Polymetallosilazanes useful in the manufacture of silicon nitride based ceramic fibers

Abstract: Polymetallosilazanes, useful as precursors in the production of metal-containing silicon nitride ceramic fibers are obtained by reaction (i) a polysilazane having a number molecular weight of 100-50,000 and having a main skeletal structure containing the following recurring unit: wherein R¹, R² and R³ are the same or different and each is hydrogen, a hydrocarbyl group, a group other than a hydrocarbyl group and having a carbon atom bonded to the silicon atom of the above formula, an alkylsilyl group, an alkylamino group or an alkoxy group, with (ii) a metal alkoxide of the formula: M(OR⁴) n wherein M is a metal, each R₄ is the same or different and is hydrogen, an alkyl group having 1-20 carbon atoms or an aryl group, and n is the valence of the metal M with the proviso that at least one of the R₄ groups is an alkyl or aryl group.

Description: This invention relates to novel polymetallosilazanes which are useful in the manufacture of metal-containing silicon nitride ceramic fibers. Ceramic fibers have been attracting much attention for their favorable properties, such as high mechanical strength and resistance to heat and chemicals, and which make the fibers useful as reinforcing materials for various composite articles such as engine parts, fan blades and aircraft structures. Japanese Examined Patent Publication No. 62-5201 discloses a fiber of a substantially amorphous Si-Ti-C-O ceramic obtained by spinning a polytitanocarbosilane, obtained by copolymerizing a polycarbosilane with polytitanosiloxane, into fibers and calcining the spun fibers. These silicon carbide-based ceramic fibers, however, contain a relatively large amount of free carbon which can react with a molten metal such as aluminum and, hence, they are not suited for use as reinforcing fibers to be incorporated into a metal matrix. European Patent Application EP-A-175 882 discloses a method for increasing the ceramic yield of a ceramic material obtained by firing a R₃S i NH- containing silazane polymer together with a boron compound which may be a boron alkoxide. Our co-pending European Patent Application No. EP-A-332357 from which the present application has been divided discloses novel inorganic fibers having a high mechanical strength and an excellent compatibility with other ceramic materials, polymers and metals. These fibers are formed of a ceramic containing Si, N, O and at least one metal M in amounts providing the following atomic ratios: N/Si : 0.3 to 3, O/Si : 0.001 to 15, M/Si : 0.001 to 5. As disclosed in the parent application, these fibers can be made by a process which comprises the steps of: providing a polymetallosilazane, spinning said polymetallosilazane into fibers; and calcining said fibers. The present invention is concerned with new polymetallosilazanes useful as the starting material in the fiber manufacturing process described in the parent application. In accordance with the present invention there is provided a polymetallosilazane having a number molecular weight of 200-500,000, obtained by reacting (i) a polysilazane having a number molecular weight of 100-50,000 and having a main skeletal structure containing the following recurring unit: wherein R¹ is hydrogen, and R² and R³ are the same or different and each is hydrogen, a hydrocarbyl group, an alkylsilyl group, an alkylamino group or an alkoxy group, with (ii) a metal alkoxide of the formula: M(OR⁴) n wherein M is a metal, each R₄ is the same or different and is hydrogen, an alkyl group having 1-20 carbon atoms or an aryl group, and n is the valence of the metal M with the proviso that at least one of the R₄ groups is an alkyl or aryl group. The metal M is preferably at least one element selected from those of the groups IIa, IIIa, IIIb, IVa, IVb, Va and Vb of the Periodic Table. Illustrative of suitable metals are Be, Mg, Ca, Sr, Ba, Sc, Y, lanthanoid elements, actinoid elements, B, Al, Ga, In, Tl, Ti, Zr, Hf, Ge, Sn, Pb, V, Nb, Ta, As, Sb and Bi. Above all, Y, B, Al, Ti and Zr are especially preferred. The hydrocarbyl group may be for example an alkyl, alkenyl, an aryl, a cycloalkyl or aralkyl group. Preferably, R² and R³ represent independently from each other hydrogen or an alkyl group with 1-5 carbon atoms, more preferably hydrogen, methyl or ethyl, and R⁴ represents an alkyl with 1-10 carbon