JP4863181B2 - Composite oxide film covering member for preventing hydrogen isotope permeation and method for producing the same - Google Patents
Composite oxide film covering member for preventing hydrogen isotope permeation and method for producing the same Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
Description
【０００１】
【発明の属する技術分野】
本発明は、水素同位体透過防止性に優れる複合酸化物皮膜被覆部材とそれの製造方法に関するものである。
【０００２】
【従来の技術】
一般に、連続的に酸化クロムによって化学的に緻密化された施工法（化学的緻密化法）によるＳｉＯ2−ＣｒＯ3からなる組成を有する皮膜（化学的緻密化皮膜）は、高硬度を有するため、耐摩耗用皮膜として用いられ、各種の機械構造部材に適用され、現在でもなお、有用な化学的緻密化法による耐摩耗性皮膜としての地位を保っている。
【０００３】
これらは、ステンレス鋼製基材に、ＣｒＯ3を化学変化させて微細なＣｒ2Ｏ3からなる硬質皮膜を形成する技術として、特開昭５９−９１７１号公報，特開昭６１−５２３７４号公報，特開昭６３−１２６６８２号公報，特開昭６３−３１７６８０号公報に開示の方法などが提案されている。
【０００４】
また、鋼鉄製基材に、ＣｒＯ3を化学変化させて微細なＣｒ2０3からなる硬質皮膜を形成する技術として、特開昭５９−９１７１号公報，特開昭６１−５２３７４号公報，特開昭６３−１２６６８２号公報，特開昭６３−３１７６８０号公報に開示の方法などが提案されている。
【０００５】
しかし、化学的緻密化皮膜も、その皮膜内部を光学顕微鏡で観察すると、微細な気孔やき裂があり、その大部分はステンレス鋼製基材表面に達している場合も少なくないことがわかっている。この微細な気孔やき裂は、水素同位体が存在する環境下では、その水素同位体が化学的繊密化皮膜内を透過しステンレス鋼製基材に到達し、さらに、ステンレス鋼製基材を透過し外部環境へ流出してしまうため、水素同位体透過防止皮膜としては利用できないという欠点があった。
【０００６】
【発明が解決しようとする課題】
本発明の目的は、上述した従来化学的緻密化法によるＳｉＯ2−Ｃｒ2Ｏ3からなる組成を有する皮膜（化学的緻密化皮膜）が有する上述した欠点を補うことのできる技術の確立を図ることにあり、優れた水素同位体透過防止性を有する複合酸化物皮膜に変成させるために有効な技術を提案するところにある。
【０００７】
即ち、このような目的を実現するために開発した本発明の考え方を整理して述べると、
（１）化学的緻密化皮膜内に発生している微細な気孔やき裂内に、水素同位体透過防止性に優れた酸化クロム−非晶質無機材料微粒子を充填することによって、水素同位体の透過を抑制する。
【０００８】
（２）化学的緻密化皮膜の微細なき裂内に、酸化クロム−非晶質無機材料微粒子を充填し、それのみならず，さらにこの化学的繊密化皮膜の表面には無機材料複合材の薄膜をも形成することによって、水素同位体の内部侵入をより一層確実に防ぐようにする。
【０００９】
（３）上述の点に関し、クロム酸水溶液ならびに焼成履歴をうけることによって非晶質無機物質を生成する材料を含む水溶液を塗布、これを加熱処理することによって固化させ析出物として得ることで微細な気孔やき裂を充填するプロセスを用いて、水素同位体の透過を抑えることができることがわかった。
【００１０】
【課題を解決するための手段】
このような知見の下に上掲の目的を実現する方法として、本発明では、化学的緻密化法によるＳｉＯ2−Ｃｒ2Ｏ3からなる組成を有する皮膜（化学的緻密化皮膜）に発生している微細な気孔やき裂に対し、水素同位体の内部侵入を抑制するため、次のような手段を採用した。
