JPS6141758A - Covering method of metallic material by spraying and heat treatment - Google Patents
Covering method of metallic material by spraying and heat treatmentInfo
- Publication number
- JPS6141758A JPS6141758A JP16209384A JP16209384A JPS6141758A JP S6141758 A JPS6141758 A JP S6141758A JP 16209384 A JP16209384 A JP 16209384A JP 16209384 A JP16209384 A JP 16209384A JP S6141758 A JPS6141758 A JP S6141758A
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- JP
- Japan
- Prior art keywords
- heat treatment
- sprayed
- gas
- corrosion resistance
- spraying
- Prior art date
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Classifications
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は溶射と熱処理との組み合わせにより金属材料の
表面に緻密な被覆を形成させ、例えば防食性を付与する
ための方法１ζ関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method 1ζ for forming a dense coating on the surface of a metal material by a combination of thermal spraying and heat treatment to impart, for example, anti-corrosion properties.
従来の技術
溶射による紡食ｙ！法にはＩ！”食の４清からみて次の
二つの方法がある。一つは１ル乏ニウムや亜鉛等の卑な
金属を溶射材として用い、その犠牲陽極作用により電気
化学的に素材を防食する方法であす、他の一つはクロム
、ステンレス鋼等の高耐食性金属、合金あるいはセラミ
ックスを溶射材として用い、溶射皮膜のＩ［８！遮断の
効果により素材を防食する方法である。Spinning by conventional technology thermal spraying! I for the law! ``From the perspective of the four principles of food, there are the following two methods.One is to use base metals such as 1-l-oligoniium or zinc as a thermal spraying material and electrochemically prevent corrosion of the material by its sacrificial anode action. Another method is to use highly corrosion-resistant metals such as chromium and stainless steel, alloys, or ceramics as a thermal spraying material, and use the I[8! blocking effect of the thermal spray coating to prevent corrosion of the material.
水溶液環境における溶射による防食方法としては、前者
によるものが一般的であり、広く用いられている。しか
し、この方法では、溶射皮膜を構成する金属覆が時間の
経過に伴って溶出したり、溶射皮膜表面が腐食生成物に
よって汚染され著しく美観を損なうことがあり、また酸
性溶液等の厳て素材の表面まで達する開孔がしばしば存
在し、その結果、環境遮断能力が劣るため、溶射後、二
次処理により環境遮断能力を高めろ必要がある。The former method is common and widely used as a corrosion prevention method by thermal spraying in an aqueous solution environment. However, with this method, the metal covering that makes up the sprayed coating may dissolve over time, or the surface of the sprayed coating may be contaminated with corrosion products, significantly impairing its aesthetic appearance. There are often open pores that reach the surface of the coating, resulting in poor environmental barrier performance, so it is necessary to improve the environmental barrier capability through secondary treatment after thermal spraying.
また、溶射皮膜自体が、バルクの金属に比べて活性化さ
れているため、その腐食活性を低下させる（１９８１）
）等が開発されている。これらの処理により溶射皮膜の
腐食活性は低下する。しかし、食塩水や硫酸等の厳しい
環境においては、溶射皮ＩＩ＋！１体の耐食性はステン
レス網等に比べて低く、水ａｌｌ！環境における防食方
法として用いられるには至っていない。In addition, since the thermal spray coating itself is more activated than the bulk metal, it reduces its corrosion activity (1981).
) etc. have been developed. These treatments reduce the corrosion activity of the sprayed coating. However, in harsh environments such as salt water and sulfuric acid, Thermal Sprayed Skin II+! The corrosion resistance of one piece is lower than that of stainless steel mesh, etc., and water all! It has not yet been used as a corrosion prevention method in the environment.
