JP2777105B2 - Carbon-based structure - Google Patents
Carbon-based structureInfo
- Publication number
- JP2777105B2 JP2777105B2 JP8113963A JP11396396A JP2777105B2 JP 2777105 B2 JP2777105 B2 JP 2777105B2 JP 8113963 A JP8113963 A JP 8113963A JP 11396396 A JP11396396 A JP 11396396A JP 2777105 B2 JP2777105 B2 JP 2777105B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- based structure
- layer
- oxidation
- resistant
- 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 - Fee Related
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 69
- 229910052799 carbon Inorganic materials 0.000 title claims description 69
- 230000003647 oxidation Effects 0.000 claims description 43
- 238000007254 oxidation reaction Methods 0.000 claims description 43
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 14
- 230000003628 erosive effect Effects 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- FFQALBCXGPYQGT-UHFFFAOYSA-N 2,4-difluoro-5-(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=C(F)C=C1F FFQALBCXGPYQGT-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical group 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 6
- DZQBLSOLVRLASG-UHFFFAOYSA-N iridium;methane Chemical compound C.[Ir] DZQBLSOLVRLASG-UHFFFAOYSA-N 0.000 claims description 6
- 230000008646 thermal stress Effects 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 62
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 239000002775 capsule Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000002679 ablation Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011301 petroleum pitch Substances 0.000 description 3
- 239000011295 pitch Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 210000004177 elastic tissue Anatomy 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 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
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 101150096674 C20L gene Proteins 0.000 description 1
- 102220543923 Protocadherin-10_F16L_mutation Human genes 0.000 description 1
- 101100445889 Vaccinia virus (strain Copenhagen) F16L gene Proteins 0.000 description 1
- 101100445891 Vaccinia virus (strain Western Reserve) VACWR055 gene Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Thermal Insulation (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高温の酸化雰囲気
下で使用された場合の耐酸化性に優れている炭素系構造
物に関し、とくに、耐酸化コーティングを施して表面に
耐酸化層が形成された炭素系構造物において耐酸化性を
より一層向上させて、高温の酸化雰囲気下で使用された
場合の重量減少率が著しく少ない耐酸化性に優れた炭素
系構造物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon-based structure having excellent oxidation resistance when used in a high-temperature oxidizing atmosphere, and more particularly to an oxidation-resistant layer formed on an oxidation-resistant coating. The present invention relates to a carbon-based structure having excellent oxidation resistance, in which the oxidation resistance of the carbon-based structure is further improved, and the weight loss rate when used in a high-temperature oxidizing atmosphere is extremely small.
【０００２】[0002]
【発明が解決しようとする課題】宇宙航空分野において
使用される地球回収型カプセルのノーズコーンには、例
えば、石英（ＳｉＯ２）のマイクロバルーンを含有して
低密度化したフェノール樹脂の複合材や、フェノール樹
脂をシリカ（ＳｉＯ２）繊維によるクロス材によって強
化した複合材などが、アブレーション材として用いられ
ている。The nose cone of the earth recovery type capsule used in the aerospace field includes, for example, a phenolic resin composite material having a low density containing quartz (SiO 2 ) microballoons or the like. A composite material obtained by reinforcing a phenol resin with a cloth material of silica (SiO 2 ) fiber is used as an ablation material.
【０００３】しかしながら、このようなアブレーション
材を使用した場合に、アブレーション材だけでカプセル
重量の１０％以上を占めるため、カプセルに搭載する実
験器具等の重量が限定されてしまうこととなるので、軽
量化の観点から、炭素系構造材に耐酸化コーティングを
施し、表面に耐酸化層が形成されたものとして、ノーズ
コーンに使用することが検討されている。However, when such an ablation material is used, the ablation material alone occupies 10% or more of the weight of the capsule, so that the weight of laboratory equipment and the like mounted on the capsule is limited. From the viewpoint of conversion, it has been studied to use a nose cone as a material having an oxidation-resistant coating formed on a carbon-based structural material and having an oxidation-resistant layer formed on the surface.
