CN117904507A - Gradient hard alloy and preparation method thereof - Google Patents
Gradient hard alloy and preparation method thereof Download PDFInfo
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- CN117904507A CN117904507A CN202410314970.2A CN202410314970A CN117904507A CN 117904507 A CN117904507 A CN 117904507A CN 202410314970 A CN202410314970 A CN 202410314970A CN 117904507 A CN117904507 A CN 117904507A
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 55
- 239000000956 alloy Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 76
- 238000005245 sintering Methods 0.000 claims description 71
- 239000000843 powder Substances 0.000 claims description 70
- 229910052786 argon Inorganic materials 0.000 claims description 38
- 239000010410 layer Substances 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 35
- 238000005422 blasting Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
- 239000002344 surface layer Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 23
- 230000004913 activation Effects 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 238000001238 wet grinding Methods 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 229910017052 cobalt Inorganic materials 0.000 claims description 17
- 239000010941 cobalt Substances 0.000 claims description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000005496 eutectics Effects 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910000997 High-speed steel Inorganic materials 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000000748 compression moulding Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 229910001018 Cast iron Inorganic materials 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000003966 growth inhibitor Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005480 shot peening Methods 0.000 claims 2
- 238000004663 powder metallurgy Methods 0.000 abstract description 3
- 239000012188 paraffin wax Substances 0.000 description 12
- 230000005389 magnetism Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000035882 stress Effects 0.000 description 7
- 229910009043 WC-Co Inorganic materials 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/04—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbonitrides
-
- 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
- B22F3/16—Both compacting and sintering in successive or repeated steps
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
-
- 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
- B22F2207/00—Aspects of the compositions, gradients
- B22F2207/01—Composition gradients
- B22F2207/03—Composition gradients of the metallic binder phase in cermets
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention belongs to the technical field of powder metallurgy, and particularly relates to a gradient hard alloy and a preparation method thereof.
Description
Technical Field
The invention belongs to the technical field of powder metallurgy, and particularly relates to a gradient hard alloy and a preparation method thereof.
Background
The hard alloy is a composite material manufactured by a hard compound (such as WC, tiC, taC, nbC and the like) of refractory metal and bonding metal (such as Co, ni and Fe) through a powder metallurgy process, and is widely applied to the application fields of metal cutting, mine tools, dies, wear-resistant parts and the like due to a series of excellent material characteristics of high hardness, high strength, good wear resistance, good thermal conductivity and the like. The working environment of the mould is usually required to bear high pressure and impact, and certain working conditions are exposed to corrosive liquid media and high temperature conditions, so that the performance requirements of the mould materials are higher and higher. Cemented carbide has found wide application in die applications, such as insert press forming dies, stainless steel high temperature resistant dies, progressive dies for leadframe materials, due to its high hardness, wear resistance and low coefficient of thermal expansion. The WC-Co alloy has higher strength and impact toughness, particularly when the cobalt content in the hard alloy is higher, the strength and toughness are higher, and the high toughness can resist crack formation and expansion caused by impact in the die pressing process, so that the high-cobalt YG hard alloy is suitable for being used under the conditions of impact and vibration. However, the high cobalt YG hard alloy has low hardness and insufficient plastic deformation resistance, and can generate the phenomena of plastic deformation, round edge of a punch, breakage and cracking, cracking and corrosion caused by thermal stress under the long-term impact and liquid cooling action in the use process, thereby causing the failure of a die. In order to solve the problems, the traditional preparation process adopts a gradient structure design method, the gradient hard alloy can keep high hardness and high wear resistance, and can fully exert the better impact toughness of the hard alloy, but cracks are easy to generate under the action of thermal stress, in order to prevent the cracks from expanding to the inside of a hard alloy matrix, a high-toughness binding phase layer, also called a surface cubic phase lack layer and a beta-removing layer, needs to be formed on the surface layer, but the surface does not contain cubic phase, so that WC grains are coarse, the cobalt content is higher than the nominal cobalt content, and the hardness and strength of the surface texture of the material are low, so that the material is not wear-resistant and fails prematurely.
Disclosure of Invention
In order to solve the problems in the prior art, the main purpose of the invention is to provide a gradient hard alloy and a preparation method thereof.
In order to solve the technical problems, according to one aspect of the present invention, the following technical solutions are provided:
the gradient hard alloy comprises a surface layer, a subsurface layer and a core part from outside to inside;
The surface layer contains WC, co and at least one of grain growth inhibitors Cr 3C2 and VC, taC, nbC,
The subsurface layer contains WC and Co,
The core contains WC, co, tiCN.
