JPH0329760B2 - - Google Patents
Info
- Publication number
- JPH0329760B2 JPH0329760B2 JP61207784A JP20778486A JPH0329760B2 JP H0329760 B2 JPH0329760 B2 JP H0329760B2 JP 61207784 A JP61207784 A JP 61207784A JP 20778486 A JP20778486 A JP 20778486A JP H0329760 B2 JPH0329760 B2 JP H0329760B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- silicon nitride
- hours
- oxide
- alkaline earth
- 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 - Lifetime
Links
- 239000000843 powder Substances 0.000 claims description 34
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 32
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 20
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 11
- 239000011812 mixed powder Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 5
- 229910000071 diazene Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は複合材料の素材として有用なβ型窒化
珪素ウイスカーの製法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing β-type silicon nitride whiskers useful as a material for composite materials.
（従来の技術及びその問題点）
窒化珪素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り、非常に高い引張強度、
弾性率を有しており、複合材料、特に高温度で用
いる金属又はセラミツクス複合材料の素材として
期待されている。(Prior art and its problems) Silicon nitride whiskers are single crystals grown in the form of fine fibers without defects, and have extremely high tensile strength and
It has a high elastic modulus and is expected to be used as a material for composite materials, especially metal or ceramic composite materials used at high temperatures.
特開昭59−147000号公報には、シリカ、カーボ
ン及び氷晶石の混合物をアンモニアと窒素との混
合雰囲気中で加熱反応させてβ型窒化珪素ウイス
カーを製造する方法が記載されている。この方法
は、生成するβ型窒化珪素ウイスカー中に原料の
シリカ及びカーボンが残留するため、これらの除
去に煩雑な操作を必要とし、さらにウイスカーの
収率が高くなるという解決すべき問題点を有して
いる。 JP-A-59-147000 describes a method for producing β-type silicon nitride whiskers by subjecting a mixture of silica, carbon, and cryolite to a heating reaction in a mixed atmosphere of ammonia and nitrogen. This method requires complicated operations to remove raw materials such as silica and carbon, which remain in the β-type silicon nitride whiskers that are produced, and also has problems that need to be resolved, such as a high whisker yield. are doing.
（発明の目的及び要旨）
本発明の目的は、β型窒化珪素ウイスカーを収
率よくかつ効率的に製造できる方法を提供するこ
とにある。(Objective and Summary of the Invention) An object of the present invention is to provide a method for producing β-type silicon nitride whiskers with high yield and efficiency.
本発明の目的は、非晶質窒化珪素及びα型窒化
珪素から選ばれる原料粉末と、原料粉末100重量
部当たり酸化物換算で0.1〜20重量部の、アルカ
リ土類金属の酸化物粉末又は焼成時に酸化物に転
化し得るアルカリ土類金属の化合物粉末（以下両
者を総称してアルカリ土類金属化合物ということ
がある）との混合粉末を、非酸化性ガス雰囲気下
で焼成することによつて達成される。 The object of the present invention is to use a raw material powder selected from amorphous silicon nitride and α-type silicon nitride, and an alkaline earth metal oxide powder or calcined powder containing 0.1 to 20 parts by weight in terms of oxide per 100 parts by weight of the raw material powder. By firing a mixed powder of an alkaline earth metal compound powder (hereinafter both may be collectively referred to as an alkaline earth metal compound) that can sometimes be converted into an oxide in a non-oxidizing gas atmosphere. achieved.
本発明で使用される非晶質窒化珪素粉末は、そ
れ自体公知の方法、たとえば四ハロゲン化珪素と
アンモニアとを液相又は気相で反応させた反応生
成物を加熱処理することによつて得ることがで
き、通常のＸ線回折によつて明確な回折現象が表
れない、いわゆる非晶質の物質である。なお、こ
の非晶質窒化珪素は珪素原子、窒素原子の他に水
素原子を含むことがある。 The amorphous silicon nitride powder used in the present invention is obtained by a method known per se, for example, by heat-treating a reaction product obtained by reacting silicon tetrahalide and ammonia in a liquid phase or a gas phase. It is a so-called amorphous material that does not show a clear diffraction phenomenon by ordinary X-ray diffraction. Note that this amorphous silicon nitride may contain hydrogen atoms in addition to silicon atoms and nitrogen atoms.
α型窒化珪素粉末は、上記の非晶質窒化珪素粉
末を仮焼する方法の他に、シリカの還元窒化法、
珪素の直接窒化法等の公知の方法で製造すること
ができる。α型窒化珪素粉末の比表面積は0.01〜
20m2／ｇ、特に２〜13m2／ｇであることが好まし
い。 In addition to the above-mentioned method of calcining the amorphous silicon nitride powder, α-type silicon nitride powder can be produced using the silica reduction nitriding method.
