WO2015156179A1 - 極低温でのhaz靱性に優れた厚鋼板 - Google Patents
極低温でのhaz靱性に優れた厚鋼板 Download PDFInfo
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
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- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
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Definitions
- the present invention relates to a thick steel plate used as a material for a structural material that requires cryogenic characteristics such as a storage tank for LNG (Liquid Natural Gas), and more particularly to a thick steel plate excellent in HAZ toughness at cryogenic temperature. It is.
- LNG Liquid Natural Gas
- the main component of natural gas is methane, which is liquefied at a very low temperature under atmospheric pressure, and the volume is reduced to about 1/600. For this reason, it is more convenient to store or transport it in a liquid rather than a gas, but on the other hand, it is necessary to hold it at an extremely low temperature, so that a material having excellent cryogenic characteristics is required for an LNG storage tank or the like.
- Thick steel plates used in LNG storage tanks and the like are ferritic steels, but these ferritic steels generally become brittle at low temperatures and may break like ceramics. However, this drawback can be overcome by increasing the amount of Ni added. On the other hand, there is always a demand for lower Ni because Ni is an expensive element. From these balances, 9% Ni steel is currently used as a material for structural materials that require excellent toughness at extremely low temperatures, such as LNG storage tanks.
- Patent Literature Various proposals have been made by 1 etc.
- Non-Patent Document 1 and Non-Patent Document 2 a technique has been adopted in which the structure is refined, or the structure is refined and the fracture start point is reduced.
- such conventional methods have not been able to sufficiently secure HAZ toughness at extremely low temperatures while reducing Ni.
- the present invention has been made as a solution to the above-mentioned conventional problems, and it is possible to achieve HAZ toughness at cryogenic temperatures that can ensure HAZ toughness at cryogenic temperatures while minimizing the amount of expensive Ni added as much as possible. It is an object to provide an excellent thick steel plate.
- the thick steel plate having excellent HAZ toughness at cryogenic temperature is, in mass%, C: 0.02 to 0.10%, Si: 0.40% or less (not including 0%), Mn: 0.00. 5 to 2.0%, P: 0.007% or less (not including 0%), S: 0.007% or less (not including 0%), Al: 0.005 to 0.05%, Ni: 5.0 to 7.5%, Ti: 0.025% or less (not including 0%), N: 0.010% or less (not including 0%), the balance being iron and inevitable impurities ([C] / 10) 0.5 ⁇ (1 + 0.7 ⁇ [Si]) ⁇ (1 + 3.33 ⁇ [Mn]) ⁇ (1 + 0.35 ⁇ [Cu]) ⁇ (1 + 0) .36 ⁇ [Ni]) ⁇ (1 + 2.16 ⁇ [Cr]) ⁇ (1 + 3 ⁇ [Mo]) ⁇ (1 + 1.75 ⁇ [V]) ⁇ (1 + 200 ⁇ [B]) ⁇ (1.7-
- the N parameter is 20 ppm or less
- the Ni—Ti balance is 0.0024 ⁇ ([Ni] ⁇ 7.5) 2 + 0.010 ⁇ [Ti] ⁇ 0, and further heated at 700 ° C. ⁇ 5 s, 700
- It is a thick steel plate excellent in HAZ toughness at cryogenic temperature, characterized in that the crystal grain size after cooling from 19 ° C. to 500 ° C. in 19 s is 4.0 ⁇ m or less.
- [] shows the mass% and is the same also in the following specifications.
- Cu 1.0% or less (excluding 0%), Cr: 1.2% or less (not including 0%), Mo: 1.0% or less (including 0%) 1) or two or more thereof.
- Nb 0.1% or less (excluding 0%)
- V 0.5% or less (not including 0%)
- B 0.005% or less (including 0%) 1)
- Zr 0.005% or less (not including 0%) is preferably contained.
- the inventors of the present invention have added Ni in order to minimize the addition amount because of the high cost of what is added to ensure toughness, while keeping the addition amount of 5.0 to 7.5% by mass as low as possible.
- the Charpy impact absorption test in order to obtain a thick steel plate excellent in HAZ toughness at a cryogenic temperature that can satisfy the condition of vE ⁇ 196 ⁇ 41 J, studies were conducted by earnest, research, and experiment.
