CN111270121B - Preparation method and application of hard alloy with net-shaped structure - Google Patents
Preparation method and application of hard alloy with net-shaped structure Download PDFInfo
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- CN111270121B CN111270121B CN202010228492.5A CN202010228492A CN111270121B CN 111270121 B CN111270121 B CN 111270121B CN 202010228492 A CN202010228492 A CN 202010228492A CN 111270121 B CN111270121 B CN 111270121B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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
- C22C29/08—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 based on tungsten carbide
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- 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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- 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
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Abstract
The invention relates to the technical field of hard alloy, and provides a preparation method and application of hard alloy with a net structure. The invention adopts a new technical route of vacuum heat curing, flexible mixing and low-pressure sintering, ensures that the agglomerate material, the matrix material, the forming agent and other added components are uniformly mixed, ensures the integrity of the spherical structure of the agglomerate in the hard alloy with the net-shaped structure and the distribution uniformity of the agglomerate in the matrix, and has no A, B-class pore defects in a metallographic structure, thereby ensuring that the comprehensive mechanical property of the hard alloy with the net-shaped structure is obviously superior to that of the traditional hard alloy. The invention can customize the net structure hard alloy meeting the requirements of various technical conditions by regulating and controlling the factors of the hard alloy cluster granules and the matrix material, the WC grain size, the granule/matrix ratio and the like. The hard alloy with the net-shaped structure is applied to products such as ground mining tools, dies and the like, and can obviously prolong the service life of the ground mining tools and the die products under complex and harsh working conditions.
Description
Technical Field
The invention relates to the technical field of hard alloy, in particular to a preparation method and application of hard alloy with a net structure.
Background
The cobalt content of the hard alloy for the ground ore and the die is generally 6-15 wt.%, and WC grains are generally medium and coarse grains. The strength and toughness of the hard alloy can be improved by increasing the cobalt content, but the hardness and the wear resistance are insufficient; the contradiction that the hardness and the wear resistance of the hard alloy are improved by reducing the cobalt content, but the strength and the toughness are insufficient makes the traditional hard alloy difficult to meet the use requirements of ground mine and die products under complex and harsh working conditions, and greatly shortens the service life of the ground mine and die products.
In order to solve the problem, improve the comprehensive mechanical property and service life of the hard alloy tool, the hard alloy with a special structure becomes a main development direction. The net structure cemented carbide is a new structure cemented carbide, and the structure thereof comprises two kinds of structures, namely, granules and a matrix. The granules contribute to hardness and wear resistance, the matrix contributes to strength and toughness, and the granules and the matrix are uniformly compounded together, so that the hard alloy with the net structure has excellent comprehensive mechanical property and can meet the use requirements of ground mines and mold products under complex and harsh working conditions.
The hard alloy with the net structure, which has complete pellet spherical structure, uniformly dispersed pellets and matrix and satisfied A, B-type pores, cannot be prepared by using the traditional powder metallurgy technology. The existing preparation technology of the hard alloy with the net structure is not mature, and large-scale production and wide application are difficult to carry out.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a cemented carbide with a net-shaped structure and an application thereof. The preparation method provided by the invention has the advantages that the hard alloy spray material is an agglomerated material, the integrity of the spherical structure of the agglomerate in the hard alloy with the net structure and the distribution uniformity of the agglomerate in a matrix are ensured through a new technical route of vacuum thermosetting, flexible mixing and low-pressure sintering, the obtained hard alloy with the net structure has no A, B-class pore defects in the metallographic structure, and the comprehensive mechanical property of the hard alloy with the net structure is obviously superior to that of the traditional hard alloy.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of hard alloy with a net structure comprises the following steps:
(1) sequentially dewaxing and carrying out vacuum thermosetting on the hard alloy spray material to obtain hard alloy agglomerate particles;
(2) flexibly mixing the hard alloy agglomerate material, the hard alloy matrix material, paraffin and alcohol, and then drying and granulating in sequence to obtain a mixture to be pressed;
(3) and sequentially carrying out compression molding and low-pressure sintering on the mixture to be pressed to obtain the hard alloy with the net structure.
Preferably, the temperature of the vacuum thermosetting is 850-1200 ℃, and the heat preservation time is 1-4 h.
