Title of Invention	"HIGH STRENGTH COLD ROLLED STEEL AND METHOD FOR MANUFACTURING THE SAME"
Abstract	The present invention relates to a high strength cold rolled steel sheet composed of ferrite grains having an average grain diemeter of 10 m or less, in which the average number per unit area of Nb(C, N) precipitates having a diemeter of 50 cm or more is 7.0x 10-2/ um2 or less, and a zone having a width of 0.2 to 2.4 um and an average area density of NbC precipitates of 60% or less of that of the cenral portion of the ferrite grains is formed along grain boundaries of the ferrite grains, for example, the steel sheet consisting of 0.004 to 0.02% of c, 1.5 % or less of si, 3% or less of mn, 0.15% or less of p, 0.02 & or less of s, 0.1 to 1.5 % of sol.Al, 0.001 to 0.007 % of N, 0.03 to 0.2 % of Nb, by mess, and the balance of fe and invitable impurities. The steel sheet of the present invention is most preferably used for automobile panel parts since it has the Ts of 340 MPa or more and superior surface strain resistance and press formability.

Title of Invention

"HIGH STRENGTH COLD ROLLED STEEL AND METHOD FOR MANUFACTURING THE SAME"

Abstract

The present invention relates to a high strength cold rolled steel sheet composed of ferrite grains having an average grain diemeter of 10 m or less, in which the average number per unit area of Nb(C, N) precipitates having a diemeter of 50 cm or more is 7.0x 10-2/ um2 or less, and a zone having a width of 0.2 to 2.4 um and an average area density of NbC precipitates of 60% or less of that of the cenral portion of the ferrite grains is formed along grain boundaries of the ferrite grains, for example, the steel sheet consisting of 0.004 to 0.02% of c, 1.5 % or less of si, 3% or less of mn, 0.15% or less of p, 0.02 & or less of s, 0.1 to 1.5 % of sol.Al, 0.001 to 0.007 % of N, 0.03 to 0.2 % of Nb, by mess, and the balance of fe and invitable impurities. The steel sheet of the present invention is most preferably used for automobile panel parts since it has the Ts of 340 MPa or more and superior surface strain resistance and press formability.

Full Text	The present invention relates to a high strength cold rolled steel sheet used for automobiles, home appliances, or the like, in particular, to a high strength cold rolled steel sheet having superior press formability and a tensile strength TS of 340 MPa or more, and to a manufacturing method thereof. Background Art Heretofore, for automobile panel parts having a complicated shape such as a side panel or a door inner panel, which are difficult to be press formed, interstitial free (IF) cold rolled steel sheets (270E, F) having superior deep drawability and stretchability and a TS of around 270 MPa, have been widely used. In recent years, due to increasing needs of lighter weight and higher strength of automobile bodies, a high strength cold rolled steel sheet having a TS of 340 MPa or more, and particularly, 390 MPa or more, has been - 2 - progressively applied to those parts which are difficult to be press formed. In addition, as is the case described above, there has also been a trend to apply a higher strength cold rolled steel sheet to inner parts or the like, in which a high strength cold rolled steel sheet has been used, so as to further reduce automobile weight by decreasing the number of reinforcement parts or by decreasing the thickness thereof. However, when the strength of the high strength cold rolled steel sheet used in automobile panels is further increased, and the thickness thereof is further decreased, the occurrence of surface strain is remarkably increased due to the increase in yield strength Y5, the decrease in work hardening coefficient n value, and the decrease in the thickness. This surface strain is a defect such as an undulation or a wrinkle brought out on a surface of steel sheet after press forming and deteriorates dimensional precision or appearance of press formed panel. Therefore, when a high strength cold rolled steel sheet is applied to parts which are difficult to be press formed such as automobile panel parts, the steel sheet must have superior resistance to surface strain and excellent stretchability, and more particularly, the steel sheet having a YS of 270 MPa or less and a na_10 of 0.20 or more is preferably desired. Here, the n1_10 is a work hardening coefficient calculated - 3 - from the stresses at strains of 1 % and 10 % of a stress- strain curve obtained from a tensile test. In order to decrease a yield ratio YR (=YS/TS), a method has been well known, in which a Ti or Nb added steel having the amount of C and N decreased as small as possible is hot rolled and coiled at a temperature of 680 °C or more to decrease the number of precipitates containing Ti or Nb and thereby to promote grain growth at annealing after cold rolling. In addition, in Japanese Unexamined Patent Application Publication No. 6-108155 and Japanese Patent No. 3291639, methods for promoting grain growth have been disclosed in which the amounts of C and S of Ti added steel are controlled to bring about Ti(C, S) precipitates in order to suppress the formation of fine TiC precipitates. The above-mentioned methods are effective for a cold rolled mild steel sheet having a TS of approximately 270 MPa. However, when the grain growth is promoted, the TS is also