CoCrNiCuMn-TiN-TiC-WC composite material and preparation method thereof
阅读说明：本技术 一种CoCrNiCuMn-TiN-TiC-WC复合材料及其制备方法 (CoCrNiCuMn-TiN-TiC-WC composite material and preparation method thereof ) 是由 邹芹 李艳国 王明智 熊建超 于 2020-06-15 设计创作，主要内容包括：本发明提供一种CoCrNiCuMn-TiN-TiC-WC复合材料及其制备方法,复合材料的原料配方为CoCrNiCuMn、TiNx、TiC和WC；其中所述TiNx中的x＝0.3～0.9或x＝1.1～1.3,所述CoCrNiCuMn的质量百分比为5～20wt.％,TiNx的质量百分比为20～50wt.％,WC的质量百分比为2～10wt.％,余量为TiC。制备方法包括以下步骤：S1、制备150nm以细的CoCrNiCuMn粉末；S2、制备150nm以细的TiNx粉末；S3、制备150nm以细的TiC粉末；S4、制备150nm以细的WC粉末；S5、混料、预压、真空热压烧结制得CoCrNiCuMn-TiN-TiC-WC复合材料。本发明公开的复合材料具有高硬度和高韧性。(The invention provides a CoCrNiCuMn-TiN-TiC-WC composite material and a preparation method thereof, wherein the raw material formula of the composite material is CoCrNiCuMn, TiNx, TiC and WC; wherein x in the TiNx is 0.3-0.9 or x is 1.1-1.3, the mass percent of the CoCrNiCuMn is 5-20 wt.%, the mass percent of the TiNx is 20-50 wt.%, the mass percent of the WC is 2-10 wt.%, and the balance is TiC. The preparation method comprises the following steps: s1, preparing fine CoCrNiCuMn powder with the particle size of 150 nm; s2, preparing TiNx powder with the fineness of 150 nm; s3, preparing fine TiC powder with the particle size of 150 nm; s4, preparing 150nm fine WC powder; s5, mixing, prepressing, and vacuum hot-pressing sintering to obtain the CoCrNiCuMn-TiN-TiC-WC composite material. The composite material disclosed by the invention has high hardness and high toughness.)
1. A CoCrNiCuMn-TiN-TiC-WC composite material is characterized in that the raw material formula is CoCrNiCuMn, TiNx, TiC and WC; wherein x in the TiNx is 0.3-0.9 or 1.1-1.3;
the mass percent of the CoCrNiCuMn is 5-20 wt.%, the mass percent of the TiNx is 20-50 wt.%, the mass percent of the WC is 2-10 wt.%, and the balance is TiC.
2. A preparation method of a CoCrNiCuMn-TiN-TiC-WC composite material is characterized by comprising the following steps:
s1, preparing fine CoCrNiCuMn powder with the particle size of 150 nm;
and ball-milling Co, Cr, Ni, Cu and Mn powder to obtain fine CoCrNiCuMn powder with the particle size of 150 nm.
S2, preparing TiNx powder with the fineness of 150 nm;
mixing Ti powder and CH according to a preset molar ratio4N2Performing ball milling on O to prepare 150nm fine TiNx powder, wherein x is 0.3-0.9 or 1.1-1.3;
s3, preparing fine TiC powder with the particle size of 150 nm;
ball-milling the TiC powder to obtain fine TiC powder with the particle size of 150 nm;
s4, preparing 150nm fine WC powder;
carrying out ball milling on WC powder to prepare fine WC powder with the particle size of 150 nm;
s5, mixing, prepressing, and vacuum hot-pressing sintering to obtain a CoCrNiCuMn-TiN-TiC-WC composite material;
weighing 5-20 wt.% of CoCrNiCuMn powder, 20-50 wt.% of 150nm fine TiNx powder and 2-10 wt.% of 150nm fine WC powder, and adding the powder into the 150nm fine TiC powder together for ball milling to obtain a mixture;
putting the mixture into a hard alloy die for prepressing to obtain a sample;
and carrying out vacuum hot-pressing sintering on the sample to obtain the CoCrNiCuMn-TiN-TiC-WC composite material.
