CN111850335A - Diamond composite sheet easy to remove cobalt and preparation method thereof - Google Patents
Diamond composite sheet easy to remove cobalt and preparation method thereof Download PDFInfo
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- CN111850335A CN111850335A CN202010732496.7A CN202010732496A CN111850335A CN 111850335 A CN111850335 A CN 111850335A CN 202010732496 A CN202010732496 A CN 202010732496A CN 111850335 A CN111850335 A CN 111850335A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C3/00—Removing material from alloys to produce alloys of different constitution separation of the constituents of alloys
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP 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
Abstract
The invention discloses an easy-to-decobalt diamond compact and a preparation method thereof. The preparation method of the diamond compact comprises the following steps: preparing auxiliary materials, wherein the auxiliary materials comprise: one or two of superfine diamond micro powder and alloy; sintering the auxiliary material, the main body diamond micro powder and the hard alloy matrix to obtain a diamond compact; the grain size of the superfine diamond micro powder is less than or equal to 3 mu m; the melting point of the alloy is less than 1643K. According to the invention, the superfine diamond micro powder is added, so that a large number of tiny gaps are formed in the diamond layer after sintering, and the gaps are beneficial for the cobalt removal acid solution to enter, so that the cobalt removal depth is improved; the melting point of the alloy is lower than 1643K, when cobalt in the hard alloy matrix is infiltrated into the diamond layer during sintering, the melted alloy is pushed to the diamond layer, the content of the alloy in the diamond layer is increased, a galvanic cell effect is generated during cobalt removal, the cobalt removal is easier, and the cobalt removal depth is increased.
Description
Technical Field
The invention relates to the field of superhard materials, in particular to a diamond compact easy to decobalt and a preparation method thereof.
Background
Polycrystalline Diamond Compact (PDC) is a composite material formed by sintering diamond micropowder and hard alloy, has the wear resistance of diamond and the impact resistance of hard alloy, and is widely applied to the fields of oil drilling, shale gas drilling, coal drilling and the like.
Because the polycrystalline layer (diamond layer) of the diamond compact contains two components of diamond and cobalt, the cobalt is a key element capable of converting the diamond into graphite; meanwhile, the expansion coefficient difference between cobalt and diamond is large, and the polycrystalline layer can crack at high temperature, so that the wear resistance of the diamond compact is reduced and the service life of the diamond compact is shortened. Therefore, before the diamond compact is used, cobalt on the surface of the diamond compact is generally removed, so that the wear resistance and the service life of the diamond compact are improved.
The cobalt removal of the diamond compact generally adopts an electrolytic method and a chemical method. The electrolytic method is to take the diamond compact as an anode and other conductive materials as a cathode to convert cobalt in the polycrystalline layer of the diamond compact into cobalt ions so as to remove the cobalt, wherein the electrolyte adopted by the electrolytic method can be acidic, neutral or alkaline. The chemical method comprises the steps of putting the diamond compact into a container filled with acid liquor, treating for a period of time at a certain temperature, and removing cobalt on the surface of the polycrystalline layer, wherein the adopted acid is mainly inorganic acid, including hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid and the like, or organic acid, such as tartaric acid, malic acid and the like, can be added into the inorganic acid, and in addition, other components, such as hydrogen peroxide, can be added, so that the cobalt removal efficiency is improved.
In addition to the above-described decobalting process, new processes have appeared in recent years, such as supercritical fluid processes and cyclic pressurization processes. The method is an improvement on the chemical method, and the cobalt removal efficiency is improved by increasing the dissolution rate of cobalt ions.
The existing cobalt removing technology of the diamond composite sheet aims at improving the cobalt removing method to improve the cobalt removing depth of a polycrystalline layer, and how to reduce the cobalt removing difficulty of the diamond composite sheet is not involved, so that the cobalt removing depth of the diamond composite sheet is limited.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an easy-to-decobalt diamond compact and a preparation method thereof, and aims to solve the problem that the decobalt depth of the diamond compact in the prior art is limited.
