CN111286663B - High-strength high-hardness microcosmic segregation non-uniform-structure hard alloy and preparation method and application thereof - Google Patents
High-strength high-hardness microcosmic segregation non-uniform-structure hard alloy and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of hard alloy, and provides high-strength high-hardness microcosmic segregation non-uniform-structure hard alloy as well as a preparation method and application thereof. The hard alloy prepared by the invention is a hard alloy with a novel organization structure, namely a microcosmic segregation non-uniform structure hard alloy. The tissue structure can obviously distinguish the higher-hardness eccentric polymer and the higher-strength matrix in the micron-scale window, and uniform tissues are shown in the millimeter-scale window and the windows above. The microcosmic segregation non-uniform-structure hard alloy prepared by the invention has the advantages of high hardness of a segregation material and high strength of a matrix material, has excellent comprehensive mechanical properties, and meets the use requirements of complex geological drilling working conditions.
Description
Technical Field
The invention relates to the technical field of hard alloy, in particular to high-strength high-hardness microcosmic segregation non-uniform-structure hard alloy and a preparation method and application thereof.
Background
The main components of cemented carbide are WC and Co, where WC contributes to wear resistance and Co contributes to toughness. The hard alloy required by the earth-mining tool not only has high wear resistance, but also has enough toughness, namely excellent comprehensive mechanical properties. However, the hardness and strength of conventional cemented carbide are a pair of spearheads, i.e., high hardness results in low toughness, whereas high toughness results. The performance of the traditional hard alloy is mainly adjusted by changing the Co content or the WC grain size, but the contradiction cannot be solved. Therefore, the comprehensive mechanical properties of the traditional hard alloy are difficult to meet the requirements of complex geological drilling working conditions.
In order to meet the requirement of complex geological drilling working condition application, a hard alloy with a net structure is developed at home and abroad (patent number: 201010100761.6], mixed crystal structure cemented carbide [ patent No.: 201611135743.5 and gradient cemented carbide [ patent No.: 201610544130.0], and the like, which suitably solves the problem of contradiction between hardness and toughness. Along with the development of geological exploration and traffic tunnel requirements, the requirement of novel-structure hard alloy with more excellent comprehensive performance is also improved.
Disclosure of Invention
The invention aims to provide a high-strength high-hardness microcosmic segregation non-uniform structure hard alloy and a preparation method and application thereof. The hard alloy provided by the invention has the advantages of high hardness of the segregation material and high strength of the matrix material, can obviously prolong the service life of the ground mineral product, and has a simple preparation method.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of high-strength high-hardness microcosmic segregation non-uniform structure hard alloy comprises the following steps:
(1) carrying out vacuum heat treatment on the hard alloy segregation material to obtain a hard alloy segregation material subjected to vacuum heat treatment; the hard alloy segregation material comprises the following components in percentage by mass: co 3 wt.% to 12 wt.%, TaC 0 to 0.8 wt.%, and balance WC; the grain size of the WC is 0.4-4.0 μm;
(2) providing a hard alloy base material; the hard alloy matrix material comprises the following components in percentage by mass: 6-20 wt% of Co, and the balance of WC; the grain size of the WC is 1.5-6.0 μm;
(3) carrying out ball milling and mixing on the hard alloy segregation material subjected to vacuum heat treatment, the hard alloy matrix material, the forming agent and alcohol to obtain mixed slurry;
(4) drying, compression molding and sintering the mixed slurry in sequence to obtain high-strength high-hardness microcosmic segregation non-uniform structure hard alloy;
the step (1) and the step (2) are not limited in time sequence.
Preferably, the preparation method of the hard alloy matrix material is any one of the following methods:
the method comprises the following steps: carrying out wet ball milling mixing on WC powder and Co powder, and taking the obtained slurry as a hard alloy matrix material;
the second method comprises the following steps: directly weighing WC powder and Co powder as hard alloy matrix materials without mixing;
the third method comprises the following steps: directly weighing the hard alloy spray drying material as a hard alloy matrix material.
Preferably, the temperature of the vacuum heat treatment is 1180-1300 ℃.
Preferably, the mass ratio of the hard alloy segregation material to the hard alloy matrix material is 5: 5-9: 1.
Preferably, the forming agent is 56# paraffin.
Preferably, the mass of the forming agent is 1.5-2.5% of the total weight of the hard alloy segregation material and the hard alloy matrix material.
