GB1561653A

GB1561653A – Silicon carbide sintered mouldings and a method for producing the same
– Google Patents

GB1561653A – Silicon carbide sintered mouldings and a method for producing the same
– Google Patents
Silicon carbide sintered mouldings and a method for producing the same

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Publication number
GB1561653A

GB1561653A
GB26012/76A
GB2601276A
GB1561653A
GB 1561653 A
GB1561653 A
GB 1561653A
GB 26012/76 A
GB26012/76 A
GB 26012/76A
GB 2601276 A
GB2601276 A
GB 2601276A
GB 1561653 A
GB1561653 A
GB 1561653A
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United Kingdom
Prior art keywords
compounds
organosilicon
molecular weight
heating
sintered
Prior art date
1975-06-25
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GB26012/76A
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1975-06-25
Filing date
1976-06-23
Publication date
1980-02-27

1975-06-25
Priority claimed from JP50077567A
external-priority
patent/JPS523611A/en

1975-09-27
Priority claimed from JP50115965A
external-priority
patent/JPS5848503B2/en

1976-06-23
Application filed by Individual
filed
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Individual

1980-02-27
Publication of GB1561653A
publication
Critical
patent/GB1561653A/en

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Expired
legal-status
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Classifications

C—CHEMISTRY; METALLURGY

C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES

C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE

C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products

C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics

C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides

C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide

C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers

Description

PATENT SPECIFICATION ( 11) 1 561 653
fn ( 21) Application No 26012/76 ( 22) Filed 23 June 1916 ( 31) Convention Application No 50/077567 ( 32) Filed 25 June 1975 ( 19) ( 31) Convention Application No 50/115965 ( 32) Filed 27 Sept 1975 in ( 33) Japan (JP) ( 44) Complete Specification published 27 Feb 1980 ( 51) INT CL 3 B 22 F 3/00 COIB 31/36 ( 52) Index at acceptance C 7 D 8 Z 12 8 Z 5 AI CIA 420 421 422 424 425 E 2 K 1 PB 5 PF 6 VC ( 54) SILICON CARBIDE SINTERED MOLDINGS AND A METHOD FOR PRODUCING THE SAME ( 71) I, HIROSHI WATANABE, President of the Research Institute for Iron, Steel and Other Metals of the Tohoku University, of 1-I Katahira, 2Chome, Sendai City, Japan, a Japanese subject, do hereby declare the invention, for which I pray that a patent may be granted to me, and the method by which it is to be
performed, to be particularly described in and by the following statement: 5
The present invention relates to sintered silicon carbide moldings and their production.
Previously proposed methods for producing sintered silicon carbide (Si C) include:
( 1) Si C powders are mixed with a clay and the resulting mixture is molded and 10 then sintered; ( 2) Si C powders are mixed with alumina, boron, silicon and the like and the resulting mixture is molded and then sintered; ( 3) Si C powders are mixed with an organic resin, such as a phenol furfural resin and the resulting mixture is molded and then sintered; and 15 ( 4) Si C powders are mixed with silicon nitride, tungsten carbide and the like and the resulting mixture is molded and then sintered.
Si C has little self-sintering ability and the sintered molding obtained from Si C powder alone has a porosity of 20-25 /n and a density far lower than the theoretical density of Si C of 3 21 g/cm 3 It is excessively oxidized at a temperature of 900 20 1,400 ‘C and its mechanical strength is low.
However, the use of various binders as in the above described processes (I)( 4) has provided Si C sintered moldings having a high density and a high oxidation resistance Particularly, high density Si C sintered moldings have been recently obtained by hot pressing Si C powders in admixture with several percent of a 25 binder, such as alumina, boron, silicon, tungsten carbide and the like Such dense Si C sintered moldings have high crushing strength and excellent resistance both to thermal shock resistance and oxidation.
However, the process necessary to produce these high strength Si C sintered moldings is complicated, the cost is prohibitive and it is not possible to produce 30 moldings of complicated shape Also the presence of materials other than Si C in the formed sintered moldings cannot be avoided For example, in the above processes (I) and ( 2), oxides of aluminium: silicon boron and the like are present.
In the above process ( 3), free carbon is formed and remains in the molding In process ( 4), silicon nitride, tungsten carbide and the like materials are present 35 Accordingly, there is a problem in using the sintered moldings obtained through these methods for a nozzle or a crucible used in the production of a highly pure Si single crystal Furthermore, there is a problem in using the sintered moldings as pipe, crucible, boat and the like for production of highly pure metals.
An object of the present invention is to obviate or mitigate the aforesaid 40 disadvantages.
According to the present invention there is provided a method for producing silicon carbide (Si C) sintered moldings, which comprises mixing a Si C powder or fibres composed of Si C with from 0 3 to 30 by weight of an organosilicon compound as a binder said organosilicon compound being selected from 45 (I) compounds having only Si-C bond, ( 2) compounds having Si-H bond in addition to Si-C bond, ( 3) compounds having Si-halide bond, ( 4) compounds having Si-Si bond, and ( 5) organosilicon high molecular weight compounds, in which silicon and 5 carbon are main skeleton components and which have been produced by polycondensation reaction of at least one of the organosilicon compounds of the above defined compounds (I)-( 4) or by polycondensation of one or more of the following compounds compounds having Si-N bond, 10 Si-OR organoalkoxy (or aroxy) silanes, compounds having Si-OH bond, compounds having Si-O-Si bond, esters of organosilicon compounds, and peroxides of organosilicon compounds, molding the mixture into a desired 15 shape and heating the molded shape at a temperature of not higher than 2200 C under a non-oxidising atmosphere to sinter the Si C and to decompose the organosilicon compounds to produce Si C.
It has been found that when Si C powder or fibres are mixed with the above defined binder and the resulting mixture is molded and then heated to sinter the 20 mixture, the binder is thermally decomposed, volatile components are volatilized and the remaining carbon and silicon react to form Si C.
Si C powders to be used in the present invention can be produced by electrically heating a mixture of silica and carbon in a silicating furnace at a high temperature When Si C powder of high purity is required, it is advantageous to use 25 highly pure silica, for example more than 99 8 Â of Si O 2 and carbon having less than 0.3 % of ash, for example, petroleum coke, retort carbon and the like.
Si C powder obtained by firing carbon having a high purity, such as sugar carbon or carbon black and metallic silicon having a high purity at a temperature higher than 1,250 C can also be advantageously used Furthermore, Si C powders 30 obtained by vapour phase cracking can be used.
However, when the use of high purity Si C sintered moldings is not necessary the commercially available Si C powders can be used.
As mentioned above, the above described four organosilicon compounds and the organosilicon high molecular weight compounds having a molecular weight of 35 600,000 can be used as the binder When the organosilicon high molecular weight compounds or the above described four organosilicon compounds are mixed with Si C powders and the mixture is molded and then heated, these organosilicon compounds are thermally decomposed and hydrogen, chlorine or a part of carbon is volatilized and the remaining carbon and silicon react at a 40 temperature of about 1,250 C to form Si C, so that when the sintered moldings are formed, the purity of Si C is not deteriorated.
The above described organosilicon compounds ( 1)-( 4) capable of being used as the binder are exemplified as follows.
