JPH11229239A - Production of high-purity silicon nitride yarn - Google Patents
Production of high-purity silicon nitride yarnInfo
- Publication number
- JPH11229239A JPH11229239A JP2984798A JP2984798A JPH11229239A JP H11229239 A JPH11229239 A JP H11229239A JP 2984798 A JP2984798 A JP 2984798A JP 2984798 A JP2984798 A JP 2984798A JP H11229239 A JPH11229239 A JP H11229239A
- Authority
- JP
- Japan
- Prior art keywords
- silicon nitride
- purity silicon
- gas
- fiber
- temperature
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高純度窒化ケイ素
繊維の製造方法に係り、特に、耐熱絶縁材に用いられる
高純度窒化ケイ素繊維の製造方法に関するものである。The present invention relates to a method for producing a high-purity silicon nitride fiber, and more particularly to a method for producing a high-purity silicon nitride fiber used for a heat-resistant insulating material.
【０００２】[0002]
【従来の技術】耐熱絶縁材料として注目されている高純
度窒化ケイ素繊維の製造方法としては、紡糸したポリカ
ルボシラン繊維に、照射線量が０．５〜９０ＭＧｙの電
離性放射線を照射して不融化処理を施し、その後、不融
化処理を施したポリカルボシラン繊維に、アンモニアな
どの窒化処理可能なガス雰囲気中、８００〜１，７００
℃の窒化処理を施すことにより、Ｓｉ−Ｎ骨格からなる
高純度窒化ケイ素繊維を作製するという方法が提案され
ている。2. Description of the Related Art As a method for producing high-purity silicon nitride fiber, which has attracted attention as a heat-resistant insulating material, a spun polycarbosilane fiber is irradiated with ionizing radiation having an irradiation dose of 0.5 to 90 MGy to render it infusible. The polycarbosilane fiber that has been subjected to the treatment and then subjected to the infusibilization treatment is subjected to a nitriding treatment in a gas atmosphere such as ammonia at 800 to 1,700.
There has been proposed a method of producing a high-purity silicon nitride fiber composed of a Si-N skeleton by performing a nitriding treatment at a temperature of ° C.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、ポリカ
ルボシラン繊維を出発原料とした従来の高純度窒化ケイ
素繊維の製造方法においては、繊維中に不純物酸素が多
量に取り込まれてしまうため、高温の熱処理中に繊維が
酸化されて劣化し、得られる高純度窒化ケイ素繊維が脆
くなってしまう。酸素を多量に含む高純度窒化ケイ素繊
維の初期引張強度は、１ＧＰａ以下であり、機械的強度
が低いという問題がある。However, in the conventional method for producing high-purity silicon nitride fiber using polycarbosilane fiber as a starting material, a large amount of impurity oxygen is incorporated into the fiber, so that high-temperature heat treatment is performed. The fibers are oxidized and deteriorated, and the resulting high-purity silicon nitride fibers become brittle. The initial tensile strength of a high-purity silicon nitride fiber containing a large amount of oxygen is 1 GPa or less, and there is a problem that the mechanical strength is low.
【０００４】そこで本発明は、上記課題を解決し、酸素
含有量が少なく、かつ、機械的強度に優れた高純度窒化
ケイ素繊維の製造方法を提供することにある。Accordingly, an object of the present invention is to solve the above problems and to provide a method for producing a high-purity silicon nitride fiber having a low oxygen content and excellent mechanical strength.
【０００５】[0005]
【課題を解決するための手段】上記課題を解決するため
に請求項１の発明は、不融化処理を施したポリカルボシ
ラン繊維に、アンモニアガス雰囲気中で窒化処理を施し
た後、不活性ガスとハロゲン系ガスとの混合ガス雰囲気
中で熱処理を施し、酸素含有量５ｗｔ％以下、引張強度
２．０ＧＰａ以上の高純度窒化ケイ素繊維を得るもので
ある。According to a first aspect of the present invention, a polycarbosilane fiber that has been subjected to an infusibilizing treatment is subjected to a nitriding treatment in an ammonia gas atmosphere and then to an inert gas. A high-purity silicon nitride fiber having an oxygen content of 5 wt% or less and a tensile strength of 2.0 GPa or more is obtained by performing a heat treatment in a mixed gas atmosphere of hydrogen and a halogen-based gas.
