JPH02129365A - Coated structural material - Google Patents
Coated structural materialInfo
- Publication number
- JPH02129365A JPH02129365A JP27939788A JP27939788A JPH02129365A JP H02129365 A JPH02129365 A JP H02129365A JP 27939788 A JP27939788 A JP 27939788A JP 27939788 A JP27939788 A JP 27939788A JP H02129365 A JPH02129365 A JP H02129365A
- Authority
- JP
- Japan
- Prior art keywords
- sic
- carbon
- coating
- temp
- si3n4
- 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
- 239000000463 material Substances 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 150000002897 organic nitrogen compounds Chemical class 0.000 claims abstract description 5
- 239000012159 carrier gas Substances 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 12
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 2
- 238000000151 deposition Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 229910005091 Si3N Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000004580 weight loss Effects 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5062—Borides, Nitrides or Silicides
- C04B41/5066—Silicon nitride
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、航空機、宇宙往還機等に使用する耐熱、耐酸
化性の被覆構造材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a heat-resistant and oxidation-resistant coating structure material used in aircraft, spacecraft, etc.
［従来の技術］
近年、高温下において優れた強度を示すカーボン繊維を
主原料としたカーボン／カーボン複合材料およびカーボ
ン／セラミックス複合材料の開発が盛んになってきてい
るが、これらの腹合材料はカーボンを原料にしているた
め高温での耐酸化性に問題があり、それゆえ、これらの
基体上に５ＩＣ９Ｓｉ ３ Ｎ ４などの高温（１２０
０℃以上）下で優れた耐酸化性を有する硬質セラミック
ス相を被覆し、耐酸化性の向上を図っている。[Prior Art] In recent years, the development of carbon/carbon composite materials and carbon/ceramic composite materials made mainly of carbon fibers, which exhibit excellent strength under high temperatures, has become active. Since carbon is used as a raw material, there is a problem with oxidation resistance at high temperatures, and therefore high temperature (120
It is coated with a hard ceramic phase that has excellent oxidation resistance at temperatures above 0°C to improve oxidation resistance.
とりわけ耐酸化性を有するセラミックス相としては、非
晶質のものよりも結晶質のＳｉＣやＳｉ３Ｎ＜が望まし
い。特にＳｉ３Ｎ４は硬度こそＳｉＣに劣るものの耐熱
衝撃性、機械的強度、耐酸化性共にＳｉＣよりも優れた
物質である。よって、ＳｉＣにＳｉ３Ｎ４を少量分散さ
せた物質は、硬度、耐熱衝撃性、機械的強度、耐酸化性
を兼ね備えた理想的物質といえる。In particular, as a ceramic phase having oxidation resistance, crystalline SiC or Si3N< is more desirable than an amorphous one. In particular, although Si3N4 is inferior to SiC in hardness, it is superior to SiC in terms of thermal shock resistance, mechanical strength, and oxidation resistance. Therefore, a material in which a small amount of Si3N4 is dispersed in SiC can be said to be an ideal material that has hardness, thermal shock resistance, mechanical strength, and oxidation resistance.
ＳｉＣおよび５ｉｘＮ４の被覆技術としては、高い成膜
速度、基材との強密着性が得られる化学蒸着法が用いら
れている。その反応系を表１に示す。As a coating technique for SiC and 5ixN4, a chemical vapor deposition method is used which provides a high film formation rate and strong adhesion to the base material. The reaction system is shown in Table 1.
表１
［発明が解決しようとする課題］
上記従来の反応系でＳｉＣ，Ｓｌ ３ Ｎ ４を得るに
は、いずれも１２００℃以上の高温を必要とし、特に結
晶質の５ＩａＮ４を得るには１２５０℃以上の雰囲気が
必要である。Table 1 [Problems to be Solved by the Invention] In order to obtain SiC and Sl 3 N 4 using the above conventional reaction system, a high temperature of 1200°C or higher is required, and in particular, a high temperature of 1250°C is required to obtain crystalline 5IaN4. The above atmosphere is necessary.
このため、被覆径室温まで冷却する際、基材を構成する
カーボン繊維の熱膨脹係数（はぼ０）より被覆層の熱膨
脹係数（ＳｉＣ： ３〜５に−ＩＳｉ３Ｎ４：２〜３
に一’）の方が大きいために、被覆層に大きな引張応力
が生じ、そのため被覆層に熱亀裂が生じ、試料の耐酸化
性が著しく低下する。Therefore, when cooling the coating diameter to room temperature, the thermal expansion coefficient of the coating layer (SiC: 3 to 5 - ISi3N4: 2 to 3
Since 1') is larger, a large tensile stress occurs in the coating layer, which causes thermal cracks in the coating layer and significantly reduces the oxidation resistance of the sample.
