Source: https://patents.google.com/patent/US8002859B2/en
Timestamp: 2019-04-21 03:37:19
Document Index: 612500697

Matched Legal Cases: ['§119', 'Application No. 60', 'Application No. 2', 'Application No. 0802233', 'Application No. 1010841', 'Application No. 08101339', 'Application No. 2', 'Application No. 0805168']

US8002859B2 - Manufacture of thermally stable cutting elements - Google Patents
Manufacture of thermally stable cutting elements Download PDF
US8002859B2
US8002859B2 US12/026,525 US2652508A US8002859B2 US 8002859 B2 US8002859 B2 US 8002859B2 US 2652508 A US2652508 A US 2652508A US 8002859 B2 US8002859 B2 US 8002859B2
US12/026,525
US20080185189A1 (en
2007-02-06 Priority to US88844907P priority Critical
2007-06-01 Priority to US94161607P priority
2008-02-05 Application filed by Smith International Inc filed Critical Smith International Inc
2008-02-05 Priority to US12/026,525 priority patent/US8002859B2/en
2008-02-20 Assigned to SMITH INTERNATIONAL, INC. reassignment SMITH INTERNATIONAL, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GRIFFO, ANTHONY
2008-08-07 Publication of US20080185189A1 publication Critical patent/US20080185189A1/en
2011-03-24 Assigned to SMITH INTERNATIONAL, INC. reassignment SMITH INTERNATIONAL, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GRIFFO, ANTHONY, KESHAVAN, MADAPUSI
2011-08-23 Publication of US8002859B2 publication Critical patent/US8002859B2/en
This application, pursuant to 35 U.S.C. §119(e), claims priority to U.S. Patent Application Ser. No. 60/888,449, filed on Feb. 6, 2007, and U.S. Patent Application No. 60/941,616, filed on Jun. 1, 2007, which are herein incorporated by reference in their entirety.
Polycrystalline diamond compact (“PDC”) cutters have been used in industrial applications including rock drilling and metal machining for many years. In a typical application, a compact of polycrystalline diamond (PCD) (or other superhard material) is bonded to a substrate material, which is typically a sintered metal-carbide to form a cutting structure. PCD comprises a polycrystalline mass of diamonds (typically synthetic) that are bonded together to form an integral, tough, high-strength mass or lattice. The resulting PCD structure produces enhanced properties of wear resistance and hardness, making PCD materials extremely useful in aggressive wear and cutting applications where high levels of wear resistance and hardness are desired.
A PDC cutter may be formed by placing a cemented carbide substrate into the container of a press. A mixture of diamond grains or diamond grains and catalyst binder is placed atop the substrate and treated under high pressure, high temperature conditions. In doing so, metal binder (often cobalt) migrates from the substrate and passes through the diamond grains to promote intergrowth between the diamond grains. As a result, the diamond grains become bonded to each other to form the diamond layer, and the diamond layer is in turn bonded to the substrate. The substrate often comprises a metal-carbide composite material, such as tungsten carbide. The deposited diamond layer is often referred to as the “diamond table” or “abrasive layer.”
A significant factor in determining the longevity of PDC cutters is the generation of heat at the cutter contact point, specifically at the exposed part of the PDC layer caused by friction between the PCD and the work material. This heat causes thermal damage to the PCD in the form of cracks (due to differences in thermal expansion coefficients) which lead to spalling of the polycrystalline diamond layer, delamination between the polycrystalline diamond and substrate, and back conversion of the diamond to graphite causing rapid abrasive wear. The thermal operating range of conventional PDC cutters is typically 750° C. or less.
As mentioned, conventional polycrystalline diamond is stable at temperatures of up to 700-750° C., after which observed increases in temperature may result in permanent damage to and structural failure of polycrystalline diamond. This deterioration in polycrystalline diamond is due to the significant difference in the coefficient of thermal expansion of the binder material, cobalt, as compared to diamond. Upon heating of polycrystalline diamond, the cobalt and the diamond lattice will expand at different rates, which may cause cracks to form in the diamond lattice structure and result in deterioration of the polycrystalline diamond. Damage is also due to graphite formation at diamond-diamond necks leading to loss of microstructural integrity and strength loss.
