WO2017183720A1 - 厚鋼板 - Google Patents
厚鋼板 Download PDFInfo
- Publication number
- WO2017183720A1 WO2017183720A1 PCT/JP2017/016090 JP2017016090W WO2017183720A1 WO 2017183720 A1 WO2017183720 A1 WO 2017183720A1 JP 2017016090 W JP2017016090 W JP 2017016090W WO 2017183720 A1 WO2017183720 A1 WO 2017183720A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- content
- mns
- less
- amount
- ctod
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- 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
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- 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
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
Definitions
- the present invention relates to a thick steel plate.
- the present invention particularly relates to a thick steel plate excellent in toughness of a heat-affected zone (hereinafter referred to as “HAZ”) used for offshore structures such as oil and natural gas drilling facilities on the sea.
- HZ heat-affected zone
- the heating temperature at the time of welding increases as it approaches the melting line.
- the austenite grains become extremely coarse in a region where the austenite grains are heated to 1400 ° C. or higher in the vicinity of the melting line. For this reason, the HAZ structure after cooling becomes coarse and the HAZ toughness deteriorates.
- a method of controlling crystal grain size in HAZ is known.
- a method for controlling the crystal grain size specifically, a method of suppressing the austenite grain coarsening in the heating process of welding by dispersing a large amount of fine pinning particles in the steel, or the ferrite transformation
- Patent Document 1 discloses that a composite inclusion made of an oxide composed of Mg, Mn and Al and MnS and having a particle size of less than 0.6 ⁇ m is dispersed in steel material by 1 ⁇ 10 6 pieces / mm 3 or more and A produced steel material is disclosed. This steel material suppresses the coarsening of prior austenite grains, and thereby ensures excellent toughness even when high heat input welding of 300 kJ / cm or more is performed.
- Patent Document 2 discloses a thick steel plate in which Mn oxide and Al oxide, which are likely to be precipitation nuclei of MnS particles, are finely dispersed in steel. This thick steel plate has good HAZ toughness even when high heat input welding of 200 kJ / cm is performed.
- Patent Document 3 discloses a plate thickness in which the particle diameter and number density of TiN particles, MnS particles and composite particles having a circle-equivalent diameter of 0.5 to 2.0 ⁇ m contained in the steel plate are controlled within a predetermined range.
- a 10-35 mm steel sheet is disclosed. This steel plate suppresses the growth of austenite grains by a pinning effect when the steel plate is heated by welding. The steel sheet further refines its structure by becoming a nucleus in which ferrite transforms when the steel sheet is cooled after welding. This steel plate improves the HAZ toughness during high heat input welding.
- An object of the present invention is to provide a thick steel plate having excellent HAZ toughness even when high heat input welding is performed.
- the present inventors have obtained the following knowledge as a result of intensive studies to solve the above-mentioned problems.
- the present inventors controlled the balance of the contents of Ti, Al, O and N in the steel making process, and the fine TiN particles dispersed in the steel caused the growth of austenite grains in the HAZ due to the pinning effect. It was found that it suppresses and suppresses the growth of coarse austenite grains.
- Control of inclusions that form the nuclei of intragranular ferrite is effective for effectively growing intragranular ferrite in austenite grains during welding. The following matters concerning the mechanism of intragranular ferrite growth were found.
- Mn is absorbed into atomic vacancies existing inside the Ti-based oxide.
- a Mn-deficient layer in which the Mn concentration decreases is formed around the inclusions, and the growth start temperature of ferrite in this portion increases.
- the present inventors have found that the amount of the MnS complex of inclusions serving as nuclei of intragranular ferrite affects the growth of intragranular ferrite. That is, when the composite MnS is large, a larger Mn concentration gradient is formed around the inclusions, so that the driving force for diffusing Mn increases. As a result, a Mn-deficient layer is easily formed. On the other hand, when the composite MnS is small, a gradient of Mn concentration is hardly formed around the inclusions. As a result, it becomes difficult to form a Mn-deficient layer.
- inclusions in steel must satisfy the following requirements in order to obtain the effect of refining crystal grains.
- the steel contains a composite inclusion in which MnS is present around the Ti oxide, and the area ratio of MnS in the cross section of the composite inclusion is 10% or more and less than 90%.
- the proportion of MnS in the length is 10% or more.
- the number density of this composite inclusion having a particle size of 0.5 to 5.0 ⁇ m is 10 to 100 / mm 2 .
- the present invention suppresses the growth of coarse crystal grains by the TiN particles, controls the composite form of the Ti-based composite oxide, and controls the amount and number density of MnS composited in the inclusions.
- intragranular ferrite is effectively precipitated.
- the present invention is based on these findings and is listed below.
- Ti_TiO (mass%): Ti content that becomes Ti oxide out of total Ti content O (mass%): O content in steel Mn_MnS (mass%): Mn amount that becomes MnS out of total Mn content R1 (%): Average value of the area ratio of MnS in the cross section of the composite inclusion R2 (%): Average value of the ratio of MnS in the circumference of the composite inclusion
- a thick steel plate having excellent HAZ toughness even when high heat input welding is performed is provided.
- the thick steel plate according to the present invention will be described.
- (A1) C 0.01 to 0.20% C has an effect of increasing the strength of the base material and the HAZ.
- the C content is 0.01% or more, preferably 0.02% or more in order to ensure the strength of the base material and HAZ and the HAZ low temperature toughness, More preferably, it is 0.05% or more, More preferably, it is 0.06% or more.
- the C content is 0.20% or less, preferably 0.15% or less, and more preferably 0.08% or less in order to ensure the strength of the base material and the HAZ and the HAZ low temperature toughness. .
