JPH04198099A - Production of silicon carbide whisker having thick diameter - Google Patents
Production of silicon carbide whisker having thick diameterInfo
- Publication number
- JPH04198099A JPH04198099A JP32268590A JP32268590A JPH04198099A JP H04198099 A JPH04198099 A JP H04198099A JP 32268590 A JP32268590 A JP 32268590A JP 32268590 A JP32268590 A JP 32268590A JP H04198099 A JPH04198099 A JP H04198099A
- Authority
- JP
- Japan
- Prior art keywords
- silicon carbide
- silicon
- gas
- group
- catalyst
- 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 61
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 229910010271 silicon carbide Inorganic materials 0.000 title description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 67
- 239000002184 metal Substances 0.000 claims abstract description 67
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 30
- 229910021332 silicide Inorganic materials 0.000 claims abstract description 27
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- DFJQEGUNXWZVAH-UHFFFAOYSA-N bis($l^{2}-silanylidene)titanium Chemical compound [Si]=[Ti]=[Si] DFJQEGUNXWZVAH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 30
- KHDSWONFYIAAPE-UHFFFAOYSA-N silicon sulfide Chemical compound S=[Si]=S KHDSWONFYIAAPE-UHFFFAOYSA-N 0.000 claims description 30
- 150000002739 metals Chemical class 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 claims description 5
- 229910021343 molybdenum disilicide Inorganic materials 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229910021352 titanium disilicide Inorganic materials 0.000 claims description 3
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 23
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 2
- 229910020343 SiS2 Inorganic materials 0.000 abstract 4
- 229910020968 MoSi2 Inorganic materials 0.000 abstract 1
- 229910020044 NbSi2 Inorganic materials 0.000 abstract 1
- 229910008479 TiSi2 Inorganic materials 0.000 abstract 1
- 229910008814 WSi2 Inorganic materials 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 41
- 230000006911 nucleation Effects 0.000 description 17
- 238000010899 nucleation Methods 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000012159 carrier gas Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 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 9
- 229910052759 nickel Inorganic materials 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 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
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000012779 reinforcing material Substances 0.000 description 6
- 239000007809 chemical reaction catalyst Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007796 conventional method Methods 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
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 229910052863 mullite Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-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
- 239000002131 composite material Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910003185 MoSx Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 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
- 239000003350 kerosene Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- -1 oxides Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011226 reinforced ceramic Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 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
- 241000238631 Hexapoda Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-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
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 239000000470 constituent Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 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
- 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
- 238000010438 heat treatment Methods 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
- 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
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 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
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 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
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000019086 sulfide ion homeostasis Effects 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
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] [Industrial Field of 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 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、溶融金属との濡れ姓がよいなど、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を介して導入し、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。Among these methods, a gas phase method in which silicon sulfide and a hydrocarbon compound are reacted in the gas phase has attracted attention. A method is to precipitate and grow silicon carbide whiskers by introducing them into a reactor maintained at 130 to 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.
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。It is also disclosed that metals such as iron, nickel, titanium, manganese, cobalt, copper, vanadium, chromium, aluminum, and silicon, or compounds thereof, are effective as nucleating materials in this method.
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か特
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 found 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, Filed earlier (Patent Application Hei 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か得
られるか、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、 ９４．９８
１（＋９８６１ ）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 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). 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: Journal of the Ceramics Association, 94.98
1 (+9861), 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、
１μｍ以上の径のものは極小量しか得られていない。本
発明の目的は、前記従来技術では有効に製造しえなかっ
た直径１μｍ以上の太い径の炭化ケイ素ウィスカーを高
収率で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 particles with a diameter of 1 μm or more has been obtained. An object of the present invention is to provide an industrially advantageous manufacturing method capable of obtaining silicon carbide whiskers having a large diameter of 1 μm or more in high yield, which could not be effectively manufactured using the conventional techniques.
