CN108941583B - Submicron diamond composite sheet and preparation process thereof - Google Patents

Submicron diamond composite sheet and preparation process thereof Download PDF

Info

Publication number
CN108941583B
CN108941583B CN201810999120.5A CN201810999120A CN108941583B CN 108941583 B CN108941583 B CN 108941583B CN 201810999120 A CN201810999120 A CN 201810999120A CN 108941583 B CN108941583 B CN 108941583B
Authority
CN
China
Prior art keywords
powder
diamond
hard alloy
pressure
cobalt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810999120.5A
Other languages
Chinese (zh)
Other versions
CN108941583A (en
Inventor
卢灿华
张涛
刘俊涛
窦明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhongnan Diamond Co Ltd
Original Assignee
Zhongnan Diamond Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhongnan Diamond Co Ltd filed Critical Zhongnan Diamond Co Ltd
Priority to CN201810999120.5A priority Critical patent/CN108941583B/en
Publication of CN108941583A publication Critical patent/CN108941583A/en
Application granted granted Critical
Publication of CN108941583B publication Critical patent/CN108941583B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/02—Local etching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/105—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing inorganic lubricating or binding agents, e.g. metal salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/142—Thermal or thermo-mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • 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
    • B22F3/001—Starting from powder comprising reducible metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • 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
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • B22F3/101—Changing atmosphere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/28—Acidic compositions for etching iron group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • 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
    • C22C2026/006—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes with additional metal compounds being carbides
    • 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
    • C22C2026/007—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes with additional metal compounds being nitrides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention discloses a submicron diamond compact and a preparation process thereof, wherein the preparation process comprises the following steps: 1) removing cobalt from the surface of the hard alloy substrate; 2) purifying the diamond micro powder; 3) preparing polycrystalline diamond powder; 4) preparing a composite component; 5) and (4) preparing the composite sheet. The submicron diamond compact prepared by the invention can effectively prevent the abnormal growth of diamond grains, thereby obtaining a finer and uniform structure to meet the requirements of finish machining and super-finish machining.

