JPH0316422B2 - - Google Patents
Info
- Publication number
- JPH0316422B2 JPH0316422B2 JP63050234A JP5023488A JPH0316422B2 JP H0316422 B2 JPH0316422 B2 JP H0316422B2 JP 63050234 A JP63050234 A JP 63050234A JP 5023488 A JP5023488 A JP 5023488A JP H0316422 B2 JPH0316422 B2 JP H0316422B2
- Authority
- JP
- Japan
- Prior art keywords
- silicon
- carbon
- sic
- fiber fabric
- composite 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.)
- Expired - Lifetime
Links
- 239000004744 fabric Substances 0.000 claims description 69
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 68
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 68
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 55
- 239000004917 carbon fiber Substances 0.000 claims description 55
- 239000000835 fiber Substances 0.000 claims description 52
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 239000011247 coating layer Substances 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- 239000002210 silicon-based material Substances 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 43
- 239000010410 layer Substances 0.000 description 29
- 238000010438 heat treatment Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009941 weaving Methods 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
- C04B30/00—Compositions for artificial stone, not containing binders
- C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、新規な構成を有するケイ素−炭素複
合繊維からなる織物乃至編物およびその製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a woven or knitted fabric made of silicon-carbon composite fibers having a novel structure and a method for producing the same.
従来技術とその問題点
炭素繊維からなる織物乃至編物（以下特に必要
でない限り単に織物という）をケイ素または炭化
ケイ素で被覆することにより、その物性改善を図
ることは、従来から試みられている。例えば、
CVD，PVD、溶射法などにより、炭素繊維織物
の表面にケイ素または炭化ケイ素の被覆層を形成
することが可能であるが、この場合には、織物の
外面に被覆層が形成されるだけで、内部に存在す
る糸や繊維の表面には、被覆層は全く形成されな
い。従つて、勿論繊維表面の改質などはまつたく
行なわれず、これらの方法では、炭素繊維織物の
物性を実質的に改善することは、出来ない。ま
た、糸の形状において、上記加工を行なつた場
合、コスト高は勿論、糸物性の変化により、製織
工程が著しく困難となり、厚物乃至三次元織物で
は、製織不能である。Prior Art and Problems There have been attempts in the past to improve the physical properties of woven or knitted fabrics (hereinafter simply referred to as woven fabrics unless otherwise required) made of carbon fibers by coating them with silicon or silicon carbide. for example,
It is possible to form a coating layer of silicon or silicon carbide on the surface of a carbon fiber fabric by CVD, PVD, thermal spraying, etc., but in this case, the coating layer is only formed on the outer surface of the fabric. No coating layer is formed on the surface of the threads or fibers present inside. Therefore, of course, the surface of the fibers cannot be modified at all, and these methods cannot substantially improve the physical properties of the carbon fiber fabric. Further, when the above-mentioned processing is performed on the shape of the thread, not only the cost increases but also the weaving process becomes extremely difficult due to changes in the physical properties of the thread, making it impossible to weave thick or three-dimensional fabrics.
問題点を解決するための手段
本発明者は、炭素繊維織物の内部の構成繊維に
までケイ素または炭化ケイ素の被覆層を形成させ
るべく鋭意研究を重ねた結果、炭素繊維織物にケ
イ素または炭化ケイ素の蒸気を接触させる場合に
は、炭素繊維織物の内部に存在する繊維の表面界
面にまでケイ素または炭化ケイ素の被覆層が形成
されること、その結果得られるケイ素−炭素複合
繊維織物の物性が著しく改善されることを見出し
た。Means for Solving the Problems The present inventor has conducted extensive research to form a coating layer of silicon or silicon carbide even on the constituent fibers inside a carbon fiber fabric, and as a result, the present inventor has found that a coating layer of silicon or silicon carbide can be formed on a carbon fiber fabric. When contacting with steam, a coating layer of silicon or silicon carbide is formed even on the surface interface of the fibers existing inside the carbon fiber fabric, and as a result, the physical properties of the resulting silicon-carbon composite fiber fabric are significantly improved. I found out that it can be done.
すなわち、本発明は、下記のケイ素−炭素複合
繊維織物およびその製造方法を提供するものであ
る：
炭素繊維からなる織物乃至編物の繊維表面に
ケイ素および／または炭化ケイ素被覆層を有
し、かつ該繊維の少なくとも一部がケイ素化合
物に変換されていることを特徴とするケイ素−
炭素複合繊維織物乃至編物。 That is, the present invention provides the following silicon-carbon composite fiber fabric and its manufacturing method: A woven or knitted fabric made of carbon fibers has a silicon and/or silicon carbide coating layer on its fiber surface, and Silicon- characterized in that at least a part of the fiber is converted into a silicon compound.
Carbon composite fiber woven or knitted fabric.
