JPS644999B2 - - Google Patents
Info
- Publication number
- JPS644999B2 JPS644999B2 JP55176244A JP17624480A JPS644999B2 JP S644999 B2 JPS644999 B2 JP S644999B2 JP 55176244 A JP55176244 A JP 55176244A JP 17624480 A JP17624480 A JP 17624480A JP S644999 B2 JPS644999 B2 JP S644999B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- silicon
- whiskers
- carbon
- reaction tube
- 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.)
- Expired
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 56
- 229910052799 carbon Inorganic materials 0.000 claims description 56
- 239000007789 gas Substances 0.000 claims description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 49
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 26
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 25
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 24
- 229910052742 iron Inorganic materials 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- 239000011651 chromium Substances 0.000 claims description 11
- 238000005121 nitriding Methods 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 8
- 238000005255 carburizing Methods 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- YOGPEMONGVRERR-UHFFFAOYSA-N [C]=O.[Si]=O Chemical compound [C]=O.[Si]=O YOGPEMONGVRERR-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-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
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 1
- 239000011225 non-oxide ceramic Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 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
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/005—Growth of whiskers or needles
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/36—Carbides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/38—Nitrides
Description
【発明の詳細な説明】
本発明は、セラミツクスウイスカーの製造法に
関し有用な長い窒化けい素ウイスカー等のセラミ
ツクスウイスカーを高収率で得ることを目的とす
るものである。ウイスカーは欠陥のない微細な繊
維状に成長した単結晶であつて、非常に高い引張
り強さを有しており、繊維強化複合材料用の基材
として重要視されている。この複合材料用基材と
してのウイスカーに要求される性質は、(1)高温で
安定なこと、(2)比強度が大きいこと、(3)比弾性率
が大きいこと、(4)軽いこと、などであり、酸化物
炭化物、窒化物などのセラミツクスウイスカーは
十分に、これらの要求に応えるものであつて、大
量に生産されるならば、極めて有望な基材として
期待されている。DETAILED DESCRIPTION OF THE INVENTION The object of the present invention is to obtain ceramic whiskers, such as long silicon nitride whiskers, useful in a process for producing ceramic whiskers, in high yield. Whiskers are defect-free single crystals grown in the form of fine fibers and have extremely high tensile strength, and are considered important as base materials for fiber-reinforced composite materials. The properties required of the whisker as a base material for composite materials are (1) stability at high temperatures, (2) high specific strength, (3) high specific modulus, (4) lightness, Ceramic whiskers such as oxide carbides and nitrides fully meet these requirements, and are expected to be extremely promising base materials if produced in large quantities.
本発明は、上記の如き、有用な複合材料用基材
としてのセラミツクウイスカーのうち、特に窒化
けい素、炭化けい素ウイスカーについてその製造
法を提供しようとするものである。 The present invention aims to provide a method for producing ceramic whiskers, particularly silicon nitride and silicon carbide whiskers, which are useful as base materials for composite materials as described above.
窒化けい素ウイスカーや炭化けい素ウイスカー
の製造については、従来から多くの試みがなされ
ているが、それらは窒化けい素粉末や炭化けい素
粉末の製造時に副産物として、何れも僅かに得ら
れる程度であり、大量生産は望めず、また有用な
長いウイスカーは容易に得られないのが現状であ
る。 Many attempts have been made to produce silicon nitride whiskers and silicon carbide whiskers, but they are only obtained in small quantities as by-products during the production of silicon nitride powder and silicon carbide powder. Currently, mass production cannot be expected, and useful long whiskers are not easily obtained.
本発明者らは、二酸化けい素（SiO2）の還
元・窒化または炭化による窒化けい素（Si3N4）
粉末または炭化けい素（SiC）粉末製造時にウイ
スカーが副生される現象から、これを多量に生産
できるような製造方法を考え、基礎実験を続けた
結果本発明に至つたものである。即ち、本発明
は、
(1) 二酸化けい素（SiO2）に金属けい素（Si）
または炭素（Ｃ）などの還元剤を混合した粉粒
体を不活性ガス中、1300℃以上に加熱して、一
酸化けい素（SiO）ガスまたは、一酸化けい素
（SiO）ガスと一酸化炭素（CO）ガスの混合ガ
スを発生させる工程。 The present inventors have developed silicon nitride (Si 3 N 4 ) by reducing and nitriding or carbonizing silicon dioxide (SiO 2 ).
