WO2012137957A1 - 耐水素脆化感受性に優れた溶接金属 - Google Patents
耐水素脆化感受性に優れた溶接金属 Download PDFInfo
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- B23K35/3053—Fe as the principal constituent
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- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
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- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3053—Fe as the principal constituent
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- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3053—Fe as the principal constituent
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- B23K9/00—Arc welding or cutting
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- B23K9/00—Arc welding or cutting
- B23K9/16—Arc welding or cutting making use of shielding gas
- B23K9/173—Arc welding or cutting making use of shielding gas and of a consumable electrode
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- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K9/00—Arc welding or cutting
- B23K9/23—Arc welding or cutting taking account of the properties of the materials to be welded
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/02—Iron or ferrous alloys
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Definitions
- the present invention relates to a weld metal having reduced sensitivity to hydrogen embrittlement in a weld metal used for a welded structure.
- gas shielded arc welding using a flux-cored wire has excellent welding workability, so a technique for ensuring low temperature cracking resistance is required for a weld metal formed by this welding method.
- Patent Document 1 discloses a technique for preventing low-temperature cracking by dispersing Mo carbide (carbide containing Mo) having a high hydrogen trap capability in a weld metal.
- Mo carbide carbide containing Mo
- Patent Document 1 discloses a technique for preventing low-temperature cracking by dispersing Mo carbide (carbide containing Mo) having a high hydrogen trap capability in a weld metal.
- this technique in order to disperse Mo carbides, it is necessary to employ a special welding technique in which submerged arc welding is performed from the inner surface side after a steel material is abutted, and it is not applicable to general welding of steel materials.
- Patent Document 2 discloses a technique for preventing cold cracking of a welded joint by dispersing Si—Mn—Ti—Al composite oxide effective for trapping diffusible hydrogen in a weld metal. Yes.
- the assumed strength level is 588.4 MPa or more in terms of tensile strength, and it cannot be said that sufficient strength can be secured.
- Patent Document 3 proposes a technique for improving cold cracking resistance by reducing the amount of diffusible hydrogen and appropriately controlling the strength and chemical composition. However, even in this technique, since a satisfactory strength level is affected by the components, the number of application points is limited in actual construction.
- Patent Document 8 also proposes a technique for achieving both strength and toughness by precisely controlling the form of oxide containing Ti, Si, and the like, and expressing a fine acicular ferrite structure starting from these oxides. .
- this technique does not take into account cold cracking resistance.
- Japanese Unexamined Patent Publication No. 2005-40816 Japanese Unexamined Patent Publication No. 2001-348649 Japanese Unexamined Patent Publication No. 11-147196 Japanese Laid-Open Patent Publication No. 8-257785 Japanese Patent No. 3208556 Japanese Unexamined Patent Publication No. 2010-274304 Japanese Unexamined Patent Publication No. 2008-87043 Japanese Unexamined Patent Publication No. 2010-115701
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a weld metal that has excellent resistance to hydrogen embrittlement resistance even if it has high strength, and does not cause cold cracking. There is.
- the weld metal according to the present invention that has solved the above problems is a weld metal formed by gas shielded arc welding using a flux-cored wire, and C: 0.02 to 0.12% ("mass" The chemical composition is the same hereinafter), Si: 0.1 to 0.80%, Mn: 0.9 to 2.5%, Ni: 0.20 to 3.5%, Mo: 0 0.05 to 1.50%, Ti: 0.040 to 0.15%, V: 0.05 to 0.60%, N: 0.015% or less (excluding 0%), and O: 0.030 % or more respectively containing the balance being iron and unavoidable impurities, the Ti containing more than 20%, the equivalent circle diameter: presence Ti-containing oxide particles of 0.15 ⁇ 1.0 .mu.m is 5000 / mm 2 or more As well as the total mass of the weld metal present as a compound in the weld metal. The amount is 0.002% or more, further, the average circle equivalent diameter of V containing carbides present in the weld metal and has a
- the “compound” is intended to include compounds such as nitrides, carbonitrides, etc. in addition to carbides.
- the V-containing carbide is intended to include not only VC but also those containing other elements (for example, Ti, Nb, Mo, etc.) up to about 25 atomic% or less.
- the above “equivalent circle diameter” is assumed to be equal in area by paying attention to the size of oxide particles or V-containing carbides observed on the observation surface of an optical microscope or a transmission electron microscope (TEM). The diameter of the circle.
- the weld metal of the present invention as other elements, Cr: 2.0% or less (not including 0%), Nb: 0.15% or less (not including 0%), Cu: 1.0% Or less (excluding 0%), Al: 0.020% or less (not including 0%), Zr: 0.10% or less (not including 0%), B: 0.0050% or less (0% It is also preferable to contain at least one of (not contained), and the characteristics of the weld metal are further improved according to the kind of the element to be contained.
- the number density of Ti-containing oxide particles of a predetermined size, the amount of V present as a compound in the weld metal, the size of the V-containing carbide present in the weld metal, etc. is controlled appropriately, so that a weld metal with excellent resistance to hydrogen embrittlement can be realized.
