CN112059193B - High-toughness wear-resistant polycrystalline diamond compact and preparation method thereof - Google Patents

High-toughness wear-resistant polycrystalline diamond compact and preparation method thereof Download PDF

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CN112059193B
CN112059193B CN202010864532.5A CN202010864532A CN112059193B CN 112059193 B CN112059193 B CN 112059193B CN 202010864532 A CN202010864532 A CN 202010864532A CN 112059193 B CN112059193 B CN 112059193B
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powder
polycrystalline diamond
graphene
layer
sintering
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CN112059193A (en
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张涛
卢灿华
朱培
宋子衡
邱林
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Zhongnan Diamond Co Ltd
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Zhongnan Diamond Co Ltd
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    • 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
    • B22F1/0003—
    • 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
    • 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
    • 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
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C23C14/0652—Silicon nitride
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • B22F2007/042—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 characterised by the layer forming method
    • 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

Abstract

The invention relates to a high-toughness wear-resistant polycrystalline diamond compact and a preparation method thereof3N 4The coating, the powder transition layer and the polycrystalline diamond layer; the polycrystalline diamond layer is composed of the following raw materials in percentage by weight: 95-98% of carbon nanotube coated diamond micro powder, 0.1-0.3% of graphene, 0.1-0.2% of carbon fiber and 1.8-4.5% of a binding agent. The invention adopts the carbon nano tube with the dual characteristics of diamond and carbon nano tube to coat the diamond micro powder and deposits Si on the surface of the hard alloy substrate3N 4The powder transition layer is arranged between the coating and the polycrystalline diamond layer, so that the excellent performance of the polycrystalline diamond layer is ensured, and meanwhile, the bonding strength between the coating and the polycrystalline diamond layer is greatly enhanced, so that the polycrystalline diamond layer has wear resistance and excellent impact toughness.

Description

High-toughness wear-resistant polycrystalline diamond compact and preparation method thereof
Technical Field
The invention belongs to the technical field of superhard composite materials, and particularly relates to a high-toughness wear-resistant polycrystalline diamond compact and a preparation method thereof.
Background
The diamond cutter which is competitively developed in various countries at present is a polycrystalline diamond-hard alloy composite sheet cutter, the polycrystalline diamond composite sheet has high hardness and good wear resistance, and has the advantages of isotropy, conductivity, weldability, economy and the like compared with single crystal diamond, so that the polycrystalline diamond composite sheet is widely applied to the field of processing nonferrous metals and non-metallic materials which are difficult to process.
Firstly, due to structural defects existing on the surface of common diamond particles and large differences between the common diamond particles and a bonding agent in strength, hardness, elastic modulus and structure, the polycrystalline diamond compact is abnormally fractured or diamond drops early in the application process, so that the service life of the polycrystalline diamond compact is shortened; the other is a polycrystalline diamond compact prepared by common diamond grains, which has a series of advantages of diamond single crystals, but has shortcomings in heat conductivity, heat resistance, oxidation resistance and chemical inertness in practical application. Thirdly, the difference between the thermal expansion coefficient, the elastic modulus and other physical performance parameters of the polycrystalline diamond layer and the hard alloy matrix is large, so that the adhesion force between the polycrystalline diamond layer and the hard alloy matrix is not strong, the impact resistance is poor, and the polycrystalline diamond layer is easy to fall off and break during working, so that the cutter fails.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a high-toughness wear-resistant polycrystalline composite sheet and a preparation method thereof, so that the impact toughness and the wear resistance of the polycrystalline diamond composite sheet are improved, and the service life of the polycrystalline diamond composite sheet is further prolonged.
In order to realize the purpose, the invention adopts the following technical scheme:
a high-toughness wear-resistant polycrystalline diamond compact comprises a hard alloy matrix and Si sequentially arranged on the hard alloy matrix3N4The coating, the powder transition layer and the polycrystalline diamond layer; the polycrystalline diamond layer is composed of the following raw materials in percentage by weight: 95-98% of carbon nanotube coated diamond micro powder, 0.1-0.3% of graphene, 0.1-0.2% of carbon fiber and 1.8-4.5% of a binding agent.
Specifically, the powder transition layer is composed of the following raw materials in percentage by weight: 40-48% of hard alloy powder, 50-56% of carbon nano tube coated diamond micro powder, 0.5-1.5% of graphene and 1.5-2.5% of a binding agent; the graphene can be selected from graphene nanosheets with the thickness of 6-8 nm and the width of 5 microns, and common commercial products can be directly purchased, for example, the graphene and the carbon fiber are purchased from Beijing Deke island gold science and technology Co.
Specifically, said Si3N4The thickness of the coating is 6-8 mu m; the mass ratio of the powder transition layer to the polycrystalline diamond layer is 0.2: 1 to 1.5.
Further, the binding agent is composed of the following raw materials in percentage by weight: 97-99% of cobalt powder, 0.5-1.5% of tungsten powder, 0.4-1.3% of titanium powder and 0.1-0.2% of rare earth elements, wherein the rare earth elements are any one of erbium, ytterbium and holmium; the particle sizes of the cobalt powder, the tungsten powder, the titanium powder and the rare earth element are 20-50 nm.
Further, the carbon nanotube coated diamond micro powder is composed of micro powder with particle size distribution of 2-4 mu m and 5-10 mu m but not including three particle size distributions of 10 mu m and 10-20 mu m; the micro powder with three particle sizes comprises the following components in percentage by weight in the carbon nano tube coated diamond micro powder: the range of 2-4 mu m accounts for 10-20%, the range of 5-10 mu m does not contain 35-40% of 10 mu m, and the range of 10-20 mu m accounts for 45-50%.
Further, the hard alloy matrix or the hard alloy powder is composed of the following raw materials in percentage by weight: 84.5-88% of tungsten carbide powder, 10.5-13.9% of cobalt powder, 0.5-1% of zirconium powder, 0.3-0.5% of tantalum carbide powder and 0.3-0.5% of niobium carbide powder; the particle size of the tungsten carbide powder is 1.2-1.6 mu m; the particle sizes of the cobalt powder, the zirconium powder, the tantalum carbide powder and the niobium carbide powder are all 0.8-1.2 mu m. The raw material powders involved in the invention are all common commercial products which can be directly purchased.
The carbon nano tube coated diamond micro powder is prepared by chemical vapor deposition of the carbon nano tube on a catalyst layer on the surface of the diamond with the catalyst layer on the surface; the carbon nano tube is of a single-layer structure or a multi-layer structure. The carbon nanotube-coated diamond micro powder can be prepared by adopting the prior art, for example, the carbon nanotube-coated diamond micro powder can be prepared by referring to chinese patent CN201610161233.9 (publication No. 105803420a, graphene and/or carbon nanotube-coated diamond composite material and preparation method and application thereof), and specifically can be: sputtering a nickel catalyst layer on the diamond by using a magnetron sputtering technology, wherein the thickness of the nickel film is 50-80 nm;depositing carbon nanotubes on the diamond containing the catalyst layer by using a chemical vapor deposition technology, applying plasma to the surface of the diamond for auxiliary growth in the deposition process, adding a magnetic field at the bottom of the diamond to restrain the plasma on the surface of the diamond, strengthening the bombardment of the plasma on the surface of the diamond, and enabling the carbon nanotubes to grow vertical to the surface of the diamond to obtain the carbon nanotube-coated diamond micropowder; the deposition parameters were: the mass flow percentage of the carbon-containing gas in the total gas in the furnace is 5-50%; the growth temperature is 400-1300 ℃, and the growth air pressure is 10 DEG3～105Pa; plasma current density of 0-30 mA/cm2(ii) a The magnetic field strength in the deposition zone is 100 gauss to 30 tesla.
