JPH02102108A - Production of raw material for silicon nitride-silicon carbide composite ceramic containing silicon carbide whisker - Google Patents
Production of raw material for silicon nitride-silicon carbide composite ceramic containing silicon carbide whiskerInfo
- Publication number
- JPH02102108A JPH02102108A JP63253793A JP25379388A JPH02102108A JP H02102108 A JPH02102108 A JP H02102108A JP 63253793 A JP63253793 A JP 63253793A JP 25379388 A JP25379388 A JP 25379388A JP H02102108 A JPH02102108 A JP H02102108A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- silicon carbide
- mixed
- raw material
- silicon
- 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
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 28
- 239000002994 raw material Substances 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims description 34
- 229910010271 silicon carbide Inorganic materials 0.000 title claims description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 26
- 239000010703 silicon Substances 0.000 title claims description 25
- 239000000919 ceramic Substances 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000843 powder Substances 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 238000010574 gas phase reaction Methods 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 20
- 239000011812 mixed powder Substances 0.000 abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 18
- 238000005245 sintering Methods 0.000 abstract description 11
- 239000000377 silicon dioxide Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 6
- 230000000704 physical effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 21
- 229910052581 Si3N4 Inorganic materials 0.000 description 14
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000003961 organosilicon compounds Chemical class 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 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
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- -1 q-balt Chemical compound 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001914 filtration Methods 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
- 229910052734 helium Inorganic materials 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
- 238000007731 hot pressing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- LCHWKMAWSZDQRD-UHFFFAOYSA-N silylformonitrile Chemical compound [SiH3]C#N LCHWKMAWSZDQRD-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、炭化ケイ素ウィスカーによって強化された窒
化ケイ素−炭化ケイ素複合セラミックスを製造するのに
好適な炭化ケイ素ウィスカーが分散された窒化ケイ素−
炭化ゲイ素混合粉末の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides a silicon nitride material in which silicon carbide whiskers are dispersed, which is suitable for producing silicon nitride-silicon carbide composite ceramics reinforced with silicon carbide whiskers.
This invention relates to a method for producing a mixed silicon carbide powder.
近年、窒化ケイ素および炭化ケイ素は高温構造材料とし
て多方面に利用されつつある。In recent years, silicon nitride and silicon carbide are being used in a wide range of applications as high-temperature structural materials.
ところで、高温構造材料として要求される物性には様々
なものがあるが、窒化ケイ素と炭化ケイ素とを比較する
と、窒化ケイ素は耐熱衝撃性や破壊靭性に、また、炭化
ケイ素は耐酸化性や高温強度にそれぞれ優れた性質を有
している。このため窒化ケイ素、炭化ケイ素はそれぞれ
の特徴を生かした分野において開発が行われている。Incidentally, there are various physical properties required for high-temperature structural materials, but when comparing silicon nitride and silicon carbide, silicon nitride has good thermal shock resistance and fracture toughness, while silicon carbide has good oxidation resistance and high temperature resistance. Each has excellent strength properties. For this reason, silicon nitride and silicon carbide are being developed in fields that take advantage of their respective characteristics.
一方、両者の利点を生かすために窒化ケイ素−炭化ケイ
素複合セラミックスの開発も試みられている。この方法
としては、例えば、
（１）窒化ケイ素粉末と炭化ケイ素粉末とを機械的に混
合してホットプレスなどで焼結する方法。On the other hand, attempts have been made to develop silicon nitride-silicon carbide composite ceramics in order to take advantage of the advantages of both. Examples of this method include: (1) A method in which silicon nitride powder and silicon carbide powder are mechanically mixed and sintered using a hot press or the like.
（２）反応焼結的な手法を用いて、予め炭化ケイ素とケ
イ素との混合物を成型した後窒化反応を行わせて窒化ケ
イ素質を生成させたり、窒化ケイ素とケイ素を生成させ
る方法。(2) A method of forming a mixture of silicon carbide and silicon in advance using a reaction sintering method and then performing a nitriding reaction to generate silicon nitride or to generate silicon nitride and silicon.
（３）有機ケイ素化合物を原料として、これにケイ素粉
末を加えて直接、あるいは熱処理後成型し、窒化反応を
行わせる方法。(3) A method in which an organosilicon compound is used as a raw material, silicon powder is added thereto, and the mixture is molded directly or after heat treatment to perform a nitriding reaction.