Description

Submicron diamond composite sheet and preparation process thereof
Technical Field
The invention belongs to the technical field of superhard materials, and particularly relates to a submicron diamond compact and a preparation process thereof.
Background
The submicron diamond composite sheet is a double-layer structure diamond composite sheet formed by sintering submicron diamond micro powder (0.1-1 mu m) and a hard alloy matrix under the conditions of high pressure and high temperature. Because it has the characteristics of small diamond grain size, uniform structure and good wear resistance, and simultaneously has the characteristics of strong impact resistance and good weldability of hard alloy, it can be extensively used in the field of fine machining and super-fine machining of non-ferrous metal material.
Currently, submicro (0.5 μm) PCD grades, DA2200, are introduced by Sumitomo Electric Carbide in the united states, which can process extremely high workpiece surface smoothness and have high strength almost comparable to that of cemented Carbide, and submicron products of 0.5 μm or less are introduced by japan, Sumitomo, element six, and the like, which improve the wear resistance, impact toughness, and workability of the tool.
The submicron diamond compact has excellent properties, however, since very small diamond particles have a large surface area to volume ratio, when an iron group element such as Co, Ni, Fe is used as a binder, since these metals are solvents for diamond, during the ultra-high pressure high temperature sintering process, including the process of dissolution and precipitation of diamond in a solution, if diamond smaller than 2 μm, particularly smaller than 1 μm, is used as a raw material, the diamond particles are easily grown to make the diamond particles non-uniform in the diamond sintered body. Such abnormally grown grains have poor quality, and may cause a change in the internal structure of the polycrystalline diamond layer and a decrease in the bonding strength between diamond particles, resulting in deteriorated performance, and thus may not be used as a blank for finishing and superfinishing tools.
Disclosure of Invention
The invention aims to provide a preparation process of a submicron diamond compact, and the submicron diamond compact prepared by the process can effectively prevent diamond grains from growing abnormally, so that a finer and uniform tissue can be obtained to meet the requirements of finish machining and super-finish machining.
In order to achieve the above object, the present invention prepares a submicron diamond compact using the following process, comprising the steps of:
1) cobalt removal of the surface of the hard alloy substrate: with HNO3：H2Etching the upper surface of the hard alloy substrate in a solution with the volume ratio of O being 1 (2.5-3) for 20-60 min, and then washing the hard alloy substrate to be neutral by water to obtain the hard alloy substrate with the cobalt removed on the surface.
2) Purifying the diamond micro powder: mixing diamond micro powder and sodium chloride according to a mass ratio of 1 (2-3), after vacuum sintering, separating the diamond micro powder from the sodium chloride through a 400-mesh screen, and then rinsing with boiling water for 8-16 h until the conductivity value of deionized water mixed with the diamond micro powder is smaller than 1 muS/cm, so as to obtain the diamond micro powder with the particle size of 0.5-1.0μm; the granularity of the diamond micro-powder is 0.5-1.0 mu m, and the granularity of the sodium chloride is 200-300 meshes.
3) Preparing polycrystalline diamond powder: mixing 88-92 wt% of the diamond micro powder purified in the step 2), 5-7 wt% of a metal binder and 3-5 wt% of a grain growth inhibitor to obtain a powder mixture, adding absolute ethyl alcohol, polyethylene glycol and hard alloy balls into the powder mixture, and mixing for 100-150 hours to obtain polycrystalline diamond powder;
4) preparing a composite component: the cobalt-removed surface of the hard alloy substrate is contacted with polycrystalline diamond, vacuum sintering is carried out, mixed gas with reducibility is introduced for reaction, and then vacuum pumping is carried out until the pressure is 3 multiplied by 10-3Pa or less, a composite module was obtained.
5) Preparing a composite sheet: and (3) placing the composite assembly obtained in the step (4) into an inner cavity of the synthesis assembly block, and sintering the synthesis assembly block in a cubic press to obtain the submicron diamond composite sheet.
The specific parameters of the vacuum sintering in the step 2) are as follows: vacuumizing to the pressure of 3 × 10-3Raising the temperature to 700-800 ℃ below Pa, and keeping the temperature for 1-2 h.
The metal binding agent in the step 3) is composed of the following raw materials in percentage by weight: 98.5-99% of cobalt powder, 0.3-0.5% of tungsten powder, 0.2-0.3% of rubidium powder, 0.3-0.4% of cerium powder and 0.2-0.3% of antimony powder, wherein the particle size of the metal binder is 60-100 nm.
The grain growth inhibitor in the step 3) consists of the following raw materials in percentage by weight: 73-84% of silicon carbide powder, 4-7% of tungsten carbide powder, 3.5-6% of titanium carbonitride powder, 3-4% of zirconium carbonitride powder, 3-5% of boron carbide powder, 0.5-1% of titanium nitride powder, 0.5-1% of vanadium carbide powder, 0.5-1% of chromium carbide powder and 0.5-1% of cubic boron nitride micro powder, wherein the grain size of the grain growth inhibitor is 60-100 nm.
In the step 3), the powder mixture, the absolute ethyl alcohol, the polyethylene glycol and the hard alloy balls are mixed according to the weight ratio of 1 (0.2-0.25) to 0.02-0.05 to 5-6; the hard alloy ball is composed of a hard alloy ball with the diameter of phi 8-phi 10mm and a hard alloy ball with the diameter of phi 3-phi 5mm according to the ratio of 1: 1, and the material grade of the hard alloy ball is YG 8.
The concrete mode for mixing the powder mixture, the absolute ethyl alcohol, the polyethylene glycol and the hard alloy balls in the step 3) is as follows: wet ball milling is carried out by adopting a clockwise and anticlockwise alternate operation mode, the rotating speed is 60-80 r/min during clockwise operation, the rotating speed is 60-80 r/min during anticlockwise operation, alternate operation is carried out, the alternate clockwise time is 5-10 min, the alternate anticlockwise time is 8-12 min, and the alternate interval standby time is 0.5-1 min.
The specific parameters of the vacuum sintering of the composite assembly in the step 4) are as follows: vacuumizing until the pressure in the furnace reaches 8 x 10-2Heating to 180-230 ℃ below Pa, preserving heat for 0.5-1 h, then continuously vacuumizing and heating to 750-800 ℃ at the same time until the pressure in the furnace is stabilized at 3 x 10-3Vacuum pumping is carried out until the pressure in the furnace is 3 multiplied by 10 below Pa-3Pa below, stopping vacuumizing, charging mixed gas with the pressure of 60-80 Mbar in the furnace into a vacuum heating furnace at the temperature of 750-800 ℃ to reduce the composite assembly for 3-4 h, and vacuumizing until the pressure in the furnace is 3 multiplied by 10-3And the mixed gas is composed of 35-40% of hydrogen and 60-65% of carbon dioxide by volume percentage below Pa.