Preferably, the liquid-solid ratio of the ball-milling mixed material is 200-300 mL/kg, the ball-material ratio is 3: 1-6: 1, and the ball-milling time is 8-24 h.
The invention also provides the high-strength high-hardness microcosmic segregation non-uniform structure hard alloy prepared by the preparation method of the scheme.
The invention also provides application of the high-strength high-hardness microcosmic segregation non-uniform structure hard alloy in the ground and mine tools.
Has the advantages that:
(1) the invention carries out vacuum heat treatment on the hard alloy segregation material to generate sufficient sintering necks among powder particles. The sintering neck enables the hard alloy segregation materials to have enough strength, so that the segregation materials are not completely crushed in the subsequent ball milling and mixing process, and micron-sized aggregates are obtained. The aggregates are high-hardness segregation tissues in the micro-segregation non-uniform structure hard alloy.
(2) The invention not only can grind the segregation body after vacuum heat treatment and WC secondary particles in the matrix through ball milling mixing to obtain micron-sized segregation aggregates and uniform matrix WC primary particles, but also fully mixes the segregation body and the matrix to ensure that the segregation body is uniformly distributed in the matrix.
(3) The components, the WC grain size and the like in the segregation material and the hard alloy matrix material are regulated and controlled, and the hard alloy prepared by combining the preparation process can obviously distinguish the segregation with higher hardness and the matrix with higher strength in a micrometer window and can show uniform tissues in a window of millimeter level and above; the hard alloy prepared by the invention is a hard alloy composite material with a novel microstructure, has the high hardness of a partial polymer material and the high strength of a matrix material, has excellent comprehensive mechanical properties, and can meet the complicated use condition of a ground and mineral product. The example result shows that the hardness of the hard alloy prepared by the invention is 87.5-92.5 HRA, and the strength is 2900-3800 MPa.
Drawings
FIG. 1 is a structural diagram of the microstructure of the micro-segregation non-uniform cemented carbide obtained in example 1, with a scale of 50 μm;
FIG. 2 is a structural diagram of the microstructure of the micro-segregation non-uniform cemented carbide obtained in example 1, with a scale of 500 μm;
FIG. 3 is a structural diagram of the microstructure of the micro-segregation non-uniform cemented carbide obtained in example 3, with a scale of 50 μm;
FIG. 4 is a structural view of the microstructure of the micro-segregation non-uniform cemented carbide obtained in example 3, with a scale of 500. mu.m.
Detailed Description
The invention provides a preparation method of high-strength high-hardness microcosmic segregation non-uniform structure hard alloy, which comprises the following steps:
(1) carrying out vacuum heat treatment on the hard alloy segregation material to obtain a hard alloy segregation material subjected to vacuum heat treatment; the hard alloy segregation material comprises the following components in percentage by mass: co 3 wt.% to 12 wt.%, TaC 0 to 0.8 wt.%, and balance WC; the grain size of the WC is 0.4-4.0 μm;
(2) providing a hard alloy base material; the hard alloy matrix material comprises the following components in percentage by mass: 6-20 wt% of Co, and the balance of WC; the grain size of the WC is 1.5-6.0 μm;
(3) mixing the hard alloy segregation material subjected to vacuum heat treatment, a hard alloy matrix material, a forming agent and alcohol, and performing ball milling and mixing to obtain mixed slurry;
(4) drying, compression molding and sintering the slurry in sequence to obtain high-strength high-hardness microcosmic segregation non-uniform structure hard alloy;
the step (1) and the step (2) are not limited in time sequence.
The invention carries out vacuum heat treatment on the hard alloy segregation material to obtain the hard alloy segregation material. In the invention, the hard alloy segregation material comprises the following components in percentage by mass: co 3 wt.% to 12 wt.%, TaC 0 to 0.8 wt.%, and balance WC, preferably including Co6 wt.% to 10 wt.%, TaC 0 to 0.5 wt.% and balance WC, more preferably including Co6 wt.% to 8 wt.%, TaC 0.1 to 0.3 wt.% and balance WC; the grain size of the WC is 0.4-4.0 μm, preferably 0.6-3.5 μm; in the invention, the cemented carbide segregation material is a cemented carbide spray material and is prepared by using a ball milling mixing-spray drying method well known to those skilled in the art.
