JP2010227949A - Weld metal and welding material - Google Patents
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Description
本発明は、溶接金属および溶接材料に関する。詳しくは、エネルギー輸送機器における高圧ガス配管など各種部材の素材として適用される鋼やオーステナイト系材料などの溶接、特に高強度鋼やオーステナイト系材料の溶接に使用され、高強度および溶接性としての「耐溶接割れ性」に優れた溶接金属を得ることができる溶接材料および上記溶接された部材の溶接金属に関する。 The present invention relates to a weld metal and a weld material. Specifically, it is used for welding steel and austenitic materials that are used as materials for various components such as high-pressure gas pipes in energy transportation equipment, especially for high-strength steel and austenitic materials. The present invention relates to a welding material capable of obtaining a weld metal excellent in “weld crack resistance” and a weld metal of the welded member.
近年、水素や天然ガスなどをエネルギーとして利用する輸送機器の実用化研究が活発に進められている。その実用化に際しては、これらのガスを高圧で貯蔵、輸送できる使用環境の整備が併せて必要であり、使用される材料には、高強度を有することが求められるため、高強度化の取り組みがなされている。 In recent years, research on practical application of transportation equipment using hydrogen, natural gas, or the like as energy has been actively promoted. For practical use, it is necessary to prepare an environment in which these gases can be stored and transported at high pressures, and the materials used are required to have high strength. Has been made.
例えば、母材については、高Mn化することでNの溶解度を高め、Vを添加したうえで必要に応じて適切な熱処理を施すことにより高強度化を試みたオーステナイト系材料の提案がなされている。具体的には、特許文献1および特許文献2に、ガスの高圧での貯蔵および輸送用部材の素材として使用可能な引張強さで1GPa以上の高強度材料が開示されている。
For example, with respect to the base material, an austenite-based material has been proposed in which the solubility of N is increased by increasing the Mn content, V is added, and an appropriate heat treatment is performed as necessary to increase the strength. Yes. Specifically,
なお、一般に、構造物として使用する場合には上述した高強度オーステナイト系材料は溶接により組み立てられる。そして、溶接の際の溶接材料としては、母材をそのまま使用することが考えられる。 In general, when used as a structure, the above-described high-strength austenitic material is assembled by welding. And it is possible to use a base material as it is as a welding material in the case of welding.
しかしながら、オーステナイト系材料の溶接金属は一般的に溶接時の高温割れ感受性が高い。このため、溶接金属には高温割れの防止が求められることになる。加えて、母材の場合、溶製後の圧延・熱処理による組織の調整を受けて高温強度の確保が図られるのに対し、溶接金属はほとんどの場合、凝固ままの組織で使用される。 However, austenitic weld metals generally have high hot cracking susceptibility during welding. For this reason, the weld metal is required to prevent hot cracking. In addition, in the case of a base material, the structure is adjusted by rolling and heat treatment after melting, and high temperature strength is ensured. On the other hand, weld metal is almost always used in a solid structure.
したがって、母材をそのまま溶接材料として使用する場合には、耐高温割れ性が十分でないばかりか、母材と同等の高い強度を得ることは極めて困難になる。このため、溶接後に「後熱処理」を実施することによって微細な粒子を析出させ、少なくとも母材と同じかそれ以上に、溶接金属を強化する必要が生じる。 Therefore, when the base material is used as a welding material as it is, not only the hot cracking resistance is sufficient, but it is extremely difficult to obtain a high strength equivalent to that of the base material. For this reason, it is necessary to reinforce the weld metal at least as much as the base material by precipitating fine particles by performing “post heat treatment” after welding.
なお、1GPa以上の引張強さを有する溶接材料としては、例えば、AWS A5.14−2005のERNiFeCr−2が既に実用化されている。また、特許文献3および特許文献4には、Al、TiおよびNbを積極活用することによって、800MPaを超える引張強さを有する溶接材料(溶接金属)が提案されている。上記特許文献4には、Tiおよび/またはAlを適正量含有させることで凝固割れを防止できることも併せて示されている。 As a welding material having a tensile strength of 1 GPa or more, for example, ERNiFeCr-2 of AWS A5.14-2005 has already been put into practical use. Patent Document 3 and Patent Document 4 propose a welding material (welded metal) having a tensile strength exceeding 800 MPa by actively utilizing Al, Ti, and Nb. Patent Document 4 also shows that solidification cracking can be prevented by containing an appropriate amount of Ti and / or Al.
しかしながら、これらの溶接材料についても、高強度化を果たすためには、溶接後に少なくとも120min以上の「後熱処理」を行うことが必要である。したがって、実際の大型構造物を考えた場合、上記のような長時間の溶接後熱処理の実施は、その適用に大きな制約を受けるとともに、製造コストも極度に増大する。 However, in order to increase the strength of these welding materials as well, it is necessary to perform “post heat treatment” for at least 120 minutes after welding. Therefore, when an actual large structure is considered, the long-time post-weld heat treatment as described above is greatly restricted in its application and the manufacturing cost is extremely increased.
本発明は、上記現状に鑑みてなされたもので、短時間の溶接後熱処理で高強度が得られ、かつ、優れた耐溶接割れ性をも具備する溶接金属とそのような溶接金属を形成するための溶接材料とを提供することを目的とするものであり、特に、近年開発が進みつつある引張強さが1GPa以上の高強度鋼や高強度オーステナイト系材料を母材とする溶接構造物をも構成できる溶接金属と前記高強度母材の溶接にも適用できる溶接材料を提供することを目的とする。 The present invention has been made in view of the above situation, and forms a weld metal having high strength obtained by a short post-weld heat treatment and also having excellent weld crack resistance, and such a weld metal. In particular, a welded structure using as a base material a high-strength steel or high-strength austenitic material having a tensile strength of 1 GPa or more, which has been developed in recent years. Another object of the present invention is to provide a welding material that can also be applied to welding of a weld metal that can also be configured and the high-strength base metal.
本発明者らは、前記した課題を解決するために、種々の検討を実施した。その結果、下記(a)の知見を得た。 The present inventors have conducted various studies in order to solve the above-described problems. As a result, the following knowledge (a) was obtained.
