JP2002069590A - High corrosion resistant clad steel - Google Patents

High corrosion resistant clad steel

Info

Publication number
JP2002069590A
JP2002069590A JP2000265046A JP2000265046A JP2002069590A JP 2002069590 A JP2002069590 A JP 2002069590A JP 2000265046 A JP2000265046 A JP 2000265046A JP 2000265046 A JP2000265046 A JP 2000265046A JP 2002069590 A JP2002069590 A JP 2002069590A
Authority
JP
Japan
Prior art keywords
less
steel
corrosion
corrosion resistance
clad steel
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
Application number
JP2000265046A
Other languages
Japanese (ja)
Inventor
Hideto Kimura
秀途 木村
Ryuichiro Ebara
隆一郎 江原
Masahiro Sato
正大 佐藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Engineering Corp
Original Assignee
NKK Corp
Nippon Kokan Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NKK Corp, Nippon Kokan Ltd filed Critical NKK Corp
Priority to JP2000265046A priority Critical patent/JP2002069590A/en
Publication of JP2002069590A publication Critical patent/JP2002069590A/en
Pending legal-status Critical Current

Links

Abstract

PROBLEM TO BE SOLVED: To provide a material having excellent corrosion resistance, mechanical properties and economical efficiency to e.g. an oxidative decomposition treatment plant using high-temperature high-pressure fluids. SOLUTION: In the high corrosion resistant clad steel, carbon steel is used as a base material and stainless steel which has a composition consisting of <=0.02% C, <=1.0% Si, <=2.0% Mn, 20-27% Cr, 17-45% of (Ni+Co), 2-5% of (Mo+1/2W), 0.01-0.3% N, 0.1-3% Cu and the balance essentially iron and satisfying relation Cr+Ni+Co+2Cu+4.1(Mo+1/2W)+24N>=62 is used as a cladding material. Further, either or both of <=0.01% B and <=0.5% Zr, one or more kinds among <=0.02% Cr, <=0.1% Al, <=0.04% La, <=0.04% Ce and <=0.1% Y, or one or more kinds among <=0.5% Ti, <=0.8% Nb, <=1.6% Ta and <=1% V can be added to the cladding material.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】この発明は、有毒廃棄物の処
理も可能な超臨界水・亜臨界水酸化プラント等における
高温高圧流体利用技術関連の装置材料に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus material related to a technology for using high-temperature and high-pressure fluid in a supercritical water / subcritical water oxidation plant capable of treating toxic waste.

【0002】[0002]

【従来の技術】全社会的に環境保全への関心が高まる
中、含塩素系有機化合物に代表される難分解性の有毒物
質の処理が今後の大きな問題としてクローズアップされ
ている。これらの分解処理の決め手となる技術として昨
今注目されているのが、高温高圧流体を利用した酸化処
理技術である。
2. Description of the Related Art With the growing interest in environmental conservation throughout the society, treatment of hardly decomposable toxic substances represented by chlorine-containing organic compounds has been highlighted as a major problem in the future. Recently, an oxidation treatment technique using a high-temperature and high-pressure fluid has attracted attention as a decisive technique for these decomposition treatments.

【0003】物質が所定の温度・圧力条件を超えると、
液体と気体が渾然一体となった超臨界流体状態となり、
その手前の亜臨界流体状態も含めて、物質の化学反応に
極めて活性な反応場を提供する。このような状態におい
て、水は非常に安定かつ安全な物質として、超臨界およ
び亜臨界の状態での廃棄物処理への応用が種々試みられ
ており、有害有機化合物の酸化分解の媒体として、現在
最も広く用いられているものの一つである。
When a substance exceeds predetermined temperature and pressure conditions,
A supercritical fluid state where liquid and gas are united together,
It provides a very active reaction field for chemical reactions of substances, including the subcritical fluid state before it. In such a state, water is a very stable and safe substance, and various applications to waste treatment in supercritical and subcritical states have been attempted.Currently, as a medium for oxidative decomposition of harmful organic compounds, water is used as a medium. It is one of the most widely used.

【0004】超臨界水による酸化分解法は、基本的技術
自体はほぼ確立された状況にあるが、実用的には材料の
耐食性に課題を残している。即ち、極めて高い反応性を
有する化学反応場に接する装置材料そのものが、現状で
は腐食損傷を激しく受けている。
The oxidative decomposition method using supercritical water is in a state where the basic technology itself has been almost established, but practically leaves a problem in the corrosion resistance of the material. That is, the equipment material itself in contact with a chemical reaction field having extremely high reactivity is currently severely damaged by corrosion.

【0005】そこで、高耐食性のNi基合金が主に使用さ
れている。また、チタン酸化物および炭・窒化物、ジル
コニウムおよびアルミニウム酸化物等のセラミクス材料
も、一般に耐食性が良好であることから、一部検討され
ている。
[0005] Therefore, Ni-base alloys having high corrosion resistance are mainly used. In addition, ceramic materials such as titanium oxide and carbon / nitride, zirconium and aluminum oxide are generally studied in part because of their good corrosion resistance.

【0006】その他、一般にクリープ強度、耐水蒸気酸
化特性、及び耐高温腐食性が必要とされるボイラ等に
は、オーステナイト系耐熱鋼が使用されてきている。特
にボイラは、使用環境が苛酷化しつつあり、十分な耐食
性と優れた高温強度を目的として、オーステナイト系耐
熱合金が開発されている。
[0006] In addition, austenitic heat-resistant steel is generally used for boilers and the like that require creep strength, steam oxidation resistance, and high-temperature corrosion resistance. In particular, the operating environment of boilers is becoming severer, and heat-resistant austenitic alloys have been developed for the purpose of sufficient corrosion resistance and excellent high-temperature strength.

【0007】例えば、特開平6-322488号公報には、質量%
で、C:0.02%未満、Si:1.5%以下(実施例では0.47〜0.50
%)、Mn:0.3〜1.5%、P:0.02%以下、S:0.005%以下、Cr:18〜2
6%、Ni:20〜40%、W:0.5〜10.0%、Nb:0.05〜0.4%(実施例で
は0.18〜0.23%)、Ti:0.01〜0.2%、B:0.003〜0.008%、N:0.
05〜0.3%(実施例では0.008〜0.147%)を含有し、さらに
必要に応じて、Mo:0.5〜2.0%および/またはMg:0.001〜0.
05%、Ca:0.001〜0.05%、希土類元素:0.001〜0.15%のうち1
種または2種以上を含有するオーステナイト系耐熱合金
が提案されている。
For example, JP-A-6-322488 discloses that
In, C: less than 0.02%, Si: 1.5% or less (0.47 to 0.50
%), Mn: 0.3-1.5%, P: 0.02% or less, S: 0.005% or less, Cr: 18-2
6%, Ni: 20 to 40%, W: 0.5 to 10.0%, Nb: 0.05 to 0.4% (0.18 to 0.23% in the example), Ti: 0.01 to 0.2%, B: 0.003 to 0.008%, N: 0 .
0.05-0.3% (0.008-0.147% in the examples), and further, if necessary, Mo: 0.5-2.0% and / or Mg: 0.001-0.
05%, Ca: 0.001-0.05%, Rare earth element: 0.001-0.15% 1
Austenitic heat-resistant alloys containing one or more species have been proposed.