- the present inventors examined from various angles about the means for improving the resistance to hydrogen embrittlement in HT780 class high strength weld metal formed by gas shielded arc welding using flux-cored wire. As a result, the hydrogen-containing embrittlement susceptibility is improved by making V-containing carbides acting as trapping sites for diffusible hydrogen exist in a proper form and by refining the structure by generating acicular ferrite from the oxide. As a result, the present invention has been completed.
- the weld metal component is controlled within a predetermined range, Ti is contained at 20% or more, and Ti-containing oxide particles having an equivalent circle diameter of 0.15 to 1.0 ⁇ m are secured at 5000 particles / mm 2 or more, V amount per total mass of weld metal present as a compound in weld metal (hereinafter sometimes referred to as “compound-type V amount”) is 0.002% or more, and further V-containing carbides present in weld metal It was found that the hydrogen embrittlement susceptibility was improved in the HT780 class weld metal by controlling the average equivalent circle diameter to 15 nm or less.
- Ti-containing oxide particles containing 20% or more of Ti and equivalent circle diameter: 0.15 to 1.0 ⁇ m: 5000 / mm 2 or more act as the starting point of intragranular transformation, so that the structure is remarkably refined and the hydrogen embrittlement susceptibility is reduced. It works effectively. In order to exhibit such an effect, the number needs to be 5000 / mm 2 or more.
- the number of Ti-containing oxide particles is preferably 8000 / mm 2 or more (more preferably 9000 / mm 2 or more).
- the upper limit of the number of Ti-containing oxide particles is not particularly limited, but is preferably 40000 pieces / mm 2 or less, more preferably 30000 pieces / mm 2 or less (more preferably 20000 pieces / mm 2 or less). It is.
- the size of the Ti-containing oxide particles to be measured is 0.15 to 1.0 ⁇ m in terms of the equivalent circle diameter. If the equivalent circle diameter is smaller than 0.15 ⁇ m, the origin of intragranular transformation is This is because the ability is lowered, and when there are a large number of particles larger than 1.0 ⁇ m, intragranular transformation occurs at a higher temperature, resulting in a decrease in strength.
- Compound-type V content in weld metal 0.002% or more
- the compound type V content is preferably 0.003% or more (more preferably 0.005% or more).
- the upper limit with preferable compound amount V is 0.05% or less, More preferably, it is 0.03% or less (more preferably 0.02% or less).
- the average equivalent circle diameter of the V-containing carbides present in the weld metal is preferably 12 nm or less, more preferably 10 nm or less.
- C is an element indispensable for ensuring the strength of the weld metal, and in order to exert such an effect, it is necessary to contain 0.02% or more. Preferably it is 0.04% or more, More preferably, it is 0.06% or more. However, if the C content exceeds 0.12%, the strength increases excessively and the hydrogen embrittlement susceptibility increases (hydrogen embrittlement susceptibility deteriorates). In addition, the upper limit with preferable C content is 0.10%, More preferably, it is 0.08% or less.
- Si 0.1 to 0.80%
- Si is a deoxidizing element and has a function of cleaning the weld metal.
- the Si content needs to be 0.1% or more.
- the content is preferably 0.25% or more, more preferably 0.28% or more.
- the Si content is excessive, the grain boundary transformation starting from the oxide is suppressed and the hydrogen embrittlement susceptibility is increased, so it is necessary to suppress it to 0.80% or less.
- it is 0.7% or less, and more preferably 0.5% or less.
- Mn is an element necessary for ensuring the strength of the weld metal, and in order to exert such an effect, it is necessary to contain 0.9% or more. Preferably it is 1.2% or more, More preferably, it is 1.5% or more. However, if the content exceeds 2.5%, the hydrogen embrittlement susceptibility increases due to an excessive increase in strength. Preferably it is 2.2% or less, More preferably, it is 2.0% or less.
- Ni is an element necessary for ensuring the strength of the weld metal, and in order to exert such effects, it is necessary to contain 0.20% or more. Preferably it is 0.5% or more, More preferably, it is 1.0% or more. However, if it exceeds 3.5%, it causes excessive hydrogen embrittlement susceptibility due to an excessive increase in strength. Preferably it is 3.0% or less, More preferably, it is 2.8% or less.
- Mo 0.05 to 1.50%
- Mo is an element necessary for improving the strength of the weld metal, and in order to exert such effects, it is necessary to contain 0.05% or more.
- it is 0.10% or more, more preferably 0.2% or more.
- it is contained excessively exceeding 1.50%, it becomes a cause of increased hydrogen embrittlement susceptibility due to an excessive increase in strength.
- it is 1.0% or less, More preferably, it is 0.50% or less.
- Ti 0.040 to 0.15%
- Ti is an element that is effective in improving the hydrogen embrittlement resistance by forming an oxide serving as a starting point of intragranular transformation and making the structure finer. In order to exhibit such an effect, it is necessary to contain 0.040% or more. Preferably it is 0.050% or more, More preferably, it is 0.055% or more. However, if the content exceeds 0.15%, hydrogen embrittlement susceptibility increases due to an excessive increase in strength. Preferably it is 0.12% or less, More preferably, it is 0.08% or less.