As a preferable embodiment of the gradient cemented carbide according to the present invention, wherein:
the WC grain size of the surface layer is 0.3-0.5 mu m, the Co content is 5-15 wt% and the thickness is 20-40 mu m;
The WC grain size of the subsurface layer is 0.6-0.8 mu m, the Co content is 8-20wt% and the thickness is 50-90 mu m;
The WC grain size of the core is 0.8-1.5 mu m, and the Co content is 5-18 wt%.
As a preferable embodiment of the gradient cemented carbide according to the present invention, wherein: the cobalt magnetism of the hard alloy is more than or equal to 10%, the magnetic force is less than or equal to 29.5KA/m, the surface hardness is more than or equal to 1910HV0.3, the subsurface hardness is more than or equal to 1760HV0.3, and the core hardness is more than or equal to 1890HV0.3.
In order to solve the above technical problems, according to another aspect of the present invention, the following technical solutions are provided:
the preparation method of the gradient hard alloy comprises the following steps:
s1, taking WC powder, co powder and TiCN powder as raw materials according to the composition of hard alloy, weighing a certain amount of forming agent, adding the forming agent and the raw materials into a ball mill together, and then adding alcohol for wet grinding to obtain a ball grinding material;
S2, performing spray drying on the ball milling material to obtain a mixture, and then performing compression molding to obtain a green body;
S3, sintering the green body in a sintering furnace for the first time to obtain a blank, and then performing surface activation pretreatment on the blank;
s4, embedding the blank subjected to surface activation pretreatment into composite powder for secondary sintering to obtain the gradient hard alloy.
As a preferable scheme of the preparation method of the gradient cemented carbide, the invention comprises the following steps: in the step S1, the mass of the forming agent is 1.6-2.5% of the mass of the raw material.
As a preferable scheme of the preparation method of the gradient cemented carbide, the invention comprises the following steps: in the step S1, the ball-to-material ratio in wet milling is (3-8) 1, the solid content is 60-90 wt%, and the wet milling time is 16-80 h.
As a preferable scheme of the preparation method of the gradient cemented carbide, the invention comprises the following steps: in the step S3, the blank surface activation pretreatment is to pretreat the blank surface through shot blasting, and the shot blasting process is as follows: the shot blasting medium is one of high-speed steel shots, cast iron shots and ceramic shots with the thickness of 60-200 mu m, the shot blasting pressure is 0.6MPa, the shot blasting time is 10-20 s, the shot blasting speed is 100-200 m/s, and the shot blasting distance is 90-120 mm.
As a preferable scheme of the preparation method of the gradient cemented carbide, the invention comprises the following steps: in the step S3, the first sintering process is as follows:
s31, heating a sintering furnace to the forming agent removal temperature of 250-350 ℃ under the conditions of hydrogen, argon, nitrogen or vacuum, and preserving heat for 1-2 hours to remove the forming agent;
s32, heating to the eutectic temperature 1340-1360 ℃ under vacuum condition, preserving heat for 0.5-1 h, and introducing argon to raise the furnace pressure to 20-80 mbar;
S33, continuously heating to the sintering temperature of 1400-1450 ℃, preserving heat for 30-120 min, introducing argon to pressurize to 10-50 bar, and sintering for 10-40 min;
S34, cooling to below the eutectic temperature point from the sintering temperature at a cooling speed of 1-10 ℃/min, and introducing high-pressure argon gas to quickly cool to room temperature along with the furnace.
As a preferable scheme of the preparation method of the gradient cemented carbide, the invention comprises the following steps: in the step S4, the composite powder is at least one of Cr 3C2 and VC, taC, nbC powder and at least one of alumina, zirconia, magnesia, yttria and calcia in a mass ratio of 1: (8-12) mixing the obtained mixture.
As a preferable scheme of the preparation method of the gradient cemented carbide, the invention comprises the following steps: in the step S4, the second sintering process is as follows: rapidly heating to 1340-1360 ℃ from room temperature, preserving heat for 0.5-1 h, introducing argon, keeping the pressure in the furnace at 20-80 mbar, continuously heating to 1380-1480 ℃ for preserving heat for 30-60 min, introducing argon, keeping the pressure in the furnace at 20-100 bar, cooling to room temperature along with the furnace, and then carrying out stress relief annealing.
