CN109811235B - High-wear-resistance hard alloy material and preparation method and application thereof - Google Patents
High-wear-resistance hard alloy material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of alloy, and discloses a high-wear-resistance hard alloy, and a preparation method and application thereof. The hard alloy is prepared by using composite powder consisting of TiC-Ni-based spherical particles and WC-Co-based powder as a raw material and adopting a low-temperature pressure maintaining method. The hard alloy has the advantages of wear resistance and toughness, the low-temperature pressure holding method can realize full densification in the alloy, and the growth of WC and TiC crystal grains in the sintering process is effectively controlled, so that the strength and the wear resistance of the hard alloy are improved.
Description
Technical Field
The invention belongs to the technical field of alloy, and particularly relates to a high-wear-resistance hard alloy, and a preparation method and application thereof.
Background
Cemented carbide is an alloy material made from a hard compound of refractory metals and a binder metal by a powder metallurgy process. Cemented carbide as a kind of special tool material has been widely used in the manufacture of cutting tools, cutters, cobalt tools and wear-resistant parts, and is widely used in the fields of military industry, aerospace, machining, metallurgy, oil drilling, mining tools, electronic communication, construction and the like.
Chinese patent application No. 201510541956.7 discloses a cemented carbide material, which is composed of the following components by weight percent: 1-20% of a binding phase and 80-99% of a hard phase, wherein the hard phase consists of WC and TiAlCN, the WC accounts for 60-98.5% of the weight of the hard alloy material, and the TiAlCN accounts for 0.5-20% of the weight of the hard alloy material. The hard alloy provided by the prior art can enable the hard phase to have higher hardness and oxidation resistance, can improve the high-temperature strength, hardness and toughness of the prepared hard alloy tool, and the TiAlCN hard phase can also refine WC hard phase grains and improve the hardness, strength and toughness of the hard alloy; the TiAlCN hard phase can form a compact oxide protective film on the surface of a tool in the high-temperature use process of hard alloy, the oxidation resistance temperature reaches over 800 ℃, the hard alloy tool is resistant to vulcanization and corrosion of various media, and the hard alloy tool can work in high-temperature and severe environments. However, the strength, hardness and wear resistance of such cemented carbide still need to be improved in order to make the cemented carbide more suitable for use.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention mainly aims to provide a high-wear-resistance hard alloy; the hard alloy has better strength, hardness and high wear resistance.
The invention also aims to provide a preparation method of the high-wear-resistance hard alloy.
Still another object of the present invention is to provide an application of the above-mentioned high wear-resistant cemented carbide.
The purpose of the invention is realized by the following technical scheme:
a high wear-resistant hard alloy consists of TiC-Ni-Mo based spherical particles and WC-Co based powder in a volume ratio of 10: 90-50: 50;
the TiC-Ni-Mo based spherical particles comprise the following components in percentage by mass: 73-90 wt% of TiC, 2-15 wt% of Ni, 0.5-6 wt% of Mo, 0.5-2 wt% of Cr3C20.5 to 2 wt% of HfC, 0.5 to 2 wt% of TiB20.5-2 wt% of La;
the WC-Co-based powder comprises the following components in percentage by mass: 70-85 wt% of WC, 10-20 wt% of Co, 0.5-5 wt% of SiC and 1-5 wt% of Ni3Al, 0.5-1.5 wt% of V, 0.5-1.5 wt% of Y, 0.5-1.5 wt% of La and 0.5-1.5 wt% of YB6。
The particle size of the TiC-Ni-Mo-based spherical particles is 5-100 microns; the TiC-Ni-Mo based spherical particles are granulated by adopting a spray granulation method or a mechanical crushing method, and then are presintered to 900-fold-1000 ℃, and are subjected to heat preservation for 30-60min and presintering molding.
The fracture toughness of the high wear-resistant hard alloy is up to 18 MPa.m1/2The wear resistance is improved by 15-30% compared with the conventional metal ceramic with uniform structure.