炭素繊維からなる織物乃至編物を、密閉容器
内においてケイ素および／または炭化ケイ素の
蒸気に接触させることを特徴とする特許請求の
範囲第１項に記載のケイ素−炭素複合繊維織物
乃至編物の製造方法。 The method for producing a silicon-carbon composite fiber woven or knitted fabric according to claim 1, characterized in that the woven or knitted fabric made of carbon fibers is brought into contact with silicon and/or silicon carbide vapor in a closed container. .
炭素繊維からなる織物乃至編物を、密閉容器
内においてケイ素および／または炭化ケイ素の
蒸気に接触させた後、1300〜2600℃で熱処理す
ることを特徴とする特許請求の範囲第１項に記
載のケイ素−炭素複合繊維織物乃至編物の製造
方法。 Silicon according to claim 1, characterized in that the woven or knitted fabric made of carbon fibers is brought into contact with silicon and/or silicon carbide vapor in a closed container, and then heat-treated at 1300 to 2600°C. - A method for producing carbon composite fiber woven or knitted fabrics.
本発明において基材として使用する炭素繊維織
物は、PAN系、ピツチ系、レーヨン系、気相成
長炭素系などのいずれであつても良い。また、織
物乃至編物の製造方法にも、一切制限はない。 The carbon fiber fabric used as the base material in the present invention may be any one of PAN type, pitch type, rayon type, vapor grown carbon type, etc. Furthermore, there are no restrictions on the method of manufacturing the woven or knitted material.
本発明のケイ素−炭素複合繊維織物は、炭素繊
維織物とSi源となる物質、または炭素繊維織物と
SiC源となる物質とを密閉容器内に入れ、Si蒸気
またはSiC蒸気が発生する温度条件下に加熱し、
発生した該蒸気と炭素繊維織物とを接触させるこ
とにより、製造される。Si源としては、Siが使用
される。Si源は、平均粒径５mm以下程度の小塊乃
至粉末の形態で使用することが好ましい。また、
SiC源としては、SiCの蒸気が形成される限り、
特に限定されないが、SiC，SiO2と炭素材料との
混合物、Siと炭素材料との混合物などが例示され
る。SiC源としてのSi成分とＣ成分との配合比
は、必要に応じて任意に選択され、特に限定され
ない。SiC源としても、平均粒径５mm以下程度の
小塊乃至粉末の形態であることが好ましい。SiC
源用の炭素材料としてピツチを使用する場合に
は、ピツチ中にSiO2などあらかじめ分散させて
おくことが好ましい。Si源およびSiC源を併用し
ても良い。また、炭素繊維織物の空隙内にSi源ま
たはSiC源の粉末を充填した状態で加熱する場合
には、織物を構成するそれぞれの糸、繊維へのSi
および／またはSiCの付着が効率良く行われ、Si
被覆層またはSiC被覆層が均一に形成される。ま
た、後記する様に、界面部分の炭素繊維の一部が
ケイ素化合物に変換される。炭素繊維織物とSiま
たはSiCの蒸気との接触時の温度は、SiCの蒸気
が形成される限り、特に限定されないが、使用す
るSi源またはSiC源材料の種類、蒸気面積、蒸気
圧など適宜考慮して、通常1300〜2600℃程度の範
囲内とする。接触時間は、所望の被覆層厚さ、織
物を構成するそれぞれの糸、繊維の太さ、織物の
形成方法などに応じて定めれば良く、特に限定さ
れない。 The silicon-carbon composite fiber fabric of the present invention combines a carbon fiber fabric and a substance that serves as a Si source, or a carbon fiber fabric and a substance that serves as a Si source.
A substance that is a SiC source is placed in a sealed container and heated under temperature conditions that generate Si vapor or SiC vapor,
It is produced by bringing the generated steam into contact with a carbon fiber fabric. Si is used as the Si source. The Si source is preferably used in the form of small lumps or powder with an average particle size of about 5 mm or less. Also,
As a SiC source, as long as SiC vapor is formed,
Examples include, but are not limited to, SiC, a mixture of SiO 2 and a carbon material, and a mixture of Si and a carbon material. The blending ratio of the Si component and the C component as a SiC source is arbitrarily selected as required and is not particularly limited. The SiC source is also preferably in the form of small lumps or powder with an average particle size of about 5 mm or less. SiC
When using pitch as a source carbon material, it is preferable to previously disperse SiO 2 in the pitch. A Si source and a SiC source may be used together. In addition, when heating the carbon fiber fabric with Si source or SiC source powder filled in the voids, Si
and/or SiC adhesion is performed efficiently and Si
The coating layer or SiC coating layer is uniformly formed. Furthermore, as will be described later, a portion of the carbon fibers at the interface are converted into silicon compounds. The temperature at which the carbon fiber fabric contacts Si or SiC vapor is not particularly limited as long as SiC vapor is formed, but the type of Si source or SiC source material used, vapor area, vapor pressure, etc. should be taken into consideration as appropriate. The temperature is usually within the range of 1300 to 2600℃. The contact time is not particularly limited, and may be determined depending on the desired thickness of the coating layer, the thickness of each thread and fiber constituting the woven fabric, the method of forming the woven fabric, and the like.