【０００６】請求項２の発明は、不融化処理を施したポ
リカルボシラン繊維に、５００℃以上のアンモニアガス
雰囲気中で窒化処理を施した後、１，０００℃以上の不
活性ガスとハロゲン系ガスとの混合ガス雰囲気中で熱処
理を施し、酸素含有量５ｗｔ％以下、引張強度２．０Ｇ
Ｐａ以上の高純度窒化ケイ繊維素を得るものである。A second aspect of the present invention is to provide an infusibilized polycarbosilane fiber which is subjected to nitriding in an ammonia gas atmosphere at 500 ° C. or more, followed by an inert gas at 1,000 ° C. or more and a halogen-based material. Heat treatment in a mixed gas atmosphere with a gas, oxygen content 5 wt% or less, tensile strength 2.0 G
It is intended to obtain a high-purity silicon nitride fibrous material of Pa or more.
【０００７】請求項３の発明は、上記窒化処理後の上記
ポリカルボシラン繊維を、大気に接触させることなく連
続して熱処理を施す請求項１記載の高純度窒化ケイ素繊
維の製造方法である。A third aspect of the present invention is the method for producing a high-purity silicon nitride fiber according to the first aspect, wherein the polycarbosilane fiber after the nitriding treatment is continuously heat-treated without being brought into contact with the atmosphere.
【０００８】請求項４の発明は、上記窒化処理温度が５
００〜１，０００℃である請求項１又は請求項２記載の
高純度窒化ケイ素繊維の製造方法である。According to a fourth aspect of the present invention, the nitriding temperature is 5
The method for producing a high-purity silicon nitride fiber according to claim 1 or 2, wherein the temperature is from 00 to 1,000 ° C.
【０００９】請求項５の発明は、上記熱処理温度が１，
０００〜１，３００℃である請求項１又は請求項２記載
の高純度窒化ケイ素繊維の製造方法である。According to a fifth aspect of the present invention, the heat treatment temperature is 1
The method for producing a high-purity silicon nitride fiber according to claim 1 or 2, wherein the temperature is from 000 to 1,300 ° C.
【００１０】請求項６の発明は、上記混合ガス中のハロ
ゲン系ガスの割合が３０体積％以下である請求項１、請
求項２、又は請求項５記載の高純度窒化ケイ素繊維の製
造方法である。The invention according to claim 6 is the method according to claim 1, wherein the proportion of the halogen-based gas in the mixed gas is 30% by volume or less. is there.
【００１１】請求項７の発明は、上記窒化処理および上
記熱処理の昇温速度が２００℃／ｈｒ以上である請求項
１乃至請求項６記載の高純度窒化ケイ素繊維の製造方法
である。The invention according to claim 7 is the method for producing a high-purity silicon nitride fiber according to any one of claims 1 to 6, wherein the heating rate of the nitriding treatment and the heat treatment is 200 ° C./hr or more.
【００１２】請求項８の発明は、上記アンモニアガスお
よび上記混合ガスを、予め、上記窒化処理温度および上
記熱処理温度に予熱しておく請求項１乃至請求項６記載
の高純度窒化ケイ素繊維の製造方法である。The invention according to claim 8 is a method for producing a high-purity silicon nitride fiber according to any one of claims 1 to 6, wherein the ammonia gas and the mixed gas are preheated to the nitriding temperature and the heat treatment temperature in advance. Is the way.
【００１３】請求項９の発明は、上記不融化処理が、
０．５〜９０ＭＧｙの電離性放射線の照射によるもので
ある請求項１又は請求項２記載の高純度窒化ケイ素繊維
の製造方法である。[0013] According to a ninth aspect of the present invention, the infusibilizing treatment comprises:
The method for producing a high-purity silicon nitride fiber according to claim 1 or 2, which is performed by irradiation of ionizing radiation of 0.5 to 90 MGy.
【００１４】上記数値範囲の限定理由を以下に述べる。The reasons for limiting the above numerical range will be described below.
【００１５】窒化処理温度を５００℃以上としたのは、
温度が５００℃よりも低いと窒化反応が生じないためで
ある。上限温度は特に限定するものではないが、１，０
００℃で窒化が完了するため、１，０００℃以上の温度
での窒化処理は無意味であり、好ましくは１，０００℃
以下とする。The reason why the nitriding temperature is set to 500 ° C. or more is as follows.
