WO2014148447A1 - Matériau acier présentant une résistance supérieure dans une zone affectée par la chaleur de soudage - Google Patents

Matériau acier présentant une résistance supérieure dans une zone affectée par la chaleur de soudage Download PDF

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WO2014148447A1
WO2014148447A1 PCT/JP2014/057205 JP2014057205W WO2014148447A1 WO 2014148447 A1 WO2014148447 A1 WO 2014148447A1 JP 2014057205 W JP2014057205 W JP 2014057205W WO 2014148447 A1 WO2014148447 A1 WO 2014148447A1
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rem
steel
mass
steel material
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崇 杉谷
正樹 島本
秀徳 名古
木村　世意
進佑 佐藤
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株式会社神戸製鋼所
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Priority to CN201480016899.4A priority Critical patent/CN105051229B/zh
Priority to EP14767775.1A priority patent/EP2977479B1/fr
Priority to KR1020157025566A priority patent/KR101718275B1/ko
Publication of WO2014148447A1 publication Critical patent/WO2014148447A1/fr

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    • C21D2211/00—Microstructure comprising significant phases
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling

Definitions

  • the present invention relates to a thick steel plate suitable for use in welded structures such as shipbuilding, construction, and bridges, and more particularly to a steel material that realizes excellent HAZ toughness even with high heat input welding.
  • a weld heat-affected zone (hereinafter also referred to as HAZ) exposed to welding heat regardless of the amount of heat becomes high temperature during welding, and the crystal grains of the steel material are likely to be coarsened.
  • HAZ weld heat-affected zone
  • the weld heat affected zone becomes higher in temperature and the cooling time becomes longer.
  • a high temperature and a long cooling time are conditions that promote the formation of a brittle upper bainite structure in the heat affected zone and the formation of an embrittled structure such as island martensite, and thus reduce the HAZ toughness of the steel material. That is already known.
  • Patent Document 1 aims at providing the steel material excellent in the welding heat affected zone toughness (HAZ toughness), and a manufacturing method. Specifically, the manufacturing method disclosed in Patent Document 1 disperses fine sulfides by adding Mg and / or REM in addition to Ca having strong sulfide-forming ability in molten steel to produce fine oxides. The HAZ structure heated to 1400 ° C. or higher is refined and good HAZ toughness is achieved even with high heat input welding of 200 kJ / cm or higher.
  • HAZ toughness welding heat affected zone toughness
  • Patent Document 2 aims to provide a high-strength welded structural steel with excellent base metal toughness and weld zone HAZ toughness and a method for producing the same.
  • the manufacturing method disclosed in Patent Document 2 includes adding one or more of Mg, Ca, and REM after adding Ti, or adding one or more of Ti, Mg, Ca, and REM.
  • Patent Document 2 as an effect of these two miniaturizations, high strength welded structural steel having good base metal toughness and welded portion HAZ toughness can be manufactured.
  • Patent Document 3 is intended to provide a thick steel plate excellent in welding heat-affected zone toughness of ultra-high heat input welding and a method for producing the same. Specifically, the production method of Patent Document 3 controls the form of dendrites formed in the solidification process in addition to adjusting the particle composition of oxides, sulfides, etc. in the molten steel. As a result, Patent Document 3 disperses dispersed particles in a steel sheet more uniformly and finely than in the past, and refines austenite grains even in HAZ during super-high heat input welding where the heat input is 300 kJ / cm or more. It is said that the HAZ toughness can be significantly improved.
  • Patent Document 4 is intended to provide a high-strength steel sheet having API standard X100 or higher having good HAZ toughness. Specifically, in the high-strength steel sheet of Patent Document 4, by limiting the amount of Ti, Mg, REM, Al, S, and N, (1) TiN-based fine precipitation containing Mg-based oxides of 0.1 ⁇ m or less. The inclusion of the material suppresses the coarsening of ⁇ grains even in the vicinity of the melting line. Furthermore, this high-strength steel sheet includes (2) a complex of MnS with an oxide mainly composed of Ti, Mg, and REM of 0.1 ⁇ m or more, and generates IGF from within relatively small ⁇ grains. It is said that the HAZ toughness can be improved by refining the structure throughout the entire HAZ.
  • Patent Document 5 aims to propose a non-tempered high-tensile steel material having both good base material toughness and weld heat-affected zone toughness.