本発明では、上記した方法で得られたケイ素−
炭素複合繊維織物を更に、1300〜2600℃で熱処理
することにより、Si被覆層またはSiC被覆層と炭
素繊維との反応を進行させることができる。この
熱処理においては、温度および時間に応じて、Si
被覆層またはSiC被覆層と炭素繊維および糸との
反応が進行して、炭素繊維の少なくとも一部が
SiC化される。この熱処理工程は、前段のSiまた
はSiC蒸気との接触工程と完全に独立した状態で
実施する必要はなく、該蒸気との接触工程を終え
た炭素繊維織物を同一密閉容器内で引き続き加熱
しても良い。この熱処理時間は、炭素繊維の表面
と被覆層との界面層のSi又はＣの拡散による固相
反応量を規制するものである。この界面相の厚さ
は、用途に応じて定められるものであるから、熱
処理時間は、特に限定されない。 In the present invention, silicon-
By further heat-treating the carbon composite fiber fabric at 1300 to 2600°C, the reaction between the Si coating layer or the SiC coating layer and the carbon fibers can proceed. In this heat treatment, Si
The reaction between the coating layer or the SiC coating layer and the carbon fibers and yarn progresses, and at least a portion of the carbon fibers are
Converted to SiC. This heat treatment step does not need to be carried out completely independently of the previous step of contacting with Si or SiC vapor, and the carbon fiber fabric that has undergone the contact step with the vapor can be continuously heated in the same closed container. Also good. This heat treatment time regulates the amount of solid phase reaction due to the diffusion of Si or C in the interface layer between the surface of the carbon fiber and the coating layer. Since the thickness of this interfacial phase is determined depending on the application, the heat treatment time is not particularly limited.
本発明によるケイ素−炭素複合繊維織物は、Si
および／またはSiC被覆層の厚さ、熱処理の程度
などにより、第１図に糸の1/4断面として概念的
に示す〜の“種の類型に大別される。第１図
において、ハツチング部分は、不定比組成層また
は界面層を示す。また、破線で示す部分は、本発
明の処理前の炭素繊維の部分である。なお、図示
した各層の厚さは、必ずしも炭素繊維における実
際の相対的な厚さを示すものではない。また、不
定比組成層または界面層においては、Siの濃度
は、表面側から内部側に向けて低くなつている。 The silicon-carbon composite fiber fabric according to the present invention has Si
Depending on the thickness of the SiC coating layer and/or the degree of heat treatment, etc., it can be roughly divided into ``types'' shown conceptually as a 1/4 cross section of the thread in Figure 1.In Figure 1, the hatched part indicates a non-stoichiometric composition layer or an interface layer. Also, the part indicated by the broken line is the part of the carbon fiber before the treatment of the present invention.The thickness of each layer shown does not necessarily correspond to the actual relative thickness of the carbon fiber. Furthermore, in the non-stoichiometric composition layer or the interface layer, the Si concentration decreases from the surface side toward the inside.
類型のものは、炭素繊維Ｃの表面まSiの被覆
層が存在しており、両層の間には、薄いSiC層が
形成されている。 In this type, a Si coating layer is present on the surface of carbon fiber C, and a thin SiC layer is formed between the two layers.
類型のものは、炭素繊維の表面に当初形成さ
れていたSi層が、熱処理により、中心部の炭素Ｃ
と反応して、中心部にSiC層が形成されたもので
あり、表面の薄いSi層と内側のSiC層とからなつ
ている。 In this type of carbon fiber, the Si layer originally formed on the surface of the carbon fiber is heated and the carbon C in the center is removed.
A SiC layer is formed in the center by the reaction, and consists of a thin Si layer on the surface and an inner SiC layer.
類型のものは、炭素繊維の表面に当初形成さ
れていたSiC層が、熱処理により、中心部の炭素
Ｃと反応して、表面のSiC層と中心部のＣ層との
間にSiCとＣとからなる混合層が形成されたもの
である。 In this type of carbon fiber, the SiC layer initially formed on the surface of the carbon fiber reacts with the carbon C in the center through heat treatment, resulting in the formation of SiC and C between the SiC layer on the surface and the C layer in the center. A mixed layer consisting of
類型のものは、炭素繊維の表面に当初形成さ
れていたSiまたはSiC層が、熱処理により、中心
部の炭素Ｃと反応して、全体がSiC層となつたも
のである。 In this type of carbon fiber, the Si or SiC layer originally formed on the surface of the carbon fiber reacts with carbon C in the center through heat treatment, and the entire surface becomes an SiC layer.
