CN114833345A - Polycrystalline diamond compact and preparation method thereof - Google Patents
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- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
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Abstract
The invention belongs to the field of diamond-containing alloys, and particularly relates to a polycrystalline diamond compact and a preparation method thereof. The polycrystalline diamond compact comprises a hard alloy substrate and a polycrystalline diamond layer compounded on the hard alloy substrate, wherein the polycrystalline diamond layer comprises polycrystalline diamond formed by mutually combining a plurality of diamond grains; coercivity of the polycrystalline diamond layer<115Oe and/or a specific magnetic saturation of > 15 G.cm 3 (ii)/g; or the polycrystalline diamond layer comprises a decobalted portion and a non-decobalted portion, the coercivity of the non-decobalted portion<115Oe and/or specific magnetic saturation intensity >)15G·cm 3 (ii) in terms of/g. The polycrystalline diamond compact provided by the invention has the advantages that the product with the coercive force and specific magnetic saturation strength meeting the performances is proved to have good wear resistance and impact resistance, and related products can meet the use requirements of equipment such as drilling tools, wire drawing machinery and the like, and belong to high-quality PDC products.
Description
Technical Field
The invention belongs to the field of diamond-containing alloys, and particularly relates to a polycrystalline diamond compact and a preparation method thereof.
Background
Polycrystalline diamond compacts are used as superabrasive cutting elements in drilling tools (e.g., cutting elements, etc.), machining equipment, bearing equipment, wire drawing machinery, and other mechanical equipment. The polycrystalline diamond compact is arranged in the sealed cavity through the diamond particles and the hard alloy matrix, the hard alloy matrix contains catalyst material cobalt, the cobalt in the hard alloy matrix becomes liquid when the polycrystalline diamond compact is subjected to composite sintering under the conditions of high pressure and high temperature, the liquid cobalt can be diffused into the diamond micro powder to fill gaps among the diamond particles, the cobalt has good wettability, the bonding among the diamond particles is promoted, and the polycrystalline diamond compact with high strength and hardness is finally obtained.
The physical performance parameters of the polycrystalline diamond compacts protected by US8616306B2, US10508502B2 and US10507565B2 are mainly characterized as follows: the polycrystalline diamond layer is a two-layer structure; the coercivity of the polycrystalline diamond layer (PCD, containing metal-solvent catalyst for short) is 115Oe or higher and the specific magnetic saturation is about 15G cm 3 (ii) a/g or less; specific magnetic permeability<0.1G·cm 3 g.Oe; average conductivity<1200S/m; with the reduction of polycrystalline diamond particles or the improvement of synthesis pressure, the comprehensive use performance, particularly the wear resistance, of the polycrystalline diamond product is greatly improved, and the coercivity of the polycrystalline diamond compact is improved and the specific magnetic saturation is reduced.
The market demand for improving the wear resistance of polycrystalline diamond compact products is increasing day by day, and practitioners of polycrystalline diamond compacts use diamond particles with fine grain sizes more often, or increase the pressure of a synthesis cavity to achieve the purpose of improving the wear resistance. After the cavity pressure is increased to a certain degree, the wear resistance of the polycrystalline diamond compact is not obviously improved any more, and the consumption cost of the top hammer facing the synthesis press is also very high. The relatively thicker diamond particles improve the shock resistance of the composite sheet to a certain extent, but the wear resistance of the polycrystalline diamond layer of the obtained composite sheet is very low, actual use requirements can not be met at many times, and the economic benefit is poor.
Disclosure of Invention
It is an object of the present invention to provide a polycrystalline diamond compact having improved wear resistance and impact performance.
A second object of the present invention is to provide a method of making the polycrystalline diamond compact described above.