atoms, more preferably 1-4 carbon atoms. The reaction for the formation of the above polymetallosilazane is preferably performed using an inert solvent at a temperature lower than the boiling point of the metal alkoxide. Details of the method for the production of the polymetallosilazane are disclosed in Japanese patent applications No. 61-226,270, No. 61-223,790 and No. 63-68221. The polymetallosilazanes of the present invention may be converted into ceramic fibers by a process comprising the steps of: (a) spinning said polymetallosilazane into fibers, and (b) calcining said fibers. As a result of the calcination, there are obtained fibers of a ceramic of a Si-M-N-O system, Si-M-N-C-O-H system or the like system. The ceramic generally shows an amorphous phase or a fine crystallites-containing amorphous phase. Such crystal phase may vary with the calcination conditions such as temperature and heating rate. For details of the preferred procedures for effecting the spinning and calcining steps, the reader is referred to the specification of the parent application EP-A-332 357 supra . As already indicated, the inorganic fibers which are thereby obtained are formed of a ceramic containing Si, N, O and at least one metal M, preferably in amounts providing the following atomic ratios: N/Si : 0.3 to 3, O/Si : 0.001 to 15, M/Si : 0.001 to 5. The ceramic fibers may further contain C and/or H in amounts providing the following atomic ratios: C/Si : 7 or less H/Si : 15 or less More preferred atomic ratios are as follows: N/Si : 0.6 to 1.4 O/Si : 0.01 to 10 M/Si : 0.01 to 2.5 C/Si : 3.5 or less H/Si : 5 or less Most preferred ranges are as follows: N/Si : 1 to 1.3 O/Si : 0.01 to 4 M/Si : 0.01 to 1 C/Si : 3.5 or less H/Si : 1 or less. The atomic ratios N/Si, O/Si, M/Si, C/Si and H/Si of the ceramic fibers are controlled by the kind of the polymetallosilazane used as starting material and the conditions for the calcination of the polymetallosilazane. The kind of the polymetallosilazane varies with the mixing ratio of the raw materials, i.e. polysilazane and metal alkoxide, and the reaction conditions under which the raw materials are reacted. It is also preferred that the ceramic fibers formed from the present polymetallosilazanes show an X-ray small angle scattering such that the ratio of the intensity of the small angle scattering of the fibers to that of air is 1 to 20, more preferably 1 to 10, most preferably 1 to 5, at scattering angles 0.5° and 1°, for reasons of exhibiting mechanical strength suitable for reinforcing materials of composite articles. The intensity of X-ray small angle scattering is related to the presence of fine pores or voids in the fibers. Namely, the presence of the fine pores causes localization of electron density, accounting for small angle scattering, as described in more detail in the parent Application EP-A-332 357, supra . The ceramic fibers obtainable from the polymetallosilazanes according to the present invention remains amorphous even heated to a high temperature and, thus, have a high mechanical strength, especially a high impact resistance at high temperatures. Even the fibers are heated to such a higher temperature as to form ceramic crystals, the mechanical strength thereof is still far greater than that of known silicon nitride-based ceramic fibers. Further, the ceramic fibers have a high electrical resistance, an extremely low free carbon content and excellent compatibility with matrix materials, especially with metals and, therefore, are particularly useful as reinforcing fibers for fiber-reinforced metal composite materials. The following examples will further illustrate the preparation of polymetallosilazanes according to the present invention, and their use in the manufacture of ceramic fibers. In the examples, the X-ray small angle scattering intensity ratio is measured by the technique described in the parent Application No. 89302178.2, supra . Reference Example 1 Preparation of Perhydropolysilazane: To a four-necked 10 liter flask equipped with a gas feed conduit, a mechanical stirrer and a Dewar condenser, an oxygen-free, dry nitrogen gas was fed to replace the air within the flask therewith. After charging 4900 ml of dry pyridine (deaerated), the flask was cooled in an ice bath. Then 744 g of dichlorosilane were added into the flask to form a white precipitate of adduct (SiH₂Cl₂·2C₅H₅N). Subsequently, with