JPH01278405A - Production of acicular silicon nitride - Google Patents
Production of acicular silicon nitrideInfo
- Publication number
- JPH01278405A JPH01278405A JP10768488A JP10768488A JPH01278405A JP H01278405 A JPH01278405 A JP H01278405A JP 10768488 A JP10768488 A JP 10768488A JP 10768488 A JP10768488 A JP 10768488A JP H01278405 A JPH01278405 A JP H01278405A
- Authority
- JP
- Japan
- Prior art keywords
- silicon nitride
- silica powder
- metals
- acicular silicon
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 27
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 4
- 229910001508 alkali metal halide Inorganic materials 0.000 claims 1
- 150000008045 alkali metal halides Chemical class 0.000 claims 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 8
- 150000004820 halides Chemical class 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 3
- 239000008246 gaseous mixture Substances 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 and co Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
−Ｑの
この発明は、針状晶窒化ケイ素のＷＡ造六方法関するも
のである。DETAILED DESCRIPTION OF THE INVENTION This invention -Q relates to six methods for producing WA of acicular silicon nitride.
ＩＬ悲炎！
例えば、特許第８３８４２１号は、弗化物、酸性弗化物
または珪弗化物を付着した非晶質シリカ粉末に炭素質物
質の粉末を混合し、窒素雰囲気中で１３００〜１６００
℃に焼成することを特徴とする針状晶窒化ケイ素の製造
方法について開示している。IL sad flame! For example, in Japanese Patent No. 838421, carbonaceous material powder is mixed with amorphous silica powder to which fluoride, acidic fluoride, or silicofluoride is attached, and the
Discloses a method for producing acicular silicon nitride, which is characterized by firing at a temperature of .degree.
ｎが ）しよ−と る 、
前述の方法を含め従来の針状晶窒化ケイ素の製造方法は
、シリカ粉末と炭素粉末の混合物を反応させる固相−固
相反応である。このため、シリカとカーボンの混合が不
十分になり易い。混合が不十分な場合、反応が不均一に
なる。反応が不均一になると、生成するウィスカーの径
が不揃いになったり、粒子状の窒化ケイ素が生成し易く
なる。The conventional method for producing acicular silicon nitride, including the method described above, is a solid-state reaction in which a mixture of silica powder and carbon powder is reacted. For this reason, silica and carbon tend to be insufficiently mixed. If mixing is insufficient, the reaction will be non-uniform. If the reaction becomes non-uniform, the diameters of the generated whiskers may become uneven, and particulate silicon nitride is likely to be produced.
ル１へ１江
前述の問題点に鑑み本発明は、収率がよく、粒状の窒化
ケイ素を含まず、しかも径のそろった針状晶窒化ケイ素
を得ることのできる針状晶窒化ケイ素の製造方法を提供
することを目的としている。In view of the above-mentioned problems, the present invention aims to produce acicular silicon nitride that has a good yield, does not contain granular silicon nitride, and can obtain acicular silicon nitride with uniform diameters. The purpose is to provide a method.
１ るた の
本発明の針状晶窒化ケイ素の製造方法においては、シリ
カ粉末あるいは、シリカ粉末に遷移金属、アルカリ金属
、アルカリ土類金属、遷移金属のハロゲン化物、アルカ
リ金属のハロゲン化物、または遷移金属のハロゲン化物
の６種のうちから選んだ少なくとも１種を加え１ζ混合
物を出発物質とする。前記混合物の混合比は、シリカ粉
末１モル部に対して前述の６種のうちから選んだ少なく
とも１種は０゜００１〜１．０モル部である。シリカ粉
末あるいは前記混合物をアンモニア（ＮＨ３）ガスと炭
化水素（Ｃ１ｌｌ−１ｎ）ガスとの混合ガス中において
、８００℃〜１６５０℃の温度で加熱することによって
針状晶窒化ケイ素を製造する。６種のうちから選んだ少
なくとも１種とは、６種の中から１種以上を任意に選ぶ
ことを意味する。もちろん、６種全部を選んでもよい。1. In the method for producing acicular silicon nitride of the present invention, silica powder, or silica powder containing a transition metal, an alkali metal, an alkaline earth metal, a halide of a transition metal, a halide of an alkali metal, or a transition metal is added to the silica powder. At least one selected from six types of metal halides is added to obtain a 1ζ mixture as a starting material. The mixing ratio of the mixture is 0.001 to 1.0 parts by mole of at least one selected from the above six types to 1 part by mole of silica powder. Acicular silicon nitride is produced by heating silica powder or the above mixture at a temperature of 800°C to 1650°C in a mixed gas of ammonia (NH3) gas and hydrocarbon (C1ll-1n) gas. At least one type selected from six types means arbitrarily selecting one or more types from among the six types. Of course, you may choose all six types.
前述の混合ガスの混合比を、Ｃｌ１ｌ ）ｌｎをＣＨ４
に換算してＮＨ３／ＣＨ４−０，５〜２０００ （体積
比）にすると右利である。The mixing ratio of the above-mentioned mixed gas is Cl1l)ln is CH4
If it is converted to NH3/CH4-0.5~2000 (volume ratio), it is right-handed.
