JPS63145727A - Production of whisker formed body - Google Patents

Abstract

PURPOSE:To obtain a formed body having superior shape retentivity and high wettability with a molten matrix, by dispersion whiskers in a soln. of an org. silicone polymer in an org. solvent, filtering the resulting dispersion liq. to form a cake and heating the cake in a nonoxidizing gas to make the org. polymer inorg. CONSTITUTION:Inorg. short fiber type whiskers of SiC, SiN or the like are added to a soln. of an org. silicone polymer such as polycarbosilane in an org. solvent and the soln. is stirred to uniformly disperse the whiskers. The resulting dispersion liq. is filtered to form a cake and this cake is dried, optionally press- formed and baked by heating to about 600-1,500 deg.C in a nonoxidizing atmosphere to make the org. silicone polymer inorg. By this treatment, a whisker formed body having a ceramic-like substance produced on the surfaces of the whiskers and at the joined parts of the whiskers is obtd. When a molten matrix is impregnated into the form body under pressure, the formed body is not deformed and a homogeneous composite body can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides a novel whisker molded body that serves as a skeleton for producing fiber-reinforced composite materials, and which has particularly excellent shape retention! The present invention relates to a method for manufacturing a whisker molded body having good strainability for an L-matrix.

(Conventional technology) In recent years, whiskers such as silicon carbide and silicon nitride have been used as skeletons for plastics, metals, and other materials due to their high strength and heat resistance.
M-fiber-reinforced composite materials using alloys, ceramics, etc. as a matrix are attracting attention.

The manufacturing method is to mix (+) whiskers with plastic matrix and
A method of mixing metals, alloys, ceramics, etc. into powder and hot pressing (for example, U.S. Patent: 1, 8:1:1,
697 specification), (2) whisker formation 71. A lj body is created, and a matrix of plastic, metal, alloy, etc. is melted into a liquid state and then press-fitted, towed, etc.
A method of unifying is known, but the former (+) has good uniform dispersibility and easy control of the whisker content.

The production of large products has advantages such as i+ (noh), and the latter (
In 2), the compounding process is short and in-tube.
It has advantages such as low construction cost.

The present invention is included in the latter method (2), in which the composite material is a skeleton of a uniform whisker molded body. Since it is known that uniformity and uniform dispersibility have a large influence, we have studied and improved how to produce whisker molded bodies. That is, it is intended to maintain the advantages of the latter (2) while facilitating uniform dispersion of the former (+) and control of whisker content.

Conventionally known methods for manufacturing whisker molded bodies include (a) pressure molding of whiskers in a dry state or in a wet state with water and Tfi solvent; for example, whiskers are dispersed in a medium and passed through a filtration process; Method of forming a whisker cake by mechanical pressure (Japanese Patent Application Laid-Open No. 59-1211
98, JP-A-6O-55000), a method of pressure-injecting gas during filtration to obtain a whisker cake and molding it under pressure (JP-A-6O-161400), a method of applying vibration to a whisker dispersion to sediment the whiskers. , a method in which the supernatant liquid is removed, dried, and then pressure molded (JP-A-59-227761) (b) A method in which whiskers are dispersed in water or an organic solvent and centrifugally dehydrated (JP-A-6O-65200) (8) ) A method in which an inorganic or organic binder is added and pressure molded, for example, a method using boric acid, an alkali metal borate, or an alkali metal aluminate (Japanese Patent Application Laid-Open No. 6O-204
660), a method using a mixture of sodium alginate and acrylic acid (JP-A-6O-210600), a method using methylcellulose (JP-A-6L-19744)
and so on.

(Problems to be solved by the invention) In the conventional technology, the molding method uses pressure (a)
Alternatively, method (0) is a general method for handling powder, and such methods may cause the edges of the molded product to chip or leave small and large cracks in the molded product. This poses a problem in terms of shape retention, or has the disadvantage of being inferior in homogeneity. Furthermore, as a result, defects may occur when a composite is manufactured. In addition, the presence of aggregates caused by the entanglement of whiskers in the molded body prevents the matrix from entering the molded body, which also causes defects when the composite is manufactured, reducing the strength of the composite. will be invited. Furthermore, although method (0) has the advantage of being able to obtain a molded body with high density, it can only produce a circular or cylindrical molded body, and is unsuitable for producing molded bodies of other complex shapes. .