stirring and cooling in the ice bath, 735 g of ammonia which had been passed successively through a sodium hydroxide-containing tube and an active carbon-containing tube was bubbled through the reaction mixture within the flask. The reaction was completed by heating the contents in the flask at 100 °C. After completion of the reaction, the reaction mixture was centrifuged and the supernatant was washed with dry pyridine, followed by filtration in a nitrogen atmosphere to give 5100 ml of a filtrate containing perhydropolysilazane. When the solvent was removed from the filtrate (5 ml) by evaporation in vacuo, 0.249 g of resinous solid was obtained. Gel permeation chromatography of the polysilazane revealed that the polysilazane had a number-average molecular weight of 980. Dried o-xylene was then added to the filtrate and the mixture was distilled in vacuo to obtain 5000 ml of an o-xylene solution containing 5.8 % by weight of the perhydropolysilazane. Example 1 To a four-necked 2 liter flask equipped with a gas feed conduit, a magnetic stirrer, a seal cap and a Dewar condenser, a dry argon gas was fed to replace the air within the flask therewith. After charging 14.7 g (72 mmol) of aluminum triisopropoxide, the 5.8 weight % solution of perhydropolysilazane in a dry o-xylene, obtained in Reference Example 1, was fed to the flask using a syringe with stirring to obtain a homogeneous solution. The solution was then heated at 80 °C for 2 hours with stirring in the atmosphere of argon. As a result, the colorless solution became light yellow. Gel permeation chromatography using a polystyrene as a standard revealed the formation of polyaluminosilazane having a number-average molecular weight of 1750 and a weight-average molecular weight of 14500. The thus obtained solution of the polyaluminosilazane was mixed with 5.0 % by weight (based on the polyaluminosilazane) of polyethylmethacrylate (molecular weight: 340000) and the mixture was stirred for 1 hour. Thereafter, the mixture was concentrated using a rotary evaporator to remove the solvent. The solvent removal was continued until the solution became suited for spinning. The spinning solution was then charged to a defoaming vessel of a dry spinning device and was allowed to quiescently stand at 60 °C for about 2 hours for defoaming. The spinning solution was then discharged at 30 °C through a nozzle with an orifice diameter of 0.1 mm to a spinning cylinder maintained at 130 °C under ambient air, while continuously winding the spun fibers around a roller at a rate of 300 m/min. The thus obtained precursor fibers had an average diameter of 10 µm. The fibers were then heated from room temperature to 1350 °C at a heating rate of 180 °C/hour in a nitrogen atmosphere while applying a tension of 500 g/mm² thereto, thereby obtaining silicon nitride-based ceramic fibers having the physical properties shown below. Tensile strength : 210-360 kg/mm² (average 280 kg/mm²) Modulus : 21-67 ton/mm² (average 26 ton/mm²) Atomic ratio: N/Si : 1.03 C/Si : 0.64 O/Si : 0.33 H/Si : 0.57 Al/Si : 0.05 Elementary analysis (wt %): Si: 48.6, Al: 2.5, N: 25.1, O: 9.3, C: 13.5, H: 1.0 Example 2 To a four-necked, 2 liter flask equipped with a gas feed conduit, a magnetic stirrer, a seal cap and a Dewar condenser, a dry nitrogen gas was fed to replace the air within the flask therewith. After charging 1000 g of the 5.8 weight % solution of perhydropolysilazane, obtained in Reference Example 1, to the flask, a solution of titanium tetraisopropoxide (7.0 g, 24.6 mmol) in 6.5 ml of dry xylene was fed to the flask using a syringe with stirring. The reaction solution was changed from colorless to light brown, purple and finally black as the reaction proceeded. After completion of the reaction, the solvent was removed by distillation in vacuo to obtain, as a dark brown solid, polytitanosilazane with a yield of 84.0 %. Gel permeation chromatography using a polystyrene as a standard revealed that the product had a number-average molecular weight of 1800 and a weight-average molecular weight of 15000. The thus obtained polytitanosilazane was dissolved in dry xylene, with which was mixed 5.0 % by weight (based on the polytitanosilazane) of polyethylmethacrylate (molecular weight: 340000) and the mixture was stirred for 1 hour. The solution was then concentrated using a rotary evaporator to remove the solvent. The solvent removal was