- V 0.05 to 0.60%
- V is an element effective for improving the hydrogen embrittlement resistance by forming V-containing carbides that serve as trapping sites for diffusion-type hydrogen.
- it is necessary to contain 0.05% or more.
- it is 0.1% or more, More preferably, it is 0.15% or more.
- the content exceeds 0.60%, the strength is excessively increased and the hydrogen embrittlement sensitivity is increased.
- N 0.015% or less (excluding 0%)
- N is an element inevitably mixed in, and is effective in improving the strength of the weld metal. However, if excessively contained, it causes an increase in the strength of hydrogen embrittlement due to an excessive increase in strength. .
- the N content needs to be 0.015% or less. Preferably it is 0.010% or less, More preferably, it is 0.006% or less. In addition, it is difficult to make N into 0% industrially.
- O is an element that is effective in improving the hydrogen embrittlement resistance by forming an oxide serving as a starting point of intragranular transformation and making the structure finer. In order to exhibit such an effect, it is necessary to contain 0.030% or more. Preferably it is 0.035% or more, More preferably, it is 0.040% or more.
- the upper limit of the O content is not particularly set, but if the content is excessive, the toughness is adversely affected, so that it is 0.10% or less (more preferably 0.080% or less). Is preferred.
- the contained elements specified in the present invention are as described above, and the balance is iron and unavoidable impurities, and the elements (for example, P, S) brought in as raw materials, materials, production facilities, etc. as the unavoidable impurities. , Sn, etc.) can be permitted.
- impurities segregate at the grain boundaries to lower the grain boundary strength and promote low temperature cracking. Therefore, in particular, P: 0.02% or less (excluding 0%), S: 0.025% or less ( It is preferable to suppress each of them. Further, inevitable impurities other than these are preferably 0.010% or less (excluding 0%) in total.
- the weld metal of the present invention as other elements, (a) Cr: 2.0% or less (not including 0%), Nb: 0.15% or less (not including 0%), and Cu: 1 1 or more selected from the group consisting of 0.0% or less (excluding 0%), (b) Al: 0.020% or less (not including 0%) and / or Zr: 0.10% or less (0 %), (C) B: 0.0050% or less (not including 0%), etc. are preferably included, and the properties of the weld metal are further improved depending on the type of element to be included. The reason for setting the range when these elements are contained is as follows.
- Cr 2.0% or less (not including 0%), Nb: 0.15% or less (not including 0%) and Cu: 1.0% or less (not including 0%)
- Cr, Nb and Cu are effective elements for improving the strength of the weld metal. Of these, Cu effectively acts to ensure low temperature toughness. However, when these elements are contained excessively, the hydrogen embrittlement susceptibility becomes high due to an excessive increase in strength. Therefore, Cr is 2.0% or less (more preferably 1.5% or less, more preferably 1.0% or less), and Nb is 0.15% or less (more preferably 0.10% or less, still more preferably). Is preferably 0.08% or less) or 1.0% or less (more preferably 0.5% or less, still more preferably 0.2% or less) of Cu. In addition, the preferable minimum for exhibiting the said effect is 0.05% or more in Cr, 0.01% or more in Nb, or 0.05% or more in Cu (both are inevitable at less than 0.01%). Impurity level).
- Al and Zr are both strong deoxidizing elements and are effective for cleaning the weld metal. However, if it is contained excessively, the oxide that becomes the starting point of the intragranular transformation is reduced, which causes the hydrogen embrittlement sensitivity to increase due to the coarsening of the structure. Therefore, it is preferable to suppress the content of Al to 0.020% or less (more preferably 0.018% or less) and Zr to 0.10% or less (more preferably 0.06% or less). In addition, the preferable minimum for exhibiting the said effect is 0.01% or more of all of Al or Zr (both are inevitable impurity levels at less than 0.01%).
- B is an element that improves the strength by suppressing the formation of ferrite from the prior austenite grain boundaries. However, if excessively contained, the strength is excessively increased and the hydrogen embrittlement susceptibility is increased. For these reasons, B is preferably suppressed to 0.0050% or less (more preferably 0.0030% or less). In addition, the preferable minimum for exhibiting the said effect is 0.0010% or more (less than 0.0008% and an inevitable impurity level).
- the wire component and the welding conditions are not particularly limited, but in order to realize the prescribed mode, A preferred range exists.
- a preferable wire component satisfies, for example, all of the following requirements. That is, for the total wire mass that combines the outer shell made of steel and the flux, (A) The amount of Ti present in the form of metal, oxide or other (total Ti amount) is 2.5 to 4.5% (mass%), (B) Al amount (total Al amount) present in the form of metal, oxide or other is 0.10% (mass%) or more, (C) Al amount present as metal (metal Al amount) is 0.01 to 0.05% (mass%) or more, (D) Zr amount (total Zr amount) present as a metal, oxide or other metal present in the form is 0.035% (mass%) or more, (E) Mg amount present as metal (metal Mg amount) is 0.4% (mass%) or more, (F) Ratio [(Mn + Ti) / Si] of Si amount (total Si amount) present in the form of metal, oxide or other and Mn + Ti amount (to
- Ti carbide has a crystal structure similar to that of V-containing carbide and is stable at higher temperatures, it is finely produced prior to V-containing carbide in the cooling process during welding and becomes a precipitation nucleus of V-containing carbide at a lower temperature. Presumed. Therefore, in order to obtain the V-containing carbide in a predetermined form, it is necessary to secure Ti generated as carbide.