decreased simultaneously as the YS is decreased, and therefore the methods are not always effective for a high strength cold rolled steel sheet having a TS of 340 MPa or more. That is, since the decrease in TS must be compensated for by addition of alloying elements such as Si, Mn, or P, problems may arise in that a manufacturing cost is increased, surface defects take place, a YS of 270 MPa or less is not obtained, and the like. For example, when the steel sheet - 4 - is strengthened by addition of Si, Mn, and P, accompanied by the grain growth of approximately 10 M m to 20 \i m in grain size, the steel sheet can only be obtained having a YS approximately 10 MPa smaller than that of a conventional high strength cold rolled steel sheet, and in addition, the resistance to the occurrence of orange peel and the anti- secondary work embrittlement of the steel sheet also deteriorates. On the other hand, in Japanese Unexamined Patent Application Publication Nos. 2001-131681, 2002-12943, and 2002-1294 6, methods have been disclosed in which, without promoting grain growth, the YS is decreased and the high n value is obtained. According to the methods described above, the amount of C is controlled to approximately 0.004 to 0.02 %, which is larger than that of a conventional ultra low carbon steel sheet, and grain refinement and precipitation strengthenings are positively applied in order to decrease the YS by approximately 20 MPa than that of a conventional ultra low carbon IF steel sheet. However, when a high strength cold rolled steel sheet having a TS of approximately 390 MPa or 440 MPa is manufactured by the methods described above, the YS exceeds 270 MPa, and it becomes difficult to perfectly suppress the occurrence of the surface strain. - 5 - Disclosure of the Invention An object of the present invention is to provide a high strength cold rolled steel sheet having a TS of 340 MPa or more, in which YS^270 MPa and n1_10^0.20 are satisfied, and a manufacturing method thereof, the steel sheet having superior surface strain resistance and press formability. This object can be achieved by a high strength cold rolled steel sheet composed of ferrite grains having an average grain diameter of 10  m or less, in which the average number per unit area (hereinafter referred to as "average area density") of Nb(C, N) precipitates having a diameter of 50 nm or more in the ferrite grains is 7.0X10 m2 or less, and a zone (hereinafter referred to as "PFZ") having a width of 0.2 to 2.4  m. and an average area density of NbC precipitates of 60 % or less of that of the central portion of the ferrite grains is formed along grain boundaries of the ferrite grains. This high strength cold rolled steel sheet can be obtained, for example, by a high strength cold rolled steel sheet consisting of 0.004 to 0.02 % of C, 1.5 % or less of Si, 3 % or less of Mn, 0.15 % or less of P, 0.02 % or less of S, 0.1 to 1.5 % of sol.Al, 0.001 to 0.007 % of N, 0.03 to 0.2 % of Nb, by mass, and the balance of Fe and inevitable - 6 - impurities. In addition, this high strength cold rolled steel sheet can be manufactured by a manufacturing method comprising the steps of: hot rolling a steel slab having the composition described above into a hot rolled steel sheet after heating the steel slab at a heating temperature SRT which satisfies the following equations (3) and (4); and pickling and cold rolling the hot rolled steel sheet, followed by annealing within a temperature range of a ferrite phase above the recrystallization temperature. SRT^1350 C "'(3) , and 1050 t;^SRT^{770+{ [sol.Al]-0. 085) °"24 X 820} C -(4)P where [sol.Al] represents the amount of sol. Al (mass%). Brief Description of the Drawings Fig. 1 shows the relationship between amount of sol.Al and YS, n value and r value. Fig. 2 shows the relationship between amount of sol.Al and slab heating temperature and YS. Embodiments of the Invention 1. Control of Precipitates Containing Nb The inventors of the present invention investigated how - 7 - to decrease the YS of a high strength cold rolled steel sheet and clarified that a high strength cold rolled steel sheet having a YS of 270 MPa or less, an n1_10 of 0.20 or more, and a TS of 340 MPa or more can be obtained when the steel sheet is composed of ferrite grains having an average grain diameter of 10 m or less, in which the average area density of Nb(C, N) precipitates having a diameter of 50 nm -2 2 or more is controlled to 7.0X10 /m or less, and a zone having a width of 0.2 to 2.4  m and an average area density of NbC precipitates of 60 % or less of that of the central portion of the ferrite grains is formed along grain boundaries of the ferrite grains. The Nb(C, N) precipitates having a diameter of 50 nm or more are formed at hot rolling to have a diameter of approximately 50 nm, do not become larger even at annealing after cold rolling, and are uniformly dispersed in the ferrite grains. On the other hand, the NbC precipitates at the center of the ferrite grains are formed at annealing, the diameter of which is approximately 10 nm, and the NbC precipitates in the PFZ are formed in such a way that fins precipitates having a diameter of approximately 2 nm uniformly formed at hot rolling are coarsened to have a diameter of approximately 50 nm by the Ostwald-ripening. The average area