(a)溶接金属において、高強度を達成するためには、Niの含有量を特定の範囲に規制するとともにTiおよびAlを含有させ、溶接後熱処理を施すことによって、Ni3TiあるいはNi3(Al、Ti)による析出強化を活用することが有効である。しかしながら、これらの元素を多量に含有させた場合においても高強度化を果たすためには、長時間の溶接後熱処理が必要となる。 (A) In order to achieve high strength in the weld metal, the content of Ni is restricted to a specific range, Ti and Al are contained, and post-weld heat treatment is performed, whereby Ni 3 Ti or Ni 3 ( It is effective to utilize precipitation strengthening by Al, Ti). However, even when these elements are contained in a large amount, a long post-weld heat treatment is required to achieve high strength.
そこで、本発明者らは、短時間、特に、120min以下の短時間での溶接後熱処理での高強度化および溶接性としての「耐溶接割れ性」を両立させるために、先ず、Tiの含有量を種々に変化させて調査、検討を行った。なお、この際の溶接金属については質量%で18〜38%のNiを含むとともに、質量%で、0.1〜0.6%のVを含むものとした。 Therefore, in order to achieve both high strength in post-weld heat treatment in a short time, in particular, a short time of 120 min or less and “weld crack resistance” as weldability, the present inventors first include Ti. Investigation and examination were conducted with various amounts. In addition, about the weld metal in this case, while containing 18 to 38% Ni by mass%, it was supposed to contain 0.1 to 0.6% V by mass%.
その結果、下記(b)および(c)の事項が明らかになった。 As a result, the following items (b) and (c) were clarified.
(b)質量%で、Tiを2.0〜6.0%含有させた場合、溶接後熱処理を実施すると、Ni3Tiがマトリックスに微細に析出して強度が増大する。 (B) When Ti is contained in an amount of 2.0 to 6.0% by mass, Ni 3 Ti precipitates finely in the matrix and increases the strength when heat treatment after welding is performed.
(c)Tiを単独で含有させただけの場合には、上記したNi3Tiによる析出強化効果を得るには、長時間の熱処理が必要である。しかも、溶接金属に「凝固割れ」および「延性低下割れ」が発生しやすい。 (C) When Ti is contained alone, long-time heat treatment is required to obtain the precipitation strengthening effect by the above-described Ni 3 Ti. In addition, “solidification cracks” and “ductility degradation cracks” tend to occur in the weld metal.
そこでさらに、質量%で、Tiを2.0〜6.0%含有させた場合における各種元素の影響について種々の調査、検討を行った。その結果、下記(d)の重要な知見を得た。 Therefore, various investigations and examinations were conducted on the influence of various elements when Ti was contained in an amount of 2.0 to 6.0% by mass. As a result, the following important knowledge (d) was obtained.
(d)質量%で、18〜38%のNiを含む溶接金属について、短時間の溶接後熱処理での高強度化および溶接性としての「耐溶接割れ性」を両立させるためには、質量%で、Tiを2.0〜6.0%含有させたうえで、C、CrおよびAlの含有量をそれぞれ、質量%で、C:0.16〜0.35%、Cr:9〜22%およびAl:0.05〜0.65%とする必要がある。 (D) For a weld metal containing 18 to 38% Ni in mass%, in order to achieve both high strength in a short post-weld heat treatment and “weld crack resistance” as weldability, mass% In addition, Ti is contained in an amount of 2.0 to 6.0%, and the contents of C, Cr, and Al are, respectively, by mass, C: 0.16 to 0.35%, Cr: 9 to 22% And Al: 0.05 to 0.65% is necessary.
なお、上記(d)の理由は次の<1>〜<6>のように考えられる。 The reason for the above (d) is considered as the following <1> to <6>.
<1>質量%で、0.05%以上のAlを含有させることによって、遷移相としてのNi3(Al、Ti)が短時間で析出し、その後、最終安定相であるNi3Tiとなるため、より短時間の熱処理で強度が向上する。 By containing 0.05% or more of Al at <1>% by mass, Ni 3 (Al, Ti) as a transition phase precipitates in a short time, and then becomes Ni 3 Ti as the final stable phase. Therefore, the strength is improved by a shorter heat treatment.
<2>しかし、上記した量のAlとTiだけを含有させた場合には、特に、Tiは溶接金属の凝固時に凝固偏析しやすい元素であることから、凝固割れ感受性が大きく増大する。 <2> However, when only the above-mentioned amounts of Al and Ti are contained, in particular, Ti is an element that easily solidifies and segregates during solidification of the weld metal, so that the solidification cracking sensitivity is greatly increased.
<3>CとCrを含有させることによって、溶接金属の凝固過程でTiを固溶するM23C6とオーステナイトの共晶凝固を生じさせ、凝固末期の液相の消失を促進させるとともに、液相中に凝固偏析して融点を降下させる有害なTiの量を軽減することになるので、凝固割れを防止することができる。 <3> By containing C and Cr, eutectic solidification of M 23 C 6 and austenite, which dissolves Ti in the solidification process of the weld metal, is generated, and the disappearance of the liquid phase at the end of solidification is promoted. Since the amount of harmful Ti that solidifies and segregates in the phase and lowers the melting point is reduced, solidification cracking can be prevented.
<4>凝固中に晶出したM23C6は、凝固後にはデンドライト境界にオーステナイトと層状組織を形成して存在する。このため、最終凝固界面積を増大させて、不純物元素の偏析を軽減する。加えて、特定面への応力集中も軽減することになるため、不純物元素が偏析して弱化した粒界に応力が作用して生じる延性低下割れの防止にも効果を有する。 <4> M 23 C 6 crystallized during solidification exists after a solidification by forming austenite and a layered structure at the dendrite boundary. For this reason, the segregation of impurity elements is reduced by increasing the final solidification interface area. In addition, since stress concentration on a specific surface is also reduced, it has an effect of preventing ductile deterioration cracks caused by stress acting on the grain boundaries where the impurity elements are segregated and weakened.