- Ti is a deoxidizing element and is mostly fixed as an oxide, by controlling Al, Zr, Mg, etc., which are more strongly deoxidized, within the above ranges [Requirements (b) to (e) ], It is considered that a part of Ti is reduced to produce Ti carbide.
- the above requirement (f) is for controlling the Ti-containing oxide particles that contribute to the refinement of the structure.
- predetermined Ti-containing oxide particles are formed, and the bainite structure is refined by intragranular transformation starting from the Ti-containing oxide particles.
- the ratio is more than 10.0 [Formula (1)]
- Ti-containing oxide particles are dispersed at high density, and further refinement of the structure is achieved, resulting in hydrogen embrittlement resistance. It also leads to improved sensitivity.
- the welding conditions for forming the weld metal it is preferable to use a mixed gas comprising a heat input of 2.5 kJ / mm or less, 20% (volume%) CO 2 as the shielding gas, and the balance of Ar. . If the heat input exceeds 2.5 kJ / mm, the cooling rate during welding decreases, and the equivalent circle diameter of the V-containing carbide exceeds a predetermined upper limit.
- the composition of the shielding gas is intended to control the oxide form to achieve the refinement of the structure.
- the flux-cored wire is used for welding, but the flux filling rate of the wire used is usually about 10 to 20%.
- a weld metal was produced by the following procedure, and various performances ( Tensile strength, hydrogen embrittlement sensitivity) were evaluated.
- Tables 1 and 2 the column indicated by “-” indicates no addition (not contained).
- the amounts of Mn, Si, Ti, and Zr indicate the total amount of Mn, the total amount of Si, the total amount of Ti, and the total amount of Zr, respectively, and the amount of Mg indicates the amount of metallic Mg.
- test piece for measuring hydrogen storage amount From the heat-treated test piece, a test piece for tensile test and a test piece for measuring hydrogen storage amount (test piece for measuring hydrogen storage amount) were collected.
- the shape of the tensile test piece is shown in FIG. 4, and the shape of the hydrogen storage amount measurement test piece is shown in FIG. Using these test pieces, the hydrogen embrittlement sensitivity was evaluated by the following method.
- Aqueous solution (0.5 mol / L or 2.5 mol / L H 2 SO 4 ) + (1 g / L-KSCN), (30 g / L-NaCl) + (1 g / L-KSCN)
- Current density 0.1 A / dm 2 , 1.0 A / dm 2 , 5.0 A / dm 2
- Charge time 24 hours
- the amount of diffusible hydrogen is determined by using a temperature-programmed desorption analyzer (manufactured by Nidec Anelva) with a built-in quadrupole mass spectrometer, did.
- Plate thickness A weld metal made under the following welding conditions by applying a 45 ° V-shaped groove to a SM490A steel plate with a thickness of 20 mm (welding materials shown in Tables 1 and 2), in accordance with JIS-Z2202. Tensile test specimens were collected, subjected to a tensile test, and those having a tensile strength exceeding 780 MPa were regarded as acceptable.
- the number density of Ti-containing oxide particles containing 20% or more of Ti and having an equivalent circle diameter of 0.15 to 1.0 ⁇ m, the amount of compound type V in the weld metal, and the average of V-containing carbides present in the weld metal was measured by the following method.
- the analysis value of Ti (% by mass) is included in the oxide particles by standardizing the analysis value (% by mass) of Si, S, Ti, Mn, Al, Zr, and Mg.
- No. 32 to 53 are examples that do not meet any of the requirements defined in the present invention, and at least one of the properties of tensile strength and resistance to hydrogen embrittlement is deteriorated.
- No. No. 32 is an example in which the heat input conditions at the time of welding are not appropriate, the average equivalent circle diameter of the V-containing carbide is large, and the hydrogen embrittlement susceptibility is high (the hydrogen embrittlement susceptibility is deteriorated).
- No. 33 is an example in which the total amount of Al in the welding material is insufficient, the amount of compound type V in the weld metal is small, and the hydrogen embrittlement sensitivity is high.
- No. 34 is an example in which the Ni content of the weld metal and the amount of metal Al in the welding material are insufficient, the amount of compound type V in the weld metal is reduced, the hydrogen embrittlement sensitivity is increased, The tensile strength is low.
- No. No. 35 is an example in which the amount of metallic Al in the welding material is excessive, and the number density of Ti-containing oxide particles in the welding metal is reduced, and the hydrogen embrittlement sensitivity is increased.
- No. 36 is an example in which the Mn content of the weld metal and the metal Mg content in the welding material are insufficient, the compound type V content in the weld metal is reduced, the hydrogen embrittlement sensitivity is increased, and the tensile strength is increased. Is low.
