CN100378035C - Boride-silicon carbide multiple phase ceramic and its preparation method - Google Patents
Boride-silicon carbide multiple phase ceramic and its preparation method Download PDFInfo
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- CN100378035C CN100378035C CNB2006100236912A CN200610023691A CN100378035C CN 100378035 C CN100378035 C CN 100378035C CN B2006100236912 A CNB2006100236912 A CN B2006100236912A CN 200610023691 A CN200610023691 A CN 200610023691A CN 100378035 C CN100378035 C CN 100378035C
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Abstract
The present invention provides boride-silicon carbide composite ceramics and a making method thereof. The present invention is characterized in that compact boride-silicon carbide composite ceramics are made by hot pressing at the mild temperature of 1700 to 1900DEG C by utilizing the activity of silicon carbide generated when polycarbon silane is decomposed; the borides mainly comprise zirconium diboride, titanium boride and hafnium boride; the technique does not need other combustion improvers so as to ensure the high temperature property of the material; and 1 to 12 wt% of one of metal powder of silicon, zirconium, titanium, hafnium, etc., or the mixture of the optional combination of metal powder of silicon, zirconium, titanium, hafnium, etc. is added in the making process to absorb the residual carbon in the decomposition process of the polycarbon silane so as to enhance the density of the composite material and improve the mechanical properties of the material. The obtained material has the microscopic structure characteristic that the active silicon carbide generated from the decomposition of the polycarbon silane wraps up the surfaces of the borides (such as zirconium diboride granules) and is combined with the boride granules under mild temperature.
Description
Technical field
The present invention relates to boride-carborundum composite-phase ceramic and preparation method thereof, comprise titanium boride-silicon carbide (TiB
2-SiC) complex phase ceramic, zirconium boride-carborundum (ZrB
2-SiC) complex phase closes pottery and hafnium boride-silicon carbide (HfB
2-SiC) complex phase ceramic and preparation method thereof.Belong to non-oxidized substance complex phase ceramic field.
Background technology
The transition metal boride pottery is with its high-melting-point; high rigidity; premium propertiess such as high conductivity and anti-glass and metal melt corrosion; at the space flight and aviation superhigh temperature ceramic material; cutting tool and high-abrasive material; electrode materials, and purposes is widely arranged with glass and the contacted container of metal melt and protecting materials aspect.If can improve the performance of boride ceramics by certain approach, improve its oxidation-resistance mutually as adding silicon carbide second, then can make the boride composite ceramics of acquisition have purposes widely.The boride complex phase ceramic generally by direct mixing method preparation, is opened clear 61-72687 as the spy, and the spy opens clear 61-21980, and the spy opens shown in the communique such as flat 5-319936, at ZrB
2In directly add SiC, B
4C, carbide such as TiC second phase, or open clear 61-48484 as the spy, the spy opens shown in the communiques such as clear 61-63573, at ZrB
2In directly add TiN, nitride such as BN second phase obtains sintered compact by hot pressing or normal pressure-sintered method then.
But, resemble ZrB
2, SiC, B
4C, TiC, TiN, the self-diffusion coefficient of non-oxide ceramicses such as BN is very little, even hot pressing also is difficult to obtain fine and close sintered compact, the intensity of material, erosion resistance etc. are difficult to reach service requirements.Add resembling Ni on a small quantity, the metal that Fe is the same can significantly improve sintering character, opens shown in the flat 05-132363 as the spy.But these metal additives can remain in the crystal boundary place of pottery, thereby reduce the mechanical behavior under high temperature and the corrosion resistance of material.