( 1) Compounds having only Si-C bond: 45 Silahydrocarbons, such as R 4 Si, R 3 Si(R’Si R 2) R’Si R 3, carbonfunctional derivatives thereof belong to this group For example, (CH 3)4 Si, (CH 2 =CH)4 Si, (CH 3)3 Si C=-C Si(CH 3)3, (CH 2)s Si(CH 2)4, (C 2 H 5)3 Si CH 2 CH 2 CI, RN si C,R RN zsi CH 2 50 (CH 3)2 si R CH C NCHX, (CH 3)2 Si c H/ cl CH 2 c CH 3 Ctt 3 (CH 3)35 i \ 5 (CR 3)3 e (CH 3)3 S’CM 2-(, ( CHR Si(CHM 3)3, 1.561 653 R R CH 2 =CH liit’i-CH=C 2 I C 12 =CH-SiJ-5 Ri-CH=C Iz R R H 3 CC 2 \Nc -CM 2 1 I H 2 C,si CH 2 R R si (CH) CMH 2 CH 2 I 1 (cu 3)As< 11 i(c H 3)2 CH 2 ( 2) Compounds having Si-H bond in addition to Si-C bond: Mono-, di-, and triorganosilanes belong to this group For example, (CH 2)s Si H 2, C 1 CH 25 i H 3, (CH 3)3 Si CH 2 Si(CH 3)2 H, R R R R M,,CH 3 I CH$ ( 2 CH cl CM 2 (C,3)2 si 's, H CM 2 ( 3) Compounds having Si-Hal bond: Organohalogensilanes. For example, CH 2 =CH Si F 3, C 2 Hs Si HCI 2, (CH 3)2 (CICH 2)Si Si(CH 3)2 C 1, (C 6 Hs)35 i Br, R R C 12 ' I I ct-Si-CH 2-CH 2-Si C I I R R C 125 ( 4) Compounds having Si-Si bond: For example, (CH 3)3 Si Si(CH 3)2 CI, (CH 3)3 Si Si(CH 3)3, (C 6 Hs)3 Si Si(C 6 Hs)2 Si(C 6 H:)2 Cl, C 2-55 \i (CH 3)2 / \ 1 CH 2 Si(CH 3)Z l Si(CH 3)2 CM 2 C 02 / "'Si (CH 3)2 (cu 3)2 s\ -Si(CH 3)2 S' ?(c 3)2 1,SI(CH 3)2 Si(CH 3)2 CH 2\ /c 3 S /' CH 2 CM 2 3 Si /Cs "%si(CH 3)2C'3 Si(c I 34)2 (C 2 Hs)25 i H 2, R R H-Si X, S'if-H R R ZI I /5 ' (C 3)2 si s C(CH 3) CH 2 1 61 653 1,561,653 CH 2 2 CH 2Si(CH 3)2 Si (CH 3)2 / \ 112 CH 3 CH 2551 (CH 3 H 2 c 52 -s,(i In the above formulae, R shows alkyl or aryl groups. In addition to the polycondensates of compounds 1-4, the polycondensates of the following compounds can be used as binders. Compounds having Si-N bond: Silylamines belong to this group. For example, R." 1 1 NH-n R/$i NHO 3 Si-OR organoalkoxy (or aroxy) silanes: For example, (CH 3)2 Si(OC 2 Hs)2, CH=CH 2 (CH 3)2 N-$i-N(CH 3)2 CH 3 C 2 Hs Si CI 2 ( O C 2 Hs), p-CIC 6 H 40 Si(CH 3)3, \si/O ' R/ \o 3 Compounds having Si-OH bond: Organosilanols. For example, (C 2 Hs)35 i C 6 Hs Si(OH)3, OH, (CH 3)2 Si(OH)2,, (HO)(CH 3)2 Si CH 2 Si(CH 3)2 (OH), R R I I HO-SI Si-ON R R Compounds having Si-O-Si bond: Organosiloxanes. For example, (CH 3)3 Si O Si(CH 3)3, HO(CH 3)2 Si O Si(CH 3)2 OH, CI 2 (CH 3)Si O Si(CH 3)CIO Si(CH 3)C 12, l(C 6 Hs)25 i Ol 4, CH 2 =C(CH 3)CO 2 CH 2 Si (CH 3)2 CH 202 C(CH 3)=CH 2 R 251-CH 2-5 i R 2 i i o o I I R 2 Si-CP 2 Si R 2 0 CS R 25/ SIR 2 o', O SI R 2 R 25 i-CH 2-Si R 2 0 O I I R 2 Si O 52 R 2 Si-C 2 Si R 2 H 2 C CH 2 I I R 2 Si-O -SIR 2 R 2 ?/ X'Si Re c\ s H 2 R 2 Si R 2 o H 2 / CH 2 R 2 SiSi R 2 1 011 Esters of organosilicon compounds: Esters formed from silanols and acids. (CH 3)2 Si(OCOCH 3)2 Peroxides of organosilicon compounds: (CH 3)3 Si OOC(CH 3)3, (CH 3)3 Si OO Si(CH 3)3 5 In the above formulae, R shows alkyl or aryl groups. From these starting materials there can be produced organo-silicon high molecular weight compounds, in which silicon and carbon are the main skeleton components For example, compounds having the following molecular structures are produced 10 l I l (a) -Si-(C)n-Si-OI (b) -Si-O-(C)n-Ol l (c) -S i-(C)nI 1 (d) The compounds having the above described skeleton components (a)-(c) as at least one partial structure in linear, ring and three dimensional structures or 15 mixtures of the compounds having the above described skeleton components (a)(c). The compounds having the above described molecular structures are, for example as follows. (a) -Si (C)n-Si-O 20 n=l, poly(silmethylenesiloxane), n=l, poly(silethylenesiloxane), n= 2, poly(silethylenesiloxane) n= 6, poly(silphenylenesiloxane) ll (b) -Si-O-(C)n-On= 1, poly(methyleneoxysiloxane), 25 n= 2 poly(ethyleneoxysiloxane),. n= 6, poly(phenyleneoxysiloxane), n= 12, poly(diphenyleneoxysiloxane) (c) -Si-(C)nn=l, polysilmethylene 30 n=', polysilethylene, n= 3, polysiltrimethylene, n= 6, polysilphenylene, n= 12, polysildiphenylene (d) The compounds having the above described skeleton components as at 35 least one partial structure in linear, ring and three dimensional structures or mixtures of the compounds having the above described skeleton components (a)(c). 1,561,653 In the organosilicon high molecular weight compounds, in which silicon and carbon are the main skeleton components, even if silicon or carbon is present in the side chain, these elements are easily decomposed and volatilized, while silicon and carbon constituting the skeleton components are not easily decomposed and volatilized by heating and silicon and carbon bond at a high temperature to form 5 Si C. The production of the organosilicon high molecular weight compounds in which silicon and carbon are the main skeleton components from the starting materials of the organosilicon compounds can be effected by polycondensation attained by subjecting the organosilicon compounds to at least one of irradiation, 10 heating and addition of a catalyst for the polycondensation. For example, some well known reaction formulae for obtaining the above described organosilicon high molecular weight compounds from the above described starting materials through at least one of addition of the catalyst, irradiation and heating, are exemplified as follows In the formulae which follow 15 the symbol Ph represent a phenyl group. Si/ S CH 3 CH 2 CH 3 CH 3 n / \ / Heatingt rCH 2312 H Si "'CC K Si-CCCCH 2C.3 CH 2 c CH 3 c,3 C 2 c C 3 LC j H H Si H + HC CH ' H 2 Pt CI 6 CH 3 013 CH 3 C 3 1 CC 3 CC 3 F CC 3 CC 3 1 1 I Cl-$;-C Hi CH 2-S;-Cl A Si-C,2 C Cc Si O-c CI-Si-C 2 CC 2 SI-CI ( 2) KOH '-I CC 3 CC 3 L CC 3 CC 3_ 1 CC 3 NH Ph $i/ + HO-CH Heabng. C, NH Ph CH 3 n CH 3 C 3 O Ph 'Sl + HO-OH Na i o-(l-l 25 -CH'3 Ch 3 LH c" 3 h 1,561,653 7 o H KOH l 5 i 6 C,653 O CH 3 CC Hc 3 CH 3 ( CHA Si CH 2 CH 3)2 CH 3 C R 3 H j (CH 3)251-CH 2-Si(CH 3)2 CH 3 CH 3 n HCH 2 (CH 3)2 _ /Si (CH 3)2 H Po imer (CH 3)2 Si-Si(CH 3)2 CU 3CH 3 Cl c Cl-Si-si-cl Heating sic H 2 sic H CH 3CH 3 CH 3 CH 3 n Other than the above described processes for producing the organosilicon high 5 molecular weight compounds, at least one organosilicon compound selected from the above described groups is polymerized within a temperature range of 2001,500 C under vacuum, an inert gas, CO gas or hydrogen gas, if necessary, under pressure to produce the organosilicon high molecular weight compounds in which silicon and carbon are the main skeleton components 10 The reason why the above described reaction should be effected within the temperature range of 200-1,500 C is as follows When the temperature is lower than 200 C, the synthesis reaction does not satisfactorily proceed, while when the temperature is higher than 1,5000 C, the decomposition reaction is violent and the yield of the organosilicon high molecular weight compound becomes small, so that 15 the temperature range must be 200 to 1,500 C and best results can be obtained within the temperature range of 300-1,2000 C. The above described synthesizing reaction can be carried out in a pressure vessel and in this case, the optimum temperature range is 350-5000 C and upon the thermal decomposition polycondensation reaction of the organosilicon compound, 20 a pressure is produced, so that it is not always necessary to apply pressure from an external source The above described polycondensation reaction may be effected by using a continuous apparatus An explanation will be made with respect to one embodiment of the continuous production apparatus, which is shown in Figure 1. The organosilicon compound is charged into a heating reaction column 2 through a 25 valve I and in the reaction column, the organosilicon compound is heated at a temperature of 300-1,500 'C preferably 500-1,2000 C and a part of the reaction product of organosilicon high molecular weight compound is discharged from the reaction system through a valve 3 and low molecular weight compounds formed in the heating reaction column 2 are fed into a fractionating column 5 through a valve 30 4 and distillation and separation are effected therein and the formed gas is discharged from the fractionating column 5 through a valve 6 and the high molecular weight compound is taken out from the fractionating column 5 through a valve 7 The low molecular weight compounds separated in the fractionating column are recycled into the heating reaction column 2 through a valve 8 35 The molecular structure of the thus obtained organosilicon high molecular weight compounds was tested by nuclear magnetic resonance absorption spectrum and infrared spectrum and the presence of -(-Si-C-) bond was recognized and it has been found that in the above described organosilicon high molecular weight compounds, the main skeleton components are constituted with silicon and 40 carbon. An explanation of a process for using the binder will be made with respect to polycarbosilane which is easily produced and has the smallest decrease of weight after heat treatment and therefore can be advantageously used. Polycarbosilane is liquid or solid and can be used directly or in a viscous 45 solution dissolved in a solvent, such as