JPH02129366A - Coated structural material - Google Patents
Coated structural materialInfo
- Publication number
- JPH02129366A JPH02129366A JP63280275A JP28027588A JPH02129366A JP H02129366 A JPH02129366 A JP H02129366A JP 63280275 A JP63280275 A JP 63280275A JP 28027588 A JP28027588 A JP 28027588A JP H02129366 A JPH02129366 A JP H02129366A
- Authority
- JP
- Japan
- Prior art keywords
- coated
- intermediate layer
- base material
- carbon
- coating
- 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
- 239000000463 material Substances 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 6
- 239000004917 carbon fiber Substances 0.000 claims abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005240 physical vapour deposition Methods 0.000 claims 1
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 12
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 23
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000011247 coating layer Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
- Physical Vapour Deposition (AREA)
- Chemical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、航空機や宇宙往還機の機体外壁部に用いる構
造材料に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a structural material used for the outer wall of an aircraft or spacecraft.
［従来の技術］
カーボン繊維を主原料としたカーボン／カーボン複合材
料、カーボン／セラミックス複合材料は１０００℃以上
の高温強度が優れていることから、航空機や宇宙往還機
の機体外壁への応用が最近注目されているが、上記材料
はいずれもカーボンを主原料としているので、高温域で
の耐酸化性に乏しい。そのため、耐酸化性向上のために
化学的蒸着方法（ＣＶＤ）によりＳｉＣやＳｉ３Ｎ４等
の優れて耐酸化性を有するセラミックス層を１３００〜
１８００℃の高温で被覆している。[Conventional technology] Carbon/carbon composite materials and carbon/ceramic composite materials made from carbon fiber as the main raw material have excellent high-temperature strength of 1000°C or higher, and have recently been applied to the outer walls of aircraft and spacecraft. Although attracting attention, all of the above-mentioned materials have carbon as their main raw material, and therefore have poor oxidation resistance in high temperature ranges. Therefore, in order to improve oxidation resistance, a ceramic layer with excellent oxidation resistance, such as SiC or Si3N4, is deposited using a chemical vapor deposition method (CVD).
It is coated at a high temperature of 1800°C.
ところが、被覆後、室温まで冷却する時基祠の主原料で
あるカーボン繊維の熱膨張係数（はとんど０）と被覆層
の熱膨張係数（ＳｉＣ３〜５に一’５ｔ）Ｎ＋：２〜３
に一’）の差により、被覆層に大きな引張応力が生じ、
熱亀裂が発生し、この亀裂を通して内部の基材が酸化さ
れ、耐酸化性は著しく低下する。この現象は被覆温度が
高いほど顕著である。このため、これを酸化する手段と
して、基材と被覆層間に中間層として比較的低温（９５
０〜１０５０℃）で、熱亀裂の少ないＴｉＣ、ＴｉＮ、
Ｔｉ （Ｃ，Ｎ）をＣＶＤ法により被覆しておき、酸化
が内部基材まで進行しないような方法が取られている。However, when cooling to room temperature after coating, the coefficient of thermal expansion of the carbon fiber, which is the main raw material of the base (almost 0), and the coefficient of thermal expansion of the coating layer (1'5t for SiC 3-5) N+: 2-2 3
A large tensile stress is generated in the coating layer due to the difference in
Thermal cracks occur, and the internal base material is oxidized through these cracks, resulting in a significant decrease in oxidation resistance. This phenomenon becomes more pronounced as the coating temperature increases. For this reason, as a means of oxidizing this, an intermediate layer is formed between the base material and the coating layer at a relatively low temperature (95%).
0~1050℃), TiC, TiN, with few thermal cracks.
A method is used in which Ti (C, N) is coated by CVD to prevent oxidation from progressing to the internal base material.