In order to achieve the above object, the polycrystalline diamond compact of the present invention employs the following technical scheme:
a polycrystalline diamond compact comprises a hard alloy substrate and a polycrystalline diamond layer compounded on the hard alloy substrate, wherein the polycrystalline diamond layer comprises polycrystalline diamond formed by mutually combining a plurality of diamond grains; coercivity of the polycrystalline diamond layer<115Oe and/or a specific magnetic saturation of > 15 G.cm 3 (ii)/g; or the polycrystalline diamond layer comprises a decobalted portion and a non-decobalted portion, the coercivity of the non-decobalted portion<115Oe and/or a specific magnetic saturation of > 15 G.cm 3 /g。
The polycrystalline diamond compact provided by the invention has the advantages that the product with the coercive force and specific magnetic saturation strength meeting the performances is proved to have good wear resistance and impact resistance, and related products can meet the use requirements of equipment such as drilling tools, wire drawing machinery and the like, and belong to high-quality PDC products.
Preferably, the coercivity of the polycrystalline diamond layer is 85-108 Oe and/or the specific magnetic saturation intensity is 16-17G-cm 3 (ii) in terms of/g. Further preferably, the number of layers of the polycrystalline diamond layer is 1, and the average grain size of diamond grains in the polycrystalline diamond layer is 10 to 40 μm or 10 to 25 μm.
More preferably, the polycrystalline diamond layer contains 90-92% by mass of C, 5.5-7.0% by mass of Co and 2.5-3.0% by mass of W.
Further preferably, the number of the polycrystalline diamond layers is 2, the polycrystalline diamond layer comprises a first polycrystalline diamond layer located on the surface and a second polycrystalline diamond layer located between the first polycrystalline diamond layer and the hard alloy substrate, the average grain size of diamond grains in the first polycrystalline diamond layer and the second polycrystalline diamond layer is 10-25 μm, and the average grain size of the diamond grains in the first polycrystalline diamond layer is smaller than that of the second polycrystalline diamond layer. The average grain size of the diamond grains in the first polycrystalline diamond layer may be 10 to 15 μm, and the average grain size of the second polycrystalline diamond layer may be 20 to 25 μm.
More preferably, the mass percentages of C, Co and W in the first polycrystalline diamond layer and the second polycrystalline diamond layer are 91-92%, 6-7% and 1.5-2.3%, respectively, and the Co content in the first polycrystalline diamond layer is higher than that in the second polycrystalline diamond layer.
More preferably, the polycrystalline diamond layer includes a cobalt-removed portion and a non-cobalt-removed portion, the cobalt-removed depth of the cobalt-removed portion is not less than the thickness of the first polycrystalline diamond layer, the coercivity of the non-cobalt-removed portion is 75-85 Oe, and the coercivity of the cobalt-removed portion is 115-135 Oe.
The preparation method of the polycrystalline diamond compact adopts the technical scheme that:
the preparation method of the polycrystalline diamond compact comprises the following steps: combining the diamond powder with a hard alloy substrate, and sintering at high temperature and high pressure under the pressure of 5-10 GPa and the temperature of 1500-1700 ℃.
According to the preparation method of the polycrystalline diamond compact, the diamond is highly combined with the diamond, basically all gap regions can be occupied by the metal solvent catalyst from the alloy substrate, the process stability is good, and the product quality is stable.
Preferably, the high-temperature and high-pressure sintering is selected from one of constant-pressure and variable-temperature sintering, constant-temperature and variable-pressure sintering and variable-temperature and variable-pressure sintering.
Further preferably, the constant pressure and temperature-changing sintering is carried out at a constant pressure of 7-7.5 GPa, the temperature-changing stage comprises a first constant temperature stage, a second constant temperature stage and a third constant temperature stage, wherein the temperature of the first constant temperature stage is 1500-1600 ℃, the temperature of the second constant temperature stage is 1600-1680 ℃, and the temperature of the third constant temperature stage is 1550-1600 ℃;
the constant temperature of constant temperature vary voltage sintering is 1600 ~ 1700 ℃, and the vary voltage stage includes first constant voltage stage, second constant voltage stage, the third constant voltage stage that pressure rises in proper order, and the pressure in first constant voltage stage, second constant voltage stage, third constant voltage stage is in proper order: 7-7.2 GPa, 7.2-7.4 GPa and 7.4-7.5 GPa;
the variable-temperature variable-pressure sintering comprises a first constant-temperature constant-pressure stage, a second constant-temperature constant-pressure stage and a third constant-temperature constant-pressure stage, wherein the temperature and the pressure of the first constant-temperature constant-pressure stage are gradually increased to 1500-1680 ℃, the pressure of the first constant-temperature constant-pressure stage is 7-7.2 GPa, the temperature of the second constant-temperature constant-pressure stage is 1680-1700 ℃, the pressure of the second constant-temperature constant-pressure stage is 7.2-7.4 GPa, and the temperature of the third constant-temperature constant-pressure stage is 1680-1700 ℃, and the pressure of the third constant-temperature constant-pressure stage is 7.4-7.5 GPa.
