The present disclosure relates to joined polycrystalline diamond and systems and methods for joining polycrystalline diamond.
Polycrystalline diamond compacts (PDCs), particularly PDC cutters, are often used in earth-boring drill bits, such as fixed cutter drill bits. PDCs include diamond formed under high-pressure, high-temperature (HTHP) conditions in a press. In many cases, a PDC includes polycrystalline diamond formed and bonded to a substrate in as few as a single HTHP press cycle. A sintering aid, sometimes referred to in the art as a catalysing material or simply a “catalyst,” is often included in the press to facilitate the diamond-diamond bonds that participate both in forming the diamond and, optionally, in bonding the diamond to the substrate.
During use (e.g. while drilling), polycrystalline diamond cutters become very hot, and residual sintering aid in the diamond can cause problems such as premature failure or wear due to factors including a mismatch between the coefficients of thermal expansion (i.e. CTE mismatch) of diamond and the sintering aid. To avoid or minimize this issue, all or a substantial portion of the residual diamond sintering aid is often removed from the polycrystalline diamond prior to use, such as via a chemical leaching process, an electrochemical process, or other methods. Polycrystalline diamond from which at least some residual sintering aid has been removed is often referred to as leached regardless of the method by which the diamond sintering aid was removed. Polycrystalline diamond sufficiently leached to avoid graphitization at temperatures up to 1200° C. at atmospheric pressure is often referred to as thermally stable. PDCs containing leached or thermally stable polycrystalline diamond are often referred to as leached or thermally stable PDCs, reflective of the nature of the polycrystalline diamond they contain.
Leaching polycrystalline diamond sometimes needs to be joined to additional polycrystalline diamond. Prior attempts at joining polycrystalline diamond have focused on mechanical clamping or brazing.
A more complete and thorough understanding of the present embodiments and advantages thereof may be acquired by referring to the following description taken in conjunction with the accompanying drawings, which are not to scale, in which like reference numbers indicate like features, and wherein:
The present disclosure relates to spark plasma sintering-joined polycrystalline diamond segments and systems and methods for joining polycrystalline diamond segments using spark plasma sintering. Two or more polycrystalline diamond segments may be joined by placing them adjacent to one another, then spark plasma sintering them such that diamond bonds and/or carbide structures form between the segments to create a single spark plasma sintering-joined polycrystalline diamond element.
Polycrystalline diamond, particularly if leached, more particularly if sufficiently leached to be thermally stable, contains pores in which the diamond bonds and/or carbide structures form. When these pores in two different polycrystalline diamond segments are adjacent one another, the diamond bonds and/or carbide structures bridge the two elements and join them, typically by a covalent bond. Due to this pore filling, the resulting polycrystalline diamond may also be denser and may have a higher impact strength along these spark plasma sintered joints. In addition, impact strength, wear resistance, or other properties affected by the degree of bonding in the polycrystalline diamond may be improve near the joint because both the diamond bonds and carbide structures provide additional covalent bonds within the polycrystalline diamond. Furthermore, spark plasma sintered polycrystalline diamond near a joint is more thermally stable than unleached polycrystalline diamond with similar pore filling by the diamond sintering aid because carbide structures and diamond bonds have a coefficient of thermal expansion closer to that of the polycrystalline diamond than diamond sintering aids do.
In addition to differences in leaching profiles, such as illustrated in
During a spark plasma sintering process, the pores 50 in both polycrystalline diamond segment 30a and polycrystalline diamond segment 30b are filled with reactant gas 80, as shown in
Finally, in spark plasma sintered polycrystalline diamond illustrated in
Although diamond bonds 90 are illustrated in
Furthermore, although each filled pore 50 in
A higher percentage of filled pores and more complete filling of filled pores 50 typically results in a stronger joint that is less likely to fail during use of polycrystalline diamond element 30. This stronger joint may be achieved by increased covalent bonding between the segments 30a and 30b. It may also result in a more dense polycrystalline diamond or higher impact strength polycrystalline diamond adjacent the joint, or polycrystalline diamond with other improver properties as discussed herein adjacent that joint.
Diamond grains 10 may be of any size suitable to form polycrystalline diamond segments 30a and 30b or polycrystalline diamond element 30. They may vary in grain size throughout the polycrystalline diamond or in different regions of the polycrystalline diamond.
