CN119320890A - Ti (titanium)5Si3/ZrB2Composite material and hot-pressed sintering method thereof - Google Patents
Ti (titanium)5Si3/ZrB2Composite material and hot-pressed sintering method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 278
- 238000005245 sintering Methods 0.000 title claims abstract description 272
- 229910052719 titanium Inorganic materials 0.000 title claims description 9
- 239000010936 titanium Substances 0.000 title description 310
- 239000000463 material Substances 0.000 title description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title 1
- 239000000843 powder Substances 0.000 claims abstract description 346
- 230000008569 process Effects 0.000 claims abstract description 228
- 239000002131 composite material Substances 0.000 claims abstract description 215
- 229910007948 ZrB2 Inorganic materials 0.000 claims abstract description 195
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 claims abstract description 195
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 144
- 238000007731 hot pressing Methods 0.000 claims abstract description 74
- 238000002156 mixing Methods 0.000 claims abstract description 66
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 61
- 229910021363 Ti-Si intermetallic compound Inorganic materials 0.000 claims abstract description 52
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005551 mechanical alloying Methods 0.000 claims abstract description 25
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims description 179
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 85
- 239000005011 phenolic resin Substances 0.000 claims description 85
- 229920001568 phenolic resin Polymers 0.000 claims description 85
- 238000010438 heat treatment Methods 0.000 claims description 84
- 239000011812 mixed powder Substances 0.000 claims description 67
- 238000000227 grinding Methods 0.000 claims description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 56
- 229910002804 graphite Inorganic materials 0.000 claims description 54
- 239000010439 graphite Substances 0.000 claims description 54
- 239000002002 slurry Substances 0.000 claims description 54
- 238000011049 filling Methods 0.000 claims description 48
- 239000011521 glass Substances 0.000 claims description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 45
- 238000001035 drying Methods 0.000 claims description 37
- 239000004816 latex Substances 0.000 claims description 32
- 229920000126 latex Polymers 0.000 claims description 32
- 239000011230 binding agent Substances 0.000 claims description 31
- 229910000831 Steel Inorganic materials 0.000 claims description 29
- 238000003825 pressing Methods 0.000 claims description 29
- 239000010959 steel Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 15
- 238000000462 isostatic pressing Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 238000011068 loading method Methods 0.000 claims description 11
- 238000009694 cold isostatic pressing Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 238000007669 thermal treatment Methods 0.000 claims description 9
- 239000010720 hydraulic oil Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 41
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 229910009871 Ti5Si3 Inorganic materials 0.000 abstract 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 46
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- 239000007791 liquid phase Substances 0.000 description 20
- 238000002844 melting Methods 0.000 description 18
- 230000008018 melting Effects 0.000 description 18
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- 230000003647 oxidation Effects 0.000 description 11
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- 238000002490 spark plasma sintering Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 229910010293 ceramic material Inorganic materials 0.000 description 8
- 238000000280 densification Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
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- 238000001764 infiltration Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910001338 liquidmetal Inorganic materials 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000005275 alloying Methods 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000004663 powder metallurgy Methods 0.000 description 5
- 239000011153 ceramic matrix composite Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910010069 TiCo Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
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- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 229910052804 chromium Inorganic materials 0.000 description 2
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- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001272 pressureless sintering Methods 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- RCKBMGHMPOIFND-UHFFFAOYSA-N sulfanylidene(sulfanylidenegallanylsulfanyl)gallane Chemical compound S=[Ga]S[Ga]=S RCKBMGHMPOIFND-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000011215 ultra-high-temperature ceramic Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- 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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- 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
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
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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
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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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
- C22C1/045—Alloys based on refractory metals
- C22C1/0458—Alloys based on titanium, zirconium or hafnium
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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
- C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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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
- C22C29/14—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on borides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0005—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with at least one oxide and at least one of carbides, nitrides, borides or silicides as the main non-metallic constituents
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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Abstract
一种Ti5Si3/ZrB2复合材料，包括有Ti5Si3金属间化合物粉末，以Ti5Si3金属间化合物为增强增韧相；ZrB2粉末，以ZrB2为基体；加入Al2O3粉末和Y2O3粉末作为烧结助剂；加入细硅粉末作为烧结助剂；其热压烧结方法包括以下步骤：采用机械合金化工艺制备Ti‑Si金属间化合物粉末；将步骤一制备的Ti‑Si金属间化合物粉末通过热处理制备出Ti5Si3粉末，并将Ti5Si3粉末和ZrB2粉末相混合；制备出Ti5Si3/ZrB2复合粉末；通过压力成型工艺制成致密的Ti5Si3/ZrB2复合粉末预制坯体；通过热压烧结工艺制备出Ti5Si3/ZrB2复合材料；热压烧结方法具有制备效率较高，制备工艺简单，可实现快速烧结制造Ti5Si3/ZrB2复合材料制品，制备的Ti5Si3/ZrB2复合材料具有较高的致密度和较高的力学性能。
A Ti5Si3 / ZrB2 composite material comprises Ti5Si3 intermetallic compound powder, with Ti5Si3 intermetallic compound as a reinforcing and toughening phase; ZrB2 powder, with ZrB2 as a matrix; Al2O3 powder and Y2O3 powder are added as sintering aids; and fine silicon powder is added as a sintering aid. The hot pressing sintering method comprises the following steps: preparing Ti -Si intermetallic compound powder by mechanical alloying process; preparing Ti5Si3 powder by heat treating the Ti - Si intermetallic compound powder prepared in step 1, and mixing the Ti5Si3 powder and ZrB2 powder to prepare Ti5Si3 / ZrB2 composite powder; forming a dense Ti5Si3 / ZrB2 composite powder preform by pressure forming process; preparing Ti5Si3 / ZrB2 composite powder by hot pressing sintering process . 2 composite material; the hot pressing sintering method has high preparation efficiency and simple preparation process, and can realize rapid sintering to manufacture Ti 5 Si 3 /ZrB 2 composite material products. The prepared Ti 5 Si 3 /ZrB 2 composite material has high density and high mechanical properties.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a Ti 5Si3/ZrB2 composite material and a hot-pressed sintering method thereof.
Background
The titanium silicon (Ti-Si) intermetallic compound mainly includes Ti 5Si3 intermetallic compound. The Ti 5Si3 intermetallic compound has high melting point (2130 ℃) and low density (4.65 g/cm 3), and excellent high-temperature properties such as high-temperature hardness, good high-temperature stability and oxidation resistance, and can be hopefully used for high-temperature structural materials with the temperature of more than 1300 ℃. The melting point of the Ti 5Si3 intermetallic compound is similar to or even higher than that of the high-temperature structural ceramics, but the density is far lower than that of some high-temperature structural ceramics and high-temperature alloys, which are equivalent to that of titanium alloys, and the Ti 5Si3 intermetallic compound has the potential of being used at high temperature. In addition, the Ti 5Si3 intermetallic compound is hopeful to be used for an electrical connection structure and a diffusion barrier layer because of low electric resistance and thermal resistance. Ti 5Si3 is an intermetallic compound with excellent properties, which are mainly characterized by high hardness, good wear resistance and a certain fracture toughness. The Ti 5Si3 intermetallic compound has a high hardness, which makes it excellent in terms of wear resistance. The TiCo/Ti 5Si3 biphase intermetallic compound alloy prepared by the laser smelting technology takes the metal silicide Ti 5Si3 as the wear-resistant reinforcing phase, and has excellent room-temperature dry sliding wear resistance. With the increase of TiCo content, the volume fraction of the primary phase Ti 5Si3 and the microhardness of the alloy are reduced, but the toughness and the wear resistance of the alloy are obviously improved. This indicates that the high hardness of Ti 5Si3 and the high toughness of TiCo combine to give the alloy excellent wear resistance. Ti 5Si3 has wide application in various fields due to its excellent properties. Ti 5Si3 exhibits a wide range of application potential in a number of fields with its high hardness, good wear resistance and by optimization of alloying principle behaviour. Ti 5Si3 is an intermetallic compound with high melting point and high specific strength, and its crystal structure belongs to a complex hexagonal structure, and has potential for use at high temperature (1600 ℃). Microstructure analysis of Ti 5Si3 shows that it has excellent physical properties such as high melting point and low density, its melting point is comparable to that of ceramics, while density is lower than that of ceramics and superalloys, close to that of titanium alloys, which makes it uniquely advantageous in certain applications. however, ti 5Si3 has larger room temperature brittleness, which limits the application range to a certain extent, but can improve the performance and widen the application field by means of alloying and the like. Ti 5Si3 has a melting point of 2130 ℃ and a density of 4.65g/cm 3, and has excellent stability under high-temperature environment, light weight and potential application value in the fields of aviation, aerospace and the like. Although Ti 5Si3 performs well at high temperatures, it is still brittle at room temperature, which limits its use in aerospace applications. The brittleness at room temperature can be improved to a certain extent by alloying, heat treatment and other methods, and the toughness and strength at room temperature can be improved. The performance of Ti 5Si3 can be effectively improved by adding a proper amount of alloying elements such as Nb and Cr, and the thermal expansion anisotropy of Ti 5Si3 can be weakened by a proper amount of Nb and Cr, so that the toughness and the hardness of the alloy are improved, and the application range of the alloy is widened. Ti 5Si3 is used as a high-performance intermetallic compound, and through proper alloying and heat treatment, the performance of the intermetallic compound under different temperatures and environments can be remarkably improved, and a new material solution is provided for various industrial and scientific fields.
Zirconium diboride (ZrB 2) is an ultra-high temperature ceramic material that is valued for its outstanding physical and chemical properties. The molecular formula of zirconium diboride is ZrB 2, each zirconium atom is combined with two boron atoms to form a dense hexagonal system structure, and the material has high stability and excellent physical properties. Zirconium diboride has a high melting point (about 3246 ℃) and is structurally stable in extremely high temperature environments, exhibiting excellent corrosion resistance, low oxidation rates and good electrical conductivity. In addition, the thermal conductivity and thermal shock stability of zirconium diboride are critical to the fabrication of the target. Zirconium diboride has a high density of about 6.09g/cm 3 and a hardness of about 25GPa, which properties make it excellent in wear and scratch resistance, suitable for industrial cutting tools and protective coating applications. Although zirconium diboride behaves as an electrical insulator at room temperature, its electrical conductivity increases at high temperatures, exhibiting semiconductor behavior, which provides potential for its use in high temperature electronic devices. It also has a relatively high thermal conductivity, a good level in ceramic materials, suitable for use in thermal management systems such as heat sinks and heat exchangers. Zirconium diboride has a low coefficient of thermal expansion, which means that its volume and shape change is small when temperature changes, providing a reliable guarantee especially in applications where dimensional stability is a high requirement. In addition, zirconium diboride may exhibit semiconductor behavior under certain conditions, providing the potential for developing new high temperature semiconductor devices. Zirconium diboride plays an indispensable role in numerous high-tech fields due to its unique physical, chemical, mechanical, thermal and electrical properties, and has applications across fields from aerospace to semiconductors. Zirconium diboride ceramic has the characteristics of high melting point and hardness, good electric conductivity and thermal conductivity, strong neutron control capability and the like, and is valued and applied in the fields of high-temperature structural ceramic materials, composite materials, refractory materials, electrode materials, nuclear control materials and the like. Such as turbine blades in the aerospace industry, magnetohydrodynamic generator motors, and the like. In addition, it has better electrical conductivity than many ceramic materials, and can be used to produce parts of complex shape by wire cutting techniques. ZrB 2 ceramic is excellent special refractory material and may be used as protecting sleeve for thermocouple, casting mold, crucible for metallurgical metal, etc. ZrB 2 has very low resistivity, and the conducting mechanism is electron conduction, so that the ZrB 2 is suitable for electric shock materials and electrode materials, and can be applied to electrodes of metal thermocouples and high-temperature heating elements. Because the hardness of ZrB 2 is extremely high, the material is a good wear-resistant material and has better application in cutters and cutting tools. ZrB 2 has very good corrosion resistance, and the corrosion resistance and the oxidation resistance of ZrB 2 are deeply researched. Zirconium diboride (ZrB 2) is a high temperature material with a relatively high melting point and hardness. The melting point is 3246 ℃, and is a very stable compound. Zirconium diboride has excellent mechanical properties, high temperature resistance, chemical stability and conductivity, and is widely applied to the fields of aviation, aerospace, energy sources, automobiles, ceramics and the like. Zirconium diboride, although being relatively expensive, has properties far superior to other materials, and is therefore widely used in high-end technical fields.
