CN100424039C - Original position reaction hot pressing synthesis TiB2-NbC-SiC refractory ceramics composite material and preparing method thereof - Google Patents
Original position reaction hot pressing synthesis TiB2-NbC-SiC refractory ceramics composite material and preparing method thereof Download PDFInfo
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- CN100424039C CN100424039C CNB2006100460138A CN200610046013A CN100424039C CN 100424039 C CN100424039 C CN 100424039C CN B2006100460138 A CNB2006100460138 A CN B2006100460138A CN 200610046013 A CN200610046013 A CN 200610046013A CN 100424039 C CN100424039 C CN 100424039C
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- 238000007731 hot pressing Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 12
- 239000002131 composite material Substances 0.000 title claims description 29
- 239000011214 refractory ceramic Substances 0.000 title claims description 27
- 238000000034 method Methods 0.000 title abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- 238000005245 sintering Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000010955 niobium Substances 0.000 claims description 11
- 229910052580 B4C Inorganic materials 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000013312 flour Nutrition 0.000 claims description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 239000000919 ceramic Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 abstract description 2
- DYOWGCNNYMLFQV-UHFFFAOYSA-N 2-acetyloxybenzoic acid;2-hydroxybenzamide;1,3,7-trimethylpurine-2,6-dione Chemical compound NC(=O)C1=CC=CC=C1O.CC(=O)OC1=CC=CC=C1C(O)=O.CN1C(=O)N(C)C(=O)C2=C1N=CN2C DYOWGCNNYMLFQV-UHFFFAOYSA-N 0.000 abstract 1
- 229910033181 TiB2 Inorganic materials 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 abstract 1
- 239000011863 silicon-based powder Substances 0.000 abstract 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 46
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 18
- 239000011159 matrix material Substances 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 101100206286 Caenorhabditis elegans tns-1 gene Proteins 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- HPNSNYBUADCFDR-UHFFFAOYSA-N chromafenozide Chemical compound CC1=CC(C)=CC(C(=O)N(NC(=O)C=2C(=C3CCCOC3=CC=2)C)C(C)(C)C)=C1 HPNSNYBUADCFDR-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
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Abstract
This invention relates to a ceramic-base compound material and its preparation method, concretely, it is a method for preparing high temperature ceramic compound material of TiB2-NbC-SiC by hot pressing of situ thermal reaction, in which, three kinds of component phases are generated in site, Nb is solutionized in TiB2 to generate Ti(Nb)B2, Ti is solutionized in NbC to generate Nb(Ti)C and SiC exists in the form of beta-SiC. The preparation method includes: taking Ti powder, Nb powder, Si powder, BC powder and graphite powder as the raw materials and absolute alcohol as the medium to ball-mill them for 16-30 h to be dried and screened and put into a graphite die to be pressed and molded(10-20MPa) to be sintered in a hot pressed kiln with Ar under 1600-1800deg.C for 1-4h, the temperature rising speed is 10-15deg.C/min and the sintering pressure is 20-40MPa.
Description
Technical field
The present invention relates to ceramic matric composite and preparation method, be specially a kind of in-situ hot pressing prepared in reaction TiB
2-NbC-SiC refractory ceramics composite material and preparation method thereof.
Background technology
TiB
2Be hexagonal system C
32The compound of type structure, it has a series of good physical and chemical performances: high-melting-point (3253K), high rigidity, high elastic coefficient, good chemical stability, electroconductibility and thermal conductivity.These excellent physical chemistry make TiB
2Have very big potential using value: as utilize its high-melting-point and high chemical stability, can prepare superhigh temperature ceramic material; Utilize its high rigidity, high strength can the good structured material of processability.But on the one hand because TiB
2In the crystal, a, b axle are covalent linkage, and the c axle is the anisotropy that the characteristic of ionic linkage causes its performance.This anisotropy can cause crystal growth preferred orientation to occur, and along with growing up of crystal grain, the unrelieved stress in the material also strengthens, and produces a large amount of tiny cracks, and the mechanical property of material is descended.Simultaneously under the acting in conjunction of ionic linkage and σ key, Ti
+With B
-All difficult migration the in sintering process, so TiB
2The atom self-diffusion coefficient very low, coking property is very poor.Though use to add the method for metal powder can low-temperature sintering the block materials of fine and close and normal temperature good mechanical property, its high-temperature mechanical property is undesirable.(Journal ofInorganic Materials, 17 (2002) 703-707) think the NbB that adds same high-melting-point, has identical crystalline structure and close lattice parameter after deliberation
2Can and TiB
2Form sosoloid, improve its coking property, and can refinement TiB
2TiB on the other hand
21000 ℃ of antioxidant property variation, and SiC can prepare TiB in antioxidant property excellence below 1400 ℃
2-SiC matrix material improves its high-temperature oxidation resistance (Materials Letters, 25 (1995) 97-100).Moreover NbC has good thermohardening and anti-thermal shock ability, can provide high temperature deformation resistance (Materials Science and Engineering A251 (1998) 276-285) for stupalith.Therefore, design TiB
2-NbC-SiC matrix material is to obtain good comprehensive mechanical performance.