  • the non-tempered high-tensile steel material of Patent Document 5 has an optimum composition range of an optimum oxide-based inclusion as follows: Ti oxide: 20 to 90% by weight, CaO and REM oxide total: 5 to 50 Weight%, Al 2 O 3 : Controlled to 70% by weight or less.
  • non-tempered high-tensile steel can effectively utilize the grain coarsening suppression ability (pinning effect) of inclusions without causing nozzle clogging or generation of harmful inclusion clusters.
  • the toughness can be improved, and further, the toughness and strength of the base material can be improved by optimally dispersing TiN or VN.
  • Japanese Patent No. 4261968 Japanese Patent No. 4762450 Japanese Patent No. 4039223 Japanese Unexamined Patent Publication No. 11-264048 Japanese Patent No. 4144121
  • Patent Documents 1 to 5 discloses that it is possible to cope with a decrease in the HAZ toughness caused by welding heat. It is difficult to improve the HAZ toughness.
  • the techniques disclosed in Patent Documents 1 to 3 are intended to refine the HAZ structure by the pinning effect of oxysulfides, but do not mention the structure refinement effect due to intragranular transformation caused by oxides. It cannot be said that it is a technology that can cope with further increase in heat input.
  • Patent Document 4 mentions a structural transformation starting from an oxide, but does not show a countermeasure against the coarse oxide and the like, and eliminates the possibility that the HAZ toughness is lowered due to the formation of the coarse oxide. It cannot be said that it is a technology that can cope with further increase in heat input.
  • the technique disclosed in Patent Document 5 is a technique for refining the HAZ structure by the pinning effect of oxysulfide, but it is not a technique that takes account of the structure transformation control starting from oxysulfide. It cannot be said that this technology can cope with large heat input.
  • the present invention has been made in view of the above-described problems, and an object of the present invention is to provide a steel material having excellent weld heat affected zone toughness (HAZ toughness) during high heat input welding.
  • HZ toughness weld heat affected zone toughness
  • the present invention has taken the following measures. That is, technical means for solving the problems in the present invention are: C: 0.02 to 0.13% (meaning mass% (mass%); the same applies to the following components); Si: 0.05 to 0.003.
  • the balance is a steel material excellent in toughness of the weld heat affected zone consisting of iron and inevitable impurities, the steel material, Including a composite oxide containing REM, Zr, Ti, Al, Ca and S, For oxides, oxides of 3 [mu] m greater is not more than 5.0 per 1 mm 2 equivalent circle diameter, and the composite oxide of the circle equivalent diameter 0.1 ⁇ 3 [mu] m, satisfies the following formula (1) Composite The number of oxides is 100 / mm 2 or more, and the average composition of the composite oxide of 0.1 to
  • Nb 0.002 to 0.10%
  • V 0.002 to 0.10%
  • B 0.0005 to 0.0050% is preferably contained.
  • a steel material excellent in the toughness (HAZ toughness) of the weld heat affected zone at the time of high heat input welding can be obtained.
  • the steel material according to the present embodiment is a steel material that exhibits excellent toughness in a weld heat affected zone (HAZ, Heat Affected Zone) affected by a very large welding energy, for example, a welding heat input exceeding 60 kJ / mm. is there.
  • HAZ weld heat affected zone
  • HAZ toughness the toughness in the HAZ
  • the steel material according to the present embodiment is a composite oxide (an oxysulfide containing Al, Ti, Zr, REM, Ca, and S) that serves as a nucleus of intragranular transformation, with its size and S concentration being appropriately controlled.
  • a composite oxide an oxysulfide containing Al, Ti, Zr, REM, Ca, and S
  • the steel material according to the present embodiment can stably exhibit excellent HAZ toughness even when welding is performed with a large heat input.
  • the steel material by this embodiment which has the above-mentioned characteristic is obtained by adding each element so that it may become the chemical composition composition explained below in the secondary refining of molten steel, for example.
  • the steel material according to the present embodiment (hereinafter simply referred to as the present steel material) has carbon C of 0.02 to 0.13%, silicon Si of 0.05 to 0.5%, and manganese Mn of 1.0 to 2.5%. 0.03% or less of phosphorus P (not including 0%), 0.01% or less of sulfur S (not including 0%), 0.002 to 0.040% of aluminum Al, and 0.02% of titanium Ti.
  • the steel material includes a composite oxide containing REM, Zr, Ti, Al, Ca, and S.
  • an oxide having an equivalent circle diameter of more than 3 ⁇ m is 5 per mm 2 .
  • the number of composite oxides satisfying the following formula (1) is 100 / mm 2 or more.