The invention provides a preparation method of the high-toughness wear-resistant polycrystalline diamond compact, which comprises the following steps:
1) depositing a transition layer: placing a hard alloy substrate in a magnetron sputtering device, taking silicon as a target material and nitrogen as a reaction gas, controlling the flow rate of the nitrogen to be 20-100 sccm, the radio frequency power to be 30-60W and the deposition pressure to be 0.3-2 Pa, and depositing Si on the surface of the clean hard alloy substrate3N4Layer of Si to obtain a layer containing3N4A coated cemented carbide substrate;
2) mixing of powder transition layers: weighing graphene according to a ratio, adding the graphene into absolute ethyl alcohol, and performing ultrasonic sweeping dispersion for 20-30 min to obtain a graphene dispersion liquid; then magnetically stirring the graphene dispersion liquid, and after 30-40 min, carrying out vacuum drying to obtain dispersed graphene powder; then weighing the carbon nanotube coated diamond micro powder, the hard alloy powder and the binding agent according to a ratio, ball-milling the carbon nanotube coated diamond micro powder, the hard alloy powder, the binding agent and the dispersed graphene powder, wherein the ball material mass ratio is 4-6: 1, the ball-milling medium is absolute ethyl alcohol, the ball-milling body is a hard alloy ball, the ball-milling tank is a hard alloy tank, the clockwise and counterclockwise alternate operation mode is adopted, the rotating speed is 35-45 r/min during clockwise operation, the rotating speed is 45-55 r/min during counterclockwise operation, the time is 20-25 min during clockwise operation, the time is 20-25 min during counterclockwise operation, the intermediate interval standby time is 4-8 min during clockwise and counterclockwise alternate operation, the ball-milling time is 25-30 h, and vacuum drying is carried out to obtain powder transition layer mixed powder;
3) mixing the polycrystalline diamond layer: weighing graphene and carbon fibers according to a ratio, respectively adding the graphene and the carbon fibers into absolute ethyl alcohol, and performing ultrasonic oscillation dispersion for 20-30 min to obtain a graphene dispersion liquid and a carbon fiber dispersion liquid; then magnetically stirring the graphene dispersion liquid, after 30-40 min, slowly adding the carbon fiber dispersion liquid drop by drop, and after 30-40 min, carrying out vacuum drying to obtain mixed powder of the dispersed graphene and the carbon fiber; then weighing the carbon nanotube coated diamond micro powder and a binding agent according to a ratio, ball-milling the carbon nanotube coated diamond micro powder, the binding agent and the mixed powder of the dispersed graphene and the carbon fiber, wherein the mass ratio of ball materials is 4-10: 1, a ball-milling medium is absolute ethyl alcohol, a ball milling body is a nickel alloy ball, a ball-milling tank is a nickel alloy tank, a clockwise and anticlockwise alternate operation mode is adopted, the rotating speed is 50-60 r/min during clockwise operation, the rotating speed is 70-80 r/min during anticlockwise operation, the time is 20-25 min during clockwise operation, the time is 20-25 min during anticlockwise operation, the intermediate interval standby time is 4-8 min during clockwise and anticlockwise alternate operation, the ball-milling time is 20-30 h, and the mixed powder of the diamond is obtained after vacuum drying;
4) assembling a composite body: firstly, paving the mixed powder of the polycrystalline diamond layer in a high-temperature resistant metal cup, and leveling; laying powder transition layer mixed powder on the polycrystalline diamond layer, and leveling; then will contain Si3N4Coated cemented carbide substrate with Si3N4Horizontally placing the coating face downwards on the mixed powder of the powder transition layer, placing the powder transition layer in a prepressing die, and prepressing for 5-8 min by using a hydraulic machine under the pressure of 10MPa to form a composite assembly;
5) and (3) purification treatment: placing the composite assembly obtained in the step 4) in a vacuum sintering furnace for sintering to obtain a purified composite assembly;
6) high-temperature high-pressure sintering: placing the purification composite component in the step 5) in a synthesis assembly block, and sintering at high temperature and high pressure by using a cubic press;
7) aging treatment: putting the polycrystalline diamond compact obtained after sintering in the step 6) into a vacuum sintering furnaceInside, the furnace is vacuumized until the pressure in the furnace is 3 multiplied by 10-3Pa, at 3X 10-3Heating to 380-430 ℃ under Pa, preserving heat for 0.5-1 h, vacuumizing again until the air pressure in the furnace is 3 multiplied by 10-5Pa, at 3X 10-5And (3) under the condition of Pa, heating to 480-530 ℃, preserving heat for 1-1.5 h, and finally cooling to room temperature and storing in vacuum.
Specifically, when the step 5) is sintered in a vacuum sintering furnace, rough vacuum is firstly carried out until the air pressure in the furnace reaches 6 multiplied by 10-2Heating to 200-300 ℃ under Pa, keeping the temperature for 20-30 min, continuously vacuumizing and heating to 850-900 ℃ until the pressure in the furnace is stabilized at 3 x 10-4Stopping vacuumizing below Pa, charging carbon monoxide gas with the furnace internal air pressure of 25-35 Mbar into a vacuum heating furnace at 850-900 ℃ to reduce the composite assembly for 0.5-1 h, and continuously vacuumizing until the furnace internal air pressure is 3 multiplied by 10-4And (3) after the temperature is increased to 1150-1200 ℃ and the temperature is kept for 2-3 min below Pa, stopping vacuumizing, intermittently filling carbon monoxide into the vacuum heating furnace, wherein the air inflation amount is the same each time and the carbon monoxide filling amount is limited to 30-40 Mbar of the air pressure in the furnace, and after the air inflation is finished each time, waiting for 10min, starting a vacuumizing system to vacuumize the vacuum heating furnace until the air pressure in the furnace is 3 multiplied by 10-4And (4) setting the vacuumizing time in advance below Pa, and starting the carbon monoxide filling program and the vacuumizing program again after vacuumizing is finished to circulate for 8-12 times to obtain the purification composite assembly.
Specifically, in the step 6), during sintering, the temperature is increased to 7GPa at the speed of 0.1-1 GPa/min, then the temperature is increased to 1370-1400 ℃ at the temperature increase rate of 20-25 ℃/min for sintering for 80-120S, then the temperature is increased to 1430-1470 ℃ at the temperature increase rate of 10-15 ℃/min for sintering for 130-180S, then the temperature is increased to 1500-1550 ℃ at the temperature increase rate of 5-10 ℃/min for sintering, the temperature is decreased to the normal temperature at the temperature decrease rate of 10-30 ℃/min after sintering for 350-500S, and the pressure is decreased from the high pressure to the normal pressure at the pressure decrease rate of 0.1-0.5 GPa/min.
The high-toughness wear-resistant polycrystalline diamond compact disclosed by the invention has the heat conductivity coefficient of more than 330W/(M.k), the wear ratio of 40-42 ten thousand and the impact frequency of not less than 65 times. The high-toughness wear-resistant polycrystalline diamond compact is made into an SNMG120404-M cutter, a cutter point arc R is 0.4, a test bar material is cut on a numerical control lathe discontinuously according to GB/T16461-1996, the used cutting test bar material is an aluminum alloy round bar, the cutting speed is 750M/min, the cutting depth is 0.13mm, and the feed rate is 0.12mm/R, when the grinding blunting standard (namely: the wear rate of a rear cutter face Vb =0.25 mm) is met, the cutting time (cutting life) reaches over 120h, and the phenomena of diamond particle falling, polycrystalline diamond layer falling and fracture do not occur, so that the cutter prepared by the compact has good cutting performance and long cutting life.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the carbon nano tubes with the dual characteristics of diamond and carbon nano tubes are adopted to coat the diamond micro powder, so that the wettability and lubricity of diamond particles and a bonding agent are improved, the contact area of diamond and the bonding agent is effectively increased, and the wear resistance and impact toughness of the polycrystalline diamond compact are greatly improved; deposition of Si on the surface of cemented carbide substrates3N 4The powder transition layer is arranged between the coating and the polycrystalline diamond layer, and the combination between the polycrystalline diamond layer and the hard alloy matrix is strengthened by adjusting the formula of the transition layer and selecting the formula of the hard alloy matrix while the excellent performance of the polycrystalline diamond layer is ensured. Compared with the polycrystalline diamond compact obtained in the prior art, the prepared polycrystalline diamond compact has both wear resistance and excellent impact toughness.
(2) According to the invention, the carbon fibers and the graphene material are added in the polycrystalline diamond layer, and the carbon nanotubes are fiber nano materials and exist in the gaps of the diamond and are distributed in a three-dimensional net shape in space, so that the effect of strengthening and toughening can be achieved; and as the graphene is considered as the material with the highest strength in the world, the graphene has a planar hexagonal structure consisting of single-layer carbon atoms, has the characteristics of excellent electrical conductivity, thermal conductivity, high Young modulus, tensile strength, high hardness, low density and the like, and has a better sintering promoting effect under high temperature and high pressure, so that the carbon fiber and the graphene material are matched for use, not only can the complementary advantages of the two materials be realized, but also the agglomeration of the two nano materials in polycrystalline diamond can be reduced, and the wear resistance and the impact resistance toughness of the polycrystalline diamond layer can be improved. The polycrystalline diamond composite sheet prepared by the invention has excellent mechanical and thermal properties, and the wear resistance, impact resistance, toughness, thermal stability and self-sharpening property of the polycrystalline diamond composite sheet are improved.
(3) When the polycrystalline diamond layer is mixed, the carbon fibers are fibrous, the diamond is in a particle and fibrous shape, the graphene is in a sheet shape, the shape difference of the carbon fibers and the diamond is large, the technical difficulty of mixing is increased, and in order to solve the problem of mixing uniformity, the mixing method combining ultrasonic oscillation, magnetic stirring and ball milling is adopted, so that the mixing uniformity is ensured, the bonding agent, the carbon fibers, the graphene and the carbon nanotube coated diamond micro powder can be fully mixed and dispersed, and the phenomenon of enrichment or segregation of powder materials is avoided.
(4) The invention adopts a progressive high-temperature high-pressure treatment method to solve the problem of local agglomeration formed by eruption type penetration of the bonding agent at the interface of the polycrystalline diamond compact, thereby greatly improving the thermal stability, impact resistance, wear resistance and the like of the polycrystalline diamond compact, further improving the anti-collapse and anti-delamination effects of the polycrystalline diamond compact in the using process and prolonging the service life.
Drawings
Fig. 1 is a schematic structural view of a high-toughness wear-resistant polycrystalline diamond compact according to the present disclosure; in the figure: 1. a hard alloy substrate; 2. si3N4Coating; 3. a powder transition layer 4 and a polycrystalline diamond layer;
fig. 2 is a diagram of a high toughness, wear resistant polycrystalline diamond compact of the present invention;
FIG. 3 is an ultrasonic flaw detection chart of a sample interface in example 1;
FIG. 4 is an ultrasonic flaw detection chart of a sample interface in example 2;
FIG. 5 is an ultrasonic flaw detection chart of a sample interface in example 3;
FIG. 6 is an ultrasonic flaw detection chart of the sample interface in comparative example 1;
FIG. 7 is an ultrasonic flaw detection chart of the sample interface in comparative example 2;
FIG. 8 is an ultrasonic flaw detection chart of the sample interface in comparative example 3;
FIG. 9 is an ultrasonic flaw detection chart of the sample interface in comparative example 4.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to be limiting.