［発明が解決しようとする課′ＸＪ］
しかしながら、ＣＶＤ法で被覆したＴＩＣやＴｉＮにも
依然として引張応力が生じているため、強度が小さく、
外層のＳｉＣやＳｉ３Ｎ４に生じる熱亀裂が中間層を通
って進行し、満足できる耐酸化性は得られていない。し
たがって本発明は引張応力の（ｊ ’ｔＥ Ｌない強靭
な中間層を設けることによって、良好な耐酸化性を有す
る被覆構造材料を得るものである。[Problem to be solved by the invention 'XJ] However, since tensile stress still occurs in TIC and TiN coated by CVD method, the strength is low
Thermal cracks that occur in the outer layer of SiC and Si3N4 propagate through the intermediate layer, making it impossible to obtain satisfactory oxidation resistance. Therefore, the present invention provides a coating structure material having good oxidation resistance by providing a strong intermediate layer with no tensile stress (j'tEL).
中間層として被覆するＴｉＣ，Ｔｉ （Ｃ，Ｎ）層に
、圧縮応力を導入する方法としては、プラズマＣＶＤ法
やイオンブレーティング法などがあるが、これらの方法
で得た被覆層にはすでに大きな圧縮応力が存在しており
、該被覆材料を外層のＳｉＣまたはＳｉ３Ｎ４の被覆に
必要な温度であるＬ２００−１８００℃に昇温するとき
に、被覆層にはさらに圧縮応力が加わることにより、被
覆層が破懐され、剥離する。Methods for introducing compressive stress into the TiC, Ti (C, N) layer coated as an intermediate layer include plasma CVD and ion blating, but the coating layer obtained by these methods already has a large amount of stress. Compressive stress is present, and when the coating material is heated to L200-1800°C, which is the temperature required for coating the outer layer of SiC or Si3N4, compressive stress is further applied to the coating layer, so that the coating layer is broken and peeled off.
［課題を解決するための手段］
本発明は、カーボン繊維を主体としたカーボン／カーボ
ン複合材料、カーボン／セラミックス複合材料を基材と
し、ＴｉＣまたはＴｉ（Ｃ−Ｎ）を中間層として被覆し
、外層としてＳｉＣまたはＳｉ３Ｎ４の少くとも一種以
上を被覆した被覆構造材料において、中間層をＴｉまた
はＴｉとＴ ｉ （Ｃｘ Ｎ＋−ｘ ）の複合相を被
覆した後、１０００〜１５００℃の温度範囲で少くとも
１０分以上保持した後、化学蒸着法により１２００〜１
８００℃の温度範囲でＳｉＣまたは５ｉｘＮ＋の少くと
も一種以上を被覆してなる被覆構造材料である。[Means for Solving the Problems] The present invention uses a carbon/carbon composite material mainly composed of carbon fibers or a carbon/ceramic composite material as a base material, and coats TiC or Ti(C-N) as an intermediate layer, In a coated structural material coated with at least one type of SiC or Si3N4 as an outer layer, after coating the intermediate layer with Ti or a composite phase of Ti and Ti (Cx N+-x), After holding both for 10 minutes or more, a chemical vapor deposition method of 1200 to 1
It is a coated structure material coated with at least one type of SiC or 5ixN+ in a temperature range of 800°C.
本発明において、予め中間層として被覆したＴ１または
ＴｉとＴｉＣの複合相、ＴｉとＴｉＮの複合層、Ｔｉと
Ｔｉ （Ｃ，Ｎ）の複合相をｒめ１０００〜１５００℃
で熱処理すると、基板から中間層に向ってカーボンが拡
散し、被覆層はそれぞれＴｉＣ，Ｔｉ （Ｃ，Ｎ）と
なり、化学蒸着時にも剥離しない、かつ大きな圧縮応力
を有する中間層が得られる。被膜の圧縮応力値は予め被
覆する中間層の組成を制御することにより制御すること
ができる。すなわち、ＴｉとＴｉＣの組成比、ＴｉとＴ
ｉＮの組成比、ＴｉとＴｉ（Ｃ，Ｎ）の組成比を制御す
る。In the present invention, T1 or a composite phase of Ti and TiC, a composite layer of Ti and TiN, or a composite phase of Ti and Ti (C,N) coated in advance as an intermediate layer is heated to 1000 to 1500°C.
Upon heat treatment, carbon diffuses from the substrate toward the intermediate layer, and the coating layers become TiC and Ti(C,N), respectively, resulting in an intermediate layer that does not peel off during chemical vapor deposition and has a large compressive stress. The compressive stress value of the coating can be controlled by controlling the composition of the intermediate layer to be coated in advance. That is, the composition ratio of Ti and TiC, Ti and T
The composition ratio of iN and the composition ratio of Ti and Ti(C,N) are controlled.