The beneficial effects of the invention are as follows:
The invention provides a gradient hard alloy and a preparation method thereof, wherein the surface layer of the gradient hard alloy has the advantages of high surface hardness, high strength, good wear resistance, no cubic phase structure of the subsurface layer, good impact resistance, capability of preventing further expansion of cracks, cubic phase in the core, good rigidity, wide application to the upper punch and lower punch materials of a high-precision die, high precision, good wear resistance, difficult punch lack and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an SEM image of a cross section of a gradient cemented carbide prepared in example 1 of the present invention.
In the figure, 1-skin layer, 2-subsurface layer, 3-core.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following description will be made clearly and fully with reference to the technical solutions in the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a gradient hard alloy and a preparation method thereof, wherein micro TiCN powder and cubic carbide powder are added into raw materials Co powder and WC powder, the hardness and plastic deformation resistance of the alloy are improved through cubic TiCN, the gradient hard alloy with a gradient structure is obtained through strong thermodynamic coupling action between Ti and N, so that the surface layer of the hard alloy keeps high toughness, the surface layer containing at least one of Cr, V, ta, nb is prepared through diffusion reaction of at least one of elements Cr, V, ta, nb, the corrosion resistance of the alloy is improved, and at least one of Cr, V, ta, nb and a bonding phase are subjected to solid solution reaction, thereby achieving the effects of grain refinement and solid solution strengthening.
According to one aspect of the invention, the invention provides the following technical scheme:
the gradient hard alloy comprises a surface layer, a subsurface layer and a core part from outside to inside;
The surface layer contains WC, co and at least one of grain growth inhibitors Cr 3C2 and VC, taC, nbC,
The subsurface layer contains WC and Co,
The core contains WC, co, tiCN.
Preferably, the WC grain size of the surface layer is 0.3-0.5 mu m, the Co content is 5-15 wt% and the thickness is 20-40 mu m; the WC grain size of the subsurface layer is 0.6-0.8 mu m, the Co content is 8-20wt% and the thickness is 50-90 mu m; the WC grain size of the core is 0.8-1.5 mu m, and the Co content is 5-18 wt%.
Preferably, the cobalt magnetism of the hard alloy is more than or equal to 10%, the magnetic force is less than or equal to 29.5KA/m, the surface hardness is more than or equal to 1910HV0.3, the subsurface hardness is more than or equal to 1760HV0.3, and the core hardness is more than or equal to 1890HV0.3.
According to another aspect of the invention, the invention provides the following technical scheme:
the preparation method of the gradient hard alloy comprises the following steps:
s1, taking WC powder, co powder and TiCN powder as raw materials according to the composition of hard alloy, weighing a certain amount of forming agent, adding the forming agent and the raw materials into a ball mill together, and then adding alcohol for wet grinding to obtain a ball grinding material;
S2, performing spray drying on the ball milling material to obtain a mixture, and then performing compression molding to obtain a green body;
S3, sintering the green body in a sintering furnace for the first time to obtain a blank, and then performing surface activation pretreatment on the blank;
s4, embedding the blank subjected to surface activation pretreatment into composite powder for secondary sintering to obtain the gradient hard alloy.
Preferably, in the step S1, the mass of the molding agent is 1.6-2.5% of the mass of the raw material; the ball-material ratio in wet milling is (3-8) 1, the solid content is 60-90 wt%, and the wet milling time is 16-80 h.
Preferably, in the step S3, the surface activation pretreatment of the blank is to pretreat the surface of the blank by shot blasting, and the shot blasting process is as follows: the shot blasting medium is one of high-speed steel shots, cast iron shots and ceramic shots with the thickness of 60-200 mu m, the shot blasting pressure is 0.6MPa, the shot blasting time is 10-20 s, the shot blasting speed is 100-200 m/s, and the shot blasting distance is 90-120 mm. Because the surface plastic deformation is generated under the action of the shot blasting and a certain compressive stress is formed, dislocation with high density can be formed in the surface strengthening layer, a plurality of microscopic channels are formed, meanwhile, the surface potential energy is increased, the surface strengthening effect provides a rapid channel for inward diffusion of atoms such as Cr, V, ta, nb and the like, and the diffusion and reaction of the atoms can be accelerated. Through shot blasting, a plurality of tiny pits are formed on the surface of the blank, the contact surface area is increased, and Cr, V, ta, nb atoms are adsorbed in the tiny pits under the action of capillary effect.