3. The method for preparing the CoCrNiCuMn-TiN-TiC-WC composite material according to claim 2, wherein the method comprises the following steps: in the step S1, the Co, Cr, Ni, Cu and Mn are mixed according to the mol ratio of 1:1:1:1:1 and ball-milled, and the purity of the Co, Cr, Ni, Cu and Mn powder is more than 99%, wherein the grain diameter of the Co powder is 1-3 μm, the grain diameter of the Cr powder is less than 75 μm, and the grain diameter of the Ni, Cu and Mn powder is less than 45 μm.
4. The method for preparing the CoCrNiCuMn-TiN-TiC-WC composite material according to claim 2, wherein the method comprises the following steps: in the step S2, the Ti powder and the CH4N2The preset molar ratio of O is 6:1 or 5:1 or 4:1 or 10:3 or 20:7 or 5:2 or 20:9 or 20:11 or 5:3 or 20:13, the particle size of the Ti powder is less than 30 mu m, the purity is more than 99.36 percent, and the CH powder is prepared by mixing the Ti powder and the CH powder4N2The purity of O was > 99% analytical purity. .
5. The method for preparing the CoCrNiCuMn-TiN-TiC-WC composite material according to claim 2, wherein the method comprises the following steps: in the step S3, the grain size of the TiC powder is 1-3 μm, and the purity is more than 99%; in the step S4, the WC powder has a particle size of 1 to 3 μm and a purity of > 99%.
6. The method for preparing the CoCrNiCuMn-TiN-TiC-WC composite material according to claim 2, wherein the method comprises the following steps:
the ball milling process in the step S1 is as follows: mixing Co, Cr, Ni, Cu and Mn in a glove box filled with argon, filling the mixture into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 300-600 r/min, the ball milling time is 20-50 h, stopping the machine for 30min for every 5h, performing heat dissipation for every 10h, scraping off the raw materials adhered to the grinding balls and the inner wall of the tank, uniformly mixing, and continuing ball milling to prepare fine CoCrNiCuMn powder with the particle size of 150 nm;
the ball milling process in the step S2 is as follows: in a glove box filled with argon, Ti powder and CH4N2Mixed charging of O into WCIn a hard alloy ball milling tank, the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 200-500 r/min, the ball milling time is 30-60 h, and the machine is stopped for 30min every 10h to dissipate heat, so that fine TiNx powder with the particle size of 150nm is prepared;
the ball milling process in the step S3 is as follows: the method comprises the following steps of putting TiC powder into a WC hard alloy ball milling tank in a glove box filled with argon, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 250-400 r/min, ball milling is carried out for 10-40 h, and the ball milling tank is stopped for 10min every 5h to carry out heat dissipation to obtain the fine TiC powder with the particle size of 150 nm;
the ball milling process in the step S4 is as follows: putting WC powder into a WC hard alloy ball milling tank in a glove box filled with argon, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 250-400 r/min, the ball milling time is 10-40 h, stopping the machine for 10min every 5h to dissipate heat, and preparing fine WC powder with the particle size of 150 nm;
the ball milling process in the step S5 is as follows: in a glove box filled with argon, 5-20 wt.% of 150nm fine CoCrNiCuMn powder, 20-50 wt.% of 150nm fine TiNx powder and 2-10 wt.% of 150nm fine WC powder are weighed, the powder and the 150nm fine TiC powder are added into the 150nm fine TiC powder in a WC hard alloy ball milling tank, the mass ratio of balls to materials is 6: 1-10: 1, the rotating speed is 200-350 r/min, the ball milling time is 1.5-5 h, and the glove box is shut down for 10min every 1h to dissipate heat, so that the mixture is prepared.
7. The method for preparing the CoCrNiCuMn-TiN-TiC-WC composite material according to claim 6, wherein the method comprises the following steps:
the ball milling processes of the steps S1, S2, S3, S4 and S5 all adopt WC hard alloy balls with the diameters of 8mm, 5mm and 2mm respectively, and the mass ratio of the three WC hard alloy balls is 3:1: 1.
8. The method for preparing the CoCrNiCuMn-TiN-TiC-WC composite material according to claim 2, wherein the method comprises the following steps: the prepressing process comprises the following steps: the prepressing pressure is 10-400 MPa, and the prepressing time is 10-120 s.