More preferably, the holding time of the three stages in the high-temperature and high-pressure sintering is 50-150 s, 50-150 s and 100-200 s in sequence.
Preferably, the diamond powder is formed by mixing diamond particles with three grain sizes of fine, medium and coarse. More preferably, the diamond particles with the three kinds of particle sizes of fine, medium and coarse have particle sizes of 2-10 μm, 16-30 μm and 40-80 μm, or 1-3, 6-12 and 16-30 μm, or 1-4, 6-12 and 16-30 μm respectively.
Drawings
Fig. 1 is a schematic structural view of a polycrystalline diamond compact according to example 3 of the present disclosure;
in the figure, 1-cemented carbide substrate, 2-boss, 3-polycrystalline diamond table, 30-non-cobalt-removed portion, 31-cobalt-removed portion.
Detailed Description
The invention mainly provides a polycrystalline diamond compact product with good wear resistance and impact performance, which is characterized in that the coercivity of the whole polycrystalline diamond layer<115Oe or specific magnetic saturation > 15G cm 3 (ii)/g; or the coercivity of the non-cobalt-depleted portion of the polycrystalline diamond layer in the presence of the cobalt-depleted portion and the non-cobalt-depleted portion<115Oe or specific magnetic saturation > 15G cm 3 /g。
Polycrystalline diamond (PCD) obtained using the method of the invention is highly diamond-to-diamond bonded and substantially all of the interstitial regions may be occupied by a metal-solvent catalyst from an alloy substrate, for example iron, nickel, cobalt or an alloy of any of the foregoing metals. The coercivity of the entire PCD layer or non-decobalted portion of the PCD may be achieved to meet the above requirements.
The mass percent of metal solvent catalyst occupying the interstitial regions in the PCD may be between 4% and 10%. In some embodiments, the mass fraction of metal solvent catalyst in the PCD may be between 4% and 7%. In other embodiments, the mass fraction of metal solvent catalyst in the PCD may be 7% to 9%.
The diamond grains may have an average grain size of 10 to 40 μm, and in some embodiments, 15 to 18 μm. In some embodiments, the average grain size of the diamond grains may be 22 μm or greater. The grain size distribution of the diamond grains may exhibit a single pattern, or may be a mixture of grains of two or more size ranges. The average grain size was determined using the intercept method: the method comprises the steps of shooting a back scattering picture through electron microscope detection of the polycrystalline diamond layer, wherein the length and the width of the picture are known, selecting 5 pictures, drawing 3 test line segments on the picture, calculating the number of cross-sections of the cross-section parts of 15 line segments and a grain interface, and determining the average grain size by using the number of the cross-sections in unit length.
Because the metal-solvent catalyst in the PCD is ferromagnetic, the amount of metal-solvent catalyst present in the PCD correlates with the measured specific magnetic saturation of the PCD. The specific magnetic saturation of PCD with relatively more metal solvent catalyst is relatively greater, while the coercivity of PCD is relatively lower.
In use of a PDC, the PCD layer is typically subjected to chemical decobalting, using an acid solution, typically a mixture of nitric acid and hydrofluoric acid. And immersing the PCD surface layer into acid liquor at a proper depth to remove the metal solvent in the PCD surface layer. The metal-solvent catalyst in the PCD table is removed from at least one external working surface (e.g., the working surface and/or the sidewall working surface of the PCD table) to a desired depth. For example, the metal-solvent catalyst is substantially completely or partially removed from the PCD table of the PDC to a specified depth from the working surface.