In this way, the use of a binder is indispensable because it is extremely difficult to manufacture a composite using a method that does not use a binder.However, in the conventionally known method (8), the bonding strength between the whiskers is low. In addition to the disadvantage of poor shape retention, high temperatures are required to inject the molten matrix, resulting in significant deformation, which may impair homogeneous compositing into the composite, or alter the quality of the binder, causing the matrix and whiskers to deteriorate. The disadvantage is that the adhesion between the interfaces is poor. In order to overcome these disadvantages, a method has been used to inorganize the binder by heating a molded body to which the binder has been added, but conventionally known binders are vitreous or carbonaceous. The drawback of low bonding strength on the matrix cannot be avoided. Particularly when the matrix is metal, a reaction occurs at the interface, resulting in an extreme decrease in the strength of the composite.

In order to solve these various disadvantages, the present inventors investigated the possibility of using a material that can be mineralized into silicon carbide or silicon nitride by heating and firing, and as a result, the present invention was developed. It is a completed invention.

(Structure of the Invention) The present invention relates to a novel whisker molding method that can solve the above-mentioned problems. That is, the present inventors dispersed whiskers in an organic solvent in which an organosilicon polymer was dissolved, filtered the wet whiskers, either left them as they were, or pressurized them to a predetermined density and shape, and then placed them in a non-oxidizing gas atmosphere. 1) By inorganicizing the organosilicon polymer, it does not deform when press-fitting into the matrix, has excellent shape retention, and has good bulging properties against the matrix, making it easier for the matrix to penetrate. We discovered that it is possible to produce molded bodies that do not adversely affect composite performance.
The present invention has been completed.

The whiskers used as the starting material of the present invention are preferably inorganic short fibers of silicon carbide, silicon nitride, etc., and the diameter thereof is easily 0.05 to 3.0 μm and the length is 3 to 200 μm.

The whiskers described above are placed in a solvent in which an organosilicon polymer is dissolved and stirred to disperse them uniformly.The organosilicon polymer used here is polycarbosilane or silicon whose main skeleton components are silicon and carbon. It is an if machine silazane city combination with ``and'' and element as the skeleton components, and the molecule 17jaoo ~ 5
,000 is preferred. Among the organosilicon polymers effective in the present invention, polycarbosilanes include:

■ Cyclic polysilane represented by the general formula (R1R2Si) n (where n is at least 4 or more, and rtl and R2 each represent any one of hydrogen, an alkyl group, a phenyl group, and a silyl group) or a general formula % formula %) linear polysilane (where n is at least 30
An organosilicon compound having a polysilane skeleton selected from the group consisting of hydrogen, an alkyl group, a phenyl group, and a silyl group, in which R' and R2 each represent one of hydrogen, an alkyl group, a phenyl group, and a silyl group, is heated in a non-oxidizing atmosphere. Polycarbosilane whose main skeleton components are silicon and carbon obtained by thermal decomposition 1 reaction at a temperature of 300 to 600°C (Japanese Patent Publication No. 57-26527) (1) Any one selected from boric acid, boric anhydride, boric acid metal salts, Nisdel borate and ([:,, I+
,,) A semi-inorganic compound obtained by mixing and heating 2Siel□ at a molar ratio of 2:3, (2) A compound represented by the general formula % (-RhoN-)3, (However, l
(3, P are monovalent hydrocarbon groups, (-(:+12
-)llsi(R'')3 (n is an integer, port 5 is a monovalent hydrocarbon group) or -N(R7)2 group (nl+ indicates hydrogen atom Y'' or monovalent hydrocarbon 1) (: 1) -Ft formula (on7), (however, Ti is
7. r, 1di represents a monovalent hydrocarbon group) and (Cr, 1li) zsi
At least one compound selected from the following three groups: polymetallosiloxane obtained by mixing and heating 2 and 2 at a molar ratio of 1:2.
A polycarbosilane compound obtained by adding 111 parts of ~15 1μ compound under the same conditions as described above (Japanese Patent Publications No. 57-266011, No. 120725 No. 120725, No. 61-239:12) ■For every 100 parts of at least one compound selected from the polycarbosilanes of ■ or ■ above, (1) a metal represented by the general formula (OR7) 4 (where M and R' are the same as above); Compound (2) General Formula (OR7). (However, M, It' are the same as above) and at least one metal compound selected from (C
,,I+5)2si(Kano)2 at a molar ratio of 1:2 and heating at least one compound selected from two groups of polymetallosiloxanes 0.1
~! A polycarbosilane compound having silicon and carbon as main skeleton components obtained by polymerizing a mixture obtained by adding 5 parts to -74126, JP-A-56-9292:
l, JP-A-56-5828, JP-A-56-1: ] 162
8), and as organic silazane polymers, ■Methyldichlorosilane, methyltrichlorosilane,
Dimethyldichlorosilane or the general formula % (I11, 11' is chlorine, !;! elementary, methyl J, t,
Ethyl", phenyl group, 1 (9 is hydrogen, chlorine, bromine, methyl group, ethyl group, phenyl J^, 1 (10 and 1 (eyes hydrogen, methyl J^, X represent chlorine and bromine, respectively) A mixture of a silicon compound represented by the formula and ammonia is reacted to produce a 1!-stranded ammonolysis product, which is further mixed with a salt catalyst capable of deprotonation to produce a silazane!■ coalescence, etc. is exemplified.