等が知られている。これらのうち、（２） 、（３）に
よる方法は一般に、焼結体の寸法安定性が良いという利
点はあるが、得られる焼結体は多孔質になり易く、緻密
な焼結体を得ることが困難である。etc. are known. Among these methods, methods (2) and (3) generally have the advantage of good dimensional stability of the sintered body, but the resulting sintered body tends to be porous and it is difficult to obtain a dense sintered body. It is difficult to do so.
このため、高密度の緻密な複合体を得るには通常前記（
１）の方法が行われている。Therefore, in order to obtain a dense and dense composite, it is usually necessary to obtain the above (
Method 1) is being used.
一方、ウィスカー強化の複合焼結体は、窒化ケイ素−炭
化ケイ素の系のみならず、酸化アルミ炭化ケイ素の光等
多方面の分野で種々開発が行われており、得られる複合
体の強度や破壊靭性に優れた焼結体が得られることが示
されている。On the other hand, whisker-reinforced composite sintered bodies have been developed in a variety of fields, including not only the silicon nitride-silicon carbide system, but also aluminum oxide silicon carbide, and the strength and fracture strength of the resulting composites. It has been shown that a sintered body with excellent toughness can be obtained.
炭化ケイ素ウィスカーを用いた炭化ケイ素ウィスカー強
化窒化ケイ素複合セラミックスの例としては、たとえば
、窯業製会誌９１．４９１ （１９８３）に窒化ケイ素
に炭化ケイ素ウィスカーを混合しホントプレス焼結する
ことにより、高温での強度低下が小さ（、信頼性を示す
ワイブル係数の大きな複合体の得られることが示されて
いる。また、こうして得られた複合焼結体は炭化ケイ素
ウィスカーの添加量と共に破壊靭性の向上することが、
窯業製会誌９４．９８１ （１９８６）に示されている
。As an example of silicon carbide whisker-reinforced silicon nitride composite ceramics using silicon carbide whiskers, for example, Ceramic Seikai Zasshi 91.491 (1983) reports that by mixing silicon nitride with silicon carbide whiskers and sintering them at high temperature, It has been shown that a composite sintered body with a small decrease in strength (and a high Weibull coefficient, which indicates reliability) can be obtained.Furthermore, the fracture toughness of the composite sintered body thus obtained improves with the addition amount of silicon carbide whiskers. That is,
It is shown in Ceramic Industry Association Journal 94.981 (1986).
しかしながら、窒化ケイ素粉末に炭化ケイ素ウィスカー
を均一に分散させることはなかなか面倒であり、上記の
文献に示されている様に、混合に際して機械的撹拌、フ
ィルター濾過を繰り返し行ったり、超音波分散を行うな
ど複雑な操作を必要とする。However, it is quite troublesome to uniformly disperse silicon carbide whiskers in silicon nitride powder, and as shown in the above-mentioned literature, mechanical stirring, repeated filter filtration, or ultrasonic dispersion is performed during mixing. Requires complex operations such as
このような複雑な操作を行なわない手段として、特開昭
６０−７２７８９号、特開昭６２−７０２６５号、特開
昭６２−１３２７７２号に、シリカと炭素を原料として
シリカ還元法により炭化ケイ素ウィスカーを含んだ窒化
ケイ素と炭化ケイ素の混合粉末を製造する方法が示され
ている。しかしながら、これらの方法では未反応のシリ
カが粉末中に残留し易く、未反応シリカが残留すると焼
結体の機械的強度などの物性に悪影響を与え好ましくな
い。As a means to avoid such complicated operations, JP-A-60-72789, JP-A-62-70265, and JP-A-62-132772 disclose silicon carbide whiskers using a silica reduction method using silica and carbon as raw materials. A method for producing a mixed powder of silicon nitride and silicon carbide containing . However, in these methods, unreacted silica tends to remain in the powder, and if unreacted silica remains, it adversely affects physical properties such as mechanical strength of the sintered body, which is not preferable.
しかして、本発明は上記のような複雑な操作を必要とせ
ず、また未反応シリカの残留がなく炭化ケイ素ウィスカ
ー強化窒化ケイ素−炭化ケイ素複合セラミックスを製造
するのに好適な炭化ケイ素ウィスカーが分散した窒化ケ
イ素−炭化ケイ素混合粉末を提供することにある。Therefore, the present invention does not require the above-mentioned complicated operations, does not require any unreacted silica, and has silicon carbide whiskers dispersed therein, which is suitable for producing silicon carbide whisker-reinforced silicon nitride-silicon carbide composite ceramics. An object of the present invention is to provide a silicon nitride-silicon carbide mixed powder.
