Composite materials including nanoparticles, earth-boring tools and components including such composite materials, polycrystalline materials including nanoparticles, and related methods
11045870 · 2021-06-29
Assignee
Inventors
- Danny E. Scott (Montgomery, TX, US)
- Anthony A. DiGiovanni (Houston, TX, US)
- Jimmy W. Eason (The Woodlands, TX, US)
Cpc classification
B22F7/08
PERFORMING OPERATIONS; TRANSPORTING
B22F1/12
PERFORMING OPERATIONS; TRANSPORTING
C22C32/0047
CHEMISTRY; METALLURGY
International classification
C22C32/00
CHEMISTRY; METALLURGY
B22D19/14
PERFORMING OPERATIONS; TRANSPORTING
B22F7/08
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A composite material comprising a plurality of hard particles surrounded by a matrix material comprising a plurality of nanoparticles. Earth boring tools including the composite material and methods of forming the composite material are also disclosed. A polycrystalline material having a catalyst material including nanoparticles in interstitial spaces between inter-bonded crystals of the polycrystalline material and methods of forming the polycrystalline material are also disclosed.
Claims
1. A polycrystalline compact cutting element for use in an earth-boring tool, the cutting element comprising a region of polycrystalline material comprising nanoparticles in interstitial spaces between inter-bonded crystals in the region of polycrystalline material, wherein the nanoparticles comprise a catalyst material, and a material selected from the group consisting of borides, nitrides, oxides, carbides, and diamond.
2. A method of forming an earth-boring tool, the method comprising: providing hard particles and carbon nanotubes within a cavity of a mold, the cavity having a shape corresponding to at least a portion of a bit body of an earth-boring tool for drilling subterranean formations, wherein the hard particles exhibit an average diameter in a range extending from about 0.5 microns to about 20.0 microns and comprise at least one material selected from the group consisting of diamond, tungsten boride, titanium boride, molybdenum boride, niobium boride, vanadium boride, hafnium boride, zirconium boride, silicon boride, tantalum boride, and chromium boride, wherein the carbon nanotubes exhibit an average diameter of about 500 nm or less; infiltrating the hard particles and the carbon nanotubes with a molten matrix material comprising a metal alloy comprising indium; cooling the molten matrix material to form a solid matrix material surrounding the hard particles wherein the carbon nanotubes comprise between about 1% and about 25% of the solid matrix material by weight and the carbon nanotubes improve formation and help prevent degradation of intergranular bonds in the solid matrix material; and disposing at least one cutter on the bit body.
3. A method of forming a component of an earth-boring tool, the method comprising: mixing hard particles, carbon nanotubes exhibiting an average diameter of about 500 nm or less, and particles comprising a metal matrix material to form a powder mixture, wherein the carbon nanotubes comprise between about 1% and about 25% of the powder mixture by weight; wherein the metal matrix material comprises indium, and wherein the hard particles exhibit an average diameter in a range extending from about 0.5 microns to about 20.0 microns and comprise at least one material selected from the group consisting of diamond, tungsten boride, titanium boride, molybdenum boride, niobium boride, vanadium boride, hafnium boride, zirconium boride, silicon boride, tantalum boride, and chromium boride; pressing the powder mixture to form a green body; and sintering the green body to a desired final density such that the carbon nanotubes improve formation and help prevent degradation of intergranular bonds in the component.
4. A method of forming a polycrystalline compact cutting element for an earth-boring tool, the method comprising: sintering a mass of hard particles interspersed with a mixture comprising carbon nanotubes and a catalyst material under high pressure, high temperature conditions, wherein the carbon nanotubes comprise between about 1% and about 25% of the mixture by weight and exhibit an average diameter of about 500 nm or less, wherein the hard particles exhibit an average diameter in a range extending from about 0.5 microns to about 20.0 microns and comprise at least one material selected from the group consisting of diamond, tungsten boride, titanium boride, molybdenum boride, niobium boride, vanadium boride, hafnium boride, zirconium boride, silicon boride, tantalum boride, and chromium boride, wherein the catalyst material comprises a metal alloy comprising indium; and causing the carbon nanotubes to improve formation and help prevent degradation of intergranular bonds in the mass.
