , wherein the plurality of grains of hard material comprises grains of diamond.
Embodiment 3 : The polycrystalline compact of Embodiment 2, wherein the interstitial material comprises at least one of carbon nitride, carbon boride, a metal carbonate, and a metal bicarbonate, and a metal carbide.
Embodiment 4: The polycrystalline compact of Embodiment 3, further comprising a catalyst material disposed in at least some interstitial spaces between the first plurality of grains and the at least a second plurality of grains of the polycrystalline hard material.
Embodiment 5: A polycrystalline compact, comprising:
a first plurality of grains of hard material having a first average grain size; and at least a second plurality of grains of hard material having a second average grains size that is at least about one hundred and fifty (150) times larger than the first average grain size of the first plurality of grains, the first plurality of grains and the at least a second plurality of grains being interspersed and interbonded to form a polycrystalline hard material,
wherein the polycrystalline hard material further comprises an interstitial material disposed in at least some interstitial spaces between the first plurality of
grains and the at least a second plurality of grains of the polycrystalline hard material, the interstitial material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
Embodiment 6: The polycrystalline compact of Embodiment 5, wherein the second average grains size of the at least a second plurality of grains is between two hundred and fifty (250) times and seven hundred and fifty (750) times larger than the first average grain size of the first plurality of grains.
Embodiment 7: The polycrystalline compact of Embodiment 5, wherein the first average grain size is between about one nanometer (1 nm) and about one hundred and fifty nanometers (150 nm), and the second average grain size is between about five microns (5 μηι) and about forty microns (40 μιη).
Embodiment 8: The polycrystalline compact of Embodiment 5, wherein the first plurality of grains comprises between about one-half of one percent (0.5%) and about thirty percent (30%) by volume of the polycrystalline hard material.
Embodiment 9: The polycrystalline compact of Embodiment 5, wherein each of the first plurality of grains and the at least a second plurality of grains comprises grains of diamond.
Embodiment 10: The polycrystalline compact of Embodiment 5, wherein each of the first plurality of grains and the at least a second plurality of grains comprises grains of cubic boron nitride.
Embodiment 11 : The polycrystalline compact of Embodiment 5, wherein the interstitial material comprises at least one of carbon nitride, carbon boride, a metal carbonate, a metal bicarbonate, and a metal carbide.
Embodiment 12: The polycrystalline compact of Embodiment 5, further comprising a catalyst material disposed in at least some interstitial spaces between the first plurality of grains and the at least a second plurality of grains of the polycrystalline hard material.
Embodiment 13: A cutting element, comprising:
a substrate; and
a polycrystalline compact on the substrate, the polycrystalline compact comprising:
a plurality of interspersed and interbonded grains of hard material forming a polycrystalline hard material, wherein the grains of the plurality of interspersed and interbonded grains comprise a first plurality of grains having a first average grain size and at least a second plurality of grains having a second average grain size at least one hundred and fifty (150) times larger than the first average grain size; and an interstitial material disposed in at least some interstitial spaces between the interbonded grains of the polycrystalline hard material, the interstitial material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
Embodiment 14: The cutting element of Embodiment 13, wherein the second average grain size of the at least a second plurality of grains is between two hundred and fifty (250) times and seven hundred and fifty (750) times larger than the first average grain size of the first plurality of grains.
Embodiment 15: The cutting element of Embodiment 13, wherein each of the first plurality of grains and the at least a second plurality of grains comprises grains of diamond.
Embodiment 16: The cutting element of Embodiment 13, wherein each of the first plurality of grains and the at least a second plurality of grains comprises grains of cubic boron nitride.
Embodiment 17: The polycrystalline compact of Embodiment 13, wherein the interstitial material comprises at least one of carbon nitride, carbon boride, a metal carbonate, a metal bicarbonate, and a metal carbide.