In order to measure and compare the performance of the examples and comparative examples, the composite sheets prepared in the following examples and comparative examples each had a diameter of phi 45mm and a thickness of 3.2 mm; the thickness of the polycrystalline diamond layer is 0.5 mm.
Example 1
As shown in fig. 1, the high-toughness wear-resistant polycrystalline diamond compact of the present embodiment includes a hard alloy substrate 1 and Si sequentially disposed on the hard alloy substrate 13N 4The coating 2, the powder transition layer 3 and the polycrystalline diamond layer 4; the polycrystalline diamond layer is composed of the following raw materials in percentage by weight: 95% of diamond micro powder coated by the carbon nano tube, 0.3% of graphene, 0.2% of carbon fiber and 4.5% of binding agent; the powder transition layer is composed of the following raw materials in percentage by weight: 40% of hard alloy powder, 56% of carbon nanotube-coated diamond micro powder, 1.5% of graphene and 2.5% of binding agent; the graphene is a graphene nanosheet with the thickness of 6-8 nm and the width of 5 micrometers; said Si3N4The thickness of the coating was 7 μm; the mass ratio of the powder transition layer to the polycrystalline diamond layer is 0.2: 1; the carbon nano tube coated diamond micro powder is prepared by chemical vapor deposition of the carbon nano tube on a catalyst layer on the surface of the diamond with the catalyst layer on the surface; the carbon nano tube is of a single-layer structure or a multi-layer structure; the binding agent is composed of the following raw materials in percentage by weight: 97% of cobalt powder, 1.5% of tungsten powder, 1.3% of titanium powder and 0.2% of rare earth element, wherein the rare earth element is erbium; the particle sizes of the cobalt powder, the tungsten powder, the titanium powder and the erbium powder are 20-50 nm; the carbon nanotube coated diamond micro powder consists of micro powder with particle size distribution of 2-4 mu m and 5-10 mu m but not including three particle size distributions of 10 mu m and 10-20 mu m; the three kinds of micro powder with the particle sizes respectively account for 2-4 mu m of carbon nano tube coated diamond micro powder10%, 40% of the particles which are 5-10 mu m but do not contain 10 mu m, and 50% of the particles which are 10-20 mu m; the hard alloy matrix or the hard alloy powder consists of the following raw materials in percentage by weight: 84.5 percent of tungsten carbide powder, 13.5 percent of cobalt powder, 1 percent of zirconium powder, 0.5 percent of tantalum carbide powder and 0.5 percent of niobium carbide powder; the particle size of the tungsten carbide powder is 1.2-1.6 mu m; the particle sizes of the cobalt powder, the zirconium powder, the tantalum carbide powder and the niobium carbide powder are all 0.8-1.2 mu m.
The preparation method of the high-toughness wear-resistant polycrystalline diamond compact comprises the following steps:
1) depositing a transition layer: placing the hard alloy matrix in a magnetron sputtering device, taking silicon as a target material and nitrogen as a reaction gas, controlling the flow rate of the nitrogen to be 20sccm, depositing under the radio frequency power of 30W, depositing under the pressure of 0.3Pa, and depositing Si on the surface of the clean hard alloy matrix3N4Layer of Si to obtain a layer containing3N4A coated cemented carbide substrate;
2) preparing the carbon nano tube coated diamond micro powder: sputtering a nickel catalyst layer on the diamond by using a magnetron sputtering technology, wherein the thickness of the nickel film is 70 nm; and then, depositing the carbon nano tubes on the diamond containing the catalyst layer by utilizing a chemical vapor deposition technology, applying plasma to the surface of the diamond for auxiliary growth in the deposition process, adding a magnetic field at the bottom of the diamond to restrain the plasma on the surface of the diamond, strengthening the bombardment of the plasma on the surface of the diamond, and enabling the carbon nano tubes to grow vertical to the surface of the diamond, wherein the deposition parameters are as follows: the mass flow percentage of the carbon-containing gas in the total gas in the furnace is 5 percent; the growth temperature is 400 ℃, and the growth pressure is 10 DEG3Pa; plasma current density 1mA/cm2(ii) a The magnetic field intensity in the deposition area is 100 gauss, and the carbon nano tube coated diamond micro powder is obtained;
3) mixing of the powder transition layer: weighing graphene according to a ratio, adding the graphene into absolute ethyl alcohol, and performing ultrasonic sweeping dispersion for 20min to obtain a graphene dispersion liquid; then magnetically stirring the graphene dispersion liquid, after 30min, carrying out vacuum drying to obtain dispersed graphene powder, then weighing the carbon nanotube coated diamond micro powder, the hard alloy powder and the binding agent according to a proportion, ball-milling the carbon nanotube coated diamond micro powder, the hard alloy powder, the binding agent and the dispersed graphene powder, wherein the ball material ratio is 4: 1, the ball-milling medium is absolute ethyl alcohol, a ball-milling body is a hard alloy ball, a ball-milling tank is a hard alloy tank, a clockwise and anticlockwise alternate operation mode is adopted, the rotating speed is 35 r/min during clockwise operation, 45 r/min during anticlockwise operation, the time is 20min during clockwise operation, the time is 20min during anticlockwise operation, the intermediate interval standby time is 4 min during clockwise and anticlockwise alternate operation, the ball-milling time is 25h, and vacuum drying is carried out to obtain powder transition layer mixed powder;
4) mixing the polycrystalline diamond layer: weighing graphene and carbon fibers according to a ratio, respectively adding the graphene and the carbon fibers into absolute ethyl alcohol, and ultrasonically oscillating and dispersing for 20min to obtain a graphene dispersion liquid and a carbon fiber dispersion liquid; then magnetically stirring the graphene dispersion liquid, after 30min, slowly adding the carbon fiber dispersion liquid drop by drop, after 30min, carrying out vacuum drying to obtain dispersed graphene and carbon fiber mixed powder, then weighing the carbon nanotube coated diamond micro powder and a binding agent according to a proportion, and carrying out ball milling on the carbon nanotube coated diamond micro powder, the binding agent and the dispersed graphene and carbon fiber mixed powder, wherein the ball material mass ratio is 4: 1, a ball milling medium is absolute ethyl alcohol, a ball milling body is a nickel alloy ball, a ball milling tank is a nickel alloy tank, a clockwise and anticlockwise alternate operation mode is adopted, the rotating speed is 50 r/min when the ball milling tank rotates clockwise, the rotating speed is 70 r/min when the ball milling tank rotates anticlockwise, the alternate operation is carried out, the ball milling time is 20h, and after vacuum drying, obtaining the diamond mixed powder;
5) assembling a composite body: laying the mixed powder of the polycrystalline diamond layer in a high-temperature resistant metal cup, and leveling; laying powder transition layer mixed powder on the polycrystalline diamond layer, and leveling; then will contain N3Si4Horizontally placing the hard alloy substrate of the coating on the mixed powder of the powder transition layer with the coating surface facing downwards, placing the hard alloy substrate in a pre-pressing die, and pre-pressing for 5min at the pressure of 10MPa by using a hydraulic machine to form to obtain a composite assembly;
6) and (3) purification treatment: placing the composite assembly obtained in the step 5) in a vacuum sintering furnace, and during sintering, firstly, roughly vacuumizing until the air pressure in the furnace reaches 6 x 10-2Heating to 200 deg.C below Pa, maintaining for 20min, and keepingContinuously vacuumizing and heating to 850 deg.C until the compressed air in furnace is stabilized at 3X 10-4Pa below, stopping vacuumizing, introducing carbon monoxide gas with an internal gas pressure of 25Mbar into a vacuum heating furnace at 850 deg.C to reduce the composite assembly for 0.5h, and continuously vacuumizing until the internal gas pressure is 3 × 10- 4Keeping the temperature below Pa and at 1150 ℃ for 2min, stopping vacuumizing, intermittently filling carbon monoxide into the vacuum heating furnace, wherein the air filling amount is the same each time and the carbon monoxide filling amount is limited to 30Mbar of the air pressure in the furnace, and waiting for 10min after the air filling is finished each time to start a vacuumizing system to vacuumize the vacuum heating furnace until the air pressure in the furnace is 3 x 10-4Setting the vacuumizing time in advance below Pa, and starting the carbon monoxide filling program and the vacuumizing program again after vacuumizing is finished to circulate for 8 times to obtain a purification composite assembly;
7) high-temperature high-pressure sintering: placing the purified composite assembly in the step 6) into a synthetic assembly block, performing high-temperature and high-pressure sintering by using a cubic press, increasing the temperature to 7GPa at the rate of 0.1GPa/min, increasing the temperature to 1370 ℃ at the rate of 20 ℃/min for sintering, sintering for 80S, increasing the temperature to 1430 ℃ at the rate of 10 ℃/min for sintering, sintering for 130S, increasing the temperature to 1500 ℃ at the rate of 5 ℃/min for sintering, decreasing the temperature to normal temperature at the rate of 10 ℃/min after sintering for 350S, and decreasing the pressure to normal pressure at the rate of 0.1 GPa/min;
8) aging treatment: putting the polycrystalline diamond compact obtained after sintering in the step 7) into a vacuum sintering furnace, and vacuumizing until the pressure in the furnace is 3 multiplied by 10-3Pa, at 3X 10-3Under the condition of Pa, heating to 380 ℃ and preserving heat for 0.5h, vacuumizing again until the air pressure in the furnace is 3 multiplied by 10-5Pa, at 3X 10-5And (3) under the condition of Pa, heating to 480 ℃, preserving the heat for 1h, and finally cooling to room temperature and storing in vacuum.