Following reusable space vehicle and hypersonic plane must adopt the novel thermal protection system material of not ablating for a long time or seldom ablating, i.e. ultrahigh-temperature pottery (UHTC) material under ultrahigh-temperature (more than 2500～2700 ℃) aerobic Service Environment.Superhigh temperature ceramic material mainly comprises ZrB
2, HfB
2, ZrC and HfC etc. with and various matrix material.But single boride ceramics can't satisfy desired physics, chemistry, mechanics and structure properties under ultrahigh-temperature simultaneously.So, select different materials to carry out reasonable combination from the material design angle, be the unique channel that addresses this problem.At present, the boride ceramics that contains SiC has become the main flow of research.
In order to obtain the material of ultrahigh-temperature excellent property, must adopt the sintering aid that high-temperature behavior is not had an influence even not add sintering aid, but must realize densification sintering.
Therefore, the research of boride-carborundum composite-phase ceramic and preparation method thereof has become an important branch of current non-oxidized substance complex phase ceramic area research.
Summary of the invention
The object of the present invention is to provide class boride-carborundum composite-phase ceramic and preparation method thereof.In the present invention, the inventor proposes to adopt the organic precursor pyrolysis method to come original position to generate SiC second phase, utilizes the high reactivity of generated in-situ SiC to promote boride ceramics densification sintering at a lower temperature and suppress growing up of boride crystal grain simultaneously.
Specifically, the organic precursor of the present invention's employing is Polycarbosilane (PCS).Its molecular formula is (SiH (CH
3)-CH
2) n, molecular weight is 1250.Carbon silicon in the split product changes than the difference with cracking temperature, and cracking temperature is when 500 ℃～1300 ℃ change, and carbon silicon is than changing between 1.72～1.44, as seen with the raising carbon silicon of cracking temperature than descending, Zong weightlessness is about 40%.Explanation will have residual carbon and occur in cracking process, scission reaction is: PCS → SiC+C+ low-molecular-weight hydrocarbon gas; So, when this PCS is added to boride (for sake of convenience following, all with ZrB
2Be example) in the pottery time, it is characterized in that the phase composite of the composite diphase material that obtains is ZrB after cracking
2-SiC-C, reaction formula is as follows: ZrB
2+ PCS=ZrB
2+ SiC+C.
The existence of carbon can stop the sintering densification of material to a certain extent in the material, but this influence is not really remarkable when the addition of PCS hangs down.The existence of carbon can improve the thermomechanical property of composite diphase material to a certain extent conversely, as heat-shock resistance etc.
In addition, the carbon that produces in cracking process also can absorb by other metallic elements that add 1-12wt%, for example, can obtain ZrB when adding metal zirconium
2-SiC-ZrC composite diphase material then can obtain ZrB when adding silicon
2-SiC complex phase ceramic:
ZrB
2+PCS+Zr＝ZrB
2+SiC+ZrC
ZrB
2+PCS+Si＝ZrB
2+SiC
Also can add the metal hafnium and absorb residual carbon, that at this moment form is ZrB
2-SiC-HfC composite ceramics:
ZrB
2+PCS+Hf＝ZrB
2+SiC+HfC
Can also add metal titanium and absorb residual carbon, that at this moment form is ZrB
2-SiC-TiC composite ceramics:
ZrB
2+PCS+Ti＝ZrB
2+SiC+TiC
In this case, because ZrB2 and TiC will change TiB at a certain temperature into
2And ZrC, reaction process is further activated, thereby the acceleration of sintering densification improve the mechanical property and the antioxidant property of material.
But itself antioxidant property of the boride of the titanium that produces when adding metal titanium or carbide is relatively poor, and too much interpolation can reduce the antioxidant property of material.So, Zr, Hf, the compound interpolation of Ti and Si will provide a valid approach for the matrix material that obtains good sintering densification performance and antioxidant property.The opposing party and, complicated phase composite can improve phase composite and the microstructure stability of complex phase ceramic under ultra-high temperature condition to a certain extent, for this class material can use the creation better condition under ultrahigh-temperature.
