JPH08252692A - Coated electrode for highly corrosion resistant and high mo stainless steel - Google Patents
Coated electrode for highly corrosion resistant and high mo stainless steelInfo
- Publication number
- JPH08252692A JPH08252692A JP8200895A JP8200895A JPH08252692A JP H08252692 A JPH08252692 A JP H08252692A JP 8200895 A JP8200895 A JP 8200895A JP 8200895 A JP8200895 A JP 8200895A JP H08252692 A JPH08252692 A JP H08252692A
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- corrosion resistance
- stainless steel
- welding
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- corrosion
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、海洋構造物、橋梁など
耐海水、耐海塩粒子性を目的とする構造物等に用いる高
耐食高Ｍｏステンレス鋼用の被覆アーク溶接棒に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated arc welding rod for high corrosion resistance and high Mo stainless steel, which is used for structures such as marine structures, bridges, etc., which are intended to resist seawater and sea salt particles. .
【０００２】[0002]
【従来の技術】近年、種々の化学プラントや石油・天然
ガスの輸送の分野あるいは海水利用技術等において、苛
酷化する使用環境に耐える耐食材料が要求されてきてお
り、これに伴い各種のオーステナイト系ステンレス鋼、
高合金が開発・適用されつつある。その中でも、耐海水
性を目的にＭｏを４〜７％程度含有した高耐食高Ｍｏス
テンレス鋼の適用が増加している。2. Description of the Related Art In recent years, in various chemical plants, transportation fields of petroleum and natural gas, seawater utilization technology, and the like, corrosion-resistant materials that can withstand harsh operating environments have been demanded. Stainless steel,
High alloys are being developed and applied. Among them, the application of high corrosion resistance and high Mo stainless steel containing Mo in an amount of 4 to 7% for the purpose of seawater resistance is increasing.
【０００３】一方、これらの材料を構造材料として適用
する場合、その多くは施工上溶接が必要となるが、一般
に凝固組織のままで使用に供される溶接部は同組成の母
材と比較して耐食性が低い。したがって、耐食構造物に
おいては、全体の耐食性を確保する上で少なくとも母材
と同程度以上の耐食性を有する溶接部の作製が必要とな
る。この観点から、最近これら高耐食ステンレス鋼を母
材とした溶接や、これら耐食構造物の補修溶接において
は、しばしば共金系の溶接材料を用いずに、インコネル
６２５（６０Ｎｉ−２２Ｃｒ−９Ｍｏ−３．５Ｎｂ、Ａ
ＷＳ−ＥＲＮｉＣｒＭｏ−３）のような高Ｃｒ−高Ｍｏ
含有の高Ｎｉ合金の溶接材料が用いられている。On the other hand, when these materials are applied as structural materials, most of them require welding for construction. Generally, the welded part used with the solidified structure as it is is compared with the base metal of the same composition. And has low corrosion resistance. Therefore, in the corrosion resistant structure, it is necessary to produce a welded portion having at least the same corrosion resistance as the base metal in order to ensure the overall corrosion resistance. From this viewpoint, recently, in welding using these high corrosion resistant stainless steels as base materials and repair welding of these corrosion resistant structures, Inconel 625 (60Ni-22Cr-9Mo-3) is often used without using a common metal welding material. .5 Nb, A
High Cr-High Mo such as WS-ERNiCrMo-3)
A high Ni alloy containing welding material is used.
【０００４】しかしながら、イコンネル６２５は、本
来、高強度、耐熱用を目的とした同組成の高Ｎｉ合金の
溶接用に発達してきた経緯から、耐食用として有害元素
のＣを固定するためにはＮｂの含有量が必要以上に多
く、このため、溶接時に高温割れが発生しやすい。さら
に、室温での機械的特性に関しては強度は高いものの延
性・靱性が低い等の欠点があり、耐食構造用溶接材料と
しては問題が多い。一方、Ｎｂ無添加の高Ｎｉ合金であ
るハステロイ２７６（６０Ｎｉ−１５Ｃｒ−１５Ｍｏ−
３．５Ｗ）では、Ｃが０．０１ｗｔ％以下であり、耐食
性は良好であるが、Ｍｏ含有量が多いために、溶接金属
中にσ相などの金属間化合物が生成し、靱性が低い欠点
がある。However, since the iconel 625 was originally developed for welding a high Ni alloy of the same composition for the purpose of high strength and heat resistance, Nb must be Nb in order to fix the harmful element C for corrosion resistance. Content is unnecessarily large, and as a result, hot cracking easily occurs during welding. Further, regarding mechanical properties at room temperature, there are drawbacks such as low ductility and toughness although having high strength, and there are many problems as a welding material for corrosion resistant structures. On the other hand, Hastelloy 276 (60Ni-15Cr-15Mo-) which is a high Ni alloy without Nb added.
At 3.5 W), C is 0.01 wt% or less and the corrosion resistance is good, but since the Mo content is large, an intermetallic compound such as a σ phase is generated in the weld metal, and the toughness is low. There is.
【０００５】また、近年、オーステナイト系ステンレス
鋼あるいは二相系ステンレス鋼において、耐食性向上の
観点からＮが添加されている。しかしながら、高Ｎｉ合
金においては、高温強度確保の観点からＴｉが添加され
ている場合が多く、このような合金にＮを添加すると、
ＴｉＮを生成し、高温強度および耐食性の両方が低下す
る。したがって、従来の高Ｎｉ合金にはＮ添加はほとん
どなされていなかった。In recent years, N has been added to austenitic stainless steel or duplex stainless steel from the viewpoint of improving corrosion resistance. However, in a high Ni alloy, Ti is often added from the viewpoint of securing high temperature strength. When N is added to such an alloy,
It produces TiN and reduces both high temperature strength and corrosion resistance. Therefore, the conventional high Ni alloy has hardly added N.
