CN100445234C - Self-sintering tantalum / charcoal carbide composite material preparation method - Google Patents
Self-sintering tantalum / charcoal carbide composite material preparation method Download PDFInfo
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- CN100445234C CN100445234C CNB200510012585XA CN200510012585A CN100445234C CN 100445234 C CN100445234 C CN 100445234C CN B200510012585X A CNB200510012585X A CN B200510012585XA CN 200510012585 A CN200510012585 A CN 200510012585A CN 100445234 C CN100445234 C CN 100445234C
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Abstract
The present invention relates to a self-sintering method of tantalum carbide / carbon composite materials. In the method, tantalic asphalt made by the patent of a making method of tantalic carbon-base composite material precursors is directly used as a self-sintering raw material, no adhesive is added, the asphalt is ground till the particle size d is no larger than 100 mum, and after compression moulding forming, carbonization and graphitization, high-strength tantalum carbide / carbon composite materials can be made. The method has the advantages of simple making process and low cost, and the made composite materials have the advantages of stable quality and high finished product rate.
Description
Technical field
The present invention relates to a kind of preparation method of tantalum/charcoal carbide composite material.
Background technology
Develop rapidly along with aerospace flight technology, more and more harsher to the requirement of military service material under extreme environment, require material under the washing away of high temperature, high velocity air in (＞2400 ℃) and the reactive atmosphere (atomic oxygen, nitrogen) have good thermochemistry, physical stability.At present; the development of supersonic flight instrument (comprising space vehicle, atmosphere reentry system, rocket propulsion system etc.) has the intensive dependency with exploitation to the warm protecting materials of superelevation, and therefore the ultrahigh-temperature structured material of research a new generation has very important meaning.
Based composite material of carbon has advantages such as good dimensional stability, high temperature specific tenacity height, easily processing, lightweight be inexpensive, by widely as high-temperature structural material.Yet the ablation in being higher than 800 ℃ oxidizing atmosphere has seriously hindered its application, therefore, must improve the anti-ablation property of raw material of wood-charcoal material, satisfies under the extreme environment the requirement of raw material of wood-charcoal material, enlarges its range of application.
The U.S. points out in 76-609 number AIAA in 1976 " solid booster rocket engine with charcoal/raw material of wood-charcoal material " report, introduces elements such as tantalum, hafnium, zirconium and form refractory carbides in the raw material of wood-charcoal material, can improve the anti-ablation and the antioxidant property of material.In 1980 80-1476 number AIAA paper, reported the ablation resistance of tantalum/charcoal carbide composite material.The U.S., Russia, France have carried out correlative study in this regard; chemical vapour deposition and the chemical gas phase reactions of adopting prepare carbide coating protection raw material of wood-charcoal material more; coating and matrix thermal expansivity do not match but these methods exist; coating is easily peeled off Problem of Failure under the high temperature, and apparatus expensive, operation are difficult, Application Areas is limited.Adopting powder to mix can reduce cost, and uniform mixing can be eliminated the influence at interface, is a kind of effective modified method.People such as Cui Hong have reported in " Northwestern Polytechnical University's journal " the 4th phase in 2004 and have added the anti-ablation property that tantalum carbide improves carbon/carbon composite that the method that adopts tantalum oxide to suspend is made soaker, introduces matrix material in resin.But there are the following problems for this method: the micro mist that is adopted is the 10-50 submicron size particle, because granularity is too high, and the density (Ta of tantalum compound
2O
5: 8.7g/cm
3Ta ℃: 14.4g/cm
3) with the density (＜2.0g/cm of carbon matrix
3) difference is bigger, is difficult to be uniformly dispersed, and causes doping constituent element and carbon matrix to have sharp interface, be prone to stress concentration in the use and destroy.Cause the quality product fluctuation big thus, the shortcoming that yield rate is low.
Summary of the invention:
The object of the invention provides the preparation method of the tantalum/charcoal carbide composite material that a kind of preparation technology is simple, quality product is excellent, yield rate is higher.
Patent " a kind of preparation method of the tantalum-containing carbon-base composite material precursor " (application number: the prepared tantalum pitch that contains 200410064579.4) that the present invention adopts the inventor to apply for, directly as the self sintering raw material, do not add any binding agent, after the moulding, only need a charing, greying just can make high strength, highdensity tantalum/charcoal carbide composite material.