［課題を解決するための手段］
本発明者らは上記課題について鋭意研究した結果、被覆
層に生じる引張応力を減少させることにより、熱亀裂数
は減少し、試料の耐酸化性が向上するという知見を得た
。すなわち、被覆する際の被覆温度を低下させれば、熱
応力が減少するという原理である。[Means for Solving the Problems] As a result of intensive research into the above problems, the present inventors have found that by reducing the tensile stress generated in the coating layer, the number of thermal cracks is reduced and the oxidation resistance of the sample is improved. I gained knowledge. That is, the principle is that if the coating temperature during coating is lowered, thermal stress will be reduced.
本発明はかかる知見に基づいてなされたもので、セラミ
ックスまたはカーボン基体上にＳｉＣまたはＳｉＣとＳ
ｉ３Ｎ４の混合相を被覆した被覆構造材料において、被
膜の炭・窒素源として低温で分解しやすい有機窒素化合
物を、金属源として化学式Ｒｘ ５ｉＣ１４−ｘ （
Ｒはアルキル、Ｘ−０，１，２，３，４）なる化合物ま
たは５ＩＨ４を、キャリアガスとしてＨ２を用い、被覆
温度７５０−１２００℃で化学蒸着法により形成してな
る被膜を有する被覆構造材料である。The present invention has been made based on this knowledge, and it is possible to form SiC or SiC and S on a ceramic or carbon substrate.
In the coating structure material that coats the mixed phase of i3N4, an organic nitrogen compound that is easily decomposed at low temperature is used as the carbon/nitrogen source of the coating, and the chemical formula Rx 5iC14-x (
R is alkyl, and a coating structure material having a coating formed by a chemical vapor deposition method using H2 as a carrier gas and a coating temperature of 750-1200°C It is.
炭・窒素源として用いる低温で分解しやすい有機窒素化
合物としては、Ｒ’ −ＣＮ ［Ｒ’ ： Ｃｌｌ３、
Ｃ１ｌ ］ （Ｃｔｌ） ２ ］が好適に用いられ、特
にアセトニトリル（Ｃ１１３ＣＮ）が良い。Organic nitrogen compounds that are easily decomposed at low temperatures and used as carbon/nitrogen sources include R'-CN [R': Cll3,
C1l ] (Ctl) 2 ] is preferably used, and acetonitrile (C113CN) is particularly preferred.
かかる炭・窒素源化合物と珪素源化合物をキャリアガス
としてＨ２を用いて化学蒸着法によりＳｉＣおよびＳｉ
３Ｎ＋を生成する反応式は下記のとおりである。The carbon/nitrogen source compound and the silicon source compound are used to form SiC and Si by chemical vapor deposition using H2 as a carrier gas.
The reaction formula for producing 3N+ is as follows.
Ｒｘ ５ｉＣＩ４−ｘ ＋Ｒ’ ＣＮ−３ＩＣ
＋Ｓｌｚ Ｎ ＜ ＋Ｈｃｌ−−− （Ｌ）Ｓｉ
Ｂ６ ＋Ｒ’−ＣＮ −ＳｉＣ＋Ｓｉ３Ｎ ４・・・（
２）上記（１）、（２）の反応では７５０℃以上で非晶
質のＳｉＣ，Ｓｌ ：ｌ Ｎ ４が成膜し、９００℃以
上で結晶質５ｉＣＳ８１３ Ｎ ４が成膜する。この場
合、１２００℃以上の高温は必要としない。Rx 5iCI4-x +R' CN-3IC
+Slz N < +Hcl--- (L)Si
B6 +R'-CN -SiC+Si3N 4...(
2) In the reactions of (1) and (2) above, amorphous SiC, Sl:l N 4 is formed at 750° C. or higher, and crystalline 5iCS813 N 4 is formed at 900° C. or higher. In this case, high temperatures of 1200° C. or higher are not required.
本発明はかかる反応によりカーボン複合材料上に、被膜
中の亀裂が少ない５ｉＣＳＳｉ ３ Ｎ ４の均一混合
相を被覆した被覆構造材料を作成することができる。The present invention can create a coated structural material in which a homogeneous mixed phase of 5iCSSi 3 N 4 with few cracks in the coating is coated on a carbon composite material by such a reaction.
［実施例コ
同一形状のＣ／Ｃコンポジットを基材とし、原料ガスと
して５ＩＣ１４、ｅｌｌコ８１０１３ 、Ｃ１１３ＯＮ
。[Example: C/C composite of the same shape was used as the base material, and raw material gases were 5IC14, ELLCO 81013, and C113ON.
.