In the invention, the temperature of the vacuum heat treatment is preferably 1180-1300 ℃, and more preferably 1200-1260 ℃; the invention has no special requirement on the time of the vacuum heat treatment, and the aim of the vacuum heat treatment can be fulfilled by adopting the time well known by the technical personnel in the field; the dewaxing and solidification are preferably carried out in a dewaxing-sintering integrated furnace. The invention generates sufficient sintering necks among powder particles through vacuum heat treatment to prepare the hard alloy segregation material with certain strength.
The invention provides a hard alloy matrix material. In the invention, the hard alloy matrix material preferably comprises the following components in percentage by mass: co6 wt.% to 20 wt.%, balance WC, more preferably comprising Co6 wt.% to 15 wt.%, balance WC; the grain size of the WC is 1.5-6.0 μm, preferably 2-5.5 μm. In the invention, preferably, WC powder and Co powder are ball-milled and mixed by a wet method, the obtained slurry is used as a hard alloy matrix material, or the WC powder and the Co powder are directly weighed as the hard alloy matrix material without mixing, or the hard alloy spray drying material is directly weighed as the hard alloy matrix material; in the present invention, the medium for wet ball milling is preferably alcohol, 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; the preparation method of the hard alloy spray-dried material has no special requirement, and the hard alloy spray-dried material is prepared by using a ball milling mixing-spray drying method.
After the hard alloy segregation material and the hard alloy matrix material are obtained, the hard alloy segregation material, the hard alloy matrix material, the forming agent and alcohol are mixed, and ball milling and mixing are carried out to obtain mixed slurry. In the invention, the forming agent is preferably No. 56 paraffin; the mass of the forming agent is preferably 1.5-2.5% of the total weight of the hard alloy segregation material and the hard alloy matrix material, and more preferably 1.8-2.2%; when the hard alloy base material is slurry, the mass of the hard alloy base material is calculated by the mass of solid matters in the slurry; the mass ratio of the hard alloy segregation material to the hard alloy matrix material is preferably 5: 5-9: 1; the alcohol is preferably industrial alcohol, the liquid-solid ratio of the ball milling mixed material is preferably 200-300 mL/kg, more preferably 220-280 mL/g, the ball-material ratio is preferably 3: 1-6: 1, and the ball milling time is preferably 8-24 h, more preferably 10-20 h. The invention grinds the vacuum heat-treated segregation and WC secondary particles in the matrix through ball milling and mixing materials to obtain micron-sized segregation aggregates and uniform matrix WC primary particles, and also fully mixes the segregation and the matrix to ensure that the segregation is uniformly distributed in the matrix.
After slurry is obtained, the slurry is sequentially dried, compression molded and sintered to obtain the high-strength high-hardness microcosmic segregation non-uniform structure hard alloy. The invention has no special requirements on the operation conditions of drying and compression molding, and the conditions known by the technicians in the field can be used; in the invention, the sintering is preferably low-pressure sintering, the sintering temperature is preferably 1400-1460 ℃, more preferably 1410-1450 ℃, and the sintering pressure is preferably 4-8 MPa, more preferably 5 MPa.
The invention also provides the high-strength high-hardness microcosmic segregation non-uniform structure hard alloy prepared by the preparation method of the scheme. According to the invention, by regulating and controlling the components of the segregation material and the hard alloy matrix material, the WC grain size, the volume ratio and the like, and combining with the hard alloy preparation process, the microstructure of the finally obtained hard alloy in a micron window can obviously distinguish a segregation structure (segregation) with higher hardness and a matrix structure (matrix) with higher strength, and uniform structures are shown in a millimeter-level window and above, so that the hard alloy composite material is a hard alloy composite material with a novel microstructure structure, has the high hardness of the segregation material and the high strength of the matrix material, and has excellent comprehensive mechanical properties; in the invention, the hardness of the high-strength high-hardness microcosmic segregation non-uniform structure hard alloy is preferably 87.5-92.5 HRA, and the strength is preferably 2900-3800 MPa.