The preparation method of the high-wear-resistance hard alloy comprises the following operation steps:
(1) the TiC-Ni-Mo based spherical particles and WC-Co based powder are filled into a graphite mould with the inner diameter of 50-100mm and are placed into a calcining furnace;
(2) introducing argon gas into the furnace body as protective gas, applying a pre-pressure of 5MPa, heating to 700-800 ℃ at a heating rate of 1-2 ℃/min, and then preserving heat for 30 min;
(3) increasing the axial pressure to 15MPa, continuously increasing the temperature to 1200 ℃ at the temperature increase rate of 1-2 ℃/min, preserving the temperature for 5min when the temperature reaches 1200 ℃, starting to increase the axial pressure at 1050 ℃, and increasing the axial pressure to 50MPa when the temperature is increased to 1200 ℃;
(4) then reducing the temperature to 1050-;
(5) after the heat preservation is finished, the temperature is reduced to 900 ℃, the temperature reduction rate is 1-2 ℃/min, and the pressure is released simultaneously;
(6) and after the temperature is reduced to 900 ℃, the material is naturally cooled to room temperature along with the furnace, and then the sintered body is taken out to obtain the high-wear-resistance hard alloy.
The high-wear-resistance hard alloy is applied to the preparation of cutting tools and special tools in the fields of infrastructure, mineral development and petroleum drilling.
Compared with the prior art, the invention has the following advantages and beneficial effects:
in the prior art, the material system is generally uniform, and if TiC-Ni-Mo based spherical particles and WC-Co based powder are prepared, micro gaps inside the TiC-Ni-Mo based spherical particles, between the TiC-Ni-Mo based spherical particles and the WC-Co based powder and between the WC-Co based powder and the WC-Co based powder are difficult to eliminate; the invention adopts a low-temperature pressure maintaining method, and the density is improved while WC and TiC crystal grains do not grow or grow a little; under the combined action of the preparation raw materials and the preparation method, micro gaps inside the TiC-Ni-Mo based spherical particles, between the TiC-Ni-Mo based spherical particles and the WC-Co based powder and between the TiC-Ni-Mo based spherical particles and the WC-Co based powder are completely eliminated, so that the complete compactness of the alloy is realized. The TiC-Ni-Mo based spherical particles acting as a hard phase in the alloyThe WC-Co base plays a role of a toughness phase in the alloy, and the wear resistance of the hard alloy is obviously improved under the characteristics of obvious hardness difference and complete compactness between the hard phase and the toughness phase. Meanwhile, the toughness of the alloy is improved under the characteristics of increased mean free path and complete compactness between hard phases. Therefore, the invention improves the wear resistance and the toughness of the hard alloy. The fracture toughness of the hard alloy in the invention is tested according to ASTM E399, and the fracture toughness of the hard alloy in the invention is up to 18MPa m1/2. The wear resistance of the cemented carbide of the present invention was tested according to ASTM B611 and the results showed that the wear resistance of the cemented carbide of the present invention was increased by 15-30% compared to conventional cermets with uniform structure.
Drawings
FIG. 1 is a diagram of a sintering process by a low-temperature pressure maintaining method.
Fig. 2 is a diagram of a conventional hot pressing sintering process.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 3 below employs the low temperature and pressure holding sintering process of the present invention as shown in fig. 1; comparative example 1 a conventional hot press sintering process is used as shown in fig. 2.