benzene, toluene, xylene, hexane, ether, tetrahydrofuran, dioxane, chloroform, methylene chloride, petroleum ether, l.56 i 653 petroleum benzene, ligroine; dimethylsulphoxide (DMSO) and dimethylformamide (DMF) The binders other than polycarbosilane may be used according to the above described process. The binder is added in an amount of 0 3-30 ,,, preferably 5-25 , more particularly 7-15 % by weight based on Si C powders The resulting mixture is 5 molded into a given shape Alternatively, a hot press process wherein the mixture is heated in a mold and the press molding is effected during the course of sintering. may be used. The sintering of the above described molding is effected by heating said molding at a temperature from room temperature to 2,2000 C -under vacuum or in 10 an atmosphere of inert gases, CO gas or hydrogen gas. If the above heat treatment is effected in air, the binder is oxidized to form Si O 2, so that the heat treatment must be effected in a non-oxidizing atmosphere (inert gases, CO gas or hydrogen gas) under vacuum, atmospheric pressure or pressure 15 When the above described heat treatment is effected under pressure in a nonoxidising atmosphere, the amount of the binder converted into Si C can be increased, so that Si C molding obtained by heating under pressure is more dense than Si C molding obtained by heating without pressure and the mechanical strength is greater The heat treatment under pressure does not require a high 20 temperature and can be effected from room temperature to 500-8000 C, at which the polycondensation of the organosilicon compounds and the organosilicon high molecular weight compounds is completed A relation of the flexural strength and the bulk density to the pressure of Si C molding obtained by heating up to 6000 C under nitrogen gas pressure and then heating up to 1,3000 C in nitrogen gas 25 atmosphere is shown in Figure 9 As seen from Figure 9, when the pressure increases, the bulk density of Si C molding and the flexural strength increase and the excellent product can be obtained If the heating is effected under vacuum, when the organosilicon compound and the organosilicon high molecular weight compound of the binder of Si C molding is polycondensed, the formed gas is 30 removed and the swelling upon the heating can be prevented. The hot press process to be used in the present invention is a process for sintering refractory substance powders in which the powder is not previously molded The powder is heated in a mold and the press molding is effected in the course of sintering and the powders are more compactly packed and a dense 35 molding can be obtained. In the hot press process industrially carried out, the temperature is usually 1,200-2,2000 C and the pressure is 140-700 Kg/cm 2 The heating of furnace is generally effected electrically by resistance heating process or high frequency induction heating process 40 In the resistance heating, the voltage is continuously varied up to 30 volts and is normally used with a resistance graphite tube for heating having a thickness of 1.3 cm, an outer diameter of 20 cm and a length of 150 cm In the high frequency induction heating, a current controller of 15,000 amps at 1,000-30,000 cycles per second can be used In a small scale hot press for producing a molding having a 45 diameter of 2 5 cm and a length of 2 5 cm, 15 KVA at 30,000 cycles is preferable and with a molding having a diameter of 35 cm and a length of 25 cm, 300 KVA at 1,000 cycles is necessary. The most simple press process is a lever type but this type is not convenient for adjusting the pressure A ram type of oil pressure or air pressure is usually used 50 If the mold is electrically conductive at a temperature of 1,200-2,600 C which is the press temperature, the heating can be directly made by a resistance or induction process, so that graphite is generally used Dense graphite having the highest strength and a high mechanical workability is suitable. A detailed explanation will be made of the self sintering of Si C upon the 55 production of Si C sintered moldings The organosilicon compounds and the organosilicon high molecular weight compounds used as the binder are thermally decomposed in the heat treatment and superfluous carbon and hydrogen volatilize and the remaining carbon and silicon react to form Si C, which bonds strongly to the Si C powders When the temperature is gradually raised over a sufficiently long 60 time, the organosilicon compound or the organosilicon high molecular weight compound which fills the grain boundary of the Si C powders decomposes and reacts to become Si C and a Si C sintered molding is formed When the binder used in the present invention is converted into Si C, microcrystalline Si C is formed and the size of the crystal grain is usually 30-70 A and the diameter of the crystal grain 65 I 1,561,653 QD is far smaller than that of the heretofore known Si C sintered moldings, so that the surface area is considerably larger and the apparent self diffusion coefficient of Si C becomes very large In Si C sintered moldings of the present invention, the self sintering ability is increased and as a result, sintered moldings having a high strength can be obtained 5 The above described Si C sintered moldings may contain free carbon and this free carbon can be removed by firing the sintered moldings at a temperature of 600-l,700 'C under an oxidizing atmosphere If the above described firing is effected at a temperature lower than 6000 C carbon cannot be removed, while when the temperature exceeds l,7000 C, the oxidation reaction of Si C becomes 10 excessive, so that such a high temperature is not preferable The time of the above described firing under an oxidizing atmosphere varies according to the firing temperature, the size of the molding and the structure of the firing furnace and when the firing temperature is low, the firing must be effected for a long time, while when the firing temperature is high, the firing time may be short When the firing is 15 effected at a low temperature for a relatively long time, the amount of Si O 2 formed is small and a good result can be obtained For example, when the crucible produced by the present invention is fired at a temperature of l,0000 C in air to remove free carbon, the preferred firing time is 1-3 hours. In the present invention, the amount of the binder added is 03-30 ,, by 20 weight as mentioned above When said amount is less than 03 %o by weight, it is difficult to obtain Si C sintered moldings, if when said amount is larger than 300,, by weight, the sintered molding is swollen and cracks are caused When the hot press process is used, l-20 %' by weight is preferable and in the cold press process where the mixture of Si C powders and the binder is press molded and then the molded 25 mixture is fired, the 5-25 % by weight is preferable. The inventors have found that Si C sintered moldings having better properties can be obtained by using Si C powders prepared by the specific production process as explained hereinafter The specific Si C powders are obtained as follows The above described any one of the organosilicon high molecular weight compounds 30 which can be used as the binder in the present invention is preliminarily heated at a temperature of 400-l,000 C under vacuum, atmospheric pressure or higher pressure in a non-oxidizing atmosphere to form Si C primary product which, if necessary, is further heated at l,000-2,200 C to form a fired product The Si C primary product or the fired product is pulverized to form Si C powders 35 A method for producing Si C powders from the organosilicon high molecular weight compounds, in which carbon and silicon are the main skeleton components, will be explained in detail hereinafter. During the above described preliminary heating, and the firing if effected, the organosilicon high molecular weight compound polycondense further to give even 40 higher molecular weights and when these higher molecular weight compounds are heated, any silicon and carbon present in the side chains of the polymer are easily decomposed and volatilized but silicon and carbon constituting the main skeleton components are not volatilized by the heating but instead bond to form Si C. The primary product is amorphous Si C and contains volatile components and 45 if the primary product is heated at a high temperature, the volatile components are volatilized and the weight is decreased and shrinkage occurs Accordingly, when the pulverized primary product is mixed with a binder, for example, polycarbosilane and the mixture is heated, the volatile components in polycarbosilane are volatilized and shrinkage occurs and simultaneously the Si C 50 primary product shrinks, so that cracks are not caused