【０００４】従来、このような耐酸化コーティングとし
ては、炭化珪素（ＳｉＣ）系のものが主体であったが、
近年、火星への突入機など、炭化珪素の耐酸化性能の限
界温度とされる１８００℃以上の高温に曝されることも
考慮して、酸化ハフニウム（ＨｆＯ２）、酸化アルミニ
ウム（Ａｌ２Ｏ３）、ストロンチウムジルコネート（Ｓ
ｒＺｒＯ３）、イットリア（Ｙ２Ｏ３）などの高融点酸
化物系のコーティング技術の研究が進められている。Conventionally, such an oxidation-resistant coating is mainly composed of silicon carbide (SiC).
In recent years, taking into account exposure to a high temperature of 1800 ° C. or more, which is the limit temperature of the oxidation resistance of silicon carbide, such as a rush machine to Mars, hafnium oxide (HfO 2 ) and aluminum oxide (Al 2 O 3) ), Strontium zirconate (S
Researches on high melting point oxide-based coating technologies such as rZrO 3 ) and yttria (Y 2 O 3 ) have been conducted.
【０００５】しかしながら、この種の高融点酸化物より
なる耐酸化層が最外層となる構造とした場合には、高温
に曝されたときに結晶成長（粗大化）が始まり、最外層
では結晶粒界にピンホールが発生し、このピンホールか
ら酸素が侵入するために、内部の炭素／炭素複合材は長
時間高温状態に保持することができないという問題点が
あった。However, in the case where the oxidation-resistant layer made of such a high-melting-point oxide is used as the outermost layer, crystal growth (coarsening) starts when exposed to a high temperature, and crystal grains are formed in the outermost layer. There is a problem that a pinhole is generated in the field and oxygen enters through the pinhole, so that the internal carbon / carbon composite material cannot be maintained at a high temperature for a long time.
【０００６】[0006]
【発明の目的】本発明は、このような従来の問題点に着
目してなされたものであって、高温の酸化雰囲気下で使
用された場合の耐酸化性により一層優れている炭素系構
造物を提供することを目的としている。SUMMARY OF THE INVENTION The present invention has been made in view of such a conventional problem, and has a carbon-based structure having more excellent oxidation resistance when used in a high-temperature oxidizing atmosphere. It is intended to provide.
【０００７】[0007]
【課題を解決するための手段】本発明に係わる炭素系構
造物は、請求項１に記載しているように、耐酸化コーテ
ィングを施して表面に耐酸化層（および／または耐エロ
ージョン層）が形成された炭素系構造物において、表面
の耐酸化層（および／または耐エロージョン層）に、高
温に曝された際に耐酸化層（および／または耐エロージ
ョン層）に形成された粗大結晶粒界やピンホール部など
のすき間部分を塞ぐリン酸アルミニウムを主体とするガ
ラスシールを設けた構成としたことを特徴としている。The carbon-based structure according to the present invention is provided with an oxidation-resistant coating and has an oxidation-resistant layer (and / or an erosion-resistant layer) on the surface. In the formed carbon-based structure, the coarse grain boundaries formed in the oxidation-resistant layer (and / or the erosion-resistant layer) when exposed to a high temperature in the oxidation-resistant layer (and / or the erosion-resistant layer) on the surface. It is characterized in that a glass seal mainly made of aluminum phosphate for closing a gap portion such as a pinhole portion or the like is provided.
【０００８】そして、本発明に係わる炭素系構造物の実
施態様においては、請求項２に記載しているように、耐
酸化層は酸素原子１対陽イオン原子１（ＭＯ）から酸素
原子３対陽イオン原子２（Ｍ２Ｏ３）までの比率の範囲
にある高融点酸化物、例えば、請求項３に記載している
ように、酸化アルミニウム（Ａｌ２Ｏ３）、ストロンチ
ウムジルコネート（ＳｒＺｒＯ３）、イットリア（Ｙ２
Ｏ３）などよりなるものとすることができる。[0008] In an embodiment of the carbon-based structure according to the present invention, as described in claim 2, the oxidation-resistant layer comprises one oxygen atom to one cation atom (MO) to three oxygen atoms. A refractory oxide in the ratio range up to 2 cation atoms (M 2 O 3 ), for example as described in claim 3
As described above, aluminum oxide (Al 2 O 3 ), strontium zirconate (SrZrO 3 ), yttria (Y 2
O 3 ).