Example 1
A high wear-resistant hard alloy is characterized in that: the high wear-resistant hard alloy consists of TiC-Ni-Mo based spherical particles and WC-Co based powder in a volume ratio of 50: 50; the TiC-Ni-Mo based spherical particles comprise the following components in percentage by mass: 73 wt% TiC, 15 wt% Ni, 6 wt% Mo, 2 wt% Cr3C22 wt% of HfC and 1 wt% of TiB21 wt% of La, TiC-Ni-Mo based spherical particles with the particle size of 5-100 microns are granulated by adopting a spray granulation method or a mechanical crushing method, and then are presintered to 900 ℃, kept for 60min and presintered to be formed; the WC-Co-based powder comprises the following components in percentage by mass: 70 wt% WC, 20 wt% Co, 2 wt% SiC, 2 wt% Ni3Al, 1.5 wt% of V, 1.5 wt% of Y, 1.5 wt% of La, 1.5 wt% of YB6. The preparation method specifically comprises the following operation steps:
(1) the TiC-Ni-Mo based spherical particles and the WC-Co based powder are filled into a graphite mold with the inner diameter of 50mm and are placed into a calcining furnace;
(2) introducing argon gas into the furnace body as protective gas, applying a pre-pressure of 5MPa, heating to 700 ℃ at a heating rate of 1 ℃/min, and then preserving heat for 30 min;
(3) continuously heating to 1200 ℃ at the heating rate of 1 ℃/min, preserving the heat for 5min when the temperature reaches 1200 ℃, starting to increase the axial pressure at 1050 ℃, and increasing the axial pressure to 50MPa when the temperature is increased to 1200 ℃;
(4) then reducing the temperature to 1050 ℃, keeping the axial pressure at 50MPa, and keeping the pressure and the heat for 48 hours;
(5) after the heat preservation is finished, the temperature is reduced to 900 ℃, the temperature reduction rate is 1 ℃/min, and the pressure is released simultaneously;
(6) and after the temperature is reduced to 900 ℃, the material is naturally cooled to room temperature along with the furnace, and then the sintered body is taken out to obtain the high-wear-resistance hard alloy.
Example 2
A high wear-resistant hard alloy is characterized in that: the high wear-resistant hard alloy is prepared from the following components in percentage by volume of 50: 50 TiC-Ni-Mo based spherical particles and WC-Co based powder; the TiC-Ni-Mo based spherical particles comprise the following components in percentage by mass: 90 wt% TiC, 2 wt% Ni, 6 wt% Mo, 0.5 wt% Cr3C20.5 wt% of HfC and 0.5 wt% of TiB20.5 wt% of La, TiC-Ni-Mo based spherical particles with the particle size of 5-100 microns are granulated by adopting a spray granulation method or a mechanical crushing method, and then are presintered to 1000 ℃, kept for 30min and presintered to form; the WC-Co-based powder comprises the following components in percentage by mass: 85 wt% WC, 10 wt% Co, 0.5 wt% SiC, 2.5 wt% Ni3Al, 0.5 wt% of V, 0.5 wt% of Y, 0.5 wt% of La, 0.5 wt% of YB6. The preparation method specifically comprises the following operation steps:
(1) the TiC-Ni-Mo based spherical particles and the WC-Co based powder are filled into a graphite mould with the inner diameter of 100mm and are placed into a calcining furnace;
(2) introducing argon gas into the furnace body as protective gas, applying a pre-pressure of 5MPa, heating to 800 ℃ at a heating rate of 2 ℃/min, and then preserving heat for 30 min;
(3) continuously heating to 1200 ℃ at the heating rate of 2 ℃/min, preserving the heat for 5min when the temperature reaches 1200 ℃, starting to increase the axial pressure at 1050 ℃, and increasing the axial pressure to 50MPa when the temperature is increased to 1200 ℃;
(4) then reducing the temperature to 1090 ℃, keeping the axial pressure at 50MPa, and keeping the pressure and the heat for 8 hours;
(5) after the heat preservation is finished, the temperature is reduced to 900 ℃, the temperature reduction rate is 2 ℃/min, and the pressure is released simultaneously;
(6) and after the temperature is reduced to 900 ℃, the material is naturally cooled to room temperature along with the furnace, and then the sintered body is taken out to obtain the high-wear-resistance hard alloy.