- the component composition of the thick steel plate is set to a predetermined component composition, and the Di value determined by the component balance that is an index of hardenability is 2.5 to 5.0, sol.
- the N parameter is set to 20 ppm or less
- the Ni—Ti balance is set to 0.0024 ⁇ ([Ni] ⁇ 7.5) 2 + 0.010 ⁇ [Ti] ⁇ 0, and further heated at 700 ° C. ⁇ 5 s, from 700 ° C. to 500 ° C.
- the inventors found that excellent HAZ toughness at a desired cryogenic temperature can be realized by setting the crystal grain size after thermal cycling to 19 ° C. to 4.0 ⁇ m or less, and completed the present invention.
- the test using a Charpy impact test piece having a size of several centimeters collected from the thick steel plate of the present invention is performed at an extremely low temperature of ⁇ 196 ° C., but the test using a large test piece of a meter size is ⁇ 165 ° C. Done in An actual LNG storage tank is used at -165 ° C. Therefore, the cryogenic temperature intended by the present invention is from ⁇ 165 ° C. to ⁇ 196 ° C.
- HZ welding heat affected zone
- the reduction of the low temperature YS attention was paid to the control of the solid solution N, which is a cause of the increase of YS due to the Cottrell atmosphere, and the amount of Ni which is said to reduce the low temperature YS of the ground.
- the Di value which is an index of hardenability
- the Di value is ([C] / 10) 0.5 ⁇ (1 + 0.7 ⁇ [Si]) ⁇ (1 + 3.33 ⁇ [Mn]) ⁇ (1 + 0.35).
- Di value In order to obtain a fine-sized structure, it is effective for convenience to define the Di value. If Di value is less than 2.5, the tissue becomes rough, vE -196 in Charpy impact absorption test decreases. On the other hand, if the Di value exceeds 5.0, and increased hardness, vE -196 is decreased in this case also the Charpy impact absorption test. Therefore, an appropriate range of the Di value that is an index of hardenability is set to 2.5 or more and 5.0 or less.
- Sol.N parameter is 20 ppm or less
- HAZ has an influence of thermal cycle, even if N is fixed by a base material, it is thermally affected by HAZ. Unstable N compounds are redissolved during thermal cycling. In HAZ, in order to fix N even after the thermal cycle, it is effective to add Ti that forms a thermally stable N compound.
- the mass (unit: ppm) of compound type Ti is calculated
- the extraction may be performed by the iodine methanol method, and the extracted electrolyte is filtered using a filter having a pore size of 0.1 ⁇ m, and the amount of Ti in the extraction residue remaining on the filter is determined by inductively coupled plasma (Inductively Coupled Plasma, ICP). ) It can be obtained by quantification by luminescence analysis.
- ICP Inductively Coupled Plasma
- Ni—Ti balance is 0.0024 ⁇ ([Ni] ⁇ 7.5) 2 + 0.010 ⁇ [Ti] ⁇ 0) If the content of Ni in the steel is increased, the low temperature YS can be reduced. However, as described above, since Ni is an expensive element, it is desirable to reduce it as much as possible. For this reason, in the present invention, the Ni—Ti balance capable of obtaining the above-described effects of adding Ti was experimentally determined. The effect of adding Ti is the same as that described in Sol. N fixation is considered to be the main, but besides that, it can be considered that there is also an effect of refining the structure size by Ti compounds, etc., and it is necessary to control the Ni—Ti balance separately from the Ti—N balance. is there.
- the Ni—Ti balance needs to be 0.0024 ⁇ ([Ni] ⁇ 7.5) 2 + 0.010 ⁇ [Ti] ⁇ 0.
- the upper limit value according to this formula is not particularly defined, but a preferable upper limit value is, for example, 0.0180.
- the crystal grain size after heating at 700 ° C. for 5 s and cooling from 700 ° C. to 500 ° C. in 19 s is 4.0 ⁇ m or less
- the crystal grain size of the HAZ has several influential factors such as the matrix structure and the crystal grain size of the matrix, as well as strain in the structure, so that the definition of the matrix structure is not sufficient. Therefore, in the present invention, the crystal grain size after the heat cycle in which 700 ° C. ⁇ 5 s is heated and 700 ° C. to 500 ° C. is cooled in 19 s is defined.
