CN1026482C - Method for manufacturing whisker reinforced silicon nitride composite material - Google Patents
Method for manufacturing whisker reinforced silicon nitride composite material Download PDFInfo
- Publication number
- CN1026482C CN1026482C CN 91100598 CN91100598A CN1026482C CN 1026482 C CN1026482 C CN 1026482C CN 91100598 CN91100598 CN 91100598 CN 91100598 A CN91100598 A CN 91100598A CN 1026482 C CN1026482 C CN 1026482C
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- CN
- China
- Prior art keywords
- sic
- composite material
- whisker
- sio
- silicon nitride
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000002131 composite material Substances 0.000 title claims abstract description 10
- 229910052581 Si3N4 Inorganic materials 0.000 title abstract description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title abstract 2
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 239000006229 carbon black Substances 0.000 claims abstract description 8
- 238000007731 hot pressing Methods 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 7
- 238000005261 decarburization Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 2
- KPHJVEBKDSTNMH-UHFFFAOYSA-N [Si].[He] Chemical compound [Si].[He] KPHJVEBKDSTNMH-UHFFFAOYSA-N 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 27
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 235000019241 carbon black Nutrition 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000010439 graphite Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000209456 Plumbago Species 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 silicon nitride compound Chemical class 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Ceramic Products (AREA)
Abstract
The present invention belongs to a method for manufacturing silicon carbide whisker reinforced silicon nitride composite material, which uses Si3N4、SiO2Carbon black and sintering aid as raw materials, 1.1-10 atmN at 1500-1900 deg.C2Synthesizing SiC crystal whisker under pressure, then decarbonizing at 600-700 ℃, and carrying out N treatment on the decarbonized composite raw material at 1700-1900 DEG C2Hot pressing for 0.5-2 hours under atmosphere to obtain compact Si3N4-SiC(w)The fracture toughness of the composite material obtained by the invention is 8.0 MPa.m1/2The normal temperature strength is 670MPa, and the high temperature strength is 621MPa measured at 1300 ℃ after being oxidized for 100 hours at 1300 ℃, which is only 7.3 percent lower than the normal temperature strength.
Description
The invention belongs to a kind of manufacture method of silicon carbide whisker excess weld metal silicon nitride compound material.High temperature resistant, corrosion-resistant, the wear-resisting structural timber that undermines performance such as anti-oxidant can be made with this method, products such as engine component, lathe tool, wortle can be used for manufacturing.
At present, the crystal whisker excess weld metal matrix material methods that add whisker that adopt more, but since whisker itself be worth expensive, the matrix material price height that obtains, the restriction of being originated again, and need very complicated technology whisker is handled and disperseed; Therefore, how obtaining in preparation process the matrix material that self generates the some amount whisker, is one of striving direction of people.Japanese Patent J63-182254 discloses a kind of crystal whisker excess weld metal Al
2O
3The manufacture method of molding is with Al
2O
3, SiO
2React at 1600 ℃ with carbon black; Be SiO
2+ 3C → SiC
(w)+ 2CO ↑, like this, matrix Al
2O
3Can not participate in the reaction and change, can obtain Al
2O
3Base SiC metal whisker composite.For Si
3N
4Base SiC metal whisker composite J63-64969,64970,64971 disclose a series of Si
3N
4-SiC
(w)The manufacture method of sintered compact is with Si powder or Si powder and Si
3N
4Be raw material, adopt at N
2Reaction sintering is prepared Si earlier in the atmosphere
3N
4The matter base substrate is then at C
3H
8+ H
2+ H
2Synthetic SiC whisker in the mixed gas of S adopts the gas pressure sintering method to prepare fine and close matrix material at last, and performance is δ b～750MPa, K
IC～8.0MPam
1/2, but do not see and introduce high-temperature behavior.This technological process is complicated, and source of the gas requires harsh, so its enforcement and application are subjected to certain limitation.
Purpose of the present invention is intended to overcome the shortcoming of above-mentioned prior art, and it is simple, easy to implement to obtain a kind of technology, and can obtain the manufacture method of the matrix material of higher high-temperature behavior.
For achieving the above object, the present invention is achieved in that Si
3N
4, SiO
2, powder mixes such as carbon black and sintering aid, at certain temperature (1500～1900 ℃), certain N
2Pressure (1.1～10atm) times synthetic SiC whiskers, decarburization 1～3h in 600～700 ℃, air then.In 1700～1900 ℃ of following hot pressing 0.5～2h, can obtain Si again
3N
4-SiC
(w)Matrix material.
Below the present invention is described in further detail.
The Si that the present invention obtains
3N
4-SiC
(w)The manufacture method of matrix material is: with weight ratio is 50～70%Si
3N
4(granularity＜0.3 μ m), 15～25%SiO
2(granularity＜100 μ m), 10～20% carbon blacks, 3～8% sintering aids mix in anhydrous ethanol medium, sieve after the oven dry.This mixing raw material is packed in the plumbago crucible, at 1.1～10atmN
2Under the pressure, 1500～1900 ℃ of synthetic 1～2h are then at Al
2O
3Coil decarburization 1～3h in interior 700 ℃ of air.To take off compound material behind the C and pack into and scribble in the graphite jig of BN, in 1700～1900 ℃, 30MPa, N
2Hot pressing 0.5～2h under the atmosphere can obtain relative density greater than 99% matrix material.