9. The method for preparing the CoCrNiCuMn-TiN-TiC-WC composite material according to claim 2, wherein the method comprises the following steps: the vacuum hot-pressing sintering process comprises the following steps:
and (3) the sintering pressure is 40-50 MPa, the vacuum degree is 40Pa, the sintering temperature is raised to 1200-1800 ℃ at the heating rate of 10-30 ℃/min, then the temperature is kept for 20-90 min, and finally the temperature is reduced and the pressure is relieved, so that the CoCrNiCuMn-TiN-TiC-WC composite material is prepared.
10. The method for preparing the CoCrNiCuMn-TiN-TiC-WC composite material according to claim 2, wherein the method comprises the following steps:
in the process of increasing the sintering temperature to 1200-1800 ℃ at the temperature increase rate of 10-30 ℃/min: heating from room temperature to 1000 ℃ at a heating rate of 10-30 ℃/min, and preserving heat at 1000 ℃ for 20 min; then raising the temperature from 1000 ℃ to 1200-1800 ℃ at a temperature raising rate of 10-30 ℃/min;
and after the temperature reduction and pressure relief, carrying out surface grinding and deburring treatment on the blank obtained by the temperature reduction and pressure relief to obtain the CoCrNiCuMn-TiN-TiC-WC composite material.
Technical Field
The invention relates to the technical field of material compounding, in particular to a CoCrNiCuMn-TiN-TiC-WC composite material and a preparation method thereof.
Background
In recent years, high-entropy alloys (HEA) have been widely studied because of their excellent properties. The HEA composed of a plurality of main elements has a series of characteristics such as high entropy effect, lattice distortion effect, retarded diffusion effect, cocktail effect and the like, so that the HEA has excellent physical, chemical and mechanical properties such as high strength, high hardness, high wear resistance, high corrosion resistance, high low-temperature toughness and the like, and therefore, the problems that the hard alloy has high hardness and insufficient toughness or even if the problems of high hardness and high toughness are met, the oxidation resistance or corrosion resistance at high temperature cannot be realized and the like can be solved.
The Ti (C0.7N0.3) -WC-Mo2C-TaC-AlCoCrFeNi system metal ceramic is prepared by the Zhugang and the like by adopting vacuum sintering. The microstructure formation and phase transformation rules of the metal ceramic in the sintering process are researched. Research results show that the introduction of the AlCoCrFeNi high-entropy alloy binding phase prolongs the process of WC diffusion solid solution forming (W, M) C annular phase on one hand, and inhibits the growth of gray outer annular phase, so that the outer annular phase which is continuously distributed is hardly observed in the structure. On the other hand, in the initial stage of sintering, a large amount of M6C type η phase is formed in the structure, and the content decreases with the increase of temperature, and the η phase gradually dissolves and disappears after 1350 ℃. The microstructure and the phase change in the sintering process of the Ti (C, N)/AlCoCrFeNi-based cermet [ J ] materials science and engineering report 2016(3):353-356 ] of Zhu-just, Xianming, Chenjialin, et al, the Ti (C, N)/AlCoCrFeNi-based cermet has complex raw material composition and poor combination of a binding phase and hardness, generates a large amount of carbon-deficient compounds in tissues and reduces the performance of the Ti (C, N) -based composite material.
Zhugang et al also studied the surface enrichment behavior of the binder phase during sintering of Ti (C, N)/AlCoCrFeNi cermets. The results show that after sintering at 1300 ℃ for 60min, the surface of the alloy sintered body is obviously enriched and a third phase, similar to M, is formed6Study on the behavior of binder phase surface enrichment during sintering of C-structured carbon-deficient phase (η) [ Zhugang, Chenjialin, Jiahailong, et al]Material guide, 2017(16).]The research shows that the AlCoCrFeNi combined Ti (C, N) cermet structure is not uniform and can not replace the traditional cermet binder.
A large number of carbon-deficient compound phases are detected in the above-mentioned research organizations, and the performance of the prepared Ti (C, N) -based composite material is not ideal, and reports of researchers on the mechanical properties of the Ti (C, N) -based composite material are not found.
