CN1164525C - Silicon carbide ceramics containing C-B-Al compound phase synthesized by reaction and its liquid-phase sinter process - Google Patents
Silicon carbide ceramics containing C-B-Al compound phase synthesized by reaction and its liquid-phase sinter process Download PDFInfo
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- CN1164525C CN1164525C CNB021110603A CN02111060A CN1164525C CN 1164525 C CN1164525 C CN 1164525C CN B021110603 A CNB021110603 A CN B021110603A CN 02111060 A CN02111060 A CN 02111060A CN 1164525 C CN1164525 C CN 1164525C
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Abstract
The present invention relates to a silicon carbide ceramic containing reaction synthesized C-B-Al compound phases and a liquid phase sintering method thereof, which is characterized in that the C-B-Al compound phases are composed of Al8B4C7. In the specific process, according to the proportion of a phenolic resin solution to B4C powder to Al of 1:0.1 to 0.6:0.4 to 1.5(mass), a sintering auxiliary agent with the mass of 2 to 15% of alpha-SiC powder is added; the specific proportion of the sintering auxiliary agent and SiC powder mixture to SiC balls to absolute alcohol is 1:3:1 (by mass); under the protection of flowing Ar, the materials are sintered at the temperature of 1800 DEG C to 1950 DEG C for 1 to 4 hours, and in the sintering process, C-B4C-Al and the sintering auxiliary agent react to synthesize Al8B4C7 so as to produce the SiC ceramic containing C-B-Al compound phases. The temperature of the present invention is 200 DEG C lower than that of the common hot pressing process using B4C and C as sintering auxiliary agents.
Description
Technical field
The present invention relates to a kind of containing with sintering process reaction synthetic C-B-Al compound (Al
8B
4C
7) the liquid phase sintering preparation method of silicon carbide ceramics of phase.Belong to the silicon carbide ceramics field.
Background technology
As everyone knows, silicon carbide ceramics has that hot strength is big, oxidation-resistance is strong, wearability is good, thermal expansivity is little, hardness is high and good holding property such as anti-thermal shock and resistance to chemical attack.Thereby it is widely used in a plurality of fields such as modern national defense, nuclear energy and space technology and automotive industry, ocean industry as the novel high-performance structured material.
Yet the high covalence key of SiC and low diffustivity make it be difficult to sintering under the situation that does not have sintering aid and impressed pressure.Since the seventies in 20th century, people have carried out a large amount of research in the hope of finding suitable sintering aid.People such as Prochazka [Prochazka S.In:Popper p, ed.SpecialCeramics 6.Stoke on Trent.U.K.:British Ceramic Research Asssociation, 1975.171-181.] be the pressureless sintering that additive has carried out β-SiC with B and C, obtained fine and close sintered compact at 2100 ℃.But the SiC-B-C system belongs to the category of solid state sintering, needs very high sintering temperature, causes grain growth easily.Mechanical property to sintered compact causes harmful effect.At the beginning of the eighties, people such as Omoril find Al
2O
3With some other rare-earth oxide can be by producing the sintering that liquid phase promote SiC.From then on, people forward in the liquid phase sintering Al to the research of silicon carbide agglomerating
2O
3, Al
2O
3-Y
2O
3(YAG), Al
2O
3-Y
2O
3-CaO[Mitomo M, Kim Y W, Hirotsuru H.J.Mater.Res., 1996,11 (7): 1601-1604.] successively be found the effective sintering aid that can be used as SiC.Except above-mentioned these oxide additions, Al-B-C[Shinozaki S, Williams R M, Juterbodk B N, et al.Am.Ceram.Soc.Bull., 1985,64 (10): 1389-1393.]-[Cao JJ, MoberlyChan W J, Ridhie T O, et al.J.Am.Ceram.Ceram.Soc., 1996,79 (2): 461-469.] also be used to SiC liquid phase sintering.Recently, people [Zhou Y, Tanaka H, Otani S, et al.J.Am.Ceram.Soc., 1999,82 (8): 1959-1964.] [Tanaka H, Zhou You.J.Mater.Res., 1999,14 (2): 518-522.] such as You Zhou uses Al respectively