Most representative compound interpolation reaction is in above-mentioned reaction:
ZrB
2+PCS+Zr+Hf+Si＝ZrB
2+ZrC+SiC+HfC
More than every in used metal-powder raw material, even it is characterized in that using thick and than the raw material of low-purity, also can obtain to have the matrix material at fine microstructure and pure interface, its reason be thing new in the reaction process generate mutually and in this course from purification effect.
More than every in employed boride (ZrB
2, TiB
2And HfB
2) raw material powder, even it is characterized in that using thicker raw material, it is to not significantly influence of sintering densification, because the active SiC that whole sintering process produces when mainly relying on the PCS cracking realizes.
In sum, be the split product one active carbide silicon-combination under mild temperature that utilizes Polycarbosilane by boride-carborundum composite-phase ceramic provided by the invention, by the hot pressed sintering densification, it is characterized in that
The active carbide silicon product that is produced by the Polycarbosilane cracking is wrapped in the surface of boride particle, in hot pressing in conjunction with boride particle.Silicon-carbide particle and residual carbon that cracking produces are distributed at the interface, and inside is the crystal grain of boride.The volume content of interfacial phase silicon carbide and residual carbon is 2% to 35%, is difficult to obtain fine and close sintered compact when surpassing this scope.
The silicon that in preparation process, adds 1～12wt%, zirconium, titanium, metal-powders such as hafnium, the perhaps arbitrary combination of these metal-powders is to absorb the residual carbon in the Polycarbosilane cracking process.The silicon-carbide particle that cracking produces and by the silicon of residual carbon and interpolation, zirconium, titanium, metal-powders such as hafnium, perhaps the arbitrary combination of the silicon carbide that arbitrary combination generated of these metal-powders or zirconium carbide or titanium carbide or hafnium carbide or these carbide is distributed at the interface, and inside is the crystal grain of boride.
The preparation method of boride of the present invention-silicon carbide compound pottery, it is characterized in that earlier Polycarbosilane being wrapped in the surface of boride particle, obtain the boride composite powder of cleaved product parcel then through cracking, or obtain the boride composite powder of cleaved product parcel by the direct mixture of boride powder and Polycarbosilane powder through cracking.The mixed powder that obtains is prepared fine and close sintered compact through hot pressed sintering.
The cracking process of the Polycarbosilane by being wrapped in the boride particle surface in advance, generate the mix products of active carbide silicon and carbon on the boride particle surface, its volume content is between 2% to 35%, this mix products evenly is wrapped in the surface of boride particle, makes this boride powder that has wrapped up active carbide silicon and carbon have good sintering activity.
The present invention is based on the hard-to-sinter that improves existing boride ceramics and suppresses crystal grain and too grow up and improve its antioxidant property and propose.The invention is characterized in the densification sintering that under mild temperature, to realize boride ceramics.
Boride (ZrB used in the present invention
2, TiB
2And HfB
2) raw material is the powder less than 10 microns, even hot pressing can only not obtain the sintered compact of about 80% density yet when not adding sintering aid.The molecular weight of the Polycarbosilane (PCS) that uses is 1250.Other raw materials Zr, Hf, Ti and Si are 320 purposes (≤45 μ m) powders, and wherein the largest particle particle diameter is about 50 microns.
Various raw material powders are prepared burden according to a certain ratio, add to have dissolved in the gasoline solution of a certain amount of PCS.Ball milling mixed 12 hours then, and compound is dry while stirring in air, obtained evenly to apply the mixed powder of PCS, as shown in Figure 1.Mixed powder carries out cracking under 600-1200 ℃ of temperature, obtain the potteryization mixed powder.The characteristics of this potteryization mixed powder are, at boride (ZrB
2, TiB
2And HfB
2) the particulate surface-coated the split product SiC+C of layer of even PCS, as shown in Figure 2.The mixed powder that obtains after the cracking hot pressed sintering under 1700-1900 ℃ differing temps of packing in the graphite jig, the protective atmosphere during hot pressing is an argon gas.Sample after dry-pressing formed also can carry out sintering densification by the normal pressure method.The microstructure of the sintered compact that obtains as shown in Figure 3, the SiC+C that reaction generates, perhaps at the Zr that adds 1-12wt%, Hf, the SiC+ZrC that Ti or Si generate when absorbing C, SiC+HfC, SiC+TiC or have only SiC, be evenly distributed between the ZrB2 particle and form three-dimensional network, and rely on the high reactivity that reacts the thing phase that generates boride (ZrB
2, TiB
2And HfB
2) particle combines and form fine and close sintered compact.The ZrB of Fig. 4 for obtaining
2The X-ray diffraction spectrum of-SiC-C matrix material demonstrates and designs the corresponding to phase composite of phase composite.Pressure is 20MPa during hot pressed sintering, is incubated 60 minutes.
