CN103964881A - Metal whisker strengthening-toughening self-healing ceramic-based composite material - Google Patents
Metal whisker strengthening-toughening self-healing ceramic-based composite material Download PDFInfo
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- CN103964881A CN103964881A CN201410151213.4A CN201410151213A CN103964881A CN 103964881 A CN103964881 A CN 103964881A CN 201410151213 A CN201410151213 A CN 201410151213A CN 103964881 A CN103964881 A CN 103964881A
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Abstract
The invention discloses a metal whisker strengthening-toughening self-healing ceramic-based composite material, and is characterized by comprising continuous fiber, metal whisker and a ceramic basal body, wherein the continuous fiber can be carbon fiber, silicon carbide fiber or C-SiC fiber, the size content is controlled within 30-50 percent, and the surface of the composite material is protected by a carbon or boron nitride coating. The metal whisker adopts metal or alloy wire whisker with good toughness and higher strength, can be one or alloy of titanium, niobium, zirconium, tungsten, rhenium and tantalum, the size content is controlled within 10-30 percent, and the metal whiskers are distributed between fiber bundles or wires. The ceramic basal body is selected from non-oxide ceramics such as silicon carbide and silicon nitride. The ceramic-based composite material is short in self-healing time and good in effect, various ceramic basal bodies, reinforced fiber and whiskers can be selected, and component design can be achieved, and high-performance parts with complex shapes can be manufactured.
Description
Technical field
The present invention relates to field of compound material, particularly relate to a kind of metal whisker highly malleablized self-healing ceramic matric composite.
Background technology
The excellent specific properties such as it is high temperature resistant, corrosion-resistant, wear-resistant that stupalith has, but exist, fragility is large, the shortcoming of easy fracture, and limited its practical ranges, therefore improve stupalith fragility, increase intensity, improve its reliability in actual applications and become the key that can it widespread use.The toughness of stupalith can be passed through whisker, fiber reinforced, and the mechanism such as yttria stabilizator and transformation toughening strengthen.Whisker-Reinforced Ceramic Based Composite is considered to solve the effective measure of high temperature application, this material commercialization be applied to cutting tool, wear part, aerospace and military device etc. at present.
Since the eighties in 20th century, the research of ceramic matric composite has obtained very big attention, and research concentrates on mechanical behavior, chemical stability and thermal shock resistance etc., less to high temperature surface crack self-healing process study.And hole and crackle that the ceramic matric composites such as silicon carbide exist have limited its work-ing life, must carry out self-healing modification to it, improve work-ing life.
For the mechanism of crack healing, differing materials is different.Engineering materials is mainly based on oxidizing reaction principle, as metallic surfaces such as stainless steel, aluminium alloys, can form oxide film, thereby prevents the further oxidation of material, plays protection, etch-proof effect.For the statement of stupalith crack healing mechanism, have nothing in common with each other at present, substantially can be divided into three kinds: 1, adsorption mechanism: when surface of fracture is bonded together, because valence f. effect causes the interatomic bond between interface.2, diffusion mechanism: driven by local surfaces Curvature change degree, it is to retake to realize by material surface long-range atom.3, chemical reaction mechanism: at healing temperature, some chemical reactions occurring, by migration and the filling to crackle of resultant, is that crackle produces healing phenomenon.At present, mainly with chemical reaction mechanism, have the greatest impact.
The manufacture method that United States Patent (USP) (US5246736) and Canadian Patent (CA2214465) have been invented multilayer Si-B-C matrix, the method adopts B4C and Si-B-C to carry out modification to the SiC matrix of carbon/silicon carbide ceramic matrix composite, the material of manufacturing can be realized the self-healing of high-temperature, but complex process, the time is long, cost is high.Northwestern Polytechnical University's (Chinese invention patent, publication number CN101503305 and 101913894A) successively adopt amorphism boron to carry out matrix modification to fiber reinforced carbon/silicon carbide ceramic matrix composite, improve compound material antioxygenic property, and on Multi-layer amorphous norbide matrix modification basis, introduce borosilicate glass matrix material interfascicular macropore is carried out to packing, realize the dual self-healing modification of matrix material.
Summary of the invention
The invention provides a kind of metal whisker highly malleablized self-healing ceramic matric composite; it is characterized in that with coating protection continuous fibre and metal whisker highly malleablized ceramic matrix; for different use temperatures, between fibrous bundle or silk, add different metal whiskers; after under certain temperature, ceramic matrix cracks; the metal whisker disperseing is oxidized rapidly and forms oxide compound healing body material; stop fast the injury of peripheral environment to fortifying fibre, keep to the full extent the applied at elevated temperature performance of this matrix material.