4C
3-B
4C-C and AlB
2-C is sintering aid has obtained better performances at 1900 ℃ low temperature a sintered compact.But because Al
4C
3And AlB
2Be difficult for obtaining and very easily decomposing, use very inconvenience as raw material.Iseki[Iseki T, Kameda T, Maruyama T.J.Mater.Sci., 1984,19:1692-1698.] and V.Laurent[Laurent V, Chatain D, Eustathopoulos N.J.Mater.Sci., 1987,22 (1): 244-250.] find that respectively the Al/SiC interface has produced Al in the time of 900 ℃
4C
3, Yamaguchi
[16]Synthesized Al Deng human aluminium powder and carbon dust reaction
4C
3This shows the synthetic Al of reaction in the sintering process
4C
3It is a solution route.But Al
4C
3Be a kind of unstable compound, difficult control the present invention relates to and how to pass through Al-B in technological process
4C-C forms, and is once synthetic in the SiC sintering process, forms Al
8B
4C
7Phase causes liquid phase sintering thus, and is low-temperature sintering.
Summary of the invention
The objective of the invention is to seek a kind of Al of containing
8B
4C
7The preparation method of the low-temp liquid-phase sintering of the silicon carbide ceramics of phase, in more detail, Al
8B
4C
7Be that reaction is synthetic in sintering process mutually, yet in sintering range, exist with liquid form again, thereby reach the purpose of liquid phase sintering.
Specifically:
(1) the present invention is with meta particle diameter d
50α-SiC of=0.5 μ m is a starting raw material, and the size distribution of using up the SiC powder that the precipitator method measure as shown in Figure 1.
(2) Al
8B
4C
7Be with Al-B mutually
4C-C is that starting raw material reacts synthetic in sintering process.Al or wherein with metallic aluminium powder form (the FM4 commodity of chemical reagent station, Shanghai packing factory, its particle diameter are tens of μ m to hundreds of μ m); Or the chemical pure isopropanol aluminium Al (OC that produces with Shanghai reagent one factory
3H
7)
3Decomposition forms, B
4C is that Beijing Chinese workers median size that boron carbide product factory produces of planting is 2.5 μ m products.The C powder is to decompose and obtain from the phenol resin solution used as binding agent.
(3) press phenol resin solution: B
42～15% (quality) that the sintering aid of C powder: Al=1: 0.1-0.6: 0.4-1.5 (quality) ratio is pressed the SiC powder add, and are dispersion medium then with the dehydrated alcohol, are abrading-ball with the SiC ball, carry out the sand milling batch mixing at sand mill.Concrete proportioning is sintering aid and SiC powders mixture: the SiC ball: dehydrated alcohol=1: 3: 1 (quality), sand mill rotating speed are 300-500 rev/min, and the sand milling time is 1-8 hour.The gained slurry after oven dry about 60 ℃, is crossed 100 mesh sieves in baking oven, dry-pressing formed on vulcanizing press afterwards, forming pressure is about 20MPa, pressurize 20s.Handle through the 200Mpa isostatic cool pressing, pressurize 2 minutes removes binding agent in 600 ℃ of left and right sides unstickings in vacuum resistance furnace again.
Under mobile Ar gas shiled, biscuit places the sintering of carbon tube furnace, and temperature rise rate below 1300 ℃ is 5 ℃-8 ℃/minute, and the temperature rise rate of other temperature ranges is 8 ℃-15 ℃/minute, and holding temperature is 1800 ℃-1950 ℃, soaking time 1-4 hour.
Obviously moulding is not necessarily on vulcanizing press, also can on general press be vulcanizing press be the press of using always.
Biscuit places sintering in the carbon tube furnace after the moulding.