<5>しかしながら、M23C6中に多量のTiが固溶すると、Ni3TiまたはNi3(Al、Ti)の析出駆動力が小さくなって、長時間の熱処理が必要となる。さらに、M23C6を晶出させることにより、凝固割れおよび延性低下割れの防止は可能となるものの、M23C6は、マトリックスであるオーステナイト相に比べて延性に乏しいため、溶接金属における延性低下が生じる。 <5> However, when a large amount of Ti is dissolved in M 23 C 6 , the driving force for precipitation of Ni 3 Ti or Ni 3 (Al, Ti) decreases, and a long-time heat treatment is required. Further, by crystallizing M 23 C 6 , it is possible to prevent solidification cracking and ductile deterioration cracking, but M 23 C 6 is poor in ductility compared to the austenite phase that is a matrix, and therefore, ductility in weld metal. A decrease occurs.
<6>上述した観点から、CおよびCrの含有量を特定の範囲、つまり、質量%で、C:0.16〜0.35%およびCr:9〜22%の範囲に調整する必要がある。 <6> From the above-mentioned viewpoint, it is necessary to adjust the contents of C and Cr to a specific range, that is, in mass%, C: 0.16-0.35% and Cr: 9-22%. .
本発明は、上記の知見に基づいて完成されたものであり、その要旨は、下記(1)に示す溶接金属および(2)に示す溶接材料にある。 The present invention has been completed based on the above findings, and the gist thereof lies in the weld metal shown in the following (1) and the weld material shown in (2).
(1)質量%で、C:0.16〜0.35%、Si:0.5%以下、Mn:2.0%以下、Ni:18〜38%、Cr:9〜22%、Ti:2.0〜6.0%、Al:0.05〜0.65%、V:0.1〜0.6%およびN:0.15%以下を含み、残部がFeおよび不純物からなり、かつ、不純物中のO、PおよびSがそれぞれ、O:0.02%以下、P:0.01%以下およびS:0.01%以下であることを特徴とする溶接金属。 (1) By mass%, C: 0.16-0.35%, Si: 0.5% or less, Mn: 2.0% or less, Ni: 18-38%, Cr: 9-22%, Ti: 2.0 to 6.0%, Al: 0.05 to 0.65%, V: 0.1 to 0.6% and N: 0.15% or less, with the balance being Fe and impurities, and A weld metal characterized in that O, P and S in the impurities are O: 0.02% or less, P: 0.01% or less and S: 0.01% or less, respectively.
なお、残部としての「Feおよび不純物」における「不純物」とは、金属材料を工業的に製造する際に、鉱石あるいはスクラップ等の原料、その他種々の要因によって混入するものを指す。 The “impurities” in the remaining “Fe and impurities” refer to materials that are mixed due to raw materials such as ores or scraps and other various factors when industrially producing metal materials.
上記の溶接金属は、残部としての「Feおよび不純物」におけるFeの一部に代えて、質量%で、Nb:5%以下を含むことができる。 The above weld metal can include Nb: 5% or less in mass%, instead of a part of Fe in “Fe and impurities” as the balance.
また、この溶接金属は、ビッカース硬さ(以下、「HV硬さ」という。)が320以上であることが望ましい。 The weld metal preferably has a Vickers hardness (hereinafter referred to as “HV hardness”) of 320 or more.
なお、「溶接金属」とは、溶接中に母材の一部と溶接材料が溶融混合し、凝固した部分を指す。 The “welded metal” refers to a portion where a part of the base metal and the welding material are melted and solidified during welding.
(2)質量%で、C:0.16〜0.35%、Si:0.5%以下、Mn:2.0%以下、Ni:18〜38%、Cr:9〜22%、Ti:2.0〜6.0%、Al:0.05〜0.65%、V:0.1〜0.6%およびN:0.15%以下を含み、残部がFeおよび不純物からなり、かつ、不純物中のO、PおよびSがそれぞれ、O:0.02%以下、P:0.01%以下およびS:0.01%以下であることを特徴とする溶接材料。 (2) By mass%, C: 0.16-0.35%, Si: 0.5% or less, Mn: 2.0% or less, Ni: 18-38%, Cr: 9-22%, Ti: 2.0 to 6.0%, Al: 0.05 to 0.65%, V: 0.1 to 0.6% and N: 0.15% or less, with the balance being Fe and impurities, and O, P, and S in the impurities are O: 0.02% or less, P: 0.01% or less, and S: 0.01% or less, respectively.
上述のとおり、残部としての「Feおよび不純物」における「不純物」とは、金属材料を工業的に製造する際に、鉱石あるいはスクラップ等の原料、その他種々の要因によって混入するものを指す。 As described above, “impurities” in the remaining “Fe and impurities” refer to materials mixed by raw materials such as ore or scrap and other various factors when industrially producing metal materials.
この溶接材料は、残部としての「Feおよび不純物」におけるFeの一部に代えて、質量%で、Nb:5%以下を含むことができる。 This welding material can contain Nb: 5% or less in mass% instead of a part of Fe in “Fe and impurities” as the balance.
ここで、上記(2)の「溶接材料」を使用して溶接が施される部材(換言すれば、「溶接構造物」の母材)、または、「溶接構造物」の母材に溶接が施されて上記(1)の「溶接金属」が形成される際のその母材として、特に、1GPa以上の引張強さを有する高強度オーステナイト系材料や高強度鋼を用いた場合に、本発明の有効性が顕著に認められ、板状、棒状や管状など溶接接合に供することができさえすれば、その母材はどのような形状でも構わない。 Here, welding is performed on a member to be welded using the “welding material” in (2) above (in other words, the base material of the “welded structure”) or the base material of the “welded structure”. When the high-strength austenitic material or high-strength steel having a tensile strength of 1 GPa or more is used as the base material when the “welded metal” of the above (1) is formed, the present invention The base material may be in any shape as long as the effectiveness of the material is remarkably recognized and it can be used for welding joining such as plate, rod or tube.
本発明の溶接金属は、短時間の溶接後熱処理で高強度が確保でき、かつ、優れた耐溶接割れ性も具備するものであるので、本発明の溶接金属を有する溶接構造物は、エネルギー輸送機器における高圧ガス配管など各種の溶接部材として好適に用いることができる。なお、本発明の溶接金属は、本発明の溶接材料を使用して溶接することによって得ることができる。 Since the weld metal of the present invention can ensure high strength by a short post-weld heat treatment and has excellent weld cracking resistance, the welded structure having the weld metal of the present invention is energy transport. It can be suitably used as various welding members such as high-pressure gas piping in equipment. The weld metal of the present invention can be obtained by welding using the welding material of the present invention.