Matrix material provided by the invention is first on continuous fortifying fibre surface, to prepare carbon or the BN protective layer of stratiform, then hybrid metal whisker is opened with organic solvent is dispersed, through heat, be solidified into the fibrous skeleton body of definite shape or utilize knitting skill that the continuous fibre of hybrid metal whisker is woven into the premolding of definite shape and prepares certain thickness carbon or BN protective layer at fiber surface, by CVI method, ceramic matrix is grown and densification on fibrous skeleton body or preform again, along with CVI step constantly repeats, in material, macrovoid size constantly reduces, it is even that pore size distribution is tending towards, finally obtain metal whisker highly malleablized self-healing ceramic matric composite.
This matrix material utilizes chemical vapor infiltration (CVI) ceramic matrix of growing on fibrous skeleton body or preform, does not destroy pattern and the mechanical property of fiber and whisker, mainly for non-oxide ceramicses such as silicon carbide, silicon nitrides.Wherein, whisker adopts the metal or alloy filament crystal of excellent toughness and higher-strength palpus, can be titanium, niobium, zirconium, tungsten, molybdenum, rhenium, tantalum or their alloy, necessarily asking that at temperature, Quick Oxidation generates oxide compound and volume increase, particular case is combined with temperature and selects, and volume content is controlled at 10%～30%.And fortifying fibre can be continuous carbon fiber, silicon carbide fiber or C-SiC fiber, volume content is controlled at 30%～50%.
Major advantage of the present invention is: after 1. under certain temperature, ceramic matrix cracks, the metal whisker disperseing is oxidized rapidly and forms oxide compound healing body material, stop fast the injury of peripheral environment to fortifying fibre, keep to the full extent the applied at elevated temperature performance of this matrix material.2. utilize CVI technology, under low pressure, low temperature, prepare matrix material, material internal residual stress is little, and fiber damaged is little, has kept to the full extent the excellent properties of each body material; 3. can select different metal whiskers for different use temperatures, when reducing material cost, simplified manufacturing technique; 4. after matrix cracks, there is coating protection on continuous fibre surface, and the metal whisker disperseing is oxidized rapidly expansion filling chink, and the self-healing time is short, effective; 5. ceramic matrix and fortifying fibre, whisker have multiple choices. can realize Composition Design and prepare complex-shaped high performance unit.
Accompanying drawing explanation
Fig. 1 is metal whisker highly malleablized self-healing ceramic matric composite self-healing process schematic diagram of the present invention.
Diagram (a): 10 is continuous fibre; 20 is fiber coat; 30 is crackle; 40 is ceramic matrix; 50 is metal whisker;
Diagram (b): 11 is continuous fibre; 12 is fiber coat; 13 is oxidation products; 14 is ceramic matrix; 15 is metal whisker;
Diagram (c): 21 is continuous fibre; 22 is fiber coat; 23 is oxidation products; 24 is ceramic matrix; 25 is metal whisker;
Embodiment
Below in conjunction with specific embodiment, further illustrate the present invention, should understand these embodiment is only not used in and limits the scope of the invention for the present invention is described, after having read the present invention, those skilled in the art all fall within the application's claims to the modification of the various equivalent form of values of the present invention and limit.
Embodiment 1
First at continuous carbon fiber surface, prepare the carbon protective layer of stratiform; thickness is 0.1～0.3 μ m, then mixes 20% Ti whisker and 40% carbon fiber, with organic solvent is dispersed, opens; through heat, be solidified into the fibrous skeleton body of definite shape, then make Si by CVI method
3n
4ceramic matrix is grown and densification on fibrous skeleton body, and along with CVI step constantly repeats, in material, macrovoid size constantly reduces, and pore size distribution is tending towards evenly, finally obtains the self-healing ceramic matric composite of Ti whisker/carbon fiber highly malleablized.
Embodiment 2
Utilize knitting skill that the continuous SiC fiber that mixes 30% niobium zirconium alloy whisker is woven into the premolding of definite shape and at fiber surface, prepare the BN protective layer of 0.5 μ m; by CVI method, SiC ceramic matrix is grown and densification on preform again; along with CVI step constantly repeats; in material, macrovoid size constantly reduces; pore size distribution is tending towards evenly, finally obtains the self-healing ceramic matric composite of niobium zirconium alloy whisker/silicon carbide fiber highly malleablized.