Is there any significant difference between these polycarbosilanes or organic silazane combinations? 1b maintains a high bonding strength at the interface with the matrix because of the oxygen contained in the polymer! The lower the number of 11, the better. Also, the polymer fraction i
- When the temperature is higher than 5,000, it becomes difficult to dissolve in solvents, and F[
5,000 or more is desirable because it becomes difficult to control the polymerization reaction, and if it is more than 800, poly 7- volatilizes and disappears during the process of heating and firing the molded product, and the effectiveness of the present invention is lost. So I don't like it. Particularly preferably the molecule -r+L
l, ranging from Ooo to 4,500.

The next solvent to be used may be any solvent as long as it can dissolve the polycarbosilanes or the organic silazane polymer, but a solvent with a boiling point in the range of 50 to 200 DEG C. is preferable for handling reasons.

The concentration of the polymer mentioned above is not limited in its range as long as it has a sufficient shape retention property of the whisker molded product, but the range is not limited to 0.
, If the ITI is less than %, the shape retention is insufficient,
If it exceeds 20%, the viscosity of the solution becomes high and it becomes difficult to handle 1), and preferably 0.1 to 20%.

Whiskers can be dispersed by simply adding them into the polymer solution, but if the whiskers are entangled and form large lumps, it is necessary to mechanically disintegrate them as appropriate to make it easier for them to be impregnated with the solution. . After adding the whiskers, it is preferable to stir them using a suitable stirring device in order to uniformly impregnate the whiskers in a short time.

The whisker dispersion solution then flows into the filtration device. Filtration is performed in a mold with a pore structure made of plastic, metal, alloy, ceramic, etc. with a filtration function, but if necessary, a material such as filter paper, filter 11, metal filter, ceramic filter, etc. may be added to the mold. may be installed. Although filtration may be performed under pressure, it is recommended to take into account the Vr value (fiber volume per unit volume: ■1) during compositing and perform it under pressure to achieve the desired density. desirable. After filtration, the whiskers are dried in a 1-1 step to remove the solvent, but since they can be dried in the subsequent firing step, this step can be omitted. Drying can be carried out by removing the whiskers from the mold, but it is preferable to dry them in the mold to prevent deformation. Further, it is sufficient to dry at room temperature and atmospheric pressure, but in cases 1 to 1 which require drying in a short period of time, heating and reduced pressure may be performed.

Next, baking is performed in order to inorganize the polymer remaining in the whiskers after drying, give shape-retaining strength to the whisker molded body, and create voids. The firing temperature is 600℃ or higher in an oxidizing gas atmosphere! ! Mechanize it and fix Whisker comrade. At temperatures below 600° C., the polymer is not sufficiently mineralized and the bonding strength between the whiskers is not high, resulting in shape retention of less than 1 minute. Moreover, if it is higher than 1500°C, sintering of silicon carbide or silicon nitride will begin, and the strength of the molded body will tend to gradually decrease, which is not preferable and is not economically advantageous. During firing, as long as the mold used to mold the whiskers is made of a material that can withstand the firing temperature, the mold may be used as is from drying to firing.

Next, reference examples showing methods for producing polycarbosilanes and organic silazane composites used in the present invention and examples of the present invention will be described.