以下、本発明の溶接金属および溶接材料に含まれる各成分元素の作用効果とその含有量の限定理由について、溶接金属と溶接材料とを区別せずに説明する。なお、以下の説明において、各元素の含有量の「%」表示は「質量%」を意味する。 Hereinafter, the effect of each component element contained in the weld metal and the weld material of the present invention and the reason for limiting the content thereof will be described without distinguishing between the weld metal and the weld material. In the following description, “%” display of the content of each element means “mass%”.
C:0.16〜0.35%
Cは、Ti、AlおよびCrとともに本発明の根幹に係る元素で、凝固割れおよび延性低下割れを防止する作用を有する。すなわち、Cは、Cr、Ti等と結合し、溶接金属が凝固する際に共晶炭化物を生成して、液相の消失を早めるとともに、最終凝固部の組織をM23C6とオーステナイトの層状組織とする。その結果、液相の残存形態が面状から点状に変化するとともに、特定面への応力集中が抑制され、また、不純物の偏析サイトとなる最終凝固界面積が増大するので、凝固割れおよび延性低下割れを防止することができる。上記のCの効果を十分に得るためには、0.16%以上のC含有量が必要である。一方、Cの含有量が過剰になり、特に、0.35%を超えると、凝固の際に炭化物とならないCが増加し、却って液相の融点が低下して凝固割れ感受性が増大する。さらには、多量の炭化物を形成するため、溶接金属の延性が低下するし、炭化物として存在するTi量が増えるので、強化に寄与するNi3TiあるいはNi3(Al、Ti)の析出駆動力の低下が生じる。そのため、Cの含有量は0.16〜0.35%とする。なお、C含有量の望ましい下限は0.18%であり、望ましい上限は0.32%である。
C: 0.16-0.35%
C is an element related to the basis of the present invention together with Ti, Al, and Cr, and has an effect of preventing solidification cracking and ductile deterioration cracking. That is, C combines with Cr, Ti, etc. to produce eutectic carbides when the weld metal solidifies, thereby accelerating the disappearance of the liquid phase, and the structure of the final solidified portion is a layered structure of M 23 C 6 and austenite. Organization. As a result, the residual form of the liquid phase changes from a planar shape to a point shape, stress concentration on a specific surface is suppressed, and the final solidification interface area that becomes a segregation site of impurities increases, so that solidification cracking and ductility Decline cracking can be prevented. In order to sufficiently obtain the above C effect, a C content of 0.16% or more is necessary. On the other hand, if the content of C becomes excessive, especially exceeding 0.35%, C that does not become carbide during solidification increases, and on the contrary, the melting point of the liquid phase decreases and the solidification cracking susceptibility increases. Furthermore, since a large amount of carbide is formed, the ductility of the weld metal is reduced, and the amount of Ti present as the carbide increases, so that the precipitation driving force of Ni 3 Ti or Ni 3 (Al, Ti) contributing to strengthening is increased. A decrease occurs. Therefore, the C content is 0.16 to 0.35%. The desirable lower limit of the C content is 0.18%, and the desirable upper limit is 0.32%.
Si:0.5%以下
Siは、脱酸剤として添加される。しかしながら、Siの含有量が多くなって0.5%を超えると、溶接金属の凝固時に柱状晶粒界に偏析し、液相の融点を下げ、凝固割れ感受性を増大させる。そのため、Siの含有量を0.5%以下とする。Si含有量は、望ましくは、0.4%以下で、さらに望ましくは、0.3%以下である。なお、Siの含有量について特に下限を設ける必要はないが、過度の低減は、脱酸効果が十分に得られず合金の清浄性が低下するとともに、製造コストの増大を招く。そのため、Si含有量の望ましい下限は0.01%である。少なくともSiを0.01%含んでおれば、脱酸効果を得ることができる。
Si: 0.5% or less Si is added as a deoxidizer. However, if the Si content increases and exceeds 0.5%, it segregates at the columnar grain boundaries during solidification of the weld metal, lowers the melting point of the liquid phase, and increases the susceptibility to solidification cracking. Therefore, the Si content is 0.5% or less. The Si content is desirably 0.4% or less, and more desirably 0.3% or less. In addition, although it is not necessary to set a minimum in particular about content of Si, excessive reduction leads to the increase in manufacturing cost while the deoxidation effect is not fully acquired but the cleanliness of an alloy falls. Therefore, the desirable lower limit of the Si content is 0.01%. If at least 0.01% of Si is contained, a deoxidizing effect can be obtained.
Mn:2.0%以下
Mnは、Siと同様、脱酸剤として添加される。しかしながら、Mnの含有量が多くなって2.0%を超えると、延性および靱性の低下を招く。そのため、Mnの含有量を2.0%以下とする。Mn含有量は、望ましくは、1.8%以下で、さらに望ましくは、1.6%以下である。なお、Mnの含有量について特に下限を設ける必要はないが、過度の低減は、脱酸効果が十分に得られず合金の清浄性が低下するとともに、製造コストの増大を招く。そのため、Mn含有量の望ましい下限は0.01%である。少なくともMnを0.01%含んでおれば、脱酸効果を得ることができる。
Mn: 2.0% or less Mn is added as a deoxidizer in the same manner as Si. However, if the Mn content increases and exceeds 2.0%, ductility and toughness are reduced. Therefore, the Mn content is set to 2.0% or less. The Mn content is desirably 1.8% or less, and more desirably 1.6% or less. In addition, although it is not necessary to set a minimum in particular about content of Mn, excessive reduction will not obtain the deoxidation effect enough, but will cause the increase in manufacturing cost while the cleanliness of an alloy falls. Therefore, the desirable lower limit of the Mn content is 0.01%. If at least 0.01% of Mn is contained, a deoxidizing effect can be obtained.