The invention provides application of the high-strength high-hardness microcosmic segregation non-uniform structure hard alloy in a ground mine tool. The hard alloy provided by the invention has excellent comprehensive mechanical properties, can meet the use requirements of complex geological drilling working conditions, and can greatly prolong the service life of a ground mine tool. 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
(1) Preparing a partial polymer material: taking a hard alloy spraying material (the Co content is 6 wt.%, the TaC content is 0.3 wt.%, the balance is WC, wherein the WC grain size is 0.6 mu m) as a segregation body raw material, and carrying out vacuum heat treatment in a dewaxing-sintering integrated furnace at 1200 ℃ to obtain a hard alloy segregation material after vacuum heat treatment;
(2) preparing a base material: putting WC powder, Co powder, 56# paraffin, alcohol and a grinding rod into a roller ball mill for grinding for 16h to obtain hard alloy slurry as a base material (the Co content is 6 wt.%, the balance is WC, and the WC grain size is 2.0 μm);
(3) preparing mixed slurry: adding 600g of the hard alloy segregation material subjected to vacuum heat treatment, 400g of the hard alloy base material (calculated by the mass of solid matters in the slurry), adding paraffin (the mass of the paraffin is 2.0 wt.% of the total weight of the hard alloy segregation material and the hard alloy base material), supplementing alcohol to enable the liquid-solid ratio of the mixed slurry to be 280mL/kg, supplementing a grinding rod to enable the ball-material ratio to be 4:1, and putting the mixed slurry into a roller ball mill for grinding for 16 hours to obtain mixed slurry;
(4) the mixed slurry is taken out, vacuum dried and molded, low-pressure sintering is carried out at 1410 ℃ and 5MPa, and then the microcosmic segregation non-uniform structure hard alloy is prepared, and the measured performance data are shown in table 1.
FIGS. 1 to 2 are structural diagrams of the microstructure of the micro-segregation non-uniform cemented carbide obtained under different magnifications, wherein the scale of FIG. 1 is 50 μm, and the scale of FIG. 2 is 500 μm. According to fig. 1 (micron-scale window), it can be seen that the microstructure of the cemented carbide can clearly distinguish the segregation tissue (segregation) with higher hardness and the matrix tissue (matrix) with higher strength, and the uniform tissue is shown in fig. 2 (millimeter-scale window).
Example 2
(1) Preparing a partial polymer material: taking a hard alloy spraying material (the Co content is 6 wt.%, the TaC content is 0.3 wt.%, the balance is WC, wherein the WC grain size is 0.6 mu m) as a segregation body raw material, and carrying out vacuum heat treatment in a dewaxing-sintering integrated furnace at 1200 ℃ to obtain a hard alloy segregation material after vacuum heat treatment;
(2) preparing a base material: spray drying materials (the Co content is 12 wt.%, the balance is WC, the WC grain size is 2.2 μm) of a production line are used as hard alloy base materials;
(3) preparing mixed slurry: 500g of the hard alloy segregation material subjected to vacuum heat treatment, 500g of the hard alloy matrix material, 18g of No. 56 paraffin, 280mL of alcohol and 6000g of grinding rod are put into a roller ball mill to be ground for 18 hours to obtain mixed slurry
(4) The mixed slurry is taken out, vacuum dried and molded, low-pressure sintering is carried out at 1410 ℃ and 5MPa, and then the microcosmic segregation non-uniform structure hard alloy is prepared, and the measured performance data are shown in table 1.
Example 3
(1) Preparing a partial polymer material: taking a hard alloy spraying material (the Co content is 6 wt.%, the balance is WC, the WC grain size is 2.0 μm) as a segregation body raw material, and carrying out vacuum heat treatment in a dewaxing-sintering integrated furnace at 1240 ℃ to obtain a hard alloy segregation material subjected to vacuum heat treatment;
(2) preparing a base material: YG11C spray material produced by a hard alloy production line is used as a hard alloy matrix material (the Co content is 11 wt.%, the balance is WC, wherein the WC grain size is 3.5 μm);
(3) preparing mixed slurry: 700g of the hard alloy segregation material subjected to vacuum heat treatment, 300g of the hard alloy matrix material, 20g of # 56 paraffin, 240mL of alcohol and 4000g of a grinding rod are put into a roller ball mill to be ground for 14 hours to obtain mixed slurry.
(4) The mixed slurry is taken out, vacuum dried and compression molded, and is prepared into the microcosmic segregation non-uniform structure hard alloy after low-pressure sintering at 1430 ℃ and 5MPa, and the measured performance data are shown in table 1.
