CN102503430A - Method for preparing reaction-sintered silicon carbide ceramic by improved tape casting process - Google Patents
Method for preparing reaction-sintered silicon carbide ceramic by improved tape casting process Download PDFInfo
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- CN102503430A CN102503430A CN2011103024165A CN201110302416A CN102503430A CN 102503430 A CN102503430 A CN 102503430A CN 2011103024165 A CN2011103024165 A CN 2011103024165A CN 201110302416 A CN201110302416 A CN 201110302416A CN 102503430 A CN102503430 A CN 102503430A
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Abstract
The invention discloses a method for preparing reaction-sintered silicon carbide ceramic by an improved tape casting process. The method comprises preparing porous carbon-containing green body by tape casting; and completely impregnating in a phenolic resin solution in vacuum, drying, carbonizing, and siliconizing in a vacuum furnace to obtain compact reaction-sintered silicon carbide ceramic. The method is based on the tape casting process and suppresses the disadvantage of high content of free silicon in the process, thus not only retains the advantage of laminate design of the tape casting process, but also reduces the residual silicon content in reaction-sintered ceramic and significantly improves the bending strength of reaction-sintered ceramic.
Description
Technical field
The present invention relates to a kind of method that adopts improvement to doctor-blade casting process preparation feedback sintered silicon carbide ceramics process modification, belong to ceramic preparation field.
Background technology
Flow casting molding is a kind of method of colloidal formation; Characteristics such as the stupalith that makes with this method has even structure, can design, safety height; At present be widely used in preparing thin flat ceramic material, advantage is more obvious in multilayer materials especially.In cut-and-try work in advance, utilize the flow casting molding method to prepare the carbon containing porous biscuit that microtexture is even, pore size distribution is narrow, and obtain fine and close reaction sintering silicon carbide ceramic through the high-temperature liquid-phase siliconising.When C/SiC ratio was 3: 10 in the biscuit, the ceramic three-point bending resistance intensity behind the reaction sintering was up to 410 ± 14MPa.
Yet contents of free si residual in the ceramic sintered bodies that this kind method obtains is higher, and when C/SiC ratio was 3: 10 in the biscuit, contents of free si was 37vol% behind the reaction sintering.And the existence of the excessive free Si use temperature of limited reactions sintered silicon carbide ceramics not only, and be unfavorable for the raising of ceramic mechanical property.Therefore need seek content and the further bending strength that improves sintered compact that a kind of method can effectively reduce free silica in the reaction sintering body.
From existing bibliographical information, reduce the silicone content that dissociates in the reaction sintering silicon carbide ceramic sintered compact and can consider from two aspects, the one, the open porosity of reduction biscuit; The 2nd, the content of carbon in the raising biscuit.But no matter select which kind of method, will consider that all the liquid phase siliconising is the process of a heat release and volumetric expansion, the increase of carbon content also is accompanied by bigger thermal stresses and volumetric expansion.If biscuit does not have certain intensity, then be easy to after the liquid phase siliconising in sintered compact, form crackle, and then ceramic body intensity is reduced.Previous work shows, and as C in the biscuit: when SiC is increased to 5: 10, occur crack-like defect in the sintered compact, bending strength also is reduced to 225 ± 79MPa.
Aspect the enhancing porous material, many investigators take the method for solvent impregnated resin, for example; People such as Furuno (Furuno, T., Imamura; Y., Kajita, minute.; 2004.Wood Sci.Tec minute nol.37,349-361.) with resin impregnating in cell walls, find that this method can significantly improve the mechanical strength of timber.
Resol be a kind of multi-functional and can with the compatible material of multiple organic or inorganic filler, it often is used as sticker, and after crosslinked certain mechanical strength can be provided.In addition, resol can decompose the carbon that stays about 55wt% being approximately under 1000 ℃ the vacuum or inert gas conditions, and this also is favourable to reaction sintering.
In the work formerly, the present inventor uses the reaction sintering silicon carbide ceramic that doctor-blade casting process has prepared structure uniform carbon containing porous biscuit and obtained good mechanical properties.On this basis; The present invention intends and further the porous biscuit is carried out the vacuum impregnation phenol resin solution; Not only improved the intensity and the carbon content of biscuit effectively, and reduced the open porosity of biscuit again, finally reduced the contents of free si of sintered compact and strengthened the mechanical strength of sintered compact.At present then rarely has report about the vacuum impregnation phenol resin solution to the technology that carbon containing porous biscuit reacts siliconising more both at home and abroad.
