CN113462944A - Boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder, cermet and preparation method - Google Patents
Boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder, cermet and preparation method Download PDFInfo
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- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 124
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 115
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 89
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 89
- 229910020630 Co Ni Inorganic materials 0.000 title claims abstract description 88
- 229910002440 Co–Ni Inorganic materials 0.000 title claims abstract description 88
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 88
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 88
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 88
- 239000000843 powder Substances 0.000 title claims abstract description 82
- 239000011195 cermet Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011812 mixed powder Substances 0.000 claims abstract description 44
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 33
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006229 carbon black Substances 0.000 claims abstract description 22
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 17
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- 239000006104 solid solution Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 238000002490 spark plasma sintering Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 241000872198 Serjania polyphylla Species 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005452 bending Methods 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000000280 densification Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
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- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 97
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
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- 239000002052 molecular layer Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910000997 High-speed steel Inorganic materials 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910000601 superalloy Inorganic materials 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—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
- C22C29/04—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 carbonitrides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
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Abstract
The invention provides boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder, cermet and a preparation method thereof, wherein the preparation method comprises the following steps: h is to be3BO3、TiO2、WO3、MoO3、Nb2O5、Ta2O5And carbon black to obtain a first mixed powder. Then adding Co into the first mixed powder3O4And NiO, and ball milling to obtain a second mixed powder. And carrying out carbothermal reduction nitridation reaction on the second mixed powder to obtain boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder. By using a deviceSintering boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder by an electric plasma sintering technology to obtain the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet. In the invention, H is added into the raw materials3BO3Powder which can play a role in microalloying Ni and Co binding phases and react with carbon and nitrogen to play a role in strengthening and toughening second phase particles. In addition, boride has better wettability with Co and Ni, and is beneficial to sintering densification. The invention improves the components and the preparation process of the Ti (C, N) -based cermet, thereby preparing the Ti (C, N) -based cermet with high hardness and high bending strength.
Description
Technical Field
The invention relates to the technical field of powder metallurgy, in particular to boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder, metal ceramic and a preparation method thereof.
Background
Cemented carbide is known as "teeth in modern industry" and is widely used in the fields of aerospace, aviation, automobiles, high-speed trains, shipbuilding, oil drilling, mining tools, military industry and the like. With the development of modern manufacturing industry, the dosage of difficult-to-machine materials with high hardness, serious work hardening tendency and low heat conductivity coefficient is increased day by day, so that the working environment of the cutter is more complex, and the cutter material is required to have comprehensive properties of high hardness, high strength, high toughness, high wear resistance and the like. Titanium carbonitride (Ti (C, N)) based cermets were developed in the early 70 th 20 th century, and cutting tools were made with Ti (C, N) as the major hard phase and nickel and cobalt as the major binder phase. It has obvious advantages compared with the WC-based hard alloy which is commonly used in the current manufacturing industry. Firstly, it has the advantages of high hardness (33GPa, the hardness of the traditional hard alloy is less than or equal to 24GPa), higher specific rigidity, red hardness, wear resistance, crater wear resistance, high-temperature chemical stability, lower friction coefficient and the like, and is particularly suitable for semi-finishing and finishing of high-speed steel and cast iron. Secondly, it contains no or few scarce strategic resources W and Co, and the production cost can be reduced by about 45-65%. It is reported that in developed countries, Ti (C, N) -based cermet is used as a tool material in a share of about 1/5 to 1/4 in total tool materials, and has reached 30% in japan, and the future demand thereof will account for 50% of the total indexable insert amount. Therefore, Ti (C, N) -based metal ceramics become an ideal substitute material of WC-based hard alloy, and have very wide application prospects.