【０００９】同じく、本発明に係わる炭素系構造物の実
施態様においては、請求項４に記載しているように、リ
ン酸アルミニウムを主体とするガラスシールはゾルゲル
法で耐酸化層の上に含浸されてなるものとすることがで
きる。[0009] Similarly, the acid in the embodiment of the carbon-based structure according to the present invention, as described in 請 Motomeko 4, glass seal composed mainly of Li <br/> phosphate aluminum by a sol-gel method Can be impregnated on the chemical layer.
【００１０】同じく、本発明に係わる炭素系構造物の実
施態様においては、請求項５に記載しているように、炭
素系構造物の基材は炭素／炭素複合材料よりなるものと
することができ、請求項６に記載しているように、基材
炭素／炭素複合材の表面に、イリジウム−炭素混合層よ
りなる熱応力緩和層（および／または界面密着強化層）
と、酸素の透過バリアー層であるイリジウム被膜と、耐
酸化層（および／または耐エロージョン層）である高融
点酸化物層と、リン酸アルミニウムを主体とするガラス
シール層が順次外表面に向けて形成されているものとす
ることができる。[0010] Similarly, in an embodiment of the carbon-based structure according to the present invention, the base material of the carbon-based structure may be made of a carbon / carbon composite material. Preferably, as described in claim 6, on the surface of the base carbon / carbon composite material, a thermal stress relaxation layer composed of an iridium-carbon mixed layer (and / or an interface adhesion strengthening layer)
And an iridium film as an oxygen permeation barrier layer, a high-melting-point oxide layer as an oxidation-resistant layer (and / or an erosion-resistant layer), and a glass seal layer mainly composed of aluminum phosphate. It can be formed.
【００１１】[0011]
【発明の効果】本発明に係わる炭素系構造物は、請求項
１に記載しているように、耐酸化コーティングを施して
表面に耐酸化層（および／または耐エロージョン層）が
形成された炭素系構造物において、表面の耐酸化層（お
よび／または耐エロージョン層）に、高温に曝された際
に耐酸化層（および／または耐エロージョン層）に形成
された成長結晶粒界やピンホール部などのすき間部分を
塞ぐリン酸アルミニウムを主体とするガラスシールを設
けた構成としたから、例えば、２０００℃程度の高温酸
化（大気等）雰囲気中に曝された場合に耐酸化層（およ
び／または耐エロージョン層）において結晶成長（粗大
化）が始まり、最外層において結晶粒界にピンホールが
発生したときでも、表面エネルギーの関係で結晶粒界や
ピンホール部にガラスシールが集まってくることによっ
て、結晶粒界やピンホールがガラスシールによってシー
ルされるので、酸素が内部に侵入しようとするのが阻止
されることから、炭素系構造物が酸素に接触して反応を
生じることにより炭素系構造物が消失するのが防止され
て、炭素系構造物を高温の酸化（大気等）雰囲気中に長
時間保持することが可能になるという耐酸化性の著しく
優れたものにできる顕著な効果がもたらされる。According to the present invention, there is provided a carbon-based structure having an oxidation-resistant layer (and / or an erosion-resistant layer) formed on its surface by applying an oxidation-resistant coating. In the system-based structure, a growth grain boundary or a pinhole portion formed in the oxidation-resistant layer (and / or the erosion-resistant layer) when exposed to a high temperature in the oxidation-resistant layer (and / or the erosion-resistant layer) on the surface. Because a glass seal mainly composed of aluminum phosphate for closing the gap portion is provided, for example, when exposed to a high-temperature oxidizing (air or the like) atmosphere of about 2000 ° C., the oxidation-resistant layer (and / or Even when crystal growth (coarsening) starts in the erosion-resistant layer) and pinholes are generated in the crystal grain boundaries in the outermost layer, the crystal grain boundaries and pinholes are not affected by the surface energy. As a result of the collection of seal, the crystal boundaries and pinholes are sealed by the glass seal, preventing oxygen from trying to enter the interior. The carbon-based structure is prevented from disappearing due to the occurrence of the carbon-containing structure, and the carbon-based structure can be held in a high-temperature oxidizing (atmosphere or the like) atmosphere for a long time. Has a remarkable effect.