【０００６】また、Ｃｕ添加による耐食性改善は、特開
昭５８−９３５９３号等の公報に開示されているが、い
ずれもステンレス鋼を目的としたものである。Ｃｏの添
加は強度向上に有効であり、特にマトリックスがオース
テナイト組織の場合には、室温におけると同様、高温強
度および高温クリープ強さを改善するが、いずれも耐熱
用鋼を目的としている。さらに、高Ｎｉ合金溶接材料と
しては、従来、特開昭５６−１２８６９６号、特開昭５
８−６６９９４号、特開昭５８−８２１９０号等の公報
に開示があるが、これらは主に耐熱用溶接金属の強度や
高温特性の改善を目的としたものである。Further, the improvement of corrosion resistance by adding Cu is disclosed in JP-A-58-93593 and the like, but all of them are aimed at stainless steel. Addition of Co is effective for improving strength, and particularly when the matrix has an austenite structure, it improves high-temperature strength and high-temperature creep strength as at room temperature, but both are intended for heat-resistant steel. Further, as a high Ni alloy welding material, there have been hitherto been disclosed in JP-A-56-128696 and JP-A-5.
Although disclosed in JP-A No. 8-66994 and JP-A No. 58-82190, these are mainly intended to improve the strength and high temperature characteristics of the heat-resistant weld metal.
【０００７】[0007]
【発明が解決しようとする課題】上述のように、従来耐
食構造に用いられてきた高Ｎｉ溶接材料は、溶接高温割
れや機械的特性の面で必ずしも十分であるとは言えな
い。本発明はこうした現状に鑑みて、高耐食高Ｍｏステ
ンレス鋼を溶接するに際して、耐食性に優れ、かつ、耐
溶接高温割れ性および機械的特性に関しても優れた被覆
アーク溶接棒を提供することを目的としている。As described above, the high Ni welding materials conventionally used for the corrosion resistant structure are not always sufficient in terms of welding hot cracking and mechanical properties. In view of these circumstances, the present invention has an object to provide a coated arc welding rod having excellent corrosion resistance when welding high-corrosion-resistant high-Mo stainless steel, and also excellent in welding hot cracking resistance and mechanical properties. There is.
【０００８】[0008]
【課題を解決するための手段】本発明は前記課題を解決
するものであって、重量％で、Ｍｏ：３．５〜８．０
％、Ｃｒ：１８．０〜２５．０％を含有し、ミクロ組織
がオーステナイト単相からなる高Ｍｏステンレス鋼用の
被覆アーク溶接棒において、重量％で、Ｃ：０．００１
〜０．０１％、Ｓｉ：０．０１〜０．２％、Ｍｎ：０．
０１〜２％、Ｃｒ：１８〜２５％、Ｎｉ：５５〜７５
％、Ｃｕ：０．１〜３％、Ｎ：０．１〜０．３％、Ｍ
ｏ、Ｗのうち１種または２種：６〜１２％、Ａｌ：０．
００１〜０．０５％を含有し、必要に応じてさらにＣ
ｏ：０．１〜５％を含有し、Ｓを０．０１％以下、Ｐを
０．０１％以下に制限し、残りがＦｅおよび不可避不純
物よりなる高Ｎｉ合金心線に、被覆剤全量に対する重量
％で、金属炭酸塩：３０〜６０％、金属ふっ化物：１５
〜３０％、金属酸化物：１５〜２０％を含有する被覆剤
を塗布したことを特徴とする高Ｍｏステンレス鋼用被覆
アーク溶接棒である。SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned problems, in which Mo: 3.5 to 8.0 in weight%.
%, Cr: 18.0 to 25.0%, in a coated arc welding rod for high Mo stainless steel having a microstructure consisting of an austenite single phase, in weight%, C: 0.001
.About.0.01%, Si: 0.01 to 0.2%, Mn: 0.
01-2%, Cr: 18-25%, Ni: 55-75
%, Cu: 0.1 to 3%, N: 0.1 to 0.3%, M
One or two of O and W: 6 to 12%, Al: 0.
001-0.05%, and if necessary, further C
o: 0.1 to 5% is contained, S is limited to 0.01% or less, P is limited to 0.01% or less, and the remainder is a high Ni alloy core wire consisting of Fe and unavoidable impurities. % By weight, metal carbonate: 30-60%, metal fluoride: 15
A coated arc welding rod for high Mo stainless steel, characterized in that a coating material containing -30% and metal oxide: 15-20% is applied.
【０００９】[0009]
【作用】本発明者らは、種々の高Ｎｉ合金心線と被覆剤
を組み合わせて溶着金属を作製し、それらの諸特性を調
べた結果、以下の知見を得た。すなわち従来のインコネ
ル６２５相当の高Ｎｉ合金溶接材料に対して、Ｎｂを含
有させず、Ｃ量を０．０１ｗｔ％以下に低減し、さらに
Ｎを添加することによって、溶接時の高温割れ感受性が
著しく改善されるとともに、機械的特性面で問題のあっ
た低延性・低靱性も大幅に改善される。そして、Ｎに関
しては０．１ｗｔ％以上添加することにより、耐溶接高
温割れ性、靱性、延性に悪影響を及ぼすことなく強度を
改善し、かつ、耐孔食性、耐隙間腐食性等の耐食性も改
善できる。また、Ｃｕの添加は、硫酸環境等、特に非酸
化性環境での耐食性改善に有効であり、一方、さらに強
度を向上させるためには、Ｃｏの添加が有効である。The present inventors have obtained the following findings as a result of making various welded metals by combining various high Ni alloy core wires and coating materials and examining their various characteristics. That is, with respect to the conventional high Ni alloy welding material equivalent to Inconel 625, Nb is not contained, the C content is reduced to 0.01 wt% or less, and N is further added, whereby the hot cracking susceptibility at the time of welding is significantly increased. In addition to being improved, low ductility and low toughness, which had problems in mechanical properties, are also greatly improved. When N is added in an amount of 0.1 wt% or more, the strength is improved without adversely affecting the weld hot cracking resistance, toughness, and ductility, and the corrosion resistance such as pitting corrosion resistance and crevice corrosion resistance is also improved. it can. Further, addition of Cu is effective for improving corrosion resistance particularly in a non-oxidizing environment such as a sulfuric acid environment, while addition of Co is effective for further improving strength.