Preferably, in the step S3, the first sintering process is as follows:
s31, heating a sintering furnace to the forming agent removal temperature of 250-350 ℃ under the conditions of hydrogen, argon, nitrogen or vacuum, and preserving heat for 1-2 hours to remove the forming agent;
s32, heating to the eutectic temperature 1340-1360 ℃ under vacuum condition, preserving heat for 0.5-1 h, and introducing argon to raise the furnace pressure to 20-80 mbar;
S33, continuously heating to the sintering temperature of 1400-1450 ℃, preserving heat for 30-120 min, introducing argon to pressurize to 10-50 bar, and sintering for 10-40 min;
S34, cooling to below the eutectic temperature point from the sintering temperature at a cooling speed of 1-10 ℃/min, and introducing high-pressure argon gas to quickly cool to room temperature along with the furnace.
Further preferably, in the step S34, the temperature is cooled from the sintering temperature to 1200 ℃ or lower at a cooling rate of 5 ℃/min or less.
Preferably, in the step S4, the composite powder is at least one of Cr 3C2 and VC, taC, nbC powder and at least one of alumina, zirconia, magnesia, yttria and calcia in a mass ratio of 1: the mixture obtained by mixing (8-12), preferably, at least one of Cr 3C2 and VC, taC, nbC powder is ball-milled and pre-treated, high-energy ball milling is carried out for 60-100 hours under the protection of nitrogen, and the ball-to-material ratio (4-10): 1, the treatment can refine granularity, improve surface activity, increase dislocation density of powder crystal grains and improve surface adsorption force and cobalt phase dissolution force.
Preferably, in the step S4, the second sintering process is as follows: rapidly heating to 1340-1360 ℃ from room temperature, preserving heat for 0.5-1 h, introducing argon, keeping the pressure in the furnace at 20-80 mbar, continuously heating to 1380-1480 ℃ for preserving heat for 30-60 min, introducing argon, keeping the pressure in the furnace at 20-100 bar, cooling to room temperature along with the furnace, and then carrying out stress relief annealing.
The technical scheme of the invention is further described below by combining specific embodiments.
Example 1
A preparation method of gradient hard alloy comprises the following steps:
S1, taking WC powder, co powder and TiCN powder (12 wt% of Co powder, 0.5wt% of TiCN powder and the balance of WC powder, wherein the FSSS granularity of the WC powder is 2.54 mu m) as raw materials according to the composition of hard alloy, weighing a certain amount of paraffin, adding the paraffin and the raw materials into a ball mill together, and then adding alcohol for wet grinding to obtain a ball abrasive; the mass of the paraffin is 2.0% of the mass of the raw material; the ball-to-material ratio in wet milling was 5:1, the solid content was 75wt%, and the wet milling time was 40h.
S2, performing spray drying on the ball milling material to obtain a mixture, and then performing compression molding to obtain a green body;
S3, sintering the green body in a sintering furnace for the first time to obtain a blank, and then performing surface activation pretreatment on the blank; the first sintering process comprises the following steps: s31, under the vacuum condition, heating the sintering furnace to the forming agent removal temperature of 300 ℃, preserving heat for 1.5h, and dewaxing; s32, heating to a eutectic temperature of 1350 ℃ under vacuum condition, preserving heat for 0.5h, and introducing argon to raise the furnace pressure to 80mbar; s33, continuously heating to the sintering temperature of 1410 ℃ and preserving heat for 90min, introducing argon to pressurize to 50bar, and sintering for 30min; s34, cooling to 1100 ℃ from the sintering temperature at a cooling rate of 5 ℃/min, and introducing high-pressure argon gas to quickly cool to room temperature along with the furnace. The blank surface activation pretreatment is to pretreat the blank surface through shot blasting, wherein the shot blasting process comprises the following steps: the shot medium was 100 μm high-speed steel shot, the shot pressure was 0.6MPa, the shot time was 15s, the shot speed was 150m/s, and the shot distance was 100mm.
S4, embedding the blank subjected to surface activation pretreatment into composite powder for secondary sintering to obtain the gradient hard alloy. The composite powder is a composition obtained by mixing Cr 3C2 powder with FSSS granularity of 0.81 mu m and aluminum oxide powder with FSSS granularity of 9 mu m according to the weight ratio of 1:10; the second sintering process comprises the following steps: rapidly heating to 1360 ℃ from room temperature, preserving heat for 1h, introducing argon, keeping the pressure in the furnace to be 60mbar, continuously heating to the sintering temperature of 1410 ℃ and preserving heat for 45min, introducing argon, keeping the pressure in the furnace to be 50bar, cooling to room temperature along with the furnace, and carrying out stress relief annealing.