However, compared with WC-based hard alloy, Ti (C, N) -based cermet has high hardness and high wear resistance, but has low strength and toughness, and is difficult to meet the performance requirements of modern manufacturing industry on cutter materials, thereby greatly limiting the application of the Ti (C, N) -based cermet. At present, the existing approach to solve the problem of insufficient toughness of Ti (C, N) -based cermet is to prepare a gradient Ti (C, N) -based coating material on the surface of a metal substrate (such as cemented carbide or high-speed steel) with low hardness and good toughness by using a physical or chemical vapor deposition (PVD or CVD) technique. The Ti (C, N) coating cutter prepared by the method combines the high strength and the high toughness of the metal matrix with the high hardness and the wear resistance of the Ti (C, N) coating, thereby having better cutting performance. However, Ti (C, N) -coated tools suffer from two distinct inherent disadvantages compared to Ti (C, N) -based cermet tools: firstly, because of the difference between the components, the structure and the thermal expansion coefficient between the Ti (C, N) coating and the substrate, cracks are easy to generate on the surface of the coating and are easy to diffuse into the coating, so that the failure of the coated cutting tool is caused. Secondly, in order to reduce the internal stress of the cutting edge of the coated tool, the cutting edge needs to be passivated before coating, so that the Ti (C, N) coated tool is not suitable for finish machining. Therefore, the Ti (C, N) -coated cutting tool cannot replace the Ti (C, N) -based metal ceramic cutting tool in the aspects of machining precision, machining efficiency, service life, application range and the like.
Disclosure of Invention
The invention aims to provide boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder which is superfine solid solution powder and has higher hardness and bending strength.
Another object of the present invention is to provide a method for preparing boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder by adding H to the raw materials3BO3And the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder can be prepared by adopting a carbothermic reduction nitridation process, is simple to operate and controllable in process, and is suitable for industrial large-scale production.
It is a third object of the present invention to provide a boron doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet having high strength, hardness and bending strength.
The fourth purpose of the invention is to provide a preparation method of boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni metal ceramic, wherein boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder is sintered by adopting a spark plasma sintering process to prepare the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni metal ceramic, and the preparation method is simple and easy to operate, has easily controlled parameters, and is suitable for industrial large-scale production.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a preparation method of boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder, which comprises the following steps:
s1, mixing H3BO3、TiO2、WO3、MoO3、Nb2O5、Ta2O5Mixing the carbon black with the mixed powder to obtain first mixed powder;
s2, adding Co into the first mixed powder3O4And NiO, and performing ball milling for 3.5-4.5 h to obtain second mixed powder;
and S3, carrying out carbothermic reduction nitridation reaction on the second mixed powder to obtain boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder.
The invention provides boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder which is prepared by the preparation method and is superfine solid solution powder.
The invention provides a preparation method of boron-doped superfine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet, which comprises the following steps: and placing the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder in a graphite die, and sintering by using discharge plasma to obtain the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet.
The invention also provides boron-doped superfine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet prepared by the preparation method.
The boron-doped superfine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder, the metal ceramic and the preparation method have the beneficial effects that:
1. the invention relates to a method for preparing a compound H3BO3Powder with TiO2、WO3、MoO3、Nb2O5、Ta2O5、NiO、 Co3O4Carbon black powder, NiO powder and Co3O4The powders are mixed to be used as raw materials, then boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni superfine solid solution powder is synthesized by using a carbothermic reduction nitridation reaction, and the superfine solid solution powder is subjected to discharge plasma sintering, so that the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni metal ceramic is obtained. The invention improves the components and the preparation process of the Ti (C, N) -based cermet to improve the hardness and the bending strength of the material, thereby preparing the Ti (C, N) -based cermet with high hardness and high toughness.
2. In the invention, H is added into the raw materials3BO3On one hand, the B element in the powder has the microalloying effect of improving the grain boundary strength and the plasticity in the Ni-based and Co-based superalloys, so the addition of the B element can play a microalloying role in Ni and Co binding phases and has a positive effect on the mechanical properties of the material. On the other hand, addition of an appropriate excess amount of B element to the raw material not only purifies the grain boundary, but also reacts with excess free carbon and nitrogen in situ to generate BC or BN, thereby exhibiting the toughening effect of the second phase particles. In addition, boride has better wettability with Co and Ni, namely, the doping of boron does not reduce the wettability between a hard phase and a bonding phase in the Ti (C, N) -based cermet, and is beneficial to sintering densification.
3. The invention adopts a carbothermic reduction nitridation method to synthesize boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni superfine solid solution powder, thereby realizing the uniform dispersion of the superfine solid solution powder and Ni and Co binder phase powder on the molecular layer. Then sintering the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni superfine solid solution powder by adopting a spark plasma sintering technology, and effectively solving the problems of low sintering density, easy aggregation and growth of crystal grains and the like so as to obtain the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni metal ceramic.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an SEM image of boron doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder of an example of the present invention.