continued until the solution became suited for spinning. The spinning solution was then charged to a defoaming vessel of a dry spinning device and was allowed to quiescently stand at 60 °C for about 2 hours for defoaming. The spinning solution was then discharged at 30 °C through a nozzle with an orifice diameter of 0.1 mm to a spinning cylinder maintained at 130 °C under ambient air, while continuously winding the spun fibers around a roller at a rate of 300 m/min. The thus obtained fibers had an average diameter of 10 µm. The fibers were then heated from room temperature to 1350 °C in a nitrogen atmosphere at a heating rate of 180 °C/hour while applying a tension of 500 g/mm² thereto, thereby obtaining silicon nitride-based ceramic fibers having the physical properties shown below. Tensile strength : 220-360 kg/mm² (average 290 kg/mm²) Modulus : 22-70 ton/mm² (average 28 ton/mm²) Atomic ratio: N/Si : 0.95 C/Si : 0.35 O/Si : 0.28 H/Si : 0.46 Ti/Si : 0.02 Elementary analysis (wt %): Si: 54.5, Ti: 1.8, N: 25.9, O: 8.7, C: 8.1, H: 1.9 The thus obtained ceramic fibers were further heated from room temperature to 1500 °C at a heating rate of 180 °C/hour. The X-ray diffraction analysis revealed that the resultant ceramic fibers were still amorphous. Example 3 To a four-necked, 2 liter flask equipped with a gas feed conduit, a magnetic stirrer, a seal cap and a Dewar condenser, a dry nitrogen gas was fed to replace the air within the flask therewith. After charging 1000 g of the 5.0 weight % solution of perhydropolysilazane, obtained in Reference Example 1, to the flask, a solution of zirconium tetraisopropoxide (18.3 g, 0.055 mmol) in 100 ml of dry o-xylene was added to the flask with stirring and the mixture was reacted at 130 °C in the atmosphere of nitrogen. Gel permeation chromatography using a polystyrene as a standard revealed that the product had a number-average molecular weight of 1850. The thus obtained polyzirconosilazane solution was then concentrated using a rotary evaporator to remove the solvent. The solvent removal was continued until the solution became suited for spinning. The spinning solution was then charged to a defoaming vessel of a dry spinning device and was allowed to quiescently stand at 60 °C for about 2 hours for defoaming. The spinning solution was then discharged at 60 °C through a nozzle with an orifice diameter of 0.1 mm to a spinning cylinder maintained at 120 °C under ambient air, while continuously winding the spun fibers around a roller at a rate of 500 m/min. The thus obtained precursor fibers had an average diameter of 8 µm. The fibers were then heated from room temperature to 1350 °C in a nitrogen atmosphere at a heating rate of 180 °C/hour while applying a tension of 500 g/mm² thereto, thereby obtaining silicon nitride-based ceramic fibers having the physical properties shown below. The X-ray diffraction analysis revealed that the ceramic fibers were amorphous. Tensile strength : 200-320 kg/mm² (average 275 kg/mm²) Modulus : 22-74 ton/mm² (average 29 ton/mm²) Atomic ratio: N/Si : 1.0 C/Si : 0.44 O/Si : 0.24 H/Si : 0.55 Zr/Si : 0.04 Elementary analysis (wt %): Si: 50.4, Zr: 7.0, N: 25.2, O: 9.5, C: 6.9, H: 1.0 Example 4 The spun fibers of polytitanosilazane obtained in Example 2 were heated from room temperature to 1350 °C in an ammoniacal atmosphere at a heating rate of 180 °C/hour while applying a tension of 500 g/m² thereto, thereby obtaining silicon nitride-based ceramic fibers having the physical properties shown below. The X-ray diffraction analysis revealed that the ceramic fibers were amorphous. Tensile strength : 200-350 kg/mm² (average 295 kg/mm²) Modulus : 23-72 ton/mm² (average 20 ton/mm²) Atomic ratio: N/Si : 1.22 O/Si : 0.28 Ti/Si : 0.02 Elementary analysis (wt %): Si: 55.3, Ti: 1.8, N: 34.0, O: 8.7, C: below 0.1, H: below 0.1 Comparative Example 1 A pyridine solution (1000 ml) containing the perhydropolysilazane, obtained in Reference Example 1, was placed in a 2 liter autoclave and heated at 120 °C for 3 hours in a nitrogen atmosphere under autogeneous pressure. A large amount of a gas was found to be produced and the pressure within the autoclave was increased by 2.0 kg/cm² as a result of the reaction. After cooling to room temperature, the pressure within the autoclave was released while feeding a nitrogen gas, and 1000 ml of ethylbenzene was mixed to the reaction mixture. The mixture was then