【0008】特開2000-129403号公報には、C:0.01〜0.2
0%(好ましくは0.035〜0.15%), Si:3.0%以下(好まし
くは0.5〜2.0%),Mn:0.01〜3.0%,Ni:15.0〜40.0%, Cr:
15.0〜30.0%,Mo:0.01〜1.0%,W:2.0〜8.0%,Nb:0.05〜0.8
%,Ti:0.2%以下,B:0.006%以下,N:0.05〜0.25% (好まし
くは0.07〜0.02%)を含有し、W/Moが2以上及びFe20〜55%
を有すること、更にTa0.01〜0.5% ,Zr0.001〜0.2%,Hf0.0
01〜0.2%の1種以上を含有するオーステナイト系耐熱合
金とそれを用いたボイラ用過熱管が提案されている。
[0008] JP-A-2000-129403 discloses that C: 0.01 to 0.2
0% (preferably 0.035 to 0.15%), Si: 3.0% or less (preferably 0.5 to 2.0%), Mn: 0.01 to 3.0%, Ni: 15.0 to 40.0%, Cr:
15.0-30.0%, Mo: 0.01-1.0%, W: 2.0-8.0%, Nb: 0.05-0.8
%, Ti: 0.2% or less, B: 0.006% or less, N: 0.05 to 0.25% (preferably 0.07 to 0.02%), W / Mo is 2 or more and Fe 20 to 55%
Having, in addition, Ta0.01-0.5%, Zr0.001-0.2%, Hf0.0
Austenitic heat-resistant alloys containing at least one of 01 to 0.2% and superheated tubes for boilers using the same have been proposed.

【0009】[0009]

【発明が解決しようとする課題】しかし、これらの材料
には次のような問題点がある。まず、Ni基合金について
は、高価であり大規模な実用プラントを想定した場合、
材料コストは膨大なものとなり、廃棄物処理との費用対
効果等のバランスに大きな課題を抱えている。セラミク
ス材料は、一般に熱衝撃による破損が起こりやすく、実
用上の信頼性に欠けるのが現状である。
However, these materials have the following problems. First, for Ni-based alloys, assuming expensive and large-scale practical plants,
Material costs have become enormous, and there is a major problem in balancing cost-effectiveness with waste treatment. At present, ceramic materials are generally easily damaged by thermal shock and lack practical reliability.

【0010】熱衝撃等に対する信頼性の観点からは、前
述のボイラ用のオーステナイト系耐熱鋼を用いることも
考えられる。しかし、これらの材料は、主として高温腐
食環境への耐久性を狙った成分設計がなされていること
から、超臨界水および亜臨界水が遷移する酸化・腐食環
境においては、主として湿食が腐食を支配する条件での
耐食性に問題を有する。即ち、特開平6-322488号公報記
載の技術、特開2000-129403号公報記載の技術ともに、
湿食に対する耐食性を向上できるCu、Mo等の元素添加の
最適化への考慮は十分なされていないか、全く添加され
ない。即ち、湿食域での全面腐食の観点から問題であ
る。
From the viewpoint of reliability against thermal shock and the like, it is conceivable to use the above-described austenitic heat-resistant steel for boilers. However, these materials are mainly designed for durability in high-temperature corrosive environments, and therefore, in oxidizing and corrosive environments where supercritical water and subcritical water transition, wet corrosion mainly causes corrosion. Has a problem in corrosion resistance under the governing conditions. That is, both the technology described in JP-A-6-322488 and the technology described in JP-A-2000-129403,
Consideration has not been given to the optimization of the addition of elements such as Cu and Mo that can improve the corrosion resistance to wet corrosion, or they are not added at all. That is, there is a problem from the viewpoint of general corrosion in a wet erosion region.

【0011】本発明は、上記の課題を解決し、高温高圧
流体を利用した有毒廃棄物の酸化分解処理プラント等に
おける装置材料、優れた耐食性と機械的性質への高い信
頼性を有し、なおかつ経済性にも優れた高耐食クラッド
鋼を提供することを目的とする。
The present invention solves the above-mentioned problems, and has high reliability in equipment materials, excellent corrosion resistance and mechanical properties in a plant for oxidative decomposition of toxic waste using high-temperature and high-pressure fluid, and It is an object of the present invention to provide a highly corrosion-resistant clad steel excellent in economy.

【0012】[0012]

【課題を解決するための手段】上記の課題は、次の発明
により解決される。その発明は、炭素鋼を母材とし、化
学成分がmass%で、C:0.02%以下、Si:1.0 %以下、Mn:2.0
%以下、Cr:20〜27%、Ni+Co:17〜45%、Mo+1/2W:2〜5%、
N:0.01〜0.3%、Cu:0.1〜3%を含み、残部が実質的に鉄で
あり、次の式を満たすステンレス鋼を合せ材とする高耐
食クラッド鋼である。
The above object is achieved by the following invention. The invention uses carbon steel as a base material, the chemical composition is mass%, C: 0.02% or less, Si: 1.0% or less, Mn: 2.0
% Or less, Cr: 20-27%, Ni + Co: 17-45%, Mo + 1 / 2W: 2-5%,
It is a highly corrosion-resistant clad steel containing N: 0.01 to 0.3% and Cu: 0.1 to 3%, with the balance being substantially iron and using stainless steel satisfying the following formula as a composite material.

【0013】Cr+Ni+Co+2Cu+4.1(Mo+1/2W)+24N≧62 式中の元素記号は各元素のmass%を示す。Cr + Ni + Co + 2Cu + 4.1 (Mo + 1 / 2W) + 24N ≧ 62 The element symbols in the formula indicate mass% of each element.