- the structure after such a heat cycle is a structure corresponding to the HAZ, and the crystal grain size after the heat cycle is 4.0 ⁇ m or less, so that the HAZ at the cryogenic temperature intended by the present invention is achieved.
- a thick steel plate with excellent toughness can be obtained.
- the aforementioned Di value, sol In addition to the N parameter, Ni-Ti balance, and crystal grain size after thermal cycling, the component composition of the thick steel plate is defined.
- the component composition will be described in detail. Hereinafter, the content of each element (chemical component) is simply described as%, but all indicate mass%.
- Component composition 0.02 to 0.10% C is effective for reducing the Ms point and obtaining a fine-sized structure.
- C In order to effectively exhibit such an action, C must be contained at least 0.02% or more.
- the minimum with preferable content of C is 0.03%, and a more preferable minimum is 0.04%.
- the upper limit is made 0.10%.
- the upper limit with preferable content of C is 0.08%, and a more preferable upper limit is 0.06%.
- Si 0.40% or less (excluding 0%) Si is an element useful as a deoxidizer. It has an effect of preventing Ti from being consumed by deoxidation and helping to fix N. However, if added excessively, the formation of a hard island-like martensite phase is promoted and the cryogenic toughness decreases, so the upper limit is made 0.40%.
- the upper limit with preferable content of Si is 0.35%, and a more preferable upper limit is 0.20%.
- the minimum of content of Si is not prescribed
- Mn 0.5 to 2.0% Mn is effective for reducing the Ms point and obtaining a fine-sized structure. In order to effectively exhibit such an action, Mn must be contained at least 0.5% or more. The minimum with preferable content of Mn is 0.6%, and a more preferable minimum is 0.7%. However, if added excessively, embrittlement due to tempering is caused, and the desired cryogenic toughness cannot be secured, so the upper limit is made 2.0%. The upper limit with preferable content of Mn is 1.5%, and a more preferable upper limit is 1.3%.
- P 0.007% or less (excluding 0%) Since P is an impurity element that causes a decrease in toughness, its content is preferably as small as possible. From the viewpoint of ensuring the desired cryogenic toughness, the P content must be suppressed to 0.007% or less, and preferably 0.005% or less. The smaller the P content, the better. However, it is difficult to make P in steel 0% industrially.
- S 0.007% or less (excluding 0%) Since S is an impurity element that causes a decrease in toughness like P, its content is preferably as small as possible. From the viewpoint of securing the desired cryogenic toughness, the S content must be suppressed to 0.007% or less, and preferably 0.005% or less. The smaller the S content, the better. However, it is difficult to industrially make S in steel 0%.
- Al 0.005 to 0.05%
- Al is an element useful as a deoxidizer. It has an effect of preventing Ti from being consumed by deoxidation and helping to fix N. It also promotes desulfurization. If the Al content is insufficient, the concentration of solute sulfur, solute nitrogen, etc. in the steel increases and the cryogenic toughness decreases, so the lower limit is made 0.005%.
- the minimum with preferable content of Al is 0.010%, and a more preferable minimum is 0.015%. However, if added excessively, oxides, nitrides, and the like are coarsened and the cryogenic toughness is also lowered, so the upper limit is made 0.05%.
- the upper limit with preferable Al content is 0.045%, and a more preferable upper limit is 0.04%.
- Ni 5.0 to 7.5%
- Ni is an element effective for improving cryogenic toughness. In order to exhibit such an action effectively, Ni must be contained at least 5.0% or more.
- a preferable lower limit of the Ni content is 5.2%, and a more preferable lower limit is 5.4%.
- the upper limit is made 7.5%.
- a preferable upper limit of the Ni content is 6.5%, a more preferable upper limit is 6.2%, and a still more preferable upper limit is 6.0%.
- Ti 0.025% or less (excluding 0%) Ti is an element effective for fixing solute N.
- a preferred lower limit is 0.003%, and a more preferred lower limit is 0.005%.
- the preferable upper limit of the Ti content is 0.025%.
- a more preferable upper limit of Ti is 0.018%, and a more preferable upper limit is 0.015%.