［課題を解決するための手段］
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
び酸処理を施した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] As a result of extensive research into a method for producing large-diameter silicon carbide whiskers by the reaction between silicon sulfide and a hydrocarbon compound, the present inventors have found that, prior to the reaction, certain metals and The present invention was completed by discovering that the above object can be achieved by forming thick stump-shaped production nuclei on a whisker production substrate using a multi-component catalyst that combines acid-treated metal silicides.
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、先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酸処理を施した
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
ばれる一種以上の酸処理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、次いて炭化水素ガスを導入し
て反応させることによって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 metals belonging to After supporting a multi-component catalyst containing one or more acid-treated metal silicides as an active ingredient, silicon sulfide gas is introduced to generate silicon nuclei, and then hydrocarbon gas is introduced to cause a reaction. After converting the silicon core into a silicon carbide core and additionally supporting a catalyst for producing silicon carbide whiskers, the raw material hydrocarbon compound and silicon sulfide gas are introduced and reacted to convert the silicon carbide core into a silicon carbide core. This is a method for producing silicon carbide whiskers with a large diameter, which is characterized by growing silicon carbide whiskers as production nuclei.
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高収率で得ることができる。According to the present invention, silicon carbide whiskers, the entire amount of which has a diameter of 1 μm or more, can be obtained in high yield.
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、収率も高々５０％前後である
ことに比へ、本発明によるウィスカーはほぼ全量が１μ
ｍ以上であり、通常は１〜５麟径という極めて太い径の
ウィスカーであり、かつ収率は９０％以上にも達する。Compared to the average diameter of silicon carbide whiskers obtained by the conventional technology, which is 0.1 to 0.5 μm and the yield is around 50% at most, the whiskers according to the present invention have almost the entire amount of 1 μm.
m or more, the whisker has an extremely large diameter, usually 1 to 5 mm, and the yield reaches 90% or more.
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あらかしめ基板上に形成し
ておくこと及び該生成核に存在しつる生成阻害因子を除
去しておくことにより可能となるのである。This is done by preparing and forming on the substrate a stump-shaped nucleus with a diameter large enough to generate silicon carbide whiskers with a large diameter, and by removing factors that inhibit the generation of tendrils present in the nucleus. It becomes possible.
以下、本発明の製造法をプロセスに従って説明する。Hereinafter, the manufacturing method of the present invention will be explained according to the process.
先ず、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（即ち、炭化ケイ素ウィス
カーの生成核、以下生成核という。）を生成させるたる
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、酸処理を施した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酸処理金属ケイ化
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。First, prior to the reaction, a catalyst (hereinafter referred to as a catalyst) for generating silicon carbide nuclei (i.e., silicon carbide whisker generation nuclei, hereinafter referred to as generation nuclei) is formed on a substrate in a reactor through the generation of silicon nuclei. , referred to as a nucleation catalyst). 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 acid-treated molybdenum disilicide, tungsten disilicide, niobium disilicide, and A multi-component catalyst containing as an active ingredient one or more acid-treated metal silicides selected from the group consisting of titanium disilicide (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.
ここで、酸処理金属ケイ化物とは、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
化チタンよりなる金属ケイ化物類を酸に浸漬あるいは酸
の蒸気に接触させたあと、水洗し乾燥させたものをいう
。酸処理することで、金属ケイ化物の８１成分を一部除
去することにより、あたかもスポンジ状を呈し、その表
面に６〜１０μｓの径を有する反応活性金属種が濃縮さ
れた状態の触媒となすか、あるいは金属ケイ化物の表面
に付着している酸化珪素や有機物等の不純物を除去し、
触媒の表面活性を増させることができる。Here, acid-treated metal silicides are metal silicides made of molybdenum disilicide, tungsten disilicide, niobium disilicide, and titanium disilicide that are immersed in acid or brought into contact with acid vapor, then washed with water and dried. refers to something that By removing part of the 81 components of the metal silicide through acid treatment, a catalyst with a sponge-like appearance and a concentration of reactive metal species with a diameter of 6 to 10 μs on its surface is created. , or remove impurities such as silicon oxide and organic substances adhering to the surface of metal silicide,
The surface activity of the catalyst can be increased.