予め被覆する中間層はカーボンの拡散しやす１．１Ｔｉ
またはＴｉとＴｉＣの複合相が望ましい。The pre-coated intermediate layer is made of 1.1Ti, which allows carbon to easily diffuse.
Alternatively, a composite phase of Ti and TiC is desirable.
また、その熱処理は１０００℃未満または１０分未満で
は効果がなく、１５００℃を越えるとＴｉ相に変質が生
じるため好ましくない。Moreover, the heat treatment is not effective if it is less than 1000°C or for less than 10 minutes, and if it exceeds 1500°C, the Ti phase will be altered, which is not preferable.
さらに、基板からのカーボンの拡散が十分でないと、中
間相にＴｉ相が残存し、Ｔｉ相が著しく酸化されるので
好ましくない。Furthermore, if the diffusion of carbon from the substrate is insufficient, the Ti phase will remain in the intermediate phase and the Ti phase will be significantly oxidized, which is not preferable.
［作 用］
本発明では、外層のＳｉＣや５ｉｚＮ４に生じた熱亀裂
の進行を強靭な中間層で防止することにより、優れた耐
酸化性を発揮する。[Function] The present invention exhibits excellent oxidation resistance by preventing the progression of thermal cracks that occur in the outer layer of SiC or 5izN4 with a tough intermediate layer.
［実施例コ
実施例Ｉ
Ｃ／Ｃコンポジットを基材として、イオンブレーティン
グ法によりＴｉまたはＴｉＣの複合相を５０〜６０μｌ
被覆した後、１３５０℃で１時間熱処理した。その後、
化学蒸着法により１５００℃でＳｉＣを１８０〜２００
ｕｔｎ被覆した。[Example 1 Example I Using a C/C composite as a base material, 50 to 60 μl of Ti or TiC composite phase was added by ion blating method.
After coating, it was heat treated at 1350°C for 1 hour. after that,
SiC is deposited at 180~200℃ at 1500℃ by chemical vapor deposition method.
utn coated.
得られた試料について４′１１４００℃で１時間大気中
にさらし、加熱前後の重量減少値を測定した。The obtained sample was exposed to the atmosphere at 4'11400°C for 1 hour, and the weight loss before and after heating was measured.
（耐酸化試験）
また、熱処理前の中間層ＴｉＣの残留応力をＸ線回折に
より測定した。なお、イオンブレーティング法で被覆し
たＴｉまたはＴｉとＴｉＣの複合相の組成についてはＥ
ＰＭＡで分析した。(Oxidation resistance test) Furthermore, the residual stress of the TiC intermediate layer before heat treatment was measured by X-ray diffraction. The composition of the Ti or Ti and TiC composite phase coated by the ion blating method is E.
Analyzed with PMA.
比較として、中間層ＴｉＣをＣＶＤ法で５０μｍの厚さ
で被覆し、その上にＳｉＣを１９０μ麿被覆したものを
作製し、同様の測定を行った。For comparison, a TiC intermediate layer was coated with a thickness of 50 μm using the CVD method, and SiC was coated thereon with a thickness of 190 μm, and the same measurements were performed.
結果を表１に示す。The results are shown in Table 1.
表１ この前後の重量減少を測定した。Table 1 Weight loss before and after this was measured.
なお、比較例の一部として、ＣＶＤ法により中間層Ｔｉ
Ｃを３５μｍ被覆後、ＣＶＤ法により５ｉ）Ｎ４を１１
０μｍ被覆したものも作製し評価した。In addition, as part of the comparative example, the intermediate layer Ti was formed by CVD method.
After coating 35 μm of C, 5i) N4 was applied to 11 by CVD method.
A sample coated with a thickness of 0 μm was also prepared and evaluated.
結果を表２に示す。The results are shown in Table 2.