A preparation method of an easy cobalt-removing diamond compact comprises the following steps:
preparing auxiliary materials, wherein the auxiliary materials comprise: one or two of superfine diamond micro powder and alloy;
putting the auxiliary material, the main body diamond micro powder and the hard alloy matrix into a metal cup, and sintering to obtain a diamond compact;
the grain size of the superfine diamond micro powder is smaller than that of the main diamond micro powder; the melting point of the alloy is less than 1643K.
The preparation method of the diamond compact easy to remove cobalt comprises the following steps of (1) preparing a diamond compact easy to remove cobalt, wherein the grain size of the superfine diamond micro powder is less than 3 mu m; the particle size of the main diamond micro powder is 10-100 mu m.
The preparation method of the diamond compact easy to remove cobalt comprises the step of preparing the diamond compact easy to remove cobalt, wherein the grain size of the superfine diamond micro powder is 0.05-1 mu m.
The preparation method of the easy cobalt removal diamond composite sheet comprises the following steps of preparing an alloy, wherein the alloy is an iron-based alloy of iron and one or more of carbon, boron, nickel, cobalt, chromium, silicon, gadolinium, manganese, molybdenum, tungsten, germanium, gallium, lutetium, neodymium, scandium, selenium, samarium, terbium, titanium, yttrium and zirconium.
The preparation method of the diamond compact with the cobalt easy to remove is characterized in that the alloy is cobalt-based alloy of cobalt and one or more of carbon, boron, tantalum, nickel, iron, silicon, titanium, vanadium, tungsten, zirconium, molybdenum and manganese.
The preparation method of the diamond compact easy to remove cobalt comprises the step of preparing a cobalt-free diamond compact, wherein the alloy is a nickel-based alloy of nickel and one or more of carbon, silicon, cobalt, iron, titanium, zirconium, yttrium, boron, tungsten, molybdenum, manganese, vanadium, chromium, tantalum, samarium and scandium.
The preparation method of the easy cobalt-removing diamond compact comprises the following steps of putting the auxiliary material, the main diamond micro powder and the hard alloy matrix into a metal cup: the auxiliary material is mixed with the main diamond micro powder and then is filled into a metal cup, the auxiliary material is placed at the bottom of the metal cup, the auxiliary material is placed between the main diamond micro powder and the hard alloy matrix, the auxiliary material is placed on the inner side surface of the metal cup, and the auxiliary material is placed on one or more of the side surfaces of the hard alloy matrix. (ii) a
The preparation method of the diamond compact easy to remove cobalt comprises the following step of enabling the weight ratio of the auxiliary material to the main diamond micro powder to be 0.1-30%.
An easy cobalt-removing diamond compact, wherein the diamond compact is prepared by the preparation method of the diamond compact according to any one of claims 1 to 8.
Has the advantages that: in the preparation method of the diamond compact, the superfine diamond micro powder is mixed with the main body diamond micro powder to obtain a mixture in which the superfine diamond micro powder is uniformly distributed on the surfaces of the main body diamond micro powder particles and in gaps among the main body diamond micro powder particles, and gaps can be generated among the superfine diamond micro powder particles to generate a large number of micro gaps in a diamond layer of the diamond compact obtained by sintering, and the gaps are beneficial to the entering of acid liquor and the dissolution of metal (cobalt) in a binder during binder removal (cobalt removal), so that the depth of the binder removal (cobalt removal depth) is improved; the melting point of the alloy is lower than 1643K, the temperature of cobalt in the hard alloy matrix infiltrated into the diamond layer is 1643K, therefore, the alloy can reach the melting point firstly during sintering and is infiltrated into the diamond layer, the temperature is continuously increased to 1643K, the cobalt in the hard alloy matrix is infiltrated into the diamond layer, the low-melting-point alloy or compound which is infiltrated into the diamond layer firstly is pushed to the direction far away from the interface, the cobalt and the low-melting-point alloy are mixed in the diamond layer, the original battery effect is generated during binder (cobalt removal), the binder (cobalt removal) is easier, and the depth of the binder (cobalt removal) is improved.