Embodiment 18: An earth-boring drill bit, comprising:
a bit body; and
a plurality of cutting elements attached to the bit body, at least one cutting element of the plurality of cutting elements comprising a hard polycrystalline material including:
a first plurality of grains having a first average grain size;
at least a second plurality of grains having a second average grain size at least one hundred and fifty (150) times larger than the first average grain size of the first plurality of grains, the first plurality of grains and the second plurality of grains being interspersed and interbonded with one another to form a polycrystalline hard material; and an interstitial material disposed in at least some interstitial spaces between the interspersed and interbonded grains of the polycrystalline hard material, the interstitial material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal .
Embodiment 19: The earth-boring drill bit of Embodiment 18, wherein the second average grain size of the at least a second plurality of grains is between two hundred and fifty (250) times and seven hundred and fifty (750) times larger than the first average grain size of the first plurality of grains.
Embodiment 20: The earth-boring drill bit of Embodiment 18, wherein each of the first plurality of grains and the at least a second plurality of grains comprises grains of diamond.
Embodiment 21 : The earth-boring drill bit of Embodiment 18, wherein each of the first plurality of grains and the at least a second plurality of grains comprises grains of cubic boron nitride.
Embodiment 22: The earth-boring drill bit of Embodiment 18, wherein the interstitial material comprises at least one of carbon nitride, carbon boride, a metal carbonate, a metal bicarbonate, and a metal carbide.
Embodiment 23 : A method of forming a polycrystalline compact, comprising:
at least partially coating each nanoparticle of a plurality of nanoparticles of hard material with a coating material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal; and
sintering the plurality of nanoparticles to form a polycrystalline hard material
comprising a plurality of grains formed from the plurality of nanoparticles,
the plurality of grains being interspersed and interbonded to form the polycrystalline hard material.
Embodiment 24: The method of Embodiment 23, further comprising selecting each nanoparticle of the plurality of nanoparticles to comprise diamond.
Embodiment 25: The method of Embodiment 24, further comprising selecting the coating material to comprise at least one of carbon nitride, carbon boride, a metal carbonate, a metal bicarbonate, and a metal carbide.
Embodiment 26: The method of Embodiment 25, wherein at least partially coating each nanoparticle of the plurality of nanoparticles comprises:
at least partially coating each nanoparticle of the plurality of nanoparticles with a reagent material capable of reacting with carbon to form the coating material; and
reacting the reagent material with carbon atoms in or on each nanoparticle of the plurality of nanoparticles to form the coating material.
Embodiment 27: A method of forming a polycrystalline compact, comprising:
at least partially coating each particle of a first plurality of particles of hard material having a first average particle size with a coating material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal;
dispersing the first plurality of particles among at least a second plurality of particles of hard material having a second average particle size larger than the first average particle size of the first plurality of particles;
sintering the first plurality of particles and the at least a second plurality of particles to form a polycrystalline hard material comprising a first plurality of grains formed from the first plurality of particles and a second plurality of grains formed from the second plurality of particles, the first plurality of grains and the second plurality of grains being interspersed and interbonded to form the polycrystalline hard material; and
selecting the first average particle size of the first plurality of particles and the
second average particle size of the second plurality of particles to cause the
second plurality of grains to have a second average grain size at least about one hundred and fifty (150) times larger than a first average grain size of the first plurality of grains.
Embodiment 28: The method of Embodiment 27, further comprising selecting the first average particle size of the first plurality of particles and the second average particle size of the second plurality of particles to cause the second average grain size of the second plurality of grains to be between two hundred and fifty (250) times and seven hundred and fifty (750) times larger than the first average grain size of the first plurality of grains.
Embodiment 29: The method of Embodiment 28, wherein at least partially coating each particle of the first plurality of particles of hard material with the coating material comprises at least partially coating each particle of the first plurality of particles of hard material with at least one of nitrogen, a nitrogen compound, a carbonate-forming metal, a metal carbonate, a bicarbonate-forming metal, a metal bicarbonate, a carbide- forming metal, and a metal carbide.
Embodiment 30: The method of Embodiment 27, further comprising selecting each particle of the first plurality of particles and each particle of the at least a second plurality of particles to comprise diamond.