Preferably, the hard alloy base material is mixed slurry or WC-Co spray drying material.
Preferably, the mass of the paraffin wax is 2-4.5 wt.% of the total weight of the cemented carbide agglomerate and the cemented carbide base material;
the adding amount of the alcohol is calculated in such a way that the liquid-solid ratio of a mixture obtained by mixing the hard alloy agglomerate material, the hard alloy matrix material, the paraffin and the alcohol is 75-120 mL/kg.
Preferably, the volume of the cemented carbide agglomerate is 50-95% of the total volume of the cemented carbide agglomerate and the cemented carbide base material.
Preferably, the temperature of the flexible mixing material is 60-76 ℃, the mixing time is 2-8 h, and the stirring speed is 30-55 rpm; the flexible blend is free of abrasive addition.
Preferably, the hard alloy spray material comprises the following components in percentage by mass: 4-10 wt% of Co, and the balance of WC; the grain size of WC in the hard alloy spray material is 1.0-4.0 μm;
the hard alloy matrix material comprises the following components in percentage by mass: co6 wt% to 15 wt%, and the balance of WC, wherein the grain size of WC in the hard alloy matrix material is 1.5 μm to 6.5 μm.
Preferably, the hard alloy spray material also comprises TaC; the mass percentage of TaC in the hard alloy spray material is 0.3-1.0 wt.%.
Preferably, the low-pressure sintering temperature is 1400-1460 ℃, and the sintering pressure is 4-8 MPa.
The invention also provides the hard alloy with the reticular structure prepared by the preparation method in the scheme.
The invention also provides application of the hard alloy with the reticular structure in the ground mine tools and die products.
Has the advantages that:
(1) the method provided by the invention adopts a new technical route of vacuum thermosetting, flexible mixing and low-pressure sintering, ensures that the agglomerate, the matrix material, the forming agent and other added components are fully and uniformly mixed, ensures the integrity of the spherical structure of the agglomerate in the hard alloy with the net structure and the distribution uniformity of the agglomerate in the matrix, ensures that the obtained hard alloy with the net structure has no A, B-type pore defects in the metallographic structure, and has the comprehensive mechanical property obviously superior to that of the traditional hard alloy corresponding to the agglomerate and the matrix material.
(2) The invention can design and customize the hard alloy with a net structure meeting the requirements of various technical conditions by regulating and controlling the factors of the hard alloy aggregate and the matrix material, the WC grain size, the aggregate/matrix ratio and the like.
(3) The hard alloy with the net-shaped structure provided by the invention has the advantages of high hardness of aggregates and high strength of a matrix, and can be applied to products such as ground mine tools, dies and the like, so that the service lives of the ground mine tools and the die products under complex and harsh working conditions can be obviously prolonged.
The embodiment result shows that the metallographic structure of the hard alloy with the net structure prepared by the method is A02B00C00, the hardness is 86.5-92 HRA, and the strength is 2800-3500 MPa.
Drawings
FIG. 1 is a topographical view of the agglomerate obtained in example 2, with a 1mm scale;
FIG. 2 is a topographical view of the agglomerate obtained in example 2, with a 100 μm scale;
FIG. 3 is a topographical view of the agglomerate obtained in example 2, with a 50 μm scale;
FIG. 4 is a graph of the morphology of the mix to be compacted obtained in example 2, with a scale of 500 μm;
FIG. 5 is a schematic representation of the topography of the mix to be compacted obtained in example 2, with a scale of 100 μm;
FIG. 6 is a diagram of the morphology of the mix to be compacted obtained in example 2, with a scale of 50 μm;
FIG. 7 is a microstructure diagram of a cemented carbide having a net structure obtained in example 2.
Detailed Description
The invention provides a preparation method of a hard alloy with a reticular structure, which comprises the following steps:
(1) sequentially dewaxing and carrying out vacuum thermosetting on the hard alloy spray material to obtain hard alloy agglomerate particles;
(2) flexibly mixing hard alloy aggregate, hard alloy matrix material, paraffin and alcohol, and then drying and granulating in sequence to obtain a mixture to be pressed;
(3) and sequentially carrying out compression molding and low-pressure sintering on the mixture to be pressed to obtain the hard alloy with the net structure.