- N 0.010% or less (excluding 0%) If N is present in a large amount as solute N, HAZ toughness is reduced. Even if solid solution N can be fixed by some method, since the total N active is preferably small from the viewpoint of the solubility product, the upper limit is made 0.010%.
- the upper limit with preferable N content is 0.006%, and a more preferable upper limit is 0.004%. The smaller the N content, the better. However, it is difficult to make N in steel 0% industrially.
- Cu, Cr, and Mo are all effective elements for reducing the Ms point and obtaining a fine-sized structure. These elements may be added alone or in combination of two or more. In order to effectively exhibit the above action, 0.05% or more is required when Cu is added, 0.05% or more when Cr is added, and 0.01% or more when Mo is added. preferable. However, if excessively added, the strength is excessively improved and the desired cryogenic toughness cannot be ensured. Therefore, when Cu is added, it is necessary to be 1.0% or less, preferably 0.8% Below, more preferably 0.7% or less.
- Nb 0.1% or less (not including 0%), V: 0.5% or less (not including 0%), B: 0.005% or less (not including 0%), Zr: 0.005 Nb, V, B, and Zr are elements that are effective for fixing solute N, though not as much as Ti. These elements may be added alone or in combination of two or more. In order to effectively exert the above action, 0.005% or more is added when Nb is added, 0.005% or more when V is added, 0.0005% or more when B is added, and Zr is added. In that case, the content is preferably 0.0005% or more. However, when excessively added, the strength is excessively increased, or coarse inclusions are formed to reduce toughness.
- Nb when added, it is necessary to be 0.1% or less, preferably Is 0.05% or less, more preferably 0.02% or less.
- V when adding V, it is necessary to set it as 0.5% or less, Preferably it is 0.3% or less, More preferably, you may be 0.2% or less.
- B when adding B, it is necessary to set it as 0.005% or less, Preferably it is 0.003% or less, More preferably, you may be 0.002% or less.
- Zr when adding Zr, it is necessary to make it 0.005% or less, Preferably it is 0.004% or less.
- Ca 0.003% or less (excluding 0%)
- REM rare earth element: one or two of 0.005% or less (not including 0%)
- Ca and REM fix solute sulfur Furthermore, it is an element that renders sulfide harmless. These elements may be added alone or in combination of two kinds. If these contents are insufficient, the concentration of solid solution sulfur in the steel increases and the toughness decreases. Therefore, when Ca is added, the content is 0.0005% or more, and when REM is added, the content is 0.0005% or more. It is preferable. However, if excessively added, sulfides, oxides, nitrides and the like are coarsened, and the toughness is also lowered. Therefore, when Ca is added, it is necessary to be 0.003% or less, preferably 0.0025. % Or less. Moreover, when adding REM, it is necessary to set it as 0.005% or less, Preferably it is set as 0.004% or less.
- REM rare earth element
- REM rare earth element
- REM is a lanthanoid element (15 elements from La of atomic number 57 to Lu of atomic number 71 in the periodic table), Sc (scandium) and Y (yttrium). It is an added element group, and these can be used alone or in combination of two or more.
- the content of REM described above is a single content when only one type of REM is contained, and the total content when two or more types are contained.
- Sc and Y have a smaller atomic weight than other REMs.
- REM usually uses an inexpensive misch metal containing a plurality of lanthanoid elements, but Sc and Y may also be used.
- Sc and Y may also be used.
- preferable elements of REM are Ce and La.
- the addition form of REM is not particularly limited, and may be added in the form of a misch metal mainly containing Ce and La (for example, Ce: about 70%, La: about 20-30%), or Ce, La alone may be added.
- the steel plate of the present invention uses steel that satisfies the above-mentioned composition, and is melted by a normal melting method to form a slab, followed by normal heating, hot rolling (rough rolling, finish rolling), and cooling. Although it can obtain by passing, the thick steel plate which satisfies the requirements of this invention reliably can be manufactured by implementing the heat processing of a base material on the conditions as shown below.
- the heat treatment of the base material is performed in the temperature range (2 phase range) from 630 ° C. to Ac3.