If the temperature is lower than 500 ° C., no nitriding reaction occurs. Although the upper limit temperature is not particularly limited,
Since nitriding is completed at 00 ° C., nitriding at a temperature of 1,000 ° C. or more is meaningless, and preferably 1,000 ° C.
The following is assumed.
【００１６】熱処理温度を１，０００℃以上としたの
は、温度が１，０００℃よりも低いと繊維中に活性なラ
ジカル（遊離基）が残存し、繊維を大気中に取出した後
に酸素が混入する原因となるためであり、上限温度は特
に限定するものではないが、１，３００℃で未反応のラ
ジカルの処理および活性基（シラザン；ＳｉＮＨ）の処
理が完了するため、１，３００℃以上の温度での熱処理
は無意味であり、好ましくは１，３００℃以下とする。The reason why the heat treatment temperature is set to 1,000 ° C. or higher is that if the temperature is lower than 1,000 ° C., active radicals (free radicals) remain in the fiber, and oxygen is removed after the fiber is taken out to the atmosphere. The upper limit temperature is not particularly limited, but the treatment of unreacted radicals and the treatment of active groups (silazane; SiNH) at 1,300 ° C. are completed. The heat treatment at the above temperature is meaningless, and is preferably 1,300 ° C. or less.
【００１７】混合ガス中のハロゲン系ガスの割合を３０
体積％以下としたのは、ハロゲン系ガスの割合が３０体
積％よりも多いと、繊維中にハロゲン元素が不純物とし
て導入されて、高温の熱処理中に繊維が酸化される原因
となり、この酸化により機械的強度が低下するためであ
る。The proportion of the halogen-based gas in the mixed gas is 30
The reason why the content is set to be not more than 30% by volume is that when the proportion of the halogen-based gas is more than 30% by volume, a halogen element is introduced as an impurity into the fiber, which causes the fiber to be oxidized during a high-temperature heat treatment. This is because the mechanical strength decreases.
【００１８】窒化処理および熱処理における昇温速度を
２００℃／ｈｒ以上としたのは、昇温速度が２００℃／
ｈｒよりも小さいと窒化ケイ素繊維中における酸素含有
量が高くなるためである。The reason why the heating rate in the nitriding treatment and the heat treatment is set to 200 ° C./hr or more is that the heating rate is 200 ° C./hr.
This is because if it is smaller than hr, the oxygen content in the silicon nitride fiber increases.
【００１９】電離性放射線の照射線量を０．５〜９０Ｍ
Ｇｙとしたのは、照射線量が０．５ＭＧｙよりも少ない
とポリカルボシラン繊維の不融化が不十分となり、窒化
処理または熱処理中に溶融してしまうためである。ま
た、照射線量が９０ＭＧｙの時、ゲル分率が１００以上
となるため、照射線量を９０ＭＧｙよりも多くしても無
意味である。The irradiation dose of ionizing radiation is 0.5 to 90 M
The reason why Gy is set is that if the irradiation dose is less than 0.5 MGy, the insolubilization of the polycarbosilane fiber becomes insufficient, and the fiber is melted during the nitriding treatment or the heat treatment. In addition, when the irradiation dose is 90 MGy, the gel fraction becomes 100 or more, so it is meaningless to increase the irradiation dose to more than 90 MGy.
【００２０】以上の構成によれば、不融化処理を施した
ポリカルボシラン繊維に、アンモニアガス雰囲気中で窒
化処理を施した後、不活性ガスとハロゲン系ガスとの混
合ガス雰囲気中で熱処理を施したため、酸素含有量が少
なく、かつ、機械的強度に優れた高純度窒化ケイ素繊維
を得ることができる。According to the above arrangement, the polycarbosilane fiber subjected to the infusibilizing treatment is subjected to a nitriding treatment in an ammonia gas atmosphere and then to a heat treatment in a mixed gas atmosphere of an inert gas and a halogen-based gas. As a result, a high-purity silicon nitride fiber having a low oxygen content and excellent mechanical strength can be obtained.
【００２１】[0021]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。Embodiments of the present invention will be described below.
