CN111172443B - High-comprehensive-performance hard alloy cutter material and preparation method thereof - Google Patents
High-comprehensive-performance hard alloy cutter material and preparation method thereof Download PDFInfo
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- CN111172443B CN111172443B CN202010112689.2A CN202010112689A CN111172443B CN 111172443 B CN111172443 B CN 111172443B CN 202010112689 A CN202010112689 A CN 202010112689A CN 111172443 B CN111172443 B CN 111172443B
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- 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
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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
- 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
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- 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
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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
- 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 hard alloy cutter material with high comprehensive performance and a preparation method thereof. Comprises the following raw materials of, by mass, WC65-90 parts and Al2O35-30 parts of Co3-10 parts of Y2O30.5-2 parts. The preparation process comprises the following steps: respectively loading all the original powder into a ball milling cylinder, respectively carrying out ball milling, mixing and then carrying out ball milling; putting the mixture of all the components after ball milling into a vacuum drying oven for drying, and packaging the sieved powder for later use; loading into a high-strength graphite mould, and then putting into a vacuum sintering furnace; under the vacuum atmosphere, the temperature is raised to 1450 ℃ in 29min, and the hot-pressing sintering molding is carried out under the conditions that the pressure is applied to 32MPa at the temperature and the heat is preserved for 30 min. The cutter material prepared by the invention has excellent comprehensive mechanical properties, and the hardness is improved while the high bending strength and the high fracture toughness are kept.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a high-comprehensive-performance hard alloy cutter material and a preparation method thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Compared with materials such as high-speed steel, diamond, ceramic and the like, the hard alloy has good strength, excellent toughness, good impact resistance and thermal shock resistance, is one of the most widely used tool materials at present, and plays a very important role in promoting industrial manufacturing and national economic development in China. The WC-Co type hard alloy has wide application in the industrial field, and the tungsten carbide (WC) has high melting point (2870 ℃), good wear resistance, chemical stability and thermal stability, is a good conductor of electricity and heat, has high hardness, simultaneously has low thermal expansion coefficient and high elastic modulus, and is suitable for being used as a cutter material. In the WC-Co type hard alloy, WC is used as a hard phase to guarantee high hardness of the material, metal Co is used to guarantee toughness of the material, and the hardness and the toughness of the material change in opposite directions along with the change of the content of WC and Co, which is the contradiction of mutual restriction between the hardness and the toughness of the WC-Co type hard alloy.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a hard alloy cutter material with high comprehensive performance and a preparation method thereof. The cutter material of the invention is prepared by adding additive phase alumina (Al) with proper proportion into WC-based hard alloy cutter material2O3) Yttrium oxide (Y)2O3) And cobalt (Co) to prepare the WC-based composite cutter material with high strength, toughness and hardness.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a high comprehensive performance hard alloy cutter material comprises, by mass, WC65-90 parts, Al2O35-30 parts of Co3-10 parts of Y2O30.5-2 parts.
The invention improves WC-Co type hard alloy, in the existing WC-Co type hard alloy, WC is taken as a hard phase to ensure the high hardness of the material, metal Co is taken as the guarantee of the toughness of the material, the hardness and the toughness of the material change in opposite directions along with the change of the content of WC and Co, which is the contradiction that the hardness and the toughness of the WC-Co type hard alloy are restricted with each other, the high temperature performance is poor, and the strength is reduced seriously at high temperatureAnd (4) heavy. Al (Al)2O3Compared with a matrix WC-Co, the material has higher hardness, excellent chemical stability, wear resistance, heat resistance, oxidation resistance and high-temperature mechanical property, but has low bending strength and fracture toughness. Therefore, the invention selects WC as the matrix phase and Al2O3Co is selected as the metal phase for the reinforcement phase, Y2O3Is a sintering aid.
As some embodiments of the present invention, WC65-90 parts by mass, Al, is composed of the following raw materials2O35-30 parts of Co4 parts of Y2O31 part.
In the invention, the WC-Co type hard alloy is doped with Al2O3And Y2O3And it was found that a certain mass part of Al was doped2O3Is beneficial to improving the mechanical property of the WC-Co hard alloy.
The invention relates to a WC-Co type hard alloy, WC and Al2O3The novel cutting tool material has good chemical compatibility, does not generate chemical reaction in the sintering process, and is favorable for improving the hardness and the high-temperature resistance of the novel cutting tool material due to high-temperature and room-temperature hardness and oxidation resistance; al (Al)2O3And Y2O3Meanwhile, the additive is added into a WC matrix material as an additive phase, which is beneficial to improving the density of the material, thereby greatly improving the hardness of the material while ensuring higher toughness.