Example 3
A high wear-resistant hard alloy is characterized in that: the high wear-resistant hard alloy consists of TiC-Ni-Mo based spherical particles and WC-Co based powder in a volume ratio of 10: 90; the TiC-Ni-Mo based spherical particles comprise the following components in percentage by mass: 80 wt% TiC, 10 wt% Ni, 2 wt% Mo, 2 wt% Cr3C22 wt% of HfC and 2 wt% of TiB22 wt% of La, TiC-Ni-Mo based spherical particles with the particle size of 5-100 microns are granulated by adopting a spray granulation method or a mechanical crushing method, and then are presintered to 950 ℃, kept for 50min and presintered to be formed; the WC-Co-based powder comprises the following components in percentage by mass: 80 wt% WC, 10 wt% Co, 5 wt% SiC, 1 wt% Ni3Al, 1.5 wt% of V, 1.5 wt% of Y, 0.5 wt% of La, 0.5 wt% of YB6. The preparation method specifically comprises the following operation steps:
(1) the TiC-Ni-Mo based spherical particles and the WC-Co based powder are filled into a graphite mold with the inner diameter of 80mm and are placed into a calcining furnace;
(2) introducing argon gas into the furnace body as protective gas, applying a pre-pressure of 5MPa, heating to 750 ℃ at a heating rate of 2 ℃/min, and then preserving heat for 30 min;
(3) continuously heating to 1200 ℃ at the heating rate of 2 ℃/min, preserving the heat for 5min when the temperature reaches 1200 ℃, starting to increase the axial pressure at 1050 ℃, and increasing the axial pressure to 50MPa when the temperature is increased to 1200 ℃;
(4) then reducing the temperature to 1090 ℃, keeping the axial pressure at 50MPa, and keeping the pressure and the heat for 24 hours;
(5) after the heat preservation is finished, the temperature is reduced to 900 ℃, the temperature reduction rate is 2 ℃/min, and the pressure is released simultaneously;
(6) and after the temperature is reduced to 900 ℃, the material is naturally cooled to room temperature along with the furnace, and then the sintered body is taken out to obtain the high-wear-resistance hard alloy.
Example 4
A high wear-resistant hard alloy is characterized in that: the high wear-resistant hard alloy consists of TiC-Ni-Mo based spherical particles and WC-Co based powder in a volume ratio of 30: 70; the TiC-Ni-Mo based spherical particles comprise the following components in percentage by mass: 85 wt% of TiC, 2-15 wt% of Ni, 3 wt% of Mo and 1 wt% of Cr3C21 wt% of HfC and 1 wt% of TiB21 wt% of La, TiC-Ni-Mo based spherical particles with the particle size of 5-100 microns are granulated by adopting a spray granulation method or a mechanical crushing method, and then are presintered to 900 ℃, kept for 40min and presintered to form; the WC-Co-based powder comprises the following components in percentage by mass: 75 wt% WC, 15 wt% Co, 3 wt% SiC, 2.5 wt% Ni3A1, 1.5 wt% V, 1.5 wt% Y, 1.5 wt% La, 1.5 wt% YB6. The preparation method specifically comprises the following operation steps:
(1) the TiC-Ni-Mo based spherical particles and the WC-Co based powder are filled into a graphite mold with the inner diameter of 50mm and are placed into a calcining furnace;
(2) introducing argon gas into the furnace body as protective gas, applying a pre-pressure of 5MPa, heating to 700 ℃ at a heating rate of 2 ℃/min, and then preserving heat for 30 min;
(3) continuously heating to 1200 ℃ at the heating rate of 1 ℃/min, preserving the heat for 5min when the temperature reaches 1200 ℃, starting to increase the axial pressure at 1050 ℃, and increasing the axial pressure to 50MPa when the temperature is increased to 1200 ℃;
(4) then reducing the temperature to 1050 ℃, keeping the axial pressure at 50MPa, and keeping the pressure and the heat for 32 h;
(5) after the heat preservation is finished, the temperature is reduced to 900 ℃, the temperature reduction rate is 2 ℃/min, and the pressure is released simultaneously;
(6) and after the temperature is reduced to 900 ℃, the material is naturally cooled to room temperature along with the furnace, and then the sintered body is taken out to obtain the high-wear-resistance hard alloy.
