WO2012036269A1 - 延性と伸びフランジ性に優れた高強度鋼板、高強度亜鉛めっき鋼板およびこれらの製造方法 - Google Patents
延性と伸びフランジ性に優れた高強度鋼板、高強度亜鉛めっき鋼板およびこれらの製造方法 Download PDFInfo
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Definitions
- the present invention relates to a high-strength steel plate, a high-strength galvanized steel plate excellent in ductility and stretch flangeability, and methods for producing them.
- This application claims priority based on Japanese Patent Application Nos. 2010-208329 and 2010-208330 filed in Japan on September 16, 2010, the contents of which are incorporated herein by reference.
- the mass is C: 0.05 to 0.20%, Si: 0.3 to 1.8%, Mn: 1.0 to 3 0.0%, S: 0.005% or less, having a composition comprising the balance Fe and inevitable impurities, a composite structure comprising ferrite, tempered martensite, residual austenite, and a low-temperature transformation phase, and the ferrite Is 30% or more by volume, the tempered martensite is 20% or more by volume, the retained austenite is 2% or more by volume, and the average grain size of the ferrite and tempered martensite is 10 ⁇ m or less.
- a high-tensile hot-dip galvanized steel sheet having excellent ductility and stretch flangeability (see, for example, Patent Document 1).
- the amounts of C, Si, Mn, P, S, Al and N are adjusted, and if necessary, Ti, Nb, V, B, Cr, Mo,
- the ferrite contains 3% or more, bainite containing carbide and 40% or more martensite containing carbide, and the ferrite, bainite, and martensite.
- a tensile strength having a structure in which the number of ferrite grains having cementite, martensite, or retained austenite in the grains is 30% or more of the total ferrite.
- Patent Document 3 the standard deviation of the hardness inside the steel plate is reduced, and the same hardness is provided throughout the steel plate.
- Patent Document 4 the hardness of the hard part is reduced by heat treatment, and the difference in hardness from the soft part is reduced.
- Patent document 5 makes a hardness difference with a soft part small by making a hard site
- the Mn concentration in the cross section in the thickness direction of the steel sheet A steel sheet having a smaller ratio between the upper limit value and the lower limit value can be given (for example, see Patent Document 6).
- the present inventor has intensively studied to solve the above problems. As a result, by increasing the micron Mn distribution inside the steel sheet, the hardness difference is large, the dispersion of the hardness distribution is limited, and the steel sheet having a sufficiently small average crystal grain size has a maximum tensile strength of 900 MPa or more. It has been found that ductility and stretch flangeability (hole expansibility) can be greatly improved while ensuring high strength.
- a plurality of measurement areas with a diameter of 1 ⁇ m or less are set, and the hardness measurement values in the plurality of measurement areas are arranged in ascending order to obtain a hardness distribution, and the hardness measurement If the whole number is multiplied by 0.02 and the number includes a decimal number, rounding it up to obtain an integer N0.02 gives the smallest measured value of N0.02
- the hardness is 2% hardness, and when the total number of hardness measurement values is 0.98 and the number includes a decimal number, an integer N0.98 obtained by rounding it down is obtained to obtain the minimum hardness When the hardness of the N0.98 largest measured value from the measured value is 98% hardness, the 98% hardness is 1.5 times or more of the 2% hardness, and between the 2% hardness and the 98% hardness.
- the hardness distribution has a kurtosis K * of -1.2 or more and -0.4 or less, and the steel High-strength steel sheet having excellent ductility and stretch flangeability, wherein the average crystal grain size in the tissue is 10 ⁇ m or less.
- the difference between the maximum value and the minimum value of the Mn concentration in the base iron at 1/8 to 3/8 thickness of the steel sheet is 0.4% or more and 3.5% or less in terms of mass%.
- [3] When the section from the 2% hardness to the 98% hardness is equally divided into 10 1/10 sections, the number of measured hardness values in each 1/10 section is the total measured value.
- the high-strength steel sheet having excellent ductility and stretch flangeability according to [1] or [2], which is in the range of 2 to 30% of the number.
- the hard phase is any one or both of a bainitic ferrite phase and a bainite phase having a volume fraction of 10 to 45% and a fresh martensite phase of 10% or less [1] ]
- the high strength steel plate excellent in ductility and stretch flangeability as described in any one of [3].
- the steel sheet structure further contains 2 to 25% of retained austenite phase, and has high ductility and stretch flangeability according to any one of [1] to [4] steel sheet.
- [6] Furthermore, in mass%, Ti: 0.005 to 0.09%, Nb: 0.005 to 0.09% of one kind or two or more kinds, characterized in that it has excellent ductility and stretch flangeability according to any one of [1] to [5] steel sheet.
- B 0.0001 to 0.01%
- Cr 0.01 to 2.0%
- Ni 0.01 to 2.0%
- Cu 0.01 to 2.0%
- Mo High strength excellent in ductility and stretch flangeability according to any one of [1] to [6], characterized by containing one or more of 0.01 to 0.8% steel sheet.
- V A high-strength steel sheet excellent in ductility and stretch flangeability according to any one of [1] to [7], characterized by containing 0.005 to 0.09%.
- the slab having the chemical component according to any one of [1] or [6] to [9] is directly or once cooled and then heated to 1050 ° C. or higher to either 800 ° C. or Ar 3 transformation point. Hot rolling at a higher temperature or higher, and rolling in a temperature range of 750 ° C.
- cooling is performed from the maximum heating temperature to the ferrite transformation temperature range or lower and primary cooling is performed for 20 to 1000 seconds in the ferrite transformation temperature range.
- cooling is performed at an average cooling rate of 10 ° C./second or higher in the bainite transformation temperature range, and secondary cooling is performed in which the martensite transformation start temperature is lower than the martensite transformation start temperature ⁇ 120 ° C. or higher.
- the steel sheet after the secondary cooling is stopped for 2 seconds to 1000 seconds within the range of the martensite transformation start temperature or lower and the second cooling stop temperature or higher.
- the heating rate in the bainite transformation temperature range is set to an average of 10 ° C./sec or higher, and the bainite transformation start temperature is reheated to a reheating stop temperature of 100 ° C. or higher.
- t (T) is the residence time (seconds) of the steel sheet at the temperature T ° C. in the cooling step after the winding.
- t (T) is the residence time (seconds) of the steel sheet at the temperature T ° C. in the cooling step after the winding.
- Ductility characterized by immersing the steel sheet in a galvanizing bath in the reheating when the high strength steel sheet is manufactured by the manufacturing method according to any one of [11] to [14]
- a method for producing high-strength galvanized steel sheets with excellent stretch flangeability [16] The steel sheet is immersed in a galvanizing bath in the bainite transformation temperature range of the third cooling when the high-strength steel sheet is manufactured by the manufacturing method according to any one of [11] to [14].
- a method for producing a high-strength galvanized steel sheet comprising: producing a high-strength steel sheet by the production method according to any one of [11] to [14]; [18] A method for producing a high-strength galvanized steel sheet, comprising producing a high-strength steel sheet by the production method according to any one of [11] to [14] and then performing hot dip galvanizing.
- the high-strength steel sheet of the present invention has a predetermined chemical composition, and in the range of 1/8 to 3/8 thickness of the steel sheet, a plurality of measurement areas having a diameter of 1 ⁇ m or less are set, and the hardness in the plurality of measurement areas Is obtained by arranging the measured values in ascending order and obtaining a hardness distribution, and by multiplying the total number of measured hardness values by 0.02 and including the decimal number, the integer N0.02 obtained by rounding it up is obtained.
- the hardness of the N0.02 largest measurement value from the minimum hardness measurement value is 2% hardness
- the total number of hardness measurement values is multiplied by 0.98, and the number includes a decimal number
- An integer N0.98 obtained by rounding down is obtained
- the hardness of the N0.98 largest measurement value is 98% hardness from the minimum hardness measurement value
- the 98% hardness is 1.5% of the 2% hardness.
- the kurtosis of the hardness distribution between the 2% hardness and the 98% hardness * Is at -0.40 or less an average the crystal grain diameter is 10 ⁇ m or less in the steel sheet structure, while ensuring high strength of more than tensile strength 900 MPa, a steel sheet excellent in ductility and stretch flangeability.
- the step of using a slab having a predetermined chemical component as a hot-rolled coil winds the steel sheet after hot rolling at 750 ° C.
- the micro Mn distribution inside the steel sheet is increased by cooling to a take-off temperature of ⁇ 100) ° C. at a cooling rate of 20 ° C./hour or less while satisfying the above formula (1).
- the steps of continuously annealing the steel sheet having a large Mn distribution are a heating process in which annealing is performed at a maximum heating temperature of 750 to 1000 ° C., and a process of cooling the steel sheet from the maximum heating temperature to the ferrite transformation temperature range or less.
- the second cooling step that stops in the range of the martensite transformation start temperature of ⁇ 120 ° C. or higher and the steel plate after the second cooling step is stopped for 2 seconds to 1000 seconds below the Ms point and in the range of the second cooling stop temperature or higher.
- the steel plate after the process and the dwell process is re-started at a bainite transformation start temperature of ⁇ 80 ° C. or more with an average heating rate in the bainite transformation temperature range of 10 ° C./second or more.
- FIG. 1 shows an example of a high-strength steel sheet according to the present invention.
- Each measured value is converted with the difference between the maximum value and the minimum value of the measured value of hardness as 100%, and is divided into a plurality of classes, It is the graph which showed the relationship with the number of the measured values in a class.
- FIG. 2 is a diagram comparing the hardness distribution of the high-strength steel sheet of the present invention with a normal distribution.
- FIG. 3 is a graph schematically showing the relationship between the transformation rate and the elapsed time of the transformation treatment when the difference between the maximum value and the minimum value of the Mn concentration in the ground iron is relatively large.
- FIG. 4 is a graph schematically showing the relationship between the transformation rate and the elapsed time of the transformation treatment when the difference between the maximum value and the minimum value of the Mn concentration in the ground iron is relatively small.
- FIG. 5 is a graph for explaining the temperature history of the cold-rolled steel sheet when passing through the continuous annealing line, and is a graph showing the relationship between the temperature of the cold-rolled steel sheet and time.
- the high-strength steel sheet of the present invention has a predetermined chemical composition, an average crystal grain size in the steel sheet structure is 10 ⁇ m or less, and has a measurement region having a diameter of 1 ⁇ m or less in the range of 1/8 to 3/8 thickness of the steel sheet.
- 98% hardness in the hardness distribution is 1.5 times or more of 2% hardness, and 2% hardness
- An example of the hardness distribution of the high-strength steel sheet of the present invention is shown in FIG.
- a hardness measurement value is obtained in a plurality of measurement regions set in a range of 1/8 thickness to 3/8 thickness of the steel sheet, and the total number of hardness measurement values is multiplied by 0.02, which is When a decimal number is included, an integer N0.02 obtained by rounding it up is obtained. Further, when the total number of hardness measurement values is multiplied by 0.98, and the number includes a decimal number, an integer N0.98 obtained by rounding down is obtained. Then, the hardness of the N0.02 largest measurement value from the measurement value of the minimum hardness in the plurality of measurement regions is set to 2% hardness.
- the hardness of the N0.98th largest measured value from the measured value of the minimum hardness in the plurality of measurement regions is set to 98% hardness.
- 98% hardness is 1.5 times or more of 2% hardness
- the kurtosis K * of the hardness distribution between 2% hardness and 98% hardness is ⁇ 0.40 or less. It is preferable that
- the reason for limiting the size of the measurement region to a diameter of 1 ⁇ m or less when setting a plurality of measurement regions is to accurately evaluate the hardness variation caused by the steel sheet structure such as ferrite phase, bainite phase, martensite phase, etc. Because.
- the average crystal grain size in the steel sheet structure is 10 ⁇ m or less. Therefore, in order to accurately evaluate the hardness variation due to the steel sheet structure, in a measurement region narrower than the average crystal grain size. It is necessary to obtain a measured value of hardness. Specifically, it is necessary to set a region having a diameter of 1 ⁇ m or less as a measurement region. When the hardness is measured using a normal Vickers tester, the indentation size is too large to accurately evaluate the hardness variation due to the structure.
- the “measured value of hardness” in the present invention means a value measured by the following method. That is, in the high-strength steel sheet of the present invention, a measurement obtained by measuring the hardness with an indentation load of 1 g using an indentation depth measurement method using a dynamic microhardness meter equipped with a Belkovic type triangular cone indenter. Use the value.
- the measurement position of the hardness is in the range of 1/8 to 3/8, centering on 1/4 of the plate thickness in the plate thickness section parallel to the rolling direction of the steel plate.
- the total number of hardness measurement values is in the range of 100 to 10,000, preferably 1000 or more.