Reactant gas 80 may include a carbide-forming metal in gas form alone or in combination with hydrogen gas (H2) and/or a hydrocarbon gas. The carbide-forming metal may include zirconium (Zr), titanium (Ti), silicon (Si), vanadium (V), chromium (Cr), boron (B), tungsten (W), tantalum (Ta), manganese (Mn), nickel (Ni), molybdenum (Mo), halfnium (Hf), rehenium (Re) and any combinations thereof. The gas form may include a salt of the metal, such as a chloride, or another compound containing the metal rather than the unreacted element, as metal compounds often form a gas more readily than do unreacted elemental metals. The hydrocarbon gas may include methane, acetone, methanol, or any combinations thereof.
Carbide structures 100 may include transitional phases of metal elements, such as zirconium carbide (ZrC), titanium carbide (TiC), silicon carbide (SiC), vanadium carbide (VC), chromium carbide (CrC), boron carbide (BC), tungsten carbide (WC), tantalum carbide (TaC), manganese carbide (MnC), nickel carbide (NiC), molybdenum carbide (MoC), halfnium carbide (HfC), rhenium carbide (ReC), and any combinations thereof.
Prior to spark plasma sintering, two polycrystalline diamond segments 30a and 30b are placed in a spark plasma sintering assembly 100, such as the assembly of
Substrate 40 may be the substrate on which leached one of polycrystalline diamond segments 30a or 30b was formed, or a second substrate to which leached polycrystalline diamond 30a or 30b was attached after leaching. Substrate 40 is typically a cemented metal carbide, such as tungsten carbide (WC) grains in a binder or infiltrant matrix, such as a metal matrix. Although
Sealed sintering can 110 includes port 120 through which reactant gas 80 enters sealed sintering can 110 before it is sealed. Reactant gas 80 may be introduced into sealed sintering can 110 before it is placed in spark plasma sintering assembly 200 of
Sealed sintering can 110 is typically formed from a metal or metal alloy or another electrically conductive material. However, it is also possible to form sealed sintering can from a non-conductive material and then place it within a conductive sleeve, such as a graphite sleeve. A conductive sleeve or non-conductive sleeve may also be used with a conductive sintering can 110 to provide mechanical reinforcement. Such sleeves or other components attached to or fitted around all or part of sintering can 110 may be considered to be part of the sintering can.
During spark plasma sintering (also sometimes referred to as field assisted sintering technique or pulsed electric current sintering) a sintering assembly, such as assembly 100 of
Presses 230 apply pressure to sintering can 100. The pressure may be up to 100 MPa, up to 80 MPa, or up to 50 MPa. Prior to or after pressure is applied, vacuum chamber 210 may be evacuated or filled with an inert gas. If sintering can 100 is filled with reactant gas 80 and sealed in vacuum chamber 210, then before substantial pressure is applied, chamber 210 is evacuated and filled with reactant gas, then port 120 is sealed. Pressure may be applied before or after chamber 210 is evacuated again and/or filled with inert gas.
After vacuum chamber 210 is prepared, a voltage and amperage is applied between electrically conductive plates 220 sufficient to heat reactant gas 80 to a temperature at which reactant gas 80 within pores 50 forms a plasma. For example, the temperature of the reactant gas may be 1500° C. or below, 1200° C. or below, 700° C. or below, between 300° C. and 1500° C., between 300° C. and 1200° C., or between 300° C. and 700° C. The temperature may be below 1200° C. or below 700° C. to avoid graphitization of diamond in polycrystalline diamond segments 30a and 30b or polycrystalline diamond element 30.
The voltage and amperage are supplied by a continuous or pulsed direct current (DC). The current passes through electrically conductive components of assembly 100, such as sealed sintering can 110 and, if electrically conductive, polycrystalline diamond segments 30a and 30b and/or substrate 40. The current density may be at least 0.5×102 A/cm2, or at least 102 A/cm2. The amperage may be at least 600 A, as high as 6000 A, or between 600 A and 6000 A. If the current is pulsed, each pulse may last between 1 millisecond and 300 milliseconds.
The passing current heats the electrically conductive components, causing reactant gas 80 to reach a temperature, as described above, at which it forms a plasma. The plasma formed from reactant gas 80 contains reactive species, such as atomic hydrogen, protons, methyl, carbon dimmers, and metal ions, such as titanium ions (Ti4+), vanadium ions (V4+), and any combinations thereof. The reactive species derived from hydrogen gas or hydrocarbon gas form diamond bonds 90. The metal reactive species form carbide structures 100. Diamond bonds 90 and/or carbide structures 100 may covalently bond to diamond grains 10.