- Si acts as a deoxidizer during the production of steel, it is effective in controlling the amount of oxygen and increases in strength by solid solution in the steel. Therefore, the Si content is 0.10% or more, and is preferably 0.13% or more in order to control the oxygen amount to an appropriate amount and ensure HAZ low temperature toughness.
- the Si content is 0.25% or less, and is preferably 0.18% or less in order to control the oxygen amount to an appropriate amount and ensure HAZ low temperature toughness.
- Mn acts as an austenite stabilizing element and suppresses the formation of coarse ferrite at grain boundaries. Therefore, the Mn content is 1.30% or more, and is preferably 1.40% or more in order to suppress the formation of coarse ferrite and prevent segregation.
- the Mn content is 2.50% or less, preferably 2.10% or less, and more preferably 2.00% or less in order to suppress the formation of coarse ferrite and prevent segregation. .
- P 0.01% or less P is an impurity element and suppresses a decrease in grain boundary strength in the HAZ due to a decrease in the P content. Therefore, the P content is 0.01% or less.
- the S content is 0.0100% or less, and is preferably 0.0050% or less in order to precipitate MnS in a composite manner and to ensure the low temperature toughness of HAZ.
- Ti 0.005 to 0.030% Ti is essential for the production of Ti-based oxides.
- the Ti content is 0.005% or more for obtaining a sufficient inclusion density, and preferably 0.009% or more for ensuring a sufficient inclusion density and HAZ toughness.
- the Ti content exceeds 0.030%, carbides such as TiC are likely to be generated, so that the HAZ toughness decreases. Therefore, the Ti content is 0.030% or less, and preferably 0.020% or less in order to ensure sufficient inclusion density and HAZ toughness.
- Al 0.003% or less
- Al is an impurity element, and the production of Ti-based oxides is suppressed by increasing the Al content. Therefore, the Al content is 0.003% or less.
- (A8) O 0.0010 to 0.0050% O is essential for the production of the Ti-based composite oxide. In order to obtain a sufficient inclusion density, the O content is 0.0010% or more.
- the O content exceeds 0.0050%, it becomes easy to form a coarse oxide that can serve as a starting point for fracture. Therefore, the O content is 0.0050% or less, and preferably 0.0030% or less in order to suppress the formation of coarse inclusions.
- N 0.0100% or less N contributes to refinement of crystal grains by combining with Ti to produce TiN.
- the N content exceeds 0.0100%, the amount of Ti necessary for TiN precipitation increases, Ti oxide is hardly formed, and TiN aggregates to become a starting point of destruction. Therefore, the N content is 0.0100% or less, preferably 0.0080% or less, more preferably 0.0050% or less in order to stably secure the Ti amount for forming the Ti oxide. is there.
- (A10) Cu 0 to 0.50% Cu may be contained as necessary to increase the strength. However, if the Cu content exceeds 0.50%, hot embrittlement occurs, and the quality of the slab surface decreases. Therefore, the Cu content is 0.50% or less, preferably 0.30% or less.
- the Cu content is preferably 0.01% or more, more preferably 0.25% or more.
- Ni may be contained as necessary in order to increase strength without reducing toughness and toughness.
- Ni is an austenite stabilizing element, when the Ni content exceeds 1.50%, intragranular ferrite is difficult to be generated. Therefore, the Ni content is 1.50% or less, and preferably 1.00% or less in order to promote the formation of intragranular ferrite.
- the Ni content is preferably 0.01% or more, more preferably 0.50% or more, and further preferably 0.60% or more.
- (A12) Cr 0 to 0.50% Cr may be contained as necessary to increase the strength. However, if the Cr content exceeds 0.50%, the HAZ toughness decreases. Therefore, the Cr content is 0.50% or less, preferably 0.30% or less.
- the Cr content is preferably 0.01% or more, more preferably 0.10% or more.
- (A13) Mo 0 to 0.50% Mo may be contained as necessary because it significantly increases the strength with a small amount. However, if the Mo content exceeds 0.50%, the HAZ toughness is significantly reduced. Therefore, the Mo content is 0.50% or less, preferably 0.30% or less.
- the Mo content is preferably 0.01% or more.
- (A14) V 0 to 0.10% V is effective in improving the strength and toughness of the base material, and may be contained as necessary. However, if the V content exceeds 0.10%, carbides such as VC are formed and the toughness is lowered. Therefore, the V content is 0.10% or less, preferably 0.05% or less.
- the V content is preferably 0.01% or more, more preferably 0.03% or more.
- Nb 0 to 0.05% Since Nb is effective in improving the strength and toughness of the base material, it may be contained as necessary. However, when the Nb content exceeds 0.05%, carbides such as NbC are easily generated, and the toughness is lowered. Therefore, the Nb content is 0.05% or less, preferably 0.03% or less.
- the Nb content is preferably 0.01% or more.
- (A16) Balance The balance other than the above is Fe and impurities. Impurities are components that are mixed due to various factors of raw materials such as ores and scraps and manufacturing processes when industrially manufacturing steel, and are allowed to be contained in amounts that do not adversely affect the present invention. Is.
- (B) Composite inclusion The steel contains a composite inclusion in which MnS is present around the Ti oxide, and the area ratio of MnS in the cross section of the composite inclusion is 10% or more and less than 90%.
- the ratio of MnS in the perimeter of the composite is 10% or more, and the number density of the composite inclusions having a particle size of 0.5 to 5.0 ⁇ m is 10 to 100 / mm 2 .
- (B1) Area ratio of MnS in the cross section of the composite inclusion in which MnS exists around the Ti oxide: 10% or more and less than 90%
- the composite inclusion appearing on an arbitrary cut surface is analyzed.