- the structure of the HAZ part after welding can be refined. That is, in the present invention, the crystal grain size after the heat cycle of heating at 700 ° C. ⁇ 5 s and cooling from 700 ° C. to 500 ° C. in 19 s can be made 4.0 ⁇ m or less.
- heat treatment is performed under conditions exceeding Ac3, the crystal grain size after the thermal cycle becomes coarse, and the predetermined toughness cannot be satisfied.
- Example 1 Using thick steel plates having the respective component compositions shown in Tables 1 and 2, small pieces of 12.5 t ⁇ 55 W ⁇ 33 L were sampled in parallel to the plate width direction from t / 4 positions (t: plate thickness) of the thick steel plates. Thereafter, two Charpy impact test pieces (V-notch test pieces of JIS Z 2242) were collected from the pieces subjected to the heat treatment described in Tables 3 and 4 and absorbed at -196 ° C. in the same manner as JIS Z 2242. Energy was measured.
- the heat cycle condition is equivalent to a heat input of 4.2 kJ / mm, and is 700 ° C. ⁇ 5 s heating ⁇ cooling from 700 ° C. to 500 ° C. in 19 s.
- the N parameter is sol.
- the crystal grain size is a region that is divided by a black contrast line segment having a width of 0.5 ⁇ m or less in a range of 150 ⁇ m in the vertical direction of the notch ⁇ 200 ⁇ m in the horizontal direction of the notch in the structure directly under the fracture surface taken with an optical microscope. was measured with the line segment method in the horizontal direction of the notch, and the average was taken as the crystal grain size.
- No. Examples 1 to 21 are invention examples that satisfy the requirements of the present invention, and the average value of the absorbed energy at ⁇ 196 ° C. was all 41 J or more, and vE ⁇ 196 ⁇ 41 J was satisfied. From this test result, No. 1 satisfying the requirements of the present invention. It can be said that all of the inventive examples 1 to 21 are thick steel plates excellent in HAZ toughness at cryogenic temperatures.
- no. Nos. 22 to 39 are comparative examples that do not satisfy any of the requirements of the present invention, and the average values of the absorbed energy at ⁇ 196 ° C. are all less than 41 J and cannot satisfy vE ⁇ 196 ⁇ 41 J. In addition, sufficient HAZ toughness at extremely low temperatures could not be secured.
- Example 2 In the above-mentioned test, three joints were manufactured for each of the inventive examples in which the average value of the absorbed energy at ⁇ 196 ° C. was 41 J or more, and the toughness was investigated.