  • the average composition of the composite oxide of 0.1 to 3 ⁇ m satisfying the above formula (1) is 20% or less of Al 2 O 3, 3 to 20% of TiO 2 , 5 to 50% of ZrO 2 , REM oxidation
  • the product is 5 to 50%
  • CaO is 5 to 50%
  • S is 1 to 15%.
  • Carbon C 0.02 to 0.13%
  • Carbon C is an element indispensable for securing the strength of the steel material (base material). Therefore, 0.02% or more, preferably 0.04% or more is added.
  • the content of C exceeds 0.13%, not only does island-like martensite (MA) form in the HAZ, leading to a reduction in the toughness of the HAZ, but also weldability due to the generation of CO gas, etc. It also has an adverse effect. Therefore, the C content is 0.13% or less, preferably 0.1% or less.
  • Silicon Si is an element that has a deoxidizing action and contributes to improving the strength of the base material by solid solution strengthening. Therefore, 0.05% or more, preferably 0.07% or more, more preferably 0.1% or more is added. However, if the Si content exceeds 0.5%, the weldability and toughness of the steel material deteriorate, so the upper limit is made 0.5%. In particular, in order to increase the HAZ toughness, it is recommended that the Si content be 0.3% or less. However, as the Si content is reduced, the HAZ toughness is improved, while the strength of the steel material may be reduced. Therefore, the Si content is 0.5% or less, preferably 0.35% or less, more preferably 0.25% or less.
  • Manganese Mn is an element that contributes to improving the strength of the base material. However, when the Mn content is less than 1.0%, the strength is lowered. Therefore, 1.0% or more, preferably 1.3% or more is added. However, if the Mn content exceeds 2.5%, the weldability of the base material is degraded. Therefore, the Mn content is set to 2.5% or less, preferably 2.0% or less.
  • Phosphorus P is an element that easily segregates, and is an element that segregates at a grain boundary in a steel material and lowers the HAZ toughness.
  • P is unavoidably contained in the base material in an amount of about 0.001%, so the content of P is specified to be 0.03% by mass or less. Preferably it is 0.02% or less, More preferably, it is 0.01% or less. However, this embodiment does not include the case where the P content is 0%.
  • Sulfur S is an element that combines with Mn to produce sulfide (MnS) and lowers the toughness of the base material and the ductility in the plate thickness direction.
  • MnS sulfide
  • S is usually unavoidably contained in the base material in an amount of about 0.0005%, so the S content is specified to be 0.01% or less. Preferably it is 0.008% or less, More preferably, it is 0.006% or less.
  • this embodiment does not include the case where the S content is 0%.
  • Aluminum Al is an element that acts as a deoxidizer. Moreover, when there is little content of Al, molten steel will become easy to be contaminated with oxygen. Therefore, 0.002% or more, preferably 0.004% or more, more preferably 0.005% or more is added. However, when Al is added excessively with respect to the base material, the added Al reduces oxides in the base material to form coarse Al oxide, so that the HAZ toughness decreases. Therefore, the Al content is 0.040% or less, preferably 0.025% or less, and more preferably 0.015% or less.
  • Titanium Ti is an element that contributes to the improvement of HAZ toughness by generating a nitride such as TiN or an oxide containing Ti in the base material. Therefore, 0.005% or more, preferably 0.010% or more, more preferably 0.014% or more is added. However, when Ti is excessively added to the base material, the base material itself is hardened by solid solution strengthening of Ti, leading to a decrease in HAZ toughness. Therefore, the Ti content is 0.040% or less, preferably 0.030% or less, and more preferably 0.025% or less.
  • Zirconium Zr is an element that contributes to the improvement of HAZ toughness by generating a complex oxide containing Zr. Therefore, 0.0003% or more, preferably 0.0005% or more, more preferably 0.0009% or more is added. However, when Zr is added excessively with respect to the base material, coarse Zr oxide (ZrO 2 ) is generated and HAZ toughness is lowered. Further, the formation of coarse Zr carbide (ZrC) reduces the toughness of the base material itself. Therefore, the Zr content is 0.020% or less, preferably 0.015% or less, and more preferably 0.010% or less.
  • REM rare earth element
  • REM is an element necessary for generation of oxides.
  • This finely dispersed oxide serves as a production nucleus for intra-grain ⁇ of HAZ and contributes to improvement of HAZ toughness. Therefore, 0.0003% or more, preferably 0.0005% or more, more preferably 0.0009% or more is added.