The high toughness wear resistant polycrystalline diamond compact prepared in this example is shown in fig. 2. The high-toughness wear-resistant polycrystalline diamond compact prepared by the embodiment is subjected to a thermal conductivity test according to the standard ASTM E1461-2007; placing a composite sheet sample in a tubular heating furnace, heating at 690 ℃ for 1min, and performing impact resistance test by adopting a drop hammer method (the drop hammer used in the test has the mass of 1kg, and the drop hammer distance is 30 cm); carrying out abrasion resistance test according to the standard JB/T3235-2013; the thermal conductivity is 350W/(M.k), the abrasion ratio is 41.5 ten thousand, the impact frequency is 66 times, and the material has excellent mechanical and thermal properties.
The high-toughness wear-resistant polycrystalline diamond compact prepared by the embodiment is prepared into an SNMG120404-M cutter, a cutter point arc R is 0.4, a test bar material is cut intermittently on a numerical control lathe according to GB/T16461-1996, the used test bar material is an aluminum alloy round bar, the cutting speed is 750M/min, the cutting depth is 0.13mm, and the feed rate is 0.12mm/R, when the grinding dull standard (namely, the wear rate of a rear cutter face is Vb =0.25 mm) is met, the cutting time (cutting service life) is 130h, and the phenomena of diamond particle falling, polycrystalline diamond layer falling and fracture do not occur, so that the cutter prepared by the compact disclosed by the invention has good cutting performance and long cutting service life.
The high-toughness wear-resistant polycrystalline diamond compact prepared by the embodiment is subjected to ultrasonic scanning inspection on the interface of the compact by an ultrasonic scanning microscope (SONIX. U.S.) and the result is shown in FIG. 3. As can be seen from fig. 3, the interface between the polycrystalline diamond layer and the hard alloy substrate of the compact of the present embodiment is well bonded, and there are no defects such as cracks, delamination, pores, and local agglomeration of the binder.
Example 2
The high-toughness wear-resistant polycrystalline diamond compact comprises a hard alloy substrate and Si sequentially arranged on the hard alloy substrate3N4The coating, the powder transition layer and the polycrystalline diamond layer; the polycrystalline diamond layer is composed of the following raw materials in percentage by weight: 98% of diamond micro powder coated by the carbon nano tube, 0.1% of graphene, 0.1% of carbon fiber and 1.8% of binding agent; the powder transition layer is composed of the following raw materials in percentage by weight: 48% of hard alloy powder, 50% of carbon nano tube coated diamond micro powder, 0.5% of graphene and 1.5% of binding agent; the graphene is a graphene nanosheet with the thickness of 6-8 nm and the width of 5 microns; said Si3N4The thickness of the coating is 8 μm; the powder transition layer andthe mass ratio of the polycrystalline diamond layer is 0.2: 1.5; the carbon nano tube coated diamond micro powder is prepared by chemical vapor deposition of the carbon nano tube on a catalyst layer on the surface of the diamond with the catalyst layer on the surface; the carbon nano tube is of a single-layer structure or a multi-layer structure; the binding agent is composed of the following raw materials in percentage by weight: 99% of cobalt powder, 0.5% of tungsten powder, 0.4% of titanium powder and 0.1% of rare earth element, wherein the rare earth element is ytterbium; the particle sizes of the cobalt powder, the tungsten powder, the titanium powder and the ytterbium powder are 20-50 nm; the carbon nanotube coated diamond micro powder consists of micro powder with particle size distribution of 2-4 mu m and 5-10 mu m but not including three particle size distributions of 10 mu m and 10-20 mu m; the weight percentage content of the micro powder with the three particle sizes in the carbon nanotube coated diamond micro powder is 20% of that of the micro powder with the three particle sizes in the range of 2-4 mu m, 35% of that of the micro powder with the three particle sizes in the range of 5-10 mu m but not 10 mu m, and 45% of that of the micro powder with the three particle sizes in the range of 10-20 mu m; the hard alloy matrix or the hard alloy powder consists of the following raw materials in percentage by weight: 88% of tungsten carbide powder, 10.9% of cobalt powder, 0.5% of zirconium powder, 0.3% of tantalum carbide powder and 0.3% of niobium carbide powder; the particle size of the tungsten carbide powder is 1.2-1.6 mu m; the particle sizes of the cobalt powder, the zirconium powder, the tantalum carbide powder and the niobium carbide powder are all 0.8-1.2 mu m.
The preparation method of the high-toughness wear-resistant polycrystalline diamond compact comprises the following steps:
1) depositing a transition layer: placing the hard alloy matrix in a magnetron sputtering device, taking silicon as a target material and nitrogen as a reaction gas, controlling the flow rate of the nitrogen gas to be 100sccm, depositing under the radio frequency power of 60W, depositing the pressure of 2Pa, and depositing Si on the surface of the clean hard alloy matrix3N4Layer of Si to obtain a layer containing3N4A coated cemented carbide substrate;
2) preparing the carbon nano tube coated diamond micro powder: sputtering a nickel catalyst layer on the diamond by using a magnetron sputtering technology, wherein the thickness of the nickel film is 60 nm; depositing carbon nanotubes on the diamond containing the catalyst layer by using a chemical vapor deposition technology, applying plasma to the surface of the diamond for auxiliary growth in the deposition process, adding a magnetic field at the bottom of the diamond to restrain the plasma on the surface of the diamond, strengthening the bombardment of the plasma on the surface of the diamond, and enabling the carbon nanotubes to grow perpendicular to the surface of the diamond, wherein the deposition parameter is: the mass flow percentage of the carbon-containing gas in the total gas in the furnace is 50 percent; the growth temperature is 1300 ℃, the growth pressure is 10 DEG5Pa; plasma current density 30mA/cm2(ii) a The magnetic field intensity in the deposition area is 30 Tesla, and the carbon nano tube coated diamond micro powder is obtained;
3) mixing of powder transition layers: weighing graphene according to a ratio, adding the graphene into absolute ethyl alcohol, and performing ultrasonic sweeping dispersion for 30min to obtain a graphene dispersion liquid; then magnetically stirring the graphene dispersion liquid, after 40min, carrying out vacuum drying to obtain dispersed graphene powder, then weighing the carbon nanotube coated diamond micro powder, the hard alloy powder and the binding agent according to a proportion, ball-milling the carbon nanotube coated diamond micro powder, the hard alloy powder, the binding agent and the dispersed graphene powder, wherein the ball material ratio is 6: 1, the ball-milling medium is absolute ethyl alcohol, the ball-milling body is a hard alloy ball, the ball-milling tank is a hard alloy tank, a clockwise and anticlockwise alternate operation mode is adopted, the rotating speed is 45 r/min during clockwise operation, 55 r/min during anticlockwise operation, the time is 25min during clockwise operation, the time is 25min during anticlockwise operation, the intermediate interval standby time is 8min during clockwise and anticlockwise alternate operation, the ball-milling time is 30h, and powder transition layer mixed powder is obtained after vacuum drying;
4) mixing the polycrystalline diamond layer: weighing graphene and carbon fibers according to a ratio, respectively adding the graphene and the carbon fibers into absolute ethyl alcohol, and ultrasonically oscillating and dispersing for 30min to obtain a graphene dispersion liquid and a carbon fiber dispersion liquid; then magnetically stirring the graphene dispersion liquid, after 40min, slowly adding the carbon fiber dispersion liquid drop by drop, after 40min, carrying out vacuum drying to obtain dispersed graphene and carbon fiber mixed powder, then weighing the carbon nanotube-coated diamond micropowder and a binding agent according to a proportion, carrying out ball milling on the carbon nanotube-coated diamond micropowder, the binding agent and the dispersed graphene and carbon fiber mixed powder, wherein the ball-material ratio is 10: 1, the ball milling medium is absolute ethyl alcohol, the ball milling body is a nickel alloy ball, the ball milling tank is a nickel alloy tank, adopting a clockwise and anticlockwise alternate operation mode, the rotating speed is 60 r/min when clockwise operating, the rotating speed is 80 r/min when anticlockwise operating clockwise for 25min, the time when anticlockwise operating is 25min, the intermediate interval stand-by time is 8min when clockwise and anticlockwise alternately operating, and the ball milling time is 30h, vacuum drying to obtain diamond mixed powder;
5) assembling a composite body: firstly, paving the mixed powder of the polycrystalline diamond layer in a high-temperature resistant metal cup, and leveling; laying powder transition layer mixed powder on the polycrystalline diamond layer, and leveling; then will contain Si3N4Horizontally placing the hard alloy substrate of the coating on the mixed powder of the powder transition layer with the coating surface facing downwards, placing the hard alloy substrate in a pre-pressing mould, and pre-pressing the hard alloy substrate for 8min at the pressure of 10Mpa by using a hydraulic machine to form a composite assembly;
6) and (3) purification treatment: placing the composite assembly obtained in the step 5) in a vacuum sintering furnace, and during sintering, firstly, roughly vacuumizing until the air pressure in the furnace reaches 6 x 10-2Heating to 300 deg.C below Pa, maintaining the temperature for 30min, continuously vacuumizing and heating to 900 deg.C until the compressed air in the furnace is stabilized at 3 × 10-4Pa below, stopping vacuum-pumping, charging carbon monoxide gas with internal gas pressure of 35Mbar into the vacuum heating furnace at 900 deg.C for reducing the composite assembly for 1 hr, and continuously vacuum-pumping until the internal gas pressure is 3 × 10-4Keeping the temperature below Pa and at 1200 ℃ for 3min, stopping vacuumizing, intermittently filling carbon monoxide into the vacuum heating furnace, wherein the air filling amount is the same each time and the carbon monoxide filling amount is limited to 40Mbar, and waiting for 10min after finishing each air filling, starting a vacuumizing system to vacuumize the vacuum heating furnace until the air pressure in the furnace is 3 x 10-4Setting the vacuumizing time in advance below Pa, and starting the carbon monoxide filling program and the vacuumizing program again to circulate for 10 times after vacuumizing is finished to obtain a purification composite assembly;
7) high-temperature high-pressure sintering: placing the purified composite assembly in the step 6) into a synthesis assembly block, performing high-temperature and high-pressure sintering by using a cubic press, increasing the temperature to 7GPa at the speed of 1GPa/min, then increasing the temperature to 1400 ℃ at the heating rate of 25 ℃/min for sintering for 120S, then increasing the temperature to 1470 ℃ at the heating rate of 15 ℃/min for sintering for 180S, increasing the temperature to 1550 ℃ at the heating rate of 10 ℃/min for sintering, decreasing the temperature to normal temperature at the cooling rate of 30 ℃/min after sintering for 500S, and decreasing the pressure from high pressure to normal pressure at the pressure reduction rate of 0.5 GPa/min;
8) aging treatment: putting the polycrystalline diamond compact obtained after sintering in the step 7) into a vacuum sintering furnace, and vacuumizing until the pressure in the furnace is 3 multiplied by 10-3Pa, at 3X 10-3Heating to 430 ℃ under Pa, preserving heat for 1h, vacuumizing again until the air pressure in the furnace is 3 multiplied by 10-5Pa, at 3X 10-5And (4) under the condition of Pa, heating to 530 ℃, preserving the heat for 1.5h, and finally cooling to room temperature and storing in vacuum.