本発明者らはかかる状況に鑑み、シリカと炭素を原料と
せず、予め主としてケイ素、炭素、窒素からなる非晶質
粉末を原料として、炭化ケイ素ウィスカーが分散混合さ
れた窒化ケイ素−炭化ケイ素混合粉末を製造する方法を
見出した。In view of this situation, the present inventors have developed a silicon nitride-silicon carbide mixed powder in which silicon carbide whiskers are dispersed and mixed, using an amorphous powder mainly composed of silicon, carbon, and nitrogen as a raw material instead of using silica and carbon as raw materials. discovered a method of manufacturing.
すなわち、本発明は、気相反応によって得られた主とし
てケイ素、炭素、窒素からなり、炭素含有量が２．０〜
２５．０重量％である非晶質の球状粉末に、０．０１〜
５．０重量％の鉄、ニッケル、コバルト、クロムの単体
、合金あるいはこれらの化合物から選ばれる少なくとも
１種を分散さ廿た粉末を非酸化性ガス雰囲気中で熱処理
することからなる炭化ケイ素ウィスカーを含む窒化ケイ
素−炭化ケイ素複合セラミンクス原料の製造法に関する
。That is, the present invention mainly consists of silicon, carbon, and nitrogen obtained by gas phase reaction, and the carbon content is 2.0 to 2.0.
0.01 to 25.0% by weight of amorphous spherical powder
Silicon carbide whiskers are produced by heat-treating powder in which 5.0% by weight of iron, nickel, cobalt, chromium alone, alloy, or at least one selected from these compounds is dispersed in a non-oxidizing gas atmosphere. The present invention relates to a method for producing a raw material for silicon nitride-silicon carbide composite ceramics containing silicon nitride-silicon carbide.
本発明の方法によって得られる混合粉末は炭化ケイ素ウ
ィスカーが分散混合された窒化ケイ素炭化ケイ素混合粉
末であり、炭化ケイ素ウィスカーによって強化された窒
化ケイ素−炭化ケイ素複合セラミックスの原料として好
適なものである。The mixed powder obtained by the method of the present invention is a silicon nitride/silicon carbide mixed powder in which silicon carbide whiskers are dispersed and mixed, and is suitable as a raw material for silicon nitride-silicon carbide composite ceramics reinforced by silicon carbide whiskers.
本発明の方法によって得られる原料粉末は、特別な処理
操作を必要とすることなく通常の乾式あるいは湿式混合
法によって、そのまま焼結助剤と混合し、常圧焼結ある
いはホットプレス、ガス圧焼結、ＩＩＩＰなどの加圧焼
結法により炭化ケイ素ウィスカーで強化された窒化ケイ
素−炭化ケイ素複合焼結体を得ることができる。The raw material powder obtained by the method of the present invention can be mixed with a sintering aid as it is by a normal dry or wet mixing method without requiring any special processing operations, and then sintered under normal pressure, hot press, or gas pressure. A silicon nitride-silicon carbide composite sintered body reinforced with silicon carbide whiskers can be obtained by a pressure sintering method such as sintering or IIIP.
本発明に用いられる非晶質の球状粉末は、たとえば特開
昭６０−２００８１２号、特開昭６０−２００８１３号
、特開昭６０−２００８１４号、特開昭６０−２２１３
１１号、特開昭６０−２３５７０７号、特開昭６１−２
４７６０８号、等に示されたシアノシラン、シラザン、
シリルアミン等の種々の有機ケイ素化合物を原料とした
気相反応によって得ることができる。具体的には、これ
らの有機ケイ素化合物の１種あるいは２種以上の混合物
を、６００〜１６００°Ｃ１好ましくは８００〜１４０
０°Ｃ２特に好ましくは９００〜１２００°Ｃの温度範
囲において非酸化性ガス雰囲気下で０．５〜１２０秒の
反応時間で気相熱分解することによって得ることができ
る。The amorphous spherical powder used in the present invention is, for example, JP-A-60-200812, JP-A-60-200813, JP-A-60-200814, JP-A-60-2213.
No. 11, JP-A-60-235707, JP-A-61-2
Cyanosilane, silazane, etc. shown in No. 47608, etc.
It can be obtained by a gas phase reaction using various organosilicon compounds such as silylamine as raw materials. Specifically, one type or a mixture of two or more of these organosilicon compounds is heated at 600 to 1600°C, preferably 800 to 140°C.
It can be obtained by vapor phase pyrolysis in a non-oxidizing gas atmosphere at a temperature range of 0°C, particularly preferably from 900 to 1200°C, for a reaction time of 0.5 to 120 seconds.
この際生成物中の炭素含有量を２．０〜２５．０重量％
に制御するにはＮＨ，やＨ２ガスを雰囲気ガス中に存在
させることが必要である。At this time, the carbon content in the product is 2.0 to 25.0% by weight.
