JP2005022970A - Manufacturing method of silicon nitride whisker - Google Patents
Manufacturing method of silicon nitride whisker Download PDFInfo
- Publication number
- JP2005022970A JP2005022970A JP2004256490A JP2004256490A JP2005022970A JP 2005022970 A JP2005022970 A JP 2005022970A JP 2004256490 A JP2004256490 A JP 2004256490A JP 2004256490 A JP2004256490 A JP 2004256490A JP 2005022970 A JP2005022970 A JP 2005022970A
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- JP
- Japan
- Prior art keywords
- silicon
- polymer compound
- whisker
- silicon nitride
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 50
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
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- 239000007787 solid Substances 0.000 claims abstract description 72
- 238000010438 heat treatment Methods 0.000 claims abstract description 53
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- 238000000034 method Methods 0.000 claims abstract description 32
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- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 58
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Images
Abstract
Description
本発明は、炭化珪素ウイスカー、或いは、窒化珪素ウイスカーの製造方法に関するものである。 The present invention relates to a method for manufacturing silicon carbide whiskers or silicon nitride whiskers.
炭化珪素、及び、窒化珪素は、耐熱性、耐薬品性、弾性率、高温強度等の点で優れた特性を有している。これらの炭化珪素、及び、窒化珪素を針状の単結晶に成長させたものが炭化珪素ウイスカー、或いは、窒化珪素ウイスカーであるが、これらの炭化珪素ウイスカー、或いは、窒化珪素ウイスカーは、微細できわめて欠陥の少ない単結晶であり、その機械的強度は理論強度に近いことから、プラスチックス、金属、セラミックス等の複合材料の強化材として注目されている。 Silicon carbide and silicon nitride have excellent characteristics in terms of heat resistance, chemical resistance, elastic modulus, high temperature strength, and the like. These silicon carbide and silicon nitride grown into needle-like single crystals are silicon carbide whiskers or silicon nitride whiskers. These silicon carbide whiskers or silicon nitride whiskers are fine and extremely Since it is a single crystal with few defects and its mechanical strength is close to the theoretical strength, it has attracted attention as a reinforcing material for composite materials such as plastics, metals, and ceramics.
炭化珪素ウイスカーの製造方法としては種々の方法が報告されており、
(1)四塩化珪素等のシリコンのハロゲン化物と、プロパン、ベンゼンなどのハイドロカーボンを水素ガスをキャリヤーガスとして反応管内に導入し反応させる方法（特許文献１）。
(2)メチルクロロジシランなどの有機珪素化合物を水素ガスをキャリヤーガスとして反応炉内に導入して反応させる方法（特許文献２）。
(3)二酸化珪素と炭素の混合物を不活性ガス中で加熱処理する方法（特許文献３）。
(4)もみ殻とカーボンブラックの混合物を非酸化性雰囲気下で加熱処理する方法（特許文献４）。
などが知られている。しかしながら、これらの方法は、スケールアップが困難である、キャリヤーガスとして水素ガスを使用する必要がある、高温で反応させる必要がある、安定した品質のものが得られないなど、工業的、経済的に不利であるという欠点を有している。
Various methods have been reported as methods for producing silicon carbide whiskers,
(1) A method in which a silicon halide such as silicon tetrachloride and a hydrocarbon such as propane and benzene are introduced into a reaction tube using hydrogen gas as a carrier gas and reacted (Patent Document 1).
(2) A method of reacting an organosilicon compound such as methylchlorodisilane by introducing it into a reaction furnace using hydrogen gas as a carrier gas (Patent Document 2).
(3) A method of heat-treating a mixture of silicon dioxide and carbon in an inert gas (Patent Document 3).
(4) A method of heat-treating a mixture of rice husk and carbon black in a non-oxidizing atmosphere (Patent Document 4).
Etc. are known. However, these methods are industrially and economically difficult to scale up, need to use hydrogen gas as a carrier gas, need to react at a high temperature, and cannot obtain a stable quality. Has the disadvantage of being disadvantageous.
また、ポリカルボシランを溶融紡糸し、不溶化後、非酸化性雰囲気で焼成することにより、炭化珪素連続繊維が合成される。この方法はすでに工業化され、その製品は市販されている。更には、炭素繊維強化炭素材へ有機珪素高分子化合物を強制含浸した後、不活性ガス雰囲気中で焼成し、含浸物を炭化珪素に転化させることにより耐酸化性を向上させる方法が提案されている（特許文献５）。しかしながら前者の炭化珪素連続繊維は結晶構造は有しておらず、非晶質構造を呈する直径十数μｍの繊維であり、後者は、詳しい性状は明記されていないものの、炭素基材に炭化珪素が多結晶微粉末として充填されているものと考えられる。このように、有機珪素高分子化合物を前駆体とした炭化珪素ウイスカーの製造については現在のところ報告がなされていない。 In addition, polycarbosilane is melt-spun, insolubilized, and then fired in a non-oxidizing atmosphere to synthesize a silicon carbide continuous fiber. This method has already been industrialized and its products are commercially available. Furthermore, a method has been proposed in which oxidation resistance is improved by forcibly impregnating a carbon fiber reinforced carbon material with an organosilicon polymer compound, followed by firing in an inert gas atmosphere and converting the impregnated material into silicon carbide. (Patent Document 5). However, the former silicon carbide continuous fiber does not have a crystal structure and is a fiber having an amorphous structure and a diameter of several tens of μm, and the latter is silicon carbide on a carbon base material, although detailed properties are not specified. Are considered to be filled as polycrystalline fine powder. Thus, there has been no report on the production of silicon carbide whiskers using an organosilicon polymer compound as a precursor at present.
一方、窒化珪素ウイスカーの製造方法としては、
(1)シリカと炭素の混合物を窒素ガス気流中で加熱処理し、原料の空隙にウイスカーを生成させる方法（特許文献６）。
(2)二酸化珪素に金属珪素または炭素などの還元剤を混合した粉粒体を不活性ガス中で加熱して一酸化珪素ガス、または、一酸化珪素ガスと一酸化炭素ガスの混合ガスを発生させ、これらガスを窒素を含む雰囲気に搬出し、窒素と反応させウイスカーを生成させる方法（特許文献７）。
(3)四塩化珪素とアンモニアを反応させて得られたシリコンジイミドを、水素ガスとアンモニアガス、及び／または、窒素ガス中において高温下で熱分解させウイスカーを生成させる方法（特許文献８）。
(4)ヘキサハロゲノジシランとアンモニアを高温で反応させウイスカーを生成させる方法（特許文献９）。
などが知られている。しかしながら、これらの方法は、高純度のウイスカーが得られない、複雑な装置を必要とする、水素ガス或いはアンモニアガスを用いるため取り扱いが面倒であるなど、工業的、経済的に不利であるという問題点を有している。
On the other hand, as a manufacturing method of silicon nitride whisker,
(1) A method in which a mixture of silica and carbon is heat-treated in a nitrogen gas stream to produce whiskers in the voids of the raw material (Patent Document 6).
(2) Heating a powder of silicon dioxide mixed with a reducing agent such as metallic silicon or carbon in an inert gas to generate silicon monoxide gas or a mixed gas of silicon monoxide gas and carbon monoxide gas And carrying out these gases to an atmosphere containing nitrogen and reacting with nitrogen to generate whiskers (Patent Document 7).
(3) A method of producing whiskers by thermally decomposing silicon diimide obtained by reacting silicon tetrachloride and ammonia in hydrogen gas and ammonia gas and / or nitrogen gas at a high temperature (Patent Document 8).
(4) A method of producing whisker by reacting hexahalogenodisilane and ammonia at a high temperature (Patent Document 9).
Etc. are known. However, these methods are disadvantageous industrially and economically, such as high-purity whiskers cannot be obtained, complicated equipment is required, and hydrogen gas or ammonia gas is difficult to handle. Has a point.
また、有機珪素高分子化合物を前駆体とする窒化珪素ウイスカーの製造方法も種々提案されている。たとえば、有機珪素高分子化合物であるポリカルボシランの粉末又は紡糸体をアンモニアガス雰囲気で１３００℃以上で焼成する方法が提案されている（特許文献１０）。しかしながら、この方法ではアンモニアガスを用いるため取り扱いが面倒であるという欠点がある。さらには、珪素含有有機高分子（特に、ポリカルボシラスチレン共重合体、ポリシラスチレン及び／又はその架橋構造物）を、高温下で微量の酸素を含有する窒素気流中で分解し、該珪素含有有機高分子の表層部に窒化珪素ウイスカーを形成させる方法が提案されている（特許文献１１）。しかし、この方法では、酸素の存在量を数〜数百ｐｐｍ程度に調整する必要があり、酸素の存在量の調整に多大な労力がかかるという問題点がある。また、窒化珪素ウイスカーは原料素材表層部に形成されるため、原料素材の比表面積が大きい方が好ましいが、この方法では、実質的には比表面積が数十ｍ2／ｋｇ程度と非常に小さく、効率良く窒化珪素ウイスカーを得ることができないという欠点がある。
本発明は、前述した従来方法の欠点を解消し、有機珪素高分子化合物を前駆体として、高純度の炭化珪素ウイスカー、或いは、窒化珪素ウイスカーを、簡単な操作で、極めて容易に製造することができる、炭素珪素ウイスカー、或いは窒素珪素ウイスカーの新規な製造方法を提供することを目的とする。 The present invention eliminates the disadvantages of the conventional methods described above, and makes it very easy to produce high-purity silicon carbide whiskers or silicon nitride whiskers with a simple operation using an organosilicon polymer compound as a precursor. An object of the present invention is to provide a novel method for producing carbon silicon whisker or nitrogen silicon whisker.
本発明者らは、このような状況に鑑み、鋭意検討を重ねた。その結果、有機珪素高分子化合物及び固体炭素を含有する成形体を、窒素ガス以外の不活性ガス雰囲気中、或いは、窒素ガス雰囲気中で加熱処理することにより、上記課題を解決でき、高純度の炭化珪素ウイスカー、或いは、窒化珪素ウイスカーを製造できることを見い出し、本発明を完成するに至った。 In view of such a situation, the present inventors made extensive studies. As a result, the above-mentioned problem can be solved by heat-treating a molded body containing an organosilicon polymer compound and solid carbon in an inert gas atmosphere other than nitrogen gas or in a nitrogen gas atmosphere, and high purity. It has been found that silicon carbide whiskers or silicon nitride whiskers can be produced, and the present invention has been completed.