Detailed Description
The invention provides an easy-to-decobalt diamond compact and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of an easy-to-decobalt diamond compact, which comprises the following steps:
preparing auxiliary materials; the auxiliary materials comprise: one or two of superfine diamond micro powder and alloy;
putting the auxiliary material, the main body diamond micro powder and the hard alloy matrix into a metal cup, and sintering at high temperature and high pressure to obtain a diamond composite sheet;
the grain size of the superfine diamond micro powder is less than 3 mu m; the melting point of the alloy is less than 1643K.
The invention provides a preparation method of a diamond compact, which reduces the difficulty of binder removal of the diamond compact, thereby improving the binder removal efficiency. That is, the present invention improves the binder removal efficiency by preparing a diamond compact that is easily binder removed.
In the preparation method of the easy-to-decobalt diamond compact, the superfine diamond micro powder is mixed with the main diamond micro powder to obtain a mixture in which the superfine diamond micro powder is uniformly distributed on the surfaces of the main diamond micro powder particles and in gaps among the main diamond micro powder particles, and the superfine diamond micro powder particles can generate intervals to generate a large amount of tiny gaps in a diamond layer of the sintered diamond compact, wherein the gaps are beneficial to the entering of acid liquor and the dissolution of metal (cobalt) in a binder during decobalting (decobalting), so that the depth of the decobalting agent (decobalting depth) is improved; the melting point of the alloy is lower than 1643K, the temperature of cobalt in the hard alloy matrix infiltrated into the diamond layer is 1643K, therefore, the alloy can reach the melting point firstly during sintering and is infiltrated into the diamond layer, the temperature is continuously increased to 1643K, the cobalt in the hard alloy matrix is infiltrated into the diamond layer, the low-melting-point alloy or compound which is infiltrated into the diamond layer firstly is pushed to the direction far away from the interface, the cobalt and the low-melting-point alloy are mixed in the diamond layer, the original battery effect is generated during binder (cobalt removal), the binder (cobalt removal) is easier, and the depth of the binder (cobalt removal) is improved.
The easy-to-decobalt diamond composite sheet comprises a hard alloy matrix and a diamond layer (polycrystalline layer) connected with the hard alloy matrix, and is prepared by putting main diamond micro powder, auxiliary materials and the hard alloy matrix in a metal cup at high temperature and high pressure (the temperature is 1400 ℃ and 1700 ℃ and the pressure is 5.5-8 GPa).
The superfine diamond micro powder is relative to the particle size of the main diamond micro powder, and the particle size of the superfine diamond micro powder is far smaller than that of the main diamond micro powder. Specifically, the particle size of the superfine diamond micro powder is less than 3 μm; the particle size of the main diamond micro powder is 10-100 mu m. The main diamond micro powder is traditional diamond micro powder, and the particle size of the main diamond micro powder is generally 10-100 mu m. The grain size of the superfine diamond micro powder is not more than 3 microns, or the maximum grain size of the superfine diamond micro powder is 3 microns.
The grain size of the superfine diamond micro powder is 0-3 mu m and is far smaller than that of the main diamond micro powder. In the process of preparing the diamond composite sheet, mixing the superfine diamond micro powder into the main body diamond micro powder to obtain a mixture, wherein the superfine diamond micro powder is adhered to the particle surface of almost every main body diamond micro powder in the mixture; and because the grain size of the superfine diamond micropowder is small, the quantity of the grains is very large, and the superfine diamond micropowder is adhered to the concave position on the surface of the main diamond grain despite the irregular surface appearance of the main diamond grain. Therefore, the ultra-fine diamond fine powder is mixed with the main body diamond fine powder to obtain the main body diamond fine powder adhered with the ultra-fine diamond fine powder. When the main body diamond micro powder coated with the superfine diamond micro powder is compacted through high pressure, the superfine diamond micro powder is positioned in the gaps of the main body diamond micro powder particles and on the particle surfaces of the main body diamond micro powder, and after high-temperature sintering, the main body diamond particles are connected together through the superfine diamond micro powder with small particle size. Because the number of the superfine diamond micro powder with small grain diameter is extremely large, the connecting points of the superfine diamond micro powder formed among the grains of the main diamond micro powder are many, and the diamond composite sheet with better wear resistance can be obtained. Therefore, compared with the prior art that limited contact points are generated on the surface of irregular main diamond micro powder to realize the connection between the main diamond micro powder particles, the main diamond micro powder particle connecting device has more connection points and better wear resistance. Therefore, the diamond compact which adopts the ultrafine diamond micro powder to provide the connection points for the main body diamond micro powder is superior to the diamond compact which adopts the irregular interface contact connection of the main body diamond micro powder in the wear resistance.