- a joint was manufactured under the following conditions with a single bevel groove (root gap: 6 mm, groove angle: 30 °).
- it is designed so that the cracks do not progress only in the low toughness HAZ part in the shape by including a multi-pass X groove, and hardly including the low toughness HAZ.
- a re-shaped groove was used.
- the thick steel plate of the present invention has excellent HAZ toughness at cryogenic temperatures, and is useful as a structural material that requires cryogenic properties such as an LNG storage tank.
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Abstract
Description
本発明において、焼き入れ性の指標であるDi値は、([C]/10)0.5×(1+0.7×[Si])×(1+3.33×[Mn])×(1+0.35×[Cu])×(1+0.36×[Ni])×(1+2.16×[Cr])×(1+3×[Mo])×(1+1.75×[V])×(1+200×[B])×(1.7-0.09×6.5)という式から求めることができる。
主要添加元素の添加量を増量することなく、低温YSを低減させて地の靱性を向上させるためには、転位に固着し転位運動を阻害する格子間元素を固定することが有効である。本発明では、これらのうち特に固溶Nの固定に着目した。
sol.Nパラメータ=全N-Tiに固定されたN=全N-(14/48)×化合物型Ti
ここで「化合物型Ti」とは、Ti化合物中に含まれるTi含有量のことを指す。
鋼中のNiの含有量を増量すれば、低温YSを低減することは可能であるが、前記したように、Niは高価な元素であることから可能な限り低減することが望ましい。そのような理由から、本発明では前記したTi添加による効果を得ることができるNi-Tiバランスを実験により求めた。Ti添加による効果は、前記したSol.N固定が主であると考えられるが、それ以外にも、Ti化合物などによる組織サイズの微細化効果もあると考えることができ、Ti-Nバランスとは別にNi-Tiバランスも制御する必要がある。
HAZの結晶粒径を細かくすることでHAZの低温靱性は向上する。しかしながら、HAZの結晶粒径には、母材組織や母材の結晶粒径の他、組織内の歪みなど幾つかの影響する要因があるため、母材組織の規定だけでは不十分である。従って、本発明では、700℃×5s加熱し、更に700℃から500℃までを19sで冷却した熱サイクル後の結晶粒径を規定する。このような熱サイクル後の組織はHAZ相当部の組織であるということができ、前記熱サイクル後の結晶粒径を4.0μm以下とすることで、本発明が意図とする極低温でのHAZ靱性に優れた厚鋼板とすることができる。
C:0.02~0.10%
Cは、Ms点を低下させ微細なサイズの組織を得るために有効である。このような作用を有効に発揮させるには、Cを少なくとも0.02%以上含有させなければならない。Cの含有量の好ましい下限は0.03%であり、より好ましい下限は0.04%である。但し、過剰に添加すると、強度の過大な上昇により極低温靱性が低下するため、その上限を0.10%とする。Cの含有量の好ましい上限は0.08%であり、より好ましい上限は0.06%である。
Siは、脱酸材として有用な元素である。Tiが脱酸に消費されることを防ぎ、N固定することを助ける作用がある。但し、過剰に添加すると、硬質の島状マルテンサイト相の生成が促進され、極低温靱性が低下するため、その上限を0.40%とする。Siの含有量の好ましい上限は0.35%であり、より好ましい上限は0.20%である。尚、Siの含有量の下限は特に規定しないが、好ましい下限は0.01%である。
Mnは、Ms点を低下させ微細なサイズの組織を得るために有効である。このような作用を有効に発揮させるには、Mnを少なくとも0.5%以上含有させなければならない。Mnの含有量の好ましい下限は0.6%であり、より好ましい下限は0.7%である。但し、過剰に添加すると、焼き戻しによる脆化をもたらし、所望の極低温靱性を確保できなくなるため、その上限を2.0%とする。Mnの含有量の好ましい上限は1.5%であり、より好ましい上限は1.3%である。
Pは、靱性低下の原因となる不純物元素であるので、その含有量はできるだけ少ないことが好ましい。所望とする極低温靱性を確保するという観点からは、Pの含有量は0.007%以下に抑制する必要があり、好ましくは0.005%以下とする。Pの含有量は少なければ少ないほど良いが、工業的に鋼中のPを0%にすることは困難である。
Sは、Pと同様に靱性低下の原因となる不純物元素であるので、その含有量はできるだけ少ないことが好ましい。所望とする極低温靱性を確保するという観点からは、Sの含有量は0.007%以下に抑制する必要があり、好ましくは0.005%以下とする。Sの含有量は少なければ少ないほど良いが、工業的に鋼中のSを0%にすることは困難である。