The sintering process in the step 5) is as follows: when the pressure is increased to 2-3 GPa, 900-1500A current is introduced, the pressure is increased to 5-6 GPa, the temperature is increased to 1400-1500 ℃, the temperature is maintained for 5-10 min, the temperature of the cavity is reduced to 750-850 ℃ at the cooling rate of 90-120 ℃/min, then the temperature of the cavity is reduced to the normal temperature at the cooling rate of 10-15 ℃/min, and the pressure of the cavity is reduced to the normal pressure at the pressure reduction rate of 0.085-0.095 GPa/min.
The submicron diamond composite sheet obtained by the preparation process comprises a hard alloy substrate and a polycrystalline diamond layer compounded on the upper surface of the hard alloy substrate, wherein the thickness of a cobalt removal layer on the upper surface of the hard alloy substrate is 50-100 mu m, and the content of cobalt in the cobalt removal layer is 1-1.2%.
The invention has the beneficial effects that:
1) according to the invention, the cobalt removal purification is carried out on the surface of the hard alloy substrate contacted with the polycrystalline diamond, the content of the metal phase cobalt at the interface of the hard alloy substrate and the diamond layer is reduced, the metal phase in the environment of the diamond near the interface is reduced, and the nucleation of the abnormal growth of the diamond grains is prevented, so that the possibility of the abnormal growth of the interface grains is reduced.
2) The invention is composed of silicon carbide, tungsten carbide, titanium carbonitride, zirconium carbonitride, boron carbide, titanium nitride, vanadium carbide, chromium carbide and cubic boron nitride, which can reduce the liquid phase of metal in diamond and metal binder and control the growth of diamond particles. The metal compounds and cubic boron nitride are partially dissolved in the metal liquid phase of the metal binder, and then precipitated on the surface of diamond crystals, thereby inhibiting abnormal growth of diamond particles. The polycrystalline diamond compact added with the grain growth inhibitor has uniform and compact structure, average granularity of less than or equal to 0.75 mu m and no abnormal growth of diamond.
3) The invention adopts a vacuum high-temperature purification method of the diamond micro powder and the sodium chloride together to fully purify the surface of the diamond; by adopting a ball milling wet type mixing method and adding a small amount of polyethylene glycol to carry out pretreatment on an initial diamond mixture, according to the characteristics of raw material composition and fine granularity of a diamond polycrystalline layer, the optimal process range is determined by adjusting parameters of a ball milling mixer, the mixing effect is further improved, and the metal bonding agent, the grain growth inhibitor and the diamond micro powder are fully mixed and dispersed. The secondary aggregate of diamond in the sample synthesized by the micro powder treated by the method is obviously reduced, the distribution of the metal phase is uniform, and the abnormal grain growth condition is reduced to a certain extent. The uniformity of the diamond compact product is further improved and enhanced.
4) According to the invention, the mixed gas of hydrogen and carbon dioxide is used for reducing the diamond micro powder and the metal bonding agent in a high vacuum state, and the foreign atoms adsorbed on the surfaces of the diamond and the bonding agent are pumped out to purify and activate the surfaces of the diamond and the bonding agent, so that the diamond and the bonding agent can easily generate chemical action, and the performances of wear resistance, thermal stability and the like of the diamond composite sheet are improved. The reduction method selects the optimal process range according to the characteristic of fine granularity of the diamond micro powder and the reduction characteristic of the metal bond material.
5) The sintering of the composite sheet adopts a mode of 'one-time pressure increasing and one-time temperature increasing', avoids the phenomenon of abnormal growth of crystal grains, adopts a scheme of slow temperature decreasing and slow pressure decreasing annealing process for reducing the stress of the sintered composite sheet during cooling and pressure releasing, has the effect of stress relieving annealing, greatly reduces the thermal residual stress of the submicron polycrystalline diamond composite sheet, and prolongs the service life of the composite sheet.
6) The performance indexes of the prepared submicron diamond compact are as follows: the average grain size of the polycrystalline diamond is less than or equal to 0.75 mu m; the abrasion ratio is 32-34 ten thousand; thermal stability: after the mixture is roasted for 2 minutes at 700 ℃, the abrasion ratio is 30-32 ten thousand, and the requirements of finish machining and super-finish machining are met.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
The normal temperature is 25 +/-5 ℃. In the following examples, the molybdenum box used in the diamond micro powder purification step and the metal cup used in the step of preparing the composite sheet assembly are common tools for holding materials in the existing production, and the structure and the using method of the synthetic assembly block applied in preparing the composite sheet are disclosed in CN107362750A, and are not described herein again.
Ct used below is the mass (weight) unit of the gemstone in carats, and 1 carat is now determined to be equal to 0.2 g or 200 mg.
The nitric acid in the invention is concentrated nitric acid sold in the market. The nitric acid concentration in the following examples is 69%.
Example 1
A preparation process of a submicron diamond compact comprises the following steps:
1) cobalt removal of the surface of the hard alloy substrate: coating a hard alloy substrate with a polytetrafluoroethylene protective materialBottom and side surfaces, then placed on HNO3：H2Etching in a solution with the volume ratio of O being 1:2.5 for 20 min, taking out the hard alloy substrate, washing the hard alloy substrate to be neutral by using ionized water to obtain the hard alloy substrate with the cobalt removed on the surface, wherein the thickness of the cobalt removed layer is 50 mu m, and the cobalt content of the cobalt removed layer is 1.0 percent (weight percentage);
wherein the material grade of the hard alloy substrate is YG10, and the specification is phi 45mm multiplied by 3.0 mm;
