Carbonate PCD and methods of making the same
10442057 ยท 2019-10-15
Assignee
Inventors
Cpc classification
B24D3/04
PERFORMING OPERATIONS; TRANSPORTING
E21B10/567
FIXED CONSTRUCTIONS
International classification
B24D3/00
PERFORMING OPERATIONS; TRANSPORTING
B24D99/00
PERFORMING OPERATIONS; TRANSPORTING
B24D18/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A polycrystalline diamond body, and a method for making a carbonate polycrystalline diamond body includes combining a first quantity of diamond particles with a first quantity of magnesium carbonate to form a first layer in an enclosure, the first layer having a working surface, and placing a second quantity of magnesium carbonate in the enclosure forming a second layer, the first layer and the second layer forming an assembly. A quantity of at least one of silicon or aluminum is mixed in with or placed adjacent to at least one of the first layer or the second layer. The assembly, including the at least one of silicon or aluminum, is sintered at high pressure and high temperature, causing the at least one of silicon or aluminum to infiltrate at least one layer of the assembly, forming a polycrystalline diamond body.
Claims
1. A method for making a carbonate polycrystalline diamond body, comprising: combining a first quantity of diamond particles with a first quantity of magnesium carbonate to form a first layer in an enclosure, the first layer having a working surface; placing a second quantity of magnesium carbonate in the enclosure, forming a second layer, the first layer and the second layer forming an assembly; silicon being mixed in with or placed adjacent to at least one of the first layer or the second layer; and sintering the assembly including the silicon at high pressure and high temperature, causing the silicon to infiltrate at least one layer of the assembly, forming a polycrystalline diamond body.
2. The method of claim 1, further comprising combining a second quantity of diamond particles with a third quantity of magnesium carbonate to form a third layer, the third quantity of magnesium carbonate being equal to or greater than the first quantity of the magnesium carbonate, the third layer being adjacent to the first layer.
3. The method of claim 2, wherein the first quantity of magnesium carbonate is present at 0.5-3 wt % based on the total weight of the first layer and the third quantity of the magnesium carbonate is present at 2-9 wt % based on the total weight of the third layer.
4. The method of claim 2, further comprising placing a substrate adjacent to the third layer, wherein the third layer is sandwiched between the substrate and the first layer.
5. The method of claim 2, wherein the quantity of silicon is mixed with the second quantity of diamond particles and the third quantity of magnesium carbonate to form the third layer; and wherein during sintering, at least a portion of the quantity of the silicon flows in a direction away from the third layer toward the working surface.
6. The method of claim 1, wherein the silicon comprises a material selected from the group consisting of elemental silicon, silicon dioxide, silicon carbide, and combinations thereof.
7. The method of claim 1, wherein prior to sintering, the silicon comprises about 1.5 wt % silicon based on the total weight of the magnesium carbonate in the first layer.
8. The method of claim 1, wherein the quantity of the silicon is mixed with the second quantity of magnesium carbonate to form the second layer, wherein during sintering, a portion of the quantity of the silicon flows in a direction away from the second layer toward the working surface.
9. The method of claim 1, wherein during sintering, the silicon reacts with magnesium carbonate to form a material selected from the group consisting of MgSiO.sub.3, Mg.sub.2SiO.sub.4, and combinations thereof.
10. The method of claim 1, wherein the sintering comprises sintering to a temperature greater than 1800 C. at a pressure equal to or greater than 65 kbar.
11. The method of claim 1, wherein the silicon comprises about 0.5 wt % SiC based on the total weight of the first layer or the second layer.
12. The method of claim 1, wherein the second layer comprises the silicon and the second layer is adjacent to the working surface.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Embodiments of the present disclosure are described with reference to the following figures.
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
DETAILED DESCRIPTION
(13) The present disclosure relates to ultra-hard materials, and more particularly in some embodiments, to ultra-hard materials formed with a carbonate catalyst having controlled thermal decomposition, and methods for forming the same. For clarity, as used herein, the term PCD refers to conventional polycrystalline diamond that has been formed with the use of a metal catalyst during an HPHT sintering process, forming a microstructure of bonded diamond crystals with the catalyst material occupying the interstitial spaces or pores between the bonded diamond crystals. The term carbonate PCD refers to PCD formed with a carbonate catalyst, forming a microstructure of bonded diamond crystals with the carbonate catalyst material occupying the interstitial spaces or pores between the bonded diamond crystals.