  • the content of REM is set to 0.020% or less, preferably 0.015% or less, more preferably 0.010% or less.
  • REM means an element containing a lanthanoid element (15 elements from La to Ln) and Sc (scandium) and Y (yttrium).
  • a lanthanoid element (15 elements from La to Ln) and Sc (scandium) and Y (yttrium).
  • Calcium Ca is an element necessary for the production of oxides. Ca also forms nuclei of HAZ in the grains and contributes to the improvement of HAZ toughness. Therefore, it is preferable to contain 0.0003% or more, preferably 0.0005% or more, more preferably 0.0007% or more.
  • the Ca content is set to 0.0080% or less, preferably 0.0060% or less, more preferably 0.0030% or less.
  • Nitrogen N is an element that precipitates nitrides (eg, ZrN, TiN, etc.). Nitride contributes to the improvement of HAZ toughness by suppressing the austenite grain coarsening during welding by the pinning effect. Since N forms a nitride and promotes refinement of austenite grains as the content increases, it effectively works to improve HAZ toughness. Therefore, 0.0030% or more, preferably 0.0040% or more, more preferably 0.0050% or more is added. However, if the N content exceeds 0.010%, the amount of solute N increases, the toughness of the base metal itself deteriorates, and the HAZ toughness also decreases. Therefore, the N content is 0.010% or less, preferably 0.0090% or less, and more preferably 0.0080% or less.
  • Oxygen O is an essential element for the formation of oxides. If the content is less than 0.0003%, a sufficient amount of oxide cannot be obtained in the base material. Preferably it is 0.0010% or more, More preferably, it is 0.0015% or more. However, if the content is more than 0.0050%, the HAZ toughness is lowered due to the coarsening of the oxide. Therefore, the content of O is set to 0.0050% or less, preferably 0.0040% or less, more preferably 0.0035% or less.
  • the content of O represents the total amount of oxygen, and means the total amount of O forming an oxide in the base material and free O dissolved in the base material.
  • This steel material contains the above-mentioned elements, and the balance consists of iron and inevitable impurities.
  • the remaining components other than the above-described elements are iron and inevitable impurities (for example, Mg, As, Se, etc.).
  • the present steel material containing the above-mentioned element includes a complex oxide (oxide and / or oxysulfide) containing REM, Zr, Ti, Al, Ca and S.
  • the composite oxides contained in this steel are Al, Ti, Zr, REM, and Al / Ti / Zr / REM / Ca / S based composite oxides containing oxides and sulfides of Ca.
  • elements such as Mn and Si and other component elements may be included.
  • Al, Ti, Zr, REM, and Ca-based oxides have good lattice matching with steel materials, and promote intragranular structure transformation (intragranular transformation) in HAZ, so they are effective in refining the HAZ structure. It is.
  • the number of oxides having an equivalent circle diameter of more than 3 ⁇ m in the above-described composite oxide is 5.0 or less per 1 mm 2 in the cross section of the steel material. Since the complex oxide having an equivalent circle diameter exceeding 3 ⁇ m is coarse, in high heat input welding where the heat input reaches 60 kJ / mm, the HAZ toughness is reduced. Therefore, the number of complex oxides exceeding 3 ⁇ m needs to be suppressed to 5.0 / mm 2 or less.
  • the above-mentioned composite oxide has a circle equivalent diameter of 0.1 ⁇ m to 3 ⁇ m (hereinafter referred to as 0.1 to 3 ⁇ m), satisfies the following formula (1), and It is contained so that the number thereof is 100 / mm 2 or more in the cross section of the steel material.
  • REM and Ca are oxysulfide-forming elements that can form oxides and sulfides. Therefore, if the S concentration (mass% S) with respect to the concentration of the oxysulfide forming elements (REM 2 O 3 and CaO) is too high, excessively generated sulfide inhibits the alignment between the oxide and the matrix. As a result, the ability of the composite oxide to contribute to the structure control (intragranular transformation ability) decreases.
  • the 2nd term which considered the conditions considered to influence these intragranular transformation is shown.
  • the S concentration (mass% S) with respect to the oxysulfide forming elements (REM 2 O 3 and CaO), and the size of the composite oxide (the equivalent circle diameter d of the composite oxide) ) Has an optimum range for producing strain energy that contributes to intragranular transformation, and it is presumed that an upper limit value and a lower limit value exist in the second term of Equation (1). Therefore, the upper limit value and the lower limit value of the second term of Expression (1) were experimentally obtained.