The high-toughness wear-resistant polycrystalline diamond compact prepared by the embodiment is subjected to a thermal conductivity test according to the standard ASTM E1461-2007; placing a composite sheet sample in a tubular heating furnace, heating at 690 ℃ for 1min, and performing impact resistance test by adopting a drop hammer method (the drop hammer used in the test has the mass of 1kg, and the drop hammer distance is 30 cm); carrying out abrasion resistance test according to the standard JB/T3235-2013; the thermal conductivity is 330W/(M.k), the abrasion ratio is 40.5 ten thousand, the impact frequency is 65 times, and the material has excellent mechanical and thermal properties.
The high-toughness wear-resistant polycrystalline diamond compact prepared by the embodiment is prepared into an SNMG120404-M cutter, a cutter point arc R is 0.4, a test bar material is cut intermittently on a numerical control lathe according to GB/T16461-1996, the used test bar material is an aluminum alloy round bar, the cutting speed is 750M/min, the cutting depth is 0.13mm, and the feed rate is 0.12mm/R, when the grinding blunting standard (namely: the wear rate of a rear cutter face Vb =0.25 mm) is reached, the cutting time (cutting service life) is 140h, and the phenomena of diamond particle falling, polycrystalline diamond layer falling and fracture do not occur, so that the cutter prepared by the compact disclosed by the invention has good cutting performance and long cutting service life.
The high-toughness wear-resistant polycrystalline diamond compact prepared by the embodiment is subjected to ultrasonic scanning inspection on the interface of the compact by an ultrasonic scanning microscope (SONIX. U.S.) and the result is shown in FIG. 4. As can be seen from fig. 4, the interface between the polycrystalline diamond layer and the cemented carbide substrate of the compact of the present embodiment is well bonded, and there are no defects such as cracks, delamination, pores, and local agglomeration of the binder.
Example 3
The high-toughness wear-resistant polycrystalline diamond compact comprises a hard alloy substrate and Si sequentially arranged on the hard alloy substrate3N 4The coating, the powder transition layer and the polycrystalline diamond layer; the polycrystalline diamond layer is composed of the following raw materials in percentage by weight: 96.5% of diamond micro powder coated by the carbon nano tube, 0.2% of graphene, 0.15% of carbon fiber and 3.15% of binding agent; the powder transition layer is composed of the following raw materials in percentage by weight: 44% of hard alloy powder, 53% of carbon nanotube-coated diamond micro powder, 1% of graphene and 2% of binding agent; the graphene is a graphene nanosheet with the thickness of 6-8 nm and the width of 5 microns; said Si3N4The thickness of the coating is 6-8 mu m; the mass ratio of the powder transition layer to the polycrystalline diamond layer is 0.2: 1.2; the carbon nano tube coated diamond micro powder is prepared by chemical vapor deposition of the carbon nano tube on a catalyst layer on the surface of the diamond with the catalyst layer on the surface; the carbon nano tube is of a single-layer structure or a multi-layer structure; the binding agent is composed of the following raw materials in percentage by weight: 98% of cobalt powder, 1% of tungsten powder, 0.85% of titanium powder and 0.15% of rare earth element, wherein the rare earth element is holmium; the particle sizes of the cobalt powder, the tungsten powder, the titanium powder and the holmium powder are 20-50 nm; the carbon nanotube coated diamond micro powder consists of micro powder with particle size distribution of 2-4 mu m and 5-10 mu m but not including three particle size distributions of 10 mu m and 10-20 mu m; the weight percentage content of the micro powder with the three particle sizes in the carbon nano tube coated diamond micro powder is 15% in the range of 2-4 mu m, 38% in the range of 5-10 mu m but not including 10 mu m, and 47% in the range of 10-20 mu m; the hard alloy matrix or the hard alloy powder consists of the following raw materials in percentage by weight: 86.25% of tungsten carbide powder, 12.2% of cobalt powder, 0.75% of zirconium powder, 0.4% of tantalum carbide powder and 0.4% of niobium carbide powder; the particle size of the tungsten carbide powder is 1.2-1.6 mu m; the particle sizes of the cobalt powder, the zirconium powder, the tantalum carbide powder and the niobium carbide powder are all 0.8-1.2 mu m.