- the indentation size measured in this way is assumed to be circular, the diameter is 1 ⁇ m or less.
- the shape of the indentation is a rectangle or triangle other than a circle, the indentation shape may have a dimension in the longitudinal direction of 1 ⁇ m or less.
- the “average crystal grain size” in the present invention means a value measured by the following method. That is, in the high-strength steel plate of the present invention, it is preferable to use a crystal grain size measured by using an EBSD (Electric Backscattering Diffraction) method.
- the observation surface of the crystal grain size is in the range of 1/8 to 3/8, centering on 1/4 of the plate thickness in the plate thickness cross section parallel to the rolling direction of the steel plate.
- a cutting method is applied to the grain boundary map obtained by regarding the observation plane as a crystal grain boundary having a boundary line where the crystal orientation difference between measurement points adjacent to the bcc crystal orientation is 15 degrees or more.
- the steel sheet structure In order to obtain a steel sheet with excellent ductility, it is important to use a structure with excellent ductility represented by ferrite as a steel sheet structure.
- a tissue having excellent ductility is soft. Therefore, in order to obtain a steel sheet having high ductility while ensuring sufficient strength, the steel sheet structure needs to include a soft structure and a hard structure typified by martensite.
- a steel sheet having a steel structure that includes both a soft structure and a hard structure the greater the difference in hardness between the soft part and the hard part, the easier the strain that accompanies the deformation accumulates in the soft part and is distributed to the hard part. Since it becomes difficult, ductility improves.
- the 98% hardness is 1.5 times or more of the 2% hardness, so the hardness difference between the soft part and the hard part is sufficiently large, thereby obtaining sufficiently high ductility. Can do.
- the 98% hardness is preferably 3.0 times or more of the 2% hardness, more preferably more than 3.0 times, and even more preferably 3.1 times or more. 4.0 times or more is more preferable, and 4.2 times or more is more preferable. If the measured value of the hardness of 98% is less than 1.5 times the measured value of the hardness of 2%, the difference in hardness between the soft part and the hard part is not sufficiently large, and the ductility becomes insufficient. .
- the measured value of 98% hardness is 4.2 times or more of the measured value of 2% hardness, the hardness difference between the soft part and the hard part is sufficiently large, and both ductility and hole expansibility are achieved. Since it improves further, it is preferable.
- the hardness difference between the soft part and the hard part is preferably as large as possible from the viewpoint of ductility.
- the regions having a large hardness difference are in contact with each other, a gap of strain accompanying deformation of the steel plate is generated at the boundary portion, and micro cracks are likely to occur.
- a micro crack becomes a starting point of a crack, so that stretch flangeability is deteriorated.
- the boundary where the regions with large hardness difference contact each other is reduced, and the regions with large hardness difference contact each other. It is effective to shorten the length of the boundary.
- the average crystal grain size measured by the EBSD method is 10 ⁇ m or less, so the boundary between the areas having a large hardness difference in the steel sheet is shortened, and the hardness difference between the soft part and the hard part is small. Deterioration of stretch flangeability due to its large size is suppressed, and excellent stretch flangeability is obtained.
- the average crystal grain size is preferably 8 ⁇ m or less, and more preferably 5 ⁇ m. When the average crystal grain size exceeds 10 ⁇ m, the effect of shortening the boundary where the regions having a large hardness difference in the steel plate contact with each other becomes insufficient, and deterioration of stretch flangeability cannot be sufficiently suppressed.
- the steel sheet structure should be composed of finely dispersed structures having various hardnesses, and the dispersion of the hardness distribution in the steel sheet should be small.
- the high-strength steel sheet according to the present invention has a hardness distribution with a kurtosis K * of ⁇ 0.40 or less, thereby reducing variations in hardness distribution in the steel sheet and having few boundaries where the areas with large hardness differences contact each other.
- the kurtosis K * is preferably ⁇ 0.50 or less, and more preferably ⁇ 0.55 or less.
- the lower limit of the kurtosis K * is not particularly defined, the effect of the present invention is exhibited. However, since it is difficult from experience to make K * less than ⁇ 1.20, this is the lower limit.
- the kurtosis K * is a value obtained from the hardness distribution by the following equation (2), and is a numerical value evaluated by comparing the hardness distribution with a normal distribution.
- the kurtosis is a negative number, it indicates that the hardness distribution curve is relatively flat, and the larger the absolute value, the greater the deviation from the normal distribution.
- Hi Hardness at the i-th largest measurement point from the minimum hardness measurement value H *: Average hardness from the minimum hardness N0.02-th largest measurement point to N0.98-th largest measurement point s *: Minimum hardness N0 Standard deviation from .02 largest measurement point to N0.98 largest measurement point
- the steel sheet structure is not sufficiently composed of finely dispersed structures having sufficiently diverse hardness, and thus the hardness distribution varies widely in the steel sheet. As a result, there are many boundaries where the regions having a large hardness difference contact each other, and the deterioration of stretch flangeability cannot be sufficiently suppressed.
- FIG. 1 shows an example of a high-strength steel sheet according to the present invention.
- Each measured value is converted with the difference between the maximum value and the minimum value of the measured value of hardness as 100%, and is divided into a plurality of classes, It is the graph which showed the relationship with the number of the measured values in a class.
- the horizontal axis indicates hardness
- the vertical axis indicates the number of measured values in each class.
- the solid line of the graph shown in FIG. 1 connects the number of measured values in each class.
- the number of measurement values in each divided range D obtained by dividing the range from 2% hardness to 98% hardness into 10 equal parts is all
- the range is preferably 2% to 30% of the number of measured values.
- the number of measurement values in each class has a peak in the division range D near the center.
- the line connecting the number of measurement values in each class has a valley in the division range D near the center. Therefore, there are many structures with a large hardness difference having different division ranges D arranged on both sides of the valley.
- the number of measured values in each divided range D is more preferably 25% or less of the total number of measured values. More preferably, it is% or less. In order to further improve the stretch flangeability, the number of measured values in each divided range D is more preferably 4% or more of the total number of measured values, and more preferably 5% or more. Further preferred.
- the hardness distribution of the high-strength steel sheet according to the present invention will be described in detail in comparison with a general normal distribution.
- the kurtosis K * of the normal distribution is generally said to be 0.
- the kurtosis of the hardness distribution of the steel sheet according to the present invention is ⁇ 0.4 or less, it is clear that the distribution is different from the normal distribution.
- the hardness distribution of the steel sheet according to the present invention is flat and has a long tail as compared with the normal distribution.
- the high-strength steel sheet of the present invention has such a hardness distribution, and the difference between 98% hardness and 2% hardness corresponding to both ends of the distribution is as large as 1.5 times or more.
- the difference in hardness between the soft part and the hard part becomes sufficiently large, and high ductility can be obtained. That is, the present inventor found that when the hardness distribution is different from the conventional one and the kurtosis is ⁇ 0.4 or less, the hole expandability is higher when the ratio of 98% hardness to 2% hardness is larger. I found it to be improved. On the other hand, the prior art states that the smaller the hardness ratio of the structure, the better the hole expanding property.
- the conventional technique is based on the assumption of a hardness distribution close to a normal distribution, and is fundamentally different from the technique presented in the present invention.
- the high-strength steel sheet of the present invention is obtained by converting the difference between the maximum value and the minimum value of the Mn concentration in the steel from 1/8 to 3/8 thickness of the steel sheet into mass%. It is preferable that it is 0.40% or more and 3.50% or less.
- the width of the hardness distribution is widened, whereby 98% hardness is 1.5 times or more, preferably 3.0 times or more, more preferably 2% hardness. More than 3.0 times, further 3.1 times or more, more preferably 4.0 times or more, and further 4.2 or more.
- the transformation of the ferrite phase will be described as an example.
- the start time of the phase transformation from austenite to ferrite becomes relatively early.
- the start time of the phase transformation from austenite to ferrite is relatively later than in the region where the Mn concentration is low. Therefore, the phase transformation from austenite to ferrite in the steel sheet proceeds more gradually as the Mn concentration in the steel sheet is more uneven and the concentration difference is larger.
- the transformation rate from the ferrite phase volume fraction from 0% to, for example, 50% is slowed down.
- the above phenomenon is the same not only in the ferrite phase but also in the tempered martensite phase and the remaining hard phase.
- FIG. 3 schematically shows the relationship between the transformation rate and the elapsed time of the transformation process.
- the transformation rate is the volume fraction of ferrite in the steel sheet structure
- the elapsed time of the transformation treatment is the elapsed time of the heat treatment causing the ferrite transformation.
- the example of the present invention shown in FIG. 3 is a case where the difference between the maximum value and the minimum value of the Mn concentration is relatively large, and the slope of the curve indicating the transformation rate of the entire steel sheet is small (the transformation speed is low).
- the difference in Mn concentration is preferably 0.60% or more, and more preferably 0.80% or more.
- the greater the difference in Mn concentration the easier it is to control the phase transformation.
- the difference in Mn concentration is preferably 3.50% or less. From the viewpoint of weldability, the difference in Mn concentration is more preferably 3.40% or less, and further preferably 3.30% or less.
- a method for determining the difference between the maximum value and the minimum value of Mn in the thickness of 1/8 to 3/8 is as follows. First, a sample is taken with a plate thickness cross section parallel to the rolling direction of the steel plate as an observation surface. Next, EPMA analysis is performed in the range from 1/8 thickness to 3/8 thickness centering on 1/4 thickness, and the amount of Mn is measured. The measurement is performed with a probe diameter of 0.2 to 1.0 ⁇ m and a measurement time per point of 10 ms or more, and the amount of Mn is measured at 1000 or more points by line analysis or surface analysis. Among the measurement results, the point where the Mn concentration exceeds 3 times the added Mn concentration is considered to be a point where inclusions such as Mn sulfide were measured.
- the point where the Mn concentration is less than 1/3 times the added Mn concentration is considered to be the measurement of inclusions such as Al oxide. Since the Mn concentration in these inclusions hardly affects the phase transformation behavior in the ground iron, the maximum value and the minimum value of the Mn concentration are obtained after removing the measurement result of inclusions from the measurement results. Then, the difference between the maximum value and the minimum value of the obtained Mn concentration is calculated.
- the method for measuring the amount of Mn is not limited to the above method.
- the Mn concentration may be measured by performing direct observation using an EMA method or a three-dimensional atom probe (3D-AP).
- the steel structure of the high-strength steel sheet of the present invention is composed of a ferrite phase with a volume fraction of 10-50%, a tempered martensite phase with 10-50%, and the remaining hard phase.
- the remaining hard phase includes one or both of a bainitic ferrite phase and a bainite phase having a volume fraction of 10 to 60% and a fresh martensite phase of 10% or less.
- the steel sheet structure may contain 2 to 25% of retained austenite phase.
- “Ferrite” Ferrite is an effective structure for improving ductility, and is preferably contained in the steel sheet structure in a volume fraction of 10 to 50%. From the viewpoint of ductility, the volume fraction of ferrite contained in the steel sheet structure is more preferably 15% or more, and further preferably 20% or more. In order to sufficiently increase the tensile strength of the steel sheet, the volume fraction of ferrite contained in the steel sheet structure is preferably 45% or less, and more preferably 40% or less. When the volume fraction of ferrite is less than 10%, sufficient ductility may not be obtained. On the other hand, since ferrite is a soft structure, when the volume fraction exceeds 50%, the yield stress may decrease.
- Bainitic ferrite and bainite are structures having a hardness between soft ferrite and hard tempered martensite and fresh martensite.
- the high-strength steel sheet of the present invention only needs to contain either bainitic ferrite or bainite, and may contain both.
- the total amount of bainitic ferrite and bainite is preferably contained in the steel sheet structure in a volume fraction of 10 to 45%.
- the total volume fraction of bainitic ferrite and bainite contained in the steel sheet structure is more preferably 15% or more, and further preferably 20% or more, from the viewpoint of stretch flangeability.
- the total volume fraction of bainitic ferrite and bainite should be 40% or less, preferably 35% or less.
- the total volume fraction of bainitic ferrite and bainite is less than 10%, the hardness distribution may be biased and stretch flangeability may deteriorate.
- the total volume fraction of bainitic ferrite and bainite exceeds 45%, it is difficult to produce appropriate amounts of both ferrite and tempered martensite, and the balance between ductility and yield stress deteriorates, which is not preferable.
- Tempered martensite is a structure that greatly improves the tensile strength, and is preferably contained in the steel sheet structure in a volume fraction of 10 to 50%. If the volume fraction of tempered martensite contained in the steel sheet structure is less than 10%, sufficient tensile strength may not be obtained. On the other hand, if the volume fraction of tempered martensite contained in the steel sheet structure exceeds 50%, it becomes difficult to secure ferrite and residual austenite necessary for improving ductility. In order to sufficiently increase the ductility of the high-strength steel plate, the volume fraction of tempered martensite is more preferably 45% or less, and further preferably 40% or less. In order to ensure the tensile strength, the volume fraction of tempered martensite is more preferably 15% or more, and further preferably 20% or more.