  • a method for obtaining the upper limit value and the lower limit value of the second term of Expression (1) will be described.
  • a heat input test simulating welding HAZ with a heat input of 60 kJ / mm was performed on the prototype material.
  • the prototype material after the heat input test was mirror-polished and corroded, and the structure was revealed by corrosion to investigate the presence of intragranular transformation caused by the composite oxide.
  • the composition and size of the composite oxide in the prototype were measured by EPMA (Electron Probe MicroAnalyzer), and the value of the second term of the formula (1) was calculated for the composite oxide of 0.1 to 3 ⁇ m.
  • the presence or absence of intragranular transformation and the calculated value of the second term are summarized as the results shown in Table 1, and the presence or absence of intragranular transformation is indicated by a circle (the value of the second term of the steel material having intragranular transformation). Based on this, the range of the second term was set to 0.008 or more and 0.289 or less.
  • the composite oxide having an equivalent circle diameter of 0.1 to 3 ⁇ m is contained in an amount of 100 / mm 2 or more after satisfying the formula (1). Further, the average composition is 20% or less of Al 2 O 3 , TiO 2 is 3% to 20% (3 to 20%), ZrO 2 is 5% to 50% (5 to 50%), REM oxide is 5% to 50% (5 to 50%), CaO is It is necessary to be 5% or more and 50% or less (5 to 50%) and S is 1% or more and 15% or less (1 to 15%).
  • the oxide composition affects the lattice matching between the oxide and the steel material in HAZ, so if the oxide composition is not controlled to the content within the above range, a composite oxide having a circle equivalent diameter of 0.1 to 3 ⁇ m. This is because it cannot contribute to the intragranular transformation in HAZ, that is, it cannot contribute to the refinement of the HAZ structure.
  • the steel material having the above chemical composition is intended for thick steel plates with a thickness of about 3.0 mm or more. In addition to small to medium heat input welding, the heat input is 50 kJ / mm or more. Since the HAZ toughness can be prevented from being lowered even in thermal welding, it can be used as a material for large structures such as bridges, high-rise buildings, and ships.
  • at least one of nickel Ni, copper Cu, chromium Cr, and molybdenum Mo is 0.05% to 1.50% (0.05 to 1.. 50%) may be contained.
  • Cu, Ni, Cr, and Mo are all elements that contribute to increasing the toughness and strength of the steel material, and can be added alone or in combination. For example, in order to effectively improve toughness and strength by adding Cu, it is preferable to contain 0.05% or more of Cu.
  • the Cu content is specified to be 0.05% or more and 1.50% or less.
  • Ni, Cr, and Mo are preferably contained in an amount of 0.05% or more. However, if the content exceeds 1.50%, the strength of the base material is excessively increased and the toughness of the base material is decreased. Therefore, the HAZ toughness is also lowered. Therefore, the contents of Ni, Cr, and Mo are also specified to be 0.05% or more and 1.50% or less.
  • Niobium Nb, Vanadium V: 0.002 to 0.10% Further, the steel material according to this embodiment may contain 0.002% or more and 0.10% or less (0.002 to 0.10%) of at least one of niobium Nb and vanadium V. Nb and V are both precipitated as carbonitrides.
  • Nb in order to effectively improve the HAZ toughness by adding Nb, it is preferable to contain Nb in an amount of 0.002% or more. However, if the content of Nb exceeds 0.10%, the precipitated carbonitrides are coarsened, and on the contrary, the HAZ toughness is reduced. Therefore, the Nb content is specified to be 0.002% or more and 0.10% or less.
  • V is preferably contained in an amount of 0.002% or more. However, if the content of V exceeds 0.10%, the precipitated carbonitrides are coarsened, and on the contrary, the HAZ toughness is lowered. Therefore, the V content is specified to be 0.002% or more and 0.10% or less.
  • the steel material according to the present embodiment may contain 0.0005% or more and 0.0050% or less (0.0005 to 0.0050%) of boron B.
  • B is an element that suppresses the formation of grain boundary ferrite and improves toughness. Therefore, in order to improve the toughness of the steel material by adding B, it is preferable to contain B in an amount of 0.0005% or more.
  • the B content is 0.0050% or less, preferably 0.0040% or less, more preferably 0.0015% or more and 0.0030% or less.
  • the steel material according to the present embodiment can be obtained by adding each element so as to have the above-described chemical component composition, for example, in the secondary refining of molten steel.