The SEM image of the cross section of the gradient cemented carbide prepared in the embodiment is shown in fig. 1, and the gradient cemented carbide sequentially comprises a surface layer 1, a subsurface layer 2 and a core 3 from outside to inside; the surface layer 1 is WC-Co-Cr 3C2, the WC grain size of the surface layer 1 is 0.4 mu m, the Co content is 12.41 weight percent, and the thickness is 28 mu m; the subsurface layer 2 is WC-Co, the WC grain size of the subsurface layer 2 is 0.65 mu m, the Co content is 13.76wt% and the thickness is 75 mu m; the core 3 was WC-Co-TiCN, the WC grain size of the core 3 was 1.0 μm, and the Co content was 15.39wt%. The cobalt magnetism of the hard alloy is 10.39%, the magnetic force is 28.71KA/m, the hardness of the surface layer 1 is 1918HV0.3, the hardness of the subsurface layer 2 is 1776HV0.3, and the hardness of the core 3 is 1902HV0.3.
Example 2
A preparation method of gradient hard alloy comprises the following steps:
s1, taking WC powder, co powder and TiCN powder (13 wt% of Co powder, 0.55wt% of TiCN powder and the balance of WC powder, wherein the FSSS granularity of the WC powder is 2.44 mu m) as raw materials according to the composition of hard alloy, weighing a certain amount of paraffin, adding the paraffin and the raw materials into a ball mill together, and then adding alcohol for wet grinding to obtain a ball grinding material; the mass of the paraffin is 2.5% of the mass of the raw material; the ball-to-material ratio in wet milling was 8:1, the solids content was 90wt%, and the wet milling time was 80h.
S2, performing spray drying on the ball milling material to obtain a mixture, and then performing compression molding to obtain a green body;
S3, sintering the green body in a sintering furnace for the first time to obtain a blank, and then performing surface activation pretreatment on the blank; the first sintering process comprises the following steps: s31, under the vacuum condition, heating a sintering furnace to the removal temperature of a forming agent of 350 ℃, preserving heat for 1h, and dewaxing; s32, heating to the eutectic temperature 1340 ℃ under vacuum condition, preserving heat for 1h, and introducing argon to raise the furnace pressure to 50mbar; s33, continuously heating to a sintering temperature of 1450 ℃, preserving heat for 30min, introducing argon, pressurizing to 10bar, and sintering for 40min; s34, cooling to 1050 ℃ from the sintering temperature at a cooling rate of 4 ℃/min, and introducing high-pressure argon gas to quickly cool to room temperature along with the furnace. The blank surface activation pretreatment is to pretreat the blank surface through shot blasting, wherein the shot blasting process comprises the following steps: the shot medium was 105 μm high-speed steel shot, the shot pressure was 0.6MPa, the shot time was 10s, the shot speed was 200m/s, and the shot distance was 90mm.
S4, embedding the blank subjected to surface activation pretreatment into composite powder for secondary sintering to obtain the gradient hard alloy. The composite powder is a composition obtained by mixing VC powder with FSSS granularity of 0.72 mu m and alumina powder with FSSS granularity of 9.5 mu m according to the weight ratio of 1:10; the second sintering process comprises the following steps: rapidly heating to 1340 ℃ from room temperature, preserving heat for 1h, introducing argon, keeping the pressure in the furnace at 80mbar, continuously heating to 1480 ℃ and preserving heat for 30min, introducing argon, keeping the pressure in the furnace at 20bar, cooling to room temperature along with the furnace, and carrying out stress relief annealing.
The gradient hard alloy prepared by the embodiment sequentially comprises a surface layer, a subsurface layer and a core part from outside to inside; the surface layer is WC-Co-VC, the WC grain size of the surface layer is 0.4 mu m, the Co content is 11.8wt% and the thickness is 25 mu m; the subsurface layer is WC-Co, the WC grain size of the subsurface layer is 0.72 mu m, the Co content is 14.56wt% and the thickness is 80 mu m; the core is WC-Co-TiCN, the WC grain size of the core is 1.2 mu m, and the Co content is 16.51wt%. The cobalt magnetism of the hard alloy is 11.1%, the magnetic force is 27.9KA/m, the surface hardness is 1921HV0.3, the subsurface hardness is 1766HV0.3, and the core hardness is 1893HV0.3.