density of NbC and Nb(C, N) - 8 - precipitates was measured as described below using a transmission electron microscope at a magnification of 5610 times and an accelerating voltage of 300 kV. As to the Nb ran or more uniformly formed in the ferrite grains, arbitrary 50 portions therein were selected, the number of Nb(C, N) precipitates existing in a circle of 2  m in diameter centered at each of the portions was measured to calculate the number per unit area (area density), and finally the average was obtained therefrom. The average area density of NbC precipitates in the central portion of the ferrite grains was obtained in the same manner as described above. As to the NbC precipitates in the PFZ, arbitrary 50 precipitates coarsened by the Ostwald-ripening were selected. For each of the NbC precipitates, a circle inscribed with the NbC and the grain boundary adjacent to the NbC was described, the number of NbC precipitates existing in the circle was measured to obtain the area density, and the average of the area density was then calculated. The width of the PFZ was obtained as the average of the diameters of the above 50 circles. The high strength cold rolled steel sheet of the present invention has the central portion of ferrite grain in which fine NbC precipitates having the diameter of - 9 - approximately 10 nm are formed at a high density and the PFZ along the grain boundary in which coarse NbC precipitates having the diameter of approximately 50 nm are formed at a low density. It is considered that a low YS and a high n value can be obtained because the soft PFZ is deformed by a low stress at the initial stage of the plastic deformation, and that a high TS can be obtained due to the hard central portion of ferrite grain. As previously mentioned, the fine NbC precipitates having a diameter of approximately 2 nm are uniformly formed at the hot rolling and coarsen into the precipitates having the diameter of approximately 50 nm on the grain boundary of recrystallized ferrite grains at annealing in a continuous annealing line (CAL) or a continuous galvanizing line (CGL) after cold rolling. Therefore, the PFZ is believed to be formed due to promotion of grain boundary migration. In order not to make ferrite grains extremely coarse, the recrystallized grains should be preferably as fine as possible, and the PFZ can be more effectively formed. 2. Chemical Composition As a high strength cold rolled steel sheet of the present invention, for example, there may be mentioned a cold rolled steel sheet consisting of 0.004 to 0.02 % of C, 1.5 % or less of Si, 3 % or less of Mn, 0.15 % or less of P, 0.02 % or less of S, 0.1 to 1.5 % of sol.Al, 0.001 to - 10 - 0.007 % of N, 0.03 to 0.2 % of Nb, by mass, and the balance of Fe and inevitable impurities. C, Nb., and sol.Al play a very important role in the control of NbC and Nb(C, N) precipitates, and the amounts of C, Nb, and sol.Al must be controlled as follows. C: Since C is combined with Nb, C plays an important role in the control of NbC and Nb(C, N) precipitates. The amount of C is set to 0.004 to 0.02 %, preferably 0.004 to 0.01 %. Nb: In order to control the NbC and Nb{C, N) precipitates, the amount of Nb is set to 0.03 % or more. However, when the amount of Nb exceeds 0.2 %, the increase in the rolling load at the hot rolling and the cold rolling causes the decrease in productivity or the increase in cost. Therefore, the amount of Nb is set to 0.2 % or less. In order to increase r value, ([Nb]/ [C])X(12/93) preferably satisfied, and the ([Nb]/[C]) X (12/93) is more preferably 1.5 to 3.0. sol.Al: Even when the amount of C is controlled to 0.004 to 0.02 %, and the amount of Nb is controlled to 0.03 to 0.2 %, Ys of 270 MPa or less may not always be obtained in some cases. It is considered to be due to coarse Nb(C, N) precipitates formed at hot rolling. As the above- mentioned, it is believed that the coarse Nb(C, N) precipitates having the diameter of approximately 50 nm - 11 - which is formed at the hot rolling have difficulties to be coarsened by the Ostwald-ripening at annealing because of the large size and the smaller solubility in ferrite than that of NbC precipitates, and the suppression of the PFZ formation leads to the suppression of the decrease in YS. Then, the inventors of the present invention investigated a method for the formation of NbC precipitates effective for forming PFZ by suppressing coarse Nb(C, N) precipitates having a diameter of 50 nm or more, and found that the addition of 0.1 % or more of sol.Al is effective. It has been believed that-N is combined with Al to form A1N. However, in steel containing 0.004 % or more of C and 0.03 % or more of Nb, precipitation of Nb(C, N) takes place at finish rolling before A1N starts to precipitate. When the amount of Al is increased to 0.1 % or more so that A1N is precipitated before Nb(C, N) is precipitated, the precipitation of NbC effective for forming the PFZ can be proceeded. Fig. 1 shows the relationship between the amount of sol.Al and YS, n value and r value. The results shown in Fig. 1 were obtained by investigating YS, r value, and n value of cold rolled steel sheets containing 0.0060 % of C, 0 to 0.45 % of Si, 1.5 to 2 % of Mn, 0.02 % of P, 0.002 % of S, 0.003 % of N, 0.0005 % of B, 0.11 % of Nb, and 0.01 to 1.7 % of sol.Al, which