【００１２】そして、請求項２に記載しているように、
耐酸化層は酸素原子１対陽イオン原子１（ＭＯ）から酸
素原子３対陽イオン原子２（Ｍ２Ｏ３）までの比率の範
囲にある高融点酸化物であるもの、例えば、請求項３に
記載しているように、酸化アルミニウム（Ａｌ
２ Ｏ ３ ），ストロンチウムジルコネート（ＳｒＺｒ
Ｏ ３ ），イットリア（Ｙ ２ Ｏ ３ ）のうちから選ばれるも
のとすることによって、炭素系構造物の耐酸化性能の限
界温度をより一層高めるものとすることが可能であり、
前記請求項１に記載しているように、ガラスシールはリ
ン酸アルミニウムを主体とするものであるようになすこ
とによって、高融点酸化物の結晶粒粗大化を防止するこ
とが可能であると共に高融点酸化物が高温に曝されて結
晶粒がたとえ粗大化してピンホールが形成されたときで
も、このリン酸アルミニウムは表面エネルギーの関係で
粗大結晶粒界やピンホールに集まってくることにより粗
大結晶粒界やピンホールの部分をシールするので、内部
への酸素の侵入を阻止することが可能であるという著し
く優れた効果がもたらされる。And, as described in claim 2,
The oxidation resistant layer is composed of one oxygen atom to one cation atom (MO).
Elementary atom 3 to cation atom 2 (M2O3)
High-melting oxide in the boxFor example, in claim 3
As noted, aluminum oxide (Al
2 O 3 ), Strontium zirconate (SrZr
O 3 ), Yttria (Y 2 O 3 )
ofLimits the oxidation resistance of carbon-based structures.
It is possible to further increase the interfacial temperature,
SaidClaim1Glass seals as described in
So that it is mainly composed of aluminum phosphate
To prevent coarsening of the crystal grains of the high melting point oxide.
And the high melting point oxide is exposed to
When the crystal grains become coarse and pinholes are formed
However, this aluminum phosphate is
Coarse due to gathering at coarse grain boundaries and pinholes
Seals large grain boundaries and pinholes, so
It is possible to prevent oxygen from entering the
Excellent effect is brought.
【００１３】そして、請求項４に記載しているように、
リン酸アルミニウムを主体とするガラスシールはゾルゲ
ル法で耐酸化層の上に含浸されてなるものとすることに
よって、請求項１の構成による効果に加えて、高融点酸
化物の表面にリン酸アルミニウムを良好に含浸させるこ
とが可能であるという著しく優れた効果がもたらされ
る。And, as described in claim 4 ,
By glass seal mainly comprising-phosphate aluminum which shall become impregnated on the oxidation-resistant layer in Sorge <br/> Le method, in addition to the effects of the first aspect, the high melting point oxides A remarkably excellent effect is that aluminum phosphate can be satisfactorily impregnated on the surface of the aluminum alloy.
【００１４】さらにまた、請求項５に記載しているよう
に、炭素系構造物の基材は炭素／炭素複合材料よりなる
ものとすることによって、耐熱性に優れそしてまた軽量
である炭素／炭素複合材の耐酸化性能をより一層向上さ
せることが可能であるという著しく優れた効果がもたら
される。Further, as described in claim 5, the base material of the carbon-based structure is made of a carbon / carbon composite material, so that the carbon / carbon material has excellent heat resistance and is lightweight. A remarkably excellent effect is obtained that the oxidation resistance of the composite material can be further improved.
【００１５】さらにまた、請求項６に記載しているよう
に、基材炭素／炭素複合材の表面に、イリジウム−炭素
混合層よりなる熱応力緩和層と、酸素の透過バリアー層
であるイリジウム被膜と、耐酸化・耐エロージョン層で
ある高融点酸化物層と、ガラスシール層が順次外表面に
向けて形成されているものとすることによって、耐熱
性，耐酸化性，耐エロージョン性に優れると共に層間の
密着強度が大で熱応力によって容易には剥離を生じがた
い耐高温特性に著しく優れた炭素系構造物を提供するこ
とが可能であるという著大なる効果がもたらされる。Further, as described in claim 6, a thermal stress relaxation layer composed of an iridium-carbon mixed layer and an iridium coating which is an oxygen permeation barrier layer are formed on the surface of the base carbon / carbon composite material. And the high-melting-point oxide layer, which is an oxidation-resistant and erosion-resistant layer, and the glass seal layer are sequentially formed on the outer surface, so that heat resistance, oxidation resistance, and erosion resistance are excellent. A remarkable effect is provided that it is possible to provide a carbon-based structure having excellent high-temperature resistance, which has high adhesion strength between layers and is not easily peeled off by thermal stress.