Use hot pressing original position synthetic technology, its principle is with raw material proportioning on request, makes it that chemical reaction take place and generates target product, uses heat pressing process to obtain fine and close material simultaneously.Its advantage is simple, the province's energy that saves time of technology, and the product original position is synthetic, has avoided outside contamination, interface cleanness.Therefore, this patent adopts hot pressing original position synthetic technology to prepare TiB
2-NbC-SiC matrix material.
Summary of the invention
The objective of the invention is to design that a kind of mechanical property is good, high temperature reliability is good, high-temperature oxidation resistance is good, simple to operate, easy control of process conditions, the synthetic TiB of reaction in hot pressing that cost is low
2-NbC-SiC refractory ceramics composite material and preparation method thereof.
Technical scheme of the present invention is:
A kind of original position is synthesized TiB
2-NbC-SiC refractory ceramics composite material is characterized in that: three kinds become the phase-splitting reaction in to generate, and Nb is solidly soluted into TiB
2Middle Ti (Nb) B that generates
2, Ti is solidly soluted into and generates Nb (Ti) C among the NbC, and silicon carbide exists with the form of β-SiC.TiB wherein
2Content be 30～65wt.%, the content of NbC is 0～60wt.%, the content of SiC is 10～35wt.% (weight percent).
By weight percentage, TiB
2Preferable content be 45～65%, the preferable content of NbC is 5～35%, the preferable content of SiC is 20～30%.
TiB is synthesized in a kind of reaction in hot pressing
2The preparation method of-NbC-SiC refractory ceramics composite material, synthetic by the reaction in hot-pressing technique, the content of NbC and SiC in the matrix wherein, Nb is at TiB
2Can regulate by the content of Nb and C in the original proportioning with the solid solubility of Ti in NbC.
Described TiB
2The preparation method of-NbC-SiC refractory ceramics composite material, with titanium valve, niobium powder, silica flour, boron carbide powder and Graphite Powder 99 is raw material, mol ratio is 2: x: 1: 1: x (0＜x≤3), ball milling 16～30 hours, dry and sieve after the coldmoulding (10～20MPa) in the graphite jig of packing into, in vacuum or be connected with sintering in the hot pressing furnace of argon gas, temperature rise rate is 10～15 ℃/minute, and sintering temperature is that 1600～1800 ℃, heat preservation sintering time are that 1～4 hour, sintering pressure are 20～40MPa.Thereby, under lower temperature, prepare superior TiB of over-all properties such as high-compactness, high rigidity, high strength, excellent toughness, high-temperature oxidation resistance be good
2-NbC-SiC refractory ceramics composite material.
The titanium valve of described adding, niobium powder, silica flour, boron carbide powder and Graphite Powder 99 size range are 200～600 orders; Described sintering processing is a hot pressed sintering; Described sintering atmosphere is that (vacuum tightness is 10 to vacuum
-4～10
-2MPa) or argon gas; Described mixing method adopts the ball milled under the alcohol medium.