2) purifying the diamond micro powder: mixing diamond micro powder and 200-mesh sodium chloride according to a mass ratio of 1:2, putting the mixture into a molybdenum box, putting the molybdenum box into a vacuum sintering furnace, vacuumizing until the pressure in the furnace is 3 multiplied by 10-3Raising the temperature to 700 ℃ below Pa, and keeping the temperature for 1 h; separating the diamond micro powder from sodium chloride by a 400-mesh screen after vacuum treatment, then boiling and rinsing the diamond micro powder for 8 hours by using deionized water until the conductivity value of the deionized water mixed with the diamond micro powder is less than 0.9 muS/cm, and drying to obtain the diamond micro powder with the particle size of 0.5-1.0μm;
3) preparing polycrystalline diamond powder: 88% of diamond micro powder purified in the step 2), 7% of metal binder and 5% of grain growth inhibitor are mixed according to the weight percentage to obtain a powder mixture, the powder mixture, absolute ethyl alcohol, polyethylene glycol and hard alloy balls are mixed according to the weight ratio of 1:0.2:0.02:5 in a ball milling tank of polytetrafluoroethylene, and then the powder mixture, the absolute ethyl alcohol, the polyethylene glycol and the hard alloy balls are placed on a ball mill to ball-mill wet-type mixture for 100 hours in a clockwise and anticlockwise alternate operation mode to obtain polycrystalline diamond powder;
wherein the metal bonding agent is composed of the following raw materials in percentage by weight: 98.5% of cobalt powder, 0.5% of tungsten powder, 0.3% of rubidium powder, 0.4% of cerium powder and 0.3% of antimony powder, wherein the particle size of the metal bonding agent is 60 nm;
the grain growth inhibitor consists of the following raw materials in percentage by weight: 73% of silicon carbide powder, 7% of tungsten carbide powder, 6% of titanium carbonitride powder, 4% of zirconium carbonitride powder, 5% of boron carbide powder, 1% of titanium nitride powder, 1% of vanadium carbide powder, 1% of chromium carbide powder and 1% of cubic boron nitride micro powder, wherein the grain size of the grain growth inhibitor is 60 nm;
the hard alloy ball is composed of a hard alloy ball with the diameter of phi 8mm and a hard alloy ball with the diameter of phi 3mm according to the ratio of 1: 1, the material grade of the hard alloy ball is YG 8;
in the ball milling wet mixing, the rotating speed is 60 r/min when the ball milling wet mixing machine runs clockwise, the rotating speed is 60 r/min when the ball milling wet mixing machine runs anticlockwise, the alternating clockwise time is 5min, the alternating anticlockwise time is 8min, and the alternating interval standby time is 0.5 min.
4) Preparing a composite component: firstly pouring the polycrystalline diamond powder with 26Ct into a metal cup, strickling, then placing the cobalt-removed surface of the hard alloy substrate on the polycrystalline diamond powder material in the metal cup, covering the metal cup, placing the metal cup in a vacuum sintering furnace, vacuumizing until the pressure in the furnace reaches 8 multiplied by 10-2Heating to 180 deg.C below Pa, maintaining for 0.5h, vacuumizing while heating to 750 deg.C until furnace pressure is stabilized at 3 × 10-3Pa below, stopping vacuumizing, reducing the composite assembly for 3h by the mixed gas with the pressure of 60Mbar in the vacuum heating furnace at 750 ℃, and vacuumizing to the pressure of 3 x 10-3Pa or less, obtaining a composite assembly;
wherein the mixed gas comprises the following components in percentage by volume: 35% of hydrogen and 65% of carbon dioxide. The polycrystalline diamond powder contains oxides, gas and impurities, the purpose of vacuumizing can be to remove the impurities sucked out along with the gas while exhausting the gas, and the mixture can be reduced after the gas is introduced for reaction.
5) Preparing a composite sheet: placing the complex assembly obtained in the step 4) in an inner cavity of a synthesis assembly block, and sintering the synthesis assembly block in a cubic press to obtain a submicron diamond composite sheet;
the sintering process is as follows: when the pressure is increased to 2GPa, 900A current is introduced, then the pressure is increased to 5GPa, the temperature is increased to 1400 ℃, the temperature is maintained for 5min, the temperature of the cavity is reduced to 750 ℃ at the cooling rate of 90 ℃/min, then the temperature of the cavity is reduced to the normal temperature at the cooling rate of 10 ℃/min, and meanwhile, the pressure of the cavity is reduced to the normal pressure at the pressure reduction rate of 0.085 GPa/min.
The performance indexes of the submicron diamond compact with the diameter of phi 45mm, the total thickness of 3mm and the thickness of the polycrystalline diamond layer of 0.5mm prepared in the embodiment are detected as follows:
the average grain size of the diamond layer of the submicron diamond compact is 0.73-0.75 mu m;
the abrasion ratio is 33 ten thousand;
thermal stability: after 2 minutes of firing at 700 c, the attrition ratio was 31.5 ten thousand.
The abrasion ratio and the thermal stability of the composite sheet are also effectively improved, the diamond layer structure is uniform and compact, and the phenomenon of grain growth is avoided. And observing the texture structure of the diamond layer by using a JSM-7610F scanning electron microscope, and measuring the size of diamond grains, wherein the test standard of the abrasion ratio is JB/T3235-2013 'method for measuring the abrasion ratio of the artificial diamond sintered body'.
Example 2
1) Cobalt removal of the surface of the hard alloy substrate: coating the bottom and side surfaces of the hard alloy substrate with polytetrafluoroethylene protective materials, and placing the hard alloy substrate on HNO3：H2Etching in a solution with the volume ratio of O being 1:3 for 60 min, taking out the hard alloy substrate, washing the hard alloy substrate to be neutral by using ionized water to obtain the hard alloy substrate with the cobalt removed on the surface, wherein the thickness of the cobalt removed layer is 100 mu m, and the cobalt content of the cobalt removed layer is 1.2 percent (weight percentage);
wherein the material grade of the hard alloy substrate is YG10, and the specification is phi 45mm multiplied by 3.0 mm;
2) purifying the diamond micro powder: mixing diamond micro powder and 300-mesh sodium chloride according to a mass ratio of 1:3, putting the mixture into a molybdenum box, putting the molybdenum box into a vacuum sintering furnace, vacuumizing until the pressure in the furnace is 3 multiplied by 10-3Raising the temperature to 800 ℃ below Pa, and keeping the temperature for 2 h; separating the diamond micro powder from sodium chloride by a 400-mesh screen after vacuum treatment, then boiling and rinsing the diamond micro powder for 16 hours by using deionized water until the conductivity value of the deionized water mixed with the diamond micro powder is less than 1 mu S/cm, and drying to obtain the diamond micro powder with the particle size of 0.5-1.0 mu m;