Due to the phenomenon in which whiskers are produced as a by-product during the production of powder or silicon carbide (SiC) powder, we devised a manufacturing method that would allow whiskers to be produced in large quantities, and continued basic experiments that led to the present invention. That is, the present invention provides the following features: (1) Metallic silicon (Si) is added to silicon dioxide (SiO 2 ).
Alternatively, powder mixed with a reducing agent such as carbon (C) is heated to 1300°C or higher in an inert gas, and monoxide is mixed with silicon monoxide (SiO) gas or silicon monoxide (SiO) gas. A process that generates a mixture of carbon (CO) gas.
(2) 上記の発生ガスを窒素（N2）ガス、二酸化
炭素（CO2）ガス、アルゴン（Ar）ガス、ヘ
リウム（He）ガス等の不活性ガスを搬送ガス
として、鉄、コバルト、ニツケル、クロムより
選ばれた金属または、それらの合金を含浸し、
1000℃以上に加熱されたカーボン反応管に送り
込み、窒化性雰囲気下で窒化けい素ウイスカー
を、あるいは、一酸化炭素（CO）ガスまたは
水素（H2）ガスを含む還元浸炭性雰囲気下で、
炭化けい素ウイスカーを析出成長させる工程。(2) The above generated gas is used as a carrier gas for inert gas such as nitrogen (N 2 ) gas, carbon dioxide (CO 2 ) gas, argon (Ar) gas, helium (He) gas, etc. Impregnated with a metal selected from chromium or an alloy thereof,
Silicon nitride whiskers are fed into a carbon reaction tube heated to 1000°C or higher under a nitriding atmosphere, or under a reducing carburizing atmosphere containing carbon monoxide (CO) gas or hydrogen (H 2 ) gas.
A process of growing silicon carbide whiskers by precipitation.
(3) 成長したウイスカーを反応管から取り出す工
程の３工程よりなる。工程(1)において、粉粒体
を1300℃以上の温度に加熱するのは、二酸化け
い素と、金属けい素または炭素との化学反応を
円滑に進めるためであり、1300℃以下の温度で
は反応が進みにくいからである。また工程(2)に
おいてカーボン反応管を1000℃以上に加熱して
いるのは、鉄、コバルト、ニツケル、クロムよ
り選ばれた金属またはそれらの合金を溶融させ
るためであり、これ以下の温度では、有用なウ
イスカーは得られないことや、一酸化けい素ガ
スの凝縮を防止するためである。(3) The process consists of three steps: removing the grown whiskers from the reaction tube. In step (1), the powder is heated to a temperature of 1300°C or higher in order to smoothly advance the chemical reaction between silicon dioxide and metal silicon or carbon. This is because it is difficult to advance. In addition, the reason why the carbon reaction tube is heated to 1000℃ or higher in step (2) is to melt metals selected from iron, cobalt, nickel, and chromium, or alloys thereof. This is to avoid obtaining useful whiskers and to prevent condensation of silicon monoxide gas.
次に、本発明の方法をその製造に使用した炉の
図面を参照して説明する。 Next, the method of the present invention will be explained with reference to drawings of a furnace used for its production.
第１図において原料ホツパー２中の原料１はバ
ルブ５の開閉操作により坩堝３内に落下供給され
る。ガス発生炉４Ａを1300℃以上の高温に保ち、
坩塙３内の原料から発生したガス８は８のガス導
入管から坩堝３内に導入した不活性ガス６を搬送
ガスとして坩堝３のあるガス発生炉４Ａと連結し
た炉４Ｂ内の、1000℃以上の温度に加熱されたカ
ーボン反応管１１へ運ばれる。該カーボン反応管
１１には、鉄、コバルト、ニツケル、クロムの中
より選ばれた金属もしくはそれらの合金が含浸さ
れており、この反応管１１は１０のガス導入管か
らN2ガス・（N2＋H2）ガスあるいはNH3ガス等
の窒化性ガスを導入した窒化性雰囲気、または、
COガスあるいはH2ガスを導入して還元浸炭性雰
囲気としている。 In FIG. 1, a raw material 1 in a raw material hopper 2 is dropped into a crucible 3 by opening and closing a valve 5. Keep the gas generator 4A at a high temperature of 1300℃ or higher,
The gas 8 generated from the raw material in the crucible 3 is heated to 1000°C in a furnace 4B connected to a gas generating furnace 4A in which the crucible 3 is located, using an inert gas 6 introduced into the crucible 3 from a gas introduction pipe 8 as a carrier gas. The carbon is transported to the carbon reaction tube 11 heated to the above temperature. The carbon reaction tube 11 is impregnated with a metal selected from iron, cobalt, nickel, and chromium or an alloy thereof, and this reaction tube 11 is supplied with N 2 gas (N 2 +H 2 ) gas or nitriding atmosphere containing nitriding gas such as NH 3 gas, or
CO gas or H 2 gas is introduced to create a reducing carburizing atmosphere.