Ni:18〜38%
Niは、安定なオーステナイト組織を得るばかりでなく、Ni3(Al、Ti)あるいはNi3Tiとして微細に分散し、溶接金属の強度を大きく向上させる作用を有する元素である。上記のNiの効果を得るためには、18%以上のNi含有量が必要である。一方、Niの含有量が多くなって38%を超えると、接ガス環境の種類によっては脆化を招く。したがって、Niの含有量は18〜38%とする。なお、Ni含有量の望ましい下限は20%であり、望ましい上限は35%である。
Ni: 18-38%
Ni is an element that not only obtains a stable austenite structure but also finely disperses as Ni 3 (Al, Ti) or Ni 3 Ti and has a function of greatly improving the strength of the weld metal. In order to obtain the above Ni effect, a Ni content of 18% or more is necessary. On the other hand, if the Ni content increases and exceeds 38%, embrittlement may occur depending on the type of gas contact environment. Therefore, the Ni content is 18 to 38%. The desirable lower limit of the Ni content is 20%, and the desirable upper limit is 35%.
Cr:9〜22%
Crは、耐食性を改善する作用のある元素であるとともに、C、TiおよびAlとともに本発明の根幹に係る元素で、凝固割れおよび延性低下割れを防止する作用を有する。すなわち、Crは、溶接金属の凝固過程でTiを固溶するM23C6とオーステナイトの共晶凝固を生じさせ、凝固末期の液相の消失を促進させるとともに、液相中に凝固偏析して融点を降下させる有害なTiの量を軽減することで凝固割れを防止する作用を有する。加えて、上記のM23C6は、凝固後にはデンドライト境界にオーステナイトと層状組織を形成して存在するため、不純物元素の偏析の軽減および特定面への応力集中の軽減がなされて、延性低下割れが防止できる。これらの効果を十分に確保するとともに、M23C6中へのTiの固溶量を適正にし、短時間の溶接後熱処理で強化に寄与するNi3TiおよびNi3(Al、Ti)を析出させるためには、本発明の上記18〜38%というNi含有量の範囲ではCrの含有量を9%以上とする必要がある。しかしながら、Crの含有量が過剰になって22%を超えると、M23C6が多量に生成して溶接金属延性の低下を招く。したがって、Crの含有量は9〜22%とする。なお、Cr含有量の望ましい下限は11%であり、望ましい上限は20%である。
Cr: 9-22%
Cr is an element that has the effect of improving the corrosion resistance, and is an element related to the basis of the present invention together with C, Ti, and Al, and has an action of preventing solidification cracking and ductile deterioration cracking. That is, Cr causes eutectic solidification of M 23 C 6 that dissolves Ti and austenite in the solidification process of the weld metal, promotes the disappearance of the liquid phase at the end of solidification, and solidifies and segregates in the liquid phase. It has the effect of preventing solidification cracking by reducing the amount of harmful Ti that lowers the melting point. In addition, the above-mentioned M 23 C 6 exists after forming austenite and a layered structure at the dendrite boundary after solidification, so that segregation of impurity elements and stress concentration on a specific surface are reduced, resulting in reduced ductility. Cracking can be prevented. Ni 3 Ti and Ni 3 (Al, Ti), which contributes to strengthening by heat treatment after welding for a short time, are deposited while ensuring these effects sufficiently and making the solid solution amount of Ti in M 23 C 6 appropriate. In order to achieve this, the Cr content needs to be 9% or more in the Ni content range of 18 to 38% of the present invention. However, when the content of Cr is excessive and exceeds 22%, a large amount of M 23 C 6 is generated and the weld metal ductility is lowered. Therefore, the Cr content is 9 to 22%. The desirable lower limit of the Cr content is 11%, and the desirable upper limit is 20%.
Ti:2.0〜6.0%
Tiは、C、Al等とともに本発明の根幹に係る元素である。すなわち、Tiは、Ni3TiあるいはNi3(Al、Ti)として微細に析出し、溶接金属の強度を増大させる作用を有する。さらに、Tiが微細な炭窒化物として粒内に析出することによっても、溶接金属を少なからず強化することができる。上記のTiの効果を得るためには、2.0%以上のTi含有量が必要である。しかしながら、Tiの含有量が過剰になって6.0%を超えると、上記の強化効果は飽和するし、Ni3TiあるいはNi3(Al、Ti)が粗大化して、溶接金属延性の低下を招く。そのため、Tiの含有量は2.0〜6.0%とする。なお、Ti含有量の望ましい下限は2.5%であり、望ましい上限は5.5%である。
Ti: 2.0-6.0%
Ti is an element related to the basis of the present invention together with C, Al and the like. That is, Ti precipitates finely as Ni 3 Ti or Ni 3 (Al, Ti) and has the effect of increasing the strength of the weld metal. Furthermore, the weld metal can be strengthened to some extent by precipitation of Ti in the grains as fine carbonitride. In order to obtain the above Ti effect, a Ti content of 2.0% or more is necessary. However, when the Ti content becomes excessive and exceeds 6.0%, the above-described strengthening effect is saturated, and Ni 3 Ti or Ni 3 (Al, Ti) is coarsened, resulting in a decrease in weld metal ductility. Invite. Therefore, the content of Ti is set to 2.0 to 6.0%. The desirable lower limit of the Ti content is 2.5%, and the desirable upper limit is 5.5%.
Al:0.05〜0.65%
Alは、Ti等とともに本発明の根幹に係る元素の一つである。すなわち、Alを含有させることにより、最終安定相であるNi3Tiに至る遷移相としてのNi3(Al、Ti)を生成し、結果として短時間の溶接後熱処理で溶接金属の強度向上を可能にする。この効果を得るためには、0.05%以上のAl含有量が必要である。しかしながら、Alの含有量が過剰になって0.65%を超えると、溶接中に酸化スラグとして浮上してしまうため、その効果は飽和するばかりか、溶接ビードの美観や溶接作業性を損なうことになる。そのため、Alの含有量は0.05〜0.65%とする。なお、Al含有量の望ましい下限は0.10%であり、望ましい上限は0.60%である。
Al: 0.05 to 0.65%
Al is one of the elements according to the present invention together with Ti and the like. That is, by containing Al, Ni 3 (Al, Ti) as a transition phase leading to Ni 3 Ti, which is the final stable phase, is generated, and as a result, the strength of the weld metal can be improved by a short post-weld heat treatment. To. In order to obtain this effect, an Al content of 0.05% or more is necessary. However, if the Al content becomes excessive and exceeds 0.65%, it will float as oxidized slag during welding, so the effect will be saturated, and the aesthetics and welding workability of the weld bead will be impaired. become. Therefore, the Al content is 0.05 to 0.65%. The desirable lower limit of the Al content is 0.10%, and the desirable upper limit is 0.60%.