According to the invention, the hard alloy spray material is sequentially dewaxed and thermally cured in vacuum to obtain hard alloy agglomerate particles. In the invention, the hard alloy spray material preferably comprises the following components in percentage by mass: 4-10 wt% of Co, and the balance of WC; more preferably comprises Co 5 wt.% to 8 wt.%, balance WC; the grain size of the WC is preferably 1-4 μm, more preferably 2-3 μm; in the present invention, the cemented carbide spray material preferably further includes TaC, and the mass percentage content of TaC in the cemented carbide spray material is preferably 0.3 wt.% to 1.0 wt.%, and more preferably 0.5 wt.%, that is, the cemented carbide spray material of the present invention may include TaC or may not include TaC, and in a specific embodiment, may be selected according to actual requirements; the preparation method of the hard alloy spray material has no special requirements, and the hard alloy spray material is prepared by using a ball milling mixing-spray drying method which is well known by the technical personnel in the field. According to the invention, the hard alloy spray material is used as a raw material, the hard alloy agglomerate material with certain strength is prepared through vacuum thermosetting, and the integrity of the spherical structure of the agglomerate in the hard alloy with the reticular structure is ensured.
In the invention, the temperature of the vacuum thermosetting is preferably 850-1200 ℃, more preferably 950-1050 ℃, and the heat preservation time of the thermosetting is preferably 1-4 h, more preferably 2-3 h; the dewaxing conditions are not particularly required in the invention, and the dewaxing is carried out according to the method of a person skilled in the art; in a particular embodiment of the present invention, the dewaxing and solidification are preferably carried out in a dewaxing-sintering integrated furnace. The invention can generate sintering necks among raw material powder particles through vacuum thermosetting, thereby ensuring that the granules have certain strength and keep complete spherical structures.
The hard alloy pellet, the hard alloy matrix material, the paraffin and the alcohol are kneaded and mixed, and then are dried and granulated in sequence to obtain a mixture to be pressed. In the invention, the hard alloy matrix material preferably comprises the following components in percentage by mass: co6 wt.% to 15 wt.%, balance WC, more preferably Co 8 wt.%, balance WC; the grain size of WC is preferably 1.5 to 6.5 μm, more preferably 3 to 4 μm. In the invention, the hard alloy agglomerate material has high hardness and good wear resistance; the hard alloy matrix material is high in strength and toughness, and the finally prepared network structure hard alloy has the high hardness of aggregates and the high strength of a matrix and excellent comprehensive mechanical properties.
In the invention, the hard alloy base material is preferably mixed slurry or WC-Co spray drying material; the mixed slurry is preferably obtained by mixing Co and WC through wet ball milling; the medium for wet ball milling is preferably alcohol, and more preferably industrial alcohol; the invention has no special requirement on the volume of the medium used in wet ball milling, and the raw materials can be uniformly ball-milled; the invention has no special requirements on the conditions of wet ball milling, and can obtain evenly mixed slurry; in the present invention, the spray-dried material is preferably prepared by a ball milling mixing-spray drying method, and the present invention has no special requirement on the specific conditions of the ball milling mixing-spray drying, and the spray-dried material is prepared according to a method well known to those skilled in the art, and in the specific embodiment of the present invention, the WC-Co spray-dried material prepared on a production line is preferably directly used. The invention can ensure that the alloy has excellent mechanical property by controlling the components of the hard alloy matrix material and the agglomerated material and the WC grain size, and can customize the hard alloy with a reticular structure meeting the requirements of various technical conditions according to the actual service working conditions and the operation process design by regulating and controlling the factors of the hard alloy agglomerated material and the matrix material, the WC grain size, the agglomerate/matrix ratio and the like.