Example 3
A preparation method of gradient hard alloy comprises the following steps:
S1, taking WC powder, co powder and TiCN powder (12 wt% of Co powder, 0.5wt% of TiCN powder and the balance of WC powder, wherein the FSSS granularity of the WC powder is 2.54 mu m) as raw materials according to the composition of hard alloy, weighing a certain amount of paraffin, adding the paraffin and the raw materials into a ball mill together, and then adding alcohol for wet grinding to obtain a ball abrasive; the mass of the paraffin is 1.6% of the mass of the raw material; the ball-to-material ratio in wet milling was 3:1, the solid content was 60wt%, and the wet milling time was 16h.
S2, performing spray drying on the ball milling material to obtain a mixture, and then performing compression molding to obtain a green body;
S3, sintering the green body in a sintering furnace for the first time to obtain a blank, and then performing surface activation pretreatment on the blank; the first sintering process comprises the following steps: s31, under the vacuum condition, heating the sintering furnace to the forming agent removal temperature of 250 ℃, preserving heat for 2 hours, and dewaxing; s32, heating to the eutectic temperature of 1360 ℃ under vacuum condition, preserving heat for 0.5h, and introducing argon to raise the furnace pressure to 20mbar; s33, continuously heating to the sintering temperature of 1400 ℃, preserving heat for 120min, introducing argon, pressurizing to 50bar, and sintering for 10min; s34, cooling to 1100 ℃ from the sintering temperature at a cooling rate of 5 ℃/min, and introducing high-pressure argon gas to quickly cool to room temperature along with the furnace. The blank surface activation pretreatment is to pretreat the blank surface through shot blasting, wherein the shot blasting process comprises the following steps: the shot medium was 100 μm high-speed steel shot, the shot pressure was 0.6MPa, the shot time was 15s, the shot speed was 150m/s, and the shot distance was 120mm.
S4, embedding the blank subjected to surface activation pretreatment into composite powder for secondary sintering to obtain the gradient hard alloy. The composite powder is a composition obtained by mixing Cr 3C2 powder with FSSS granularity of 0.75 mu m and aluminum oxide powder with FSSS granularity of 9 mu m according to the weight ratio of 1:8; the second sintering process comprises the following steps: and (3) rapidly heating to 1350 ℃ from room temperature, preserving heat for 0.5h, introducing argon, keeping the pressure in the furnace at 20mbar, continuously heating to 1380 ℃ for preserving heat for 60min, introducing argon, keeping the pressure in the furnace at 100bar, cooling to room temperature along with the furnace, and carrying out stress relief annealing.
The gradient hard alloy prepared by the embodiment sequentially comprises a surface layer, a subsurface layer and a core part from outside to inside; the surface layer is WC-Co-Cr 3C2, the WC grain size of the surface layer is 0.45 mu m, the Co content is 11.58wt% and the thickness is 32 mu m; the subsurface layer is WC-Co, the WC grain size of the subsurface layer is 0.76 mu m, the Co content is 15.15wt% and the thickness is 81 mu m; the core is WC-Co-TiCN, the WC grain size of the core is 1.5 mu m, and the Co content is 14.47wt%. The cobalt magnetism of the hard alloy is 10.54%, the magnetic force is 27.88KA/m, the surface layer hardness is 1925HV0.3, the subsurface layer hardness is 1771HV0.3, and the core hardness is 1899HV0.3.
Example 4
A preparation method of gradient hard alloy comprises the following steps:
s1, taking WC powder, co powder and TiCN powder (12.5 wt% of Co powder, 0.6wt% of TiCN powder and the balance of WC powder, wherein the FSSS granularity of the WC powder is 2.57 mu m) as raw materials according to the composition of hard alloy, weighing a certain amount of paraffin, adding the paraffin and the raw materials into a ball mill together, and then adding alcohol for wet grinding to obtain a ball grinding material; the mass of the paraffin is 1.6% of the mass of the raw material; the ball-to-material ratio in wet milling was 3:1, the solid content was 60wt%, and the wet milling time was 16h.
