JPS58223696A - Silicon nitride fiber and its production - Google Patents
Silicon nitride fiber and its productionInfo
- Publication number
- JPS58223696A JPS58223696A JP57100739A JP10073982A JPS58223696A JP S58223696 A JPS58223696 A JP S58223696A JP 57100739 A JP57100739 A JP 57100739A JP 10073982 A JP10073982 A JP 10073982A JP S58223696 A JPS58223696 A JP S58223696A
- Authority
- JP
- Japan
- Prior art keywords
- silicon nitride
- whiskers
- fibers
- compound
- fiber
- 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
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
- C30B29/38—Nitrides
Abstract
Description
【発明の詳細な説明】
本発明は窒化ケイ累つイヌカ一番こ関するものであり、
特に窒化ケイ素つイヌノＪ−が集合してなる繊組とその
製法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silicon nitride compound,
In particular, the present invention relates to a fiber assembly made of silicon nitride and a combination of silicon nitride and its manufacturing method.
窒化ケイ素つイヌカーは耐高／１′１□Ｙ性に優れ、比
重が小さく、強度１弾性率が大きい特性を有し、繊組強
化複合ヰ］料、特に高温度で用いる金属またはセラミッ
ク複合材料用の素材として期待されているＯ
しかしながら、このような優れた才、−性をＶ＋するに
もかかわらす窒化ケイ素ウィスカーはまだ実用げ・Ｊに
広く使わイするに（才至っていない。その理由の一つは
、窒化ケイ素ウィスカーを」−業的に生産する技術が未
熟で大量生産されていないことがあ０、もう一つの大き
な理由は窒化ケイ素つイヌカーの長さ／径の比は太きい
が、長さの絶体価が小さく、同じく繊維強化複合月料用
に用いられる仄素繊翔。Silicon nitride inuka has excellent high resistance/1'1□Y properties, low specific gravity, and high strength and elastic modulus, and is suitable for fiber-reinforced composite materials, especially metal or ceramic composite materials used at high temperatures. However, despite these excellent qualities and negative properties, silicon nitride whiskers are still not practical enough to be widely used in J. One reason is that the technology to commercially produce silicon nitride whiskers is immature and they are not mass-produced.Another major reason is that silicon nitride whiskers have a large length/diameter ratio. The absolute value of the fiber is small, and it is also used for fiber-reinforced composite materials.
ガラス繊維などに比べ、非常に収扱いにくいことがあげ
られる。Compared to glass fiber, etc., it is extremely difficult to handle.
これらの点を改良すべく、取扱いやすい長いウィスカー
を工業的に製造する方法を（ｉｆｌｉ立することがｉ＋
’ｆ：来の研究の大きな流れてあり、いくつかの提案が
なされてきた。が、ウィスカーを長ぐするのは至鋪のわ
ざてあり炭素繊糺のような連Ｍ、ｌ、、長繊独に比し収
扱いにくいガ１点は克服されてない。In order to improve these points, we developed a method for industrially manufacturing long whiskers that are easy to handle (ifli standing is i +
'f: There is a major trend in future research, and several proposals have been made. However, elongating the whiskers is a very difficult task, and one problem that has not been overcome is that they are difficult to manage compared to long fibers such as carbon fiber.
従来、提案された多くの窒化ケイ素ウィスカーの製法で
は生成するウィスカーは反兄、７二）内壁に月７５．析
出し、これを回収する（例えば特開昭５６−１００１１
５）のが菖’／Ｊモてあり、回収の際、反１．１“−・
管内から剥離させるので得られたウィスカーの配列は全
く不規則であった。In many of the methods for manufacturing silicon nitride whiskers that have been proposed so far, the whiskers produced are anti-hybrid, 72) 75. precipitate and collect it (for example, JP-A-56-10011)
5) There is an irises/J model, and when it is collected, the anti-1.1"-・
Since the whiskers were peeled from inside the tube, the arrangement of the whiskers obtained was completely irregular.