発明が解決しようとするｌ１１理点
本発明者らは優れた耐食性を示す表面処理方法を開発す
るためにｓｕｉｇＦ究を重ねた結果、酸化時の体積膨張
が著しいり四ムを溶射しその皮膜を酸化性ＩＦＩＩ！気
で熱処理することによりその目的を達成しうろことを見
出し、この知見に基づいて本発間履点を解決するための
手段
すなわち、本発明は、酸化時の体Ｗ！Ｗ張が著し提供す
るものである。11 Points to be Solved by the Invention The present inventors have conducted extensive research to develop a surface treatment method that exhibits excellent corrosion resistance.As a result, the volumetric expansion during oxidation was significant, and the resulting film was thermally sprayed. Oxidizing IFII! It has been discovered that the object can be achieved by heat treatment with air, and based on this knowledge, the present invention provides a means to solve the problem of the oxidation of the body during oxidation. Authored and provided by W. Zhang.
クロムの溶射皮膜は、醜素含有ガス中で高１で熱処理す
ることにより、溶射皮膜の表面及びその内部で酸化を受
け、体ｌＩ膨張がおこり、溶射皮膜の空孔率を減少させ
るため、溶射皮膜の防食性が向上する。また、溶射皮膜
は活性化されているため、それ自体の耐食性ばバルクの
金属に比べて低いが、高１１ａ化することにより溶射皮
膜が安定化されろため、ｉ１食性も向上する。Thermal sprayed chromium coatings undergo oxidation on the surface and inside of the sprayed coating by heat treatment at high temperature in a gas containing ugliness, causing body expansion and reducing the porosity of the sprayed coating. The corrosion resistance of the film is improved. Furthermore, since the thermal sprayed coating is activated, its own corrosion resistance is lower than that of bulk metal, but since the thermal sprayed coating is stabilized by increasing the 11a height, the i1 corrosion resistance is also improved.
したがって、溶射材として、酸化の原体積膨彊が著しい
クロム粉末を用い、それを溶射した後高ａＷｉ化させる
ことによって、素材の耐食性は向上するものと考えられ
る。Therefore, it is thought that the corrosion resistance of the material can be improved by using chromium powder, which has a remarkable original volumetric expansion due to oxidation, as a thermal spraying material and increasing the aWi after thermal spraying.
耐食性の評価は０．５Ｍ硫ｙａＷＩ液中及び０．５Ｍ食
塩水中における電位ステップ法による１ノ一ド分極曲線
の測定及び塩水噴震試験によって打った。０．５Ｍ硫酸
ＷＩ液は耐全面前食性の評価を行要する時間の長短によ
って耐食性の評価を行った。Corrosion resistance was evaluated by measuring one-node polarization curves using the potential step method in 0.5M sulfur yaWI solution and 0.5M saline, and by salt water jet tests. The corrosion resistance of the 0.5M sulfuric acid WI solution was evaluated based on the length of time required to evaluate the overall pre-corrosion resistance.
溶射溶融粒子は溶射時には酸化を受けないことが好まし
く、このため本発明におけろ溶射法としては不活性ガス
を１−クガス及び粉末供給ガスとして用いるプラズマ１
溶射法が適しているが、アーク溶射法並びにレーザー溶
射法によっても可能である。また、熱処理は通常、酸化
性芥囲気中で、：電熱炉や赤外線加熱炉等の炉を月いて
行うが、ガニ°−バーナーやプラズマトーチ等を泪いて
も行うこ１′
とができる。It is preferable that the thermally sprayed molten particles do not undergo oxidation during thermal spraying, and for this reason, in the thermal spraying method of the present invention, plasma 1 is used in which an inert gas is used as a gas and a powder supply gas.
Thermal spraying is suitable, but arc spraying and laser spraying are also possible. The heat treatment is usually carried out in an oxidizing atmosphere using a furnace such as an electric heating furnace or an infrared heating furnace, but it can also be carried out using a crab burner, a plasma torch, or the like.