【0014】ここでさらに、合せ材にはmass%で、下記
〜のいずれかを添加してもよい。 B:0.01%以下、Zr:0.5%以下のうち1種以上 Ca:0.02%以下、Al:0.1%以下、La:0.04%以下、Ce:0.
04%以下、Y:0.1%以下のうち1種以上 Ti:0.5%以下、Nb:0.8%以下、Ta:1.6%以下、V:1%以
下のうち1種以上 また、上記、、を適宜組合せて添加することもで
きる。
Here, any one of the following items (1) to (3) may be added to the composite material in mass%. B: 0.01% or less, Zr: 0.5% or less, at least one of Ca: 0.02% or less, Al: 0.1% or less, La: 0.04% or less, Ce: 0.
04% or less, Y: 0.1% or less, one or more of Ti: 0.5% or less, Nb: 0.8% or less, Ta: 1.6% or less, V: 1% or less Can also be added.

【0015】この発明は、超臨界水による酸化分解法に
用いる材料として、高価なNi基合金の代わりに、鉄基の
ステンレス鋼を合せ材とするクラッド鋼を適用すること
を検討する中でなされた。種々の添加元素の組合せにつ
いて鋭意検討を行った結果、Niの添加量を大幅に増加す
ることなく、酸化分解処理における耐食性を確保するこ
とに成功した。
The present invention has been made while studying the use of a clad steel using iron-based stainless steel as a composite material instead of an expensive Ni-based alloy as a material used in the oxidative decomposition method using supercritical water. Was. As a result of intensive studies on the combinations of various additive elements, we succeeded in securing the corrosion resistance in the oxidative decomposition treatment without greatly increasing the amount of Ni added.

【0016】本発明のクラッド鋼の母材は、普通鋼、高
張力鋼等の、機械的性質、経済性に優れた炭素鋼を選択
して使用することができる。
As the base material of the clad steel of the present invention, carbon steel having excellent mechanical properties and economic efficiency, such as ordinary steel and high tensile steel, can be selected and used.

【0017】本発明の合せ材における化学成分の限定理
由について以下に述べる。
The reasons for limiting the chemical components in the composite of the present invention will be described below.

【0018】C: 0.02%以下 CはCrと結合して炭化物を形成し、Crによる鋼の耐高温
腐食性向上効果を減少させるため、その含有量は少ない
ことが望ましい。C量が0.02%以下であれば、耐食性の劣
化は僅かであるため、添加量を0.02%以下とする。
C: 0.02% or less C is preferably combined with Cr to form carbides and reduce the effect of Cr on improving the high-temperature corrosion resistance of steel, so that its content is small. If the C content is 0.02% or less, the deterioration of corrosion resistance is slight, so the addition amount is set to 0.02% or less.

【0019】Si: 1.0 %以下 Siは脱酸剤として有効であるが、1.0 %を超えると金属
間化合物の析出を著しく加速し、熱間加工性を低下させ
る。従って、Siの添加量を1.0 %以下とする。
Si: 1.0% or less Si is effective as a deoxidizing agent, but if it exceeds 1.0%, the precipitation of intermetallic compounds is remarkably accelerated, and the hot workability is reduced. Therefore, the addition amount of Si is set to 1.0% or less.

【0020】Mn: 2.0%以下 Mnは脱酸剤であり、熱間加工性を向上させるため2.0%
以下を含んでもよい。2.0%を超えると耐食性を低下さ
せる。従って、Mnの添加量を2.0%以下とする。
Mn: 2.0% or less Mn is a deoxidizing agent, and is used in an amount of 2.0% to improve hot workability.
It may include: If it exceeds 2.0%, the corrosion resistance is reduced. Therefore, the addition amount of Mn is set to 2.0% or less.

【0021】Cr: 20〜27% Crは鋼の耐高温腐食性を向上させる重要な働きを持つ。
高温高圧酸化プロセス環境においては、20%未満の添加
ではその効果は十分ではない。一方、Crを27%を超えて
添加すると、脆い金属間化合物が析出し易くなり、高温
における機械的性質や加工性が劣化する。従って、Crの
添加量を20〜27%の範囲内とする。
Cr: 20-27% Cr has an important function of improving the high-temperature corrosion resistance of steel.
In a high-temperature and high-pressure oxidation process environment, the effect is not sufficient if added less than 20%. On the other hand, if Cr is added in excess of 27%, brittle intermetallic compounds tend to precipitate, and mechanical properties and workability at high temperatures deteriorate. Therefore, the added amount of Cr is set in the range of 20 to 27%.

【0022】Ni+Co: 17〜45% Niは高温において生じる鋼表面の保護皮膜中に入り、保
護皮膜の密着性を改善することを通じて、高温高圧酸化
プロセス環境での耐食性を向上させる。この効果に関し
て、CoはNiと等価であるため、合計してNi+Coの添加量
として扱う。Ni+Coの添加量が17%未満では、耐食性の向
上効果は顕著ではない。一方、Ni+Co を45%を超えて添
加してもその効果は飽和するばかりか、経済性を損なう
ようになる。従って、Ni+Coの添加量を17〜45%の範囲内
とする。
Ni + Co: 17-45% Ni enters the protective coating on the steel surface generated at high temperatures and improves the corrosion resistance in a high temperature and high pressure oxidation process environment by improving the adhesion of the protective coating. Regarding this effect, since Co is equivalent to Ni, the total is treated as the addition amount of Ni + Co. If the addition amount of Ni + Co is less than 17%, the effect of improving corrosion resistance is not significant. On the other hand, if Ni + Co is added in excess of 45%, the effect is not only saturated, but also the economic efficiency is impaired. Therefore, the added amount of Ni + Co is set in the range of 17 to 45%.

【0023】Mo+1/2W: 2〜5% Moは孔食型の腐食に対して鋼材の耐食性を向上させる顕
著な効果を有する。その効果は、2%未満のMoの添加では
顕著ではなく、一方、5%を超えて添加すると、耐高温酸
化性が劣化する。また、Wはmass%ではその1/2の量、即ち
1/2WでMoと等価であるため、合計してMo+1/2Wの添加量
として扱う。従って、Mo+1/2Wの添加量を2〜5%の範囲内
とする。
Mo + 1 / 2W: 2-5% Mo has a remarkable effect of improving the corrosion resistance of steel against pitting corrosion. The effect is not remarkable when less than 2% of Mo is added, while when more than 5% is added, the high-temperature oxidation resistance is deteriorated. W is 1/2 of mass%, that is, W
Since it is equivalent to Mo at 1/2 W, it is treated as the addition amount of Mo + 1/2 W in total. Therefore, the added amount of Mo + 1 / 2W is set in the range of 2 to 5%.