【００２２】本発明の高純度窒化ケイ素繊維の製造方法
は、先ず、照射線量が０．５〜９０ＭＧｙの電離性放射
線を、紡糸したポリカルボシラン繊維に照射して、ポリ
カルボシラン繊維に不融化処理を施す。ここで、電離性
放射線としては、電子線、α線、γ線、Ｘ線などが挙げ
られる。In the method for producing a high-purity silicon nitride fiber according to the present invention, first, an ionizing radiation having an irradiation dose of 0.5 to 90 MGy is irradiated on the spun polycarbosilane fiber so as to make the polycarbosilane fiber infusible. Perform processing. Here, examples of the ionizing radiation include an electron beam, α-ray, γ-ray, and X-ray.
【００２３】次に、不融化処理を施したポリカルボシラ
ン繊維を、室温のアンモニアガス雰囲気内に搬送した
後、２００℃／ｈｒ以上の昇温速度で５００℃以上（好
ましくは５００〜１，０００℃）の温度に加熱して、ポ
リカルボシラン繊維に窒化処理を施す。Next, the infusibilized polycarbosilane fiber is conveyed into an ammonia gas atmosphere at room temperature, and is then heated at a temperature rising rate of 200 ° C./hr or more to 500 ° C. or more (preferably 500 to 1,000). (° C.) to perform a nitriding treatment on the polycarbosilane fiber.
【００２４】次に、この窒化処理後、ポリカルボシラン
繊維に大気を接触させることなく、かつ、連続して熱処
理を施す。Next, after the nitriding treatment, the polycarbosilane fiber is subjected to a continuous heat treatment without contacting the atmosphere.
【００２５】この熱処理は、窒化処理を施したポリカル
ボシラン繊維を、不活性ガス中に３０体積％以下のハロ
ゲン系ガスを混入した混合ガス雰囲気内に搬送した後、
２００℃／ｈｒ以上の昇温速度で１，０００℃以上（好
ましくは１，０００〜１，３００℃）の温度に加熱する
ものである。ここで、ハロゲン系ガスとしては、塩素ガ
ス、フッ素ガスなどが挙げられ、不活性ガスとしては、
窒素ガス、アルゴンガスなどが挙げられる。In the heat treatment, the polycarbosilane fiber subjected to the nitriding treatment is transferred into a mixed gas atmosphere in which 30% by volume or less of a halogen-based gas is mixed in an inert gas.
The heating is performed at a temperature rising rate of 200 ° C./hr or more to a temperature of 1,000 ° C. or more (preferably 1,000 to 1,300 ° C.). Here, examples of the halogen-based gas include chlorine gas and fluorine gas, and examples of the inert gas include:
Examples include nitrogen gas and argon gas.
【００２６】この時、窒化処理温度および熱処理温度と
同じ温度に予熱しておいたアンモニアガスおよび混合ガ
スを用いてもよく、その場合、ポリカルボシラン繊維の
表面温度が下がらないため、窒化処理中および熱処理中
におけるポリカルボシラン繊維内への酸素混入を更に抑
制することができると共に、高純度窒化ケイ素繊維の機
械的強度が更に向上する。At this time, an ammonia gas or a mixed gas preheated to the same temperature as the nitriding temperature and the heat treatment temperature may be used. In this case, since the surface temperature of the polycarbosilane fiber does not drop, the nitriding In addition, oxygen contamination into the polycarbosilane fiber during the heat treatment can be further suppressed, and the mechanical strength of the high-purity silicon nitride fiber is further improved.
【００２７】熱処理後、室温まで徐冷して高純度窒化ケ
イ繊維素を得る。After the heat treatment, the mixture is gradually cooled to room temperature to obtain a high-purity silicon nitride fiber.
【００２８】すなわち、不融化処理後のポリカルボシラ
ン繊維に対する従来の熱処理は一工程であったのに対
し、本発明の高純度窒化ケイ素繊維の製造方法における
熱処理は、アンモニアガス雰囲気中で窒化処理を施すと
共に、不活性ガス中にハロゲン系ガスを混入した混合ガ
ス雰囲気中で熱処理を施すという具合に、二工程に分離
させているため、酸素含有量が５ｗｔ％以下、かつ、引
張強度が２．０ＧＰａ以上の高純度窒化ケイ素繊維を得
ることができる。That is, while the conventional heat treatment for the polycarbosilane fiber after the infusibilization treatment was one step, the heat treatment in the method for producing a high-purity silicon nitride fiber of the present invention is a nitridation treatment in an ammonia gas atmosphere. And the heat treatment is performed in a mixed gas atmosphere in which a halogen-based gas is mixed in an inert gas, so that the oxygen content is 5 wt% or less and the tensile strength is 2 A high-purity silicon nitride fiber of 0.0 GPa or more can be obtained.