The Ti 5Si3 intermetallic compound has high strength, high toughness, high melting point, high hardness and good wear resistance, and has corrosion resistance and high-temperature oxidation resistance, and is widely applied to the engineering field. The Ti 5Si3 intermetallic compound has higher mechanical property, and can be used as a reinforcing phase and a toughening phase of a ceramic material to improve the mechanical property and high-temperature oxidation resistance of the ceramic material. Zirconium diboride ceramic materials have high strength and high hardness, good wear resistance, high-temperature oxidation resistance and the like, and are widely applied to the engineering field. However, zirconium diboride ceramics have higher brittleness and lower fracture toughness, so that a reinforcing and toughening phase needs to be added into a ZrB 2 matrix. The compatibility of the Ti 5Si3 intermetallic compound and the ZrB 2 is good, and the Ti 5Si3 intermetallic compound can be added into the ZrB 2 matrix to form the Ti 5Si3/ZrB2 composite material through compounding, so that the mechanical property of the ZrB 2 ceramic material is greatly improved and enhanced. The Ti 5Si3/ZrB2 composite material has the high strength, high toughness, high hardness and high wear resistance of Ti 5Si3 intermetallic compound, and also has the high hardness and high wear resistance of ZrB 2 ceramic. The Ti 5Si3/ZrB2 composite will have excellent properties. The Ti 5Si3/ZrB2 composite material has higher mechanical property, higher hardness and wear resistance, higher high-temperature oxidation resistance, corrosion resistance and the like. The preparation of Ti 5Si3/ZrB2 composite materials has become a major research focus and hotspot. For the preparation process of intermetallic compound/ceramic matrix composite materials, some researchers use a liquid metal infiltration method to prepare intermetallic compound/ceramic matrix composite materials. Since the melting point of the Ti 5Si3 intermetallic compound is high, the melting point of the Ti 5Si3 intermetallic compound is 2130 ℃, and a liquid phase is required to be formed at a high temperature, so that the liquid phase is difficult to be formed. And the Ti 5Si3 intermetallic compound and the ZrB 2 ceramic have the problems of poor wettability and the like, and the Ti 5Si3 intermetallic compound is difficult to permeate into the ZrB 2 ceramic preform, so that the Ti 5Si3/ZrB2 composite material cannot be prepared by adopting a liquid metal infiltration method. Therefore, the Ti 5Si3/ZrB2 composite material can only be prepared by adopting a powder metallurgy process. The powder metallurgy process mainly comprises a normal pressure sintering process, a hot pressing sintering process, a spark plasma sintering process and a hot isostatic pressing sintering process. The normal pressure sintering process, namely the pressureless sintering process, cannot prepare a compact Ti 5Si3/ZrB2 composite material because no pressure is used for sintering, and the finally obtained Ti 5Si3/ZrB2 composite material sintered block with extremely high porosity cannot obtain a compact sintered block, so that the obtained composite material is poor in mechanics and cannot be applied to the engineering field, and therefore, the preparation cannot be carried out by adopting the normal pressure sintering process. Although compact Ti 5Si3/ZrB2 composite materials can be prepared by the spark plasma sintering process, the spark plasma sintering process has very complex preparation process, relatively short sintering time, high sintering cost, very high price of spark plasma sintering equipment and high preparation cost, and can not be prepared by the spark plasma sintering process. The hot isostatic pressing sintering process requires a hot isostatic pressing machine, and the hot isostatic pressing machine has high equipment price, high sintering cost and very complex preparation process, so that the hot isostatic pressing sintering process cannot be adopted for preparation. Therefore, the Ti 5Si3/ZrB2 composite material can be prepared only by adopting a hot press sintering process with relatively low sintering cost. The Ti 5Si3/ZrB2 composite material sintered block with higher density can be prepared by the hot-press sintering process, and the Ti 5Si3/ZrB2 composite material sintered block prepared by the hot-press sintering process has higher mechanical property, higher density, uniform and compact microstructure, excellent wear resistance, excellent corrosion resistance, excellent high-temperature oxidation resistance and the like. Therefore, the preparation of the Ti 5Si3/ZrB2 composite material by adopting the hot-press sintering process is the most suitable sintering process. The hot-press sintering process has the advantages of high sintering speed and high density of sintered products, and can realize mass production. The hot-press sintering process utilizes resistance heating to heat raw material powder in a die, applies axial pressure to the raw material powder in the die, and maintains the temperature and pressure for a certain time to obtain a compact sintered product. In order to realize rapid molding and sintering of the composite material, the invention provides a method for preparing the Ti 5Si3/ZrB2 composite material by adopting a hot pressing sintering process.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a Ti 5Si3/ZrB2 composite material and a hot-pressing sintering method thereof, and overcomes the defects that the operation process of the traditional liquid metal infiltration process is too complex, the preparation cost is higher, the shape and the size of the prepared product are limited and the like. The invention adopts the hot-pressing sintering process, has the characteristics of simplifying the production process, reducing the production cost, simultaneously being capable of preparing a sintering product with a complex shape, and the prepared Ti 5Si3/ZrB2 composite material has higher density and higher mechanical property.
The invention provides a method for preparing Ti 5Si3/ZrB2 composite material blocks by adopting a hot-pressing sintering process. The hot-press sintering process includes loading the prepared Ti 5Si3/ZrB2 composite powder into graphite mold, sintering in hot-press sintering furnace, applying certain axial pressure to the sintered blank under the action of high temperature and high heat, maintaining temperature and pressure for certain time, and sintering to obtain the composite material product. the hot-press sintering process has low cost and simple preparation process, can realize rapid molding and sintering to prepare composite material products, is suitable for industrial production, and is favorable for realizing industrialization. The invention provides a method for preparing the Ti 5Si3/ZrB2 composite material block by adopting a hot-pressing sintering process. Firstly preparing Ti 5Si3 intermetallic compound powder by adopting a mechanical alloying process and a heat treatment process, mixing the Ti 5Si3 intermetallic compound powder with ZrB 2 powder, adding 10 parts by weight of Al 2O3 powder and Y 2O3 powder sintering aid, adding 10 parts by weight of fine silicon powder serving as sintering aid, mixing by a wet ball mill, drying to prepare Ti 5Si3/ZrB2 composite powder, filling the prepared Ti 5Si3/ZrB2 composite powder into a graphite mold, and preparing the Ti 5Si3/ZrB2 composite material block by a hot-press sintering process. the method adopted by the invention has the advantage of rapid molding by using a hot-press sintering process, so that Ti 5Si3 intermetallic compound particles and ZrB 2 particles can be sintered into compact Ti 5Si3/ZrB2 composite material blocks under the action of heating and pressing sintering, and therefore, the Ti 5Si3/ZrB2 composite material blocks are prepared by using the hot-press sintering process.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The Ti 5Si3/ZrB2 composite material comprises the following components in parts by weight:
10-70 parts of Ti 5Si3 intermetallic compound powder, and taking Ti 5Si3 intermetallic compound as a reinforcing and toughening phase;
30-90 parts of ZrB 2 powder, and taking ZrB 2 as a matrix;
10 parts of Al 2O3 powder and Y 2O3 powder as sintering aids;
fine silicon powder as a sintering aid 10 parts.
The Ti 5Si3 intermetallic compound powder is prepared by adopting a mechanical alloying and heat treatment process, the Ti-Si intermetallic compound powder is prepared by adopting a mechanical alloying process ball milling for 80 hours, the prepared Ti-Si intermetallic compound powder is subjected to a heat treatment process, wherein the heat treatment process is carried out at the temperature of 1000-1400 ℃ for 1 hour, the heat treatment process is carried out under the vacuum condition, and the Ti 5Si3 intermetallic compound powder is prepared by the heat treatment process.
The molar ratio of Ti to Si in the Ti 5Si3 intermetallic compound powder is 63:37.
The hot-press sintering method of the Ti 5Si3/ZrB2 composite material comprises the following steps of:
preparing Ti-Si intermetallic compound powder by adopting a mechanical alloying process, wherein the specific method comprises the following steps of:
Filling Ti powder and Si powder into a ball milling tank of a QM-1SP2 planetary ball mill, wherein the ball milling tank adopts a polytetrafluoroethylene ball milling tank, grinding balls adopt agate grinding balls, the mass ratio of the agate grinding balls to mixed powder is 10:1, the molar ratio of the Ti powder to the Si powder is 63:37, the planetary ball mill is started for mechanical ball milling after the four ball milling tanks are fixed, the mechanical ball milling time is 80h, the rotating speed of the ball mill is 400r/min, the dry ball milling is adopted, and an intermittent ball milling mode is adopted, argon is filled into the ball milling tank as a protective gas, so that Ti-Si intermetallic compound powder is prepared, the purity of the Ti powder is 99%, the granularity is 75-100 mu m, and the purity of the Si powder is 99%, and the granularity is 75-100 mu m;
step two, carrying out a heat treatment process on the Ti-Si intermetallic compound powder prepared in the step one, wherein the specific method comprises the following steps:
placing Ti-Si intermetallic compound powder and 10 parts of phenolic resin binder into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, mixing for 24 hours through mechanical ball milling, mixing to prepare slurry through wet ball milling, placing the slurry into a glass beaker, then placing the glass beaker into a drying oven, drying for 24 hours at 100 ℃, placing the mixed powder into a steel mold capable of preparing strip-shaped samples, pressing the steel mold into strip-shaped samples with the size of 50mm multiplied by 5mm multiplied by 6mm under the pressure of 100MPa for 3 minutes by a pressure forming machine, placing the strip-shaped samples into a graphite crucible, placing the graphite crucible into a vacuum sintering furnace, wherein the heat treatment temperature is 1000-1400 ℃ and the heat preservation time is 1 hour, performing heat treatment under the vacuum condition with the vacuum degree of 10 -2 Pa to obtain porous tissue loose Ti 5Si3 intermetallic compound powder strip-shaped samples, taking out the Ti 5Si3 intermetallic compound strips, crushing the Ti 5Si3 intermetallic compound strips, preparing the strip-shaped samples into the strip-shaped samples with the size of 50mm multiplied by 5mm multiplied by 6mm, placing the strip-shaped samples into the graphite crucible, placing the graphite crucible into a vacuum sintering furnace, wherein the graphite crucible is subjected to heat treatment at 1000 ℃ at the temperature of 1000 ℃ and the temperature of 1400 ℃ and the thermal treatment temperature is lower than the thermal treatment temperature, and the phenolic resin is completely decomposed by 34, and the phenolic resin is completely, the phenolic resin powder is not decomposed in the process, and the phenolic resin powder has no residual phenolic resin is completely;
Mixing 10-70 parts of the Ti 5Si3 intermetallic compound powder prepared in the second step with 30-90 parts of ZrB 2 powder to obtain composite powder, adding 3-9 parts of Al 2O3 powder and 1-7 parts of Y 2O3 powder serving as sintering aids in the composite powder, adding 10 parts of fine silicon powder serving as sintering aids, mixing to obtain mixed powder A consisting of Ti 5Si3 powder, zrB 2 powder, al 2O3 powder, Y 2O3 powder and fine silicon powder, carrying out wet ball milling on the mixed powder A by a mechanical ball mill, loading the mixed powder A into a ball milling tank, carrying out mechanical ball milling and mixing for 24 hours by adding 100-400 ml of absolute ethyl alcohol and 30-60 agate balls with the diameter of 10-16 mm into the ball milling tank, preparing slurry, loading the slurry into a glass beaker, and drying for 24 hours at 100 ℃ to prepare Ti 5Si3/ZrB2 composite powder, wherein the mixed powder A is prepared by mixing the Ti 5Si3 intermetallic compound powder in the ball milling tank by 10-70 parts by weight of Ti 5Si3/ZrB2;
Step four, mixing the Ti 5Si3/ZrB2 composite powder prepared in the step three with 10 parts of phenolic resin binder, then filling the mixture into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, carrying out mechanical ball milling and mixing for 24 hours to prepare slurry, filling the slurry into a glass beaker, and then putting the glass beaker into a baking oven to be dried at 100 ℃ for 24 hours to obtain Ti 5Si3/ZrB2 mixed powder B containing the phenolic resin binder; the mixed powder B is filled into a steel mould capable of preparing a wafer sample to be pressed into the wafer sample, the pressing is carried out for 3 minutes by adopting a forming press under the pressure of 100 MPa-200 MPa to prepare the wafer sample with the diameter of 40mm and the height of about 10mm, the wafer sample is filled into latex gloves and wrapped by the latex gloves and is put into a cold isostatic pressing machine, the medium in the cold isostatic pressing machine is hydraulic oil, the pressure of 100 MPa-200 MPa in the cold isostatic pressing machine is maintained for 5 minutes, the sample is taken out after the pressure maintaining time is finished, and a compact Ti 5Si3/ZrB2 composite powder prefabricated blank body is prepared by isostatic pressing of the cold isostatic pressing machine to obtain the wafer sample with the diameter of 40mm and the height of 8mm, and the compactness of the Ti 5Si3/ZrB2 composite powder prefabricated blank body can be obviously improved by a cold isostatic pressing process;
and fifthly, placing the Ti 5Si3/ZrB2 composite powder prefabricated blank prepared in the step four into a graphite mold, and placing the graphite mold into a vacuum hot-pressing sintering furnace for vacuum hot-pressing sintering process, wherein the vacuum hot-pressing sintering process is prepared by the steps of sintering at 1500-1800 ℃, hot-pressing at 35MPa, keeping the temperature for 2 hours, keeping the vacuum degree at 10 -2 Pa and heating at 10-35 ℃ per minute, and cooling along with the furnace after the vacuum hot-pressing sintering is finished to obtain the Ti 5Si3/ZrB2 composite material. The method comprises the steps of obtaining a sintered wafer sample with the diameter of 40mm and the height of 6mm of a Ti 5Si3/ZrB2 composite material through a hot-pressing sintering process, namely a sintered block of the Ti 5Si3/ZrB2 composite material, wherein the weight part of a Ti 5Si3 intermetallic compound in the Ti 5Si3/ZrB2 composite material is 10-70 parts, a small amount of phenolic resin is completely decomposed and volatilized in a high-temperature hot-pressing sintering process, and no phenolic resin remains in the obtained sintered block.