The preparation method of the high-toughness wear-resistant polycrystalline diamond compact comprises the following steps:
1) depositing a transition layer: placing the hard alloy matrix in a magnetron sputtering device, taking silicon as a target material and nitrogen as reaction gas, and controlling the flow of the nitrogen gas60sccm, RF power of 45W, deposition pressure of 1.1Pa, and deposition of Si on the surface of clean cemented carbide substrate3N4Layer of Si to obtain a layer containing3N4A coated cemented carbide substrate;
2) preparing the carbon nano tube coated diamond micro powder: sputtering a nickel catalyst layer on the diamond by using a magnetron sputtering technology, wherein the thickness of the nickel film is 80 nm; and then, depositing the carbon nano tubes on the diamond containing the catalyst layer by utilizing a chemical vapor deposition technology, applying plasma to the surface of the diamond for auxiliary growth in the deposition process, adding a magnetic field at the bottom of the diamond to restrain the plasma on the surface of the diamond, strengthening the bombardment of the plasma on the surface of the diamond, and enabling the carbon nano tubes to grow vertical to the surface of the diamond, wherein the deposition parameters are as follows: the mass flow percentage of the carbon-containing gas in the total gas in the furnace is 25 percent; the growth temperature is 850 ℃, the growth pressure is 10 DEG4Pa; plasma current density 15 mA/cm2(ii) a The magnetic field intensity in the deposition area is 10 Tesla, and the carbon nano tube coated diamond micro powder is obtained;
3) mixing of powder transition layers: weighing graphene according to a ratio, adding the graphene into absolute ethyl alcohol, and carrying out ultrasonic wave sweeping dispersion for 25min to obtain a graphene dispersion liquid; then magnetically stirring the graphene dispersion liquid, drying in vacuum after 35min to obtain dispersed graphene powder, then weighing the carbon nanotube coated diamond micro powder, the hard alloy powder and the binding agent according to a proportion, ball-milling the carbon nanotube coated diamond micro powder, the hard alloy powder, the binding agent and the dispersed graphene powder, wherein the ball material mass ratio is 5: 1, a ball-milling medium is absolute ethyl alcohol, a ball-milling body is a hard alloy ball, a ball-milling tank is a hard alloy tank, a clockwise and anticlockwise alternate operation mode is adopted, the rotating speed is 40 r/min during clockwise operation, 50 r/min during anticlockwise operation, 22min during clockwise operation, 22min during anticlockwise operation, the intermediate interval standby time is 6 min during clockwise and anticlockwise alternate operation, the ball-milling time is 27h, and vacuum drying is carried out to obtain powder transition layer mixed powder;
4) mixing the polycrystalline diamond layer: weighing graphene and carbon fibers according to a ratio, respectively adding the graphene and the carbon fibers into absolute ethyl alcohol, and ultrasonically oscillating and dispersing for 25min to obtain a graphene dispersion liquid and a carbon fiber dispersion liquid; then magnetically stirring the graphene dispersion liquid, after 35min, slowly adding the carbon fiber dispersion liquid drop by drop, after 35min, carrying out vacuum drying to obtain dispersed graphene and carbon fiber mixed powder, then weighing the carbon nanotube-coated diamond micro powder and a binding agent according to a proportion, carrying out ball milling on the carbon nanotube-coated diamond micro powder, the binding agent and the dispersed graphene and carbon fiber mixed powder, wherein the ball material mass ratio is 7: 1, the ball milling medium is absolute ethyl alcohol, the ball milling body is a nickel alloy ball, the ball milling tank is a nickel alloy tank, adopting a clockwise and anticlockwise alternate operation mode, the rotating speed is 55 r/min when clockwise operating, the rotating speed is 75 r/min when anticlockwise operating, the time when clockwise operating is 22min, the time when anticlockwise operating is 22min, the intermediate interval standby time is 6 min when clockwise and anticlockwise alternately operating, and the ball milling time is 25h, vacuum drying to obtain diamond mixed powder;
5) assembling a composite body: firstly, paving the mixed powder of the polycrystalline diamond layer in a high-temperature resistant metal cup, and leveling; laying powder transition layer mixed powder on the polycrystalline diamond layer, and leveling; then will contain Si3N4Horizontally placing the hard alloy substrate of the coating on the mixed powder of the powder transition layer with the coating surface facing downwards, placing the hard alloy substrate in a pre-pressing die, and pre-pressing for 7min at the pressure of 10MPa by using a hydraulic machine to form to obtain a composite assembly;
6) and (3) purification treatment: placing the composite assembly obtained in the step 5) in a vacuum sintering furnace, and during sintering, firstly, roughly vacuumizing until the air pressure in the furnace reaches 6 x 10-2Heating to 250 deg.C under Pa for 25min, vacuumizing while heating to 870 deg.C until the compressed air in the furnace is stabilized at 3 × 10-4Pa below, stopping vacuumizing, charging carbon monoxide gas with gas pressure of 30Mbar into vacuum heating furnace at 870 deg.C for reducing the complex assembly for 0.75 hr, and continuously vacuumizing until the gas pressure in the furnace is 3 × 10-4Keeping the temperature below Pa and 1175 ℃ for 2.5min, stopping vacuumizing, intermittently filling carbon monoxide into the vacuum heating furnace, keeping the same aeration quantity and the carbon monoxide filling quantity within 35Mbar of the air pressure in the furnace, waiting for 10min after each aeration is finished, and starting the vacuumizing systemVacuumizing the vacuum heating furnace until the air pressure in the furnace is 3 multiplied by 10-4Setting the vacuumizing time in advance below Pa, and starting the carbon monoxide filling program and the vacuumizing program again after vacuumizing for 9 times to obtain a purification composite assembly;
7) high-temperature high-pressure sintering: placing the purified composite assembly obtained in the step 6) into a synthetic assembly block, performing high-temperature and high-pressure sintering by using a cubic press, increasing the temperature to 7GPa at the speed of 0.5GPa/min, then increasing the temperature to 1380 ℃ at the heating rate of 22 ℃/min for sintering, sintering for 100S, then increasing the temperature to 1450 ℃ at the heating rate of 12 ℃/min for sintering, sintering for 150S, increasing the temperature to 1530 ℃ at the heating rate of 7 ℃/min for sintering, decreasing the temperature to normal temperature at the cooling rate of 20 ℃/min after sintering for 425S, and decreasing the pressure from high pressure to normal pressure at the pressure reduction rate of 0.3 GPa/min;
8) and (3) aging treatment: putting the polycrystalline diamond compact obtained after sintering in the step 7) into a vacuum sintering furnace, and vacuumizing until the pressure in the furnace is 3 multiplied by 10-3Pa, at 3X 10-3Heating to 400 ℃ under Pa, keeping the temperature for 0.75h, and vacuumizing again until the air pressure in the furnace is 3 multiplied by 10-5Pa, at 3X 10-5And (3) under the condition of Pa, heating to 500 ℃, preserving the heat for 1.2h, and finally cooling to room temperature and storing in vacuum.
The high-toughness wear-resistant polycrystalline diamond compact prepared by the embodiment is subjected to a thermal conductivity test according to the standard ASTM E1461-2007; placing a composite sheet sample in a tubular heating furnace, heating at 690 ℃ for 1min, and performing impact resistance test by adopting a drop hammer method (the drop hammer used in the test has the mass of 1kg, and the drop hammer distance is 30 cm); carrying out abrasion resistance test according to the standard JB/T3235-2013; the heat conductivity coefficient is 340W/(M.k), the abrasion ratio is 41.5 ten thousand, the impact frequency is 70 times, and the material has excellent mechanical and thermal properties.
According to the SNMG120404-M cutter manufactured by the high-toughness wear-resistant polycrystalline diamond composite sheet, a cutter point circular arc R is 0.4, a test bar material is discontinuously cut on a numerical control lathe according to the GB/T16461-1996, the used test bar material is an aluminum alloy round bar, the cutting speed is 750M/min, the cutting depth is 0.13mm, and the feed rate is 0.12mm/R, when the cutting time (cutting life) reaches the dull grinding standard (namely, the wear loss of a rear cutter face is Vb =0.25 mm), the phenomena of diamond particle falling, polycrystalline diamond layer falling and fracture do not occur, and the cutter manufactured by the composite sheet has good cutting performance and long cutting life.
The high-toughness wear-resistant polycrystalline diamond compact prepared in the embodiment is subjected to ultrasonic scanning inspection on the interface of the compact through a U.S. SONIX ultrasonic scanning microscope, and the result is shown in FIG. 5. As can be seen from fig. 5, the interface between the polycrystalline diamond layer and the cemented carbide substrate of the compact of the present embodiment is well bonded, and there are no defects such as cracks, delamination, pores, and local agglomeration of the binder.
Comparative example 1
The high-toughness wear-resistant polycrystalline diamond compact of the comparative example comprises a hard alloy matrix and Si sequentially arranged on the hard alloy matrix3N4A coating, a powder transition layer, and a polycrystalline diamond layer; the polycrystalline diamond layer is composed of the following raw materials in percentage by weight: 90% of diamond micro powder coated by the carbon nano tube, 1% of graphene, 1% of carbon fiber and 8% of binding agent; the powder transition layer is composed of the following raw materials in percentage by weight: 35% of hard alloy powder, 60% of carbon nanotube-coated diamond micro powder, 2% of graphene and 3% of binding agent; the graphene is a graphene nanosheet with the thickness of 6-8 nm and the width of 5 micrometers; said Si3N4The thickness of the coating was 7 μm; the mass ratio of the powder transition layer to the polycrystalline diamond layer is 0.2: 1; the carbon nano tube coated diamond micro powder is prepared by chemical vapor deposition of the carbon nano tube on a catalyst layer on the surface of the diamond with the catalyst layer on the surface; the carbon nano tube is of a single-layer structure or a multi-layer structure; the binding agent is composed of the following raw materials in percentage by weight: 93% of cobalt powder, 3% of tungsten powder, 3% of titanium powder and 1% of rare earth element, wherein the rare earth element is erbium; the particle sizes of the cobalt powder, the tungsten powder, the titanium powder and the erbium powder are 20-50 nm; the carbon nanotube coated diamond micro powder consists of micro powder with particle size distribution of 2-4 mu m and 5-10 mu m but not including three particle size distributions of 10 mu m and 10-20 mu m; the micro powder with the three particle sizes is respectively in the weight percentage of the diamond micro powder coated by the carbon nano tubeThe content is 10% in the range of 2-4 mu m, 40% in the range of 5-10 mu m but not including 10 mu m, and 50% in the range of 10-20 mu m; the hard alloy matrix or the hard alloy powder consists of the following raw materials in percentage by weight: 80% of tungsten carbide powder, 16% of cobalt powder, 2% of zirconium powder, 1% of tantalum carbide powder and 1% of niobium carbide powder; the particle size of the tungsten carbide powder is 1.2-1.6 mu m; the particle sizes of the cobalt powder, the zirconium powder, the tantalum carbide powder and the niobium carbide powder are all 0.8-1.2 mu m.
The preparation method of the high-toughness wear-resistant polycrystalline diamond compact is the same as that in example 1.
The high-toughness wear-resistant polycrystalline diamond compact prepared by the comparative example is subjected to performance test by the same test method as that of example 1; the thermal conductivity is 300W/(M.k), the abrasion ratio is 35 ten thousand, the impact frequency is 55 times, and the performance index is obviously reduced compared with that of the embodiment 1.
The method for manufacturing and testing the cutter from the high-toughness wear-resistant polycrystalline diamond compact prepared by the comparative example is the same as that of example 1, the cutting time (cutting life) is 90 hours, and the phenomenon that diamond particles fall off occurs on the cutter. The cutting time was significantly reduced compared to example 1, indicating poorer cutting performance and shorter cutting life.