【００２９】[0029]
【実施例】（実施例１）先ず、紡糸装置を用いて直径１
８μｍのポリカルボシラン繊維を作製した後、このポリ
カルボシラン繊維に、Ｈｅガス雰囲気中で１５ＭＧｙの
電離性放射線を照射して不融化処理を施す。(Example 1) First, using a spinning apparatus, a diameter of 1 mm was used.
After producing an 8 μm polycarbosilane fiber, the polycarbosilane fiber is irradiated with 15 MGy of ionizing radiation in a He gas atmosphere to be infusibilized.
【００３０】次に、この不融化処理を施したポリカルボ
シラン繊維を室温のアンモニアガス雰囲気内に搬送した
後、無張力下において、３００℃／ｈｒ以上の昇温速度
で１，０００℃の温度に加熱して、ポリカルボシラン繊
維に窒化処理を施す。Next, the polycarbosilane fiber subjected to the infusibilizing treatment is conveyed into an ammonia gas atmosphere at room temperature, and then, under no tension, at a temperature increase rate of 300 ° C./hr or more at a temperature of 1,000 ° C. To perform a nitriding treatment on the polycarbosilane fiber.
【００３１】窒化処理後、このポリカルボシラン繊維
を、大気に接触させることなく、かつ、連続して、窒素
ガス中に３０体積％の塩素ガスを混入した混合ガス気流
中に搬送する。その後、３００℃／ｈｒ以上の昇温速度
で１，３００℃の温度に加熱して、ポリカルボシラン繊
維に熱処理を施す。After the nitriding treatment, the polycarbosilane fibers are continuously conveyed into a mixed gas stream in which 30% by volume of chlorine gas is mixed in nitrogen gas without being brought into contact with the atmosphere. Thereafter, the polycarbosilane fiber is heated by heating to a temperature of 1,300 ° C. at a rate of 300 ° C./hr or more.
【００３２】その後、室温まで徐冷して、無色透明の繊
維を得る。Thereafter, the mixture is gradually cooled to room temperature to obtain colorless and transparent fibers.
【００３３】（実施例２）窒素ガス中に１０体積％の塩
素ガスを混入した混合ガスを用いる以外は実施例１と同
様にして、無色透明の繊維を得る。Example 2 A colorless and transparent fiber is obtained in the same manner as in Example 1 except that a mixed gas obtained by mixing 10% by volume of chlorine gas in nitrogen gas is used.
【００３４】（実施例３）窒化処理温度を８００℃とす
る以外は実施例２と同様にして、無色透明の繊維を得
る。(Example 3) A colorless and transparent fiber is obtained in the same manner as in Example 2 except that the nitriding temperature is set to 800 ° C.
【００３５】（実施例４）熱処理温度を１，２００℃と
する以外は実施例３と同様にして、無色透明の繊維を得
る。Example 4 A colorless and transparent fiber is obtained in the same manner as in Example 3 except that the heat treatment temperature is set to 1,200 ° C.
【００３６】（実施例５）熱処理温度を１，０００℃と
する以外は実施例２と同様にして、無色透明の繊維を得
る。Example 5 A colorless and transparent fiber was obtained in the same manner as in Example 2 except that the heat treatment temperature was changed to 1,000 ° C.
【００３７】（比較例１）混合ガスではなく１００体積
％の窒素ガスを用いる以外は実施例１と同様にして、無
色透明の繊維を得る。Comparative Example 1 A colorless and transparent fiber was obtained in the same manner as in Example 1 except that 100% by volume of nitrogen gas was used instead of the mixed gas.
【００３８】（比較例２）窒化処理温度を４００℃とす
る以外は実施例２と同様にして、黒色の繊維を得る。Comparative Example 2 A black fiber is obtained in the same manner as in Example 2 except that the nitriding temperature is set to 400 ° C.
【００３９】（比較例３）昇温速度を１００℃／ｈｒと
する以外は実施例１と同様にして、無色透明の繊維を得
る。(Comparative Example 3) A colorless and transparent fiber was obtained in the same manner as in Example 1 except that the heating rate was 100 ° C / hr.