- Residual austenite Residual austenite is an effective structure for improving ductility and is preferably contained in the steel sheet structure in a volume fraction of 2 to 25%. If the volume fraction of retained austenite contained in the steel sheet structure is 2% or more, more sufficient ductility can be obtained. If the volume fraction of retained austenite is 25% or less, it is not necessary to add a large amount of an austenite stabilizing element typified by C or Mn, and weldability is improved.
- the steel structure of the high-strength steel sheet of the present invention preferably contains retained austenite because it is effective for improving ductility. However, when sufficient ductility is obtained, retained austenite is contained. It does not have to be.
- the steel sheet structure preferably contains 10% or less in volume fraction.
- the volume fraction of fresh martensite is preferably 5% or less, and more preferably 2% or less.
- the steel structure of the high-strength steel sheet of the present invention may contain other structures such as pearlite and coarse cementite.
- other structures such as pearlite and coarse cementite.
- pearlite or coarse cementite increases in the steel structure of the high-strength steel plate, ductility deteriorates. From this, the total volume fraction of pearlite and coarse cementite contained in the steel sheet structure is preferably 10% or less, more preferably 5% or less.
- the volume fraction of each structure included in the steel sheet structure of the high-strength steel sheet of the present invention can be measured, for example, by the method shown below.
- the volume fraction of retained austenite can be regarded as the volume fraction by performing an X-ray analysis using a plane parallel to the plate surface of the steel sheet and a thickness of 1/4 as an observation surface, and calculating the area fraction. .
- the volume fractions of ferrite, bainitic ferrite, bainite, tempered martensite and fresh martensite were collected by taking a sample with the plate thickness section parallel to the rolling direction of the steel sheet as the observation surface, polishing the observation surface, Etching and observing the range of 1/8 to 3/8 thickness centered on 1/4 of the plate thickness with a field emission scanning electron microscope (FE-SEM: Field Emission Scanning Electron Microscope) Can be regarded as a volume fraction.
- FE-SEM Field Emission Scanning Electron Microscope
- the area of the observation surface observed with the FE-SEM can be a square with a side of 30 ⁇ m, for example, and the structures on each observation surface can be distinguished as shown below.
- Ferrite is a massive crystal grain and is an area where there is no iron-based carbide having a major axis of 100 nm or more.
- the volume fraction of ferrite is the sum of the volume fraction of ferrite remaining at the maximum heating temperature and the ferrite newly generated in the ferrite transformation temperature range.
- Bainitic ferrite is a collection of lath-like crystal grains and does not contain iron-based carbide having a major axis of 20 nm or more in the lath.
- Bainite is a collection of lath-shaped crystal grains, and has a plurality of iron-based carbides having a major axis of 20 nm or more inside the lath, and further, these carbides are a single variant, that is, an iron-based material that extends in the same direction. It belongs to the carbide group.
- the iron-based carbide group extending in the same direction means that the difference in the extension direction of the iron-based carbide group is within 5 °.
- Tempered martensite is an aggregate of lath-like crystal grains, and has a plurality of iron-based carbides having a major axis of 20 nm or more inside the lath, and further, these carbides are a plurality of variants, that is, a plurality of elongated in different directions. It belongs to the iron-based carbide group. Note that bainite and tempered martensite can be easily distinguished by observing the iron-based carbide inside the lath-like crystal grains using FE-SEM and examining the elongation direction.
- C: 0.050 to 0.400% is contained to increase the strength of the high-strength steel plate.
- the C content is preferably 0.350% or less, and more preferably 0.300% or less.
- the C content is less than 0.050%, the strength is lowered, and the maximum tensile strength of 900 MPa or more cannot be ensured.
- the C content is preferably 0.060% or more, and more preferably 0.080% or more.
- Si: 0.10-2.50% Si is added to suppress martensite temper softening and increase the strength of the steel sheet.
- the Si content is preferably 2.20% or less, and more preferably 2.00% or less.
- the Si content is less than 0.10%, the hardness of the tempered martensite is significantly lowered, and the maximum tensile strength of 900 MPa or more cannot be ensured.
- the lower limit value of Si is preferably 0.30% or more, and more preferably 0.50% or more.
- Mn 1.00 to 3.50%
- Mn is an element that increases the strength of the steel sheet, and since the hardness distribution inside the steel sheet can be controlled by controlling the Mn distribution inside the steel sheet, it is added to the steel sheet of the present invention.
- the Mn content exceeds 3.50%, a coarse Mn-concentrated portion is formed at the center of the plate thickness of the steel sheet, and embrittlement is likely to occur, and troubles such as cracking of the cast slab are likely to occur.
- the Mn content exceeds 3.50%, the weldability is also deteriorated. Therefore, the content of Mu needs to be 3.50% or less.
- the Mn content is preferably 3.20% or less, and more preferably 3.00% or less.
- the Mn content is less than 1.00%, a large amount of soft structure is formed during cooling after annealing, so it becomes difficult to ensure the maximum tensile strength of 900 MPa or more. It is necessary to make content of 1.00% or more.
- the Mn content is preferably 1.30% or more, and more preferably 1.50% or more.
- P 0.001 to 0.030%
- P tends to segregate in the central part of the plate thickness of the steel sheet, causing the weld to become brittle.
- the P content exceeds 0.030%, the welded portion is significantly embrittled, so the P content is limited to 0.030% or less.
- the lower limit of the content of P is not particularly defined, the effect of the present invention is exhibited. However, since the content of P is less than 0.001% is accompanied by a significant increase in production cost, 0.001 % Is the lower limit.
- S 0.0001 to 0.0100% S adversely affects weldability and manufacturability during casting and hot rolling. Therefore, the upper limit value of the S content is set to 0.0100% or less. Further, since S is combined with Mn to form coarse MnS to reduce stretch flangeability, the content is preferably 0.0050% or less, and more preferably 0.0025% or less. The lower limit of the content of S is not particularly defined, and the effect of the present invention is exhibited. However, if the content of S is less than 0.0001%, a significant increase in production cost is caused, so 0.0001% Is the lower limit.
- Al: 0.001% to 2.500% is an element that suppresses the formation of iron-based carbides and increases strength. However, if the Al content exceeds 2.50%, the ferrite fraction in the steel sheet is excessively increased and the strength is lowered, so the upper limit of the Al content is 2.500%.
- the Al content is preferably 2.000% or less, and more preferably 1.600% or less.
- the lower limit of the Al content is not particularly defined, and the effect of the present invention is exhibited. However, if the Al content is 0.001% or more, the effect as a deoxidizer is obtained. % Is the lower limit. In order to obtain a sufficient effect as a deoxidizer, the Al content is preferably 0.005% or more, and more preferably 0.010% or more.
- N 0.0001 to 0.0100% N forms coarse nitrides and deteriorates stretch flangeability, so the amount added needs to be suppressed.
- N content exceeds 0.0100%, this tendency becomes remarkable, so the N content range is set to 0.0100% or less. Further, N is better because it causes blowholes during welding.
- the lower limit of the content of N is not particularly defined, and the effect of the present invention is exhibited. However, if the content of N is less than 0.0001%, a significant increase in manufacturing cost is caused, so 0.0001% Is the lower limit.
- O 0.0001-0.0080% Since O forms an oxide and deteriorates stretch flangeability, it is necessary to suppress the addition amount. When the content of O exceeds 0.0080%, the deterioration of stretch flangeability becomes remarkable, so the upper limit of the O content is set to 0.0080% or less.
- the O content is preferably 0.0070% or less, and more preferably 0.0060% or less.
- the lower limit of the content of O is not particularly defined, the effects of the present invention are exhibited. However, if the content of O is less than 0.0001%, a significant increase in manufacturing cost is caused, so 0.0001% Was the lower limit.
- the high-strength steel sheet of the present invention may further contain the following elements as necessary.
- Ti 0.005-0.090%
- Ti is an element that contributes to increasing the strength of the steel sheet by strengthening precipitates, strengthening fine grains by suppressing the growth of ferrite crystal grains, and dislocation strengthening by suppressing recrystallization.
- the Ti content is preferably 0.090% or less.
- the Ti content is more preferably 0.080% or less, and further preferably 0.070% or less.
- the lower limit of the Ti content is not particularly defined, and the effects of the present invention are exhibited.
- the Ti content is preferably 0.005% or more.
- the Ti content is more preferably 0.010% or more, and further preferably 0.015% or more.
- Nb 0.005 to 0.090%
- Nb is an element that contributes to increasing the strength of the steel sheet by strengthening precipitates, strengthening fine grains by suppressing the growth of ferrite crystal grains, and dislocation strengthening by suppressing recrystallization.
- the Nb content is preferably 0.090% or less.
- the Nb content is more preferably 0.070% or less, and further preferably 0.050% or less.
- the lower limit of the Nb content is not particularly defined, and the effects of the present invention are exhibited.
- the Nb content is preferably 0.005% or more.
- the Nb content is more preferably 0.010% or more, and further preferably 0.015% or more.
- V 0.005-0.090%
- V is an element that contributes to increasing the strength of the steel sheet by strengthening precipitates, strengthening fine grains by suppressing the growth of ferrite crystal grains, and dislocation strengthening by suppressing recrystallization.
- the Nb content is preferably 0.090% or less.
- the lower limit of the content of V is not particularly limited, and the effect of the present invention is exhibited.
- the content of V is preferably 0.005% or more.
- B 0.0001 to 0.0100% Since B delays the phase transformation from austenite in the cooling process after hot rolling, the addition of B can effectively promote the distribution of Mn. If the B content exceeds 0.0100%, the hot workability is impaired and the productivity is lowered. Therefore, the B content is preferably 0.0100% or less. From the viewpoint of productivity, the B content is more preferably 0.0050% or less, and further preferably 0.0030% or less. The lower limit of the content of B is not particularly defined, and the effect of the present invention is exhibited. However, in order to sufficiently obtain the effect of delaying the phase transformation due to B, the content of B should be 0.0001% or more. preferable. In order to delay the phase transformation, the B content is more preferably 0.0003% or more, and more preferably 0.0005% or more.
- Mo 0.01-0.80% Since Mo delays the phase transformation from austenite in the cooling process after hot rolling, the distribution of Mn can be effectively advanced by adding Mo. If the Mo content exceeds 0.80%, the hot workability is impaired and the productivity is lowered. Therefore, the Mo content is preferably 0.80% or less. Although the lower limit of the content of Mo is not particularly defined, the effect of the present invention is exhibited. However, in order to sufficiently obtain the effect of delaying the phase transformation by Mo, the content of Mo should be 0.01% or more. preferable.
- Cr, Ni, and Cu are elements that improve the contribution of strength, and one or more of them can be added in place of part of C and / or Si. If the content of each element exceeds 2.00%, the pickling property, weldability, hot workability, etc. may deteriorate, so the content of Cr, Ni and Cu is 2.00% or less respectively. It is preferable that The lower limit of the content of Cr, Ni and Cu is not particularly specified, and the effect of the present invention is exhibited. However, in order to sufficiently obtain the effect of increasing the strength of the steel sheet, the content of Cr, Ni and Cu is set to 0 respectively. 0.01% or more is preferable.
- Total of 0.0001 to 0.5000% of one or more of Ca, Ce, Mg, and REM Ca, Ce, Mg, and REM are effective elements for improving moldability, and one or more of them can be added. However, if the total content of one or more of Ca, Ce, Mg, and REM exceeds 0.5000%, the ductility may be adversely affected, so the total content of each element is 0.5000. % Or less is preferable.
- the lower limit of the content of one or more of Ca, Ce, Mg and REM is not particularly defined, and the effect of the present invention is exhibited, but in order to sufficiently obtain the effect of improving the formability of the steel sheet,
- the total content of each element is preferably 0.0001% or more.
- the total content of one or more of Ca, Ce, Mg and REM is more preferably 0.0005% or more, and further preferably 0.0010% or more.
- REM is an abbreviation for Rare Earth Metal and refers to an element belonging to the lanthanoid series.
- REM and Ce are often added by misch metal and may contain a lanthanoid series element in combination with La and Ce. Even if these lanthanoid series elements other than La and Ce are included as inevitable impurities, the effect of the present invention is exhibited. Even if the metal La or Ce is added, the effect of the present invention is exhibited.
- the high-strength steel plate of the present invention may be a high-strength galvanized steel plate by forming a galvanized layer or an alloyed galvanized layer on the surface. Since the galvanized layer is formed on the surface of the high-strength steel plate, the steel sheet has excellent corrosion resistance. Moreover, since the alloyed galvanized layer is formed on the surface of the high-strength steel plate, it has excellent corrosion resistance and excellent paint adhesion.