and a sintered molding having a high strength can be obtained. Furthermore, Si C powders obtained by further firing the primary product behave precisely the same as those obtained by firing the binder of the present invention, so that the adhesion of the binder to Si C powders is good and there is no 55 formation of cracks. The atmosphere from the preliminary heating is carried out under vacuum or in inert gas, CO gas, hydrogen gas, vapour of an organosilicon compound gas or a hydrocarbon vapour The temperature of the preliminary heating is 400-I, 000 C, preferably 500-8000 C 60 When the preliminary heating is effected under pressure, the yield of Si C primary product can be increased When the preliminary heating is effected under vacuum, the gases generated in polycondensation and decomposition reactions of the above described organosilicon high molecular weight compounds can be easily I 561 653 removed but the yield when the preliminary heating is effected under pressure, is larger than that in the case under vacuum. The preliminary heating may be carried out by what we call a "delayed process' or by a fluid bed process An embodiment of production apparatus in the S delayed process is shown in Figure 2 101 and 102 are reaction columns, 103 is a 5 heating furnace, 104 is a fractionating column and 105 is a valve In this apparatus, the organosilicon high molecular weight compound is charged through the valve and rapidly heated within a temperature range of 400-1,0000 C at the heating furnace 103 and then fed into the reaction column 101 or 102 In the reaction column, the decomposition reaction proceeds and hydrogen gas, low molecular 10 weight hydrocarbons, low molecular weight organosilicon compounds and other gases, and a liquid are formed and Si C primary product remains in the reaction column 101 or 102 The above described gases and the liquid are fed into the fractionating column 104, in which the gases and the liquid are separated and the gases are discharged from the fractionating column and the liquid is recycled into 15 the heating furnace 103. Si C primary product produced by the above described delayed process or the fired Si C obtained by firing the Si C primary product at a high temperature contains a large number of pores and the specific gravity is small The bulk density of the above described fired Si C is 1 5-2 2 g/cc and is significantly lower than the specific 20 gravity of Si C crystal of 3 21 The yield of Si C primary product in the above described delayed process varies according to the average molecular weight of the starting material of the organosilicon high molecular weight compounds and the reaction pressure. When the reaction pressure is 1 atmosphere, the relationship between the yield 25 of Si C primary product and the average molecular weight of the organosilicon high molecular weight compound is shown in Figure 4 As seen from Figure 4, the yield of Si C primary product increases, as the average molecular weight of the organosilicon high molecular weight compound increases but when the average molecular weight approaches 5,000, the yield becomes substantially constant The 30 relation of the yield of Si C primary product to the reaction pressure is shown in Figure 5 As seen from Figure 5, as the reaction pressure increases, the yield of Si C primary product increases but when the reaction pressure becomes more than 8 Kg/cm 2, the yield becomes substantially constant. An embodiment of apparatus in the fluid bed process is shown in Figure 3 201 35 is a compressor for feeding an inert gas, 202 and 203 are fluidized beds, 204 and 205 are tubes for flowing Si C primary product, 206 is a fractionating column and 207 is a valve. In the above described apparatus, the organosilicon high molecular weightcompound is charged into the fluidized bed 203 heated within a range of 400 40 1,0000 C through the valve 207 Si C primary product produced in this fluidized bed 203 is fed into the fluidized bed 202 from the lower portion of the fluidized bed 203 through a tube 205 and dried by air fed from the compressor 201 and fed again into the fluidized bed 203 through the tube 204 and mixed with the starting material of the organosilicon high molecular weight compound and the mixture is reacted The 45 gases formed in the fluidized bed 202 are discharged from the reaction system and the gases and the liquid formed in the fluidized bed 203 are separated in the fractionating column 206 and the separated gas is discharged from the reaction system and the liquid is recycled into the fluidized bed 203. Si C primary product produced by the above described fluid bed process and 50 Si C obtained by firing the primary product have a circular onion-shaped structure and have a bulk specific gravity of 1 7-2 7, which is greater than that of the product formed in the previously described delayed process The yield of Si C primary product in the fluid bed process is 5-20 % and does not vary greatly with the average molecular weight of the starting material used or the reaction pressure 55 A structure of Si C powders formed by the above described preliminary heating is explained hereinafter X-ray diffraction patterns of Si C powders obtained by the preliminary heating at 8000 C are shown in Figure 6 As seen from this diffraction patterns, there are two broad diffraction peaks, the center of which is 20 36 5 ' and 20- 650, respectively and this X-ray diffraction pattern shows that the structure of 60 Si C primary product is amorphous The peak of 20- 26 5 ' is based on ( 002) plane of graphite and it is recognized that graphite crystal coexists in silicon carbide heated at 800 GC. The above described Si C primary product may be heated at a temperature of lo 1,561 653 700-2,200 'C, preferably 1,000-2,0000 C under vacuum or an atmosphere of inert gas, CO gas or hydrogen gas to form heat-treated silicon carbide. If the above described heating were effected in air, the Si C primary product would be oxidized to form Si O 2 so that said heat treatment must be effected under vacuum or an atmosphere of inert gas, CO gas or hydrogen gas Moreover, the 5 above described heat treatment may be effected by embedding Si C primary product in coke granules. In the above described heat treatment, when the heating temperature is higher than 2,200 'C, the reaction of formation of Si C is too violent, so that the heat treatment should be effected at a temperature lower than 2,200 'C 10 The heat-treated silicon carbides obtained by varying the above described heating temperature were pulverized and the X-ray diffraction of resulting powders was determined and the obtained results are shown in Figure 6 As shown in Figure 6, in the powders heat-treated at 1,5000 C, Si C crystal does not fully grow but in the powders heat-treated at a temperature higher than 2,0000 C, Si C crystal grows fully 15 and is /3-Si C Furthermore, the coexistence of graphite crystal shown by the diffraction peak of 20 = 26 5 ' is recognized in the above described heattreated Si C as shown in the X-ray diffraction pattern. The silicon carbide sintered moldings are produced from the above described Si C primary product or the heat-treated Si C in the following manner The above 20 described Si C primary product or the heat-treated Si C is pulverized to form granules and powders and the compounding ratio of the resulting granules and powders are adjusted depending upon the form of the moldings and then the organosilicon compound or the organosilicon high molecular weight compound as a binder is added thereto in the described manner and the mixture is mixed and 25 then press molded into a molding having a given shape, after which the molded mixture is heated from room temperature to 2,2000 C in at least one of the atmospheres of inert gases, CO gas, hydrogen gas, if necessary under pressure or vacuum When the above described heating is effected under pressure, the yield of Si C of the binder can be increased, so that Si C sintered moldings having a high 30 strength can be obtained, while when the above described heating is effected under vacuum, the formed gas is conveniently volatilized but the yield of Si C is decreased. In the above described heating, if the temperature is gradually raised in a sufficient time, the yield of Si C from the binder is improved and the shrinkage of 35 the molding can be uniformly effected, so that the dense molding can be obtained. The above described Si C sintered moldings may contain free carbon This free carbon may be removed by heating such Si C sintered moldings at a temperature of 600-I,7000 C under an oxidizing atmosphere as already explained. The inventors have found a method for producing Si C fibers having