  • the steel manufacturing method (manufacturing conditions) shown, that is, the method of adding each element will be described. In the following description, steel was melted using a vacuum melting furnace (capacity 150 kg), cast into a 150 kg ingot, and cooled to obtain steels shown in examples and comparative examples described later.
  • the desulfurization method for adjusting the S concentration is not particularly limited, but a molten steel having a low S concentration may be used in advance.
  • the grounds for the dissolved oxygen amount and the S concentration are as follows. First, when the amount of dissolved oxygen exceeds 0.005%, the oxide generated in the molten steel becomes coarse. In addition, when the value of (mass% Of / mass% S) is large, the sulfide necessary for the oxide is not sufficiently generated. Further, when the value of (mass% Of / mass% S) is small, not only the desired oxide cannot be obtained, but also the sulfide is generated to a level that inhibits intragranular transformation because the S concentration is too high. End up.
  • Ti was added to the molten steel before REM and Zr. If Ti is added before Al, all Ti oxides are reduced by Al in the subsequent steps. Therefore, Ti must be added after Al is added. After the addition of Ti, the molten steel was held for 2 to 15 minutes without adding other elements.
  • the dissolved oxygen amount (mass% Of) is 0.005% or less, and the value of (mass% Of / mass% S) is 0.2 ⁇ mass% Of / mass%.
  • S ⁇ 9.6
  • the amount of Zr added is 10 ppm to 120 ppm and the amount of REM added is 30 ppm to 150 ppm. This is because if either one of Zr and REM is excessive, a coarse composite oxide having an equivalent circle diameter exceeding 3 ⁇ m is formed, and if either one of the elements is too small, A fine complex oxysulfide having an equivalent diameter of 0.1 to 3 ⁇ m is insufficient. That is, the amount of Zr and REM added affects the particle size distribution of the composite oxide.
  • REM has the property of easily forming oxides and sulfides
  • Zr has the property of forming oxides but not sulfides. Therefore, in order to optimize the balance between the oxide and the sulfide, it is necessary to add Zr and REM according to mass% Of and mass% S. Therefore, the ratio (add [Zr] / add [REM]) between the Zr addition amount and the REM addition amount is determined so as to satisfy the following expression (2).
  • the deoxidizing elements Al, REM, Zr, and Ca are preferably not added all at once to the molten steel, but divided into two or more times or continuously in small amounts.
  • REM, Ca, Zr, Ti added to molten steel is not specifically limited,
  • REM pure La, pure Ce, and pure Y, pure Ca, pure Zr, pure Ti, and also Fe -Si-La alloy, Fe-Si-Ce alloy, Fe-Si-Ca alloy, Fe-Si-La-Ce alloy, Fe-Ca alloy, Ni-Ca alloy and the like may be added.
  • Misch metal is a mixture of rare earth elements, and specifically contains about 40 to 50% of Ce and about 20 to 40% of La.
  • misch metal often contains Ca as an impurity, when the misch metal contains Ca, it is necessary to satisfy the range of the Ca content defined in the present embodiment.
  • composition (content) of the component elements described so far, the relational expression regarding the content of the component elements, the manufacturing conditions, and the like are referred to as “conditions defined in the present embodiment”.
  • “Casting / Rolling” Molten steel whose components were adjusted as described above was cast into an ingot. The cast ingot was processed by hot rolling to produce a thick steel plate having a thickness of 30 mm to 80 mm. In actual operation, the molten steel obtained by adjusting the components may be continuously cast according to a conventional method to form a slab and then hot rolled according to a conventional method.
  • Each of these three V-notch specimens is subjected to a Charpy impact test at ⁇ 40 ° C., the absorbed energy (vE-40) is measured, and the average value and minimum value of the measurement results of the three V-notch specimens are measured. The value was determined.
  • test piece thin steel plate having an average value of vE-40 exceeding 140 J was evaluated as a steel plate excellent in HAZ toughness.
  • Measurement method of composite oxide composition of 0.1 to 3 ⁇ m A test piece is cut out from the surface of the thick steel plate at a depth t / 4 (t: thickness of the thick steel plate) (taken so that the axis of the test piece passes through the position of the depth t / 4), and the rolling direction and A cross section parallel to the plate thickness direction is mirror-polished and 0.1 to 3 ⁇ m using an electron probe microprobe X-ray analyzer (EPMA, trade name JXA-8500F) manufactured by JEOL Datum. The composite oxide composition of was measured.