【００１１】
（１）化学的緻密化皮膜の表面に対して直接，焼成することによって非晶質無機物質を生成する材料を含む水溶液を塗布，噴霧もしくはこの水溶液中に化学的緻密化皮膜を浸漬して引き上げた後，焼成する方法。
【００１２】
（２）化学的緻密化皮膜において，直接その表面に，焼成履歴を受けることによって非晶質無機物質を生成する材料を含む水溶液を塗布，噴霧もしくはこの水溶液中に化学的緻密化皮膜を浸漬して引き上げた後，焼成する方法を複数回繰り返すことによって，該化学的繊密化皮膜の微細気孔や亀裂内部へ非晶質無機物質を充填するだけでなく，余剰の非晶質無機物質を化学的繊密化皮膜の最外層表面にも薄く被覆する方法。
【００１３】
即ち、本発明要旨構成を列挙して述べると、下記のとおりである。
（１）本発明は，ステンレス鋼などの金属材料鋼基材の表面に，化学的緻密化皮膜を設けるとともに，該皮膜の気孔やき裂内に非晶質無機物質を充填することによって形成する複合酸化物皮膜被覆部材である。
【００１４】
（２）また，本発明は，ステンレス鋼などの金属材料基材の表面に，化学的緻密化皮膜を設けるとともに，該皮膜の気孔やき裂内に非晶質無機物質を充填させ，かつ，その表面には非晶質無機物質層を形成させることによって得られる複合酸化物皮膜被覆部材である。
【００１５】
（３）なお，本発明においては上記非晶質無機物質充填材としては，焼成することによって非晶質無機物質を生成する材料を含む水溶液を塗布，噴霧もしくはこの水溶液中に浸漬した後，加熱，焼成することによって生成させたものであり，珪酸塩ガラス，ほう珪酸塩ガラス，あるいはリン酸塩ガラスを主として含むものが好ましい。
【００１６】
（４）次に，本発明にかかる部材は，ステンレス鋼などの金属材料基材の表面に化学的緻密化皮膜を設けるとともに，該皮膜の表面に，焼成履歴を受けることによって非晶質無機物質を生成する材料を含む水溶液を塗布，噴霧もしくはこの水溶液中に化学的緻密化皮膜を浸漬した後，加熱，焼成することによって，該化学的緻密化皮膜の気孔やき裂内に非晶質無機物質を充填して水素同位体透過防止用複合酸化物皮膜を形成させることによって製造するか，
（５）ステンレス鋼などの金属材料基材の表面に化学的緻密化皮膜を設けるとともに，該皮膜の表面に，焼成履歴を受けることによって非晶質無機物質を生成する材料を含む水溶液を塗布，噴霧もしくはこの水溶液中に化学的緻密化皮膜を浸漬した後，加熱，焼成することによって，該化学的緻密化皮膜の気孔やき裂内に非晶質無機物質を充填させると同時にその化学的緻密化皮膜表面にも該非晶質無機物質層を生成被覆させることによって製造する。
【００１７】
【発明の実施の形態】
本発明の水素同位体透過防止性に優れる複合酸化物皮膜の作用機構について具体的に説明する。
【００１８】
（１）ステンレス鋼製基材の表面に被覆されたＳｉＯ2−Ｃｒ2Ｏ3からなる組成を有する皮膜（化学的緻密化皮膜）は、化学的緻密化法により図１に示す施工流れにより形成する。しかし、形成された化学的緻密化皮膜は非常に硬く、耐摩耗性に優れているものの、その皮膜内には微細な気孔やき裂が存在し、そのうちには基材に直接達するような開口き裂もある。
【００１９】
この微細な気孔やき裂は、水素同位体が存在する環境下では、その水素同位体が化学的緻密化皮膜内を透過し、ステンレス鋼製基材に到達し、さらに、ステンレス鋼製基材をも透過して外部環境へ流出してしまうため、水素同位体透過防止皮膜としては利用できないという欠点があった。
【００２０】
そこで本発明では，この化学的緻密化皮膜の表面に直接，焼成履歴を受けることによって非晶質無機物質を生成する材料を含む水溶液とクロム酸水溶液の混合物を塗布，噴霧もしくはこの水溶液中に化学的緻密化皮膜を浸漬した後，加熱，焼成することによって，該化学的緻密化皮膜の気孔やき裂内に非晶質無機物質を侵入，充填させる。焼成履歴を受けることによって非晶質無機物質を生成する材料を含む水溶液とは，硼酸塩化合物，珪酸塩化合物，リン酸塩化合物を含む水溶液である。
【００２１】