【００１０】以下に、本発明において各成分等の範囲を
限定した理由を述べる。なお、本発明において％は、特
に明記しない限り、重量％を意味する。第一に高Ｎｉ合
金心線の成分限定理由を述べる。The reasons for limiting the range of each component in the present invention will be described below. In the present invention,% means% by weight unless otherwise specified. First, the reasons for limiting the components of the high Ni alloy core wire will be described.
【００１１】Ｃ：Ｃは強化元素として０．００１％以上
添加する。一方、Ｃは高Ｎｉ溶接金属においては特にＣ
ｒと結合しやすく、粒界等に炭化物として析出し、耐食
性や延性・靱性を阻害するとともに、Ｍｏ、Ｗとも結合
して耐溶接高温割れ性も低下させる。したがってＣはで
きるだけ低減する必要があり、０．０１％を上限とし
た。C: C is added as a strengthening element in an amount of 0.001% or more. On the other hand, C is especially C in the high Ni weld metal.
It easily binds with r, precipitates as carbides at grain boundaries, etc., and inhibits corrosion resistance, ductility, and toughness, and also binds with Mo and W to reduce weld hot cracking resistance. Therefore, C needs to be reduced as much as possible, and 0.01% is made the upper limit.
【００１２】Ｓｉ：Ｓｉは、溶製時に脱酸元素として
０．０１％以上含有されるが、多量に含有すると溶接熱
サイクル中に高Ｃｒ−高Ｍｏ系の金属間化合物であるσ
相の析出を著しく助長し、その結果、耐食性や延性・靱
性が低下する。したがって、Ｓｉについてもできるだけ
低減するために、０．２％を上限とした。Si: Si is contained in an amount of 0.01% or more as a deoxidizing element during melting, but if it is contained in a large amount, it is a high Cr-high Mo intermetallic compound during the welding thermal cycle.
It significantly promotes the precipitation of phases, resulting in deterioration of corrosion resistance, ductility and toughness. Therefore, in order to reduce Si as much as possible, the upper limit is 0.2%.
【００１３】Ｍｎ：Ｍｎは脱酸元素であり、同時にＮの
固溶も促進するため０．０１％以上の含有が必要である
が、一方、多量に含有すると耐食性等に有害な金属間化
合物の析出も助長するため、２％を上限とした。Mn: Mn is a deoxidizing element and at the same time needs to be contained in an amount of 0.01% or more to promote solid solution of N. On the other hand, if contained in a large amount, it is an intermetallic compound which is harmful to corrosion resistance and the like. Since precipitation is also promoted, the upper limit was 2%.
【００１４】Ｃｒ：Ｃｒは耐食性を付与する主要元素で
あり、その効果を十分ならしめるためには１８％以上が
必要である。一方、多量に含有すると心線の製造性が著
しく低下するとともに、耐食性に有害な金属間化合物の
析出を助長する。それらを考慮して上限を２５％とし
た。Cr: Cr is a main element that imparts corrosion resistance, and 18% or more is necessary to fully bring out the effect. On the other hand, when contained in a large amount, the manufacturability of the core wire is remarkably reduced, and the precipitation of intermetallic compounds harmful to the corrosion resistance is promoted. Taking these into consideration, the upper limit was set to 25%.
【００１５】Ｎｉ：Ｎｉはマトリックスを構成する主要
元素である。耐食性の確保、凝固のまま組織中でのＭ
ｏ、Ｗの偏析の低減の観点から、少なくとも５５％以上
の含有が必要であるが、Ｃｒ等合金元素を表記の量含有
するためには７５％が上限である。Ni: Ni is the main element forming the matrix. Securing corrosion resistance, M in tissue as solidified
From the viewpoint of reducing segregation of o and W, it is necessary to contain at least 55% or more, but in order to contain alloy elements such as Cr in the indicated amounts, 75% is the upper limit.
【００１６】Ｃｕ：Ｃｕは、硫黄環境等の非酸化環境や
中性環境での耐食性を改善する元素であり、０．１％以
上の添加が必要であるが、多量に含有すると熱間加工性
を低下させるため溶接材料の製造性を害する上、塩化物
含有酸化性環境での耐食性も害することから、これらを
考慮して上限を３％とした。Cu: Cu is an element that improves the corrosion resistance in a non-oxidizing environment such as a sulfur environment and in a neutral environment, and it is necessary to add 0.1% or more, but if it is contained in a large amount, hot workability Therefore, the manufacturability of the welding material is impaired and the corrosion resistance in the chloride-containing oxidizing environment is impaired as well, so the upper limit was made 3% in consideration of these.
【００１７】Ｎ：Ｎはマトリックスに固溶して、耐食
性、強度を向上させる。その効果を十分ならしめるには
０．１％以上必要であるが、一方、０．３％を超えて含
有させるとワイヤの製造性が著しく低下し、また、窒化
物等の析出により溶接金属の耐食性も低下するため、こ
れを上限とした。N: N forms a solid solution in the matrix to improve corrosion resistance and strength. 0.1% or more is necessary to make the effect sufficiently effective. On the other hand, if the content exceeds 0.3%, the manufacturability of the wire is remarkably reduced, and the precipitation of nitride etc. causes the weld metal Corrosion resistance also decreases, so this was made the upper limit.