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. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder, the cermet, and the preparation method according to the embodiments of the present invention will be described in detail below.
The preparation method of boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder provided by the embodiment of the invention comprises the following steps:
s1, mixing H3BO3、TiO2、WO3、MoO3、Nb2O5、Ta2O5And carbon black to obtain a first mixed powder. The addition of a proper excess of B element to the raw material not only purifies the grain boundary, but also reacts with excess free carbon and nitrogen in situ to form BC or BN, thereby strengthening and toughening the second phase particles.
Further, in a preferred embodiment of the present invention, the TiO is2The carbon black, theWO3The MoO3、Nb2O5And Ta2O5The weight ratio of (A) to (B) is 10-15: 4-8: 2-4: 1-2: 0.8-1.2: 1.
Further, in a preferred embodiment of the present invention, in the first mixed powder, the H is3BO3The weight percentage of the component (A) is 0.1-3%.
S2, adding Co into the first mixed powder3O4And NiO, and performing ball milling for 3.5-4.5 h to obtain second mixed powder.
And S3, carrying out carbothermic reduction nitridation reaction on the second mixed powder to obtain boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder. NiO and Co are added into the raw materials3O4The boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni superfine solid solution powder can be synthesized by simultaneously carrying out carbothermic reduction nitridation reaction on the raw material powder, so that the uniform dispersion of the solid solution powder and Ni and Co binder phase powder on the molecular layer is realized. On the other hand, the B element has the microalloying effect of improving the grain boundary strength and the plasticity in the Ni-based and Co-based superalloys, so the addition of the B element can play a microalloying role in Ni and Co binder phases and has a positive influence on the mechanical properties of the material. In addition, boride has better wettability with Co and Ni, namely, the doping of boron does not reduce the wettability between a hard phase and a bonding phase in the Ti (C, N) -based cermet, and is beneficial to sintering densification.
Further, in a preferred embodiment of the present invention, in the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder, the weight percentage of Co element is 7-8%, and the weight percentage of Ni element is 7-8%. Preferably, the weight percentage of the Co element is 7.5%, and the weight percentage of the Ni element is 7.5%.
Further, in a preferred embodiment of the present invention, the temperature of the carbothermic reduction nitridation reaction is 1300-1800 ℃, the reaction time is 1-3 h, and the nitrogen partial pressure of the reaction is 1-3 kPa.
The embodiment of the invention also provides boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder which is prepared according to the preparation method. The boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder is superfine solid solution powder, and can realize uniform dispersion with Ni and Co binder phase powder on a molecular layer.
The invention also provides a preparation method of the boron-doped superfine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet, which comprises the following steps: and (3) placing the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder in a graphite die, and sintering by using discharge plasma to obtain the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet. The spark plasma sintering has the characteristics of high heating efficiency, high heating rate, strong self-purification effect, low sintering temperature, short time and the like, and has better effect when being applied to the preparation of ultrafine-grained Ti (C, N) -based cermet.
Further, in a preferred embodiment of the present invention, the step of spark plasma sintering comprises: heating to 1200-1600 ℃ in the atmosphere, and keeping the temperature for 5-20 min under the pressure of 10-80 MPa, wherein the atmosphere is vacuum, nitrogen or argon.
The invention utilizes a carbothermic reduction nitridation method to synthesize boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni superfine solid solution powder. Then sintering the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder by adopting a spark plasma sintering process to prepare the high-strength, high-hardness and high-toughness ultrafine grain (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni ceramic.
The invention also provides a boron-doped superfine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet prepared according to the preparation method.
Further, in the preferred embodiment of the present invention, the compactness of the boron-doped ultra-fine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet reaches more than 95%, and both the grain size and the hard phase size are less than 500 nm.
In conclusion, the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder is superfine solid solution powder. The superfine solid solution powder is subjected to spark plasma sintering to obtain boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet. The boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet can improve the hardness and the bending strength of the Ti (C, N) -based cermet by comprehensively exerting the performance advantages of strengthening and toughening measures such as grain refinement, solutionizing, second-phase and binder-phase microalloying and the like at the same time.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The boron-doped ultrafine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder and the cermet provided by the embodiment are prepared according to the following steps:
s1, mixing H3BO3、TiO2、WO3、MoO3、Nb2O5、Ta2O5And carbon black to obtain a first mixed powder. Wherein, TiO2Carbon black and WO3、MoO3、Nb2O5、Ta2O5The weight ratio of carbon black is 12.5:6.25:3:1.25:1: 1. In the first mixed powder, H3BO3Is 3% by weight.