(14) A region of a carbonate PCD material 10 is schematically illustrated in
(15) In some embodiments, a carbonate PCD body is formed by subjecting an ultra-hard diamond element such as a volume of diamond particles to an HPHT sintering process in the presence of a carbonate catalyst such as magnesium carbonate (MgCO.sub.3). In an embodiment, the carbonate PCD body is formed by mixing diamond particles 14 with the carbonate catalyst 16 before HPHT sintering to create the carbonate PCD body. The formed carbonate PCD body is subsequently heat-treated under vacuum or at atmospheric pressure at a temperature of approximately 1100 C. to 1200 C. to convert a portion of the carbonate catalyst into an oxide, while releasing a gas. Heat treatment may occur in a furnace, such as vacuum furnace. In embodiments including a MgCO.sub.3 carbonate catalyst, the oxide is magnesium oxide (MgO), while the gas is carbon dioxide (CO.sub.2). In some embodiments including an MgCO.sub.3 carbonate catalyst, the MgCO.sub.3 carbonate catalyst contains a SiO.sub.2 impurity in the range of 1.5 wt % to 1.8 wt %. In some embodiments, the MgCO.sub.3 carbonate catalyst contains 1.5 wt % SiO.sub.2.
(16) With reference to
(17) Generally, when a non-metal catalyst such as a carbonate is used in forming a carbonate PCD body, the diamond remains stable while being converted to polycrystalline diamond form during HPHT sintering with increasing temperatures up to 1200 C., without being converted to carbon dioxide, carbon monoxide, or graphite. However, during subsequent heat-treatment cycles of the formed carbonate PCD under atmospheric pressure or vacuum (after HPHT sintering) for the purpose of decomposing the carbonate catalyst, the PCD may develop cracks at temperatures between 800 C. and 1200 C., and may be subject to graphitization. This threshold temperature of 1200 C. is very close to the thermally stable temperature of PCD under vacuum. In some embodiments, by controlling the thermal decomposition of the carbonate catalyst, a crack-free working surface 23 of the carbonate PCD body is formed. Thus, in order to prevent or reduce thermal degradation of the PCD after HPHT sintering and during heat-treatment cycles below the threshold 1200 C. (ranging from temperatures between 1100 C.-1200 C.), various embodiments provide for a MgCO.sub.3 carbonate catalyst that infiltrates the diamond particles during HPHT sintering and fully (or mostly) decomposes at a temperature below the 1200 C. threshold during subsequent heat-treatment cycles.
(18) Generally, a carbonate catalyst such as MgCO.sub.3 may begin to decompose at a temperature of approximately 400 C. at ambient pressure. The thermal decomposition temperature of MgCO.sub.3 is related to the pressure. For example, MgCO.sub.3 will remain in its major phase without fully decomposing when heat-treated after HPHT sintering for one hour under vacuum to a temperature of 1200 C., as for example shown in
(19) TABLE-US-00001 TABLE 1 Phase Content for FIG. 6 X-Ray Diffraction Pattern Diamond MgCO.sub.3 MgO Content 97.29% 1.75% 0.97%
(20) However, by mixing the components of the first, second, and/or third layer with a Si and/or Al compound before sintering, according to various embodiments disclosed herein, full (or nearly full) thermal decomposition of the MgCO.sub.3 carbon catalyst during a post-HPHT sintering heat-treatment temperature below 1200 C. may be realized. When the Si and/or Al compound mixed into the first, second, and/or third layer, according to embodiments of the present disclosure, reacts with the MgCO.sub.3 catalyst, MgSiO.sub.3, Mg.sub.2SiO.sub.4, MgAl.sub.2O.sub.4 and/or combinations thereof is formed. The compounds formed as a result of the reaction of the Si and/or Al compounds with the MgCO.sub.3 promote thermal decomposition of the MgCO.sub.3 at a lower temperature than the temperature of thermal decomposition under vacuum during heat-treatment cycles when Si and/or Al is/are not included. According to various embodiments, the MgCO.sub.3 will enter the full thermal decomposition phase at or below the 1200 C. threshold for thermal degradation of the carbonate PCD, itself, and thus cause a reduction in the cracks often formed in the carbonate PCD at heat treatment cycles of temperatures between 800 C. and 1200 C. As shown in
(21) TABLE-US-00002 TABLE 2 Phase Content for FIG. 7 X-Ray Diffraction Pattern Phase Diamond MgCO.sub.3 MgO MgSiO.sub.3 Mg.sub.2SiO.sub.4 With <0.2 wt % Si 97.3% 2.7% With ~1.5 wt % Si 96.8% 0.45% 1.38% 1.2%