The specific magnetic saturation and coercivity of the PCD were determined by a unit with an authoritative certification authority in China. Specific magnetic saturation intensity analyzer, specification and model: d60-25, manufacturer: sitelam, france, air gap field: 10000Oe, sensitivity: 1mg cobalt, error: 1%, detection standard: GB/T23369-2009. The coercive force instrument is of the specification and model: SJ-CM-2000, manufacturer: korean tin, measurement range: 0-800Oe, precision: 0.5%, detection standard: GB/T3848 and 2017. And removing the hard alloy part of the PDC by cutting and grinding, and reserving the PCD layer, or grinding and removing the cobalt-removed layer on the surface of the PCD according to the requirement. The coercivity and specific magnetic saturation of the whole PCD layer or the non-cobalt-removed part of PCD were measured. The sample volume of the test portion is at least 0.050cm 3 。
It should be noted that due to various physical processes, such as grain growth, diamond particle fracture, high carbon content, the diamond grain size after sintering may differ from the average grain size of the diamond particles before sintering. The carbon dissolved in the metal solvent catalyst is bonded and grown after being separated out.
Cobalt from the cemented carbide tungsten carbide matrix, a component of the cemented carbide matrix during high temperature high pressure synthesis (HPHT), liquefies and sweeps from a region near the volume of the diamond particles into the interstitial regions between the diamond particles during high temperature high pressure processing. Cobalt acts as a catalyst to promote intergrowth of diamond particles to form bonded diamond particles. In the following examples, cemented carbide was used in a diameter of 15.88mm and a height of 11 mm.
In the following examples, no metallic binder was added to the diamond dust and the binder cobalt detected in the PCD layer penetrated the PCD as a cemented carbide substrate.
Specific examples of polycrystalline diamond compacts and methods of making the same
Example 1
The polycrystalline diamond compact of this embodiment includes a cemented carbide substrate and a single-layer polycrystalline diamond layer formed on the cemented carbide substrate, and the polycrystalline diamond layer includes polycrystalline diamond formed by bonding a plurality of diamond crystal grains to each other, and binder cobalt exists in the interstitial regions between a plurality of diamond crystal grains.
The average grain size of the polycrystalline diamond layer was 25 μm. The coercive force of the polycrystalline diamond layer was 105Oe, and the specific saturation magnetization was 12.5G cm 3 (ii) in terms of/g. The mass percentages of C, Co and W elements in the polycrystalline diamond layer are respectively 92%, 5.5% and 2.5% through energy spectrum detection.
The polycrystalline diamond compact of this example was prepared as follows, resulting in a single layer product:
(1) uniformly mixing diamond micro powder with the particle size of 2-10 microns, 16-30 microns and 40-80 microns according to the mass ratio of 10:40:50 to obtain diamond powder.
(2) The mixed diamond powder is next to the cemented carbide substrate, the diamond powder and the cemented carbide are sealed by a metal cup (such as a niobium cup), the entire cup is enclosed in a pressure transmission medium to form a single assembly, and the single assembly is placed into a cubic press. The synthesis process comprises the following steps: the sintering temperature curve under constant pressure is a segmented process, the synthesis pressure adopts 7GPa, the sintering temperature of the first stage is up to 1500 ℃, and the heat preservation time is 50S; the sintering temperature of the second stage reaches 1680 ℃, and the heat preservation time is 100S; the sintering temperature in the third stage reaches 1600 ℃, and the heat preservation time is 100S. And directly stopping heating after the heating stage is finished, naturally cooling for 200S under the synthetic pressure, and then reducing the pressure for 150S.
In the synthesis process, a metal solvent catalyst Co in the hard alloy substrate enters gaps of diamond particles, so that the diamond particles are combined and sintered together with the hard alloy substrate to obtain the Polycrystalline Diamond Compact (PDC).
According to the sample preparation method for testing a part of samples in the specific embodiment, the cemented carbide substrate of the PDC is completely removed by cutting and grinding, and the measured coercive force of the remaining PCD layer (the thickness is 1.5mm, and the diameter is 15.88mm) is between 100 and 108 Oe.