The preparation method of the cutter material comprises the steps of respectively carrying out ball milling on the raw materials, mixing the ball-milled raw materials, drying, repeatedly carrying out ball milling and drying on the mixture after drying, and then carrying out vacuum sintering on the dried mixture to obtain the cutter material.
The ball milling is carried out firstly and then mixed and then the ball milling is carried out, and the purpose is as follows: the dispersibility of each component is improved, and the fusibility of each raw material component after mixing is facilitated.
The invention has the beneficial effects that:
the method has the advantages of simple equipment, good safety, lower cost, stable preparation process, simple operation and treatment and high production efficiency. The prepared WC-based composite cutter material has excellent comprehensive mechanical properties, high bending strength and fracture toughness and high hardness.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a scanning electron micrograph of a polished surface of the WC-based composite cutting tool material of example 1, wherein A is WC and B is Al2O3。
FIG. 2 is a scanning electron micrograph of a polished surface of the WC-based composite cutting tool material of example 2, wherein A is WC and B is Al2O3。
FIG. 3 is a scanning electron micrograph of a polished surface of the WC-based composite cutting tool material of example 3, wherein A is WC and B is Al2O3。
FIG. 4 is a SEM photograph of the polished surface of the WC-based composite cutting tool material of example 4, wherein A is WC and B is Al2O3。
FIG. 5 is a SEM photograph of the polished surface of the WC-based composite cutting tool material of example 5, wherein A is WC and B is Al2O3。
FIG. 6 is a SEM photograph of the polished surface of the WC-based composite cutting tool material of example 6, wherein A is WC and B is Al2O3。
FIG. 7 is a representation of a WC-based composite tool material conducted in example 6; FIG. 7(a) is a scanning electron micrograph of a polished surface, and EDS energy spectrum analysis was performed on the gray phase A point and the black phase B point in the drawing, and the results are shown in FIG. 7(B) and FIG. 7(c), respectively.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. Furthermore, it will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
A high comprehensive performance hard alloy cutter material comprises, by mass, WC65-90 parts, Al2O35-30 parts of Co3-10 parts of Y2O30.5-2 parts.
As some embodiments of the invention, the high-comprehensive-performance hard alloy cutter material comprises the following raw materials of, by mass, 65-90 parts of WC and Al2O35-30 parts of Co4 parts of Y2O31 part.
The preparation method of the cutter material comprises the following specific steps:
respectively carrying out ball milling on the raw materials, mixing the ball-milled raw materials, drying, repeatedly carrying out ball milling and drying on the mixture after drying, and then carrying out vacuum sintering on the dried mixture to obtain the cutter material.
In some embodiments of the invention, the WC has a particle size of 0.3 to 0.5 μm, Al2O3Has a particle diameter of 0.4-0.6 μm, Co has a particle diameter of 0.4-0.6 μm, and Y2O3The particle diameter of (A) is 0.8-1.2 μm.
In some embodiments of the invention, the ball milling is performed using a ball mill, and Al is2O3When the powder is separately ball-milled, the ball-milling balls are alumina balls, when the other powder is separately ball-milled and secondly mixed ball-milled, the ball-milling balls are tungsten carbide balls, the ball-material ratio of the first ball-milling to the second ball-milling is 9-11:1, and the ball-milling medium is alcohol.
In some embodiments of the invention, the ball milling time of the feedstock is 40 to 50 hours. The ball milling time of the raw materials refers to the time of ball milling of each raw material separately for the first time and the time of ball milling of the mixture for the second time.
In some embodiments of the invention, the drying temperature of the raw material is 100-.
In some embodiments of the present invention, the pressure of vacuum sintering is 30-40MPa, and the temperature of vacuum sintering is 1300-1600 ℃, preferably 1400-1500 ℃.
In some embodiments of the invention, the temperature rise time of the vacuum sintering is 20-40min, and the heat preservation time is 20-40 min.
The present invention will be further described with reference to the following examples.
Example 1
A high-comprehensive-performance hard alloy cutter material comprises, by mass, WC65 parts and Al2O330 parts of Co4 parts of Y2O31 part.