(4) according to people such as S.Shinozaki [Shinozaki S, Hangas J, Carduner K R, et al.J.Mater.Res., 1993,8 (7): 1635-1643.] achievement in research, when temperature is higher than 660 ℃ of the fusing points of aluminium, liquid and gasiform aluminium will be diffused into the zone of rich carbon, when temperature is higher, in the triangle crystalline region, Al will generate Al with the C reaction
4C
3When temperature rises to more than 1800 ℃, according to SiC-Al
4C
3-B
4The phasor of C system [Mitomo M, Kim Y W, Hirotsuru H.J.Mater.Res., 1996,11 (7): 1601-1604.] will have Al
8B
4C
7Liquid phase occurs, and has Al in this XRD figure with 1850 ℃ and 1900 ℃ agglomerating A2B1 materials shown in Fig. 2 (b) and 2 (c)
8B
4C
7Conform to, and A1B2, A1B1, A3B1, A4B1 also have similar pattern in the sintered compact of this temperature spot, show to have generated Al in the sintering process
8B
4C
7Just because of Al
8B
4C
7Liquid phase, appearance, promoted sintering.Wherein A2B1, A1B2 etc. are shown in Table 1 concrete the composition.
Fig. 3 and Fig. 5 show the variation of different sintering temperatures (1800 ℃, 1850 ℃, 1900 ℃ and 1950 ℃) (being incubated 1 hour) folding strength and relative density respectively, as can be seen from the figure, raising along with sintering temperature, the relative density of sample is in rising trend, and folding strength reaches maximum value in the time of 1900 ℃, sharply descends afterwards.This is because when 1800 ℃ of sintering, because temperature is lower, can't form enough amount of liquid phase, does not contain Al in the XRD figure sample of Fig. 2 (a)
8B
4C
7This point also has been described, because mass transfer velocity is very slow, pore is got rid of difficulty, and material does not have sintering, and the Photomicrograph shown in Fig. 4 (a) has also shown loose porous structure, and corresponding density and intensity are all very low.And when sintering temperature was 1850 ℃ and 1900 ℃, mass transfer velocity was accelerated, and SiC crystal grain begins to grow up, and the microstructure of Fig. 4 (b), Fig. 4 (c) is much then fine and close, fracture mode transcrystalline and also deposits along brilliant.When sintering temperature is 1950 ℃, be incubated 1 hour, crystal grain is looked very big, shows as transgranular fracture, shown in Fig. 4 (d).
It can also be seen that from Fig. 5 when sintering temperature was 1850 ℃ and 1900 ℃, higher A2B1, the A4B1 of Al content had higher relative density and intensity.Because according to Al
8B
4C
7Molecular formula is when the Al/B mol ratio is 2/1, when promptly specimen coding is A2B1, with generating the liquid phase of maximum ratio, also will more help the raising of sintering character, but because the volatility of liquid phase, in sintering process, will lose inevitably, therefore, when sintering temperature is 1950 ℃, be incubated 1 hour, because the continuing of the serious volatilization of liquid phase and crystal grain grows up, though at this moment the density of material increases, be deleterious to the mechanical property of material, so the intensity of sample becomes downtrending on the contrary.
In sum, silicon carbide ceramics provided by the invention has the following advantages:
(1) Al that contains of SiC pottery
8B
4C
7Phase is to generate at 1800 ℃ of-1900 ℃ of sintering range internal reactions.
(2) ratio at Al/B is 3/1 and 4/1 scope, when 1850 ℃ of-1900 ℃ of sintering, shows best performance, and XRD shows Al
8B
4C
7Exist mutually.
(3) contain Al
8B
4C
7The optimal sintering temperature of the SiC pottery of phase is 1850 ℃-1900 ℃, and relative density reaches more than 90%, and best soaking time is 1 hour.Than using B usually
4C
7Hang down about 200 ℃ with C for 2050-2100 ℃ as the hot pressed sintering temperature of sintering aid, so be a kind of technological process that Practical significance is arranged very much.
Description of drawings
Fig. 1 is the size distribution figure of SiC powder.