In the first step, the average grain size of the Ti-Si intermetallic compound powder prepared after ball milling for 60 hours by adopting mechanical alloying technology is 10-15 mu m, the grain size of the powder is extremely fine, the grain size of the Ti 5Si3 intermetallic compound powder obtained after the heat treatment technology is still 10-15 mu m, and the Ti 5Si3 intermetallic compound powder with an ordered structure is obtained.
And step three, wherein the granularity of the ZrB 2 powder is 3-5 mu m, and the mass part of the Ti 5Si3 intermetallic compound powder in the Ti 5Si3/ZrB2 composite powder is 10-70 parts.
The beneficial effects of the invention are as follows:
For the preparation process of intermetallic compound/ceramic matrix composite materials, some researchers use a liquid metal infiltration method to prepare intermetallic compound/ceramic matrix composite materials. Since the melting point of the Ti 5Si3 intermetallic compound is high, the melting point of the Ti 5Si3 intermetallic compound is 2130 ℃, and a liquid phase is required to be formed at a high temperature, so that the liquid phase is difficult to be formed. And the Ti 5Si3 intermetallic compound and the ZrB 2 ceramic have the problems of poor wettability and the like, and the Ti 5Si3 intermetallic compound is difficult to permeate into the ZrB 2 ceramic preform, so that the Ti 5Si3/ZrB2 composite material cannot be prepared by adopting a liquid metal infiltration method. Therefore, the Ti 5Si3/ZrB2 composite material can only be prepared by adopting a powder metallurgy process. The traditional liquid metal melting infiltration process method has higher cost, the preparation process is complex, the shape and the size of the prepared product are limited, and the large-scale production and the industrialization are difficult to realize. The Ti 5Si3/ZrB2 composite material can only be prepared by adopting a powder metallurgy process. The powder metallurgy process mainly comprises a normal pressure sintering process, a hot pressing sintering process, a spark plasma sintering process and a hot isostatic pressing sintering process. The normal pressure sintering process, namely the pressureless sintering process, cannot prepare a compact Ti 5Si3/ZrB2 composite material because no pressure is used for sintering, and the finally obtained Ti 5Si3/ZrB2 composite material sintered block with extremely high porosity cannot obtain a compact sintered block, so that the obtained composite material is poor in mechanics and cannot be applied to the engineering field, and therefore, the preparation cannot be carried out by adopting the normal pressure sintering process. Although compact Ti 5Si3/ZrB2 composite materials can be prepared by the spark plasma sintering process, the spark plasma sintering process has very complex preparation process, relatively short sintering time, high sintering cost, very high price of spark plasma sintering equipment and high preparation cost, and can not be prepared by the spark plasma sintering process. The hot isostatic pressing sintering process requires a hot isostatic pressing machine, and the hot isostatic pressing machine has high equipment price, high sintering cost and very complex preparation process, so that the hot isostatic pressing sintering process cannot be adopted for preparation. Therefore, the Ti 5Si3/ZrB2 composite material can be prepared only by adopting a hot press sintering process with relatively low sintering cost. the invention adopts mechanical alloying and heat treatment processes to prepare Ti 5Si3 intermetallic compound powder, mixes the prepared Ti 5Si3 intermetallic compound powder with ZrB 2 powder, adds 10 parts by weight of Al 2O3 powder and Y 2O3 powder sintering aid and 10 parts by weight of fine silicon powder as sintering aid, prepares Ti 5Si3/ZrB2 composite powder by wet ball milling mixing and drying, and prepares Ti 5Si3/ZrB2 composite material block by hot-press sintering process. The hot-press sintering process can realize rapid molding, has low sintering cost and simple preparation process, can manufacture sintered products with complex shapes, is easy for industrial production, and is beneficial to realizing industrialization. The hot-press sintering process is to heat the raw material powder by resistance heating, apply axial pressure to the raw material powder and keep the temperature and pressure for a certain time to realize the molding of the sintered product. Meanwhile, in the sintering process of the Ti 5Si3/ZrB2 composite material, the hot pressing sintering temperature is 1500-1800 ℃, the hot pressing pressure is 35MPa, the heat preservation time is 2 hours, and the Ti 5Si3 alloy particles and the ZrB 2 particles are bonded together to form a compact sintered block. The sintering aid is added with 10 parts by weight of Al 2O3 powder and Y 2O3 powder, and the Al 2O3 powder and the Y 2O3 powder are reacted at high temperature in the sintering process to form a liquid phase Y 3Al5O12, namely YAG phase, so that the liquid phase is formed to promote the densification of the ceramic composite material matrix, the effect of filling pores is achieved, the relative density of the ceramic composite material is improved, and the mechanical property of the ceramic composite material is improved. The effect of adding 10 parts by mass of fine silicon powder sintering auxiliary agent is that the fine silicon powder sintering auxiliary agent forms liquid phase silicon liquid at high temperature in the sintering process, the melting point of silicon powder is 1410 ℃, and the liquid phase silicon liquid is formed at high temperature to promote densification of a ceramic composite material matrix, so that the effect of filling pores is achieved, the relative density of the ceramic composite material is improved, and the mechanical property of the ceramic composite material is improved. The sintered product with higher density and uniform and compact microstructure can be obtained through the hot-press sintering process, and meanwhile, the sintered product also has higher mechanical property. The Ti 5Si3/ZrB2 composite material prepared by the hot-pressed sintering process has higher mechanical property, good wear resistance, high-temperature oxidation resistance and other excellent properties. Therefore, the Ti 5Si3/ZrB2 composite material block prepared by adopting the hot-pressing sintering process has the advantages of low preparation cost and high performance, can realize rapid forming, and can also prepare parts with complex shapes according to engineering requirements, so that the preparation method has important significance and practical value.
The hot-press sintering process is to prepare compact sintered blocks by heating, pressurizing and sintering and preserving heat for a certain time. The hot-press sintering process has the advantages of high sintering speed, high density of the sintered sample and rapid forming. The hot-press sintering process is to fill the dry powder into the mould and then heat the mould from the uniaxial direction while pressurizing, so that the forming and sintering are completed simultaneously. The hot pressing sintering process is characterized in that the hot pressing sintering process is carried out simultaneously due to the fact that heating and pressurizing are carried out, powder is in a thermoplastic state, contact diffusion flow of particles is facilitated, mass transfer process is facilitated, forming pressure is low, sintering temperature can be reduced, sintering time is shortened, crystal grains are prevented from growing up, and products with fine crystal grains, high density, high mechanical property and high mechanical property are obtained. The ceramic product with ultra-high purity can be produced without adding sintering auxiliary agent or forming auxiliary agent. The hot-press sintering process has the defects of complex hot-press sintering process, complex hot-press sintering equipment and high requirement on die materials. Various sintered products can be prepared by a hot press sintering process. The hot-press sintering equipment needs a special hot-press sintering furnace, and the common hot-press sintering furnace mainly comprises a heating furnace, a pressurizing device, a die and a temperature and pressure measuring device. A reducing atmosphere or an inert atmosphere is required depending on the nature of the material. The mold requires high strength and high temperature resistance. High strength sintered bodies can also be obtained by hot press sintering processes. The sintering product with higher density can be prepared by the hot-press sintering process and has higher mechanical property. The hot press sintering process is to prepare a compact sintered sample by heating and pressing sintering. The compact sintered product can be prepared by the hot-press sintering process, and the prepared sintered product has uniform and compact microstructure, higher mechanical property and the like.
Drawings
FIG. 1 is an X-ray diffraction pattern of a block of Ti 5Si3/ZrB2 composite material prepared by a hot press sintering process according to the method provided by the invention.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples.
Example 1
The Ti 5Si3/ZrB2 composite material comprises the following components in parts by weight:
10 parts of Ti 5Si3 intermetallic compound powder, wherein Ti 5Si3 intermetallic compound is used as a reinforcing and toughening phase;
90 parts of ZrB 2 powder, 10 parts of Al 2O3 powder and Y 2O3 powder serving as sintering aids and 10 parts of fine silicon powder serving as sintering aids, wherein ZrB 2 is taken as a matrix.
The Ti 5Si3 intermetallic compound powder is prepared by adopting a mechanical alloying and heat treatment process, the Ti-Si intermetallic compound powder is prepared by adopting a mechanical alloying process ball milling for 80 hours, and the prepared Ti-Si intermetallic compound powder is subjected to a heat treatment process, wherein the heat treatment process is carried out under the vacuum condition at the temperature of 1000 ℃ for 1 hour, and the Ti 5Si3 intermetallic compound powder is prepared by the heat treatment process.
The molar ratio of Ti to Si in the Ti 5Si3 intermetallic compound powder is 63:37.
Example 2
The Ti 5Si3/ZrB2 composite material comprises the following components in parts by weight:
40 parts of Ti 5Si3 intermetallic compound powder, wherein Ti 5Si3 intermetallic compound is used as a reinforcing and toughening phase;
60 parts of ZrB 2 powder, 10 parts of Al 2O3 powder and Y 2O3 powder serving as sintering aids and 10 parts of fine silicon powder serving as sintering aids, wherein ZrB 2 is taken as a matrix.