【0024】N:0.01〜0.3% Nは孔食型の腐食に対する鋼材の耐食性を向上させる効
果を持つと同時に、鋼のオーステナイト組織を安定化さ
せ、脆い金属間化合物が析出するのを抑止する効果を有
する。これらの効果を得るには、0.01%以上の添加が必
要であるが、0.3%を超える添加では製鋼コストが上昇し
経済性が損なわれる。従って、Nの添加量を0.01〜0.3%
の範囲内とする。
N: 0.01 to 0.3% N has the effect of improving the corrosion resistance of steel against pitting corrosion, and at the same time stabilizes the austenitic structure of steel and suppresses the precipitation of brittle intermetallic compounds. Having. To obtain these effects, addition of 0.01% or more is necessary. However, addition of more than 0.3% increases steelmaking cost and impairs economic efficiency. Therefore, the addition amount of N is 0.01-0.3%
Within the range.

【0025】Cu: 0.1〜3% Cuは鋼の耐酸性を向上させるが、0.1%未満の添加ではそ
の効果は十分ではなく、3%を超えて添加すると熱間加工
性を劣化させる。従って、Cuの添加量を0.1〜3%の範囲
内とする。本発明における合せ材としては、以上の化学
成分を基本成分とし、さらに各種特性を向上させるた
め、下記元素の添加が可能である。
Cu: 0.1-3% Although Cu improves the acid resistance of steel, its effect is not sufficient if added less than 0.1%, and hot workability is deteriorated if added over 3%. Therefore, the addition amount of Cu is set in the range of 0.1 to 3%. In the present invention, the following elements can be added to the composite material in order to further improve various properties with the above chemical components as basic components.

【0026】B,Zr: B≦0.01%,Zr≦0.5%のうち1種以上 Bは、少量の添加により粒界強度の向上に効果がある
が、0.01%を超えて添加すると溶接高温割れの傾向を著
しくする。従って、Bを添加する場合は0.01%以下とす
る。Zrも、同様に粒界強度の向上に効果があるが、0.5%
を超えて添加すると溶接高温割れの傾向を著しくする。
従って、Zr を添加する場合は0.5%以下とする。
B, Zr: one or more of B ≦ 0.01% and Zr ≦ 0.5% B is effective in improving the grain boundary strength by adding a small amount, but when added in an amount exceeding 0.01%, the hot cracking of the weld may occur. Make the tendency remarkable. Therefore, when B is added, the content is set to 0.01% or less. Zr is also effective in improving the grain boundary strength, but 0.5%
If added in excess of, the tendency of welding hot cracking will be marked.
Therefore, when Zr is added, the content is set to 0.5% or less.

【0027】Ca,Al,La,Ce,Y: Ca≦0.02%,Al≦0.1%,La≦
0.04%,Ce≦0.04%,Y≦0.1%のうち1種以上 Ca,Al,La,Ce,Yは、1種以上を少量添加することによ
り、表面に緻密な酸化膜を形成し、あるいはCr酸化物中
に取り込まれて、耐高温酸化性を向上させる。しかし、
Caでは0.02%、Alでは0.1%、Laでは0.04%、Ceでは0.04
%、Yでは0.1%を超えて添加すると、鋼の熱間加工性を劣
化させ表面疵も発生しやすくなる。従って、Ca,Al,La,C
e,Yを添加する場合は、Ca:0.02%以下、Al:0.1%以下、L
a:0.04%以下、Ce:0.04%以下、Y:0.1%以下のうち1種以
上を選択して添加する。
Ca, Al, La, Ce, Y: Ca ≦ 0.02%, Al ≦ 0.1%, La ≦
At least one of 0.04%, Ce ≦ 0.04%, Y ≦ 0.1% Ca, Al, La, Ce, Y forms a dense oxide film on the surface or Incorporated into oxides to improve high temperature oxidation resistance. But,
0.02% for Ca, 0.1% for Al, 0.04% for La, 0.04% for Ce
%, And in Y exceeding 0.1%, the hot workability of the steel is degraded and surface flaws are likely to occur. Therefore, Ca, Al, La, C
When adding e and Y, Ca: 0.02% or less, Al: 0.1% or less, L
a: 0.04% or less, Ce: 0.04% or less, Y: 0.1% or less.

【0028】Ti,Nb,Ta,V: Ti≦0.5%,Nb≦0.8%,Ta≦1.6
%,V≦1%のうち1種以上 Ti,Nb,Ta,V は、鋼中の炭素と結合して炭化物を形成
し、Cr炭化物の生成を抑制することにより、耐食性劣化
を減じることができる。しかし、Tiでは0.5%、Nbでは0.
8%、Taでは1.6%、Vでは1%を超えて添加すると、脆い金
属間化合物が析出しやすくなる。従って、Ti,Nb,Ta,Vを
添加する場合は、Ti:0.5%以下、Nb:0.8%以下、Ta:1.6%
以下、V:1%以下のうち1種以上を選択して添加する。
Ti, Nb, Ta, V: Ti ≦ 0.5%, Nb ≦ 0.8%, Ta ≦ 1.6
%, V ≦ 1% One or more of Ti, Nb, Ta, V combine with carbon in steel to form carbides and suppress the formation of Cr carbides, thereby reducing corrosion resistance deterioration . However, 0.5% for Ti and 0 for Nb.
Addition of more than 8%, 1.6% for Ta, and 1% for V facilitates precipitation of brittle intermetallic compounds. Therefore, when adding Ti, Nb, Ta, V, Ti: 0.5% or less, Nb: 0.8% or less, Ta: 1.6%
Hereinafter, one or more of V: 1% or less are selected and added.

【0029】化学成分の限定式: Cr+Ni+Co+2Cu+4.1(Mo+
1/2W)+24N≧62 高温高圧水酸化環境における腐食速度に及ぼす化学成分
の影響については、次の式(1)の耐食性指数Rにより評価
することができる。
Limited formula of chemical components: Cr + Ni + Co + 2Cu + 4.1 (Mo +
1 / 2W) + 24N ≧ 62 The effect of chemical components on the corrosion rate in a high-temperature, high-pressure hydroxylated environment can be evaluated by the corrosion resistance index R of the following equation (1).

【0030】 R = Cr+Ni+Co+2Cu+4.1(Mo+1/2W)+24N (1) ここで、元素記号は各元素のmass%を示す。R = Cr + Ni + Co + 2Cu + 4.1 (Mo + 1 / 2W) + 24N (1) Here, the element symbols indicate mass% of each element.