Further, the ultrafine diamond fine powder is present between the main diamond fine powder particles, and thus, fine voids (pores) are formed between the main diamond fine powder particles by spacing the ultrafine diamond fine powder particles, and the number of the ultrafine diamond fine powder is extremely large, so that many such voids are formed. In addition, the ultrafine diamond particles are also connected with each other during sintering to form a large number of micro voids. The voids are filled with binder upon completion of sintering, and the voids facilitate the entry of acid and the dissolution of binder metal ions (cobalt ions) upon binder removal (decobalting), thereby improving binder removal efficiency and binder removal depth.
In one embodiment of the present invention, the ultra-fine diamond powder is a submicron ultra-fine diamond powder. In another embodiment of the present invention, the ultra fine diamond powder has a particle size of 0.05 to 3 μm. In another embodiment of the invention, the grain size of the ultra-fine diamond micro powder is one or more of 0-0.5 μm, 0-1 μm, 0-2 μm, 0.5-1 μm and 0.5-3 μm. It should be noted that the mechanical properties and the depth of the binder removal of the diamond compact can be controlled by controlling the particle size of the ultra-fine diamond powder and the amount ratio of the ultra-fine diamond powder to the main diamond powder.
The melting point of the alloy is 1643K lower than the temperature of cobalt in the hard alloy matrix infiltrated into the diamond layer. Based on this, the alloy may be referred to as a low melting point alloy in the present invention. The alloy may also be replaced by a low melting point compound having a melting point below 1643K. The low-melting-point alloy or compound has a low melting point, which means that the melting point of the low-melting-point alloy or compound is lower than the temperature at which cobalt in the hard alloy is infiltrated into the diamond layer. The alloy of the present invention may be used as a binder for a diamond layer.
In the sintering process, because the low-melting-point alloy or compound can be used as a binder of the diamond layer, the low-melting-point alloy or compound is firstly melted and infiltrated in the diamond layer, and then the diamond micro powder is partially sintered; then, after the sintering temperature is continuously increased and reaches the melting point of cobalt in the hard alloy matrix (the melting point of a binder of the hard alloy matrix), the cobalt in the hard alloy matrix is infiltrated to the diamond layer, at the moment, the melted low-melting-point alloy is pushed to the direction far away from the interface by the cobalt infiltrated from the hard alloy matrix, so that the content of the low-melting-point alloy or compound is far higher or near lower relative to the interface, the content of the low-melting-point alloy or compound in the diamond layer is increased, the galvanic effect is generated when the binder is removed, the corrosion rate of metal in the binder is increased, and the post-treatment of binder removal is facilitated. Therefore, the diamond composite sheet prepared by the invention can be deeper than the traditional sintered diamond composite sheet in binder removal depth. And after binder removal (cobalt removal) post-treatment, most of the binder in the area with high binder content is removed, so that the influence of local metal (cobalt) with high expansion coefficient on the polycrystalline layer is eliminated.
In addition, the sintering quality of the polycrystalline layer of the diamond compact has an obvious relationship with the content of the binder: the content of the binder is low, diamond particles in the diamond layer cannot be completely sintered, and the particles are not bonded sufficiently; the content of the binder is high, the prepared polycrystalline layer is too loose, the connecting point positions among diamond particles are few, and the bonding among the particles is poor. In contrast, the content of the binder is 10 to 20 percent higher than that of the normally sintered diamond compact, and the connection state among diamond particles of the diamond layer is better than that of the normally sintered diamond compact. The binder of the invention is infiltrated in the form of low melting point alloy or compound, the binder content of the polycrystalline layer is relatively higher in the diamond layer, and the connection among diamond particles of the diamond layer is good.