In order to control this, it is necessary to have NH or H2 gas present in the atmospheric gas.
すなわち、原料として用いる有機ケイ素化合物中のＳｉ
、Ｃ，Ｎの原子比が求める非晶質粉末の組成と同様な場
合には雰囲気ガスとして窒素、アルゴン、ヘリウムなど
の不活性ガスを選択するのが好ましく、また、原料とし
て用いる有機ケイ素化合物中のＳｉ、Ｃ，Ｎの原子比が
求める非晶質粉末の組成と大きく異なる場合には、その
組成に応じて雰囲気ガス中にＮＨ，やＨ２ガスを存在さ
せる。That is, Si in the organosilicon compound used as a raw material
, C, and N are similar to the composition of the desired amorphous powder, it is preferable to select an inert gas such as nitrogen, argon, or helium as the atmospheric gas. If the atomic ratio of Si, C, and N is significantly different from the desired composition of the amorphous powder, NH or H2 gas is made to exist in the atmospheric gas depending on the composition.
このようにして得られる非晶質粉末は主としてケイ素、
炭素、窒素からなり、その他に水素あるいはハロゲンを
含む有機ケイ素化合物を用いた場合には、ハロゲンを含
む組成となる。いずれの場合も得られる非晶質粉末は球
状粉末で、粒径はミクロンサイズであり、好ましい条件
で製造された場合にはサブミクロンサイズの粒度分布の
狭い粉末を得ることができる。このようにして得られる
粉末はそのまま本発明の原料として使用することもでき
るが、空気あるいは水分との反応性が高いので、１００
０−１４５０℃の温度で熱処理して安定化させることが
好ましい。このような処理によって得られる非晶質の球
状粉末は、本発明に使用するのに好適な原料である。The amorphous powder obtained in this way mainly contains silicon,
If an organosilicon compound consisting of carbon and nitrogen and also containing hydrogen or halogen is used, the composition will contain halogen. In either case, the amorphous powder obtained is a spherical powder with a particle size of microns, and when produced under preferable conditions, a submicron-sized powder with a narrow particle size distribution can be obtained. The powder thus obtained can be used as it is as a raw material for the present invention, but since it is highly reactive with air or moisture,
Preferably, it is stabilized by heat treatment at a temperature of 0-1450°C. The amorphous spherical powder obtained by such treatment is a suitable raw material for use in the present invention.
このようにして得られた炭素含有量が２．０〜２５．０
重量％である非晶質粉末を、そのまま結晶化させると大
部分が等軸状の窒化ケイ素と炭化ケイ素との混合粉末と
なり、本発明の目的である炭化ケイ素ウィスカーを含む
窒化ケイ素と炭化ケイ素との混合粉末を得ることはでき
ない。The carbon content obtained in this way is 2.0 to 25.0
If an amorphous powder of 10% by weight is directly crystallized, it will become a mixed powder of mostly equiaxed silicon nitride and silicon carbide, which is the object of the present invention. It is not possible to obtain a mixed powder of
そこで、本発明においては、炭化ケイ素ウィスカーの生
成を促進する鉄、ニッケル、ｑバルト、クロムの単体、
合金あるいはこれらの化合物から選ばれる少なくとも１
４ｍを上記の非晶質粉末に分散させる。上記金属の化合
物の例としては、上記金属のハロゲン化物、硝酸塩、炭
酸塩、あるいはカルボニル化合物などが例示される。具
体的には、ＦｅＣｌ２５ 、ＦｅＣ１ｚ 、Ｆｅ（ＮＯ
３）ｓ、Ｆｅ（ＣＯｉ）ｚ、Ｆｅ （Ｃｏ） ａ、Ｎｉ
Ｃ１２ｚ 、Ｎｉ （ＮＯｚ） ｚ、ＣｏＣｆｆ１２
、Ｃｏ（Ｎｏ、）ｓなどが例示される。Therefore, in the present invention, elements of iron, nickel, q-balt, chromium, which promote the formation of silicon carbide whiskers,
At least one selected from alloys or these compounds
4m is dispersed in the above amorphous powder. Examples of the metal compounds include halides, nitrates, carbonates, and carbonyl compounds of the metals. Specifically, FeCl25, FeC1z, Fe(NO
3) s, Fe(COi)z, Fe(Co)a, Ni
C12z, Ni (NOz)z, CoCff12
, Co(No,)s, etc. are exemplified.