本発明者らは、このような不規則、乱雑な配列のウィス
カー集合体ではなく、例えば短いワラが集合して長いナ
ワが形成される場合のように、多数のウィスカーが集合
して長い繊維状物を形成するならば取扱い易さが向上す
ることに青目し、種ノｌの実験を行った。The present inventors discovered that rather than such irregular and disorderly arrangement of whisker aggregates, for example, when short straw aggregates to form a long nape, a large number of whiskers aggregate to form a long fibrous structure. I realized that it would be easier to handle if I formed a product, so I conducted a preliminary experiment.
その結果、Ｓｉ成分を含有する有機基、？、１１または
活性炭繊組をＹ化合物の存在下、窒素を含む非酸化性雰
囲気中、１３００〜＋ ６００ ’Ｃに加熱すると、皮
付された線繊ｉｆ１を中心に多数のウィスカーが集合し
た集合体、つまり拡大観察するとウィスカー状物が多数
集合しあたかも毛皮のような外観を有するウィスカー集
合体が生成するという新事実を見出し７だ。As a result, an organic group containing a Si component, ? , 11 or the activated carbon fiber set is heated to 1300 to +600'C in a non-oxidizing atmosphere containing nitrogen in the presence of a Y compound, an aggregate of many whiskers is formed around the coated wire fiber if1. In other words, we discovered a new fact that when observed under magnification, a large number of whisker-like objects aggregate to form a whisker aggregate that looks like fur.
本発明の目的は、ウィスカーの優れた特性を有し、しか
も取扱いやすい形態のウィスカー集合体およびその製法
を提供することにある。An object of the present invention is to provide a whisker aggregate that has excellent whisker characteristics and is easy to handle, and a method for producing the same.
本発明はウィスカーが集合してなることを特徴とする窒
化ケイ素繊維とその製法である。The present invention is a silicon nitride fiber characterized by being formed by aggregation of whiskers, and a method for producing the same.
本発明の窒化ケイ素繊維を構成するウィスカーは、径０
３μす、上、長さ３０μす、上、長さく！：径の比が５
０以上であり、特に径０５〜３μ、長さ１００〜５００
０μである。The whiskers constituting the silicon nitride fiber of the present invention have a diameter of 0.
3μ, top, length 30μ, top, length! : Diameter ratio is 5
0 or more, especially diameter 05-3μ, length 100-500
It is 0μ.
このようなウィスカーが集合してウィスカー集合体型繊
維を構成するが、その集合は多数のウィスカーが変性さ
れた原繊維を中心にして放射状に着生または配列してい
る形の集合であり、いわば毛皮状の外観を呈する集合で
ある。この繊組の径はみかけ」二、０１〜．５ Ｆａｌ
ｌ、 、特に０２〜２顧が取扱い易い。繊維の長さに限
定はない。These whiskers aggregate to form a whisker aggregate type fiber, which is an aggregate in which many whiskers are attached or arranged radially around a modified fibril, so to speak. It is a set that has the appearance of The diameter of this fiber braid is "2, 01~. 5 Fal
1, especially 02-2 models are easy to handle. There is no limit to the length of the fibers.
このようなウィスカー集合体型紙ｉｆｆ、の製法に−〕
いて次に説明する。For the manufacturing method of such whisker aggregate type paper if-]
This will be explained next.
本発明の製法はＳ］酸成分含有する有機繊維または活性
炭繊糺をＹ化合物の存在下、窒素を含む非酸化性雰囲気
中、１３００〜Ｉ ６００ ’Ｃに加熱することを特徴
とする窒化ケイ素ウィスカー集合体型繊維の製法である
。The method for producing silicon nitride whiskers of the present invention is to heat organic fibers or activated carbon fibers containing an acid component to 1300 to 600'C in the presence of a Y compound in a non-oxidizing atmosphere containing nitrogen. This is a method for producing aggregate type fibers.