In the invention, the paraffin is preferably 52# to 68# paraffin; the alcohol is preferably industrial alcohol; the mass of the paraffin is preferably 2-4.5 wt.% of the total mass of the cemented carbide agglomerate and the cemented carbide base material, and more preferably 2.5-4 wt.%; the amount of the alcohol added is preferably such that the liquid-solid ratio of a mixture obtained by mixing the cemented carbide agglomerate, the cemented carbide base material, the paraffin and the alcohol is 75 to 120mL/kg, and more preferably 80 to 110 mL/kg. In the invention, the volume of the hard alloy agglomerate is preferably 50-95% of the total volume of the hard alloy agglomerate and the hard alloy matrix, and more preferably 60-80%; when the base material is slurry, the volume of the base material is calculated by the volume of the solid matter of the corresponding alloy in the slurry; the invention can further ensure the mechanical property of the obtained hard alloy by controlling the volume ratio of the hard alloy agglomerate material to the matrix material.
In the invention, the temperature of the flexible mixing is preferably 60-76 ℃, more preferably 65-70 ℃, the mixing time is preferably 2-8 h, more preferably 3-6 h, and the stirring speed is preferably 30-55 rpm, more preferably 35-50 rpm; the flexible mixed material is added without an abrasive body; in the invention, the drying temperature is preferably 80-90 ℃, more preferably 85-88 ℃, the drying time is preferably 2-4 h, more preferably 2.5-3.5 h, and the drying is preferably carried out under a vacuum condition. In a specific embodiment of the invention, the flexible mixing is specifically kneaded mixing, the flexible mixing and drying are preferably performed in an automatic kneader, and in the invention, after the kneaded mixing is completed, the temperature in a cylinder of the automatic kneader is raised to 80-90 ℃ to dry the material, and the material is continuously vacuumized in the drying process. In the invention, the flexible mixing is realized by shearing and kneading high-viscosity materials under the stirring state, no grinding body is added in the flexible mixing process, so that the granules are not broken and the integrity of a spherical structure is kept, and the mixing technology can ensure that the granules, a matrix and a forming agent are uniformly mixed, so that the hard alloy with a net structure, which is uniform in distribution of the granules and the matrix, free of A, B pores and excellent in comprehensive mechanical property, is obtained.
The granulation is carried out according to the methods known to those skilled in the art, without any particular requirement.
After the mixture to be pressed is obtained, the mixture to be pressed is sequentially subjected to compression molding and low-pressure sintering to obtain the hard alloy with the net structure. The invention has no special requirement on the operation condition of the compression molding, and the condition which is well known by the technicians in the field can be used; in the invention, the temperature of the low-pressure sintering is preferably 1400-1460 ℃, more preferably 1410-1450 ℃, and the pressure of the low-pressure sintering is preferably 4-8 MPa, more preferably 5-6 MPa; the pressure during the low pressure sintering is preferably provided by Ar. In the invention, Ar with certain pressure in the low-pressure sintering process can ensure the sufficient densification of the net-shaped alloy, thereby obtaining the hard alloy with the net-shaped structure without A, B types of pore defects in a metallographic structure.
The invention provides the hard alloy with the net structure prepared by the preparation method in the scheme. The metallographic structure of the hard alloy with the reticular structure is A02B00C00, the hardness is 89-92 HRA, the strength is 2800-3650 MPa, the high hardness of the agglomerate and the high strength of the matrix are achieved, and A, B types of pores are not formed in the metallographic structure of the alloy.
The invention also provides application of the hard alloy with the reticular structure in the ground and mine tools and die products. The hard alloy with the net-shaped structure is applied to ground mine tools and mold products, so that the service life of the ground mine tools and the mold products under complex and severe working conditions can be obviously prolonged. The present invention is not particularly limited to the specific method of use described, and may be applied using methods well known to those skilled in the art.
The embodiments of the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The hard alloy spraying material (the components are 5 wt.% Co, the balance is WC, the grain size of the WC is 1.0 mu m) is thermally cured in a vacuum furnace at 960 ℃ for 3 hours to be used as an agglomerate material;
using a WC-Co spray drying material (the components are 8 wt.% Co, and the balance is WC, wherein the WC grain size is 3.0 mu m) prepared by a production line as a base material;
putting 70% of agglomerate material by volume and 30% of matrix material by volume into a full-automatic kneader, supplementing paraffin to 2.5 wt.% of the total weight of the agglomerate material and the matrix material, and adding alcohol to enable the liquid-solid ratio of the mixed slurry to reach 105 mL/kg; mixing for 6 hours in a full-automatic kneader at 70 ℃ to carry out flexible mixing, wherein the stirring speed is 55 rpm; vacuumizing and drying at 80 ℃ for 3.5h, and granulating to obtain a uniform hard alloy mixture with a net structure to be pressed;
the mixture of the hard alloy with the reticular structure is subjected to compression molding, and is subjected to low-pressure sintering at the temperature of 1410 ℃ and the pressure of 6MPa to obtain a reticular hard alloy sample, and the performance of the tested hard alloy is shown in Table 1.