distilled at 70 °C under vacuo to leave white powder (reformed perhydropolysilazane) having a number-average molecular weight of 2500. Toluene was then added little by little to the reformed product for dissolution until there was obtained a solution exhibiting a desired spinnability. The solution was then charged to a defoaming vessel of a dry spinning device and was allowed to quiescently stand at 60 °C for about 4 hours for defoaming. The spinning solution was then discharged at 40 °C through a nozzle with an orifice diameter of 0.08 mm to a spinning cylinder maintained at 100 °C in the atmosphere of argon, while continuously winding the spun fibers around a roller at a rate of 1000 m/min. The thus obtained fibers had an average diameter of 10 µm. The fibers were then heated from room temperature to 1350 °C at a heating rate of 180 °C/hour in a nitrogen atmosphere while applying a tension of 500 g/mm² thereto, thereby obtaining silicon nitride-based ceramic fibers having the physical properties shown below. Tensile strength : 150-230 kg/mm² (average 200 kg/mm²) Modulus : 15-32 ton/mm² (average 20 ton/mm²) Crystal phase : amorphous (weak diffraction pattern attributed to alpha-type silicon nitride crystals was observed) Atomic ratio: N/Si : 0.96 C/Si : 0.02 O/Si : 0.07 H/Si : 0.08 Elementary analysis (wt %): Si: 65.4, N: 31.4, O: 2.5, C: 0.5, H: 0.2 Example 5 The spun fibers of polyaluminosilazane obtained in Example 1 were heated from room temperature to 600 °C in an ammoniacal atmosphere and to 1300 °C at a heating rate of 300 °C/hour while applying a tension of 500 g/mm² thereto, thereby obtaining silicon nitride-based ceramic fibers having the physical properties shown below. Tensile strength : 180-350 kg/mm² (average 280 kg/mm²) Modulus : 20-65 ton/mm² (average 25 ton/mm²) Crystal phase : amorphous; X-ray small angle scattering intensity ratio: 1° : 7.5 0.5° : 6.2 Atomic ratio (based on elementary analysis): N/Si : 1.02 C/Si : 0.64 O/Si : 0.35 H/Si : 0.07 Al/Si : 0.09 The thus obtained silicon nitride-based ceramic fibers were woven to form a plain weave cloth, and then impregnated with a commercially available epoxy resin (Bisphenol A-type resin) followed by deaeration at about 40 °C and pre-curing at about 95 °C, thereby to obtain prepreg sheets. These sheets were laminated, treated by a hot press at a pressure of 30 kg/cm² to remove an excess resin and heated at 170 °C for 4 hours for curing. The resulting composite sheet had a resin content of 60 vol. %, a tensile strength of 90 kg/mm², a modulus of 11.0 ton/mm², an interlayer shearing strength of 12.9 kg/mm² and a specific resistivity of 10¹⁴ ohm·cm. Example 6 The spun fibers obtained in Example 2 were heated from room temperature to 600 °C in an ammoniacal atmosphere and to 1100 °C at a heating rate of 300 °C/hour while applying a tension of 500 g/mm² thereto, thereby obtaining silicon nitride-based ceramic fibers having the physical properties shown below. Tensile strength : 210-350 kg/mm² (average 285 kg/mm²) Modulus : 20-65 ton/mm² (average 29 ton/mm²) Crystal phase : amorphous X-ray small angle scattering intensity ratio: 1° : 9.3 0.5° : 7.0 Atomic ratio (based on elementary analysis): N/Si : 0.96 C/Si : 0.31 O/Si : 0.22 H/Si : 0.07 Ti/Si : 0.02 The thus obtained silicon nitride-based ceramic fibers were cut into a length of 6 mm and mixed homogeneously with Nylon 6,6 powder. The mixture was then shaped into a sheet with a hot press machine at 290 °C and 150 kg/cm². The resulting composite sheet had a resin content of 50 vol. %, a tensile strength of 12.4 kg/mm², a modulus of 2.5 ton/mm², and and a specific resistivity of 10¹⁵ ohm·cm. Comparative Example 2 A composite sheet was prepared in the same manner as that in Example 5 except that carbon fibers were used in place of the ceramic fibers. The physical properties of the fibers and the composite sheet are summarized below. Carbon Fibers Tensile strength: average 276 kg/mm² Modulus : average 27 ton/mm² X-ray small angle scattering intensity ratio: 1° : 70 0.5° : 100 Composite Sheet Tensilestrength: 73 kg/mm² Modulus : 6.7 ton/mm² Inter-layer shearing strength: 6.4 kg/mm² Specific resistivity: 8.2x10⁻¹ ohm·cm Comparative Example 3 A composite sheet was prepared in the same manner as that in Example 6 except that carbon fibers were used in place of the ceramic fibers. The physical properties of the fibers and the composite