- the area ratio of MnS in the cross-sectional area of the composite inclusion By measuring the area ratio of MnS in the cross-sectional area of the composite inclusion, the amount of MnS in the composite inclusion is defined.
- the area ratio of MnS in the cross section of the composite inclusion is less than 10%, the amount of MnS in the composite inclusion is small and a sufficient Mn-deficient layer cannot be formed. For this reason, formation of intragranular ferrite becomes difficult.
- the composite inclusion is mainly MnS, and the ratio of the Ti-based oxide decreases. For this reason, Mn absorptivity falls, and since sufficient Mn deficiency layer cannot be formed, generation of intragranular ferrite becomes difficult.
- Ratio of MnS in the circumference of the composite inclusion 10% or more MnS in the composite inclusion is formed around the Ti-based oxide. If the ratio of MnS to the circumference of the composite inclusion is less than 10%, the initial Mn-deficient region formed at the interface between MnS and the matrix is small. For this reason, even if it welds, since the formation amount of an intragranular ferrite is not enough, favorable low-temperature HAZ toughness cannot be obtained. Therefore, the ratio of MnS to the circumference of the composite inclusion matrix is 10% or more.
- the ratio of MnS the larger the initial Mn-deficient layer, and the easier formation of intragranular ferrite. For this reason, although the upper limit of the ratio of MnS is not defined, it is usually 80% or less.
- (B3) Particle size of composite inclusion 0.5 to 5.0 ⁇ m
- the particle size of the composite inclusion is less than 0.5 ⁇ m, the amount of Mn that can be absorbed from the periphery of the composite inclusion is small, and as a result, it becomes difficult to form a Mn-deficient layer necessary for the formation of intragranular ferrite.
- the particle size of the composite inclusion is larger than 5.0 ⁇ m, the composite inclusion becomes a starting point of destruction.
- the “particle diameter” is the equivalent circle diameter.
- the first term represented by (Ti_TiO / O) represents the balance between the Ti content and the O content to be Ti oxide. This first term is calculated by subtracting the Ti amount necessary for TiN generation calculated from the N content in the steel from the total Ti content. The larger the value of the first term, the easier the Ti oxide is formed. When the value of the first term is negative, Ti oxide is not formed.
- the second term represented by (Mn_MnS) represents the amount of Mn that becomes MnS.
- the second term is calculated from the S content in the steel. The larger the value of the second term, the more MnS becomes complex.
- the value X obtained from the equation (i) indicates the ease of formation of the Ti oxide composited with MnS and the degree of MnS composite of the formed composite inclusion.
- the larger the value X the more complex inclusions in which MnS is combined are formed, and a fine structure is easily formed at the weld. As a result, the steel material is excellent in toughness.
- the value X obtained from the formula (i) is less than 0.04, the Ti amount necessary for forming the Ti oxide, the S amount and Mn amount necessary for forming MnS, or the proportion of MnS is insufficient. . That is, it is a state in which inclusions effective for intragranular transformation are not formed. For this reason, the value X is 0.04 or more, preferably 0.50 or more, and more preferably 1.00 or more in order to form an effective Ti oxide.
- the value X obtained from the formula (i) exceeds 9.70, it becomes easy to aggregate due to the formation of excess Ti oxide. As a result, coarse inclusions are formed, which becomes a starting point of destruction. Furthermore, since inclusions of simple MnS are easily formed, intragranular transformation is not promoted. As a result, the coarse microstructure increases and the CTOD characteristics deteriorate. Therefore, the value X is 9.70 or less, more preferably 5.00 or less, and further preferably 4.00 or less.
- the plate thickness of the thick steel plate is preferably 100 mm or less.
- the yield stress of the thick steel plate according to the present invention is 400 to 500 MPa.
- the manufacturing method of the thick steel plate which concerns on this invention is not restrict
- it can be manufactured by heating a slab having the chemical composition described above, followed by hot rolling and finally cooling.
- the ausfoam reduction rate that is, the reduction rate at 950 ° C. or less before accelerated cooling is preferably 20% or more.
- the rolling reduction at 950 ° C. or less before accelerated cooling is less than 20%, most of the dislocations introduced immediately after rolling by rolling may disappear due to recrystallization, and thus may not function as a nucleus of transformation. As a result, the structure after transformation becomes coarse and embrittlement due to solute nitrogen often becomes a problem. For this reason, the rolling reduction at 950 ° C. or less before accelerated cooling is preferably 20% or more.
- the flow rate of Ar gas was adjusted between 100 and 200 L / min, and the blowing time was adjusted between 5 and 15 min.
- each element was added with an RH vacuum degassing device to adjust the components, and a 300 mm slab was cast by continuous casting.
- the cast slab was heated in the range of 1000 to 1100 ° C. in a heating furnace. After heating, hot rolling was performed at 760 ° C. or higher until the thickness reached 2t (t: final finished plate thickness), and then hot rolled at a temperature range of 730 to 750 ° C. to the final finished plate thickness t. After hot rolling, water cooling was performed at ⁇ 2 to ⁇ 3 ° C./sec to 200 ° C. or lower to prepare a specimen.
- the MnS area ratio was calculated by measuring the cross-sectional area of the entire composite inclusion and the cross-sectional area of the MnS portion in the entire composite inclusion from the image.
- the ratio of MnS to the circumference of the composite inclusion was calculated by measuring the circumference of the Ti oxide in the composite inclusion and the length of the MnS interface in contact with the Ti oxide from the image.