- a slab having the above-described chemical component (composition) is cast.
- a slab produced by a continuous casting slab, a thin slab caster or the like can be used.
- the method for producing a high-strength steel sheet of the present invention is compatible with a process such as continuous casting-direct rolling (CC-DR) in which hot rolling is performed immediately after casting.
- the slab heating temperature needs to be 1050 ° C. or higher.
- the finish rolling temperature falls below the Ar3 transformation point, resulting in two-phase rolling of ferrite and austenite, and the hot rolled sheet structure becomes a heterogeneous mixed grain structure, which has undergone cold rolling and annealing processes.
- the heterogeneous structure is not eliminated and the ductility and bendability are poor.
- slab heating temperature shall be 1050 degreeC or more. There is a need to.
- the upper limit of the slab heating temperature is not particularly defined, and the effect of the present invention is exhibited. However, since it is not economically preferable to make the heating temperature excessively high, the upper limit of the slab heating temperature is 1350 ° C. or less. It is desirable.
- Ar 3 901-325 ⁇ C + 33 ⁇ Si-92 ⁇ (Mn + Ni / 2 + Cr / 2 + Cu / 2 + Mo / 2) + 52 ⁇ Al
- C, Si, Mn, Ni, Cr, Cu, Mo, and Al are the content [% by mass] of each element.
- the hot rolling finish rolling temperature has a lower limit of 800 ° C. or a higher Ar 3 point, and an upper limit of 1000 ° C.
- the finish rolling temperature is less than 800 ° C.
- the hot rolling may be a two-phase rolling of ferrite and austenite, and the structure of the hot rolled steel sheet may be a heterogeneous mixed grain structure.
- the upper limit of the finish rolling temperature is not particularly defined, and the effect of the present invention is exhibited.
- the slab heating temperature must be excessively high in order to secure the temperature. I must.
- the upper limit temperature of the finish rolling temperature is desirably 1000 ° C. or less.
- Mn distribution of the steel sheet can be obtained by diffusing Mn from ferrite to austenite by treating the microstructure during slow cooling after winding as a two-phase structure of ferrite and austenite and treating at a high temperature for a long time.
- the volume fraction of austenite is from 1/8 to 3/8 thickness when the steel sheet is wound. It needs to be 50% or more. When the volume fraction of austenite in the thickness of 1/8 to 3/8 is less than 50%, the austenite disappears immediately after winding due to the progress of phase transformation. Mn concentration distribution cannot be obtained.
- the volume fraction of austenite is preferably 70% or more, and more preferably 80% or more. On the other hand, even if the volume fraction of austenite is 100%, phase transformation proceeds after winding, ferrite is generated, and distribution of Mn starts. Therefore, there is no upper limit on the volume fraction of austenite.
- the cooling rate from completion of hot rolling to winding is required to be 10 ° C./second or more on average.
- the cooling rate is less than 10 ° C./second, ferrite transformation proceeds during cooling, and the volume fraction of austenite during winding may be less than 50%.
- the cooling rate is preferably 13 ° C./second or more, and more preferably 15 ° C./second or more.
- the upper limit of the cooling rate is not particularly defined, and the effect of the present invention is exhibited.
- special equipment is required to make the cooling rate higher than 200 ° C./second, and the manufacturing cost increases remarkably. It is preferable to set it to less than second.
- the winding temperature is 750 ° C. or lower.
- the winding temperature is preferably 720 ° C. or less, and more preferably 700 ° C. or less.
- the winding temperature is set to the Bs point or higher.
- the winding temperature is preferably 500 ° C. or higher, more preferably 550 ° C. or higher, and further preferably 600 ° C. or higher.
- a small piece is cut out from the slab before hot rolling.
- the small piece is rolled or compressed at the same temperature and reduction rate as the final pass of hot rolling, cooled at the same cooling rate from hot rolling to winding and immediately cooled with water, and then the phase fraction of the small piece is measured.
- the sum of the volume fractions of martensite, tempered martensite and retained austenite as quenched was taken as the volume fraction of austenite at the time of winding.
- the cooling process of the steel sheet after winding is important for controlling the distribution of Mn.
- the austenite fraction at the time of winding is set to 50% or more, and the following formula (3) is satisfied and the temperature from the winding temperature to (winding temperature ⁇ 100) ° C. is cooled at a rate of 20 ° C./hour or less.
- the inventive Mn distribution is obtained.
- Equation (3) is an index representing the progress of the distribution of Mn between ferrite and austenite.
- the larger the value on the left side the more the distribution of Mn proceeds.
- the value on the left side is preferably 2.5 or more, and more preferably 4.0 or more.
- the upper limit of the value on the left side is not particularly defined, and the effect of the present invention is exhibited. However, in order to increase the value above 50.0, heat retention for a long time is required, and the manufacturing cost increases significantly. It is preferably 0 or less.
- T C Winding temperature (° C.)
- T Steel plate temperature (° C.)
- T Residence time at temperature T (seconds)
- the cooling rate from the coiling temperature to (coiling temperature ⁇ 100) ° C. exceeds 20 ° C./hour, the phase transformation proceeds excessively and austenite in the steel sheet can disappear, so
- the cooling rate to a temperature of ⁇ 100) ° C. is set to 20 ° C./hour or less.
- the cooling rate from the coiling temperature to (coiling temperature ⁇ 100) ° C. is preferably 17 ° C./hour or less, and more preferably 15 ° C./hour or less.
- the lower limit of the cooling rate is not particularly defined, and the effect of the present invention is exhibited.
- heat retention for a long time is required, and the manufacturing cost is remarkably increased. It is preferable to set it as °C / hour or more.
- the hot-rolled steel sheet thus manufactured is pickled. Since pickling can remove oxides on the surface of steel sheets, it can improve the chemical conversion properties of cold-rolled high-strength steel sheets as final products, and improve the hot-plating properties of cold-rolled steel sheets for hot-dip galvanized or galvannealed steel sheets. It is important for that. Moreover, pickling may be performed once or may be performed in a plurality of times.
- the pickled hot-rolled steel sheet is cold-rolled at a reduction rate of 35 to 80% and passed through a continuous annealing line or a continuous hot dip galvanizing line.
- the rolling reduction is preferably 40% or more, and more preferably 45% or more.
- the rolling reduction is 80% or less.
- the rolling reduction is preferably 75% or less.
- the effect of the present invention is exhibited without particularly defining the number of rolling passes and the rolling reduction for each pass. Further, cold rolling may be omitted.
- FIG. 5 is a graph for explaining the temperature history of the cold-rolled steel sheet when passing through the continuous annealing line, and is a graph showing the relationship between the temperature of the cold-rolled steel sheet and time.
- the “ferrite transformation temperature range” shows the range from (Ae3 ⁇ 50 ° C.) to Bs point
- the “bainite transformation temperature range” shows the range from Bs point to Ms point
- “Temperature range” indicates Ms point to room temperature.
- the Bs point is calculated by the following formula.
- Bs point [° C.] 820-290C / (1-VF) -37Si-90Mn-65Cr-50Ni + 70Al
- VF represents the volume fraction of ferrite
- C, Mn, Cr, Ni, Al, and Si are addition amounts [mass%] of the respective elements.
- Ms point [° C.] 541-474C / (1-VF) -15Si-35Mn-17Cr-17Ni + 19Al
- VF represents the volume fraction of ferrite
- C, Si, Mn, Cr, Ni, and Al are addition amounts [mass%] of the respective elements.
- a small piece of cold-rolled steel sheet before passing through a continuous annealing line is cut out, The change in volume of the ferrite of the small piece is measured by annealing with the same temperature history as when passing the small piece through the continuous annealing line, and the numerical value calculated using the result is used as the volume fraction VF of the ferrite.
- a heating process is performed in which annealing is performed at a maximum heating temperature (T 1 ) of 750 ° C. to 1000 ° C.
- T 1 maximum heating temperature
- the amount of austenite becomes insufficient at the maximum heating temperature T 1 is lower than 750 ° C. in the heating step can not be secured a sufficient amount of the hard tissue phase transformation during the subsequent cooling.
- the maximum heating temperature T 1 of is preferably set to 770 ° C. or higher.
- the maximum heating temperature T 1 of this point is preferably set to 900 ° C. or less.
- a first cooling step of cooling the cold-rolled steel sheet from the maximum heating temperature T 1 of up to less ferrite transformation temperature range is held for 20 seconds to 1000 seconds in the ferrite transformation temperature range.
- it is necessary to stop in the ferrite transformation temperature range for 20 seconds or longer in the first cooling step preferably 30 seconds or longer, and more preferably 50 seconds or longer. preferable.
- the time for retaining in the ferrite transformation temperature range exceeds 1000 seconds, the ferrite transformation proceeds excessively and untransformed austenite is reduced, so that a sufficient hard structure cannot be obtained.
- the cold-rolled steel sheet after the ferrite transformation is stopped for 20 seconds to 1000 seconds in the ferrite transformation temperature range in the first cooling step is cooled at the second cooling rate, and the Ms point (martense)
- the second cooling step is performed to stop the temperature within the range of the Ms point of ⁇ 120 ° C. or higher.
- the second cooling stop temperature T 2 for stopping the second cooling step is more than Ms point, it does not produce martensite.
- the second cooling stop temperature T 2 is less than the Ms point of ⁇ 120 ° C., most of the untransformed austenite becomes martensite, and a sufficient amount of bainite cannot be obtained in the subsequent steps.
- the second cooling process stop temperature T 2 is preferably Ms point ⁇ 80 ° C. or higher, and more preferably Ms point ⁇ 60 ° C. or higher.
- the bainite transformation is a temperature range between the ferrite transformation temperature range and the martensitic transformation temperature range. It is preferable to prevent the bainite transformation from proceeding excessively in the temperature range. For this reason, the second cooling rate in the bainite transformation temperature region needs to be 10 ° C./second or more on average, preferably 20 ° C./second or more, and more preferably 50 ° C./second or more.
- the second cooling stop is performed below the Ms point in order to further advance the martensitic transformation.
- a dwell process is carried out in which the dwell is carried out for 2 seconds to 1000 seconds within a temperature range. In the stopping process, it is necessary to stop for 2 seconds or more in order to sufficiently advance the martensitic transformation.
- the retention time in the retention step exceeds 1000 seconds, hard lower bainite is generated, untransformed austenite is reduced, and bainite having a hardness close to ferrite cannot be obtained.
- the reheating process which reheats a steel plate is performed.
- the temperature T 3 (reheating stop temperature) at which reheating is stopped in the reheating step is set so that the dispersion of hardness distribution in the steel sheet is small, so that the Bs point (bainite transformation start temperature (the upper limit of the bainite transformation temperature range) Value)) -100 ° C or higher.
- the reheating stop temperature T 3 is preferably set to a Bs point of ⁇ 60 ° C. or higher, and more preferably set to a Bs point or higher as shown in FIG.
- the heating rate in the bainite transformation temperature range needs to be 10 ° C./second or more on average, preferably 20 ° C./second or more, and more preferably 40 ° C./second or more. If the heating rate in the bainite transformation temperature range in the reheating process is small, the bainite transformation will proceed excessively in the low temperature range, so that hard bainite with a large hardness difference from ferrite is likely to be produced, and in the steel sheet It is difficult to produce ferrite that can reduce variation in hardness distribution and soft bainite having a small hardness difference. Therefore, in the reheating step, it is preferable that the rate of temperature increase in the bainite transformation temperature range is large.
- the time for stopping in the bainite transformation temperature region in the second cooling step and the bainite transformation region in the reheating step is 25 seconds or less, and more preferably 20 seconds or less.
- a third step of cooling the steel plate from the re-heating stop temperature T 3 to below the bainite transformation temperature range performed.
- the 3rd cooling process in order to advance bainite transformation, it is made to stop for 30 seconds or more in a bainite transformation temperature range.
- the bainite transformation temperature region is retained for 60 seconds or longer in the third cooling step, and 120 seconds or longer is more preferable.
- there is no particular upper limit for the time of retention in the bainite transformation temperature range but it is preferably 2000 seconds or less, and more preferably 1000 seconds or less.
- the time for retaining in the bainite transformation temperature range is 2000 seconds or less, it becomes possible to cool to room temperature before the bainite transformation of untransformed austenite is completed, and the untransformed austenite becomes martensite or retained austenite. Thereby, the yield stress and ductility of a high-strength cold-rolled steel sheet can be further improved.
- the 4th cooling process which cools a steel plate from the temperature below a bainite transformation temperature range to room temperature is performed after a 3rd cooling process.