Reference Example 1゜ 2.3 kg (100 mol) of metallic sodium and xylene +1 were heated to 110°C, and 6.5 g of dimethyldichlorosilane was gradually added dropwise over 3 hours to this while stirring vigorously, and xylene was added. After the reaction, the precipitate was filtered. After washing 6 times with water, a white powder of dimethylpolysilane [(c++:+)2sD, 2.5%
g (yield 86%) was obtained.

Reference Example 2゜ 100g of linear polysilane synthesized in Reference Example 1 was added to three
1 Place in a flask and attach a stirrer, a thermometer, and a ring tube. After replacing the inside of the system with nitrogen and hydrogen, the temperature was raised to 420°C at a rate of 10°C/h and maintained at 420°C for 5 hours to complete the reaction. 38 g of brown polycarbosilane was obtained.

Reference Example 3 200 g of dimethylpolysilane obtained in Reference Example 1 and 20 g of B-trimethyl-N-triphenylborazine were mixed with a thermometer,
When heated in a four-piece flask equipped with a volatile gas distillation exhaust pipe, a stirrer, and an inert gas inlet pipe, thermal decomposition 1r reaction started at about 250°C, and as volatile components were generated, a transparent gas was formed. It became a liquid, but when this temperature was gradually raised to )-H and the reaction was carried out at 380°C for 2 hours and then cooled, a yellow-green transparent resinous substance with a melting point of 135-142°C +4:1 was obtained. g (Yield -165%) is 1"-1'J h Ta is Koh Ha Si41.3%,
8 1.2:1%, N 1.50%TeSi:B=
It was an organometallic copolymer containing approximately -7 theoretical amounts of B and N at a molar ratio of 12.9:l.

Reference example 4゜Ammonolysis TI! [Methyldichlorosilane: methyltrichlorosilane: dimethyldichlorosilane = 75: 15: 10 (mol %)] Hexane 8 was placed in a dry four-eye IIl flask equipped with a stirrer, a thermometer, an N112 inlet tube, and a deep cooling condenser.
After charging 50mj2, methyldichlorosilane 4:]
, Ig, 2 g of methyltrichlorosilane l+, and 6.5 g of dimethyldichlorosilane were added, and the mixture was cooled to -20°C.

Excess gaseous ammonia was added to this solution at a rate of 12ffi/llr for 4 hours (total addition of NI+3 2.1 moles). The reaction mixture was warmed to room temperature while unreacted N1
The cooler was changed to an air-cooled condenser so that 13 could escape. Next, by-product ammonium chloride was removed from the reaction mixture by filtration in a dry box. 200 cakes in history
Wash with 11 IIL of hexane, and extract the filtrate under reduced pressure (60
The hexane was stripped at 0.degree. C./1 mmtlg). The residue (ammonolysis product) was a clear fluid liquid, and 26 g was obtained.

Asuke training: 100 mfi five 11 flasks, stirrer, thermometer,
A droplet tube was placed in a dry box containing 0.2 g (5 mmol) of potassium hydride and Nal! 125 mM of dehydrated IF was injected into the flask. This flask was taken out of the try box and connected to a nitrogen pipe. At room temperature, while stirring the mixture and dispersing 11, 10 g of the product obtained by dissolving ammonolycyst in 75 mQ of TIIF was slowly added over 15 minutes from a dropping funnel. During this addition, evolution of large ITh gas was observed, and the gas evolution stopped after 1 hour. When 3 g of methyl iodide was added, a white precipitate appeared. After stirring for an additional 30 minutes, most of the TIIF solvent was removed under reduced pressure and 80 ml of hexane was added to the remaining white slurry. This mixture was filtered and the filtrate was collected under reduced pressure F (1n
onllg) When hexane is removed at 70°C, 9.
1g of viscous solid (silazane city combination) is j! I was beaten.

This stuff is hard.Viscosity (benzene, 20℃) 0.0
7. It had a melting point of 90°C and was soluble in hexane, benzene, TIIF and other organic solvents. Also, from 11 dogs, 3400cl' was N11.2980cm-'C
-H, 2150cm-1 to 5i-11, 1260cm-
' to 5iCI1. Absorption of each of these was observed. In addition, the molecule '+t fl! by the Hensen freezing point depression F method is calculated. '1 constant was 1020.