発明者らの実験によれば，硼酸塩化合物水溶液とクロム酸水溶液との混合物を塗布などの処理を施した化学的緻密化皮膜の場合は５５０〜７２０℃，クロム酸水溶液−リン酸塩化合物水溶液混合物を塗布などの処理を施した化学的緻密化皮膜の場合は２５０〜７５０℃の温度で０．５〜２時間加熱すると，水溶液中に含まれる水分は蒸発するとともに微細粒子からなるクロム酸化物は加熱残渣物として，気孔，き裂内に充填されるとともに，化学的緻密化皮膜の表面に生成することがわかった。
【００２２】
すなわちクロム酸は中間体を経てＣｒ2Ｏ3（酸化クロム）となり，同時に存在する硼酸塩化合物，珪酸塩化合物，リン酸塩化合物水溶液はそれぞれ水分を放出して非晶質無機物質となるのである。上記水溶液から析出したＣｒ2Ｏ3はきわめて微細で硬く，耐摩耗性と耐食性に優れるものである。リン酸塩化合物，硼酸塩化合物，珪酸塩化合物はいずれも非晶質で一部ガラス状を呈し，皮膜内気孔，き裂内に析出，これらを封止する。さらに，皮膜構成粒子間の密着性を向上させる。
【００２３】
本発明によれば，微細Ｃｒ2Ｏ3の折出と硼酸塩化合物，珪酸塩化合物，リン酸塩化合物が現出する非晶質物質がＣｒ2Ｏ3微細粒の結合を強めていると考えられる。これらが水素同素体の侵入経路の遮断に寄与する。
【００２４】
なお，クロム酸と，硼酸塩化合物，珪酸塩化合物，リン酸塩化合物水溶液を主成分とする処理液を塗布，噴霧，あるいはこれへの浸漬などをおこなった後これを加熱する工程を複数回繰り返すと，化学的緻密化皮膜の気孔，亀裂内部へのＣｒ2０3と非晶質無機物の充填にとどまらず余剰の酸化クロム−非晶質無機化合物複合層に覆われているため、この皮膜によって水素同位体透過防止性を維持することとなる。表１は、水素同位体透過防止用複合酸化物皮膜施工条件を示したものである。
【００２５】
【表１】
また、図２は、本発明に係る水素同位体透過防止用複合酸化物皮膜の断面構造例を示したものである。ここで１はステンレス鋼製基材、２は化学的緻密化皮膜、３は化学的緻密化皮膜に存在している貫通気孔（亀裂）、４は該気孔部，即ちき裂内に充填された酸化クロム−非晶質無機物複合微粒子であり、５は化学的緻密化皮膜の表面を覆っている酸化クロム−非晶質無機物複合微粒子の層を示している。なお、この断面構造から明らかなように、上記酸化クロム−非晶質無機物複合微粒子層は、その微粒子の化学的緻密化皮膜のき裂内にも完全に充填された状態になっているので、極めて高い密着性を発揮する。
【００２７】
【実施例】
（実施例１）
この実施例では、ＳＳ４００鋼製基材の表面に施工した化学的緻密化皮膜及びその気孔，き裂中に酸化クロム−非晶質無機物複合微粒子層を充填，被覆処理した水素同位体透過防止用複合酸化物皮膜について、これら皮膜被覆部材の耐食性をめっきの耐食性試験方法（キャス試験：ＪＩＳＨ８５０２）に基づき実施した。
【００２８】
（１）本発明の水素同位体透過防止用複合酸化物皮膜：皮膜部基材（ＳＳ４００鋼）表面に化学的緻密化皮膜を施工後、５５％クロム酸水溶液と１５％ほう酸水溶液を１：１に混合して得た水溶液中に浸漬した後引き上げて、７５０℃で１時間の熱処理を施す工程を６回繰り返して複合酸化物皮膜（５０μｍ）としたものを用いた。
【００２９】
（２）比較例の化学的緻密化皮膜：上記の化学的緻密化皮膜（５０μｍ）だけをそのまま用いた。
（３）キャス試験結果：キャス試験結果を表２に示した。この結果から明らかなように、比較例の無処理化学的緻密化皮膜は、皮膜の亀裂部分を通って環境からの水溶液が侵入して基材の炭素鋼を腐食し、これが化学的緻密化皮膜の表面に赤さびとして多量に認められた。
【００３０】
これに対し本発明の処理を施した水素同位体透過防止用複合酸化物皮膜は、全く赤さびの発生は認められなかった。すなわち、化学的緻密化皮膜の気孔，き裂内に酸化クロム−ほう珪酸ガラス複合微粒子層が充填された結果、水溶液の侵入が抑制され、優れた耐食性を発揮したものと考えられる。
【００３１】
【表２】
（実施例２）
この実施例では、本発明にかかる処理を施して得られた水素同位体透過防止用複合酸化物皮膜の重水素透過性を調査した。