- the cooling rate in the fourth cooling step is not particularly defined, it is preferable to set the average cooling rate to 1 ° C./second or more in order to make untransformed austenite martensite or retained austenite.
- the re-heating stop temperature T 3 in the reheating step was 460 ° C. ⁇ 600 ° C.
- the cold-rolled steel sheet after immersion in a zinc plating bath by performing alloying treatment to stop for more than 2 seconds reheating stop temperature T 3, a plating layer on the surface it may be alloyed.
- a Zn—Fe alloy formed by alloying the zinc plating layer is formed on the surface, and a high-strength galvanized steel sheet having the alloyed zinc plating layer on the surface is obtained.
- strength galvanized steel plate is not limited to said example, For example, in the bainite transformation temperature range of a 3rd cooling process, except having immersed a steel plate in a galvanization bath, it mentioned above. You may manufacture a high intensity
- the cold-rolled steel sheet after being immersed in the galvanizing bath is heated again to 460 ° C. to 600 ° C. and retained for 2 seconds or longer.
- the plating layer on the surface may be alloyed by applying an alloying treatment. Even when such an alloying treatment is performed, a Zn-Fe alloy formed by alloying the zinc plating layer is formed on the surface, and a high-strength galvanized steel sheet having the alloyed zinc plating layer on the surface is obtained. .
- the annealed cold-rolled steel sheet may be rolled for the purpose of shape correction.
- the rolling rate after annealing exceeds 10%, the soft ferrite part is work-hardened and the ductility is significantly deteriorated. Therefore, the rolling rate is preferably less than 10%.
- the present invention is not limited to the above example.
- the steel sheet before annealing is plated with one or more kinds selected from Ni, Cu, Co, and Fe. May be.
- a first cooling step for cooling the cold-rolled steel plate, a second cooling step for cooling the cold-rolled steel plate after the first cooling step, a holding step for holding the cold-rolled steel plate after the second cooling step, and a post-holding step A reheating step of reheating the cold-rolled steel sheet to the reheating stop temperature, and a step of cooling the cold-rolled steel sheet after the reheating step from the reheating stop temperature to less than the bainite transformation temperature range, in the bainite transformation temperature range.
- a third cooling step for retaining for 30 seconds or more and a fourth cooling step for cooling the steel sheet from a temperature below the bainite transformation temperature range to room temperature were performed.
- a liquid circulation type electroplating apparatus is used for the steel sheet after the pretreatment, and a plating bath made of zinc sulfate, sodium sulfate, and sulfuric acid is used until a predetermined plating thickness is obtained at a current density of 100 A / dm 2. Electrolytic treatment was performed and Zn plating was performed.
- the cold rolled steel sheets of Experimental Examples 64 to 68 when passing through the continuous annealing line, in the reheating process, the cold rolled steel sheets were immersed in a galvanizing bath to obtain high strength galvanized steel sheets.
- the cold rolled steel sheets of Experimental Example 69 to Experimental Example 73 the cold rolled steel sheets after being immersed in the galvanizing bath in the reheating step are shown in Table 12 as “reheating stop temperature T 3 ” shown in Table 11.
- the surface plating layer was alloyed to obtain a high-strength galvanized steel sheet having the alloyed galvanized layer.
- the cold rolled steel sheets of Experimental Examples 74 to 77 when passing through the continuous annealing line, in the third cooling step, the cold rolled steel sheets were immersed in a galvanizing bath to obtain high strength galvanized steel sheets.
- the cold rolled steel sheets of Experimental Example 78 to Experimental Example 82 the cold rolled steel sheet after being immersed in the galvanizing bath in the third cooling step was reheated to the “alloying temperature Tg” shown in Table 12, By applying an alloying treatment for retaining at the “residence time” shown in FIG. 12, the surface plating layer was alloyed to obtain a high-strength galvanized steel sheet having the alloyed galvanized layer.
- the volume fraction of ferrite, bainitic ferrite, bainite, tempered martensite, and fresh martensite is obtained by taking a sample with the thickness cross section parallel to the rolling direction of the steel sheet as the observation surface, polishing the observation surface, and performing nital etching. In the 1 / 8th to 3 / 8th thickness centered on 1/4 of the plate thickness, set an area with a side of 30 ⁇ m, and observe the area fraction by FE-SEM. Rate. The results are shown in Tables 13, 14, 17, 26 and 32, respectively.
- the plate thickness section parallel to the rolling direction of the steel plate is finished to be a mirror surface, and EPMA in the range of 1/8 to 3/8 centering on 1/4 of the plate thickness.
- Analysis was performed and the amount of Mn was measured. The measurement was performed with a probe diameter of 0.5 ⁇ m and a measurement time per point of 20 ms, and the amount of Mn was measured at 40,000 points by surface analysis. The results are shown in Tables 15, 16, 18, 27, 28 and 33. After removing the inclusion measurement results from the measurement results, the maximum value and the minimum value of the Mn concentration were determined, and the difference between the maximum value and the minimum value of the calculated Mn concentration was calculated. The results are shown in Tables 15, 16, 18, 27, 28, and 33, respectively.
- the hardness was measured at an indentation load of 1 g using an indentation depth measurement method using a dynamic microhardness meter equipped with a Belkovic type triangular pan indenter.
- the measurement position of the hardness was in the range of 1/8 to 3/8, centering on 1/4 of the plate thickness in the plate thickness section parallel to the rolling direction of the steel plate.
- the number of measured values was in the range of 100 to 10,000, preferably 1000 or more.
- the average crystal grain size was measured by using an EBSD (Electric Backscattering Diffraction) method.
- the observation surface of the crystal grain size was in the range of 1/8 to 3/8, centering on 1/4 of the plate thickness in the plate thickness section parallel to the rolling direction of the steel plate.
- the crystal grain size was measured by regarding the boundary line where the crystal orientation difference between the measurement points adjacent to the bcc crystal orientation on the observation surface was 15 degrees or more as the crystal grain boundary.
- the average crystal grain size was calculated by applying a cutting method to the obtained result (map) of the grain boundary. The results are shown in Tables 13, 14, 17, 26 and 32, respectively.