3) preparing polycrystalline diamond powder: mixing 92 wt% of the diamond micro powder purified in the step 2), 5 wt% of a metal binder and 3 wt% of a grain growth inhibitor to obtain a powder mixture, pouring the powder mixture into a polytetrafluoroethylene ball milling tank, mixing the powder mixture, absolute ethyl alcohol, polyethylene glycol and hard alloy balls according to the weight ratio of 1:0.25:0.05:6, and then placing the powder mixture on a ball mill to perform ball milling wet mixing for 150 hours in a clockwise and anticlockwise alternating operation mode to obtain polycrystalline diamond powder;
wherein the metal bonding agent is composed of the following raw materials in percentage by weight: 99% of cobalt powder, 0.3% of tungsten powder, 0.2% of rubidium powder, 0.3% of cerium powder and 0.2% of antimony powder, wherein the particle size of the metal binder is 100 nm;
the grain growth inhibitor consists of the following raw materials in percentage by weight: 84% of silicon carbide powder, 4% of tungsten carbide powder, 3.5% of titanium carbonitride powder, 3% of zirconium carbonitride powder, 3% of boron carbide powder, 0.5% of titanium nitride powder, 0.5% of vanadium carbide powder, 0.5% of chromium carbide powder and 0.5% of cubic boron nitride micro powder, wherein the grain size of the grain growth inhibitor is 100 nm;
the hard alloy ball is composed of a hard alloy ball with the diameter of phi 10mm and a hard alloy ball with the diameter of phi 5mm according to the ratio of 1: 1, the material grade of the hard alloy ball is YG 8;
in the ball milling wet mixing, the rotating speed is 80 r/min when the ball milling wet mixing material is operated clockwise, the rotating speed is 80 r/min when the ball milling wet mixing material is operated anticlockwise, the ball milling wet mixing material is alternately operated, the alternate clockwise time is 10min, the alternate anticlockwise time is 12min, and the alternate interval standby time is 1 min.
4) Preparing a composite component: firstly pouring the polycrystalline diamond powder with 26Ct into a metal cup, strickling, then placing the cobalt-removed surface of the hard alloy substrate on the polycrystalline diamond powder material in the metal cup, covering the metal cup, placing the metal cup in a vacuum sintering furnace, vacuumizing until the pressure in the furnace reaches 8 multiplied by 10-2Heating to 230 deg.C under Pa for 1 hr, vacuumizing while heating to 800 deg.C until the furnace pressure is stabilized at 3 × 10-3Pa below, stopping vacuumizing, reducing the composite assembly with mixed gas at 800 deg.C for 4 hr, and vacuumizing to pressure of 3 × 10-3Pa or less, obtaining a composite assembly;
wherein the mixed gas comprises the following components in percentage by volume: 40% of hydrogen and 60% of carbon dioxide.
5) Preparing a composite sheet: placing the complex assembly obtained in the step 4) in an inner cavity of a synthesis assembly block, and sintering the synthesis assembly block in a cubic press to obtain a submicron diamond composite sheet;
the sintering process is as follows: when the pressure is increased to 3GPa, 1500A current is introduced, then the pressure is increased to 6GPa, the temperature is increased to 1500 ℃, the temperature is maintained for 10min, the temperature of the cavity is reduced to 850 ℃ at the cooling rate of 120 ℃/min, then the temperature of the cavity is reduced to the normal temperature at the cooling rate of 15 ℃/min, and meanwhile, the pressure of the cavity is reduced to the normal pressure at the pressure reduction rate of 0.095 GPa/min.
The performance indexes of the submicron diamond compact with the diameter of phi 45mm, the total thickness of 3mm and the thickness of the polycrystalline diamond layer of 0.5mm prepared in the embodiment are detected as follows:
the average grain size of the diamond layer of the submicron diamond compact is 0.73-0.74 mu m;
the abrasion ratio is 33 ten thousand; thermal stability:
after 2 minutes of firing at 700 c, the attrition rate was 32 ten thousand.
The abrasion ratio and the thermal stability of the composite sheet are also effectively improved, the diamond layer structure is uniform and compact, and the phenomenon of grain growth is avoided. And observing the texture structure of the diamond layer by using a JSM-7610F scanning electron microscope, and measuring the size of diamond grains, wherein the test standard of the abrasion ratio is JB/T3235-2013 'method for measuring the abrasion ratio of the artificial diamond sintered body'.
Example 3
1) Cobalt removal of the surface of the hard alloy substrate: coating the bottom and side surfaces of the hard alloy substrate with polytetrafluoroethylene protective materials, and placing the hard alloy substrate on HNO3：H2Etching in a solution with the volume ratio of O being 1:2.75 for 40min, taking out the hard alloy substrate, washing the hard alloy substrate to be neutral by using ionized water to obtain the hard alloy substrate with the cobalt removed on the surface, wherein the thickness of the cobalt removed layer is 75 mu m, and the cobalt content of the cobalt removed layer is 1.1 percent (weight percentage);
wherein the material grade of the hard alloy substrate is YG10, and the specification is phi 45mm multiplied by 3.0 mm;
2) purifying the diamond micro powder: mixing the diamond micro powder and 250-mesh sodium chloride according to the mass ratio of 1:2.5, and mixingThen the mixture is put into a molybdenum box and is placed in a vacuum sintering furnace, and the vacuum sintering furnace is vacuumized until the air pressure in the furnace is 3 multiplied by 10-3Raising the temperature to 750 ℃ below Pa, and keeping the temperature for 1.5 h; separating the diamond micro powder from sodium chloride by a 400-mesh screen after vacuum treatment, then boiling and rinsing the diamond micro powder for 16 hours by using deionized water until the conductivity value of the deionized water mixed with the diamond micro powder is less than 0.5 muS/cm, and drying to obtain the diamond micro powder with the particle size of 0.5-1.0μm;
3) preparing polycrystalline diamond powder: mixing 90 wt% of the diamond micro powder purified in the step 2), 6 wt% of a metal binder and 4 wt% of a grain growth inhibitor to obtain a powder mixture, pouring the powder mixture into a polytetrafluoroethylene ball milling tank, mixing the powder mixture, absolute ethyl alcohol, polyethylene glycol and hard alloy balls according to the weight ratio of 1:0.225:0.035:5.5, and then placing the powder mixture on a ball mill to ball mill wet-type mixed materials for 125 hours by adopting a clockwise and anticlockwise alternate operation mode to obtain polycrystalline diamond powder;
wherein the metal bonding agent is composed of the following raw materials in percentage by weight: 98.75% of cobalt powder, 0.4% of tungsten powder, 0.25% of rubidium powder, 0.35% of cerium powder and 0.25% of antimony powder, wherein the particle size of the metal bonding agent is 80 nm;
the grain growth inhibitor consists of the following raw materials in percentage by weight: 78.5% of silicon carbide powder, 5.5% of tungsten carbide powder, 4.75% of titanium carbonitride powder, 3.5% of zirconium carbonitride powder, 4% of boron carbide powder, 0.75% of titanium nitride powder, 0.75% of vanadium carbide powder, 0.75% of chromium carbide powder and 0.75% of cubic boron nitride micro powder, wherein the grain size of the grain growth inhibitor is 80 nm;