【００１８】Ｍｏ，Ｗのうち１種または２種：Ｍｏ，Ｗ
はいずれもマトリックスに固溶して、耐食性、強度を向
上させる。その効果を十分ならしめるためには１種また
は２種の合計として６％以上必要であるが、一方、１２
％を超えて含有すると、耐食性、延性・靱性に有害な金
属間化合物の生成を著しく助長するため、上限を１２％
とした。One or two of Mo and W: Mo and W
Both form a solid solution in the matrix to improve corrosion resistance and strength. In order to fully bring out the effect, it is necessary that the total amount of one kind or two kinds is 6% or more.
If it is contained in excess of 10%, the production of intermetallic compounds harmful to corrosion resistance, ductility and toughness is remarkably promoted, so the upper limit is 12%.
And
【００１９】Ａｌ：Ａｌは脱酸元素として０．００１％
以上添加されるが、０．０５％を超えて含有させると耐
食性、熱間加工性を低下させるため、０．００１〜０．
０５％と限定した。Al: Al is 0.001% as a deoxidizing element
Although it is added as described above, if it is contained in an amount of more than 0.05%, the corrosion resistance and the hot workability are deteriorated.
Limited to 05%.
【００２０】Ｓ、Ｐはいずれも不可避的不純物元素であ
り、両者とも溶接高温割れ感受性を著しく阻害する元素
である。また、多層溶接や補修溶接等の多重熱サイクル
中に粒界脆化も助長する。また、Ｓは熱間加工性に著し
く影響をおよぼす。したがって、両元素ともできるだけ
低減する必要があり、いずれも上限を０．０１％とし
た。Both S and P are unavoidable impurity elements, and both are elements which significantly impede the hot cracking susceptibility. It also promotes grain boundary embrittlement during multiple thermal cycles such as multi-layer welding and repair welding. Further, S significantly affects the hot workability. Therefore, it is necessary to reduce both elements as much as possible, and the upper limit of both elements is set to 0.01%.
【００２１】また、本発明は必要に応じて、１．０〜５
％のＣｏを添加する。Ｃｏは通常Ｎｉ合金では不可避的
に０．１％未満含有されるが、０．１％以上添加するこ
とにより、強度の改善が図られる。他方、５％を超えて
含有すると心線の製造性が低下する。したがって、上限
を５％とした。上記成分の残部はＦｅ等の不可避的不純
物である。In the present invention, if necessary, 1.0 to 5
% Co is added. Co is usually unavoidably contained in the Ni alloy in an amount of less than 0.1%, but the addition of 0.1% or more improves the strength. On the other hand, if the content exceeds 5%, the manufacturability of the core wire deteriorates. Therefore, the upper limit is set to 5%. The balance of the above components is inevitable impurities such as Fe.
【００２２】第二に、本発明で使用する被覆アーク溶接
棒における被覆剤の成分限定理由を述べる。 金属炭酸塩：金属炭酸塩は、立向姿勢でのスラグの流動
性を若干良くし、棒焼けに防止にも効果がある。しか
し、過剰になるとスパッタが増加するので、３０〜６０
％に制限する。なお、ここでいう金属炭酸塩とは、Ｃａ
ＣＯ3 、ＭｇＣＯ3 、ＢａＣＯ3 、Ｌｉ2 ＣＯ3 などを
いう。Secondly, the reasons for limiting the components of the coating agent in the coated arc welding rod used in the present invention will be described. Metal carbonate: Metal carbonate slightly improves the fluidity of the slag in the vertical position and is also effective in preventing stick burning. However, if it becomes excessive, the spatter increases, so 30-60
Limit to%. The metal carbonate referred to here is Ca
CO 3, MgCO 3, BaCO 3 , refers to such Li 2 CO 3.
【００２３】金属ふっ化物：金属ふっ化物は、アークの
集中性を損なわずに適度にアークの吹付けを強くするた
め、融合不良などの溶接欠陥防止に効果的である。この
ような効果は、添加量が１５％以上で顕著に現れるが、
３０％を超えるとアークの吹付けが強くなり過ぎるの
で、１５〜３０％に制限する。なお、ここでいう金属ふ
っ化物とは、ＣａＦ2 やＢａＦ2 などをいう。Metal Fluoride: The metal fluoride is effective for preventing welding defects such as defective fusion because it appropriately strengthens the arc spraying without impairing the concentration of the arc. Such an effect remarkably appears when the added amount is 15% or more,
If it exceeds 30%, the arc spraying becomes too strong, so it is limited to 15 to 30%. The metal fluoride referred to here is CaF 2 , BaF 2, or the like.
【００２４】金属酸化物：金属酸化物は、スラグの被包
性を良くし、特に下向や水平すみ肉姿勢におけるビード
形状が良好になる。また、生産性確保のために添加され
る。しかし、１５％未満では効果が不十分であり、ま
た、２０％を超えるとスパッタが増加し、立向姿勢での
スラグの流動性も悪くなるので、１５〜２０％に制限す
る。なお、ここでいう金属酸化物とは、ＳｉＯ2 、Ｃａ
Ｏ、ＴｉＯ2 などをいう。Metal oxide: The metal oxide improves the encapsulation property of the slag, and particularly the bead shape in the downward or horizontal fillet posture. It is also added to ensure productivity. However, if it is less than 15%, the effect is insufficient, and if it exceeds 20%, the spatter increases and the fluidity of the slag in the vertical position deteriorates. Therefore, it is limited to 15 to 20%. The metal oxide mentioned here means SiO 2 , Ca.
O, TiO 2 and the like.