本発明の製法において、Ｓｉ成分とは金属Ｓｉ、Ｓｊ水
酸化物、Ｓ１酸化物もしくは加水分解または熱分解によ
りこれらを生成するＳｉ化合物を意味する。In the production method of the present invention, the Si component means metal Si, Sj hydroxide, S1 oxide, or a Si compound that produces these by hydrolysis or thermal decomposition.
本発明において有機繊維とは、２００〜１５００６Ｃｏ
）ｉ’ｉｏ’１度範囲のいずれかの温度に少くとも非酸
化性雰囲気中で加熱した場合に炭素質残留物となる４１
機物を主成分とする繊維をいう。In the present invention, organic fibers refer to 200 to 15006 Co
) i'io' forms a carbonaceous residue when heated to any temperature in the range of 1 degree in at least a non-oxidizing atmosphere41
A fiber whose main component is textiles.
これら自機物の例をあ（ヂれは、セルロース、キチン、
アルギン酸澱粉などの多糖類あるいはその誘Ｊｒｐ 体
、ポリビニルアルコール、ポリアクリロニトリル、ポリ
塩化ビニル、ポリ塩化ビニリデン、ポリブタジェン、ポ
リ西′１酸ビニルあるいはこれらを１−成分とする共１
１合体などビニル車合体およびその誘）！７体、右曲ピ
ッチ、フェノール樹脂など熱硬１ヒ樹脂、グルテン、大
豆蛋白などの蛋白質など数多くのものがある。Here are some examples of these organic materials (cellulose, chitin,
Polysaccharides such as starch alginate or their derivatives, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, polybutadiene, polyvinyl nitrate, or polysaccharides containing these as one component.
1) Vinyl car combinations (such as 1 combinations)! There are many types, including 7 types, right-handed pitches, thermoset resins such as phenolic resins, proteins such as gluten and soybean protein.
また、本発明において活性炭繊維とは繊維状の〆占性炭
であり、一般に知られている通り、微多孔をｆｌする炭
素質繊維てあり、多くの市販品が利用できる。Furthermore, in the present invention, the activated carbon fibers are fibrous carbon fibers, and as is generally known, they are microporous carbon fibers, and many commercially available products are available.
また、上記有機繊維または活性炭繊維は織物状または織
物状でも用いることができる。Further, the above organic fiber or activated carbon fiber can also be used in the form of a fabric or fabric.
Ｓｉ成分を含イｊする有機繊維は神々の方法、例えば混
合紡糸、含浸法て作ることができる。具体例をあげれは
、ケイ酸水溶液とアルギン酸、ポリビニルアルコールな
ど水溶性ポリマーの混合水溶液から湿式紡糸することに
より作ることがてきるし、ケイ酸−ポリアクリロニトリ
ルのジメチルフォルムアミド溶液から作ることもできる
。またη機繊維をケイ酸溶液またはエチルシリケート溶
液に渥〆責してＳ１分を含浸させてもよい。Organic fibers containing Si components can be produced using special methods such as mixed spinning and impregnation methods. For example, it can be made by wet spinning from a mixed aqueous solution of silicic acid and a water-soluble polymer such as alginic acid or polyvinyl alcohol, or it can be made from a dimethylformamide solution of silicic acid and polyacrylonitrile. Alternatively, the η fiber may be impregnated with S1 by soaking it in a silicic acid solution or an ethyl silicate solution.
有機繊維中のＣ，！：Ｓｌ成分中の８１の割合は、モル
化としてＣ／Ｓｉ が１５〜４５、特に１８〜３が好
ましい。Ｃ／Ｓｉが小さいと１皇料の状態での強度が小
さく取扱いにくい。Ｃ／Ｓｉが大きい場合は取扱陣やす
いが、反応後残留するＣの除去が必要となる場合がある
。C in organic fibers! :The ratio of 81 in the Sl component is preferably such that the molar ratio of C/Si is 15 to 45, particularly 18 to 3. If C/Si is small, the strength in the state of 1-koryo is small and it is difficult to handle. When C/Si is large, it is easier for the handling staff, but it may be necessary to remove residual C after the reaction.