the hard alloy ball is composed of a hard alloy ball with the diameter phi of 9mm and a hard alloy ball with the diameter phi of 4mm according to the weight ratio of 1: 1, the material grade of the hard alloy ball is YG 8;
in the ball milling wet mixing, the rotating speed is 70 r/min when the ball milling wet mixing material is operated clockwise, the rotating speed is 70 r/min when the ball milling wet mixing material is operated anticlockwise, the ball milling wet mixing material is alternately operated, the alternate clockwise time is 7min, the alternate anticlockwise time is 10min, and the alternate interval standby time is 0.7 min.
4) Preparing a composite component: firstly, pouring 26Ct polycrystalline diamond powder into a metal cup, strickling, and then removing the hard alloy substratePlacing cobalt with surface facing downwards on the polycrystalline diamond powder material in a metal cup, covering the metal cup cover, placing in a vacuum sintering furnace, vacuumizing until the pressure in the furnace reaches 8 × 10-2Heating to 205 deg.C below Pa, maintaining for 0.75 hr, vacuumizing while heating to 775 deg.C until furnace pressure is stabilized at 3 × 10-3Pa below, stopping vacuumizing, reducing the composite assembly with mixed gas at 775 deg.C for 3.5 hr, and vacuumizing to 3 × 10-3Pa or less, obtaining a composite assembly;
wherein the mixed gas comprises the following components in percentage by volume: 37.5% of hydrogen and 62.5% of carbon dioxide.
5) Preparing a composite sheet: placing the complex assembly obtained in the step 4) in an inner cavity of a synthesis assembly block, and sintering the synthesis assembly block in a cubic press to obtain a submicron diamond composite sheet;
the sintering process is as follows: when the pressure is increased to 2.5GPa, the current of 1200A is introduced, then the pressure is increased to 5.5GPa, the temperature is increased to 1450 ℃, after 7.5min, the temperature of the cavity is reduced to 800 ℃ at the cooling rate of 105 ℃/min, then the temperature of the cavity is reduced to the normal temperature at the cooling rate of 12.5 ℃/min, and simultaneously the pressure of the cavity is reduced to the normal pressure at the pressure reduction rate of 0.09 GPa/min.
The performance indexes of the submicron diamond compact with the diameter of phi 45mm, the total thickness of 3mm and the thickness of the polycrystalline diamond layer of 0.5mm, which are prepared in the embodiment, are detected as follows:
the average grain size of the diamond layer of the submicron diamond composite sheet is 0.74-0.75 mu m, and no grain growth phenomenon exists;
the abrasion ratio is 34 ten thousand;
thermal stability: after 2 minutes of firing at 700 c, the attrition ratio was 31.8 ten thousand.
The abrasion ratio and the thermal stability of the composite sheet are also effectively improved and enhanced. The diamond layer has uniform and compact structure and no grain growth phenomenon. And observing the texture structure of the diamond layer by using a JSM-7610F scanning electron microscope, and measuring the size of diamond grains, wherein the test standard of the abrasion ratio is JB/T3235-2013 'method for measuring the abrasion ratio of the artificial diamond sintered body'.
Comparative example 1
The difference from the embodiment 1 is that:
1) the thickness of the cobalt-removing layer on the surface of the hard alloy substrate is 49 mu m, and the cobalt content of the cobalt-removing layer is 1.3 w%;
2) the powder mixture consists of the following materials in percentage by weight: 87% of diamond micro powder, 7.5% of metal bonding agent and 5.5% of grain growth inhibitor;
the composite sheet described in comparative example 1 has an average grain size equal to 1 μm; the abrasion ratio is 28 ten thousand; thermal stability: after 2 minutes of firing at 700 c, the attrition rate was 25 ten thousand. It has poor wear resistance and thermal stability. There is a grain growth phenomenon.
Comparative example 2
The difference from the embodiment 1 is that:
1) the metal bonding agent comprises the following raw materials in percentage by weight: 99.4% of cobalt powder, 0.2% of tungsten powder, 0.1% of rubidium powder, 0.2% of cerium powder and 0.1% of antimony powder, wherein the particle size of the metal binder is 60-100 nm;
2) the grain growth inhibitor consists of the following raw materials in percentage by weight: 85% of silicon carbide powder, 3.9% of tungsten carbide powder, 3.3% of titanium carbonitride powder, 2.9% of zirconium carbonitride powder, 2.8% of boron carbide powder, 0.45% of titanium carbide powder, 0.4% of titanium nitride powder, 0.45% of vanadium carbide powder, 0.4% of chromium carbide powder and 0.4% of cubic boron nitride micropowder, and the grain size of the grain growth inhibitor is 110 nm.
The composite sheet described in comparative example 2 has an average grain size equal to 1.2 μm; the abrasion ratio is 29 ten thousand; thermal stability: after 2 minutes of firing at 700 c, the attrition rate was 26 ten thousand. It has poor wear resistance and thermal stability. There is a grain growth phenomenon.
Comparative example 3
The difference from the embodiment 3 is that:
1）HNO3：H2the volume ratio of O is 1: 2.4, etching time is 19 min;
the composite sheet prepared in comparative example 3 had an average grain size equal to 0.95 μm; the abrasion ratio is 30 ten thousand; thermal stability: after 2 minutes of firing at 700 c, the attrition rate was 27 ten thousand. It has poor wear resistance and thermal stability. There is a grain growth phenomenon.
Comparative example 4
The difference from the embodiment 3 is that:
1) the mass ratio of the diamond micro powder to 350-mesh analytically pure sodium chloride is 1: 3.5 mixing; raising the temperature to 810 ℃ and preserving the heat for 2.5 h; after vacuum treatment, the diamond micro powder is boiled and rinsed by deionized water for 17 hours until the conductivity value of the deionized water mixed with the diamond micro powder is 2 muS/cm;
comparative example 4. the composite sheet obtained in comparative example 4 has an average grain size of 0.95 μm or less; the abrasion ratio is 27 ten thousand; thermal stability: after 2 minutes of firing at 700 c, the attrition rate was 24 ten thousand. It has poor wear resistance and thermal stability. There is a grain growth phenomenon.
It can be clearly seen that the average grain size of the submicron diamond compact prepared in examples 1-3 is less than or equal to 0.75 μm, which not only has good wear resistance, but also effectively improves and enhances the thermal stability of the compact, and the diamond layer has uniform and compact structure and no grain growth phenomenon.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention, and it is intended to cover in the appended claims all such changes and modifications that are within the scope of the invention.