5. The method of claim 4, wherein sintering a mass of hard particles comprises sintering a mass of diamond particles.
6. The polycrystalline compact cutting element of claim 1, wherein the polycrystalline material comprises a material selected from the group consisting of diamond, boron carbide, boron nitride, silicon nitride, aluminum nitride, and carbides or borides of the group consisting of W, Ti, Mo, Nb, V, Hf, Zr, Si, Ta, and Cr.
7. The polycrystalline compact cutting element of claim 6, wherein the polycrystalline material comprises diamond.
8. The polycrystalline compact cutting element of claim 1, wherein the inter-bonded crystals and nanoparticles comprise different materials from one another.
9. The polycrystalline compact cutting element of claim 1, wherein the nanoparticles comprise a material selected from the group consisting of carbon nanotubes, fullerenes, adamantanes, and amorphous carbon.
10. The polycrystalline compact cutting element of claim 1, wherein the nanoparticles comprise particles having an average aspect ratio of one hundred to one (100:1) or less.
11. The polycrystalline compact cutting element of claim 1, wherein the nanoparticles further comprise a material selected from the group consisting of vanadium carbide and titanium diboride.
12. The polycrystalline compact cutting element of claim 1, wherein the nanoparticles comprise a coating of the catalyst material.
13. The polycrystalline compact cutting element of claim 1, wherein the nanoparticles further comprise a coating material selected from the group consisting of tin oxide, tungsten, nickel, and titanium.
14. The polycrystalline compact cutting element of claim 1, wherein the polycrystalline material further comprises a material selected from the group consisting of silver, gold, and indium within the interstitial spaces.
15. The polycrystalline compact cutting element of claim 1, wherein the catalyst material comprises a material selected from the group consisting of cobalt, iron, and nickel.
16. The polycrystalline compact cutting element of claim 1, wherein the nanoparticles further comprise diamond.
17. The polycrystalline compact cutting element of claim 16, wherein the diamond is coated with the catalyst material.
18. The polycrystalline compact cutting element of claim 1, wherein the polycrystalline material further comprises a matrix material within the interstitial spaces, the matrix material comprising the nanoparticles dispersed therein.
19. The polycrystalline compact cutting element of claim 18, wherein the nanoparticles have a higher hardness than the matrix material.
Description
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
(1) While the specification concludes with claims particularly pointing out and distinctly claiming what are regarded as embodiments of the present disclosure, advantages of the disclosure may be more readily ascertained from the description of some embodiments provided below, when read in conjunction with the accompanying drawings, in which:
(2)
(3)
(4)
(5)
DETAILED DESCRIPTION
(6) The illustrations presented herein are not meant to be actual views of any particular material, apparatus, or method, but are merely idealized representations which are employed to describe embodiments of the present disclosure. Additionally, elements common between figures may retain the same numerical designation.
(7)
(8) The nanoparticles 54 may have an average particle diameter of about five hundred nanometers (500 nm) or less. For example, in some embodiments, the nanoparticles 54 may have a diameter less than about one hundred nanometers (100 nm). By way of example and not limitation, the matrix material 52 may comprise between about one percent (1%) to about twenty-five percent (25%) by weight nanoparticles 54.
(9) As known in the art, the average particle size of the nanoparticles 54 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 bit body 12 (
(10) The material of the nanoparticles 54 may be selected to improve a desired characteristic of the matrix material 52. For example, the material of the nanoparticles 54 may be selected to improve at least one of the strength, yield point, ductility, impact strength, and abrasivity of the matrix material 52. As a non-limiting example, in some embodiments, the nanoparticles 54 may comprise a harder material (e.g., as determined by a Vickers hardness test) than the matrix material 52. By selecting the nanoparticles 54 to comprise a harder material than the matrix material 52, at least one of the hardness, abrasion resistance, and strength of bit body 12 (
(11) The nanoparticles 54 may comprise, for example, at least one of borides, nitrides, oxides, carbides, and refractory metals. In some embodiments, the nanoparticles 54 may comprise, for example, at least one of diamond, polycrystalline cubic boron nitride, silicon nitride, silicon carbide, titanium carbide, tungsten carbide, tantalum carbide, or another hard material. The nanoparticles 54 may not be hard particles in some embodiments of the disclosure. For example, the nanoparticles 54 may comprise one or more of carbides, ceramics, oxides, intermetallics, clays, minerals, glasses, elemental constituents, various forms of carbon, such as carbon nanotubes, fullerenes, adamantanes, amorphous carbon, etc. Furthermore, in some embodiments, the nanoparticles 54 may comprise a carbon allotrope and may have an average aspect ratio of about one hundred to one (100:1) or less. In further embodiments, the nanoparticles 54 may comprise vanadium carbide or titanium diboride.