【0031】式(1)の値により、塩素イオンを含む高温
高圧水酸化環境での装置材料の腐食速度は、図1に示す
ように良好に整理される。この図より、式(1)の値が62
以上においては、腐食速度は0.5g/m2h以下となり、上記
装置材料として許容される耐食性レベルを確保できる。
それとともに、腐食速度の変動も急速に収束し、安定し
た耐食性能を示すようになる。以上から、式(1)の値が6
2以上となるように化学成分を規定する。これは、不等
式で表すと、 Cr+Ni+Co+2Cu+4.1(Mo+1/2W)+24N≧62 (2) となる。
According to the value of the equation (1), the corrosion rate of the apparatus material in a high-temperature and high-pressure hydroxylation environment containing chlorine ions is well arranged as shown in FIG. From this figure, the value of equation (1) is 62
In the above, the corrosion rate is 0.5 g / m 2 h or less, and the level of corrosion resistance that is permissible as the device material can be secured.
At the same time, fluctuations in the corrosion rate rapidly converge, and stable corrosion resistance is exhibited. From the above, the value of equation (1) is 6
Define chemical components to be 2 or more. This is represented by the following equation: Cr + Ni + Co + 2Cu + 4.1 (Mo + 1 / 2W) + 24N ≧ 62 (2)

【0032】なお、これらの手段において「残部が実質
的に鉄である」とは、本発明の作用・効果を無くさない
限り、不可避的不純物をはじめ、他の微量元素を含有す
るものが本発明の範囲に含まれることを意味する。
In these means, "the balance is substantially iron" means that the substance containing other trace elements including unavoidable impurities is used in the present invention as long as the function and effect of the present invention are not lost. Is included in the range.

【0033】[0033]

【発明の実施の形態】本発明の実施に当たっては、上記
の合せ材の化学成分に基づき、通常のステンレス鋼と同
様の方法で製造したステンレス鋼を合せ材とし、炭素鋼
を母材としてクラッド鋼を製造できる。すなわち、これ
ら両者を組合せて、所謂サンドイッチ型あるしはオープ
ン型等、自由な形状のスラブとして溶接組立し、界面を
真空脱気・封止した後、加熱圧延して鋼板として製造す
る。
DESCRIPTION OF THE PREFERRED EMBODIMENTS In carrying out the present invention, a stainless steel manufactured by the same method as ordinary stainless steel based on the chemical composition of the above-mentioned composite material is used as a composite material, and a carbon steel is used as a base material and a clad steel is used. Can be manufactured. That is, these two are combined, welded and assembled as a free-form slab such as a so-called sandwich type or open type, vacuum degassed and sealed at the interface, and then heated and rolled to produce a steel sheet.

【0034】本発明の合せ材に用いるステンレス鋼の化
学成分は、超臨界水・亜臨界水環境での装置材料の腐食
と実用性に関する検討に基づくものである。検討を通
じ、高温高圧水環境での媒体の酸化性はもとより、分解
処理過程で発生する塩酸による局所的な腐食が、材料損
傷を加速している可能性が大きいことが明らかとなっ
た。
The chemical composition of the stainless steel used in the composite according to the present invention is based on a study on the corrosion and practicality of equipment materials in a supercritical water / subcritical water environment. Through investigations, it was clarified that not only the oxidizing property of the medium in the high-temperature and high-pressure water environment but also the local corrosion due to hydrochloric acid generated in the decomposition process is likely to accelerate the material damage.

【0035】そもそも、本発明の対象とする含塩素系で
酸化力も大きい環境では、高温腐食と湿食、特に局部腐
食に近い腐食機構が、重複して材料損傷を速めていると
考えられる。しかし、耐高温腐食性の向上と、局部腐食
環境での耐食性向上は、合金設計の観点からは多くの点
で相容れないものであり、両立させることが難しい。
In the first place, in an environment containing chlorine and containing a large amount of oxidizing power, which is the object of the present invention, it is considered that corrosion mechanisms close to high-temperature corrosion and wet corrosion, particularly local corrosion, accelerate material damage. However, improvement of high-temperature corrosion resistance and improvement of corrosion resistance in a local corrosion environment are incompatible in many aspects from the viewpoint of alloy design, and it is difficult to achieve both.

【0036】そこで、新たな視点からの耐食性向上技術
について鋭意検討を行い、その過程で、高温で生じた酸
化皮膜の安定性が、従来言われているCr含有量のみなら
ず、Niの含有量に基づき影響されることを見出した。検
討の結果、酸化皮膜がCr酸化物主体でしかもNiが含まれ
ると、皮膜の合せ材母相への密着性と保護性が向上する
傾向があることを突き止めた。
In view of the above, the inventors of the present invention have intensively studied a technique for improving the corrosion resistance from a new point of view. In the process, the stability of the oxide film generated at a high temperature is determined not only by the conventional Cr content but also by the Ni content. Was found to be affected. As a result of the investigation, it was found that when the oxide film was mainly composed of Cr oxide and contained Ni, the adhesion and protection of the film to the matrix of the composite material tended to be improved.

【0037】この傾向について考察すると、密着性向上
には、酸化皮膜自体の延性の僅かな増加、酸化物と母相
(ステンレス鋼)の線膨張率差の縮小が関連している。
また、保護性の向上には、Fe-Cr系酸化物と比較した場
合の、Ni-Cr系酸化物中での酸素等の拡散速度の減少等
が関連していると考察される。従来、高価にして敬遠さ
れながらも、Ni基合金を高温高圧水プラントの用途に適
用せざるを得なかった背景がここにある。
Considering this tendency, a slight increase in the ductility of the oxide film itself and a reduction in the difference in the coefficient of linear expansion between the oxide and the parent phase (stainless steel) are related to the improvement in adhesion.
Further, it is considered that the improvement of the protection is related to a decrease in the diffusion rate of oxygen and the like in the Ni-Cr-based oxide as compared with the Fe-Cr-based oxide. Heretofore, this has been the reason why Ni-based alloys had to be applied to high-temperature and high-pressure water plant applications, albeit expensive and shunned.

【0038】そこで、酸化皮膜へのNiの固溶が高温腐食
と湿食の重畳した環境への耐性に有効である以上、皮膜
の特性を改善するに十分なNi量があればよいことにな
る。このようなNi添加量の最小量さえ確保すれば、鉄基
のステンレス鋼であっても、十分優れた耐食性が発揮で
きる筈であり、これを合せ材としてクラッド鋼とすれば
経済性は飛躍的に向上するとの考え方に基づき実験を継
続した。
Therefore, as long as the solid solution of Ni in the oxide film is effective for resistance to an environment where high temperature corrosion and wet corrosion are superimposed, it is sufficient if there is a sufficient amount of Ni to improve the characteristics of the film. . As long as such a minimum amount of Ni is secured, even iron-based stainless steel should be able to exhibit sufficiently excellent corrosion resistance. The experiment was continued based on the idea that it would improve.