Embodiment 31 : The method of Embodiment 30, wherein at least partially coating each particle of the first plurality of particles of hard material with the coating material comprises:
at least partially coating each particle of the first plurality of particles with a reagent material capable of reacting with carbon to form the coating material; and reacting the reagent material with carbon atoms in or on each particle of the first plurality of particles to form the coating material.
Embodiment 32: The method of Embodiment 27, further comprising selecting each particle of the first plurality of particles and each particle of the at least a second plurality of particles to comprise cubic boron nitride.
Embodiment 33: The method of Embodiment 27, wherein sintering the first plurality of particles and the at least a second plurality of particles to form the polycrystalline hard material comprises subjecting the first plurality of particles and
the at least a second plurality of particles to a high temperature/high pressure (HTHP) process.
Embodiment 34: The method of Embodiment 33, wherein sintering the first plurality of particles and the at least a second plurality of particles to form the polycrystalline hard material comprises subjecting the first plurality of particles and the at least a second plurality of particles to a pressure greater than about five gigapascals (5.0 GPa) and a temperature greater than about 1,000 °C.
Embodiment 35: The method of Embodiment 34, wherein subjecting the first plurality of particles and the at least a second plurality of particles to a pressure greater than about five gigapascals (5.0 GPa) and a temperature greater than about 1 ,000 °C comprises subjecting the first plurality of particles and the at least a second plurality of particles to a pressure greater than about six and one half gigapascals (6.5 GPa) and a temperature greater than about 1,500 °C for less than about two minutes (2.0 min).
Embodiment 36: The method of Embodiment 27, further comprising:
selecting the first average particle size of the first plurality of particles to cause the first average grain size of the first plurality of grains to be between about one nanometer (1 nm) and about one hundred and fifty nanometers (150 nm), and selecting the second average particle size of the second plurality of particles to cause the second average grain size of the second plurality of grains to be between about five microns (5 μπι) and about forty microns (40 μπι).
Embodiment 37: The method of Embodiment 27, further comprising forming the first plurality of grains to comprise between about one-half of one percent (0.5%) and about thirty percent (30%) by volume of the polycrystalline hard material.
Embodiment 38: The method of Embodiment 27, further comprising catalyzing the formation of inter-granular bonds between the grains of the first plurality of grains and the second plurality of grains.
The foregoing description is directed to particular embodiments for the purpose of illustration and explanation. It will be apparent, however, to one skilled in the art that many modifications and changes to the embodiments set forth above
are possible without departing from the scope of the embodiments disclosed herein as hereinafter claimed, including legal equivalents. It is intended that the following claims be interpreted to embrace all such modifications and changes.
Claims
What is claimed is: 1. A polycrystalline compact, comprising:
a first plurality of grains of hard material having a first average grain size; and at least a second plurality of grains of hard material having a second average grains size that is at least about one hundred and fifty (150) times larger than the first average grain size of the first plurality of grains, the first plurality of grains and the at least a second plurality of grains being interspersed and interbonded to form a polycrystalline hard material,
wherein the polycrystalline hard material further comprises an interstitial material disposed in at least some interstitial spaces between the first plurality of grains and the at least a second plurality of grains of the polycrystalline hard material, the interstitial material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal.
2. The polycrystalline compact of claim 1, wherein the second average grains size of the at least a second plurality of grains is between two hundred and fifty (250) times and seven hundred and fifty (750) times larger than the first averag grain size of the first plurality of grains.
3. The polycrystalline compact of claim 1, wherein the first average grain size is between about one nanometer (1 nm) and about one hundred and fifty nanometers (150 nm), and the second average grain size is between about five microns (5 μιη) and about forty microns (40 μηι).
4. The polycrystalline compact of claim 1 , wherein the first plurality of grains comprises between about one-half of one percent (0.5%) and about thirty percent (30%) by volume of the polycrystalline hard material.