Ｓｉ分を含自する繊維をＹ化合物の存イ１−で加熱する
ことに、より［」曲物が得られる。Ｙ化合物の（Ｙイ■
。By heating the fiber containing Si in the presence of the Y compound, a curved material can be obtained. Y compound (Yi■
.
は繊＆、ｔｌとＹ化合物の粉末を混合した状態でもよい
し、Ｙ化合物の近傍に繊維をおいてもよいが、最も好ま
しいのは繊維にＹ化合物を含浸などの手段て含有させて
おく方法である。Ｙ化合物が存在するとライヌカ−集合
体型繊維が生成するが、その作用機作は明らかでない。may be a mixture of fiber &, tl and powder of the Y compound, or the fiber may be placed near the Y compound, but the most preferred method is to impregnate the fiber with the Y compound by means such as impregnation. It is. When the Y compound is present, linuka-aggregate type fibers are produced, but its mechanism of action is not clear.
Ｙ化合物としては塩酸塩、硝酸塩、有機酸塩が含浸に便
利であり効果も太きい。酸化物も］吏えるが含浸させる
には不便である。As Y compounds, hydrochlorides, nitrates, and organic acid salts are convenient for impregnation and have great effects. Oxides are also available, but are inconvenient for impregnation.
Ｙ化合物の含有は微量でよく８１１モルあたり０．００
０１〜００５モル、特に０００１〜０．０１モルがｂｆ
ましい。The content of the Y compound is only a trace amount, which is 0.00 per mole of 811.
01-005 mol, especially 0001-0.01 mol is bf
Delicious.
反ルと１はシリカ還元窒化法による窒化ケイ素合成に通
常１小われる’１ｊｊｔ度、雰囲気でおこなえばよい。The reaction may be carried out in an atmosphere at a temperature of 1 degree, which is usually 1 degree less for silicon nitride synthesis by silica reduction nitridation method.
すなわち、窒素を含む非酸化性雰囲気中１３００〜＋
６００ ’Ｃに加熱すれはよい。That is, 1300~+ in a non-oxidizing atmosphere containing nitrogen.
It is best to heat it to 600'C.
本発明によれば、ウィスカ〜でありながら巨視的に（４
長い繊維状を呈するウィスカー集合体を得ることができ
る。そしてこの集合体は巨視的には長い繊組状であるの
で強化月料として他物質と組合せて使用する場合、取扱
いが便利な利点がある。According to the present invention, although it is a whisker, macroscopically (4
A whisker aggregate exhibiting a long fibrous shape can be obtained. Macroscopically, this aggregate is in the form of long fibers, so it has the advantage of being convenient to handle when used in combination with other substances as a reinforcing material.
以下、実施例によりさらに説明する。なお以下の実施例
において、部はすべて重量部である。This will be further explained below with reference to Examples. In addition, in the following examples, all parts are parts by weight.
実施例１
アルギン酸アンモニウムおよびケイ酸混合水溶液から紡
糸したアルギン酸／ケイ酸繊Ｍｔ（ｃ ／ ｓｉ Ｄ２
＝２．２／Ｉ（モル比）、篠６０μ）１部を塩化イツト
リウム水溶液（濃度００５モル）１００部に４０°０２
時間浸漬した後、窒素雰囲気中、１５１０℃、４時間加
熱した。窒化ケイ索ウィスカーが集合し、毛皮状の外観
を呈する集合体繊維（ウィスカー径約０５〜１μ、ウィ
スカー長、約１００μ、集合体繊細径約０２〜０．４
Ｗｂ ） ０．０６部を得た。Example 1 Alginic acid/silicic acid fiber Mt (c/si D2) spun from ammonium alginate and silicic acid mixed aqueous solution
= 2.2/I (molar ratio), 1 part of Shino 60μ) was added to 100 parts of yttrium chloride aqueous solution (concentration 0.005 mol) at 40°02
After being immersed for an hour, it was heated at 1510° C. for 4 hours in a nitrogen atmosphere. Nitride silicon wire whiskers are aggregated to form aggregate fibers that have a fur-like appearance (whisker diameter approximately 05 to 1μ, whisker length approximately 100μ, aggregate fine diameter approximately 02 to 0.4).