FIGS. 3 to 4 are structural diagrams of the microstructure of the micro-segregation non-uniform cemented carbide obtained under different magnifications, wherein the scale of FIG. 3 is 50 μm, and the scale of FIG. 4 is 500 μm. According to fig. 3 (micron-sized window), it can be seen that the microstructure of the cemented carbide can clearly distinguish the segregation tissue (segregation) with higher hardness and the matrix tissue (matrix) with higher strength, and the uniform tissue is shown in fig. 4 (millimeter-sized window).
Example 4
(1) Preparing a partial polymer material: taking a hard alloy spraying material (the Co content is 6 wt.%, the balance is WC, the WC grain size is 3.2 mu m) as a segregation raw material, and carrying out vacuum heat treatment in a dewaxing-sintering integrated furnace at 1260 ℃ to obtain a hard alloy segregation material subjected to vacuum heat treatment;
(2) preparing a base material: putting WC powder, Co powder, 56# paraffin, alcohol and a grinding rod into a roller ball mill for grinding for 16h to obtain hard alloy slurry as a base material (the Co content is 10 wt.%, the balance is WC, and the WC grain size is 5.5 mu m);
(3) preparing mixed slurry: adding 800g of the hard alloy segregation material subjected to vacuum heat treatment, 200g of the hard alloy base material (calculated by the mass of solid matters in the slurry), adding paraffin (the mass of the paraffin is 2.5 wt.% of the total weight of the hard alloy segregation material and the hard alloy base material), supplementing alcohol to enable the liquid-solid ratio of the mixed slurry to be 220mL/kg, supplementing a grinding rod to enable the ball-material ratio to be 4:1, and putting the mixed slurry into a roller ball mill for grinding for 16 hours to obtain mixed slurry;
(4) the mixed slurry is taken out, vacuum dried, compression molded and sintered under the temperature of 1450 ℃ and the pressure of 5MPa to prepare the microcosmic segregation non-uniform hard alloy, and the measured performance data are shown in table 1.
Example 5
(1) Preparing a partial polymer material: taking a hard alloy spraying material (the Co content is 8 wt.%, the balance is WC, the WC grain size is 3.0 μm) as a segregation raw material, and carrying out vacuum heat treatment in a dewaxing-sintering integrated furnace at 1260 ℃ to obtain a hard alloy segregation material subjected to vacuum heat treatment;
(2) preparing a base material: WC powder and Co powder are directly used as a hard alloy matrix material without mixing (the Co content is 11 wt.%, the balance is WC, and the WC grain size is 3.5 mu m);
(3) preparing mixed slurry: putting 900g of the hard alloy segregation material subjected to vacuum heat treatment, 100g of the hard alloy matrix material, 22g of No. 56 paraffin, 220mL of alcohol and 3000g of a grinding rod into a roller ball mill for grinding for 12 hours to obtain mixed slurry;
(4) the ball milling material is taken out, vacuum dried, compression molded, sintered under the low pressure of 1450 ℃ and 5MPa, and then the microcosmic segregation non-uniform structure hard alloy is prepared, and the measured performance data are shown in table 1.
Example 6
(1) Preparing a partial polymer material: taking a hard alloy spraying material (the Co content is 11 wt.%, the balance is WC, the WC grain size is 3.5 μm) as a segregation raw material, and carrying out vacuum heat treatment in a dewaxing-sintering integrated furnace at 1260 ℃ to obtain a hard alloy segregation material subjected to vacuum heat treatment;
(2) preparing a base material: putting WC powder and Co powder (the Co content is 15 wt.%, the balance is WC, wherein the WC grain size is 4.0 μm), 56# paraffin, alcohol and a grinding rod into a roller ball mill for grinding for 16h to obtain hard alloy slurry as a base material;
(3) preparing mixed slurry: adding 900g of the hard alloy segregation material subjected to vacuum heat treatment, 100g of the hard alloy base material (calculated by the mass of solid matters in the slurry), adding paraffin (the mass of the paraffin is 2.5 wt% of the total weight of the hard alloy segregation material and the hard alloy base material), supplementing alcohol to enable the liquid-solid ratio of the mixed slurry to be 220mL/kg, supplementing a grinding rod to enable the ball-material ratio to be 4:1, and putting the mixed slurry into a roller ball mill for grinding for 16 hours to obtain mixed slurry;
(4) the mixed slurry is taken out, vacuum dried, compression molded and sintered under the temperature of 1450 ℃ and the pressure of 5MPa to prepare the microcosmic segregation non-uniform hard alloy, and the measured performance data are shown in table 1.