In order to overcome this problem, strong acids may be used to “leach” the cobalt from the diamond lattice structure (either a thin volume or entire tablet) to at least reduce the damage experienced from heating diamond-cobalt composite at different rates upon heating. Examples of “leaching” processes can be found, for example, in U.S. Pat. Nos. 4,288,248 and 4,104,344. Briefly, a strong acid, typically nitric acid or combinations of several strong acids (such as nitric and hydrofluoric acid) may be used to treat the diamond table, removing at least a portion of the co-catalyst from the PDC composite. By leaching out the cobalt, thermally stable polycrystalline (TSP) diamond may be formed. In certain embodiments, only a select portion of a diamond composite is leached, in order to gain thermal stability without losing impact resistance. As used herein, the term TSP includes both of the above (i.e., partially and completely leached) compounds. Interstitial volumes remaining after leaching may be reduced by either furthering consolidation or by filling the volume with a secondary material, such by processes known in the art and described in U.S. Pat. No. 5,127,923, which is herein incorporated by reference in its entirety.
A polycrystalline diamond body may be formed in a conventional manner, such as by a high pressure, high temperature sintering of “green” particles to create intercrystalline bonding between the particles. “Sintering” may involve a high pressure, high temperature (HPHT) process. Examples of high pressure, high temperature (HPHT) process can be found, for example, in U.S. Pat. Nos. 4,694,918; 5,370,195; and 4,525,178. Briefly, to form the polycrystalline diamond object, an unsintered mass of diamond crystalline particles is placed within a metal enclosure of the reaction cell of a HPHT apparatus. A suitable HPHT apparatus for this process is described in U.S. Pat. Nos. 2,947,611; 2,941,241; 2,941,248; 3,609,818; 3,767,371; 4,289,503; 4,673,414; and 4,954,139. A metal catalyst, such as cobalt or other Group VIII metals, may be included with the unsintered mass of crystalline particles to promote intercrystalline diamond-to-diamond bonding. The catalyst material may be provided in the form of powder and mixed with the diamond grains, or may be infiltrated into the diamond grains during HPHT sintering An exemplary minimum temperature is about 1200° C. and an exemplary minimum pressure is about 35 kilobars. Typical processing is at a pressure of about 45 kbar and 1300° C. Those of ordinary skill will appreciate that a variety of temperatures and pressures may be used, and the scope of the present invention is not limited to specifically referenced temperatures and pressures.
The diamond powder may be combined with the desired catalyst material, and the reaction cell is then placed under processing conditions sufficient to cause the intercrystalline bonding between the diamond particles. It should be noted that if too much additional non-diamond material is present in the powdered mass of crystalline particles, appreciable intercrystalline bonding is prevented during the sintering process. Such a sintered material where appreciable intercrystalline bonding has not occurred is not within the definition of PCD. Following such formation of intercrystalline bonding, a polycrystalline diamond body may be formed that has, in one embodiment, at least about 80 percent by volume diamond, with the remaining balance of the interstitial regions between the diamond grains occupied by the catalyst material. In other embodiments, such diamond content may comprise at least 85 percent by volume of the formed diamond body, and at least 90 percent by volume in yet another embodiment. However, one skilled in the art would appreciate that other diamond densities may be used in alternative embodiments. Thus, the polycrystalline diamond bodies being leached in accordance with the present disclosure include what is frequently referred to in the art as “high density” polycrystalline diamond. One skilled in the art would appreciate that conventionally, as diamond density increases, the leaching time (and potential inability to effectively leach) similarly increases.
In a particular embodiment, the polycrystalline diamond body is formed using solvent catalyst material provided as an infiltrant from a substrate, for example, a WC—Co substrate, during the HPHT process. In such embodiments where the polycrystalline diamond body is formed with a substrate, it may be desirable to remove the polycrystalline diamond portion from the substrate prior to leaching so that leaching agents may attack the diamond body in an unshielded manner, i.e., from all sides of the diamond body without substantial restriction.