上記の金属単体、合金あるいは化合物は、前記非晶質粉
末と均一に分散するように添加させる伜。The above metal element, alloy, or compound is added so as to be uniformly dispersed with the amorphous powder.
とが必要である。この添加方法としては、たとえば、非
晶質粉末と乾式あるいは湿式混合したり、非晶質粉末を
気相反応で製造する際に同時に上記金属、金属化合物等
を供給して気相反応により生成される非晶質粉末中に分
散させる方法などがある。is necessary. Examples of ways to add this include dry or wet mixing with the amorphous powder, or simultaneous supply of the above metals, metal compounds, etc. when producing the amorphous powder by a gas phase reaction. There are methods such as dispersing it in an amorphous powder.
これらの金属あるいは金属化合物の量は０．０１〜５．
０重量％が好適であり、上記の量よりも少ない場合は炭
化ケイ素ウィスカーの生成に有効でなく、量が多い場合
には焼結体の機械的強度等の物性が低下するなどの悪影
習を与える傾向があり、好ましくない。The amount of these metals or metal compounds is 0.01 to 5.
0% by weight is preferable; if the amount is less than the above amount, it is not effective in generating silicon carbide whiskers, and if the amount is too much, it may cause negative effects such as a decrease in physical properties such as mechanical strength of the sintered body. This is not desirable as it tends to give
以上のようにして得られる金属あるいは金属化合物が分
散された非晶質粉末は、非酸化性ガス雰囲気中で、１３
００〜１６００℃で熱処理することによって結晶化し、
炭化ケイ素ウィスカーを含む窒化ケイ素−炭化ケイ素混
合粉末が得られる。The amorphous powder in which the metal or metal compound is dispersed is prepared as described above in a non-oxidizing gas atmosphere.
Crystallized by heat treatment at 00 to 1600°C,
A silicon nitride-silicon carbide mixed powder containing silicon carbide whiskers is obtained.
また、必要に応じ、ウィスカーの生成空間を助けるため
に熱処理温度で蒸発し得るＮａＣＩｔなどのアルカリ金
属ハロゲン化物あるいはアルカリ出金属ハロゲン化物を
添加することもできる。Further, if necessary, an alkali metal halide or an alkaline metal halide, such as NaCIt, which can be evaporated at the heat treatment temperature, can be added to assist the generation space of whiskers.
本発明において、熱処理するに際して使用される非酸化
性ガスは、Ｈｅ、静、Ｎ２、ＮＨ，あるいはＨ２ガスの
単体あるいは混合ガスが用いられる。特にＨ，やＮＨ，
を用いることは結晶化を促進し反応速度を高めるので有
効である。In the present invention, the non-oxidizing gas used in the heat treatment may be a single gas or a mixture of He, static, N2, NH, or H2 gas. Especially H, and NH,
The use of is effective because it promotes crystallization and increases the reaction rate.
本発明の方法における熱処理温度は、１３００〜１６ｏ
ｏ’ｃ、好ましくは１３５０−１５５０℃が好適である
。The heat treatment temperature in the method of the present invention is 1300 to 16o
o'c, preferably 1350-1550°C.
１３００°Ｃよりも低い温度では結晶化速度が極めて遅
く、１６００°Ｃよりも筒い温度では結晶化の速度は速
いが粒成長を起こし易く微細な粉末が得られ難く好まし
くない。処理時間は、適用される温度、処理量等により
異なるが、−殻内には０．５〜１０時間程度で実施され
る。このように制御された雰囲気、温度、時間のもとで
熱処理を行うことによって、本発明の目的とする炭化ケ
イ素ウィスカーを含む窒化ケイ素−炭化ケイ素混合粉末
が得られる。At temperatures lower than 1300°C, the crystallization rate is extremely slow, and at temperatures higher than 1600°C, although the crystallization rate is fast, grain growth tends to occur and it is difficult to obtain fine powder, which is not preferred. The treatment time varies depending on the applied temperature, amount of treatment, etc., but it is carried out for about 0.5 to 10 hours in the shell. By performing heat treatment under such controlled atmosphere, temperature, and time, a silicon nitride-silicon carbide mixed powder containing silicon carbide whiskers, which is the object of the present invention, can be obtained.
この混合粉末中の等軸状粒子の粒径は２ミクロン以下で
あり、好ましい条件で熱処理された場合にはサブミクロ
ンの大きさのものが得られる。The particle size of the equiaxed particles in this mixed powder is 2 microns or less, and when heat treated under preferable conditions, submicron particles can be obtained.