In one implementation of the invention, the alloy is an iron-based alloy that can be used as a binder for the diamond layer. Specifically, the iron-based alloy is a low-melting-point alloy formed by iron and one or more of carbon, boron, nickel, cobalt, chromium, silicon, gadolinium, manganese, tungsten, germanium, gallium, lutetium, neodymium, scandium, selenium, samarium, terbium, titanium, yttrium and zirconium. The melting point of the binary alloy formed by iron and the elements is shown in the following table 1:
TABLE 1 melting point of iron-based binary alloys
The melting point of the iron-based binary alloy in the table 1 is 1643K lower than the temperature of cobalt in the hard alloy matrix infiltrating to the polycrystalline diamond layer, so that the iron-based binary alloy can be melted in the polycrystalline layer or infiltrated to the polycrystalline layer before the cobalt in the hard alloy matrix infiltrates to the polycrystalline layer, and the depth of binder removal is further effectively increased; meanwhile, the alloy in the auxiliary material can also be two or more than two iron-based binary alloys, so that the added alloy is gradually melted, and the effect of gradual sintering is achieved.
The alloy in the auxiliary material can also be an iron-based ternary alloy and an iron-based ternary or higher alloy, and specifically can be a ternary to eight-element alloy which is composed of Fe and at least two of Ni, Cr, Mo, Mn, C, Si and B and takes Fe as a main component, such as Fe-Si-B alloy, Fe-Cr-C-Si-B alloy, Fe-Cr-Mn-C-Si-B alloy, Fe-Ni-Cr-Mo-Mn-C-Si-B alloy and the like. In the iron-based binary to eight-element alloy, the content of Cr is 2-40%, the content of Ni is 5-32%, the content of Mo is 1.5-5%, the content of Mn is 0.1-1.5%, the content of C is 0.01-4.5%, the content of Si is 0.1-4.5%, the content of B is 0.1-4%, and the balance of Fe. The melting point of the iron-based ternary alloy or the alloy with more than iron-based ternary alloy is 1173-1523K and is lower than 1643K. The iron-based alloy may be an iron-based alloy containing an introduced element, for example, an iron-based alloy containing an element such as Nb, Nd, Co, Ni, Sm, Y, Sc, Gd, Ge, Ga, Lu, etc., in addition to an Fe — Si — B ternary alloy, and having a melting point of 1573K or less, wherein the content of Si is 1 to 15%, the content of B is 0.1 to 24%, the content of the introduced element is 0.1 to 10%, and the balance is Fe.
In one implementation of the invention, the alloy is an iron-based alloy comprising iron, silicon, boron; wherein, the weight percentage of silicon in the iron-based alloy is 0.1-4.5%, and the weight percentage of boron is 0.1-4%.
In one implementation of the invention, the alloy is a cobalt-based alloy that can be used as a binder for the diamond layer. Specifically, the cobalt-based alloy is an alloy with a low melting point formed by cobalt and one or more of carbon, tantalum, nickel, silicon, titanium, vanadium, tungsten, zirconium, molybdenum and manganese. Wherein the melting point of the cobalt-based binary alloy is shown in the following table 2:
TABLE 2 melting point of cobalt-based binary alloys
| Alloy (I) | Melting Point/K |
| Co-Mn | 1434 |
| Co-Si | 1477 |
| Co-B | 1383 |
| Co-V | 1521 |
| Co-Zr | 1505 |
| Co-Ti | 1443 |
The melting point of the cobalt-based binary alloy is 1643K lower than the temperature of cobalt in the hard alloy matrix infiltrating to the diamond layer, so that the cobalt-based binary alloy can be melted or infiltrated in the diamond layer before the cobalt in the hard alloy matrix infiltrates to the diamond layer, and the depth of binder removal is further effectively increased; meanwhile, the alloy in the auxiliary material is two or more than two binary cobalt-based alloys, so that the alloy is gradually melted, and the effect of gradual sintering is achieved.