【００２５】また、本発明方法で使用する被覆アーク溶
接棒の被覆剤においては、上記の成分の他に、溶接時の
金属蒸発に伴う成分調整を行うために、Ｍｎ，Ｃｒ，Ｍ
ｏなどの金属粉を添加することができるが、金属粉の合
計が２０％を超えると靱性・延性が低下するため、上限
は２０％が好ましい。さらに、被覆剤は心線に均一に塗
布し、かつ、溶融金属および溶融スラグからの熱影響を
少なくする必要から、均等性および耐熱性の観点から被
覆率は２５〜４５％が好ましい。In addition, in the coating agent for the coated arc welding rod used in the method of the present invention, in addition to the above components, Mn, Cr, and M are added in order to adjust the components associated with metal evaporation during welding.
Although metal powders such as o can be added, if the total of the metal powders exceeds 20%, the toughness and ductility will decrease, so the upper limit is preferably 20%. Furthermore, since it is necessary to apply the coating agent evenly to the core wire and to reduce the heat effect from the molten metal and molten slag, the coating rate is preferably 25 to 45% from the viewpoint of uniformity and heat resistance.
【００２６】本発明では、耐海水性・耐海塩粒子性を目
的とする構造物等の溶接に一般的に良く使用される被覆
アーク溶接を対象とする。溶接は、自動、半自動、手動
のいずれでも良く、特に限定されるものではない。さら
に、それら構造物の補修溶接あるいは肉盛等にも適用で
きる。The present invention is directed to covered arc welding, which is commonly used for welding structures and the like for the purpose of resistance to seawater and sea salt particles. Welding may be automatic, semi-automatic, or manual, and is not particularly limited. Further, it can be applied to repair welding or overlaying of those structures.
【００２７】本発明が対象とする高Ｍｏステンレス鋼
は、Ｍｏ量が３．５〜８．０％、Ｃｒ量が１８．０〜２
５．０％であって、適量のＮｉを含有することによりミ
クロ組織がオーステナイト単相のもので、高耐食性が要
求されるステンレス鋼である。ここで、Ｍｏ量が３．５
％未満、Ｃｒ量が１８％未満では、十分な耐食性が確保
できない。また、Ｍｏ量が８％超、Ｃｒ量が２５％超で
は金属間化合物が析出し、延性・靱性が十分ではなくな
る。The high Mo stainless steel targeted by the present invention has a Mo content of 3.5-8.0% and a Cr content of 18.0-2.
The stainless steel is 5.0% and has a microstructure of austenite single phase by containing a proper amount of Ni and is required to have high corrosion resistance. Here, the amount of Mo is 3.5
%, And the Cr content is less than 18%, sufficient corrosion resistance cannot be secured. On the other hand, if the Mo content exceeds 8% and the Cr content exceeds 25%, an intermetallic compound precipitates and ductility and toughness become insufficient.
【００２８】高Ｍｏ鋼ではあっても、該ステンレス鋼の
組織がフェライト単相、あるいはフェライト＋オーステ
ナイト二相からなる場合には、ステンレス鋼自体の耐食
性および延性・靱性が必ずしも高くなく、さらに、溶接
金属中でもＮｉ量が低下して脆弱な金属間化合物が析出
しやすくなるので好ましくない。なお、ミクロ組織は、
エッチングの後に直接組織観察する方法もしくはフェラ
イトメーターのような磁気的測定により判定するのが好
ましい。Even if it is a high Mo steel, if the structure of the stainless steel is ferrite single phase or ferrite + austenite dual phase, the corrosion resistance and ductility / toughness of the stainless steel itself are not necessarily high, and further, welding Even in metals, the amount of Ni decreases and brittle intermetallic compounds tend to precipitate, which is not preferable. The microstructure is
It is preferable to judge by a method of directly observing the structure after etching or by a magnetic measurement such as a ferrite meter.
【００２９】本発明が対象とする高Ｍｏステンレス鋼に
おいては、Ｍｏ量およびＣｒ量が前述の範囲であり、適
量のＮｉを含有することによりミクロ組織がオーステナ
イト単相であれば、他の成分は特に限定されるものでは
なく、いずれも適用可能であるが、Ｃ：０．００５〜
０．０２％、Ｓｉ：０．３〜０．７％、Ｍｎ：０．３〜
１．０％、Ｐ：０．０３％以下、Ｓ：０．００３％以
下、Ｃｒ：１８〜２２％、Ｍｏ：５．５〜６．５％含有
するものであることが好ましい。In the high Mo stainless steel targeted by the present invention, if the amount of Mo and the amount of Cr are within the above ranges and the microstructure is an austenite single phase by containing an appropriate amount of Ni, the other components are It is not particularly limited, and any of them is applicable, but C: 0.005 to
0.02%, Si: 0.3 to 0.7%, Mn: 0.3 to
1.0%, P: 0.03% or less, S: 0.003% or less, Cr: 18-22%, Mo: 5.5-6.5% are preferable.