【００４０】実施例１〜５および比較例１〜３の各繊維
を、メノウ乳鉢に入れて粉砕した後、蛍光Ｘ線分析によ
り元素分析測定を行う。また、引張試験機を用いて常温
における各繊維の単繊維引張強度を測定する。Each of the fibers of Examples 1 to 5 and Comparative Examples 1 to 3 is ground in an agate mortar, and then subjected to elemental analysis by fluorescent X-ray analysis. In addition, the single fiber tensile strength of each fiber at room temperature is measured using a tensile tester.
【００４１】実施例１〜５および比較例１〜３の各繊維
の処理条件および各測定結果を表１に示す。Table 1 shows the processing conditions and measurement results for each fiber of Examples 1 to 5 and Comparative Examples 1 to 3.
【００４２】[0042]
【表１】 [Table 1]
【００４３】表１に示すように、実施例１〜５の各繊維
は、窒化処理および熱処理の各処理条件を規定範囲内に
制御しているため、各繊維の酸素含有量は、いずれも５
ｗｔ％以下（それぞれ２．０ｗｔ％、２．１ｗｔ％、
２．８ｗｔ％、２．８ｗｔ％、３．０ｗｔ％）であると
共に、各繊維の引張強度も、いずれも２．０ＧＰａ以上
（それぞれ３．０ＧＰａ、２．８ＧＰａ、２．７ＧＰ
ａ、２．７ＧＰａ、２．５Ｐａ）であり、高純度窒化ケ
イ素繊維が得られた。As shown in Table 1, each of the fibers of Examples 1 to 5 controls the respective nitriding treatment and heat treatment conditions within a specified range.
wt% or less (2.0 wt%, 2.1 wt%, respectively)
2.8 wt%, 2.8 wt%, 3.0 wt%) and the tensile strength of each fiber is 2.0 GPa or more (3.0 GPa, 2.8 GPa, 2.7 GPa, respectively).
a, 2.7 GPa, 2.5 Pa), and a high-purity silicon nitride fiber was obtained.
【００４４】これに対して、比較例１の繊維は、引張強
度は２．０ＧＰａ以上（２．１ＧＰａ）であるものの、
熱処理の雰囲気ガスが１００体積％の窒素ガスであり、
規定（不活性ガス中に３０体積％以下のハロゲン系ガス
を混入した混合ガス）以外の雰囲気ガスを用いているた
め、酸素含有量が８．０ｗｔ％と高くなった。On the other hand, although the fiber of Comparative Example 1 has a tensile strength of 2.0 GPa or more (2.1 GPa),
The atmosphere gas for the heat treatment is 100% by volume nitrogen gas,
Since an atmosphere gas other than the regulation (a mixed gas containing 30 vol% or less of a halogen-based gas in an inert gas) was used, the oxygen content was increased to 8.0 wt%.
【００４５】また、比較例２の繊維は、窒化処理温度が
４００℃であり、規定（５００℃以上）外の温度である
ため、炭素含有量が５０ｗｔ％となっており、得られた
繊維は炭化ケイ素繊維であった。The fiber of Comparative Example 2 had a nitriding temperature of 400 ° C., which was out of the specified range (500 ° C. or higher), so that the carbon content was 50 wt%. It was a silicon carbide fiber.
【００４６】さらに、比較例３の繊維は、引張強度は
２．０ＧＰａ以上（２．１ＧＰａ）であるものの、昇温
速度が１００℃／ｈｒであり、規定（２００℃／ｈｒ以
上）外であるため、酸素含有量が８．０ｗｔ％と高くな
った。Further, the fiber of Comparative Example 3 has a tensile strength of 2.0 GPa or more (2.1 GPa), but a heating rate of 100 ° C./hr, which is out of the specified range (200 ° C./hr or more). Therefore, the oxygen content was increased to 8.0 wt%.