The alloy in the auxiliary material is ternary cobalt-based alloy or ternary or higher cobalt-based alloy, specifically, the ternary cobalt-based alloy or ternary or higher cobalt-based alloy is ternary to ten-element cobalt-based alloy which is composed of Co, Fe, Ni, Cr, Mo, Mn, W, C, Si and B and takes Co as a main component, for example, ternary Co-Si-B alloy to ten-element Co-Fe-Ni-Cr-Mo-Mn-W-C-Si-B alloy. Wherein, in the binary to ten-element cobalt-base alloy, the content of Fe is 0.5-3%, the content of Ni is 1.5-25%, the content of Cr is 5-35%, the content of Mo is 0.3-30%, the content of Mn is 0.1-2%, the content of W is 0.15-15%, the content of C is 0.01-3%, the content of Si is 0.5-4%, the content of B is 0.5-5%, and the balance of Co. The melting point of the cobalt-based alloy is below 1573K and below 1643K. For example, the binder is a cobalt-based alloy containing cobalt, silicon, boron; the weight percentage of silicon in the cobalt-based alloy is 0.5-4%, and the weight percentage of boron in the cobalt-based alloy is 0.5-5%.
In the traditional sintering mode of the diamond compact, the binder is Co-C-W three-phase eutectic, and the melting point is 1643K. The melting point of the cobalt-based alloy is lower than 1643K, and with the rise of temperature, the low-melting-point alloy is melted and then infiltrates into the diamond layer, and the diamond micro powder particles are partially sintered; then, after the temperature is increased to the melting point of the binder of the hard alloy matrix 1643K, cobalt can infiltrate from the interface to the diamond layer, the low-melting-point alloy or compound which is firstly infiltrated into the diamond layer can be pushed to the direction far away from the interface by the cobalt infiltrated by the matrix, and the cobalt content of the polycrystalline layer infiltrated by the hard alloy matrix is lower than that of the cobalt-based alloy, so that the phenomenon that the cobalt content is far higher or near lower relative to the interface is formed. Because metals with different activities exist in the diamond layer, galvanic cell effect can be generated in the acidic liquid without the binding agent to improve the corrosion rate of the metals, and after the content of the binding agent is higher, the binding agent can be easily removed by post treatment.
In one implementation of the invention, the alloy in the auxiliary material is a nickel-based alloy, which is used as a binder for the diamond layer. The nickel-based alloy can be a low-melting-point alloy or compound formed by nickel and one or more elements of carbon, silicon, titanium, zirconium, yttrium, boron, tungsten, molybdenum, vanadium, chromium, iron, tantalum, samarium and scandium. Wherein the melting point of the binary nickel-based alloy is shown in the following table 3:
TABLE 3 melting points of the nickel-based binary alloys
| Alloy (I) | Melting Point/K |
| Ni-Si | 1416 |
| Ni-B | 1368 |
| Ni-V | 1475 |
| Ni-Zr | 1443 |
| Ni-Ti | 1577 |
| Ni-Ta | 1603 |
| Ni-Sm | 1553 |
| Ni-Sc | 1413 |
| Ni-Cr | 1614 |
The melting point of the nickel-based binary alloy is 1643K lower than the temperature of cobalt in the hard alloy matrix infiltrating to the polycrystalline diamond layer, so that the nickel-based binary alloy can be melted or infiltrated in the diamond layer before the cobalt in the hard alloy matrix infiltrates to the polycrystalline layer, and the depth of the binder removal is further effectively increased; meanwhile, the alloy in the auxiliary material can also be two or more than two nickel-based binary alloys, namely, the two or more than two nickel-based binary alloys are matched for use, so that the nickel-based alloy can be gradually melted, and the effect of gradual sintering is achieved.
The alloy in the auxiliary material is ternary nickel-based alloy and nickel-based alloy with more than ternary. Specifically, the ternary nickel-based alloy and the ternary or higher nickel-based alloy are ternary to nine-element alloys which are composed of Ni and two or more elements of Fe, Co, Cr, Mo, Mn, W, C, Si and B and mainly contain nickel. For example, the nickel-based alloys are ternary Ni-Si-B alloys, quaternary Ni-Cr-Mo-Fe alloys through to nine-membered Ni-Fe-Cr-Mo-Mn-W-C-Si-B alloys. In the binary to nine-element nickel-based alloy, the content of Fe is 0.5-15%, the content of Co is 1.5-11%, the content of Cr is 0.1-20%, the content of Mo is 0.1-33%, the content of Mn is 0.1-1%, the content of W is 0.3-6%, the content of C is 0.03-2%, the content of Si is 1-5%, the content of B is 0.5-5%, and the balance of Ni. The melting point of the nickel-based alloy is 1273-1573K and is lower than 1643K.