an 40 extremely high strength from the organosilicon high molecular weight compounds, in which silicon and carbon are the main skeleton components and filed as British Patent Application ( 16063/76 (Serial No 1,551,342), British Patent Specification No. A brief explanation will be made with respect to one embodiment for 45 producing Si C fibers. The content of low molecular weight impurities contained in the organosilicon high molecular weight compounds is reduced by the process, the thus treated high molecular weight compounds are spun by a melt or dry spinning process into filaments having a diameter of 5-100,, if necessary the spun filaments are heat 50 treated in air at a temperature lower than 3000 C, the filaments are preliminarily heated under vacuum at a temperature of 350-800 C to volatilize the remaining low molecular weight compounds, and then the thus treated filaments are baked at a temperature of 800-2,0000 C under vacuum or in an atmosphere of inert gas, CO gas or hydrogen gas to form Si C fibers 55 The inventors have further found that the thus formed Si C fibers are preferable for the aggregate of Si C sintered moldings instead of Si C powders. The compounding ratio of the binder to Si C fibers is the same as in the case of Si C powders. Si C fibers can be used in any form of staple fibers and long filaments When 60 Si C fibers are used as staple fibers, the following merits can be obtained When the above described Si C primary product or the fired Si C block is pulverized to form Si C powders, over-pulverizing occurs and it is impossible to obtain only the powders having a given particle size but when a bundle of fibers are cut by a cutter to a given length, the fibers having the given length can be easily obtained When 65 I 1,561,653 1 1 l l the Si C staple fibers having a uniform length are used as the aggregate, the compounding ratio of the binder is always constant and the physical properties of the obtained sintered moldings are uniform. The strength of Si C sintered moldings obtained by aligning the long Si C fibers, adding the binder of the organosilicon high molecular weight compound thereto 5 and heating the mixture, is very large in the fiber direction and a flexural strength of 20 Kg/mm 2 is easily obtained. Heretofore, Si C sintered moldings having a high strength of more than 5 Kg/mm 2 of flexural strength have not been obtained, unless the bulk density is more than 3 05 g/cm 3 as in KT Si C of Carborundum Co, the hot pressed Si C of Norton 10 Co and the self sintered Si C of GE Co The relation between the bulk density and the flexural strength of Si C sintered molding of the present invention is shown in Figure 7 As shown in Figure 7, even though the bulk density is as low as 2 35 g/cm 3, the flexural strength is 5 5 Kg/mm 2 and when the bulk density is increased to 2 5 g/cm 3, the flexural strength increases to 17 Kg/mm 2 The flexural strength of 17 15 Kg/mm 2 is as same as the flexural strength ( 17 Kg/mm 2) of the KT Si C molding A merit of the present invention is that Si C moldings having a high strength at a bulk density of lower than 3 05 g/cm 3 are produced. Oxidation resistance of Si C sintered moldings of the present invention is excellent and even if Si C sintered moldings are heated at a high temperature in air, 20 the weight increase due to oxidation is far smaller than that of the conventional Si C sintered moldings Si C sintered molding of the present invention (bulk density: 2 5 g/cm 3) and Si C sintered molding of Norton Co (bulk density: 3 29 g/cm 3) were subjected to oxidation test and the obtained results are shown in Figure 8. Si C sintered molding of the present invention with a low bulk density of 2 5 25 g/cm 3 contains 32 % of fine pores, while the bulk density of the conventional Si C sintered moldings is 3 29 g/cm 3 and no fine pores are present Nevertheless, as seen from Figure 8, even if Si C sintered molding of the present invention is heated at the high temperature for a long time in air, the weight increase is about half of the conventional Si C sintered molding This is because in Si C sintered molding of the 30 present invention, Si C powders are bonded by Si C formed from the organosilicon high molecular weight compound of the binder, while in the conventional Si C sintered molding, Si C powders are bonded by alumina, boron, metallic silicon and the like The oxidation resistance of SIC sintered moldings of the present invention is high 35 Furthermore, Si C moldings of the present invention do not shrink upon heat treatment and the shape before heating can be maintained even after heating. Therefore, Si C sintered molding having a high precision or a high dimension precision can be obtained In the conventional Si C sintered moldings, it has been impossible to obtain complicated shapes and the dimension precision is very poor 40 Up to now it has been considered that Si C sintered moldings having a high dimension precision cannot be obtained. The present invention will be explained in more detail. For a better understanding of the invention, reference is taken to the accompanying drawings, wherein: 45 Figure 1 shows a diagrammatic view of an apparatus for producing the organosilicon high molecular weight compounds, in which silicon and carbon are the main skeleton components, from organosilicon compounds; Figures 2 and 3 show diagrammatic views of apparatuses of the delayed process and the fluid bed process for producing Si C primary product from the 50 organosilicon high molecular weight compounds, respectively; Figures 4 and 5 are graphs showing the relation between the average molecular weight of the organosilicon high molecular weight compound and the yield of Si C primary product in the delayed process and the relation between the reaction pressure and the yield of Si C primary product in the delayed process, respectively; 55 Figure 6 shows X-ray diffraction patterns of silicon carbides heattreated at various temperatures; Figure 7 is a graph showing the relation between the flexural strength and the bulk density of Si C sintered moldings of the present invention; Figure 8 is a graph showing the relation between the weight increase due to 60 oxidation and the time of Si C sintered moldings of the present invention and Norton Co: and Figure 9 is a graph showing the relation between the heating pressure and the flexural strength and the bulk density of Si C sintered molding of the present invention 65 I 1,561,653 The following examples are given for the purpose of illustration of this invention and are not intended as limitations thereof In the examples, ",, ' and "parts" mean by weight unless otherwise indicated. Example I Dodecamethylcyclohexasilane was heat treated in an autoclave at 400 C for 36 hours under argon to form a liquid polycarbosilane having an average molecular weight of 800 30 g of powdery Si C of 99 90 / purity having a particle size of about 400 meshes was thoroughly kneaded together with 5 g of the above obtained polycarbosilane, and the resulting mixture was press molded into a crucible Then the crucible was fired by heating the crucible from room temperature to 1, 800 C in 10 8 hours under a vacuum of 1 x 10-4 mm Hg to obtain a Si C sintered crucible having a bulk density of 2 3 g/cm 3 When the resulting Si C sintered crucible was used in the melting of metallic silicon, the crucible had a remarkably longer life and the purity of the melted metallic silicon was improved. Example 2 15 In an autoclave, 10 g of linear polydimethylsilane produced from dimethyldichlorosilane was heated at 400 C for 30 hours under a pressure of 30 atmosphere under argon to form 6 3 g of polycarbosilane The average molecular weight of the polycarbosilane was adjusted to 1,500 50 g of powdery Si C of 99 750, purity produced from metallic silicon and carbon and having a particle size of less 20 than 325 meshes was kneaded together with 5 g of the above obtained polycarbosilane as a binder, and the resulting mixture was charged into a graphite mold for producing a nozzle, and gradually heated up to l,500 C in 10 hours under vacuum ( 1 x 10-4 mm Hg) by a high-frequency induction furnace, while applying a pressure of 200 Kg/cm 2 to the mixture by a hot press, to form a Si C sintered nozzle 25 having a bulk density of 2 4 g/cm 3 The resulting Si C sintered nozzle was further kept at 1,000 C for 3 hours in air in order to decrease the carbon content into a very small amount. A metallic silicon ribbon was produced by using the above obtained Si C sintered nozzle When the Si C nozzle was compared with Si C nozzles produced by 30 conventional processes, the Si C sintered nozzle had a longer life metallic silicon had a higher purity. Example 