Wb) 0.06 part was obtained.
生成物の電子顕微鏡写真を第１図に示した。An electron micrograph of the product is shown in FIG.
比較例１
実施例１において、塩化イツトリウム水溶液に浸漬する
操作を省略した他は、実施例１と同様に実験した。灰色
化した繊維およびその破砕物が生成し、ウィスカー集合
体は生成しなかった。Comparative Example 1 An experiment was carried out in the same manner as in Example 1, except that the operation of immersing the sample in the yttrium chloride aqueous solution was omitted. Grayed fibers and their crushed materials were produced, but no whisker aggregates were produced.
実施例２
ポリビニルアルコール／ケイ酸繊維（Ｇ／ｉ−ｉ］０２
＝５／ｌ（モル比））１部を硝酸イソ１１ウム水溶液（
ａ度０．０１ モ／Ｉ／ ） ５００部ニ４０℃、２時
間音〆青した後、空気中２００ ’Ｃ１１６時間加熱し
た後、窒素雰囲気中１５１０°Ｃ１４時間加熱した。Example 2 Polyvinyl alcohol/silicic acid fiber (G/i-i]02
= 5/l (molar ratio)) was added to 1 part of iso-11ium nitrate aqueous solution (
After cooling 500 parts at 40°C for 2 hours, heating in air at 200°C for 116 hours, and then heating at 1510°C in nitrogen atmosphere for 14 hours.
窒化ケイ素ウィスカー集合体００４部が得られた。004 parts of silicon nitride whisker aggregates were obtained.
第１図は本発明に係る窒化ケイ素集合体繊維の″屯ｒ顕
ｔｊ：ｌｋ鏡写貝である。
出 願 人 ノ１ｕ ダ ウ 株 式 会
老１代 理 人 シ：９ ｍ
善 卸ｌｏｏ）ＬFIG. 1 is a mirror image of the silicon nitride aggregate fiber according to the present invention. Applicant: Dow Co., Ltd.
Elderly 1st generation person: 9 m
good wholesale loo)L
Claims (1)
イ素系繊維。 ２）Ｓ】成分を含有する有機繊維をＹ化合物のｑイ（Ｉ
・、窒素を含む非酸化性雰囲気中、１３００〜１６００
℃に加熱することを特徴とする窒化ケイ素ウィスカー集
合体型繊維の製法。[Claims] I) A silicon nitride-based fiber characterized by comprising a collection of whiskers. 2) The organic fiber containing the component qi (I) of the Y compound is
・1300-1600 in a non-oxidizing atmosphere containing nitrogen
A method for producing silicon nitride whisker aggregate type fibers, which is characterized by heating to ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57100739A JPS58223696A (en) | 1982-06-14 | 1982-06-14 | Silicon nitride fiber and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57100739A JPS58223696A (en) | 1982-06-14 | 1982-06-14 | Silicon nitride fiber and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58223696A true JPS58223696A (en) | 1983-12-26 |
Family
ID=14281928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57100739A Pending JPS58223696A (en) | 1982-06-14 | 1982-06-14 | Silicon nitride fiber and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58223696A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0310265A1 (en) * | 1987-09-30 | 1989-04-05 | The Standard Oil Company | Formation of fibrous silicon carbide and silicon nitride |
-
1982
- 1982-06-14 JP JP57100739A patent/JPS58223696A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0310265A1 (en) * | 1987-09-30 | 1989-04-05 | The Standard Oil Company | Formation of fibrous silicon carbide and silicon nitride |
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