- the MnS area ratio and the ratio of MnS to the circumference of the composite inclusion were obtained by analyzing 20 pieces of each sample material by EPMA and calculating the average value. The results are shown in Table 1.
- the number of composite inclusions is determined by an automatic inclusion analyzer combined with SEM-EDX, and the composite inclusions whose particle size is in the range of 0.5 to 5.0 ⁇ m from the shape measurement data of the detected composite inclusions.
- the number density was calculated by calculating the number of. The results are shown in Table 1.
- ⁇ Tensile test> A JIS No. 4 tensile test piece is taken from the 1/4 t position where the thickness of the prepared specimen is t, and a tensile test is performed at room temperature to obtain the yield stress (YP) and tensile strength ( TS) was measured.
- ⁇ All three test pieces are gauge over. ⁇ : Of the three test pieces, 0 to 2 are over gauge, and all the test pieces that are not over gauge have a CTOD value of 0.4 mm or more. X: Three test pieces. Among the pieces, the CTOD value of one or more test pieces is less than 0.4 mm. “Gauge over” means that the attached clip gauge is fully opened. In addition, the CTOD characteristic of a joint at ⁇ 20 ° C., which is normally required, has a CTOD value of 0.4 mm or more.
- Example 9 although the CTOD test result was acceptable, YP and TS were low because the C content was close to the lower limit of the range of the present invention.
- Example 10 although the CTOD test result was acceptable, YP and TS were low because the Si content was close to the lower limit of the range of the present invention.
- Example 11 although the CTOD test result was acceptable, the YP and TS were low because the Mn content was close to the lower limit of the range of the present invention.
- Example 12 has a low P content, but does not affect the results of the CTOD test.
- Example 13 since the S content was close to the lower limit of the range of the present invention, the MnS composite amount decreased, and the MnS area ratio in the cross section of the composite inclusion and the ratio of MnS in the circumference of the composite inclusion decreased. did. As a result, in the CTOD test, only one test piece was not gauge over.
- Example 14 since the Ti content was close to the lower limit of the range of the present invention, the number density of composite inclusions was low. As a result, in the CTOD test, only one test piece was not gauge over.
- Example 15 the hard content increased because the C content was close to the upper limit of the range of the present invention. Therefore, in the CTOD test, although the two test pieces were not gauge over, the CTOD value was 0.4 mm or more.
- Example 16 was segregated because the Mn content was close to the upper limit of the range of the present invention. As a result, in the CTOD test, the two test pieces were not gauge over, but the CTOD value was 0.4 mm or more.
- Example 17 the toughness decreased because the P content was close to the upper limit of the range of the present invention.
- the two test pieces were not gauge over, but the CTOD value was 0.4 mm or more.
- Example 18 since the S content was close to the upper limit of the range of the present invention, the toughness was lowered. As a result, in the CTOD test, the two test pieces were not gauge over, but the CTOD value was 0.4 mm or more.
- Example 19 since the Ti content was close to the upper limit of the range of the present invention, the toughness decreased due to an increase in carbides such as TiC. As a result, in the CTOD test, the two test pieces were not gauge over, but the CTOD value was 0.4 mm or more.
- Example 20 since the Al content was close to the upper limit of the range of the present invention, the inclusions that formed intragranular ferrite nuclei decreased, and as a result, the toughness decreased. Therefore, in the CTOD test, although the two test pieces were not gauge over, the CTOD value was 0.4 mm or more.
- Example 21 since the N content was close to the upper limit of the range of the present invention, TiN increased and as a result, toughness decreased. Therefore, in the CTOD test, although the two test pieces were not gauge over, the CTOD value was 0.4 mm or more.
- Example 22 since the Cu content was within the range of the present invention, the result of the CTOD test was acceptable. In addition, since Cu content exceeded 0.3%, the surface quality of the slab fell and the surface repair was needed in manufacture.
- Example 23 although the Ni content is in the range of the present invention and exceeds 0.4%, the result of the CTOD test was acceptable, but there was little intragranular ferrite in the microstructure, and the toughness was compared. It was very low.
- Example 24 although the Cr content was within the range of the present invention and exceeded 0.3%, the CTOD test result was acceptable, but the toughness was relatively low.
- Example 25 had a Mo content within the range of the present invention, but exceeded 0.30%. Therefore, although the result of the CTOD test was acceptable, the toughness was relatively low.
- Example 26 although the V content is within the range of the present invention and exceeds 0.05%, the result of the CTOD test was acceptable, but a relatively large amount of VC precipitated and the toughness was relatively low. It was.
- Example 27 the Nb content was within the range of the present invention, but exceeded 0.03%, so a relatively large amount of NbC was precipitated, and as a result, the toughness was relatively low.
- Comparative Example 10 had a low Ti content, and the number density of composite inclusions was less than the range of the present invention. Therefore, the intragranular ferrite did not grow sufficiently and the toughness was lowered. Therefore, in the CTOD test, there was a test piece having a CTOD value of less than 0.4 mm.
- Example 3 As in Example 1, the test numbers shown in Table 3 were used. Steels having the chemical compositions of Examples 31 to 61 and Comparative Examples 21 to 32 were melted in an actual production process to prepare test materials. In the same manner as in Example 1, the MnS area ratio in the cross section of the composite inclusion, the ratio of MnS in the circumference of the composite inclusion, and the number density of the composite inclusion were calculated. The results are shown in Table 3.
- Example 2 In addition, as in Example 1, a tensile test and a CTOD test were performed. The test results are shown in Table 4.
- Example 39 although the result of the CTOD test was acceptable, YP and TS were low because the C content was close to the lower limit of the range of the present invention.