Summary of the invention
The object of the present invention is to provide a kind of method of improving casting molding processes preparation feedback sintered silicon carbide ceramics that adopts.The present invention be directed in the casting molding processes preparation feedback sintered silicon carbide ceramics technology high, the relatively low deficiency of bending strength of free silicone content, provide a kind of simple, effective means to make improvements.It is characterized in that: adopt vacuum-impregnated method, phenol resin solution is impregnated into by in the porous biscuit that obtains after casting films lamination, the unsticking, then remain on the hole wall behind the phenolic resin curing; Again through in warm unsticking, the decolorizing carbon that forms after the resol cracking remains in the biscuit, has not only reduced the open porosity of biscuit but also has increased the carbon content in the biscuit.The reaction sintering silicon carbide ceramic that the biscuit that obtains thus carries out obtaining after the liquid phase siliconising is with respect to the sample of impregnated phenolic resin not, and free silicone content reduces greatly in the sintered compact, and bending strength obviously increases.
The concrete technology that the present invention adopts comprises the steps:
1) prepares different C/SiC porous carbon containing biscuit with doctor-blade casting process than, even aperture distribution;
2) with the vacuum impregnation of above-mentioned resulting porous carbon containing biscuit in the different concns phenol resin solution;
3) after flooding fully, the unnecessary phenolic aldehyde solution in carbon containing porous biscuit surface that is impregnated with phenol resin solution is blotted with filter paper;
4) have the biscuit of unnecessary phenolic aldehyde solution to blot on the surface after, be placed into that drying makes phenolic resin curing in the loft drier;
5) dried biscuit is heated up under vacuum condition make resol be cracked into decolorizing carbon;
The carbonaceous biscuit that 6) will obtain is placed on the silicon chip, vacuum condition reaction siliconising down, and temperature of reaction is between 1420-1550 ℃.
Above-mentioned steps 1) the C/SiC mass ratio in is between 1: 10-10: between 1;
Preferable, the C/SiC mass ratio is between 1.4-7 in the said step 1): between 1;
Said step 2) resol in is phenol formaldehyde resin, polyvinyl acetal modified phenolic resins, polyamide modified resol, epoxy modified phenolic resin, organic-silicon-modified resin and other modified version resins etc.;
Described resol organic solution is any one in ethanol, Virahol, propyl carbinol, n-Octanol, acetone, butanone, toluene, YLENE, normal hexane, the hexanaphthene organic solvent;
Preferable, the organic solution concentration of described resol is 5-70wt%, preferential 10wt%-60wt%;
Preferable, said step 2) vacuum impregnation in is earlier to porous biscuit vacuum suction, and then in the porous biscuit, adds phenol resin solution; Make the solution of porous biscuit vacuum impregnation at resol.
Preferable, said step 2) vacuum tightness in is for being lower than 0.1MPa;
Preferable, said step 2) the vacuum suction time in is 2-30 minute;
Preferable, the drying oven temperature is between 50-170 ℃ in the said step 4), is preferably 70-160 ℃;
Preferable, the exsiccant time is 2-72 hour in the said step 4), is preferably 2-24 hour;
Preferable, temperature rise rate is preferably 0.3-5 ℃/minute for being lower than 10 ℃/minute in the said step 5);
Preferable, cracking temperature is 700 ℃-1200 ℃ in the said step 5), is preferably 800-1000 ℃; Temperature rise rate is less than 10 ℃/minute;
Preferable, soaking time is 10-300 minute in the said step 5), is preferably 10-120 minute;
Preferable, the reaction siliconising is accomplished in carbon tube furnace in the said step 6), and vacuum tightness is between the 1-20Pa.
Above-mentioned steps 2) be one-period to technology described in the step 5), this cycle can only carry out once also can repeating repeatedly.
The present invention is used for the basis that is prepared as of silicon carbide reaction-sintered biscuit with casting molding processes; The high deficiency of contents of free si to existing in this technology is improved; But not only kept the advantage of casting technique stack-design, and reduced in the reaction-sintered ceramic content of residual Si and the bending strength that significantly improves sintered compact effectively.