S2, performing spray drying on the ball milling material to obtain a mixture, and then performing compression molding to obtain a green body;
S3, sintering the green body in a sintering furnace for the first time to obtain a blank, and then performing surface activation pretreatment on the blank; the first sintering process comprises the following steps: s31, under the vacuum condition, heating the sintering furnace to the forming agent removal temperature of 300 ℃, preserving heat for 2 hours, and dewaxing; s32, heating to a eutectic temperature of 1350 ℃ under vacuum condition, preserving heat for 0.5h, and introducing argon to raise the furnace pressure to 80mbar; s33, continuously heating to the sintering temperature of 1410 ℃ and preserving heat for 90min, introducing argon to pressurize to 50bar, and sintering for 30min; s34, cooling to 1100 ℃ from the sintering temperature at a cooling rate of 5 ℃/min, and introducing high-pressure argon gas to quickly cool to room temperature along with the furnace. The blank surface activation pretreatment is to pretreat the blank surface through shot blasting, wherein the shot blasting process comprises the following steps: the shot medium was 100 μm high-speed steel shot, the shot pressure was 0.6MPa, the shot time was 15s, the shot speed was 150m/s, and the shot distance was 100mm.
S4, embedding the blank subjected to surface activation pretreatment into composite powder for secondary sintering to obtain the gradient hard alloy. The composite powder is a composition obtained by mixing Cr 3C2 powder with FSSS granularity of 0.81 mu m and aluminum oxide powder with FSSS granularity of 9 mu m according to the weight ratio of 1:12; the second sintering process comprises the following steps: and (3) rapidly heating to 1350 ℃ from room temperature, preserving heat for 0.5h, introducing argon, keeping the pressure in the furnace at 20mbar, continuously heating to 1380 ℃ for preserving heat for 60min, introducing argon, keeping the pressure in the furnace at 100bar, cooling to room temperature along with the furnace, and carrying out stress relief annealing.
The gradient hard alloy prepared by the embodiment sequentially comprises a surface layer, a subsurface layer and a core part from outside to inside; the surface layer is WC-Co-Cr 3C2, the WC grain size of the surface layer is 0.42 mu m, the Co content is 13.14wt% and the thickness is 21 mu m; the subsurface layer is WC-Co, the WC grain size of the subsurface layer is 0.60 mu m, the Co content is 12.87wt% and the thickness is 67 mu m; the core is WC-Co-TiCN, the WC grain size of the core is 0.9 mu m, and the Co content is 14.74wt%. The cobalt magnetism of the hard alloy is 10.87%, the magnetic force is 29.1KA/m, the surface hardness is 1913HV0.3, the subsurface hardness is 1760HV0.3, and the core hardness is 1907HV0.3.
Comparative example 1
The difference from example 1 is that steps S3-S4 are not performed and the green body is dewaxed and sintered in a hot isostatic pressing sintering furnace at 300 c for 2h at 1410 c for 1.5h.
The hard alloy prepared in the comparative example has a homogeneous structure containing WC-Co-TiCN, the cobalt magnetism is 8.9%, the magnetic force is 34.24KA/m, and the hardness is 1887HV0.3.
Comparative example 2
The difference from example 1 is that steps S3-S4 are not performed, the green body is dewaxed and sintered in a hot isostatic pressing sintering furnace, nitrogen partial pressure sintering is adopted, the dewaxing temperature is 300 ℃, the dewaxing time is 2h, the nitrogen partial pressure is 50mbar, the sintering final temperature is 1410 ℃, and the sintering time is 1.5h.
The cemented carbide prepared in this comparative example was a homogeneous structure of WC-Co-TiCN of the core and an outside cubic phase lacking layer, the thickness of the cubic phase lacking layer was 20 μm, the cobalt magnetism was 8.1%, the magnetic force was 32.21KA/m, the core hardness was 1913HV0.3, and the cubic phase lacking layer hardness was 1810HV0.3.
Comparative example 3
The difference from example 1 is that the surface activation pretreatment of the blank is not performed after the blank is obtained by the first sintering in step S3.
The hard alloy prepared in the comparative example comprises a surface layer, a subsurface layer and a core part from outside to inside; the surface layer is WC-Co-Cr 3C2, the thickness is only 5 μm, the cobalt magnetism is 9.5%, the magnetic force is 29.9KA/m, and the hardness is 1878HV0.3.
Comparative example 4
The difference from example 1 is that in step S4, alumina powder having an FSSS particle size of 9 μm is used instead of the composite powder.
The cemented carbide prepared in this comparative example was a homogeneous structure of WC-Co-TiCN in the core and an outside cubic phase lacking layer having a thickness of 24 μm, a cobalt magnetism of 9.6%, a magnetic force of 31.8KA/m, and a hardness of 1854HV0.3.