また、ウィスカーは径が０．１〜２ミクロン、アスペク
ト比が５〜１００程度のものであり、等軸状粒子と混じ
りあった状態で分散して存在している。さらにまた、従
来のシリカと炭素とを原料としていないので、生成物中
にシリカ分を殆ど含有しない高純度な混合粉末である。The whiskers have a diameter of 0.1 to 2 microns and an aspect ratio of about 5 to 100, and are present in a dispersed state mixed with equiaxed particles. Furthermore, since the conventional silica and carbon are not used as raw materials, the product is a highly pure mixed powder containing almost no silica.
次に、本発明の実施例を示す。Next, examples of the present invention will be shown.
実施例 １
気相反応によって得られた非晶質の球状粉末（Ｃ： ９
．６ ｗｔＸ 、Ｎ ： ３０．２ ｗｔＸ、Ｏ： ０
．９ ｗｔＸ、残部ケイ素および５００ ｐｐｍ以下の
重金属不純物） ２ｇと塩化第二鉄０．０１ ｇを乾
式混合した。この混合物をアルミナ製容器に充填し、Ａ
ｒ：］（ｚ＝ １２ ： ８８（Ｖｏｌχ）の混合ガス
雰囲気中で、１５２０°Ｃ，４時間熱処理した。Example 1 Amorphous spherical powder (C: 9
．． 6 wtX, N: 30.2 wtX, O: 0
．． 9 wtX, balance silicon and 500 ppm or less of heavy metal impurities) and 0.01 g of ferric chloride were dry mixed. Fill this mixture into an alumina container and
Heat treatment was performed at 1520° C. for 4 hours in a mixed gas atmosphere of r: ] (z = 12:88 (Volχ).
得られた生成物は、等軸状の粒子とウィスカーの混合粉
末であり、ウィスカーは粒子間に分散した状態で存在し
ている。等軸状粒子の粒径は０．１〜２．０μｍ、ウィ
スカーは直径０．１〜０．５ ／／Ｉ１１、アスペクト
比が１０〜８０であった。またＸ線回折によれば、生成
物の大部分がα−５ｉＪ４とβ−５ｉＣであり、わずか
にβ−５ｉＪ４が認められた。The obtained product is a mixed powder of equiaxed particles and whiskers, and the whiskers exist in a dispersed state between the particles. The particle size of the equiaxed particles was 0.1-2.0 μm, the whisker diameter was 0.1-0.5 //I11, and the aspect ratio was 10-80. Moreover, according to X-ray diffraction, most of the products were α-5iJ4 and β-5iC, with only a small amount of β-5iJ4 observed.
ＴＥＭ （透過型電子顕微鏡）観察によればウィスカー
はβ−３ｉＣであった。なお、生成物中の酸素含有量は
０．５χ未満であった。According to TEM (transmission electron microscope) observation, the whiskers were β-3iC. Note that the oxygen content in the product was less than 0.5χ.
実施例 ２
実施例１における塩化第二鉄の代わりに塩化コバルトを
用いた以外は実施例１と同様の方法により等軸状粒子と
ウィスカーとの混合わ）末を得た。Example 2 A mixed powder of equiaxed particles and whiskers was obtained in the same manner as in Example 1 except that cobalt chloride was used instead of ferric chloride in Example 1.
等軸状粒子の粒径は０．０５〜２．０μｍ、ウィスカー
は直径０．１〜０．５μｍ、アスペクト比がｌθ〜１０
０であり、Ｘ線回折によれば、生成物の大部分がα−５
ｉＪ４とβ−５ｉＣであることが認められた。なお、生
成物中の酸素含有量は０．５χ未満であった。The particle size of the equiaxed particles is 0.05 to 2.0 μm, the diameter of the whisker is 0.1 to 0.5 μm, and the aspect ratio is lθ to 10.
0, and according to X-ray diffraction, the majority of the product is α-5
It was recognized that they were iJ4 and β-5iC. Note that the oxygen content in the product was less than 0.5χ.
実施例 ３
気相反応によって得られた非晶質の球状粉末（Ｃ： ２
０．９ ｗｔＸ、Ｎ ： １８．１誓ｔχ、Ｏ： １．
５ ｗｔＸ、残部ケイ素およびｓｏｏ ｐｐｍ以下の重
金属不純物）３ｇと塩化ニッケル０．０１ ｇをエタノ
ール中湿式混合後、乾燥して粉末を得た。この混合粉末
をアルミナ製容器に充填し、Ｈ２雰囲気中でｔｓｏｏ℃
、３時間熱処理した。Example 3 Amorphous spherical powder (C: 2
0.9 wtX,N: 18.1wtχ,O: 1.