Above are only two embodiments of the present invention, but design concept of the present invention is not limited to this, allly utilizes this design to carry out the change of unsubstantiality to the present invention, all should belong to the behavior of invading the scope of protection of the invention.In every case be the content that does not depart from technical solution of the present invention, any type of simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (5)
1. a metal whisker highly malleablized self-healing ceramic matric composite, is characterized in that being comprised of continuous fibre, metal whisker and ceramic matrix.
2. ceramic matric composite according to claim 1, is characterized in that described continuous fibre can be carbon fiber, silicon carbide fiber or C-SiC fiber, and volume content is controlled at 30%～50%.
3. ceramic matric composite according to claim 1, it is characterized in that described metal whisker employing has the metal or alloy filament crystal palpus of excellent toughness and higher-strength, can be titanium, niobium, zirconium, tungsten, molybdenum, rhenium, tantalum or their alloy, volume content be controlled at 10%～30%.
4. ceramic matric composite according to claim 1, is characterized in that described ceramic matrix selects the non-oxide ceramicses such as silicon carbide, silicon nitride.
5. ceramic matric composite according to claim 1, is characterized in that there are carbon or boron nitride coating protection in continuous fibre surface, and metal whisker is distributed between fibrous bundle or silk.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410151213.4A CN103964881A (en) | 2013-07-23 | 2014-04-15 | Metal whisker strengthening-toughening self-healing ceramic-based composite material |
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| CN201310309162.9 | 2013-07-23 | ||
| CN201310309162 | 2013-07-23 | ||
| CN201410151213.4A CN103964881A (en) | 2013-07-23 | 2014-04-15 | Metal whisker strengthening-toughening self-healing ceramic-based composite material |
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| CN103964881A true CN103964881A (en) | 2014-08-06 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107171003A (en) * | 2017-06-15 | 2017-09-15 | 常州翊迈新材料科技有限公司 | Conductive super-corrosion-resistant functional coating material |
| CN110256082A (en) * | 2019-05-17 | 2019-09-20 | 浙江理工大学 | Reaction-sintered prepares monocrystalline silicon carbide nanofiber/carbon/silicon carbide ceramic matrix composite method |
| CN113149677A (en) * | 2021-04-29 | 2021-07-23 | 陕西科技大学 | Nickel wire toughened silicon nitride-based ceramic with wood-like ring structure and preparation method and application thereof |
| CN116462525A (en) * | 2023-06-19 | 2023-07-21 | 中国人民解放军国防科技大学 | A continuous carbon fiber reinforced ultra-high temperature ceramic matrix composite material and its preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503305A (en) * | 2009-02-03 | 2009-08-12 | 西北工业大学 | Process for preparing self-sealing silicon carbide ceramic based composite material |
-
2014
- 2014-04-15 CN CN201410151213.4A patent/CN103964881A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503305A (en) * | 2009-02-03 | 2009-08-12 | 西北工业大学 | Process for preparing self-sealing silicon carbide ceramic based composite material |
Non-Patent Citations (1)
| Title |
|---|
| 王俊山等: "难熔金属及其化合物与C/C复合材料相互作用研究", 《宇航材料工艺》, 31 December 2006 (2006-12-31), pages 50 - 55 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107171003A (en) * | 2017-06-15 | 2017-09-15 | 常州翊迈新材料科技有限公司 | Conductive super-corrosion-resistant functional coating material |
| CN107171003B (en) * | 2017-06-15 | 2020-05-05 | 常州翊迈新材料科技有限公司 | Conductive super-corrosion-resistant functional coating material |
| CN110256082A (en) * | 2019-05-17 | 2019-09-20 | 浙江理工大学 | Reaction-sintered prepares monocrystalline silicon carbide nanofiber/carbon/silicon carbide ceramic matrix composite method |
| CN110256082B (en) * | 2019-05-17 | 2021-11-02 | 浙江理工大学 | Method for preparing single crystal silicon carbide nanofibers/silicon carbide ceramic matrix composites by reaction sintering |
| CN113149677A (en) * | 2021-04-29 | 2021-07-23 | 陕西科技大学 | Nickel wire toughened silicon nitride-based ceramic with wood-like ring structure and preparation method and application thereof |
| CN116462525A (en) * | 2023-06-19 | 2023-07-21 | 中国人民解放军国防科技大学 | A continuous carbon fiber reinforced ultra-high temperature ceramic matrix composite material and its preparation method |
| CN116462525B (en) * | 2023-06-19 | 2023-09-05 | 中国人民解放军国防科技大学 | Continuous carbon fiber reinforced ultrahigh-temperature ceramic matrix composite material and preparation method thereof |
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Application publication date: 20140806 |