The high-toughness wear-resistant polycrystalline diamond compact prepared by the comparative example is subjected to ultrasonic scanning inspection on the interface of the compact by an American SONIX ultrasonic scanning microscope, and the result is shown in FIG. 6. As can be seen from fig. 6, delamination defects (delamination areas are white edge portions) appear at the interface between the polycrystalline diamond layer and the cemented carbide substrate of the compact.
Comparative example 2
The high-toughness wear-resistant polycrystalline diamond compact of the comparative example comprises a hard alloy matrix and Si sequentially arranged on the hard alloy matrix3N 4The coating, the powder transition layer and the polycrystalline diamond layer; the polycrystalline diamond layer is composed of the following raw materials in percentage by weight: 98.2% of diamond micro powder coated by the carbon nano tube, 0% of graphene, 0% of carbon fiber and 1.8% of binding agent; the powder transition layer is composed of the following raw materials in percentage by weight: 52 percent of hard alloy powder and 45 percent of carbon nano tube coated diamond micropowder,0% of graphene and 3% of a binding agent; the graphene nanosheet is 6-8 nm in thickness and 5 mu m in width; said Si3N4The thickness of the coating was 7 μm; the mass ratio of the powder transition layer to the polycrystalline diamond layer is 0.2: 1.6; the carbon nano tube coated diamond micro powder is prepared by chemical vapor deposition of the carbon nano tube on a catalyst layer on the surface of the diamond with the catalyst layer on the surface; the carbon nano tube has a single-layer structure or a multi-layer structure; the binding agent is composed of the following raw materials in percentage by weight: 99% of cobalt powder, 0.5% of tungsten powder, 0.4% of titanium powder and 0.1% of rare earth element, wherein the rare earth element is ytterbium; the particle sizes of the cobalt powder, the tungsten powder, the titanium powder and the ytterbium powder are 20-50 nm; the carbon nanotube coated diamond micro powder consists of micro powder with particle size distribution of 2-4 mu m and 5-10 mu m but not including three particle size distributions of 10 mu m and 10-20 mu m; the weight percentage content of the micro powder with the three particle sizes in the carbon nano tube coated diamond micro powder is 20% in the range of 2-4 mu m, 35% in the range of 5-10 mu m but not including 10 mu m, and 45% in the range of 10-20 mu m; the hard alloy matrix or the hard alloy powder consists of the following raw materials in percentage by weight: 92% of tungsten carbide powder, 7% of cobalt powder, 0.5% of zirconium powder, 0.3% of tantalum carbide powder and 0.2% of niobium carbide powder; the particle size of the tungsten carbide powder is 1.2-1.6 mu m; the particle sizes of the cobalt powder, the zirconium powder, the tantalum carbide powder and the niobium carbide powder are all 0.8-1.2 mu m.
The preparation method of the high-toughness wear-resistant polycrystalline diamond compact is the same as that in example 1.
The high-toughness wear-resistant polycrystalline diamond compact prepared by the comparative example is subjected to performance test by the same test method as that of example 1; the thermal conductivity is 280W/(M.k), the abrasion ratio is 36 ten thousand, the impact frequency is 58 times, and the performance index is obviously reduced compared with that of the embodiment 1.
The method for manufacturing and testing the cutter from the high-toughness wear-resistant polycrystalline diamond compact prepared by the comparative example is the same as that of example 1, the cutting time (cutting life) is 80 hours, and the phenomenon that diamond particles fall off occurs on the cutter. Compared with example 1, the cutting mileage is significantly reduced, indicating that the cutting performance is poor and the cutting life is short.
The high-toughness wear-resistant polycrystalline diamond compact prepared by the comparative example is subjected to ultrasonic scanning inspection on the interface of the compact by an American SONIX ultrasonic scanning microscope, and the result is shown in figure 7. As can be seen from fig. 7, crack defects (crack regions are linear edge portions) appear at the interface between the polycrystalline diamond layer and the cemented carbide substrate of the compact.
Comparative example 3
The high-toughness wear-resistant polycrystalline diamond compact of the comparative example, the materials, the proportion and the preparation method thereof refer to example 2; the difference lies in that: the carbon nanotube coated diamond micro powder related in the raw material is uniformly replaced by the diamond micro powder, and the step 2) for preparing the carbon nanotube coated diamond micro powder is omitted).
The performance of the high-toughness wear-resistant polycrystalline diamond compact prepared by the comparative example is tested by the same test method as that of example 1; the thermal conductivity was 285W/(M.k), the wear ratio was 38 ten thousand, and the number of impacts was 59, and the performance index was significantly lower than that of example 1.
The method for manufacturing and testing the cutter from the high-toughness wear-resistant polycrystalline diamond compact prepared by the comparative example is the same as that of example 1, the cutting time (cutting life) is 100 hours, and the phenomenon that diamond particles fall off occurs on the cutter. The cutting time was significantly reduced compared to example 1, indicating poorer cutting performance and shorter cutting life.
The high-toughness wear-resistant polycrystalline diamond compact prepared by the comparative example is subjected to ultrasonic scanning inspection on the interface of the compact by an American SONIX ultrasonic scanning microscope, and the result is shown in figure 8. As can be seen from fig. 8, delamination defects (delamination areas are white edge portions) are present at the interface between the polycrystalline diamond layer and the cemented carbide substrate of the compact.
Comparative example 4
The materials and the proportion of the high-toughness wear-resistant polycrystalline diamond compact of the comparative example are the same as those of the example 3; the preparation method comprises the following steps:
1) depositing a transition layer: the same as in example 3;
2) mixing of powder transition layers: weighing the carbon nanotube coated diamond micro powder, the hard alloy powder, the binding agent and the graphene according to a proportion, carrying out ball milling, wherein the ball material mass ratio is 5: 1, the ball milling medium is absolute ethyl alcohol, the ball milling body is a hard alloy ball, the ball milling tank is a hard alloy tank, adopting a clockwise and anticlockwise alternate operation mode, the rotating speed is 40 r/min during clockwise operation, 50 r/min during anticlockwise operation, 22min during clockwise operation, 22min during anticlockwise operation, the alternate interval standby time is 6 min, and the ball milling time is 27h, and carrying out vacuum drying to obtain powder transition layer mixed powder;
3) mixing the polycrystalline diamond layer: weighing the carbon nanotube coated diamond micro powder, the carbon fiber, the binding agent and the graphene according to a proportion, carrying out ball milling, wherein the ball material mass ratio is 7: 1, the ball milling medium is absolute ethyl alcohol, the ball milling body is a hard alloy ball, the ball milling tank is a hard alloy tank, adopting a clockwise and anticlockwise alternate operation mode, the rotating speed is 55 r/min when the ball milling tank is operated clockwise, the rotating speed is 75 r/min when the ball milling tank is operated anticlockwise, the time when the ball milling tank is operated clockwise is 22min, the standby time at alternate intervals is 6 min, the ball milling time is 25h, and carrying out vacuum drying to obtain powder transition layer mixed powder;
4) assembling a composite body: the same as in example 3;
5) and (3) purification treatment: the same as in example 3;
6) high-temperature high-pressure sintering: and (3) placing the purified composite assembly in the step 6) into a synthesis assembly block, and sintering at high temperature and high pressure by using a cubic press, wherein during sintering, the temperature is increased to 7GPa at the rate of 0.5GPa/min, then the temperature is increased to 1530 ℃ at the rate of 10 ℃/min for sintering, after 650S is sintered, the temperature is reduced to normal temperature at the rate of 20 ℃/min, and the pressure is reduced to normal pressure at the rate of 0.3 GPa/min. 7) Aging treatment: the same as in example 3.
The high-toughness wear-resistant polycrystalline diamond compact prepared by the comparative example is subjected to performance test by the same test method as that of example 1; the heat conductivity is 310W/(M.k), the abrasion ratio is 38 ten thousand, the impact frequency is 62 times, and the performance index is obviously reduced compared with the example 1.
The method for manufacturing and testing the cutter from the high-toughness wear-resistant polycrystalline diamond compact prepared by the comparative example is the same as that of example 1, the cutting time (cutting life) is 100 hours, and the phenomenon that diamond particles fall off occurs on the cutter. The cutting time was significantly reduced compared to example 1, indicating poorer cutting performance and shorter cutting life.
The high-toughness wear-resistant polycrystalline diamond compact prepared by the comparative example is subjected to ultrasonic scanning inspection on the interface of the compact by an American SONIX ultrasonic scanning microscope, and the result is shown in figure 9. As can be seen from fig. 9, delamination defects (delamination areas are white edge portions) are present at the interface between the polycrystalline diamond layer and the cemented carbide substrate of the compact.
Through the comparative analysis of the cutting performance of the embodiment and the comparative example, it can be obviously obtained that the high-toughness wear-resistant polycrystalline diamond compact composite sheet produced by the technical scheme of the invention does not have the phenomena of diamond particle falling, polycrystalline diamond layer falling and fracture when the standard cutting blade is manufactured into an intermittent aluminum alloy round rod, and the cutter not only has good cutting performance, but also has long cutting service life.
As can be seen from the interface ultrasonic flaw detection images of the examples and the comparative examples, the interface between the polycrystalline diamond layer and the hard alloy matrix of the composite sheet is well combined, and the composite sheet has no defects such as cracks, delamination, air holes, inclusions and the like.
It should be noted that: the materials used in the invention, which are not mentioned in manufacturers and models, are all sold on the conventional market. The manufacturer of the embodiments, the diameter, thickness of the compact, the thickness of the polycrystalline diamond layer, etc., are not intended to limit the present invention.