本発明におけろ酸化性雰ｌｆ！１９にとしては、酸素含
有率が１〜３０％程度の酸素含有ガスを月いることがで
きるが、通常は空気が使用される。熱処理濃度としては
、６００〜１３００℃が用いられ、６００℃未満では十
分な酸化を行うことができなで異なるが、５分から３時
間のｌ１ＩＩ１１である。溶射皮膜は５５μｍ以上にす
ることが望ましく、熱処５；よ＆Ｉ化化上；；さシτ溶
射皮門の１１以上となるように行うのが望ましい。In the present invention, an oxidizing atmosphere! Although an oxygen-containing gas having an oxygen content of about 1 to 30% can be used as the gas, air is usually used. The heat treatment concentration used is 600 to 1300°C, and is different because sufficient oxidation cannot be performed below 600°C, but it is 11II11 for 5 minutes to 3 hours. It is desirable that the thermal spray coating has a thickness of 55 μm or more, and the heat treatment is preferably performed so that the thickness of the thermal spray coating is 11 or more.
本発明の方法においては、溶射と熱処理を別々の工程で
行ってもよいし、また一つの工程で行ってもよい。一つ
の工程で行う場合では、プラズマ−熱で酸化される。In the method of the present invention, thermal spraying and heat treatment may be performed in separate steps or in one step. In the case of one-step oxidation, plasma-thermal oxidation is performed.
発明の効果
本発明の方法によれば、耐食性に優れた緻密な被覆を容
易に形成することができ、しかも溶射と熱処理とを一つ
の工程で行う実施態様に従えば、熱処理炉を使用しなく
ても酸化処理が行える。この場合には、任意の形状の素
材に対して防食処理を行うことができ、かつ作業効率に
も優れているなめ、利用範囲は大幅に拡大され、１巣的
に極めて望ましいものといえる。Effects of the Invention According to the method of the present invention, a dense coating with excellent corrosion resistance can be easily formed, and if an embodiment is followed in which thermal spraying and heat treatment are performed in one process, a heat treatment furnace is not required. Oxidation treatment can be performed even if the In this case, it is possible to perform anti-corrosion treatment on materials of any shape, and the work efficiency is also excellent, so the scope of use is greatly expanded and it can be said to be extremely desirable.
実施例 次に実施例により本発明をさらに詳細に説明する。Example Next, the present invention will be explained in more detail with reference to Examples.
例１
低合金鋼にブラスト処理を行った後、アルゴンく□
１．を含む窒素気流中で１３００℃で５分間の熱処理、
：
を行った。耐食性の評価は電位ステップ法により：：：
行った。すなわち、脱酸素を行った２５℃の０゜５Ｍ硫
酸ＩＩＦ液中において、５分毎にＯ，ＩＶずつ電位を増
加させながら１ノ一ド分極曲尊を測定した。溶射後熱処
理した低合金鋼の不働態保持ｆ４流密度は、約１μＡ／
ｃｊと非常に小さく、鉄鋼またはクロムにみられるよう
な活性態の存在は認められず、耐食性が非常に優れてい
るといえる。Example 1 After blasting low alloy steel, use argon gas □ 1. Heat treatment at 1300°C for 5 minutes in a nitrogen stream containing
: I did. Corrosion resistance was evaluated by the potential step method. That is, in a deoxidized 0.5 M sulfuric acid IIF solution at 25.degree. C., one node polarization curve was measured while increasing the potential by O and IV every 5 minutes. The passivity-retaining f4 flow density of low-alloy steel heat-treated after thermal spraying is approximately 1 μA/
cj, which is extremely small, and the existence of active states found in steel or chromium is not observed, so it can be said that the corrosion resistance is extremely excellent.
比較例１
例１に示した低合金鋼を、溶射−熱処理を全く行わない
まま、例１と全く同一の手順・条件で耐食性の評価を行
った。当試料では、活性態電位域で０．２Ａ／ｃｊ、不
働態電位域では、０．２ｍＡ／−の電流密度を示した。Comparative Example 1 Corrosion resistance of the low alloy steel shown in Example 1 was evaluated under exactly the same procedure and conditions as in Example 1, without any thermal spraying or heat treatment. This sample showed a current density of 0.2 A/cj in the active potential range and 0.2 mA/- in the passive potential range.