sheet are summarized below. Carbon Fibers Tensile strength: average 278 kg/mm² Modulus : average 27 ton.mm² X-ray small angle scattering intensity ratio: 1° : 70 0.5° : 100 Composite Sheet Tensile strength: 7.8 kg/mm² Modulus : 1.8 ton/mm² Specific resistivity: 6.5 x 10⁻² ohm.cm From the results shown in Examples 5 and 6 and Comparative Examples 2 and 3, it is appreciated that the composite materials prepared from the ceramic fibers obtained from the polymetallosilazanes of the present invention have superior tensile strength, modulus and inter-layer shearing strength in comparison with conventional ones. In particular, the composite laminate sheets obtainable starting with polymetallosilazanes of the present invention exhibit excellent inter-layer shearing strength, indicating the excellent compatibility of the ceramic fibers used therein. The high resistivity of the composite sheets indicates that they are suited as a lightweight, insulating material. Example 7 The silicon nitride-based ceramic fibers obtained in Example 5 were placed on a pure aluminum foil having a thickness of 0.5 mm with their axes being in parallel with each other. After covering the surface of the fiber layer with another aluminum foil, it was passed between a pair of heat rollers of 670°C to obtain a laminate. Such laminates (27 sheets) were superimposed one over another, heated at 670°C for 10 minutes under vacuum, and then pressed at 600°C using a hot press machine to obtain a silicon nitride fiber-reinforced composite aluminum material in which the fibers are distributed in the matrix of aluminum. The composite material contained 30 % by volume of the fibers and had a tensile strength of 80 kg/mm² and modulus of 11 ton/mm². The observation of the cross section of the composite material by a scanning electron microscope showed that the fibers were in close contact with the metal matrix without any substance in the interface. Comparative Example 4 Example 7 was repeated in the same manner as described except that commercially available silicon carbide fibers having the properties shown below were used in place of the ceramic fibers obtained in Example 5. Silicon Carbide Fibers Tensile strength: average 250 kg/mm² Modulus : average 20 ton/mm² X-ray small angle scattering intensity ratio: 1° : 14.3 0.5° : 7.2 Atomic ratio: C/Si : 1.25 O/Si : 0.44 The composite material contained 30 % by volume of the fibers and had a tensile strength of 36 kg/mm² and modulus of 6.9 ton/mm². The low mechanical strengths of the composite material are considered to be attributed to the reduction of the mechanical strengths of the conventional silicon carbide fibers during the heat treatment at 670 °C in the presence of molten aluminum. Example 8 The silicon nitride-based ceramic fibers obtained in Example 6 were arranged into a sheet-like form with their axes being oriented in parallel with each other, over which titanium metal was covered by means of a melt-injection device to a thickness of 0.1-10 µm. The resulting sheets were superimposed one over the other while filling the interstices between them with titanium powder. The resultant laminate was subjected to press molding for consolidation and the consolidated body was pre-calcined at 520 °C for 3 hours in the atmosphere of hydrogen and then subjected to hot press at 1150 °C for 3 hours under 200 kg/cm² in the atmosphere of argon, thereby to obtain silicon nitride fiber-reinforced titanium composite material. This composite material contained 45 % by volume of the fibers and had a tensile strength of 165 kg/mm² and modulus of 17 ton/mm². Comparative Example 5 Example 8 was repeated in the same manner as described except that commercially available silicon carbide fibers as used in Comparative Example 4 were used in place of the ceramic fibers obtained in Example 6. The composite material contained 30 % by volume of the fibers and had a tensile strength of 112 kg/mm² and modulus of 17 ton/mm². Example 9 The silicon nitride-based ceramic fibers obtained in Example 5 were cut into a length of 10 mm and the chopped fibers (45 volume %) were mixed with borosilicate glass powder (7740) with an average diameter of 44 µm. The mixture was dispersed in isopropanol to form a slurry. The silicon nitride-based ceramic fibers obtained in Example 5 were arranged into a sheet-like form with their axes being in parallel with each other. The resulting