Description of drawings
Fig. 1 compares for the microtexture of biscuit before and after impregnated phenolic resin of mentioning among the embodiment 2.Wherein (a) is microtexture and the pore size distribution before the biscuit impregnated phenolic resin, (b) is microtexture and pore size distribution behind the biscuit impregnated phenolic resin.
Embodiment
Through concrete instance, the present invention is further specified below:
Comparative Examples 1: with the C/SiC ratio be 3: 10 casting films lamination after 500 ℃ of unstickings, the density and the carbon content of the porous biscuit for preparing are respectively 1.43g/cm
3, 24wt%.Again after siliconising in 1450 ℃/30 minutes, the sintered density that obtains is 2.89g/cm with this biscuit
3, contents of free si is 37vol%, three-point bending resistance intensity is 410 ± 14MPa.
Embodiment 1: the porous biscuit that with the C/SiC ratio is 3: 10; In vacuum tightness is that dipping concentration is the phenol resin solution of 30wt% under the 0.1MPa condition; After 80 ℃ of dryings 12 hours were again with temperature rise rate carbonization in 5 ℃/minute to 800 ℃/1 hour, the density and the carbon content of biscuit were respectively 1.57g/cm
3, 25wt%, be respectively 10% and 4% with respect to biscuit increasing amount before the impregnated phenolic resin not.
Embodiment 2: the porous biscuit that with the C/SiC ratio is 3: 10; In vacuum tightness is that dipping concentration is the phenol resin solution of 50wt% under the 0.1MPa condition; After 80 ℃ of dryings 12 hours were again with temperature rise rate carbonization in 5 ℃/minute to 800 ℃/1 hour, the density and the carbon content of biscuit were respectively 1.60g/cm
3, 26wt%, be respectively 11% and 8% with respect to biscuit increasing amount before the impregnated phenolic resin not, microtexture such as Fig. 1 before and after the dipping.Can find out that the biscuit after the impregnated phenolic resin still can keep the pore structure that is communicated with, and still keeps narrow pore size distribution.
Embodiment 3: with the C/SiC ratio is 1.4: 10 porous biscuit, is that dipping concentration is the phenol resin solution of 50wt% under the 0.1MPa condition in vacuum tightness, then 80 ℃ of dryings 12 hours again with temperature rise rate carbonization in 5 ℃/minute to 800 ℃/1 hour.Afterwards with the porous biscuit after the carbonization again vacuum tightness be in the carbon tube furnace of 6Pa through reaction siliconising in 1450 ℃/30 minutes, the sintered compact three-point bending resistance intensity that obtains is 430 ± 45MPa, silicone content is 24vol%.Increase by 28% with respect to the intensity level behind the biscuit sintering of impregnated phenolic resin (Comparative Examples) not, contents of free si reduces by 44%.
Embodiment 4: the porous biscuit that with the C/SiC ratio is 2: 10; Dipping concentration is the phenol resin solution of 50wt%; With step drying, carbonization, reaction siliconising among the embodiment 4, the sintered compact three-point bending resistance intensity that obtains is 549 ± 86MPa then, and silicone content is 20vol%.Increase by 50% with respect to the intensity level behind the biscuit sintering of impregnated phenolic resin (Comparative Examples) not, contents of free si reduces by 49%.
Embodiment 5: the porous biscuit that with the C/SiC ratio is 3: 10; Dipping concentration is the phenol resin solution of 50wt%; With step drying, carbonization, reaction siliconising among the embodiment 4, the sintered compact three-point bending resistance intensity that obtains is 598 ± 112MPa then, and silicone content is 17vol%.Increase by 46% with respect to the intensity level behind the biscuit sintering of impregnated phenolic resin (Comparative Examples) not, contents of free si reduces by 54%.
Claims (4)
1. one kind is adopted the method for improving casting molding processes moulding reaction sintering silicon carbide ceramic, it is characterized in that comprising the steps:
1) prepares different C/SiC ratios, aperture equally distributed porous carbon containing biscuit with doctor-blade casting process;
2) above-mentioned resulting porous carbon containing biscuit unsticking final vacuum is immersed in the organic solution of resol;
3) after flooding fully, the unnecessary phenolic aldehyde solution in carbon containing porous biscuit surface that will contain phenol resin solution blots with filter paper;
4) biscuit is after the unnecessary phenolic aldehyde solution in surface blots, and is placed into that drying makes phenolic resin curing in the loft drier;
5) dried biscuit is heated up under vacuum condition make phenolic aldehyde be cracked into decolorizing carbon;
6) the carbon containing biscuit that obtains is placed on the silicon chip, vacuum condition reaction siliconising down, temperature of reaction is between 1420-1550 ℃.