  • EPMA electron probe microprobe X-ray analyzer
  • the observation conditions at this time were an acceleration voltage of 20 kV, a sample current of 0.01 ⁇ A, a magnification of 5000 times, an observation area of 0.4 mm 2 or more, and the component composition at the center of the composite oxide with wavelength dispersion of characteristic X-rays Quantitative analysis was performed by spectroscopy.
  • the elements to be quantified are Si, Mn, S, Al, Ti, Zr, La, Ce, Ca, and O (oxygen), and the relationship between the X-ray intensity and element concentration of each element using a known substance.
  • the amount of elements contained in the composite oxide was quantified based on the X-ray intensity and calibration curve obtained from the composite oxide to be analyzed.
  • each element other than S was converted to a single oxide, and the composition of the oxide was calculated.
  • S was calculated with a single concentration.
  • mass conversion is performed as the single oxide and S single element concentration in this way, and the average of a plurality of composite oxides is used as the composite oxide composition.
  • the REM oxide is present in the steel material in the form of M 2 O 3 , M 3 O 5 , MO 2, etc., but all the REM oxide is converted to M 2 O 3 . Converted. Similarly, all Ti was converted to TiO 2 .
  • Measurement method of equivalent circle diameter and number of composite oxide In the composition measurement of the composite oxide using the above-described EPMA, the area of the composite oxide was measured and the composite oxide was assumed to be a circle, and the diameter of the circle corresponding to the measured area was calculated as the equivalent circle diameter.
  • the magnification is 200 times
  • the observation area is 50 mm 2 or more
  • other conditions are the number of composite oxides whose equivalent circle diameter is 5 ⁇ m or less. The measurement was performed under the same conditions as in the measurement.
  • Table 2 shows steel No. which is an example of the steel according to the present embodiment.
  • 1-No. The chemical composition of 31 is shown.
  • Steel No. 1-No. All 31 component compositions satisfy the conditions defined in this embodiment.
  • Table 3 below shows steel material No. which is an example of this steel material.
  • 1-No. 31 production conditions are shown.
  • Steel No. 1-No. All the 31 manufacturing conditions also satisfy the conditions defined in this embodiment.
  • the selected addition order and addition method are shown in the remarks column.
  • Table 4 below shows steel No. which is an example of this steel.
  • 1-No. 31 shows the composite oxide particle size and number distribution, the composite oxide average composition, and the HAZ toughness test results.
  • the number of composite oxides having a circle equivalent diameter exceeding 3 ⁇ m is 5.0 pieces / mm 2 or less, and the number of composite oxides having a circle equivalent diameter of 0.1 to 3 ⁇ m is 100 pieces / mm 2 or more. It is.
  • the steel material No. 1-No. In all cases 31, the average composition of the composite oxide having an equivalent circle diameter of 0.1 to 3 ⁇ m satisfies the conditions defined in this embodiment.
  • steel material No. 1-No. All 31 can be evaluated as having a HAZ toughness test result of 140 J or more and exhibiting excellent HAZ toughness.
  • Table 5 below shows steel No. as a comparative example that does not satisfy the conditions specified in the present embodiment.
  • 32-No. 67 component compositions are shown.
  • Steel No. No. 32 does not satisfy the conditions specified by the present embodiment for the Al content.
  • Steel No. In 34 and 35 the Ti content does not satisfy the conditions defined in this embodiment.
  • Steel No. In 40 and 41 the REM content does not satisfy the conditions defined in the present embodiment.
  • Steel No. In Nos. 44 and 45 the Zr content does not satisfy the conditions defined in this embodiment.
  • the Ca content does not satisfy the conditions defined in this embodiment.
  • the S content does not satisfy the conditions defined in the present embodiment.
  • Table 6 below shows steel Nos. That do not satisfy the conditions specified in this embodiment. 32-No. 67 manufacturing conditions are shown. Steel No. In 33, 36, 37, 42, 43, 46, 47, 50, and 51, “addition order of complex oxide forming elements” is marked with “x”, and complex oxide forming elements (Al and Ti) are added. Is added in a different order than the order described above. Steel No. Nos. 38 and 39 indicate that the holding time of the molten steel after addition of Ti does not satisfy the conditions defined in the present embodiment. Steel No. 52 indicates that the value of (mass% Of / mass% S) does not satisfy the condition defined in the present embodiment. Steel No.
  • steel material No. 32-No. 67 does not satisfy the conditions defined in the present embodiment in one or both of the component composition shown in Table 5 and the production conditions shown in Table 6.