このようにした反応管１１内で窒化性雰囲気ガ
スと発生ガス８、または、還元浸炭性雰囲気ガス
と発生ガス８とを接触させることにより、反応管
内に窒化けい素ウイスカー１２、あるいは、炭化
けい素ウイスカー１２を析出成長させるのであ
る。結晶生成に寄与しなかつたガスは炉４Ｂの端
部の接続管１３から捕集ビン１６に回収される。
なお、１４はボルト１５で着脱可能にするために
炉４Ｂに取り付けた蓋部材である。 By bringing the nitriding atmospheric gas and the generated gas 8 into contact with each other or the reducing carburizing atmospheric gas and the generated gas 8 in the reaction tube 11, silicon nitride whiskers 12 or silicon carbide are formed in the reaction tube. The whiskers 12 are caused to grow by precipitation. Gas that does not contribute to crystal formation is collected into a collection bottle 16 from a connecting pipe 13 at the end of the furnace 4B.
Note that 14 is a lid member attached to the furnace 4B so as to be detachable with bolts 15.
上記のように本発明で用いる炉４は、原料から
発生するガス８を供給するガス発生炉４Ａとウイ
スカー１２を析出成長させるカーボン反応管１１
を有する炉４Ｂとからなる。 As described above, the furnace 4 used in the present invention includes a gas generating furnace 4A that supplies gas 8 generated from raw materials, and a carbon reaction tube 11 that deposits and grows whiskers 12.
It consists of a furnace 4B having a
炉４Ｂ内の反応管１１は析出面積を大きくする
ためにカーボン反応管を増やすことや、カーボン
反応管内にウイスカーを析出成長させたのち、カ
ーボン反応管を抜き出し、新たにカーボン反応管
を挿入するか、あるいは、抜き出したカーボン反
応管からウイスカーを回収したのち、再び挿入す
ることにより、ウイスカーの生成が行なえるよう
にしている。 For the reaction tube 11 in the furnace 4B, the number of carbon reaction tubes may be increased to increase the deposition area, or after whiskers are deposited and grown in the carbon reaction tube, the carbon reaction tube is taken out and a new carbon reaction tube is inserted. Alternatively, whiskers can be generated by collecting the whiskers from the carbon reaction tube that has been taken out and then reinserting the tube.
また、本発明では、二酸化けい素を主原料と
し、反応に寄与する還元剤として、金属けい素や
炭素を必要とする。この場合反応は、二酸化けい
素と金属けい素、あるいは炭素との界面での反応
が律速であるため、原料の形状は微細で表面積の
大きい粉末が有効であり、さらには、二酸化けい
素と還元剤との混合比は大きいほど反応が促進さ
れやすく最終的にウイスカーの収率を増加するこ
とができる。しかしその重量比は、二酸化けい素
１重量部に対して、還元剤0.4〜４重量部が適当
である。本発明で、窒化けい素ウイスカー、炭化
けい素ウイスカーの生成反応にあずかる一酸化け
い素（SiO）ガスを得る手段とてしては、前述の
ように二酸化けい素を還元するか、または炭化け
い素を酸化する方法。 Further, in the present invention, silicon dioxide is used as the main raw material, and metal silicon and carbon are required as reducing agents that contribute to the reaction. In this case, the rate of the reaction is determined by the reaction at the interface between silicon dioxide and metal silicon or carbon, so it is effective to use a powder with a fine shape and a large surface area as the raw material. The larger the mixing ratio with the agent, the more easily the reaction is promoted and the final yield of whiskers can be increased. However, the appropriate weight ratio is 0.4 to 4 parts by weight of the reducing agent to 1 part by weight of silicon dioxide. In the present invention, as a means for obtaining silicon monoxide (SiO) gas that participates in the production reaction of silicon nitride whiskers and silicon carbide whiskers, silicon dioxide is reduced as described above, or silicon carbide is A method of oxidizing elements.