The Ti 5Si3 intermetallic compound powder is prepared by adopting a mechanical alloying and heat treatment process, the Ti-Si intermetallic compound powder is prepared by adopting a mechanical alloying process to ball mill for 80 hours, and the prepared Ti-Si intermetallic compound powder is subjected to a heat treatment process, wherein the heat treatment process is carried out at the temperature of 1250 ℃ for 1 hour, the heat treatment process is carried out under the vacuum condition, and the Ti 5Si3 intermetallic compound powder is prepared by the heat treatment process.
The molar ratio of Ti to Si in the Ti 5Si3 intermetallic compound powder is 63:37.
Example 3
The Ti 5Si3/ZrB2 composite material comprises the following components in parts by weight:
70 parts of Ti 5Si3 intermetallic compound powder, and taking Ti 5Si3 intermetallic compound as a reinforcing and toughening phase;
30 parts of ZrB 2 powder, 10 parts of Al 2O3 powder and Y 2O3 powder serving as sintering aids and 10 parts of fine silicon powder serving as sintering aids, wherein ZrB 2 is taken as a matrix.
The Ti 5Si3 intermetallic compound powder is prepared by adopting a mechanical alloying and heat treatment process, the Ti-Si intermetallic compound powder is prepared by adopting a mechanical alloying process ball milling for 80 hours, and the prepared Ti-Si intermetallic compound powder is subjected to a heat treatment process, wherein the heat treatment process is carried out at 1400 ℃ for 1 hour under vacuum condition, and the Ti 5Si3 intermetallic compound powder is prepared by the heat treatment process.
The molar ratio of Ti to Si in the Ti 5Si3 intermetallic compound powder is 63:37.
Example 4
The hot-press sintering method of the Ti 5Si3/ZrB2 composite material comprises the following steps of:
preparing Ti-Si intermetallic compound powder by adopting a mechanical alloying process, wherein the specific method comprises the following steps of:
Filling Ti powder and Si powder into a ball milling tank of a QM-1SP2 planetary ball mill, wherein the ball milling tank adopts a polytetrafluoroethylene ball milling tank, grinding balls adopt agate grinding balls, the mass ratio of the agate grinding balls to mixed powder is 10:1, the molar ratio of the Ti powder to the Si powder is 63:37, the planetary ball mill is started for mechanical ball milling after the four ball milling tanks are fixed, the mechanical ball milling time is 80h, the rotating speed of the ball mill is 400r/min, the dry ball milling is adopted, and an intermittent ball milling mode is adopted, argon is filled into the ball milling tank as a protective gas, so that Ti-Si intermetallic compound powder is prepared, the purity of the Ti powder is 99%, the granularity is 75-100 mu m, and the purity of the Si powder is 99%, and the granularity is 75-100 mu m;
step two, carrying out a heat treatment process on the Ti-Si intermetallic compound powder prepared in the step one, wherein the specific method comprises the following steps:
Placing Ti-Si intermetallic compound powder and 10 parts of phenolic resin binder into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, mixing for 24 hours through mechanical ball milling, preparing slurry through wet ball milling, placing the slurry into a glass beaker, then placing the glass beaker into a drying oven, drying for 24 hours at 100 ℃, then placing the mixed powder into a steel mould capable of preparing strip-shaped samples, pressing the steel mould into strip-shaped samples with the size of 50mm multiplied by 5mm multiplied by 6mm under the pressure of 100MPa for 3 minutes by a pressure forming machine, placing the strip-shaped samples into a graphite crucible, placing the graphite crucible into a vacuum sintering furnace, wherein the heat treatment temperature is 1000 ℃, the heat preservation time is 1 hour, performing heat treatment under the vacuum condition with the vacuum degree of 10 -2 Pa to obtain porous tissue loose Ti 5Si3 intermetallic compound powder samples, taking out the Ti 5Si3 intermetallic compound strips, crushing and grinding the Ti 5Si3 intermetallic compound samples into Ti 5Si3 intermetallic compound powder, preparing the strip-shaped samples with the size of 50mm multiplied by the pressure forming machine, placing the strip-shaped samples into the graphite crucible, placing the graphite crucible into a vacuum sintering furnace, wherein the heat treatment temperature is 1000 ℃ and the heat treatment temperature is 1h, the heat treatment time is 1h, and the thermal treatment is carried out under the condition that the phenolic resin is not completely volatilized by the phenolic resin, and the phenolic resin is completely decomposed in the process, and the phenolic resin is not left in the process;
Mixing 10 parts of the Ti 5Si3 intermetallic compound powder prepared in the second step with 90 parts of ZrB 2 powder to obtain composite powder, adding 3 parts of Al 2O3 powder and 7 parts of Y 2O3 powder serving as sintering aids into the composite powder, adding 10 parts of fine silicon powder serving as sintering aids, mixing to obtain mixed powder consisting of Ti 5Si3 powder, zrB 2 powder, al 2O3 powder, Y 2O3 powder and fine silicon powder, carrying out wet ball milling mixing process on the mixed powder by mechanical ball milling, filling the mixed powder into a ball milling tank, carrying out mechanical ball milling mixing for 24 hours by adding 100 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 10mm into the ball milling tank to prepare slurry, filling the slurry into a glass beaker, and then drying for 24 hours at 100 ℃ to prepare Ti 5Si3/ZrB2 composite powder, wherein the mass part of the Ti 5Si3 intermetallic compound powder in the Ti 5Si3/ZrB2 composite powder is 10 parts;
mixing the Ti 5Si3/ZrB2 composite powder prepared in the step three with 10 parts of phenolic resin binder, filling the mixture into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, carrying out mechanical ball milling and mixing for 24 hours to prepare slurry, filling the slurry into a glass beaker, then putting the glass beaker into a baking oven, drying at 100 ℃ for 24 hours to obtain Ti 5Si3/ZrB2 composite powder containing the phenolic resin binder, filling the mixed powder into a steel mold capable of preparing a wafer sample, pressing the steel mold into a wafer sample, wherein the pressing adopts a molding press for 3 minutes under the pressure of 100MPa, pressing the wafer sample into a wafer sample with the diameter of 40mm and the height of about 10mm, filling the wafer sample into latex gloves, wrapping the latex gloves, sealing the latex gloves, putting the latex gloves into a cold isostatic press, taking out the sample in the cold isostatic press, and carrying out isostatic pressing on the sample after the end of the pressure maintaining time in the cold isostatic press for 5 minutes under the pressure of 100MPa, and carrying out isostatic pressing on the obtained Ti 5Si3/ZrB2 composite powder with the diameter of 40mm, and obtaining a compact wafer sample which can be remarkably improved by 5Si3/ZrB2 mm;
And fifthly, placing the Ti 5Si3/ZrB2 composite powder prefabricated blank wafer sample prepared in the step four into a graphite mold, placing the graphite mold into a vacuum hot-pressing sintering furnace for vacuum hot-pressing sintering process, wherein the preparation method of the vacuum hot-pressing sintering process comprises the steps of carrying out the hot-pressing sintering process under the vacuum condition at the sintering temperature of 1500 ℃ under the hot-pressing pressure of 35MPa for 2 hours at the heat preservation time of 10 -2 Pa, and at the heating rate of 10 ℃ per minute in the sintering process, and cooling along with the furnace after the sintering process is finished, thereby preparing the Ti 5Si3/ZrB2 composite material. The sintered wafer sample with the diameter of 40mm and the height of about 6mm can be obtained through the hot-press sintering process, namely the sintered block of the Ti 5Si3/ZrB2 composite material. Wherein the mass fraction of the Ti 5Si3 intermetallic compound in the Ti 5Si3/ZrB2 composite material is 10. Wherein a small amount of phenolic resin is completely decomposed and volatilized in the high-temperature hot-press sintering process, and no phenolic resin remains in the obtained sintered block.
Example 5
The hot-press sintering method of the Ti 5Si3/ZrB2 composite material comprises the following steps of:
preparing Ti-Si intermetallic compound powder by adopting a mechanical alloying process, wherein the specific method comprises the following steps of:
Filling Ti powder and Si powder into a ball milling tank of a QM-1SP2 planetary ball mill, wherein the ball milling tank adopts a polytetrafluoroethylene ball milling tank, grinding balls adopt agate grinding balls, the mass ratio of the agate grinding balls to mixed powder is 10:1, the molar ratio of the Ti powder to the Si powder is 63:37, the planetary ball mill is started for mechanical ball milling after the four ball milling tanks are fixed, the mechanical ball milling time is 80h, the rotating speed of the ball mill is 400r/min, the dry ball milling is adopted, and an intermittent ball milling mode is adopted, argon is filled into the ball milling tank as a protective gas, so that Ti-Si intermetallic compound powder is prepared, the purity of the Ti powder is 99%, the granularity is 75-100 mu m, and the purity of the Si powder is 99%, and the granularity is 75-100 mu m;
step two, carrying out a heat treatment process on the Ti-Si intermetallic compound powder prepared in the step one, wherein the specific method comprises the following steps:
Placing Ti-Si intermetallic compound powder and 10 parts of phenolic resin binder into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, mixing for 24 hours through mechanical ball milling, preparing slurry through wet ball milling, placing the slurry into a glass beaker, then placing the glass beaker into a drying oven, drying for 24 hours at 100 ℃, then placing the mixed powder into a steel mould capable of preparing strip-shaped samples, pressing the steel mould into strip-shaped samples with the pressure of 120MPa for 3 minutes by a pressure forming machine, placing the strip-shaped samples into a graphite crucible, placing the graphite crucible into a vacuum sintering furnace, wherein the heat treatment temperature is 1100 ℃, the heat preservation time is 1 hour, performing heat treatment under the vacuum condition with the vacuum degree of 10 -2 Pa, obtaining porous-tissue loose Ti 5Si3 intermetallic compound powder samples, taking out the Ti 5Si3 intermetallic compound strips, crushing and grinding the Ti 5Si3 intermetallic compound samples into Ti 5Si3 intermetallic compound powder, preparing the strip-shaped samples with the size of 50mm x 5mm and placing the strip-shaped samples into the graphite crucible, wherein a small amount of the thermal treatment process has no residual phenolic resin in the phenolic resin, and the phenolic resin is completely decomposed in the process, and the phenolic resin is not completely decomposed;
Mixing 20 parts of the Ti 5Si3 intermetallic compound powder prepared in the second step with 80 parts of ZrB 2 powder to obtain composite powder, adding 4 parts by weight of Al 2O3 powder and 6 parts by weight of Y 2O3 powder serving as sintering aids into the composite powder, adding 10 parts of fine silicon powder serving as sintering aids, mixing to obtain mixed powder consisting of Ti 5Si3 powder, zrB 2 powder, al 2O3 powder, Y 2O3 powder and fine silicon powder, carrying out a wet ball milling mixing process on the mixed powder through mechanical ball milling, loading the mixed powder into a ball milling tank, adding 150ml of anhydrous ethanol and 35 agate grinding balls with the diameter of 11mm into the ball milling tank, carrying out mechanical ball milling mixing for 24 hours, preparing slurry, loading the slurry into a glass beaker, and drying for 24 hours at 100 ℃ to obtain Ti 5Si3/ZrB2 composite powder, wherein the mass of the Ti 5Si3 intermetallic compound powder in the Ti 5Si3/ZrB2 composite powder is 20 parts;
Mixing the Ti 5Si3/ZrB2 composite powder prepared in the step three with 10 parts of phenolic resin binder, filling the mixture into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, carrying out mechanical ball milling and mixing for 24 hours to prepare slurry, filling the slurry into a glass beaker, then putting the glass beaker into a baking oven, drying at 100 ℃ for 24 hours to obtain Ti 5Si3/ZrB2 mixed powder containing the phenolic resin binder, filling the mixed powder into a steel mould capable of preparing a wafer sample, pressing the mixed powder into a wafer sample by adopting a forming press for 3 minutes under the pressure of 120MPa, pressing the wafer sample into a wafer sample with the diameter of 40mm and the height of about 10mm, filling the wafer sample into latex gloves, packaging the latex gloves, sealing the latex gloves, putting the latex gloves into a cold isostatic press, taking out the sample in the cold isostatic press after the pressure of 120MPa for 5 minutes, and carrying out isostatic pressing on the cold isostatic press to obtain a prefabricated Ti 5Si3/ZrB2 composite powder with the diameter of 40mm, and the density of the wafer sample can be remarkably improved by a compact process of 35 mm;
And fifthly, placing the Ti 5Si3/ZrB2 composite powder prefabricated blank disc sample prepared in the step four into a graphite mold, placing the graphite mold into a vacuum hot-pressing sintering furnace for vacuum hot-pressing sintering process, wherein the preparation method of the vacuum hot-pressing sintering process comprises the steps of performing the hot-pressing sintering process under the vacuum condition, wherein the sintering temperature is 1550 ℃, the hot-pressing pressure is 35MPa, the heat preservation time is 2h, the vacuum degree is 10 -2 Pa, the heating rate in the sintering process is 15 ℃ per minute, cooling the furnace after the sintering process is finished, and obtaining the Ti 5Si3/ZrB2 composite material, wherein the sintered disc sample with the diameter of 40mm and the height of about 6mm can be obtained through the hot-pressing sintering process, and the sintered disc sample is the Ti 5Si3/ZrB2 composite material sintered block. The Ti 5Si3 intermetallic compound comprises 20 parts by weight of the Ti 5Si3/ZrB2 composite material, wherein a small amount of phenolic resin is completely decomposed and volatilized in the high-temperature hot-pressing sintering process, and no phenolic resin remains in the obtained sintered block.