Even though use the thicker Zr of raw material particle size, Hf, Ti and Si powder also can obtain to have the matrix material at fine microstructure and pure interface, but, when the addition of these powders hanged down, thick excessively particle was difficult to obtain uniform dispersion, finally is difficult to obtain the uniform sintered compact of phase composite.Because the addition of these raw materials is lower among the present invention, for this reason, also used the tiny Zr of particle diameter among the present invention, Hf, Ti and Si powder compare experiment, and their particle diameter is between the 5-10 micron.
Because the sintering densification process among the present invention does not rely on boride (ZrB
2, TiB
2And HfB
2) activity, so the particle diameter of boride raw material is not the significant effects factor, this point has great importance for the sintering of boride coarse grain powder.
Boride-carborundum composite-phase ceramic of the present invention has the advantage of easy-sintering densification under 1700-1900 ℃ of temperature, compares with traditional technology and can reduce sintering temperature, reduces the preparation energy consumption, has very strong industrial applicibility.Simultaneously by adding separately or compound interpolation zirconium, hafnium, metal-powder such as titanium or silicon absorbs or partially absorbs the carbon that produces because of the Polycarbosilane cracking, can conveniently regulate the mechanics and the thermal property of composite diphase material, and the Properties Control approach of a flexibility is provided for industrial applications.The composite diphase material of preparation has excellent mechanical property and thermal property, for material application at high temperature provides the assurance on the rerum natura.Boride-carborundum composite-phase ceramic of the present invention is particularly suitable for the industrial application under the high temperature corrosion condition.Therefore industrial applicibility of the present invention is conspicuous.
Description of drawings
Fig. 1 applies the boride powder of PCS (with ZrB
2Be example)
The boride powder that cleaved product S iC+C coats after Fig. 2 PCS cracking is (with ZrB
2Be example)
The microstructure synoptic diagram of Fig. 3 sintered compact
The ZrB that Fig. 4 prepares with method provided by the present invention
2The X-ray diffraction spectrum of-SiC-C matrix material
The ZrB that Fig. 5 embodiment 1 obtains
2The scanning electron microscope pattern of-SiC-C matrix material
Embodiment
The present invention will describe in detail with the following examples, but the present invention is not limited by the following examples.
Embodiment 1
For preparation contains ZrB
2-(SiC+C) composite diphase material of 20% volume content is with ZrB
2Powder 8.8 gram adds in the gasoline solution that is dissolved with 1.2 gram PCS, with zirconia ball mix grinding 12 hours, pours in the kiver limit then into and stirs and allow gasoline vaporising, obtains to apply ZrB
2Powder.This coating powders carries out cracking under 800 ℃ in the argon gas atmosphere that flows, obtain the potteryization mixed powder.The 1800 ℃ of hot pressed sinterings in argon shield atmosphere of then this powder being packed in the graphite jig, hot pressing pressure is 20MPa, soaking time is 60min.The performance of the material that obtains is listed in the table 1.