【００１６】[0016]
【実施例】本発明に係わる炭素系構造物の実施例につい
て比較例と共に説明するが、本発明はこの実施例にのみ
限定されるものでないことは言うまでもない。EXAMPLES Examples of the carbon-based structure according to the present invention will be described together with comparative examples, but it goes without saying that the present invention is not limited to these examples.
【００１７】実施例１ 図１に示すように、この実施例１による炭素系構造物１
では、ピッチ粉末をマトリックス前躯体とする石油ピッ
チ系の高弾性繊維（縦糸２Ａおよび横糸２Ｂ）による炭
素／炭素複合材２を基材とし、そのうえに、熱応力緩和
層および界面密着強化層として機能する３０体積％イリ
ジウム−炭素混合層（３０体積％Ｉｒ−Ｃ混合層）３を
形成し、さらにこのうえに、酸素の透過バリアー層とし
て機能するイリジウム被覆（Ｉｒ被覆）４を設け、さら
にこのうえに耐酸化・耐エロージョン層として機能する
ＳｒＺｒＯ３高融点酸化物層５を設け、さらにその上
に、ガラスシールとして機能するリン酸アルミニウム被
覆６をゾルゲル法によって高融点酸化物層５に含浸付着
させたものとした。 Embodiment 1 As shown in FIG. 1, a carbon-based structure 1 according to Embodiment 1
In this example, a carbon / carbon composite material 2 made of petroleum pitch-based high elasticity fibers (warp yarns 2A and weft yarns 2B) having pitch powder as a matrix precursor is used as a base material, and further functions as a thermal stress relaxation layer and an interface adhesion reinforcing layer. A 30 volume% iridium-carbon mixed layer (30 volume% Ir-C mixed layer) 3 is formed, and an iridium coating (Ir coating) 4 serving as an oxygen permeation barrier layer is further provided thereon. An SrZrO 3 high melting point oxide layer 5 functioning as an oxidation / erosion resistance layer was provided, and an aluminum phosphate coating 6 functioning as a glass seal was further impregnated and adhered to the high melting point oxide layer 5 by a sol-gel method. It was taken.
【００１８】次いで、このようにして得た炭素系構造物
１において、後記する温度２０００℃での大気中曝露試
験を行った後における試料の表面および断面を走査顕微
鏡によって観察したところ、それぞれ図２および図３に
示した結果であった。Next, in the carbon-based structure 1 thus obtained, the surface and cross section of the sample after an atmospheric exposure test at a temperature of 2000 ° C. to be described later were observed with a scanning microscope. And the results shown in FIG.
【００１９】この結果、温度２０００℃での大気曝露試
験後においては、図２および図３に示すように、コーテ
ィング層ならびに基材である炭素／炭素複合材のいずれ
においてもほとんど問題は認められなかった。As a result, after the air exposure test at a temperature of 2000 ° C., as shown in FIGS. 2 and 3, almost no problem was found in any of the coating layer and the carbon / carbon composite material as the base material. Was.
【００２０】また、後記する比較例２の図６および図７
と比較して明らかであるように、リン酸アルミニウムを
被覆することによって、高融点酸化物であるストロンチ
ウムジルコネート（ＳｒＺｒＯ３）の結晶粒粗大化挙動
も明らかに小さいことが認められた。これはリン酸アル
ミニウムがストロンチウムジルコネートの結晶微細化剤
としても働くためであると考えられた。FIGS. 6 and 7 of Comparative Example 2 to be described later.
As is clear from comparison with the above, it was recognized that the coating with aluminum phosphate also significantly reduced the crystal grain coarsening behavior of strontium zirconate (SrZrO 3 ), which is a high melting point oxide. This was thought to be because aluminum phosphate also served as a crystal refiner for strontium zirconate.