発明の効果
本発明のケイ素−炭素複合繊維織物は、耐酸化
性、機械的強度などに優れているので、例えば、
セラミツクス（ガラス、窒化物、炭化物など）、
金属（アルミニウム、チタンなど）などと組み合
わせて得られる複合材料における強化基材とし
て、有用である。Effects of the Invention The silicon-carbon composite fiber fabric of the present invention has excellent oxidation resistance and mechanical strength, so for example,
Ceramics (glass, nitride, carbide, etc.),
It is useful as a reinforcing base material in composite materials obtained in combination with metals (aluminum, titanium, etc.).
実施例
以下実施例を示し、本発明の特徴とするところ
をより一層明らかにする。Examples Examples will be shown below to further clarify the features of the present invention.
実施例 １
PAN系炭素繊維の織物3.0ｇの空隙内にSi粉末
（200メツシユ通過）3.0ｇを充填し、密閉黒鉛容
器内に入れ、昇温速度８℃／分で1700℃まで昇温
し、同温度で20分間保持した。Example 1 3.0 g of Si powder (passed through 200 meshes) was filled into the voids of 3.0 g of PAN-based carbon fiber fabric, placed in a sealed graphite container, and heated to 1700°C at a heating rate of 8°C/min. It was kept at the same temperature for 20 minutes.
上記の過程において、炭素繊維の表面に先ずSi
が堆積し、これが炭素と反応して、SiとＣとの間
にSiCからなる界面層が形成され、第１図の類型
に相当するケイ素−炭素複合繊維織物が得られ
た。 In the above process, Si is first applied to the surface of the carbon fiber.
was deposited and reacted with carbon to form an interfacial layer of SiC between Si and C, resulting in a silicon-carbon composite fiber fabric corresponding to the type shown in FIG.
また、得られたケイ素−炭素複合繊維織物を粉
砕し、粉末をＸ線回折に供した結果は、第１表に
示す通りであつた。 Further, the obtained silicon-carbon composite fiber fabric was pulverized and the powder was subjected to X-ray diffraction, and the results were as shown in Table 1.
第 １ 表
2θ 該当物質 相対強度
26.4 Ｃ 100
28.4 Si 30
35.6 SiC 80
41.4 SiC 20
47.3 Si ５
54.6 Ｃ 20
実施例 ２
ピツチ系炭素繊維の織物5.0ｇとSi塊（平均粒
径３mm）15ｇとを密閉黒鉛容器内に収容し、昇温
速度15℃／分で2100℃まで昇温し、同温度で30分
間保持した。 Table 1 2θ Applicable substance Relative strength 26.4 C 100 28.4 Si 30 35.6 SiC 80 41.4 SiC 20 47.3 Si 5 54.6 C 20 Example 2 5.0 g of pitch carbon fiber fabric and 15 g of Si lumps (average particle size 3 mm) are sealed. It was placed in a graphite container, heated to 2100°C at a heating rate of 15°C/min, and held at the same temperature for 30 minutes.
上記の過程において、炭素繊維の表面に先ずSi
が堆積し、これが炭素と反応して、SiとＣとの間
にSiCからなる界面層が形成され、次いでこの界
面層の厚さが次第に増大して、最終的に第１図の
類型に相当するケイ素−炭素複合繊維織物が得
られた。 In the above process, Si is first applied to the surface of the carbon fiber.
is deposited and reacts with carbon to form an interfacial layer consisting of SiC between Si and C.Then, the thickness of this interfacial layer gradually increases, and finally it corresponds to the type shown in Figure 1. A silicon-carbon composite fiber fabric was obtained.
また、得られたケイ素−炭素複合繊維織物を粉
砕し、粉末をＸ線回折に供した結果は、第２表に
示す通りであつた。 Further, the obtained silicon-carbon composite fiber fabric was pulverized and the powder was subjected to X-ray diffraction, and the results were as shown in Table 2.
第 ２ 表
2θ 該当物質 相対強度
28.4 Si 20
35.6 SiC 100
41.4 SiC 25
47.3 Si ３
実施例 ３
PAN系炭素繊維の織物3.0ｇとSiC粉末（100メ
ツシユ通過）5.0ｇとを密閉黒鉛容器内に収容し、
昇温速度15℃／分で1800℃まで昇温し、同温度で
30分間保持した。 Table 2 2θ Applicable substance Relative strength 28.4 Si 20 35.6 SiC 100 41.4 SiC 25 47.3 Si 3 Example 3 3.0 g of PAN-based carbon fiber fabric and 5.0 g of SiC powder (passed through 100 meshes) were placed in a sealed graphite container. ,
The temperature was raised to 1800℃ at a heating rate of 15℃/min, and at the same temperature
Hold for 30 minutes.
上記の過程において、炭素繊維の表面に先ず
SiCが堆積し、これが炭素とわずかに反応して、
Si／Ｃの不定比組成を有する界面層（SiC＋Ｃ）
が形成され、第１図の類型に相当するケイ素−
炭素複合繊維織物が得られた。 In the above process, the surface of the carbon fiber is first
SiC is deposited, which reacts slightly with carbon,
Interface layer with non-stoichiometric composition of Si/C (SiC+C)
is formed, and silicon corresponding to the type shown in Figure 1 is formed.