are - 12 - heated at 1150 0C and 1250 0C, followed by the hot rolling to 3 mm thick in the y region and coiling at 560 0C, and subsequently cold rolled to 0.8 mm thick, followed by annealing at 820 0C for 80 seconds. Since the increases in TS by the addition of one percent of Si, Mn, and sol.Al were 86 MPa, 33 MPa, and 32.5 MPa, respectively, the amounts of Si, Mn, and Al were controlled so as to obtain a constant TS of approximately 440 MPa. That is, ([Si]+[Mn]/2.6+[sol.Al]/2,6) was controlled to 1.25 %. Here, [M] represents the amount of element M (mass%) . YS, r value, and n value are also examined in a conventional ultra low carbon cold rolled steel sheet manufactured under the same conditions as described above using a steel containing 0.0020 % of C, 0.75 % of Si, 2 % of Mn, 0.02 % Of P, 0.002 % of S, 0.003 % of N, 0.0005 % of B, 0.015 % of Nb, and 0.03 % of Ti. The cold rolled steel sheets containing 0.004 % or more of C and 0.03 % or more of Nb have lower YS, higher n value, and higher r values than the conventional ultra low carbon cold rolled steel sheet. In particular, when the amount of sol.Al is 0.1 to 1.5 %, YS becomes 270 MPa or less and n1-10 becomes 0.20 or more. In addition, when the amount of sol.Al is 0.2 to 0.6 %, the YS is further decreased to 260 MPa or less in both cases of heating temperatures of 1250 and 1150 0C. The ferrite grains were sufficiently fine as - 13 - is the case in which the amount of sol.Al is 0.1 % or less. When the amount of sol.Al is less than 0.1 %, a large number of Nb(C, N) precipitates having a diameter of 50 nm or more, which inhibit the formation of PFZ, are observed. On the other hand, when the amount of sol.Al is 0.1 to 1.5 %, the coarse Nb(C, N) precipitates are remarkably decreased to an average area density of 0 to 7.0X10 /m , and the PFZ is remarkably formed. The reason why the r value is remarkably increased when the amount of sol.Al is controlled to 0.1 % or more is not clear. It is, however, inferred that Al has influences on the formation of deformation band at cold rolling or on the amount of solute C. Si: Si is an element for the solid solution strengthening, which may be added when it is necessary. However, the amount of Si which exceeds 1.5 % deteriorates the ductility and the anti-secondary work embrittlement, and increases the YS. The amount of Si is set to 1.5 % or less. In addition, since the addition of Si deteriorates the conversion treatment properties of a cold rolled steel sheet and appearance of a hot dip galvanized steel sheet, the amount of Si is preferably set to 0.5 % or less. In order to strengthen the steel sheet, the amount of Si is preferably set to 0,003 % or more. Mn: Since Mn is also an element for the solid solution - 14 - strengthening and an element for preventing the red shortness, Mn may be added when it is necessary. However, when the amount of Mn exceeds 3 %, the decrease in ductility and the increase in YS occur. The amount of Mn is set to 3 % or less. In order to obtain the superior appearance of the galvanized steel sheet, the amount of Mn is preferably set to 2 % or less. The amount of Mn is preferably set to 0.1 % or more for the solid solution strengthening. P: P is an effective element for strengthening the steel. However, the excessive addition of P deteriorates the anti-secondary work embrittlement and the ductility, and causes the increase in YS. Therefore, the amount of P is set to 0.15 % or less. In order to prevent the deterioration of alloying treatment properties and adhesion failure of coating of the galvanized steel sheet, the amount of P is preferably set to 0.1 % or less. The amount of P is preferably set to 0.01 % or more to increase the strength of the steel sheet. S: S exists as a sulfide in the steel sheet. Since the excessive amount of S decreases the ductility, the amount of S is set to 0.02 % or less. 0.004 % or more of S is desirable for the descaling preferably set to, and 0.01 % or less of S is favorable for the ductility. N: Since N is necessary to precipitate as A1N with the addition of 0.1 to 1.5 % of sol.Al, the amount of N is set - 15 - to 0.007 % or less. The amount of N is preferably decreased as small as possible. However, since the amount of N can not be decreased to less than 0.001 % by the steel smelting process, the amount of N is set to 0.001 % or more. The balance is Fe and inevitable impurities. In addition to the elements described above, at least one element selected from the group consisting of 0.0001 to 0.003 % of B, 0.5 % or less of Cu, 0.5 % or less of Ni, 0.3 % or less of Mo, 0.5 % or less of Cr, 0.04 % or less of Ti, 0.2 % or less of Sb, and 0.2 % or less of Sn is preferably added for the following reasons. B: The amount of B is set to 0.0001 % or more in order to improve the anti-secondary embrittlement. When the amount of B exceeds 0.003 %, the effect saturates, and the rolling load at hot rolling is increased. Therefore, the amount of B is set to 0.0001 to 0.003 %. Cu, Ni, Mo, and Cr: In order to increase the TS, the anti-secondary work erabrittlement, and the r value, 0.5 % or less of Cu, 0.5 % or less of Ni, 0.3 % or less of Mo, and 0.5 % or less of Cr may be added. Cu, Cr, and Ni are the expensive elements, and when the amount of each element exceeds 0.5 %, the surface appearance deteriorates. Although