Advantage of the present invention is:
1. low-temperature sintering, technology is simple, and cost is low.The present invention is a raw material with titanium valve, niobium powder, silica flour, boron carbide powder and Graphite Powder 99, and synthetic 1600～1800 ℃ of hot pressing by reaction in, sintering and densification are carried out simultaneously.The agglomerating TiB of institute
2-NbC-SiC refractory ceramics composite material can be by titanium boride, niobium carbide and silicon carbide three phase composites, and wherein Nb is solidly soluted into TiB
2In and Ti be solidly soluted into and form sosoloid among the NbC.With respect to earlier synthetic three phase ceramics, the remix sintering had both made technical process become simply, greatly reduced sintering temperature again.
2. good, mechanical behavior under high temperature of mechanical property and high-temperature oxidation resistance are good.Because it is synthetic that three-phase is an original position, the good interface relation is arranged, and the existence meeting refinement TiB of NbC and SiC
2Crystal grain, thereby the mechanical property of raising matrix.In addition, silicon carbide is to improving TiB
2High-temperature oxidation resistance, and NbC also obtains performance to the advantage of the high temperature rigidity that improves material.
3, the matrix material of the present invention's acquisition can use in the temperature below 1400 ℃, mainly as thermal structure spare, be applied to condition harshnesses such as high temperature, corrodibility is strong, in the high Working environment of mechanical property requirements, comprise machinery, metallurgy, Aeronautics and Astronautics field.
Description of drawings
Fig. 1 (a)-(b) is TiB
2The X-ray diffraction phase composition of-NbC-SiC refractory ceramics composite material is analyzed.
Fig. 2 (a)-(c) is TiB
2The distribution mutually of-NbC-SiC refractory ceramics composite material glazed surface (back scattering phase).
Fig. 3 is TiB
2The Young's modulus of-NbC-SiC refractory ceramics composite material is in a vacuum with the variation of temperature curve.
Fig. 4 is TiB
2The high temperature oxidation change in resistance curve (respectively being incubated 2 hours) of-NbC-SiC refractory ceramics composite material.
Embodiment
Below by example in detail the present invention is described in detail.
Embodiment 1 (TNS-1)
With size range is 200～600 purpose titanium valve 102.42g, niobium powder 9.30g, silica flour 30.45g, boron carbide powder 59.46g and graphite 1.20g.Ball milling is 16 hours in raw spirit medium, agate jar, and dry (water content is less than 0.05wt.%) also crosses 200 mesh sieves, coldmoulding in the graphite jig of packing into afterwards, and the pressure that applies is 10MPa, puts into the hot pressing furnace hot pressed sintering.Temperature rise rate is 10 ℃/minute, is heated to 1700 ℃ of insulations 4 hours, and exerting pressure is 35MPa.Whole sintering process all is to carry out under argon shield, and the reaction product of acquisition is TiB through X-ray diffraction analysis
2, NbC and SiC.TiB
2The about 65.3wt.% of content, the about 0.4wt.% of the content of NbC, the about 34.3wt.% of the content of SiC.The density that Archimedes's method records is 3.88g/cm
3The Vickers' hardness of TNS-1 matrix material is 21.5 ± 2.4GPa; Young's modulus is 362GPa; Flexural strength is 603.1 ± 44.7MPa; Fracture toughness property is 5.4 ± 0.3MPam
1/2
Embodiment 2 (TNS-2)
With size range is 200～600 purpose titanium valve 91.35g, niobium powder 43.37g, silica flour 26.89g, boron carbide powder 52.50g and graphite 5.60g.Ball milling is 24 hours in raw spirit medium, agate jar, and dry (water content is less than 0.05wt.%) also crosses 200 mesh sieves, coldmoulding in the graphite jig of packing into afterwards, and the pressure that applies is 15MPa, puts into the hot pressing furnace hot pressed sintering.Temperature rise rate is 15 ℃/minute, is heated to 1750 ℃ of insulations 2 hours, and exerting pressure is 30MPa.Whole sintering process all is to carry out under argon shield, and the reaction product of acquisition is TiB through X-ray diffraction analysis
2, NbC and SiC.TiB
2The about 57.8wt.% of content, the about 15.0wt.% of the content of NbC, the about 27.2wt.% of the content of SiC.The density that Archimedes's method records is 4.33g/cm