Reference Example 5 Ammonolysis [Methyldichlorosilane: Methyltrichlorosilane: 1
．． 2-bis(methyldichlorosilyl)ethane = 75:
10: 15 (mol%)] Stirrer, thermometer, Nl+,
Equipped with 3 inlet tubes and deep-cooled condenser, dry iIL
Add hexane 850II1 to a four-eye flask. After charging I2, methyldichlorosilane 4:1. Ig, 7.5 g of methyltrichlorosilane, and 19.2 g of 1,2-bis(methyldichlorosilyl)ethane were added, and the mixture was cooled to -20°C. Excess gaseous ammonia at 45 Q/llr
was added to this f8 solution for 1.5 hours at a rate of (N11. total addition - 13.0 mol). The reaction mixture was warmed to room temperature and
At that time, the cold N1 reactor was replaced with an air-cooled condenser so that unreacted N113 could escape. Next, ammonium chloride, a by-product of the reaction (μ), was removed by filtration in a try box. The cake was washed with 200+1 hexane, and the hexane was stripped from the filtrate under reduced pressure (60° C./1 ml mm 1 liter). .Residue (ammonolysis product)
31 g of a clear fluid liquid was obtained.

Kesukeiko Sumire: 125 ml of 100ml flask equipped with a stirrer, a thermometer, and a dropping funnel, and dehydrated with 0.2 g (5 mmol) of potassium hydride and 1l of Na in a dry box. was injected into the flask. This flask was taken out of the dry box and connected to a nitrogen pipe. At room temperature F, while stirring the mixture to disperse 8+1, 10 g of the product obtained in the ammonolysis step dissolved in 75 mff1 of TIIF was slowly added through a funnel over 15 minutes. During this addition person:I
After 1 hour, the gas evolution stopped. When 3 g of methyl iodide was added, a white precipitate of 1 was formed. After stirring for 30 minutes, most of the Ti1l' The solvent was removed under reduced pressure and 801 nQ of hexane was added to the remaining white slurry. The mixture was filtered and the filtrate was removed under reduced pressure at F.
(l mmmm1 l When hexane is removed at 70°C, 9.1 g of viscous solid (silazane! ■ combined) is
It was done.

This product has an intrinsic viscosity (benzene, 20°C) of 0.06,
It has a melting point of 90°C and is soluble in hexane, benzene, TIIF and other organic solvents. Also, from IR:
N11 at 1400cm-'. C-1 at 2980cm-'
t, 2150 cm-', Si-■, 1260 cm-
Absorption of 5iC1l was observed in '. Furthermore, the molecular weight was determined to be ++jo by benzene freezing point depression method.

Example! .

Too g of the polycarbosilane obtained in Reference Example 2 was dissolved in 900 g of xylene to obtain a 10% by weight solution. 78 g of silicon carbide whiskers were added to this solution and stirred for 30 minutes using a stirring device to uniformly disperse the mixture. Next, this dispersion was filtered into a thick square metal container with an inner dimension of Oma+X 30 mm and a pore at the bottom, and then left as it was to give about 150 g/g/ml from the top of the cake. cm2
It was compressed and molded. Next, the metal container containing the whiskers was placed in the dry lb box 71. It was placed in an Ij electric furnace and dried at 200° C. for 1 hour in static gas. cooling? &2 Take out the whisker molded body from the metal container and heat it at 800°C at atmospheric pressure F in a static atmosphere in a box-shaped electric furnace.
After firing for 1 hour at
] Ox 150 mm, vr value l IS , 0% whisker molded body 1ii was produced. This molded product had no damage at the edges and was extremely easy to handle. The whisker molded body obtained in this way is
The strength was measured using a room I11 three-point bending strength measuring machine, and the whisker molded product had a high strength of 15g/C112.

Example 2 The whisker molded product obtained in Example 1 was placed in a mold, and the mold was maintained at about 500°C. After that, molten aluminum alloy (^C4G) at 800℃ was injected and the temperature reached 1000g/
High-pressure casting was performed using Cl112 to obtain a prismatic composite.

The tensile strength of this composite was measured and was 61Kg/mm.
2, the elastic modulus was +0.5 L/ma+2. Next, the fractured surface of the composite was observed under an electron microscope, and no defective inclusions or void formation was found at all.

Examples 3 to 10° Whiskers were produced in the same manner as in Example 1, except that the molding conditions and the polycarbosilane concentration in the polycarbosilane solution were changed as shown in Table 1. A molded product was prepared and its three-point bending strength was measured, and it showed high values as shown in Table 1. Further, the molded bodies of Examples 3.5 and 6 were composited with He1 alloy (8C4C) and the tensile strength was measured, and high strength composites as shown in Table 1 could be obtained.