3 In an autoclave, 10 g of linear polydimethylsiloxane synthesized from dimethyldichlorosilane was heated at 430 C for 30 hours under pressure of 30 atm 35 under argon to form 6 3 g of polycarbosilane The average molecular weight of the polycarbosilane was adjusted to 1,500 50 g of powdery Si C was kneaded together with a solution of 8 g of the above obtained polycarbosilane in 50 ml of xylene. After the xylene was removed under a reduced pressure, the resulting mixture was heated and molded into a rod The rod was heated from room temperature to 40 600 C in 12 hours in a pressure of 40 Kg/cm 2 of argon and then heated from 600 C to 1,300 C for 7 hours under argon to obtain a Si C sintered rod having a bulk density of 2 42 g/cm 3 The Si C sintered rod was further kept at 900 C for 4 hours in air to form an Si C sintered rod having a bulk density of 2 42 g/cm 3 and a flexural strength of 12 Kg/mm 2 45 When the resulting Si C sintered rod was used as a heating element, the life of the heating element was about 30 , longer than that of conventional Si C heating elements. Example 4 1,3-Disilacyclobutane was heated in an autoclave at 350 C for 40 hours under 50 argon to obtain a solid organosilicon high molecular weight compound having an average molecular weight of 15,000 50 g of powdery Si C was kneaded together with 2 0 g of powders of the above obtained organosilicon high molecular weight compound as a binder, and the resulting mixture was charged into a graphite molding and gradually heated up to 1,750 C in 12 hours under argon by a high 55 frequency induction furnace, while applying a pressure of 700 Kg/cm 2 to the mixture by a hot press, to obtain a Si C sintered nozzle having a density of 2 40 g/cm 3. When high purity silicon was gradually extruded through the resulting Si C nozzle, a semiconductor was obtained 60 1,561,653 Example 5 Dodecamethylcyclohexasilane was heat treated in an autoclave at 450 C for 36 hours under argon to form a liquid organosilicon high molecular weight compound The organosilicon high molecular weight compound was dissolved in nhexane, and acetone was added to the solution to obtain an acetoneinsoluble solid 5 organosilicon high molecular weight compound having an average molecular weight of 3,200 50 g of commercially available powdery Si C having an average particle size of 320 meshes was kneaded together with 2 5 g of powders of the above obtained solid acetone-insoluble organosilicon high molecular weight compound as a binder, and the resulting mixture was charged into a graphite mold for producing 10 a pipe and gradually heated up to 1,750 C in 12 hours under vacuum (lx IO-4 mm Hg) by a high-frequency induction furnace, while applying a pressure of 200 Kg/cm 2 to the mixture by a hot press, to form a Si C sintered pipe having a bulk density of 2 40 g/cm 3. When the resulting Si C sintered pipe was used in a still for zinc, the life of the 15 Si C sintered pipe was considerably longer than that of conventional Si C pipes. Example 6 Octaphenylcyclotetrasilane was heated in an autoclave at 420 C for 20 hours under argon to form a solid organosilicon high molecular weight compound 50 g of powdery Si C of 99 5 % purity having a particle size of 400 meshes was kneaded 20 together with 1 0 g of powders of the above obtained organosilicon high molecular weight compound as a binder, and the resulting mixture was charged in a graphite mold for producing a nozzle and gradually heated up to l,750 C under argon by a high-frequency induction furnace, while applying a pressure of S t/cm 2 to the mixture by a hot press, to form an Si C sintered nozzle having a bulk density of 2 45 25 g/cm 3. When melted high purity silicon was extruded through the resulting Si C sintered nozzle, a semiconductor was obtained. Example 7 A solution of 3 g of octaphenyltrisilane l(C 6 Hs)3 Si Si(C 6 Hs)2 Si(C 6 Hs)3 l in 30 benzene was thoroughly kneaded together with 30 g of powdery Si C of 99 9 % purity having an average particle size of 450 meshes After the solvent was evaporated, the resulting mixture was press molded into a cylindrical rod The rod-shaped molding was fired by heating the molding from room temperature to l,300 C in 8 hours under argon to obtain a Si C sintered rod having a bulk density of 2 35 g/cm 3 The 35 Si C sintered rod was kept at 800 C for 3 hours in air The thus treated Si C sintered rod contained less than 0 2 % of free carbon and other impurities. When the Si C sintered rod was used as a heating element, the life of the heating element was at least 20 % longer than that of the conventional Si C heating elements 40 Example 8 A solution of 4 g of p-bis(dimethylvinylsilyl)-benzene ICH 2 =CH Si(CH 3)2 C 6 H 4 Si(CH 3)2 CH=CH 2 l in xylene was thoroughly kneaded together with 30 g of powdery Si C of 99 9 % purity having an average particle size of 450 meshes After the solvent was evaporated, the resulting mixture was charged 45 into a graphite mold for producing a pipe and gradually heated up to l, 400 C in 12 hours under argon by a high-frequency induction furnace, while applying a pressure of 700 Kg/cm 2 to the mixture by a hot press, to form a Si C sintered pipe having a bulk density of 2 45 g/cm 3. Further, Si C sintered moldings can be obtained in the same manner as 50 described in this example by using organohalogenosilane or organohydrosilane having relatively high melting point and boiling point as a binder in place of the above described silicon compound. Example 9 A mixture consisting of about 78 % of dimethyldichlorosilane, about 8 of 55 methyltrichlorosilane, about 3 % of trimethylchlorosilane, about 2 %,, of methyldichlorosilane and about 9 % of the product obtained by direct synthesis of methyl chloride and silicon, was used as a starting material, and an organosilicon high molecular weight compound was produced by means of the apparatus shown in Figure 1 in the following manner Air in the whole apparatus was firstly purged 60 with nitrogen gas, and the above described mixture was fed into a reaction column 2 heated to 750 C at a rate of 15 I/hr to effect a polycondensation reaction therein. 1,561,653 The reaction product was fed into a fractionating column 5, and was separated into gas, liquid, and organosilicon high molecular weight compound therein The gas containing large amounts of propane and hydrogen was exhausted from the reaction system through a valve The liquid was recycled into the reaction column 2 The organosilicon high molecular weight compound was partly taken out from 5 the reaction column 2 and further taken out from the fractionating column 5. Then, by using the apparatus shown in Figure 2, the resulting organosilicon high molecular weight compound was fed into a heating furnace 103 at a rate of 3 l/hr, and rapidly heated up to 5500 C therein, and then fed into a reaction column 101 kept at atmospheric pressure The gas-liquid mixture formed in the reaction 10 column 101 was separated into gas and liquid in a fractionating column 104 The gas was exhausted from the reaction system, and the liquid was recycled and again heated in the heating furnace 103 The Si C primary product block obtained in this reaction was taken out from the reaction column 101 and pulverized into granules and powders Among the resulting granules and powders, 30 parts of Si C granules 15 having a particle size of 50-100 meshes, 30 parts of Si C granules having a particle size of 200-250 meshes and 25 parts of Si C powders having a particle size of less than 325 mesh were mixed together with 15 parts of the above obtained organosilicon high molecular weight compound, which had previously been dissolved in n-hexane After the n-hexane was evaporated, the resulting mixture 20 was press molded into a brick The brick was fired by heating the brick up to 1,800 'C in nitrogen gas to form a silicon carbide brick having a bulk density of 2 2 g/cm 3 and a flexural strength of 6 Kg/mm 2. Example 10 The Si C primary product block obtained in Example 9 was fired by heating the 25 block up to 800 OC under argon, and pulverized into granules and powders Among the resulting granules and powders, 60 parts of Si C granules having a particle size of 150-200 mesh and 25 parts of Si C powders having a particle size of less than 325 meshes were mixed together with 15 parts of an organosilicon high molecular weight compound (polycarbosilane synthesized from polysilane) as a binder while 30 heating, and the resulting mixture was press molded into a crucible The crucibleshaped molding was placed in coke granules, heated from room temperature to 5000 C in 6 hours, then from 5000 C to 9001 C in 10 hours and further up to 1,800 C in 4 hours to form a silicon carbide crucible consisting mainly