The metallographic structure of the hard alloy prepared in the embodiment 2 and the embodiments 4 to 6 is observed, and the results show that the microstructure of the hard alloy can obviously distinguish a segregation structure (segregation) with higher hardness and a matrix structure (matrix) with higher strength in the micron-sized window, and a uniform structure is shown in the millimeter-sized window.
Comparative example 1
Referring to the segregation material components in the comparative example 1, 1000g of a hard alloy spray material (with a Co content of 6 wt.%, a TaC content of 0.3 wt.%, and the balance of WC, wherein the grain size of WC is 0.6 μm), 20g of 56# paraffin, 300mL of alcohol, and 6000g of a grinding rod are put into a roller ball mill and ground for 36 hours to obtain a mixed slurry; and spray drying to obtain the hard alloy mixture. And (3) carrying out compression molding on the mixture, and sintering at 1410 ℃ and 5MPa to obtain a hard alloy comparison sample. The difference of this comparative example is that a single structure sample with uniform WC-6Co-0.3TaC components was prepared using 0.6. mu. mWC powder, and the test performance is shown in Table 1.
Comparative example 2
Referring to the base material components in comparative example 1, 1000g of a cemented carbide raw material (with a Co content of 6 wt.%, balance being WC, wherein the grain size of WC is 2.0 μm), 20g of 56# paraffin, 250mL of alcohol, and 4000g of a grinding rod were put into a roller ball mill and ground for 28 hours to obtain a mixed slurry; 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. The difference of the comparative example is that 2.0 μm WC powder is used to prepare a single structure sample with uniform WC-6Co components, and the test performance is shown in Table 1.
Comparative example 3
Referring to the segregation material components in the comparative example 4, 1000g of a hard alloy spray material (with a Co content of 6 wt.%, balance being WC, wherein the grain size of WC is 3.2 μm), 20g of 56# paraffin, 220mL of alcohol, and 3000g of a grinding rod are put into a roller ball mill to be ground for 20 hours to obtain a mixed slurry; and spray drying to obtain the hard alloy mixture. And (3) compression molding the mixture, and sintering at 1450 ℃ and under 5MPa to obtain a hard alloy comparison sample. The difference of the comparative example is that 3.2 μm WC powder is used to prepare a single structure sample with uniform WC-6Co components, and the test performance is shown in Table 1.
Comparative example 4
Referring to the ingredients of the segregation material in the comparative example 5, 1000g of a hard alloy spray material (with a Co content of 8 wt.%, and the balance being WC, wherein the grain size of WC is 3.0 μm), 20g of 56# paraffin, 220mL of alcohol, and 3000g of a grinding rod are put into a roller ball mill to be ground for 24 hours, so as to obtain a mixed slurry; and spray drying to obtain the hard alloy mixture. And (3) compression molding the mixture, and sintering at 1450 ℃ and under 5MPa to obtain a hard alloy comparison sample. The difference of the comparative example is that 3.0 μm WC powder is used to prepare a single structure sample with uniform WC-8Co components, and the test performance is shown in Table 1.
Comparative example 5
Referring to the base material components in comparative example 4, 1000g of a cemented carbide raw material (with a Co content of 10 wt.%, balance being WC, wherein the grain size of WC is 5.5 μm), 20g of 56# paraffin, 220mL of alcohol, and 6000g of a grinding rod were put into a roller ball mill and ground for 18 hours to obtain a mixed slurry; and spray drying to obtain the hard alloy mixture. And (3) compression molding the mixture, and sintering at 1450 ℃ and under 5MPa to obtain a hard alloy comparison sample. The difference of this comparative example is that 5.5 μm WC powder was used to prepare a single structure sample with homogeneous WC-10Co composition, and the test performance is shown in Table 1.
Comparative example 6
Referring to the base material components in comparative example 5, 1000g of cemented carbide raw material (with a Co content of 11 wt.%, balance being WC, wherein the grain size of WC is 3.5 μm), 20g of 56# paraffin, 250mL of alcohol, and 3000g of grinding rod were put into a roller ball mill and ground for 28 hours to obtain mixed slurry; and spray drying to obtain the hard alloy mixture. And (3) compression molding the mixture, and sintering at 1450 ℃ and under 5MPa to obtain a hard alloy comparison sample. The difference of this comparative example is that 3.5 μm WC powder was used to prepare a single structure sample with homogeneous WC-11Co composition, and the test performance is shown in Table 1.