Example 6
The hot-press sintering method of the Ti 5Si3/ZrB2 composite material comprises the following steps of:
preparing Ti-Si intermetallic compound powder by adopting a mechanical alloying process, wherein the specific method comprises the following steps of:
Filling Ti powder and Si powder into a ball milling tank of a QM-1SP2 planetary ball mill, wherein the ball milling tank adopts a polytetrafluoroethylene ball milling tank, grinding balls adopt agate grinding balls, the mass ratio of the agate grinding balls to mixed powder is 10:1, the molar ratio of the Ti powder to the Si powder is 63:37, the planetary ball mill is started for mechanical ball milling after the four ball milling tanks are fixed, the mechanical ball milling time is 80h, the rotating speed of the ball mill is 400r/min, the dry ball milling is adopted, and an intermittent ball milling mode is adopted, argon is filled into the ball milling tank as a protective gas, so that Ti-Si intermetallic compound powder is prepared, the purity of the Ti powder is 99%, the granularity is 75-100 mu m, and the purity of the Si powder is 99%, and the granularity is 75-100 mu m;
step two, carrying out a heat treatment process on the Ti-Si intermetallic compound powder prepared in the step one, wherein the specific method comprises the following steps:
Placing Ti-Si intermetallic compound powder and 10 parts of phenolic resin binder into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, mixing for 24 hours through mechanical ball milling, preparing slurry through wet ball milling, placing the slurry into a glass beaker, then placing the glass beaker into a drying oven, drying for 24 hours at 100 ℃, then placing the mixed powder into a steel mould capable of preparing strip-shaped samples, pressing the steel mould into strip-shaped samples with the pressure of 140MPa for 3 minutes by a pressure forming machine, placing the strip-shaped samples into a graphite crucible, placing the graphite crucible into a vacuum sintering furnace, wherein the heat treatment temperature is 1200 ℃, the heat preservation time is 1 hour, performing heat treatment under the vacuum condition with the vacuum degree of 10 -2 Pa, obtaining porous-tissue loose Ti 5Si3 intermetallic compound powder samples, taking out the Ti 5Si3 intermetallic compound strips, crushing and grinding the Ti 5Si3 intermetallic compound samples into Ti 5Si3 intermetallic compound powder, preparing the strip-shaped samples with the size of 50mm x 5mm and placing the strip-shaped samples into a graphite crucible, wherein a small amount of the thermal treatment process has no residual phenolic resin in the phenolic resin, and the phenolic resin is completely decomposed in the process, and the phenolic resin is not completely decomposed;
Mixing 30 parts of the Ti 5Si3 intermetallic compound powder prepared in the second step with 70 parts of ZrB 2 powder to obtain composite powder, adding 5 parts by weight of Al 2O3 powder and 5 parts by weight of Y 2O3 powder serving as sintering aids, adding 10 parts by weight of fine silicon powder serving as sintering aids, mixing to obtain mixed powder consisting of Ti 5Si3 powder, zrB 2 powder, al 2O3 powder, Y 2O3 powder and fine silicon powder, carrying out wet ball milling on the mixed powder by mechanical ball milling, loading the mixed powder into a ball milling tank, adding 200 milliliters of absolute ethyl alcohol and 40 agate grinding balls with the diameter of 12mm into the ball milling tank, carrying out mechanical ball milling and mixing for 24 hours, preparing slurry, loading the slurry into a glass beaker, and then putting the glass beaker into an oven, and drying for 24 hours at 100 ℃ to obtain Ti 5Si3/ZrB2 composite powder, wherein the mass part of the Ti 5Si3 intermetallic compound powder in the Ti 5Si3/ZrB2 composite powder is 30 parts;
mixing the Ti 5Si3/ZrB2 composite powder prepared in the step three with 10 parts of phenolic resin binder, filling the mixture into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, carrying out mechanical ball milling and mixing for 24 hours to prepare slurry, filling the slurry into a glass beaker, then putting the glass beaker into a baking oven, drying at 100 ℃ for 24 hours to obtain Ti 5Si3/ZrB2 mixed powder containing the phenolic resin binder, filling the mixed powder into a steel mould capable of preparing a wafer sample, pressing the mixed powder into a wafer sample by adopting a forming press for 3 minutes under the pressure of 140MPa, pressing the wafer sample into a wafer sample with the diameter of 40mm and the height of about 10mm, filling the wafer sample into latex gloves, packaging the latex gloves, sealing the latex gloves, putting the latex gloves into a cold isostatic press, taking out the sample in the cold isostatic press, and carrying out isostatic pressing forming by the cold isostatic press to obtain a prefabricated powder composite 5Si3/ZrB2 with the diameter of 40mm, wherein the diameter of the prefabricated wafer sample is remarkably improved by a compact process of 5Si3/ZrB2 mm;
And fifthly, placing the Ti 5Si3/ZrB2 composite powder prefabricated blank wafer sample prepared in the step four into a graphite mold, placing the graphite mold into a vacuum hot-pressing sintering furnace for vacuum hot-pressing sintering process, wherein the preparation method of the vacuum hot-pressing sintering process comprises the steps of carrying out the hot-pressing sintering process under the vacuum condition at the sintering temperature of 1600 ℃, the hot-pressing pressure of 35MPa and the heat preservation time of 2 hours, wherein the vacuum degree of 10 -2 Pa, the heating rate of 20 ℃ per minute in the sintering process, and cooling along with the furnace after the sintering process is finished, thereby preparing the Ti 5Si3/ZrB2 composite material. A sintered wafer sample with the diameter of 40mm and the height of about 6mm can be obtained through a hot-press sintering process, namely the sintered block of the Ti 5Si3/ZrB2 composite material, wherein the mass fraction of the Ti 5Si3 intermetallic compound in the Ti 5Si3/ZrB2 composite material is 30 parts. Wherein a small amount of phenolic resin is completely decomposed and volatilized in the high-temperature hot-press sintering process, and no phenolic resin remains in the obtained sintered block.
Example 7
The hot-press sintering method of the Ti 5Si3/ZrB2 composite material comprises the following steps of:
preparing Ti-Si intermetallic compound powder by adopting a mechanical alloying process, wherein the specific method comprises the following steps of:
Filling Ti powder and Si powder into a ball milling tank of a QM-1SP2 planetary ball mill, wherein the ball milling tank adopts a polytetrafluoroethylene ball milling tank, grinding balls adopt agate grinding balls, the mass ratio of the agate grinding balls to mixed powder is 10:1, the molar ratio of the Ti powder to the Si powder is 63:37, the planetary ball mill is started for mechanical ball milling after the four ball milling tanks are fixed, the mechanical ball milling time is 80h, the rotating speed of the ball mill is 400r/min, the dry ball milling is adopted, and an intermittent ball milling mode is adopted, argon is filled into the ball milling tank as a protective gas, so that Ti-Si intermetallic compound powder is prepared, the purity of the Ti powder is 99%, the granularity is 75-100 mu m, and the purity of the Si powder is 99%, and the granularity is 75-100 mu m;
step two, carrying out a heat treatment process on the Ti-Si intermetallic compound powder prepared in the step one, wherein the specific method comprises the following steps:
Placing Ti-Si intermetallic compound powder and 10 parts of phenolic resin binder into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, mixing for 24 hours through mechanical ball milling, preparing slurry through wet ball milling, placing the slurry into a glass beaker, then placing the glass beaker into a drying oven, drying for 24 hours at 100 ℃, then placing the mixed powder into a steel mould capable of preparing strip-shaped samples, pressing the steel mould into strip-shaped samples with the pressure of 150MPa for 3 minutes through a pressure forming machine, placing the strip-shaped samples into a graphite crucible, placing the graphite crucible into a vacuum sintering furnace, wherein the heat treatment temperature is 1250 ℃, the heat preservation time is 1 hour, performing heat treatment under the vacuum condition with the vacuum degree of 10 -2 Pa, obtaining porous-tissue loose Ti 5Si3 intermetallic compound powder samples, taking out the Ti 5Si3 intermetallic compound strips, crushing and grinding the Ti 5Si3 intermetallic compound samples into Ti 5Si3 intermetallic compound powder, preparing the strip-shaped samples with the size of 50mm x 5mm x 6mm, placing the strip-shaped samples into the graphite crucible into a vacuum sintering furnace, wherein the heat treatment temperature is 1250 ℃, the heat treatment temperature is 1h, the heat treatment is 10 Pa, and the phenolic resin is not completely volatilized in the phenolic resin, and the phenolic resin is completely decomposed;
Mixing 40 parts of the Ti 5Si3 intermetallic compound powder prepared in the second step with 60 parts of ZrB 2 powder to obtain composite powder, adding 6 parts of Al 2O3 powder and 4 parts of Y 2O3 powder serving as sintering aids into the composite powder, adding 10 parts of fine silicon powder serving as sintering aids, mixing to obtain mixed powder composed of Ti 5Si3 powder, zrB 2 powder, al 2O3 powder, Y 2O3 powder and fine silicon powder, carrying out wet ball milling mixing process on the mixed powder through mechanical ball milling, filling the mixed powder into a ball milling tank, adding 250 milliliters of anhydrous ethanol and 45 agate grinding balls with the diameter of 13mm into the ball milling tank, carrying out mechanical ball milling mixing for 24 hours, preparing slurry, filling the slurry into a glass beaker, and then drying at 100 ℃ for 24 hours to obtain Ti 5Si3/ZrB2 composite powder, wherein the mass part of the Ti 5Si3 intermetallic compound powder in the Ti 5Si3/ZrB2 composite powder is 40 parts.