【００２１】比較例１ 図４に示すように、この比較例１による炭素系構造物１
１では、ピッチ粉末をマトリックス前躯体とする石油ピ
ッチ系の高弾性繊維（縦糸１２Ａおよび横糸１２Ｂ）に
よる炭素／炭素複合材１２を基材とし、表面の耐酸化コ
ーティングは施さないものとした。 Comparative Example 1 As shown in FIG. 4, the carbon-based structure 1 according to Comparative Example 1
In No. 1, a carbon / carbon composite material 12 made of petroleum pitch-based highly elastic fibers (warp yarns 12A and weft yarns 12B) having pitch powder as a matrix precursor was used as a base material, and the surface was not subjected to oxidation-resistant coating.
【００２２】比較例２ 図５に示すように、この比較例２による炭素系構造物２
１では、ピッチ粉末をマトリックス前躯体とする石油ピ
ッチ系の高弾性繊維（縦糸２２Ａおよび横糸２２Ｂ）に
よる炭素／炭素複合材２２を基材とし、そのうえに、熱
応力緩和層および界面密着強化層として機能する３０体
積％イリジウム−炭素混合層（３０体積％Ｉｒ−Ｃ混合
層）２３を形成し、さらにこのうえに、酸素の透過バリ
アー層として機能するイリジウム被覆（Ｉｒ被覆）２４
を設け、さらにこのうえに耐酸化・耐エロージョン層と
して機能するＳｒＺｒＯ３高融点酸化物層２５を設けた
ものとした。 Comparative Example 2 As shown in FIG. 5, the carbon-based structure 2 according to Comparative Example 2
In No. 1, a carbon / carbon composite material 22 made of petroleum pitch-based highly elastic fibers (warp yarns 22A and weft yarns 22B) having a pitch powder as a matrix precursor is used as a base material, and further functions as a thermal stress relaxation layer and an interface adhesion reinforcing layer. A 30 volume% iridium-carbon mixed layer (30 volume% Ir-C mixed layer) 23 is formed, and an iridium coating (Ir coating) 24 serving as an oxygen permeation barrier layer is further formed thereon.
And a SrZrO 3 high melting point oxide layer 25 functioning as an oxidation-resistant and erosion-resistant layer.
【００２３】次いで、このようにして得た炭素系構造物
２１において、後記する温度２０００℃での大気中曝露
試験を行った後における試料の表面および断面を走査顕
微鏡によって観察したところ、それぞれ図６および図７
に示した結果であった。Next, the surface and the cross section of the carbon-based structure 21 obtained in this manner after an atmospheric exposure test at a temperature of 2000 ° C., which will be described later, were observed with a scanning microscope. And FIG.
The results are shown in FIG.
【００２４】この結果、温度２０００℃での大気曝露試
験後においては、図６および図７に示すように、コーテ
ィング層は残存しているものの、基材である炭素／炭素
複合材はほとんど消失していた。As a result, after the air exposure test at a temperature of 2000 ° C., as shown in FIGS. 6 and 7, although the coating layer remains, the carbon / carbon composite material as the base material almost disappears. I was
【００２５】評価試験例 この評価試験では、図８に示すように、クセノンランプ
３１、楕円形鏡面３２、放射温度計３３，３４、試料３
５Ｓを支持する試料台３５、電子天秤（熱天秤）３６、
ガス供給器３７、ガラス分析計３８などをそなえたクセ
ノンランプ集光炉３９を使用し、このクセンノンランプ
集光炉３９内において、試料３５Ｓを大気雰囲気中で２
０００℃に曝し、電子天秤３６によって重量減少の時間
経過による変化を測定した。この結果を図９に示す。 Evaluation Test Example In this evaluation test, as shown in FIG. 8, a xenon lamp 31, an elliptical mirror surface 32, radiation thermometers 33 and 34, a sample 3
A sample stage 35 supporting 5S, an electronic balance (thermal balance) 36,
A xenon lamp condenser furnace 39 having a gas supply device 37, a glass analyzer 38, and the like is used.
The sample was exposed to 000 ° C., and the change with time of the weight loss was measured by the electronic balance 36. The result is shown in FIG.