Preparation method of the present invention comprises the steps:
1) pre-feed: with charred residue content (GB8729-89) is 80～85wt%, volatile content is 9～14wt%, the pitch that contains tantalum 2～10wt% is that (concrete preparation method sees patent " a kind of preparation method of tantalum-containing carbon-base composite material precursor " to the self sintering raw material, application number: 200410064579.4), be ground to granularity d≤100 μ m, compression molding under 50～100MPa makes elementary moulding product;
2) charing, greying: with elementary moulding product under normal pressure, inert atmosphere protection; with 10～15 ℃/hour speed charing to 1200～1300 ℃ and constant temperature 1～2 hour; after this place it in and carry out graphitization processing in the graphitizing furnace; in argon gas atmosphere; rise to 2400～2600 ℃ with 100～200 ℃/speed at one hour rating; and, can make product 2400～2600 ℃ of constant temperature 1～2 hour.
Described patent " a kind of preparation method of tantalum-containing carbon-base composite material precursor ", application number: 200410064579.4 concrete preparation method is as follows:
Described pitch be with the coal-tar pitch of 60 ℃～80 ℃ of softening temperatures or petroleum pitch in inert atmosphere, water-less environment, is coal-tar pitch or petroleum pitch with tantalum chloride by mass ratio: mix tantalum chloride=100: 1～20, in 260 ℃～420 ℃, boost certainly or 0.3～1.0Mpa pressure under, at the uniform velocity the mechanical stirring reaction is 4～10 hours, promptly makes pitch.
The present invention has following advantage:
1, employing prepares matrix material from sintered powder, and preparation technology is simple, does not need any additives, constant product quality, and cost is low, the yield rate height.
2, employing is introduced tantalum by pitch in carbon matrix, after overmolding prepared material, tantalum was converted into that tantalum carbide is meticulous to be dispersed in the carbon matrix, compared with the material of the adulterated method preparation of micro mist, the matrix material material of pressing this patent preparation is more even, has better character.
Embodiment:
Embodiment 1
With charred residue is 80wt%, volatilization is divided into 14.0wt%, (this raw material is by the coal-tar pitch of 68 ℃ of softening temperatures as the self sintering raw material to contain the pitch of tantalum 2.0wt%, with tantalum chloride in 100: 4 ratio, 350 ℃ down reaction produced in 8 hours, concrete grammar is seen patent " a kind of preparation method of tantalum-containing carbon-base composite material precursor ", application number: 200410064579.4), after this pitch is ground to granularity d≤100 μ m, in 50MPa compression moulding under room temperature on the compression molding forming machine, obtain blank of material.Under the protection of rare gas element, be warming up to 1200 ℃, and 1200 ℃ of constant temperature 2 hours with 10 ℃/hour speed, make elementary moulding product thus.After this product is placed in the graphitizing furnace, under argon shield, rises to 2400 ℃ with 100 ℃/speed at one hour rating, and at 2400 ℃ of constant temperature 2 hours, the target product that can make.The density of this material is 1.85g/cm
3, the bending strength on the vertical pressing direction is 50.8MPa, ultimate compression strength is 110.3MPa.
Embodiment 2
With charred residue is 93wt%, the pitch that volatilization is divided into 9.0wt%, contain tantalum 5.35wt% is as self sintering raw material (this raw material is reacted down by 100: 10 ratio, at 400 ℃ by the coal-tar pitch of 68 ℃ of softening temperatures and tantalum chloride and produced in 6 hours, and the method among concrete grammar and the embodiment 1 is similar).After this pitch is ground to granularity d≤10 μ m,, obtain blank of material in 70MPa compression moulding under room temperature on the compression molding forming machine.Then under the protection of rare gas element, and be warming up to 1300 ℃ and, make elementary moulding product thus 1300 ℃ of constant temperature 1 hour with 12 ℃/hour speed.After this product is placed in the graphitizing furnace, under argon shield, rises to 2500 ℃ with 150 ℃/speed at one hour rating, and at 2500 ℃ of constant temperature 1 hour, the target product that can make.The density of this material is 1.91g/cm
3, the bending strength on the vertical pressing direction is 59.7MPa, ultimate compression strength is 119.7MPa.