of Si C The crucible was further heated at 9000 C for 4 hours in air to obtain a silicon carbide crucible 35 Example 11 Air in the whole apparatus shown in Figure 1 was firstly purged with nitrogen gas in order to produce an organosilicon high molecular weight compound from hexamethyldisilane as a starting material The starting material was fed into a reaction column 2 at a rate of 12 I/hr and heated to 740 'C to carry out a 40 polycondensation reaction therein The reaction product was fed into a fractionating column 5 and separated into gas, liquid and the organosilicon high molecular weight compound therein The gas was exhausted from the reaction system, and the liquid was recycled into the reaction column 2 The organosilicon high molecular weight compound was partly taken out from the reaction column 2 45 and further taken out from the fractionating column 5. By the use of the apparatus shown in Figure 3, the above obtained organosilicon high molecular weight compound was used as a starting material, and a Si C primary product block was produced in a reaction column 203 heated to 6800 C The resulting Si C primary product block was placed in coke granules and 50 fired by heating the block up to 1,1000 C, and then pulverized into granules and powders Among the resulting granules and powders, 58 parts of Si C granules having a particle size of 150-200 meshes and 30 parts of Si C powders having a particle size of less than 325 mesh were mixed together with 12 parts of an organosilicon high molecular weight compound, which had previously been 55 dissolved in n-hexane After the n-hexane was evaporated, the resulting mixture was press molded into a tube The tube-shaped molding was heated in coke granules from room temperature to 1,3000 C in 12 hours to form a silicon carbide tube having a bulk density of 2 3 g/CM 3 and a flexural strength 6 0 Kg/mm 2. Example 12 60 p-B is(oxydimethylsilyl)benzene, l 5 1,561,653 CH 3 C/I 3 was polymerized into an organosilicon high molecular weight compound having an average molecular weight of 5,000 in the presence of potassium hydroxide catalyst. A Si C primary product was produced from the above obtained organosilicon high molecular weight compound by means of the apparatus shown in Figure 2 Air 5 in the whole apparatus was firstly purged with nitrogen gas The above described starting material was fed into a heating furnace 103 at a rate of 51/hr, rapidly heated up to 5600 C therein and then fed into a reaction column 101 kept at atmospheric pressure The gas-liquid mixture formed in the reaction column 101 was separated into gas and liquid in a fractionating column 104, and the liquid was recycled into 10 the heating furnace 103 The Si C primary product formed in the reaction column 101 had a bulk density of 1 4 g/cm 3, and the yield of the product based on the starting material was 25 % After the Si C primary product was fired by heating the product up to l,1000 C in nitrogen gas, the product was further fired at 1,0000 C for 4 hours in air to remove free carbon, and then pulverized into granules and 15 powders Among the resulting granules and powders, 20 parts of Si C granules having a particle size of 30-60 mesh, 10 parts of Si C granules having a particle size of 100-325 mesh, 20 parts of Si C granules having a particle size of 200325 mesh and 35 parts of Si C powders having a particle size of less than 325 meshes were mixed together with 15 parts of an organosilicon high molecular weight compound 20 dissolved in toluene After removing the toluene, the resulting mixture was molded into a rod having a diameter of 10 mm and a length of 40 cm The rodshaped molding was placed in coke granules and fired by heating the molding from room temperature to 1,3000 C in 48 hours to form a silicon carbide rod having a bulk density of 2 30 g/cm 3 and a flexural strength of as high as 6 0 Kg/mm 2 25 Example 13 A mixture of N,N'-diphenyldiaminodimethylsilane, \ H \S NH CH 3 NH Ph and p-dihydroxybenzene was heated and reacted to obtain an organosilicon high molecular weight compound having an average molecular weight of 8,000 A Si C 30 primary product was produced from the organosilicon high molecular weight compound by means of the apparatus shown in Figure 2 Air in the whole apparatus was firstly purged with nitrogen gas The above described starting material was fed into a heating furnace 103 at a rate of 4 I/hr rapidly heated up to 550 'C therein and then fed into a reaction column 101 kept at 4 atm The gas-liquid mixture formed in 35 the reaction column 101 was fed into a fractionating column 104 and separated into gas and liquid therein, and the liquid was recycled into the heating furnace 103 The Si C primary product formed in the reaction column 101 had a bulk density of 1 5 ggcm 3, and the yield of the product based on the starting material was about 35 %. After the Si C primary product was fired by heating the product up to 1, 300 C in 40 nitrogen gas, the product was pulverized into granules and powders Among the resulting granules and powders, 80 parts of Si C powders having a particle size of less than 325 meshes was mixed together with 20 parts of the above described organosilicon high molecular weight compound while heating, and the resulting mixture was press molded into a boat The boat-shaped molding was placed in coke 45 granules and fired by heating the molding up to 2,200 C in 12 hours to form a silicon carbide boat having a bulk density of 2 2 g/CM 3 and a flexural strength of 8 Kg/mm 2. Example 14 Dodecamethylcyclohexasilane was heat treated in an autoclave at 4000 C for 50 48 hours to obtain an organosilicon high molecular weight compound The organosilicon high molecular weight compound was treated with a solvent, andonly polycarbosilane having an average molecular weight of 1,500 was gathered. The polycarbosilane was melted and extruded into air through a nozzle, and the I 1,561,653 extruded fibers was drawn to obtain fibers having a diameter of 10-20 microns by means of a melt spinning process The fibers were heated at 200 C for 3 hours in air to be made infusible, and then the infusible fibers were fired by heating the fibers up to 1 300 C under vacuum to obtain silicon carbide fiber The silicon carbide fibers were cut into a length of 2-3 mm, and 100 g of the short cut fibers and 15 g 5 of the described polycarbosilane were mixed by means of a V-type mixer The resulting mixture was charged into a metal mold heated to 300 C, compressed under a pressure of 500 Kg/cm 2, and kept for 30 minutes After the polycarbosilane was completely melted and filled in the space between the short cut fibers, the metal mold was left to stand to be cooled to room temperature, and then the 10 molding was taken out from the mold to obtain a dense molding The resulting molding was heated at 200 C for 24 hours in air and then heated up to 1 200 C in 8 hours in nitrogen gas to obtain a sintered body having a bulk density of 2 3 g/cm 3, a porosity of 38,, and a flexural strength of 9 Kg/cm 2. Example 15 15 In an autoclave of 1 I capacity, 250 g of polydimethylsilane, which is obtained by reacting dimethyldichlorosilane and metallic sodium, was reacted at 470 C for 14 hours After completion of the reaction, the reaction product was taken out from the autoclave in the form of an n-hexane solution After the n-hexane solution was filtered, the filtrate was concentrated by heating the filtrate up to 280 C under 20 a reduced pressure by a vacuum pump to obtain polycarbosilane The resulting polycarbosilane was heated up to 320 C and spun into polycarbosilane fibers having an average diameter of 13 1 um by means of a spinning apparatus provided with a spinneret having a diameter of 300,um The resulting polycarbosilane fibers were heated up to 190 C in 5 hours in air to be made infusible The resulting 25 infusible fibers were heated up to 1,400 C in nitrogen gas at a rate of 100 C/hr and then kept at 1,400 C for 1 hour to obtain silicon carbide fibers having an average diameter of 10 ptm, a strength of 400 Kg/mm 2, a modulus of elasticity of 2 7 x 104 Kg/mm 2 The silicon carbide fibers were cut into a length of 200 mm 93 parts of the silicon carbide fibers were arranged in a mold having a dimension of 10 x 10 x 200 30 mm and 7 parts of the above obtained polycarbosilane dissolved in nhexane was fed into the mold After the n-hexane was evaporated, the resulting mixture was press molded into a molding, and the molding was fired by heating the molding up to 1,500 C at a rate of 100 C/hr in nitrogen gas to form a Si C molding having a bulk density of 2 0 g/cm 3, a flexural strength in the length direction of fiber of as high as 35 21 Kg/mm 2. As described above, the silicon carbide