【0039】実験では、Cr,Ni,Fe他の元素の添加量を変
化させて組合わせた組成の合金を準備した。検討を通
じ、ある量以上にNiを添加しても、酸化皮膜の組成は飽
和し、密着性は飽和するという知見が得られた。添加量
としては、Crを20%以上とする必要があること、これと
ほぼ同量のNiの添加が、皮膜特性の飛躍的な向上をもた
らすこと等を明らかにした。さらに、酸化皮膜の安定性
の向上に役立つ元素として、N,Mo,Cu等もあることが明
らかとなった。
In the experiment, an alloy having a composition which was prepared by changing the amounts of Cr, Ni, Fe and other elements was prepared. Through the investigation, it was found that even if Ni was added in a certain amount or more, the composition of the oxide film was saturated and the adhesion was saturated. It was clarified that the content of Cr should be 20% or more, and that the addition of approximately the same amount of Ni would bring about a dramatic improvement in the film properties. Further, it has been clarified that N, Mo, Cu, and the like are also useful elements for improving the stability of the oxide film.

【0040】しかし、MoおよびWの添加については、耐
局部腐食性の向上は期待できるものの、クラッド鋼の製
造時の熱履歴により耐食性が劣化する傾向があった。こ
れは、特に900〜1100℃の最終圧下後の冷却過程におい
て、結晶粒界にCr,Ni等との金属間化合物を析出しやす
くし、耐食性に有効な化学成分を減少させるためであ
る。このように、MoおよびWの添加量には制限があるこ
とが明らかとなった。
However, with respect to the addition of Mo and W, although an improvement in the local corrosion resistance can be expected, the corrosion resistance tends to deteriorate due to the heat history during the production of the clad steel. This is because the intermetallic compound with Cr, Ni, or the like is easily precipitated at the crystal grain boundaries, particularly in the cooling process after the final reduction at 900 to 1100 ° C., and the chemical components effective for corrosion resistance are reduced. Thus, it became clear that the addition amounts of Mo and W are limited.

【0041】実際の装置材料として役立つためには、材
料の加工性、延性、溶接性等が優れていることは極めて
重要である。その観点からは、合せ材の金属組織がオー
ステナイト組織となることを想定して添加元素を設定す
れば、クラッド鋼の曲げ加工性や耐剥離性は良好である
ほか、溶接性も良好である。
In order to be useful as an actual device material, it is extremely important that the material has excellent workability, ductility, weldability, and the like. From this viewpoint, if the additive element is set on the assumption that the metal structure of the composite material is an austenitic structure, the bending workability and the peeling resistance of the clad steel are good, and the weldability is also good.

【0042】本発明は、以上の考え方に基づき、高温高
圧水環境での耐食性に優れたクラッド鋼を提供する。化
学成分については、好ましくは次のようにするとよい。
The present invention provides a clad steel having excellent corrosion resistance in a high-temperature and high-pressure water environment based on the above concept. The chemical components are preferably as follows.

【0043】P: 0.002〜0.02% Pは不純物であり、低いほどよく、含有量が0.02%を超え
ると溶接性を劣化させる。しかし、0.002%未満まで低下
させると脱P処理のコストが増加する。従って、Pを0.00
2〜0.02%の範囲とすることが好ましい。
P: 0.002 to 0.02% P is an impurity, and the lower the better, the better, and if the content exceeds 0.02%, the weldability deteriorates. However, if the content is reduced to less than 0.002%, the cost of the de-P treatment increases. Therefore, P is 0.00
It is preferable to be in the range of 2 to 0.02%.

【0044】S: 0.01%以下 Sは不純物であり、低いほどよく、含有量が0.01%を超え
ると熱間加工性を劣化させる。従って、Sを0.01%以下と
することが好ましい。
S: 0.01% or less S is an impurity, and the lower the better, the better. If the content exceeds 0.01%, the hot workability deteriorates. Therefore, it is preferable that S is set to 0.01% or less.

【0045】N: 0.15〜0.3% Nは好ましくは、0.15%以上添加することにより、鋼のオ
ーステナイト組織をより安定化させ、脆い金属間化合物
の析出抑止効果が確実に得られる。
N: 0.15 to 0.3% N is preferably added in an amount of 0.15% or more, whereby the austenite structure of the steel is further stabilized, and the effect of preventing precipitation of brittle intermetallic compounds is surely obtained.

【0046】本発明の高耐食クラッド鋼の適用形態とし
ては、プラント設備の反応容器用の構造体ないし流通管
として用いることが、最も適している。さらに、反応容
器の内部構造や制御装置のケーシング等として用いて
も、好適な耐食性と機械的性質を発揮しうる。
As the application form of the high corrosion resistant clad steel of the present invention, it is most suitable to use it as a structure or a flow pipe for a reaction vessel of plant equipment. Furthermore, suitable corrosion resistance and mechanical properties can be exhibited even when used as the internal structure of a reaction vessel or a casing of a control device.

【0047】[0047]

【実施例】合せ材として、表1に示す化学成分を有する
ステンレス鋼を真空誘導溶解にて溶製し、鋳造後1200℃
に均熱し、熱間圧延を施して30mm厚の鋼板を製造した。
熱間圧延後の鋼板については、耳割れ状況及び表面疵の
発生状況をまず評価した。
EXAMPLE As a composite material, stainless steel having the chemical components shown in Table 1 was melted by vacuum induction melting, and after casting, 1200 ° C.
And then hot-rolled to produce a 30 mm thick steel sheet.
For the steel sheet after hot rolling, the state of edge cracking and the state of occurrence of surface flaws were first evaluated.

【0048】引き続き表面欠陥等の研削除去および接合
予定面の研磨調整を実施した後、同様に接合予定面を研
磨調整した90mm厚の炭素鋼スラブと組合せて、90mm+30m
m+30mm+90mm計240mm厚さに重ね合せた。これら2組のク
ラッドの界面を真空脱気して四周を溶接封止して、サン
ドイッチ型クラッドスラブとなした。
Subsequently, after grinding and removal of surface defects and the like and polishing adjustment of the surface to be joined were carried out, 90 mm + 30 m in combination with a 90 mm thick carbon steel slab which was similarly polished and adjusted to the surface to be joined.
m + 30mm + 90mm, superimposed on a total of 240mm thickness. The interface between these two sets of clads was evacuated by vacuum and the four circumferences were welded and sealed to form a sandwich-type clad slab.