Finally, it should be noted that: the above embodiments are merely illustrative and not restrictive of the technical solutions of the present invention, and any equivalent substitutions and modifications or partial substitutions made without departing from the spirit and scope of the present invention should be included in the scope of the claims of the present invention.

Claims (8)

1. A high-toughness wear-resistant polycrystalline diamond compact is characterized by comprising a hard alloy matrix and Si sequentially arranged on the hard alloy matrix3N4The coating, the powder transition layer and the polycrystalline diamond layer; the polycrystallineThe diamond layer consists of the following raw materials in percentage by weight: 95-98% of carbon nanotube coated diamond micro powder, 0.1-0.3% of graphene, 0.1-0.2% of carbon fiber and 1.8-4.5% of a binding agent;
the powder transition layer is composed of the following raw materials in percentage by weight: 40-48% of hard alloy powder, 50-56% of carbon nano tube coated diamond micro powder, 0.5-1.5% of graphene and 1.5-2.5% of a binding agent.
2. The high toughness, wear resistant polycrystalline diamond compact of claim 1, wherein the Si is3N4The thickness of the coating is 6-8 mu m; the mass ratio of the powder transition layer to the polycrystalline diamond layer is 0.2: 1 to 1.5.
3. The high toughness, wear resistant polycrystalline diamond compact of claim 1 wherein the binder is comprised of the following raw materials in weight percent: 97-99% of cobalt powder, 0.5-1.5% of tungsten powder, 0.4-1.3% of titanium powder and 0.1-0.2% of rare earth elements, wherein the rare earth elements are any one of erbium, ytterbium and holmium; the particle sizes of the cobalt powder, the tungsten powder, the titanium powder and the rare earth element are 20-50 nm.
4. The high-toughness wear-resistant polycrystalline diamond compact according to claim 1, wherein the carbon nanotube coated diamond micro powder consists of micro powder with particle size distribution of 2-4 μm and 5-10 μm but not including three particle size distributions of 10 μm and 10-20 μm; the micro powder with three particle sizes comprises the following components in percentage by weight in the carbon nano tube coated diamond micro powder: the range of 2-4 mu m accounts for 10-20%, the range of 5-10 mu m does not contain 35-40% of 10 mu m, and the range of 10-20 mu m accounts for 45-50%.
5. The high toughness, wear resistant polycrystalline diamond compact of claim 1 wherein the cemented carbide substrate or cemented carbide powder is comprised of the following raw materials in weight percent: 84.5-88% of tungsten carbide powder, 10.5-13.9% of cobalt powder, 0.5-1% of zirconium powder, 0.3-0.5% of tantalum carbide powder and 0.3-0.5% of niobium carbide powder; the particle size of the tungsten carbide powder is 1.2-1.6 mu m; the particle sizes of the cobalt powder, the zirconium powder, the tantalum carbide powder and the niobium carbide powder are all 0.8-1.2 mu m.
6. The method of making a high toughness, wear resistant polycrystalline diamond compact of any of claims 1 to 5,
the method comprises the following steps:
1) depositing a transition layer: placing a hard alloy substrate in a magnetron sputtering device, taking silicon as a target material and nitrogen as a reaction gas, controlling the flow rate of the nitrogen to be 20-100 sccm, the radio frequency power to be 30-60W and the deposition pressure to be 0.3-2 Pa, and depositing Si on the surface of the clean hard alloy substrate3N4Layer of Si to obtain a layer containing3N4A coated cemented carbide substrate;
2) mixing of powder transition layers: weighing graphene according to a ratio, adding the graphene into absolute ethyl alcohol, and carrying out ultrasonic wave sweeping dispersion for 20-30 min to obtain a graphene dispersion liquid; then magnetically stirring the graphene dispersion liquid, and after 30-40 min, carrying out vacuum drying to obtain dispersed graphene powder; then weighing the carbon nanotube coated diamond micro powder, the hard alloy powder and the binding agent according to a proportion, ball-milling the carbon nanotube coated diamond micro powder, the hard alloy powder, the binding agent and the dispersed graphene powder, wherein the ball material mass ratio is 4-6: 1, the ball-milling medium is absolute ethyl alcohol, a clockwise and anticlockwise alternate operation mode is adopted, the rotating speed is 35-45 r/min during clockwise operation, the rotating speed is 45-55 r/min during anticlockwise operation, the time is 20-25 min during clockwise operation, the time is 20-25 min during anticlockwise operation, the ball-milling time is 25-30 h, and vacuum drying is carried out to obtain powder transition layer mixed powder;
3) mixing the polycrystalline diamond layer: weighing graphene and carbon fibers according to a ratio, respectively adding the graphene and the carbon fibers into absolute ethyl alcohol, and ultrasonically oscillating and dispersing for 20-30 min to obtain a graphene dispersion liquid and a carbon fiber dispersion liquid; then, magnetically stirring the graphene dispersion liquid, after 30-40 min, dropwise adding the carbon fiber dispersion liquid, and after 30-40 min, performing vacuum drying to obtain mixed powder of the dispersed graphene and the carbon fiber; then weighing the carbon nanotube-coated diamond micro powder and a binding agent according to a ratio, ball-milling the carbon nanotube-coated diamond micro powder, the binding agent and the dispersed graphene and carbon fiber mixed powder in a ball-milling manner, wherein the mass ratio of ball materials is 4-10: 1, the ball-milling medium is absolute ethyl alcohol, the ball-milling manner adopts a clockwise and anticlockwise alternate operation mode, the rotating speed is 50-60 r/min during clockwise operation, the rotating speed is 70-80 r/min during anticlockwise operation, the time is 20-25 min during clockwise operation, the time is 20-25 min during anticlockwise operation, the ball-milling time is 20-30 h, and vacuum drying is carried out to obtain diamond mixed powder;
4) assembling a composite body: laying the mixed powder of the polycrystalline diamond layer in a metal cup, and leveling; laying powder transition layer mixed powder on the polycrystalline diamond layer, and leveling; then will contain Si3N4Coated cemented carbide substrate with Si3N4Horizontally placing the coating face downwards on the mixed powder of the powder transition layer, placing the powder transition layer in a prepressing die, and prepressing for 5-8 min by using a hydraulic machine under the pressure of 10MPa to form a composite assembly;
5) and (3) purification treatment: placing the composite assembly obtained in the step 4) in a vacuum sintering furnace for sintering to obtain a purified composite assembly;
6) high-temperature high-pressure sintering: placing the purification composite component in the step 5) in a synthesis assembly block, and sintering at high temperature and high pressure by using a cubic press;
7) aging treatment: putting the polycrystalline diamond compact obtained after sintering in the step 6) into a vacuum sintering furnace, and vacuumizing until the pressure in the furnace is 3 multiplied by 10-3Pa, at 3X 10-3Heating to 380-430 ℃ under Pa, preserving heat for 0.5-1 h, vacuumizing again until the air pressure in the furnace is 3 multiplied by 10-5Pa, at 3X 10-5And under the condition of Pa, heating to 480-530 ℃, preserving the heat for 1-1.5 h, and finally cooling to room temperature and storing in vacuum.
7. The method for preparing the high-toughness wear-resistant polycrystalline diamond compact according to claim 6, wherein in the step 5) of sintering in a vacuum sintering furnace, rough vacuum is firstly carried out until the pressure in the furnace reaches 6 x 10-2Heating to 200-300 ℃ under Pa, keeping the temperature for 20-30 min, continuously vacuumizing and heating to 850-900 ℃ until the air pressure in the furnace is stabilized at 3 in a predetermined volume10-4Stopping vacuumizing, charging carbon monoxide gas with the furnace internal air pressure of 25-35 Mbar into a vacuum heating furnace at the temperature of 850-900 ℃ to reduce the composite assembly for 0.5-1 h, and continuously vacuumizing until the furnace internal air pressure is 3 multiplied by 10-4And (3) after the temperature is increased to 1150-1200 ℃ and the temperature is kept for 2-3 min below Pa, stopping vacuumizing, intermittently filling carbon monoxide into the vacuum heating furnace, wherein the air inflation amount is the same each time and the carbon monoxide filling amount is limited to 30-40 Mbar of the air pressure in the furnace, and after the air inflation is finished each time, waiting for 10min, starting a vacuumizing system to vacuumize the vacuum heating furnace until the air pressure in the furnace is 3 multiplied by 10-4And (5) below Pa, starting the carbon monoxide filling program and the vacuumizing program again after vacuumizing is finished, and circulating for 8-12 times to obtain the purification composite assembly.
8. The preparation method of the high-toughness wear-resistant polycrystalline diamond compact according to claim 6, wherein in the step 6), during sintering, the sintering pressure is increased to 7GPa at a rate of 0.1-1 GPa/min, then the temperature is increased to 1370-1400 ℃ at a temperature increase rate of 20-25 ℃/min for sintering for 80-120S, then the temperature is increased to 1430-1470 ℃ at a temperature increase rate of 10-15 ℃/min for sintering, the temperature is increased to 130-180S at a temperature increase rate of 5-10 ℃/min for sintering at 1500-1550 ℃, after sintering for 350-500S, the temperature is decreased to normal temperature at a temperature decrease rate of 10-30 ℃/min, and the pressure is decreased to normal pressure at a pressure decrease rate of 0.1-0.5 GPa/min.
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