The surface superfine crystal structure of the gradient hard alloy has the advantages of high surface hardness, high strength, good wear resistance, no cubic phase structure of the subsurface layer, good impact resistance, capability of preventing further expansion of cracks, cubic phase in the core, good rigidity, wide application to upper and lower punch materials of a high-precision die, high precision, good wear resistance, difficult punch shortage and the like, and simple preparation method and easy production implementation.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the content of the present invention or direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (10)
1. The gradient hard alloy is characterized by sequentially comprising a surface layer, a subsurface layer and a core part from outside to inside;
The surface layer contains WC, co and at least one of grain growth inhibitors Cr 3C2 and VC, taC, nbC,
The subsurface layer contains WC and Co,
The core contains WC, co, tiCN.
2. The gradient cemented carbide according to claim 1,
The WC grain size of the surface layer is 0.3-0.5 mu m, the Co content is 5-15 wt% and the thickness is 20-40 mu m;
The WC grain size of the subsurface layer is 0.6-0.8 mu m, the Co content is 8-20wt% and the thickness is 50-90 mu m;
The WC grain size of the core is 0.8-1.5 mu m, and the Co content is 5-18 wt%.
3. The gradient cemented carbide according to claim 1, wherein the cemented carbide has a cobalt magnetic force of 10% or more, a magnetic force of 29.5KA/m or less, a surface hardness of 1910HV0.3% or more, a subsurface hardness of 1760HV0.3 or more, and a core hardness of 1890HV0.3 or more.
4. A method of producing a gradient cemented carbide according to any one of claims 1-3, comprising the steps of:
s1, taking WC powder, co powder and TiCN powder as raw materials according to the composition of hard alloy, weighing a certain amount of forming agent, adding the forming agent and the raw materials into a ball mill together, and then adding alcohol for wet grinding to obtain a ball grinding material;
S2, performing spray drying on the ball milling material to obtain a mixture, and then performing compression molding to obtain a green body;
S3, sintering the green body in a sintering furnace for the first time to obtain a blank, and then performing surface activation pretreatment on the blank;
s4, embedding the blank subjected to surface activation pretreatment into composite powder for secondary sintering to obtain the gradient hard alloy.
5. The method of producing a gradient cemented carbide according to claim 4, wherein in step S1, the mass of the forming agent is 1.6-2.5% of the mass of the raw material.
6. The method of producing a gradient cemented carbide according to claim 4, wherein in step S1, the ball-to-material ratio in wet milling in step S1 is (3-8): 1, the solid content is 60-90 wt%, and the wet milling time is 16-80 hours.
7. The method for preparing a gradient cemented carbide according to claim 4, wherein in the step S1, the blank surface activation pretreatment in the step S3 is a pretreatment of the blank surface by shot peening, and the shot peening process is as follows: the shot blasting medium is one of high-speed steel shots, cast iron shots and ceramic shots with the thickness of 60-200 mu m, the shot blasting pressure is 0.6MPa, the shot blasting time is 10-20 s, the shot blasting speed is 100-200 m/s, and the shot blasting distance is 90-120 mm.
8. The method of manufacturing a gradient cemented carbide according to claim 4, wherein in step S1, the first sintering process in step S3 is:
s31, heating a sintering furnace to the forming agent removal temperature of 250-350 ℃ under the conditions of hydrogen, argon, nitrogen or vacuum, and preserving heat for 1-2 hours to remove the forming agent;
s32, heating to the eutectic temperature 1340-1360 ℃ under vacuum condition, preserving heat for 0.5-1 h, and introducing argon to raise the furnace pressure to 20-80 mbar;
S33, continuously heating to the sintering temperature of 1400-1450 ℃, preserving heat for 30-120 min, introducing argon to pressurize to 10-50 bar, and sintering for 10-40 min;
S34, cooling to below the eutectic temperature point from the sintering temperature at a cooling speed of 1-10 ℃/min, and introducing high-pressure argon gas to quickly cool to room temperature along with the furnace.
9. The method according to claim 4, wherein in the step S1, in the step S4, the composite powder is at least one of Cr 3C2 and VC, taC, nbC powder and at least one of alumina, zirconia, magnesia, yttria and calcia is in a mass ratio of 1: (8-12) mixing the obtained mixture.
10. The method of manufacturing a gradient cemented carbide according to claim 4, wherein in step S1, the second sintering process in step S4 is: rapidly heating to 1340-1360 ℃ from room temperature, preserving heat for 0.5-1 h, introducing argon, keeping the pressure in the furnace at 20-80 mbar, continuously heating to 1380-1480 ℃ for preserving heat for 30-60 min, introducing argon, keeping the pressure in the furnace at 20-100 bar, cooling to room temperature along with the furnace, and then carrying out stress relief annealing.
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