【００３０】[0030]
【実施例】以下、実施例にて本発明を説明する。表１に
母材として用いた高Ｍｏステンレス鋼板の化学成分およ
びミクロ組織を示す。はＡＳＴＭ−Ａ２４０−Ｓ３１
２５４相当の高耐食オーステナイト系ステンレス鋼であ
り、は高耐海水性を目的に実験室的に溶製したステ
ンレス鋼である。板厚はいずれも５ｍｍであり、開先角
度：８０°、ルートフェース：０．５ｍｍのＹ開先を設
け、表２に成分を示す供試心線と、表３に示す被覆剤を
表４に示す組み合わせにより作製した被覆アーク溶接棒
を用いて溶接継手を作成した。EXAMPLES The present invention will be described below with reference to examples. Table 1 shows the chemical composition and microstructure of the high Mo stainless steel sheet used as the base material. Is ASTM-A240-S31
It is a high-corrosion-resistant austenitic stainless steel equivalent to 254, and is a stainless steel melted in a laboratory for the purpose of high seawater resistance. The plate thickness is 5 mm in each case, a Y-groove with a groove angle of 80 ° and a root face of 0.5 mm is provided, and the test core wire showing the components in Table 2 and the coating material shown in Table 3 are shown in Table 4. Welded joints were prepared using the covered arc welding rods produced by the combination shown in.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 [Table 2]
【００３３】[0033]
【表３】 [Table 3]
【００３４】[0034]
【表４】 [Table 4]
【００３５】下向姿勢で溶接条件は溶接電流：１４０Ａ
（ＡＣ）、アーク電圧：２２〜２６Ｖ、溶接速度：２０
〜２５ｃｍ／ｍｉｎとした。また、立向姿勢での溶接条
件は溶接電流：１００Ａ（ＡＣ）、アーク電圧：２０〜
２４Ｖ、溶接速度：５〜１０ｃｍ／ｍｉｎとした。な
お、表１のステンレス鋼は、圧延の後に１１５０℃で溶
体化熱処理を施して、臨界孔食発生温度を７０℃以上と
したステンレス鋼である。表４には各被覆アーク溶接棒
を適用したステンレス鋼板の記号を記した。Welding current: 140A in the downward posture
(AC), arc voltage: 22 to 26 V, welding speed: 20
˜25 cm / min. Further, the welding conditions in the vertical posture are as follows: welding current: 100 A (AC), arc voltage: 20-
24V, welding speed: 5 to 10 cm / min. The stainless steels in Table 1 are stainless steels that have been subjected to solution heat treatment at 1150 ° C after rolling to have a critical pitting corrosion temperature of 70 ° C or higher. Table 4 shows the symbols of stainless steel plates to which each coated arc welding rod is applied.
【００３６】作製した溶接継手では、それぞれ耐食性、
機械的特性を調べた。耐食性については、耐孔食性、耐
粒界腐食性および全面腐食性を調べた。耐孔食性は、塩
化物環境での臨界孔食発生温度（ＣＰＴ）を求め評価し
た。腐食環境としては、ＪＩＳ−Ｇ０５７８−１９８１
に定める６％塩化第二鉄＋０．０５Ｎ塩酸水溶液を用い
た。臨界孔食発生温度は、５℃間隔で管理された腐食環
境に２４時間浸漬し、孔食の発生しない最高温度を求
め、それと定めた。また、耐粒界腐食性および全面腐食
性については、それぞれ６５％沸騰硝酸および１０％沸
騰硫酸中に、前者は４８時間、後者は６時間浸漬して、
腐食減量によって評価した。それぞれの耐食性評価試験
の試験片は、いずれも溶接部を中央に含むよう３０×３
０ｍｍの大きさを採取し、余盛を削除して元厚（５ｍ
ｍ）のまま用いた。The produced welded joints have corrosion resistance,
The mechanical properties were investigated. Regarding corrosion resistance, pitting corrosion resistance, intergranular corrosion resistance and general corrosion resistance were examined. The pitting corrosion resistance was evaluated by determining the critical pitting corrosion generation temperature (CPT) in a chloride environment. As a corrosive environment, JIS-G0578-1981
6% ferric chloride + 0.05N hydrochloric acid aqueous solution defined in 1. The critical pitting corrosion temperature was determined by immersing in a corrosive environment controlled at 5 ° C. intervals for 24 hours to find the maximum temperature at which pitting corrosion did not occur. Regarding the intergranular corrosion resistance and general corrosion resistance, the former was immersed in 65% boiling nitric acid and 10% boiling sulfuric acid for 48 hours and the latter for 6 hours, respectively.
It was evaluated by the corrosion weight loss. Each of the test pieces for each corrosion resistance evaluation test was 30 × 3 so that the welded part was included in the center.
The size of 0 mm is sampled, the extra scale is removed, and the original thickness (5 m
m) was used as it was.
【００３７】一方、機械的特性は、溶接継手引張試験、
溶接金属のシャルピー衝撃試験、および溶接継手の表・
裏曲げ試験から評価した。継手引張試験は、溶接継手か
ら余盛を削除した試験片（１号試験片、ＪＩＳ−Ｚ３１
２１−１９６１）を採取し、引張強度を求めた。シャル
ピー衝撃試験は、溶接方向に垂直方向からサブサイズシ
ャルピー試験片（５ｔ×１０ｗ×５５Ｌｍｍ）を採取
し、０℃にて試験し、吸収エネルギーを求めた。曲げ試
験は、溶接継手から溶接方向に垂直方向から余盛を削除
した試験片（５ｔ×３０ｗ×２５０Ｌｍｍ）を採取し、
溶接部を表または裏からローラ曲げ（ＪＩＳ−Ｚ３１２
４−１９６０、曲げ半径：Ｒ＝１０ｍｍ）し、溶接継手
の曲げ延性を評価した。On the other hand, the mechanical properties are as follows:
Charpy impact test of weld metal and table of welded joint
Evaluated from the back bending test. The joint tensile test is a test piece (No. 1 test piece, JIS-Z31
21-1961) was sampled and the tensile strength was determined. In the Charpy impact test, a subsize Charpy test piece (5t × 10w × 55Lmm) was sampled from the direction perpendicular to the welding direction and tested at 0 ° C. to determine the absorbed energy. In the bending test, a test piece (5t × 30w × 250Lmm) from which a surplus was removed from the weld joint in the direction perpendicular to the welding direction was taken,
Roll-bend the welded part from the front or back (JIS-Z312
4-1960, bending radius: R = 10 mm), and the bending ductility of the welded joint was evaluated.