Mixing the Ti 5Si3/ZrB2 composite powder prepared in the step three with 10 parts of phenolic resin binder, filling the mixture into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, carrying out mechanical ball milling and mixing for 24 hours to prepare slurry, filling the slurry into a glass beaker, then putting the glass beaker into a baking oven, drying at 100 ℃ for 24 hours to obtain Ti 5Si3/ZrB2 composite powder containing the phenolic resin binder, filling the mixed powder into a steel mold capable of preparing a wafer sample, pressing the steel mold into a wafer sample, wherein the pressing adopts a molding press for 3 minutes under the pressure of 150MPa, pressing the wafer sample into a wafer sample with the diameter of 40mm and the height of about 10mm, filling the wafer sample into latex gloves, wrapping the latex gloves, sealing the latex gloves, putting the latex gloves into a cold isostatic press, taking out the sample in the cold isostatic press, and carrying out isostatic pressing on the sample after the end of the pressure maintaining time in the cold isostatic press for 5 minutes under the pressure of 150MPa, and carrying out isostatic pressing on the obtained Ti 5Si3/ZrB2 composite powder by isostatic pressing of the cold isostatic press, thus obtaining a preform with the diameter of 40mm, and the compact wafer sample with the height of 5Si3/ZrB2 mm;
And fifthly, placing the Ti 5Si3/ZrB2 composite powder prefabricated blank wafer sample prepared in the step four into a graphite mold, placing the graphite mold into a vacuum hot-pressing sintering furnace for vacuum hot-pressing sintering process, wherein the preparation method of the vacuum hot-pressing sintering process comprises the steps of sintering at 1650 ℃, hot-pressing at 35MPa, maintaining for 2 hours, performing the hot-pressing sintering process under the vacuum condition, maintaining the vacuum degree at 10 -2 Pa, heating at 23 ℃ per minute in the sintering process, and cooling with the furnace after the sintering process is finished to prepare the Ti 5Si3/ZrB2 composite material. The sintered wafer sample with the diameter of 40mm and the height of about 6mm can be obtained through the hot-press sintering process, namely the sintered block of the Ti 5Si3/ZrB2 composite material. The Ti 5Si3 intermetallic compound comprises 40 parts by weight of the Ti 5Si3/ZrB2 composite material, wherein a small amount of phenolic resin is completely decomposed and volatilized in the high-temperature hot-pressing sintering process, and no phenolic resin remains in the obtained sintered block.
Example 8
The hot-press sintering method of the Ti 5Si3/ZrB2 composite material comprises the following steps of:
preparing Ti-Si intermetallic compound powder by adopting a mechanical alloying process, wherein the specific method comprises the following steps of:
Filling Ti powder and Si powder into a ball milling tank of a QM-1SP2 planetary ball mill, wherein the ball milling tank adopts a polytetrafluoroethylene ball milling tank, grinding balls adopt agate grinding balls, the mass ratio of the agate grinding balls to mixed powder is 10:1, the molar ratio of the Ti powder to the Si powder is 63:37, the planetary ball mill is started for mechanical ball milling after the four ball milling tanks are fixed, the mechanical ball milling time is 80h, the rotating speed of the ball mill is 400r/min, the dry ball milling is adopted, and an intermittent ball milling mode is adopted, argon is filled into the ball milling tank as a protective gas, so that Ti-Si intermetallic compound powder is prepared, the purity of the Ti powder is 99%, the granularity is 75-100 mu m, and the purity of the Si powder is 99%, and the granularity is 75-100 mu m;
step two, carrying out a heat treatment process on the Ti-Si intermetallic compound powder prepared in the step one, wherein the specific method comprises the following steps:
Placing Ti-Si intermetallic compound powder and 10 parts of phenolic resin binder into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, mixing for 24 hours through mechanical ball milling, preparing slurry through wet ball milling, placing the slurry into a glass beaker, then placing the glass beaker into a drying oven, drying for 24 hours at 100 ℃, then placing the mixed powder into a steel mould capable of preparing strip-shaped samples, pressing the steel mould into strip-shaped samples with the pressure of 160MPa for 3 minutes by a pressure forming machine, placing the strip-shaped samples into a graphite crucible, placing the graphite crucible into a vacuum sintering furnace, wherein the heat treatment temperature is 1300 ℃, the heat preservation time is 1 hour, performing heat treatment under the vacuum condition with the vacuum degree of 10 -2 Pa, obtaining porous-tissue loose Ti 5Si3 intermetallic compound powder samples, taking out the Ti 5Si3 intermetallic compound strips, crushing and grinding the Ti 5Si3 intermetallic compound samples into Ti 5Si3 intermetallic compound powder, preparing the strip-shaped samples with the size of 50mm x 5mm and placing the strip-shaped samples into a graphite crucible, wherein a small amount of the thermal treatment process has no residual phenolic resin in the phenolic resin, and the phenolic resin is completely decomposed in the process, and the phenolic resin is not completely decomposed;
Mixing 50 parts of the Ti 5Si3 intermetallic compound powder prepared in the second step with 50 parts of ZrB 2 powder to obtain composite powder, adding 7 parts of Al 2O3 powder and 3 parts of Y 2O3 powder serving as sintering aids into the composite powder, adding 10 parts of fine silicon powder serving as sintering aids, mixing to obtain mixed powder consisting of Ti 5Si3 powder, zrB 2 powder, al 2O3 powder, Y 2O3 powder and fine silicon powder, carrying out wet ball milling on the mixed powder through mechanical ball milling, loading the mixed powder into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 50 agate grinding balls with the diameter of 14mm into the ball milling tank, carrying out mechanical ball milling and mixing for 24 hours to obtain slurry, loading the slurry into a glass beaker, and then drying at 100 ℃ for 24 hours in an oven to obtain Ti 5Si3/ZrB2 composite powder, wherein the mass part of the Ti 5Si3 intermetallic compound powder in the Ti 5Si3/ZrB2 composite powder is 50 parts;
mixing the Ti 5Si3/ZrB2 composite powder prepared in the step three with 10 parts of phenolic resin binder, filling the mixture into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, carrying out mechanical ball milling and mixing for 24 hours to prepare slurry, filling the slurry into a glass beaker, then putting the glass beaker into a baking oven, drying at 100 ℃ for 24 hours to obtain Ti 5Si3/ZrB2 mixed powder containing the phenolic resin binder, filling the mixed powder into a steel mould capable of preparing a wafer sample, pressing the mixed powder into a wafer sample by adopting a forming press for 3 minutes under the pressure of 160MPa, pressing the wafer sample into a wafer sample with the diameter of 40mm and the height of about 10mm, filling the wafer sample into latex gloves, packaging the latex gloves, sealing the latex gloves, putting the latex gloves into a cold isostatic press, taking out the sample in the cold isostatic press, and carrying out isostatic pressing forming by the cold isostatic press to obtain a prefabricated powder composite 5Si3/ZrB2 with the diameter of 40mm, wherein the diameter of the prefabricated wafer sample is remarkably improved by a compact process of 5Si3/ZrB2 mm;
And fifthly, placing the Ti 5Si3/ZrB2 composite powder prefabricated blank wafer sample prepared in the step four into a graphite mold, placing the graphite mold into a vacuum hot-pressing sintering furnace for vacuum hot-pressing sintering process, wherein the preparation method of the vacuum hot-pressing sintering process comprises the steps of sintering at 1700 ℃, hot-pressing at 35MPa, keeping the temperature for 2 hours, performing the hot-pressing sintering process under the vacuum condition, keeping the vacuum degree at 10 -2 Pa, heating at 25 ℃ per minute in the sintering process, and cooling with the furnace after the sintering process is finished to prepare the Ti 5Si3/ZrB2 composite material. The sintered wafer sample with the diameter of 40mm and the height of about 6mm can be obtained through a hot-pressing sintering process, namely the sintered block of the Ti 5Si3/ZrB2 composite material, wherein the mass fraction of the Ti 5Si3 intermetallic compound in the Ti 5Si3/ZrB2 composite material is 50 parts, a small amount of phenolic resin is completely decomposed and volatilized in the high-temperature hot-pressing sintering process, and no residual phenolic resin exists in the obtained sintered block.
Example 9
The hot-press sintering method of the Ti 5Si3/ZrB2 composite material comprises the following steps of:
preparing Ti-Si intermetallic compound powder by adopting a mechanical alloying process, wherein the specific method comprises the following steps of:
Filling Ti powder and Si powder into a ball milling tank of a QM-1SP2 planetary ball mill, wherein the ball milling tank adopts a polytetrafluoroethylene ball milling tank, grinding balls adopt agate grinding balls, the mass ratio of the agate grinding balls to mixed powder is 10:1, the molar ratio of the Ti powder to the Si powder is 63:37, the planetary ball mill is started for mechanical ball milling after the four ball milling tanks are fixed, the mechanical ball milling time is 80h, the rotating speed of the ball mill is 400r/min, the dry ball milling is adopted, and an intermittent ball milling mode is adopted, argon is filled into the ball milling tank as a protective gas, so that Ti-Si intermetallic compound powder is prepared, the purity of the Ti powder is 99%, the granularity is 75-100 mu m, and the purity of the Si powder is 99%, and the granularity is 75-100 mu m;
step two, carrying out a heat treatment process on the Ti-Si intermetallic compound powder prepared in the step one, wherein the specific method comprises the following steps:
Placing Ti-Si intermetallic compound powder and 10 parts of phenolic resin binder into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, mixing for 24 hours through mechanical ball milling, preparing slurry through wet ball milling, placing the slurry into a glass beaker, then placing the glass beaker into a drying oven, drying for 24 hours at 100 ℃, then placing the mixed powder into a steel mould capable of preparing strip-shaped samples, pressing the steel mould into strip-shaped samples with the pressure of 180MPa for 3 minutes through a pressure forming machine, placing the strip-shaped samples into a graphite crucible, placing the graphite crucible into a vacuum sintering furnace, wherein the heat treatment temperature is 1350 ℃, the heat preservation time is 1 hour, performing heat treatment under the vacuum condition with the vacuum degree of 10 -2 Pa, obtaining porous-tissue loose Ti 5Si3 intermetallic compound powder samples, taking out the Ti 5Si3 intermetallic compound strips, crushing and grinding the Ti 5Si3 intermetallic compound samples into Ti 5Si3 intermetallic compound powder, preparing the strip-shaped samples with the size of 50mm x 5mm and placing the strip-shaped samples into a graphite crucible, wherein a small amount of the phenolic resin is completely decomposed in a high-temperature phenolic resin, and the phenolic resin is not completely volatilized during the process, and the phenolic resin is not completely decomposed;
Mixing 60 parts of the Ti 5Si3 intermetallic compound powder prepared in the second step with 40 parts of ZrB 2 powder to obtain composite powder, adding 8 parts of Al 2O3 powder and 2 parts of Y 2O3 powder serving as sintering aids into the composite powder, adding 10 parts of fine silicon powder serving as sintering aids, mixing to obtain mixed powder consisting of Ti 5Si3 powder, zrB 2 powder, al 2O3 powder, Y 2O3 powder and fine silicon powder, carrying out wet ball milling on the mixed powder through mechanical ball milling, filling the mixed powder into a ball milling tank, adding 350 milliliters of absolute ethyl alcohol and 55 agate grinding balls with the diameter of 15mm into the ball milling tank, carrying out mechanical ball milling and mixing for 24 hours to obtain slurry, filling the slurry into a glass beaker, and then drying at 100 ℃ for 24 hours to obtain Ti 5Si3/ZrB2 composite powder, wherein the mass of the Ti 5Si3 intermetallic compound powder in the Ti 5Si3/ZrB2 composite powder is 60 parts;
Mixing the Ti 5Si3/ZrB2 composite powder prepared in the step three with 10 parts of phenolic resin binder, filling the mixture into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, carrying out mechanical ball milling and mixing for 24 hours to prepare slurry, filling the slurry into a glass beaker, then putting the glass beaker into a baking oven, drying at 100 ℃ for 24 hours to obtain Ti 5Si3/ZrB2 mixed powder containing the phenolic resin binder, filling the mixed powder into a steel mould capable of preparing a wafer sample, pressing the mixed powder into a wafer sample by adopting a forming press for 3 minutes under the pressure of 180MPa, pressing the wafer sample into a wafer sample with the diameter of 40mm and the height of about 10mm, filling the wafer sample into latex gloves, packaging the latex gloves, sealing the latex gloves, putting the latex gloves into a cold isostatic press, taking out the sample in the cold isostatic press, and carrying out isostatic pressing forming by the cold isostatic press to obtain a prefabricated powder composite 5Si3/ZrB2 with the diameter of 40mm, wherein the diameter of the prefabricated wafer sample is remarkably improved by a compact process of 5Si3/ZrB2 mm;
And fifthly, placing the Ti 5Si3/ZrB2 composite powder prefabricated blank wafer sample prepared in the step four into a graphite mold, placing the graphite mold into a vacuum hot-pressing sintering furnace for vacuum hot-pressing sintering process, wherein the preparation method of the vacuum hot-pressing sintering process comprises the steps of carrying out the hot-pressing sintering process under the vacuum condition at the sintering temperature of 1750 ℃, the hot-pressing pressure of 35MPa and the heat preservation time of 2 hours, wherein the vacuum degree of 10 -2 Pa, the heating rate of 30 ℃ per minute in the sintering process, and cooling along with the furnace after the sintering process is finished, thereby preparing the Ti 5Si3/ZrB2 composite material. The sintered wafer sample with the diameter of 40mm and the height of about 6mm can be obtained through the hot-press sintering process, namely the sintered block of the Ti 5Si3/ZrB2 composite material. The Ti 5Si3 intermetallic compound comprises 60 parts by weight of the Ti 5Si3/ZrB2 composite material, wherein a small amount of phenolic resin is completely decomposed and volatilized in the high-temperature hot-pressing sintering process, and no phenolic resin remains in the obtained sintered block.