Preparation of the cutter material of example 1: all the raw powders were loaded into a polyurethane ball mill cylinder, Al2O3The powder takes alumina balls as ball milling balls, other powder takes tungsten carbide balls as ball milling balls and alcohol as ball milling media, and the powder is sealed and then put on a roller ball mill for wet ball milling for 48 hours; putting the mixture of all the components subjected to ball milling into a vacuum drying oven for drying at the drying temperature of 100 ℃, sieving with a 100-mesh sieve after drying, and packaging the sieved powder for later use; weighing the components according to the proportion listed in the attached table of the embodiment, putting the components into a polyurethane ball grinding cylinder, taking tungsten carbide balls as ball grinding balls with the ball-material ratio of 10:1 and alcohol as a ball grinding medium, sealing, and putting the ball grinding cylinder on a roller ball mill for wet ball grinding for 48 hours; putting the ball-milled mixture into a vacuum drying box for drying; taking out the packaged powder, weighing the mixed powder according to the dosage required by cutter preparation, putting the mixed powder into a high-strength graphite mould, and then putting the mould into a vacuum sintering furnace; under the vacuum atmosphere, the temperature is raised to 1450 ℃ in 29min, and the hot-pressing sintering molding is carried out under the conditions that the pressure is applied to 32MPa at the temperature and the heat is preserved for 30 min. After the heat preservation is finished, hot-pressing sintering molding is carried out according to the process conditions of the parameter attached table of the embodiment. The sintering process comprises the following steps: the sintering temperature is 1450 ℃, the heat preservation time is 30min, and the heat preservation pressure is 32 MPa.
From FIG. 1, it can be seen that the main components of WC and Al obtained in the preparation of example 12O3The tool material (2) has a grey phase of WC and a black phase of Al2O3The prepared material has less pores, so thatBetter density, uneven distribution of partial components and obvious growth of partial crystal grains.
Example 2
A high-comprehensive-performance hard alloy cutter material comprises, by mass, WC70 parts and Al2O325 parts of Co4 parts of Y2O31 part.
The cutter material of example 2 was prepared in the same manner as in example 1. From FIG. 2, it can be seen that the main components of WC and Al obtained in the preparation of example 22O3The tool material (2) has a grey phase of WC and a black phase of Al2O3The prepared material has the characteristics of less pores, better compactness, uneven distribution of partial components and obvious growth of partial crystal grains.
Example 3
A high-comprehensive-performance hard alloy cutter material comprises, by mass, WC75 parts and Al2O320 parts of Co4 parts of Y2O31 part.
The cutter material of example 3 was prepared in the same manner as in example 1. From FIG. 3, it can be obtained that example 3 was prepared to have WC and Al as main components2O3The tool material (2) has a grey phase of WC and a black phase of Al2O3The prepared material has less pores and better density, and part of Al2O3Uneven distribution and local agglomeration.
Example 4
A high-comprehensive-performance hard alloy cutter material comprises, by mass, WC80 parts and Al2O315 parts of Co4 parts of Y2O31 part.
The cutter material of example 4 was prepared in the same manner as in example 1. From FIG. 4, it can be seen that the main components of WC and Al obtained in example 42O3The tool material (2) has a grey phase of WC and a black phase of Al2O3The prepared material has the characteristics of relatively uniform component distribution, obvious growth of partial crystal grains, less air holes and better compactness。
Example 5
A high-comprehensive-performance hard alloy cutter material comprises, by mass, WC85 parts and Al2O310 parts of Co4 parts of Y2O31 part.
The cutter material of example 5 was prepared in the same manner as in example 1. From FIG. 5, it can be seen that the main components of WC and Al obtained in the preparation of example 52O3The tool material (2) has a grey phase of WC and a black phase of Al2O3The prepared material has the characteristics of uniform component distribution, larger grain size, more uniform grain size distribution, fewer air holes and better density.
Example 6
A high-comprehensive-performance hard alloy cutter material comprises, by mass, WC90 parts and Al2O35 parts of Co4 parts of Y2O31 part.