Alは、脱酸材として有用な元素である。Tiが脱酸に消費されることを防ぎ、N固定することを助ける作用がある。また、脱硫を促進する。Alの含有量が不足すると、鋼中の固溶硫黄、固溶窒素などの濃度が上昇し、極低温靱性が低下するため、その下限を0.005%とする。Alの含有量の好ましい下限は0.010%であり、より好ましい下限は0.015%である。但し、過剰に添加すると、酸化物や窒化物などが粗大化し、やはり極低温靱性が低下するため、その上限を0.05%とする。Alの含有量の好ましい上限は0.045%であり、より好ましい上限は0.04%である。
Niは、極低温靱性の向上に有効な元素である。このような作用を有効に発揮させるためには、Niを少なくとも5.0%以上含有させなければならない。Niの含有量の好ましい下限は5.2%であり、より好ましい下限は5.4%である。但し、高価な元素であるNiを過剰に添加すると、原料のコスト高を招くため、その上限を7.5%とする。Niの含有量の好ましい上限は6.5%であり、より好ましい上限は6.2%、更に好ましい上限は6.0%である。
Tiは、固溶Nの固定に有効な元素である。好ましい下限は0.003%、より好ましい下限は0.005%である。一方で、過剰に添加すると、粗大介在物を形成し靭性を低下させるため、Tiの含有量の好ましい上限を0.025%とする。Tiのより好ましい上限は0.018%であり、更に好ましい上限は0.015%である。
Nは、固溶Nとして多量に存在するとHAZ靭性を低下させる。たとえ何らかの方法により固溶Nを固定できるとしても、溶解度積の観点からは全N能動は小さい方が好ましいため、その上限を0.010%とする。Nの含有量の好ましい上限は0.006%であり、より好ましい上限は0.004%である。尚、Nの含有量は少なければ少ないほど良いが、工業的に鋼中のNを0%にすることは困難である。
Cu、CrおよびMoは、いずれもMs点を低下させ微細なサイズの組織を得るために有効な元素である。これらの元素は単独で添加しても良いし、2種類以上を併用しても良い。上記作用を有効に発揮させるためには、Cuを添加する場合は0.05%以上、Crを添加する場合は0.05%以上、Moを添加する場合は0.01%以上とすることが好ましい。但し、過剰に添加すると、強度の過度な向上を招き、所望とする極低温靱性を確保できなくなるため、Cuを添加する場合は1.0%以下とする必要があり、好ましくは0.8%以下、より好ましくは0.7%以下とする。また、Crを添加する場合は1.2%以下とする必要があり、好ましくは1.1%以下、より好ましくは0.9%以下とする。また、Moを添加する場合は1.0%以下とする必要があり、好ましくは0.8%以下、より好ましくは0.6%以下とする。
Nb、V、B、およびZrは、Tiほどではないものの、いずれも固溶Nを固定するのに有効な元素である。これらの元素は単独で添加しても良いし、2種以上を併用しても良い。上記作用を有効に発揮させるためには、Nbを添加する場合は0.005%以上、Vを添加する場合は0.005%以上、Bを添加する場合は0.0005%以上、Zrを添加する場合は0.0005%以上とすることが好ましい。但し、過剰に添加すると、強度の過度な上昇を招くか、もしくは、粗大介在物を形成して靱性を低下させるため、Nbを添加する場合は、0.1%以下とする必要があり、好ましくは0.05%以下、より好ましくは0.02%以下とする。また、Vを添加する場合は、0.5%以下とする必要があり、好ましくは0.3%以下、より好ましくは0.2%以下とする。また、Bを添加する場合は、0.005%以下とする必要があり、好ましくは0.003%以下、より好ましくは0.002%以下とする。また、Zrを添加する場合は、0.005%以下とする必要があり、好ましくは0.004%以下とする。
Ca、およびREMは、固溶硫黄を固定し、更に硫化物を無害化する元素である。これらの元素は単独で添加しても良いし、2種を併用しても良い。これらの含有量が不足すると、鋼中の固溶硫黄濃度が上昇し、靱性が低下するため、Caを添加する場合は0.0005%以上、REMを添加する場合は0.0005%以上とすることが好ましい。但し、過剰に添加すると、硫化物、酸化物や窒化物などが粗大化し、やはり靱性が低下するため、Caを添加する場合は、0.003%以下とする必要があり、好ましくは0.0025%以下とする。また、REMを添加する場合は、0.005%以下とする必要があり、好ましくは0.004%以下とする。
(2/3)×(1/88)×(226)×(1/4.8)×[REM(Sc,Y)]+(2/3)×(1/140)×(327)×(1/7)×[REM(others)]≦0.0015
尚、前式中、[REM(Sc,Y)]はScおよびYの添加量(質量%)であり、[REM(others)]はScおよびY以外のREMの添加量(質量%)である。
本発明の厚鋼板は、前記成分組成を満足する鋼を用い、通常の溶製法により溶製し、スラブとした後、通常の加熱、熱間圧延(粗圧延、仕上げ圧延)、冷却という工程を経ることで得ることができるが、母材の熱処理を次に示すような条件で実施することにより、確実に本発明の要件を満足する厚鋼板を製造することができる。
表1,2に示す各成分組成の厚鋼板を用い、それら厚鋼板のt/4位置(t:板厚)から、板幅方向に平行に12.5t×55W×33Lの小片を採取した。その後、表3、表4に記載の熱処理を付与した小片からシャルピー衝撃試験片(JIS Z 2242のVノッチ試験片)を2本毎採取し、JIS Z 2242の要領で、-196℃での吸収エネルギーを測定した。尚、熱サイクル条件は、入熱4.2kJ/mm相当で、700℃×5s加熱→700℃から500℃までを19sで冷却することである。測定の結果、-196℃での吸収エネルギーの平均値が41J以上、すなわち、vE-196≧41Jを満足するものを極低温靭性に優れると評価した。試験結果を表3,4に示す。