【００３３】
（１）本発明の水素同位体透過防止用複合酸化物皮膜：皮膜部基材（ＳＵＳ３１６Ｌ：外径３０．０ｍｍ×厚さ０．９ｍｍの管材内面に化学的緻密化皮膜を施工後、ＣｒＯ３とリン酸を主成分とする水溶液中に浸漬した後引き上げて、４５０℃で１時間の熱処理を６回繰り返して複合酸化物皮膜（５０μｍ）としたものを用いた。
【００３４】
（２）比較例の皮膜：比較例の皮膜として、無処理の前記化学的緻密化皮膜のみのものを用いた。
（３）重水素透過試験：図３に示した重水素透過試験試験装置を用い、６００℃における重水素透過量を測定し、透過低減率（皮膜未施工時の重水素透過量に対する皮膜施工時の重水素透過量の比）を求めた。
【００３５】
（４）重水素透過試験結果：その試験結果を図４及び表３に取りまとめた。化学的緻密化皮膜は、重水素透過低減率が６００℃において約１／５０であったのに対し、水素同位体透過防止用複合酸化物皮膜は、重水素透過低減率が６００℃において約１／１０００であった。
【００３６】
【表３】
【発明の効果】
以上説明したように本発明によれば、化学的緻密化皮膜を有する部材について、この部材表面に生成した気孔や，き裂を有する該化学的緻密化皮膜を、クロム酸水溶液および非晶質無機物質を生成する材料を含む水溶液を塗布等した後，加熱することによって、酸化クロム−非晶質無機物質複合材微粒子を生成させてこれを該気孔や，き裂中に充填すると同時に、さらには皮膜表面に一定の厚さで被覆することで、従来から十分でないとされていた化学的緻密化皮膜の水素同位体透過防止性を向上させることができる。この結果、ガス透過防止性が要求される機械構造物あるいは部材に対する水素同位体透過防止用複合酸化物皮膜の適用分野が拡大される。
【図面の簡単な説明】
【図１】 ステンレス鋼製基材の表面に化学的緻密化皮膜を形成するための施工流れ図である。
【図２】 ステンレス鋼製基材の表面に形成された化学的緻密化皮膜上に、クロム酸ならびに焼成によって非晶質無機物質を生成する材料を含む水溶液を主成分とする処理液を用いて酸化クロム−非晶質無機物質複合皮膜を形成した水素同位体透過防止用複合酸化物皮膜被覆部材の部分断面図である。
【符号の説明】
１：ステンレス鋼製基材、
２：化学的緻密化皮膜、
３：化学的緻密化皮膜に存在している貫通気孔（き裂）
４：該気孔部，即ち，き裂内に充填された酸化クロム−非晶質無機物質複合材微粒子
５：化学的緻密化皮膜の表面を覆っている酸化クロム−非晶質無機物質複合材層
【図３】 ＳＵＳ３１６Ｌ基材管内面に皮膜施工したものを試験管とし、試験管の内側に重水素を既定濃度含むアルゴンカスを流し、試験管を透過した重水素を試験管外側に純アルゴンカスを流すことにより質量分析計に導き、重水素濃度を測定する重水素透過試験装置の部分概略図である。
【符号の説明】
１：ＳＵＳ３１６Ｌ基材管（内径３０．０ｍｍ×厚さ０．９ｍｍ）で内面に皮膜を５０μｍ厚さ施工した試験管
２：ハステロイ−×基材管（内径５０．０ｍｍ×厚さ３．０ｍｍ）を用いた測定管
３：試験管を透過した重水素透過量を測定する質量分析計
４：重水素含有アルゴンカス中に含まれる重水素、
５：試験管の重水素の透過
６：試験管内への重水素含有アルゴンカス供給ライン
７：試験管内からの重水素含有アルゴンガス排出ライン
８：試験管を透過した重水素を質量分析計へ導くための測定管内純アルゴンガス供給ライン
９：試験管を透過した重水素を質量分析計へ導くための測定管内純アルゴンガス排出ライン
【図４】 試験管の内側に重水素を既定濃度含むアルゴンガスを流し始め、試験管を透過した重水素量の変化を経時的に示した、６００℃における重水素透過試験結果の図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a composite oxide film-coated member excellent in hydrogen isotope permeation-preventing property and a method for producing the same.