Embodiment 2
For preparation contains ZrB
2-(SiC+C) composite diphase material of 20% volume content, with 1.2 gram PCS powder directly with 8.8 gram ZrB
2Powder mixes.This mixed powder carries out cracking under 800 ℃ in the argon gas atmosphere that flows, obtain the potteryization mixed powder.The 1800 ℃ of hot pressed sinterings in argon shield atmosphere of then this powder being packed in the graphite jig, hot pressing pressure is 20MPa, soaking time is 60min.The performance of the material that obtains is listed in the table 1.
Embodiment 3
By obtaining sample with example 1 identical mode, different is at 1700 ℃ of hot pressed sinterings.The performance of the material that obtains is listed in the table 1.
Embodiment 4
By obtaining sample with example 1 identical mode, different is the residual carbon that generates when adding 0.3 gram, 320 purpose silica flours with absorption PCS cracking in compound, and generates the SiC phase.The performance of the material that obtains is listed in the table 1.
Embodiment 5
By obtaining sample with example 1 identical mode, different is the residual carbon that generates when adding 1 gram, 320 purpose zirconium powders with absorption PCS cracking in compound, and generates the ZrC phase.The performance of the material that obtains is listed in the table 1.
Embodiment 6
By obtaining sample with example 1 identical mode, different is the residual carbon that generates when adding 0.5 gram, 320 purpose titanium valves with absorption PCS cracking in compound, and generates the TiC phase.The performance of the material that obtains is listed in the table 1.
Embodiment 7
By obtaining sample with example 1 identical mode, different is the residual carbon that generates when adding 0.9 gram, 320 purpose hafnium powder with absorption PCS cracking in compound, and generates the HfC phase.The performance of the material that obtains is listed in the table 1.
Embodiment 8
By obtaining sample with example 1 identical mode, the residual carbon that different is adds 0.3 gram 5-10 micron in compound silica flour generates when absorbing the PCS cracking, and generate the SiC phase.The performance of the material that obtains is listed in the table 1.
Embodiment 9
By obtaining sample with example 1 identical mode, the residual carbon that different is adds 1 gram 5-10 micron in compound zirconium powder generates when absorbing the PCS cracking, and generate the ZrC phase.The performance of the material that obtains is listed in the table 1.
Embodiment 10
By obtaining sample with example 1 identical mode, the residual carbon that different is adds 0.5 gram 5-10 micron in compound titanium valve generates when absorbing the PCS cracking, and generate the TiC phase.The performance of the material that obtains is listed in the table 1.
Embodiment 11
By obtaining sample with example 1 identical mode, the residual carbon that different is adds 0.9 gram 5-10 micron in compound hafnium powder generates when absorbing the PCS cracking, and generate the HfC phase.The performance of the material that obtains is listed in the table 1.
Embodiment 12
By obtaining sample with example 1 identical mode, different is only to add 2% volume (SiC+C) in compound.The performance of the material that obtains is listed in the table 1.
Embodiment 13
By obtaining sample with example 1 identical mode, different is to add 35% volume (SiC+C) in compound.The performance of the material that obtains is listed in the table 1.
Embodiment 14
For preparation contains TiB
2-(SiC+C) composite diphase material of 20% volume content is with TiB
2Powder 8.5 gram adds in the gasoline solution that is dissolved with 1.5 gram PCS, with zirconia ball mix grinding 12 hours, pours in the shallow beaker limit then into and stirs and allow gasoline vaporising, obtains to apply TiB
2Powder.This coating powders carries out cracking under 800 ℃ in the argon gas atmosphere that flows, obtain the potteryization mixed powder.The 1800 ℃ of hot pressed sinterings in argon shield atmosphere of then this powder being packed in the graphite jig, hot pressing pressure is 20MPa, soaking time is 60min.The performance of the material that obtains is listed in the table 1.
Embodiment 15
By obtaining sample with example 14 identical modes, the residual carbon that different is adds 0.3 gram 5-10 micron in compound silica flour generates when absorbing the PCS cracking, and generate the SiC phase.The performance of the material that obtains is listed in the table 1.