sintered molding obtained by the present invention can be used for example as firebrick, refractory block. refractory granule, crucible, boat, pipe, heating element, electric resistor, abrasive material, heat exchanger and acid proof vessel 40 Claims (1) WHAT I CLAIM IS:- 1 A method for producing silicon carbide (Si C) sintered moldings, which comprises mixing a Si C powder or fibers composed of Si C with from 0 3 to 30 %,, by weight of an organosilicon compound as a said organosilicon compound being selected from 45 (I) compounds having only Si-C bond, ( 2) compounds having Si-H bond in addition to Si-C bond, ( 3) compounds having Si-halide bond, ( 4) compounds having Si-Si bond, and ( 5) organosilicon high molecular weight compounds in which silicon and 50 carbon are main skeleton components and which have been produced by polycondensation reaction of at least one of the organosilicon compounds of the above defined compounds ( 1)-( 4) or by polyconde'sation of one or more of the following compounds; compounds having Si-N bond, 55 Si-OR organoalkoxy (or aroxy) silanes, compounds having Si-OH bond, compounds having Si-O-Si bond, esters of organosilicon compounds, and peroxides of organosilicon compounds, molding the mixture into a desired 60 shape and heating the molded shape at a temperature of not higher than 2, 200 C under a non-oxidising atmosphere to sinter the Si C and to decompose the organosilicon compound to produce Si C. 1.561 653 2 A method as claimed in claim 1, wherein the formed Si C sintered molding is heated at a temperature of 600-1,7000 C under an oxidizing atmosphere to remove free carbon contained in the Si C sintered molding. 3 A method as claimed in claim I or 2, wherein the mixture of Si C powders or fiber and the binder is press molded by a hot press process, during which sintering 5 is effected. 4 A method as claimed in claim I or 2 or 3, wherein the sintering of the Si C moulded shape is effected in a non-oxidizing atmosphere of inert gas, carbon monoxide gas or hydrogen gas under pressure. 5 A method according to any preceding claim, in which the Si C powder is 10 produced by preliminarily heating an organosilicon high molecular weight compound obtained by sub jecting an organosilicon compound defined in claim I to polvcondensation reaction in the presence of a polymerization catalyst or under irradiation or heating, at a temperature of 200-1,5000 C in a nonoxidizing atmosphere to form a Si C primary product and pulverizing the primary product to 15 form the Si C powder. 6 The method as claimed in claim 5, wherein after the preliminarily heating to produce the primary Si C product, and prior to pulverising the primary product is heated at a temperature of 700-2,2000 C under reduced pressure or in an atmosphere of inert gas, CO gas or hydrogen gas to form a fired product and then 20 the pulverizing step is effected. 7 A method according to any of claims I to 4, in which the Si C fibres are obtained by spinning a organosilicon high molecular weight compound produced by polycondensation of an organosilicon compound as defined in claim I, in which carbon and silicon are the main skeleton components, in a melt spinning process, a 25 dry spinning process or a wet spinning process into filaments having a diameter of 5-100 p M, heating the formed filaments at a temperature lower than 3000 C in air to form non-fused filaments, preliminarily heating the non-fused filaments at a temperature of 350-8000 C under vacuum to volatilize the low molecular weight contaminants and then pyrolysing the thus treated filaments at a temperature of 30 800-2,000 C under a vacuum or an atmosphere of inert gas, CO gas or hydrogen gas. 8 A method for producing Si C sintered moldings, substantially as hereinbefore described with reference to any one of the Examples. 9 A silicon carbide sintered molding whenever produced by the method 35 according to any one of the preceding claims. FITZPATRICKS, Chartered Patent Agents, 14-18 Cadogan Street, Glasgow, G 2 6 QW, and Warwick House, Warwick Court, London, WCIR 5 DJ. Printed for Her Majesty's Stationery Office, by the Courier Press, Leamington Spa 1980 Published by The Patent Office 25 Southampton Buildings London WC 2 A IAY from which copies may be obtained. 1,561,653 GB26012/76A 1975-06-25 1976-06-23 Silicon carbide sintered mouldings and a method for producing the same Expired GB1561653A (en) Applications Claiming Priority (2) Application Number Priority Date Filing Date Title JP50077567A JPS523611A (en) 1975-06-25 1975-06-25 Manufacture of silicon carbide sintered mold articles JP50115965A JPS5848503B2 (en) 1975-09-27 1975-09-27 silicon carbide material Publications (1) Publication Number Publication Date GB1561653A true GB1561653A (en) 1980-02-27 Family ID=26418645 Family Applications (1) Application Number Title Priority Date Filing Date GB26012/76A Expired GB1561653A (en) 1975-06-25 1976-06-23 Silicon carbide sintered mouldings and a method for producing the same Country Status (7) Country Link US (1) US4117057A (en) CA (1) CA1083789A (en) DE (1) DE2628342C3 (en) FR (1) FR2317039A1 (en) GB (1) GB1561653A (en) IT (1) IT1066600B (en) SE (3) SE434735B (en) Cited By (1) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title US4737327A (en) * 1983-02-07 1988-04-12 Kurosaki Refractories Co., Ltd. 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Process for producing silicon carbide sintered product Also Published As Publication number Publication date SE452456B (en) 1987-11-30 US4117057A (en) 1978-09-26 DE2628342B2 (en) 1981-02-05 DE2628342A1 (en) 1977-01-13 CA1083789A (en) 1980-08-19 SE7607297L (en) 1976-12-26 SE434735B (en) 1984-08-13 FR2317039A1 (en) 1977-02-04 IT1066600B (en) 1985-03-12 FR2317039B1 (en) 1981-03-06 SE8201112L (en) 1982-02-23 DE2628342C3 (en) 1981-10-29 SE8201111L (en) 1982-02-23 Similar Documents Publication Publication Date Title GB1561653A (en) 1980-02-27 Silicon carbide sintered mouldings and a method for producing the same CA1102483A (en) 1981-06-02 Organosilicon high molecular weight compounds US4164528A (en) 1979-08-14 Method for producing metal nitride sintered moldings US3892583A (en) 1975-07-01 Production of shaped articles of silicon carbide and silicon nitride US4110386A (en) 1978-08-29 Silicon carbide sintered moldings and a method for producing said moldings US5358910A (en) 1994-10-25 Porous silicon carbide ceramics using filled polysiloxanes GB1579981A (en) 1980-11-26 Method for producing silicon carbide sintered mouldings consisting mainly of sic GB1590011A (en) 1981-05-28 Method of producing dense sintered silicon carbide body from polycarbosilane US4336215A (en) 1982-06-22 Sintered ceramic body and process for production thereof US4962069A (en) 1990-10-09 Highly densified bodies from preceramic polysilazanes filled with silicon carbide powders AU691626B2 (en) 1998-05-21 Preparation of high density zirconium diboride ceramics with preceramic polymer binders US4556526A (en) 1985-12-03 Process for production of sintered ceramic body US20020165332A1 (en) 2002-11-07 Preceramic polymers to hafnium carbide and hafnium nitride ceramic fibers and matrices CA1287432C (en) 1991-08-06 Preceramic polymers derived from cyclic silazanes and halogenated disilanes and a method for their preparation EP0698589A1 (en) 1996-02-28 Preparation of high density titanium carbide ceramics with preceramic polymer binders US5508238A (en) 1996-04-16 Monolithic ceramic bodies using modified hydrogen silsesquioxane resin AU690699B2 (en) 1998-04-30 Preparation of high density titanium diboride ceramics with preceramic polymer binders EP0695729B1 (en) 1999-04-07 Preparation of high density zirconium carbide ceramics with preceramic polymer binders US5863848A (en) 1999-01-26 Preparation of substantially crystalline silicon carbide fibers from borosilazanes JP3142886B2 (en) 2001-03-07 Method for producing SiC-based ceramic precursor KR950006726B1 (en) 1995-06-21 Method for producing polycarbosilane Baney et al. 1984 The conversion of methylchloropolysilanes and polydisilylazanes to silicon carbide and silicon carbide/silicon nitride ceramics, respectively CA2086266A1 (en) 1997-03-12 Preparation of substantially crystalline silicon carbide fibers from borosilazanes Yajima et al. 1983 Process for the production of metal nitride sintered bodies and resultant silicon nitride and aluminum nitride sintered bodies CA2031064A1 (en) 1991-06-29 High density silicon carbide sintered bodies from borosiloxanes Legal Events Date Code Title Description 1980-05-29 PS Patent sealed [section 19, patents act 1949] 1996-02-21 PCNP Patent ceased through non-payment of renewal fee Effective date: 19950623
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