- Example 40 although the result of the CTOD test was acceptable, YP and TS were low because the Si content was close to the lower limit of the range of the present invention.
- Example 41 although the result of the CTOD test was acceptable, the YP and TS were low because the Mn content was close to the lower limit of the range of the present invention.
- Example 43 since the S content was close to the lower limit of the range of the present invention, the MnS composite amount decreased, and the MnS area ratio in the cross section of the composite inclusion and the ratio of MnS in the circumference of the composite inclusion decreased. did. As a result, in the CTOD test, only one test piece was not gauge over.
- Example 44 since the Ni content was close to the lower limit of the range of the present invention, the toughness decreased. As a result, in the CTOD test, only one test piece was not gauge over.
- Example 45 since the Ti content was close to the lower limit of the range of the present invention, the number density of the composite inclusions was low. As a result, in the CTOD test, only one test piece was not gauge over.
- Example 46 since the O content was close to the lower limit of the range of the present invention, the number density of the composite inclusions was low. As a result, in the CTOD test, only one test piece was not gauge over.
- Example 47 since the C content was close to the upper limit of the range of the present invention, the hard structure increased. Therefore, in the CTOD test, although all the test pieces were not gauge over, the CTOD value was 0.4 mm or more.
- Example 48 since the Si content was close to the upper limit of the range of the present invention, the hard structure increased. Therefore, in the CTOD test, although all the test pieces were not gauge over, the CTOD value was 0.4 mm or more.
- Example 49 segregation occurred because the Mn content was close to the upper limit of the range of the present invention. Therefore, in the CTOD test, although all the test pieces were not gauge over, the CTOD value was 0.4 mm or more.
- Example 50 since the P content was close to the upper limit of the range of the present invention, the toughness decreased due to segregation. Therefore, in the CTOD test, although all the test pieces were not gauge over, the CTOD value was 0.4 mm or more.
- Example 51 since the S content was close to the upper limit of the range of the present invention, the toughness decreased due to segregation. Therefore, in the CTOD test, although all the test pieces were not gauge over, the CTOD value was 0.4 mm or more.
- Example 52 since the Ni content was close to the upper limit of the range of the present invention, the toughness was reduced by suppressing the formation of intragranular transformed ferrite. Therefore, in the CTOD test, although all the test pieces were not gauge over, the CTOD value was 0.4 mm or more.
- Example 53 since the Ti content was close to the upper limit of the range of the present invention, the toughness decreased due to an increase in carbides such as TiC. Therefore, in the CTOD test, although all the test pieces were not gauge over, the CTOD value was 0.4 mm or more.
- Example 54 since the Al content was close to the upper limit of the range of the present invention, inclusions serving as intragranular ferrite formation nuclei decreased, and as a result, toughness decreased. Therefore, in the CTOD test, although all the test pieces were not gauge over, the CTOD value was 0.4 mm or more.
- Example 55 since the N content was close to the upper limit of the range of the present invention, TiN increased, and as a result, toughness decreased. Therefore, in the CTOD test, although all the test pieces were not gauge over, the CTOD value was 0.4 mm or more.
- Example 56 since the O content was close to the upper limit of the range of the present invention, the toughness decreased due to an increase in coarse oxides. Therefore, in the CTOD test, although all the test pieces were not gauge over, the CTOD value was 0.4 mm or more.
- Example 57 had a relatively low toughness although the result of the CTOD test was acceptable because the Cu content was within the scope of the present invention.
- Example 58 had a relatively low toughness although the result of the CTOD test was acceptable because the Cr content was within the scope of the present invention.
- Example 59 had relatively low toughness although the result of the CTOD test was acceptable because the Mo content was within the scope of the present invention.
- Example 60 since the V content is within the range of the present invention, the result of the CTOD test was acceptable, but the toughness was relatively low.
- Example 61 since the Nb content is within the range of the present invention, the result of the CTOD test was acceptable, but the toughness was relatively low.
- Comparative Example 28 the Cu content was outside the range of the present invention, so the strength increased and as a result, the toughness decreased. Therefore, in the CTOD test, there was a test piece having a CTOD value of less than 0.4 mm.