SiO2＋Ｃ→SiO＋CO ……(1)
SiO2＋So→2SiO ……(2)
2SiO2＋SiC→3SiO＋CO ……(3)
SiC＋CO→SiO＋2C ……(4)
の反応によるものである。これらのうち、混合・
反応性原料の価格等を考慮すると、式(1)の、二酸
化けい素を炭素で還元する方法が最も有利とな
る。生成した一酸化けい素（SiO）ガスは、N2、
CO2、Ar、He等の不活性ガスにより、ガス発生
炉４Ａとは別に設けられた炉４Ｂのカーボン反応
管１１内へ送られると共にガス導入管１０より、
窒化性雰囲気ガスまたは還元浸炭性雰囲気ガスが
新たに導入され、カーボン反応管内で、次の(5)・
(6)式の反応が連続的に起こり、容易に窒化けい素
ウイスカーまたは炭化けい素ウイスカーが得られ
る。本発明では、カーボン反応管に鉄、コバル
ト、ニツケルの中から選ばれた金属もしくは、そ
れらの合金を含浸させているが、その方法は、例
えば塩化第二鉄、塩化コバルト、塩化ニツケル、
塩化クロムあるいは、それらの混合物の水溶液
を、カーボン反応管に、これらの塩化物の水溶液
を浸らせ、水分を乾燥後、水素気流中、1000℃以
上の温度で１時間還元することにより、鉄、コバ
ルト、ニツケル、クロムの各金属もしくは、それ
らの合金を、カーボン反応管内に均一に含浸させ
ることができる。窒化けい素ウイスカー、炭化け
い素ウイスカーはそれぞれウイスカーの先端に小
球体をもつておりこの小球体がウイスカー成長の
原動力になつていると考え、小球体の解析を行つ
た。 This is due to the following reaction: SiO 2 +C→SiO+CO (1) SiO 2 +So→2SiO (2) 2SiO 2 +SiC→3SiO+CO (3) SiC+CO→SiO+2C (4). Among these, mixed
Considering the price of reactive raw materials, etc., the method of formula (1) in which silicon dioxide is reduced with carbon is the most advantageous. The generated silicon monoxide (SiO) gas is
Inert gas such as CO 2 , Ar, He, etc. is sent into the carbon reaction tube 11 of the furnace 4B, which is provided separately from the gas generation furnace 4A, and from the gas introduction tube 10.
A nitriding atmosphere gas or a reducing carburizing atmosphere gas is newly introduced, and the following (5).
The reaction of formula (6) occurs continuously, and silicon nitride whiskers or silicon carbide whiskers are easily obtained. In the present invention, the carbon reaction tube is impregnated with a metal selected from iron, cobalt, and nickel, or an alloy thereof.
Iron, iron, Cobalt, nickel, chromium, or an alloy thereof can be uniformly impregnated into the carbon reaction tube. Silicon nitride whiskers and silicon carbide whiskers each have a spherule at the tip of the whisker, and we analyzed the spherules, believing that these spherules are the driving force behind whisker growth.
その結果小球体は鉄を含むシリコン合金であり
ウイスカーの成長時は液相、即ち液滴になつてお
り、さらにウイスカーには鉄は含まれていないこ
とがわかつた。これらの結果よりウイスカーの析
出、成長には鉄が析出核あるいは触媒として重要
な働きをしていると考えられる。 As a result, it was found that the spherules are a silicon alloy containing iron and are in a liquid phase, that is, droplets, when the whiskers grow, and that the whiskers do not contain iron. These results suggest that iron plays an important role as a precipitation nucleus or catalyst in whisker precipitation and growth.
この鉄の働きについて更に詳しく説明すると
(i) 一酸化けい素ガスが微粒鉄粉末表面の析出カ
ーボンでで還元され、シリコンが鉄中に溶入
し、シリコン−鉄の共晶温度（1208℃）で溶融
し、液滴となる。 To explain the function of iron in more detail, (i) silicon monoxide gas is reduced by carbon precipitated on the surface of fine iron powder, silicon dissolves into iron, and silicon-iron eutectic temperature (1208℃) It melts into droplets.
SiO＋Ｃ（onFe）→Si（inFe）＋CO↑ ……(5)
(ii) COガスは鉄と接触してカーボンをシリコン
−鉄液滴に供給し、過飽和になつたカーボンは
液滴表面に析出する。SiO + C (onFe) → Si (inFe) + CO↑ ...(5) (ii) CO gas contacts iron and supplies carbon to silicon-iron droplets, and supersaturated carbon is deposited on the droplet surface. .