V:0.1〜0.6%
Vは、微細な炭窒化物として粒内に析出することによって溶接金属を強化する作用を有する元素である。この効果を得るためには、0.1%以上のV含有量が必要である。しかしながら、Vの含有量が過剰になって0.6%を超えると前記の効果が飽和してコストが嵩むばかりであるし、炭窒化物の粗大化が生じて却って強化効果が損なわれることもある。したがって、Vの含有量は0.1〜0.6%とする。なお、V含有量の望ましい下限は0.15%であり、望ましい上限は0.55%である。
V: 0.1-0.6%
V is an element having an action of strengthening the weld metal by being precipitated in the grains as fine carbonitride. In order to obtain this effect, a V content of 0.1% or more is necessary. However, if the content of V is excessive and exceeds 0.6%, the above effects are saturated and the cost is increased, and the strengthening effect may be impaired due to coarsening of carbonitrides. is there. Therefore, the V content is 0.1 to 0.6%. The desirable lower limit of the V content is 0.15%, and the desirable upper limit is 0.55%.
N:0.15%以下
Nは、マトリックスに固溶するとともに微細な窒化物を形成して溶接金属の強度を高める作用を有する元素である。しかしながら、Nの含有量が過剰になって0.15%を超えると、TiNやAlNとして析出し、高強度化に必要なNi3(Al、Ti)やNi3Tiの析出を抑制してしまう。そのため、Nの含有量を0.15%以下とする。なお、Nの含有量について特に下限を設ける必要はないが、極端な低減は製鋼コストの著しい増大を招く。そのため、N含有量の望ましい下限は0.001%である。少なくともNを0.001%含んでおれば、強度向上効果を得ることができる。
N: 0.15% or less N is an element having an action of increasing the strength of the weld metal by forming a fine nitride while forming a solid solution in the matrix. However, if the N content becomes excessive and exceeds 0.15%, it precipitates as TiN or AlN and suppresses the precipitation of Ni 3 (Al, Ti) and Ni 3 Ti necessary for increasing the strength. . Therefore, the N content is 0.15% or less. In addition, although there is no need to set a lower limit in particular for the N content, an extreme reduction causes a significant increase in steelmaking costs. Therefore, the desirable lower limit of the N content is 0.001%. If at least N is contained by 0.001%, an effect of improving the strength can be obtained.
本発明の溶接金属の1つは、以上に述べた元素のほか、残部がFeおよび不純物からなる化学組成を有するものである。また、本発明の溶接材料の1つも、以上に述べた元素のほか、残部がFeおよび不純物からなる化学組成を有するものである。 One of the weld metals of the present invention has a chemical composition in which the balance is composed of Fe and impurities in addition to the elements described above. One of the welding materials of the present invention also has a chemical composition in which the balance is composed of Fe and impurities in addition to the elements described above.
既に述べたように、残部としての「Feおよび不純物」における「不純物」とは、金属材料を工業的に製造する際に、鉱石あるいはスクラップ等の原料、その他種々の要因によって混入するものを指す。なお、不純物中の特定元素の含有量規制については後述する。 As already described, the “impurities” in the remaining “Fe and impurities” refer to materials that are mixed due to raw materials such as ore or scrap and other various factors when industrially producing metal materials. In addition, content regulation of the specific element in an impurity is mentioned later.
本発明の溶接金属および溶接材料の他の一つは、いずれも、上記残部としての「Feおよび不純物」におけるFeの一部に代えて、5%以下のNbを含有する化学組成を有するものである。 The other one of the weld metal and welding material of the present invention has a chemical composition containing 5% or less of Nb in place of a part of Fe in the “Fe and impurities” as the balance. is there.
以下、任意元素であるNbの作用効果と、含有量の限定理由について説明する。 Hereinafter, the effect of Nb which is an arbitrary element and the reason for limiting the content will be described.
Nb:5%以下
Nbは、Ni3Nbとして微細に析出し、溶接金属の強度を増大させる作用を有する。さらに、Nbが微細な炭窒化物として粒内に析出することによっても、溶接金属を少なからず強化することができる。したがって、強度増大のためにNbを含有してもよい。しかしながら、5%を超える量のNbを含有させても上記の効果が飽和してコストが嵩むばかりである。したがって、Nbを含有させる場合の含有量を5%以下とした。なお、Nbの含有量は4%以下とすることが好ましい。
Nb: 5% or less Nb precipitates finely as Ni 3 Nb and has the effect of increasing the strength of the weld metal. Furthermore, the weld metal can be strengthened to some extent when Nb is precipitated in the grains as fine carbonitride. Therefore, you may contain Nb for intensity | strength increase. However, even if Nb is contained in an amount exceeding 5%, the above effect is saturated and the cost is increased. Therefore, the content when Nb is contained is set to 5% or less. The Nb content is preferably 4% or less.
一方、前記したNbの強度向上効果を確実に得るためには、Nb含有量の下限を0.1%とすることが好ましく、0.5%とすればさらに好ましい。 On the other hand, in order to reliably obtain the above-described effect of improving the strength of Nb, the lower limit of the Nb content is preferably 0.1%, and more preferably 0.5%.
次に、不純物元素の含有量規制について説明する。 Next, the content restriction of the impurity element will be described.
本発明の溶接金属および溶接材料においては、不純物中のO、PおよびSの含有量をそれぞれ、下記のとおりに規制する。 In the weld metal and the weld material of the present invention, the contents of O, P and S in the impurities are regulated as follows.
O:0.02%以下
Oは、不純物として存在し、多量に含まれると、溶接材料の加工性や溶接金属の延性を劣化させる。そのため、Oの含有量は可能な限り低減することが好ましいが、0.02%以下であれば、本発明の溶接金属や溶接材料の特性に顕著な劣化は認められない。したがって、Oの含有量を0.02%以下とする。
O: 0.02% or less O exists as an impurity, and when it is contained in a large amount, the workability of the welding material and the ductility of the weld metal are deteriorated. Therefore, it is preferable to reduce the O content as much as possible. However, if the content is 0.02% or less, no remarkable deterioration is observed in the characteristics of the weld metal or the weld material of the present invention. Therefore, the content of O is set to 0.02% or less.