- the thick steel plate of the present invention can be suitably used for welded structures such as offshore structures, in particular, thick steel plates having a thickness of 50 mm or more.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Abstract
Description
鋼中に、Ti酸化物の周囲にMnSが存在する複合介在物を含み、前記複合介在物の断面における前記MnSの面積率が10%以上90%未満であり、前記複合介在物の周長に占める前記MnSの割合が10%以上であり、粒径0.5~5.0μmの前記複合介在物の個数密度が10~100個/mm2である、厚鋼板。
O(質量%):鋼中のO含有量
Mn_MnS(質量%):全Mn含有量のうち、MnSとなるMn量
R1(%):複合介在物の断面におけるMnSの面積率の平均値
R2(%):複合介在物の周長に占めるMnSの割合の平均値
各元素の作用効果と、含有量の限定理由を説明する。本明細書において、化学組成または濃度に関する「%」は、特に断りがない限り「質量%」を意味する。
Cは、母材およびHAZの強度を高める作用を有する。400~500MPaの強度を確保するために、C含有量は、0.01%以上であり、母材およびHAZの強度およびHAZ低温靱性を確保するために好ましくは、0.02%以上であり、より好ましくは0.05%以上であり、さらに好ましくは0.06%以上である。
Siは、鋼材の製造中に脱酸剤として作用することから、酸素量の制御に有効であるとともに、鋼中に固溶して強度を増加させる。したがって、Si含有量は、0.10%以上であり、適正な酸素量に制御するとともにHAZ低温靱性を確保するために好ましくは0.13%以上である。
Mnは、オーステナイト安定化元素として作用し、粒界における粗大なフェライトの生成を抑制する。したがって、Mn含有量は、1.30%以上であり、粗大なフェライトの生成を抑制するとともに偏析を防止するために、好ましくは1.40%以上である。
Pは不純物元素であり、P含有量が低下することによりHAZにおいて粒界強度の低下を抑制する。したがって、P含有量は、0.01%以下である。
Sは、MnSを複合析出させる。したがって、S含有量は、0.0010%以上であり、MnSを複合析出させるとともにHAZの低温靱性を確保するために好ましくは0.0020%以上である。
Tiは、Ti系酸化物の生成に必須である。Ti含有量は、充分な介在物密度を得るために0.005%以上であり、充分な介在物密度を確保するとともにHAZ靱性を確保するために好ましくは0.009%以上である。
Alは不純物元素であり、Al含有量が増加することによりTi系酸化物の生成が抑制される。したがって、Al含有量は0.003%以下である。
Oは、Ti系複合酸化物の生成に必須である。充分な介在物密度を得るため、O含有量は、0.0010%以上である。
Nは、Tiと結合してTiNを生成することにより、結晶粒の微細化に寄与する。しかし、N含有量が0.0100%を超えると、TiN析出に必要なTi量が増加し、Ti酸化物が形成されにくくなるとともに、TiNが凝集して破壊の起点になる。したがって、N含有量は、0.0100%以下であり、Ti酸化物を形成するTi量を安定して確保するために好ましくは0.0080%以下であり、より好ましくは0.0050%以下である。
Cuは、強度を高めるため、必要に応じて含有してもよい。しかし、Cu含有量が0.50%を超えると、熱間脆化が生じ、スラブ表面の品質が低下する。したがって、Cu含有量は、0.50%以下であり、好ましくは0.30%以下である。
Niは、靭性靱性を低下させずに強度を高めるため、必要に応じて含有してもよい。しかし、Niはオーステナイト安定化元素であるため、Ni含有量が1.50%を超えると、粒内フェライトが生成し難くなる。したがって、Ni含有量は、1.50%以下であり、粒内フェライトの生成を促進させるために好ましくは1.00%以下である。
Crは、強度を高めるため、必要に応じて含有してもよい。しかし、Cr含有量が0.50%を超えると、HAZ靱性が低下する。したがって、Cr含有量は、0.50%以下であり、好ましくは0.30%以下である。
Moは、少量の含有で強度を顕著に高めるため、必要に応じて含有してもよい。しかし、Mo含有量が0.50%を超えると、HAZ靱性が著しく低下する。したがって、Mo含有量は、0.50%以下であり、好ましくは0.30%以下である。
Vは、母材の強度および靱性の向上に有効であるため、必要に応じて含有してもよい。しかし、V含有量が0.10%を超えると、VCなどの炭化物を形成し、靱性が低下する。したがって、V含有量は、0.10%以下であり、好ましくは0.05%以下である。
Nbは、母材の強度および靱性の向上に有効であるため、必要に応じて含有してもよい。しかし、Nb含有量が0.05%を超えると、NbCなどの炭化物を生成し易くなり、靱性が低下する。したがって、Nb含有量は、0.05%以下であり、好ましくは0.03%以下である。
上記以外の残部はFeおよび不純物である。不純物とは、鋼を工業的に製造する際に、鉱石、スクラップ等の原料、製造工程の種々の要因によって混入する成分であって、本発明に悪影響を与えない量での含有を許容されるものである。
鋼中に、Ti酸化物の周囲にMnSが存在する複合介在物を含み、この複合介在物の断面におけるMnSの面積率が10%以上90%未満であり、複合介在物の周長に占めるMnSの割合が10%以上であり、粒径0.5~5.0μmの前記複合介在物の個数密度が10~100個/mm2である。
任意の切断面に現出した複合介在物を分析する。その複合介在物の断面積におけるMnSの面積率を測定することにより、複合介在物中のMnS量を規定する。複合介在物の断面におけるMnSの面積率が10%未満であると、複合介在物中のMnS量が少なく、充分なMn欠乏層を形成できない。このため、粒内フェライトの生成が困難になる。
複合介在物中のMnSは,Ti系酸化物の周囲に形成される。複合介在物の周長に占めるMnSの割合が10%未満であれば、MnSとマトリクスとの界面に形成される初期Mn欠乏領域が小さい。このため、溶接しても粒内フェライトの形成量が十分でないので、良好な低温HAZ靭性を得られない。したがって、複合介在物のマトリクスとの周長に占めるMnSの割合は10%以上である。
複合介在物の粒径が0.5μm未満では、複合介在物の周囲から吸収できるMn量が少なく、その結果、粒内フェライトの生成に必要なMn欠乏層の形成が困難になる。一方、複合介在物の粒径が5.0μmより大きいと、複合介在物が破壊の起点となる。ここで「粒径」とは円相当直径である。
安定した粒内フェライトを生成させるためには、各複合介在物が旧オーステナイト内に少なくとも1つ程度含まれる必要がある。そのため、複合介在物の個数密度は10個/mm2以上である。一方、複合介在物が過剰に多いと破壊の起点になり易い。そのため、複合介在物の個数密度は100個/mm2以下である。