Example 2
The polycrystalline diamond compact of this example is consistent with the polycrystalline diamond compact of example 1 in specification and structure, and the difference is only that the average grain size of the polycrystalline diamond layer is 10 μm. The coercivity of the polycrystalline diamond layer was 95 Oe; specific magnetic saturation intensity of 16G cm 3 (ii) in terms of/g. The content of C, Co and W in the polycrystalline diamond layer is 90%, 7% and 3% by weight respectively.
The difference between the method of manufacturing the polycrystalline diamond compact of this example and the method of example 1 is described as follows:
(1) uniformly mixing diamond micro powder with the particle size of 1-3 microns, 6-12 microns and 16-30 microns according to the mass ratio of 10:30:60 to obtain diamond powder.
(2) The synthesis process comprises the following steps: the constant pressure of the sintering temperature curve is a segmented process, the sintering temperature is maintained at 1700 ℃, the total time is 400s, the first-stage pressure is 7GPa, and the pressure maintaining time is 100 s; the pressure of the second stage is 7.2GPa, and the pressure maintaining time is 100 s; and (3) sintering the Polycrystalline Diamond Compact (PDC) with the pressure of 7.5GPa and the dwell time of 200s in the third stage.
According to the sample preparation method for testing part of samples in the specific embodiment, the cemented carbide substrate of the PDC is completely removed by cutting and grinding, the coercivity of the remaining PCD layer (thickness of 1.5mm) is measured to be 85-100Oe, and the specific magnetic saturation is measured to be 16-17G cm 3 /g。
Example 3
The polycrystalline diamond compact of this embodiment includes the carbide substrate and compounds first, the second polycrystalline diamond layer on the carbide substrate, first, the second polycrystalline diamond layer integrated into one piece, and the second polycrystalline diamond layer combines on the carbide substrate, and first polycrystalline diamond layer combines on the second polycrystalline diamond layer.
Referring to fig. 1, a central boss 2 is provided on a side of a cemented carbide substrate 1 facing a polycrystalline diamond table, first and second polycrystalline diamond layers form the polycrystalline diamond table 3, and the polycrystalline diamond table includes an un-cobalt-removed portion 30 connected to the cemented carbide substrate, and a cobalt-removed portion 31 connected to the un-cobalt-removed portion. The non-cobalt removing part 30 is an inverted circular groove and comprises a groove body, the groove body is provided with a groove opening end and a non-groove opening end deviating from the groove opening end, the groove opening end comprises a groove wall surface and a groove bottom surface, the groove wall surface and the groove bottom surface are matched with a central boss, and the cylindrical cobalt removing part 31 is connected to the end surface of the non-groove opening end.
The average grain size of the first polycrystalline diamond layer was 15 μm. The mass percentages of the elements C, Co and W in the first polycrystalline diamond layer are respectively 92%, 6.5% and 1.5% (the content before cobalt removal).
The average grain size of the second polycrystalline diamond layer was 25 μm. The mass percentage contents of the elements C, Co and W in the second polycrystalline diamond layer are 91.5%, 6.2% and 2.3% respectively (the contents before cobalt removal).
The preparation method of the polycrystalline diamond compact of the embodiment comprises the following steps:
(1) uniformly mixing diamond micro powder with the particle sizes of 1-3 microns, 6-12 microns and 16-30 microns according to a mass ratio of 10:25:65 to form first diamond powder; uniformly mixing diamond micro powder with the particle size of 2-10 microns, 16-30 microns and 40-80 microns according to the mass ratio of 10:40:50 to form second diamond powder.
(2) Assembling the hard alloy substrate, the second diamond powder and the first diamond powder in sequence, forming a second diamond layer and a first diamond layer correspondingly after sintering the second diamond powder and the first diamond powder, then encapsulating the second diamond layer and the first diamond layer in a pressure transmission medium to form a single assembly, and putting the single assembly into a cubic press. The synthesis process adopts a variable temperature and pressure sintering process: in the first stage, the sintering temperature is 1500 ℃, the pressure is kept at 7GPa, and the time is 100 s; the sintering temperature of the second stage is 1680 ℃, the pressure is kept at 7.2GPa, and the time is 100 s; the sintering temperature of the third stage is 1680 ℃, the pressure is kept at 7.5GPa, and the time is 200 s. And directly stopping heating after the heating stage is finished, naturally cooling for 200S under the synthetic pressure, and then reducing the pressure for 150S.