Example 10
The hot-press sintering method of the Ti 5Si3/ZrB2 composite material comprises the following steps of:
preparing Ti-Si intermetallic compound powder by adopting a mechanical alloying process, wherein the specific method comprises the following steps of:
Filling Ti powder and Si powder into a ball milling tank of a QM-1SP2 planetary ball mill, wherein the ball milling tank adopts a polytetrafluoroethylene ball milling tank, grinding balls adopt agate grinding balls, the mass ratio of the agate grinding balls to mixed powder is 10:1, the molar ratio of the Ti powder to the Si powder is 63:37, the planetary ball mill is started for mechanical ball milling after the four ball milling tanks are fixed, the mechanical ball milling time is 80h, the rotating speed of the ball mill is 400r/min, the dry ball milling is adopted, and an intermittent ball milling mode is adopted, argon is filled into the ball milling tank as a protective gas, so that Ti-Si intermetallic compound powder is prepared, the purity of the Ti powder is 99%, the granularity is 75-100 mu m, and the purity of the Si powder is 99%, and the granularity is 75-100 mu m;
step two, carrying out a heat treatment process on the Ti-Si intermetallic compound powder prepared in the step one, wherein the specific method comprises the following steps:
Placing Ti-Si intermetallic compound powder and 10 parts of phenolic resin binder into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, mixing for 24 hours through mechanical ball milling, preparing slurry through wet ball milling, placing the slurry into a glass beaker, then placing the glass beaker into a drying oven, drying for 24 hours at 100 ℃, then placing the mixed powder into a steel mould capable of preparing strip-shaped samples, pressing the steel mould into strip-shaped samples with the pressure of 200MPa for 3 minutes through a pressure forming machine, placing the strip-shaped samples into a graphite crucible, placing the graphite crucible into a vacuum sintering furnace, wherein the heat treatment temperature is 1400 ℃, the heat preservation time is 1 hour, performing heat treatment under the vacuum condition with the vacuum degree of 10 -2 Pa, obtaining porous-tissue loose Ti 5Si3 intermetallic compound powder samples, taking out the Ti 5Si3 intermetallic compound strips, crushing and grinding the Ti 5Si3 intermetallic compound samples into Ti 5Si3 intermetallic compound powder, preparing the strip-shaped samples with the size of 50mm x 5mm and placing the strip-shaped samples into a graphite crucible, wherein a small amount of the thermal treatment process has no residual phenolic resin in the phenolic resin, and the thermal process has no residual phenolic resin in the process of completely decomposing the Ti 5Si3 intermetallic compound powder;
Mixing 70 parts of the Ti 5Si3 intermetallic compound powder prepared in the second step with 30 parts of ZrB 2 powder to obtain composite powder, adding 9 parts of Al 2O3 powder and 1 part of Y 2O3 powder serving as sintering aids into the composite powder, adding 10 parts of fine silicon powder serving as sintering aids, mixing to obtain mixed powder consisting of Ti 5Si3 powder, zrB 2 powder, al 2O3 powder, Y 2O3 powder and fine silicon powder, carrying out wet ball milling mixing process on the mixed powder by mechanical ball milling, filling the mixed powder into a ball milling tank, adding 400 milliliters of absolute ethyl alcohol and 60 agate grinding balls with the diameter of 16mm into the ball milling tank, carrying out mechanical ball milling mixing for 24 hours to prepare slurry, filling the slurry into a glass beaker, and then drying for 24 hours at 100 ℃ to prepare Ti 5Si3/ZrB2 composite powder, wherein the mass part of the Ti 5Si3 intermetallic compound powder in the Ti 5Si3/ZrB2 composite powder is 70 parts;
mixing the Ti 5Si3/ZrB2 composite powder prepared in the step three with 10 parts of phenolic resin binder, filling the mixture into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, carrying out mechanical ball milling and mixing for 24 hours to prepare slurry, filling the slurry into a glass beaker, then putting the glass beaker into a baking oven, drying at 100 ℃ for 24 hours to obtain Ti 5Si3/ZrB2 mixed powder containing the phenolic resin binder, filling the mixed powder into a steel mould capable of preparing a wafer sample, pressing the mixed powder into a wafer sample by adopting a forming press for 3 minutes under the pressure of 200MPa, pressing the wafer sample into a wafer sample with the diameter of 40mm and the height of about 10mm, filling the wafer sample into latex gloves, packaging the latex gloves, sealing the latex gloves, putting the latex gloves into a cold isostatic press, taking out the sample in the cold isostatic press, and carrying out isostatic pressing forming by the cold isostatic press to obtain a prefabricated powder composite 5Si3/ZrB2 with the diameter of 40mm, wherein the density of the prefabricated wafer sample can be remarkably improved by a compact process of 5Si3/ZrB2 mm;
And fifthly, placing the Ti 5Si3/ZrB2 composite powder prefabricated blank wafer sample prepared in the step four into a graphite mold, placing the graphite mold into a vacuum hot-pressing sintering furnace for vacuum hot-pressing sintering process, wherein the preparation method of the vacuum hot-pressing sintering process comprises the steps of carrying out the hot-pressing sintering process under the vacuum condition at the sintering temperature of 1800 ℃, the hot-pressing pressure of 35MPa and the heat preservation time of 2 hours, wherein the vacuum degree of 10 -2 Pa, the heating rate of 35 ℃ per minute in the sintering process, and cooling along with the furnace after the sintering process is finished, thereby preparing the Ti 5Si3/ZrB2 composite material. The sintered wafer sample with the diameter of 40mm and the height of about 6mm can be obtained through the hot-press sintering process, namely the sintered block of the Ti 5Si3/ZrB2 composite material. The Ti 5Si3 intermetallic compound comprises 70 parts by weight of the Ti 5Si3/ZrB2 composite material, wherein a small amount of phenolic resin is completely decomposed and volatilized in the high-temperature hot-pressing sintering process, and no phenolic resin remains in the obtained sintered block.
And step three, during the hot-press sintering process, ti 5Si3 intermetallic compound particles and ZrB 2 particles form a compact Ti 5Si3/ZrB2 composite material sintered block through a hot-press sintering process. The Ti 5Si3 particles and the ZrB 2 particles have good wettability and can be well bonded together to form a compact sintered block. And the higher the content of the Ti 5Si3 intermetallic compound is, the more compact the Ti 5Si3/ZrB2 composite material is. The sintering aid is added with 10 parts by weight of Al 2O3 powder and Y 2O3 powder, and the Al 2O3 powder and the Y 2O3 powder are reacted at high temperature in the sintering process to form a liquid phase Y 3Al5O12, namely YAG phase, so that the liquid phase is formed to promote the densification of the ceramic composite material matrix, the effect of filling pores is achieved, the relative density of the ceramic composite material is improved, and the mechanical property of the ceramic composite material is improved. The effect of adding 10 parts by weight of fine silicon powder sintering auxiliary agent is that the fine silicon powder sintering auxiliary agent forms liquid phase silicon liquid at high temperature in the sintering process, and the liquid phase silicon liquid is formed to promote densification of a ceramic composite material matrix, plays a role of filling pores, improves the relative density of the ceramic composite material and improves the mechanical property of the ceramic composite material. Therefore, the Ti 5Si3/ZrB2 composite material block with higher density can be prepared by the hot-pressing sintering process. And because the hot-press sintering process is carried out at a higher sintering temperature and a higher hot-press pressure, the grains in the sintered block are kept fine, so the Ti 5Si3/ZrB2 composite block prepared by the hot-press sintering process has higher mechanical property and a uniform and compact microstructure.
As can be seen from examples 4 to 10, the hot press sintering process adopted in examples 4 to 10 has the advantages of simple preparation process, low cost and high sintering efficiency, and can realize rapid prototyping. The hot-pressing sintering process has low cost and simple preparation process, and can prepare compact composite material blocks. The main advantages of the present invention over existing technology are therefore:
1) The invention adopts a mechanical alloying process and a heat treatment process to prepare Ti 5Si3 intermetallic compound powder, mixes the prepared Ti 5Si3 intermetallic compound powder with ZrB 2 powder, adds 10 parts by weight of Al 2O3 powder and Y 2O3 powder sintering aid and 10 parts by weight of fine silicon powder as sintering aid, prepares Ti 5Si3/ZrB2 composite powder by wet ball milling mixing and drying, and prepares Ti 5Si3/ZrB2 composite material block by hot-press sintering process. The sintering aid is added with 10 parts by weight of Al 2O3 powder and Y 2O3 powder, and the Al 2O3 powder and the Y 2O3 powder are reacted at high temperature in the sintering process to form a liquid phase Y 3Al5O12, namely YAG phase, so that the liquid phase is formed to promote the densification of the ceramic composite material matrix, the effect of filling pores is achieved, the relative density of the ceramic composite material is improved, and the mechanical property of the ceramic composite material is improved. the effect of adding 10 parts by weight of fine silicon powder sintering auxiliary agent is that the fine silicon powder sintering auxiliary agent forms liquid phase silicon liquid at high temperature in the sintering process, and the liquid phase silicon liquid is formed to promote densification of a ceramic composite material matrix, plays a role of filling pores, improves the relative density of the ceramic composite material and improves the mechanical property of the ceramic composite material. The preparation process of hot-pressing sintering has low cost, simple preparation process and high sintering efficiency, can realize rapid molding sintering, and can also prepare the Ti 5Si3/ZrB2 composite material block with uniform and compact tissue structure.
2) The Ti 5Si3/ZrB2 composite material prepared by adopting the hot-press sintering process has a uniform and compact microstructure, has higher mechanical properties, and simultaneously has the properties of high melting point, high hardness, high elastic modulus and the like of the Ti 5Si3 intermetallic compound. The Ti 5Si3/ZrB2 composite material prepared by the hot-pressed sintering process has higher density and uniform and compact microstructure. The Ti 5Si3/ZrB2 composite material prepared by the hot-pressed sintering process has higher mechanical property and higher hardness, higher wear resistance, good high-temperature oxidation resistance and the like. The invention develops a new preparation process for low-cost manufacture of the Ti 5Si3/ZrB2 composite material, and lays a foundation for popularization and promotion of wide application of the Ti 5Si3/ZrB2 composite material in the engineering field.
3) In the preparation process of the Ti 5Si3/ZrB2 composite material block, 10 parts by weight of Al 2O3 powder and Y 2O3 powder sintering auxiliary agent are added, and the effect of the addition is that the Al 2O3 powder and the Y 2O3 powder sintering auxiliary agent react at high temperature in the sintering process to form a liquid phase Y 3Al5O12, namely YAG phase, so that the liquid phase is formed to promote the densification of the ceramic composite material matrix, the effect of filling pores is achieved, and the mechanical property of the ceramic composite material is improved. In the heat treatment process of the Ti-Si intermetallic compound powder, 10 parts by weight of phenolic resin binder is added into the Ti-Si intermetallic compound powder to improve the strength and hardness of the strip-shaped sample blank after pressure forming, prevent the sample from breaking and damaging when the sample is taken and put into a graphite crucible, ensure the integrity of the sample, decompose the phenolic resin binder into gas at high temperature and volatilize, only a small amount of residual carbon is mixed in the Ti 5Si3 intermetallic compound powder after the heat treatment process, and the final product cannot be influenced. The phenolic resin binder with the mass portion of 10 parts is added into the Ti 5Si3/ZrB2 composite powder to improve the strength and hardness of the wafer sample preform body pressed after pressure molding, prevent the wafer sample preform body from breaking and damaging during sample taking and placing in a graphite mold, ensure the integrity of the sample, decompose the phenolic resin binder into gas at high temperature to volatilize, only a small amount of residual carbon is mixed in the sample after hot-pressed sintering, and the final product is not affected.