Example 2
A hard alloy spraying material (the components are 6 wt.% of Co, 0.5 wt.% of TaC and the balance of WC, wherein the grain size of the WC is 2.0 mu m) is kept in a vacuum furnace at 1020 ℃ for 2h to be used as an agglomerate;
using a WC-Co spray drying material (the components are 8 wt.% Co, and the balance is WC, wherein the WC grain size is 3.0 mu m) prepared by a production line as a base material;
putting 80% of agglomerate material by volume and 20% of matrix material by volume into a full-automatic kneader, supplementing paraffin to 3.5 wt.% of the total weight of the agglomerate material and the matrix material, and adding alcohol to ensure that the liquid-solid ratio of the mixed slurry is 90 mL/kg; mixing for 4.5h at 65 ℃ in a full-automatic kneader to carry out flexible mixing, wherein the stirring speed is 35 rpm; vacuumizing and drying at 85 ℃ for 3h, and granulating to obtain a uniform and to-be-pressed hard alloy mixture with a net structure;
the hard alloy mixture with the reticular structure is subjected to compression molding, and is subjected to low-pressure sintering at the temperature of 1430 ℃ and the pressure of 5MPa to obtain a reticular hard alloy sample, and the performance of the tested hard alloy is shown in Table 1.
FIGS. 1 to 3 are graphs of the morphology of the resulting agglomerated material at different magnifications; as can be seen from FIGS. 1 to 3, the cemented carbide aggregate obtained by the present invention maintains an intact spherical structure.
FIGS. 4 to 6 are the morphology diagrams of the mixtures to be pressed obtained under different magnifications; as can be seen from the figures 4-6, the mixture to be pressed obtained by the invention keeps a complete spherical structure, is uniform in shape and has a good kneading effect.
FIG. 7 is a view showing a microstructure of the obtained cemented carbide having a net structure, with a scale of 100 μm; as can be seen from fig. 7, the metallographic structure of the obtained cemented carbide having a mesh structure was a02B00C 00.
Example 3
The hard alloy spraying material (the components are 8 wt.% Co, the balance is WC, wherein the grain size of the WC is 1.0 mu m) is kept in a vacuum furnace at 960 ℃ for 3 hours to be used as an agglomerate material;
using a WC-Co spray drying material (the components are 8 wt.% Co, and the balance is WC, wherein the WC grain size is 3.0 mu m) prepared by a production line as a base material;
putting 60% volume of agglomerate and 40% volume of matrix into a full-automatic kneader, supplementing paraffin to 3 wt.% of paraffin based on the total weight of the agglomerate and the matrix, and adding alcohol to make the liquid-solid ratio of the mixed slurry 105 mL/kg; mixing for 6 hours in a full-automatic kneader at 70 ℃ to carry out flexible mixing, wherein the stirring speed is 55 rpm; vacuumizing and drying at 80 ℃ for 3.5h, and granulating to obtain a uniform hard alloy mixture with a net structure to be pressed;
the mixture of the hard alloy with the reticular structure is subjected to compression molding, and is subjected to low-pressure sintering at the temperature of 1410 ℃ and the pressure of 5MPa to obtain a reticular hard alloy sample, and the performance of the tested hard alloy is shown in Table 1.