CO→Ｃ（inFe）＋CO2 ……(6)
Ｃ（inFe）→Ｃ（onFe） ……(7)
(iii) (1)と(2)の反応でシリコン−鉄合金の液滴中に
固溶したシリコンとカーボンは液滴内で反応し
て炭化けい素として析出する。 CO→C(inFe)+CO 2 ……(6) C(inFe)→C(onFe) ……(7) (iii) Due to the reaction of (1) and (2), solidification occurs in the silicon-iron alloy droplet. The dissolved silicon and carbon react within the droplet and precipitate as silicon carbide.
Si（inFe）＋Ｃ（inFe）→SiC ……(8)
炭化けい素ウイスカーは上記(5)〜(8)の反応が連
続的に行われることにより成長しているものと
考えられる。 Si(inFe)+C(inFe)→SiC (8) It is thought that silicon carbide whiskers grow by continuously performing the reactions (5) to (8) above.
なお、窒化けい素ウイスカーの場合は窒化性雰
囲気により窒素ガスが液滴中に固溶しており、別
に固溶しているシリコンと反応して窒化けい素を
析出する。 In the case of silicon nitride whiskers, nitrogen gas is solidly dissolved in the droplets due to the nitriding atmosphere, and reacts with silicon that is otherwise solidly dissolved to precipitate silicon nitride.
N2→2N（inFe） ……(9)
3Si（inFe）＋4N（inFe）→Si3N4 ……(10)
窒化けい素ウイスカーは上記(5)(6)(7)(9)(10)の反応
が連続的に行われることにより成長しているもの
と考えられる。 N 2 → 2N (inFe) ……(9) 3Si (inFe) + 4N (inFe) → Si 3 N 4 ……(10) Silicon nitride whiskers are the above (5) (6) (7) (9) (10) It is thought that the growth is caused by the continuous reaction of ).
上に述べた鉄の働きをまとめると、シリコンが
溶入してウイスカー生成温度で液相になり、浸炭
性雰囲気よりのカーボンを溶入し、過飽和分は表
面に析出する。なお、窒化性雰囲気より窒素ガス
も溶入する。この様な特性を個々に持つ元素は沢
山あり、アルミニウム、ベリリウム、カルシウ
ム、コバルト、クロム、鉄、モリブテン、ニツケ
ル、タンタル、チタン、ウラン、バナジウム、タ
ングステン、ジルコニウムが挙げられるが、シリ
コン、カーボン、窒素が溶入するものとして鉄、
ニツケル、コバルト、クロムおよびこれらの合金
がウイスカー成長上に効果があることがわかつ
た。中でも、カーボン反応管に、鉄を均一に含浸
させた場合には、他の場合にくらべて、特に長い
結晶性ウイスカーを多量に得ることができた。ま
た、鉄、コバルト、ニツケル、クロムもしくは、
それらの合金を含浸させずに、ウイスカーをカー
ボン反応管に得ようとしたが、短いウイスカー
が、わずかに得られたにすぎなかつた。 To summarize the above-mentioned functions of iron, silicon infiltrates and becomes a liquid phase at the whisker formation temperature, carbon from the carburizing atmosphere infiltrates, and supersaturated content precipitates on the surface. Note that nitrogen gas also infiltrates from the nitriding atmosphere. There are many elements that individually have these properties, including aluminum, beryllium, calcium, cobalt, chromium, iron, molybdenum, nickel, tantalum, titanium, uranium, vanadium, tungsten, and zirconium, but also silicon, carbon, and nitrogen. iron as something to be welded into,
Nickel, cobalt, chromium, and their alloys were found to be effective on whisker growth. Among these, when the carbon reaction tube was uniformly impregnated with iron, a large amount of particularly long crystalline whiskers could be obtained compared to other cases. Also, iron, cobalt, nickel, chromium or
Attempts were made to obtain whiskers in carbon reaction tubes without impregnating these alloys, but only a few short whiskers were obtained.