(3) The diameter of the polycrystalline diamond table on the polycrystalline diamond compact obtained after sintering is 15.88mm, the total thickness is 2.2mm, and the thickness of the first polycrystalline diamond composite layer is 1.0 mm. And then, carrying out cobalt removal (chemical cobalt removal by using acid liquor) on the PCD layer of the polycrystalline diamond composite sheet, wherein the cobalt removal depth (the thickness from the surface to the substrate direction) is 1.1mm, and the cobalt of the first polycrystalline diamond composite layer is completely removed.
The coercivity 80Oe was determined for the remaining non-decobalted portion of the PCD (0.6 mm thick) following the method of sampling the test portion of the sample in the specific embodiment by cutting and grinding to completely remove the cemented carbide substrate of the PDC and the decobalted portion. While the coercivity of the original PCD layer, corresponding to the decobalted portion, was measured at 120 Oe.
Example 4
The polycrystalline diamond compact of the present example has the same specifications and structure as those of example 3, and the differences are described below:
the average grain size of the first polycrystalline diamond layer was 12 μm and the average grain size of the second polycrystalline diamond layer was 25 μm.
The mass percentages of C, Co and W elements in the first polycrystalline diamond layer are 91%, 7% and 2% respectively (the contents before cobalt removal). The mass percentages of C, Co and W elements in the second polycrystalline diamond layer are respectively 92%, 6% and 2% (the content before cobalt removal).
The difference between the method for manufacturing the polycrystalline diamond compact of this example and example 3 is described as follows:
(1) uniformly mixing diamond micro powder with the particle sizes of 1-4 microns, 6-12 microns and 16-30 microns according to a mass ratio of 15:20:65 to form first diamond powder; uniformly mixing diamond micro powder with the particle size of 2-10 microns, 16-30 microns and 40-80 microns according to the mass ratio of 10:40:50 to form second diamond powder.
(2) The synthesis process comprises the following steps: the pressure is a segmented process under the constant sintering temperature curve, the sintering temperature is maintained at 1600 ℃, the total time is 400S, the pressure of the first stage is 7GPa, and the holding time is 100S; the pressure of the second stage is 7.2GPa, and the holding time is 100 s; the third stage pressure was 7.5GPa with a holding time of 200 s.
(3) The decobalting control was identical to example 3.
The remaining non-decobalted portion of the PCD (0.6 mm thick) was then measured for coercivity 85Oe by cutting and grinding to completely remove the cemented carbide substrate of the PDC and the decobalted portion, as per the sample preparation method for the test portion of the sample in the specific embodiment. While the coercivity 130Oe was determined for the original PCD layer corresponding to the cobalt removed portion.
Second, Experimental example
Experimental example 1 Single layer Material product comparison
The single-layer products of examples 1 and 2 are mainly used for drilling cutting elements which are important on drilling bit tools for drilling and production of oil, natural gas, coal and the like.
Example 1 single-ply product, coercivity was measured at 104Oe, and impact average score 30 (10 samples, all around 30 scores), impact performance was evaluated as follows: vertical impact energy 40J, impact primary score 1, impact secondary score 2, until PCD broke or stop 50 times. The coercivity of the same-sized product in the market as that of example 1 was 147Oe, and the average score of impact was 25 (the number of samples was 10, and the scores were all around 25).
Example 2 single-ply product, coercivity was measured at 95Oe, and impact average score 18 (number of samples 10, all around 18). The coercivity of the commercial product of the same specification corresponding to the average particle size of example 2 was 141Oe, and the impact average score was 15 (the number of samples was 10, and the scores were all around 15).