3The Vickers' hardness of TNS-2 matrix material is 20.6 ± 2.0GPa; Young's modulus is 421GPa; Flexural strength is 522.4 ± 30.2MPa; Fracture toughness property is 6.0 ± 0.2MPam
1/2
Embodiment 3 (TNS-3)
With size range is 200～600 purpose titanium valve 84.62g, niobium powder 116.18g, silica flour 24.92g, boron carbide powder 48.65g and graphite 15.00g.Ball milling is 30 hours in raw spirit medium, agate jar, and dry (water content is less than 0.05wt.%) also crosses 200 mesh sieves, coldmoulding in the graphite jig of packing into afterwards, and the pressure that applies is 20MPa, puts into the hot pressing furnace hot pressed sintering.Temperature rise rate is 15 ℃/minute, is heated to 1800 ℃ of insulations 1 hour, and exerting pressure is 20MPa.Whole sintering process all is to carry out under argon shield, and the reaction product of acquisition is TiB through X-ray diffraction analysis
2, NbC and SiC.TiB
2The about 44.3wt.% of content, the about 38.9wt.% of the content of NbC, the about 16.8wt.% of the content of SiC.The density that Archimedes's method records is 4.69g/cm
3The Vickers' hardness of TNS-3 matrix material is 17.0 ± 1.6GPa; Young's modulus is 380GPa; Flexural strength is 525.1 ± 22.4MPa; Fracture toughness property is 5.5 ± 0.2MPam
1/2
Comparative example
Adopt the TiB of three kinds of prepared heterogeneity phase contents of present method
2-NbC-SiC refractory ceramics composite material and Guojun Zhang etc. are by reaction hot-pressing synthetic TiB
2-SiC matrix material (Materials Letters, 25 (1995) 97-100) is compared.TiB in the document
2The preparation temperature of-SiC matrix material is 2000 ℃, and Vickers' hardness is 16.5GPa; Flexural strength 3322 ± 26MPa.Not only preparation temperature is higher, and the relevant mechanical properties index also is lower than TiB
2-NbC-SiC refractory ceramics composite material.
Following mask body is introduced TiB
2The phase composition of-NbC-SiC refractory ceramics composite material, microstructure, high-temperature elastic modulus and high-temperature oxidation resistance.
Fig. 1 (a)-(b) is TiB
2The X-ray diffraction phase composition of-NbC-SiC refractory ceramics composite material is analyzed.Fig. 1 (b) is that the part among Fig. 1 (a) is amplified.With increasing of Nb in the original proportioning and C content, the TiB that generates
2Be offset to low angle with the peak position of NbC.This is because Nb is solidly soluted into TiB
2In many more, can make big more that its lattice parameter becomes.Simultaneously, with the minimizing of Ti solid solution in NbC, it is big more that its lattice parameter also becomes.Fig. 2 (a)-(c) is TiB
2The distribution mutually of-NbC-SiC refractory ceramics composite material glazed surface (back scattering phase).Fig. 2 (a), Fig. 2 (b) are SiC with black among Fig. 2 (c) mutually, and grey form and aspect are TiB
2Fig. 2 (b) is NbC with white among Fig. 2 (c) mutually, increases with the increase of Nb in the original proportioning and C content.SiC even dispersion among Fig. 2 (a) is distributed in TiB
2In the matrix, and reuniting appears in the SiC among Fig. 2 (b) and Fig. 2 (c).Fig. 3 is TiB
2The Young's modulus of-NbC-SiC refractory ceramics composite material is in a vacuum with the variation of temperature curve.Before 900 ℃, the Young's modulus of three kinds of matrix materials descends all very little, about 20GPa.Descending with the increase Young's modulus of temperature after 900 ℃ has aggravation trend, also only respectively is 18.5%, 16.9% and 17.8% but descend up to the Young's modulus of 1400 ℃ of three kinds of matrix materials.This shows TiB
2-NbC-SiC refractory ceramics composite material has good high-temperature stability.Fig. 4 is TiB
2The high temperature oxidation change in resistance curve of-NbC-SiC refractory ceramics composite material.The matrix material of three kinds of heterogeneities all shows excellent oxidation-resistance before 1000 ℃; Between 1000～1400 ℃, be reduction trend with the increase of NbC content in the matrix and the minimizing oxidation resistance of SiC content.But the gain in weight of TNS-3 also only is 282.59g/m in the time of 1400 ℃
2, prove TiB
2-NbC-SiC refractory ceramics composite material has good high-temperature oxidation resistance.