金属ケイ化物をスポンジ類似形状とし表面の金属濃度を
高めることで、Ｈ２Ｓとの反応により生成するＭｏＳｘ
等の金属硫化物によるウィスカーの収率向上を図ること
ができ、さらにＭ ｏ Ｓ ｉ ２等の金属ケイ化物の
粒径が６〜１０μｓであるため、ＭｏＳｘ等の金属硫化
物の粒径も同程度になると考えられ、この粒径のウィス
カー径への寄与率は一般に５０％程度であるため大径（
１〜５戸）のウィスカーが生成可能となる。By making the metal silicide into a sponge-like shape and increasing the metal concentration on the surface, MoSx generated by reaction with H2S
Furthermore, since the particle size of metal silicides such as MoS i 2 is 6 to 10 μs, the particle size of metal sulfides such as MoSx can also be improved. The contribution rate of this particle size to the whisker diameter is generally about 50%, so the large diameter (
1 to 5) whiskers can be generated.
不純物の存在は生成されるケイ素質の核の生成を阻害す
るため、最終的に得られるウィスカーの収率およびウィ
スカーの直径に影響を及ぼし得る。従って、ウィスカー
の直径が太い状態のままで収率を向上させる手段として
、前記触媒形状とするか不純物を除去することが有効に
なる。使用できる酸としては、フッ化水素酸、硫酸、硝
酸等の無機酸、酢酸、蓚酸、マロン酸等の有機酸あるい
はこれらの混合酸等のいずれでも良い。中でも、金属ケ
イ化物のＳ１成分を一部除去する作用の優れた酸として
はフッ化水素酸を挙げることができる。具体的には、０
．１〜５０Ｍ程度の酸に１〜６０分間（１０〜３０℃）
程度浸漬（必要により攪拌）するか、酸の０．１〜１０
％蒸気（１００〜３００℃）に１〜５分間程度接触させ
ることにより、酸処理を行なうことができるが、用いる
ことのできる酸処理金属ケイ化物は、その処理方法を問
わず、不純物が５．０００ｐ ｐ ｍ未満の処理物を好
適に用いることができる。The presence of impurities inhibits the formation of the siliceous cores that are produced, and thus can affect the final whisker yield and whisker diameter. Therefore, as a means to improve the yield while keeping the diameter of the whiskers large, it is effective to use the catalyst shape described above or to remove impurities. Examples of acids that can be used include inorganic acids such as hydrofluoric acid, sulfuric acid, and nitric acid, organic acids such as acetic acid, oxalic acid, and malonic acid, and mixed acids thereof. Among these, hydrofluoric acid can be cited as an acid that has an excellent effect of partially removing the S1 component of metal silicides. Specifically, 0
．． 1-60 minutes in 1-50M acid (10-30℃)
Immerse to a certain degree (stirring if necessary) or add 0.1 to 10% of acid.
% steam (100 to 300°C) for about 1 to 5 minutes, however, the acid-treated metal silicide that can be used has impurities of 5.5%, regardless of the treatment method. A treated product having a concentration of less than 000 ppm can be suitably used.
この多元触媒はＢ群の酸処理金属ケイ化物とＡ群の各金
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
合物あるいは一般弐Ｍ ｆｃ２Ｈ５）で表されるメタロ
センなどの有機化合物を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
群の酸処理金属ケイ化物とＡ群各金属との混合物あるい
はＢ群の酸処理金属ケイ化物とＡ群各金属の一部合金の
形として担持させる。各金属の使用割合は、Ａ群の金属
とＢ群の酸処理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１ｏ／１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高収率で得
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群の酸処理金属ケイ化物として酸処理を施した二ケイ
化モリブデン（ＭｏＳｉｉ）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
。This multi-component catalyst is composed of the acid-treated metal silicide of group B and the elemental metal of each metal component of group A, or inorganic compounds such as oxides, carbides, sulfides, halides, sulfates, and nitrates of these metals, or general After an organic compound such as metallocene represented by fc2H5) is mixed and deposited on a substrate as a carrier, B is produced by a thermal decomposition reaction and/or a reduction reaction.