Example 11~+2゜Execution except that the polycarbosilane obtained in Reference Example 2 and the organosilazane monopolymer obtained in Reference Example 3.4 were used instead of the polycarbosilane solution shown in Example 1. A whisker molded body was created using a method similar to that shown in Example 1,
When the three-point bending strength of the molded product was measured, it showed high values as shown in Table 2.

Table 2 Comparative Example 1° Whiskers were immersed in the polycarbosilane solution shown in Example 1 at 11°1 and formed Jl, +71. A whisker molded body with Vf (/f 17.5%) was prepared in the same manner as shown in Example 1, and the three-point bending strength was determined to be 4!1, which was 1.5K) <7 cm2. Met.

Comparative example 2゜Comparative example! A composite body was prepared using the whisker molded body obtained in the same manner as shown in Example 2.

After the composite was fractured, the fractured surface was observed using an electron microscope. As a result, the formation of voids was observed, and the whiskers were not uniformly dispersed, making it impossible to obtain a good composite.

[Effects of the invention] The whisker molded product obtained in this way has excellent shape retention compared to a molded product obtained only by pressurized molding without using a binder, and it is also easy to use general-purpose resin. Because the bonding strength between the whiskers is higher than that of the molded product used as a binder, the shape retention is extremely good, and there is no deformation when the molten matrix is press-fitted, ensuring homogeneous compounding into the composite. The 4r advantage is obtained. In addition, the inorganic substance generated on the surface of the whiskers is silicon carbide or silicon nitride, which has good compatibility with the matrix, and allows the matrix to penetrate easily. It penetrates and forms silicon carbide or silicon nitride substances in that area, filling it up.
), there will be no defects when the composite is manufactured, and
A composite material with high strength can be obtained.

Claims (1)