これは、例１の溶射−熱処理低合金鋼に比べて、活性態
電位域で約５桁、不働態電位域で約２桁大きな値であフ
な。このこ゛、≠
“−た。当試料では、−０，ｇＶ付近で０．ＯＩＡ／−
のピーク電流密度を有する活性態が認められ、−０，３
Ｖより責な電位では電流密度は約１＋ｏＡ／ｄであつた
。耐食性評価試験後の溶射皮膜は剥離しやすく、溶射皮
膜の下地の低合金鋼に？Ｉａの鯖の発生が目？１ＬＩｌ
ｌ察により認められた。This is approximately 5 orders of magnitude larger in the active state potential range and about 2 orders of magnitude larger in the passive state potential range than the thermally sprayed and heat treated low alloy steel of Example 1. This means that ≠ "-.In this sample, 0.OIA/- at around -0,gV
An active state with a peak current density of −0,3
At potentials greater than V, the current density was approximately 1+oA/d. Thermal sprayed coating after corrosion resistance evaluation test is easy to peel off, and does it affect the low alloy steel underlying the thermal sprayed coating? The appearance of mackerel in Ia is the eye? 1LIl
It was confirmed by inspection.
例２
例１と同一の手順・条件でクロムの溶射及び熱処理を行
った低合金鋼に対して、脱酸素を行った１ 。Example 2 Low alloy steel that had been thermally sprayed with chromium and heat treated using the same procedure and conditions as Example 1 was deoxidized.
２５℃、０．５Ｍ食塩水中で電位ステップ法により５分
毎に０．０５〜Ｏ，ＩＶずつ電位を増加させて耐孔食性
試験を行った。A pitting corrosion resistance test was carried out at 25° C. in 0.5 M saline by increasing the potential by 0.05 to 0.0 IV every 5 minutes using the potential step method.
自然浸Ｉｊｌｉｉ位は約Ｏ，ＯＶであり、目視観察によ
れば孔食の発生は認められず、また１μＡ／ｃｊという
非常に低い不働態保持ｆ４流密度を示した。The natural immersion level Ijlii was approximately O, OV, no pitting corrosion was observed by visual observation, and a very low passivation f4 flow density of 1 μA/cj was exhibited.
わないまま、例２と全く同一の手順・条件で耐食性の評
価を行った。当試料の自然浸慣電位は約−〇、５ｖであ
り、電位が増加するのに伴ｔ％Ｆ！ ！！ ９度は急激
に増加した。耐食性評価試験後のａｙ：ｉ蜆観察により
、試料表面に微小な食孔の発生が認められた。このこと
は溶射−熱処理を行わない低合金鋼の耐食性が非常に劣
っていることを示す。Corrosion resistance was evaluated under exactly the same procedure and conditions as in Example 2, without any modification. The natural immersion potential of this sample is approximately -0.5V, and as the potential increases, t%F! ! ! 9 degrees increased rapidly. Ay:I observation after the corrosion resistance evaluation test revealed the occurrence of minute pits on the sample surface. This shows that the corrosion resistance of low alloy steel without thermal spraying and heat treatment is very poor.
例８
例１と同一の手順・条件でクロム溶射及び熱処理を行ま
た低合金鋼に対して、塩水噴霧試験による耐食性の評価
を行った。塩水噴霧試験は、Ｊ１５２！！７１に準じて
行った。すなわち、３６℃の恒温槽中に５％の食塩水を
噴霧したが、その噴霧量は８０−当たり１〜２ ｗｄ
／ ｈ ｒであった。Example 8 Chromium spraying and heat treatment were carried out under the same procedure and conditions as in Example 1, and the corrosion resistance of the low alloy steel was evaluated by a salt spray test. Salt spray test is J152! ! 71. That is, 5% saline was sprayed into a constant temperature bath at 36°C, and the amount of spray was 1 to 2 wd per 80°C.
/hr.
１０８０時間の塩水噴霧試験後、目視観察をした結果、
当試料の表面には錆の発生は全く認められなかった。As a result of visual observation after 1080 hours of salt spray test,
No rust was observed on the surface of this sample.