以上のように、本発明によれば、一酸化けい素
（SiO）ガスまたは一酸化けい素（SiO）ガス及び
一酸化炭素（CO）ガスを多量に発生させる工程
と、一酸化けい素（SiO）ガスを用いて、窒化性
ガス雰囲気下におかれたカーボン反応管内で、窒
化けい素（Si3N4）ウイスカーを、また、還元浸
炭性ガス雰囲気下で炭化けい素（SiC）ウイスカ
ーを析出、成長させる工程にわけ、反応管には
鉄、コバルト、ニツケル、クロムの中から選ばれ
た金属もしくはそれらの合金を均一に含浸させた
ことにより、長い、結晶性の良い窒化けい素ウイ
スカーおよび、炭化けい素ウイスカーが高収率
で、多量に得られることが特徴である。且つ、原
料として安価なものを使用することにより、製造
コストを低下せしめることができるので、本発明
は窒化けい素や、炭化けい素等の非酸化物セラミ
ツクスウイスカーが経済的に得られるという実用
上大きな価値を有する。 As described above, according to the present invention, the process of generating a large amount of silicon monoxide (SiO) gas or silicon monoxide (SiO) gas and carbon monoxide (CO) gas, ) gas to deposit silicon nitride (Si 3 N 4 ) whiskers in a carbon reaction tube placed in a nitriding gas atmosphere, and silicon carbide (SiC) whiskers in a reducing carburizing gas atmosphere. During the growth process, the reaction tube is uniformly impregnated with a metal selected from iron, cobalt, nickel, and chromium, or an alloy thereof, resulting in long, well-crystalline silicon nitride whiskers and It is characterized by the fact that silicon carbide whiskers can be obtained in high yield and in large quantities. In addition, by using inexpensive materials as raw materials, manufacturing costs can be reduced, so the present invention has practical advantages in that non-oxide ceramic whiskers such as silicon nitride and silicon carbide can be obtained economically. have great value.
以下、本発明を実施例により説明する。 The present invention will be explained below using examples.
実施例 １
主原料として粒度15ｍμの二酸化けい素
（SiO2）粉末を用い、還元剤として40ｍμの炭素
（Ｃ）粉末を重量比でSiO2：Ｃ＝10：４の比率で
配合しボールミルを用いて、72時間均一に混合し
た粉末をプレス圧１Kg／cm2で成型した後、、これ
を粉砕し、10メツシユ程度に造粒した粉末を最終
原料とした。そしてこの原料300ｇを原料ホツパ
ー２から坩堝３に投入し、1600℃に加熱し、発生
したガス８をアルゴンガス６により、窒素ガス９
を導入したカーボン反応管１１内で、窒化けい素
ウイスカーを析出成長させた。この時カーボン反
応管は、塩化第二鉄溶液中に１時間浸し、十分乾
燥後、水素気流中1200℃で１時間還元し、鉄をカ
ーボン反応管内に均一に含浸させて使用し、1400
℃に保持した。Example 1 Silicon dioxide (SiO 2 ) powder with a particle size of 15 mμ was used as the main raw material, carbon (C) powder with a particle size of 40 mμ was mixed as a reducing agent at a weight ratio of SiO 2 :C = 10:4, and a ball mill was used. The powder was homogeneously mixed for 72 hours and then molded at a press pressure of 1 kg/cm 2 , and then pulverized and granulated to about 10 meshes, which was used as the final raw material. Then, 300g of this raw material was put into the crucible 3 from the raw material hopper 2 and heated to 1600°C, and the generated gas 8 was mixed with argon gas 6 and nitrogen gas 9
Silicon nitride whiskers were precipitated and grown in the carbon reaction tube 11 into which was introduced. At this time, the carbon reaction tube was immersed in a ferric chloride solution for 1 hour, thoroughly dried, and then reduced in a hydrogen stream at 1200°C for 1 hour to uniformly impregnate iron into the carbon reaction tube.
It was kept at ℃.
３時間反応させた後、カーボン反応管を取り出
し、生成した窒化けい素ウイスカーを回収したと
ころ、約30ｇの窒化けい素ウイスカーが得られ
た。得られた窒化けい素ウイスカーは、太さ１〜
5μ長さ50〜300ｍ〓・平均200ｍ〓・長いものでは３
mmに達していた。 After reacting for 3 hours, the carbon reaction tube was taken out and the generated silicon nitride whiskers were collected, and about 30 g of silicon nitride whiskers were obtained. The obtained silicon nitride whiskers have a thickness of 1~
5μ Length 50-300m〓・Average 200m〓・3 for long ones
It had reached mm.