Claims (7)

1. A preparation process of a submicron diamond compact is characterized by comprising the following steps:
1) cobalt removal of the surface of the hard alloy substrate: at HNO3：H2Etching the upper surface of the hard alloy substrate for 20-60 min in a solution with the volume ratio of O being 1 (2.5-3), and then washing with water to obtain the hard alloy substrate with the cobalt removed on the surface;
2) purifying the diamond micro powder: mixing the diamond micro powder and sodium chloride according to a mass ratio of 1 (2-3), after vacuum sintering, separating the diamond micro powder from the sodium chloride, and then rinsing with boiling water for 8-16 h to obtain purified diamond micro powder;
3) preparing polycrystalline diamond powder: mixing 88-92 wt% of the diamond micro powder purified in the step 2), 5-7 wt% of a metal binder and 3-5 wt% of a grain growth inhibitor to obtain a powder mixture, adding absolute ethyl alcohol, polyethylene glycol and hard alloy balls into the powder mixture, and mixing for 100-150 hours to obtain polycrystalline diamond powder;
4) preparing a composite component: the cobalt-removed surface of the hard alloy substrate is contacted with polycrystalline diamond powder, vacuum sintering is carried out, mixed gas with reducibility is introduced for reaction, and then vacuum pumping is carried out until the gas pressure is 3 multiplied by 10-3Pa or less, obtaining a composite assembly;
5) preparing a composite sheet: placing the complex assembly obtained in the step 4) in an inner cavity of a synthesis assembly block, and sintering the synthesis assembly block in a cubic press to obtain a submicron diamond composite sheet;
the metal binding agent in the step 3) is composed of the following raw materials in percentage by weight: 98.5-99% of cobalt powder, 0.3-0.5% of tungsten powder, 0.2-0.3% of rubidium powder, 0.3-0.4% of cerium powder and 0.2-0.3% of antimony powder, wherein the particle size of the metal binder is 60-100 nm;
the grain growth inhibitor in the step 3) consists of the following raw materials in percentage by weight: 73-84% of silicon carbide powder, 4-7% of tungsten carbide powder, 3.5-6% of titanium carbonitride powder, 3-4% of zirconium carbonitride powder, 3-5% of boron carbide powder, 0.5-1% of titanium nitride powder, 0.5-1% of vanadium carbide powder, 0.5-1% of chromium carbide powder and 0.5-1% of cubic boron nitride micro powder, wherein the grain size of the grain growth inhibitor is 60-100 nm;
the submicron diamond compact comprises a hard alloy substrate and a polycrystalline diamond layer compounded on the cobalt-removed surface of the hard alloy substrate.
2. The process for preparing a submicron diamond compact according to claim 1, wherein the specific parameters of the vacuum sintering in step 2) are: vacuumizing to the pressure of 3 × 10-3Raising the temperature to 700-800 ℃ below Pa, and keeping the temperature for 1-2 h.
3. The process for preparing a submicron diamond compact according to claim 1, wherein in the step 3), the powder mixture, the absolute ethyl alcohol, the polyethylene glycol and the hard alloy ball are mixed according to the weight ratio of 1 (0.2-0.25) to (0.02-0.05) to (5-6); the hard alloy ball is composed of a hard alloy ball with the diameter of phi 8-phi 10mm and a hard alloy ball with the diameter of phi 3-phi 5mm according to the ratio of 1: 1 by weight ratio.
4. The preparation process of the submicron diamond compact of claim 1, wherein the specific mixing mode of the powder mixture, the absolute ethyl alcohol, the polyethylene glycol and the hard alloy ball in the step 3) is as follows: wet ball milling is carried out by adopting a clockwise and anticlockwise alternate operation mode, the rotating speed is 60-80 r/min during clockwise operation, the rotating speed is 60-80 r/min during anticlockwise operation, alternate operation is carried out, the alternate clockwise time is 5-10 min, the alternate anticlockwise time is 8-12 min, and the alternate interval standby time is 0.5-1 min.
5. The process for making a sub-micron diamond compact of claim 1, wherein the specific parameters for vacuum sintering the composite assembly in step 4) are: vacuumizing until the pressure in the furnace reaches 8 x 10-2Heating to 180-230 ℃ below Pa, preserving heat for 0.5-1 h, then continuously vacuumizing and heating to 750-800 ℃ at the same time until the pressure in the furnace is stabilized at 3 x 10-3Pa below, stopping vacuumizing, charging mixed gas with the pressure of 60-80 Mbar in the furnace into a vacuum heating furnace at the temperature of 750-800 ℃ to reduce the composite assembly for 3-4 h, and vacuumizing until the pressure in the furnace is 3 multiplied by 10-3Pa below; the mixed gas consists of 35-40% of hydrogen and 60-65% of carbon dioxide by volume percentage.
6. The process for preparing a submicron diamond compact according to claim 1, wherein the sintering process in step 5) is as follows: when the pressure is increased to 2-3 GPa, 900-1500A current is introduced, the pressure is increased to 5-6 GPa, the temperature is increased to 1400-1500 ℃, the temperature is maintained for 5-10 min, the temperature of the cavity is reduced to 750-850 ℃ at the cooling rate of 90-120 ℃/min, then the temperature of the cavity is reduced to the normal temperature at the cooling rate of 10-15 ℃/min, and the pressure of the cavity is reduced to the normal pressure at the pressure reduction rate of 0.085-0.095 GPa/min.
7. The submicron diamond compact obtained by the preparation process according to any one of claims 1 to 6, wherein the thickness of the cobalt-removed layer on the upper surface of the cemented carbide substrate is 50 to 100 μm, and the cobalt content of the cobalt-removed layer is 1 to 1.2%.
CN201810999120.5A 2018-08-30 2018-08-30 Submicron diamond composite sheet and preparation process thereof Active CN108941583B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810999120.5A CN108941583B (en) 2018-08-30 2018-08-30 Submicron diamond composite sheet and preparation process thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810999120.5A CN108941583B (en) 2018-08-30 2018-08-30 Submicron diamond composite sheet and preparation process thereof