It is supported in the form of a mixture of the acid-treated metal silicide of Group A and each metal of Group A, or a partial alloy of the acid-treated metal silicide of Group B and each metal of Group A. The ratio of each metal to be used is that the molar ratio of group A metal to group B acid-treated metal silicide is 0.1/
The preferred range is 1 to 5/1 and the ratio of the largest component in Group A to the remaining components is 10/1 or less in terms of molar ratio. 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 obtained in high yield. Among these multi-component catalysts, iron (Fe) and nickel (Ni) are used as group A metals,
A particularly excellent combination is the use of acid-treated molybdenum disilicide (MoSii) as the acid-treated metal silicide of group B, as it has high reactivity and is 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、ムライト等のセラミックス材料あるいは黒鉛
、ガラス状炭素等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等の３１０２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５ｕｃｈ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, and among these, materials containing the 3102 component such as mullite ceramics are particularly suitable. This is presumed to be because 5uch, 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
壁な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 structure such as a mullite ball 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Ｓこ限定は
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のもの
が好適に用いられる。The reactor used in the method of the present invention is not particularly limited, but for example, a hydrocarbon compound as shown in FIG.
A structure in which a reaction tube equipped with an inlet pipe for silicon sulfide and catalyst components and an outlet pipe for exhaust gas is installed in a horizontal electric furnace is preferably used.
横型か好ましいのは粉末状の酸処理金属ケイ化物を担体
上に担持させやすいためである。The horizontal type is preferable because it makes it easier to support the powdered acid-treated metal silicide on the carrier.
生成核形成触媒の担持方法としては、前記Ｂ群の酸処理
金属ケイ化物を担体上に予め担持させておき、Ａ群の各
金属の単体またはその金属化合物を１．１００〜１．５
００℃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、ニラケロセン等
の昇華性のある物質は蒸気圧を利用し、加熱状態で窒素
等の不活性ガスや水素等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Ａ群の金属成
分は、還元性ガスによフて還元され、金属の形でＢ群の
酸処理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 for supporting the nucleation catalyst, the acid-treated metal silicide of group B is supported on the carrier in advance, and each element of group A metal or its metal compound is supported at a concentration of 1.100 to 1.5.
It is introduced into a reactor maintained at a high temperature of 00°C and supported on a carrier. In this case, sublimable substances such as ferrocene and nirakerosene are carried by utilizing vapor pressure and introducing an inert gas such as nitrogen or a reducing gas such as hydrogen into the system as a carrier gas in a heated state. 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 a catalytic action together with the acid-treated 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群の金属はＩ Ｃ１〜５００ ｍｇ／ｍ”、Ｂ群の酸
処理金属ケイ化物は１００〜ｌ、 ０００ｍｇ／ｍ２が
好ましい。Ａ群の金属の担持量カ月Ｏｍｇ／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５ ００ ｍｇ／ｍ２を超
えてもそれ以上の効果はない、Ｂ群の酸処理金属ケイ化
物は担持量が１００ ｍｇ／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、０（１（ｌ
ｍｇ／ｍ”を超えてもそれ以上の効果はない。The supported amount of the nucleation catalyst is preferably 1 to 500 mg/m2 for group A metals and 100 to 1,000 mg/m2 for acid-treated metal silicides of group B per unit area of the base material of the carrier. If the supported amount of the group metal is less than 0 mg/m2 per month, it is difficult to obtain large diameter nuclei, so there is little effect in increasing the diameter of the whisker, and if it exceeds 500 mg/m2, there is no further effect.B Similarly, acid-treated metal silicides in the group have little effect in increasing the whisker diameter when the supported amount is less than 100 mg/m2, and 1,0(1(l)
There is no further effect even if it exceeds "mg/m".