fiber layer was covered with a layer of the above slurry. Such fiber layers and the slurry layers were alternately overlaid, and the resulting laminate was dried and press molded by a hot press machine at a pressure of 750 kg/cm² and a temperature of 1350 °C for 10 minutes in the atmosphere of argon, thereby to obtain a composite material. The composite material had an anti-bending strength of 18.7 kg/mm² at room temperature. For the purpose of comparison, the above procedure was repeated in the same manner as described except that commercially available silicon carbide fibers were used in place of the ceramic fibers obtained in Example 5. This composite material had an anti-bending strength of 14 kg/mm² at room temperature. Example 10 The polytitanosilazane fibers obtained in Example 6 (15 volume %) were mixed in an alumina ball mill with a mixture containing 98 parts by weight of Al₂O₃ particles with a diameter of 0.5 µm and 2 parts by weight of TiO₂. As a result, the fibers in the thus obtained mixture had an average length of about 0.5 mm. This mixture was then pyrolized and sintered in a hot press machine at 2000°C to obtain a silicon nitride fiber-reinforced, sintered alumina plate with a size of 40 x 10 x 3 mm. Then, the plate was subjected to a spalling test which was conducted by heating the plate in a furnace at 1500°C for 20 minutes and immediately forcibly cooling the heated plate. Such a heating and cooling treatment was repeated until cracks were formed in the plate. The repetition number was 10 in the above sintered alumina plate. For the purpose of comparison, a sintered alumina plate was prepared in the same manner as described above except that no fibers were added. Spalling test for this comparative sample revealed that the formation of cracks when the heating and cooling treatment was repeated twice. As will be appreciated from the foregoing, the inorganic fibers formed from the polymetallosilazanes according to the present invention have both a high tensile strength and a modulus. Preferred physical properties of these inorganic fibers are as summarized below: Physical property Preferred More Preferred Tensile strength (Kg/mm²) 100-450 200-450 Modulus (ton/mm²) 10-90 20-90 Diameter (µm) 3-30 3-20

Claims: A polymetallosilazane having a number molecular weight of 200-500,000, obtained by reacting (i) a polysilazane having a number molecular weight of 100-50,000 and having a main skeletal structure containing the following recurring unit: wherein R¹ is hydrogen, and R² and R³ are the same or different and each is hydrogen, a hydrocarbyl group, an alkylsilyl group, an alkylamino group or an alkoxy group, with (ii) a metal alkoxide of the formula: M(OR⁴) n wherein M is a metal, each R₄ is the same or different and is hydrogen, an alkyl group having 1-20 carbon atoms or an aryl group, and n is the valence of the metal M with the proviso that at least one of the R₄ groups is an alkyl or aryl group. A polymetallosilazane as set forth in Claim 1, wherein said metal M is selected from metals of the groups IIa, IIIa, IIIb, IVa, IVb, Va and Vb of the Periodic Table. A polymetallosilazane as set forth in Claim 2, wherein said metal M is selected from Be, Mg, Ca, Sr, Ba, Sc, Y, lanthanoid elements, actinoid elements, B, Al, Ga, In, Tl, Ti, Zr, Hf, Ge, Sn, Pb, V, Nb, Ta, As, Sb and Bi. A polymetallosilazane as set forth in Claim 3, wherein said metal M is selected from Y, B, Al, Ti and Zr. A polymetallosilazane as set forth in any preceding claim, wherein said hydrocarbyl group is an alkyl, alkenyl, aryl, cycloalkyl or aralkyl group. A polymetallosilazane as set forth in any preceding claim, wherein R² and R³ are independently selected from hydrogen and C₁-C₅ alkyl groups, and R⁴ is a C₁-C₁₀ alkyl group. A polymetallosilazane as set forth in Claim 6, wherein R² and R³ are independently selected from hydrogen, methyl or ethyl, and R⁴ is a C₁-C₄ alkyl group.

Inventors: AOKI HIROYUKI, ARAI MIKIRO, FUNAYAMA OSAMU, HAINO MUTSUO, ISODA TAKESHI, KATAHATA TOSHIO, KAYA HIROSHI, NISHIMURA GENSHIRO, SUZUKI TADASHI, TASHIRO YUUJI, AOKI, HIROYUKI, ARAI, MIKIRO, FUNAYAMA, OSAMU, HAINO, MUTSUO, ISODA, TAKESHI, KATAHATA, TOSHIO, KAYA, HIROSHI, NISHIMURA, GENSHIRO, SUZUKI, TADASHI, TASHIRO, YUUJI
Applicants: TOA NENRYO KOGYO KK, TOA NENRYO KOGYO KABUSHIKI KAISHA
Application year: 1989
Main classification: D01F9
IPC codes: C08G77, C04B35, D01F9, C08G79