5. The polycrystalline compact of claim 1, wherein each of the first plurality of grains and the at least a second plurality of grains comprises grains of diamond.
6. The polycrystalline compact of claim 1 , wherein the interstitial material comprises at least one of carbon nitride, carbon boride, a metal carbonate, a metal bicarbonate, and a metal carbide.
7. The polycrystalline compact of claim 1, further comprising a catalyst material disposed in at least some interstitial spaces between the first plurality of grains and the at least a second plurality of grains of the polycrystalline hard material.
8. A cutting element, comprising:
a substrate; and
a polycrystalline compact as recited in any one of claims 1 through 7.
9. An earth-boring drill bit, comprising:
a bit body; and
a plurality of cutting elements attached to the bit body, at least one cutting element of the plurality of cutting elements comprising acutting element as recited in claim 8.
10. A method of forming a polycrystalline compact, comprising:
at least partially coating each particle of a first plurality of particles of hard material having a first average particle size with a coating material comprising at least one of a boride, a carbide, a nitride, a metal carbonate, a metal bicarbonate, and a non-catalytic metal;
dispersing the first plurality of particles among at least a second plurality of particles of hard material having a second average particle size larger than the first average particle size of the first plurality of particles;
sintering the first plurality of particles and the at least a second plurality of particles to form a polycrystalline hard material comprising a first plurality of grains formed from the first plurality of particles and a second plurality of grains formed from the second plurality of particles, the first plurality of grains and the second plurality of grains being interspersed and interbonded to form the polycrystalline hard material; and
selecting the first average particle size of the first plurality of particles and the
second average particle size of the second plurality of particles to cause the second plurality of grains to have a second average grain size at least about one hundred and fifty (150) times larger than a first average grain size of the first plurality of grains.
1 1. The method of claim 10, further comprising selecting the first average particle size of the first plurality of particles and the second average particle size of the second plurality of particles to cause the second average grain size of the second plurality of grains to be between two hundred and fifty (250) times and seven hundred and fifty (750) times larger than the first average grain size of the first plurality of grains.
12. The method of claim 1 1 , wherein at least partially coating each particle of the first plurality of particles of hard material with the coating material comprises at least partially coating each particle of the first plurality of particles of hard material with at least one of nitrogen, a nitrogen compound, a
carbonate-forming metal, a metal carbonate, a bicarbonate-forming metal, a metal bicarbonate, a carbide- forming metal, and a metal carbide.
13. The method of claim 10, further comprising selecting each particle of the first plurality of particles and each particle of the at least a second plurality of particles to comprise diamond.
14. The method of claim 13, wherein at least partially coating each particle of the first plurality of particles of hard material with the coating material comprises:
at least partially coating each particle of the first plurality of particles with a reagent material capable of reacting with carbon to form the coating material; and reacting the reagent material with carbon atoms in or on each particle of the first plurality of particles to form the coating material.
15. The method of claim 10, wherein sintering the first plurality of particles and the at least a second plurality of particles to form the polycrystalline hard material comprises subjecting the first plurality of particles and the at least a second plurality of particles to a high temperature/high pressure (HTHP) process.
16. The method of claim 15, wherein sintering the first plurality of particles and the at least a second plurality of particles to form the polycrystalline hard material comprises subjecting the first plurality of particles and the at least a second plurality of particles to a pressure greater than about five gigapascals (5.0 GPa) and a temperature greater than about 1 ,000 °C.
17. The method of claim 16, wherein subjecting the first plurality of particles and the at least a second plurality of particles to a pressure greater than about five gigapascals (5.0 GPa) and a temperature greater than about 1 ,000 °C comprises subjecting the first plurality of particles and the at least a second plurality of particles to a pressure greater than about six and one half gigapascals (6.5 GPa) and a temperature greater than about 1,500 °C for less than about two minutes (2.0 min).