(i)式中、(Ti_TiO/O)で示される第1項は、Ti酸化物になるTi含有量およびO含有量のバランスを表す。この第1項は、全Ti含有量から、鋼中のN含有量より算出されるTiN生成に必要なTi量を差し引くことにより、算出される。この第1項の値が大きいほど、Ti酸化物が形成され易くなる。この第1項の値が負になるときは、Ti酸化物が形成されない。
本発明に係る厚鋼板は、以上のような複合介在物を有するため、板厚が50mm以上であっても、HAZ低温靱性が優れる。すなわち、板厚が50mm以上の厚鋼板を低パス回数で溶接するためには溶接時の入熱量を増加させる必要がある。しかし、本発明に係る厚鋼板は、大入熱溶接を行った場合であっても、優れたHAZ低温靭性を有する。
本発明に係る厚鋼板の製造方法は特に制限されない。例えば、上記で説明した化学組成を有するスラブを加熱した後、熱間圧延し、最後に冷却することにより製造できる。
表1に示す試験No.実施例1~28,比較例1~18の化学組成を有する鋼を実際の製造工程で溶製した。この製造工程では、RH真空脱ガス処理前にArガスを上部より溶鋼内に吹き込み、溶鋼の表面のスラグと溶鋼とを反応させることにより、スラグ内のトータルFe量を調整した。
複合介在物分析用の試験片は、前記供試材の板厚をtとするときの板厚1/4t部より採取したものを用いた。複合介在物は、電子プローブマイクロアナライザー(EPMA)を用い、複合介在物を面分析したマッピング画像から、MnS面積率および複合介在物の周長に占めるMnSの割合を測定した。
複合介在物の個数は、SEM-EDXを組み合わせた自動介在物分析装置により行い、検出された複合介在物の形状測定データから、粒径が0.5~5.0μmの範囲である複合介在物の個数を算出することにより、個数密度を算出した。結果を表1に示す。
作成した供試材の板厚をtとするときの1/4t位置よりJIS 4号引張試験片を採取し、室温で引張試験を実施し、圧延母材の降伏応力(YP)および引張強度(TS)を測定した。
作成した供試材からCTOD試験用の試験片をn=3で採取した。各試験片に開先加工を施し、サブマージアーク溶接(SAW)にて入熱5.0kJ/mmにて多層溶接を行った。作成した溶接継手のHAZにノッチ加工を施し、試験温度-20℃でBS7448規格準拠にて、CTOD試験を行った。試験結果の良否は、下記の基準に基づいて判定した。下記の基準のうち、判定が◎または○であった試験片を合格とした。結果を表2に示す。
○:3本の試験片うち、0~2本がゲージオーバー、かつ、ゲージオーバーでない試験片すべてのCTOD値が0.4mm以上
×:3本の試験片のうち、1本以上の試験片のCTOD値が0.4mm未満
なお、ゲージオーバーとは、取り付けたクリップゲージが限界まで開ききることをいう。また、通常要求される-20℃における継手のCTOD特性は、CTOD値が0.4mm以上であるため、CTOD値の基準を0.4mmとした。
Claims (3)
- 化学組成が、質量%で、
C:0.01~0.20%、
Si:0.10~0.25%、
Mn:1.30~2.50%、
P:0.01%以下、
S:0.0010~0.0100%、
Ti:0.005~0.030%、
Al:0.003%以下、
O:0.0010~0.0050%、
N:0.0100%以下、
Cu:0~0.50%、
Ni:0~1.50%、
Cr:0~0.50%、
Mo:0~0.50%、
V:0~0.10%、
Nb:0~0.05%、および、
残部:Feおよび不純物であり、かつ、
鋼中に、Ti酸化物の周囲にMnSが存在する複合介在物を含み、
前記複合介在物の断面における前記MnSの面積率が10%以上90%未満であり、
前記複合介在物の周長に占める前記MnSの割合が10%以上であり、
粒径0.5~5.0μmの前記複合介在物の個数密度が10~100個/mm2である、厚鋼板。 - 質量%で、
Cu:0.01~0.50%、
Ni:0.01~1.50%、
Cr:0.01~0.50%、
Mo:0.01~0.50%、
V:0.01~0.10%、および、
Nb:0.01~0.05%
から選択される1種以上を含有する、請求項1に記載の厚鋼板。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP17786057.4A EP3447162B1 (en) | 2016-04-21 | 2017-04-21 | Thick steel plate |
KR1020187033428A KR20180132909A (ko) | 2016-04-21 | 2017-04-21 | 후강판 |
CN201780024463.3A CN109072383B (zh) | 2016-04-21 | 2017-04-21 | 厚钢板 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016085147A JP6747032B2 (ja) | 2016-04-21 | 2016-04-21 | 厚鋼板 |
JP2016085148A JP6662174B2 (ja) | 2016-04-21 | 2016-04-21 | 厚鋼板 |
JP2016-085147 | 2016-04-21 | ||
JP2016-085148 | 2016-04-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017183720A1 true WO2017183720A1 (ja) | 2017-10-26 |
Family
ID=60116163
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/016090 WO2017183720A1 (ja) | 2016-04-21 | 2017-04-21 | 厚鋼板 |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP3447162B1 (ja) |
KR (1) | KR20180132909A (ja) |
CN (1) | CN109072383B (ja) |
WO (1) | WO2017183720A1 (ja) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6743996B1 (ja) * | 2019-11-13 | 2020-08-19 | 日本製鉄株式会社 | 鋼材 |
CN114729414B (zh) * | 2019-11-13 | 2024-03-29 | 日本制铁株式会社 | 钢材 |
JP6813128B1 (ja) * | 2019-11-13 | 2021-01-13 | 日本製鉄株式会社 | 鋼材 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01191765A (ja) * | 1988-01-26 | 1989-08-01 | Nippon Steel Corp | 微細粒チタン酸化物、硫化物を分散した溶接部靭性の優れた低温用高張力鋼 |
JPH06136439A (ja) * | 1992-10-22 | 1994-05-17 | Kobe Steel Ltd | 溶接継手靱性の優れた溶接構造用鋼板の製造方法 |