- No. 37 is an example in which the Mo content of the weld metal and the metal Zr content in the weld material are insufficient, the compound type V content in the weld metal is reduced, the hydrogen embrittlement sensitivity is increased, and the tensile strength is increased. Is low.
- No. No. 38 is an example in which the C content and the compound type V content of the weld metal are low, and the hydrogen embrittlement sensitivity is high and the tensile strength is low.
- No. No. 39 is an example in which the C content of the weld metal is excessive. The tensile strength is excessively increased and the hydrogen embrittlement sensitivity is increased.
- No. 40 is an example in which the Si content of the weld metal is excessive [the welding material (Ti + Mn / Si) is also small], and the number density of the Ti-containing oxide particles is low and the hydrogen embrittlement sensitivity is low. Is high.
- No. No. 41 is an example in which the Mn content of the weld metal is excessive, the tensile strength is excessively increased and the hydrogen embrittlement sensitivity is increased.
- No. 42 is an example in which the Ni content of the weld metal is excessive, the (Ti + Mn / Si) of the welding material is also small, the number density of Ti-containing oxide particles is low, and the tensile strength is low.
- the hydrogen embrittlement susceptibility is increased due to excessive increase.
- No. 43 is an example in which the Mo content of the weld metal is excessive [(Ti + Mn / Si) of the welding material is also small], and the number density of the Ti-containing oxide particles is reduced and the tensile strength is reduced.
- the hydrogen embrittlement susceptibility is increased due to excessive increase.
- No. No. 44 is an example in which the Ti content of the weld metal is insufficient (the total Ti content in the welding material is small), and the number density of the Ti-containing oxide particles is low and the hydrogen embrittlement sensitivity is high.
- No. No. 45 is an example in which the Ti content of the weld metal is excessive, and the tensile strength is excessively increased and the hydrogen embrittlement sensitivity is increased.
- No. 46 is an example in which the Si content of the weld metal is excessive and the V content is insufficient [(Ti + Mn / Si) of the welding material is also small], and the number density of Ti-containing oxide particles The amount of compound type V in the weld metal decreases, the tensile strength increases excessively, and the hydrogen embrittlement sensitivity increases.
- No. 47 is an example in which the V content of the weld metal is excessive, the tensile strength is excessively increased, and the hydrogen embrittlement sensitivity is increased.
- No. No. 48 is an example in which the Cr content of the weld metal is excessive, and (Ti + Mn / Si) of the welding material is also reduced, so that the number density of the Ti-containing oxide particles is lowered and the hydrogen embrittlement sensitivity is reduced. It is high.
- No. No. 49 is an example in which the Nb content of the weld metal is excessive, the tensile strength is excessively increased and the hydrogen embrittlement sensitivity is increased.
- No. 50 is an example in which the Cu content of the weld metal is excessive [the welding material (Ti + Mn / Si) is also small], and the number density of the Ti-containing oxide particles is low and the hydrogen embrittlement sensitivity is low. Is high.
- No. No. 51 is an example in which the Al content of the weld metal is excessive, and the number density of the Ti-containing oxide particles is lowered and the hydrogen embrittlement sensitivity is increased.
- No. No. 52 is an example in which the Zr content of the weld metal is excessive, and the number density of the Ti-containing oxide particles is lowered and the hydrogen embrittlement sensitivity is increased.
- No. 53 is an example in which the B content of the weld metal is excessive. The tensile strength is excessively increased and the hydrogen embrittlement sensitivity is increased.
- the weld metal of the present invention is used for welded structures and can reduce sensitivity to hydrogen embrittlement.