The used raw material of the present invention is Si
3N
4, SiO
2And carbon black, when at high temperature synthesizing the SiC whisker for assurance, Si
3N
4The unlikely decomposition of matrix needs to adopt N
2Protect, but because N
2Participation, Si
3N
4, SiO
2C and N
2Between at high temperature (1600 ℃) down very complicated chemical reaction may take place, sum up and get up to mainly contain following three reactions:
△G
0 1＝137500+3TlgT-92.44T Cal
△G
0 2＝98500-75.21T Cal
△G
0 3＝314000+9TlgT-202.11T Cal
As calculated, above-mentioned three standard free energies variations that are reflected under 1600 ℃ are respectively:
△G
0 1＝-17251Cal
△G
0 2＝-42368Cal
△G
0 3＝-9309Cal
This shows, consider that from the thermodynamics angle above-mentioned three reactions all may take place.Work as N
2Preponderated than the reaction of (1) (2) when pressure was 1atm, promptly as the Si of matrix material
3N
4To be transformed into SiC(with C reaction but not be the whisker shape), make SiC content be higher than expectation quantity; Like this, be the generation of inhibited reaction (2), should increase N
2Pressure, but the meeting of the trend of reaction (3) so increase, i.e. SiO
2Be transformed into Si
2N
4, be difficult to obtain estimating the SiC whisker of quantity.So,, guarantee SiO for the generation of inhibited reaction (2), (3)
2All generate the SiC that estimates quantity, must select suitable pressure range with the C reaction.Be defined as 1.1～10atm through experiment.
Consider Si simultaneously
3N
4If the phase composite of raw material is N
2Pressure excessive (＞3atm), then can promote α → β → Si
3N
4Phase transformation, make α-Si
3N
4Content reduces, β-Si
3N
4Content increases.
In 1500～1900 ℃ of scopes, when temperature during less than 1600 ℃, SiO
2Though the reaction of+3C → SiC+2CO can take place, react abundant inadequately, and particulate state SiC is more; After 1650 ℃, react completely, but the whisker surface deterioration.
In sum, synthetic Si
3N
4-SiC
(w)The optimal processing parameter of compound material is: 1600～1650 ℃, and 2～2.5atmN
2Pressure.
Employed sintering aid is among the present invention: Y
2O
3, Al
2O
3And La
2O
3
After the synthetic SiC whisker,, therefore have remaining C and exist, also need in air 600～700 ℃ of decarburization 1～3h because C is excessive.And then will take off compound material after the C and pack into and scribble in the graphite jig of BN, in 1700～1900 ℃, 30MPa, N
2Protection (1atm) is hot pressing 0.5～2h down, can obtain fine and close matrix material.
Introduce embodiments of the invention below in conjunction with effect.
Embodiment 1, raw material: 62wt%Si
3N
4(mean particle size is 0.25 μ m, α-Si
3N
4Account for 94%, β-Si
3N
4Be that 5.2% free Si and other impurity are 0.8%), 18.18wt%SiO
2(granularity＜100 μ m), 16.1wt% carbon ink, sintering aid Y
2O
3And Al
2O
3Respectively be 1.86%.
Above-mentioned raw materials ball milling in anhydrous ethanol medium is mixed, sieves after the oven dry, in the plumbago crucible of packing in 1600 ℃, 2.5tmN
2Synthetic 2 h under the pressure, 700 ℃ of decarburization 2h in air atmosphere again take off compound material behind the C and carry out X-ray diffraction analysis and prove by α-Si
3N
4, β-Si
3N
4And β-SiC composition, under scanning electron microscope, can observe tangible whisker, diameter is 0.1～0.5 μ m, length is tens μ m.SiC content adopts infrared absorption determining C constituent content to convert out in the compound material.With the synthetic compound material at 1800 ℃, 1atmN
2Hot pressing 1h under the atmosphere.
Embodiment 2: proportioning raw materials is 69.44wt%Si
3N
4, 13.2wt%SiO
2, 13.20wt% carbon black, Y
2O
3And AL
2O
3Respectively be 2.08%.Manufacture method is with embodiment 1.
Embodiment 3: proportioning raw materials is with embodiment 1, in 1600 ℃, and 2atmN
2Following Synthetic 2 h, 700 ℃ are taken off C2h, and 1800 ℃, 1atmN
2Following hot pressing 1h.
Comparative Examples is Si same as the previously described embodiments
3N
4Raw material is in 1800 ℃, 1atmN
2Following hot pressing 1h.
The measurement of material mechanical performance: the normal temperature bending strength adopts three-point bending method, and specimen size is 3 * 4 * 36mm, and span is 30mm, and loading velocity is 0.5mm/min; Fracture toughness property adopts the coped beam method, and specimen size is 2 * 4 * 22mm, and kerf width is 84 μ m; High-temperature bending strength is 1300 ℃ of oxidation 100h, 1300 ℃ of intensity that record.