5 wtX, balance silicon and heavy metal impurities below soo ppm) and 0.01 g of nickel chloride were wet mixed in ethanol and dried to obtain a powder. This mixed powder was filled into an alumina container and heated to 20°C in an H2 atmosphere.
, heat treated for 3 hours.
得られた生成物は、等軸状粒子とウィスカーの混合粉末
であり、ウィスカーは粒子間に分散した状態で存在して
いる。等軸状粒子の粒径は０．１〜０．５ μｍ 、ウ
ィスカーは直径０．１〜０．５ ／１ｍ 、アスペクト
比が５〜５０であった。またＸ線回折によれば、生成物
の大部分がα−５ｉＪｎとβ−３ｉＣであり、わずかに
β−５ｉ３Ｎ４が認められた。The obtained product is a mixed powder of equiaxed particles and whiskers, and the whiskers exist in a dispersed state between the particles. The particle size of the equiaxed particles was 0.1-0.5 μm, the whisker diameter was 0.1-0.5/1 m, and the aspect ratio was 5-50. Moreover, according to X-ray diffraction, most of the products were α-5iJn and β-3iC, with only a small amount of β-5i3N4.
なお、生成物中の酸素含有量は０．５χ未満であった。Note that the oxygen content in the product was less than 0.5χ.
実施例 イ
有機ケイ素化合物を非酸化性雰囲気で気相反応させる際
にニッケル化合物（ＮｉＣｌ ｚ）を同時に供給して得
られたニッケル２０００ ｐｐｍを含む非晶質粉末（Ｃ
： ５．２ ｗｔＸ、Ｎ ： ３３．８ ｗｔＸ、Ｏ：
２．１ｗｔχ残部ケイ素および５００ ｐｐｍ以下の
重金属不純物）５ｇを黒鉛容器に充填し、Ｈｔ： Ｎ
ｔ−５０：５０（Ｖｏｌχ）の混合ガス雰囲気中で１５
００°Ｃ１２時間熱処理した。 得られた生成物は、等
軸状粒子とウィスカーの混合粉末であり、ウィスカーは
粒子間に分散した状態で存在している。等軸状粒子の粒
径は０゜２〜１μｍ、ウィスカーは直径０．２〜０．５
μｍ、アスペクト比が５〜１００であった。またＸ線回
折によれば、生成物は大部分のα−５ｉ：＋Ｎ４とβ−
５ｉＣであり、わずかにβ−３ｉＪ、が認められた。Example A: Amorphous powder containing 2000 ppm of nickel (C
: 5.2 wtX,N : 33.8 wtX,O:
Fill a graphite container with 5 g of Ht:N
15 in a mixed gas atmosphere of t-50:50 (Volχ)
Heat treatment was performed at 00°C for 12 hours. The obtained product is a mixed powder of equiaxed particles and whiskers, and the whiskers exist in a dispersed state between the particles. The particle size of equiaxed particles is 0°2 to 1 μm, and the diameter of whiskers is 0.2 to 0.5
μm, and the aspect ratio was 5 to 100. Also, according to X-ray diffraction, the product consists mostly of α-5i:+N4 and β-
5iC, and a slight amount of β-3iJ was observed.
なお、生成物中の酸素含有量は０．５ｚ未満であった。Note that the oxygen content in the product was less than 0.5z.
本発明の方法によって得られる混合粉末は炭化ケイ素ウ
ィスカーが分散混合された窒化ケイ素−炭化ケイ素混合
粉末であり、炭化ケイ素ウィスカーによって強化された
窒化ケイ素−炭化ケイ素複合セラミックスの原料として
好適なものである。The mixed powder obtained by the method of the present invention is a silicon nitride-silicon carbide mixed powder in which silicon carbide whiskers are dispersed and mixed, and is suitable as a raw material for silicon nitride-silicon carbide composite ceramics reinforced by silicon carbide whiskers. .
この様な原料粉末は、特別な処理操作を必要とすること
なく通常の乾式あるいは湿式混合法によって、そのまま
焼結助剤と混合し、常圧焼結あるいはホットプレス、ガ
ス圧焼結、ＩＩＩＰなどの加圧焼結法により炭化ケイ素
ウィスカーで強化された窒化ケイ素−炭化ケイ素複合焼
結体を得ることができる。Such raw material powders can be mixed with sintering aids as they are by ordinary dry or wet mixing methods without requiring any special processing operations, and subjected to atmospheric pressure sintering, hot pressing, gas pressure sintering, IIIP, etc. A silicon nitride-silicon carbide composite sintered body reinforced with silicon carbide whiskers can be obtained by the pressure sintering method.