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Abstract
Description
Tiを20%以上含有し、円相当直径:0.15~1.0μmのTi含有酸化物粒子が粒内変態の起点として作用することで、組織を著しく微細化し、水素脆化感受性を低下させるのに有効に作用する。こうした効果を発揮させるためには、その個数は5000個/mm2以上とする必要がある。Ti含有酸化物粒子の個数は、8000個/mm2以上であることが好ましい(より好ましくは、9000個/mm2以上)。Ti含有酸化物粒子の個数の上限は、特に規定するものではないが、好ましくは40000個/mm2以下であり、より好ましくは30000個/mm2以下(更に好ましくは20000個/mm2以下)である。尚、測定対象とするTi含有酸化物粒子の大きさを、円相当直径で0.15~1.0μmとしたのは、円相当直径が0.15μmよりも小さいと粒内変態の起点としての能力が低下するためであり、また1.0μmより大きいものが多数存在すると、粒内変態がより高温で起こり、強度の低下をもたらすからである。
化合物型V量が0.002%未満となると、拡散性水素トラップサイトとなるV含有炭化物の量が不足する。尚、化合物型V量は0.003%以上であることが好ましい(より好ましくは0.005%以上)。また化合物型V量の好ましい上限は0.05%以下であり、より好ましくは0.03%以下(更に好ましくは0.02%以下)である。
上記で化合物型V量が確保されていても、V含有炭化物の平均円相当直径が15nmを超えると、V含有炭化物粒子が粗大となり、V含有炭化物粒子数が減少するため、トラップ効果が十分に発揮されなくなる。溶接金属中に存在するV含有炭化物の平均円相当直径は、12nm以下であることが好ましく、より好ましくは10nm以下である。
Cは、溶接金属の強度を確保するために欠くことのできない元素であり、こうした効果を発揮させるには、0.02%以上含有させる必要がある。好ましくは0.04%以上であり、より好ましくは0.06%以上である。しかしながら、C含有量が0.12%を超えると、強度が過大に上昇して水素脆化感受性が高くなる(耐水素脆化感受性が劣化する)。尚、C含有量の好ましい上限は、0.10%であり、より好ましくは0.08%以下である。
Siは、脱酸元素であり、溶接金属を清浄化する作用を有する。こうした効果を発揮させるためには、Si含有量は0.1%以上とする必要がある。好ましくは0.25%以上、より好ましくは0.28%以上含有させるのがよい。しかしながら、Si含有量が過剰になると、酸化物を起点とする粒界変態が抑制され、水素脆化感受性が高くなるので、0.80%以下に抑える必要がある。好ましくは0.7%以下であり、より好ましくは0.5%以下に抑えるのが良い。
Mnは、溶接金属の強度を確保する上で必要な元素であり、こうした効果を発揮させるには、0.9%以上含有させる必要がある。好ましくは1.2%以上、より好ましくは1.5%以上である。しかしながら、2.5%を超えて過剰に含有させると、強度の過大な上昇による水素脆化感受性が高くなる原因となる。好ましくは2.2%以下であり、より好ましくは2.0%以下である。
Niは、溶接金属の強度を確保する上で必要な元素であり、こうした効果を発揮させるには、0.20%以上含有させる必要がある。好ましくは0.5%以上、より好ましくは1.0%以上である。しかしながら、3.5%を超えて過剰に含有させると、強度の過大な上昇による水素脆化感受性が高くなる原因となる。好ましくは3.0%以下であり、より好ましくは2.8%以下である。
Moは、溶接金属の強度を向上する上で必要な元素であり、こうした効果を発揮させるには、0.05%以上含有させる必要がある。好ましくは0.10%以上、より好ましくは0.2%以上である。しかしながら、1.50%を超えて過剰に含有させると、強度の過大な上昇による水素脆化感受性が高くなる原因となる。好ましくは1.0%以下であり、より好ましくは0.50%以下である。
Tiは、粒内変態の起点となる酸化物を形成し、組織を微細化することで耐水素脆化特性の改善に有効な元素である。こうした効果を発揮させるには、0.040%以上含有させる必要がある。好ましくは0.050%以上、より好ましくは0.055%以上である。しかしながら、0.15%を超えて過剰に含有させると、強度の過大な上昇による水素脆化感受性が高くなる原因となる。好ましくは0.12%以下であり、より好ましくは0.08%以下である。
Vは、拡散型水素のトラップサイトとなるV含有炭化物を形成することで、耐水素脆化特性の改善に有効な元素である。こうした効果を発揮させるには、0.05%以上含有させる必要がある。好ましくは0.1%以上、より好ましくは0.15%以上である。しかしながら、0.60%を超えて過剰に含有させると、強度を過大に上昇させ、水素脆化感受性が高くなる原因となる。
Nは、不可避的に混入してくる元素であり、溶接金属の強度を向上する上で有効であるが、過剰に含有させると、強度の過大な上昇により水素脆化感受性が高くなる原因となる。こうしたことから、N含有量は0.015%以下とする必要がある。好ましくは0.010%以下であり、より好ましくは0.006%以下である。尚、Nは工業的に0%とすることは困難である。
Oは、粒内変態の起点となる酸化物を形成し、組織を微細化することで耐水素脆化特性の改善に有効な元素である。こうした効果を発揮させるには、0.030%以上含有させる必要がある。好ましくは0.035%以上、より好ましくは0.040%以上である。尚、O含有量の上限については、特に設定するものではないが、含有量が過剰になると、靭性に悪影響を及ぼすため、0.10%以下(より好ましくは0.080%以下)であることが好ましい。
Cr,NbおよびCuは、溶接金属の強度を向上する上で有効な元素である。このうちCuは、低温靭性の確保にも有効に作用する。しかしながら、これらの元素を過剰に含有させると、強度の過大な上昇により水素脆化感受性が高くなる原因となる。こうしたことから、Crで2.0%以下(より好ましくは1.5%以下、更に好ましくは1.0%以下)、Nbで0.15%以下(より好ましくは0.10%以下、更に好ましくは0.08%以下)、またはCuで1.0%以下(より好ましくは0.5%以下、更に好ましくは0.2%以下)に、夫々抑制することが好ましい。尚、上記効果を発揮させるための好ましい下限は、Crで0.05%以上、Nbで0.01%以上、またはCuで0.05%以上である(いずれも、0.01%未満で不可避的不純物レベル)。