Abscissa is a particle size among the figure, and unit is μ m; Ordinate is an accumulating weight percentage ratio.
Fig. 2 is the differing temps sintering, is incubated the XRD figure of 1 hour A2B1.
(a) 1800 ℃, (b) 1850 ℃, (c) 1900 ℃, (d) 1950 ℃ among the figure.
Fig. 3 is the variation diagram of folding strength with sintering temperature.
Abscissa is sintering temperature (being incubated 1 hour), and ordinate is folding strength (Mpa).
Fig. 4 is the SEM photo of agglomerated material section
(a) A4B1,1800 ℃ of sintering, 6000X;
(b) A3B1,1850 ℃ of sintering, 4000X;
(c) A4B1,1900 ℃ of sintering, 2000X;
(d) A3B1,1950 ℃ of sintering, 2000X.
Fig. 5 is the sintering temperature of agglomerated material and the relation of relative density, and abscissa is a sintering temperature, and ordinate is a relative density.
Numbering among Fig. 2,3,4,5, see Table 1 concrete the composition.
Embodiment
Further specify outstanding feature of the present invention and obvious improvement below by specific embodiment, but the present invention is confined to embodiment by no means.
The concrete proportioning of embodiment 1～6 is as shown in table 1, example 1～5 be the Al source with the Al powder, embodiment 6 is the aluminium source with the aluminum isopropylate.
Table 1 embodiment gathers
| Embodiment | Numbering | SiC | Al/g | Al(OC 3H 7)/g | B 4C/g | Resol | The Al/B ratio |
| 1 | A1B2 | 133.5 | 6.36 | 0 | 7.94 | 4.41 | 1/2 |
| 2 | A1B1 | 133.5 | 8.13 | 0 | 5.97 | 4.80 | 1/1 |
| 3 | A2B1 | 133.5 | 9.44 | 0 | 4.52 | 5.10 | 2/1 |
| 4 | A3B1 | 133.5 | 9.98 | 0 | 3.92 | 5.22 | 3/1 |
| 5 | A4B1 | 133.5 | 10.26 | 0 | 3.60 | 5.28 | 4/1 |
| 6 | D-A2B1 | 133.5 | 0 | 71.44 | 4.52 | 5.10 | 2/1 |
Prescription with embodiment 1 is an example, sintering aid and SiC powder: SiC ball: dehydrated alcohol=1: 3: 1 (quality), the sand mill rotating speed is 400 rev/mins, 2 hours sand milling time, the gained slurry in baking oven 60 ℃ of oven dry, cross behind 100 mesh sieves on vulcanizing press with the 20Mpa pressure forming,, in vacuum resistance, remove binding agent at 600 ℃ again through static pressure such as 200Mpa.
Under mobile Ar gas shiled, place the carbon tube furnace sintering, under 1300 ℃, heat up with 5 ℃/time speed, be raised to 1900 ℃ of temperature with 10 ℃/time then, be incubated 1 hour, agglomerated material relative density 98.5%, folding strength reaches 210Mpa, KiC=4.4Mpa m
1/2
Claims (8)
1, a kind of lqiuid phase sintering method that contains the silicon carbide ceramics of the synthetic C-B-Al compound phase of reaction comprises initial SiC proportioning raw materials, moulding, sintering process, it is characterized in that:
(1) will be by phenol resin solution: B
42～15% (quality) that the sintering aid of C powder: Al=1: 0.1-0.6: 0.4-1.5 (quality) ratio is pressed α-SiC powder add;
(2) with the dehydrated alcohol being dispersion medium, is abrading-ball with the SiC ball, and concrete proportioning is sintering aid and SiC powders mixture: SiC ball: dehydrated alcohol=1: 3: 1 (quality);
(3) the oven dry slurry, sieve 600 ℃ of sticking binding agents that remove in a vacuum after the moulding;
(4) under mobile Ar gas shiled, agglomerated material, sintering temperature is 1800 ℃-1950 ℃, soaking time 1-4 hour, at sintering process C-B
4The synthetic Al of C-Al sintering aid reaction
8B
4C
7, the SiC pottery of generation carbon containing boron aluminum compound phase.