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.
先ずキャリアガス中に０．５〜４Ｖｏ１％の硫化ケイ素
ガスを含む混合ガスを１．２５０〜１．４５０℃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〜
０．１０ｃｍ／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。First, a gas mixture containing 0.5 to 4 Vo1% silicon sulfide gas in a carrier gas is placed in a reactor kept at 1.250 to 1.450°C at a gas flow rate of 0.02 to 0.02 in the reaction zone.
It takes 2 to 4 hours at 0.10 cm/sec, and the total amount of silicon sulfide supplied is 1 of the nucleation catalyst supported on the substrate.
It is introduced in an amount of ~30 times (in terms of molar ratio) to generate silicon nuclei on the substrate. 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.
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０．５〜１．０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〜ｌＯ＠
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てあり、ま
た１０倍量を超えてもそれ以上の効果はない。この生成
核は、顕微鏡観察によれば、直径１μｍ以上の切り株状
の形態を有するものが生体であり、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。Next, a mixed gas containing 5 to 30 Vo1% hydrocarbon gas in the carrier gas was passed at the same temperature at a gas rate of 0.02 to 0.
．． It takes 0.5 to 1.0 hours at 10 cm/sec, and the total amount of hydrocarbon supplied is 1 to 1 O@ compared to that of silicon sulfide.
amount (in terms of molar ratio) to change the previously formed silicon core into a silicon carbide core (product nucleus). If the total supply of hydrocarbons is that of silicon sulfide,
If the amount is less than 1 times, the formation of silicon carbide nuclei will be insufficient, and if the amount exceeds 10 times, no further effect will be obtained. According to microscopic observation, this generated nucleus has a stump-like form with a diameter of 1 μm or more in living organisms, and silicon carbide whiskers are generated in the form of growing stumps, so thick whiskers are used. Obtainable.
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.
即ち、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
するたけて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 a catalyst at this stage in order to make the reaction proceed smoothly. −
Once formed, the product nuclei remain intact even after the generated silicon carbide whiskers are recovered, and can be used repeatedly as they are as long as the reaction catalyst is added.
反応触媒としては、キャリアガス導入等の装置の構造上
、前記Ｂ群の酸処理金属ケイ化物とＡ群の金属の中から
選ばれる一種以上を適当な化合物の形で導入し担持させ
ることが好ましいか、それらに限らず、酸処理を施して
いない金属ケイ化物やＭｏ、 Ｎｂ、 Ｗ等も用いつる
。その中でも鉄やニッケルは使いやすい触媒である。担
持方法としては例えば、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 ’Ｃ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
触媒の担持量は、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０．０００２〜０００１モルが好まし
い。As the reaction catalyst, it is preferable to introduce and support one or more selected from the acid-treated metal silicide of group B and the metal of group A in the form of an appropriate compound, due to the structure of the equipment for introducing carrier gas, etc. However, metal silicides, Mo, Nb, W, etc. that have not been subjected to acid treatment can also be used. Among them, iron and nickel are easy to use catalysts. For example, in the case of iron or nickel, hydrogen gas heated to around 80°C in the form of ferrocene or nilakerosene is introduced as a carrier, and in the case of cobalt, cobalt chloride is heated to around 250°C. Nitrogen gas may be introduced as a carrier. The amount of the additional catalyst supported is preferably 0.0002 to 0001 mol in total of the metal components per 1 mol of silicon sulfide to be reacted.
担持量が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。If the supported amount is less than 0.0002 mol, the yield of silicon carbide whiskers will be low, and if it exceeds 0.001 mol, there will be no further effect.
次に反応帯域の温度を１，１３０〜１．５００℃、好ま
しくはｌ、 ２００〜ｌ、 ４５０°Ｃ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 reaction zone temperature is 1,130 to 1,500°C, preferably 1,200 to 450°C, and the reaction is started.