AlとZrは、いずれも強脱酸元素であり、溶接金属を清浄化させるのに有効である。しかしながら、過剰に含有させると、粒内変態の起点となる酸化物を減少させ、組織粗大化によって水素脆化感受性が高くなる原因となる。こうしたことから、Alで0.020%以下(より好ましくは0.018%以下)、Zrで0.10%以下(より好ましくは0.06%以下)に、夫々抑制することが好ましい。尚、上記効果を発揮させるための好ましい下限は、AlまたはZrのいずれも0.01%以上である(いずれも、0.01%未満で不可避的不純物レベル)。
Bは、旧オーステナイト粒界からのフェライト生成を抑制することで、強度を向上させる元素であるが、過剰に含有させると、強度を過大に上昇させ、水素脆化感受性が高くなる原因となる。こうしたことから、Bは0.0050%以下(より好ましくは0.0030%以下)に抑制することが好ましい。尚、上記効果を発揮させるための好ましい下限は、0.0010%以上である(0.0008%未満で不可避的不純物レベル)。
(a)金属、酸化物その他の形態で存在するTi量(全Ti量)が2.5~4.5%(質量%)、
(b)金属、酸化物その他の形態で存在するAl量(全Al量)が0.10%(質量%)以上、
(c)金属として存在するAl量(金属Al量)が0.01~0.05%(質量%)以上、
(d)金属、酸化物その他の形態で存在する金属として存在するZr量(全Zr量)が0.035%(質量%)以上、
(e)金属として存在するMg量(金属Mg量)が0.4%(質量%)以上、
(f)金属、酸化物その他の形態で存在するSi量(全Si量)と、Mn+Ti量(全Mn量と全Ti量の合計)との比[(Mn+Ti)/Si]が、下記(1)式の関係を満足すること。
(Mn+Ti)/Si>10.0 …(1)
SM490A鋼板を、図1に示す開先形状に加工し、下記の溶接条件でガスシールドアーク溶接を実施し、溶接金属を作製した。
シールドガス:20体積%CO2-80体積%Ar混合ガス
電流-電圧-溶接速度:270A-29V-3.0~4.5mm/秒
入熱条件:
(ア)1.74kJ/mm(270A-29V-4.5mm/秒)
(イ)2.37kJ/mm(270A-29V-3.3mm/秒)
(ウ)2.61kJ/mm(270A-29V-3.0mm/秒)
予熱-パス間温度:105~150℃
積層法:3層13パス
上記で得られた水素吸蔵量測定用試験片を用い、拡散性水素量=1.5~3.0ppmとなるような水素チャージ条件を選定した。このとき採用したチャージ条件は、下記の通りである。
電流密度:0.1A/dm2、1.0A/dm2、5.0A/dm2
チャージ時間:24時間
水溶液:(350g/L-ZnSO4・7H2O)+(20.6g/L-H2SO4(97%))+(60g/L-Na2SO4)
浴温:60℃
電流密度:50A/dm2
めっき時間:3分
S=(1-Eh/E0)×100(%)…(2)
板厚:20mmのSM490A鋼板に、45°V字開先を施し、下記の溶接条件で作製した溶接金属について(溶接材料については、表1、2に示したもの)、JIS-Z2202に準拠した引張り試験片を採取し、引張り試験を行い、引張り強度にして780MPaを超えるものを合格とした。
(溶接条件)
シールドガス:20体積%CO2-80体積%Ar混合ガス
電流-電圧-溶接速度:270A-29V-4.5mm/秒
入熱量:1.74kJ/mm
予熱-パス間温度:105~150℃
積層法:8層17パス
SSRT試験用に作製した溶接金属(前記「溶接金属の作製」の欄)の最終パスより、直径:5mmの丸棒試験片を採取し、輪切り断面を鏡面研磨した後、光学顕微鏡にて1000倍の画像を2視野撮影した。画像解析ソフト(「Image-Pro Plus」Media Cybernetics社製)によって、円相当直径:0.15~1.0μmの酸化物粒子を選定すると共に、撮影した酸化物中央部の組成をSEM-EDS(Energy-dispersive X-ray spectroscopy)にて分析した。検出された元素のうち、Tiの分析値(質量%)をSi,S,Ti,Mn,Al,Zr,Mgの分析値(質量%)の合計で規格化することで、酸化物粒子に含まれるTi濃度(質量%)を算出し、20%以上のTiを含有する酸化物粒子であって、円相当直径が0.15~1.0μmのものの個数密度を算出した。
SSRT試験用に作製した溶接金属(前記「溶接金属の作製」の欄)の最終パスより、直径:5mm×長さ30mmの丸棒試験片を採取し、10体積%アセチルアセトン-1体積%テトラメチルアンモニウムクロライド-メタノール溶液により電解抽出し、フィルター孔径:0.1μmのフィルターで濾過して残渣を得た後、この残渣をICP発光分析にかけ、化合物型V量を求めた。
SSRT試験用に作製した溶接金属(前記「溶接金属の作製」の欄)の最終パスより、直径:5mmの丸棒試験片を採取し、輪切り断面から抽出レプリカTEM試験片を作製し、30万倍の画像を1視野撮影し、写りこんだV含有炭化物のうち、画像解析ソフト(「Image-Pro Plus」Media Cybernetics社製)によって、面積が10nm2以上のものの全粒子の円相当直径を測定し、平均値を算出した。このとき、観察された化合物粒子について、TEMに付属のEDS(エネルギー分散型X線分析装置)にて元素分析を行い、V含有炭化物の判定を行った。
本出願は、2011年4月8日出願の日本特許出願(特願2011-086727)に基づくものであり、その内容はここに参照として取り込まれる。
Claims (2)
- フラックス入りワイヤを用い、ガスシールドアーク溶接によって形成される溶接金属であって、
C:0.02~0.12%(「質量%」の意味。化学成分組成について、以下同じ)、Si:0.1~0.80%、Mn:0.9~2.5%、Ni:0.20~3.5%、Mo:0.05~1.50%、Ti:0.040~0.15%、V:0.05~0.60%、N:0.015%以下(0%を含まない)およびO:0.030%以上を夫々含有し、残部が鉄および不可避的不純物からなり、