【0049】このクラッドスラブを1150℃に均熱し、圧
下比10で熱間圧延を施し、全体を24mm厚の板となした
後、母材厚9mm、合せ材厚3mmのクラッド鋼2組に切断分
離して製品とした。クラッド鋼の合せ材表層より、135m
mL×5mmw×1mmtの試験片を圧延方向に切り出し、表面研
磨仕上げで腐食試験に供した。
The clad slab was soaked at 1150 ° C., hot-rolled at a reduction ratio of 10 to form a 24 mm thick plate, and then cut into two sets of clad steel having a base material thickness of 9 mm and a laminated material thickness of 3 mm. The product was separated. 135m from the surface of the clad steel cladding
A test piece of ML x 5 mm w x 1 mm t was cut out in the rolling direction and subjected to a corrosion test with a surface polished finish.

【0050】[0050]

【表1】 [Table 1]

【0051】腐食試験は、トリクロロエチレン分解処理
プラントの反応容器環境を模擬し、2%トリクロロエチレ
ン、等モルの水酸化ナトリウム、及び等モルの過酸化水
素を加えた純水中に浸積して行った。測定は、温度550
℃、圧力35MPaで1時間保持して腐食量を測定し、減肉速
度に換算して評価した。以上の評価結果についても、表
1にまとめて示す。
The corrosion test simulated a reaction vessel environment of a trichlorethylene decomposition treatment plant, and was immersed in pure water to which 2% trichlorethylene, equimolar sodium hydroxide, and equimolar hydrogen peroxide were added. . Measurements were taken at a temperature of 550
The temperature was maintained at 35 ° C. and a pressure of 35 MPa for 1 hour, the amount of corrosion was measured, and the conversion was converted into a wall thinning rate and evaluated. Table 1 also shows the above evaluation results.

【0052】本発明鋼合せ材の熱間加工性は、割れや疵
の発生がなく(表では○印)良好に圧延できた。また、
トリクロロエチレン分解処理プラントの反応容器模擬環
境の腐食速度(表では腐食速度*の欄)は、目標とする
0.6g/m2h(=0.66mm/year)未満の腐食速度が達成できてい
る。
The hot workability of the laminated steel according to the present invention was satisfactory without any cracks or flaws (marked with ○ in the table). Also,
The target corrosion rate (corrosion rate * column in the table) of the simulated reaction vessel environment of the trichlorethylene decomposition plant
A corrosion rate of less than 0.6 g / m 2 h (= 0.66 mm / year) has been achieved.

【0053】この腐食速度の目標値(=0.66mm/year)が維
持できれば、装置寿命を5年と想定した場合の減肉相当
厚さは3.3mmであって、適用可能なクラッド鋼の板厚と
しては、例えば、6mm+3.3mm〜11mm+3.3mmが考えられ、
実用プラント向けに好適である。これは、1 ton/dayの
工業的処理プラントで想定されている肉厚10〜15mm の
ソリッド反応容器と同等の耐食性と機械的性質を備え、
素材コストはソリッド使用の場合に比較して30〜40%と
推定される。
If the target value of the corrosion rate (= 0.66 mm / year) can be maintained, the equivalent thickness of the reduced thickness is 3.3 mm, assuming that the equipment life is 5 years, and the applicable clad steel thickness For example, 6 mm + 3.3 mm to 11 mm + 3.3 mm can be considered,
Suitable for practical plants. It has the same corrosion resistance and mechanical properties as a solid reaction vessel with a wall thickness of 10 to 15 mm, which is assumed for an industrial treatment plant of 1 ton / day,
The material cost is estimated to be 30-40% compared to the case of using solids.

【0054】合せ材の化学成分が本発明の範囲に入らな
い比較鋼についても、同様に合せ材の真空溶解・鋳造・
熱間圧延の工程を経て、耳割れ・表面疵の評価を行っ
た。その後、表面機械加工および接合予定面の調整・母
材炭素鋼とのスラブと組立・界面脱気・クラッド圧延と
いう工程を経て、合せ材表層の耐食性の評価を実施し
た。比較鋼の合せ材の化学成分及び評価結果を、表2に
まとめて示す。
For comparative steels whose chemical components do not fall within the scope of the present invention, similarly, vacuum melting, casting,
After the hot rolling process, the evaluation of the edge crack and the surface flaw was performed. After that, through the steps of surface machining, adjustment of the surface to be joined, slab and assembling with base carbon steel, interfacial deaeration, and clad rolling, the corrosion resistance of the surface layer of the composite material was evaluated. Table 2 summarizes the chemical components and evaluation results of the composite material of the comparative steel.

【0055】[0055]

【表2】 [Table 2]

【0056】比較鋼の合せ材の熱間加工性については、
割れ、表面疵が発生したものがあり、表に×印、△印で
示す。割れが発生したもの(×印)は、金属間化合物の
析出に関連すると思われる高温での低延性割れ、もしく
は粒界強度の不足に起因すると思われる耳割れが発生し
たものである。表面疵が発生したもの(△印)も、同様
の原因によるものと思われる。比較鋼の耐食性について
は、腐食速度の上記目標値0.6g/m2hを超えるものもあ
る。
Regarding the hot workability of the composite material of the comparative steel,
Some of them have cracks and surface flaws. Those with cracks (x marks) are those with low ductile cracks at high temperatures, which are thought to be related to the precipitation of intermetallic compounds, or ear cracks, which are thought to be due to insufficient grain boundary strength. It is considered that the surface flaw (marked by △) is caused by the same cause. Regarding the corrosion resistance of the comparative steels, there are those in which the corrosion rate exceeds the above target value of 0.6 g / m 2 h.

【0057】このように、表1に示す発明鋼では、添加
元素の適切な組合せにより、全ての例について熱間加工
性、耐食性の双方とも良好である。一方、表2に示す比
較鋼では、合せ材の熱間加工性もしくは耐食性のいずれ
かに難があり、双方を両立させることができない。以上
より、本発明の用途に対して本発明の規定が有効である
ことがわかる。
As described above, in the steels of the invention shown in Table 1, both the hot workability and the corrosion resistance are good in all the examples by the proper combination of the additional elements. On the other hand, in the comparative steels shown in Table 2, either the hot workability or the corrosion resistance of the composite material is difficult, and the two cannot be compatible. From the above, it can be seen that the provisions of the present invention are effective for the uses of the present invention.