A carbon composite fiber fabric was obtained.
また、得られたケイ素−炭素複合繊維織物を粉
砕し、粉末をＸ線回折に供した結果は、第３表に
示す通りであつた。 Further, the obtained silicon-carbon composite fiber fabric was pulverized and the powder was subjected to X-ray diffraction, and the results were as shown in Table 3.
第 ３ 表
2θ 該当物質 相対強度
26.4 Ｃ 100
35.6 SiC 80
41.4 SiC 20
54.6 Ｃ 20
第２図は、本実施例により得られたケイ素−炭
素複合繊維織物の繊維糸の断面形状を示す走査型
電子顕微鏡写真（炭素繊維の断面直径：約7μm）
である。繊維の表面に約0.8μmの均一なSiC被覆
層が形成されており、破断面は、その被覆膜を通
つて同一平面を有していることから、繊維糸と膜
との間にSi／Ｃの不定比組成を有する界面層が存
在していることが明らかである。 Table 3 2θ Applicable substance Relative strength 26.4 C 100 35.6 SiC 80 41.4 SiC 20 54.6 C 20 Figure 2 is a scanning electron microscope image showing the cross-sectional shape of the fiber yarn of the silicon-carbon composite fiber fabric obtained in this example. Photo (Cross-sectional diameter of carbon fiber: approx. 7μm)
It is. A uniform SiC coating layer of about 0.8 μm is formed on the surface of the fiber, and the fracture surface has the same plane through the coating film, so there is no Si/SiC coating between the fiber thread and the membrane. It is clear that an interfacial layer with a non-stoichiometric composition of C is present.
次に、本実施例で得られたケイ素−炭素複合繊
維織物を750℃に保持しつつ、N280％−O220％の
混合ガスを流量800ml／分で流通させて、耐酸化
性を測定した。結果を曲線Ａとして第３図に示
す。無処理の炭素繊維織物についての同様な試験
結果を示す曲線Ｂに比して、酸化による重量減少
はほとんど認められない。 Next, while maintaining the silicon-carbon composite fiber fabric obtained in this example at 750°C, a mixed gas of 80% N 2 - 20% O 2 was passed through at a flow rate of 800 ml/min to improve its oxidation resistance. It was measured. The results are shown as curve A in FIG. Compared to curve B showing similar test results for untreated carbon fiber fabric, almost no weight loss due to oxidation is observed.
また、本実施例で得られたケイ素−炭素複合繊
維織物の曲げ強度を測定した。結果を第４図に
（）として示す。無処理の炭素繊維織物につい
ての結果およびCVD法によるSiC被覆した炭素繊
維織物についての結果（CVD）に比して、本発
明品の曲げ強度が著しく向上していることが明ら
かである。 In addition, the bending strength of the silicon-carbon composite fiber fabric obtained in this example was measured. The results are shown in parentheses in Figure 4. It is clear that the bending strength of the product of the present invention is significantly improved compared to the results for untreated carbon fiber fabrics and the results for carbon fiber fabrics coated with SiC by CVD method (CVD).
実施例 ４
ピツチ系炭素繊維の織物5.0ｇとSi塊（平均粒
径３mm）15ｇとを密閉黒鉛容器内に収容し、昇温
速度15℃／分で2100℃まで昇温し、同温度で３時
間保持した。Example 4 5.0 g of pitch-based carbon fiber fabric and 15 g of Si lumps (average particle size 3 mm) were placed in a sealed graphite container, heated to 2100°C at a rate of 15°C/min, and heated to 2100°C at the same temperature. Holds time.
上記の過程において、炭素繊維の表面に先ずSi
が堆積し、これが2100℃での保持により炭素と反
応して、SiとＣとの間にSiCからなる界面層が形
成され、次いでこの界面層の厚さが次第に増大し
て、最終的には炭素繊維の全てがSiCとなつた第
１図の類型に相当するケイ素−炭素複合繊維織
物が得られた。 In the above process, Si is first applied to the surface of the carbon fiber.
is deposited, which reacts with carbon when held at 2100°C to form an interface layer consisting of SiC between Si and C, and then the thickness of this interface layer gradually increases until finally A silicon-carbon composite fiber fabric corresponding to the type shown in FIG. 1 in which all of the carbon fibers were SiC was obtained.
また、得られたケイ素−炭素複合繊維織物を粉
砕し、粉末をＸ線回折に供した結果は、第４表に
示す通りであつた。 Further, the obtained silicon-carbon composite fiber fabric was pulverized and the powder was subjected to X-ray diffraction, and the results were as shown in Table 4.