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、プロパン等のパラフィン系炭化水素化合物、エチ
レン、プロピレン等のオレフィン系炭化水素化合物、ア
セチレン、アリレン等のアセチレン系炭化水素化合物、
ベンゼン、トルエン等の芳香族炭化水素化合物、シクロ
パラフィン、シクロオレフィン等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, and acetylene, arylene, etc. acetylenic hydrocarbon compounds,
Examples include aromatic hydrocarbon compounds such as benzene and toluene, alicyclic hydrocarbon compounds such as cycloparaffins and cycloolefins, and mixtures thereof.
炭化水素化合物は、水素等の還元性ガスまたはこれらの
還元性ガスを窒素等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。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.
また、硫化ケイ素は、予めフェロシリコンと硫黄とを反
応させる等の方法で製造したものを加熱気化させ、キャ
リアガスと共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、キャリアガスて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。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 produced by holding metal silicon at the tip of an introduction tube maintained at 1.000 to 1.400°C in a reactor, and introducing hydrogen sulfide gas diluted with a carrier gas to cause the reaction. If it is produced, it is convenient because there is no need to provide a separate silicon sulfide production device or vaporization device.
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てもよい水素など
の還元性ガスを用いるか、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 less active gas such as nitrogen or a reducing gas such as hydrogen which may be diluted with an inert gas, or a reducing gas such as hydrogen which may be diluted with an inert gas, or Particularly preferred is hydrogen or a mixed gas of hydrogen and nitrogen.
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、反応温度等の他の条件との組
み合わせで適宜窓められる。通常、原料混合物およびキ
ャリアガスを含む全ガス中の炭化水素化合物の濃度は１
〜５ ｍｏ１％、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, shape, and reaction temperature of the reactor. Typically, the concentration of hydrocarbon compounds in the total gas including the feed mixture and carrier gas is 1
~5 mo1%, silicon sulfide concentration is 5-30 mo1%
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、００６〜０．２４ｃｍ／ｓｅｃとする。通ガ
ス速度が０．０６ｃｍ／ｓｅｃ未満ては単位時間当たり
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 less than 0.06 cm/sec, 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 are 0
It grows to the desired size in 5 to 1 hour and can be collected 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核の上に成長して
いくので、従来の方法では得ることが難しかった太い径
のウィスカーを高収率で得ることができる。In the method of the present invention, silicon carbide whiskers grow on the nuclei formed in advance on the substrate in the reactor, so thick whiskers, which are difficult to obtain with conventional methods, can be produced with high yield. You can get it at a high rate.
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１〜５μｍ、長さ１、０００〜１０．０００
ｐｍかつアスペクト比１．０００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
維強化セラミックス等の各種複合材料の補強材として好
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 5 μm, and a length of 1,000 to 10,000 μm.
pm and an aspect ratio of 1.000 or more, and is suitable as a reinforcing material 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.
以下の実施例および比較例は、実施例１．２および比較
例１．２をそれぞれ表１に示す条件に基づき触媒の使用
比率等を変え下記の手順にしたがって実施した。なお、
条件により下記の手順の一部を省略したものもある。The following Examples and Comparative Examples were carried out in accordance with the following procedure by changing the ratio of catalyst used, etc., based on the conditions shown in Table 1 for Example 1.2 and Comparative Example 1.2, respectively. In addition,
Depending on the conditions, some of the steps below may be omitted.
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てシールした内径５２ｍｍ、長さｌ
、 ５００ｍｍのムライト製反応管４を設置し、内径１
０ｍｍのアルミナ管を右端のゴム栓に３本（導入管５〜
７）、左端のゴム栓に１本（排ガス導出管８）取り付け
たものを反応器とした。As shown in Fig. 1, a horizontal electric furnace 1 with an inner diameter of 52 mm and a length l whose left and right ends were sealed with silicone rubber plugs 2.