Further, one skilled in the art would appreciate that the same techniques used with polycrystalline diamond may be applied to polycrystalline cubic boron nitride (PCBN). Similar to polycrystalline diamond, PCBN may be formed by sintering boron nitride particles (typically CBN) via a HPHT process, similar to those for PCD, to sinter “green” particles to create intercrystalline bonding between the particles. CBN refers to an internal crystal structure of boron atoms and nitrogen atoms in which the equivalent lattice points are at the corner of each cell. Boron nitride particles typically have a diameter of approximately one micron and appear as a white powder. Boron nitride, when initially formed, has a generally graphite-like, hexagonal plate structure. When compressed at high pressures (such as 106 psi), CBN particles will be formed with a hardness very similar to diamond, and a stability in air at temperatures of up to 1400° C.
In various embodiments, a formed PCD body having a catalyst material in the interstitial spaces between bonded diamond grains is subjected to a leaching process in conjunction with at least one accelerating technique, whereby the catalyst material is removed from the PCD body. As used herein, the term “removed” refers to the reduced presence of catalyst material in the PCD body, and is understood to mean that a substantial portion of the catalyst material no longer resides in the PCD body. However, one skilled in the art would appreciate that trace amounts of catalyst material may still remain in the microstructure of the PCD body within the interstitial regions and/or adhered to the surface of the diamond grains.
While conventional leaching techniques may require many weeks for sufficient removal of catalyst material from a PCD body to occur, in accordance with the present disclosure, accelerating techniques may be applied to the leaching process to decrease the amount of treatment time required to reach the same level of catalyst removal. In a particular embodiment, the leaching of a PCD body may be accelerated by subjecting the leaching environment and thus the PCD body to an elevated pressure. As used herein, the term “elevated pressure” refers to pressures greater than atmospheric pressure. Suitable pressure levels may include elevated pressure levels ranging from about 5 to 345 bar (or, alternatively, 100 to 5000 psi), and in one embodiment, pressure levels used may range from about 5 to 100 bar (or, alternatively, 100 to 1500 psi). However, one skilled in the art would appreciate that the particular pressure may be dependent, for example, on the particular equipment used, the temperature selected, amount (and type) of leaching agent present, and total system volume.
Further, in addition to elevated pressures, elevated temperatures may also be a technique by which the leaching of a PCD body may be accelerated. As used herein, the term “elevated temperature” refers to a temperature that is close to or above the boiling point of the liquid in which the PCD body to be leached is submersed. Suitable temperature levels may range from at or near the boiling point to three times the boiling point of the leaching agent solution, for example, from about 90 to 350° C. in one embodiment, and from about 175 to 225° C. in another embodiment. In one or more other embodiments, elevated temperature levels may range up to 300° C. Further, one skilled in the art would appreciate that the selection of an elevated temperature may be dependent, for example, on the type of leaching agent selected, so that, for example, the boiling point may be reached while still avoiding flash boiling of the leaching agent. Further, the source of the elevated temperatures is not a limitation of the scope of the present disclosure. Thus, one skilled in the art would appreciate that such heating may be provided, for example, conventional resistance-based heating such as conventional oven or furnace heating or a volumetric-based heating such as microwave heating.
Referring to FIG. 2, a pressure vessel according to one embodiment of the present disclosure is shown. Pressure vessel 200 includes a container body 213 (which may be comprised of two parts, body 215 and liner 217) having an opening 219 at the top end thereof. Container body 213 is closed by closure 221, which includes closure portion 223 and holding collar 225 which threadably engages with body 215. Closure portion 223 includes sealing section 222 and boss 224. Body 215 is of a material of construction which of sufficient strength (tensile strength) and other physical characteristics, including dimensions, so that it can withstand internal pressures in ranges likely to be encountered in various heating and digestion operations in which the container may be employed. Such pressure ranges may range, for example, up to 5000 psi. However, a venting means 239 is provided for the container 200 so that if pressures generated within the container 200 exceed the limits for which the container is designed, the generated pressures will vent from the container to the external environment. Such venting means 239 may include a rupturable diaphragm (not shown separately), which under normal pressures seals the interior of the container 200 from the passageways 241 leading to the exterior environment. Most suitable synthetic organic polymeric plastic materials for such body 213 are any of the polyether imides, such as those sold under the ULTEM® trademark by General Electric Corporation, but others of the “engineering plastics,” fiber reinforced plastics, such as glass fiber reinforced polyesters or polyethers, or other polymers known to be of good strengths and/or transmissive of microwaves (when microwave heating is used) may also be used. Further, one skilled in the art would appreciate that any configuration of a sealed, but ventable container may be used for forming a pressure vessel such as the one shown in FIG. 2 may be used to leach polycrystalline diamond bodies in accordance with the present disclosure.