針状晶窒化ケイ素は基本的には■の反応で作られる。Acicular silicon nitride is basically produced by the reaction (2).
３Ｓｉ ０２ ＋４ＮＨ３
→Ｓｉ ３ Ｈ４＋６Ｈ２０・・・■
ＳｉＯ２にＦｅ、Ｎｉ、ｃｏ等ノ遷移金属、アルカリ金
属、アルカリ土類金属あるいはこれらのハロゲン化物を
添加することにより、添加しない場合に比べ、より速く
反応を進行させ、かつ生成するＳｉ ３Ｎ、ｓの形態を
針状晶（ライスｈ−＞とすることができる。これらの添
加物の添加市が、Ｓ’１０２１モル部に対し、０．００
１モル部より少ないと、触媒としての効果が得られない
１また、１モル部を超えると、原料シリカと化合し、ガ
ラス相を生成し、反応速度を著しく低下させる。3Si 02 +4NH3 →Si 3 H4+6H20... ■ By adding transition metals such as Fe, Ni, and co, alkali metals, alkaline earth metals, or halides of these to SiO2, the reaction is faster than when no addition is made. The form of Si 3N,s produced can be made into acicular crystals (rice h->).
If it is less than 1 part by mole, no effect as a catalyst can be obtained.If it exceeds 1 part by mole, it will combine with the raw material silica to form a glass phase, significantly reducing the reaction rate.
■の反応により生成するＨ２０の分圧を下げ、■の反応
をよりすみやかに進行させるために炭化水素（Ｃｍ Ｈ
ｎ ）ガスを用いる（第０式参照）。Hydrocarbons (Cm H
n) Using gas (see equation 0).
Ｉｆ−１２０４−〇＋＋＋ ）−Ｉｎ→■ ｃｏ＋
（ｍ ＋’ｉＭ Ｈ２＝■このように、反応ガス
としては、Ｎ Ｈ３とＣｌ１ｌ １−（ｎの混合ガスを
用いる。ＮＨ３とＣＩｒＩＨｎの混合割合について述べ
ると、ＣｍＨｎをＣＨ４に換算して、ＮＨ３／ＣＨ４が
０゜５（ｖｏｌ比）より小さい場合には、ＮＨ３の分圧
が低くなりすぎて反応の進行が著しく遅くなる。ＮＨ３
／ＣＨ４＞２０００の場合には、Ｃ１１−Ｉｎを添加す
る効果がほとんどなくなる。If-1204-〇+++ )-In→■ co+
(m +'iM H2=■ In this way, a mixed gas of NH3 and Cl1l 1-(n is used as the reaction gas. Regarding the mixing ratio of NH3 and CIrIHn, converting CmHn into CH4, NH3 /CH4 is less than 0°5 (vol ratio), the partial pressure of NH3 becomes too low and the reaction progresses significantly.NH3
When /CH4>2000, the effect of adding C11-In is almost lost.
次に反応温度について）ホベる。反応温度が８００℃よ
り低温では実質的に反応が進行しない。１６５０℃より
高湿ではＳｉＣが生成し、得られる針状晶窒化ケイ素の
純度が低下する。Next, regarding the reaction temperature). When the reaction temperature is lower than 800°C, the reaction does not substantially proceed. If the humidity is higher than 1650° C., SiC is generated and the purity of the obtained acicular silicon nitride is reduced.
火ＩＬ
実施例１
平均粒径０．０２μｍのシリカ粉末３ｇを窒化ケイ素製
ルツボに入れ、さらにそのルツボを黒鉛製ルツボに入れ
て、画周波誘導炉中にセットした。このルツボをＮＨ３
と０３Ｈ８との混合気体からなる雰囲気中において、１
４００℃で４時間保持し、針状晶窒化ケイ素を得た。得
られた生成物についてＸ線回折およびＳＥＭによる形状
観察を行った。その結果を表１に示す。Fire IL Example 1 3 g of silica powder with an average particle size of 0.02 μm was placed in a silicon nitride crucible, and the crucible was further placed in a graphite crucible, which was then set in a cutting frequency induction furnace. This crucible is NH3
In an atmosphere consisting of a gas mixture of and 03H8, 1
The temperature was maintained at 400° C. for 4 hours to obtain acicular silicon nitride. The shape of the obtained product was observed by X-ray diffraction and SEM. The results are shown in Table 1.
平均粒径０．０２μｍのシリカ粉末３ｇにＮａ ＣＱを
対シリカモル比で０．０５加えた。Na CQ was added to 3 g of silica powder with an average particle size of 0.02 μm in a molar ratio of 0.05 to silica.