Because spark plasma sintering heats assembly 100 internally as the direct current passes, it is quicker than external heating methods for forming a plasma. Assembly 100 may also be pre-heated or jointly heated by an external source, however. The voltage and amperage may only need to be applied for 20 minutes or less, or even for 10 minutes or less, or 5 minutes or less to form spark plasma sintering-joined polycrystalline diamond. The rate of temperature increase of assembly 100 or a component thereof while the voltage and amperage are applied may be at least 300° C./minute, allowing short sintering times. These short sintering times avoid or reduce thermal degradation of the polycrystalline diamond.
The resulting PDC containing spark plasma sintering-joined polycrystalline diamond element 30 and substrate 40 may in the form of a cutter 300 as shown in
Substrate 40 may include reinforcing components, and may have different carbide grain sizes.
If polycrystalline diamond segments 30a and/or 30b in PDC cutter 300 are thermally stable prior to joining or attachment to substrate 40, they may remain thermally stable after attachment, or experience a much lesser decrease in thermal stability than is typically experienced if an elemental metal or metal alloy is reintroduced during attachment because the carbide structures do not negatively affect thermal stability to the degree elemental metals or metal alloys do.
Furthermore, if there is reason to further leach polycrystalline diamond element 30 after its formation by joining or after its attachment to substrate 40, such additional leaching may be performed.
In
In
A PDC cutter such as cutter 300 may be incorporated into an earth-boring drill bit, such as fixed cutter drill bit 400 of
Drilling action associated with drill bit 400 may occur as bit body 420 is rotated relative to the bottom of a wellbore. At least some PDC cutters 300 disposed on associated blades 410 contact adjacent portions of a downhole formation during drilling. These cutters 300 are oriented such that the polycrystalline diamond contacts the formation.
Spark plasma sintered PDC other than that in PCD cutters may be attached to other sites of drill bit 400 or other earth-boring drill bits. Suitable attachment sites include high-wear areas, such as areas near nozzles, in junk slots, or in dampening or depth of cut control regions.
The present disclosure provides an embodiment A relating to a method of joining polycrystalline diamond segments via a diamond bond by placing at least two leached polycrystalline diamond segments including pores formed by removal of a diamond sintering aid adjacent one another with a reactant gas including a hydrocarbon gas form in an assembly, and applying to the assembly a voltage and amperage sufficient to heat the reactant gas to a temperature of 1500° C. or less at which the reactant gas forms a plasma, which plasma forms diamond bonds and carbide structures in at least a portion of the polycrystalline diamond pores. The diamond bonds covalently bond the polycrystalline diamond segments to one another to forma polycrystalline diamond element.
The present disclosure further includes an embodiment B relating to a PDC element including polycrystalline diamond segments adjacent one another and covalently bonded to one another by diamond bonds in pores formed by removal of a diamond sintering aid. The PDC element may be formed using the method of embodiment A.
The present disclosure further includes an embodiment C relating to a fixed cutter drill bit including a bit body and a PDC element of embodiment B or formed using embodiment A.
The present disclosure further includes the following elements, which may be combined with any of elements A, B, or C or with one another unless mutually exclusive: i) one or both leached polycrystalline diamond segments may include a leached portion in which less than 2% of the volume is occupied by a diamond sintering aid; ii) the hydrocarbon gas may include methane, acetone, methanol, or any combinations thereof; ii-a) the plasma may include methyl, carbon dimmers, or a combination thereof; iii) the reactant gas may include a carbide-forming metal in gas form; iii-a) the carbide-forming metal in gas form may include a metal salt; iii-b) the plasma may include metal ions; iv) the reactant gas may include a hydrocarbon gas; iv-a) the plasma may include atomic hydrogen, a proton, or a combination thereof; v) the temperature may be 1200° C. or less; vi) the temperature may be 700° C. or less; vii) the voltage and amperage may be supplied by a continuous direct current or a pulsed direct current; viii) the voltage and amperage may be applied for 20 minutes or less; ix) the assembly or any component thereof may have a rate of temperature increase while the voltage and amperage are applied of least 300° C./minute; x) diamond bonds, carbide structures, or both may be formed in at least 25% of the pores of the polycrystalline diamond; xi) the PDC element may be a cutter; xii) the PDC element may be an erosion-resistant element.
Although the present disclosure and its advantages have been described in detail, it should be understood that various changes, substitutions and alternations can be made herein without departing from the spirit and scope of the disclosure as defined by the following claims.
Filing Document | Filing Date | Country | Kind |
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PCT/US2015/043771 | 8/5/2015 | WO | 00 |