From the comparison results, it can be seen that, for a single-layer product, controlling the coercivity of the entire polycrystalline diamond layer to be less than 115Oe contributes to improving the impact resistance of the product.
Experimental example 2 double layer Material product comparison
The double-layer material products of the embodiments 3 and 4 are also used for important wear-resistant cutting elements on drill bit tools for drilling and mining such as oil, natural gas, coal and the like.
Referring to example 3, diamond micro powder with the particle sizes of 1-3 μm, 6-12 μm and 16-30 μm is uniformly mixed according to the mass ratio of 10:25:65 to form single-layer diamond powder, the single-layer diamond powder is assembled according to the sequence of a hard alloy substrate and the diamond powder, the sintered diamond powder correspondingly forms a diamond layer, then the diamond layer is packaged in a pressure transmission medium to form a single assembly, the single assembly is placed in a cubic press to manufacture a single-layer material product with the average grain size of 15 μm, the synthesis process is the same as example 3, the diameter of a polycrystalline diamond table on a polycrystalline diamond composite sheet obtained after sintering is 15.88mm, and the total thickness of the polycrystalline diamond composite layer is 2.2 mm.
The impact properties of the two-layer material product and the single-layer material product were compared in the following manner, and the impact property evaluation manner was as follows: vertical impact energy 40J, impact primary score 1, impact secondary score 2, until PCD broke or stop 50 times. The average impact score of the single-layer material product is 20 (the number of samples is 10, and the scores are all around 20); the average score of the double-layer material product can be increased to 40 (the number of samples is 10, and the scores are all around 40), which shows that the impact performance of the double-layer material product adopting the method is improved by 100 percent.
Referring to example 4, diamond micro powder with the particle sizes of 1-4 μm, 6-12 μm and 16-30 μm is uniformly mixed according to the mass ratio of 15:20:65 to form single-layer diamond powder, the single-layer diamond powder is assembled according to the sequence of the hard alloy substrate and the diamond powder, the sintered diamond powder correspondingly forms a diamond layer, then the diamond layer is packaged in a pressure transmission medium to form a single assembly, the single assembly is placed in a cubic press to manufacture a single-layer material product with the average grain size of 12 μm, the synthesis process is the same as example 4, the diameter of a polycrystalline diamond table on a polycrystalline diamond composite sheet obtained after sintering is 15.88mm, and the total thickness of the polycrystalline diamond composite layer is 2.2 mm.
The impact performance was evaluated in the above manner, and the average impact score of the single-layer product was 18 (the number of samples was 10, and the scores were all around 18); the average score of the double-layer material product can be increased to 32 (the number of samples is 10, and the scores are all around 32), which indicates that the impact performance of the double-layer material product adopting the method is improved by 80 percent.
Claims (13)
1. A polycrystalline diamond compact is characterized by comprising a hard alloy substrate and a polycrystalline diamond layer compounded on the hard alloy substrate, wherein the polycrystalline diamond layer comprises polycrystalline diamond formed by mutually combining a plurality of diamond grains; coercivity of the polycrystalline diamond layer<115Oe and/or a specific magnetic saturation of > 15 G.cm 3 (ii)/g; or the polycrystalline diamond layer comprises a decobalted portion and a non-decobalted portion, the coercivity of the non-decobalted portion<115Oe and/or a specific magnetic saturation of > 15 G.cm 3 /g。
2. The polycrystalline of claim 1The diamond compact is characterized in that the coercivity of the polycrystalline diamond layer is 85-108 Oe and/or the specific magnetic saturation intensity is 16-17G-cm 3 /g。
3. A polycrystalline diamond compact according to claim 2, wherein the number of layers in the polycrystalline diamond layer is 1 and the average grain size of the diamond grains in the polycrystalline diamond layer is 10 to 40 μm or 10 to 25 μm.
4. A polycrystalline diamond compact according to claim 2 or claim 3, wherein the polycrystalline diamond layer comprises 90 to 92%, 5.5 to 7.0% and 2.5 to 3.0% by weight of C, Co and W, respectively.