2. by the described method of claim 1, it is characterized in that:
A) the said C/SiC ratio of step 1) is 1: 10-10: 1;
B) step 2) described resol comprises a kind of in phenol formaldehyde resin, polyvinyl acetal modified phenolic resins, polyamide modified resol, epoxy modified phenolic resin and the organic-silicon-modified resin;
C) step 2) solvent is in ethanol, Virahol, propyl carbinol, n-Octanol, acetone, butanone, toluene, YLENE, normal hexane, the hexanaphthene organic solvent any one in the said phenol resin solution;
D) step 2) the organic solution concentration of said resol is 5wt%-70wt%;
E) step 2) said vacuum-impregnated vacuum tightness is lower than 0.1MPa; The vacuum suction time is 2-30 minute;
F) the said drying temperature of step 4) is that be 2-72 hour time of drying between 50 ℃-170 ℃;
G) the said phenolic aldehyde cracking temperature of step 5) is 700 ℃-1200 ℃, and temperature rise rate is less than 10 ℃/minute; Cracking soaking time 10-300 minute;
H) the described reaction siliconising of step 6) is accomplished in carbon tube furnace, and vacuum tightness is between the 1-20Pa.
3. by claim 1 or 2 described methods, it is characterized in that:
A) in the step 1) mass ratio of C/SiC between (1.4-7): 1;
B) concentration of the organic solution of resol is 10wt%-60wt% step 2);
C) drying temperature is 70-160 ℃ in the step 4); Be 2-24 hour time of drying;
D) cracking temperature is 800-1000 ℃ in the step 5);
E) the cracking soaking time is 10-120 minute in the step 5).
4. by the described method of claim 1, it is characterized in that step 2) be one-period to technology described in the step 5), this cycle can carry out once, also can repeat repeatedly.
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Cited By (6)
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| CN103980003A (en) * | 2014-05-27 | 2014-08-13 | 彭达鸿 | Method for preparing silicified graphite via vacuum vapor deposition reaction method |
| CN105254306A (en) * | 2015-09-30 | 2016-01-20 | 西北工业大学 | Method for preparing high-thermal-conductivity silicon nitride ceramics |
| CN111132951A (en) * | 2017-09-28 | 2020-05-08 | 西格里碳素欧洲公司 | Ceramic component |
| CN111716494A (en) * | 2020-06-17 | 2020-09-29 | 宁波伏尔肯科技股份有限公司 | Method for preparing layered complex phase ceramic by using reaction sintering method |
| CN114276143A (en) * | 2022-01-18 | 2022-04-05 | 中国科学院上海硅酸盐研究所 | SiC-SiO based on 3D printing2Two-step sintering method of ceramic green body |
| CN114394844A (en) * | 2021-12-28 | 2022-04-26 | 华中科技大学 | Method for preparing silicon carbide ceramic by 3D printing of waste and silicon carbide ceramic |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103980003A (en) * | 2014-05-27 | 2014-08-13 | 彭达鸿 | Method for preparing silicified graphite via vacuum vapor deposition reaction method |
| CN103980003B (en) * | 2014-05-27 | 2015-10-28 | 彭达鸿 | Vacuum vapor deposition reaction method prepares the method for silicated graphite |
| CN105254306A (en) * | 2015-09-30 | 2016-01-20 | 西北工业大学 | Method for preparing high-thermal-conductivity silicon nitride ceramics |
| CN111132951A (en) * | 2017-09-28 | 2020-05-08 | 西格里碳素欧洲公司 | Ceramic component |
| CN111716494A (en) * | 2020-06-17 | 2020-09-29 | 宁波伏尔肯科技股份有限公司 | Method for preparing layered complex phase ceramic by using reaction sintering method |
| CN114394844A (en) * | 2021-12-28 | 2022-04-26 | 华中科技大学 | Method for preparing silicon carbide ceramic by 3D printing of waste and silicon carbide ceramic |
| CN114276143A (en) * | 2022-01-18 | 2022-04-05 | 中国科学院上海硅酸盐研究所 | SiC-SiO based on 3D printing2Two-step sintering method of ceramic green body |
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