It can be manufactured by a known method such as direct silicon nitridation. The specific surface area of α-type silicon nitride powder is 0.01~
It is preferably 20 m 2 /g, especially 2 to 13 m 2 /g.
アルカリ土類金属の酸化物の具体例としては、
酸化マグネシウム、酸化カルシウム、酸化バリウ
ム、酸化ストロンチウムが挙げられる。 Specific examples of alkaline earth metal oxides include:
Examples include magnesium oxide, calcium oxide, barium oxide, and strontium oxide.
焼成時にアルカリ土類金属の酸化物に転化し得
る化合物としては、窒化珪素ウイスカー成長時に
一部又は全部が酸化物に転化し得る化合物であれ
ばいかなる化合物を使用してもよく、中でもアル
カリ土類金属の水酸化物、炭酸塩が便利に採用さ
れる。そのような例として、水酸化カルシウム、
水酸化バリウム、炭酸カルシウム、炭酸バリウム
ウ、炭酸ストロンチウムが挙げられる。 As the compound that can be converted into an oxide of an alkaline earth metal during firing, any compound that can be partially or completely converted into an oxide during silicon nitride whisker growth may be used. Metal hydroxides and carbonates are conveniently employed. Such examples include calcium hydroxide,
Examples include barium hydroxide, calcium carbonate, barium carbonate, and strontium carbonate.
アルカリ土類金属化合物粉末の配合量は、非晶
質窒化珪素及びα型窒化珪素から選ばれる原料粉
末100重量部当たり、酸化物換算で、0.5〜10重量
部である。アルカリ土類金属化合物粉末の配合量
が下限より小さいウイスカーの収率が小さくな
り、その配合量が上限より多いとウイスカー同志
の融着が起こるようになる。 The blending amount of the alkaline earth metal compound powder is 0.5 to 10 parts by weight in terms of oxide per 100 parts by weight of the raw material powder selected from amorphous silicon nitride and α-type silicon nitride. If the amount of alkaline earth metal compound powder blended is smaller than the lower limit, the yield of whiskers will be lower, and if the blended amount is more than the upper limit, fusion of whiskers will occur.
原料粉末とアルカリ土類金属化合物粉末との混
合粉末の調製法については特に制限はなく、それ
自体公知の方法、たとえば両者を乾式混合する方
法、不活性液体中で両者を湿式混合した後に不活
性液体を除去する方法等を採用することができ
る。混合装置としては、Ｖ型混合機、ボールミ
ル、又は振動ボールミルが好ましく使用される。
上記混合物の別の調製法としては、非晶質窒化珪
素粉末の前駆体、たとえばシリコンジイミド又は
シリコンテトラミドにアルカリ土類金属化合物粉
末を混合分散させ、この分散物を加熱処理する方
法を採用することもできる。上記調製法におい
て、非晶質窒化珪素又はその前駆体を使用する場
合、これらは酸素又は水分に対してきわめて敏感
であるので、制御された不活性雰囲気下で取り扱
う必要がある。 There are no particular restrictions on the method of preparing the mixed powder of the raw material powder and the alkaline earth metal compound powder, and methods known per se may be used, such as dry mixing of the two, wet mixing of the two in an inert liquid, and then inert mixing. A method of removing the liquid, etc. can be adopted. As the mixing device, a V-type mixer, a ball mill, or a vibrating ball mill is preferably used.
Another method for preparing the above mixture is to mix and disperse alkaline earth metal compound powder into a precursor of amorphous silicon nitride powder, such as silicon diimide or silicon tetraamide, and heat-treat the dispersion. You can also do it. If amorphous silicon nitride or its precursors are used in the above preparation method, they must be handled under a controlled inert atmosphere since they are very sensitive to oxygen or moisture.
焼成時の非酸化性ガスを構成する非酸化性ガス
の具体例としては、窒素、アルゴン、アンモニア
あるいはこれらの混合ガスが挙げられる。焼成条
件は、混合粉末が1000℃から最高温度の間を平均
して、２〜20時間で加熱されるように設定する。
焼成時の最高温度は1600〜1800℃の範囲内の温度
である。 Specific examples of the non-oxidizing gas constituting the non-oxidizing gas during firing include nitrogen, argon, ammonia, or a mixed gas thereof. The firing conditions are set so that the mixed powder is heated between 1000° C. and the maximum temperature in an average of 2 to 20 hours.