2, by the described lqiuid phase sintering method that contains the silicon carbide ceramics of the synthetic C-B-Al compound phase of reaction of claim 1, it is characterized in that described α-SiC meta particle diameter d
50=0.5 μ m.
3,, it is characterized in that described Al source or decompose forming with metallic aluminium powder or with chemical pure isopropanol aluminium by the described lqiuid phase sintering method that contains the silicon carbide ceramics of the synthetic C-B-Al compound phase of reaction of claim 1; Phenol resin solution is to originate as the C powder.
4, by the described lqiuid phase sintering method that contains the silicon carbide ceramics of the synthetic C-B-Al compound phase of reaction of claim 1, it is characterized in that described batch mixing carries out in sand mill, rotating speed is 300-500 rev/min, and the sand milling time is 1-8 hour.
5, by the described lqiuid phase sintering method that contains the silicon carbide ceramics of the synthetic C-B-Al compound phase of reaction of claim 1, it is characterized in that described slurry, cross 100 mesh sieves 60 ℃ of oven for drying; On the sheet-leveling machine with the 20MPa pressure forming, again through the 200Mpa isostatic cool pressing.
6, by the described lqiuid phase sintering method that contains the silicon carbide ceramics of the synthetic C-B-Al compound phase of reaction of claim 1, it is characterized in that described sintering process is to carry out in carbon tube furnace; Temperature rise rate below 1300 ℃ is 5-8 ℃/minute, is warming up to sintering temperature with 8-15 ℃ of/minute clock rate then.
7,, it is characterized in that the ratio of Al/B in the described sintering aid or be 1/1 or 2/1 or 3/1 or 4/1 by the described lqiuid phase sintering method that contains the silicon carbide ceramics of the synthetic C-B-Al compound phase of reaction of claim 1.
8, by claim 1 or the 7 described lqiuid phase sintering methods that contain the silicon carbide ceramics of the synthetic C-B-Al compound phase of reaction, the ratio that it is characterized in that Al/B is 3/1 or 4/1, and sintering temperature is 1850-1900 ℃, is incubated 1 hour.
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Cited By (2)
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|---|---|---|---|---|
| CN101462932B (en) * | 2009-01-21 | 2012-04-18 | 成都欣华源科技有限责任公司 | Method for preparing aldehyde by hydroformylation of light olefins |
| CN102583424A (en) * | 2012-02-16 | 2012-07-18 | 中国地质大学（北京） | Al8B4C7 abrasive and preparation method thereof |
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| CN1331560C (en) * | 2004-10-13 | 2007-08-15 | 中国科学院上海硅酸盐研究所 | Low temperature sintering reticular silicon carbide ceramic filtering device with high fire resisting level and its preparation method |
| CN104030687B (en) * | 2014-04-28 | 2015-12-09 | 宁波东联密封件有限公司 | A kind of silicon carbide ceramics and low-temperature sintering method thereof |
| CN107474202A (en) * | 2017-07-06 | 2017-12-15 | 首都航天机械公司 | A kind of synthetic method of high temperature resistant phenolic resin containing carborane |
| CN109852850A (en) * | 2019-03-20 | 2019-06-07 | 中国工程物理研究院材料研究所 | A kind of preparation method of structure-function integration neutron absorber material |
| CN110627507B (en) * | 2019-09-18 | 2022-02-25 | 广东工业大学 | Low-temperature silicon carbide ceramic and preparation method and application thereof |
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2002
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462932B (en) * | 2009-01-21 | 2012-04-18 | 成都欣华源科技有限责任公司 | Method for preparing aldehyde by hydroformylation of light olefins |
| CN102583424A (en) * | 2012-02-16 | 2012-07-18 | 中国地质大学（北京） | Al8B4C7 abrasive and preparation method thereof |
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