(12) In further embodiments, the nanoparticles 54 may comprise vanadium carbide or titanium diboride. In some embodiments, the nanoparticles 54 may not be distinguishable from the matrix material 52 within the particle-matrix composite material, while in other embodiments, the nanoparticles 54 may maintain all or some of their original structure and integrity and be distinguishable within the matrix material 52. For example, the nanoparticles 54 may partially or fully melt and/or dissolve within the matrix material 52 during formation of the particle-matrix composite material 15. Such melting may result in alloying of the material of the nanoparticles 54 with the matrix material 52. In some embodiments, the material of the nanoparticles 54 may become evenly dispersed throughout the matrix material 52. In other embodiments, the matrix material 52 may be interspersed with areas of greater concentration of the material of the nanoparticles 54 where the nanoparticles 54 melted or dissolved. In some embodiments, the nanoparticles 54 may comprise a material that reacts with the matrix material 52. The entire thickness of each nanoparticle of the plurality of nanoparticles 54 may react with the matrix material 52 or, alternatively, only an outer portion of each of the plurality of nanoparticles 54 may react with the matrix material 52 and an inner portion of each of the plurality of nanoparticles 54 may remain unreacted. In further embodiments, the plurality of nanoparticles 54 may help to create a spinodal decomposition of the matrix material 52.
(13) In some embodiments of the present disclosure, the nanoparticles 54 may be coated, metallized, functionalized, or derivatized to include functional groups. Derivatizing the nanoparticles 54 may increase the stability of the nanoparticles 54 in liquid-based processing steps, which may help to hinder or prevent agglomeration of the nanoparticles during formation of the particle-matrix composite material 15. Such methods of forming derivatized nanoparticles are described in U.S. Provisional Patent Application No. 61/324,142, filed Apr. 14, 2010, and entitled “Method of Preparing Polycrystalline Diamond From Derivatized Nanodiamond,” the disclosure of which provisional patent application is incorporated herein in its entirety by this reference.
(14) As previously discussed, the nanoparticles 54 may comprise a coating. In some embodiments, the coating may be inert or resistant to dissolving within the matrix material 52 to help maintain the integrity of the nanoparticle 54. In some embodiments, the coating on the nanoparticles 54 may comprise a material configured to enhance the wettability of the nanoparticles 54 to the matrix material 52 and/or to prevent any detrimental chemical reaction from occurring between the nanoparticles 54 and the surrounding matrix material 52. By way of example and not limitation, each nanoparticle of the nanoparticles 54 may comprise a coating of at least one of tin oxide (SnO.sub.2), tungsten, nickel, and titanium. Furthermore, in some embodiments, trace amounts of at least one of silver, gold, and indium may, optionally, be included in the matrix material 52 to enhance the wettability of the matrix material relative to the nanoparticles 54.