Mo increases the TS without decreasing the anti- secondary work embrittlement, the amount of Mo exceeding 0.3 % increases the YS. When Cu, Cr, and Ni are added, the - 16 - amount of each element is preferably set to 0.03 % or more. When Mo is added, the amount of Mo is desirably set to 0.05 % or more. When Cu is added, Ni is preferably added with the same amount as Cu. Ti: In order to improve the r value, 0.04 % or less of Ti may be added. The amount of Ti exceeding 0.04 % increases the coarse precipitates containing Ti, which lead to the decrease in the TS and the prevention of the decrease in the YS by the suppression of A1N precipitation. When Ti is added, the amount of Ti is preferably set to 0.005 % or more. Sb and Sn: In order to improve the surface appearance, the coating adhesion, the fatigue resistance, and the toughness of the galvanized steel sheet, 0.2 % or less of Sb and 0.2 % or less of Sri are effectively added so that 0.002 [Sb]+1/2X [Sn]^0.2 is satisfied. Here, [Sb] and [Sn] represent the amounts'1 of Sb and Sn (mass%) , respectively. Since the addition of Sb and Sn prevents the surface nitridation or oxidation at slab heating, at coiling after hot rolling, at annealing in a CAL or a CGL, or at additional intermediate annealing, the coating adhesion is improved in addition to the suppression of the irregular coating. Furthermore, since the adhesion of zinc oxides to the steel sheet in a coating bath can be prevented, the surface appearance of the galvanized steel sheet is also - 17 - improved. When the amounts of Sb and Sn exceed 0.2 %, they deteriorate the coating adhesion and the toughness of the galvanized steel sheet. 3. Manufacturing Method The high strength cold rolled steel sheet can be manufactured by a manufacturing method comprising the steps of: hot rolling a steel slab having a chemical composition within the range of the present invention into a hot rolled steel sheet after heating the steel slab at a heating temperature SRT which satisfies the following equations (3) and (4); and pickling and cold rolling the hot rolled steel sheet, followed by annealing within a temperature range of a ferrite phase above the recrystallization temperature. SRT 1050 0C^SRTS{770+([sol.Al]-0.0B5)°24X820} 0C -(4), where [sol.Al] represents the amount of sol. Al (mass%). As shown in Fig. 1, when the amount of sol.Al is 0.1 to 0.6 %, the lower YS can be obtained at the heating temperature SRT of 1150 0C as compared with that of 1250 0C. The relation between the amount of sol.Al and SRT and YS was investigated by using the cold rolled steel sheets shown in Fig. 1. As shown in Fig. 2, when the amount of sol.Al is 0.1 to 0.6 %, and SRT {770+([sol.Al]-0. 085) °'24X820} 0C is satisfied, the low YS such as 260 MPa or less can be - 18 - obtained. It is believed to be caused by the suppression of Nb(C, N) precipitation at hot rolling, accompanied by the suppression of A1N dissolution at heating by controlling the SRT. Fine ferrite grains having a grain diameter of 10  m or less were obtained. When the SRT is less than 1050 0C, the hot rolling load is increased, so that the productivity is decreased, and when the SRT is more than 1350 0C, the surface oxidation apparently occurs, so that the surface quality deteriorates. Therefore, SRT1350 0C, and 1050 t:SRT {770+ ([sol.Al] - 0.085)°"24X820} 0C must be satisfied. In order to obtain the superior surface quality, the scales formed at slab heating and at hot rolling should be preferably sufficiently removed. The heating by the use of a bar heater at hot rolling may also be performed. The coiling temperature after hot rolling has influences on the formation of PFZ and the r value. In order to effectively form the PFZ, fine NbC must be precipitated, and in order to obtain a high r value, the amount of solute C must be sufficiently decreased. In view of the effective formation of PFZ and the high r value, the coiling temperature is preferably set to 480 to 700 0C, more preferably 500 to 600 0C. The high cold rolling reduction is desirable. However, the cold rolling reduction which exceeds 85 % increases the - 19 - rolling load, so that the productivity decreases. Therefore, the cold rolling reduction is preferably 85 % or less. The high annealing temperature promotes the precipitation of coarser NbC existing in the vicinity of grain boundary, which causes the low YS and the high n value. Therefore, the annealing temperature is preferably set to 820 °C or more. When the annealing temperature is lower than the recrystallization temperature, the sufficiently low YS and the high n value can not be obtained. Therefore, the annealing temperature must be at least not less than the recrystallization temperature. However, when the annealing temperature exceeds the Ac1 transformation temperature, ferrite grains become very fine by the ferrite transformation from the austenite, which leads to increase the YR. Therefore, the annealing temperature must be the temperature of the AC1 transformation temperature or less. When the annealing time is increased, grain boundary migration occurs more significantly to promote the formation of PFZ. Therefore, the soaking time is preferably set to 4 0 seconds or more. A cold rolled steel sheet after annealing may be galvanized by electrogalvanizing or hot dip galvanizing. The