比較例３
例１に示した低合金鋼を、溶射−熱処理を全く行わない
で、例３と全（同一の手順・条件で＃１食性の評価を行
った。３０分間の塩水噴霧試験の結・”４３と同一の手
順・条件で耐食性の評価を行った。Comparative Example 3 The low-alloy steel shown in Example 1 was evaluated for #1 corrosion under the same procedure and conditions as Example 3 without any thermal spraying or heat treatment.・Corrosion resistance was evaluated using the same procedure and conditions as “43.”
４時間の塩水噴霧試験後には当試料表面に点状の謂の発
生が認められた。After the 4-hour salt water spray test, so-called dots were observed on the surface of the sample.
例４
空気気流中９００℃で５分間、熱処理を行った他は、例
１と同一の手順・条件で溶射及び熱処理を行ったクロム
溶射−熱処理低合金鋼に対して、例１と全く同一の手順
・条件で耐食性の評価を行った。Example 4 The same method as in Example 1 was applied to chromium sprayed-heat treated low alloy steel which was thermally sprayed and heat treated under the same procedure and conditions as in Example 1, except that it was heat treated at 900°C for 5 minutes in an air stream. Corrosion resistance was evaluated using different procedures and conditions.
当試料では、不働態保持電流密度は約１０μＡ／ｄと非
常に小さく、１ノ一ド分極曲林には活性態は認められな
かった。このことは、比較例１に示した溶射及び熱処理
を行わない低合金鋼と比較して当試料の耐食性が著しく
高いことを示してｔする。In this sample, the passive state holding current density was very small, about 10 μA/d, and no active state was observed in the one-node polarized curved forest. This indicates that the corrosion resistance of this sample is significantly higher than that of the low alloy steel shown in Comparative Example 1 which is not subjected to thermal spraying and heat treatment.
例５ □鴨□Ｗｆｉｔ、工、。１−一同。ゆ４．よゆ。Example 5 □Duck□Wfit, Engineering. 1-Everyone. Yu4. Yoyu.
１≦ｊ１１
− ゛・耐食性の評価を行い、熱処理濃度の耐食性：ζ
及１を一子影響ｅ贋べた。ＳＯＯ及び６００℃で３時間
熱処理したクロム溶射−熱処理低合金鋼の−０，２〜０
０ＳＶの電位範囲におけるｔ４流密度は、それぞれ１ｓ
ａＡ／ｃｊ、３０μ人／−であった。このなめ工業的に
意味のある熱処理温度はｓｏｏ′ｃ息上であるといえる
。。1≦j11 − ゛・Evaluate corrosion resistance, and calculate corrosion resistance of heat treatment concentration: ζ
1 was forged under the influence of Kazuko. Chromium spray heat treated at SOO and 600℃ for 3 hours -0,2~0 on heat treated low alloy steel
The t4 flow density in the potential range of 0SV is 1s, respectively.
aA/cj, 30μ people/-. It can be said that this heat treatment temperature, which is meaningful in the licking industry, is above soo'c. .
比較例４
厚さが異なる他は例１と同一の手順・条件でり一同−の
手順・条件で耐食性の評価を行うな、その結果、０，６
Ｖにおける電ｍ密度は皮膜の厚さが増加するに従って一
様に減少することがわかった。Comparative Example 4 Corrosion resistance was evaluated using the same procedure and conditions as Example 1 except for the difference in thickness.
It was found that the electric m density at V decreases uniformly as the film thickness increases.
また、皮膜厚さが４０．５５．８５及び１７０μｍの試
料のａｍ密度は、それぞれ７０，１０．１書考例
通常使用されている耐食性材料である５ＵＳ３０４ステ
ンレス鋼に対して例１と全く同一の手順・条件で硫酸溶
液中における耐食性の評価を行った。In addition, the am densities of samples with film thicknesses of 40, 55, 85 and 170 μm are exactly the same as in Example 1 for 5US304 stainless steel, which is a commonly used corrosion-resistant material. Corrosion resistance in sulfuric acid solution was evaluated according to the procedure and conditions.