すなわち、本発明によれば、主鎖が珪素原子のみからなる有機珪素高分子化合物、及び／または、主鎖が珪素原子と炭素原子のみからなる有機珪素高分子化合物と、固体炭素を含有する成形体を、窒素ガス以外の不活性ガス雰囲気中で加熱処理することを特徴とする炭化珪素ウイスカーの製造方法が提供され、また、好ましくは、前記成形体が、主鎖が珪素原子のみからなる有機珪素高分子化合物、及び／または、主鎖が珪素原子と炭素原子のみからなる有機珪素高分子化合物、固体炭素、重合性不飽和化合物、及び、重合開始剤を含有する組成物を重合させて得られた重合体であることを特徴とする前記炭化珪素ウイスカーの製造方法が提供され、また、好ましくは、前記成形体が、多孔質体であることを特徴とする前記炭化珪素ウイスカーの製造方法が提供され、また、好ましくは、前記多孔質体が、主鎖が珪素原子のみからなる有機珪素高分子化合物、及び／または、主鎖が珪素原子と炭素原子のみからなる有機珪素高分子化合物、固体炭素、重合性不飽和化合物、乳化剤、重合開始剤、及び、水を混合、撹拌して得られるＷ／Ｏ型エマルジョンを重合させた後、水を蒸発させて得られるものであることを特徴とする前記炭化珪素ウイスカーの製造方法が提供され、また、好ましくは、前記多孔質体が、主鎖が珪素原子のみからなる有機珪素高分子化合物、及び／または、主鎖が珪素原子と炭素原子のみからなる有機珪素高分子化合物を溶媒に溶解した後、固体炭素と混合、及び／または、固体炭素に含浸し、次いで、溶媒を除去することにより得られるものであることを特徴とする前記炭化珪素ウイスカーの製造方法が提供され、また、好ましくは、前記重合性不飽和化合物の主成分がスチレン系化合物であることを特徴とする前記炭化珪素ウイスカーの製造方法が提供され、また、好ましくは、前記固体炭素が、繊維状炭素であることを特徴とする前記炭素珪素ウイスカーの製造方法が提供され、また好ましくは、前記加熱処理を１１００〜１５５０℃の温度領域で行うことを特徴とする前記炭化珪素ウイスカーの製造方法が提供され、また、好ましくは、前記不活性ガスが、アルゴンガスであることを特徴とする炭化珪素ウイスカーの製造方法が提供される。 That is, according to the present invention, an organosilicon polymer compound whose main chain is composed only of silicon atoms and / or an organosilicon polymer compound whose main chain is composed only of silicon atoms and carbon atoms, and a molding containing solid carbon A method for producing a silicon carbide whisker characterized in that the body is heat-treated in an inert gas atmosphere other than nitrogen gas, and preferably, the molded body is an organic material whose main chain is composed only of silicon atoms. Obtained by polymerizing a composition containing a silicon polymer compound and / or an organic silicon polymer compound whose main chain is composed only of silicon atoms and carbon atoms, solid carbon, a polymerizable unsaturated compound, and a polymerization initiator. The method for producing the silicon carbide whisker is characterized in that the silicon carbide whisker is characterized in that the molded body is a porous body. Preferably, the porous body is composed of an organic silicon polymer compound whose main chain is composed only of silicon atoms, and / or an organic silicon high compound whose main chain is composed only of silicon atoms and carbon atoms. It is obtained by polymerizing a W / O emulsion obtained by mixing and stirring a molecular compound, solid carbon, a polymerizable unsaturated compound, an emulsifier, a polymerization initiator, and water, and then evaporating the water. The method for producing the silicon carbide whisker is characterized in that, preferably, the porous body is an organosilicon polymer compound whose main chain is composed only of silicon atoms, and / or the main chain is silicon atoms. And an organic silicon polymer compound consisting only of carbon atoms in a solvent, mixed with solid carbon and / or impregnated in solid carbon, and then removed from the solvent. A method for producing the silicon carbide whisker is provided, and preferably, the main component of the polymerizable unsaturated compound is a styrenic compound, and the method for producing the silicon carbide whisker is provided. Preferably, the method for producing the carbon silicon whisker is characterized in that the solid carbon is fibrous carbon, and preferably, the heat treatment is performed in a temperature range of 1100 to 1550 ° C. The method for producing silicon carbide whisker is provided, and preferably, the method for producing silicon carbide whisker is characterized in that the inert gas is argon gas.
更に、主鎖が珪素原子のみからなる有機珪素高分子化合物、及び／または、主鎖が珪素原子と炭素原子のみからなる有機珪素高分子化合物と、固体炭素を含有する成形体を、窒素ガス雰囲気中で加熱処理することを特徴とする窒化珪素ウイスカーの製造方法が提供され、また、好ましくは、前記成形体が、主鎖が珪素原子のみからなる有機珪素高分子化合物、及び／または、主鎖が珪素原子と炭素原子のみからなる有機珪素高分子化合物、固体炭素、重合性不飽和化合物、及び、重合開始剤を含有する組成物を重合させて得られた重合体であることを特徴とする前記窒化珪素ウイスカーの製造方法が提供され、また、好ましくは、前記成形体が、多孔質体であることを特徴とする前記窒化珪素ウイスカーの製造方法が提供され、また、好ましくは、前記多孔質体が、主鎖が珪素原子のみからなる有機珪素高分子化合物、及び／または、主鎖が珪素原子と炭素原子のみからなる有機珪素高分子化合物、固体炭素、重合性不飽和化合物、乳化剤、重合開始剤、及び、水を混合、撹拌して得られるＷ／Ｏ型エマルジョンを重合させた後、水を蒸発させて得られるものであることを特徴とする前記窒化珪素ウイスカーの製造方法が提供され、また、好ましくは、前記多孔質体が、主鎖が珪素原子のみからなる有機珪素高分子化合物、及び／または、主鎖が珪素原子と炭素原子のみからなる有機珪素高分子化合物を溶媒に溶解した後、固体炭素と混合、及び／または、固体炭素に含浸し、次いで、溶媒を除去することにより得られるものであることを特徴とする前記窒化珪素ウイスカーの製造方法が提供され、また、好ましくは、前記重合性不飽和化合物の主成分がスチレン系化合物であることを特徴とする前記窒化珪素ウイスカーの製造方法が提供され、また、好ましくは、前記固体炭素が繊維状炭素であることを特徴とする前記窒化珪素ウイスカーの製造方法が提供され、また、好ましくは、前記加熱処理を１１００〜１６００℃の温度領域で行うことを特徴とする窒化珪素ウイスカーの製造方法が提供される。 Further, an organic silicon polymer compound whose main chain is composed only of silicon atoms and / or an organic silicon polymer compound whose main chain is composed only of silicon atoms and carbon atoms, and a molded body containing solid carbon, and a nitrogen gas atmosphere A method for producing a silicon nitride whisker characterized in that it is heat-treated in the inside is provided, and preferably, the molded body is an organosilicon polymer compound whose main chain is composed only of silicon atoms, and / or a main chain. Is a polymer obtained by polymerizing a composition containing an organosilicon polymer compound composed of only silicon atoms and carbon atoms, solid carbon, a polymerizable unsaturated compound, and a polymerization initiator. A method for producing the silicon nitride whisker is provided, and preferably, the method for producing the silicon nitride whisker is characterized in that the molded body is a porous body. The porous body is an organosilicon polymer compound whose main chain consists only of silicon atoms, and / or an organosilicon polymer compound whose main chain consists only of silicon atoms and carbon atoms, solid carbon, polymerizable unsaturated The silicon nitride whisker is obtained by polymerizing a W / O emulsion obtained by mixing and stirring a compound, an emulsifier, a polymerization initiator, and water, and then evaporating the water. A production method is provided, and preferably, the porous body is an organosilicon polymer compound whose main chain is composed only of silicon atoms, and / or an organosilicon polymer whose main chain is composed only of silicon atoms and carbon atoms. Production of the silicon nitride whisker, wherein the compound is obtained by dissolving a compound in a solvent, mixing with solid carbon and / or impregnating the solid carbon, and then removing the solvent And a method for producing the silicon nitride whisker, wherein the main component of the polymerizable unsaturated compound is a styrene compound, and preferably the solid carbon is A method for producing the silicon nitride whisker characterized in that it is fibrous carbon, and preferably, the heat treatment is performed in a temperature range of 1100 to 1600 ° C. Is provided.
以上説明したように、本発明によれば、反応ガスとして取り扱いにくい水素ガス、或いは、アンモニアガスを用いなくても、有機珪素高分子化合物、固体炭素を含有する成形体を、取り扱いが容易な窒素ガス雰囲気中で加熱するという簡単な操作で、窒化珪素ウイスカーを製造できる。更に、本発明によれば、窒化珪素ウイスカーは、加熱処理時に形成される加熱処理物の表面、及び／或いは、内部に生成するため、窒化珪素ウイスカーの生成に必要な反応ガスを別の空間まで搬出させる等といった複雑な製造装置を必要としない。また、本発明によって得られる窒化珪素ウイスカーは品質的に非常に安定したものである。このように、本発明によれば、高品質な窒化珪素ウイスカーの低コストでの供給が可能である。 As described above, according to the present invention, a nitrogen gas that is difficult to handle as a reaction gas or a compact containing an organosilicon polymer compound and solid carbon can be easily handled without using ammonia gas. A silicon nitride whisker can be manufactured by a simple operation of heating in a gas atmosphere. Furthermore, according to the present invention, since the silicon nitride whisker is generated on the surface and / or inside of the heat-treated product formed during the heat treatment, the reaction gas necessary for generating the silicon nitride whisker is transferred to another space. There is no need for complicated manufacturing equipment such as unloading. The silicon nitride whisker obtained by the present invention is very stable in quality. Thus, according to the present invention, it is possible to supply high-quality silicon nitride whiskers at a low cost.
以下、本発明について詳細に説明する。本発明における、主鎖が珪素原子のみからなる有機珪素高分子化合物、及び／または、主鎖が珪素原子と炭素原子のみからなる有機珪素高分子化合物（以下、有機珪素高分子化合物と略す）は、近年セラミックスの前駆体として知られるようになった高分子化合物である（YAJIMA et al:Chemistry Letter,PP.931-943,1975）。主鎖が珪素原子のみからなる有機珪素高分子化合物としては、ジメチルジクロロシランとフェニルメチルジクロロシランから合成されるポリシラスチレンに代表されるポリシラン等が挙げられる。また、主鎖が珪素原子と炭素原子のみからなる有機珪素高分子化合物としては、テトラメチルシランの熱分解、ポリ（ジメチルシラン）のオートクレーブ中での熱分解、ポリ（ジメチルシラン）の常圧下での熱分解、ドデカメチルシクロヘキサシランのオートクレーブ中、加圧下での熱分解などにより得られるポリカルボシラン等が挙げられる。 Hereinafter, the present invention will be described in detail. In the present invention, the organosilicon polymer compound whose main chain consists only of silicon atoms and / or the organosilicon polymer compound whose main chain consists only of silicon atoms and carbon atoms (hereinafter abbreviated as organosilicon polymer compound) Recently, it is a polymer compound that has become known as a precursor of ceramics (YAJIMA et al: Chemistry Letter, PP.931-943, 1975). Examples of the organosilicon polymer compound whose main chain is composed only of silicon atoms include polysilanes represented by polysilastyrene synthesized from dimethyldichlorosilane and phenylmethyldichlorosilane. In addition, organosilicon polymer compounds whose main chain consists only of silicon atoms and carbon atoms include thermal decomposition of tetramethylsilane, thermal decomposition of poly (dimethylsilane) in an autoclave, and normal pressure of poly (dimethylsilane). And polycarbosilane obtained by thermal decomposition under pressure in an autoclave of dodecamethylcyclohexasilane.
これらの有機珪素高分子化合物のうち、その数平均分子量が５００〜５００００のもの、より好ましくは、数平均分子量が１０００〜３００００のものを使用するのが望ましい。数平均分子量が５００未満であると該有機珪素高分子化合物のうち、加熱処理中に分解ガスとなって揮発してしまう部分が多くなり、ウイスカーの収率が低下するため好ましくない。また、逆に数平均分子量が５００００を超えると、後述するような有機結合材、或いは、有機溶媒に対する溶解度が低くなるため、有機珪素高分子化合物と固体炭素とを均一に混合させるのが困難となったり、あるいは、有機溶媒に溶解させたときの溶液粘度が高くなるため、固体炭素に含浸させるのが困難となり、その結果、均質なウイスカーが得られなくなり好ましくない。 Among these organosilicon polymer compounds, those having a number average molecular weight of 500 to 50,000, more preferably those having a number average molecular weight of 1,000 to 30,000 are desirably used. When the number average molecular weight is less than 500, the organosilicon polymer compound is not preferable because the portion that becomes a decomposition gas and volatilizes during the heat treatment increases and the whisker yield decreases. On the other hand, when the number average molecular weight exceeds 50000, the solubility in an organic binder or an organic solvent as described later is lowered, and it is difficult to uniformly mix the organosilicon polymer compound and solid carbon. Or the viscosity of the solution when dissolved in an organic solvent becomes high, so that it becomes difficult to impregnate solid carbon, and as a result, a homogeneous whisker cannot be obtained.