excellent press formability can also be obtained in the galvanized steel sheet where pure zinc coating, alloy zinc coating, and zinc-nickel alloy coating may be applied. Even - 20 - when the organic film is deposited after the coating, the superior press can also be obtained. Example 1 Several types of steel A to V having the chemical compositions listed in Table 1 were smelt and continuously cast into the slabs having a thickness of 230 mm. These slabs were heated to 1090 to 1325 °C and hot rolled to 3.2 mm thick under the hot rolling conditions listed in Table 2. These hot rolled steel sheets were cold rolled to 0.8 mm thick, followed by annealing in a continuous annealing line (CAL), a hot dip galvanizing line (CGL), or a box annealing furnace (BAF) under the annealing conditions shown in Table 2, and subsequently, temper rolling with the elongation of 0.5 %. The hot dip zinc coating was performed at 4 60 °C in the CGL, followed by the alloying treatment of the coated layer at 500 °C in an in-line alloying furnace. The amount of the coating per one surface was 45 g/m2 . The tensile tests were performed using JIS No. 5 test pieces cut from the direction of 0° , the direction of 45° , and the direction of 90° to the rolling direction, respectively. The averages of YS, n10, r value, and TS were obtained by the following equation, respectively. The average V=([V0]+2[V45]+[V90])/4, - 21 - where [V0], [V45] and [V90] show the value of the properties obtained in the direction of 0° , 45° and 90° to the rolling direction, respectively. The ferrite grain diameter was measured by the point- counting method in the rolling direction, the thickness direction, and the direction of 45° to the rolling direction at the cross section parallel to the rolling direction, and the average of the ferrite grain sizes was obtained. The sizes of NbC and Nb(C, N) and the average area density thereof were obtained by the method previously mentioned. The results are shown in Table 2. Samples Nos. 1 to 19 of the present invention have the YS of 27 0 MPa or less, the n1-10 of 0.20 or more, and the high r value of 1.8 or more. In particular, the samples Nos. 2 to 6, 9 to 11, 15 to 17, and 19 have the YS of 260 MPa.or less because the amounts of sol.Al are 0.1 to 0.6 % and the temperature are within the present invention. In case of samples of the present invention, the average area density of coarse Nb(C, N) precipitates having a diameter of 50 nm or more, which prevents the formation of PFZ, is 7.0X10 / m2 or less, and the PFZ having a width of 0.2 to 2.4  m was formed in the vicinity of the ferrite grain boundary. On the other hand, samples Nos. 20 to 27 of the comparative examples have the high YS and the low n value - 22 - because the average area density of coarse Nb{C, N) precipitates having a diameter of 50 run or more or the width of the PFZ is out of the invention. Sample No. 20 in which the amount of sol.Al is small has the YS of more than 27 0 MPa, the n value of less than 0.20, ant the r value of less than 1.8. Sample No. 21 in which the amount of sol.Al is excessive has the YS of more than 270 MPa and the n value of less than 0.20. Samples Nos. 23, 24, 25, and 26 in which C, Si, Mn, and P are out of the range of the present invention have the YS of excessively larger than 270 MPa. Sample No. 27 in which the amount of Nb is small has the n value of less than 0.20 and the excessively low r value. Sample No. 22 as the conventional ultra low carbon high strength cold rolled steel sheet has the YS of much larger than 270 MPa, and the n value of less than 0.20. In each of samples Nos. 1 to 19 of the present invention, the ferrite grains are fine having a diameter of less than 10  m as compared with that of sample No. 22 of the conventional example, 11.4 m. Therefore, each of samples Nos. 1 to 19 of the present invention has the superior resistance to the occurrence of the orange peel and the anti-secondary work embrittlement. - 23 - - 24 - - 25 - We claim :- 1. A high strength cold rolled steel sheet composed of ferrite grains having an average grain diameter of 10  m or less, in which the average number per unit area (hereinafter referred to as "average area density") of Nb{C, N) precipitates having a diameter of 50 nm or more is 7.0X10 /  m or less, and a zone having a width of 0.2 to 2.4  m and an average area density of NbC precipitates of 60 % or less of that of the central portion of the ferrite grains is formed along grain boundaries of the ferrite grains. 2. The high strength cold rolled steel sheet according to Claim 1 consisting of 0-004 to 0.02 % of C, 1.5 % or less of Si, 3 % or less of Mn, 0.15 % or less of P, 0.02 % or less of S, 0.1 to 1.5 % of sol.Al, 0.001 to 0.007 % of N, 0.03 to 0.2 % of Nb, by mass, and the balance of Fe and inevitable impurities. 3. The high strength cold rolled steel sheet according to Claim 2, wherein the amount of sol.Al is 0.2 to 0.6 %. 4. The high strength cold rolled steel sheet according to Claim 2, wherein the following equation (1) is satisfied; ([Nb]/[C])X (12/93)^1 -{1), - 26 - where [Nb] and [C] represent the amounts of Nb and C (mass%), respectively. 5. The high strength cold rolled steel sheet according to Claim 3, wherein the following equation (1) is satisfied; ([Nb]/[C]) X (12/93) >1 -(1), where [Nb] and [C] represent the amounts of Nb and C (mass%), respectively. 