Inside body 215, as a part of the container body means 213, is liner 217, which is essentially or completely transparent to microwave radiation and is also resistant to damage from chemical attack by strong chemicals, such as strong acids, often employed as leaching agents. Materials of construction suitable for manufacture of such liners, such as fluorinated alkylenes or perfluorocarbons, e.g., polytetrafluoroethylene and other polymers of this type sold under the tradename TEFLON® or other tradenames may be employed, with the preferred materials being TEFLON PFA and TEFLON FEP, but other chemically resistant plastics, such as chloroprene, silicone, ethylene, propylene and other suitable polymers, under the proper circumstances, may also be used. However, at elevated temperature, such polymers and others which are satisfactorily resistant to chemical reactions with the materials being heated or by the digestion mixes are not usually sufficiently strong to resist pressures that may be developed in the container and therefore such are normally employed only as liners within strengthening body members which are made of other, stronger materials. Further, one skilled in the art would appreciate that, in alternative embodiments, the liner and body of the vessel may be made of a single material, without the need for a separate liner. For example, when using microwave heating, if microwave- and other radiant energy-transmissive materials that are available or may become available are satisfactorily resistant to chemical damage from the contained materials and are strong enough to resist pressures developed during the heatings of such materials in the closed container the container body means may be made of one piece of one material, without the need for a separate liner.
The electrical charges may then be converted by the piezoelectric crystal into acoustic energy (e.g. mechanical energy) such that an acoustic signal may be produced. The piezoelectric crystal may be comprised of many materials, ceramics and quartz crystals being most common. Specifically, in one embodiment, the piezoelectric crystal may be comprised of Kézite K600, available from Keramos of Piezo Technologies, which is a modified lead zirconate titanate piezoelectric ceramic.
Further, as mentioned above, while the above discussion has applied to PCD cutting elements, those having ordinary skill in the art will appreciate that these techniques may be more generally applied to any material that requires the leaching of a material (such as a catalyst) from its surrounding matrix. In particular, embodiments disclosed herein apply to “free-standing” PCD bodies, such as, PCD wafers having no carbide substrate. Such PCD bodies may have been formed “free-standing” or may have been detached from a carbide substrate prior to leaching. In a particular embodiment, the PCD bodies may be at least 1 mm thick, and at least 1.5 or 2 mm thick in alternate embodiments.
Further when such “free-standing” PCD bodies are leached, in particular embodiments, the leached PCD bodies may be attached (or reattached) to a substrate, to facilitate attached to a bit, cutting tool, or other end use, for example. Such methods of reattachment may include sintering a leached PCD body with a substrate in a second HPHT sintering step, such as discussed in U.S. Patent Applications No. 60/941,616, filed on Jun. 1, 2007, which is assigned to the present assignee and herein incorporated by reference in its entirety. Further, as discussed in U.S. Patent Applications No. 60/941,616, the interstitial regions (or at least a portion thereof) previously occupied by the catalyzing material that has been removed by the leaching process may optionally be filled with a variety of infiltrants or replacement materials using any number of techniques, including liquid-phase sintering under HPHT conditions, pressure techniques. The type of infiltrant or replacement material is not a limitation on the scope of the present disclosure. Rather any type of infiltrant or replacement materials may be used, including, for example, non-refractory metals such as copper or other Group IB metals or alloys thereof, Group VIII metals such as cobalt, nickel, and iron, ceramics, silicon, and silicon-containing compounds, ultra-hard materials such as diamond and cBN. In a particular embodiment, the source of infiltrant or replacement material may be a substrate that is attached to the leached PCD body during an HPHT process. Substrates useful in this regard may include those substrates that are used to form conventional PCD, including those formed from metals, ceramics, and/or cermet materials that contain a desired infiltrant, such as a substrate formed from WC—Co. Further, in specific embodiments, the substrate may be formed of a cermet such as WC and a binder material including Group IB metals or alloys thereof such as Cu, Ag, Au, Cu—W, Cu—Ti, Cu—Nb, or the like. In such an embodiment where it is preferred that a catalyst material such as cobalt does not infiltrate into the leached PCD, it may be desirable to use a substrate having at least one infiltrant material with a melting temperature below 1200° C., and limiting the HPHT sintering temperatures accordingly so that such the replacement material infiltrates into the PCD body without causing any catalyst material present in the substrate to melt and enter the PCD body.