The red bayberry and the like are sintered by microwaves to prepare the Ti (C, N)/CoNiFeCuMnx (x is 0.3-1), so that the performance of the Ti (C, N) hard alloy is improved. [ Myrica rubra; korean ice; longjiaping, a preparation method of high-entropy alloy binding phase Ti (C, N) base cermet, CN109022990A, university of Country Engineers, 2018.12.18. ]
The Liu Ying and the like are sintered at low pressure, high-entropy alloy is used as a binder, and carbide and titanium carbonitride solid solution are used as hard phases to prepare the titanium carbonitride-based hard alloy. [ Liu Ying; leaf golden text; zhahao, titanium carbonitride based cermet based on high entropy alloy binder phase and preparation method thereof CN102787266A university Sichuan 2012.11.21. ]
In the two researches, only Ti (C, N) and high-entropy alloy are mixed and sintered, and the problems of poor bonding property of the high-entropy alloy and the Ti (C, N) and the like are not solved.
Disclosure of Invention
According to the technical problem, the invention provides a CoCrNiCuMn-TiN-TiC-WC composite material and a preparation method thereof.
The CoCrNiCuMn is used as a binder of the CoCrNiCuMn-TiN-TiC-WC composite material, TiNx and TiC are used as hard phases, WC is used as a reinforcing phase, and the CoCrNiCuMn-TiN-TiC-WC composite material is prepared by adopting a vacuum hot-pressing sintering method. Aims to reduce the sintering temperature and improve the comprehensive performance.
The technical means adopted by the invention are as follows:
a CoCrNiCuMn-TiN-TiC-WC composite material comprises the following raw materials of CoCrNiCuMn, TiNx, TiC and WC; wherein x in the TiNx is 0.3-0.9 or 1.1-1.3;
the mass percent of the CoCrNiCuMn is 5-20 wt.%, the mass percent of the TiNx is 20-50 wt.%, the mass percent of the WC is 2-10 wt.%, and the balance is TiC.
The invention also discloses a preparation method of the CoCrNiCuMn-TiN-TiC-WC composite material, which comprises the following steps:
s1, preparing fine CoCrNiCuMn powder with the particle size of 150 nm;
and ball-milling Co, Cr, Ni, Cu and Mn powder to obtain fine CoCrNiCuMn powder with the particle size of 150 nm.
S2, preparing TiNx powder with the fineness of 150 nm;
mixing Ti powder and CH according to a preset molar ratio4N2Performing ball milling on O to prepare 150nm fine TiNx powder, wherein x is 0.3-0.9 or 1.1-1.3;
s3, preparing fine TiC powder with the particle size of 150 nm;
ball-milling the TiC powder to obtain fine TiC powder with the particle size of 150 nm;
s4, preparing 150nm fine WC powder;
carrying out ball milling on WC powder to prepare fine WC powder with the particle size of 150 nm;
s5, mixing, prepressing, and vacuum hot-pressing sintering to obtain a CoCrNiCuMn-TiN-TiC-WC composite material;
weighing 5-20 wt.% of CoCrNiCuMn powder, 20-50 wt.% of 150nm fine TiNx powder and 2-10 wt.% of 150nm fine WC powder, and adding the powder into the 150nm fine TiC powder together for ball milling to obtain a mixture;
putting the mixture into a hard alloy die for prepressing to obtain a sample;
and carrying out vacuum hot-pressing sintering on the sample to obtain the CoCrNiCuMn-TiN-TiC-WC composite material.
Further, in the step S1, Co, Cr, Ni, Cu, and Mn are mixed at a molar ratio of 1:1:1:1:1 and ball milled, and the purity of Co, Cr, Ni, Cu, and Mn powder is greater than 99%, wherein the particle size of Co powder is 1 to 3 μm, the particle size of Cr powder is less than 75 μm, and the particle size of Ni, Cu, and Mn powder is less than 45 μm.
Further, in the step S2, the Ti powder and the CH4N2The preset molar ratio of O is 6:1 or 5:1 or 4:1 or 10:3 or 20:7 or 5:2 or 20:9 or 20:11 or 5:3 or 20:13, the particle size of the Ti powder is less than 30 mu m, the purity is more than 99.36 percent, and the CH powder is prepared by mixing the Ti powder and the CH powder4N2The purity of O was > 99% analytical purity. .