P:0.01%以下
Pは、不純物として含まれ、溶接金属の凝固時に最終凝固部の融点を低下させ、凝固割れ感受性を著しく増大させてしまう。さらに、結晶粒界に偏析して延性低下割れ感受性をも高めてしまう。そのため、Pの含有量は可能な限り低減することが好ましいが、P含有量の極度の低減は製鋼コストの増大を招くし、0.01%以下であれば、本発明の溶接金属や溶接材料の特性に顕著な劣化は認められない。したがって、Pの含有量を0.01%以下とする。
P: 0.01% or less P is contained as an impurity, and lowers the melting point of the final solidified portion during solidification of the weld metal, and remarkably increases the susceptibility to solidification cracking. Furthermore, it segregates at the grain boundaries and increases the susceptibility to ductile drop cracking. Therefore, it is preferable to reduce the P content as much as possible. However, extreme reduction of the P content leads to an increase in steelmaking cost, and if it is 0.01% or less, the weld metal or welding material of the present invention. There is no noticeable deterioration in the characteristics. Therefore, the P content is 0.01% or less.
S:0.01%以下
Sは、Pと同様に不純物として含まれ、溶接金属の凝固時に最終凝固部の融点を低下させ、凝固割れ感受性を著しく増大させてしまう。さらに、結晶粒界に偏析して延性低下割れ感受性をも高めてしまう。そのため、Sの含有量は可能な限り低減することが好ましいが、Pの場合と同様に、S含有量の極度の低減は製鋼コストの増大を招くし、0.01%以下であれば、本発明の溶接金属や溶接材料の特性に顕著な劣化は認められない。したがって、Sの含有量を0.01%以下とする。
S: 0.01% or less S is contained as an impurity in the same manner as P, and lowers the melting point of the final solidified portion during solidification of the weld metal, and remarkably increases the susceptibility to solidification cracking. Furthermore, it segregates at the grain boundaries and increases the susceptibility to ductile drop cracking. Therefore, it is preferable to reduce the S content as much as possible. However, as in the case of P, the extreme reduction of the S content leads to an increase in steelmaking costs. There is no noticeable deterioration in the characteristics of the weld metal or welding material of the invention. Therefore, the S content is 0.01% or less.
なお、溶接構造物としては、母材の一部と溶接材料が溶融混合した結果得られた「溶接金属」の化学組成が上述した要件を満たしておればよい。このため、「溶接材料」の化学組成については、用いる「母材」の化学組成に応じて選ぶ必要はあるが、「溶接金属の組成における母材組成の割合」として定義される「母材希釈率」は開先形状や溶接方法・溶接条件により異なるが、一般的には30〜60%程度である。したがって、前述の(2)に記載した溶接材料の化学組成範囲において、母材による希釈を考慮した上で、溶接材料の組成を選定することが望ましい。 In addition, as a welded structure, the chemical composition of the “welded metal” obtained as a result of melting and mixing a part of the base material and the welding material only needs to satisfy the above-described requirements. For this reason, the chemical composition of the “welding material” needs to be selected according to the chemical composition of the “base metal” used, but the “base metal dilution” defined as “the ratio of the base metal composition in the composition of the weld metal” The “rate” varies depending on the groove shape, welding method and welding conditions, but is generally about 30 to 60%. Therefore, in the chemical composition range of the welding material described in (2) above, it is desirable to select the composition of the welding material in consideration of dilution by the base material.
なお、母材としては、1GPa以上の引張強さを有する高強度材料が好適であり、その形状は、板状、棒状や管状など溶接接合に供することができさえすればどのような形状でも構わないことは既に述べたとおりである。 As the base material, a high-strength material having a tensile strength of 1 GPa or more is suitable, and the shape may be any shape as long as it can be used for welding joining such as a plate shape, a rod shape, or a tubular shape. It is as already mentioned that there is nothing.
以下、実施例によって本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these Examples.
表1に示す化学組成を有する材料を実験室溶解して鋳込んだインゴットから、熱間鍛造、熱間圧延、熱処理および機械加工により、板厚10mm、幅50mm、長さ100mmの鋼板を溶接母材用として作製した。 A steel plate having a thickness of 10 mm, a width of 50 mm, and a length of 100 mm is welded to a weld mother from an ingot in which a material having the chemical composition shown in Table 1 is melted and cast in a laboratory by hot forging, hot rolling, heat treatment and machining. It was produced as a material.
また、同じインゴットから、熱間鍛造、熱間圧延および機械加工により、外径1.2mm、長さ1000mmの溶接ワイヤ(溶接材料)を作製した。 Further, from the same ingot, a welding wire (welding material) having an outer diameter of 1.2 mm and a length of 1000 mm was produced by hot forging, hot rolling and machining.
上記の溶接母材用鋼板の長手方向に、図1に示す開先加工を施して、厚さ25mm、幅200mm、長さ200mmの市販のSM400A鋼板上に、JIS Z 3224(1999)に記載された「DNiCrFe−3」の被覆アーク溶接棒を用いて四周を拘束溶接した。 It is described in JIS Z 3224 (1999) on a commercially available SM400A steel plate having a thickness of 25 mm, a width of 200 mm, and a length of 200 mm by performing the groove processing shown in FIG. Further, four-circle restraint welding was performed using a coated arc welding rod of “DNiCrFe-3”.
次いで、上記の溶接母材用鋼板に施した開先内に、この溶接母材用鋼板と同じ化学組成を有する前述の外径1.2mmの溶接ワイヤを用いて、TIG溶接により平均入熱を約10kJ/cmとして多層溶接を行った。なお、このTIG溶接の際には拘束されているために、溶接による熱応力が生じて割れが発生しやすくなる。 Next, the average heat input by TIG welding is performed using the above-described welding wire having an outer diameter of 1.2 mm, which has the same chemical composition as that of the steel sheet for the weld base material, in the groove formed on the steel sheet for the weld base material. Multi-layer welding was performed at about 10 kJ / cm. In addition, since it is restrained in the case of this TIG welding, the thermal stress by welding arises and it becomes easy to generate | occur | produce a crack.