特許出願人 三菱瓦斯化学株式会社 代理人 弁理士 小 堀 貞 文Patent applicant: Mitsubishi Gas Chemical Co., Ltd. Agent: Patent Attorney Sadafumi Kohori
Claims (1)
素からなり、炭素含有量が２．０〜２５．０重量％であ
る非晶質の球状粉末に、０．０１〜５．０重量％の鉄、
ニッケル、コバルト、クロムの単体、合金あるいはこれ
らの化合物から選ばれる少なくとも１種を分散させた粉
末を非酸化性ガス雰囲気中で熱処理することを特徴とす
る炭化ケイ素ウィスカーを含む窒化ケイ素−炭化ケイ素
複合セラミックス原料の製造法。0.01 to 5.0 weight % of iron is added to an amorphous spherical powder obtained by gas phase reaction, mainly consisting of silicon, carbon, and nitrogen, with a carbon content of 2.0 to 25.0 weight %. ,
A silicon nitride-silicon carbide composite containing silicon carbide whiskers, which is characterized by heat-treating a powder in which at least one selected from nickel, cobalt, chromium, an element, an alloy, or a compound thereof is dispersed in a non-oxidizing gas atmosphere. Manufacturing method for ceramic raw materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63253793A JPH02102108A (en) | 1988-10-11 | 1988-10-11 | Production of raw material for silicon nitride-silicon carbide composite ceramic containing silicon carbide whisker |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63253793A JPH02102108A (en) | 1988-10-11 | 1988-10-11 | Production of raw material for silicon nitride-silicon carbide composite ceramic containing silicon carbide whisker |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02102108A true JPH02102108A (en) | 1990-04-13 |
Family
ID=17256226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63253793A Pending JPH02102108A (en) | 1988-10-11 | 1988-10-11 | Production of raw material for silicon nitride-silicon carbide composite ceramic containing silicon carbide whisker |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02102108A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515770A (en) * | 2011-11-25 | 2012-06-27 | 中原工学院 | Method for preparing nano SiC reinforced MoSi2 composite material |
| CN107382324A (en) * | 2017-08-18 | 2017-11-24 | 深圳市赛普戴蒙德科技有限公司 | Carbon/silicon carbide ceramic matrix composite and preparation method thereof |
-
1988
- 1988-10-11 JP JP63253793A patent/JPH02102108A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515770A (en) * | 2011-11-25 | 2012-06-27 | 中原工学院 | Method for preparing nano SiC reinforced MoSi2 composite material |
| CN107382324A (en) * | 2017-08-18 | 2017-11-24 | 深圳市赛普戴蒙德科技有限公司 | Carbon/silicon carbide ceramic matrix composite and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4226841A (en) | Method of producing silicon carbide powder | |
| US5912399A (en) | Chemical synthesis of refractory metal based composite powders | |
| JPH0336783B2 (en) | ||
| JPH0134925B2 (en) | ||
| US4346068A (en) | Process for preparing high-purity α-type silicon nitride | |
| US4888084A (en) | Method for the preparation of titanium nitride whiskers | |
| US5234643A (en) | Silicon nitride ceramics containing crystallized grain boundary phases | |
| JPH0280318A (en) | Synthesis of refractory metal boride having predetermined particle dimension | |
| JPH02102108A (en) | Production of raw material for silicon nitride-silicon carbide composite ceramic containing silicon carbide whisker | |
| Real et al. | Synthesis of silicon carbide whiskers from carbothermal reduction of silica gel by means of the constant rate thermal analysis (CRTA) method | |
| JPS5839764B2 (en) | Method for producing aluminum nitride powder | |
| JPH08176695A (en) | Production of titanium nitride sinter | |
| JPS6212663A (en) | Method of sintering b4c base fine body | |
| JPH09221367A (en) | Conductive silicon carbide material composite material and its production | |
| JPS6212664A (en) | Method of sintering b4c base composite body | |
| JP3280059B2 (en) | Method for producing activated silicon carbide | |
| JPS5849611A (en) | Powder containing 2h type silicon carbide and its preparation | |
| JPH06172036A (en) | Production of silicon nitride powder | |
| JPH04321505A (en) | Production of aluminum nitride | |
| KR860000992B1 (en) | Process for the production of a hard solid solution containing molybdenum | |
| JPH05238900A (en) | Production of alumina whisker | |
| JPS6183606A (en) | Production of easily sinterable aluminum nitride powder | |
| JPS5891028A (en) | Manufacture of silicon carbide powder | |
| JP2695070B2 (en) | Method for producing silicon nitride-silicon carbide composite sintered body | |
| JPH0535694B2 (en) |