Further, in the step S3, the grain size of the TiC powder is 1 to 3 μm, and the purity is greater than 99%; in the step S4, the WC powder has a particle size of 1 to 3 μm and a purity of > 99%.
Further, the ball milling process in the step S1 is as follows: mixing Co, Cr, Ni, Cu and Mn in a glove box filled with argon, filling the mixture into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 300-600 r/min, the ball milling time is 20-50 h, stopping the machine for 30min for every 5h, performing heat dissipation for every 10h, scraping off the raw materials adhered to the grinding balls and the inner wall of the tank, uniformly mixing, and continuing ball milling to prepare fine CoCrNiCuMn powder with the particle size of 150 nm;
the ball milling process in the step S2 is as follows: in a glove box filled with argon, Ti powder and CH4N2Mixing O, putting into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 200-500 r/min, the ball milling time is 30-60 h, and stopping the machine for 30min every 10h to dissipate heat to obtain TiNx powder with the particle size of 150nm or less;
the ball milling process in the step S3 is as follows: the method comprises the following steps of putting TiC powder into a WC hard alloy ball milling tank in a glove box filled with argon, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 250-400 r/min, ball milling is carried out for 10-40 h, and the ball milling tank is stopped for 10min every 5h to carry out heat dissipation to obtain the fine TiC powder with the particle size of 150 nm;
the ball milling process in the step S4 is as follows: putting WC powder into a WC hard alloy ball milling tank in a glove box filled with argon, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 250-400 r/min, the ball milling time is 10-40 h, stopping the machine for 10min every 5h to dissipate heat, and preparing fine WC powder with the particle size of 150 nm;
the ball milling process in the step S5 is as follows: in a glove box filled with argon, 5-20 wt.% of 150nm fine CoCrNiCuMn powder, 20-50 wt.% of 150nm fine TiNx powder and 2-10 wt.% of 150nm fine WC powder are weighed, the powder and the 150nm fine TiC powder are added into the 150nm fine TiC powder in a WC hard alloy ball milling tank, the mass ratio of balls to materials is 6: 1-10: 1, the rotating speed is 200-350 r/min, the ball milling time is 1.5-5 h, and the glove box is shut down for 10min every 1h to dissipate heat, so that the mixture is prepared.
Further, the ball milling processes of the steps S1, S2, S3, S4 and S5 all adopt WC cemented carbide balls with three outer diameters of 8mm, 5mm and 2mm respectively, and the mass ratio of the three WC cemented carbide balls is 3:1: 1.
Further, the prepressing process comprises the following steps: the prepressing pressure is 10-400 MPa, and the prepressing time is 10-120 s.
Further, the vacuum hot-pressing sintering process comprises the following steps:
and (3) applying pressure to the sample to 40-50 MPa, keeping the vacuum degree at 40Pa, raising the sintering temperature to 1200-1800 ℃ at the temperature rise rate of 10-30 ℃/min, then preserving the heat for 20-90 min, and finally cooling and releasing the pressure to obtain the CoCrNiCuMn-TiN-TiC-WC composite material.
Further, in the process of raising the sintering temperature to 1200-1800 ℃ at a temperature raising rate of 10-30 ℃/min: heating from room temperature to 1000 ℃ at a heating rate of 10-30 ℃/min, and preserving heat at 1000 ℃ for 20 min; then raising the temperature from 1000 ℃ to 1200-1800 ℃ at a temperature raising rate of 10-30 ℃/min;
further, after the temperature reduction and pressure relief, carrying out surface grinding and deburring treatment on a blank obtained by the temperature reduction and pressure relief to obtain the CoCrNiCuMn-TiN-TiC-WC composite material.
Compared with the prior art, the invention has the following advantages:
1. the CoCrNiCuMn high-entropy alloy has excellent comprehensive performance, exceeds the traditional metal binders such as Ni, Co, Fe and the like, and can improve the hardness and toughness of the composite material.