Tiを20%以上含有し、円相当直径:0.15~1.0μmのTi含有酸化物粒子が5000個/mm2以上存在すると共に、溶接金属中に化合物として存在する溶接金属全質量当たりのV量が0.002%以上であり、
更に、溶接金属中に存在するV含有炭化物の平均円相当直径が15nm以下であることを特徴とする耐水素脆化感受性に優れた溶接金属。 - 更に、下記元素の少なくとも1種を含有することを特徴とする請求項1記載の溶接金属。
Cr:2.0%以下(0%を含まない)、
Nb:0.15%以下(0%を含まない)
Cu:1.0%以下(0%を含まない)
Al:0.020%以下(0%を含まない)
Zr:0.10%以下(0%を含まない)
B:0.0050%以下(0%を含まない)
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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US14/110,556 US9592575B2 (en) | 2011-04-08 | 2012-04-06 | Weld metal having excellent resistance to hydrogen embrittlement susceptibility |
SG2013069125A SG193455A1 (en) | 2011-04-08 | 2012-04-06 | Weld metal having excellent resistance to hydrogen embrittlement |
KR1020137026262A KR101503634B1 (ko) | 2011-04-08 | 2012-04-06 | 내수소 취화 감수성이 우수한 용접 금속 |
CN201280015931.8A CN103476542B (zh) | 2011-04-08 | 2012-04-06 | 耐氢脆敏感性优异的焊接金属 |
RU2013149796/02A RU2553169C1 (ru) | 2011-04-08 | 2012-04-06 | Металл сварного шва, обладающий высокой устойчивостью к водородному охрупчиванию |
EP12767441.4A EP2695702A4 (en) | 2011-04-08 | 2012-04-06 | WELDING METAL WITH EXCELLENT RESISTANCE TO HYDROGEN INJURY |
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EP (1) | EP2695702A4 (ja) |
JP (1) | JP5606985B2 (ja) |
KR (1) | KR101503634B1 (ja) |
CN (1) | CN103476542B (ja) |
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WO2014136601A1 (ja) * | 2013-03-08 | 2014-09-12 | 株式会社神戸製鋼所 | 溶接金属及びこれを備えた溶接構造体 |
CN104955608A (zh) * | 2013-01-11 | 2015-09-30 | 株式会社神户制钢所 | 耐氢脆化敏感性优异的焊接金属和埋弧焊用实芯焊丝 |
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JP5798060B2 (ja) * | 2011-11-21 | 2015-10-21 | 株式会社神戸製鋼所 | 耐焼戻し脆化特性に優れた溶接金属 |
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CN104955608A (zh) * | 2013-01-11 | 2015-09-30 | 株式会社神户制钢所 | 耐氢脆化敏感性优异的焊接金属和埋弧焊用实芯焊丝 |
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WO2014136601A1 (ja) * | 2013-03-08 | 2014-09-12 | 株式会社神戸製鋼所 | 溶接金属及びこれを備えた溶接構造体 |
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KR101778422B1 (ko) | 2013-03-08 | 2017-09-13 | 가부시키가이샤 고베 세이코쇼 | 용접 금속 및 이것을 구비한 용접 구조체 |
EP3424637A1 (en) * | 2013-03-08 | 2019-01-09 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Weld metal and welded structure provided with same |
Also Published As
Publication number | Publication date |
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CN103476542B (zh) | 2016-08-17 |
RU2013149796A (ru) | 2015-05-20 |
JP2012218034A (ja) | 2012-11-12 |
JP5606985B2 (ja) | 2014-10-15 |
EP2695702A1 (en) | 2014-02-12 |
US20140086786A1 (en) | 2014-03-27 |
KR101503634B1 (ko) | 2015-03-18 |
SG193455A1 (en) | 2013-10-30 |
CN103476542A (zh) | 2013-12-25 |
EP2695702A4 (en) | 2014-08-27 |
KR20130122985A (ko) | 2013-11-11 |
US9592575B2 (en) | 2017-03-14 |
RU2553169C1 (ru) | 2015-06-10 |
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