【００４７】[0047]
【発明の効果】以上要するに本発明によれば、不融化処
理を施したポリカルボシラン繊維に、アンモニアガス雰
囲気中で窒化処理を施した後、不活性ガスとハロゲン系
ガスとの混合ガス雰囲気中で熱処理を施すことで、酸素
含有量が５ｗｔ％以下、かつ、引張強度が２．０ＧＰａ
以上の高純度窒化ケイ素繊維を得ることができるという
優れた効果を発揮する。In summary, according to the present invention, the polycarbosilane fiber which has been subjected to the infusibilizing treatment is subjected to nitriding treatment in an ammonia gas atmosphere and then to a mixed gas atmosphere of an inert gas and a halogen-based gas. The oxygen content is 5 wt% or less and the tensile strength is 2.0 GPa
An excellent effect that the above-described high-purity silicon nitride fiber can be obtained is exhibited.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 瀬口 忠男 群馬県高崎市綿貫町1233番地 日本原子力 研究所 高崎研究所内 (72)発明者 神村 誠二 茨城県日立市日高町５丁目１番１号 日立 電線株式会社パワーシステム研究所内 (72)発明者 渡辺 清 茨城県日立市日高町５丁目１番１号 日立 電線株式会社パワーシステム研究所内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tadao Seguchi 1233 Watanukicho, Takasaki City, Gunma Prefecture Inside the Japan Atomic Energy Research Institute Takasaki Research Laboratory (72) Inventor Seiji Kamimura 5-1-1 Hidakacho Hitachi, Hitachi City, Ibaraki Hitachi (72) Inventor Kiyoshi Watanabe 5-1-1 Hidakacho, Hitachi City, Ibaraki Prefecture Power Systems Laboratory, Hitachi Cable, Ltd.
Claims (9)
維に、アンモニアガス雰囲気中で窒化処理を施した後、
不活性ガスとハロゲン系ガスとの混合ガス雰囲気中で熱
処理を施し、酸素含有量５ｗｔ％以下、引張強度２．０
ＧＰａ以上の高純度窒化ケイ素繊維を得ることを特徴と
する高純度窒化ケイ素繊維の製造方法。Claims: 1. After subjecting a polycarbosilane fiber subjected to an infusibilizing treatment to a nitriding treatment in an ammonia gas atmosphere,
Heat treatment is performed in a mixed gas atmosphere of an inert gas and a halogen-based gas, and the oxygen content is 5 wt% or less and the tensile strength is 2.0
A method for producing a high-purity silicon nitride fiber, which comprises obtaining a high-purity silicon nitride fiber of GPa or more.
維に、５００℃以上のアンモニアガス雰囲気中で窒化処
理を施した後、１，０００℃以上の不活性ガスとハロゲ
ン系ガスとの混合ガス雰囲気中で熱処理を施し、酸素含
有量５ｗｔ％以下、引張強度２．０ＧＰａ以上の高純度
窒化ケイ繊維素を得ることを特徴とする高純度窒化ケイ
素繊維の製造方法。2. A polycarbosilane fiber subjected to an infusibilizing treatment is subjected to a nitriding treatment in an ammonia gas atmosphere at 500 ° C. or more, and then a mixed gas of an inert gas and a halogen-based gas at 1,000 ° C. or more. A method for producing a high-purity silicon nitride fiber, comprising performing a heat treatment in an atmosphere to obtain a high-purity silicon nitride fiber having an oxygen content of 5 wt% or less and a tensile strength of 2.0 GPa or more.
繊維を、大気に接触させることなく連続して熱処理を施
す請求項１記載の高純度窒化ケイ素繊維の製造方法。3. The method for producing a high-purity silicon nitride fiber according to claim 1, wherein the polycarbosilane fiber after the nitriding treatment is continuously subjected to a heat treatment without being brought into contact with the atmosphere.
℃である請求項１又は請求項２記載の高純度窒化ケイ素
繊維の製造方法。4. The nitriding temperature is 500 to 1,000.
The method for producing a high-purity silicon nitride fiber according to claim 1 or 2, wherein the temperature is ° C.
０℃である請求項１又は請求項２記載の高純度窒化ケイ
素繊維の製造方法。5. The heat treatment temperature is 1,000 to 1,30.
The method for producing a high-purity silicon nitride fiber according to claim 1 or 2, wherein the temperature is 0 ° C.
が３０体積％以下である請求項１、請求項２、又は請求
項５記載の高純度窒化ケイ素繊維の製造方法。6. The method for producing a high-purity silicon nitride fiber according to claim 1, wherein the proportion of the halogen-based gas in the mixed gas is 30% by volume or less.
度が２００℃／ｈｒ以上である請求項１乃至請求項６記
載の高純度窒化ケイ素繊維の製造方法。7. The method for producing a high-purity silicon nitride fiber according to claim 1, wherein a temperature rising rate of the nitriding treatment and the heat treatment is 200 ° C./hr or more.