Embodiment 16
The composite diphase material that contains HfB2-(SiC+C) 20% volume content for preparation, HfB2 powder 9.3 grams are added in the gasoline solution that is dissolved with 0.7 gram PCS, with zirconia ball mix grinding 12 hours, pour in the shallow beaker limit then into and stir and allow gasoline vaporising, obtain to apply the HfB2 powder.This coating powders carries out cracking under 800 ℃ in the argon gas atmosphere that flows, obtain the potteryization mixed powder.The 1800 ℃ of hot pressed sinterings in argon shield atmosphere of then this powder being packed in the graphite jig, hot pressing pressure is 20MPa, soaking time is 60min.The performance of the material that obtains is listed in the table 1.
Embodiment 17
By obtaining sample with example 16 identical modes, the residual carbon that different is adds 0.3 gram 5-10 micron in compound silica flour generates when absorbing the PCS cracking, and generate the SiC phase.The performance of the material that obtains is listed in the table 1.
Table 1
| Embodiment | Phase composite | Density (%TD) | Hardness (GPa) | Flexural strength (MPa) |
| 1 | ZrB 2，SiC，C | 98.5 | 13 | 356 |
| 2 | ZrB 2，SiC，C | 96.8 | 12 | 323 |
| 3 | ZrB 2，SiC，C | 95.1 | 10 | 261 |
| 4 | ZrB 2，SiC | 99.3 | 16 | 482 |
| 5 | ZrB 2，SiC，ZrC | 99.1 | 15.6 | 463 |
| 6 | ZrB 2，SiC，TiC | 99.2 | 15.5 | 487 |
| 7 | ZrB 2，SiC，HfC | 99.2 | 15.5 | 458 |
| 8 | ZrB 2，SiC | 99.7 | 17 | 512 |
| 9 | ZrB 2，SiC，ZrC | 99.3 | 16.3 | 485 |
| 10 | ZrB 2，SiC，TiC | 99.5 | 16.2 | 498 |
| 11 | ZrB 2，SiC，HfC | 99.4 | 16.3 | 471 |
| 12 | ZrB 2，SiC，C | 89.2 | 5.1 | 127 |
| 13 | ZrB 2，SiC，C | 82.7 | 4.3 | 113 |
| 14 | TiB 2，SiC，C | 92.3 | 9.0 | 265 |
| 15 | TiB 2，SiC | 98.7 | 18.1 | 521 |
| 16 | HfB 2，SiC，C | 99.1 | 17.2 | 435 |
| 17 | HfB 2，SiC | 99.8 | 17.8 | 482 |
Claims (12)
1. boride-carborundum composite-phase ceramic is characterized in that: the active carbide silicon product that is produced by the Polycarbosilane cracking is wrapped in the surface of boride particle, in hot pressing in conjunction with boride particle; Silicon-carbide particle and residual carbon that cracking produces are distributed at the interface, and inside is the crystal grain of boride.
2. by the described boride-carborundum composite-phase ceramic of claim 1, it is characterized in that the silicon carbide of Polycarbosilane cracking generation and the volume content of residual carbon are 2-35%.
3. by the described boride-carborundum composite-phase ceramic of claim 1, it is characterized in that the boride that uses is ZrB
2, TiB
2Or HfB
2, their particle diameter is less than 10 microns; The particle diameter of Zr, Hf, Ti and Si≤45 μ m is 50 μ m to the maximum.
4. by the described boride-carborundum composite-phase ceramic of claim 1, the molecular weight that it is characterized in that Polycarbosilane is 1250.