これにアセトンを加えてメノウ乳バチで混合し、その後
、乾燥した。得られた混合物を実施例１と同様の方法で
針状晶窒化ケイ素を製造した。ただし、加熱温度は１４
５０℃である（実施例２）。Acetone was added to this, mixed with an agate milk drum, and then dried. Acicular silicon nitride was produced from the resulting mixture in the same manner as in Example 1. However, the heating temperature is 14
50° C. (Example 2).
実施例３では、ＮａＦを対シリカモル比で０．５加え、
実施例１と同様の方法で針状晶窒化ケイ素を製造した。In Example 3, NaF was added at a molar ratio of 0.5 to silica,
Acicular silicon nitride was produced in the same manner as in Example 1.
同様に表１に示す条件で実施例４〜６において針状晶窒
化ケイ素を製造し、形状観察を行った。Similarly, acicular silicon nitride was produced in Examples 4 to 6 under the conditions shown in Table 1, and the shapes were observed.
また、表１に示す条件で比較例１〜４において針状晶窒
化ケイ素の製造を試み、形状観察を行った。Further, production of acicular silicon nitride was attempted in Comparative Examples 1 to 4 under the conditions shown in Table 1, and the shapes were observed.
この結果、実施例１〜５によれば、長さ及び径の比較的
そろった針状晶窒化ケイ素が収率よく得られることが明
らかになった。As a result, it was revealed that according to Examples 1 to 5, acicular silicon nitride having relatively uniform length and diameter could be obtained in good yield.
１１匹１１
本発明の針状晶窒化ケイ素の製造方法によれば、収率よ
く短時間で、粒状の窒化ケイ素を含まず、比較的径のそ
ろった針状晶窒化ケイ素を得ることができる。According to the method for producing acicular silicon nitride of the present invention, acicular silicon nitride containing no particulate silicon nitride and having a relatively uniform diameter can be obtained in a high yield and in a short time.
Claims (1)
素（ＣｍＨｎ）ガスとの混合ガス中において、８００℃
〜１６５０℃の温度で加熱することを特徴とする針状晶
窒化ケイ素の製造方法。 ２、前記混合ガスの混合比が、炭化水素 （ＣｍＨｎ）をＣＨ＿４に換算して、ＮＨ＿３とＣＨ＿
４の体積比が０．５〜２０００であることを特徴とする
請求項１記載の針状晶窒化ケイ素の製造方法。 ３、シリカ粉末がさらにシリカ粉末１モル 部に対し、触媒として遷移金属、アルカリ金属、アルカ
リ土類金属、遷移金属のハロゲン化物、アルカリ金属の
ハロゲン化物またはアルカリ土類金属のハロゲン化物の
６種の中から選んだ少なくとも１種０．００１〜１．０
モル部を含む、第１項または第２項に記載の針状晶窒化
ケイ素の製造方法。[Claims] 1. Silica powder was heated at 800°C in a mixed gas of ammonia (NH_3) gas and hydrocarbon (CmHn) gas.
A method for producing acicular silicon nitride, the method comprising heating at a temperature of ~1650°C. 2. The mixing ratio of the mixed gas is NH_3 and CH_4, converting hydrocarbons (CmHn) into CH_4.
2. The method for producing acicular silicon nitride according to claim 1, wherein the volume ratio of 4 to 4 is 0.5 to 2000. 3. The silica powder further contains 6 types of transition metals, alkali metals, alkaline earth metals, transition metal halides, alkali metal halides, or alkaline earth metal halides as a catalyst per 1 mole part of silica powder. At least one selected from among 0.001 to 1.0
The method for producing acicular silicon nitride according to item 1 or 2, including a molar part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10768488A JPH01278405A (en) | 1988-05-02 | 1988-05-02 | Production of acicular silicon nitride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10768488A JPH01278405A (en) | 1988-05-02 | 1988-05-02 | Production of acicular silicon nitride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01278405A true JPH01278405A (en) | 1989-11-08 |
| JPH0511047B2 JPH0511047B2 (en) | 1993-02-12 |
Family
ID=14465348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10768488A Granted JPH01278405A (en) | 1988-05-02 | 1988-05-02 | Production of acicular silicon nitride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01278405A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5814290A (en) * | 1995-07-24 | 1998-09-29 | Hyperion Catalysis International | Silicon nitride nanowhiskers and method of making same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5673603A (en) * | 1979-11-14 | 1981-06-18 | Toshiba Corp | Manufacture of silicon nitride |
| JPS63162516A (en) * | 1986-12-26 | 1988-07-06 | Toshiba Ceramics Co Ltd | Production of silicon nitride |
-
1988
- 1988-05-02 JP JP10768488A patent/JPH01278405A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5673603A (en) * | 1979-11-14 | 1981-06-18 | Toshiba Corp | Manufacture of silicon nitride |
| JPS63162516A (en) * | 1986-12-26 | 1988-07-06 | Toshiba Ceramics Co Ltd | Production of silicon nitride |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5814290A (en) * | 1995-07-24 | 1998-09-29 | Hyperion Catalysis International | Silicon nitride nanowhiskers and method of making same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0511047B2 (en) | 1993-02-12 |
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