WO2014199488A1 (ja) * | 2013-06-13 | 2014-12-18 | 新日鐵住金株式会社 | 溶接用超高張力鋼板 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2940647B2 (ja) * | 1991-08-14 | 1999-08-25 | 新日本製鐵株式会社 | 溶接用低温高靱性鋼の製造方法 |
EP1221493B1 (en) * | 2000-05-09 | 2005-01-12 | Nippon Steel Corporation | THICK STEEL PLATE BEING EXCELLENT IN CTOD CHARACTERISTIC IN WELDING HEAT AFFECTED ZONE AND HAVING YIELD STRENGTH OF 460 Mpa OR MORE |
JP5181639B2 (ja) * | 2006-12-04 | 2013-04-10 | 新日鐵住金株式会社 | 低温靱性に優れた高強度厚肉ラインパイプ用溶接鋼管及びその製造方法 |
JP4969275B2 (ja) * | 2007-03-12 | 2012-07-04 | 株式会社神戸製鋼所 | 溶接熱影響部の靭性に優れた高張力厚鋼板 |
JP4612735B2 (ja) * | 2007-12-06 | 2011-01-12 | 新日本製鐵株式会社 | 脆性破壊伝播停止特性と大入熱溶接熱影響部靭性に優れた厚手高強度鋼板の製造方法、及び、脆性破壊伝播停止特性と大入熱溶接熱影響部靭性に優れた厚手高強度鋼板 |
TWI365915B (en) * | 2009-05-21 | 2012-06-11 | Nippon Steel Corp | Steel for welded structure and producing method thereof |
CN104451389A (zh) * | 2014-11-13 | 2015-03-25 | 南京钢铁股份有限公司 | 一种100mm厚抗大线能量焊接E36海洋工程用钢板 |
-
2017
- 2017-04-21 CN CN201780024463.3A patent/CN109072383B/zh active Active
- 2017-04-21 WO PCT/JP2017/016090 patent/WO2017183720A1/ja active Application Filing
- 2017-04-21 EP EP17786057.4A patent/EP3447162B1/en active Active
- 2017-04-21 KR KR1020187033428A patent/KR20180132909A/ko not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01191765A (ja) * | 1988-01-26 | 1989-08-01 | Nippon Steel Corp | 微細粒チタン酸化物、硫化物を分散した溶接部靭性の優れた低温用高張力鋼 |
JPH06136439A (ja) * | 1992-10-22 | 1994-05-17 | Kobe Steel Ltd | 溶接継手靱性の優れた溶接構造用鋼板の製造方法 |
WO2014199488A1 (ja) * | 2013-06-13 | 2014-12-18 | 新日鐵住金株式会社 | 溶接用超高張力鋼板 |
Also Published As
Publication number | Publication date |
---|---|
EP3447162A4 (en) | 2019-10-02 |
EP3447162B1 (en) | 2020-12-30 |
EP3447162A1 (en) | 2019-02-27 |
CN109072383B (zh) | 2021-02-09 |
CN109072383A (zh) | 2018-12-21 |
KR20180132909A (ko) | 2018-12-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5201665B2 (ja) | 大入熱溶接時の熱影響部の靭性に優れた溶接用高張力厚鋼板 | |
JP6245417B1 (ja) | 鋼材 | |
JP6665659B2 (ja) | 厚鋼板およびその製造方法 | |
WO2017183719A1 (ja) | 高張力鋼および海洋構造物 | |
JP5842314B2 (ja) | 大入熱溶接用鋼 | |
JP6645373B2 (ja) | 厚鋼板とその製造方法 | |
JP2003213366A (ja) | 母材および大小入熱溶接熱影響部の靭性に優れた鋼材 | |
WO2017183720A1 (ja) | 厚鋼板 | |
JP4041447B2 (ja) | 大入熱溶接継手靭性に優れた厚鋼板 | |
JP5435837B2 (ja) | 高張力厚鋼板の溶接継手 | |
JP5708349B2 (ja) | 溶接熱影響部靭性に優れた鋼材 | |
JP6665658B2 (ja) | 高強度厚鋼板 | |
JPWO2010038470A1 (ja) | 母材および溶接熱影響部の低温靭性に優れかつ強度異方性の小さい鋼板およびその製造方法 | |
JP4074536B2 (ja) | 母材および溶接熱影響部の靱性に優れた鋼材 | |
JP4276576B2 (ja) | 大入熱溶接熱影響部靭性に優れた厚手高強度鋼板 | |
JP6187270B2 (ja) | 溶接熱影響部靱性に優れた鋼材 | |
JP6662174B2 (ja) | 厚鋼板 | |
JP4299769B2 (ja) | 入熱20〜100kJ/mmの大入熱溶接用高HAZ靭性鋼材 | |
JP6747032B2 (ja) | 厚鋼板 | |
JP2009179844A (ja) | 溶接熱影響部の靭性に優れた高張力厚鋼板 | |
JP2002371338A (ja) | レーザー溶接部の靭性に優れた鋼 | |
JP5213517B2 (ja) | 溶接熱影響部靭性に優れた鋼材 | |
JPH07278736A (ja) | 溶接熱影響部靱性の優れた鋼材 | |
JP4522042B2 (ja) | 高パス間温度溶接性に優れた鋼材およびその溶接継手 | |
WO2024127494A1 (ja) | 溶接継手および溶接構造体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20187033428 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2017786057 Country of ref document: EP |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17786057 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017786057 Country of ref document: EP Effective date: 20181121 |