, A 500 mm mullite reaction tube 4 was installed, and the inner diameter was 1.
Three 0mm alumina tubes are attached to the rubber stopper on the right end (introduction tube 5~
7) A reactor was constructed by attaching one pipe (exhaust gas outlet pipe 8) to the rubber stopper at the left end.
成ノ〉 虫媒の礼′
反応管中心部の均熱帯（長さ４５０ｍｍ程度の範囲）に
、フッ化水素酸５０Ｍ溶液（２０℃）に６０分間浸漬す
ることにより酸処理を施した二ケイ化モリブデン粉末（
粉末度１〜３００４ｍ） ５ Ｑｍｇ （６８０ｍｇ／
ｍ２）を室温で担持させておき、つついて反応器を第２
図に示すような温度分布となるように加熱しておき、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°Ｃ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。Narino〉 Thanks to the insect pollinator' Disilicide was acid-treated by immersing it in a 50M solution of hydrofluoric acid (20°C) for 60 minutes in a soaking zone (approximately 450 mm in length) at the center of the reaction tube. Molybdenum powder (
Powderness 1-3004m) 5 Qmg (680mg/
m2) was supported at room temperature, and the reactor was moved to the second
It was heated so that the temperature distribution was as shown in the figure, and on the other hand, sufficient amounts of ferrocene and nirakerosene were placed in a 50 ml container and heated to 80°C. Vaporized ferrocene and nilakerosene were introduced into the reactor from the introduction tube 5 by passing through the reactor for a minute, and a predetermined amount of iron and nickel were supported on the inner wall (0.25 m2) of the reaction tube.
！底叔Ω工滅
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。先ず
、導入管７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７よ
り１．５ｍｌ／ｍｉｎの硫化水素と７５ ｍｌ／ｍｉｎ
の水素の混合ガス（通ガス速度０．０６ｃｍ／５ｅｃ）
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１０ｍｌ／ｍｉｎのメタンと６６、５ｍｌ／ｍｉｎ
の水素よりなる混合ガス（通ガス速度０、０６ｃｍ／５
ｅｃ）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。! A reactor carrying the nucleation catalyst was heated to a temperature distribution as shown in FIG. 2, and nucleation was performed. First, metal silicon is fixed on the tip of the introduction tube 7, and this tip is maintained in a temperature range of 1.200°C, and hydrogen sulfide is added through the introduction tube 7 at a rate of 1.5 ml/min and 75 ml/min.
mixed gas of hydrogen (gas flow rate 0.06cm/5ec)
was introduced over a period of 3 hours to generate silicon sulfide and silicon cores. Next, the introduction pipe 6
10ml/min of methane and 66,5ml/min
A mixed gas consisting of hydrogen (gas flow rate 0, 06 cm/5
ec) was introduced over a period of 0.5 hours to form silicon carbide nuclei.
叉妄股崖９１１
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８０°Ｃに加温しておき、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
内壁に所定量の鉄およびニッケルを担持させた。Confusion cliff 911 The device for introducing ferrocene and nira-kerosene used for product nucleation is heated to 80°C, and by passing hydrogen at 50 ml/min for 30 minutes, vaporized ferrocene and nira-kerosene are introduced from the inlet tube 5 into the reactor. A predetermined amount of iron and nickel were supported on the inner wall of the reaction tube.
叉−一且
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（通
ガス速度０．１２ｃｍ／５ｅｃ） Ｌ／、反応させた。Gaseous methane and silicon sulfide (S
iS) was introduced together with a carrier gas over a period of 2 hours (gas flow rate: 0.12 cm/5 ec) L/, and the reaction was carried out.