表２
実施例２
カーボン繊維とＳｉＣセラミックスの複合材料であるＣ
／セラミックス複合材料を基材として、イオンブレーテ
ィング法によりＴｉを３０〜４０μｍ被覆した後、８０
０〜１４００℃で０．１〜２時間真空で熱処理後、さら
にＣＶＤ法によりＳｉ３Ｎ４を１００〜１２０μ信被覆
した。Table 2 Example 2 C, a composite material of carbon fiber and SiC ceramics
/ After coating a ceramic composite material as a base material with 30 to 40 μm of Ti using the ion blating method,
After heat treatment in vacuum at 0 to 1400°C for 0.1 to 2 hours, a layer of Si3N4 of 100 to 120 μm was coated by CVD.
得られた試料についてＸ線回折による生成相同定を行い
、１８００℃で２時間大気中にさらし、［発明の効果コ
本発明材料は、高温で優れた耐酸化性を有する高温高強
度材料であり、航空機や宇宙往還機の機体外壁部に適用
してａ用である。The resulting sample was identified by X-ray diffraction and exposed to the atmosphere for 2 hours at 1800°C. It is suitable for use on the outer walls of aircraft and spacecraft.
Claims (2)
合材料、カーボン／セラミックス複合材料を基材とし、
ＴｉＣまたはＴｉ（Ｃ・Ｎ）を中間層として被覆し、外
層としてＳｉＣまたはＳｉ＿３Ｎ＿４の少くとも一種以
上を被覆した被覆構造材料において、中間層をＴｉまた
はＴｉとＴｉ（Ｃ＿ｘＮ＿１＿−＿ｘ）の複合相を被覆
した後、１０００〜１５００℃の温度範囲で少くとも１
０分以上保持した後、化学蒸着法により １２００〜１８００℃の温度範囲でＳｉＣまたはＳｉ＿
３Ｎ＿４の少くとも一種以上を被覆してなることを特徴
とする被覆構造材料。(1) Carbon/carbon composite material based on carbon fiber, carbon/ceramic composite material as base material,
In a coated structural material coated with TiC or Ti(C/N) as an intermediate layer and at least one type of SiC or Si_3N_4 as an outer layer, the intermediate layer is made of Ti or a composite phase of Ti and Ti (C_xN_1_-_x). After coating, at least 1
After holding for more than 0 minutes, SiC or Si_
A coated structural material characterized by being coated with at least one type of 3N_4.
求項（１）記載の被覆構造材料。（３）中間層の複合相
の被覆方法が物理蒸着法である請求項（１）記載の被覆
構造材料。(2) The covering structure material according to claim (1), wherein the residual stress existing in the intermediate layer is compressive stress. (3) The coated structural material according to claim (1), wherein the method for coating the composite phase of the intermediate layer is a physical vapor deposition method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63280275A JP2685151B2 (en) | 1988-11-08 | 1988-11-08 | Coating structural material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63280275A JP2685151B2 (en) | 1988-11-08 | 1988-11-08 | Coating structural material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02129366A true JPH02129366A (en) | 1990-05-17 |
| JP2685151B2 JP2685151B2 (en) | 1997-12-03 |
Family
ID=17622720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63280275A Expired - Lifetime JP2685151B2 (en) | 1988-11-08 | 1988-11-08 | Coating structural material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2685151B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014521832A (en) * | 2011-07-23 | 2014-08-28 | ビーコ・エーエルディー インコーポレイテッド | Textiles containing fibers deposited with materials using atomic layer deposition to improve stiffness and strength |
| CN113387724A (en) * | 2021-06-10 | 2021-09-14 | 西北工业大学 | High-temperature-resistant long-life composite coating on surface of carbon/carbon composite material and preparation method thereof |
-
1988
- 1988-11-08 JP JP63280275A patent/JP2685151B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014521832A (en) * | 2011-07-23 | 2014-08-28 | ビーコ・エーエルディー インコーポレイテッド | Textiles containing fibers deposited with materials using atomic layer deposition to improve stiffness and strength |
| CN113387724A (en) * | 2021-06-10 | 2021-09-14 | 西北工业大学 | High-temperature-resistant long-life composite coating on surface of carbon/carbon composite material and preparation method thereof |
| CN113387724B (en) * | 2021-06-10 | 2022-09-02 | 西北工业大学 | High-temperature-resistant long-life composite coating on surface of carbon/carbon composite material and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2685151B2 (en) | 1997-12-03 |
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