CN101417878B - TaC-SiC ceramic composite material synthesized by hot pressing at in-situ reaction - Google Patents
TaC-SiC ceramic composite material synthesized by hot pressing at in-situ reaction Download PDFInfo
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- CN101417878B CN101417878B CN2007101576704A CN200710157670A CN101417878B CN 101417878 B CN101417878 B CN 101417878B CN 2007101576704 A CN2007101576704 A CN 2007101576704A CN 200710157670 A CN200710157670 A CN 200710157670A CN 101417878 B CN101417878 B CN 101417878B
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Abstract
The invention relates to a ceramic matrix composite material and a synthetic method thereof, which are concretely an in-situ reactive synthesized TaC-SiC ceramic composite material by hot pressing and a synthetic method thereof. The method aims at solving the problems that the oxidation resistance of TaC is not ideal and loose surface oxide layers are easy to form in an oxidizing atmosphere, and the like. Two composition phases of TaC and SiC are in-situ formed and the percentage content of SiC is 0 to 50vol. percent. The concrete synthetic method is as follows: tantalum powders, silicon powders and graphite powders are used as materials which are ball milled for 10 to 40 hours under dry condition in a resin tank, after sieving the materials are put in a graphite die for cold molding (5 to 20 MPa), and then the materials are sintered in vacuum or a hot pressing furnace introduced with argon, with the sintering temperature of 1950 to 2150 DEG C, heat preserving sintering time of 1 to 2 hours and sintering pressure of 30 to 40 MPa. The synthetic method can synthesize the TaC-SiC ceramic composite materials by in-situ reaction, the prepared TaC-SiC ceramic composite materials are mainly used for structural components of ablation resistance under high temperature and anti-oxidation and the materials are applied to the aerospace field.
Description
Technical field
The present invention relates to ceramic matric composite, be specially a kind of TaC-SiC ceramic composite material synthesized by hot pressing at in-situ reaction.
Background technology
Transition metal carbides TaC has the NaCl type crystal structure and since the existence of covalent linkage it have high Young's modulus (560GPa), high hardness (15GPa) and high fusing point (3985 ℃).Utilize its high fusing point, TaC can be used as the anti-ablator of high temperature, for example is applied as the throat liner material of aerospace engine jet pipe.Lockheed Martin Corporation (U.S.) once developed a kind of TaC pottery larynx lining that ablate, pure compression molding (density is 95%) hardly, and than traditional carbon-to-carbon material, the production cycle shortens (airborne weapon, 2 (2004) 48) greatly.But the antioxidant property of very important is TaC is undesirable, is easy to form loose surface oxide layer in oxidizing atmosphere.
Summary of the invention
The object of the present invention is to provide a kind of easy control of process conditions, TaC-SiC ceramic composite material synthesized by hot pressing at in-situ reaction that cost is low, undesirable with the antioxidant property that solves TaC, in oxidizing atmosphere, be easy to form loose problems such as surface oxide layer.
Technical scheme of the present invention is:
A kind of TaC-SiC ceramic composite material synthesized by hot pressing at in-situ reaction, TaC become the phase-splitting reaction in to generate with two kinds of SiC, percentage composition meter by volume, and the content of SiC is 0～50% (preferable range is 10～30%), all the other are TaC; The SiC type is a cube phase β-SiC.
The synthetic method of above-mentioned TaC-SiC ceramic composite material synthesized by hot pressing at in-situ reaction, synthetic by the reaction in hot-pressing technique, wherein the content of TaC and SiC in the matrix can be regulated by the content of Ta, Si and C in the original proportioning.Concrete synthetic method is:
With tantalum powder, silica flour and Graphite Powder 99 is raw material, ball milling is 10～40 hours in resin container, the coldmoulding (5～20MPa) in the graphite jig of packing into after sieving, 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 1950～2150 ℃, heat preservation sintering time are that 1～2 hour, sintering pressure are 30～40MPa.Thereby, under lower temperature, synthesize the TaC-SiC ceramic composite of high-compactness fast.
The tantalum powder of described adding, silica flour 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 drying conditions.
Advantage of the present invention is:
1. technology is simple.The present invention is a raw material with tantalum powder, silica flour and Graphite Powder 99, and synthetic 1950～2150 ℃ of hot pressing by reaction in, sintering and densification are carried out simultaneously.The agglomerating TaC-SiC of institute ceramic composite is by tantalum carbide and silicon carbide two phase composites.With respect to earlier synthetic two phase ceramics, the remix sintering makes technical process become simple.
2. the TaC-SiC matrix material of the present invention's acquisition is applied to the aerospace field mainly as the anti-ablation of high temperature, oxidation resistant structural part.