Example 4
A hard alloy spraying material (the components are 6 wt.% of Co, 0.5 wt.% of TaC and the balance of WC, wherein the grain size of the WC is 2.0 mu m) is kept in a vacuum furnace at 1020 ℃ for 2h to be used as an agglomerate;
performing ball milling mixing on the ultra-coarse WC powder and the Co powder for 16 hours by using a traditional ball milling mixing technology to obtain hard alloy mixed slurry (the components are 10 wt.% of Co, the balance is WC, and the grain size of the WC is 6.0 mu m) serving as a base material;
putting 50% by volume of the agglomerate and 50% by volume of the matrix (based on the volume of the solid matter corresponding to the alloy in the slurry) into a full-automatic kneader, supplementing paraffin to the total weight of the agglomerate and the matrix (based on the mass of the solid matter corresponding to the alloy in the slurry) of 4 wt.%, and supplementing alcohol to make the liquid-solid ratio of the mixed slurry be 90 mL/kg; mixing for 4 hours in a full-automatic kneader at 65 ℃ to carry out flexible mixing, wherein the stirring speed is 40 rpm; vacuumizing and drying at 85 ℃ for 3h, and granulating to obtain a uniform and to-be-pressed hard alloy mixture with a net structure;
the hard alloy mixture with the reticular structure is subjected to compression molding, and is subjected to low-pressure sintering at the temperature of 1430 ℃ and the pressure of 5MPa to obtain a reticular hard alloy sample, and the performance of the tested hard alloy is shown in Table 1.
Example 5
The hard alloy spraying material (the components are 8 wt.% Co, the balance is WC, wherein the grain size of the WC is 3.0 mu m) is kept at 1050 ℃ in a vacuum furnace for 2 hours to be used as an aggregate;
performing ball milling mixing on coarse WC powder and Co powder for 18h by using a traditional ball milling mixing technology to obtain hard alloy mixed slurry (the components are 15 wt.% Co, the balance is WC, and the grain size of the WC is 4.0 mu m) serving as a base material;
putting 90% by volume of the agglomerate and 10% by volume of the matrix (based on the volume of the solid matter corresponding to the alloy in the slurry) into a full-automatic kneader, supplementing paraffin to the total weight of the agglomerate and the matrix (based on the mass of the solid matter corresponding to the alloy in the slurry) of 4 wt.%, and supplementing alcohol to make the liquid-solid ratio of the mixed slurry be 80 mL/kg; mixing for 3.5h at 70 ℃ in a full-automatic kneader to carry out flexible mixing, wherein the stirring speed is 50 rpm; vacuumizing and drying at 88 ℃ for 2.5h, and granulating to obtain a uniform hard alloy mixture with a net structure to be pressed;
the hard alloy mixture with the reticular structure is subjected to compression molding, and is subjected to low-pressure sintering at the temperature of 1450 ℃ and the pressure of 5MPa to obtain a reticular hard alloy sample, wherein the tested performance of the hard alloy is shown in Table 1.
Comparative example 1
Reference is made to the composition of the reticulated cemented carbide agglomerate grains of example 1, i.e. 5 wt.% Co, with the balance being WC, wherein the WC grain size is 1.0 μm. Except that this comparative example was a single homogeneous composition structure. Wet grinding and spray drying to obtain the hard alloy mixture. And (3) carrying out compression molding on the mixture, and sintering at 1410 ℃ and 6MPa to obtain a hard alloy comparison sample, wherein the test performance of the hard alloy comparison sample is shown in table 1.
Comparative example 2
Reference is made to the composition of the reticulated cemented carbide agglomerate of example 2, namely 6 wt.% Co, 0.5TaC, with the balance WC, wherein the WC grain size is 2.0 μm. Except that this comparative example was a single homogeneous composition structure. Wet grinding and spray drying to obtain the hard alloy mixture. And (3) carrying out compression molding on the mixture, and sintering at 1430 ℃ and 5MPa to obtain a hard alloy comparison sample, wherein the test performance of the hard alloy comparison sample is shown in table 1.
Comparative example 3
Reference is made to the composition of the reticulated cemented carbide agglomerate grains of example 3, i.e. 8 wt.% Co, with the balance being WC, wherein the WC grain size is 1.0 μm. Except that this comparative example was a single homogeneous composition structure. Wet grinding and spray drying to obtain the hard alloy mixture. And (3) carrying out compression molding on the mixture, and sintering at 1410 ℃ and 6MPa to obtain a hard alloy comparison sample, wherein the test performance of the hard alloy comparison sample is shown in table 1.