溶接施工後、溶接金属部を中央部に有するミクロ試験片、側曲げ試験片および時効硬さ試験片を採取し、それぞれの試験に供した。 After welding, a micro test piece, a side bend test piece and an aging hardness test piece having a weld metal part at the center were collected and used for each test.
ミクロ試験片は、バフ研磨にて鏡面仕上げした後、光学顕微鏡にて100〜500倍の倍率にて溶接金属部を全て観察し、「凝固割れ」および「延性低下割れ」の発生有無を観察した。なお、「凝固割れ」および「延性低下割れ」の双方ともが発生しないことを目標とした。 The micro test piece was mirror-finished by buffing, and then all the weld metal parts were observed with an optical microscope at a magnification of 100 to 500 times, and the occurrence of "solidification cracking" and "ductility-reducing cracking" was observed. . The target was that neither “solidification cracking” nor “ductility degradation cracking” occurred.
側曲げ試験片は、板厚の2倍の曲げ半径で180゜曲げを行い、溶接金属の割れ発生有無および延性を調べた。なお、割れ発生がないことを目標とした。 The side bend specimen was bent 180 ° with a bending radius twice the plate thickness, and the presence or absence of cracks in the weld metal and the ductility were examined. The goal was to prevent cracking.
加えて、時効硬さ試験片を用いて溶接後熱処理を模擬した時効熱処理を行い、試験力を98Nとして、HV硬さ試験を行った。なお、時効熱処理は750℃での時間が1〜180minの範囲で行い、ASTM E140に記載の換算式から溶接金属の目標引張強さである1GPaに相当するHV硬さ320に到達するのに必要な時効時間を調査した。そして、時効時間が120min以下であることを目標とした。 In addition, an aging hardness test piece was used to perform an aging heat treatment simulating post-weld heat treatment, and a test force was set to 98 N, and an HV hardness test was performed. The aging heat treatment is performed at a temperature of 750 ° C. for 1 to 180 minutes, and it is necessary to reach the HV hardness 320 corresponding to 1 GPa which is the target tensile strength of the weld metal from the conversion formula described in ASTM E140. Aging time was investigated. And it aimed at aging time being 120 min or less.
表2に、ミクロ試験片における「凝固割れ」および「延性低下割れ」の発生有無の観察結果、側曲げ試験片における割れ発生有無の観察結果ならびに750℃で時効熱処理した場合のHV硬さ320に到達するのに必要な時間を示す。 Table 2 shows the observation results of occurrence of “solidification cracks” and “ductility-reducing cracks” in micro test pieces, observation results of occurrence of cracks in side bending test pieces, and HV hardness 320 when aging heat treatment is performed at 750 ° C. Indicates the time required to reach.
表2から、試験番号1〜5における化学組成が本発明で規定する範囲にある鋼の場合、凝固割れおよび延性低下割れのない健全な溶接継手が得られ、かつ、十分な曲げ延性も有することが明らかである。加えて、60min以下という短時間の時効熱処理によって溶接金属のHV硬さが320以上となり、短時間の溶接後熱処理で溶接金属の強化が可能であることがわかる。
From Table 2, in the case of steel whose chemical compositions in
これに対して、試験番号6におけるCおよびTiの含有量が本発明で規定する範囲から外れた鋼の場合、凝固割れおよび延性低下割れが発生し、しかも、側曲げ試験片に割れが生じて曲げ延性にも劣っていた。これは、M23C6の生成量が少なく、凝固過程での液相の消失促進の効果が得られず、かつ、偏析サイトの増大による不純物元素の分散が十分でないことに基づくものである。さらに、この試験番号6における鋼の場合、Tiの含有量が本発明で規定する範囲を下回っていたため、180minの時効熱処理を行っても溶接金属は目標とする硬さが得られなかった。 On the other hand, in the case of the steel in which the C and Ti contents in Test No. 6 deviate from the range specified in the present invention, solidification cracks and ductile deterioration cracks occurred, and cracks occurred in the side bend specimens. The bending ductility was also inferior. This is based on the fact that the amount of M 23 C 6 produced is small, the effect of promoting the disappearance of the liquid phase during the solidification process cannot be obtained, and the dispersion of the impurity elements due to the increase in segregation sites is not sufficient. Furthermore, in the case of the steel in this test number 6, since the Ti content was below the range specified in the present invention, the target hardness of the weld metal could not be obtained even after aging heat treatment for 180 minutes.
試験番号7におけるAlの含有量が本発明で規定する範囲から外れた鋼の場合、750℃での時効熱処理で溶接金属はHV320という目標硬さまで硬化したものの180minという長時間の時効熱処理が必要であった。 In the case of steel in which the Al content in the test number 7 is out of the range specified in the present invention, the weld metal is hardened to a target hardness of HV320 by aging heat treatment at 750 ° C., but a long aging heat treatment of 180 min is required. there were.
試験番号8におけるCの含有量が本発明で規定する上限から外れた鋼の場合、側曲げ試験片に割れが生じて曲げ延性に劣っていた。これは、過剰のM23C6が生成したことに基づく。 In the case of steel in which the C content in Test No. 8 deviated from the upper limit specified in the present invention, the side bending test piece was cracked and inferior in bending ductility. This is based on the formation of excess M 23 C 6 .
本発明の溶接金属は、短時間の溶接後熱処理で高強度が確保でき、かつ、優れた耐溶接割れ性も具備するものである。このため、本発明の溶接金属を有する溶接構造物は、エネルギー輸送機器における高圧ガス配管など各種の溶接部材として好適に用いることができる。なお、本発明の溶接金属は、本発明の溶接材料を使用して溶接することによって得ることができる。 The weld metal of the present invention can ensure high strength by a short post-weld heat treatment and has excellent weld crack resistance. For this reason, the welding structure which has the weld metal of this invention can be used suitably as various welding members, such as high-pressure gas piping in an energy transport apparatus. The weld metal of the present invention can be obtained by welding using the welding material of the present invention.
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