【００２６】図９に示すように、本発明実施例の場合に
は、耐酸化層の最外層にガラスシール材としてリン酸ア
ルミニウム被膜を施すことによって、高融点酸化物層の
結晶粗大化を防止することができるだけでなく、結晶粒
界部やピンホール部にもリン酸アルミニウムが集積する
ため、結晶粒界部やピンホール部から侵入しようとする
酸素の拡散を防止することができるので、これによっ
て、重量減少がほとんどみられず、すこぶる優れた耐酸
化性を有し、大気中において２０００℃域での使用が可
能である炭素系構造物の耐酸化コーティングを形成する
ことができ、例えば、火星突入型カプセルのノーズコー
ンなど酸化雰囲気中２０００℃域での使用が可能である
炭素質構造材料を提供することが可能であった。As shown in FIG. 9, in the case of the embodiment of the present invention, the outermost layer of the oxidation-resistant layer is coated with an aluminum phosphate film as a glass sealing material, thereby preventing the crystal of the high-melting-point oxide layer from becoming coarse. In addition to this, aluminum phosphate accumulates in the crystal grain boundaries and pinholes, which prevents diffusion of oxygen that tends to enter from the crystal grain boundaries and pinholes. By this, it is possible to form an oxidation-resistant coating of a carbon-based structure that has little weight loss, has extremely excellent oxidation resistance, and can be used in the 2000 ° C. range in the atmosphere. It has been possible to provide a carbonaceous structural material that can be used in an oxidizing atmosphere at a temperature of 2000 ° C., such as a nose cone of a Mars rush type capsule.
【図１】本発明の一実施例による炭素系構造物の断面を
模型的に示す説明図である。FIG. 1 is an explanatory view schematically showing a cross section of a carbon-based structure according to one embodiment of the present invention.
【図２】図１に示した炭素系構造物に対して大気中２０
００℃での曝露試験を行ったのちの表面走査電子顕微鏡
観察結果を示す模写図である。FIG. 2 shows that the carbon-based structure shown in FIG.
It is a mimetic diagram showing the result of surface scanning electron microscope observation after performing an exposure test at 00 ° C.
【図３】図１に示した炭素系構造物に対して大気中２０
００℃での曝露試験を行ったのちの断面走査電子顕微鏡
観察結果を示す模写図である。FIG. 3 shows that the carbon-based structure shown in FIG.
It is a mimetic diagram showing a section scanning electron microscope observation result after performing an exposure test at 00 ° C.
【図４】比較例１による炭素系構造物の断面を模型的に
示す説明図である。FIG. 4 is an explanatory diagram schematically showing a cross section of a carbon-based structure according to Comparative Example 1.
【図５】比較例２による炭素系構造物の断面を模型的に
示す説明図である。FIG. 5 is an explanatory diagram schematically showing a cross section of a carbon-based structure according to Comparative Example 2.
【図６】図５に示した炭素系構造物に対して大気中２０
００℃での曝露試験を行ったのちの表面走査電子顕微鏡
観察結果を示す模写図である。FIG. 6 shows that the carbon-based structure shown in FIG.
It is a mimetic diagram showing the result of surface scanning electron microscope observation after performing an exposure test at 00 ° C.
【図７】図５に示した炭素系構造物に対して大気中２０
００℃での曝露試験を行ったのちの断面走査電子顕微鏡
観察結果を示す模写図である。FIG. 7 shows that the carbon-based structure shown in FIG.
It is a mimetic diagram showing a section scanning electron microscope observation result after performing an exposure test at 00 ° C.
【図８】評価試験例で使用したクセノンランプ集光炉の
概略構成を示す説明図である。FIG. 8 is an explanatory diagram showing a schematic configuration of a xenon lamp condenser furnace used in an evaluation test example.
【図９】評価試験により得た経過時間による重量減少率
の変化を例示するグラフである。FIG. 9 is a graph exemplifying a change in a weight loss rate according to elapsed time obtained by an evaluation test.