2. The non-stoichiometric ratio TiNx promotes sintering and lowers the sintering temperature of the composite material.
3. WC can improve the wettability of the hard phase and the binding phase, thereby improving the hardness and the fracture toughness of the alloy.
4. The CoCrNiCuMn high-entropy alloy adopted by the application has excellent mechanical properties, and is different from the high-entropy alloy adopted by the previous research. Furthermore, the present invention combines the advantages of the non-stoichiometric compounds TiNx and WC. The non-stoichiometric compound is changed into the covalent bond compound which is difficult to sinter, the densification can be fully realized at a lower sintering temperature, and the mass transfer capacity is good in the sintering process, so that the hard phase and the binding phase in the hard alloy can form good interface combination. WC can improve the wettability of the hard phase and the binding phase, thereby improving the hardness and the fracture toughness of the alloy.
For the reasons, the invention can be widely popularized in the fields of composite materials and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a scanning electron microscope (FESEM) image of a CoCrNiCuMn-TiN-TiC-WC composite material in the embodiment of the invention:
wherein (a) is example 1; (b) example 4 was used.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A CoCrNiCuMn-TiN-TiC-WC composite material comprises the following raw materials of CoCrNiCuMn, TiNx, TiC and WC; wherein x in the TiNx is 0.3-0.9 or 1.1-1.3;
the mass percent of the CoCrNiCuMn is 5-20 wt.%, the mass percent of the TiNx is 20-50 wt.%, the mass percent of the WC is 2-10 wt.%, and the balance is TiC.
The invention also discloses a preparation method of the CoCrNiCuMn-TiN-TiC-WC composite material, which comprises the following steps:
s1, preparing fine CoCrNiCuMn powder with the particle size of 150 nm;
and ball-milling Co, Cr, Ni, Cu and Mn powder to obtain fine CoCrNiCuMn powder with the particle size of 150 nm.
S2, preparing TiNx powder with the fineness of 150 nm;
mixing Ti powder and CH according to a preset molar ratio4N2Performing ball milling on O to prepare 150nm fine TiNx powder, wherein x is 0.3-0.9 or 1.1-1.3;
s3, preparing fine TiC powder with the particle size of 150 nm;
ball-milling the TiC powder to obtain fine TiC powder with the particle size of 150 nm;
s4, preparing 150nm fine WC powder;
carrying out ball milling on WC powder to prepare fine WC powder with the particle size of 150 nm;
s5, mixing, prepressing, and vacuum hot-pressing sintering to obtain a CoCrNiCuMn-TiN-TiC-WC composite material;
weighing 5-20 wt.% of CoCrNiCuMn powder, 20-50 wt.% of 150nm fine TiNx powder and 2-10 wt.% of 150nm fine WC powder, and adding the powder into the 150nm fine TiC powder together for ball milling to obtain a mixture;
putting the mixture into a hard alloy die for prepressing to obtain a sample;
and carrying out vacuum hot-pressing sintering on the sample to obtain the CoCrNiCuMn-TiN-TiC-WC composite material.
Further, in the step S1, Co, Cr, Ni, Cu, and Mn are mixed at a molar ratio of 1:1:1:1:1 and ball milled, and the purity of Co, Cr, Ni, Cu, and Mn powder is greater than 99%, wherein the particle size of Co powder is 1 to 3 μm, the particle size of Cr powder is less than 75 μm, and the particle size of Ni, Cu, and Mn powder is less than 45 μm.
Further, in the step S2, the Ti powder and the CH4N2The preset molar ratio of O is 6:1 or 5:1 or 4:1 or 10:3 or 20:7 or 5:2 or 20:9 or 20:11 or 5:3 or 20:13, the particle size of the Ti powder is less than 30 mu m, the purity is more than 99.36 percent, and the CH powder is prepared by mixing the Ti powder and the CH powder4N2The purity of O was > 99% analytical purity. .
Further, in the step S3, the grain size of the TiC powder is 1 to 3 μm, and the purity is greater than 99%; in the step S4, the WC powder has a particle size of 1 to 3 μm and a purity of > 99%.