By embodiment 1, embodiment 2, embodiment 3 and comparative example as seen, the TiB of present method preparation
2-NbC-SiC refractory ceramics composite material has superior characteristics of over-all properties such as high-compactness, high rigidity, high strength, excellent toughness, high-temperature oxidation resistance be good.
Claims (4)
1. TiB is synthesized in a reaction in hot pressing
2The preparation method of-NbC-SiC refractory ceramics composite material, it is characterized in that: with titanium valve, niobium powder, silica flour, boron carbide powder and Graphite Powder 99 is raw material, mol ratio between each raw material is 2: x: 1: 1: x, 0＜x≤3 wherein, raw material powder ball milling 16～30 hours, the coldmoulding in the graphite jig of packing into, the pressure that applies is 10～20MPa, in vacuum or be connected with sintering in the hot pressing furnace of argon gas, temperature rise rate is 10～15 ℃/minute, sintering temperature is 1600～1800 ℃, and the heat preservation sintering time is that 1～4 hour, sintering pressure are 20～40MPa.
2. according to the described TiB of claim 1
2The preparation method of-NbC-SiC refractory ceramics composite material is characterized in that: the content of NbC and SiC, Nb is at TiB
2In solid solubility and the solid solubility of Ti in NbC, regulate according to the content of Nb and C in the original proportioning.
3. according to the described TiB of claim 1
2The preparation method of-NbC-SiC refractory ceramics composite material is characterized in that: the titanium valve of described adding, niobium powder, silica flour, boron carbide powder and Graphite Powder 99 size range are 200～600 orders.
4. according to the described TiB of claim 1
2The preparation method of-NbC-SiC refractory ceramics composite material is characterized in that: adopting alcohol is medium ball milling in the agate jar.
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| CN101417878B (en) * | 2007-10-24 | 2011-06-29 | 中国科学院金属研究所 | TaC-SiC ceramic composite material synthesized by hot pressing at in-situ reaction |
| US20190203344A1 (en) * | 2017-03-24 | 2019-07-04 | Kennametal Inc. | Evaporator boats for metallization installations |
| CN107382353A (en) * | 2017-08-10 | 2017-11-24 | 巩义市泛锐熠辉复合材料有限公司 | A kind of preparation method of fibre reinforced titanium diboride based composites |
| CN113149658B (en) * | 2021-04-28 | 2023-02-07 | 武汉理工大学 | Titanium nitride-based composite ceramic material and preparation method thereof |
| CN114438360B (en) * | 2021-12-31 | 2022-06-21 | 哈尔滨工业大学 | In-situ synthesized (TiNb) C reinforced superfine crystal TiNbMo refractory concentrated alloy-based composite material and preparation method thereof |
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| JPH04132667A (en) * | 1990-09-21 | 1992-05-06 | Agency Of Ind Science & Technol | Method for increasing strength of titanium boride/silicon carbide compound ceramics |
| CN1680215A (en) * | 2005-01-14 | 2005-10-12 | 李根法 | Eutectic composite powdery-sintering assistant for manufacturing structural ceramic and production thereof |
| JP4132667B2 (en) * | 1998-01-30 | 2008-08-13 | シマヅ リサーチ ラボラトリー（ヨーロッパ）リミティド | Time-of-flight mass spectrometer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04132667A (en) * | 1990-09-21 | 1992-05-06 | Agency Of Ind Science & Technol | Method for increasing strength of titanium boride/silicon carbide compound ceramics |
| JP4132667B2 (en) * | 1998-01-30 | 2008-08-13 | シマヅ リサーチ ラボラトリー（ヨーロッパ）リミティド | Time-of-flight mass spectrometer |
| CN1680215A (en) * | 2005-01-14 | 2005-10-12 | 李根法 | Eutectic composite powdery-sintering assistant for manufacturing structural ceramic and production thereof |
Non-Patent Citations (1)
| Title |
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| TiB2材料的研究现状及其应用. 向军辉.陶瓷工程，第29卷第4期. 1996 * |
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