【００３８】また、それぞれの被覆アーク溶接棒の溶接
高温割れ感受性をＣ型ジグ拘束突合せ溶接割れ試験（Ｊ
ＩＳ−Ｚ３１５５−１９７４）により調べた。試験片と
しては、上記溶接継手特性評価に用いたのと同じ３種の
耐食ステンレス鋼を用い、被覆アーク溶接により溶接部
の割れを調べた。Further, the susceptibility of each coated arc welding rod to high temperature cracking was evaluated by the C-type jig restraint butt welding cracking test (J
IS-Z3155-1974). As the test piece, the same three kinds of corrosion-resistant stainless steels as those used for the evaluation of the welded joint characteristics were used, and cracks in the welded portion were examined by covered arc welding.
【００３９】表５にそれぞれの溶接作業性および腐食試
験の結果を示し、表６に機械試験および高温割れ試験の
結果を示す。表５，表６から明らかなように、本発明例
であるＮｏ．１〜５は、溶接作業性、耐食性、機械的特
性および耐高温割れ性に優れ、多数の要求特性を同時に
満足できることがわかる。Table 5 shows the results of welding workability and corrosion test, and Table 6 shows the results of mechanical test and hot cracking test. As is clear from Table 5 and Table 6, No. It can be seen that Nos. 1 to 5 are excellent in welding workability, corrosion resistance, mechanical properties, and high temperature crack resistance, and can satisfy many required properties at the same time.
【００４０】[0040]
【表５】 [Table 5]
【００４１】[0041]
【表６】 [Table 6]
【００４２】まず、耐孔食性に関してであるが、本発明
の溶接棒で溶接した溶接継手の臨界孔食発生温度はいず
れも７０〜８０℃の範囲で、比較例Ｎｏ．６，７より高
く、母材同等の優れた耐孔食性を有しているといえる。
次に、耐粒界腐食性については、６５％沸騰硝酸試験の
結果では、本発明法による溶接部はいずれも母材の結果
と同等の１．４６〜１．７９ｇ／ｍ2 ・ｈｒの腐食速度
を示し、良好な耐粒界腐食性を有しているといえる。さ
らに、全面腐食性については、本発明法による溶接継手
は、いずれも比較心線ｄ，ｅを用いた溶接継手より耐食
性に優れており、母材と比較しても同等以上の耐全面腐
食性を示した。これは、高Ｎｉ，Ｍｏ，ＷおよびＣｕ添
加の効果によるものである。First, concerning the pitting corrosion resistance, the critical pitting corrosion generation temperature of the welded joints welded with the welding rod of the present invention is in the range of 70 to 80 ° C. It can be said that it has higher pitting corrosion resistance than that of the base metal, which is higher than those of Nos. 6 and 7.
Next, regarding the intergranular corrosion resistance, according to the result of the 65% boiling nitric acid test, all the welded parts according to the method of the present invention have the same corrosion of 1.46 to 1.79 g / m 2 · hr as the result of the base metal. It exhibits a high speed and can be said to have good intergranular corrosion resistance. Further, regarding the general corrosion resistance, the welded joints according to the method of the present invention are superior in corrosion resistance to the welded joints using the comparative cores d and e, and even if compared with the base metal, the same or more general corrosion resistance is obtained. showed that. This is due to the effect of adding high Ni, Mo, W and Cu.
【００４３】他方、機械的特性に関しては、まず、シャ
ルピー衝撃試験の結果では、比較心線ｄを用いた溶接金
属は非常に低い吸収エネルギーを示したのに対し、本発
明による溶接金属はいずれも十分高い吸収エネルギーが
得られた。また、強度に関しては、本発明心線ａ，ｂに
よる溶接部は比較心線ｄと同等であり、これはまた母材
ともほぼ同等である。さらに、心線ｃによる溶接部はこ
れより約３〜５ｋｇｆ／ｍｍ2 程度高い引張強度を示
し、Ｃｏ添加による強度改善が認められる。曲げ試験で
は、本発明による溶接部は、表曲げ、裏曲げのいずれの
面にも割れ、欠陥等は認められず、曲げ延性は良好であ
った。しかるに、比較例Ｎｏ．６，７による溶接部は、
曲げ表面に多数の微小な割れが見られる。On the other hand, regarding the mechanical properties, first, in the result of the Charpy impact test, the weld metal using the comparative core wire d showed a very low absorbed energy, whereas all the weld metals according to the present invention. A sufficiently high absorbed energy was obtained. In terms of strength, the welded portions according to the present invention core wires a and b are equivalent to the comparative core wire d, and this is also substantially equivalent to the base metal. Further, the welded portion by the core wire c shows a tensile strength higher by about 3 to 5 kgf / mm 2 than this, and the strength improvement by the addition of Co is recognized. In the bending test, the welded part according to the present invention showed no cracks, defects or the like on either side of front bending and back bending, and had good bending ductility. However, in Comparative Example No. The welded part by 6 and 7 is
Many small cracks are seen on the bent surface.
【００４４】これらのことより本発明による溶接部は、
母材のタイプにかかわらず溶接作業性と腐食性のみなら
ず機械的特性にも優れていることが示され、耐食構造用
溶接材料として本発明が有効であることが明らかになっ
た。さらに、溶接高温割れ試験結果からもわかるよう
に、比較例Ｎｏ．６，７は割れ感受性が極めて高いのに
対し、本発明例では優れた耐高温割れ性を示した。特
に、比較例による試験溶接ビードでは、通常この試験に
おいて割れやすいとされるクレータのみならず、それ以
外の部分にもかなり長い割れが見られた。一方、本発明
例による溶接ビードでは、クレータに若干の割れが見ら
れたが他は全く割れが認められず、実用上の耐割れ性は
十分であるといえる。From the above, the welded portion according to the present invention is
It was shown that not only the workability and corrosivity but also the mechanical properties are excellent regardless of the type of base material, and it became clear that the present invention is effective as a welding material for corrosion resistant structures. Further, as can be seen from the results of the welding hot crack test, Comparative Example No. Nos. 6 and 7 had extremely high cracking susceptibility, while the examples of the present invention showed excellent high temperature cracking resistance. In particular, in the test weld bead according to the comparative example, not only the crater which is usually liable to be cracked in this test, but also a considerably long crack was observed in other portions. On the other hand, in the weld bead according to the example of the present invention, some cracks were observed in the crater, but no other cracks were observed, and it can be said that the practical crack resistance is sufficient.