18. The method of claim 10, further comprising:
selecting the first average particle size of the first plurality of particles to cause the first average grain size of the first plurality of grains to be between about one nanometer (1 nm) and about one hundred and fifty nanometers (150 nm), and selecting the second average particle size of the second plurality of particles to cause the second average grain size of the second plurality of grains to be between about five microns (5 μιη) and about forty microns (40 μηι).
19. The method of claim 10, further comprising forming the first plurality of grains to comprise between about one-half of one percent (0.5%) and about thirty percent (30%) by volume of the polycrystalline hard material.
20. The method of claim 10, further comprising catalyzing the formation of inter-granular bonds between the grains of the first plurality of grains and the second plurality of grains.
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EP10816117.5A EP2475838A4 (en) | 2009-09-11 | 2010-09-10 | Polycrystalline compacts having material disposed in interstitial spaces therein, cutting elements and earth-boring tools including such compacts, and methods of forming such compacts |
ZA2012/01748A ZA201201748B (en) | 2009-09-11 | 2012-03-09 | Polycrystalline compacts having material disposed in interstitial spaces therein,cutting elements and earth-boring tools including such compacts,and methods of forming such compacts |
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US12/558,184 US8727042B2 (en) | 2009-09-11 | 2009-09-11 | Polycrystalline compacts having material disposed in interstitial spaces therein, and cutting elements including such compacts |
US12/558,184 | 2009-09-11 |
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EP2632637B1 (en) | 2010-10-29 | 2016-06-08 | Baker Hughes Incorporated | Polycrystalline compacts including nanoparticulate inclusions, cutting elements and earth-boring tools including such compacts, and methods of forming same |
WO2012064399A1 (en) | 2010-11-08 | 2012-05-18 | Baker Hughes Incorporated | Polycrystalline compacts including nanoparticulate inclusions, cutting elements and earth-boring tools including such compacts, and methods of forming same |
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- 2010-09-10 EP EP10816117.5A patent/EP2475838A4/en not_active Withdrawn
- 2010-09-10 WO PCT/US2010/048343 patent/WO2011031912A2/en active Application Filing
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2012
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- 2012-09-14 US US13/619,931 patent/US9085946B2/en active Active
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2014
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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GB2483163A (en) * | 2010-08-27 | 2012-02-29 | Element Six Abrasives Sa | Method of making polycrystalline diamond material |
GB2483163B (en) * | 2010-08-27 | 2014-08-06 | Element Six Abrasives Sa | Method of making polycrystalline diamond material |
US9114504B2 (en) | 2010-08-27 | 2015-08-25 | Element Six Abrasives S.A. | Method of making polycrystalline diamond material |
US10702975B2 (en) | 2015-01-12 | 2020-07-07 | Longyear Tm, Inc. | Drilling tools having matrices with carbide-forming alloys, and methods of making and using same |
WO2017161282A1 (en) * | 2016-03-18 | 2017-09-21 | Baker Hughes Incorporated | Methods of forming a cutting element including a multi-layered cutting table, and related cutting elements and earth-boring tools |
US10605008B2 (en) | 2016-03-18 | 2020-03-31 | Baker Hughes, A Ge Company, Llc | Methods of forming a cutting element including a multi-layered cutting table, and related cutting elements and earth-boring tools |
Also Published As
Publication number | Publication date |
---|---|
US8727042B2 (en) | 2014-05-20 |
US9187961B2 (en) | 2015-11-17 |
US20130008093A1 (en) | 2013-01-10 |
WO2011031912A4 (en) | 2011-08-04 |
US9878425B2 (en) | 2018-01-30 |
WO2011031912A3 (en) | 2011-06-16 |
ZA201201748B (en) | 2012-11-28 |
CA2773500A1 (en) | 2011-03-17 |
US20160008956A1 (en) | 2016-01-14 |
EP2475838A4 (en) | 2015-07-08 |
US20110061942A1 (en) | 2011-03-17 |
CA2773500C (en) | 2015-07-07 |
US9085946B2 (en) | 2015-07-21 |
US20140231150A1 (en) | 2014-08-21 |
EP2475838A2 (en) | 2012-07-18 |
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