前記した試験で、-196℃での吸収エネルギーの平均値が41J以上と良好な結果を得ることができた発明例について、継手を3本ずつ作製して靱性を調査した。
・溶接材料:NIC-70S(KOBE)
・パス数:BP:5~6/FP:3
・入熱:平均で35kJ/cm、24.5~41.4kJ/cmの間
・パス間:100℃未満
本出願は、2014年4月8日出願の日本特許出願(特願2014-079378)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)
- 質量%で、C:0.02~0.10%、Si:0.40%以下(0%を含まない)、Mn:0.5~2.0%、P:0.007%以下(0%を含まない)、S:0.007%以下(0%を含まない)、Al:0.005~0.05%、Ni:5.0~7.5%、Ti:0.025%以下(0%を含まない)、N:0.010%以下(0%を含まない)を含有し、残部が鉄および不可避的不純物でなる厚鋼板であって、
([C]/10)0.5×(1+0.7×[Si])×(1+3.33×[Mn])×(1+0.35×[Cu])×(1+0.36×[Ni])×(1+2.16×[Cr])×(1+3×[Mo])×(1+1.75×[V])×(1+200×[B])×(1.7-0.09×6.5)から求められるDi値が、2.5以上5.0以下、
sol.Nパラメータが、20ppm以下、
Ni-Tiバランスが、0.0024×([Ni]-7.5)2+0.010-[Ti]≧0であり、
更には、700℃×5s加熱し、700℃から500℃までを19sで冷却した後の結晶粒径が、4.0μm以下であることを特徴とする極低温でのHAZ靱性に優れた厚鋼板。
但し、前記した各式中、[ ]は質量%を示す。 - 更に、下記(a)~(c)の少なくとも一つを含有する請求項1記載の極低温でのHAZ靱性に優れた厚鋼板。
(a)質量%で、Cu:1.0%以下(0%を含まない)、Cr:1.2%以下(0%を含まない)、Mo:1.0%以下(0%を含まない)の1種または2種以上
(b)質量%で、Nb:0.1%以下(0%を含まない)、V:0.5%以下(0%を含まない)、B:0.005%以下(0%を含まない)、Zr:0.005%以下(0%を含まない)の1種または2種以上
(c)質量%で、Ca:0.003%以下(0%を含まない)、REM:0.005%以下(0%を含まない)の1種または2種
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CN103374681B (zh) * | 2012-04-13 | 2015-07-29 | 株式会社神户制钢所 | 极低温韧性优异的厚钢板 |
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JP5833991B2 (ja) * | 2012-08-23 | 2015-12-16 | 株式会社神戸製鋼所 | 極低温靱性に優れた厚鋼板 |
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2015
- 2015-03-31 EP EP15776770.8A patent/EP3130687A4/en not_active Withdrawn
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- 2015-03-31 KR KR1020167027394A patent/KR101843677B1/ko active IP Right Grant
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US20210010114A1 (en) * | 2017-12-24 | 2021-01-14 | Posco | Low-temperature steel material having excellent toughness in welding portion thereof and manufacturing method therefor |
US11591679B2 (en) * | 2017-12-24 | 2023-02-28 | Posco Co., Ltd | Low-temperature steel material having excellent toughness in welding portion thereof and manufacturing method therefor |
Also Published As
Publication number | Publication date |
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EP3130687A4 (en) | 2017-08-30 |
CN106133172A (zh) | 2016-11-16 |
KR20160130442A (ko) | 2016-11-11 |
JP6196929B2 (ja) | 2017-09-13 |
KR101843677B1 (ko) | 2018-03-29 |
EP3130687A1 (en) | 2017-02-15 |
JP2015199983A (ja) | 2015-11-12 |
CN106133172B (zh) | 2018-01-02 |
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