【００４５】[0045]
【発明の効果】上記の実施例からもわかるように、本発
明は溶接作業性、耐食性および機械的特性、耐溶接高温
割れ性に優れた高Ｍｏステンレス鋼用の被覆アーク溶接
棒を提供することを可能としたものであり、産業の発展
に貢献するところが極めて大である。As can be seen from the above examples, the present invention provides a coated arc welding rod for high Mo stainless steel, which is excellent in welding workability, corrosion resistance and mechanical characteristics, and high temperature crack resistance in welding. It is a very important factor to contribute to the development of industry.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 三宅 聰之 千葉県富津市新富20−１ 新日本製鐵株式 会社技術開発本部内 (72)発明者 緒方 雅人 千葉県富津市新富20−１ 新日本製鐵株式 会社技術開発本部内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiyuki Miyake 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel Co., Ltd. Technology Development Division (72) Inventor Masato Ogata 20-1 Shintomi, Futtsu-shi, Chiba Japan Steel Engineering Co., Ltd.
Claims (2)
ｒ：１８．０〜２５．０％を含有し、ミクロ組織がオー
ステナイト単相からなる高Ｍｏステンレス鋼用の被覆ア
ーク溶接棒において、重量％で、 Ｃ ：０．００１〜０．０１％、 Ｓｉ：０．０１〜０．２％、 Ｍｎ：０．０１〜２％、 Ｃｒ：１８〜２５％、 Ｎｉ：５５〜７５％、 Ｃｕ：０．１〜３％、 Ｎ ：０．１〜０．３％、 Ｍｏ、Ｗのうち１種または２種：６〜１２％、 Ａｌ：０．００１〜０．０５％、を含有し、 Ｓを０．０１％以下、 Ｐを０．０１％以下、に制限し、残りがＦｅおよび不可
避不純物よりなる高Ｎｉ合金心線に、被覆剤全量に対す
る重量％で、 金属炭酸塩 ：３０〜６０％、 金属ふっ化物：１５〜３０％、 金属酸化物 ：１５〜２０％、を含有する被覆剤を塗布
したことを特徴とする高Ｍｏステンレス鋼用被覆アーク
溶接棒。1. Mo: 3.5-8.0%, C by weight
r: 18.0 to 25.0%, in a coated arc welding rod for high Mo stainless steel having a microstructure consisting of an austenite single phase, in weight%, C: 0.001 to 0.01%, Si : 0.01-0.2%, Mn: 0.01-2%, Cr: 18-25%, Ni: 55-75%, Cu: 0.1-3%, N: 0.1-0. 3%, 1 or 2 kinds of Mo and W: 6 to 12%, Al: 0.001 to 0.05%, S is 0.01% or less, P is 0.01% or less, In the high Ni alloy core wire consisting of Fe and unavoidable impurities, the balance is 30% to 60% of metal carbonate, 15% to 30% of metal fluoride, and 15% of metal oxide. ˜20%, coated arc containing high Mo stainless steel, characterized in that Sebbo.
項１に記載の高Ｍｏステンレス鋼用被覆アーク溶接棒。2. The coated arc welding rod for high Mo stainless steel according to claim 1, wherein the high Ni alloy core wire further contains, by weight, Co: 0.1 to 5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8200895A JPH08252692A (en) | 1995-03-15 | 1995-03-15 | Coated electrode for highly corrosion resistant and high mo stainless steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8200895A JPH08252692A (en) | 1995-03-15 | 1995-03-15 | Coated electrode for highly corrosion resistant and high mo stainless steel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08252692A true JPH08252692A (en) | 1996-10-01 |
Family
ID=13762503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8200895A Withdrawn JPH08252692A (en) | 1995-03-15 | 1995-03-15 | Coated electrode for highly corrosion resistant and high mo stainless steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08252692A (en) |
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| JP2000052089A (en) * | 1998-08-14 | 2000-02-22 | Nippon Steel Corp | Austenite system stainless steel filler rod with excellent high temperature characteristic |
| JP2002248598A (en) * | 2001-02-26 | 2002-09-03 | Nippon Steel Corp | Coated welding electrode for high corrosion resistant stainless steel |
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- 1995-03-15 JP JP8200895A patent/JPH08252692A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000052089A (en) * | 1998-08-14 | 2000-02-22 | Nippon Steel Corp | Austenite system stainless steel filler rod with excellent high temperature characteristic |
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| WO2006003954A1 (en) * | 2004-06-30 | 2006-01-12 | Sumitomo Metal Industries, Ltd. | Ni BASE ALLOY MATERIAL TUBE AND METHOD FOR PRODUCTION THEREOF |
| AU2005258507B2 (en) * | 2004-06-30 | 2008-04-17 | Nippon Steel Corporation | Ni base alloy material tube and method for production thereof |
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| JP2011063863A (en) * | 2009-09-18 | 2011-03-31 | Sumitomo Metal Ind Ltd | Ni-BASED ALLOY MATERIAL |
| WO2011034100A1 (en) * | 2009-09-18 | 2011-03-24 | 住友金属工業株式会社 | Ni-BASED ALLOY MATERIAL |
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| CN103374671A (en) * | 2012-04-30 | 2013-10-30 | 海恩斯国际公司 | Acid and alkali resistant nickel-chromium-molybdenum-copper alloys |
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| JP2014040669A (en) * | 2013-10-10 | 2014-03-06 | Nippon Yakin Kogyo Co Ltd | High corrosion-resistant alloy excellent in intergranular corrosion resistance |
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