- tensile test pieces according to JIS Z 2201 were taken from the high-strength steel plates of Experimental Examples 1 to 134, and a tensile test was performed according to JIS Z 2241. Maximum tensile strength (TS) and ductility (EL). was measured. The results are shown in Tables 15, 16, 18, 27, 28 and 33.
- the measured value of 98% hardness is 1.5 times or more the measured value of 2% hardness, and 2%
- the kurtosis (K *) between the measured value of hardness and the measured value of 98% hardness is ⁇ 0.40 or less
- the average crystal grain size is 10 ⁇ m or less
- the maximum tensile strength (TS) is 10 ⁇ m or less
- TS maximum tensile strength
- ⁇ stretch flangeability
- Experimental Example 39 is an example in which the average cooling rate in the bainite transformation temperature range is small in the second cooling step, and the bainite transformation proceeds excessively in the same step. In Experimental Example 39, there was no tempered martensite, so the tensile strength TS was insufficient.
- the high-strength steel sheet of the present invention has a predetermined chemical component, 98% hardness is 1.5 times or more of 2% hardness, and the kurtosis K * of the hardness distribution between 2% hardness and 98% hardness is Since it is ⁇ 0.40 or less and the average crystal grain size in the steel sheet structure is 10 ⁇ m or less, the steel sheet is excellent in ductility and stretch flangeability while ensuring high strength with a tensile strength of 900 MPa or more. Therefore, the industrial contribution of the present invention is extremely remarkable, such as ensuring the strength of the steel sheet without impairing workability.
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Abstract
Description
本願は、2010年9月16日に、日本に出願された特願2010-208329号及び特願2010-208330号に基づき優先権を主張し、その内容をここに援用する。
通常、鋼板の強度を向上させると、延性や伸びフランジ性が低下して、加工性が劣化する。しかしながら、近年、高強度鋼板においても十分な加工性を有することが要求されている。
本発明は、このような事情に鑑みてなされたものであって、引張最大強度900MPa以上の高強度を確保しながら、優れた延性と伸びフランジ性が得られる加工性に優れた高強度鋼板およびその製造方法を提供することを課題とするものである。
C:0.05~0.4%、
Si:0.1~2.5%、
Mn:1.0~3.5%、
P:0.001~0.03%、
S:0.0001~0.01%、
Al:0.001~2.5%、
N:0.0001~0.01%、
O:0.0001~0.008%、
を含有し、残部が鉄および不可避的不純物からなる鋼であり、
鋼板組織が、体積分率で10~50%のフェライト相と、10~50%の焼戻しマルテンサイト相と、残部硬質相とからなり、
鋼板の1/8厚~3/8厚の範囲において、直径1μm以下の測定領域を複数設定して、前記複数の測定領域における硬度の測定値を小さい順に並べて硬度分布を得るとともに、硬度の測定値の全数に0.02を乗じた数であって該数が小数を含む場合はこれを切り上げて得た整数N0.02を求め、最小硬度の測定値からN0.02番目に大きな測定値の硬度を2%硬度とし、また、硬度の測定値の全数に0.98を乗じた数であって該数が小数を含む場合はこれを切り下げて得た整数N0.98を求め、最小硬度の測定値からN0.98番目に大きな測定値の硬度を98%硬度としたとき、前記98%硬度が前記2%硬度の1.5倍以上であり、前記2%硬度と前記98%硬度の間における前記硬度分布の尖度K*が-1.2以上、-0.4以下であり、前記鋼板組織における平均結晶粒径が10μm以下であることを特徴とする延性と伸びフランジ性に優れた高強度鋼板。
[2] 鋼板の1/8厚~3/8厚における地鉄中のMn濃度の最大値と最小値の差が質量%に換算して0.4%以上3.5%以下であることを特徴とする[1]に記載の延性と伸びフランジ性に優れた高強度鋼板。
[3] 前記2%硬度から98%硬度までの区間を10等分して10個の1/10区間を設定したとき、各1/10区間における硬度の測定値の数が、全測定値の数の2~30%の範囲にあることを特徴とする[1]または[2]に記載の延性と伸びフランジ性に優れた高強度鋼板。
[4] 前記硬質相が、体積分率で10~45%のベイニティックフェライト相若しくはベイナイト相のいずれか一方または両方と、10%以下のフレッシュマルテンサイト相であることを特徴とする[1]乃至[3]の何れか一項に記載の延性と伸びフランジ性に優れた高強度鋼板。
[5] 鋼板組織として、さらに、2~25%の残留オーステナイト相を含有することを特徴とする[1]乃至[4]の何れか一項に記載の延性と伸びフランジ性に優れた高強度鋼板。
[6] さらに、質量%で、
Ti:0.005~0.09%、
Nb:0.005~0.09%の1種または2種以上を含有することを特徴とする[1]乃至[5]の何れか一項に記載の延性と伸びフランジ性に優れた高強度鋼板。
[7] さらに、質量%で、
B:0.0001~0.01%、
Cr:0.01~2.0%、
Ni:0.01~2.0%、
Cu:0.01~2.0%、
Mo:0.01~0.8%の1種または2種以上を含有することを特徴とする[1]乃至[6]の何れか一項に記載の延性と伸びフランジ性に優れた高強度鋼板。
[8] さらに、質量%で、
V:0.005~0.09%含有することを特徴とする[1]乃至[7]の何れか一項に記載の延性と伸びフランジ性に優れた高強度鋼板。
[9] さらに、質量%で、
Ca、Ce、Mg、REMの1種または2種以上を合計で0.0001~0.5%含有することを特徴とする[1]乃至[8]の何れか一項に記載の延性と伸びフランジ性に優れた高強度鋼板。
[10] [1]乃至[9]の何れか一項に記載の高強度鋼板の表面に亜鉛めっき層が形成されてなることを特徴とする延性と伸びフランジ性に優れた高強度亜鉛めっき鋼板。
[11] [1]または[6]~[9]のいずれか1項に記載の化学成分を有するスラブを、直接又は一旦冷却した後1050℃以上に加熱し、800℃またはAr3変態点の何れか高い温度以上で熱間圧延し、圧延後の圧延材の組織中のオーステナイト相が50体積%以上となるように750℃以下の温度域にて巻き取る熱間圧延工程と、
前記熱間圧延後の鋼板を、下記(1)式を満たしつつ巻き取り温度から(巻き取り温度-100)℃までを20℃/時以下の速度で冷却する冷却工程と、
前記冷却後の鋼板を連続焼鈍する工程と、を備え、
前記連続焼鈍する工程は、
前記鋼板を最高加熱温度750~1000℃で焼鈍し、
次いで、前記最高加熱温度からフェライト変態温度域以下まで冷却するとともにフェライト変態温度域で20~1000秒停留させる第1次冷却を行い、
次いで、ベイナイト変態温度域における冷却速度を平均10℃/秒以上として冷却し、マルテンサイト変態開始温度以下、マルテンサイト変態開始温度-120℃以上の範囲で停止する第2次冷却を行い、
次いで、第2次冷却後の鋼板を、マルテンサイト変態開始温度以下、第2冷却停止温度以上の範囲で2秒~1000秒停留し、
次いで、ベイナイト変態温度域における昇温速度を平均10℃/sec以上として、ベイナイト変態開始温度-100℃以上の再加熱停止温度に再加熱し、
次いで、前記再加熱後の鋼板を、前記再加熱停止温度からベイナイト変態温度域未満まで冷却するとともにベイナイト変態温度域で30秒以上停留させる第3冷却を行う
工程であることを特徴とする延性と伸びフランジ性に優れた高強度鋼板の製造方法。
[12] 前記熱間圧延後の巻き取り温度をBs点以上750℃以下とすることを特徴とする[11]に記載の延性と伸びフランジ性に優れた高強度鋼板の製造方法。
[13] 前記冷却工程と前記連続焼鈍工程との間に、酸洗してから圧下率35~80%の圧下率で冷延する冷延工程を備えたことを特徴とする[11]または[12]に記載の延性と伸びフランジ性に優れた高強度鋼板の製造方法。
[14] 前記第2次冷却におけるベイナイト変態温度域に停留する時間と、前記再加熱におけるベイナイト変態域に停留する時間との合計が、25秒以下であることを特徴とする[11]乃至[13]の何れか一項に記載の延性と伸びフランジ性に優れた高強度鋼板の製造方法。
[15] [11]乃至[14]の何れか一項に記載の製造方法で高強度鋼板を製造する際の前記再加熱において、前記鋼板を亜鉛めっき浴に浸漬することを特徴とする延性と伸びフランジ性に優れた高強度亜鉛めっき鋼板の製造方法。
[16] [11]乃至[14]の何れか一項に記載の製造方法で高強度鋼板を製造する際の前記第3次冷却のベイナイト変態温度域において、前記鋼板を亜鉛めっき浴に浸漬することを特徴とする延性と伸びフランジ性に優れた高強度亜鉛めっき鋼板の製造方法。
[17] [11]乃至[14]の何れか一項に記載の製造方法で高強度鋼板を製造した後、亜鉛電気めっきを施すことを特徴とする高強度亜鉛めっき鋼板の製造方法。
[18] [11]乃至[14]の何れか一項に記載の製造方法で高強度鋼板を製造した後、溶融亜鉛めっきを施すことを特徴とする高強度亜鉛めっき鋼板の製造方法。
そして、Mn分布を大きくさせた鋼板を連続焼鈍する工程が、最高加熱温度750~1000℃で焼鈍する加熱工程と、最高加熱温度からフェライト変態温度域以下まで鋼板を冷却する工程であって、フェライト変態温度域で20~1000秒停留させる第1冷却工程と、第1冷却工程後の鋼板を、ベイナイト変態温度域における冷却速度を平均10℃/秒以上として冷却し、マルテンサイト変態開始温度以下、マルテンサイト変態開始温度-120℃以上の範囲で停止する第2冷却工程と、第2冷却工程後の鋼板を、Ms点以下、第2冷却停止温度以上の範囲で2秒~1000秒停留させる停留工程と、停留工程後の鋼板を、ベイナイト変態温度域における昇温速度を平均10℃/秒以上として、ベイナイト変態開始温度-80℃以上の再加熱停止温度に再加熱する再加熱工程と、再加熱工程後の鋼板を、再加熱停止温度からベイナイト変態温度域未満まで冷却する工程であって、ベイナイト変態温度域で30秒以上停留させる第3冷却工程とから構成されるので、鋼板組織が制御されて、鋼板内部の硬度差が大きく、平均結晶粒径が十分に小さいものとなり、引張最大強度900MPa以上の高強度を確保でき、かつ、優れた延性と伸びフランジ性(穴拡げ性)を有する加工性に優れた高強度冷延鋼板が得られる。
更に、亜鉛めっき層を形成する工程を追加することで、引張最大強度900MPa以上の高強度を確保でき、かつ、優れた延性と伸びフランジ性(穴拡げ性)を有する加工性に優れた高強度亜鉛めっき鋼板が得られる。
以下、硬度の規定について説明するが、まず、2%硬度及び98%硬度について説明する。鋼板の1/8厚~3/8厚の範囲に設定された複数の測定領域において硬度の測定値を求め、硬度の測定値の全個数に0.02を乗じた数であって該数が小数を含む場合はこれを切り上げて得た整数N0.02を求める。また、硬度の測定値の全個数に0.98を乗じた数であって該数が小数を含む場合はこれを切り下げて得た整数N0.98を求める。そして、複数の測定領域における最小硬度の測定値からN0.02番目に大きな測定値の硬度を2%硬度とする。また、複数の測定領域における最小硬度の測定値からN0.98番目に大きな測定値の硬度を98%硬度とする。そして、本発明の高強度鋼板では、98%硬度が2%硬度の1.5倍以上であり、2%硬度と98%硬度の間における前記硬度分布の尖度K*が-0.40以下であることが好ましい。
H*:最小硬度からN0.02番目に大きな測定点からN0.98番目に大きな測定点までの平均硬度
s*:最小硬度からN0.02番目に大きな測定点からN0.98番目に大きな測定点までの標準偏差
本発明の高強度鋼板は、上述の硬度分布を得るために、鋼板の1/8厚~3/8厚における地鉄中のMn濃度の最大値と最小値の差が質量%に換算して0.40%以上3.50%以下であることが好ましい。
以上の現象は、フェライト相のみならず、焼き戻しマルテンサイト相及び残部硬質相においても同様である。
測定結果のうち、Mn濃度が添加Mn濃度の3倍を超える点はMn硫化物などの介在物を測定した点と考えられる。また、Mn濃度が添加Mn濃度の1/3倍未満の点は、Al酸化物などの介在物を測定した点と考えられる。これら介在物中のMn濃度は、地鉄中の相変態挙動にほとんど影響しないため、測定結果から介在物の測定結果を除いた上で、Mn濃度の最大値と最小値をそれぞれ求める。そして、求めたMn濃度の最大値と最小値の差を算出する。
Mn量の測定方法は上記の手法に限らない。例えばEMA法や三次元アトムプローブ(3D-AP)を用いた直接観察を行って、Mn濃度を測定しても良い。
また、本発明の高強度鋼板の鋼板組織は、体積分率で10~50%のフェライト相と、10~50%の焼戻しマルテンサイト相と、残部硬質相とからなる。また、残部硬質相には、体積分率で10~60%のベイニティックフェライト相あるいはベイナイト相の何れか一方または両方と、10%以下のフレッシュマルテンサイト相が含まれる。更に、鋼板組織として、2~25%の残留オーステナイト相を含有していてもよい。本発明の高強度鋼板がこのような鋼板組織を有するものである場合、鋼板内部の硬度差がより一層大きく、かつ、平均結晶粒径が十分に小さいものとなり、より一層、高強度で、優れた延性と伸びフランジ性(穴拡げ性)を有するものとなる。
フェライトは、延性の向上に有効な組織であり、鋼板組織に体積分率で10~50%含まれていることが好ましい。鋼板組織に含まれるフェライトの体積分率は、延性の観点から15%以上含まれることがより好ましく、20%以上含まれることがさらに好ましい。また、鋼板の引張強度を十分高めるには、鋼板組織に含まれるフェライトの体積分率を45%以下とすることが好ましく、40%以下とすることがさらに好ましい。フェライトの体積分率が10%未満である場合、十分な延性が得られない恐れがある。一方、フェライトは軟質な組織であるため、体積分率が50%を超えると降伏応力が低下する場合がある。