FIG. 1 is an X-ray diffraction pattern of a block of Ti 5Si3/ZrB2 composite material prepared by a hot press sintering process according to the method provided by the invention. FIG. 1 is an XRD pattern of a block of Ti 5Si3/ZrB2 composite material prepared by a hot press sintering process. As can be seen from fig. 1, there are diffraction peaks of the Ti 5Si3 intermetallic compound phase and diffraction peaks of the ZrB 2 ceramic phase in the XRD pattern. In addition, there is a small amount of diffraction peak of Y 3Al5O12 phase, namely, diffraction peak of YAG phase. Wherein, during sintering, al 2O3 powder and Y 2O3 powder sintering auxiliary react at high temperature to form liquid phase Y 3Al5O12, namely YAG phase, and the liquid phase is formed to promote densification of the ceramic composite material matrix, thereby improving the relative density of the ceramic composite material and the mechanical property of the ceramic composite material. The XRD pattern has diffraction peaks of Ti 5Si3 intermetallic compound phase and diffraction peaks of ZrB 2 ceramic phase, which shows that in the preparation process of hot-pressed sintering technology, the Ti 5Si3 intermetallic compound and the ZrB 2 ceramic do not react to generate other impurity phases, and the Ti 5Si3 intermetallic compound and the ZrB 2 ceramic have good compatibility, so that the Ti 5Si3 intermetallic compound and the ZrB 2 ceramic can be sintered together to form a compact Ti 5Si3/ZrB2 composite material through the hot-pressed sintering technology, wherein the Ti 5Si3 intermetallic compound is a reinforced and toughened phase, and the ZrB 2 ceramic is taken as a matrix. The Ti 5Si3 intermetallic compound plays a role in strengthening and toughening the ZrB 2 ceramic, and the Ti 5Si3 intermetallic compound can remarkably improve the mechanical property of the ZrB 2 ceramic. The Ti 5Si3/ZrB2 composite material has excellent properties of Ti 5Si3 intermetallic compound and ZrB 2 ceramic. The invention develops a new preparation process for low-cost manufacture of the Ti 5Si3/ZrB2 composite material, and the preparation of the Ti 5Si3/ZrB2 composite material by adopting the hot-press sintering process has the advantages of high preparation efficiency, low preparation cost and higher density and uniform and compact microstructure of the Ti 5Si3/ZrB2 composite material prepared by adopting the hot-press sintering process. The Ti 5Si3/ZrB2 composite material prepared by the hot-pressed sintering process has higher mechanical property and higher hardness, and has good wear resistance, good high-temperature oxidation resistance and the like. The invention develops a new preparation process for low-cost manufacture of the Ti 5Si3/ZrB2 composite material, and lays a foundation for popularization and promotion of wide application of the Ti 5Si3/ZrB2 composite material in the engineering field.
Claims (6)
1. The Ti 5Si3/ZrB2 composite material is characterized by comprising the following components in parts by weight:
10-70 parts of Ti 5Si3 intermetallic compound powder, and taking Ti 5Si3 intermetallic compound as a reinforcing and toughening phase;
30-90 parts of ZrB 2 powder, and taking ZrB 2 as a matrix;
10 parts of Al 2O3 powder and Y 2O3 powder as sintering aids;
fine silicon powder as a sintering aid 10 parts.
2. The Ti 5Si3/ZrB2 composite material according to claim 1, wherein the Ti 5Si3 intermetallic compound is prepared by adopting a mechanical alloying and heat treatment process, ti-Si intermetallic compound powder is prepared by adopting a mechanical alloying ball milling process for 80 hours, and the prepared Ti-Si intermetallic compound powder is subjected to a heat treatment process, wherein the heat treatment process is carried out at a temperature of 1000-1400 ℃ for 1 hour, the heat treatment process is carried out under a vacuum condition, and the Ti 5Si3 intermetallic compound powder is prepared by the heat treatment process.
3. The Ti 5Si3/ZrB2 composite according to claim 1 wherein the molar ratio of Ti to Si in the Ti 5Si3 intermetallic compound is 63:37.
4. The hot press sintering method of the Ti 5Si3/ZrB2 composite material as claimed in claim 1, which is characterized by comprising the following steps in parts by mass:
preparing Ti-Si intermetallic compound powder by adopting a mechanical alloying process, wherein the specific method comprises the following steps of:
Filling Ti powder and Si powder into a ball milling tank of a QM-1SP2 planetary ball mill, wherein the ball milling tank adopts a polytetrafluoroethylene ball milling tank, grinding balls adopt agate grinding balls, the mass ratio of the agate grinding balls to mixed powder is 10:1, the molar ratio of the Ti powder to the Si powder is 63:37, the planetary ball mill is started for mechanical ball milling after the four ball milling tanks are fixed, the mechanical ball milling time is 80h, the rotating speed of the ball mill is 400r/min, the dry ball milling is adopted, and an intermittent ball milling mode is adopted, argon is filled into the ball milling tank as a protective gas, so that Ti-Si intermetallic compound powder is prepared, the purity of the Ti powder is 99%, the granularity is 75-100 mu m, and the purity of the Si powder is 99%, and the granularity is 75-100 mu m;
step two, carrying out a heat treatment process on the Ti-Si intermetallic compound powder prepared in the step one, wherein the specific method comprises the following steps:
placing Ti-Si intermetallic compound powder and 10 parts of phenolic resin binder into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, mixing for 24 hours through mechanical ball milling, mixing to prepare slurry through wet ball milling, placing the slurry into a glass beaker, then placing the glass beaker into a drying oven, drying for 24 hours at 100 ℃, placing the mixed powder into a steel mold capable of preparing strip-shaped samples, pressing the steel mold into strip-shaped samples with the size of 50mm multiplied by 5mm multiplied by 6mm under the pressure of 100MPa for 3 minutes by a pressure forming machine, placing the strip-shaped samples into a graphite crucible, placing the graphite crucible into a vacuum sintering furnace, wherein the heat treatment temperature is 1000-1400 ℃ and the heat preservation time is 1 hour, performing heat treatment under the vacuum condition with the vacuum degree of 10 -2 Pa to obtain porous tissue loose Ti 5Si3 intermetallic compound powder strip-shaped samples, taking out the Ti 5Si3 intermetallic compound strips, crushing the Ti 5Si3 intermetallic compound strips, preparing the strip-shaped samples into the strip-shaped samples with the size of 50mm multiplied by 5mm multiplied by 6mm, placing the strip-shaped samples into the graphite crucible, placing the graphite crucible into a vacuum sintering furnace, wherein the graphite crucible is subjected to heat treatment at 1000 ℃ at the temperature of 1000 ℃ and the temperature of 1400 ℃ and the thermal treatment temperature is lower than the thermal treatment temperature, and the phenolic resin is completely decomposed by 34, and the phenolic resin is completely, the phenolic resin powder is not decomposed in the process, and the phenolic resin powder has no residual phenolic resin is completely;
Mixing 10-70 parts of the Ti 5Si3 intermetallic compound powder prepared in the second step with 30-90 parts of ZrB 2 powder to obtain composite powder, adding 3-9 parts of Al 2O3 powder and 1-7 parts of Y 2O3 powder serving as sintering aids, adding 10 parts of fine silicon powder serving as sintering aids, mixing to obtain mixed powder A consisting of Ti 5Si3 powder, zrB 2 powder, al 2O3 powder, Y 2O3 powder and fine silicon powder, carrying out wet ball milling on the mixed powder A by a mechanical ball milling process, loading the mixed powder A into a ball milling tank, carrying out mechanical ball milling and mixing for 24 hours by adding 100-400 milliliters of absolute ethyl alcohol and 30-60 agate grinding balls with the diameter of 10-16 mm into the ball milling tank, preparing slurry, loading the slurry into a glass beaker, and drying for 24 hours at 100 ℃ to prepare Ti 5Si3/ZrB2 composite powder, wherein the mass of the Ti 5Si3 intermetallic compound powder in the Ti 5Si3/ZrB2 composite powder is 10-70 parts;
Step four, mixing the Ti 5Si3/ZrB2 composite powder prepared in the step three with 10 parts of phenolic resin binder, then filling the mixture into a ball milling tank, adding 300 milliliters of absolute ethyl alcohol and 30 agate grinding balls with the diameter of 15mm, carrying out mechanical ball milling and mixing for 24 hours to prepare slurry, filling the slurry into a glass beaker, and then putting the glass beaker into a baking oven to be dried at 100 ℃ for 24 hours to obtain Ti 5Si3/ZrB2 mixed powder B containing the phenolic resin binder; the mixed powder B is filled into a steel mould capable of preparing a wafer sample to be pressed into the wafer sample, the pressing is carried out for 3 minutes by adopting a forming press under the pressure of 100 MPa-200 MPa to prepare the wafer sample with the diameter of 40mm and the height of about 10mm, the wafer sample is filled into latex gloves and wrapped by the latex gloves and is put into a cold isostatic pressing machine, the medium in the cold isostatic pressing machine is hydraulic oil, the pressure of 100 MPa-200 MPa in the cold isostatic pressing machine is maintained for 5 minutes, the sample is taken out after the pressure maintaining time is finished, and a compact Ti 5Si3/ZrB2 composite powder prefabricated blank body is prepared by isostatic pressing of the cold isostatic pressing machine to obtain the wafer sample with the diameter of 40mm and the height of 8mm, and the compactness of the Ti 5Si3/ZrB2 composite powder prefabricated blank body can be obviously improved by a cold isostatic pressing process;
and fifthly, placing the Ti 5Si3/ZrB2 composite powder prefabricated blank prepared in the step four into a graphite mold, and placing the graphite mold into a vacuum hot-pressing sintering furnace for vacuum hot-pressing sintering process, wherein the vacuum hot-pressing sintering process is prepared by the steps of sintering at 1500-1800 ℃, hot-pressing at 35MPa, keeping the temperature for 2 hours, keeping the vacuum degree at 10 -2 Pa and heating at 10-35 ℃ per minute, and cooling along with the furnace after the vacuum hot-pressing sintering is finished to obtain the Ti 5Si3/ZrB2 composite material. The method comprises the steps of obtaining a sintered wafer sample with the diameter of 40mm and the height of 6mm of a Ti 5Si3/ZrB2 composite material through a hot-pressing sintering process, namely a sintered block of the Ti 5Si3/ZrB2 composite material, wherein the weight part of a Ti 5Si3 intermetallic compound in the Ti 5Si3/ZrB2 composite material is 10-70 parts, a small amount of phenolic resin is completely decomposed and volatilized in a high-temperature hot-pressing sintering process, and no phenolic resin remains in the obtained sintered block.
5. The hot press sintering method of a Ti 5Si3/ZrB2 composite material according to claim 4, wherein in the first step, the average grain size of the Ti-Si intermetallic compound powder prepared by ball milling for 60 hours by mechanical alloying is 10-15 μm, the grain size of the powder is extremely fine, the grain size of the Ti 5Si3 intermetallic compound powder obtained by heat treatment is still 10-15 μm, and the Ti 5Si3 intermetallic compound powder with an ordered structure is obtained.
6. The hot press sintering method of a Ti 5Si3/ZrB2 composite material according to claim 4, wherein in the third step, the grain size of the ZrB 2 powder is 3-5 μm, and the mass fraction of Ti 5Si3 intermetallic compound powder in the Ti 5Si3/ZrB2 composite powder is 10-70 parts.
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