塩化第２鉄のかわりに、塩化コバルト、塩化ニ
ツケル、塩化クロムの溶液を用いて、コバルト、
ニツケル、クロムを含浸させたカーボン反応管を
使用した場合にも窒化けい素ウイスカーが得ら
れ、コバルトの場合、太さ0.5〜３ｍ〓長さ30〜
300ｍμ、平均150ｍμ、長いもので２mm、またク
ロムの場合、太さ0.5〜3μ、長さ30〜300μ、平均
200μｍ長いもので２mmの窒化けい素ウイスカー
が得られた。ニツケルと鉄をカーボン反応管に含
浸させた後、還元性雰囲気中で加熱して合金化さ
せ、前記と同様の処理を行つた。太さ0.5〜0.8μ
ｍ、長さ30〜300μｍ、平均200μｍ長いもので３
mmの窒化けい素ウイスカーが得られた。 Instead of ferric chloride, cobalt,
Silicon nitride whiskers can also be obtained when using a carbon reaction tube impregnated with nickel or chromium, and in the case of cobalt, the thickness is 0.5 to 3 m and the length is 30 to 30 m.
300mμ, average 150mμ, 2mm long, and in the case of chrome, thickness 0.5-3μ, length 30-300μ, average
Silicon nitride whiskers of 2 mm in length were obtained with a length of 200 μm. After impregnating nickel and iron into a carbon reaction tube, they were heated in a reducing atmosphere to form an alloy, and the same treatment as above was performed. Thickness 0.5~0.8μ
m, length 30-300μm, average 200μm long 3
mm silicon nitride whiskers were obtained.
鉄、コバルト、ニツケル、クロムより選ばれた
金属または、それらの合金をカーボン反応管に含
浸させずに反応させた場合、太さ0.1〜0.5ｍμ、
長さ20〜100ｍμ、平均70ｍμの短い窒化けい素
ウイスカーしか得られなかつた。 When a metal selected from iron, cobalt, nickel, and chromium or an alloy thereof is reacted without impregnating it in a carbon reaction tube, the thickness is 0.1 to 0.5 mμ,
Only short silicon nitride whiskers with a length of 20 to 100 mμ and an average of 70 mμ were obtained.
実施例 ２
実施例１と同様に、原料粉末を配合、造粒した
粉末400ｇを使用し、水素ガス９を導入したカー
ボン反応管１１内で、炭化けい素ウイスカーを析
出成長させた。この時、カーボン反応管には実施
例１と同様にして鉄を含浸して使用し1700℃に保
持した。２時間反応させた後、カーボン反応管を
取り出し、生成したウイスカーを回収したところ
約30ｇの炭化けい素ウイスカーは、太さ２〜５ｍ
μ、長さ100〜500ｍμ、平均350ｍμ、長いもの
では４mmに達していた。Example 2 In the same manner as in Example 1, silicon carbide whiskers were precipitated and grown in a carbon reaction tube 11 into which hydrogen gas 9 was introduced, using 400 g of powder obtained by blending and granulating raw material powders. At this time, the carbon reaction tube was impregnated with iron in the same manner as in Example 1 and was maintained at 1700°C. After reacting for 2 hours, the carbon reaction tube was taken out and the generated whiskers were collected. Approximately 30 g of silicon carbide whiskers were 2 to 5 m thick.
μ, length: 100 to 500 mμ, average 350 mμ, the longest one reaching 4 mm.
鉄のかわりに、コバルトを含浸させたカーボン
反応管を使用した場合には、太さ、0.5〜３ｍμ
長さ100〜400ｍμ平均250ｍμの炭化けい素ウイ
スカーが、また、ニツケルを含浸させたカーボン
反応管を使用した場合には、太さ0.5〜３ｍμ、
長さ100〜350ｍμ、平均200ｍμの炭化けい素ウ
イスカーが得られた。 If a carbon reaction tube impregnated with cobalt is used instead of iron, the thickness will be 0.5 to 3 mμ.
Silicon carbide whiskers with a length of 100 to 400 mμ and an average of 250 mμ, and a thickness of 0.5 to 3 mμ when using a carbon reaction tube impregnated with nickel.
Silicon carbide whiskers with a length of 100 to 350 mμ and an average of 200 mμ were obtained.
鉄、コバルト、ニツケルより選ばれた金属また
は、それらの合金をカーボン反応管に含浸させず
に反応させた場合、太さ、0.2〜0.5ｍμ長さ30〜
150ｍμ、平均100ｍμの短い炭化けい素ウイスカ
ーしか得られなかつた。 When a metal selected from iron, cobalt, and nickel or an alloy thereof is reacted without impregnating it in a carbon reaction tube, the thickness is 0.2 to 0.5 mm, and the length is 30 to
Only short silicon carbide whiskers of 150 mμ and an average of 100 mμ were obtained.