(22) In some embodiments, by increasing the percentage by weight of MgCO.sub.3 premixed with the diamond particles of the second layer, or as part of an additional third layer, thermal decomposition of the MgCO.sub.3 at a lower temperature is promoted, causing thermal decomposition under vacuum during heat-treatment cycles. The additional percentage by weight of MgCO.sub.3 results in the formation of larger pore channels in the carbonate PCD during HPHT sintering, allowing the CO.sub.2 gas formed during subsequent thermal decomposition of the MgCO.sub.3 to more easily release from the PCD body. As shown in Table 3 below, in one embodiment, the phase ratio of MgO to MgCO.sub.3, after heat-treating a carbonate PCD body under vacuum at a temperature of 1100 C. (after HPHT sintering), increases as the percentage by weight of MgCO.sub.3 premixed with the diamond particles or as part of a third layer is increased. In one embodiment including a 3% premixed percentage by weight of MgCO.sub.3, the phase ratio is approximately 0.07, while in another embodiment including a 5% premixed percentage by weight of MgCO.sub.3, the ratio increases to 1.63, and in another embodiment including a 7% premixed percentage by weight of MgCO.sub.3, the ratio increases to 13.85.
(23) TABLE-US-00003 TABLE 3 Phase Ratio After Heat Treating at 1100 C. for MgCO.sub.3 PCD Measured by X-ray Diffraction Premixed Amount Phase Ratio of MgCO.sub.3 (MgO/MgCO.sub.3) 3% 0.07 5% 1.63 7% 13.85
(24) However, an increase in the percentage by weight of MgCO.sub.3 premixed into a layer, while promoting thermal decomposition of the catalyst at a lower temperature, can also decrease the wear resistance of the PCD body surface as a result of the formation of larger pore channels on the surface carbonate PCD body and as a result of the decrease in diamond density. In various embodiments, the increased percentage by weight of MgCO.sub.3 is added to the second layer, and/or as part of the additional third layer, while the first layer, which will form a working surface of the carbonate PCD, optionally includes a comparably decreased percentage by weight of MgCO.sub.3. As a result of the increased percentage by weight of MgCO.sub.3 premixed into the second and/or third layers, these layers may be generally thicker than the first layer, which contains a lesser quantity of the MgCO.sub.3 premixed into the layer. In these embodiments, the higher concentration of the MgCO.sub.3 catalyst premixed into the second and/or third layers may promote thermal degradation of the MgCO.sub.3 catalyst at a lower temperature than the temperature at which thermal degradation of the MgCO.sub.3 of the first layer will occur because of the formation of larger pore channels in the second and/or third layers due to the higher concentration of the MgCO.sub.3 catalyst, making it easier for CO.sub.2 gas to be released from these layers. Accordingly, in some embodiments, the MgCO.sub.3 catalyst in the second and/or third layers, which will be heat-treated after HPHT sintering, may be more fully decomposed at a lower temperature than the MgCO.sub.3 catalyst in the first layer. The result of this variance in thermal decomposition properties of the layers after HPHT sintering and initial heat-treatment cycles due to the difference in the MgCO.sub.3 catalyst concentrations in the layers is that the carbonate PCD may form minimal to no cracks at the working surface side of the first layer during subsequent heat-treatment cycles because the CO.sub.2 decomposed from the first layer can be quickly released through the thinner first layer, rather than remain trapped inside the thicker second and/or third layers. However, because the Si and/or Al compounds may promote thermal decomposition of the MgCO.sub.3 catalyst at a lower temperature are not catalysts, in order to decrease wear resistance at the working surface, the amount of these compounds that accumulates at the working surface after mixing these Si and/or Al compounds into the first, second, and/or third layer, in some embodiments, may be minimized or reduced. In some embodiments, infiltrating the first layer at the working surface side with additional MgCO.sub.3 catalyst that has not been premixed with diamond particles, for example by placing the third layer or another fourth layer of MgCO.sub.3 catalyst adjacent to the first layer so that the first layer is sandwiched between the third or fourth layer and the second layer, allows for the formation of a working surface with minimal cracks, and maintained wear resistance. In some embodiments, after HPHT sintering and subsequent heat-treatment cycles, the additional MgCO.sub.3 catalyst in the third or fourth layer, adjacent to the first layer, may fully decompose, allowing the Si and/or Al compound to infiltrate through the remaining layers, and resulting in the formation of a working surface having reduced to no cracks.