メタンは２０ ｍｌ／ｍｉｎのメタンガスを１１５ｍｌ
／ｍｉｎの水素ガスと共に導入管６より導入し、硫化ケ
イ素は、導入管７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
７より３ ｍｌ／ｍｉｎの硫化水素と１５ｍｌ／ｍｉｎ
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。For methane, 115 ml of methane gas at 20 ml/min
Silicon sulfide is introduced from the introduction tube 6 together with hydrogen gas at a temperature of 3 ml/min hydrogen sulfide and 15 ml/min
A mixed gas of 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、顕微鏡し察の結果、ウィス
カーの直径は１〜５μｍ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 examination of the obtained product, the diameter of whiskers was 1 to 5 μm, and the presence of whiskers smaller than 1 μm was not observed. Further, as a result of X-ray diffraction measurement, it was confirmed that the obtained product was a β-type silicon carbide whisker.
比較例として、生成核形成触媒として酸処理金属ケイ化
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共に表１に示す。酸
処理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〜（１
，５ｕＩであった。As a comparative example, silicon carbide whiskers were produced in the same manner as in the examples without using an acid-treated metal silicide as a nucleation catalyst, and the results are shown in Table 1 together with the examples. When acid-treated metal silicide is not used, the diameter of the obtained silicon carbide whiskers is 01 to (1) as a result of microscopic observation.
, 5uI.
更に、ウィスカーの収率においても表１の結果から本発
明の方法に基づ〈実施例１．２ては、比較例１．２に比
較して炭化ケイ素ウィスカーが極めて高収率で得られた
ことがわかる。なお、ここで示した収率は、次の式によ
り計算した。Furthermore, regarding the yield of whiskers, based on the method of the present invention, as shown in Table 1, silicon carbide whiskers were obtained in an extremely high yield in Example 1.2 compared to Comparative Example 1.2. I understand that. Note that the yield shown here was calculated using the following formula.
収率（％） ＝ （（ＳｉＣウィスカー収量）／消費Ｓ
１量から計算したＳｉＣ量））ｘｌＯ○（以下余白）
［発明の効果］
本発明の方法によれば、前記Ｂ群の酸処理金属ケイ化物
を核生成触媒として用いることにより、従来の方法に比
へて太い径の炭化ケイ素ウィスカーを高収率で得ること
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。Yield (%) = ((SiC whisker yield)/Consumption S
SiC amount calculated from 1 amount)) Silicon carbide whiskers with a relatively large diameter can be obtained in high yield. 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 ５〜７・・・導入管８・・・
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 5-7...Introduction tube 8...
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、先ず反応系内の基板上に、触媒として
周期律表第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、酸処理を施した二
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
れる一種以上の酸処理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つて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 catalyst belonging to Group VIII of the periodic table is placed on a substrate in the reaction system. Group consisting of metal and copper (A
2 or more metals selected from Group B) and one or more acids selected from the group consisting of acid-treated molybdenum disilicide, tungsten disilicide, niobium disilicide, and titanium disilicide (Group B). After supporting a multi-component catalyst containing treated metal silicide as an active ingredient, silicon sulfide gas is introduced to generate silicon cores, and then hydrocarbon gas is introduced and reacted to generate silicon cores. After converting into silicon carbide cores and additionally supporting a catalyst for producing silicon carbide whiskers, the raw material hydrocarbon compound and silicon sulfide gas are introduced and reacted, and the silicon carbide cores are used as production nuclei to carbonize. A method for producing silicon carbide whiskers with a large diameter, characterized by growing silicon whiskers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32268590A JPH04198099A (en) | 1990-11-28 | 1990-11-28 | Production of silicon carbide whisker having thick diameter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32268590A JPH04198099A (en) | 1990-11-28 | 1990-11-28 | Production of silicon carbide whisker having thick diameter |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04198099A true JPH04198099A (en) | 1992-07-17 |
Family
ID=18146477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32268590A Pending JPH04198099A (en) | 1990-11-28 | 1990-11-28 | Production of silicon carbide whisker having thick diameter |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04198099A (en) |
-
1990
- 1990-11-28 JP JP32268590A patent/JPH04198099A/en active Pending
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