S2, adding Co into the first mixed powder3O4And NiO, and ball milling for 4h to obtain a second mixed powder.
S3, heating the second mixed powder to 1800 ℃ under the nitrogen partial pressure of 3kPa, and reacting for 3h to obtain boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder. Wherein, in the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder, the weight percentage of Co element is 7.5 percent, and the weight percentage of Ni element is 7.5 percent.
S4, placing boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder in a graphite mold, heating to 1600 ℃ under vacuum, and keeping the temperature for 5min under the pressure of 80MPa to obtain the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet.
The boron-doped ultra-fine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder prepared in this example was measured for hardness on a small-load Vickers hardness tester and bending strength on an electronic universal material tester, respectively, and had a hardness of 93.5HRA and a bending strength of 1730 MPa.
Example 2
This example provides a boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder and cermet, which is prepared according to the following steps:
s1, mixing H3BO3、TiO2、WO3、MoO3、Nb2O5、Ta2O5And carbon black to obtain a first mixed powder. Wherein, TiO2Carbon black and WO3、MoO3、Nb2O5、Ta2O5The weight ratio of carbon black is 12.5:6.25:3:1.25:1: 1. In the first mixed powder, H3BO3Is 0.1% by weight.
S2, adding Co into the first mixed powder3O4And NiO, and ball milling for 4h to obtain a second mixed powder.
S3, heating the second mixed powder to 1800 ℃ under the nitrogen partial pressure of 3kPa, and reacting for 3h to obtain boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder. Wherein, in the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder, the weight percentage of Co element is 7.5 percent, and the weight percentage of Ni element is 7.5 percent.
S4, placing boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder in a graphite mold, heating to 1600 ℃ under vacuum, and keeping the temperature for 5min under the pressure of 80MPa to obtain the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet.
The boron-doped ultra-fine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder prepared in this example was measured for hardness on a small-load Vickers hardness tester and bending strength on an electronic universal material tester, respectively, and had a hardness of 92.4HRA and a bending strength of 1708 MPa.
Example 3
The boron-doped ultrafine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder and the cermet provided by the embodiment are prepared according to the following steps:
s1, mixing H3BO3、TiO2、WO3、MoO3、Nb2O5、Ta2O5And carbon black to obtain a first mixed powder. Wherein, TiO2Carbon black and WO3、MoO3、Nb2O5、Ta2O5The weight ratio of carbon black is 12.5:6.25:3:1.25:1: 1. In the first mixed powder, H3BO3Is 3% by weight.
S2, adding into the first mixed powderCo3O4And NiO, and ball milling for 4h to obtain a second mixed powder.
S3, heating the second mixed powder to 1800 ℃ under the nitrogen partial pressure of 3kPa, and reacting for 3h to obtain boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder. Wherein, in the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder, the weight percentage of Co element is 7.5 percent, and the weight percentage of Ni element is 7.5 percent.
S4, placing boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder in a graphite mold, heating to 1200 ℃ in a nitrogen atmosphere, and keeping the temperature for 20min under the pressure of 80MPa to obtain the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet.
The boron-doped ultra-fine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder prepared in this example was measured for hardness on a small-load Vickers hardness tester and bending strength on an electronic universal material tester, respectively, and had a hardness of 92.1HRA and a bending strength of 1711 MPa.
Example 4
The boron-doped ultrafine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder and the cermet provided by the embodiment are prepared according to the following steps:
s1, mixing H3BO3、TiO2、WO3、MoO3、Nb2O5、Ta2O5And carbon black to obtain a first mixed powder. Wherein, TiO2Carbon black and WO3、MoO3、Nb2O5、Ta2O5The weight ratio of carbon black is 12.5:6.25:3:1.25:1: 1. In the first mixed powder, H3BO3Is 3% by weight.
S2, adding Co into the first mixed powder3O4And NiO, and ball milling for 4h to obtain a second mixed powder.