3.SiC have excellent high temperature oxidation resistance, can the highlyest in 1600 ℃ air, use.Therefore, the present invention's design strengthens TaC and improves its high-temperature oxidation resistance with SiC.TaC and SiC are by the reaction in synthetic among the present invention.Use reaction in hot pressing 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 dense material simultaneously.Its advantage is that technology is simple, the product original position is synthetic, has avoided outside contamination, interface cleanness.
Description of drawings
Fig. 1 is that the X-ray diffraction phase composition of TaC-SiC ceramic composite is analyzed.Wherein (a) is TAS0, (b) is TAS5, (c) is TAS10, (d) is TAS20, (e) is TAS30, (f) is TAS40, (g) is TAS50.
Fig. 2 is the density of TaC-SiC ceramic composite and the density change curve with SiC content.
Fig. 3 (a)-(e) is the distribution mutually (secondary electron phase) of TaC-SiC ceramic composite glazed surface.Wherein, Fig. 3 (a) is TAS10, and Fig. 3 (b) is TAS20, and Fig. 3 (c) is TAS30, and Fig. 3 (d) is TAS40, and Fig. 3 (e) is TAS50.
Fig. 4 is the change curve of the Vickers' hardness of TaC-SiC ceramic composite with SiC content.
Fig. 5 is the flexural strength of TaC-SiC ceramic composite and the fracture toughness property change curve with SiC content.
Fig. 6 is that the Young's modulus of TaC-SiC ceramic composite is with the variation of temperature curve.
Embodiment
Below by example in detail the present invention is described in detail, for ease of comparing, single-phase TaC also adopts same technology synthetic.
Embodiment 1 (TaC-5vol.%SiC, TAS5)
With size range is 200～600 purpose tantalum powder 90.3g, silica flour 0.80g and Graphite Powder 99 5.71g, and ball milling is 40 hours in resin container, 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 15 ℃/minute, is heated to 1950 ℃ 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 TaC through X-ray diffraction analysis, because diffraction peak does not appear in the content of SiC less.The density that Archimedes's method records is 12.58g/cm
3, be 90.4% of theoretical density.Vickers' hardness is 6.3GPa, and flexural strength is 309MPa, and fracture toughness property is 2.9MPam
1/2, Young's modulus is 353GPa.
Embodiment 2 (TaC-10vol.%SiC, TAS10)
With size range is 200～600 purpose tantalum powder 91.67g, silica flour 1.71g and Graphite Powder 99 6.12g, and ball milling is 10 hours in resin container, 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 2050 ℃ of insulations 1 hour, and exerting pressure is 40MPa.Whole sintering process all is to carry out under argon shield, and the reaction product of acquisition is TaC and β-SiC through X-ray diffraction analysis.The density that Archimedes's method records is 12.69g/cm
3, be 95.0% of theoretical density.Vickers' hardness is 8.9GPa, and flexural strength is 341MPa, and fracture toughness property is 2.6MPam
1/2, Young's modulus is 410GPa.
Enforcement 3 (TaC-20vol.%SiC, TAS20)
With size range is 200～600 purpose tantalum powder 90.55g, silica flour 3.75g and Graphite Powder 99 6.85g, and ball milling is 20 hours in resin container, crosses 200 mesh sieves, coldmoulding in the graphite jig of packing into afterwards, and the pressure that applies is 5MPa, puts into the hot pressing furnace hot pressed sintering.Temperature rise rate is 10 ℃/minute, is heated to 1950 ℃ of insulations 1 hour, and exerting pressure is 40MPa.Whole sintering process all is to carry out under argon shield, and the reaction product of acquisition is TaC and β-SiC through X-ray diffraction analysis.The density that Archimedes's method records is 11.70g/cm
3, be 95.7% of theoretical density.Vickers' hardness is 8.4GPa, and flexural strength is 309MPa, and fracture toughness property is 3.9MPam
1/2, Young's modulus is 398GPa.
Embodiment 4 (TaC-30vol.%SiC, TAS30)
With size range is 200～600 purpose tantalum powder 79.2g, silica flour 5.65g and Graphite Powder 99 6.9g, and ball milling is 30 hours in resin container, 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 2150 ℃ of insulations 2 hours, and exerting pressure is 35MPa.Whole sintering process all is to carry out under argon shield, and the reaction product of acquisition is TaC through X-ray diffraction analysis, β-SiC and a small amount of TaSi
2The density that Archimedes's method records is 11.26 g/cm
3, being 101.4% of theoretical density, this is attributed to than SiC density (3.22g/cm
3) high TaSi
2(density, 9.84g/cm
3) influence.Vickers' hardness is 13.9GPa, and flexural strength is 289MPa, and fracture toughness property is 5.5MPam
1/2, Young's modulus is 459GPa.