(25) A method for forming the carbonate PCD body with a distribution of Si and/or Al elements is shown in
(26) In some embodiments, the method includes introducing a third layer 26 including a Silicon (Si) and/or Aluminum (Al) compound, as well as a carbonate catalyst adjacent to the non-working surface 21 of the second layer (block 103). In various embodiments, this Si and/or Al compound includes Al, Si, SiO.sub.2, Al.sub.2O.sub.3, SiC, Al.sub.3C, and/or combinations thereof. In some embodiments, the Si and/or Al compound is included at about 1.5 wt % (with respect to the weight of the carbonate catalyst). In other embodiments, the Si and/or Al compound is SiC included at 0.5 wt % (with respect to the weight of the layer). In other embodiments, instead of using a third layer, the Si and/or Al compound can be combined directly with the second layer 24 forming a mixture of diamond particles, mixed with the second percentage of carbonate catalyst, and mixed with the Si and/or Al compound for forming the second layer 24. In other embodiments, the Si and/or Al compound is introduced to the separate third layer 26, the Si and/or Al compound is applied as separate layer 29 adjacent to the second layer 24, and disposed at an opposite surface from the first layer working surface 23, and adjacent to the non-working surface 21, as, for example, shown in
(27) In other embodiments, as shown in
(28) With reference again to
(29) By way of example,
(30)
(31)
(32) In some embodiments, where the Si and/or Al compound is directly mixed with the particles and catalyst of the second layer or in the separate third layer adjacent to the second layer prior to HPHT sintering, the resulting carbonate PCD after HPHT sintering has a first layer or working surface with a higher concentration of the Si and/or Al compound. And, as a result of the first layer including the working surface having a percentage of the carbonate catalyst less than that of the second layer prior to HPHT sintering, a greater percentage of the carbonate catalyst may be thermally decomposed at the first layer working surface, than at the second layer or non-working surface, during heat-treatment cycles. The higher concentration of the Si and/or Al compound formed at the first layer including the working surface results in a lower thermal decomposition temperature for the carbonate catalyst than there would be otherwise without the Si and/or Al compound at the working surface and throughout the remainder of the carbonate PCD, including throughout the second layer. In other embodiments, the decomposition temperature of the first layer may be lower than, equal to, or even greater than the decomposition temperature of the second layer, as a result of the Si and/or Al compound introduced prior to HPHT sintering. However, the resulting thermal decomposition temperature of the first layer will be less than the thermal decomposition temperature for a carbonate catalyst not including a Si and/or Al compound. The result is a diamond compact including a carbonate PCD body with a distribution of Si and/or Al elements.
(33) A diamond compact 30 according to an embodiment is shown in
(34) The diamond compact 30 shown in
(35) In other embodiments, rather than the carbonate catalyst, and/or the Si and/or Al compounds being mixed in or pre-mixed with the diamond particles of the first layer, and/or the second layer, the carbonate catalyst and/or the Si and/or Al compounds may be applied as separate layer(s) adjacent to the first layer or the second layer, or the third layer, or any other layer including or not including diamond particles. The separate layer(s) including the carbonate catalyst and/or the Si and/or Al compounds may then infiltrate into the corresponding adjacent layer during HPHT sintering.
(36) Although only a few embodiments have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the embodiments without materially departing from embodiments disclosed herein. Accordingly, all such modifications are intended to be included within the scope of this disclosure. In the claims, means-plus-function clauses are intended to cover the structures described herein as performing the recited function and not only structural equivalents, but also equivalent structures. Thus, although a nail and a screw may not be structural equivalents in that a nail employs a cylindrical surface to secure wooden parts together, whereas a screw employs a helical surface, in the environment of fastening wooden parts, a nail and a screw may be equivalent structures.