Comparative example 1
A high wear-resistant hard alloy is characterized in that: the high wear-resistant hard alloy is prepared from the following components in percentage by volume of 50: 50 TiC-Ni-Mo based spherical particles and WC-Co based powder; the TiC-Ni-Mo based spherical particles comprise the following components in percentage by mass: 73 wt% TiC, 15 wt% Ni, 6 wt% Mo, 2 wt% Cr3C22 wt% of HfC and 1 wt% of TiB21 wt% of La, TiC-Ni-Mo based spherical particles with the particle size of 5-100 microns are granulated by adopting a spray granulation method or a mechanical crushing method, and then are presintered to 900 ℃, kept for 60min and presintered to be formed; the WC-Co-based powder comprises the following components in percentage by mass: 70 wt% WC, 20 wt% Co, 2 wt% SiC, 2 wt% Ni3Al, 1.5 wt% of V, 1.5 wt% of Y, 1.5 wt% of La, 1.5 wt% of YB6. The preparation method specifically comprises the following operation steps:
(1) the TiC-Ni-Mo based spherical particles and the WC-Co based powder are filled into a graphite mold with the inner diameter of 50mm and are placed into a calcining furnace;
(2) introducing argon gas into the furnace body as protective gas, applying a pre-pressure of 5MPa, heating to 750 ℃ at a heating rate of 1 ℃/min, and then preserving heat for 30 min;
(3) continuously heating to 1200 ℃ at the heating rate of 1 ℃/min, keeping the pressure and preserving the heat for 60min when the temperature reaches 1200 ℃, starting to increase the axial pressure at 1050 ℃, and increasing the axial pressure to 50MPa when the temperature is increased to 1200 ℃; keeping the pressure during the heat preservation process;
(4) after the heat preservation is finished, the temperature is reduced to 900 ℃, the temperature reduction rate is 1 ℃/min, and the pressure is released simultaneously;
(5) and after the temperature is reduced to 900 ℃, the material is naturally cooled to room temperature along with the furnace, and then the sintered body is taken out to obtain the high-wear-resistance hard alloy.
Comparative example 2
A high wear-resistant hard alloy is characterized in that: the high wear-resistant hard alloy consists of TiC-Ni-Mo based spherical particles and WC-Co based powder in a volume ratio of 50: 50; the TiC-Ni-Mo based spherical particles comprise the following components in percentage by mass: the TiC-Ni-Mo based spherical particles are prepared by 79 wt% of TiC, 15 wt% of Ni and 6 wt% of Mo, the particle size of the TiC-Ni-Mo based spherical particles is 5-100 micrometers, the particles are granulated by a mechanical crushing method, and then the particles are presintered to 900 ℃, the temperature is kept for 60min, and the presintering molding is carried out; the WC-Co-based powder comprises the following components in percentage by mass: 80 wt% of WC and 20 wt% of Co. The preparation method specifically comprises the following operation steps:
(1) the TiC-Ni-Mo spherical particles and WC-Co powder are filled into a graphite die with the inner diameter of 50mm and are placed into a calcining furnace;
(2) introducing argon gas into the furnace body as protective gas, applying a pre-pressure of 5MPa, heating to 700 ℃ at a heating rate of 1 ℃/min, and then preserving heat for 30 min;
(3) continuously heating to 1200 ℃ at the heating rate of 1 ℃/min, preserving the heat for 5min when the temperature reaches 1200 ℃, starting to increase the axial pressure at 1050 ℃, and increasing the axial pressure to 50MPa when the temperature is increased to 1200 ℃;
(4) then reducing the temperature to 1090 ℃, keeping the axial pressure at 50MPa, and keeping the pressure and the heat for 48 h;
(5) after the heat preservation is finished, the temperature is reduced to 900 ℃, the temperature reduction rate is 1 ℃/min, and the pressure is released simultaneously;
(6) and after the temperature is reduced to 900 ℃, the material is naturally cooled to room temperature along with the furnace, and then the sintered body is taken out to obtain the high-wear-resistance hard alloy.