Embodiment 3
With charred residue is 85wt%, volatilization is divided into 12wt%, (this raw material is by the coal-tar pitch of 68 ℃ of softening temperatures as the self sintering raw material to contain the pitch of tantalum 8.48wt%, with tantalum chloride in 100: 16 ratio, 450 ℃ down reaction produced in 4 hours, method among concrete grammar and the embodiment 1 is similar), after this pitch is ground to granularity d≤100 μ m, in 90MPa compression moulding under room temperature on the compression molding forming machine, obtain blank of material.Then under the protection of rare gas element, be warming up to 1200 ℃, and 1200 ℃ of constant temperature 2 hours with 15 ℃/hour speed, make elementary moulding product thus.After this product is placed in the graphitizing furnace, under argon shield, rises to 2600 ℃ with 200 ℃/speed at one hour rating, and at 2600 ℃ of constant temperature 2 hours, the target product that can make.The density of this material is 1.98g/cm
3, the bending strength on the vertical pressing direction is 62.8MPa, ultimate compression strength is 125.4MPa.
Embodiment 4
With charred residue is 92wt%, volatilization is divided into 10.0wt%, the pitch that contains tantalum 10.0wt% as the self sintering raw material (this raw material by the coal-tar pitch of 68 ℃ of softening temperatures and tantalum chloride in 100: 20 ratio, 500 ℃ down reaction produced in 2 hours, method among concrete grammar and the embodiment 1 is similar), after this pitch is ground to granularity d≤10 μ m, in 100MPa compression moulding under room temperature on the compression molding forming machine, obtain blank of material.Under the protection of rare gas element, be warming up to 1300 ℃, and 1300 ℃ of constant temperature 1 hour with 10 ℃/hour speed, make elementary moulding product thus.After this product is placed in the graphitizing furnace, under argon shield, rises to 2600 ℃ with 100 ℃/speed at one hour rating, and at 2600 ℃ of constant temperature 2 hours, the target product that can make.The density of this material is 2.05g/cm
3, the bending strength on the vertical pressing direction is 70.0MPa, ultimate compression strength is 130.3MPa.
Claims (1)
1, a kind of preparation method of self-sintering tantalum/charcoal carbide composite material is characterized in that comprising the steps:
1) pre-feed: with charred residue content is 80～85wt%, and volatile content is 9～14wt%, and the pitch that contains tantalum 2～10wt% is ground to granularity d≤100 μ m as from raw materials for sintering, and compression molding under 50～100MPa makes elementary moulding product;
2) charing, greying: with elementary moulding product under normal pressure, inert atmosphere protection, with 10～15 ℃/hour speed charing to 1200～1300 ℃ and constant temperature 1～2 hour, after this place it in and carry out graphitization processing in the graphitizing furnace, under argon shield, rise to 2400～2600 ℃ with 100～200 ℃/speed at one hour rating, and, can make product 2400～2600 ℃ of constant temperature 1～2 hour;
Described pitch be with the coal-tar pitch of 60 ℃～80 ℃ of softening temperatures or petroleum pitch in inert atmosphere, water-less environment, is coal-tar pitch or petroleum pitch with tantalum chloride by mass ratio: mix tantalum chloride=100: 1～20, in 260 ℃～420 ℃, boost certainly or 0.3～1.0MPa pressure under, at the uniform velocity the mechanical stirring reaction is 4～10 hours, promptly makes pitch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510012585XA CN100445234C (en) | 2005-06-07 | 2005-06-07 | Self-sintering tantalum / charcoal carbide composite material preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510012585XA CN100445234C (en) | 2005-06-07 | 2005-06-07 | Self-sintering tantalum / charcoal carbide composite material preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1730438A CN1730438A (en) | 2006-02-08 |
| CN100445234C true CN100445234C (en) | 2008-12-24 |
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| CNB200510012585XA Expired - Fee Related CN100445234C (en) | 2005-06-07 | 2005-06-07 | Self-sintering tantalum / charcoal carbide composite material preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101328064B (en) * | 2007-06-22 | 2010-08-25 | 中国科学院金属研究所 | In situ reaction heat synthesized TaC-TaSi2 ceramic composite material |
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Non-Patent Citations (2)
| Title |
|---|
| "添加难熔金属碳化物提高C/C 复合材料抗烧蚀性能的研究". 崔红等.西北工业大学学报，第18卷第4期. 2000 |
| "添加难熔金属碳化物提高C/C 复合材料抗烧蚀性能的研究". 崔红等.西北工业大学学报，第18卷第4期. 2000 * |
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| CN1730438A (en) | 2006-02-08 |
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