The maximum temperature during firing is within the range of 1600-1800°C.
混合粉末の焼成の際に使用される炉については
特に制限はなく、たとえば高周波誘導加熱方式又
は抵抗加熱方式によるバツチ式炉、ロータリー
炉、プツシヤー炉等を使用することができる。 There is no particular restriction on the furnace used for firing the mixed powder, and for example, a batch type furnace, rotary furnace, pusher furnace, etc. using a high frequency induction heating method or a resistance heating method can be used.
（発明の効果）
本発明によれば、使用原料の残留がない高純度
のβ型窒化珪素ウイスカーを収率よく製造するこ
とができる。本発明で得られるβ型窒化珪素ウイ
スカーは、金属又はセラミツクスの強化用材料と
して用いることができ、特に窒化珪素焼結体及び
サイアロン焼結体の強化用材料として好適に使用
することができる。(Effects of the Invention) According to the present invention, highly pure β-type silicon nitride whiskers with no residual raw materials can be produced with good yield. The β-type silicon nitride whiskers obtained in the present invention can be used as a material for reinforcing metals or ceramics, and can be particularly suitably used as a material for reinforcing silicon nitride sintered bodies and sialon sintered bodies.
（実施例） 以下に実施例を示す。(Example) Examples are shown below.
実施例 １
シリコンジイミドを1200℃で加熱分解して得ら
れた非晶質窒化珪素粉末50ｇと、純度99.9％の酸
化カルシウム（CaCO3）粉末1.78ｇとを、窒素ガ
ス雰囲気下ボールミルで２時間混合した。混合粉
末を、内径120mm、内容積450mlの黒鉛製ルツボに
入れ、高周波誘導炉中にセツトし、窒素ガス雰囲
気下で、室温から1200℃を1.5時間、1200〜1400
℃を４時間、1400〜1700℃を３時間で昇温し、さ
らに1700℃に10時間保持して、焼成した。Example 1 50 g of amorphous silicon nitride powder obtained by thermally decomposing silicon diimide at 1200°C and 1.78 g of calcium oxide (CaCO 3 ) powder with a purity of 99.9% were mixed in a ball mill under a nitrogen gas atmosphere for 2 hours. did. The mixed powder was placed in a graphite crucible with an inner diameter of 120 mm and an inner volume of 450 ml, set in a high frequency induction furnace, and heated from room temperature to 1200°C for 1.5 hours at 1200 to 1400°C under a nitrogen gas atmosphere.
The temperature was raised to 1400-1700°C for 4 hours, 3 hours to 1700°C, and then kept at 1700°C for 10 hours for firing.
得られた粉末をＸ線回折によつて調べたとこ
ろ、その結晶形態は第１図に示すようにβ型であ
り、また走査型電子顕微鏡による観察では、長さ
10〜20μｍ、径0.5〜1.0μｍのウイスカーであるこ
とが認められた。原料窒化珪素を基準にしたウイ
スカーの収率（以下単に収率という）は90％であ
つた。 When the obtained powder was examined by X-ray diffraction, its crystal form was β type as shown in Figure 1, and observation with a scanning electron microscope revealed that the length was
It was observed that the whiskers were 10 to 20 μm in diameter and 0.5 to 1.0 μm in diameter. The whisker yield (hereinafter simply referred to as yield) based on the raw material silicon nitride was 90%.
実施例 ２
シリコンジイミドを1200℃で加熱分解して得ら
れた非晶質窒化珪素粉末200ｇと酸化バリウム
（BaO：和光純薬製、試薬第１級）10ｇとを窒素
雰囲気下にナイロン製ボールポツトを用いて２時
間振動ミル混合した。混合物を内径290mm、高さ
70mmの黒鉛製ルツボに入れ、抵抗加熱式高温炉中
にセツトした。窒素雰囲気下に室温から1200℃を
２時間、1200〜1400℃を４時間、1400〜1800℃を
４時間で昇温し、さらに1800℃で３時間保持し
た。Example 2 200 g of amorphous silicon nitride powder obtained by thermally decomposing silicon diimide at 1200°C and 10 g of barium oxide (BaO: manufactured by Wako Pure Chemical Industries, Ltd., grade 1 reagent) were placed in a nylon ball pot under a nitrogen atmosphere. Mixing was carried out using a vibratory mill for 2 hours. Mixture inner diameter 290mm, height
It was placed in a 70 mm graphite crucible and set in a resistance heating high temperature furnace. Under a nitrogen atmosphere, the temperature was raised from room temperature to 1200°C for 2 hours, 1200-1400°C for 4 hours, 1400-1800°C for 4 hours, and further held at 1800°C for 3 hours.