6. The high strength cold rolled steel sheet according to Claim 2 further containing 0.0001 to 0.003 % of B. 7. The high strength cold rolled steel sheet according to Claim 5 further containing .0.0001 to 0.003 % of B. 8. The high strength cold rolled steel sheet according to Claim 2 further containing at least one element selected from the group consisting of 0.5 % or less of Cu, 0.5 % or less of Ni, 0.3 % or less of Mo, 0.5 % or less of Cr, and 0.04 % or less of Ti. 9. The high strength cold rolled steel sheet according to Claim 7 further containing at least one element selected from the group consisting of 0.5 % or less of Cu, 0.5 % or less of Ni, 0.3 % or less of Mo, 0.5 % or less of Cr, and - 27 - 0.04 % or less of Ti. 10. The high strength cold rolled steel sheet according to Claim 2 further containing at least one element selected from the group consisting of 0.2 % or less of Sb and 0.2 % or less of Sn, wherein the following equation (2) is satisfied; 0.002 where [Sb] and [Sn] represent the amounts of Sb and Sn (mass%), respectively. 11. The high strength cold rolled steel sheet according to Claim 9 further containing at least one element selected from the group consisting of 0.2 % or less of Sb and 0.2 % or less of Sn, wherein the following equation (2) is satisfied; 0.002 where [Sb] and [Sn] represent the amounts of Sb and Sn mass%), respectively. 12. A method for manufacturing a high strength cold rolled steel sheet comprising the steps of: hot rolling a steel slab having the chemical composition according to any one of Claims 2 to 11 into a hot rolled steel sheet after heating the steel slab at a - 28 - heating temperature SRT which satisfies the following equations (3) and (4); and pickling and cold rolling the hot rolled steel sheet, followed by annealing within a temperature range of a ferrite phase above the recrystallization temperature, SRT - 29 - 1050 °C where [sol.Al] represents the amount of sol. Al (mass%). The present invention relates to a high strength cold rolled steel sheet composed of ferrite grains having an average grain diemeter of 10 m or less, in which the average number per unit area of Nb(C, N) precipitates having a diemeter of 50 cm or more is 7.0x 10-2/ um2 or less, and a zone having a width of 0.2 to 2.4 um and an average area density of NbC precipitates of 60% or less of that of the cenral portion of the ferrite grains is formed along grain boundaries of the ferrite grains, for example, the steel sheet consisting of 0.004 to 0.02% of c, 1.5 % or less of si, 3% or less of mn, 0.15% or less of p, 0.02 & or less of s, 0.1 to 1.5 % of sol.Al, 0.001 to 0.007 % of N, 0.03 to 0.2 % of Nb, by mess, and the balance of fe and invitable impurities. The steel sheet of the present invention is most preferably used for automobile panel parts since it has the Ts of 340 MPa or more and superior surface strain resistance and press formability.

Full Text

The present invention relates to a high strength cold
rolled steel sheet used for automobiles, home appliances, or
the like, in particular, to a high strength cold rolled
steel sheet having superior press formability and a tensile
strength TS of 340 MPa or more, and to a manufacturing
method thereof.
Background Art
Heretofore, for automobile panel parts having a
complicated shape such as a side panel or a door inner panel,
which are difficult to be press formed, interstitial free
(IF) cold rolled steel sheets (270E, F) having superior deep
drawability and stretchability and a TS of around 270 MPa,
have been widely used.
In recent years, due to increasing needs of lighter
weight and higher strength of automobile bodies, a high
strength cold rolled steel sheet having a TS of 340 MPa or
more, and particularly, 390 MPa or more, has been
- 2 -

progressively applied to those parts which are difficult to
be press formed. In addition, as is the case described
above, there has also been a trend to apply a higher
strength cold rolled steel sheet to inner parts or the like,
in which a high strength cold rolled steel sheet has been
used, so as to further reduce automobile weight by
decreasing the number of reinforcement parts or by
decreasing the thickness thereof.
However, when the strength of the high strength cold
rolled steel sheet used in automobile panels is further
increased, and the thickness thereof is further decreased,
the occurrence of surface strain is remarkably increased due
to the increase in yield strength Y5, the decrease in work
hardening coefficient n value, and the decrease in the
thickness. This surface strain is a defect such as an
undulation or a wrinkle brought out on a surface of steel
sheet after press forming and deteriorates dimensional
precision or appearance of press formed panel. Therefore,
when a high strength cold rolled steel sheet is applied to
parts which are difficult to be press formed such as
automobile panel parts, the steel sheet must have superior
resistance to surface strain and excellent stretchability,
and more particularly, the steel sheet having a YS of 270
MPa or less and a na_10 of 0.20 or more is preferably desired.
Here, the n1_10 is a work hardening coefficient calculated
- 3 -

from the stresses at strains of 1 % and 10 % of a stress-
strain curve obtained from a tensile test.