5. the method for preparing boride-carborundum composite-phase ceramic as claimed in claim 1, it is characterized in that earlier Polycarbosilane being wrapped in the surface of boride particle, obtain the boride composite powder of cleaved product parcel then through cracking, the mixed powder that obtains is prepared fine and close sintered compact through hot pressed sintering, and processing step is:
1. form than thing one carborundum composite-phase ceramic by the boron of desire preparation, boride is joined in the gasoline solution that has dissolved the aequum Polycarbosilane, ball milling mixed 12 hours then, and compound is dry while stirring in air, obtained evenly to apply the mixed powder of Polycarbosilane;
2. mixed powder carries out cracking under 600-1200 ℃ of temperature, obtains the potteryization mixed powder, makes it in the surface-coated of boride particle the split product SiC and the C of layer of even Polycarbosilane;
3. the mixed powder that obtains after the cracking is packed in the graphite jig at 1700-1900 ℃ of hot pressed sintering, and the protective atmosphere during hot pressing is an argon gas;
On the boride particle surface, the volume content that generates SiC and residual C was between the 2-35% when described Polycarbosilane usage quantity was its cracking.
6. by the preparation method of the described boride-carborundum composite-phase ceramic of claim 5, pressure is 20MPa when it is characterized in that hot pressed sintering, and the time is 60min.
7. boride-carborundum composite-phase ceramic has following two features:
1. the active carbide silicon product that is produced by the Polycarbosilane cracking is wrapped in the surface of boride particle, in hot pressing in conjunction with boride particle; Silicon-carbide particle and residual carbon that cracking produces are distributed at the interface, and inside is the crystal grain of boride;
2. adding mass percent in the compound of Polycarbosilane and boride powder is the silicon of 1-12%, zirconium, the arbitrary combination of any one or they in titanium and the hafnium, the powder that is added generates corresponding carbide through reaction, the distribution of carbides that generates is at the interface, and inside is the crystal grain of boride.
8. by the described boride-carborundum composite-phase ceramic of claim 7, it is characterized in that the silicon carbide of Polycarbosilane cracking generation and the volume content of residual carbon are 2-35%.
9. by the described boride-carborundum composite-phase ceramic of claim 7, it is characterized in that the boride that uses is ZrB
2, TiB
2Or HfB
2, their particle diameter is less than 10 microns; The particle diameter of Zr, Hf, Ti and Si≤45 μ m is 50 μ m to the maximum.
10. by the described boride-carborundum composite-phase ceramic of claim 7, the molecular weight that it is characterized in that Polycarbosilane is 1250.
11. prepare the method for boride-carborundum composite-phase ceramic as claimed in claim 7, it is characterized in that in boride powder and Polycarbosilane compound, adding silicon, zirconium, the arbitrary combination of any one or they in titanium and the hafnium, mixture obtain the boride composite powder of cleaved product parcel through cracking; The mixed powder that obtains is prepared fine and close sintered compact through hot pressed sintering, and processing step is:
1. form by boride one carborundum composite-phase ceramic of desire preparation, boride is joined in the gasoline solution that has dissolved the aequum Polycarbosilane, ball milling mixed 12 hours then, and compound is dry while stirring in air, obtained evenly to apply the mixed powder of Polycarbosilane; And in Polycarbosilane and boride compound, add silicon, zirconium, the powder of any one in titanium and the hafnium or the arbitrary combination between them;
2. mixed powder carries out cracking under 600-1200 ℃ of temperature, obtains the potteryization mixed powder, makes it in the surface-coated of boride particle the split product SiC+C of layer of even Polycarbosilane;
3. the mixed powder that obtains after the cracking is packed in the graphite jig at 1700-1900 ℃ of hot pressed sintering, and the protective atmosphere during hot pressing is an argon gas; Simultaneously, the silicon of adding, zirconium, any one in titanium and the hafnium or the arbitrary combination between them generate corresponding carbide through reaction;
When described Polycarbosilane usage quantity was its cracking, the volume content that generates SiC and residual C on the boride particle surface was between the 2-35%;
Any one or the mass percent that makes up between them are 1-12% among described compound Zr, Si, Ti and the Hf, and the distribution of carbides that reaction generates is at the crystal boundary place; Be evenly distributed on and form three-dimensional network between the boride particle.