１ 炭素系構造物 ２ 炭素／炭素複合材 ３ イリジウム−炭素混合層（耐酸化層） ４ イリジウム被覆層（耐酸化層） ５ 高融点酸化物層（耐酸化・耐エロージョン層） ６ リン酸アルミニウム被覆（ガラスシール） DESCRIPTION OF SYMBOLS 1 Carbon-based structure 2 Carbon / carbon composite material 3 Iridium-carbon mixed layer (oxidation-resistant layer) 4 Iridium coating layer (oxidation-resistant layer) 5 High-melting-point oxide layer (oxidation-resistant and erosion-resistant layer) 6 Aluminum phosphate coating (Glass seal)
フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C04B 41/80 - 41/90 F16L 59/00Continuation of front page (58) Field surveyed (Int.Cl. 6 , DB name) C04B 41/80-41/90 F16L 59/00
Claims (6)
化層が形成された炭素系構造物において、表面の耐酸化
層に、高温に曝された際に耐酸化層に形成された粗大結
晶粒界やピンホール部などのすき間部分を塞ぐリン酸ア
ルミニウムを主体とするガラスシールを設けたことを特
徴とする炭素系構造物。1. A carbon-based structure having an oxidation-resistant layer formed on its surface by applying an oxidation-resistant coating, wherein coarse crystal grains formed on the oxidation-resistant layer when exposed to a high temperature. Phosphoric acid that blocks gaps such as
A carbon-based structure provided with a glass seal mainly made of luminium .
（ＭＯ）から酸素原子３対陽イオン原子２（Ｍ２Ｏ３）
までの比率の範囲にある高融点酸化物である請求項１に
記載の炭素系構造物。2. The oxidation-resistant layer comprises one oxygen atom and one cation atom.
From (MO), 3 oxygen atoms to 2 cation atoms (M 2 O 3 )
The carbon-based structure according to claim 1, which is a high-melting-point oxide having a ratio in the range up to.
２ Ｏ ３ ），ストロンチウムジルコネート（ＳｒＺｒ
Ｏ ３ ），イットリア（Ｙ ２ Ｏ ３ ）のうちから選ばれる請
求項２に記載の炭素系構造物。3. The high melting point oxide is aluminum oxide (Al).
2 O 3 ), strontium zirconate (SrZr
O 3), yttria (Y 2 O 3) carbon-based structure according to請<br/> sought to claim 2 selected from among the.
シールはゾルゲル法で耐酸化層の上に含浸されてなる請
求項１ないし３のいずれかに記載の炭素系構造物。4. A glass mainly comprising-phosphate aluminum
The carbon-based structure according to any one of claims 1 to 3 , wherein the seal is impregnated on the oxidation-resistant layer by a sol-gel method.
料よりなる請求項１ないし４のいずれかに記載の炭素系
構造物。5. The carbon-based structure according to claim 1, wherein the base material of the carbon-based structure is made of a carbon / carbon composite material.
ウム−炭素混合層よりなる熱応力緩和層と、酸素の透過
バリアー層であるイリジウム被膜と、耐酸化・耐エロー
ジョン層である高融点酸化物層と、ガラスシール層が順
次外表面に向けて形成されている請求項５に記載の炭素
系構造物。6. A thermal stress relieving layer composed of an iridium-carbon mixed layer, an iridium coating which is a barrier layer for oxygen, and a high melting point which is an oxidation-resistant and erosion-resistant layer on the surface of the base carbon / carbon composite material. The carbon-based structure according to claim 5, wherein the oxide layer and the glass seal layer are sequentially formed toward the outer surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8113963A JP2777105B2 (en) | 1996-05-08 | 1996-05-08 | Carbon-based structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8113963A JP2777105B2 (en) | 1996-05-08 | 1996-05-08 | Carbon-based structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09301788A JPH09301788A (en) | 1997-11-25 |
| JP2777105B2 true JP2777105B2 (en) | 1998-07-16 |
Family
ID=14625600
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8113963A Expired - Fee Related JP2777105B2 (en) | 1996-05-08 | 1996-05-08 | Carbon-based structure |
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| Country | Link |
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| JP (1) | JP2777105B2 (en) |
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| JP4913934B2 (en) * | 2000-01-07 | 2012-04-11 | 富士重工業株式会社 | Oxidation resistant coating film of carbon fiber reinforced carbon composite material and repair method thereof |
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|---|---|---|---|---|
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| JP3034084B2 (en) * | 1991-08-12 | 2000-04-17 | 川崎重工業株式会社 | Oxidation resistant carbon fiber reinforced carbon composite material and method for producing the same |
| JP3548605B2 (en) * | 1994-08-18 | 2004-07-28 | 東海カーボン株式会社 | Oxidation-resistant treatment of carbon fiber reinforced carbon composites |
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|---|---|
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