(15) The particle-matrix composite material 15 including the nanoparticles 54 of the present disclosure may be used to form at least one component of an earth-boring tool. For example, an embodiment of an earth-boring rotary drill bit 10 of the present disclosure is shown in
(16) Referring again to
(17) As shown in
(18) The drill bit 10 may include a plurality of cutting structures on the face 18 thereof. By way of example and not limitation, a plurality of polycrystalline diamond compact (PDC) cutters 34 may be provided on each of the blades 30, as shown in
(19) The metal blank 16 shown in
(20) The rotary drill bit 10 shown in
(21) In some embodiments, the bit body 12 may be formed using so-called “suspension” or “dispersion” casting techniques. For example, a mold (not shown) may be provided that includes a mold cavity having a size and shape corresponding to the size and shape of the bit body 12. The mold may be formed from, for example, graphite or any other high-temperature refractory material, such as a ceramic. The mold cavity of the mold may be machined using a five-axis machine tool. Fine features may be added to the cavity of the mold using hand-held tools. Additional clay work also may be required to obtain the desired configuration of some features of the bit body 12. Where necessary, preform elements or displacements (which may comprise ceramic components, graphite components, or resin-coated sand compact components) may be positioned within the mold cavity and used to define the internal fluid passageways 42, cutting element pockets 36, junk slots 32, and other external topographic features of the bit body 12.
(22) After forming the mold, a suspension may be prepared that includes a plurality of hard particles 50 and the nanoparticles 54 suspended within molten matrix material 52 (
(23) Optionally, a metal blank 16 (
(24) The suspension comprising the hard particles 50, the nanoparticles 54, and molten matrix material 52 may be poured into the mold cavity of the mold. As the molten matrix material 52 (e.g., the metal alloy materials) may be susceptible to oxidation, the infiltration process may be carried out under vacuum. In additional embodiments, the molten matrix material 52 may be substantially flooded with an inert gas or a reductant gas to prevent oxidation of the molten matrix material 52. In some embodiments, pressure may be applied to the suspension during casting to facilitate the casting process and to substantially prevent formation of voids within the bit body 12.
(25) After casting the suspension within the mold, the molten matrix material 52 may be allowed to cool and solidify, forming the solid matrix material 52 of the particle-matrix composite material 15 including the nanoparticles 54 around the hard particles 50.
(26) In some embodiments, the bit body 12 may be formed using so-called “infiltration” casting techniques. For example, a mold (not shown) may be provided that includes a mold cavity having a size and shape corresponding to the size and shape of the bit body 12. The mold may be formed from, for example, graphite or any other high-temperature refractory material, such as a ceramic. The mold cavity of the mold may be machined using a five-axis machine tool. Fine features may be added to the cavity of the mold using hand-held tools. Additional clay work also may be required to obtain the desired configuration of some features of the bit body 12. Where necessary, preform elements or displacements (which may comprise ceramic components, graphite components, or resin-coated sand compact components) may be positioned within the mold cavity and used to define the internal fluid passageways 42, cutting element pockets 36, junk slots 32, and other external topographic features of the bit body 12.
(27) After forming the mold, a plurality of hard particles 50 (
(28) Molten matrix material 52 having a composition as previously described herein then may be prepared by heating the matrix material 52 to a temperature sufficient to cause the matrix material 52 to melt, thereby forming a molten matrix material 52. In some embodiments, the nanoparticles 54 may be added to the molten matrix material 52, in addition to or in lieu of nanoparticles 54 previously placed within the mold cavity. The molten matrix material 52 including, optionally, the nanoparticles 54 then may be allowed or caused to infiltrate the spaces between the hard particles 50 and optionally, the nanoparticles 54, within the mold cavity. Optionally, pressure may be applied to the molten matrix material 52 to facilitate the infiltration process as necessary or desired. As the molten materials may be susceptible to oxidation, the infiltration process may be carried out under vacuum. In additional embodiments, the molten materials may be substantially flooded with an inert gas or a reductant gas to prevent oxidation of the molten materials. In some embodiments, pressure may be applied to the molten matrix material 52, hard particles 50, and nanoparticles 54 to facilitate the infiltration process and to substantially prevent the formation of voids within the bit body 12 being formed.
(29) After the hard particles 50 and nanoparticles 54 have been infiltrated with the molten matrix material 52, the molten matrix material 52 may be allowed to cool and solidify, forming a solid matrix material 52 of the particle-matrix composite material 15.