5. The polycrystalline diamond compact of claim 1, wherein the number of layers of polycrystalline diamond layers is 2, the polycrystalline diamond compact comprises a first polycrystalline diamond layer on the surface and a second polycrystalline diamond layer between the first polycrystalline diamond layer and the cemented carbide substrate, the diamond grains in the first polycrystalline diamond layer and the second polycrystalline diamond layer have an average grain size of 10 to 25 μm, and the diamond grains in the first polycrystalline diamond layer have an average grain size smaller than that of the second polycrystalline diamond layer.
6. The polycrystalline diamond compact of claim 5, wherein the first polycrystalline diamond layer and the second polycrystalline diamond layer comprise 91-92%, 6-7% and 1.5-2.3% by weight of C, Co and W, respectively, and the content of Co in the first polycrystalline diamond layer is higher than that in the second polycrystalline diamond layer.
7. A polycrystalline diamond compact according to claim 5 or claim 6, wherein the polycrystalline diamond layer comprises a cobalt-depleted portion and a non-cobalt-depleted portion, the cobalt-depleted portion having a cobalt depletion depth of no less than the thickness of the first polycrystalline diamond layer, the non-cobalt-depleted portion having a coercivity of 75 to 85Oe, the cobalt-depleted portion having a coercivity of 115 to 135 Oe.
8. A method of making a polycrystalline diamond compact according to any one of claims 1 to 7, comprising the steps of: combining the diamond powder with a hard alloy substrate, and sintering at high temperature and high pressure under the pressure of 5-10 GPa and the temperature of 1500-1700 ℃.
9. The method of making a polycrystalline diamond compact according to claim 8, wherein the high temperature and high pressure sintering is selected from one of constant pressure and temperature variable sintering, constant temperature and pressure variable sintering, and variable temperature and pressure variable sintering.
10. The method for preparing a polycrystalline diamond compact according to claim 9, wherein the constant pressure and temperature-varying sintering is performed at a constant pressure of 7-7.5 GPa, and the temperature-varying stage comprises a first constant temperature stage, a second constant temperature stage and a third constant temperature stage, wherein the temperature of the first constant temperature stage is 1500-1600 ℃, the temperature of the second constant temperature stage is 1600-1680 ℃, and the temperature of the third constant temperature stage is 1550-1600 ℃;
the constant temperature of constant temperature vary voltage sintering is 1600 ~ 1700 ℃, and the vary voltage stage includes first constant voltage stage, second constant voltage stage, the third constant voltage stage that pressure rises in proper order, and the pressure in first constant voltage stage, second constant voltage stage, third constant voltage stage is in proper order: 7-7.2 GPa, 7.2-7.4 GPa, 7.4-7.5 GPa;
the variable-temperature variable-pressure sintering comprises a first constant-temperature constant-pressure stage, a second constant-temperature constant-pressure stage and a third constant-temperature constant-pressure stage, wherein the temperature and the pressure of the first constant-temperature constant-pressure stage are gradually increased to 1500-1680 ℃, the pressure of the first constant-temperature constant-pressure stage is 7-7.2 GPa, the temperature of the second constant-temperature constant-pressure stage is 1680-1700 ℃, the pressure of the second constant-temperature constant-pressure stage is 7.2-7.4 GPa, and the temperature of the third constant-temperature constant-pressure stage is 1680-1700 ℃, and the pressure of the third constant-temperature constant-pressure stage is 7.4-7.5 GPa.
11. The method of preparing a polycrystalline diamond compact according to claim 10, wherein the three stages of the high temperature and high pressure sintering are maintained for 50 to 150 seconds, and 100 to 200 seconds in sequence.
12. A method of making a polycrystalline diamond compact according to any one of claims 8 to 11, wherein the diamond powder is a blend of fine, medium and coarse diamond particles.
13. The method of preparing a polycrystalline diamond compact according to claim 12, wherein the diamond particles of the fine, medium, and coarse particle sizes are 2 to 10 μm, 16 to 30 μm, and 40 to 80 μm, or 1 to 3, 6 to 12, and 16 to 30 μm, or 1 to 4, 6 to 12, and 16 to 30 μm, respectively.
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