[0002]
[Prior art]
In general, a film (chemically densified film) having a composition composed of SiO 2 —CrO 3 by a construction method (chemical densification method) continuously chemically densified with chromium oxide has high hardness. They are used as anti-friction耗用coating is applied to various mechanical structural member, yet still has maintained its position as the abrasion-resistant films according to useful chemical densification method.
[0003]
These stainless steel substrate, a technique of forming a hard film composed of fine Cr 2 O 3 and the CrO 3 is chemically changed, JP 59-9171, JP-Sho 61-52374 JP JP-A-63-126682 and JP-A-63-317680 propose methods disclosed therein.
[0004]
Further, as a technique for chemically changing CrO 3 on a steel substrate to form a hard film composed of fine Cr 2 O 3 , Japanese Patent Laid-Open Nos. 59-9171 and 61-52374 are disclosed. Methods disclosed in Japanese Unexamined Patent Publication No. 63-126682 and Japanese Unexamined Patent Publication No. 63-317680 have been proposed.
[0005]
However, chemical densified films also have microscopic pores and cracks when observed inside the film with an optical microscope, and most of them reach the surface of the stainless steel substrate. . In the environment where hydrogen isotopes exist, these fine pores and cracks pass through the chemically densified film and reach the stainless steel substrate. Since it permeates and flows out to the external environment, there is a drawback that it cannot be used as a hydrogen isotope permeation preventive film.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to establish a technique capable of compensating for the above-described drawbacks of a film having a composition composed of SiO 2 —Cr 2 O 3 by the conventional chemical densification method described above (chemical densification film). In particular, an effective technique for transforming into a complex oxide film having excellent hydrogen isotope permeation-preventing properties is proposed.
[0007]
In other words, to summarize and describe the idea of the present invention that has been developed to achieve such purposes,
(1) By filling the fine pores and cracks generated in the chemically densified film with fine particles of chromium oxide-amorphous inorganic material excellent in hydrogen isotope permeation prevention properties, Suppresses transmission.
[0008]
(2) The fine cracks of the chemically densified film are filled with fine particles of chromium oxide-amorphous inorganic material. In addition, the surface of the chemically densified film is made of an inorganic material composite material. By forming a thin film as well, the internal penetration of hydrogen isotopes is more reliably prevented.
[0009]
(3) With regard to the above-mentioned points, it is possible to apply a chromic acid aqueous solution and an aqueous solution containing a material that generates an amorphous inorganic substance by receiving a firing history, and heat-treat this to solidify and obtain a fine precipitate. It was found that hydrogen isotope permeation can be suppressed by using a process of filling pores and cracks.
[0010]
[Means for Solving the Problems]
As a method for realizing the above-mentioned object based on such knowledge, in the present invention, it occurs in a film (chemically densified film) having a composition composed of SiO 2 —Cr 2 O 3 by a chemical densification method. In order to suppress the intrusion of hydrogen isotopes into the fine pores and cracks, the following measures were adopted.
[0011]
(1) directly to the surface of the chemical densified coating, an aqueous solution containing a material that generates an amorphous inorganic substance by sintering the coating, and immersion spray or chemical densification coating in the aqueous solution A method of firing after raising.
[0012]
(2) In a chemically densified film, an aqueous solution containing a material that generates an amorphous inorganic substance by receiving a firing history is directly applied to the surface, sprayed, or immersed in this aqueous solution. after raising Te, by repeating a plurality of times a process of firing, as well as Hama charging the amorphous inorganic material into fine pores and cracks inside the said chemical繊密of film, the amorphous inorganic material surplus A method of thinly coating the outermost surface of a chemically densified film.