S3, heating the second mixed powder to 1300 ℃ under the nitrogen partial pressure of 3kPa, and reacting for 3h to obtain boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder. Wherein, in the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder, the weight percentage of Co element is 7.5 percent, and the weight percentage of Ni element is 7.5 percent.
S4, placing boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder in a graphite mold, heating to 1600 ℃ under vacuum, and keeping the temperature for 20min under the pressure of 10MPa to obtain the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet.
The boron-doped ultra-fine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder prepared in this example was measured for hardness on a small-load Vickers hardness tester and bending strength on an electronic universal material tester, respectively, and had a hardness of 93HRA and a bending strength of 1722 MPa.
Example 5
The boron-doped ultrafine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder and the cermet provided by the embodiment are prepared according to the following steps:
s1, mixing H3BO3、TiO2、WO3、MoO3、Nb2O5、Ta2O5And carbon black to obtain a first mixed powder. Wherein, TiO2Carbon black and WO3、MoO3、Nb2O5、Ta2O5The weight ratio of carbon black is 12.5:6.25:3:1.25:1: 1. In the first mixed powder, H3BO3The weight percentage of (B) is 2%.
S2, adding Co into the first mixed powder3O4And NiO, and ball milling for 4.5h to obtain a second mixed powder.
S3, heating the second mixed powder to 1800 ℃ under the nitrogen partial pressure of 3kPa, and reacting for 3h to obtain boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder. Wherein, in the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder, the weight percentage of Co element is 7.5 percent, and the weight percentage of Ni element is 7.5 percent.
S4, placing boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder in a graphite mold, heating to 1500 ℃ in vacuum, and keeping the temperature for 15min under the pressure of 60MPa to obtain the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet.
The boron-doped ultra-fine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder prepared in this example was measured for hardness on a small-load Vickers hardness tester and bending strength on an electronic universal material tester, respectively, and had a hardness of 92.8HRA and a bending strength of 1725 MPa.
Test example 1
Boron-doped ultra-fine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder was measured by scanning electron microscopy. FIG. 1 shows an SEM image of boron-doped ultra-fine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder provided in example 1. As can be seen from FIG. 1, the boron-doped ultra-fine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder has a fine particle size, is uniformly dispersed, and has an average size of 130 nm.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the 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.
Claims (10)
1. A preparation method of boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder is characterized by comprising the following steps:
s1, mixing H3BO3、TiO2、WO3、MoO3、Nb2O5、Ta2O5Mixing the carbon black with the mixed powder to obtain first mixed powder;
s2, adding Co into the first mixed powder3O4And NiO, and performing ball milling for 3.5-4.5 h to obtain second mixed powder;
and S3, carrying out carbothermic reduction nitridation reaction on the second mixed powder to obtain boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder.
2. The method according to claim 1, wherein the TiO is added in step S12The carbon black and the WO3The MoO3The Nb2O5And said Ta2O5The weight ratio of (A) to (B) is 10-15: 4-8: 2-4: 1-2: 0.8-1.2: 1.
3. The method of claim 1, wherein the method comprisesCharacterized in that, in the first mixed powder, the H3BO3The weight percentage of the component (A) is 0.1-3%.
4. The method according to claim 1, wherein the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder contains Co in an amount of 7-8 wt% and Ni in an amount of 7-8 wt%.
5. The method according to claim 1, wherein in step S3, the carbothermic nitridation reaction is performed at 1300-1800 ℃ for 1-3 h with a nitrogen partial pressure of 1-3 kPa.
6. The boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder is prepared by the preparation method according to any one of claims 1 to 5, and is an ultrafine solid solution powder.
7. A preparation method of boron-doped superfine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet is characterized by comprising the following steps: placing the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni powder of claim 6 in a graphite mold, and sintering by spark plasma to obtain the boron-doped (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet.
8. The method of claim 7, wherein the step of spark plasma sintering comprises: heating to 1200-1600 ℃ in the atmosphere, and keeping the temperature for 5-20 min under the pressure of 10-80 MPa, wherein the atmosphere is vacuum, nitrogen or argon.
9. A boron-doped ultra-fine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet prepared by the process according to any one of claims 7 to 8.
10. The boron-doped ultrafine (Ti, W, Mo, Nb, Ta) (C, N) -Co-Ni cermet according to claim 9, characterized in that it has a compactness of more than 95% and a grain size and hard phase size of less than 500 nm.
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