また、本発明における固体炭素は特に限定されるものではなく、例えば繊維状炭素である炭素繊維、黒鉛繊維など、或いは、粉末状炭素であるカーボンブラック、活性炭、木炭粉、コークス粉、黒鉛粉末などを用いることができる。なかでも繊維状炭素を用いると、繊維同士の絡み合いにより、成形体を加熱処理する際の収縮をより少なくすることができ、炭化珪素ウイスカー、窒化珪素ウイスカーが生長するために必要な空間が十分得られるため特に好ましい。その際、繊維状炭素は糸状のものをそのまま使用しても差し支えないが、組成物中に均一に混合させるためには、短くチョップしたチョップド・ファイバー、或いは、ミリングしたミルド・ファイバーを用いるのが好ましい。これらの固体炭素は単独で、或いは、適宜組み合わせて用いることができる。これらの固体炭素は、大気中で加熱処理することにより簡単に燃焼除去できるため、生成した炭化珪素ウイスカー及び窒化珪素ウイスカーとの分離が容易である。本発明のごとく、成形体が固体炭素を含有することによって、より高品質の炭化珪素ウイスカー、或いは、窒化珪素ウイスカーが得られるようになる。その機構は現在のところ明確ではないが、有機珪素高分子化合物と固体炭素との共存効果により、発生した有機珪素高分子化合物の分解ガスが炭化珪素、窒化珪素単結晶の成長に適しており、その結果、欠陥の少ない単結晶が得られるためではないかと考えられる。 Further, the solid carbon in the present invention is not particularly limited. For example, carbon fiber that is fibrous carbon, graphite fiber, or carbon black, activated carbon, charcoal powder, coke powder, graphite powder that is powdered carbon, and the like. Can be used. In particular, when fibrous carbon is used, shrinkage when the molded body is heat-treated can be reduced due to the entanglement of the fibers, and sufficient space is obtained for the growth of silicon carbide whiskers and silicon nitride whiskers. This is particularly preferable. At that time, the fibrous carbon may be used as it is, but in order to mix it uniformly in the composition, a short chopped fiber or a milled milled fiber is used. preferable. These solid carbons can be used alone or in appropriate combination. Since these solid carbons can be easily burned and removed by heat treatment in the atmosphere, separation from the generated silicon carbide whiskers and silicon nitride whiskers is easy. As in the present invention, when the compact contains solid carbon, a higher quality silicon carbide whisker or silicon nitride whisker can be obtained. The mechanism is not clear at present, but due to the coexistence effect of the organosilicon polymer compound and solid carbon, the generated decomposition gas of the organosilicon polymer compound is suitable for the growth of silicon carbide and silicon nitride single crystals, As a result, it is considered that a single crystal with few defects is obtained.
本発明における成形体は、成形体中に有機珪素高分子化合物と固体炭素とを効率的に包含できていること、そして、少なくとも実質的にウイスカーが生成し始める温度領域において、該成形体が多孔質構造体となっていることが望まれる。このような成形体を得るために、例えば、以下のような有機結合材が用いられ、また、それぞれ併記するような手段により成形体を形成させる。
(1)重合性不飽和化合物
有機珪素高分子化合物、固体炭素、重合開始剤等と混合して得られる組成物を重合させる。
(2)熱可塑性合成樹脂
加熱により溶融させ、有機珪素高分子化合物、固体炭素等と混合した後、冷却固化せしめる。
(3)デンプン
水に分散後、加熱糊化させ、次いで、有機珪素高分子化合物、固体炭素等と混合した後、冷却する。
(4)ゼラチン
水に分散後、加熱溶解させ、次いで、有機珪素高分子化合物、固体炭素等と混合した後、冷却する。
これらの手段のうちでも、(1)の重合性不飽和化合物を用いる手段がより均質な成形体が得られる点でより好ましく用いられる。また、これらの有機結合材は、加熱処理により分解除去されやすく、加熱処理過程において、成形体に連続気孔構造をもたらす。
The molded body in the present invention can efficiently contain an organosilicon polymer compound and solid carbon in the molded body, and the molded body is porous at least in a temperature region where whisker begins to be generated. It is desired to be a quality structure. In order to obtain such a molded body, for example, the following organic binder is used, and the molded body is formed by the means described below.
(1) Polymerizable unsaturated compound An organic silicon polymer compound, solid carbon, a composition obtained by mixing with a polymerization initiator, and the like are polymerized.
(2) The thermoplastic synthetic resin is melted by heating, mixed with an organosilicon polymer compound, solid carbon, etc., and then cooled and solidified.
(3) Disperse in starch water, heat gelatinize, mix with organosilicon polymer compound, solid carbon, etc., then cool.
(4) Disperse in gelatin water, dissolve by heating, then mix with organosilicon polymer compound, solid carbon, etc., then cool.
Among these means, the means (1) using the polymerizable unsaturated compound is more preferably used in that a more uniform molded product can be obtained. In addition, these organic binders are easily decomposed and removed by heat treatment, and provide a continuous pore structure in the molded body in the heat treatment process.
次に、有機珪素高分子化合物、固体炭素、重合性不飽和化合物、重合開始剤を含有する組成物を重合させて得られる重合体について説明する。本発明において用いられる重合性不飽和化合物は、有機珪素高分子化合物を溶解し、分子中に二重結合を有し、ラジカル重合又はレドックス重合しうるものであれば特に限定しない。このような重合性不飽和化合物としては、スチレン、α−メチルスチレン、ジビニルベンゼン等のスチレン系化合物、メチル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート等の（メタ）アクリル酸エステル類、（メタ）アクリル酸類〔但し、ここにおいて、（メタ）アクリルはアクリルまたはメタクリルを表すものとする〕、ジアリルフタレート、不飽和ポリエステル類等が挙げられる。これらは単独で、或いは、適宜組み合わせて用いることができる。中でも、スチレン系化合物を主成分とした前記重合性不飽和化合物は、有機珪素高分子化合物の溶解性が高く、さらには、重合後の重合物としての炭化率が低く、加熱処理過程でそのほとんどがガスとなって揮散し、ウイスカーが成長するために必要な空間が十分形成されるため特に好ましい。このような重合性不飽和化合物は、該有機珪素高分子化合物１００重量部に対し１００〜２０００重量部、特に３００〜１３００重量部用いることが望ましい。 Next, a polymer obtained by polymerizing a composition containing an organosilicon polymer compound, solid carbon, a polymerizable unsaturated compound, and a polymerization initiator will be described. The polymerizable unsaturated compound used in the present invention is not particularly limited as long as it dissolves an organosilicon polymer compound, has a double bond in the molecule, and can undergo radical polymerization or redox polymerization. Such polymerizable unsaturated compounds include styrene compounds such as styrene, α-methylstyrene, divinylbenzene, methyl (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like. Examples include (meth) acrylic acid esters, (meth) acrylic acids (where (meth) acrylic represents acryl or methacrylic), diallyl phthalate, unsaturated polyesters, and the like. These can be used alone or in appropriate combination. Among them, the polymerizable unsaturated compound mainly composed of a styrenic compound has high solubility of the organosilicon polymer compound, and further has a low carbonization rate as a polymerized product after polymerization. It is particularly preferable because it is volatilized as a gas and a space necessary for growing whiskers is sufficiently formed. Such a polymerizable unsaturated compound is desirably used in an amount of 100 to 2000 parts by weight, particularly 300 to 1300 parts by weight, based on 100 parts by weight of the organosilicon polymer compound.
一方、重合開始剤としては、通常のラジカル重合開始剤、レドックス重合開始剤が特に制限なく使用できる。これらの例として、過酸化ベンゾイル、過酸化ラウロイル、ｔ−ブチルパーオキシオクトエート、ｐ−メンタンヒドロパーオキサイド、ジ−ミリスチルパーオキシジカーボネート、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサンなどの過酸化物系ラジカル重合開始剤、アゾビスイソブチロニトリル、アゾビス−２，４−ジメチルバレロニトリルなどのアゾ系ラジカル重合開始剤、或いは、これらのラジカル重合開始剤とアミン系化合物、有機金属化合物とのレドックス重合開始剤等が挙げられる。重合開始剤の添加量は、重合性不飽和化合物１００重量部に対して０．０５〜５重量部が望ましい。 On the other hand, as the polymerization initiator, ordinary radical polymerization initiators and redox polymerization initiators can be used without particular limitation. Examples of these include benzoyl peroxide, lauroyl peroxide, t-butyl peroxyoctoate, p-menthane hydroperoxide, di-myristyl peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclohexane, etc. Peroxide radical polymerization initiators, azo radical polymerization initiators such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, or these radical polymerization initiators and amine compounds, organic metals Examples thereof include a redox polymerization initiator with a compound. The addition amount of the polymerization initiator is desirably 0.05 to 5 parts by weight with respect to 100 parts by weight of the polymerizable unsaturated compound.
更に、組成物を調製する際、粘度調整剤として重合性不飽和化合物に溶解し得る有機高分子化合物を含有させておくと、重合中に、固体炭素が沈降しないため、重合体中に固体炭素が均一に分散した重合体を得ることができ、その結果、均質なウイスカーが得られ好ましい。本発明で粘度調製剤として用いることのできる有機高分子化合物は、前述した重合性不飽和化合物に溶解し得るものであれば特に限定はされないが、ポリスチレン、石油樹脂、クマロン樹脂、ジアリルフタレート樹脂、メタクリル樹脂等を用いることができる。これらは単独で、或いは、適宜組み合わせて用いることができる。また、これらの有機高分子化合物は、重合性不飽和化合物と同様に、重合性不飽和化合物の重合後は固体炭素と有機珪素高分子化合物との有機結合材として作用する。 Furthermore, when an organic polymer compound that can be dissolved in a polymerizable unsaturated compound is contained as a viscosity modifier when preparing the composition, solid carbon does not settle during the polymerization, so solid carbon is contained in the polymer. Can be obtained, and as a result, a homogeneous whisker can be obtained. The organic polymer compound that can be used as a viscosity adjusting agent in the present invention is not particularly limited as long as it can be dissolved in the polymerizable unsaturated compound described above, but polystyrene, petroleum resin, coumarone resin, diallyl phthalate resin, A methacrylic resin or the like can be used. These can be used alone or in appropriate combination. In addition, these organic polymer compounds act as an organic binder between solid carbon and an organosilicon polymer compound after polymerization of the polymerizable unsaturated compound, similarly to the polymerizable unsaturated compound.
重合体の製造方法としては、まず、上記したような、有機珪素高分子化合物、固体炭素、重合性不飽和化合物、重合開始剤、そして必要により粘度調整剤を用いて組成物を調製する。その手順については特に制限はないが、有機珪素高分子化合物、粘度調整剤はあらかじめ重合性不飽和化合物に溶解させておくことが好ましい。次いで、得られた組成物を重合硬化させる。重合温度、重合時間は、用いた重合性不飽和化合物、重合開始剤の種類によって適宜設定される。 As a method for producing a polymer, first, a composition is prepared using an organosilicon polymer compound, solid carbon, a polymerizable unsaturated compound, a polymerization initiator, and, if necessary, a viscosity modifier as described above. Although there is no restriction | limiting in particular about the procedure, It is preferable to melt | dissolve an organosilicon polymer compound and a viscosity modifier in a polymerizable unsaturated compound previously. Next, the obtained composition is polymerized and cured. The polymerization temperature and polymerization time are appropriately set depending on the type of polymerizable unsaturated compound and polymerization initiator used.
また本発明では、成形体が多孔質体であることが好ましい。成形体を多孔質体とすることにより、後述する理由により良好なウイスカーが得られる。成形体を多孔質体とするためには、発泡剤を用いる方法、撹拌、或いは、バブリング等の方法によって気体を混入させる方法、また、可溶性物質を混合しておき、成形の後、該可溶性物質を溶解除去する方法など、従来から広く知られている方法を利用することができる。 In the present invention, the molded body is preferably a porous body. By making the compact into a porous body, good whiskers can be obtained for the reasons described later. In order to make a molded body into a porous body, a method using a foaming agent, a method in which gas is mixed by a method such as stirring or bubbling, or a soluble material is mixed, and after the molding, the soluble material is mixed. Conventionally well-known methods such as a method for dissolving and removing the lysate can be used.
またさらに、多孔質体として、有機珪素高分子化合物、固体炭素、重合性不飽和化合物、乳化剤、重合開始剤、及び、水を混合、撹拌して得られるＷ／Ｏ型エマルジョンを重合させた後、水を蒸発させて得られた多孔質体、あるいは、有機珪素高分子化合物を溶媒に溶解した後、固体炭素と混合、及び／または、固体炭素に含浸し、次いで、溶媒を除去することにより得られたものであることが特に好ましい。特に、前者の多孔質体においては、多孔質体内には、均一な大きさをした球形の気孔が多孔質体全体に分布するため、該多孔質体の比表面積は概して数百〜数千ｍ2／ｋｇと非常に大きく、多孔質体全体に効率よく均質なウイスカーが生成するのに適している。また、後者の多孔質体においても、気孔は連続気孔であるため、多孔質体全体に効率よくウイスカーが生成するのに適している。
Furthermore, after polymerizing a W / O emulsion obtained by mixing and stirring an organic silicon polymer compound, solid carbon, a polymerizable unsaturated compound, an emulsifier, a polymerization initiator, and water as a porous body. The porous body obtained by evaporating water or the organosilicon polymer compound is dissolved in a solvent, mixed with solid carbon, and / or impregnated with solid carbon, and then the solvent is removed. It is particularly preferred that it is obtained. In particular, in the former porous body, since spherical pores of uniform size are distributed throughout the porous body, the specific surface area of the porous body is generally several hundred to several thousand
まず、有機珪素高分子化合物、固体炭素、重合性不飽和化合物、乳化剤、重合開始剤、及び、水を混合撹拌して得られるＷ／Ｏ型エマルジョンを重合させた後、水を蒸発させることによって得られる多孔質体について説明する。用いられる重合性不飽和化合物は、前記した有機珪素高分子化合物、固体炭素、重合性不飽和化合物を含有する組成物を調製する際に用いられるものを使用することができる。すなわち、重合体有機珪素高分子化合物を溶解し、分子中に二重結合を有し、ラジカル重合又はレドックス重合しうるものであれば特に限定しない。このような重合性不飽和化合物としては、スチレン、α−メチルスチレン、ジビニルベンゼン等のスチレン系化合物、メチル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート等の（メタ）アクリル酸エステル類、（メタ）アクリル酸類〔但し、ここにおいて、（メタ）アクリルはアクリルまたはメタクリルを表すものとする〕、ジアリルフタレート、不飽和ポリエステル類等が挙げられる。これらは単独で、或いは、適宜組み合わせて用いることができる。中でも、スチレン系化合物を主成分とした前記重合性不飽和化合物は、有機珪素高分子化合物の溶解性が高いため特に好ましい。 First, by polymerizing a W / O emulsion obtained by mixing and stirring an organic silicon polymer compound, solid carbon, a polymerizable unsaturated compound, an emulsifier, a polymerization initiator, and water, by evaporating the water The obtained porous body will be described. As the polymerizable unsaturated compound to be used, those used in preparing a composition containing the aforementioned organosilicon polymer compound, solid carbon, and polymerizable unsaturated compound can be used. That is, it is not particularly limited as long as it dissolves a polymer organic silicon polymer compound, has a double bond in the molecule, and can undergo radical polymerization or redox polymerization. Such polymerizable unsaturated compounds include styrene compounds such as styrene, α-methylstyrene, divinylbenzene, methyl (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like. Examples include (meth) acrylic acid esters, (meth) acrylic acids (where (meth) acrylic represents acryl or methacrylic), diallyl phthalate, unsaturated polyesters, and the like. These can be used alone or in appropriate combination. Among these, the polymerizable unsaturated compound containing a styrene compound as a main component is particularly preferable because the organosilicon polymer compound has high solubility.
また、乳化剤としては、従来からよく知られ、広く一般に用いられているＷ／Ｏ型エマルジョンを生成する作用を有するものが用いられる。このような乳化剤としてはＨ．Ｌ．Ｂ．が３．５〜６．０程度の界面活性剤があり、例えばソルビタンセスキオレート、ソルビタンモノオレート、ソルビタンモノステアレートなどのソルビタンの高級脂肪酸エステル、グリセロールステアレート、ポリグリセロールオレートなどの高級脂肪酸エステルなどが挙げられる。これらは適宜組み合わせて用いることもできる。このような乳化剤は、重合性不飽和化合物１００重量部に対し１０〜５０重量部、特に２０〜３０重量部使用することが好ましい。 Moreover, as an emulsifier, what has the effect | action which produces | generates the W / O type emulsion well known conventionally and widely used is used. Such emulsifiers include H.E. L. B. There are surfactants having a ratio of about 3.5 to 6.0, for example, higher fatty acid esters of sorbitan such as sorbitan sesquioleate, sorbitan monooleate, sorbitan monostearate, higher fatty acid esters such as glycerol stearate, polyglycerol oleate, etc. Is mentioned. These can also be used in combination as appropriate. Such an emulsifier is preferably used in an amount of 10 to 50 parts by weight, particularly 20 to 30 parts by weight, based on 100 parts by weight of the polymerizable unsaturated compound.
重合開始剤としては、前記した有機珪素高分子化合物、固体炭素、重合性不飽和化合物を含有する組成物の重合の際に用いられるものを使用することができる。即ち通常のラジカル重合開始剤、レドックス重合開始剤が特に制限なく使用できるが、Ｗ／Ｏ型エマルジョンの著しい相分離、水分の蒸発を避けるため１００℃以下で作用するラジカル重合開始剤、レドックス重合開始剤を用いるのが好ましい。これらの例として、過酸化水素、過硫酸アンモニウム、過硫酸カリウム、過酸化ベンゾイル、過酸化ラウロイル、ｔ−ブチルパーオキシオクトエート、ｐ−メンタンヒドロパーオキサイド、ジ−ミリスチルパーオキシジカーボネート、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサンなどの過酸化物系ラジカル重合開始剤、アゾビスイソブチロニトリル、アゾビス−２，４−ジメチルバレロニトリルなどのアゾ系ラジカル重合開始剤、或いは、これらのラジカル重合開始剤とアミン系化合物、有機金属化合物からなるレドックス重合開始剤等が挙げられる。重合開始剤の添加量も、前記同様に、重合性不飽和化合物１００重量部に対して０．０５〜５重量部が好ましい。 As a polymerization initiator, what is used in the case of superposition | polymerization of the composition containing an above-described organosilicon polymer compound, solid carbon, and a polymerizable unsaturated compound can be used. That is, normal radical polymerization initiators and redox polymerization initiators can be used without any particular limitation, but radical polymerization initiators that operate at 100 ° C. or lower to prevent remarkable phase separation of W / O type emulsions and evaporation of water, redox polymerization initiation. It is preferable to use an agent. Examples of these include hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide, lauroyl peroxide, t-butyl peroxyoctoate, p-menthane hydroperoxide, di-myristyl peroxydicarbonate, 1,1. -Peroxide radical polymerization initiators such as bis (t-butylperoxy) cyclohexane, azo radical polymerization initiators such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, or these Examples thereof include a redox polymerization initiator composed of a radical polymerization initiator, an amine compound, and an organometallic compound. Similarly to the above, the addition amount of the polymerization initiator is preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the polymerizable unsaturated compound.
次いで、上記したような、重合性不飽和化合物、乳化剤、重合開始剤と有機珪素高分子化合物、固体炭素、水を用いて多孔質体を製造する。その手順について説明する。まず、有機珪素高分子化合物、固体炭素、重合性不飽和化合物、乳化剤、重合開始剤、及び、水を混合、撹拌してＷ／Ｏ型エマルジョンを生成させる。この際、各原材料の添加順序については特に制限はないが、有機珪素高分子化合物はあらかじめ重合性不飽和化合物に溶解させておくことが好ましい。混合、攪拌には、かい十字型、プロペラ型、タービン型等の攪拌羽根を備えた攪拌機、ボールミル、コロイドミルなどの混合機、ニーダー、スクリュー押出機等の混練機を使用することができる。水の添加量は、得られる多孔質体の気孔率と極めて関係が深く、水の添加量が大きくなると気孔率は大きくなり、逆に添加量が小さくなると気孔率は小さくなる。 Next, a porous body is produced using a polymerizable unsaturated compound, an emulsifier, a polymerization initiator and an organic silicon polymer compound, solid carbon, and water as described above. The procedure will be described. First, an organic silicon polymer compound, solid carbon, a polymerizable unsaturated compound, an emulsifier, a polymerization initiator, and water are mixed and stirred to form a W / O emulsion. At this time, the order of addition of the raw materials is not particularly limited, but the organosilicon polymer compound is preferably dissolved in advance in the polymerizable unsaturated compound. For mixing and stirring, a stirrer equipped with stirring blades such as a cross-shaped, propeller and turbine types, a mixer such as a ball mill and a colloid mill, and a kneader such as a kneader and a screw extruder can be used. The amount of water added is very closely related to the porosity of the resulting porous body. When the amount of water added increases, the porosity increases. Conversely, when the amount added decreases, the porosity decreases.
次いで、得られたＷ／Ｏ型エマルジョンを重合硬化させる。重合温度、重合時間は、Ｗ／Ｏ型エマルジョンの著しい相分離、水の蒸発を避けるため１００℃以下で１〜４８時間とするのが好ましい。このようにして得られた重合物を熱風乾燥、内部加熱乾燥、真空乾燥、凍結乾燥等の方法で乾燥して重合物中に分散した水を蒸発させることにより、有機珪素高分子化合物と固体炭素を含有する多孔質体が得られる。 Next, the obtained W / O emulsion is polymerized and cured. The polymerization temperature and polymerization time are preferably 1 to 48 hours at 100 ° C. or lower in order to avoid significant phase separation of the W / O emulsion and water evaporation. The polymer obtained in this way is dried by a method such as hot air drying, internal heat drying, vacuum drying, freeze drying, and the like, and the water dispersed in the polymer is evaporated to obtain an organosilicon polymer compound and solid carbon. A porous body containing is obtained.
次に、有機珪素高分子化合物を溶媒に溶解した後、固体炭素と混合、及び／または、固体炭素に含浸し、次いで、溶媒を除去することにより得られる多孔質体について説明する。有機珪素高分子化合物を溶解させうる溶媒としては、キシレン、トルエン、ベンゼン等の芳香族系溶媒、クロロホルム、四塩化炭素、１，１，１−トリクロロエタン、１，１，２，２−テトラクロロエタン等の脂肪族系ハロゲン化炭化水素溶媒、エーテル、テトラヒドロフラン等のエーテル系溶媒、ヘキサン等の脂肪族系炭化水素溶媒等が挙げられる。このような溶媒を用いて、固体炭素に溶液状態で有機珪素高分子化合物を混合、及び／または、含浸した後、溶媒を揮発することにより、成形体は固体炭素を核、或いは、骨格とし、その間に有機珪素高分子化合物が固定された連続気孔を有する多孔質構造体とすることができる。またこの際、有機珪素高分子化合物は固体炭素同士の結合材としても作用する。 Next, a porous body obtained by dissolving an organosilicon polymer compound in a solvent, mixing with solid carbon, and / or impregnating the solid carbon, and then removing the solvent will be described. Solvents that can dissolve the organosilicon polymer compound include aromatic solvents such as xylene, toluene, and benzene, chloroform, carbon tetrachloride, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, and the like. Aliphatic hydrocarbon solvents such as ether, ether solvents such as ether and tetrahydrofuran, and aliphatic hydrocarbon solvents such as hexane. Using such a solvent, solid carbon is mixed and / or impregnated with an organosilicon polymer compound in a solution state, and then the solvent is volatilized, whereby the compact has a solid carbon as a nucleus or a skeleton, A porous structure having continuous pores in which the organosilicon polymer compound is fixed in the meantime can be obtained. At this time, the organosilicon polymer compound also acts as a binder between the solid carbons.
多孔質体の気孔率は特に限定するものではないが、多孔質体の気孔率は、３５〜８０％が好ましく、更には、４０〜７０％がより好ましい。気孔率が３５〜８０％であると、ウイスカーが生長するのに必要な空間が十分得られると同時に、多孔質体自身の十分な強度が得られるため、取り扱い時につぶれることがなく好ましい。 The porosity of the porous body is not particularly limited, but the porosity of the porous body is preferably 35 to 80%, and more preferably 40 to 70%. When the porosity is 35 to 80%, a space necessary for growing whiskers can be sufficiently obtained, and at the same time, sufficient strength of the porous body can be obtained.
また、炭化珪素ウイスカー、或いは、窒化珪素ウイスカーの生成を促進させる目的で、以上述べた成形体に、鉄、コバルト、ニッケル、マンガン、タングステン、アルミニウム、及びこれらの金属の酸化物、塩化物、硝酸塩、炭酸塩等の化合物を含有させてもよい。これらの金属及びこれらの金属の化合物が触媒の作用をし、炭化珪素ウイスカー、或いは、窒化珪素ウイスカーの生成が促進される。 In addition, for the purpose of promoting the formation of silicon carbide whiskers or silicon nitride whiskers, the above-described molded body is made of iron, cobalt, nickel, manganese, tungsten, aluminum, and oxides, chlorides, and nitrates of these metals. Further, a compound such as carbonate may be contained. These metals and compounds of these metals act as a catalyst, and the production of silicon carbide whiskers or silicon nitride whiskers is promoted.
以上のようにして得られた成形体を窒素ガス以外の不活性ガス雰囲気中で加熱処理すると炭化珪素ウイスカーが、窒素ガス雰囲気中で加熱処理すると窒化珪素ウイスカーが生成する。 When the molded body obtained as described above is heat-treated in an inert gas atmosphere other than nitrogen gas, silicon carbide whiskers are produced, and when heat-treated in a nitrogen gas atmosphere, silicon nitride whiskers are produced.
次に、加熱処理方法について詳細に説明する。本発明の炭化珪素ウイスカーの製造において、窒素ガス以外の不活性ガス雰囲気中での加熱処理温度は、１１００〜１５５０℃、更には、１２００〜１５００℃が好ましい。１１００〜１５５０℃での加熱処理により、均質で良好な炭化珪素ウイスカーが得られる。不活性ガスとしては、窒素ガスまたは該ガスを主成分とする不活性ガス以外のものであり、アルゴン、ヘリウム、ネオンなどの単独ガスもしくは混合ガスが挙げられるが、なかでも、安価であるアルゴンガスが特に好ましい。不活性ガスは、成形体を入れた炉内に単に充填しておいてもよいし、また、炉内を所望の流速で流すようにしていてもよい。 Next, the heat treatment method will be described in detail. In the production of the silicon carbide whisker of the present invention, the heat treatment temperature in an inert gas atmosphere other than nitrogen gas is preferably 1100 to 1550 ° C, and more preferably 1200 to 1500 ° C. A uniform and good silicon carbide whisker is obtained by heat treatment at 1100 to 1550 ° C. The inert gas is other than nitrogen gas or an inert gas containing the gas as a main component, and includes a single gas or a mixed gas such as argon, helium, neon, etc. Among them, an inexpensive argon gas Is particularly preferred. The inert gas may be simply filled in a furnace containing the molded body, or may flow through the furnace at a desired flow rate.
本発明の窒化珪素ウイスカーの製造において、窒素ガス雰囲気中での加熱処理温度は、１１００〜１６００℃、更には１３００〜１５００℃が好ましい。１１００〜１６００℃での加熱処理により、均質で良好な窒化珪素ウイスカーが得られる。なお、窒素ガスは、成形体を入れた炉内に単に充填しておいてもよいし、また、炉内を所望の流速で流すようにしてもよいが、炉内を所望の流速で流すようにした方が有機珪素高分子化合物の分解ガスと窒素ガスとの反応が効率よく行われるため好ましい。 In the production of the silicon nitride whisker of the present invention, the heat treatment temperature in the nitrogen gas atmosphere is preferably 1100 to 1600 ° C, more preferably 1300 to 1500 ° C. By heat treatment at 1100 to 1600 ° C., uniform and good silicon nitride whiskers can be obtained. Nitrogen gas may be simply filled in the furnace containing the molded body, or it may flow through the furnace at a desired flow rate, but it flows through the furnace at a desired flow rate. This is preferable because the reaction between the decomposition gas of the organosilicon polymer compound and the nitrogen gas is efficiently performed.
なお、成形体の加熱処理に先立ち、成形体中に含まれる有機結合材を分解除去するための予備加熱を行ってもよい。該予備加熱工程において用いられるガスとしては、アルゴン、ヘリウム、ネオン、窒素などの不活性ガスが単独で、或いは、混合ガスの状態で用いられる。予備加熱を行う温度は、有機結合材、有機珪素高分子化合物の種類によって異なるが、一般的には、５００〜９００℃の範囲、特に５００〜６００℃の範囲で行うことが好ましい。またその際、有機結合材の分解ガスにより成形体に膨れやクラックが生じないように昇温速度を調整することが望ましい。 Prior to the heat treatment of the molded body, preliminary heating for decomposing and removing the organic binder contained in the molded body may be performed. As the gas used in the preheating step, an inert gas such as argon, helium, neon, or nitrogen is used alone or in a mixed gas state. The temperature at which the preheating is performed varies depending on the type of the organic binder and the organosilicon polymer compound, but in general, it is preferably performed in the range of 500 to 900 ° C, particularly in the range of 500 to 600 ° C. At this time, it is desirable to adjust the temperature rising rate so that the molded body does not swell or crack due to the decomposition gas of the organic binder.
［作用］
本発明において調製される成形体が、有機結合材あるいは粘度調整剤等の有機成分を含有する場合、該成形体を、窒素ガス以外の不活性ガス雰囲気中、或いは、窒素ガス雰囲気中で加熱処理すると、これらの有機成分は徐々に分解し始め、６００℃までにそのほとんどがガスとなって分解除去される。その際、成形体が多孔質体であると有機結合材の分解ガスは多孔質体の気孔を通じて効率よく排出されるため、有機結合材の除去が容易である。またこの時点において、有機珪素高分子化合物も同様に側鎖の水素やメチル基がガスとなって分解し始めるものの、６００℃付近ではまだその分解は激しくない。一方、成形体に含まれる固体炭素はほとんど分解作用を受けず、成形体は、固体炭素を核、或いは、骨格とし、その固体炭素間に有機珪素高分子化合物が固定された連続気孔を有する多孔質構造体となる。また、有機珪素高分子化合物を溶媒に溶解した後、固体炭素と混合、及び／または、固体炭素に含浸し、次いで、溶媒を除去することにより得られた成形体においては、既に成形体に形成されている多孔質構造が保たれたまま、加熱処理される。
[Action]
When the molded body prepared in the present invention contains an organic component such as an organic binder or a viscosity modifier, the molded body is heated in an inert gas atmosphere other than nitrogen gas or in a nitrogen gas atmosphere. Then, these organic components begin to decompose gradually, and most of them are decomposed and removed by 600 ° C. At this time, if the molded body is a porous body, the decomposition gas of the organic binder is efficiently discharged through the pores of the porous body, so that the organic binder can be easily removed. At this point, the organosilicon polymer compound also begins to decompose with hydrogen and methyl groups in the side chain as gases, but the decomposition is not yet intense at around 600 ° C. On the other hand, the solid carbon contained in the molded body is hardly decomposed, and the molded body has a continuous pore in which the solid silicon is a nucleus or a skeleton, and an organic silicon polymer compound is fixed between the solid carbons. It becomes a quality structure. In addition, a molded body obtained by dissolving an organosilicon polymer compound in a solvent and then mixing with and / or impregnating solid carbon and then removing the solvent is already formed into a molded body. Heat treatment is performed while maintaining the porous structure.
このようにして多孔質構造となった成形体（以下、加熱処理物と呼ぶ）を、引き続き窒素ガス以外の不活性ガス雰囲気中で加熱処理すると、固体炭素との共存効果により発生した有機珪素高分子化合物の分解ガスは、その加熱処理物内の気孔内で炭化珪素ウイスカーとして析出し、更に生長する。また、加熱処理物は連続気孔構造を有するため、有機珪素高分子化合物の分解ガスは局所的にとどまることがなく加熱処理物内全体に拡散し、加熱処理物内全体に均質な炭化珪素ウイスカーが得られると同時に、有機珪素高分子化合物の分解ガスが加熱処理物の表面にも流出するため、該加熱処理物の表面にも炭化珪素ウイスカーが析出し更に生長する。 When the molded body having a porous structure in this way (hereinafter referred to as a heat-treated product) is subsequently heat-treated in an inert gas atmosphere other than nitrogen gas, the high organic silicon generated due to the coexistence effect with solid carbon is obtained. The decomposition gas of the molecular compound precipitates as silicon carbide whiskers in the pores in the heat-treated product, and further grows. In addition, since the heat-treated product has a continuous pore structure, the decomposition gas of the organosilicon polymer compound does not stay locally but diffuses throughout the heat-treated product, and uniform silicon carbide whiskers are formed throughout the heat-treated product. At the same time, the decomposition gas of the organosilicon polymer compound flows out to the surface of the heat-treated product, so that silicon carbide whiskers are deposited on the surface of the heat-treated product and further grow.
一方、前述したようにして多孔質構造となった加熱処理物を窒素ガス雰囲気中で加熱処理すると、固体炭素との共存効果により発生した有機珪素高分子化合物の分解ガスは、その加熱処理物内の気孔内で窒素ガスと反応して窒化珪素ウイスカーとして析出する。その際、加熱処理物は連続気孔構造を有するため、有機珪素高分子化合物の分解ガスは局所的にとどまることがなく加熱処理物全体に拡散するとともに、該気孔を通して加熱処理物内に連続的に窒素ガスが供給されるため、有機珪素高分子化合物の分解ガスと窒素ガスとの反応が連続的に効率よく行われ、加熱処理物内全体に均質な窒化珪素ウイスカーが得られる。更に、有機珪素高分子化合物の分解ガスは気孔を通して加熱処理物の表面にも流出するため、加熱処理物の表面にも窒化珪素ウイスカーが析出し更に生長する。 On the other hand, when the heat-treated product having a porous structure as described above is heat-treated in a nitrogen gas atmosphere, the decomposition gas of the organosilicon polymer compound generated by the coexistence effect with the solid carbon is generated in the heat-treated product. It reacts with nitrogen gas in the pores and precipitates as silicon nitride whiskers. At that time, since the heat-treated product has a continuous pore structure, the decomposition gas of the organosilicon polymer compound does not stay locally but diffuses throughout the heat-treated product and continuously into the heat-treated product through the pores. Since the nitrogen gas is supplied, the reaction between the decomposition gas of the organosilicon polymer compound and the nitrogen gas is continuously and efficiently performed, and a uniform silicon nitride whisker is obtained in the entire heat-treated product. Furthermore, since the decomposition gas of the organosilicon polymer compound flows out to the surface of the heat-treated product through the pores, silicon nitride whiskers are deposited on the surface of the heat-treated product and further grow.
以下、実施例により本発明を更に詳細に説明する。なお、有機珪素高分子化合物、固体炭素、重合性不飽和化合物、乳化剤、粘度調整剤、重合開始剤として以下のものを用いた。
・有機珪素高分子化合物
ポリカルボシラン（数平均分子量 約２５００、日本カーボン株式会社製）
ポリシラスチレン（数平均分子量 約２０００、和光純薬工業株式会社製
・固体炭素
ミルド炭素繊維（ピッチ系、日本板硝子株式会社製）
チョップド炭素繊維（ピッチ系、株式会社ドナック製）
フェルト炭素繊維（ピッチ系、株式会社ドナック製）
・重合性不飽和化合物
スチレン
トリメチロールプロパントリメタクリレート（ＴＭＰＴ）
・乳化剤
ソルビタンセスキオレート
・粘度調整剤
ポリスチレン（石津製薬株式会社製）
石油樹脂（Ｃ５系石油樹脂、ハイレッツＴ−１００Ｘ、三井石油化学工業株式会社製）
・重合開始剤
過酸化ベンゾイル（ＢＰＯ）
過硫酸アンモニウム（ＡＰＳ）
Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the following were used as an organosilicon polymer compound, solid carbon, a polymerizable unsaturated compound, an emulsifier, a viscosity modifier, and a polymerization initiator.
・ Organic silicon polymer compound Polycarbosilane (Number average molecular weight approx. 2500, manufactured by Nippon Carbon Co., Ltd.)
Polysilastyrene (Number average molecular weight: approx. 2000, manufactured by Wako Pure Chemical Industries, Ltd., solid carbon, milled carbon fiber (pitch-based, manufactured by Nippon Sheet Glass Co., Ltd.)
Chopped carbon fiber (pitch-based, manufactured by Donac Co., Ltd.)
Felt carbon fiber (pitch-based, manufactured by Donac Co., Ltd.)
・ Polymerizable unsaturated compounds Styrene Trimethylolpropane trimethacrylate (TMPT)
・ Emulsifier Sorbitan sesquioleate ・ Viscosity modifier Polystyrene (Ishizu Pharmaceutical Co., Ltd.)
Petroleum resin (C5 petroleum resin, Hiretsu T-100X, manufactured by Mitsui Petrochemical Co., Ltd.)
・ Polymerization initiator Benzoyl peroxide (BPO)
Ammonium persulfate (APS)
１．炭化珪素ウイスカーの製造
１．１ 有機珪素高分子化合物、固体炭素、重合性不飽和化合物、重合開始剤を含有する組成物を重合して得られた重合体からの製造。
1. Production of silicon carbide whisker 1.1 Production from a polymer obtained by polymerizing a composition containing an organosilicon polymer compound, solid carbon, a polymerizable unsaturated compound and a polymerization initiator.
ポリカルボシランのスチレン溶液（ポリカルボシラン：１００重量部、スチレン：３３３重量部）４３３重量部、トリメチロールプロパントリメタクリレート（ＴＭＰＴ）３７重量部、ミルド炭素繊維４７０重量部、過酸化ベンゾイル（ＢＰＯ）３．７重量部をポリエチレン製の容器に入れ、プロペラ型攪拌羽根で攪拌し組成物を得た。得られた組成物を型枠に移し込み、６０℃で２４時間重合硬化した後脱型し、成形体を得た。次いで、得られた成形体を雰囲気炉に挿入し、５５０℃で窒素ガスを毎分１リットルの流量で流しながら４時間予備加熱処理することにより、重合体に含まれる重合性不飽和化合物が重合して生成した重合体、及び、重合開始剤を除去した。そして、更に、アルゴンガスを毎分０．５リットルの流速で流しながら１４００℃で５時間加熱処理を行なった。得られた加熱処理物を走査型電子顕微鏡により観察したところ、内部及び表面にウイスカー状のものが生成していた。次いで、大気中で６５０℃で４時間加熱処理して残留する炭素成分を燃焼除去した。得られた淡緑色の生成物を走査型電子顕微鏡により観察したところ、表１に示すように長さが１０〜２５μｍ、直径が０．２〜０．４μｍのウイスカーであることが確認された。更に、このウイスカーのＸ線回折分析を行なったところ、図１に示すような回折線が得られ、β−ＳｉＣであることが確認された。 Styrene solution of polycarbosilane (polycarbosilane: 100 parts by weight, styrene: 333 parts by weight) 433 parts by weight, 37 parts by weight of trimethylolpropane trimethacrylate (TMPT), 470 parts by weight of milled carbon fiber, benzoyl peroxide (BPO) 3.7 parts by weight were put in a polyethylene container and stirred with a propeller-type stirring blade to obtain a composition. The obtained composition was transferred to a mold, polymerized and cured at 60 ° C. for 24 hours, and then demolded to obtain a molded body. Next, the obtained molded body was inserted into an atmosphere furnace, and preheated for 4 hours while flowing nitrogen gas at a flow rate of 1 liter at 550 ° C. per minute, whereby the polymerizable unsaturated compound contained in the polymer was polymerized. The polymer produced in this manner and the polymerization initiator were removed. Further, heat treatment was performed at 1400 ° C. for 5 hours while flowing argon gas at a flow rate of 0.5 liters per minute. When the obtained heat-treated product was observed with a scanning electron microscope, whisker-like products were generated inside and on the surface. Subsequently, the remaining carbon component was burned and removed by heat treatment at 650 ° C. for 4 hours in the atmosphere. When the obtained light green product was observed with a scanning electron microscope, it was confirmed that the whisker had a length of 10 to 25 μm and a diameter of 0.2 to 0.4 μm as shown in Table 1. Furthermore, when X-ray diffraction analysis of this whisker was performed, a diffraction line as shown in FIG. 1 was obtained, and it was confirmed that it was β-SiC.
表１に示す組成からなる組成物を実施例１と同様にして重合硬化、成形し、成形体を作製した。次いで、加熱処理温度を１３５０℃に変える以外は実施例１と同様にして成形体を加熱処理して、淡緑色の生成物を得た。得られた生成物を走査電子顕微鏡により観察したところ、表１に示すように、長さが１０〜２５μｍ、直径が０．２〜０．３μｍのウイスカーであることが確認された。更に、このウイスカーのＸ線回折分析を行なったところ、図１に示したと同様な回折線が得られ、β−ＳｉＣであることが確認された。 A composition comprising the composition shown in Table 1 was polymerized and cured in the same manner as in Example 1 to produce a molded body. Next, the green body was heat-treated in the same manner as in Example 1 except that the heat treatment temperature was changed to 1350 ° C. to obtain a light green product. When the obtained product was observed with a scanning electron microscope, as shown in Table 1, it was confirmed that the whisker had a length of 10 to 25 μm and a diameter of 0.2 to 0.3 μm. Further, when X-ray diffraction analysis of this whisker was performed, a diffraction line similar to that shown in FIG. 1 was obtained, and it was confirmed that it was β-SiC.
表１に示す組成からなる組成物を実施例１と同様にして重合硬化、成形し、成形体を作製した。次いで、加熱処理温度を１２５０℃に変える以外は実施例１と同様にして成形体を加熱処理して、淡緑色の生成物を得た。得られた生成物を走査電子顕微鏡により観察したところ、表１に示すように、長さが１０〜１５μｍ、直径が０．４〜０．６μｍのウイスカーであることが確認された。更に、このウイスカーのＸ線回折分析を行なったところ、図１に示したと同様な回折線が得られ、β−ＳｉＣであることが確認された。 A composition comprising the composition shown in Table 1 was polymerized and cured in the same manner as in Example 1 to produce a molded body. Subsequently, the green body was heat-treated in the same manner as in Example 1 except that the heat treatment temperature was changed to 1250 ° C., to obtain a light green product. When the obtained product was observed with a scanning electron microscope, as shown in Table 1, it was confirmed that the whisker had a length of 10 to 15 μm and a diameter of 0.4 to 0.6 μm. Further, when X-ray diffraction analysis of this whisker was performed, a diffraction line similar to that shown in FIG. 1 was obtained, and it was confirmed that it was β-SiC.
１．２ 有機珪素高分子化合物、固体炭素、重合性不飽和化合物、乳化剤、重合開始剤、及び、水を混合、撹拌して得られるＷ／Ｏ型エマルジョンを重合させた後、水を蒸発させて得られた多孔質体からの製造。 1.2 Polymerize W / O emulsion obtained by mixing and stirring organic silicon polymer compound, solid carbon, polymerizable unsaturated compound, emulsifier, polymerization initiator, and water, and then evaporate water. From a porous material obtained in this way.
ポリカルボシランのスチレン溶液（ポリカルボシラン：１００重量部、スチレン：１４４重量部）２４４重量部、トリメチロールプロパントリメタクリレート（ＴＭＰＴ）１６重量部、ソルビタンセスキオレート（ＳＳＯ）４０重量部、ミルド炭素繊維４７０重量部をポリエチレン製の容器に入れ、プロペラ型攪拌羽根で攪拌し分散混合物を得た。次いで、これに、過硫酸アンモニウム（ＡＰＳ）１．６重量部を溶かした水４７０重量部を徐々に加えながら、更に激しく攪拌したところ安定なＷ／Ｏ型エマルジョンが得られた。得られたＷ／Ｏ型エマルジョンを型枠に流し込み、６０℃で２４時間重合硬化した後脱型し、６０℃で乾燥してポリカルボシランと固体炭素を含む多孔質体が得られた。次いで、得られた多孔質体を雰囲気炉に挿入し、５５０℃で窒素ガスを毎分１リットルの流量で流しながら４時間予備加熱処理することにより、多孔質体に含まれる重合性不飽和化合物が重合して生成した重合体、乳化剤、及び、重合開始剤を除去した。そして、更に、アルゴンガスを毎分０．５リットルの流速で流しながら１３００℃で５時間加熱処理を行なった。加熱処理後、大気中で６５０℃で４時間加熱処理して残留する炭素成分を燃焼除去した。得られた淡緑色の生成物の電子顕微鏡写真を撮影したところ、表２に示すように、長さが１０〜２５μｍ、直径が０．２〜０．４μｍのウイスカーであることが確認された。更に、このウイスカーのＸ線回折を行なったところ、図２に示すような回折線が得られ、β−ＳｉＣであることが確認された。 Styrene solution of polycarbosilane (polycarbosilane: 100 parts by weight, styrene: 144 parts by weight) 244 parts by weight, trimethylolpropane trimethacrylate (TMPT) 16 parts by weight, sorbitan sesquiolate (SSO) 40 parts by weight, milled carbon fiber 470 parts by weight was placed in a polyethylene container and stirred with a propeller-type stirring blade to obtain a dispersion mixture. Next, 470 parts by weight of water in which 1.6 parts by weight of ammonium persulfate (APS) was dissolved was gradually added to this, and further stirred vigorously to obtain a stable W / O type emulsion. The obtained W / O emulsion was poured into a mold, polymerized and cured at 60 ° C. for 24 hours, demolded, and dried at 60 ° C. to obtain a porous body containing polycarbosilane and solid carbon. Next, the obtained porous body is inserted into an atmospheric furnace, and preheated for 4 hours while flowing nitrogen gas at a flow rate of 1 liter per minute at 550 ° C., so that the polymerizable unsaturated compound contained in the porous body The polymer, the emulsifier, and the polymerization initiator produced by polymerization were removed. Further, heat treatment was performed at 1300 ° C. for 5 hours while flowing argon gas at a flow rate of 0.5 liters per minute. After the heat treatment, the remaining carbon component was burned and removed by heat treatment in the atmosphere at 650 ° C. for 4 hours. When an electron micrograph of the obtained pale green product was taken, it was confirmed that the whisker had a length of 10 to 25 μm and a diameter of 0.2 to 0.4 μm as shown in Table 2. Further, when X-ray diffraction of this whisker was performed, a diffraction line as shown in FIG. 2 was obtained, and it was confirmed to be β-SiC.
表２に示す組成からなる分散混合物を実施例４と同様にして重合硬化、成形して多孔質体を作製した。次いで得られた多孔質体の加熱処理温度を１５００℃に変える以外実施例４と全く同様にして加熱処理を行ない淡緑色の生成物を得た。得られた淡緑色の生成物を走査電子顕微鏡により観察したところ、表２に示すように、長さが１０〜１５μｍ、直径が０．３〜０．６μｍのウイスカーであることが確認された。更に、このウイスカーのＸ線回折分析を行なったところ、図２に示したと同様な回折線が得られ、β−ＳｉＣであることが確認された。 A dispersion mixture having the composition shown in Table 2 was polymerized and cured in the same manner as in Example 4 to prepare a porous body. Subsequently, heat treatment was performed in the same manner as in Example 4 except that the heat treatment temperature of the obtained porous body was changed to 1500 ° C., and a light green product was obtained. When the obtained pale green product was observed with a scanning electron microscope, as shown in Table 2, it was confirmed that the whisker had a length of 10 to 15 μm and a diameter of 0.3 to 0.6 μm. Further, when X-ray diffraction analysis of this whisker was performed, a diffraction line similar to that shown in FIG. 2 was obtained, and it was confirmed that the whisker was β-SiC.
表２に示す組成からなる分散混合物を実施例４と同様にして重合硬化、成形して多孔質体を作製した。次いで得られた多孔質体の加熱処理温度を１４００℃に変える以外実施例４と全く同様にして加熱処理を行ない淡緑色の生成物を得た。得られた淡緑色の生成物を走査電子顕微鏡により観察したところ、表２に示すように、長さが２０〜３０μｍ、直径が０．２〜０．４μｍのウイスカーであることが確認された。更に、このウイスカーのＸ線回折分析を行なったところ、図２に示したと同様な回折線が得られ、β−ＳｉＣであることが確認された。 A dispersion mixture having the composition shown in Table 2 was polymerized and cured in the same manner as in Example 4 to prepare a porous body. Subsequently, heat treatment was performed in the same manner as in Example 4 except that the heat treatment temperature of the obtained porous body was changed to 1400 ° C., and a light green product was obtained. When the obtained light green product was observed with a scanning electron microscope, as shown in Table 2, it was confirmed that the whisker had a length of 20 to 30 μm and a diameter of 0.2 to 0.4 μm. Further, when X-ray diffraction analysis of this whisker was performed, a diffraction line similar to that shown in FIG. 2 was obtained, and it was confirmed that the whisker was β-SiC.
［比較例１］
ミルド炭素繊維を添加しない以外は実施例４と全く同様にしてポリカルボシランを含む多孔質体を得た。次いで、実施例４と全く同様にして加熱処理を行なった。得られた生成物の電子顕微鏡写真を撮影したところ、ウイスカーの生成は全く認められなかった。更に生成物のＸ線回折を行なったところ、２θで３５．７゜、４１．５゜、６０．０゜、７１．８゜、７５．５゜にピークが認められたものの非常にブロードであり、非晶質のβ−ＳｉＣであることが確認された。
[Comparative Example 1]
A porous body containing polycarbosilane was obtained in the same manner as in Example 4 except that no milled carbon fiber was added. Next, heat treatment was performed in the same manner as in Example 4. When an electron micrograph of the obtained product was taken, no whisker formation was observed. Further, X-ray diffraction of the product revealed that peaks were observed at 25.7 at 35.7 °, 41.5 °, 60.0 °, 71.8 ° and 75.5 °, but it was very broad. Was confirmed to be amorphous β-SiC.
１．３ 有機珪素高分子化合物を溶媒に溶解した後、固体炭素と混合、及び／または、固体炭素に含浸し、次いで、溶媒を除去することにより得られた多孔質体からの製造。 1.3 Production from a porous material obtained by dissolving an organosilicon polymer compound in a solvent, mixing with solid carbon, and / or impregnating the solid carbon, and then removing the solvent.
ポリカルボシラン１００重量部とクロロホルム５００重量部をポリエチレン製の容器に入れ、プロペラ型攪拌羽根で攪拌し、ポリカルボシランを完全に溶解した。次いで、これにミルド炭素繊維２５０重量部を加えた後、激しく攪拌して混合物を得た。得られた混合物を６０℃で２４時間乾燥してクロロホルムを完全に揮散させた。得られた組成物は多孔質状の固形でありハンドリングが容易であった。次いで、得られた多孔質体を雰囲気炉に挿入し、１３５０℃でアルゴンガスを毎分０．５リットルの流量で流しながら５時間加熱処理を行なった。得られた加熱処理物を走査型電子顕微鏡により観察したところ、内部及び表面にウイスカー状のものが生成していた。次いで、大気中で６５０℃で４時間加熱処理して残留する炭素成分を燃焼除去した。得られた淡緑色の生成物を走査型電子顕微鏡により観察したところ、表３に示すように長さが１０〜２５μｍ、直径が０．３〜０．６μｍのウイスカー状であることが確認された。更に、このウイスカー状の生成物のＸ線回折を行なったところ、図３に示すような回折線が得られ、β−ＳｉＣであることが確認された。 100 parts by weight of polycarbosilane and 500 parts by weight of chloroform were put into a polyethylene container and stirred with a propeller-type stirring blade to completely dissolve the polycarbosilane. Next, 250 parts by weight of milled carbon fiber was added thereto, and then the mixture was vigorously stirred to obtain a mixture. The obtained mixture was dried at 60 ° C. for 24 hours to completely evaporate chloroform. The resulting composition was a porous solid and easy to handle. Next, the obtained porous body was inserted into an atmospheric furnace, and heat treatment was performed at 1350 ° C. for 5 hours while flowing argon gas at a flow rate of 0.5 liters per minute. When the obtained heat-treated product was observed with a scanning electron microscope, whisker-like products were generated inside and on the surface. Subsequently, the remaining carbon component was burned and removed by heat treatment at 650 ° C. for 4 hours in the atmosphere. When the obtained light green product was observed with a scanning electron microscope, as shown in Table 3, it was confirmed to be a whisker shape having a length of 10 to 25 μm and a diameter of 0.3 to 0.6 μm. . Furthermore, when X-ray diffraction of this whisker-like product was performed, a diffraction line as shown in FIG. 3 was obtained, and it was confirmed that it was β-SiC.
表３に示す組成の混合物から実施例７と同様にして多孔質体を作製した。次いで、加熱処理温度を１２５０℃に変える以外は実施例７と同様にして加熱処理を行い、淡緑色の生成物を得た。得られた生成物を走査電子顕微鏡により観察したところ、表３に示すように、長さが１０〜２０μｍ、直径が０．２〜０．４μｍのウイスカーであることが確認された。更に、このウイスカーのＸ線回折を行なったところ、図３に示したと同様な回折線が得られ、β−ＳｉＣであることが確認された。 A porous body was produced from the mixture having the composition shown in Table 3 in the same manner as in Example 7. Subsequently, heat treatment was performed in the same manner as in Example 7 except that the heat treatment temperature was changed to 1250 ° C., and a light green product was obtained. When the obtained product was observed with a scanning electron microscope, as shown in Table 3, it was confirmed that the whisker had a length of 10 to 20 μm and a diameter of 0.2 to 0.4 μm. Furthermore, when X-ray diffraction of this whisker was performed, a diffraction line similar to that shown in FIG. 3 was obtained, and it was confirmed that the whisker was β-SiC.
表３に示す組成の混合物から実施例７と同様にして多孔質体を作製した。次いで、加熱処理温度を１３５０℃に変える以外は実施例７と同様にして加熱処理を行い、淡緑色の生成物を得た。得られた生成物を走査電子顕微鏡により観察したところ、表３に示すように、長さが１０〜２５μｍ、直径が０．３〜０．７μｍのウイスカーであることが確認された。更に、このウイスカーのＸ線回折を行なったところ、図３に示したと同様な回折線が得られ、β−ＳｉＣであることが確認された。 A porous body was produced from the mixture having the composition shown in Table 3 in the same manner as in Example 7. Subsequently, heat treatment was performed in the same manner as in Example 7 except that the heat treatment temperature was changed to 1350 ° C., and a light green product was obtained. When the obtained product was observed with a scanning electron microscope, as shown in Table 3, it was confirmed that the whisker had a length of 10 to 25 μm and a diameter of 0.3 to 0.7 μm. Furthermore, when X-ray diffraction of this whisker was performed, a diffraction line similar to that shown in FIG. 3 was obtained, and it was confirmed that the whisker was β-SiC.
２．窒化珪素ウイスカーの製造
２．１ 有機珪素高分子化合物、固体炭素、重合性不飽和化合物、重合開始剤を含有する組成物を重合して得られた成形体からの製造。
2. 2. Production of silicon nitride whisker 2.1 Production from a molded product obtained by polymerizing a composition containing an organosilicon polymer compound, solid carbon, a polymerizable unsaturated compound, and a polymerization initiator.
ポリカルボシラン及びポリスチレンのスチレン溶液（ポリカルボシラン：１００重量部、ポリスチレン：４００重量部、スチレン：９００重量部）１４００重量部、トリメチロールプロパントリメタクリレート（ＴＭＰＴ）１００重量部、ミルド炭素繊維５００重量部、過酸化ベンゾイル（ＢＰＯ）１０重量部をポリエチレン製の容器に入れ、プロペラ型攪拌羽根で攪拌し組成物を得た。得られた組成物を型枠に移し込み、６０℃で２４時間重合硬化した後脱型し、成形体を得た。次いで、得られた成形体を雰囲気炉に挿入し、１３５０℃で窒素ガスを毎分１リットルの流量で流しながら５時間加熱処理を行なった。得られた加熱処理物を走査型電子顕微鏡により観察したところ、内部及び表面にウイスカー状のものが生成していた。次いで、大気中で６５０℃で４時間加熱処理して残留する炭素成分を燃焼除去した。得られた灰白色の生成物を走査型電子顕微鏡により観察したところ、表４に示すように、長さが１０〜３０μｍ、直径が０．３〜０．９μｍのウイスカーであることが確認された。更に、このウイスカーのＸ線回折分析を行なったところ、図４に示すような回折線が得られ、α−Ｓｉ3Ｎ4であることが確認された。 Polycarbosilane and polystyrene styrene solution (polycarbosilane: 100 parts by weight, polystyrene: 400 parts by weight, styrene: 900 parts by weight) 1400 parts by weight, trimethylolpropane trimethacrylate (TMPT) 100 parts by weight, milled carbon fiber 500 parts by weight Part and 10 parts by weight of benzoyl peroxide (BPO) were put in a polyethylene container and stirred with a propeller type stirring blade to obtain a composition. The obtained composition was transferred to a mold, polymerized and cured at 60 ° C. for 24 hours, and then demolded to obtain a molded body. Next, the obtained molded body was inserted into an atmospheric furnace, and heat treatment was performed at 1350 ° C. for 5 hours while flowing nitrogen gas at a flow rate of 1 liter per minute. When the obtained heat-treated product was observed with a scanning electron microscope, whisker-like products were generated inside and on the surface. Subsequently, the remaining carbon component was burned and removed by heat treatment at 650 ° C. for 4 hours in the atmosphere. When the obtained grayish white product was observed with a scanning electron microscope, as shown in Table 4, it was confirmed that the whisker had a length of 10 to 30 μm and a diameter of 0.3 to 0.9 μm. Further, when X-ray diffraction analysis of this whisker was performed, a diffraction line as shown in FIG. 4 was obtained, and it was confirmed to be α-Si 3 N 4.
表４に示す組成からなる組成物を実施例１０と同様にして重合硬化、成形し、成形体を作製した。次いで、実施例１０と同様にして成形体を加熱処理して、灰白色の生成物を得た。得られた生成物を走査電子顕微鏡により観察したところ、表４に示すように、長さが１０〜４０μｍ、直径が０．５〜１．５μｍのウイスカーであることが確認された。更に、このウイスカーのＸ線回折分析を行なったところ、図４に示したと同様な回折線が得られ、α−Ｓｉ3Ｎ4であることが確認された。 A composition comprising the composition shown in Table 4 was polymerized and cured in the same manner as in Example 10 to produce a molded body. Subsequently, the molded body was heat-treated in the same manner as in Example 10 to obtain an off-white product. When the obtained product was observed with a scanning electron microscope, as shown in Table 4, it was confirmed that the whisker had a length of 10 to 40 μm and a diameter of 0.5 to 1.5 μm. Further, when X-ray diffraction analysis of this whisker was performed, a diffraction line similar to that shown in FIG. 4 was obtained, and it was confirmed that it was α-Si 3 N 4 .
表４に示す組成からなる組成物を実施例１０と同様にして重合硬化、成形し、成形体を作製した。次いで、加熱処理温度を１４５０℃に変える以外は実施例１０と同様にして成形体を加熱処理して、灰白色の生成物を得た。得られた生成物を走査電子顕微鏡により観察したところ、表４に示すように、長さが３０〜５０μｍ、直径が０．８〜２．０μｍのウイスカーであることが確認された。更に、このウイスカーのＸ線回折分析を行なったところ、図４に示したと同様な回折線が得られ、α−Ｓｉ3Ｎ4であることが確認された。 A composition comprising the composition shown in Table 4 was polymerized and cured in the same manner as in Example 10 to produce a molded body. Next, the molded body was heat-treated in the same manner as in Example 10 except that the heat treatment temperature was changed to 1450 ° C., and an off-white product was obtained. When the obtained product was observed with a scanning electron microscope, as shown in Table 4, it was confirmed to be a whisker having a length of 30 to 50 μm and a diameter of 0.8 to 2.0 μm. Further, when X-ray diffraction analysis of this whisker was performed, a diffraction line similar to that shown in FIG. 4 was obtained, and it was confirmed that it was α-Si 3 N 4 .
２．２ 有機珪素高分子化合物、固体炭素、重合性不飽和化合物、乳化剤、重合開始剤、及び、水を混合、撹拌して得られるＷ／Ｏ型エマルジョンを重合させた後、水を蒸発させて得られた多孔質体からの製造。 2.2 Polymerize W / O emulsion obtained by mixing and stirring organosilicon polymer compound, solid carbon, polymerizable unsaturated compound, emulsifier, polymerization initiator and water, and then evaporating water. From a porous material obtained in this way.
ポリカルボシランのスチレン溶液（ポリカルボシラン：１００重量部、スチレン：２７０重量部）３７０重量部、トリメチロールプロパントリメタクリレート（ＴＭＰＴ）３０重量部、ソルビタンセスキオレート（ＳＳＯ）７５重量部、ミルド炭素繊維４７０重量部をポリエチレン製の容器に入れ、プロペラ型攪拌羽根で攪拌し分散混合物を得た。次いで、これに、過硫酸アンモニウム（ＡＰＳ）３重量部を溶かした水９７０重量部を徐々に加えながら、更に激しく攪拌したところ安定なＷ／Ｏ型エマルジョンが得られた。得られたＷ／Ｏ型エマルジョンを型枠に流し込み、６０℃で２４時間重合硬化した後脱型し、６０℃で乾燥してポリカルボシランと固体炭素を含む多孔質体を得た。次いで、得られた多孔質体を雰囲気炉に挿入し、１４００℃で窒素ガスを毎分１リットルの流量で流しながら５時間加熱処理を行なった。得られた加熱処理物を走査型電子顕微鏡により観察したところ、内部及び表面にウイスカー状のものが生成していた。次いで、大気中で６５０℃で４時間加熱処理して残留する炭素成分を燃焼除去した。得られた灰白色の生成物を走査電子顕微鏡により観察したところ、表５に示すように長さが１０〜２０μｍ、直径が０．３〜０．６μｍのウイスカーであることが確認された。更に、このウイスカーのＸ線回折を行なったところ、図５に示すような回折線が得られ、α−Ｓｉ3Ｎ4であることが確認された。 Styrene solution of polycarbosilane (polycarbosilane: 100 parts by weight, styrene: 270 parts by weight) 370 parts by weight, trimethylolpropane trimethacrylate (TMPT) 30 parts by weight, sorbitan sesquiolate (SSO) 75 parts by weight, milled carbon fiber 470 parts by weight was placed in a polyethylene container and stirred with a propeller-type stirring blade to obtain a dispersion mixture. Next, 970 parts by weight of water in which 3 parts by weight of ammonium persulfate (APS) was dissolved was gradually added to this, and further stirred vigorously to obtain a stable W / O type emulsion. The obtained W / O emulsion was poured into a mold, polymerized and cured at 60 ° C. for 24 hours, demolded, and dried at 60 ° C. to obtain a porous body containing polycarbosilane and solid carbon. Next, the obtained porous body was inserted into an atmospheric furnace, and heat treatment was performed at 1400 ° C. for 5 hours while flowing nitrogen gas at a flow rate of 1 liter per minute. When the obtained heat-treated product was observed with a scanning electron microscope, whisker-like products were generated inside and on the surface. Subsequently, the remaining carbon component was burned and removed by heat treatment at 650 ° C. for 4 hours in the atmosphere. When the obtained grayish white product was observed with a scanning electron microscope, it was confirmed that the whisker had a length of 10 to 20 μm and a diameter of 0.3 to 0.6 μm as shown in Table 5. Further, when X-ray diffraction of this whisker was performed, a diffraction line as shown in FIG. 5 was obtained, and it was confirmed to be α-Si 3 N 4.
表５に示す組成からなる分散混合物を実施例１３と同様にして重合硬化、成形して多孔質体を作製した。次いで、加熱処理温度を１３００℃に変える以外は実施例１３と同様にして多孔質体を加熱処理して、灰白色の生成物を得た。得られた生成物を走査電子顕微鏡により観察した結果、表５に示すように、長さが１０〜４０μｍ、直径が０．３〜０．９μｍのウイスカーであることが確認された。更に、このウイスカーのＸ線回折を行なったところ、図５に示したと同様な回折線が得られ、α−Ｓｉ3Ｎ4であることが確認された。 A dispersion mixture having the composition shown in Table 5 was polymerized and cured in the same manner as in Example 13 to prepare a porous body. Next, the porous body was heat-treated in the same manner as in Example 13 except that the heat treatment temperature was changed to 1300 ° C., and an off-white product was obtained. As a result of observing the obtained product with a scanning electron microscope, as shown in Table 5, it was confirmed that the whisker had a length of 10 to 40 μm and a diameter of 0.3 to 0.9 μm. Further, when X-ray diffraction of this whisker was performed, a diffraction line similar to that shown in FIG. 5 was obtained, and it was confirmed that the whisker was α-Si 3 N 4 .
表５に示す組成からなる分散混合物を実施例１３と同様にして重合硬化、成形して多孔質体を作製した。次いで、加熱処理温度を１５００℃に変える以外は実施例１３と同様にして多孔質体を加熱処理して、灰白色の生成物を得た。得られた生成物を走査電子顕微鏡により観察した結果、表５に示すように、長さが２０〜４０μｍ、直径が０．３〜０．８μｍのウイスカーであることが確認された。更に、このウイスカーのＸ線回折を行なったところ、図５に示したと同様な回折線が得られ、α−Ｓｉ3Ｎ4であることが確認された。 A dispersion mixture having the composition shown in Table 5 was polymerized and cured in the same manner as in Example 13 to prepare a porous body. Subsequently, the porous body was heat-treated in the same manner as in Example 13 except that the heat treatment temperature was changed to 1500 ° C., and an off-white product was obtained. As a result of observing the obtained product with a scanning electron microscope, as shown in Table 5, it was confirmed that the whisker had a length of 20 to 40 μm and a diameter of 0.3 to 0.8 μm. Further, when X-ray diffraction of this whisker was performed, a diffraction line similar to that shown in FIG. 5 was obtained, and it was confirmed that the whisker was α-Si 3 N 4 .
［比較例２］
ミルド炭素繊維を使用しない以外は実施例１３と全く同様にして多孔質体を得た。次いで、得られた多孔質体に対して実施例１３と同様にして１４００℃で窒素ガスを毎分１リットルの流量で流しながら５時間加熱処理を行なった。得られた加熱処理物を走査電子顕微鏡により観察したところ、内部には全くウイスカーは認められず、表面に極僅か毛玉状のウイスカーが生成しているだけであった。
[Comparative Example 2]
A porous body was obtained in the same manner as in Example 13 except that milled carbon fiber was not used. Subsequently, the obtained porous body was subjected to a heat treatment in the same manner as in Example 13 at 1400 ° C. for 5 hours while flowing nitrogen gas at a flow rate of 1 liter per minute. When the obtained heat-treated product was observed with a scanning electron microscope, no whisker was found inside, and only a slight hairball-like whisker was formed on the surface.
［比較例３］
ポリカルボシランのみを粉末のままで、実施例１３と同様にして１４００℃で窒素ガスを毎分１リットルの流量で流しながら５時間加熱処理を行なった。得られた生成物を走査電子顕微鏡により観察したがウイスカーの生成は全く認められなかった。
[Comparative Example 3]
Heat treatment was carried out for 5 hours while flowing only nitrogen gas at a flow rate of 1 liter / min at 1400 ° C. in the same manner as in Example 13 while maintaining only the polycarbosilane. When the obtained product was observed with a scanning electron microscope, no whisker formation was observed.
２．３ 有機珪素高分子化合物を溶媒に溶解した後、固体炭素と混合、及び／または、固体炭素に含浸し、次いで、溶媒を除去することにより得られた多孔質体からの製造。 2.3 Production from a porous body obtained by dissolving an organosilicon polymer compound in a solvent, mixing with solid carbon, and / or impregnating the solid carbon, and then removing the solvent.
ポリシラスチレン１００重量部とクロロホルム１０００重量部をポリエチレン製の容器に入れ、プロペラ型攪拌羽根で攪拌し、ポリシラスチレンを完全に溶解した。次いで、これにミルド炭素繊維５００重量部を加えた後、激しく攪拌して混合物を得た。得られた混合物を６０℃で２４時間乾燥してクロロホルムを完全に揮散させた。得られた組成物は多孔質状の固形でありハンドリングが容易であった。次いで、得られた多孔質体を雰囲気炉に挿入し、１３５０℃で窒素ガスを毎分１リットルの流量で流しながら５時間加熱処理を行なった。得られた加熱処理物を走査型電子顕微鏡により観察したところ、内部及び表面にウイスカー状のものが生成していた。次いで、大気中で６５０℃で４時間加熱処理して残留する炭素成分を燃焼除去した。得られた灰白色の生成物を走査型電子顕微鏡により観察したところ、表６に示すように長さが２５〜４０μｍ、直径が０．５〜１．５μｍのウイスカー状であることが確認された。更に、このウイスカー状の生成物のＸ線回折を行なったところ、図６に示すような回折線が得られ、α−Ｓｉ3Ｎ4であることが確認された。 100 parts by weight of polysilastyrene and 1000 parts by weight of chloroform were placed in a polyethylene container and stirred with a propeller-type stirring blade to completely dissolve the polysilastyrene. Next, 500 parts by weight of milled carbon fiber was added thereto, followed by vigorous stirring to obtain a mixture. The obtained mixture was dried at 60 ° C. for 24 hours to completely evaporate chloroform. The resulting composition was a porous solid and easy to handle. Next, the obtained porous body was inserted into an atmospheric furnace, and heat treatment was performed at 1350 ° C. for 5 hours while flowing nitrogen gas at a flow rate of 1 liter per minute. When the obtained heat-treated product was observed with a scanning electron microscope, whisker-like products were generated inside and on the surface. Subsequently, the remaining carbon component was burned and removed by heat treatment at 650 ° C. for 4 hours in the atmosphere. When the obtained grayish white product was observed with a scanning electron microscope, as shown in Table 6, it was confirmed that the whisker shape had a length of 25 to 40 μm and a diameter of 0.5 to 1.5 μm. Furthermore, when X-ray diffraction of this whisker-like product was performed, a diffraction line as shown in FIG. 6 was obtained, and it was confirmed to be α-Si 3 N 4 .
表６に示す組成の混合物から実施例１６と同様にして多孔質体を作製した。次いで、加熱処理温度を１４５０℃に変える以外は実施例１６と同様にして組成物を加熱処理して、灰白色の生成物を得た。得られた生成物を走査電子顕微鏡により観察したところ、表６に示すように、長さが１５〜２５μｍ、直径が０．５〜１．０μｍのウイスカーであることが確認された。更に、このウイスカーのＸ線回折を行なったところ、図６に示したと同様な回折線が得られ、α−Ｓｉ3Ｎ4、であることが確認された。 A porous body was produced from the mixture having the composition shown in Table 6 in the same manner as in Example 16. Subsequently, the composition was heat-treated in the same manner as in Example 16 except that the heat treatment temperature was changed to 1450 ° C., and an off-white product was obtained. When the obtained product was observed with a scanning electron microscope, as shown in Table 6, it was confirmed that the whisker had a length of 15 to 25 μm and a diameter of 0.5 to 1.0 μm. Further, when X-ray diffraction of this whisker was performed, a diffraction line similar to that shown in FIG. 6 was obtained, and it was confirmed that it was α-Si 3 N 4 .
表６に示す組成の混合物から実施例１６と同様にして多孔質体を作製した。次いで、加熱処理温度を１３５０℃に変える以外は実施例１６と同様にして組成物を加熱処理して、灰白色の生成物を得た。得られた生成物を走査電子顕微鏡により観察したところ、表６に示すように、長さが１０〜２０μｍ、直径が０．５〜１．０μｍのウイスカーであることが確認された。更に、このウイスカーのＸ線回折を行なったところ、図６に示したと同様な回折線が得られ、α−Ｓｉ3Ｎ4であることが確認された。 A porous body was produced from the mixture having the composition shown in Table 6 in the same manner as in Example 16. Subsequently, the composition was heat-treated in the same manner as in Example 16 except that the heat treatment temperature was changed to 1350 ° C., and an off-white product was obtained. When the obtained product was observed with a scanning electron microscope, as shown in Table 6, it was confirmed that the whisker had a length of 10 to 20 μm and a diameter of 0.5 to 1.0 μm. Further, when X-ray diffraction of this whisker was performed, a diffraction line similar to that shown in FIG. 6 was obtained, and it was confirmed that it was α-Si 3 N 4 .
Claims (8)
The method for manufacturing a silicon nitride whisker according to claim 1, wherein the heat treatment is performed in a temperature range of 1100 to 1600 ° C.
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