[0013]
That is, the gist of the present invention is listed and described as follows.
(1) The present invention is a composite formed by providing a chemically densified film on the surface of a metal material steel substrate such as stainless steel and filling an amorphous inorganic substance in pores or cracks of the film. It is an oxide film covering member.
[0014]
(2) Further, the present invention provides a chemically densified film on the surface of a metal material base material such as stainless steel, fills pores or cracks in the film with an amorphous inorganic substance, and It is a complex oxide film covering member obtained by forming an amorphous inorganic substance layer on the surface.
[0015]
(3) As the above-mentioned amorphous inorganic material filler in the present invention, an aqueous solution containing a material that generates an amorphous inorganic substance by sintering the coating, after immersed into a spray or in the aqueous solution, It is produced by heating and baking, and preferably contains mainly silicate glass, borosilicate glass, or phosphate glass.
[0016]
(4) Next, the member according to the present invention is provided with a chemically densified film on the surface of a metal material base material such as stainless steel, and the surface of the film is subjected to a firing history to thereby form an amorphous inorganic substance. Applying, spraying, or immersing the chemical densified film in this aqueous solution, followed by heating and baking, an amorphous inorganic substance in the pores or cracks of the chemically densified film Or by forming a composite oxide film for preventing hydrogen isotope permeation,
(5) A chemical densified film is provided on the surface of a metal material substrate such as stainless steel, and an aqueous solution containing a material that generates an amorphous inorganic substance by receiving a firing history is applied to the surface of the film. By spraying or immersing the chemically densified film in this aqueous solution, followed by heating and baking, the pores and cracks of the chemically densified film are filled with the amorphous inorganic substance and at the same time the chemical densified It is produced by forming and coating the amorphous inorganic material layer on the surface of the film.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
The action mechanism of the composite oxide film excellent in hydrogen isotope permeation-preventing property of the present invention will be specifically described.
[0018]
(1) A film (chemically densified film) having a composition composed of SiO 2 —Cr 2 O 3 coated on the surface of a stainless steel substrate is formed by the chemical densification method according to the construction flow shown in FIG. To do. However, although the formed chemically densified film is very hard and has excellent wear resistance, there are fine pores and cracks in the film, and some of the openings that directly reach the substrate. There is also a crack.
[0019]
In the environment where hydrogen isotopes exist, these fine pores and cracks penetrate the chemically densified film and reach the stainless steel substrate. In other words, the hydrogen isotope permeation film flows out to the external environment and cannot be used as a hydrogen isotope permeation preventive film.
[0020]
Therefore, in the present invention, a mixture of an aqueous solution containing a material that forms an amorphous inorganic substance by receiving a firing history directly on the surface of the chemically densified film and a chromic acid aqueous solution are applied, sprayed, or chemically applied to the aqueous solution. After immersing the mechanically densified film, heating and baking are performed, so that an amorphous inorganic substance enters and fills the pores and cracks of the chemically densified film. An aqueous solution containing a material that generates an amorphous inorganic substance by receiving a firing history is an aqueous solution containing a borate compound, a silicate compound, and a phosphate compound.
[0021]
According to the experiments by the inventors, in the case of a chemically densified film obtained by applying a mixture of a borate compound aqueous solution and a chromic acid aqueous solution to a treatment such as 550 to 720 ° C., a chromic acid aqueous solution-phosphate compound aqueous solution. In the case of a chemically densified film obtained by subjecting the mixture to a treatment such as coating, when heated at a temperature of 250 to 750 ° C. for 0.5 to 2 hours, the water contained in the aqueous solution evaporates and the chromium oxide composed of fine particles As a heating residue, it was found that it was filled in the pores and cracks and formed on the surface of the chemically densified film.
[0022]
In other words, chromic acid becomes Cr 2 O 3 (chromium oxide) through an intermediate, and simultaneously existing borate compound, silicate compound, and phosphate compound aqueous solution release amorphous water to become amorphous inorganic substance. . Cr 2 O 3 deposited from the aqueous solution is extremely fine and hard, and has excellent wear resistance and corrosion resistance. The phosphate compound, borate compound, and silicate compound are all amorphous and partially glassy, and precipitate in the pores and cracks in the film and seal them. Furthermore, the adhesion between the film-constituting particles is improved.