得られた粉末をＸ線回折によつて調べたところ
その結晶形態はβ型であり、また走査型電子顕微
鏡による観察では、長さ５〜15μｍ、径0.2〜0.7μ
ｍのウイスカーであることが認められた。ウイス
カーの収率は87％であつた。 When the obtained powder was examined by X-ray diffraction, its crystal form was found to be β type, and when observed using a scanning electron microscope, it was found to have a length of 5 to 15 μm and a diameter of 0.2 to 0.7 μm.
It was recognized that the whisker was M. The whisker yield was 87%.
実施例 ３
シリコンジイミドを1200℃で加熱分解して得ら
れた非晶質窒化珪素粉末60ｇと、純度99.9％の炭
酸ストロンチウム（SrCO3）2.56ｇとを、窒素ガ
ス雰囲気下ボールミルで１時間混合した。混合粉
末を、内径120mm、高さ50mmの黒鉛製ルツボに入
れ、高周波誘導炉中にセツトし、窒素ガス雰囲気
下で、室温から1200℃を２時間、1200〜1445℃を
3.5時間、1445〜1650℃を２時間で昇温し、さら
に1650℃に20時間保持して、焼成した。Example 3 60 g of amorphous silicon nitride powder obtained by thermally decomposing silicon diimide at 1200°C and 2.56 g of strontium carbonate (SrCO 3 ) with a purity of 99.9% were mixed in a ball mill under a nitrogen gas atmosphere for 1 hour. . The mixed powder was placed in a graphite crucible with an inner diameter of 120 mm and a height of 50 mm, set in a high frequency induction furnace, and heated from room temperature to 1200°C for 2 hours and then from 1200 to 1445°C under a nitrogen gas atmosphere.
The temperature was raised from 1445 to 1650°C over 2 hours for 3.5 hours, and the temperature was further maintained at 1650°C for 20 hours for firing.
得られた粉末をＸ線回折によつて調べたところ
その結晶形態はβ型であり、また走査型電子顕微
鏡による観察では、，粉末の75％は長さ10〜20μ
ｍ、径0.5〜1.0μｍのウイスカーであり、残り20
％はβ型粒状窒化珪素であることが認められた。
ウイスカー状及び粒状窒化珪素の合計収率は91％
であつた。 When the obtained powder was examined by X-ray diffraction, its crystal morphology was found to be β type, and observation using a scanning electron microscope revealed that 75% of the powder had a length of 10 to 20 μm.
m, whiskers with a diameter of 0.5 to 1.0 μm, and the remaining 20
% was found to be β-type granular silicon nitride.
Total yield of whisker-like and granular silicon nitride is 91%
It was hot.
実施例 ４
比表面積4.8m2／ｇのα型窒化珪素粉末50ｇ、
酸化カルシウム（CaO：和光純薬製、試薬第１
級）粉末1.5ｇ及びエタノール250c.c.を、ボールミ
ル混合機で10時間湿式混合した後、減圧乾燥し
た。混合粉末を、内径120mm、高さ50mmの黒鉛製
ルツボに入れ、高周波誘導炉中にセツトし、窒素
ガス雰囲気下で、室温から1200℃を２時間、1200
〜1750℃を5.5時間で昇温し、さらに1750℃に５
時間保持して、焼成した。Example 4 50 g of α-type silicon nitride powder with a specific surface area of 4.8 m 2 /g,
Calcium oxide (CaO: manufactured by Wako Pure Chemical Industries, Ltd., Reagent No. 1
1.5 g of powder) and 250 c.c. of ethanol were wet mixed in a ball mill mixer for 10 hours, and then dried under reduced pressure. The mixed powder was placed in a graphite crucible with an inner diameter of 120 mm and a height of 50 mm, set in a high frequency induction furnace, and heated from room temperature to 1200°C for 2 hours at 1200°C under a nitrogen gas atmosphere.
Raise the temperature to ~1750℃ in 5.5 hours, then further increase the temperature to 1750℃ for 5.5 hours.
It was kept for a while and baked.
得られた粉末をＸ線回折によつて調べたとこ
ろ、その結晶形態はβ型であり、また走査型電子
顕微鏡による観察では、長さ10〜15μｍ、径0.5〜
0.7μｍのウイスカーであることが認められた。収
率は97％であつた。 When the obtained powder was examined by X-ray diffraction, its crystal form was β type, and observation using a scanning electron microscope revealed that it had a length of 10 to 15 μm and a diameter of 0.5 to 0.5 μm.
It was recognized that it was a 0.7 μm whisker. The yield was 97%.