ＣＨ３（ＮＨ）２ ＣＮ、 Ｈ２を用い、７５０〜１
０００℃の温度範囲で、化学蒸着法により ＳｉＣと５
ｉｘＮ＋の混合膜を被覆した。これらの試料については
、Ｘ線回折およびＥＰＭＡによる生成相の同定、膜中の
残留応力測定を行った。Using CH3(NH)2CN, H2, 750~1
SiC and 5 by chemical vapor deposition in the temperature range of 000℃
A mixed film of ixN+ was coated. For these samples, the generated phase was identified by X-ray diffraction and EPMA, and the residual stress in the film was measured.
また、試料を１５００℃で１時間大気中にさらし、熱処
理前後の重量減少率から試料の耐酸化性を評価した。In addition, the samples were exposed to the atmosphere at 1500° C. for 1 hour, and the oxidation resistance of the samples was evaluated from the weight loss rate before and after the heat treatment.
比較例として５ＩＣＩ４ 、ＣＨ４、ＮＨ３、Ｈ２と原
料ガスとして１５００℃でＳｉＣおよびＳｉ３Ｎ４を被
覆した試料も作成した。結果を表２に示す。As a comparative example, a sample was also prepared in which 5ICI4, CH4, NH3, H2 and SiC and Si3N4 were coated at 1500° C. as the raw material gas. The results are shown in Table 2.
表
（注）α：非晶質
Ｃ：結晶質
［発明の効果］
本発明では、表面亀裂の少ない結晶質の５ＩＣ１Ｓｉ３
Ｎ＋の均一混合膜がカーボン複合材料上に被覆されてお
り、その結果、高温下で優れた強度、耐酸化性を有する
被覆構造材料が得られるので、航空機、宇宙往還機の機
体外壁部に使用すると効果的である。Table (Note) α: Amorphous C: Crystalline [Effects of the invention] In the present invention, crystalline 5IC1Si3 with few surface cracks is used.
A homogeneous mixed N+ film is coated on the carbon composite material, resulting in a coated structural material that has excellent strength and oxidation resistance under high temperatures, so it can be used on the exterior walls of aircraft and spacecraft. Then it is effective.
Claims (3)
はＳｉＣとＳｉ＿３Ｎ＿４の混合相を被覆した被覆構造
材料において、被膜の炭・窒素源として低温で分解しや
すい有機窒素化合物を、金属源として化学式Ｒ＿ｘＳｉ
Ｃｌ＿４＿−＿ｘ（Ｒはアルキル、Ｘ＝０、１、２、３
、４）なる化合物またはＳｉＨ＿４を、キャリアガスと
してＨ＿２を用い、被覆温度７５０〜１２００℃で化学
蒸着法により形成してなる被膜を有することを特徴とす
る被覆構造材料。(1) In a coating structure material in which SiC or a mixed phase of SiC and Si_3N_4 is coated on a ceramic or carbon substrate, an organic nitrogen compound that is easily decomposed at low temperature is used as the carbon/nitrogen source of the coating, and the chemical formula R_xSi is used as the metal source.
Cl_4_-_x (R is alkyl, X=0, 1, 2, 3
, 4) or SiH_4 by chemical vapor deposition at a coating temperature of 750 to 1200°C using H_2 as a carrier gas.
の被覆構造材料。(2) The covering structure material according to claim (1), wherein Si_3N_4 is crystalline.
ＣＮ）を用いる請求項（１）記載の被覆構造材料。(3) Acetonitrile (CH_3
The covering structure material according to claim (1), using CN).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27939788A JPH02129365A (en) | 1988-11-07 | 1988-11-07 | Coated structural material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27939788A JPH02129365A (en) | 1988-11-07 | 1988-11-07 | Coated structural material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02129365A true JPH02129365A (en) | 1990-05-17 |
Family
ID=17610551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27939788A Pending JPH02129365A (en) | 1988-11-07 | 1988-11-07 | Coated structural material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02129365A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113748489A (en) * | 2019-04-17 | 2021-12-03 | 韩国东海炭素株式会社 | Preparation method of silicon carbide-silicon nitride composite material and silicon carbide-silicon nitride composite material based on same |
-
1988
- 1988-11-07 JP JP27939788A patent/JPH02129365A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113748489A (en) * | 2019-04-17 | 2021-12-03 | 韩国东海炭素株式会社 | Preparation method of silicon carbide-silicon nitride composite material and silicon carbide-silicon nitride composite material based on same |
| JP2022520899A (en) * | 2019-04-17 | 2022-04-01 | トカイ カーボン コリア カンパニー，リミティド | Silicon Carbide-Silicon Nitride Composite Material Manufacturing Method and Silicon Carbide-Silicon Nitride Composite Material |
| US11697620B2 (en) | 2019-04-17 | 2023-07-11 | Tokai Carbon Korea Co., Ltd | Method for preparing silicon-carbide-silicon-nitride composite material, and silicon-carbide- silicon-nitride composite material according to same |
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