[0023]
According to the present invention, it is considered that the formation of fine Cr 2 O 3 and the amorphous material in which the borate compound, silicate compound, and phosphate compound appear enhance the bonding of Cr 2 O 3 fine particles. It is done. These contribute to blocking the invasion pathway of the hydrogen allotrope.
[0024]
The process of applying, spraying, or immersing the treatment liquid mainly composed of chromic acid and an aqueous solution of borate compound, silicate compound, and phosphate compound is repeated several times. And the pores of the chemically densified film, and not only the Cr 2 0 3 and the amorphous inorganic substance inside the crack, but also the extra chromium oxide-amorphous inorganic compound composite layer is covered by this film. The hydrogen isotope permeation preventing property will be maintained. Table 1 shows the construction conditions of the composite oxide film for preventing hydrogen isotope permeation.
[0025]
[Table 1]
FIG. 2 shows an example of a cross-sectional structure of a composite oxide film for preventing hydrogen isotope permeation according to the present invention. Here, 1 is a stainless steel substrate, 2 is a chemically densified film, 3 is a through pore (crack) existing in the chemically densified film, and 4 is filled in the pore part, that is, the crack.
[0027]
【Example】
Example 1
In this example, a chemically densified film applied on the surface of a SS400 steel base material and its pores and cracks were filled with a chromium oxide-amorphous inorganic composite fine particle layer and coated with a coating to prevent hydrogen isotope permeation. For the composite oxide film, the corrosion resistance of these film-coated members was measured based on a plating corrosion resistance test method (Cass test: JISH8502).
[0028]
(1) The composite oxide film for preventing hydrogen isotope permeation according to the present invention: After applying a chemically densified film on the surface of the film base (SS400 steel), a 55% chromic acid aqueous solution and a 15% boric acid aqueous solution were mixed 1: 1. Raise after immersion in an aqueous solution obtained by mixing the used was a compound oxide film (50 [mu] m) is repeated 6 times a step of performing heat treatment of 1 hour at 750 ° C..
[0029]
(2) Chemically densified film of Comparative Example: Only the above chemically densified film (50 μm) was used as it was.
(3) Cast test results: Table 2 shows the cast test results. As is clear from this result, the non-processed chemical densified film of the comparative example corrodes the carbon steel of the base material by the penetration of the aqueous solution from the environment through the cracked part of the film, and this is the chemical densified film. A large amount of red rust was observed on the surface.
[0030]
On the other hand, the generation of red rust was not observed at all in the composite film for preventing hydrogen isotope permeation subjected to the treatment of the present invention. That is, it is considered that the chromium oxide-borosilicate glass composite fine particle layer was filled in the pores and cracks of the chemically densified film, so that the penetration of the aqueous solution was suppressed and the excellent corrosion resistance was exhibited.
[0031]
[Table 2]
(Example 2)
In this example, the deuterium permeability of the composite oxide film for preventing hydrogen isotope permeation obtained by performing the treatment according to the present invention was investigated.
[0033]
(1) Composite oxide film for preventing hydrogen isotope permeation according to the present invention: film base material (SUS316L: after applying a chemical densified film on the inner surface of a pipe having an outer diameter of 30.0 mm and a thickness of 0.9 mm, CrO 3 Then, it was dipped in an aqueous solution containing phosphoric acid as a main component, pulled up, and subjected to heat treatment at 450 ° C. for 1 hour six times to obtain a composite oxide film (50 μm).
[0034]
(2) Film of Comparative Example: As the film of the comparative example, only the untreated chemical densified film was used.
(3) Deuterium permeation test: Using the deuterium permeation test test device shown in FIG. 3, measure the deuterium permeation amount at 600 ° C. Of deuterium permeation amount).
[0035]
(4) Deuterium permeation test results: The test results are summarized in FIG. 4 and Table 3. The chemically densified film had a deuterium permeation reduction ratio of about 1/50 at 600 ° C., whereas the hydrogen oxide isotope permeation prevention composite oxide film had a deuterium permeation reduction ratio of about 1 at 600 ° C. / 1000.