【0058】[0058]

【発明の効果】本発明の高耐食クラッド鋼は、合せ材の
化学成分を適切に調製することにより、超臨界水・亜臨
界水酸化プラントに適用することが可能である。その結
果、反応容器用構造体、流通管、反応容器の内部構造等
に好適な耐食性と機械的性質を発揮でき、しかも経済性
の障害を克服しうる。すなわち、工業的な有害廃棄物の
SCWO(超臨界水酸化)処理プラントの装置製造に見通し
が得られ、産業上極めて有益な効果が得られると同時
に、環境関連産業の創成に貢献できる。
The highly corrosion-resistant clad steel of the present invention can be applied to a supercritical water / subcritical water oxidation plant by appropriately adjusting the chemical composition of the composite material. As a result, it is possible to exhibit corrosion resistance and mechanical properties suitable for the structure for the reaction vessel, the flow pipe, the internal structure of the reaction vessel, and the like, and to overcome economical obstacles. In other words, industrial hazardous waste
The prospect of manufacturing equipment for SCWO (Supercritical Water Oxidation) treatment plant can be obtained, and extremely beneficial effects on the industry can be obtained, and at the same time, it can contribute to the creation of an environment-related industry.

【図面の簡単な説明】[Brief description of the drawings]

【図1】合せ材の耐食性指数Rと高温高圧水酸化環境で
の腐食速度の関係を示す図。
FIG. 1 is a graph showing a relationship between a corrosion resistance index R of a composite material and a corrosion rate in a high-temperature and high-pressure hydroxylation environment.

Claims (4)

【特許請求の範囲】[Claims] 【請求項1】 炭素鋼を母材とし、化学成分がmass%
で、C:0.02%以下、Si:1.0 %以下、Mn:2.0%以下、Cr:20
〜27%、Ni+Co:17〜45%、Mo+1/2W:2〜5%、N:0.01〜0.3
%、Cu:0.1〜3%を含み、残部が実質的に鉄であり、各元
素のmass%をそれぞれの元素記号で表すとき次の式を満
たすステンレス鋼を合せ材とする高耐食クラッド鋼。 Cr+Ni+Co+2Cu+4.1(Mo+1/2W)+24N≧62
Claims: 1. A carbon steel as a base material having a chemical composition of mass%
In, C: 0.02% or less, Si: 1.0% or less, Mn: 2.0% or less, Cr: 20
~ 27%, Ni + Co: 17-45%, Mo + 1 / 2W: 2-5%, N: 0.01-0.3
%, Cu: 0.1 to 3%, the balance being substantially iron, and when the mass% of each element is represented by each element symbol, a high corrosion resistant clad steel using a stainless steel satisfying the following formula as a composite material. Cr + Ni + Co + 2Cu + 4.1 (Mo + 1 / 2W) + 24N ≧ 62
【請求項2】 合せ材の化学成分が、請求項1記載の化
学成分に加えてさらに、mass%で、B:0.01%以下、Zr:0.5
%以下のうち1種以上を含むことを特徴とする高耐食ク
ラッド鋼。
2. The chemical composition of the composite material further comprises, in addition to the chemical composition of claim 1, a mass%, B: 0.01% or less, Zr: 0.5
% High-corrosion-resistant clad steel containing at least one selected from the group consisting of:
【請求項3】 合せ材の化学成分が、請求項1または請
求項2記載の化学成分に加えてさらに、mass%で、Ca:0.
02%以下、Al:0.1%以下、La:0.04%以下、Ce:0.04%以下、
Y:0.1%以下のうち1種以上を含むことを特徴とする高耐
食クラッド鋼。
3. The chemical composition of the composite material further comprises, in addition to the chemical composition of claim 1 or 2, a mass%, Ca: 0.
02% or less, Al: 0.1% or less, La: 0.04% or less, Ce: 0.04% or less,
Y: High corrosion resistant clad steel containing at least one of 0.1% or less.
【請求項4】 合せ材の化学成分が、請求項1ないしは
請求項3記載の化学成分に加えてさらに、Ti:0.5%以
下、Nb:0.8%以下、Ta:1.6%以下、V:1%以下のうち1種以
上を含むことを特徴とする高耐食クラッド鋼。
4. The chemical composition of the composite material further comprises Ti: 0.5% or less, Nb: 0.8% or less, Ta: 1.6% or less, V: 1% in addition to the chemical components described in claim 1 or 3. A highly corrosion-resistant clad steel comprising at least one of the following:
JP2000265046A 2000-09-01 2000-09-01 High corrosion resistant clad steel Pending JP2002069590A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2000265046A JP2002069590A (en) 2000-09-01 2000-09-01 High corrosion resistant clad steel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2000265046A JP2002069590A (en) 2000-09-01 2000-09-01 High corrosion resistant clad steel

Publications (1)

Publication Number Publication Date
JP2002069590A true JP2002069590A (en) 2002-03-08

Family

ID=18752374

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2000265046A Pending JP2002069590A (en) 2000-09-01 2000-09-01 High corrosion resistant clad steel

Country Status (1)

Country Link
JP (1) JP2002069590A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004005569A1 (en) * 2002-07-09 2004-01-15 Fujikin Incorporated Parts for fluid
WO2004005568A1 (en) * 2002-07-09 2004-01-15 Fujikin Incorporated Parts for fluid
WO2004005570A1 (en) * 2002-07-09 2004-01-15 Fujikin Incorporated Pipe joint
JP2014001413A (en) * 2012-06-15 2014-01-09 Nippon Steel & Sumitomo Metal Ni-BASED ALLOY

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004005569A1 (en) * 2002-07-09 2004-01-15 Fujikin Incorporated Parts for fluid
WO2004005568A1 (en) * 2002-07-09 2004-01-15 Fujikin Incorporated Parts for fluid
WO2004005570A1 (en) * 2002-07-09 2004-01-15 Fujikin Incorporated Pipe joint
JP2004044633A (en) * 2002-07-09 2004-02-12 Nippon Steel Corp Pipe joint
EP1536029A1 (en) * 2002-07-09 2005-06-01 Fujikin Incorporated Parts for fluid
EP1536030A1 (en) * 2002-07-09 2005-06-01 Fujikin Incorporated Pipe joint
EP1553199A1 (en) * 2002-07-09 2005-07-13 Fujikin Incorporated Parts for fluid
EP1553199A4 (en) * 2002-07-09 2005-08-31 Fujikin Kk Parts for fluid
EP1536030A4 (en) * 2002-07-09 2005-08-31 Fujikin Kk Pipe joint
EP1536029A4 (en) * 2002-07-09 2005-08-31 Fujikin Kk Parts for fluid
CN1307321C (en) * 2002-07-09 2007-03-28 株式会社富士金 Parts for fluid
CN1320151C (en) * 2002-07-09 2007-06-06 株式会社富士金 Pipe joint
JP2014001413A (en) * 2012-06-15 2014-01-09 Nippon Steel & Sumitomo Metal Ni-BASED ALLOY

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