Finally, some performance tests were performed on the cemented carbides obtained in examples 1-4 of the present invention and comparative examples 1-2, and the data obtained are presented in the form of table 1 herein, which shows that the best solution can be obtained by using the formulation and method of the present invention. The data show that the wear resistance of the cemented carbide of the present invention was tested according to ASTM B611, which is mentioned in the specification, and the wear resistance of the cemented carbide of the present invention was improved by 50-120% compared to the conventional cermet.
Table 1 composite cemented carbide property test data
| Sample (I) | Abrasion resistance Krev | Hardness HV30 |
| Example 1 | 2.6 | 2060 |
| Example 2 | 2.2 | 2030 |
| Example 3 | 2.4 | 2050 |
| Example 4 | 2.1 | 2000 |
| Comparative example 1 | 1.4 | 1730 |
| Comparative example 2 | 1.6 | 1760 |
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (2)
1. The preparation method of the high-wear-resistance hard alloy is characterized by comprising the following operation steps:
(1) the TiC-Ni-Mo based spherical particles and WC-Co based powder are filled into a graphite mould with the inner diameter of 50-100mm and are placed into a calcining furnace;
(2) introducing argon gas into the furnace body as protective gas, applying a pre-pressure of 5MPa, heating to 700-800 ℃ at a heating rate of 1-2 ℃/min, and then preserving heat for 30 min;
(3) increasing the axial pressure to 15MPa, continuously increasing the temperature to 1200 ℃ at the temperature increase rate of 1-2 ℃/min, preserving the temperature for 5min when the temperature reaches 1200 ℃, starting to increase the axial pressure at 1050 ℃, and increasing the axial pressure to 50MPa when the temperature is increased to 1200 ℃;
(4) then reducing the temperature to 1050-;
(5) after the heat preservation is finished, the temperature is reduced to 900 ℃, the temperature reduction rate is 1-2 ℃/min, and the pressure is released simultaneously;
(6) after the temperature is reduced to 900 ℃, the material is naturally cooled to room temperature along with the furnace, and then the sintered body is taken out to obtain the high wear-resistant hard alloy;
the obtained high wear-resistant hard alloy is prepared from the following components in percentage by volume of 10: 90-50: 50 TiC-Ni-Mo based spherical particles and WC-Co based powder;
the TiC-Ni-Mo based spherical particles comprise the following components in percentage by mass: 73-90 wt% of TiC, 2-15 wt% of Ni, 0.5-6 wt% of Mo, 0.5-2 wt% of Cr3C20.5 to 2 wt% of HfC, 0.5 to 2 wt% of TiB20.5-2 wt% of La;
the WC-Co-based powder comprises the following components in percentage by mass: 70-85 wt% of WC, 10-20 wt% of Co, 0.5-5 wt% of SiC and 1-5 wt% of Ni3Al, 0.5-1.5 wt% of V, 0.5-1.5 wt% of Y, 0.5-1.5 wt% of La and 0.5-1.5 wt% of YB6。
2. The method for preparing the high-wear-resistance hard alloy according to claim 1, wherein the method comprises the following steps: the particle size of the TiC-Ni-Mo-based spherical particles is 5-100 microns; the TiC-Ni-Mo based spherical particles are granulated by adopting a spray granulation method or a mechanical crushing method, and then are presintered to 900-fold-1000 ℃, and are subjected to heat preservation for 30-60min and presintering molding.
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