ベイニティックフェライトとベイナイトは、軟質なフェライトと硬質な焼戻しマルテンサイトおよびフレッシュマルテンサイトとの間の硬度を持つ組織である。本発明の高強度鋼板では、ベイニティックフェライトまたはベイナイトの何れか一方が含まれていればよく、両方が含まれていても良い。鋼板内部の硬さ分布を平坦にするにはベイニティックフェライト及びベイナイトの合計量が鋼板組織に体積分率で10~45%含まれていることが好ましい。鋼板組織に含まれるベイニティックフェライトおよびベイナイトの体積分率の合計は、伸びフランジ性の観点から15%以上含まれることがより好ましく、20%以上含まれることがさらに好ましい。また、延性と降伏応力のバランスを良好にするために、ベイニティックフェライトおよびベイナイトの体積分率の合計を40%以下、好ましくは35%以下にするとよりよい。
焼戻しマルテンサイトは、引張強度を大きく向上させる組織であり、鋼板組織に体積分率で10~50%含まれていることが好ましい。鋼板組織に含まれる焼戻しマルテンサイトの体積分率が、10%未満であると、十分な引張強度が得られない恐れがある。一方、鋼板組織に含まれる焼戻しマルテンサイトの体積分率が50%を超えると、延性の向上に必要なフェライトおよび残留オーステナイトを確保することが困難となる。高強度鋼板の延性を十分に高めるには、焼戻しマルテンサイトの体積分率を45%以下とすることがより好ましく、40%以下とすることが更に好ましい。また、引張強度を確保するためには、焼戻しマルテンサイトの体積分率を15%以上とすることがより好ましく、20%以上とすることが更に好ましい。
残留オーステナイトは延性の向上に有効な組織であり、鋼板組織に体積分率で2~25%含まれていることが好ましい。鋼板組織に含まれる残留オーステナイトの体積分率が2%以上であれば、より十分な延性が得られる。また、残留オーステナイトの体積分率が25%以下であれば、CやMnに代表されるオーステナイト安定化元素を多量に添加する必要がなく、溶接性が向上する。なお、本発明の高強度鋼板の鋼板組織には、残留オーステナイトが含まれていることが、延性の向上に有効であるため好ましいが、十分な延性が得られる場合には、残留オーステナイトが含まれていなくてもよい。
フレッシュマルテンサイトは、引張強度を大きく向上させるが、一方で破壊の起点となって伸びフランジ性を劣化させるため、鋼板組織に体積分率で10%以下含まれていることが好ましい。伸びフランジ性を高めるにはフレッシュマルテンサイトの体積分率を5%以下とすることがより好ましく、2%以下とすることが更に好ましい。
本発明の高強度鋼板の鋼板組織には、パーライトや粗大なセメンタイトなどの上記以外の組織が含まれていてもよい。しかし、高強度鋼板の鋼板組織中にパーライトや粗大なセメンタイトが多くなると、延性が劣化する。このことから、鋼板組織に含まれるパーライトおよび粗大なセメンタイトの体積分率は、合計で10%以下であることが好ましく、5%以下であることがより好ましい。
また、ベイナイトは、ラス状の結晶粒の集合であり、ラスの内部に長径20nm以上の鉄系炭化物を複数有し、さらにそれらの炭化物が単一のバリアント、すなわち同一の方向に伸張した鉄系炭化物群に属するものである。ここで、同一の方向に伸長した鉄系炭化物群とは、鉄系炭化物群の伸長方向の差異が5°以内であるものを意味している。
なお、FE-SEMを用いてラス状結晶粒内部の鉄系炭化物を観察し、その伸長方向を調べることによって、ベイナイトと焼戻しマルテンサイトは容易に区別しうる。
したがって、フレッシュマルテンサイトの体積分率は、FE-SEMにて観察された腐食されていない領域の面積分率と、X線によって測定した残留オーステナイトの面積分率との差分として求められる。
次に、本発明の高強度鋼板の化学成分(組成)について説明する。なお、以下の説明における[%]は[質量%]である。
Cは、高強度鋼板の強度を高めるために含有される。しかし、Cの含有量が0.400%を超えると溶接性が不十分となる。溶接性の観点から、Cの含有量は0.350%以下であることが好ましく、0.300%以下であることがより好ましい。一方、Cの含有量が0.050%未満であると強度が低下し、900MPa以上の引張最大強度を確保することが出来ない。強度を高めるため、Cの含有量は0.060%以上であることが好ましく、0.080%以上であることがより好ましい。
Siは、マルテンサイトの焼戻し軟化を抑制し、鋼板を高強度化するために添加される。しかし、Siの含有量が2.50%を超えると鋼板が脆化し、延性が劣化する。延性の観点から、Siの含有量は2.20%以下であることが好ましく、2.00%以下であることがより好ましい。一方、Siの含有量が0.10%未満では焼戻しマルテンサイトの硬さが大幅に低下し、900MPa以上の引張最大強度を確保することが出来ない。強度を高めるため、Siの下限値は0.30%以上であることが好ましく、0.50%以上がより好ましい。
Mnは鋼板の強度を高める元素であり、鋼板内部のMn分布を制御することで鋼板内部の硬度分布を制御することができることから、本発明の鋼板に添加される。しかし、Mnの含有量が3.50%を超えると鋼板の板厚中央部に粗大なMn濃化部が生じ、脆化が起こりやすくなり、鋳造したスラブが割れるなどのトラブルが起こりやすい。また、Mnの含有量が3.50%を超えると溶接性も劣化する。したがって、Muの含有量は、3.50%以下とする必要がある。溶接性の観点から、Mnの含有量は3.20%以下であることが好ましく、3.00%以下であることがより好ましい。一方、Mnの含有量が1.00%未満であると、焼鈍後の冷却中に軟質な組織が多量に形成されてしまうため、900MPa以上の引張最大強度を確保することが難しくなるため、Mnの含有量を1.00%以上とする必要がある。強度を高めるため、Mnの含有量は1.30%以上であることが好ましく、1.50%以上であることがより好ましい。
Pは鋼板の板厚中央部に偏析する傾向があり、溶接部を脆化させる。Pの含有量が0.030%を超えると溶接部が大幅に脆化するため、Pの含有量を0.030%以下に限定した。Pの含有量の下限は、特に定めることなく本発明の効果は発揮されるが、Pの含有量を0.001%未満とすることは製造コストの大幅な増加を伴うことから、0.001%を下限値とする。
Sは、溶接性ならびに鋳造時および熱延時の製造性に悪影響を及ぼす。このことから、Sの含有量の上限値を0.0100%以下とした。また、SはMnと結びついて粗大なMnSを形成して伸びフランジ性を低下させるため、0.0050%以下とすることが好ましく、0.0025%以下とすることがより好ましい。Sの含有量の下限は、特に定めることなく本発明の効果は発揮されるが、Sの含有量を0.0001%未満とすることは製造コストの大幅な増加を伴うため、0.0001%を下限値とする。
Alは鉄系炭化物の生成を抑えて強度を高める元素である。しかし、Alの含有量が2.50%を超えると鋼板中のフェライト分率が過度に高まり、かえって強度が低下するため、Alの含有量の上限を2.500%とする。Alの含有量は2.000%以下とすることが好ましく、1.600%以下とすることがより好ましい。Alの含有量の下限は、特に定めることなく本発明の効果は発揮されるが、Alの含有量が0.001%以上であれば脱酸剤としての効果が得られることから、0.001%を下限とする。脱酸材として十分な効果を得るため、Alの含有量を0.005%以上とすることが好ましく、0.010%以上とすることがより好ましい。
Nは、粗大な窒化物を形成し、伸びフランジ性を劣化させることから、添加量を抑える必要がある。Nの含有量が0.0100%を超えると、この傾向が顕著となることから、N含有量の範囲を0.0100%以下とした。また、Nは、溶接時のブローホール発生の原因になることから少ない方が良い。Nの含有量の下限は、特に定めることなく本発明の効果は発揮されるが、Nの含有量を0.0001%未満にすると、製造コストの大幅な増加を招くことから、0.0001%を下限値とする。
Oは、酸化物を形成し、伸びフランジ性を劣化させることから、添加量を抑える必要がある。Oの含有量が0.0080%を超えると、伸びフランジ性の劣化が顕著となることから、O含有量の上限を0.0080%以下とした。Oの含有量は0.0070%以下であることが好ましく0.0060%以下であることがさらに好ましい。Oの含有量の下限は、特に定めることなく本発明の効果は発揮されるが、Oの含有量を0.0001%未満とすることは製造コストの大幅な増加を伴うため、0.0001%を下限とした。
Tiは、析出物強化、フェライト結晶粒の成長抑制による細粒強化および再結晶の抑制を通じた転位強化にて、鋼板の強度上昇に寄与する元素である。しかし、Tiの含有量が0.090%を超えると、炭窒化物の析出が多くなり成形性が劣化するため、Tiの含有量は0.090%以下であることが好ましい。成形性の観点から、Tiの含有量は0.080%以下であることがより好ましく、0.070%以下であることがさらに好ましい。Tiの含有量の下限は、特に定めることなく本発明の効果は発揮されるが、Tiによる強度上昇効果を十分に得るにはTiの含有量は0.005%以上であることが好ましい。鋼板の高強度化には、Tiの含有量は0.010%以上であることがより好ましく、0.015%以上であることがさらに好ましい。
Nbは、析出物強化、フェライト結晶粒の成長抑制による細粒強化および再結晶の抑制を通じた転位強化にて、鋼板の強度上昇に寄与する元素である。しかし、Nbの含有量が0.090%を超えると、炭窒化物の析出が多くなり成形性が劣化するため、Nbの含有量は0.090%以下であることが好ましい。成形性の観点から、Nbの含有量を0.070%以下であることがより好ましく、0.050%以下であることがさらに好ましい。Nbの含有量の下限は、特に定めることなく本発明の効果は発揮されるが、Nbによる強度上昇効果を十分に得るにはNbの含有量は0.005%以上であることが好ましい。鋼板の高強度化には、Nbの含有量は0.010%以上であることがより好ましく、0.015%以上であることがさらに好ましい。
Vは、析出物強化、フェライト結晶粒の成長抑制による細粒強化および再結晶の抑制を通じた転位強化にて、鋼板の強度上昇に寄与する元素である。しかし、Vの含有量が0.090%を超えると、炭窒化物の析出が多くなり成形性が劣化するため、Nbの含有量は0.090%以下であることが好ましい。Vの含有量の下限は、特に定めることなく本発明の効果は発揮されるが、Vによる強度上昇効果を十分に得るにはVの含有量は0.005%以上であることが好ましい。
Bは、熱間圧延後の冷却プロセスにおいてオーステナイトからの相変態を遅延することから、Bを添加することでMnの分配を効果的に進めることができる。Bの含有量が0.0100%を超えると、熱間での加工性が損なわれ生産性が低下することから、Bの含有量は0.0100%以下であることが好ましい。生産性の観点から、Bの含有量は0.0050%以下であることがより好ましく、0.0030%以下であることがさらに好ましい。Bの含有量の下限は、特に定めることなく本発明の効果は発揮されるが、Bによる相変態の遅延効果を十分に得るには、Bの含有量を0.0001%以上とすることが好ましい。相変態の遅延には、Bの含有量が0.0003%以上であることがより好ましく、0.0005%以上であることがより好ましい。
Moは、熱間圧延後の冷却プロセスにおいてオーステナイトからの相変態を遅延することから、Moを添加することでMnの分配を効果的に進めることができる。Moの含有量が0.80%を超えると、熱間での加工性が損なわれ生産性が低下することから、Moの含有量は0.80%以下であることが好ましい。Moの含有量の下限は、特に定めることなく本発明の効果は発揮されるが、Moによる相変態の遅延効果を十分に得るには、Moの含有量は0.01%以上であることが好ましい。
Cr、NiおよびCuは強度の寄与に向上する元素であり、1種又は2種以上をCおよび/またはSiの一部に替えて添加することができる。各元素の含有量がそれぞれ2.00%を超えると、酸洗性や溶接性、熱間加工性などが劣化することがあるため、Cr、NiおよびCuの含有量はそれぞれ2.00%以下であることが好ましい。Cr、NiおよびCuの含有量の下限は、特に定めることなく本発明の効果は発揮されるが、鋼板の高強度化効果を十分に得るには、Cr、NiおよびCuの含有量をそれぞれ0.01%以上であることが好ましい。
Ca、Ce、Mg、REMは、成形性の改善に有効な元素であり、1種又は2種以上を添加することができる。しかし、Ca、Ce、MgおよびREMの1種または2種以上の含有量が合計が0.5000%を超えると、却って延性を損なう恐れがあるため、各元素の含有量の合計が0.5000%以下であることが好ましい。Ca、Ce、MgおよびREMの1種または2種以上の含有量の下限は、特に定めることなく本発明の効果は発揮されるが、鋼板の成形性を改善する効果を十分に得るには、各元素の含有量の合計が0.0001%以上であることが好ましい。成形性の観点から、Ca、Ce、MgおよびREMの1種または2種以上の含有量の合計が0.0005%以上であることがより好ましく、0.0010%以上であることがさらに好ましい。なお、REMとは、Rare Earth Metalの略であり、ランタノイド系列に属する元素をさす。本発明において、REMやCeはミッシュメタルにて添加されることが多く、LaやCeの他にランタノイド系列の元素を複合で含有する場合がある。不可避不純物として、これらLaやCe以外のランタノイド系列の元素を含んだとしても本発明の効果は発揮される。また、金属LaやCeを添加したとしても本発明の効果は発揮される。
次に、本発明の高強度鋼板の製造方法について説明する。
本発明の高強度鋼板を製造するには、まず、上述した化学成分(組成)を有するスラブを鋳造する。
熱間圧延に供するスラブは、連続鋳造スラブや薄スラブキャスターなどで製造したものを用いることができる。本発明の高強度鋼板の製造方法は、鋳造後に直ちに熱間圧延を行う連続鋳造-直接圧延(CC-DR)のようなプロセスに適合する。
Ar3=901-325×C+33×Si-92×(Mn+Ni/2+Cr/2+Cu/2+Mo/2)+52×Al
一方、仕上げ圧延温度の上限は特に定めることなく、本発明の効果は発揮されるが、仕上げ圧延温度を過度に高温とした場合、その温度を確保するためにスラブ加熱温度を過度に高温にしなければならない。このことから、仕上げ圧延温度の上限温度は、1000℃以下とすることが望ましい。
また、(3)式および冷却速度を満たす範囲で、巻き取り後に鋼板を再加熱しても構わない。
伸びフランジ性を高めるには、次工程においてMnを分配させる際、Mn濃度の高い領域と低い領域を細かく分散させることが好ましい。このためには冷間圧延における圧下率を高め、昇温中にフェライトを再結晶させ、粒径を細かくすることが効果的である。この観点から、圧下率は40%以上であることが好ましく、45%以上であることがより好ましい。
一方、圧下率が80%以下の冷延は、冷延荷重が大きくなりすぎず、冷延が困難とならない。このことから、圧下率80%以下を上限とする。冷延荷重の観点から、圧下率は75%以下であることが好ましい。
なお、圧延パスの回数、各パス毎の圧下率については特に規定することなく本発明の効果は発揮される。また、冷間圧延は省略してもよい。
図5は、連続焼鈍ラインを通板させる際の冷延鋼板の温度履歴を説明するためのグラフであり、冷延鋼板の温度と時間との関係を示したグラフである。なお、図5においては「フェライト変態温度域」として、(Ae3点-50℃)~Bs点の範囲を示し、「ベイナイト変態温度域」としてBs点~Ms点の範囲を示し、「マルテンサイト変態温度域」としてMs点~室温を示している。
Bs点[℃]=820-290C/(1-VF)-37Si-90Mn-65Cr-50Ni+70Al
上記式において、VFはフェライトの体積分率を示し、C、Mn、Cr、Ni、Al、Siはそれぞれの元素の添加量[質量%]である。
Ms点[℃]=541-474C/(1-VF)-15Si-35Mn-17Cr-17Ni+19Al
以上の工程により、高い延性と伸びフランジ性を有する高強度冷延鋼板が得られる。
すなわち、再加熱工程において、冷延鋼板を亜鉛めっき浴に浸漬すること以外は、上述した冷延鋼板を連続焼鈍ラインに通板させる場合と同様にして、高強度亜鉛めっき鋼板を製造できる。
このことにより、表面に亜鉛めっき層の形成された高い延性と伸びフランジ性を有する高強度亜鉛めっき鋼板が得られる。