12. by the preparation method of described boride one carborundum composite-phase ceramic of claim 11, pressure is 20Mpa when it is characterized in that the sinter burning, the time is 60min.
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| CN113511900A (en) * | 2021-05-28 | 2021-10-19 | 中国科学院上海硅酸盐研究所 | Preparation method of zirconium boride reinforced SiC-AlN solid solution main phase nano multiphase ceramic sintered body |
| CN116023147A (en) * | 2022-12-14 | 2023-04-28 | 先进能源科学与技术广东省实验室 | Polycarbosilane and silicon composition, application thereof, siC ceramic and SiC ceramic matrix composite |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4289720A (en) * | 1977-08-03 | 1981-09-15 | The Foundation: The Research Institute For Special Inorganic Materials | Process for producing a thermal-resistant ceramic fired body |
| CN1031535A (en) * | 1987-07-10 | 1989-03-08 | 罗纳·布郎克化学股份有限公司 | Its method for making of polycarbosilane composition and silicon carbide be the basis product and the effect in the Ceramic Production process |
| JPH02244A (en) * | 1987-10-30 | 1990-01-05 | Sumitomo Chem Co Ltd | Production of aminophenol ether |
| JPH02241A (en) * | 1987-12-01 | 1990-01-05 | Simes Spa | Compound having beta-blocking activity and preparation thereof |
| JPH02245A (en) * | 1987-12-03 | 1990-01-05 | F Hoffmann La Roche Ag | Preparation of benzaldehyde |
| US5449646A (en) * | 1994-07-29 | 1995-09-12 | Dow Corning Corporation | Preparation of high density zirconium diboride ceramics with preceramic polymer binders |
| CN1562885A (en) * | 2004-04-14 | 2005-01-12 | 哈尔滨工业大学 | Method preparing BN/SiO2 composite ceramics through dipping, and cracking precursor body |
-
2006
- 2006-01-26 CN CNB2006100236912A patent/CN100378035C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4289720A (en) * | 1977-08-03 | 1981-09-15 | The Foundation: The Research Institute For Special Inorganic Materials | Process for producing a thermal-resistant ceramic fired body |
| CN1031535A (en) * | 1987-07-10 | 1989-03-08 | 罗纳·布郎克化学股份有限公司 | Its method for making of polycarbosilane composition and silicon carbide be the basis product and the effect in the Ceramic Production process |
| JPH02244A (en) * | 1987-10-30 | 1990-01-05 | Sumitomo Chem Co Ltd | Production of aminophenol ether |
| JPH02241A (en) * | 1987-12-01 | 1990-01-05 | Simes Spa | Compound having beta-blocking activity and preparation thereof |
| JPH02245A (en) * | 1987-12-03 | 1990-01-05 | F Hoffmann La Roche Ag | Preparation of benzaldehyde |
| US5449646A (en) * | 1994-07-29 | 1995-09-12 | Dow Corning Corporation | Preparation of high density zirconium diboride ceramics with preceramic polymer binders |
| CN1562885A (en) * | 2004-04-14 | 2005-01-12 | 哈尔滨工业大学 | Method preparing BN/SiO2 composite ceramics through dipping, and cracking precursor body |
Non-Patent Citations (3)
| Title |
|---|
| 国外硼化物系结构陶瓷的研究动向. 安时天.中国建材科技，第4期. 1987 * |
| 用聚碳硅烷作粘结剂制备碳化硅烧结体. 杨一明.炭素，第4期. 1987 * |
| 碳化硅-硼化锆复相陶瓷的增强研究. 江东亮.硅酸盐学报，第18卷第2期. 1990 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11180419B2 (en) | 2018-12-23 | 2021-11-23 | Shanghai Jiao Tong University | Method for preparation of dense HfC(Si)—HfB2 composite ceramic |
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