Publications (2)

Publication Number Publication Date
CN108941583A CN108941583A (en) 2018-12-07
CN108941583B true CN108941583B (en) 2021-08-20

Family

ID=64473636

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810999120.5A Active CN108941583B (en) 2018-08-30 2018-08-30 Submicron diamond composite sheet and preparation process thereof

Country Status (1)

Country Link
CN (1) CN108941583B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111872375B (en) * 2020-07-17 2022-07-05 苏州思珀利尔工业技术有限公司 Preparation method of cobalt powder coated diamond pellet, cobalt powder coated diamond and application thereof
CN111850335B (en) * 2020-07-27 2022-04-29 深圳市海明润超硬材料股份有限公司 Diamond composite sheet easy to remove cobalt and preparation method thereof
CN114700494A (en) * 2021-12-14 2022-07-05 河南晶锐新材料股份有限公司 Preparation method of polycrystalline diamond compact

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6302225B1 (en) * 1998-04-28 2001-10-16 Sumitomo Electric Industries, Ltd. Polycrystal diamond tool
CN103722174A (en) * 2013-12-30 2014-04-16 中原工学院 Self-sharpening polycrystalline diamond compact and preparation method thereof
CN104942280A (en) * 2015-06-23 2015-09-30 中南钻石有限公司 High-performance polycrystalline diamond sintering body, preparation method thereof and binding agent
CN104959616A (en) * 2015-06-23 2015-10-07 中南钻石有限公司 Sandwich-type polycrystalline diamond compact and preparation method thereof and used binding agent
CN106563809A (en) * 2016-11-14 2017-04-19 中石化石油机械股份有限公司江钻分公司 Polycrystalline diamond-hard alloy composite sheet and preparation method thereof
CN106623946A (en) * 2015-10-29 2017-05-10 李涛 Method for manufacturing diamond compact
CN106735246A (en) * 2016-11-18 2017-05-31 富耐克超硬材料股份有限公司 A kind of multilayer composite polycrystal-diamond and preparation method thereof
CN107867016A (en) * 2017-11-22 2018-04-03 深圳先进技术研究院 A kind of composite polycrystal-diamond and preparation method thereof
CN108115142A (en) * 2017-12-25 2018-06-05 富耐克超硬材料股份有限公司 Diamond compact and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7556763B2 (en) * 1999-12-08 2009-07-07 Diamicron, Inc. Method of making components for prosthetic joints

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6302225B1 (en) * 1998-04-28 2001-10-16 Sumitomo Electric Industries, Ltd. Polycrystal diamond tool
CN103722174A (en) * 2013-12-30 2014-04-16 中原工学院 Self-sharpening polycrystalline diamond compact and preparation method thereof
CN104942280A (en) * 2015-06-23 2015-09-30 中南钻石有限公司 High-performance polycrystalline diamond sintering body, preparation method thereof and binding agent
CN104959616A (en) * 2015-06-23 2015-10-07 中南钻石有限公司 Sandwich-type polycrystalline diamond compact and preparation method thereof and used binding agent
CN106623946A (en) * 2015-10-29 2017-05-10 李涛 Method for manufacturing diamond compact
CN106563809A (en) * 2016-11-14 2017-04-19 中石化石油机械股份有限公司江钻分公司 Polycrystalline diamond-hard alloy composite sheet and preparation method thereof
CN106735246A (en) * 2016-11-18 2017-05-31 富耐克超硬材料股份有限公司 A kind of multilayer composite polycrystal-diamond and preparation method thereof
CN107867016A (en) * 2017-11-22 2018-04-03 深圳先进技术研究院 A kind of composite polycrystal-diamond and preparation method thereof
CN108115142A (en) * 2017-12-25 2018-06-05 富耐克超硬材料股份有限公司 Diamond compact and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
硬质合金球上纳米金刚石膜的形貌与力学性能;张廷飞等;《人工晶体学报》;20130615;第42卷(第06期);第1016-1020页 *

Also Published As

Publication number Publication date
CN108941583A (en) 2018-12-07

Similar Documents

Publication Publication Date Title
CN108941583B (en) Submicron diamond composite sheet and preparation process thereof
CN108950560B (en) Double-sided heat-resistant polycrystalline diamond compact and preparation process thereof
EP1942204B1 (en) Sputtering target
CN108950561B (en) Titanium-plated cubic boron nitride composite sheet and preparation process thereof
TWI458845B (en) Tungsten sintered body sputtering target
TWI413703B (en) Tantalum sputtering target
TWI487583B (en) Production method of high purity tungsten powder
EP2604718B1 (en) Tantalum sputtering target
US11046581B2 (en) Polycrystalline cubic boron nitride and method for manufacturing the same
JPH04146987A (en) Alumina-zirconia lapping compound, production thereof, and composition for abrasion
TWI500778B (en) Tantalum sputtering target
CN103878555B (en) Cubic boron nitride base ultra-high pressure sintered material control surface coated cutting tool
WO2002014452A1 (en) Diamond abrasive material particles and production method therefor
WO2004069399A1 (en) Cubic boron nitride, catalyst for synthesizing cubic boron nitride, and process for producing cubic boron nitride
JP3698664B2 (en) Method for producing high purity silicon nitride powder
CN113621892A (en) Hard alloy milling cutter with high impact resistance and preparation method thereof
CN103467101A (en) Rare earth green silicon carbide, application thereof and rare earth green silicon carbide abrasive grinding tool
CN109609793A (en) The preparation method of the hard alloy containing ruthenium
JP2005248309A (en) Cemented carbide and coated cemented carbide
CN109485425A (en) A kind of tungsten carbide composite and preparation method thereof
JP3285621B2 (en) Method for producing silicon nitride powder
CN114196883B (en) Low-defect fine-grain alloy steel and casting method and application thereof
EP4039766A1 (en) Easily crushable diamond abrasive grains and method for manufacturing same
JP3367567B2 (en) Method for producing easily crushable and high α-type silicon nitride
JP2010207954A (en) Cemented carbide end-mill excellent in chipping resistance in high speed cutting

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant