JPH04119999A - Production of large-diameter silicon carbide whisker - Google Patents
Production of large-diameter silicon carbide whiskerInfo
- Publication number
- JPH04119999A JPH04119999A JP2235854A JP23585490A JPH04119999A JP H04119999 A JPH04119999 A JP H04119999A JP 2235854 A JP2235854 A JP 2235854A JP 23585490 A JP23585490 A JP 23585490A JP H04119999 A JPH04119999 A JP H04119999A
- Authority
- JP
- Japan
- Prior art keywords
- silicon carbide
- silicon
- group
- catalyst
- gas
- 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.)
- Pending
Links
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- KHDSWONFYIAAPE-UHFFFAOYSA-N silicon sulfide Chemical compound S=[Si]=S KHDSWONFYIAAPE-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 28
- 229910021332 silicide Inorganic materials 0.000 claims abstract description 21
- 150000002739 metals Chemical class 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021343 molybdenum disilicide Inorganic materials 0.000 claims abstract description 5
- DFJQEGUNXWZVAH-UHFFFAOYSA-N bis($l^{2}-silanylidene)titanium Chemical compound [Si]=[Ti]=[Si] DFJQEGUNXWZVAH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 239000010955 niobium Substances 0.000 claims abstract description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910021352 titanium disilicide Inorganic materials 0.000 claims abstract description 3
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 22
- 239000004480 active ingredient Substances 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000758 substrate Substances 0.000 abstract description 10
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 239000010703 silicon Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 40
- 230000006911 nucleation Effects 0.000 description 18
- 238000010899 nucleation Methods 0.000 description 18
- 239000012159 carrier gas Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007809 chemical reaction catalyst Substances 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 6
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 6
- 239000012779 reinforcing material Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052863 mullite Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011226 reinforced ceramic Substances 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- -1 alicyclic hydrocarbon compounds Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000019086 sulfide ion homeostasis Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、各種複合材料の補強材として有用な炭化ケイ
素ウィスカーの製造法、さらに詳しくは、ウィスカーの
成長過程を制御することによる径の太い炭化ケイ素ウィ
スカーの製造法に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for producing silicon carbide whiskers useful as reinforcing materials for various composite materials, and more specifically, a method for producing silicon carbide whiskers useful as reinforcing materials for various composite materials, and more specifically, a method for producing silicon carbide whiskers that have a large diameter by controlling the growth process of the whiskers. This invention relates to a method for producing silicon carbide whiskers.
［従来の技術］
炭化ケイ素ウィスカーは、高い強度と弾性率を有し、高
温における金属との反応性が低い、酸化雰囲気下での耐
熱性が高い、溶融金属との濡れ性がよいなど、複合材料
の補強材として優れた特性を有しており、広い分野にお
いて活用が期待されている材料である。[Prior art] Silicon carbide whiskers have high strength and elastic modulus, low reactivity with metals at high temperatures, high heat resistance in oxidizing atmospheres, and good wettability with molten metals. It has excellent properties as a reinforcing material, and is expected to be used in a wide range of fields.
従来、炭化ケイ素ウィスカーの製造方法として、固相法
、気相法など種々の方法が知られている。Conventionally, various methods such as a solid phase method and a gas phase method are known as methods for producing silicon carbide whiskers.
これらの方法の中で、硫化ケイ素と炭化水素化合物を気
相で反応させる気相法が注目されており、例えば特開昭
６３−２０６３９９および特開昭６３−３１９３００に
は、硫化ケイ素ガスを１．１３０−１，５００℃に保持
された反応器にキャリアガスな介して導入し、空間に浮
遊した生成核の存在下に炭化水素化合物と接触させるこ
とにより炭化ケイ素ウィスカーを析出、成長させる方法
が提案されている。また、この方法においては、生成核
材として鉄、ニッケル、チタン、マンガン、コバルト、
銅、バナジウム、クロム、アルミニウムおよびシリコン
などの金属またはその化合物が有効であることも開示さ
れている。Among these methods, a gas phase method in which silicon sulfide and a hydrocarbon compound are reacted in the gas phase has attracted attention. There is a method in which silicon carbide whiskers are precipitated and grown by introducing them into a reactor maintained at 130-1,500°C via a carrier gas and bringing them into contact with a hydrocarbon compound in the presence of product nuclei floating in the space. Proposed. In addition, in this method, iron, nickel, titanium, manganese, cobalt,
Metals such as copper, vanadium, chromium, aluminum and silicon or their compounds are also disclosed to be effective.
一方、本発明者らは、硫化ケイ素と炭化水素化合物とを
気相で反応させる際の触媒として、鉄、ニッケル、コバ
ルト、ロジウム、パラジウム、オスミウム、イリジウム
、白金である周期律表第■族に属する金属および銅より
なる群から選ばれる二種類以上の金属とモリブデン、ル
テニウム、レニウムおよびタングステンよりなる群から
選ばれる一種以上の金属とを有効成分とする多元触媒が
特に有効であることを見いだし、先に出願した（特願平
１−２７１５５２）。On the other hand, the present inventors have discovered that iron, nickel, cobalt, rhodium, palladium, osmium, iridium, and platinum, which are group I of the periodic table, can be used as catalysts for reacting silicon sulfide and hydrocarbon compounds in the gas phase. We have discovered that a multi-component catalyst containing as active ingredients two or more metals selected from the group consisting of metals and copper and one or more metals selected from the group consisting of molybdenum, ruthenium, rhenium and tungsten is particularly effective, The application was filed earlier (Japanese Patent Application No. 1-271552).
［発明が解決しようとする課題］
ところで、複合材料用の補強材として用いられる炭化ケ
イ素ウィスカーのうち、繊維強化金属（ＦＭＲ）用の補
強材としては従来の細い径のもので良好な補強効果が得
られるが、繊維強化セラミックス（ＦＲＣ）用の補強材
としては１μｍ以上の太い径の炭化ケイ素ウィスカーの
方が靭性改良の面で好ましい効果が得られるとの報告（
例えば、上野和夫、袖岡賢；窯業協会誌、９４．９８１
（＋９８６） ’）があり、また、作業環境上の観点か
らも径の太い炭化ケイ素ウィスカーの製造方法が望まれ
ている。[Problems to be Solved by the Invention] By the way, among the silicon carbide whiskers used as reinforcing materials for composite materials, conventional thin diameter ones have good reinforcing effects as reinforcing materials for fiber reinforced metal (FMR). However, it has been reported that as a reinforcing material for fiber reinforced ceramics (FRC), silicon carbide whiskers with a larger diameter of 1 μm or more have a more favorable effect in terms of improving toughness (
For example, Kazuo Ueno, Ken Sodeoka; Ceramics Association Journal, 94.981
(+986) '), and from the viewpoint of the working environment, a method for producing silicon carbide whiskers with a large diameter is desired.
しかしながら、前記従来技術で得られる炭化ケイ素ウィ
スカーは、０．５μｍ以下の径のものが大部分であり、
ＩＬＬｍ以上の径のものは極小量しか得られていない０
本発明の目的は、前記従来技術では有効に製造し得なか
った直径１μｍ以上の太い径の炭化ケイ素ウィスカーを
安定して得ることができる工業的に有利な製造法を提供
することにある。However, most of the silicon carbide whiskers obtained by the conventional technique have a diameter of 0.5 μm or less,
Only a very small amount of those with diameters larger than ILLm have been obtained.
An object of the present invention is to provide an industrially advantageous manufacturing method capable of stably obtaining silicon carbide whiskers having a large diameter of 1 μm or more, which could not be effectively manufactured using the conventional techniques.
［課題を解決すための手段１
本発明者らは、硫化ケイ素と炭化水素化合物との反応に
より径の太い炭化ケイ素ウィスカーを製造する方法につ
いて鋭意検討の結果、反応に先立ち、特定の金属類およ
び金属ケイ化物類を組み合わせた多元触媒を用い、ウィ
スカー生成基板上に太い切り株状の生成核を形成してお
くことにより前記目的が達成できることを見いだし、本
発明を完成した。[Means for Solving the Problems 1] As a result of extensive research into a method for producing large-diameter silicon carbide whiskers by reacting silicon sulfide with a hydrocarbon compound, the present inventors found that, prior to the reaction, certain metals and The inventors have discovered that the above object can be achieved by forming thick, stump-shaped nuclei on a whisker-generating substrate using a multi-component catalyst that combines metal silicides, and have completed the present invention.
本発明は、炭化水素化合物および硫化ケイ素を金属系触
媒の存在下に気相で反応させて炭化ケイ素ウィスカーを
製造する方法において、まず反応系内の基板上に、触媒
として周期律表第■族に属する金属および銅よりなる群
（Ａ群）から選ばれる二種以上の金属と、ニケイ化モリ
ブデン、ニケイ化タングステン、ニケイ化ニオブおよび
ニケイ化チタンよりなる群（Ｂ群）から選ばれる一種以
上の金属ケイ化物とを有効成分とする多元触媒な担持さ
せたのち、硫化ケイ素ガスを導入してケイ素質を核を生
成させ、次いで炭化水素ガスを導入して反応させること
によって該ケイ素質の核を炭化ケイ素の核に変化させ、
さらに炭化ケイ素ウィスカー生成用の触媒を追加担持さ
せたのち、原料の炭化水素化合物と硫化ケイ素ガスを導
入して反応させ、前記炭化ケイ素の核を生成核として炭
化ケイ素ウィスカーを成長させることを特徴とする径の
太い炭化ケイ素ウィスカーの製造法である。The present invention provides a method for producing silicon carbide whiskers by reacting a hydrocarbon compound and silicon sulfide in the gas phase in the presence of a metal catalyst. two or more metals selected from the group consisting of copper and metals belonging to After supporting a multi-component catalyst containing a metal silicide as an active ingredient, silicon sulfide gas is introduced to generate silicon nuclei, and then hydrocarbon gas is introduced and reacted to generate the silicon nuclei. Changed to silicon carbide core,
Furthermore, after additionally supporting a catalyst for producing silicon carbide whiskers, a raw material hydrocarbon compound and silicon sulfide gas are introduced and reacted, and silicon carbide whiskers are grown using the silicon carbide nuclei as production nuclei. This is a method for producing silicon carbide whiskers with large diameters.
本発明によれば、はぼ全量が直径１μｍ以上の径を有す
る炭化ケイ素ウィスカーを安定的に得ることができる。According to the present invention, silicon carbide whiskers whose entire amount has a diameter of 1 μm or more can be stably obtained.
従来技術により得られる炭化ケイ素ウィスカーの平均径
が０．１〜０．５μｍであることに比べ、本発明による
ウィスカーはほぼ全量が１μｍ以上であり、通常は３〜
１０μｍ径という極めて太い径のウィスカーである。こ
れは太い径の炭化ケイ素ウィスカーを生成するに足る径
の太い切り株状の生成核を予め基板上に形成しておくこ
とにより可能となるのである。Compared to silicon carbide whiskers obtained by conventional techniques, which have an average diameter of 0.1 to 0.5 μm, almost all of the whiskers according to the present invention have an average diameter of 1 μm or more, and usually 3 to 0.5 μm.
The whisker has an extremely large diameter of 10 μm. This is made possible by forming in advance on the substrate a stump-shaped nucleus with a diameter large enough to produce silicon carbide whiskers with a large diameter.
以下、本発明の製造法をプロセスにしたがって説明する
。Hereinafter, the manufacturing method of the present invention will be explained according to the process.
まず、反応に先立ち、反応器内の基板上にケイ素質の核
の生成を経て炭化ケイ素の核（すなわち、炭化ケイ素ウ
ィスカーの生成核、以下生成核という。）を生成させる
ための触媒（以下、生成核形成触媒という。）を担持さ
せる。この触媒としては、周期律表第■族に属する金属
および銅よりなる群（Ａ群）から選ばれる二種以上の金
属とニケイ化モリブデン、ニケイ化タングステン、ニケ
イ化ニオブおよびニケイ化チタンよりなる群（Ｂ群）か
ら選ばれる一種以上の金属ケイ化物とを有効成分とする
多元触媒を使用する。十分な生成核を形成するには上記
Ａ群とＢ群の組み合わせによる多元触媒が非常に有効な
のである。この多元触媒はＢ群の金属ケイ化物とＡ群の
核金属成分の単体金属またはこれらの金属の酸化物、炭
化物、硫化物、ハロゲン化物、硫酸塩、硝酸塩などの無
機化合物あるいは一般式Ｍ （Ｃ２Ｈｅ ）で表される
メタロセンなどの有機化合物な担体である基板上に混合
付着させたのち熱分解反応および／または還元反応によ
り、Ｂ群の金属ケイ化物とＡ群各金属との混合物あるい
はＢ群の金属ケイ化物とＡ群各金属の一部合金の形とし
て担持させる。First, before the reaction, a catalyst (hereinafter referred to as (referred to as a nucleation catalyst) is supported. This catalyst includes two or more metals selected from the group (group A) consisting of metals belonging to Group I of the periodic table and copper, and the group consisting of molybdenum disilicide, tungsten disilicide, niobium disilicide, and titanium disilicide. A multi-component catalyst containing as an active ingredient one or more metal silicides selected from (Group B) is used. In order to form sufficient product nuclei, a multi-catalyst using a combination of the above-mentioned groups A and B is very effective. This multi-component catalyst is a group B metal silicide, a group A nuclear metal component, an elemental metal, or an inorganic compound such as an oxide, carbide, sulfide, halide, sulfate, or nitrate of these metals, or a compound with the general formula M (C2He ) A mixture of metal silicides of group B and each metal of group A or a mixture of group B metal silicides and each metal of group A is formed by a thermal decomposition reaction and/or reduction reaction after being mixed and deposited on a substrate which is an organic compound carrier such as metallocene represented by It is supported in the form of a partial alloy of metal silicide and each metal of Group A.
各金属の使用割合は、Ａ群の金属とＢ群の金属ケイ化物
の比率がモル比で０．１／１〜５／１かつＡ群中の最大
成分と残りの成分の比率がモル比で１０／ｌ以下となる
ような範囲が好ましい。金属成分の構成比率が前記の範
囲を外れると生成核の形成が不十分で径の太い炭化ケイ
素ウィスカーを安定して得ることができない、これらの
多元触媒の中で、Ａ群の金属として鉄（Ｆｅ）およびニ
ッケル（Ｎｉ）を使用し、Ｂ群の金属ケイ化物としてニ
ケイ化モリブデン（ＭｏＳｉｚ）を使用したものが、反
応性も高く、取り扱いも容易で特に優れた組み合わせで
ある。The ratio of each metal to be used is such that the ratio of group A metal to group B metal silicide is 0.1/1 to 5/1 in molar ratio, and the ratio of the largest component in group A to the remaining component is in molar ratio. The range is preferably 10/l or less. If the composition ratio of the metal components is outside the above range, the formation of nuclei will be insufficient and silicon carbide whiskers with a large diameter cannot be stably obtained. Among these multi-component catalysts, iron ( A particularly excellent combination is one in which molybdenum disilicide (MoSiz) is used as the group B metal silicide with Fe) and nickel (Ni), and is highly reactive and easy to handle.
生成核形成触媒を担持させる基板（担体）の材質として
は、生成核の形成および炭化ケイ素ウィスカーの生成反
応に悪影響をおよぼすものでなければ特に制限はなく、
アルミナ、ムライトなどのセラミックス材料あるいは黒
鉛、ガラス状炭素などの炭素材料などが用いられるが、
その中でムライト系のセラミックスなどの５ｉｎ２成分
を含有する材料が特に好適である。これは、材料の構成
成分の一部であるＳｉＣ２が生成核の形成および炭化ケ
イ素ウィスカーの生成に好結果を与えるためと推定され
る。The material of the substrate (carrier) on which the nucleation catalyst is supported is not particularly limited as long as it does not adversely affect the formation of the nucleation and the silicon carbide whisker production reaction.
Ceramic materials such as alumina and mullite, and carbon materials such as graphite and glassy carbon are used.
Among these, materials containing a 5in2 component such as mullite ceramics are particularly suitable. This is presumed to be because SiC2, which is a part of the constituent components of the material, gives good results to the formation of product nuclei and the production of silicon carbide whiskers.
炭化ケイ素ウィスカーは担体上に形成された生成核上で
生成し、成長するので、担体の形状としては得られたウ
ィスカーの単離の容易なものがよい。通常は反応器の器
壁をそのまま利用すればよく、反応容積を大きくする場
合にはムライト製ボールなどの簡単な構造の充填物を入
れるか、管状の反応器を組み合わせた多管反応器を使用
すればよい。Since silicon carbide whiskers are generated and grow on nuclei formed on a carrier, the shape of the carrier is preferably such that the resulting whiskers can be easily isolated. Normally, the wall of the reactor can be used as is, but if the reaction volume is to be increased, a simple packing such as mullite balls can be used, or a multi-tubular reactor combined with tubular reactors can be used. do it.
本発明の方法で使用する反応装置としては特に限定はな
いが、例えば、第１図に示すような炭化水素化合物、硫
化ケイ素および触媒成分の導入管と排ガスの導出管を備
えた反応管を、横型の電気炉中に設置した構成ものが好
適に用いられる。横型が好ましいのは粉末状の金属ケイ
化物な担体上に担持させやすいためである。Although there are no particular limitations on the reaction apparatus used in the method of the present invention, for example, a reaction tube equipped with an inlet tube for hydrocarbon compounds, silicon sulfide, and catalyst components and an outlet tube for exhaust gas as shown in FIG. A structure installed in a horizontal electric furnace is preferably used. The horizontal type is preferred because it can be easily supported on a powdered metal silicide support.
生成核形成触媒の担持方法としては、前記Ｂ群の金属ケ
イ化物な担体上に予め反応管を回転させるなどの方法よ
り担持させておき、Ａ群の各金属の単体またはその金属
化合物を１，１００〜１．４００℃の高温度に保持され
た反応器内へ導入し、担体上に担持させる。この場合、
フェロセン、ニラケロセンなどの昇華性のある物質は蒸
気圧を利用し、加熱状態で窒素などの不活性ガスや水素
などの還元性ガスをキャリアガスとして系内に導入して
担持させる。蒸気圧の低い化合物の場合には溶液あるい
はスラリーの形で反応器内へ噴霧する方法が好適である
。各成分はそれぞれ単独で反応器内へ導入してもよいが
、予め混合した状態で導入してもよい。各種化合物の形
で反応器内へ担持されたＡ群の金属成分は、還元性ガス
によって還元され、金属の形でＢ群の金属ケイ化物と共
に触媒作用を示すものと思われる。As a method of supporting the nucleation catalyst, it is supported on the group B metal silicide support by a method such as rotating a reaction tube in advance, and each element of group A metal or its metal compound is It is introduced into a reactor maintained at a high temperature of 100 to 1.400°C and supported on a carrier. in this case,
Sublimable substances such as ferrocene and nirakerosene are supported by using vapor pressure and introducing an inert gas such as nitrogen or a reducing gas such as hydrogen as a carrier gas into the system under heating. In the case of compounds with low vapor pressure, it is preferable to spray them into the reactor in the form of a solution or slurry. Each component may be introduced into the reactor individually, or may be introduced in a pre-mixed state. It is believed that the metal components of group A supported in the reactor in the form of various compounds are reduced by the reducing gas and exhibit catalytic activity together with the metal silicides of group B in the form of metals.
生成核形成触媒の担持量は、担体の基材単位面積当たり
Ａ群金属はｌ Ｏ〜５００ｍｇ／ｍ２．Ｂ群金属ケイ化
物は１００〜１，０００ｍｇ／ｍ２が好ましい。Ａ群金
属の担持量が１０ｍｇ／ｍ２未満では径の太い生成核が
得られにくいためウィスカーの径を太くする効果が少な
く、また５００ｍ ｇ ／ ｍ ２を超えてもそれ以上
の効果はない。Ｂ群金属ケイ化物は使用量力ｔｌｏｏｍ
ｇ／ｍ２未満では同様にウィスカーの径を太くする効果
が少なく、また１、０００ｍｇ／ｍ”を超えてもそれ以
上の効果はない。The supported amount of the nucleation catalyst is 1 O to 500 mg/m2 of group A metal per unit area of the base material of the carrier. The amount of Group B metal silicide is preferably 100 to 1,000 mg/m2. If the supported amount of group A metal is less than 10 mg/m2, it is difficult to obtain a large-diameter nucleus, so that the effect of increasing the diameter of the whisker is small, and if it exceeds 500 mg/m2, no further effect is obtained. The amount of Group B metal silicide used is
If it is less than 1,000 mg/m2, the effect of increasing the whisker diameter will be small, and if it exceeds 1,000 mg/m, there will be no further effect.
次に、前記生成核形成触媒を担持させた基板上に必要に
よりキャリアガスで希釈した硫化ケイ素ガスつづいて炭
化水素ガスを導入し、生成核を形成させる。ここで使用
するガスは、後記の炭化ケイ素ウィスカーの生成反応の
場合と同様のものを使用し、導入の方法もそれに準じて
行えばよい。Next, a silicon sulfide gas diluted with a carrier gas if necessary, followed by a hydrocarbon gas are introduced onto the substrate supporting the nucleation catalyst to form nucleations. The gas used here is the same as in the case of the silicon carbide whisker production reaction described later, and the method of introduction may be carried out in accordance therewith.
まずキャリアガス中に０．５〜４Ｖｏ １％の硫化ケイ
素ガスを含む混合ガスを１，２５０〜１．３５０℃に保
持した反応器内に反応帯域における通ガス速度０．０２
〜０１１０ｃｍ／ｓｅｃで２〜４時間を要し、硫化ケイ
素の総供給量が基板上に担持している生成核形成触媒の
１〜３０倍量（モル比換算）となるように導入して基板
上にケイ素質の核を生成させる。硫化ケイ素の総供給量
が生成核形成触媒に対して、１倍量未満ではケイ素質核
形成上の効果がなく、また３０倍量を超えてもそれ以上
の効果はない。次いでキャリアガス中に５〜３０Ｖｏ１
％の炭化水素ガスを含む混合ガスを同一温度で通ガス速
度０．０２〜０．１０ｃｍ／ｓｅｃで０５〜１０時間を
要し、炭化水素の総供給量が硫化ケイ素のそれに対し１
〜１０倍量（モル比換算）となるように導入して、先に
形成させたケイ素質の核を炭化ケイ素の核（生成核）に
変化させる。炭化水素の総供給量が硫化ケイ素のそれに
対して、１倍量未満では炭化ケイ素核の形成が不十分で
あり、また１０倍量を超えてもそれ以上の効果はない。First, a mixed gas containing silicon sulfide gas of 0.5 to 4 Vo 1% in the carrier gas was introduced into a reactor maintained at 1,250 to 1.350°C at a gas flow rate of 0.02 in the reaction zone.
It takes 2 to 4 hours at ~0110 cm/sec, and the total amount of silicon sulfide supplied is 1 to 30 times the amount (in terms of molar ratio) of the nucleation catalyst supported on the substrate. A silicon core is generated on top. If the total amount of silicon sulfide supplied is less than 1 times the amount of the generated nucleation catalyst, there will be no effect on the formation of siliceous nuclei, and if it exceeds 30 times the amount of the generated nucleation catalyst, no further effect will be obtained. Then add 5 to 30 Vol in the carrier gas.
It takes 0.5 to 10 hours to pass a mixed gas containing % of hydrocarbon gas at the same temperature at a gas flow rate of 0.02 to 0.10 cm/sec, and the total amount of hydrocarbon supplied is 1% to that of silicon sulfide.
It is introduced in an amount of ~10 times (in terms of molar ratio) to convert the previously formed silicon core into a silicon carbide core (product nucleus). If the total amount of hydrocarbon supplied is less than 1 times that of silicon sulfide, the formation of silicon carbide nuclei will be insufficient, and if it exceeds 10 times that of silicon sulfide, no further effect will be obtained.
この生成核は、顕微鏡観察によれば、直径１μｍ以上の
切り林状の形態を有するものが主体であり、炭化ケイ素
ウィスカーはこの切り株が成長するような形で生成して
いくので太い径のウィスカーを得ることができる。According to microscopic observation, these generated nuclei mainly have a tree-like shape with a diameter of 1 μm or more, and silicon carbide whiskers are generated in the form of growing tree stumps, so they are thick-diameter whiskers. can be obtained.
次に、このようにして生成核を形成した基板上に炭化ケ
イ素ウィスカー生成反応用の触媒（反応触媒）を追加担
持させる。ここで、追加担持とは本工程を前述生成核形
成の工程で用いた生成核形成触媒とは別に炭化ケイ素ウ
ィスカーを製造する毎に、反応触媒を新たに担持させる
ことをいう。Next, a catalyst for the silicon carbide whisker production reaction (reaction catalyst) is additionally supported on the substrate on which the production nuclei have been formed in this manner. Here, the term "additional support" refers to newly supporting a reaction catalyst each time silicon carbide whiskers are produced, in addition to the nucleation catalyst used in the above-mentioned nucleation step.
すなわち、前記の生成核形成触媒も炭化ケイ素ウィスカ
ー生成反応の触媒として機能するが、反応を円滑に進行
させるためにはこの段階で触媒を追加するのが好ましい
。−旦形成させた生成核は、生成した炭化ケイ素ウィス
カーを回収したあともそのまま残っており、反応触媒を
追加するだけでそのまま繰り返し使用することができる
。That is, although the above-mentioned nucleation catalyst also functions as a catalyst for the silicon carbide whisker production reaction, it is preferable to add the catalyst at this stage in order to make the reaction proceed smoothly. - The product nuclei once formed remain as they are even after the silicon carbide whiskers are collected, and can be used repeatedly as is by simply adding a reaction catalyst.
反応触媒としては、好ましくは前記Ｂ群の金属ケイ化物
とＡ群の金属の中から選ばれる１種以上を適当な化合物
の形で導入し担持させる。担持方法としては例λば、鉄
またはニッケルの場合にはフェロセンあるいはニラケロ
センの形で８０℃付近に加温した水素ガスをキャリアー
として導入し、またコバルトの場合には塩化コバルトを
２５０℃付近に加温した窒素ガスをキャリアーとして導
入すればよい。追加する触媒の担持ｍは、反応させる硫
化ケイ素１モルに対し金属成分の合計量で０．０００２
〜０．００１モルが好ましい。担持■が０．０００２モ
ル未満では炭化ケイ素ウィスカーの収率が低く、また０
、００１モルを超えてもそれ以上の効果はない。As the reaction catalyst, one or more selected from the group B metal silicides and the group A metals are preferably introduced and supported in the form of a suitable compound. For example, in the case of iron or nickel, hydrogen gas heated to around 80°C in the form of ferrocene or kerosene is introduced as a carrier, and in the case of cobalt, cobalt chloride is added to around 250°C. Warmed nitrogen gas may be introduced as a carrier. The supporting amount of the additional catalyst (m) is 0.0002 in terms of the total amount of metal components per mol of silicon sulfide to be reacted.
~0.001 mol is preferred. If the supported amount is less than 0.0002 mol, the yield of silicon carbide whiskers will be low;
, 001 mole, there is no further effect.
次に反応帯域の温度を１，１３０〜１．５００℃、好ま
しくは１，２００〜１，４００℃とした反応器内へ原料
の炭化水素化合物および硫化ケイ素を導入して反応を開
始させる。Next, the raw material hydrocarbon compound and silicon sulfide are introduced into a reactor whose temperature in the reaction zone is 1,130 to 1,500°C, preferably 1,200 to 1,400°C, to start the reaction.
本発明の方法において、炭化ケイ素ウィスカー製造用原
料として使用する炭化水素化合物としては、メタン、エ
タン、プロパンなどのパラフィン系炭化水素化合物、エ
チレン、プロピレンなとのオレフィン系炭化水素化合物
、アセチレン、アリレンなどのアセチレン系炭化水素化
合物、ベンゼン、トルエンなどの芳香族炭化水素化合物
、シクロパラフィン、シクロオレフィンなどの脂環族炭
化水素化合物あるいはこれらの混合物が挙げられる。In the method of the present invention, hydrocarbon compounds used as raw materials for producing silicon carbide whiskers include paraffinic hydrocarbon compounds such as methane, ethane, and propane, olefinic hydrocarbon compounds such as ethylene and propylene, acetylene, arylene, etc. Examples include acetylenic hydrocarbon compounds, aromatic hydrocarbon compounds such as benzene and toluene, alicyclic hydrocarbon compounds such as cycloparaffin and cycloolefin, or mixtures thereof.
炭化水素化合物は、水素などの還元性ガスまたはこれら
の還元性ガスを窒素などの不活性ガスで希釈した混合物
よりなるキャリアガスとともに、反応器内に導入される
。キャリアガスとしては水素ガスまたは水素と窒素の混
合ガスが特に好ましい。また、硫化ケイ素は、予めフェ
ロシリコンと硫黄とを反応させるなどの方法で製造した
ものを加熱気化させ、キャリアガスとともに系内へ導入
することによって供給される。あるいは、この硫化ケイ
素は、金属ケイ素を反応器の１．０００〜１．４００℃
に保持された導入管の先端部に保持し、キャリアガスで
希釈した硫化水素ガスを導入して反応させることによっ
て生成させれば、別に硫化ケイ素の製造装置や気化装置
を設ける必要がないので好都合である。The hydrocarbon compound is introduced into the reactor together with a carrier gas consisting of a reducing gas such as hydrogen or a mixture of these reducing gases diluted with an inert gas such as nitrogen. As the carrier gas, hydrogen gas or a mixed gas of hydrogen and nitrogen is particularly preferred. Further, silicon sulfide is supplied by heating and vaporizing silicon sulfide produced in advance by a method such as reacting ferrosilicon and sulfur, and introducing the same into the system together with a carrier gas. Alternatively, this silicon sulfide can be heated to 1.000 to 1.400°C in a reactor.
If hydrogen sulfide gas diluted with a carrier gas is introduced into the tip of an inlet tube held at the tip of the inlet tube and generated by reaction, there is no need to install a separate silicon sulfide production device or vaporization device, which is convenient. It is.
炭化水素化合物および硫化ケイ素を反応器へ導入させる
ためのキャリアガスとしては、窒素のような活性の低い
ガスまたは不活性ガスで希釈されていでもよい水素など
の還元性ガスを用いるが、このうち水素または水素と窒
素の混合ガスが特に好ましい。As a carrier gas for introducing hydrocarbon compounds and silicon sulfide into the reactor, a reducing gas such as hydrogen, which may be diluted with a low-activity gas such as nitrogen or an inert gas, is used. Alternatively, a mixed gas of hydrogen and nitrogen is particularly preferred.
炭化水素化合物と硫化ケイ素の使用割合は、硫化ケイ素
１モルに対し炭化水素化合物１〜１０モルの範囲が好ま
しい。炭化水素化合物のモル比が１未満では反応率が低
くなり、また、１０モル比を超えても反応率はそれ以上
向上せず、炭化水素化合物のロスが多くなる。The ratio of the hydrocarbon compound and silicon sulfide used is preferably in the range of 1 to 10 moles of hydrocarbon compound per 1 mole of silicon sulfide. If the molar ratio of the hydrocarbon compound is less than 1, the reaction rate will be low, and if the molar ratio exceeds 10, the reaction rate will not improve any further, and the loss of the hydrocarbon compound will increase.
反応器内へ導入する原料混合物の濃度および通ガス速度
は反応器の大きさ、形状、反応温度などの他の条件との
組み合わせで適宜定められる。通常、原料混合物および
キャリアガスな含む全ガス中の炭化水素化合物の濃度は
１〜５ｍ０１％、硫化ケイ素の濃度は５〜３０ｍｏ１％
の範囲とするのが好ましい。The concentration of the raw material mixture introduced into the reactor and the gas passing rate are appropriately determined in combination with other conditions such as the size and shape of the reactor, and the reaction temperature. Usually, the concentration of hydrocarbon compounds in the raw material mixture and all gases including carrier gas is 1 to 5 mol%, and the concentration of silicon sulfide is 5 to 30 mol%.
It is preferable to set it as the range of.
原料混合物の反応帯域における滞留時間を左右する通ガ
ス速度は、０．０６〜０．２４ｃｍ／ｓｅｃとする。通
ガス速度が０．０６ｃｍ／ＳｅＣ未渦では単位時間当た
りの炭化ケイ素ウィスカーの生成量が少なく、また、０
．２４ｃｍ／ｓｅｃを超えると炭化ケイ素ウィスカーの
収率が大幅に低下する。通常、炭化ケイ素ウィスカーは
０．５〜１時間で目的の大きさまで成長し、常法に従っ
て回収され得る。The gas passing rate, which influences the residence time of the raw material mixture in the reaction zone, is 0.06 to 0.24 cm/sec. When the gas flow rate is 0.06 cm/SeC without vortex, the amount of silicon carbide whiskers produced per unit time is small;
．． If it exceeds 24 cm/sec, the yield of silicon carbide whiskers will decrease significantly. Typically, silicon carbide whiskers grow to a desired size in 0.5 to 1 hour and can be recovered by conventional methods.
本発明の方法においては、炭化ケイ素ウィスカーは、予
め反応器内の基板上に形成された生成量の上に成長して
いくので、従来の方法では得ることが難しかった太い径
のウィスカーを得ることができる。In the method of the present invention, silicon carbide whiskers grow on top of the amount previously formed on the substrate in the reactor, making it possible to obtain whiskers with a large diameter, which was difficult to obtain with conventional methods. I can do it.
本発明の方法によって得られる炭化ケイ素ウィスカーは
、ウィスカー中に触媒粒子の混入がほとんど無く高純度
で、直径が１〜１０μｍ、長さ１．０００〜１０．００
０μｍかつアスペクト比１００’Ｏ以上の形状を有して
おり、繊維強化プラスチックス、繊維強化金属あるいは
繊維強化セラミ・シクスなどの各種複合材料として好適
である。The silicon carbide whiskers obtained by the method of the present invention have high purity with almost no catalyst particles mixed in the whiskers, have a diameter of 1 to 10 μm, and a length of 1.000 to 10.00 μm.
It has a shape of 0 μm and an aspect ratio of 100'O or more, and is suitable for various composite materials such as fiber-reinforced plastics, fiber-reinforced metals, and fiber-reinforced ceramics.
［実 施 例］
以下、実施例により本発明の方法をさらに具体的に説明
する。[Example] Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.
第１図に示すような、横型電気炉１中に、左、右端をシ
リコンゴム栓２．３でシールした内径５２ｍｍ、長さ１
，５００ｍｍのムライト製反応管４を設置し、内径１０
ｍｍのアルミナ管を右端のゴム栓に４本（導入管５〜８
）、左端のゴム栓に１本（排ガス導出管９）取り付けた
ものを反応器として用い、表１に示す反応条件および以
下に説明する要領で炭化ケイ素ウィスカーを製造した。As shown in Fig. 1, a horizontal electric furnace 1 with an inner diameter of 52 mm and a length of 1.
, a 500 mm mullite reaction tube 4 was installed, with an inner diameter of 10
Four mm alumina tubes are attached to the rubber plugs on the right end (introduction tubes 5 to 8
), one (exhaust gas outlet pipe 9) attached to the rubber stopper on the left end was used as a reactor, and silicon carbide whiskers were produced under the reaction conditions shown in Table 1 and in the manner described below.
生成核形成触媒の調製
反応管中心部の均熱帯（長さ４５．０ ｍ ｍ程度の範
囲）にニケイ化モリブデン粉末（粉末度１〜３００μｍ
）５０ｍｇ （６８０ｍｇ／ｍ” ）などを表１に示す
配合に従い室温で担持させておき、つづいて反応器を第
２図に示すような温度分布となるように加熱しておく一
方、充分量のフェロセンおよびニラケロセンを５０ｍ１
の容器に入れ、８０℃に加温しておき、キャリアガスと
して５０ｍ１／ｍｉｎの水素を３０分間通すことによっ
て気化フェロセンおよびニラケロセンを導入管５から反
応器内へ導入し、反応管内壁（０，２５ｍ２）に所定量
の鉄およびニッケルを担持させた。Preparation of Nucleation Catalyst Molybdenum disilicide powder (powder size 1 to 300 μm
) 50 mg (680 mg/m”) etc. were supported at room temperature according to the formulation shown in Table 1, and then the reactor was heated to achieve the temperature distribution shown in Figure 2. 50ml of ferrocene and nilakerosene
vaporized ferrocene and nirakerosene were introduced into the reactor from the introduction tube 5 by passing hydrogen at 50 ml/min as a carrier gas for 30 minutes, and the inner wall of the reaction tube (0, 25 m2) was loaded with predetermined amounts of iron and nickel.
生成核の形成
生成核形成触媒を担持させた反応器を、第２図のような
温度分布に加熱しておき、生成核の形成を行った。まず
、導入管８の先端部に金属ケイ素を固定しておき、この
先端部を１，２００℃の温度領域に保持し、導入管８よ
り１．５ｍｌ／ｍｉｎの硫化水素と７５ｍ１／ｍｉｎの
水素の混合ガス（通ガス速度０．０６ｃｍ／秒）を３時
間を要して導入することにより硫化ケイ素を生成させな
がらケイ素質の核を生成させた。次に、導入管６より１
０ ｍ １ ／ ｍ ｉ ｎのメタンと６６．５ｍ １
／ ｍ ｉ ｎの水素のよりなる混合ガス（通ガス速
度０．０６ｃｍ／秒）を０．５時間を要して導入し、炭
化ケイ素の生成核を形成させた。Formation of Product Nuclei A reactor carrying a product nucleation catalyst was heated to a temperature distribution as shown in FIG. 2, and product nuclei were formed. First, metal silicon is fixed to the tip of the introduction tube 8, and this tip is maintained in a temperature range of 1,200°C. By introducing a mixed gas of (gas flow rate: 0.06 cm/sec) over a period of 3 hours, silicon cores were generated while silicon sulfide was generated. Next, from the introduction pipe 6,
0 m 1 / min of methane and 66.5 m 1
A mixed gas (gas flow rate: 0.06 cm/sec) consisting of hydrogen of / min was introduced over a period of 0.5 hours to form nuclei of silicon carbide.
反応触媒の調製
生成核形成に用いたフェロセンおよびニラケロセンの導
入装置を６０℃に加温しておき、５０ｐｎ ｌ ／ ｍ
ｉ ｎの水素を３０分間通すことによって気化フェロ
センおよびニラケロセンを導入管５から反応器内へ導入
し、反応管内壁に所定量の鉄およびニッケルを担持させ
た。Preparation of reaction catalyst The introduction device for ferrocene and nilakerosene used for nucleation was heated to 60°C, and 50 pn l/m
Vaporized ferrocene and nilakerosene were introduced into the reactor from the introduction tube 5 by passing hydrogen of i.
反 応
反応触媒を担持させ、第２図のような温度分布に加熱さ
れた反応器内に、気体状のメタンおよび硫化ケイ素（Ｓ
ｉＳ）をキャリアガスとともに２時間を要して導入しく
通ガス速度０．１２ｃｍ／秒）、反応させた。メタンは
２０ｍ１／ｍｉｎのメタンガスを１１５ｍ１／ｍｉｎの
水素ガスとともに導入管６より導入し、硫化ケイ素は、
導入管８の先端部に金属ケイ素を固定しておき、この先
端部を１，２００℃の温度域に保持し、導入管８より３
ｍ １ ／ ｍ ｉ ｎの硫化水素と１５ｍ１／ｍｉ
ｎの水素の混合ガスを導入することにより硫化ケイ素を
生成させながら導入した。Gaseous methane and silicon sulfide (S
iS) was introduced together with a carrier gas over a period of 2 hours (at a gas flow rate of 0.12 cm/sec), and reacted. For methane, 20 m1/min of methane gas was introduced through the introduction pipe 6 along with 115 m1/min of hydrogen gas, and silicon sulfide was
Metallic silicon is fixed to the tip of the introduction tube 8, and this tip is maintained at a temperature range of 1,200°C.
m 1 / min hydrogen sulfide and 15 m 1 /mi
A mixed gas of n hydrogen was introduced while producing silicon sulfide.
反応終了後、室温まで冷却し、生成したウィスカーを回
収した。得られた生成物は、顕微鏡観察の結果、ウィス
カーの直径は３〜１０μｍであり、１μｍ未満のものの
存在は認められなかった。また、Ｘ線回折測定の結果、
得られた生成物はβ型の炭化ケイ素ウィスカーであるこ
とが確認された。After the reaction was completed, the mixture was cooled to room temperature and the generated whiskers were collected. As a result of microscopic observation of the obtained product, the diameter of whiskers was 3 to 10 μm, and the presence of whiskers smaller than 1 μm was not observed. In addition, as a result of X-ray diffraction measurement,
The obtained product was confirmed to be β-type silicon carbide whiskers.
比較例として、生成核形成触媒として金属ケイ化物を使
用しないで、実施例と同一の方法で炭化ケイ素ウィスカ
ーを製造した結果を実施例とともに表１に示す。金属ケ
イ化物を使用しない場合は、得られた炭化ケイ素ウィス
カーの直径は、顕微鏡観察の結果０１〜０．５μｍであ
った。As a comparative example, silicon carbide whiskers were produced in the same manner as in the examples without using a metal silicide as a nucleation catalyst, and the results are shown in Table 1 together with the examples. When no metal silicide was used, the diameter of the silicon carbide whiskers obtained was 01 to 0.5 μm as determined by microscopic observation.
（以下余白）
表
［発明の効果］
本発明の方法によれば、前記Ｂ群の金属ケイ化物を核生
成触媒として用いることにより、従来の方法に比べて太
い径の炭化ケイ素ウィスカーを安定して得ることができ
る。また、−度形成させた生成核は、生成したウィスカ
ーを回収したのち、反応用触媒を追加するだけでそのま
ま繰り返し使用が可能であり、本発明の方法は工業的に
極めて有利な方法ということができる。(Margins below) Table [Effects of the Invention] According to the method of the present invention, by using the metal silicide of group B as a nucleation catalyst, silicon carbide whiskers with a large diameter can be stably produced compared to conventional methods. Obtainable. In addition, the generated nuclei can be used repeatedly by simply adding a reaction catalyst after collecting the generated whiskers, and the method of the present invention is said to be an extremely advantageous method industrially. can.
第１図は、本発明の実施に用いることのできる反応器の
一例を示す装置の模式断面図、第２図は、実施例におい
て加熱された反応器内の温度分布を示すグラフである。
１・・・横型電気炉、２．３・・・シリコンゴム栓、４
・・・反応管、 ５〜８・・・導入管、９・・・排
ガス導出管。FIG. 1 is a schematic cross-sectional view of an apparatus showing an example of a reactor that can be used in the practice of the present invention, and FIG. 2 is a graph showing the temperature distribution inside the heated reactor in an example. 1...Horizontal electric furnace, 2.3...Silicone rubber stopper, 4
...Reaction tube, 5-8...Introduction pipe, 9...Exhaust gas outlet pipe.
Claims (1)
在下に気相で反応させて炭化ケイ素ウィスカーを製造す
る方法において、まず反応系の基板上に、触媒として周
期律表VIII族に属する金属および銅よりなる群（Ａ群）
から選ばれる二種以上の金属と、二ケイ化モリブデン、
二ケイ化タングステン、二ケイ化ニオブおよび二ケイ化
チタンよりなる群（Ｂ群）から選ばれる一種以上の金属
ケイ化物とを有効成分とする多元触媒を担持させたのち
、硫化ケイ素ガスを導入してケイ素質の核を生成させ、
次いで炭化水素ガスを導入して反応させることによって
該ケイ素質の核を炭化ケイ素の核に変化させ、さらに炭
化ケイ素ウィスカー生成用の触媒を追加担持させたのち
、原料の炭化水素化合物と硫化ケイ素ガスを導入して反
応させ、前記炭化ケイ素の核を生成核として炭化ケイ素
ウィスカーを成長させることを特徴とする径の太い炭化
ケイ素ウィスカーの製造法。1. In a method for producing silicon carbide whiskers by reacting a hydrocarbon compound and silicon sulfide in the gas phase in the presence of a metal catalyst, first, a metal belonging to Group VIII of the Periodic Table and Group consisting of copper (group A)
two or more metals selected from, molybdenum disilicide,
After supporting a multi-component catalyst containing as an active ingredient one or more metal silicides selected from the group consisting of tungsten disilicide, niobium disilicide and titanium disilicide (group B), silicon sulfide gas is introduced. to generate a silicon core,
Next, hydrocarbon gas is introduced and reacted to change the silicon core into a silicon carbide core, and after additionally supporting a catalyst for producing silicon carbide whiskers, the raw material hydrocarbon compound and silicon sulfide gas are combined. 1. A method for producing silicon carbide whiskers having a large diameter, the method comprising: introducing and reacting silicon carbide to grow silicon carbide whiskers using the silicon carbide nuclei as production nuclei.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2235854A JPH04119999A (en) | 1990-09-07 | 1990-09-07 | Production of large-diameter silicon carbide whisker |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2235854A JPH04119999A (en) | 1990-09-07 | 1990-09-07 | Production of large-diameter silicon carbide whisker |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04119999A true JPH04119999A (en) | 1992-04-21 |
Family
ID=16992238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2235854A Pending JPH04119999A (en) | 1990-09-07 | 1990-09-07 | Production of large-diameter silicon carbide whisker |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04119999A (en) |
-
1990
- 1990-09-07 JP JP2235854A patent/JPH04119999A/en active Pending
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