図面は本発明の実施に用いる装置の一例を示す
ものであり、第１図縦断面図、第２図は主要部の
縦断面図である。
１……原料、２……原料ホツパー、３……坩
堝、４……炉、５……バルブ、６……不活性ガ
ス、７……導入管、８……ガス、９……水素ガ
ス、１０……ガス導入管、１１……反応管、１２
……ウイスカー、１３……接続管、１４……蓄部
材、１５……ボルト、１６……捕集ビン。
The drawings show an example of an apparatus used to carry out the present invention, and FIG. 1 is a longitudinal cross-sectional view, and FIG. 2 is a longitudinal cross-sectional view of the main parts. 1... Raw material, 2... Raw material hopper, 3... Crucible, 4... Furnace, 5... Valve, 6... Inert gas, 7... Inlet pipe, 8... Gas, 9... Hydrogen gas, 10...Gas introduction tube, 11...Reaction tube, 12
...Whisker, 13...Connecting pipe, 14...Storage member, 15...Bolt, 16...Collection bottle.
Claims (1)
剤を混合した粉粒体を不活性ガス中で1300℃以上
で加熱して一酸化けい素ガスまたは一酸化けい素
一酸化炭素ガスの混合ガスを発生させ、この発生
ガスを、窒素を含む窒化性雰囲気下／または一酸
化炭素ガスを含む還元浸炭性雰囲気下で、その内
表面に鉄、ニツケル、コバルト、クロムより選ば
れた金属またはそれらの合金が含浸され、1000℃
以上に加熱された反応管に不活性ガスとともに送
り込み、該反応管表面に窒化けい素／または炭化
けい素のセラミツクスウイスカーを析出成長させ
ることを特徴とするセラミツクスウイスカーの製
造法。1 Heat a powder mixture of silicon dioxide and a reducing agent of metal silicon or carbon in an inert gas at 1300℃ or higher to generate a mixed gas of silicon monoxide gas or silicon monoxide carbon monoxide gas. The generated gas is coated with a metal selected from iron, nickel, cobalt, and chromium or an alloy thereof on the inner surface under a nitriding atmosphere containing nitrogen or a reducing carburizing atmosphere containing carbon monoxide gas. is impregnated and heated to 1000℃
A method for producing ceramic whiskers, which comprises feeding ceramic whiskers together with an inert gas into a reaction tube heated as described above, and depositing and growing ceramic whiskers of silicon nitride/silicon carbide on the surface of the reaction tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55176244A JPS57101000A (en) | 1980-12-12 | 1980-12-12 | Preparation of ceramic whisker |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55176244A JPS57101000A (en) | 1980-12-12 | 1980-12-12 | Preparation of ceramic whisker |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57101000A JPS57101000A (en) | 1982-06-23 |
| JPS644999B2 true JPS644999B2 (en) | 1989-01-27 |
Family
ID=16010159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55176244A Granted JPS57101000A (en) | 1980-12-12 | 1980-12-12 | Preparation of ceramic whisker |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57101000A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1275088A (en) * | 1985-12-30 | 1990-10-09 | Peter D. Shalek | Prealloyed catalyst for growing silicon carbide whiskers |
| JPS63159299A (en) * | 1986-12-20 | 1988-07-02 | Kobe Steel Ltd | Production of silicon carbide whisker |
| JPH0717369B2 (en) * | 1987-10-20 | 1995-03-01 | 工業技術院長 | Method for producing fibrous silicon / oxygen / carbon compound |
| FR2684091B1 (en) * | 1991-11-21 | 1994-02-25 | Pechiney Recherche | METHOD FOR MANUFACTURING METAL CARBIDES WITH A LARGE SPECIFIC SURFACE UNDER ATMOSPHERIC PRESSURE INERATED GAS SCANNING. |
| CN109594100B (en) * | 2018-12-07 | 2021-04-02 | 东华大学 | C3N4Cu/Sn loaded alloy material and preparation and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5213169B2 (en) * | 1972-06-23 | 1977-04-12 | ||
| JPS5234715B2 (en) * | 1973-05-17 | 1977-09-05 | ||
| JPS5417720A (en) * | 1977-07-08 | 1979-02-09 | Ricoh Co Ltd | Diazo type copying method |
| JPS56100125A (en) * | 1980-01-14 | 1981-08-11 | Sumitomo Electric Ind Ltd | Manufacture of silicon carbide whisker |
| JPS56100115A (en) * | 1980-01-14 | 1981-08-11 | Sumitomo Electric Ind Ltd | Manufacture of silicon nitride whisker |
-
1980
- 1980-12-12 JP JP55176244A patent/JPS57101000A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57101000A (en) | 1982-06-23 |
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