Further, the ball milling process in the step S1 is as follows: mixing Co, Cr, Ni, Cu and Mn in a glove box filled with argon, filling the mixture into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 300-600 r/min, the ball milling time is 20-50 h, stopping the machine for 30min for every 5h, performing heat dissipation for every 10h, scraping off the raw materials adhered to the grinding balls and the inner wall of the tank, uniformly mixing, and continuing ball milling to prepare fine CoCrNiCuMn powder with the particle size of 150 nm;
the ball milling process in the step S2 is as follows: in a glove box filled with argon, Ti powder and CH4N2Mixing O, putting into a WC hard alloy ball milling tank, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 200-500 r/min, the ball milling time is 30-60 h, and stopping the machine for 30min every 10h to dissipate heat to obtain TiNx powder with the particle size of 150nm or less;
the ball milling process in the step S3 is as follows: the method comprises the following steps of putting TiC powder into a WC hard alloy ball milling tank in a glove box filled with argon, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 250-400 r/min, ball milling is carried out for 10-40 h, and the ball milling tank is stopped for 10min every 5h to carry out heat dissipation to obtain the fine TiC powder with the particle size of 150 nm;
the ball milling process in the step S4 is as follows: putting WC powder into a WC hard alloy ball milling tank in a glove box filled with argon, wherein the mass ratio of balls to materials is 10: 1-20: 1, the rotating speed is 250-400 r/min, the ball milling time is 10-40 h, stopping the machine for 10min every 5h to dissipate heat, and preparing fine WC powder with the particle size of 150 nm;
the ball milling process in the step S5 is as follows: in a glove box filled with argon, 5-20 wt.% of 150nm fine CoCrNiCuMn powder, 20-50 wt.% of 150nm fine TiNx powder and 2-10 wt.% of 150nm fine WC powder are weighed, the powder and the 150nm fine TiC powder are added into the 150nm fine TiC powder in a WC hard alloy ball milling tank, the mass ratio of balls to materials is 6: 1-10: 1, the rotating speed is 200-350 r/min, the ball milling time is 1.5-5 h, and the glove box is shut down for 10min every 1h to dissipate heat, so that the mixture is prepared.
Further, the ball milling processes of the steps S1, S2, S3, S4 and S5 all adopt WC cemented carbide balls with three outer diameters of 8mm, 5mm and 2mm respectively, and the mass ratio of the three WC cemented carbide balls is 3:1: 1.
Further, the prepressing process comprises the following steps: the prepressing pressure is 10-400 MPa, and the prepressing time is 10-120 s.
Further, the vacuum hot-pressing sintering process comprises the following steps:
and (3) applying pressure to the sample to 40-50 MPa, keeping the vacuum degree at 40Pa, raising the sintering temperature to 1200-1800 ℃ at the temperature rise rate of 10-30 ℃/min, then preserving the heat for 20-90 min, and finally cooling and releasing the pressure to obtain the CoCrNiCuMn-TiN-TiC-WC composite material.
Further, in the process of raising the sintering temperature to 1200-1800 ℃ at a temperature raising rate of 10-30 ℃/min: heating from room temperature to 1000 ℃ at a heating rate of 10-30 ℃/min, and preserving heat at 1000 ℃ for 20 min; then raising the temperature from 1000 ℃ to 1200-1800 ℃ at a temperature raising rate of 10-30 ℃/min;
further, after the temperature reduction and pressure relief, carrying out surface grinding and deburring treatment on a blank obtained by the temperature reduction and pressure relief to obtain the CoCrNiCuMn-TiN-TiC-WC composite material.
The raw materials for preparing TiNx and the mass ratios thereof in all the following examples are shown in Table 1:
TABLE 1 preparation of TiNxThe raw materials and the mass ratio thereof
The raw materials for preparing CoCrNiCuMn and the mass ratios thereof in all the following examples are shown in Table 2:
table 2 raw materials for preparing CoCrNiCuMn and mass ratio thereof
The ball mill model adopted by the ball milling is QM-3SP4 model (China).
The hot-pressing sintering adopts a hot-pressing sintering instrument, and the model number of the hot-pressing sintering instrument is ZRY-120 (China).
The detection equipment provided by the invention is an instrument used by a conventional detection means in a college laboratory, such as an X-ray diffractometer, a sclerometer, a scanning electron microscope and the like.