The measuring result such as the table 1 of the present invention and Comparative Examples show.
As can be seen from Table 1, because the existence of SiC whisker, the fracture toughness property of material has obtained very big improvement, by 5.7MPam
1/2Bring up to 8.0MPam
1/2, improved approximately 40% than matrix, simultaneously, the high-temperature behavior of material has had significant raising: Si
3N
4The hot strength of material is that 383MPa(is without 1300 ℃ * 100h oxidation), compare with normal temperature strength (750MPa) and to have reduced by 48.9%; And the hot strength of matrix material of the present invention is that 621MPa(is through 1300 ℃ * 100h oxidation), (670MP) compares with normal temperature strength, only reduced about 7.3%.
Compared with the prior art, the present invention directly adopts Si
3N
4Be matrix, use SiO simultaneously
2With the synthetic SiC whisker of carbon black, because the temperature higher (greater than 1550 ℃) that synthetic SiC whisker needs, all selecting the material that can not react with it and change in the prior art for use is matrix, as AL
2O
3Deng, and the present invention calculates and analyzes by thermodynamic argument, by selecting suitable atmosphere, pressure and synthesis temperature, has solved this difficult problem dexterously, has both guaranteed Si
3N
4Matrix can not change because of reaction takes place to decompose, and can obtain being uniformly distributed in the SiC whisker of the expectation quantity in the matrix again.The Si that the present invention obtains
3N
4-SiC
(w)Method for composite material, with J63-64969,64970,64971 all methods are compared, have advantages such as technology is simple, easy to implement, the source of the gas requirement is single, can eliminate the harm that obnoxious flavour causes in composite material manufacturing process, and can obtain having the matrix material of excellent high-temperature behavior.
Table 1
1300℃×100h
Krc(MPa) after the oxidation
SiCvol%????δ（MPa）
·m
1/2） δ
b1300℃
（MPa）
Si
3N
40 750 5.7 383°
Embodiment 1 15 670 8.0 621
Embodiment 2 10 640 7.0-
Embodiment 3 19 622 6.5-
* without 1300 ℃ * 100h oxidation.
Claims (2)
1, a kind of manufacture method of crystal whisker excess weld metal helium silicon composite, this method comprises: synthetic through 1～2 hour high temperature after required raw material is mixed, in 600～700 ℃ of insulations decarburization in 1～3 hour,, can obtain fine and close Si then again in 1700～1900 ℃ of following hot pressing 0.5～2 hour
3N
4-SiC
(w)Matrix material is characterized in that: the content of raw material is (wt%): Si
3N
450～70, SiO
215～25, carbon black 10～20, sintering aid 3～8, described sintering aid are Y
2O
3, Al
2O
3And La
2O
3, under 1500～1900 ℃, 1.1～2.5atmN
2Synthetic compound material under the pressure.
2, manufacture method according to claim 1 is characterized in that: the optimal processing parameter of described synthetic compound material is 1600～1650 ℃, 2～2.5atmN
2Pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91100598 CN1026482C (en) | 1991-02-04 | 1991-02-04 | Method for manufacturing whisker reinforced silicon nitride composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91100598 CN1026482C (en) | 1991-02-04 | 1991-02-04 | Method for manufacturing whisker reinforced silicon nitride composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1052652A CN1052652A (en) | 1991-07-03 |
| CN1026482C true CN1026482C (en) | 1994-11-09 |
Family
ID=4904718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91100598 Expired - Fee Related CN1026482C (en) | 1991-02-04 | 1991-02-04 | Method for manufacturing whisker reinforced silicon nitride composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1026482C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100381398C (en) * | 2005-07-29 | 2008-04-16 | 南京理工大学 | Preparation method of AlN Si3N4-SiC ceramic material |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055324C (en) * | 1994-06-30 | 2000-08-09 | 中国科学院金属研究所 | Amorphous in-situ synthesized nm silicon nitride crystal whisker |
| CN1057515C (en) * | 1997-10-24 | 2000-10-18 | 清华大学 | Method for deoxidisation and reinforcement of solid organic procursor of silicon nitride material |
| CN1112337C (en) * | 1999-05-28 | 2003-06-25 | 清华大学 | Preparation of silicon nitride-based composite material with superhigh tenacity |
| CN109320276B (en) * | 2018-10-15 | 2021-04-02 | 西北工业大学 | Preparation method of silicon nitride whiskers and silicon nitride nanowires reinforced silicon nitride-based wave-transmitting ceramics |
| CN112159236B (en) * | 2020-10-19 | 2021-06-11 | 江苏贝色新材料有限公司 | High-thermal-conductivity silicon nitride ceramic substrate and preparation method thereof |
-
1991
- 1991-02-04 CN CN 91100598 patent/CN1026482C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100381398C (en) * | 2005-07-29 | 2008-04-16 | 南京理工大学 | Preparation method of AlN Si3N4-SiC ceramic material |
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| Publication number | Publication date |
|---|---|
| CN1052652A (en) | 1991-07-03 |
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