In one implementation mode of the invention, the weight ratio of the auxiliary material to the main diamond micro powder is 0.1-30%, so that the diamond compact with good binder removal effect and good wear resistance is prepared. The alloy in the auxiliary materials is specifically alloy powder, alloy sheets and alloy rings. For example, the alloy in the auxiliary materials is one or more of iron-based alloy powder or iron compound with the particle size of 0.05-300 microns, cobalt-based alloy powder or cobalt compound with the particle size of 0.05-300 microns, nickel-based alloy powder or nickel compound with the particle size of 0.05-300 microns, iron-based alloy sheet, iron-based alloy ring, cobalt-based alloy sheet, cobalt-based alloy ring, nickel-based alloy sheet and nickel-based alloy ring.
In addition, the auxiliary material, the main body diamond micro powder and the hard alloy matrix are put into a metal cup, and the auxiliary material, the main body diamond micro powder and the hard alloy matrix are put into the metal cup to be internally and externally installed to form a kit for high-temperature and high-pressure sintering, wherein the kit comprises: the auxiliary material is mixed with the main diamond micro powder and then is filled into a metal cup, the auxiliary material is placed at the bottom of the metal cup, the auxiliary material is placed between the main diamond micro powder and the hard alloy matrix, the auxiliary material is placed on the inner side surface of the metal cup, and the auxiliary material is placed on one or more of the side surfaces of the hard alloy matrix. For example, the ultra-fine diamond fine powder is mixed with the main diamond fine powder and then is put into a metal cup; the alloy powder or the alloy ring is placed at the bottom of the metal cup, placed on the side face of the hard alloy matrix, the auxiliary material is placed between the main body diamond micro powder and the hard alloy matrix, and the auxiliary material is placed on one or more of the inner side faces of the metal cup.
It should be noted that, in the present invention, the auxiliary material may include the ultra-fine diamond powder without the low-melting-point alloy or the low-melting-point alloy without the ultra-fine diamond powder, or may include both the ultra-fine diamond powder and the low-melting-point alloy, because both the ultra-fine diamond powder and the low-melting-point alloy can improve the depth of the binder removal.
The invention also provides the diamond compact easy to remove cobalt, wherein the diamond compact is prepared by the preparation method of the diamond compact. The diamond compact has good binder removal effect.
The technical solution of the present invention will be described below by specific examples.
Example 1
Mixing the ultra-fine diamond micro powder with the maximum grain size of 0.5 mu m into the main diamond micro powder with the grain size of 20 mu m, wherein the adding amount of the ultra-fine diamond micro powder is 8 percent of the weight of the main diamond micro powder, uniformly mixing, putting the mixture, the traditional Co-C-W binder and the hard alloy matrix into a metal cup, and synthesizing a diamond composite sheet (blank) at the high temperature of 1600 ℃ and the high pressure of 8GPa after the treatment of a kit; carrying out binder removal (cobalt removal) treatment on the prepared diamond composite sheet in mixed acid solution of hydrofluoric acid and nitric acid for 10 days, cutting the diamond composite sheet, and carrying out SEM detection on the diamond composite sheet to obtain an average binder removal depth of 673 microns; under the same binder removal condition, the average binder removal depth of the comparative sample is 332 μm, and the treatment depth of the diamond compact prepared in the embodiment is increased by 102%.