実施例 ５
シリコンジイミドを1200℃で加熱分解して得ら
れた非晶質窒化珪素粉末150ｇと、純度99％の酸
化マグネシウム（MgO）粉末６ｇとを、窒素ガ
ス雰囲気下に密閉型Ｖ型混合機に入れ、４時間混
合した。混合粉末を内径290mm、高さ70mmの黒鉛
製ルツボに入れ、抵抗加熱式高温炉中にセツト
し、窒素ガス雰囲気下で、室温から1200℃を２時
間、1200〜1400℃を４時間、1400〜1820℃を４時
間で昇温し、さらに1820℃に２時間保持して、焼
成した。Example 5 150 g of amorphous silicon nitride powder obtained by thermally decomposing silicon diimide at 1200°C and 6 g of magnesium oxide (MgO) powder with a purity of 99% were mixed in a closed V-type mixer under a nitrogen gas atmosphere. and mixed for 4 hours. The mixed powder was placed in a graphite crucible with an inner diameter of 290 mm and a height of 70 mm, set in a resistance heating high temperature furnace, and heated from room temperature to 1200°C for 2 hours, from 1200 to 1400°C for 4 hours, and from 1400 to 1400°C for 4 hours in a nitrogen gas atmosphere. The temperature was raised to 1820°C over 4 hours, and the temperature was further maintained at 1820°C for 2 hours for firing.
得られた粉末をＸ線回折によつて調べたとこ
ろ、その結晶形態はβ型であり、また走査型電子
顕微鏡による観察では、長さ５〜30μｍ、径0.1〜
1.0μｍのウイスカーであることが認められた。収
率は87％であつた。 When the obtained powder was examined by X-ray diffraction, its crystal form was β type, and observation using a scanning electron microscope revealed that it had a length of 5 to 30 μm and a diameter of 0.1 to 0.1 μm.
It was recognized that it was a 1.0 μm whisker. The yield was 87%.
第１図は、実施例１で得られたβ型窒化珪素ウ
イスカーのＸ線回折図である。
FIG. 1 is an X-ray diffraction diagram of the β-type silicon nitride whiskers obtained in Example 1.
Claims (1)
る原料粉末と、原料粉末100重量部当たり酸化物
換算で0.5〜10重量部の、アルカリ土類金属の酸
化物粉末又は焼成時に酸化物に転化し得るアルカ
リ土類金属の化合物粉末との混合粉末を、非酸化
性ガス雰囲気下で1000℃から最高温度の間を２〜
20時間で加熱し、最高温度1600〜1800℃の範囲で
焼成することを特徴とするβ型窒化珪素ウイスカ
ーの製法。1 Raw material powder selected from amorphous silicon nitride and α-type silicon nitride, and 0.5 to 10 parts by weight of alkaline earth metal oxide powder or converted to oxide during firing, in terms of oxide per 100 parts by weight of raw material powder. A mixed powder with a compound powder of an alkaline earth metal that can
A method for producing β-type silicon nitride whiskers, characterized by heating for 20 hours and firing at a maximum temperature in the range of 1,600 to 1,800°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20778486A JPS6365000A (en) | 1986-09-05 | 1986-09-05 | Production of beta-type silicon nitride whisker |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20778486A JPS6365000A (en) | 1986-09-05 | 1986-09-05 | Production of beta-type silicon nitride whisker |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6365000A JPS6365000A (en) | 1988-03-23 |
| JPH0329760B2 true JPH0329760B2 (en) | 1991-04-25 |
Family
ID=16545447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20778486A Granted JPS6365000A (en) | 1986-09-05 | 1986-09-05 | Production of beta-type silicon nitride whisker |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6365000A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63235437A (en) * | 1986-10-24 | 1988-09-30 | Ube Ind Ltd | Beta-type silicon-nitride whisker compact and its production |
| US5814290A (en) * | 1995-07-24 | 1998-09-29 | Hyperion Catalysis International | Silicon nitride nanowhiskers and method of making same |
| CN104499053A (en) * | 2014-12-17 | 2015-04-08 | 青岛桥海陶瓷新材料科技有限公司 | Method for preparing silicon nitride crystal whisker |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6340711A (en) * | 1986-08-06 | 1988-02-22 | Ngk Insulators Ltd | Production of beta-type silicon nitride |
-
1986
- 1986-09-05 JP JP20778486A patent/JPS6365000A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6340711A (en) * | 1986-08-06 | 1988-02-22 | Ngk Insulators Ltd | Production of beta-type silicon nitride |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6365000A (en) | 1988-03-23 |
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