Comparative example 7
Referring to the base material components in comparative example 2, 1000g of a cemented carbide raw material (with a Co content of 12 wt.%, balance being WC, wherein the grain size of WC is 2.2 μm), 20g of 56# paraffin, 260mL of alcohol, and 3000g of a grinding rod were put into a roller ball mill and ground for 24 hours to obtain a mixed slurry; 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. The difference of the comparative example is that 2.2 μm WC powder is used to prepare a single structure sample with uniform WC-12Co components, and the test performance is shown in Table 1.
Comparative example 8
Referring to the base material components in comparative example 6, 1000g of a cemented carbide raw material (with a Co content of 15 wt.%, balance being WC, wherein the grain size of WC is 4.0 μm), 22g of 56# paraffin, 300mL of alcohol, and 6000g of a grinding rod were put into a roller ball mill and ground for 24 hours to obtain a mixed slurry; and spray drying to obtain the hard alloy mixture. And (3) compression molding the mixture, and sintering at 1450 ℃ and under 5MPa to obtain a hard alloy comparison sample. The difference of the comparative example is that 4.0 μm WC powder is used to prepare a single structure sample with uniform WC-15Co components, and the test performance is shown in Table 1.
TABLE 1 shows properties of the cemented carbide of examples 1-6 and comparative examples 1-8
According to the data in the table 1, the hardness of the microcosmic segregation non-uniform hard alloy is 87.5-92.5 HRA, the strength is 2900-3800 MPa, the high hardness of the segregation material and the high strength of the matrix material are both achieved, the microcosmic segregation non-uniform hard alloy has excellent comprehensive mechanical properties, the complex service condition of the ground and mine products can be met, and the service life of the ground and mine products can be greatly prolonged.
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 (6)
1. A preparation method of high-strength high-hardness microcosmic segregation non-uniform structure hard alloy is characterized by comprising the following steps:
(1) carrying out vacuum heat treatment on the hard alloy segregation material to obtain a hard alloy segregation material subjected to vacuum heat treatment; the hard alloy segregation material comprises the following components in percentage by mass: co 3 wt.% to 12 wt.%, TaC 0 to 0.8 wt.%, and balance WC; the grain size of the WC is 0.4-4.0 μm; the temperature of the vacuum heat treatment is 1180-1300 ℃; the hard alloy segregation material is a hard alloy spray material and is prepared by ball milling mixing and spray drying;
(2) providing a hard alloy base material; the hard alloy matrix material comprises the following components in percentage by mass: co6 wt-20 wt.%, balance WC; the grain size of the WC is 1.5-6.0 μm;
(3) carrying out ball milling and mixing on the hard alloy segregation material subjected to vacuum heat treatment, the hard alloy matrix material, the forming agent and alcohol to obtain mixed slurry; the mass ratio of the hard alloy segregation material to the hard alloy matrix material is 5: 5-9: 1; the liquid-solid ratio of the ball-milling mixed material is 200-300 mL/kg, the ball-material ratio is 3: 1-6: 1, and the ball-milling time is 8-24 hours;
(4) drying, compression molding and sintering the mixed slurry in sequence to obtain high-strength high-hardness microcosmic segregation non-uniform structure hard alloy;
the step (1) and the step (2) are not limited in time sequence.
2. The method according to claim 1, wherein the cemented carbide base material is prepared by any one of the following methods:
the method comprises the following steps: carrying out wet ball milling mixing on WC powder and Co powder, and taking the obtained slurry as a hard alloy matrix material;
the second method comprises the following steps: directly weighing WC powder and Co powder as hard alloy matrix materials without mixing;
the third method comprises the following steps: directly weighing the hard alloy spray drying material as a hard alloy matrix material.
3. The method according to claim 1, wherein the forming agent is 56# paraffin.
4. The preparation method according to claim 3, wherein the mass of the forming agent is 1.5-2.5% of the total weight of the cemented carbide segregation material and the cemented carbide base material.
5. The high-strength high-hardness micro-segregation non-uniform structure hard alloy prepared by the preparation method of any one of claims 1 to 4.
6. Use of the high strength, high hardness, micro-segregation, non-uniform structure cemented carbide according to claim 5 in earth-mining tools.
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