当試料−Ｃ’Ｌｔ、−ｏ、ｉｖ付近１４０．１ｍＡ／ｃ
ｊのピーク電流密度を有する活性態が認められ、０゜２
■より責な電位では、不働態保持電流密度は約が０．６
ｖ付近に食孔発生に伴う電流密度の急激な増加が認めら
れた。このことば、例１に記した溶射−熱処理低合金鋼
は５Ｕ３３０４ステンレス鋼より耐食性が優れているこ
とを示す。This sample -C'Lt, -o, iv vicinity 140.1 mA/c
An active state with a peak current density of 0°2 was observed.
■At more aggressive potentials, the passivation current density is approximately 0.6
A rapid increase in current density was observed near v due to the occurrence of pitting. This statement indicates that the sprayed and heat treated low alloy steel described in Example 1 has superior corrosion resistance to 5U3304 stainless steel.
Claims (1)
ス中で熱処理を行うことを特徴とする金属材料の被覆方
法A method for coating metal materials, which comprises spraying chromium powder onto the surface of the metal material and then heat-treating it in an oxygen-containing gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16209384A JPS6141758A (en) | 1984-07-31 | 1984-07-31 | Covering method of metallic material by spraying and heat treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16209384A JPS6141758A (en) | 1984-07-31 | 1984-07-31 | Covering method of metallic material by spraying and heat treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6141758A true JPS6141758A (en) | 1986-02-28 |
| JPH0348265B2 JPH0348265B2 (en) | 1991-07-23 |
Family
ID=15747937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16209384A Granted JPS6141758A (en) | 1984-07-31 | 1984-07-31 | Covering method of metallic material by spraying and heat treatment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6141758A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996027694A1 (en) * | 1995-03-08 | 1996-09-12 | Tocalo Co., Ltd. | Member having composite coating and process for producing the same |
| US20130302639A1 (en) * | 2012-05-10 | 2013-11-14 | Korea Hydro And Nuclear Power Co., Ltd. | Zirconium alloy for improving resistance to oxidation at very high temperature and fabrication method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3911730B2 (en) * | 1995-09-20 | 2007-05-09 | 株式会社日立プラントテクノロジー | Pump and manufacturing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4510081Y1 (en) * | 1966-08-24 | 1970-05-11 | ||
| JPS5198637A (en) * | 1975-02-26 | 1976-08-31 | ||
| JPS57114680A (en) * | 1980-08-16 | 1982-07-16 | Kernforschungsanlage Juelich | Porous oxide diaphragm for alkali electrolysis and production and use thereof |
-
1984
- 1984-07-31 JP JP16209384A patent/JPS6141758A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4510081Y1 (en) * | 1966-08-24 | 1970-05-11 | ||
| JPS5198637A (en) * | 1975-02-26 | 1976-08-31 | ||
| JPS57114680A (en) * | 1980-08-16 | 1982-07-16 | Kernforschungsanlage Juelich | Porous oxide diaphragm for alkali electrolysis and production and use thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996027694A1 (en) * | 1995-03-08 | 1996-09-12 | Tocalo Co., Ltd. | Member having composite coating and process for producing the same |
| GB2313847A (en) * | 1995-03-08 | 1997-12-10 | Tocalo Co Limited | Member having composite coating and process for producing the same |
| GB2313847B (en) * | 1995-03-08 | 1998-12-09 | Tocalo Co Ltd | Member having composite coating and process for producing the same |
| US6129994A (en) * | 1995-03-08 | 2000-10-10 | Tocalo Co., Ltd. | Member having composite coating and process for producing the same |
| US20130302639A1 (en) * | 2012-05-10 | 2013-11-14 | Korea Hydro And Nuclear Power Co., Ltd. | Zirconium alloy for improving resistance to oxidation at very high temperature and fabrication method thereof |
| US9421740B2 (en) * | 2012-05-10 | 2016-08-23 | Korea Atomic Energy Research Institute | Zirconium alloy for improving resistance to oxidation at very high temperature and fabrication method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0348265B2 (en) | 1991-07-23 |
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