Embodiment 5 (TaC-40vol.%SiC, TAS40)
With size range is 200～600 purpose tantalum powder 67.9g, silica flour 7.55g and Graphite Powder 99 6.95g, and ball milling is 20 hours in resin container, crosses 200 mesh sieves, coldmoulding in the graphite jig of packing into afterwards, and the pressure that applies is 5MPa, puts into the hot pressing furnace hot pressed sintering.Temperature rise rate is 10 ℃/minute, is heated to 1950 ℃ of insulations 1 hour, and exerting pressure is 30MPa.Whole sintering process all is to carry out under argon shield, and the reaction product of acquisition is TaC through X-ray diffraction analysis, β-SiC and a small amount of TaSi
2The density that Archimedes's method records is 10.28g/cm
3, being 103.0% of theoretical density, this is attributed to than SiC density (3.22g/cm
3) high TaSi
2(density, 9.84g/cm
3) influence.Vickers' hardness is 14.9GPa, and flexural strength is 331MPa, and fracture toughness property is 5.5MPam
1/2, Young's modulus is 465GPa.
Embodiment 6 (TaC-50vol.%SiC, TAS50)
With size range is 200～600 purpose tantalum powder 67.92g, silica flour 11.28g and Graphite Powder 99 8.4g, and ball milling is 20 hours in resin container, crosses 200 mesh sieves, coldmoulding in the graphite jig of packing into afterwards, and the pressure that applies is 5MPa, puts into the hot pressing furnace hot pressed sintering.Temperature rise rate is 10 ℃/minute, is heated to 2050 ℃ of insulations 1 hour, and exerting pressure is 30MPa.Whole sintering process all is to carry out under argon shield, and the reaction product of acquisition is TaC through X-ray diffraction analysis, β-SiC and a small amount of TaSi
2The density that Archimedes's method records is 8.93g/cm
3, being 100.1% of theoretical density, this is attributed to than SiC density (3.22g/cm
3) high TaSi
2(density, 9.84g/cm
3) influence.Vickers' hardness is 13.9GPa, and flexural strength is 340MPa, and fracture toughness property is 5.2MPam
1/2, Young's modulus is 438GPa.
Comparative example (single-phase TaC, TAS0)
With size range is 200～600 purpose tantalum powder 101.84g and Graphite Powder 99 6.08g, and ball milling is 40 hours in resin container, 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 15 ℃/minute, is heated to 2050 ℃ of insulations 1 hour, and exerting pressure is 30MPa.Whole sintering process all is to carry out under argon shield, and the reaction product of acquisition is TaC through X-ray diffraction analysis.The density that Archimedes's method records is 10.93g/cm
3, be 75.5% of theoretical density.Vickers' hardness is 1.4GPa, and flexural strength is 69MPa, and fracture toughness property is 1.2MPam
1/2, Young's modulus is 136GPa.As seen synthetic TaC-SiC ceramic composite can be realized densification and enhancement by adding SiC under the same process condition, obtains room-temperature mechanical property preferably.
Following mask body is introduced the phase composition of TaC-SiC ceramic composite, density, and microstructure, Vickers' hardness, flexural strength and fracture toughness property, and high-temperature elastic modulus is with the variation relation of SiC content.
Fig. 1 (a)-(g) is that the X-ray diffraction phase composition of TaC-SiC ceramic composite is analyzed.With the increase of SiC content in the matrix material, the diffraction peak of SiC is grow gradually.(a) be single-phase TaC; (b) diffraction peak that does not have SiC in is because the diffraction peak of TaC is bigger by force, has hidden the diffraction peak of SiC.(e)-(g) contain a spot of TaSi in the show sample in
2Fig. 2 is the density of matrix material and the change curve that density increases with the SiC volumn concentration.When showing among the figure that content as SiC is greater than 10vol.%, the density of matrix material is all more than 95%, and its density is on a declining curve with the increase of SiC content.But, just there is a spot of TaSi in the sample of preparation when the content of SiC during greater than 30vol.%
2, because its density (9.84g/cm
3) greater than the density (3.22g/cm of SiC
3), the density value that causes being calculated is greater than 1.Fig. 3 (a)-(e) is the pattern of TaC-SiC ceramic composite glazed surface and distribute mutually (secondary electron phase).Greyish white form and aspect among the figure are TaC, and black is SiC mutually, and the SiC particle is uniform distribution in the TaC matrix, and a little reunion is arranged.Fig. 3 (a) and (b) in have a small amount of sealed porosity, corresponding their lower densityes.And scheme not have in (c)-(e) existence of sealed porosity, the increase of this explanation SiC content has promoted the densification of material.On the other hand, low melting point TaSi
2The existence of (2040 ℃) also may promote the densification of sample.Fig. 4 is the change curve of the Vickers' hardness of TaC-SiC ceramic composite with SiC content.With the increase of SiC content, the hardness of matrix material is in rising trend.The variation of this hardness is corresponding with the variation of density on the one hand; Be that (hardness, 26GPa) content increases the SiC higher than TaC hardness (15GPa), also improves the hardness of matrix material on the other hand.Fig. 5 is the flexural strength of TaC-SiC ceramic composite and the change curve that fracture toughness property increases with SiC content.The fracture toughness property of matrix material is in rising trend with the increase of SiC content.As the SiC content fracture toughness property value of tending towards stability 5.5MPam during greater than 30vol.%
1/2Flexural strength has maximum 341MPa at SiC content during for 10vol.%, and the raising with SiC content descends then.Fig. 6 is that the Young's modulus of TaC-SiC ceramic composite is with the variation of temperature curve.The high temperature rigid of TAS10 shown in the figure and TAS30 all is maintained to 1400 ℃, has shown high temperature application, and the TAS50 high temperature rigid is poor slightly.From above interpretation of result as can be seen, when the content of SiC was 10～30vol.%, matrix material can obtain better comprehensive mechanical property.
By embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6 and comparative example as seen, present method can original position be synthesized the TaC-SiC ceramic composite, when SiC content is 10～30vol.%, has better comprehensive mechanical property.
Claims (5)
1. TaC-SiC ceramic composite material synthesized by hot pressing at in-situ reaction is characterized in that: percentage composition meter by volume, and the content of 0＜SiC≤50%, all the other are TaC; TaC becomes the phase-splitting reaction in to generate with two kinds of SiC, with tantalum powder, silica flour and Graphite Powder 99 is raw material, ball milling is 10～40 hours in resin container, the coldmoulding in the graphite jig of packing into after sieving, forming pressure 5～20MPa, sintering in being connected with the hot pressing furnace of argon gas, temperature rise rate are 10～15 ℃/minute, and sintering temperature is that 1950～2150 ℃, heat preservation sintering time are that 1～2 hour, sintering pressure are 30～40MPa.
2. according to the described TaC-SiC ceramic composite of claim 1, it is characterized in that: per-cent meter by volume, the content of SiC is 10～30%.
3. according to the described TaC-SiC ceramic composite of claim 1, it is characterized in that: the content of TaC and SiC, regulate according to the content of tantalum powder, silica flour and Graphite Powder 99 in the original proportioning.
4. according to the described TaC-SiC ceramic composite of claim 1, it is characterized in that: the tantalum powder of described adding, silica flour and Graphite Powder 99 size range are 200～600 orders.
5. according to the described TaC-SiC ceramic composite of claim 1, it is characterized in that: ball milling under the drying conditions in resin container.
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| CN104651771A (en) * | 2015-03-04 | 2015-05-27 | 中国科学院上海硅酸盐研究所 | High-temperature-resistant ablation-resistant tantalum carbide composite coating and preparation method thereof |
| CN106431413A (en) * | 2016-09-29 | 2017-02-22 | 芜湖市三山区绿色食品产业协会 | Anti-corrosion and anti-abrasion sintered silicon carbide sealing piece and preparing method thereof |
| CN110818420B (en) * | 2019-11-25 | 2021-08-17 | 武汉科技大学 | SiC-doped TaxHf1-xC ceramic and preparation method thereof |
| CN115521151A (en) * | 2022-09-28 | 2022-12-27 | 中国科学院上海硅酸盐研究所 | Discharge plasma sintering method of silicon carbide/tantalum carbide toughened ceramic |
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| CN1730435A (en) * | 2005-06-07 | 2006-02-08 | 中国科学院山西煤炭化学研究所 | The hot-forming method for preparing tantalum/charcoal carbide composite material |
| CN101024575A (en) * | 2006-02-17 | 2007-08-29 | 中国科学院金属研究所 | Method for preparing tantalum-aluminium-carbon ceramic by in-situ heat-pressing/solid-liquid phase reaction |
| CN101033134A (en) * | 2006-03-10 | 2007-09-12 | 中国科学院金属研究所 | Original position reaction hot pressing synthesis TiB2-NbC-SiC refractory ceramics composite material and preparing method thereof |
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| CN1730435A (en) * | 2005-06-07 | 2006-02-08 | 中国科学院山西煤炭化学研究所 | The hot-forming method for preparing tantalum/charcoal carbide composite material |
| CN101024575A (en) * | 2006-02-17 | 2007-08-29 | 中国科学院金属研究所 | Method for preparing tantalum-aluminium-carbon ceramic by in-situ heat-pressing/solid-liquid phase reaction |
| CN101033134A (en) * | 2006-03-10 | 2007-09-12 | 中国科学院金属研究所 | Original position reaction hot pressing synthesis TiB2-NbC-SiC refractory ceramics composite material and preparing method thereof |
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