(30) In some embodiments, the bit body 12 may be formed using so-called particle compaction and sintering techniques such as, for example, those disclosed in application Ser. No. 11/271,153, filed Nov. 10, 2005, now U.S. Pat. No. 7,802,495, issued Sep. 28, 2010, and in application Ser. No. 11/272,439, filed Nov. 10, 2005, now U.S. Pat. No. 7,776,256, issued Aug. 17, 2010, each assigned to the Assignee of the present disclosure and the disclosure of which is incorporated herein in its entirety by reference. Briefly, a powder mixture may be pressed to form a green bit body or billet, which then may be sintered one or more times to form a bit body 12 having a desired final density.
(31) The powder mixture may include a plurality of hard particles 50, a plurality of nanoparticles 54, and a plurality of particles comprising a matrix material 52, as previously described herein. Optionally, the powder mixture may further include additives commonly used when pressing powder mixtures such as, for example, binders for providing lubrication during pressing and for providing structural strength to the pressed powder component, plasticizers for making the binder more pliable, and lubricants or compaction aids for reducing inter-particle friction. Furthermore, the powder mixture may be milled, which may result in the hard particles 50 being at least partially coated with the matrix material 52 and nanoparticles 54.
(32) The powder mixture may be pressed (e.g., axially within a mold or die, or substantially isostatically within a mold or container) to form a green bit body. The green bit body may be machined or otherwise shaped to form features such as blades, fluid courses, internal longitudinal bores, cutting element pockets, etc., prior to sintering. In some embodiments, the green bit body (with or without machining) may be partially sintered to form a brown bit body, and the brown bit body may be machined or otherwise shaped to form one or more such features prior to sintering the brown bit body to a desired final density.
(33) The sintering processes may include conventional sintering in a vacuum furnace, the sintering in a vacuum furnace followed by a conventional hot isostatic pressing process, and sintering immediately followed by isostatic pressing at temperatures near the sintering temperature (often referred to as “sinter-HIP”). Furthermore, the sintering processes may include subliquidus phase sintering. In other words, the sintering processes may be conducted at temperatures proximate to but below the liquidus line of the phase diagram for the matrix material. For example, the sintering processes described herein may be conducted using a number of different methods known to one of ordinary skill in the art, such as the Rapid Omnidirectional Compaction (ROC) process, the CERACON® process, hot isostatic pressing (HIP), or adaptations of such processes.
(34) When the bit body 12 is formed by particle compaction and sintering techniques, the bit body 12 may not include a metal blank 16 and may be secured to the shank 20 by, for example, one or more of brazing, welding, and mechanical interlocking.
(35) The particle-matrix composite material 15 (
(36) The particle-matrix composite material 15 (
(37) Referring to
(38) In further embodiments, the nanoparticles 54 may also be used to form a polycrystalline diamond table 35 such as in the polycrystalline diamond compact (PDC) cutters 34 of the drill bit 10 of
(39) By incorporating nanoparticles into the particle-matrix phase of composite materials, the composite materials may be tailored to exhibit a desired characteristic. For example, the composite material may exhibit an improved hardness, wear resistance, erosion resistance, fracture resistance, strength, yield point, ductility, impact strength, abrasivity, improved magnetic susceptibility, amongst other desirable improvements. While not wishing to be bound by any particular theory, it is believed that the presence of the nanoparticles may serve to tie up grain boundaries and dislocations in the composite material.
(40) While the present disclosure is described herein in relation to embodiments of concentric earth-boring rotary drill bits that include fixed-cutters and to embodiments of methods for forming such drill bits and cutters, the present disclosure also encompasses other types of earth-boring tools such as, for example, core bits, eccentric bits, bicenter bits, reamers, mills, roller cone bits and hybrid bits employing both fixed and movable cutting structures, as well as methods for forming such tools. Thus, as employed herein, the term “bit body” includes and encompasses bodies of all of the foregoing structures, as well as components and subcomponents of such structures.
(41) While the present disclosure has been described herein with respect to certain embodiments, those of ordinary skill in the art will recognize and appreciate that it is not so limited. Rather, many additions, deletions and modifications to the embodiments described and illustrated herein may be made without departing from the scope of the invention as hereinafter claimed, including legal equivalents. In addition, features from one embodiment may be combined with features of another embodiment while still being encompassed within the scope of the invention as contemplated by the inventors. Further, the invention has utility in drill bits and core bits having various different bit profiles, as well as various different cutter types.