In accordance with one embodiment, a plurality of PDC bodies are placed inside of a pressure vessel which contains a selected amount of leaching agent. The bodies are then exposed for a selected time to elevated temperatures, for example 200° C., and experience elevated pressure levels, for example, 500 psi (or around 34 bar).
In accordance with another embodiment, a PCD body (16 mm, 2.5 mm thick), including cobalt as a binder catalyst material in the interstitial spaces of the microstructure is disposed in pressure vessel (125 mL capacity pressure bomb from Parr Instruments) containing a HNO3/HF/H2O mixture (1:1:1 ratio) in an amount of 10 mL per PCD body. The sealed pressure vessel is then placed in an oven and heated to 180-200° C. Increasing temperature causes the generation of pressures within the vessel (for example, ranging from 10 to 50 bar). After 4 days of sitting in the pressure vessel at the increased temperature, the leaching agent was replenished, with a cool down prior to removing the vessel from the oven. The pressure vessel was then placed back into the oven and reheated to 180-200° C. for an additional 4 days, with a final cool down prior to removing the vessel from the oven. Radiographs of samples taken prior to leaching and after 4 and 8 days of leaching showed that a generally uniform leach through the entire PDC body was achieved by leaching for 8 days at temperature as described above. Conventional leaching techniques, such baths may take as much as twelve weeks (for low density diamond) or more (greater diamond density and/or thickness) to achieve this desired removal. However, use of the pressure vessel at the elevated temperatures described above reduced the leach time to less than 2 weeks for the same desired amount of removal.
7. The method of claim 6, wherein the elevated temperature ranges from 175° C. to 225° C. and the elevated pressure ranges from 5 to 100 bar.
8. The method of claim 1, wherein the polycrystalline abrasive body is disposed in the leaching agent unshielded.
US12/026,525 2007-02-06 2008-02-05 Manufacture of thermally stable cutting elements Active 2029-08-25 US8002859B2 (en)
US88844907P true 2007-02-06 2007-02-06
US94161607P true 2007-06-01 2007-06-01
US12/026,525 US8002859B2 (en) 2007-02-06 2008-02-05 Manufacture of thermally stable cutting elements
US13/155,043 US8470060B2 (en) 2007-02-06 2011-06-07 Manufacture of thermally stable cutting elements
US13/925,320 US9387571B2 (en) 2007-02-06 2013-06-24 Manufacture of thermally stable cutting elements
US13/155,043 Continuation US8470060B2 (en) 2007-02-06 2011-06-07 Manufacture of thermally stable cutting elements
US20080185189A1 US20080185189A1 (en) 2008-08-07
US8002859B2 true US8002859B2 (en) 2011-08-23
US12/026,525 Active 2029-08-25 US8002859B2 (en) 2007-02-06 2008-02-05 Manufacture of thermally stable cutting elements
US12/026,398 Active US8028771B2 (en) 2007-02-06 2008-02-05 Polycrystalline diamond constructions having improved thermal stability
US12/399,369 Active 2030-02-17 US10124468B2 (en) 2007-02-06 2009-03-06 Polycrystalline diamond constructions having improved thermal stability
US13/155,043 Active US8470060B2 (en) 2007-02-06 2011-06-07 Manufacture of thermally stable cutting elements
US13/925,320 Active 2028-02-17 US9387571B2 (en) 2007-02-06 2013-06-24 Manufacture of thermally stable cutting elements
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