The cutter material of example 6 was prepared in the same manner as in example 1. From FIGS. 6 and 7, it can be seen that the main components of WC and Al in example 6 are2O3The tool material (2) has a grey phase of WC and a black phase of Al2O3The prepared material has the characteristics of uniform component distribution, fine crystal grains, uniform particle size distribution, few pores and good density. It can be seen from FIGS. 7(B) and 7(C) that the elemental composition of spectrum A includes tungsten (W) and carbon (C), and the elemental composition of spectrum B includes aluminum (Al) and oxygen (O), and since the material is designed such that the system does not chemically react, it is inferred that in FIG. 7(a), the main component of the gray phase A is WC, and the main component of the black phase B is Al2O3。
The cutter materials of example 1, example 2, example 3, example 4, example 5, example 6 were subjected to a performance test, and the parameters obtained were as shown in table 1:
TABLE 1 cutter Material Performance test results
As can be seen from Table 1, along with Al2O3The content is reduced, the hardness of the composite cutter material is firstly reduced and then increased, and Al2O3When the content is 5 parts, the hardness is the highest and is 22.78 +/-2.0 GPa; having a fracture toughness of Al2O3The highest content is 13.04 +/-1.1 MPa.m when the content is 20 parts1/2(ii) a Its bending strength is in Al2O3The highest content is 1193.6 +/-30 MPa when the content is 10 parts. In Al2O3When the content is 5 parts and 10 parts, the cutter material has better comprehensive mechanical property, higher bending strength and fracture toughness and higher hardness.
90 parts of WC-5 parts of Al prepared by the invention2O3-1 part of Y2O3Fracture toughness of-4 parts of Co cutter material is 12.34 +/-1.1 MPa.m1/2The bending strength is 1002 +/-45 MPa, the Vickers hardness is 22.78 +/-2.0 GPa, and the prior Al2O3Compared with the cutter material obtained by compounding Co and WC, the fracture toughness and hardness of the composite cutter material are respectively improved by 25% and 12%. Solves the problem of the contradiction between the hardness and the toughness of the existing WC-Co composite cutter material.
90 parts of WC-5 parts of Al prepared by the invention2O3-1 part of Y2O3Compared with the hard alloy cutter grade YG3(97 parts WC-3 parts Co, mass parts), the hardness of the-4 parts Co cutter material is improved by 58.2 percent compared with that of YG3 on the premise of ensuring that the bending strength is not reduced. 85 parts of WC-10 parts of Al prepared by the invention2O3-1 part of Y2O34 parts of Co cutter material, the hardness (18.98 +/-0.85 GPa) of the Co cutter material is 31.8 percent higher than that (14.4GPa) of YG3, and the bending strength is equivalent. In a word, the cutter material prepared by the invention not only has higher obdurability, but also obviously improves the hardness of the WC-based hard alloy cutter and is beneficial to improving the high-temperature resistance of the WC-based hard alloy cutter.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A high comprehensive performance hard alloy cutter material is characterized in that: comprises the following raw materials of, by mass, WC65-90 parts and Al2O35-30 parts of Co3-10 parts of Y2O30.5-2 parts;
the preparation method comprises the following steps: respectively carrying out ball milling on the raw materials, mixing the ball-milled raw materials, drying, repeatedly carrying out ball milling and drying on the mixture after drying, and then carrying out vacuum sintering on the dried mixture to obtain a cutter material;
ball milling was carried out using a ball mill, Al2O3When the powder is separately ball-milled, the ball-milling balls are alumina balls, when the other powder is separately ball-milled and secondly mixed ball-milled, the ball-milling balls are tungsten carbide balls, the ball-material ratio of the first ball-milling to the second ball-milling is 9-11:1, and the ball-milling medium is alcohol;
the pressure of vacuum sintering is 30-40MPa, and the temperature of vacuum sintering is 1300-1600 ℃;
the heating time of vacuum sintering is 20-40min, and the heat preservation time is 20-40 min.
2. The cemented carbide tool material as claimed in claim 1, wherein: comprises the following raw materials of, by mass, WC65-90 parts and Al2O35-30 parts of Co4 and Y2O31 part.
3. The cemented carbide tool material as claimed in claim 1, wherein: WC grain size of 0.3-0.5 μm, Al2O3Has a particle diameter of 0.4-0.6 μm, Co has a particle diameter of 0.4-0.6 μm, and Y2O3The particle diameter of (A) is 0.8-1.2 μm.
4. The cemented carbide tool material as claimed in claim 1, wherein: the ball milling time of the raw materials is 40-50 h.
5. The cemented carbide tool material as claimed in claim 1, wherein: the drying temperature of the raw materials is 100-140 ℃, and the drying time is 3-4 h.
6. The cemented carbide tool material as claimed in claim 1, wherein: the temperature of vacuum sintering is 1400-1500 ℃.
7. Use of a cemented carbide tool material according to any one of claims 1-6 in the field of milling tools.
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