第 ４ 表
2θ 該当物質 相対強度
35.6 SiC 100
41.4 SiC 25
第５図は、本実施例により得られたケイ素−炭
素複合繊維織物の繊維糸の断面形状を示す走査型
電子顕微鏡写真である。繊維の内部まで全面にわ
たつて完全にSiC層が形成されていることが明ら
かである。 Table 4 2θ Applicable substance Relative strength 35.6 SiC 100 41.4 SiC 25 FIG. 5 is a scanning electron micrograph showing the cross-sectional shape of the fiber yarn of the silicon-carbon composite fiber fabric obtained in this example. It is clear that the SiC layer is completely formed all over the inside of the fiber.
次に、本実施例で得られたケイ素−炭素複合繊
維織物を750℃に保持しつつ、N280％−O220％の
混合ガスを流量800ml／分で流通させて、耐酸化
性を測定した。結果を曲線Ｃとして第６図に示
す。無処理の炭素繊維織物についての同様な試験
結果を示す曲線Ｄに比して、酸化による重量減少
は全く認められない。本実施例品の場合には、表
面層でのSiC→SiO2の反応により、むしろ若干の
重量増加が認められる。 Next, while maintaining the silicon-carbon composite fiber fabric obtained in this example at 750°C, a mixed gas of 80% N 2 - 20% O 2 was passed through at a flow rate of 800 ml/min to improve its oxidation resistance. It was measured. The results are shown as curve C in FIG. Compared to curve D, which shows similar test results for untreated carbon fiber fabric, no weight loss due to oxidation is observed. In the case of the product of this example, a slight increase in weight is rather observed due to the reaction of SiC→SiO 2 in the surface layer.
実施例 ５
予めSiO2粉末（平均粒径2μm）120ｇをピツチ
（軟化点87℃，QI＝0.01％）100ｇに分散させ、オ
ートクレーブ中で温度300℃、圧力40Kg／cm2の条
件下にPAN系炭素繊維織物200ｇの空隙内に含浸
させた後、昇温速度２℃／分で1000℃まで昇温
し、初圧40Kg／cm2で加圧炭化処理した。Example 5 120 g of SiO 2 powder (average particle size 2 μm) was dispersed in 100 g of pitch (softening point 87°C, QI = 0.01%) in advance, and a PAN system was prepared in an autoclave at a temperature of 300°C and a pressure of 40 kg/cm 2 . After it was impregnated into the voids of 200 g of carbon fiber fabric, the temperature was raised to 1000° C. at a rate of 2° C./min and carbonized under pressure at an initial pressure of 40 Kg/cm 2 .
次いで、炭化処理した炭素繊維織物を密閉黒鉛
容器内に収容し、昇温速度15℃／分で2500℃まで
昇温し、同温度で30分間保持した。 Next, the carbonized carbon fiber fabric was placed in a sealed graphite container, and the temperature was raised to 2500°C at a heating rate of 15°C/min and held at the same temperature for 30 minutes.
上記の過程において、炭素繊維の表面に先ず
SiCが堆積し、これが2500℃での保持により炭素
とわずかに反応して、Si／Ｃの不定比組成を有す
る界面層が形成され、第１図の類型に相当する
ケイ素−炭素複合繊維織物が得られた。 In the above process, the surface of the carbon fiber is first
SiC is deposited, and when kept at 2500°C, it slightly reacts with carbon to form an interfacial layer with a non-stoichiometric composition of Si/C, resulting in a silicon-carbon composite fiber fabric corresponding to the type shown in Figure 1. Obtained.
また、得られたケイ素−炭素複合繊維織物を粉
砕し、粉末をＸ線回折に供した結果は、第５表に
示す通りであつた。 Further, the obtained silicon-carbon composite fiber fabric was pulverized and the powder was subjected to X-ray diffraction, and the results were as shown in Table 5.
第 ５ 表
2θ 該当物質 相対強度
26.4 Ｃ 50
35.6 SiC 100
41.4 SiC 25
54.6 Ｃ 10
実施例 ６
予めSi粉末（200ムツシユ通過）28ｇをピツチ
（軟化点87℃，QI＝0.01％）18ｇに分散させ、オ
ートクレーブ中で温度300℃、圧力40Kg／cm2の条
件下にピツチ系炭素繊維の織物20ｇの空隙内に含
浸させた後、昇温速度２℃／分で800℃まで昇温
し、初圧40Kg／cm2で炭化処理した。 Table 5 2θ Applicable substance Relative strength 26.4 C 50 35.6 SiC 100 41.4 SiC 25 54.6 C 10 Example 6 28 g of Si powder (passed through 200 mushrooms) was dispersed in 18 g of pitch (softening point 87°C, QI = 0.01%), After impregnating into the voids of 20g of pitch-based carbon fiber fabric in an autoclave at a temperature of 300℃ and a pressure of 40Kg/ cm2 , the temperature was raised to 800℃ at a heating rate of 2℃/min, and the initial pressure was 40Kg. / cm2 .