[0036]
[Table 3]
【Effect of the invention】
As described above, according to the present invention, a chemically densified film having pores or cracks formed on the surface of a member having a chemically densified film is treated with an aqueous chromic acid solution and an amorphous inorganic substance. After application of an aqueous solution containing a material that generates a substance, heating is performed to generate chromium oxide-amorphous inorganic substance composite fine particles, which are filled in the pores and cracks, and further, By covering the surface of the film with a certain thickness, it is possible to improve the hydrogen isotope permeation-preventing property of a chemically densified film that has been considered to be insufficient. As a result, the field of application of the composite oxide film for preventing hydrogen isotope permeation to mechanical structures or members that require gas permeation prevention is expanded.
[Brief description of the drawings]
FIG. 1 is a construction flowchart for forming a chemically densified film on the surface of a stainless steel substrate.
[Fig. 2] Using a treatment liquid mainly composed of an aqueous solution containing chromic acid and a material that generates an amorphous inorganic substance by firing on a chemically densified film formed on the surface of a stainless steel substrate. It is a fragmentary sectional view of the composite oxide film covering member for hydrogen isotope permeation prevention which formed chromium oxide-amorphous inorganic substance composite film.
[Explanation of symbols]
1: stainless steel substrate,
2: Chemically densified film,
3: Through pores (cracks) present in the chemically densified film
4: Chromium oxide-amorphous inorganic material composite fine particles filled in the pores, that is, cracks 5: Chromium oxide-amorphous inorganic material composite layer covering the surface of the chemically densified film FIG. 3 shows a test tube made of SUS316L base material pipe coated on the inner surface. Argon degas containing a predetermined concentration of deuterium is allowed to flow inside the test tube. It is the partial schematic of the deuterium permeation | transmission test apparatus which leads to a mass spectrometer by this and measures a deuterium density | concentration.
[Explanation of symbols]
1: SUS316L base tube (inner diameter: 30.0 mm × thickness: 0.9 mm), test tube with inner surface coated with a thickness of 50 μm 2: Hastelloy- × base material tube (inner diameter: 50.0 mm × thickness: 3.0 mm) Measuring
5: Deuterium permeation through test tube 6: Deuterium-containing argon gas supply line 7 into the test tube 7: Deuterium-containing argon
Claims (6)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001058253A JP4863181B2 (en) | 2001-03-02 | 2001-03-02 | Composite oxide film covering member for preventing hydrogen isotope permeation and method for producing the same |
| EP20020090080 EP1236813B1 (en) | 2001-03-02 | 2002-02-28 | Members coated with composite oxide coatings for preventing the permeation of hydrogen isotopes and a process for producing such members |
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|---|---|---|---|
| JP2001058253A JP4863181B2 (en) | 2001-03-02 | 2001-03-02 | Composite oxide film covering member for preventing hydrogen isotope permeation and method for producing the same |
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| JP2002256450A JP2002256450A (en) | 2002-09-11 |
| JP4863181B2 true JP4863181B2 (en) | 2012-01-25 |
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| KR101518618B1 (en) * | 2013-11-27 | 2015-05-13 | 주식회사 포스코 | The coating method of improving adhesion for steel sheet and steel sheet treated with tem |
| CN107217281B (en) * | 2017-05-26 | 2018-10-16 | 华中科技大学 | Compound resistance tritium coating of one kind and preparation method thereof |
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| US3956531A (en) * | 1967-06-01 | 1976-05-11 | Kaman Sciences Corporation | Chromium oxide densification, bonding, hardening and strengthening of bodies having interconnected porosity |
| US5820976A (en) * | 1988-12-05 | 1998-10-13 | Adiabatics, Inc. | Thin insulative ceramic coating and process |
| US5360634A (en) * | 1988-12-05 | 1994-11-01 | Adiabatics, Inc. | Composition and methods for densifying refractory oxide coatings |
| JPH02194183A (en) * | 1989-01-20 | 1990-07-31 | Japan Atom Energy Res Inst | Ceramic-coated zirconium alloy article and its production |
| JP3220012B2 (en) * | 1996-06-27 | 2001-10-22 | トーカロ株式会社 | Hard plating film coated member and method of manufacturing the same |
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| JP2002256450A (en) | 2002-09-11 |
| EP1236813A2 (en) | 2002-09-04 |
| EP1236813A3 (en) | 2003-08-13 |
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