  • Table 7 shows steel No. as a comparative example that does not satisfy the conditions specified in this embodiment.
  • 32-No. 67 shows the particle size and number distribution of the composite oxide, the average composition of the composite oxide, and the HAZ toughness test results.
  • Steel No. 32-No. 55 the average composition of the composite product does not satisfy the conditions defined in this embodiment.
  • Steel No. In 56 and 57 the number of complex oxides having a circle equivalent diameter exceeding 3 ⁇ m exceeds 5.0 / mm 2 .
  • Steel No. 58-No. In No. 67 one or both of the number of composite oxides having an equivalent circle diameter exceeding 3 ⁇ m and the number of composite oxides having an equivalent circle diameter of 0.1 to 3 ⁇ m do not satisfy the conditions defined in this embodiment.
  • Steel No. 32-No. For each of 55 a condition that is not satisfied among the conditions defined in the present embodiment is shown in “Remarks”.
  • FIG. 1 shows the HAZ toughness of the steel material according to the present embodiment shown in Table 4 and the steel material No. of the comparative example shown in Table 7.
  • 6 is a graph showing the HAZ toughness of 59, 61-67.
  • the number of composite oxides having an equivalent circle diameter of 3 ⁇ m is less than 5.0 / mm 2 .
  • Nos. 59, 61 to 67 are examples in which the number of complex oxides with equivalent circle diameters of 0.1 to 3 ⁇ m was less than 100, and in any case, the HAZ toughness test results were much lower than 140J.
  • HAZ toughness test result is significantly lower than 140J.
  • FIG. 3 shows the HAZ toughness of the steel according to the present embodiment shown in Table 4 and the steel No. of the comparative example shown in Table 7. It is a graph which shows the HAZ toughness of 56,57.
  • the number of complex oxides having equivalent circle diameters of 0.1 to 3 ⁇ m is 100 or more.
  • 56 and 57 are examples in which the number of composite oxides having an equivalent circle diameter of 3 ⁇ m exceeds 5.0 / mm 2 , and the HAZ toughness test result is significantly lower than 140J in both cases.
  • the steel material has a configuration that satisfies the conditions defined in the present embodiment, it can exhibit excellent HAZ toughness even in high heat input welding.
  • the embodiment disclosed this time should be considered as illustrative in all points and not restrictive.
  • matters that are not explicitly disclosed, for example, operating conditions and operating conditions, various parameters, dimensions, weights, volumes, and the like of a component deviate from a range that a person skilled in the art normally performs. Instead, values that can be easily assumed by those skilled in the art are employed.
  • the present steel material is manufactured in secondary refining
  • a steel material that exhibits the same HAZ toughness can be obtained even if it is manufactured using a converter or an electric furnace. Therefore, the production of the present steel material using a converter or an electric furnace is also included in the technical scope of the present invention.
  • the steel sheet of the present invention realizes excellent HAZ toughness even with high heat input welding, and is therefore suitable for use in welded structures such as shipbuilding, construction, and bridges.

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Abstract

La présente invention concerne un matériau acier qui satisfait à une composition chimique prédéterminée et dont un reste comprend du fer et des impuretés inévitables. Ledit matériau acier contient un oxyde complexe qui contient REM, Zr, Ti, Al, Ca, et S, l'oxyde complexe ne possède pas plus de 5,0/mm2 d'oxydes dont un diamètre équivalent en cercle est supérieur à 3 μm, et en ce qui concerne des oxydes complexes dont un diamètre équivalent en cercle est de 0,1 à 3 μm, il y a au moins 100/mm2 d'oxydes complexes qui satisfont à la formule (1), et en outre la composition moyenne des oxydes complexes qui mesurent 0,1 à 3 μm qui satisfont à la formule (1) est telle qu'il n'y a pas plus de 20 % de Al2O3, 3 à 20 % de TiO2, 5 à 50 % de ZrO2, 5 à 50 % d'oxyde REM, 5 à 50 % de CaO, et 1 à 15 % de S. 0,008 ≤ (1/d)×{mass%S/(mass%CaO + mass%REM2O3)} ≤ 0,289 …(1) (d étant le diamètre équivalent en cercle de chaque oxyde complexe, et étant 0,1 à 3 μm)
PCT/JP2014/057205 2013-03-22 2014-03-17 Matériau acier présentant une résistance supérieure dans une zone affectée par la chaleur de soudage WO2014148447A1 (fr)

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