次いで、炭化処理した炭素繊維織物を密閉黒鉛
容器内に収容し、昇温速度20℃／分で1500℃まで
昇温し、同温度で２時間保持した。 Next, the carbonized carbon fiber fabric was placed in a sealed graphite container, heated to 1500°C at a rate of 20°C/min, and held at the same temperature for 2 hours.
上記の過程において、炭素繊維の表面に先ず
SiCが堆積し、これが1500での保持により炭素と
わずかに反応して、Si／Ｃの不定比組成を有する
界面層が形成され、第１図の類型に相当するケ
イ素−炭素複合繊維織物が得られた。 In the above process, the surface of the carbon fiber is first
SiC is deposited, which reacts slightly with carbon by holding at 1500° C. to form an interfacial layer having a non-stoichiometric composition of Si/C, resulting in a silicon-carbon composite fiber fabric corresponding to the type shown in Figure 1. It was done.
また、得られたケイ素−炭素複合繊維織物を粉
砕し、粉末をＸ線回折に供した結果は、第６表に
示す通りであつた。 Further, the obtained silicon-carbon composite fiber fabric was pulverized and the powder was subjected to X-ray diffraction, and the results were as shown in Table 6.
第 ６ 表
2θ 該当物質 相対強度
26.4 Ｃ 100
35.6 SiC 60
41.4 SiC 15
54.6 Ｃ 20
実施例 ７
予めSiO2粉末（平均粒径5μm）5.0ｇをノボラ
ツク型フエノール樹脂７ｇに分散させ、オートク
レーブ中で温度150℃でレーヨン系炭素繊維の編
物4.0ｇの空隙内に含浸硬化させた後、密閉黒鉛
容器内に収容し、昇温速度0.3℃／分で1300℃ま
で昇温し、同温度で15時間保持した。 Table 6 2θ Applicable substance Relative strength 26.4 C 100 35.6 SiC 60 41.4 SiC 15 54.6 C 20 Example 7 5.0 g of SiO 2 powder (average particle size 5 μm) was dispersed in 7 g of novolak type phenolic resin in advance, and the mixture was heated in an autoclave at a temperature of 150 After impregnating and curing the voids of 4.0 g of knitted rayon-based carbon fiber at ℃, it was placed in a sealed graphite container, heated to 1300 ℃ at a heating rate of 0.3 ℃/min, and held at the same temperature for 15 hours. .
上記の過程において、炭素繊維の表面に先ず
SiCが堆積し、これが1300℃での保持により炭素
とわずかに反応して、Si／Ｃの不定比組成を有す
る界面層が形成され、第１図の類型に相当する
ケイ素−炭素複合繊維織物が得られた。 In the above process, the surface of the carbon fiber is first
SiC is deposited, and when held at 1300°C, it slightly reacts with carbon to form an interfacial layer with a non-stoichiometric composition of Si/C, resulting in a silicon-carbon composite fiber fabric corresponding to the type shown in Figure 1. Obtained.
また、得られたケイ素−炭素複合繊維織物を粉
砕し、粉末をＸ線回折に供した結果は、第７表に
示す通りであつた。 Further, the obtained silicon-carbon composite fiber fabric was pulverized and the powder was subjected to X-ray diffraction, and the results were as shown in Table 7.
第 ７ 表 2θ 該当物質 相対強度 26.4 Ｃ 80 35.6 SiC 80 41.4 SiC 20 54.6 Ｃ 18 Table 7 2θ Applicable substance Relative intensity 26.4 C 80 35.6 SiC 80 41.4 SiC 20 54.6 C 18
第１図は、本発明によるケイ素−炭素複合繊維
織物の構成繊維のケイ素化の状況を〜の４種
の類型に大別して概念的に示す断面である。第２
図および第５図は、本発明実施例により得られた
ケイ素−炭素複合繊維織物の繊維の断面形状を示
す走査型電子顕微鏡写真である。第３図および第
６図は、本発明実施例により得られたケイ素−炭
素複合繊維織物の耐酸化性を示すグラフである。
第４図は、本発明実施例により得られたケイ素−
炭素複合繊維織物の曲げ強度を示すグラフであ
る。
FIG. 1 is a cross-sectional view conceptually showing the state of siliconization of the constituent fibers of the silicon-carbon composite fiber fabric according to the present invention, roughly divided into four types. Second
The figure and FIG. 5 are scanning electron micrographs showing the cross-sectional shape of the fibers of the silicon-carbon composite fiber fabric obtained in the example of the present invention. FIGS. 3 and 6 are graphs showing the oxidation resistance of the silicon-carbon composite fiber fabrics obtained according to the examples of the present invention.
FIG. 4 shows silicon-
It is a graph showing the bending strength of carbon composite fiber fabric.