[Claims] 1. Whiskers are dispersed in an organic solvent solution containing an organosilicon polymer, and then this dispersion is filtered to obtain a cake, which is heated as it is or after pressure molding in a non-oxidizing atmosphere. - A method for manufacturing a whisker molded body, which comprises firing to inorganicize an organic silicon polymer to generate a ceramic substance on the whisker surface and whisker joints. 2. The manufacturing method according to claim 1, wherein the whisker is silicon carbide or silicon nitride. 3. The organosilicon polymer has the general formula (R^1R^2Si)
Cyclic polysilane represented by __n (where n is at least 4, R^1 and R^2 are each a hydrogen atom, an alkyl group, a phenyl group, or a silyl group ▲ Numerical formula, chemical formula, table, etc. are available ▼ A linear polysilane represented by (where n is at least 30
In the above, R^1 and R^2 each represent one of a hydrogen atom, an alkyl group, a phenyl group, and a silyl group)
A polycarbosilane whose main skeleton components are silicon and carbon obtained by subjecting an organosilicon compound having a polysilane skeleton selected from among these to a thermal decomposition polymerization reaction at a temperature of 300 to 600°C in an inert gas atmosphere. The molecular weight is 800-5
3. A method according to claim 1 or claim 2, characterized in that it is in the range of ,000. 4. Organosilicon polymer has the general formula (R^1R^2Si)
Cyclic polysilane represented by __n (however, n, R^1, R
^2 are the same as above) or ▲There are mathematical formulas, chemical formulas, tables, etc.▼
are the same as above), per 100 parts by weight of an organosilicon compound having a polysilane skeleton selected from among (1) boric acid, boric anhydride, boric acid metal salts, and boric esters. One kind (C_6H_5
) A semi-inorganic compound obtained by mixing and heating _2SiCl_2 at a molar ratio of 2:3, (2) A compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R^3R^4 is Monovalent hydrocarbon group, (-
CH_2-)_nSi(R^5)_3 (n is an integer, R^
5 is a monovalent hydrocarbon group) or -N(R^6)_2 group [
R^6 represents a hydrogen atom or a monovalent hydrocarbon group] (3) General formula (OR^7), (where M is Ti, Zr,
R^7 represents a monovalent hydrocarbon group) and (C_6H_5)_2Si(O
H)_2 and polymetallosiloxane obtained by mixing and heating at a molar ratio of 1:2, at least one compound selected from the following three groups: 0.1
A polycarbosilane compound having silicon and carbon as main skeleton components obtained by thermally decomposing and polymerizing a mixture containing 15 parts by weight at a temperature of 300 to 600°C in an inert gas atmosphere, Claim 1 or 2, characterized in that the molecular weight is in the range of 800 to 5,000.
The method described in section. 5. The organosilicon polymer has the general formula [1] (R^1R^2
Si) cyclic polysilane represented by _n (where n is at least 4 and R^1 and R^2 each represent any one of a hydrogen atom, an alkyl group, a phenyl group, and a silyl group) or a general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Chain polysilane shown by (however, n is at least 30
In the above, R^1 and R^2 each represent one of a hydrogen atom, an alkyl group, a phenyl group, and a silyl group)
A polycarbosilane compound whose main skeleton components are silicon and carbon obtained by subjecting an organosilicon compound having a polysilane skeleton selected from among these to a thermal decomposition polymerization reaction at a temperature of 300 to 600°C in an inert gas atmosphere. , and [2] 100 parts by weight of the organosilicon compound having a polysilane skeleton, (1) any one selected from boric acid, boric anhydride, boric acid metal salts, and boric acid esters and (C_6H_5
)_2 A semi-inorganic compound obtained by mixing and heating SiCl_2 at a molar ratio of 2:3, (2) A compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R^3, R^ 4 is a monovalent hydrocarbon group, (
-CH_2-)_nSi(R^5)_3 (n is an integer, R
^5 is a monovalent hydrocarbon group) or -N(R^6)_2 group [R^6 is a hydrogen atom or a monovalent hydrocarbon group]) (3) General formula (OR^7)_4( However, M is Ti, Zr
, R^7 represents a monovalent hydrocarbon group) and (C_6H_5)_2Si(
Polymetallosiloxane obtained by mixing and heating OH)_2 at a molar ratio of 1:2, at least one compound selected from the following three groups: 0.1
Selected from polycarbosilane compounds whose main skeleton components are silicon and carbon obtained by subjecting a mixture formed by adding ~15 parts by weight to a thermal decomposition polymerization reaction at a temperature of 300 to 600°C in an inert gas atmosphere. (1) General formula (OR^7)_4 (however, M
, R^7 is the same as above); (2) at least one metal compound selected from the general formula (OR^7)_4 (where M and R^7 are the same as above); and (C_6H_5 )_2Si(OH)_2 at a molar ratio of 1:2, polymetallosiloxane obtained by mixing and heating, at least one compound selected from the following two groups: 0.1
A polycarbosilane compound having silicon and carbon as main skeleton components obtained by polymerizing a mixture obtained by adding ~15 parts by weight at a temperature of 100 to 300°C in an inert gas atmosphere, and having a molecular weight of 5. A method according to any one of claims 1 to 4, characterized in that . 6. An organosilicon polymer is obtained by polymerizing an ammonolysis product obtained by reacting a mixture of methyldichlorosilane, methyltrichlorosilane, and dimethyldichlorosilane with ammonia using a basic catalyst capable of further deprotonation. 3. The method according to claim 1 or 2, wherein the method is an organic silazane polymer. 7. Organosilicon polymers include methyldichlorosilane, methyltrichlorosilane, and the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R^8 is chlorine, bromine, methyl group, ethyl group, phenyl group, R ^9 is hydrogen, chlorine, bromine, methyl group, ethyl group, phenyl group, R^1^0 and R^1^1 are hydrogen, methyl group, X is chlorine and bromine, respectively). Claim 1, characterized in that it is an organic silazane polymer obtained by polymerizing an ammonolysis product obtained by reacting a mixture of and ammonia with a basic catalyst capable of further deprotonation. or the method described in Section 2. 8. Any one of claims 1 to 5, characterized in that the concentration of the organosilicon polymer in the organic solvent solution containing the organosilicon polymer is in the range of 0.1 to 30% by weight. Method described. 9. The method according to any one of claims 1 to 6, characterized in that the heating and firing temperature during mineralization of the organosilicon polymer is in the range of 600 to 1500°C. . 10. Any one of claims 1 to 7, wherein the non-oxidizing atmosphere when mineralizing the organosilicon polymer is argon, nitrogen, helium, ammonia, or carbon monoxide. Method described in Crab. 11. Any one of claims 1 to 8, characterized in that the ceramic substance generated on the whisker surface and the whisker joint is a silicon carbide substance, a silicon nitride substance, or a mixture thereof. The method described in.