Example 2
Putting main diamond micro powder with the particle size of 20 mu m into a metal cup, then putting Co-based alloy powder Co-1.5C-27.5Cr-2Si-W-2Fe-5.5Mo-2.5Ni (the number in front of the elements in the alloy is the mass percent of the elements, and the balance is Co) with the particle size of 5 mu m and the weight of 10% of the main diamond micro powder, finally putting the alloy into a hard alloy substrate, and synthesizing a diamond composite sheet (blank) at the high temperature of 1643 ℃ and the high pressure of 5.5-8GPa after the treatment of a kit; removing the binder of the prepared diamond composite sheet in mixed acid solution of hydrofluoric acid and nitric acid for 14 days, cutting the diamond composite sheet, and detecting by SEM, wherein the average binder removal depth is 1050 mu m; under the same binder removal condition, the average binder removal depth of the control sample was 538 μm, and the binder removal depth of the diamond compact prepared in this example increased by 95%.
Example 3
Putting an alloy ring with the components of Ni-15Cr-7.3Si-1.4B (the number before the element is the mass percent of the element, and the balance of Ni) and the thickness of 0.1mm into a metal cup, then putting main diamond micro powder with the particle size of 20 mu m into the alloy ring, then putting the main diamond micro powder into a hard alloy substrate, and synthesizing a diamond composite sheet (blank) at the high temperature of 1643 ℃ and the high pressure of 5.5-8GPa after the processing of a kit; removing the binder of the prepared diamond composite sheet in mixed acid solution of hydrofluoric acid and nitric acid for 14 days, cutting the diamond composite sheet, and performing SEM detection to obtain a binder removal depth of 821 microns after average; under the same conditions, the mean debinding depth of the control sample was 565 μm, and the debinding depth increased by 45%.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (9)
1. A preparation method of an easy cobalt-removing diamond compact is characterized by comprising the following steps:
preparing auxiliary materials, wherein the auxiliary materials comprise: one or two of superfine diamond micro powder and alloy;
putting the auxiliary material, the main body diamond micro powder and the hard alloy matrix into a metal cup, and sintering to obtain a diamond compact;
wherein the particle size of the ultra-fine diamond micro powder is smaller than that of the main diamond micro powder; the melting point of the alloy is less than 1643K.
2. The preparation method of the cobalt-easy-to-remove diamond compact sheet as claimed in claim 1, wherein the grain size of the ultra-fine diamond micro powder is less than 3 μm; the particle size of the main diamond micro powder is 10-100 mu m.
3. The method for preparing the cobalt-easy-to-remove diamond compact sheet as claimed in claim 1, wherein the grain size of the ultra-fine diamond micro powder is 0.05-1 μm.
4. The method for preparing an easy cobalt removal diamond compact according to claim 1, wherein the alloy is an iron-based alloy of iron and one or more of carbon, boron, nickel, cobalt, chromium, silicon, gadolinium, manganese, molybdenum, tungsten, germanium, gallium, lutetium, neodymium, scandium, selenium, samarium, terbium, titanium, yttrium, and zirconium.
5. The preparation method of the cobalt-easy-to-remove diamond compact of claim 1, wherein the alloy is cobalt-based alloy of cobalt and one or more of carbon, boron, tantalum, nickel, iron, silicon, titanium, vanadium, tungsten, zirconium, molybdenum and manganese.
6. The method for preparing the cobalt-easy-to-remove diamond compact according to claim 1, wherein the alloy is nickel-based alloy of nickel and one or more of carbon, silicon, cobalt, iron, titanium, zirconium, yttrium, boron, tungsten, molybdenum, manganese, vanadium, chromium, tantalum, samarium and scandium.
7. The method of making a diamond compact of claim 1, wherein placing the adjunct, the bulk diamond micro powder, and the cemented carbide substrate into a metallic cup comprises: the auxiliary material is mixed with the main diamond micro powder and then is filled into a metal cup, the auxiliary material is placed at the bottom of the metal cup, the auxiliary material is placed between the main diamond micro powder and the hard alloy matrix, the auxiliary material is placed on the inner side surface of the metal cup, and the auxiliary material is placed on one or more of the side surfaces of the hard alloy matrix.
8. The preparation method of the diamond compact with the cobalt easy to remove of the claim 1, wherein the weight ratio of the auxiliary material to the main diamond micro powder is 0.1-30%.
9. An easy cobalt-removing diamond compact, which is prepared by the method for preparing the diamond compact according to any one of claims 1 to 8.
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