Comparative example 4
Reference is made to the composition of the matrix material of the cemented carbide mesh of example 1, i.e. 8 wt.% Co, with the balance being WC, wherein the WC grain size is 3.0 μm. Except that this comparative example was a single homogeneous composition structure. The mixture is molded and pressed and sintered at 1450 ℃ and 5MPa to obtain a hard alloy comparison sample, and the test performance of the hard alloy comparison sample is shown in table 1.
Comparative example 5
Reference is made to the composition of the matrix material of the cemented carbide in example 4, i.e. 10 wt.% Co, with the balance WC, wherein the WC grain size is 6.0 μm. Except that this comparative example was a single homogeneous composition structure. Wet grinding, vacuum drying, and sieving and granulating to obtain the hard alloy mixture. The mixture is molded and pressed and sintered at 1450 ℃ and 5MPa to obtain a hard alloy comparison sample, and the test performance of the hard alloy comparison sample is shown in table 1.
Comparative example 6
Reference is made to the composition of the matrix material of the cemented carbide in comparative example 5, namely 15 wt.% Co, with the balance being WC, wherein the WC grain size is 4.0 μm. Except that this comparative example was a single homogeneous composition structure. Wet grinding, vacuum drying, and sieving and granulating to obtain the hard alloy mixture. The mixture is molded and pressed and sintered at 1450 ℃ and 5MPa to obtain a hard alloy comparison sample, and the test performance of the hard alloy comparison sample is shown in table 1.
Table 1 shows properties of the cemented carbide of examples 1 to 5 and comparative examples 1 to 6
According to the data in the table 1, the hardness of the network structure hard alloy provided by the invention is 86.5-92 HRA, the strength is 2850-3500 MPa, and the high hardness of the agglomerate material and the high strength of the matrix material are both achieved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The preparation method of the hard alloy with the net structure is characterized by comprising the following steps:
(1) sequentially dewaxing and carrying out vacuum thermosetting on the hard alloy spray material to obtain hard alloy agglomerate particles;
(2) flexibly mixing the hard alloy agglomerate material, the hard alloy matrix material, paraffin and alcohol, and then drying and granulating in sequence to obtain a mixture to be pressed;
(3) sequentially carrying out compression molding and low-pressure sintering on the mixture to be pressed to obtain the hard alloy with the net structure;
the temperature of the vacuum thermosetting is 850-1200 ℃, and the heat preservation time is 1-4 h; the temperature of the flexible material mixing is 60-76 ℃, the material mixing time is 2-8 h, and the stirring speed is 30-55 rpm; the flexible mixed material is added without an abrasive body; the flexible mixed material is a kneading mixed material; the sintering pressure of the low-pressure sintering is 4 MPa-8 MPa.
2. The method according to claim 1, wherein the cemented carbide base material is a mixed slurry or a WC-Co spray-dried material.
3. The method according to claim 1, wherein the paraffin wax has a mass of 2 to 4.5 wt.% based on the total weight of the cemented carbide agglomerate and the cemented carbide base material;
the adding amount of the alcohol is calculated in such a way that the liquid-solid ratio of a mixture obtained by mixing the hard alloy agglomerate material, the hard alloy matrix material, the paraffin and the alcohol is 75-120 mL/kg;
the volume of the hard alloy cluster particles is 50-95% of the total volume of the hard alloy cluster particles and the hard alloy matrix material.
4. The preparation method according to claim 1, wherein the hard alloy spray material comprises the following components in percentage by mass: co4 wt-10 wt.%, balance WC; the grain size of WC in the hard alloy spray material is 1.0-4.0 μm;
the hard alloy matrix material comprises the following components in percentage by mass: co6 wt-15 wt%, balance WC, and the grain size of WC in the hard alloy matrix is 1.5-6.5 μm.
5. The method according to claim 1, wherein the sintering temperature of the low-pressure sintering is 1400 ℃ to 1460 ℃.
6. The method of claim 4, wherein the cemented carbide feedstock further comprises TaC; the mass percentage of TaC in the hard alloy spray material is 0.3-1.0 wt.%.
7. The hard alloy with the net structure prepared by the preparation method of any one of claims 1 to 6.
8. Use of the reticulated cemented carbide of claim 7 in earth-mining tools, mould products.
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