このような合金化処理を行うことで、亜鉛めっき層が合金化されてなるZn-Fe合金が表面に形成され、表面に合金化した亜鉛めっき層を有する高強度亜鉛めっき鋼板が得られる。
このことにより、表面に亜鉛めっき層の形成された高い延性と伸びフランジ性を有する高強度亜鉛めっき鋼板が得られる。
このような合金化処理を行った場合にも、亜鉛めっき層が合金化されてなるZn-Fe合金が表面に形成され、表面に合金化した亜鉛めっき層を有する高強度亜鉛めっき鋼板が得られる。
例えば、本発明の高強度亜鉛めっき鋼板の製造方法においては、めっき密着性を向上させるために、焼鈍前の鋼板にNi、Cu、Co、Feから選ばれる1種あるいは複数種よりなるめっきを施してもよい。
連続焼鈍ラインを通板させるに際しては、表5~12、23~25、30~31に示す条件(加熱工程の最高加熱温度、第1冷却工程のフェライト変態温度域での停留時間、第2冷却工程のベイナイト変態温度域における冷却速度、第2冷却工程の停止温度、停留工程の停留時間、再加熱工程のベイナイト変態温度域における昇温速度および再加熱停止温度、第3冷却工程のベイナイト変態温度域での停留時間、第4冷却工程の冷却速度、第2冷却工程においてベイナイト変態温度域に停留する時間と再加熱工程においてベイナイト変態域に停留する時間との合計(合計停留時間))で、以下に示す方法により、実験例1~実験例134の高強度冷延鋼板を得た。
以上の工程により、実験例1~実験例134の高強度冷延鋼板及び高強度熱延鋼板を得た。
まず、連続焼鈍ラインを通板させた鋼板に対して、めっきの前処理として、アルカリ脱脂、水洗、酸洗、並びに水洗を順に実施した。その後、前処理後の鋼板に対し、液循環式の電気めっき装置を用い、めっき浴として硫酸亜鉛、硫酸ナトリウム、硫酸からなるものを用い、電流密度100A/dm2で所定のめっき厚みになるまで電解処理して、Znめっきを施した。
また、実験例69~実験例73の冷延鋼板については、再加熱工程において亜鉛めっき浴に浸漬した後の冷延鋼板を、表11に示す「再加熱停止温度T3」で表12に示す「停留時間」で停留させる合金化処理を施すことにより、表面のめっき層を合金化させて、合金化した亜鉛めっき層を有する高強度亜鉛めっき鋼板とした。
また、実験例78~実験例82の冷延鋼板については、第3冷却工程において亜鉛めっき浴に浸漬した後の冷延鋼板を、表12に示す「合金化温度Tg」まで再々加熱し、表12に示す「停留時間」で停留させる合金化処理を施すことにより、表面のめっき層を合金化させて、合金化した亜鉛めっき層を有する高強度亜鉛めっき鋼板とした。
残留オーステナイトの体積分率は、鋼板の板面に平行かつ1/4厚の面を観察面としてX線解析を行い、面積分率を算出し、それを持って体積分率とした。
フェライト、ベイニティックフェライト、ベイナイト、焼戻しマルテンサイトおよびフレッシュマルテンサイトの体積分率は、鋼板の圧延方向に平行な板厚断面を観察面として試料を採取し、観察面を研磨、ナイタールエッチングし、板厚の1/4を中心とした1/8厚~3/8厚において、一辺30μmの領域を設定し、FE-SEMで観察して面積分率を測定し、それを持って体積分率とした。
その結果を表13、14、17、26、32にそれぞれ示す。
より詳細には、実験例56は、鋼WにおいてCの含有量が本特許で規定する下限を下回っている。このため、実験例56では、軟質組織の割合が高く、引張強度TSが不足した。
Claims (18)
- 質量%で、
C:0.05~0.4%、
Si:0.1~2.5%、
Mn:1.0~3.5%、
P:0.001~0.03%、
S:0.0001~0.01%、
Al:0.001~2.5%、
N:0.0001~0.01%、
O:0.0001~0.008%、
を含有し、残部が鉄および不可避的不純物からなる鋼であり、
鋼板組織が、体積分率で10~50%のフェライト相と、10~50%の焼戻しマルテンサイト相と、残部硬質相とからなり、
鋼板の1/8厚~3/8厚の範囲において、直径1μm以下の測定領域を複数設定して、前記複数の測定領域における硬度の測定値を小さい順に並べて硬度分布を得るとともに、硬度の測定値の全数に0.02を乗じた数であって該数が小数を含む場合はこれを切り上げて得た整数N0.02を求め、最小硬度の測定値からN0.02番目に大きな測定値の硬度を2%硬度とし、また、硬度の測定値の全数に0.98を乗じた数であって該数が小数を含む場合はこれを切り下げて得た整数N0.98を求め、最小硬度の測定値からN0.98番目に大きな測定値の硬度を98%硬度としたとき、前記98%硬度が前記2%硬度の1.5倍以上であり、前記2%硬度と前記98%硬度の間における前記硬度分布の尖度K*が-1.2以上、-0.4以下であり、前記鋼板組織における平均結晶粒径が10μm以下であることを特徴とする延性と伸びフランジ性に優れた高強度鋼板。 - 鋼板の1/8厚~3/8厚における地鉄中のMn濃度の最大値と最小値の差が質量%に換算して0.4%以上3.5%以下であることを特徴とする請求項1に記載の延性と伸びフランジ性に優れた高強度鋼板。
- 前記2%硬度から98%硬度までの区間を10等分して10個の1/10区間を設定したとき、各1/10区間における硬度の測定値の数が、全測定値の数の2~30%の範囲にあることを特徴とする請求項1または請求項2に記載の延性と伸びフランジ性に優れた高強度鋼板。
- 前記硬質相が、体積分率で10~45%のベイニティックフェライト相若しくはベイナイト相のいずれか一方または両方と、10%以下のフレッシュマルテンサイト相であることを特徴とする請求項1乃至請求項3の何れか一項に記載の延性と伸びフランジ性に優れた高強度鋼板。
- 鋼板組織として、さらに、2~25%の残留オーステナイト相を含有することを特徴とする請求項1乃至請求項4の何れか一項に記載の延性と伸びフランジ性に優れた高強度鋼板。
- さらに、質量%で、
Ti:0.005~0.09%、
Nb:0.005~0.09%の1種または2種以上を含有することを特徴とする請求項1乃至請求項5の何れか一項に記載の延性と伸びフランジ性に優れた高強度鋼板。 - さらに、質量%で、
B:0.0001~0.01%、
Cr:0.01~2.0%、
Ni:0.01~2.0%、
Cu:0.01~2.0%、
Mo:0.01~0.8%の1種または2種以上を含有することを特徴とする請求項1乃至請求項6の何れか一項に記載の延性と伸びフランジ性に優れた高強度鋼板。 - さらに、質量%で、
V:0.005~0.09%含有することを特徴とする請求項1乃至請求項7の何れか一項に記載の延性と伸びフランジ性に優れた高強度鋼板。 - さらに、質量%で、
Ca、Ce、Mg、REMの1種または2種以上を合計で0.0001~0.5%含有することを特徴とする請求項1乃至請求項8の何れか一項に記載の延性と伸びフランジ性に優れた高強度鋼板。 - 請求項1乃至請求項9の何れか一項に記載の高強度鋼板の表面に亜鉛めっき層が形成されてなることを特徴とする延性と伸びフランジ性に優れた高強度亜鉛めっき鋼板。
- 請求項1または請求項6~9のいずれか1項に記載の化学成分を有するスラブを、直接又は一旦冷却した後1050℃以上に加熱し、800℃またはAr3変態点の何れか高い温度以上で熱間圧延し、圧延後の圧延材の組織中のオーステナイト相が50体積%以上となるように750℃以下の温度域にて巻き取る熱間圧延工程と、
前記熱間圧延後の鋼板を、下記(1)式を満たしつつ巻き取り温度から(巻き取り温度-100)℃までを20℃/時以下の速度で冷却する冷却工程と、
前記冷却後の鋼板を連続焼鈍する工程と、を備え、
前記連続焼鈍する工程は、
前記鋼板を最高加熱温度750~1000℃で焼鈍し、
次いで、前記最高加熱温度からフェライト変態温度域以下まで冷却するとともにフェライト変態温度域で20~1000秒停留させる第1次冷却を行い、
次いで、ベイナイト変態温度域における冷却速度を平均10℃/秒以上として冷却し、マルテンサイト変態開始温度以下、マルテンサイト変態開始温度-120℃以上の範囲で停止する第2次冷却を行い、
次いで、第2次冷却後の鋼板を、マルテンサイト変態開始温度以下、第2冷却停止温度以上の範囲で2秒~1000秒停留し、
次いで、ベイナイト変態温度域における昇温速度を平均10℃/sec以上として、ベイナイト変態開始温度-100℃以上の再加熱停止温度に再加熱し、
次いで、前記再加熱後の鋼板を、前記再加熱停止温度からベイナイト変態温度域未満まで冷却するとともにベイナイト変態温度域で30秒以上停留させる第3冷却を行う
工程であることを特徴とする延性と伸びフランジ性に優れた高強度鋼板の製造方法。
- 前記熱間圧延後の巻き取り温度をBs点以上750℃以下とすることを特徴とする請求項11に記載の延性と伸びフランジ性に優れた高強度鋼板の製造方法。
- 前記冷却工程と前記連続焼鈍工程との間に、酸洗してから圧下率35~80%の圧下率で冷延する冷延工程を備えたことを特徴とする請求項11または請求項12に記載の延性と伸びフランジ性に優れた高強度鋼板の製造方法。
- 前記第2次冷却におけるベイナイト変態温度域に停留する時間と、前記再加熱におけるベイナイト変態域に停留する時間との合計が、25秒以下であることを特徴とする請求項11乃至請求項13の何れか一項に記載の延性と伸びフランジ性に優れた高強度鋼板の製造方法。
- 請求項11乃至請求項14の何れか一項に記載の製造方法で高強度鋼板を製造する際の前記再加熱において、前記鋼板を亜鉛めっき浴に浸漬することを特徴とする延性と伸びフランジ性に優れた高強度亜鉛めっき鋼板の製造方法。
- 請求項11乃至請求項14の何れか一項に記載の製造方法で高強度鋼板を製造する際の前記第3次冷却のベイナイト変態温度域において、前記鋼板を亜鉛めっき浴に浸漬することを特徴とする延性と伸びフランジ性に優れた高強度亜鉛めっき鋼板の製造方法。
- 請求項11乃至請求項14の何れか一項に記載の製造方法で高強度鋼板を製造した後、亜鉛電気めっきを施すことを特徴とする高強度亜鉛めっき鋼板の製造方法。
- 請求項11乃至請求項14の何れか一項に記載の製造方法で高強度鋼板を製造した後、溶融亜鉛めっきを施すことを特徴とする高強度亜鉛めっき鋼板の製造方法。
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EP11825267.5A EP2617849B1 (en) | 2010-09-16 | 2011-09-16 | High-strength cold-rolled steel sheet with excellent ductility and stretch flangeability, high-strength galvanized steel sheet, and method for producing both |
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CN201180044334.3A CN103097566B (zh) | 2010-09-16 | 2011-09-16 | 延展性和拉伸凸缘性优异的高强度钢板、高强度镀锌钢板以及它们的制造方法 |
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MX2013002906A MX339219B (es) | 2010-09-16 | 2011-09-16 | Lamina de acero de alta resistencia y lamina de acero revestida con zinc de alta resistencia que tiene excelente ductilidad y capacidad de embridado por estiramiento y metodo de fabricacion de las mismas. |
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US13/822,746 US9139885B2 (en) | 2010-09-16 | 2011-09-16 | High-strength steel sheet and high-strength zinc-coated steel sheet which have excellent ductility and stretch-flangeability and manufacturing method thereof |
ES11825267.5T ES2617477T3 (es) | 2010-09-16 | 2011-09-16 | Lámina de acero laminada en frío de alta resistencia con excelente ductilidad y expansibilidad, y lámina de acero galvanizada de alta resistencia, y método para fabricar las mismas |
EP15202459.2A EP3034644B1 (en) | 2010-09-16 | 2011-09-16 | High-strength steel sheet and high-strength zinc-coated steel sheet which have excellent ductility and stretch-flangeability and manufacturing method thereof |
BR112013006143-0A BR112013006143B1 (pt) | 2010-09-16 | 2011-09-16 | chapa de aço de alta resistência e chapa de aço revestida com zinco de alta resistência que têm excelente ductilidade e capacidade de estiramento-flangeamento e método de fabricação das mesmas |
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Also Published As
Publication number | Publication date |
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BR112013006143B1 (pt) | 2018-12-18 |
EP2617849A4 (en) | 2014-07-23 |
ES2711891T3 (es) | 2019-05-08 |
KR20130032917A (ko) | 2013-04-02 |
MX2013002906A (es) | 2013-05-22 |
CN103097566A (zh) | 2013-05-08 |
US20130167980A1 (en) | 2013-07-04 |
US9139885B2 (en) | 2015-09-22 |
PL2617849T3 (pl) | 2017-07-31 |
ES2617477T3 (es) | 2017-06-19 |
KR101329840B1 (ko) | 2013-11-14 |
JPWO2012036269A1 (ja) | 2014-02-03 |
EP3034644B1 (en) | 2018-12-12 |
CA2811189A1 (en) | 2012-03-22 |
EP2617849B1 (en) | 2017-01-18 |
EP2617849A1 (en) | 2013-07-24 |
JP5021108B2 (ja) | 2012-09-05 |
BR112013006143A2 (pt) | 2016-06-14 |
MX339219B (es) | 2016-05-17 |
CA2811189C (en) | 2014-04-22 |
EP3034644A1 (en) | 2016-06-22 |
PL3034644T3 (pl) | 2019-04-30 |
CN103097566B (zh) | 2015-02-18 |
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