Claims (1)
にケイ素および／または炭化ケイ素被覆層を有
し、かつ該繊維の少なくとも一部がケイ素化合
物に変換されていることを特徴とするケイ素−
炭素複合繊維織物乃至編物。 炭素繊維からなる織物乃至編物を、密閉容器
内においてケイ素および／または炭化ケイ素の
蒸気に接触させることを特徴とする特許請求の
範囲第１項に記載のケイ素−炭素複合繊維織物
乃至編物の製造方法。 炭素繊維からなる織物乃至編物を密閉容器内
においてケイ素および／または炭化ケイ素の蒸
気に接触させた後、1300〜2600℃で熱処理する
ことを特徴とする特許請求の範囲第１項に記載
のケイ素−炭素複合繊維織物乃至編物の製造方
法。[Claims] 1. A woven or knitted fabric made of carbon fibers, characterized in that the fiber surface has a silicon and/or silicon carbide coating layer, and at least a portion of the fibers are converted into a silicon compound. Silicon-
Carbon composite fiber woven or knitted fabric. The method for producing a silicon-carbon composite fiber woven or knitted fabric according to claim 1, characterized in that the woven or knitted fabric made of carbon fibers is brought into contact with silicon and/or silicon carbide vapor in a closed container. . The silicon-based material according to claim 1, wherein the woven or knitted fabric made of carbon fibers is brought into contact with silicon and/or silicon carbide vapor in a closed container, and then heat-treated at 1300 to 2600°C. A method for producing carbon composite fiber woven or knitted fabrics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63050234A JPH01229874A (en) | 1988-03-02 | 1988-03-02 | Woven and knitted cloth consisting of silicon-carbon conjugated fiber and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63050234A JPH01229874A (en) | 1988-03-02 | 1988-03-02 | Woven and knitted cloth consisting of silicon-carbon conjugated fiber and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01229874A JPH01229874A (en) | 1989-09-13 |
| JPH0316422B2 true JPH0316422B2 (en) | 1991-03-05 |
Family
ID=12853321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63050234A Granted JPH01229874A (en) | 1988-03-02 | 1988-03-02 | Woven and knitted cloth consisting of silicon-carbon conjugated fiber and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01229874A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5572426B2 (en) * | 2010-03-12 | 2014-08-13 | グンゼ株式会社 | Method for producing carbon fiber reinforced silicon carbide composite material |
| US9005702B2 (en) * | 2012-07-18 | 2015-04-14 | The Boeing Company | Re-usable high-temperature resistant softgoods for aerospace applications |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5029528A (en) * | 1973-02-15 | 1975-03-25 | ||
| JPS5322198A (en) * | 1976-08-12 | 1978-03-01 | Agency Of Ind Science & Technol | Production of water-containing calcium borate |
| JPS5831167A (en) * | 1981-08-19 | 1983-02-23 | 工業技術院長 | Surface coated carbon fiber |
| JPS5959976A (en) * | 1982-09-22 | 1984-04-05 | 信越化学工業株式会社 | Production of silicon carbide coated carbon fiber |
| JPS59112028A (en) * | 1982-12-15 | 1984-06-28 | Mitsubishi Rayon Co Ltd | Carbon fiber coated with silica compound and ceramic reinforced therewith |
| JPS59179875A (en) * | 1983-03-26 | 1984-10-12 | 工業技術院長 | Surface coated carbon fiber and production thereof |
| JPS605682A (en) * | 1983-06-23 | 1985-01-12 | Mitsubishi Electric Corp | Charge transfer solid-state image pickup device |
| JPS6082344A (en) * | 1983-10-11 | 1985-05-10 | 株式会社クラレ | Inorganic composite material |
| JPH01104879A (en) * | 1987-10-15 | 1989-04-21 | Ibiden Co Ltd | Composite carbon fiber and its production |
-
1988
- 1988-03-02 JP JP63050234A patent/JPH01229874A/en active Granted
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5029528A (en) * | 1973-02-15 | 1975-03-25 | ||
| JPS5322198A (en) * | 1976-08-12 | 1978-03-01 | Agency Of Ind Science & Technol | Production of water-containing calcium borate |
| JPS5831167A (en) * | 1981-08-19 | 1983-02-23 | 工業技術院長 | Surface coated carbon fiber |
| JPS5959976A (en) * | 1982-09-22 | 1984-04-05 | 信越化学工業株式会社 | Production of silicon carbide coated carbon fiber |
| JPS59112028A (en) * | 1982-12-15 | 1984-06-28 | Mitsubishi Rayon Co Ltd | Carbon fiber coated with silica compound and ceramic reinforced therewith |
| JPS59179875A (en) * | 1983-03-26 | 1984-10-12 | 工業技術院長 | Surface coated carbon fiber and production thereof |
| JPS605682A (en) * | 1983-06-23 | 1985-01-12 | Mitsubishi Electric Corp | Charge transfer solid-state image pickup device |
| JPS6082344A (en) * | 1983-10-11 | 1985-05-10 | 株式会社クラレ | Inorganic composite material |
| JPH01104879A (en) * | 1987-10-15 | 1989-04-21 | Ibiden Co Ltd | Composite carbon fiber and its production |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01229874A (en) | 1989-09-13 |
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