を、予め、上記窒化処理温度および上記熱処理温度に予
熱しておく請求項１乃至請求項６記載の高純度窒化ケイ
素繊維の製造方法。8. The method for producing a high-purity silicon nitride fiber according to claim 1, wherein the ammonia gas and the mixed gas are preheated to the nitriding temperature and the heat treatment temperature in advance.
の電離性放射線の照射によるものである請求項１又は請
求項２記載の高純度窒化ケイ素繊維の製造方法。9. The method according to claim 1, wherein the infusibilizing treatment is performed at 0.5 to 90 MGy.
The method for producing a high-purity silicon nitride fiber according to claim 1 or 2, which is performed by irradiation with ionizing radiation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2984798A JPH11229239A (en) | 1998-02-12 | 1998-02-12 | Production of high-purity silicon nitride yarn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2984798A JPH11229239A (en) | 1998-02-12 | 1998-02-12 | Production of high-purity silicon nitride yarn |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11229239A true JPH11229239A (en) | 1999-08-24 |
Family
ID=12287392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2984798A Pending JPH11229239A (en) | 1998-02-12 | 1998-02-12 | Production of high-purity silicon nitride yarn |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11229239A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2075012A1 (en) * | 2001-12-21 | 2009-07-01 | PSIMEDICA Limited | Medical fibres |
| CN104818609A (en) * | 2015-05-14 | 2015-08-05 | 中国人民解放军国防科学技术大学 | Polycarbosilane fiber low-oxygen non-melting method |
-
1998
- 1998-02-12 JP JP2984798A patent/JPH11229239A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2075012A1 (en) * | 2001-12-21 | 2009-07-01 | PSIMEDICA Limited | Medical fibres |
| CN104818609A (en) * | 2015-05-14 | 2015-08-05 | 中国人民解放军国防科学技术大学 | Polycarbosilane fiber low-oxygen non-melting method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6372192B1 (en) | Carbon fiber manufacturing via plasma technology | |
| US9045347B2 (en) | Stiochiometric silicon carbide fibers from thermo-chemically cured polysilazanes | |
| US8987402B2 (en) | Stoichiometric silicon carbide fibers from thermo-chemically cured polysilazanes | |
| JP2002097074A (en) | Manufacture of silicon carbide composite material by applying radiation to silicon-based polymer | |
| Kamimura et al. | Development of silicon nitride fiber from Si-containing polymer by radiation curing and its application | |
| Mittal et al. | Denitrogenation behavior and tensile strength increase during carbonization of stabilized PAN fibers | |
| JP2525286B2 (en) | Method for producing super heat resistant silicon carbide fiber | |
| US3972984A (en) | Process for the preparation of carbon fiber | |
| US5322822A (en) | Ultra-high-strength refractory silicon carbide fiber and process for producing same | |
| JPH11229239A (en) | Production of high-purity silicon nitride yarn | |
| JPH06192917A (en) | Production of silicon carbide fiber | |
| JP2963021B2 (en) | Method for producing silicon carbide fiber | |
| US5051215A (en) | Curing preceramic polymers by exposure to nitrogen dioxide | |
| Raman et al. | Synthesis of silicon carbide through the sol—gel process from rayon fibers | |
| JP3155687B2 (en) | Method for producing silicon nitride fiber | |
| JP3279144B2 (en) | High heat resistant ceramic fiber and method for producing the same | |
| JPH01139819A (en) | Ceramics fiber and production thereof | |
| JP3198014B2 (en) | Method and apparatus for producing continuous silicon nitride fiber that can be woven | |
| JP2001207377A (en) | Surface-modified carbon fiber | |
| JPH0941225A (en) | Production of silicon carbide fiber | |
| JP2574179B2 (en) | Method for producing super heat resistant high strength silicon carbide fiber | |
| JP2001295140A (en) | Silicon carbine fiber having carbon film on surface of fiber, and method for producing the same | |
| JP3457774B2 (en) | Method for producing highly elastic carbon fiber having excellent interfacial adhesion to resin | |
| JP3002698B2 (en) | Manufacturing method of graphite fiber | |
| JPS6119817A (en) | Silicon oxide fiber and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040528 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040608 |
|
| A02 | Decision of refusal |
Effective date: 20041026 Free format text: JAPANESE INTERMEDIATE CODE: A02 |