In order to decrease a yield ratio YR (=YS/TS), a
method has been well known, in which a Ti or Nb added steel
having the amount of C and N decreased as small as possible
is hot rolled and coiled at a temperature of 680 °C or more
to decrease the number of precipitates containing Ti or Nb
and thereby to promote grain growth at annealing after cold
rolling. In addition, in Japanese Unexamined Patent
Application Publication No. 6-108155 and Japanese Patent No.
3291639, methods for promoting grain growth have been
disclosed in which the amounts of C and S of Ti added steel
are controlled to bring about Ti(C, S) precipitates in order
to suppress the formation of fine TiC precipitates.
The above-mentioned methods are effective for a cold
rolled mild steel sheet having a TS of approximately 270 MPa.
However, when the grain growth is promoted, the TS is also
decreased simultaneously as the YS is decreased, and
therefore the methods are not always effective for a high
strength cold rolled steel sheet having a TS of 340 MPa or
more. That is, since the decrease in TS must be compensated
for by addition of alloying elements such as Si, Mn, or P,
problems may arise in that a manufacturing cost is increased,
surface defects take place, a YS of 270 MPa or less is not
obtained, and the like. For example, when the steel sheet
- 4 -

is strengthened by addition of Si, Mn, and P, accompanied by
the grain growth of approximately 10 M m to 20 \i m in grain
size, the steel sheet can only be obtained having a YS
approximately 10 MPa smaller than that of a conventional
high strength cold rolled steel sheet, and in addition, the
resistance to the occurrence of orange peel and the anti-
secondary work embrittlement of the steel sheet also
deteriorates.
On the other hand, in Japanese Unexamined Patent
Application Publication Nos. 2001-131681, 2002-12943, and
2002-1294 6, methods have been disclosed in which, without
promoting grain growth, the YS is decreased and the high n
value is obtained. According to the methods described above,
the amount of C is controlled to approximately 0.004 to
0.02 %, which is larger than that of a conventional ultra
low carbon steel sheet, and grain refinement and
precipitation strengthenings are positively applied in order
to decrease the YS by approximately 20 MPa than that of a
conventional ultra low carbon IF steel sheet.
However, when a high strength cold rolled steel sheet
having a TS of approximately 390 MPa or 440 MPa is
manufactured by the methods described above, the YS exceeds
270 MPa, and it becomes difficult to perfectly suppress the
occurrence of the surface strain.
- 5 -

Disclosure of the Invention
An object of the present invention is to provide a high
strength cold rolled steel sheet having a TS of 340 MPa or
more, in which YS^270 MPa and n1_10^0.20 are satisfied, and
a manufacturing method thereof, the steel sheet having
superior surface strain resistance and press formability.
This object can be achieved by a high strength cold
rolled steel sheet composed of ferrite grains having an
average grain diameter of 10  m or less, in which the
average number per unit area (hereinafter referred to as
"average area density") of Nb(C, N) precipitates having a
diameter of 50 nm or more in the ferrite grains is 7.0X10
m2 or less, and a zone (hereinafter referred to as "PFZ")
having a width of 0.2 to 2.4  m. and an average area density
of NbC precipitates of 60 % or less of that of the central
portion of the ferrite grains is formed along grain
boundaries of the ferrite grains.
This high strength cold rolled steel sheet can be
obtained, for example, by a high strength cold rolled steel
sheet consisting of 0.004 to 0.02 % of C, 1.5 % or less of
Si, 3 % or less of Mn, 0.15 % or less of P, 0.02 % or less
of S, 0.1 to 1.5 % of sol.Al, 0.001 to 0.007 % of N, 0.03 to
0.2 % of Nb, by mass, and the balance of Fe and inevitable
- 6 -

impurities.
In addition, this high strength cold rolled steel sheet
can be manufactured by a manufacturing method comprising the
steps of: hot rolling a steel slab having the composition
described above into a hot rolled steel sheet after heating
the steel slab at a heating temperature SRT which satisfies
the following equations (3) and (4); and pickling and cold
rolling the hot rolled steel sheet, followed by annealing
within a temperature range of a ferrite phase above the
recrystallization temperature.
SRT^1350 *C "'(3) , and
1050 t;^SRT^{770+{ [sol.Al]-0. 085) °"24 X 820} *C -(4)P
where [sol.Al] represents the amount of sol. Al (mass%).
Brief Description of the Drawings
Fig. 1 shows the relationship between amount of sol.Al
and YS, n value and r value.
Fig. 2 shows the relationship between amount of sol.Al
and slab heating temperature and YS.
Embodiments of the Invention
1. Control of Precipitates Containing Nb
The inventors of the present invention investigated how
- 7 -

to decrease the YS of a high strength cold rolled steel
sheet and clarified that a high strength cold rolled steel
sheet having a YS of 270 MPa or less, an n1_10 of 0.20 or
more, and a TS of 340 MPa or more can be obtained when the
steel sheet is composed of ferrite grains having an average
grain diameter of 10 m or less, in which the average area
density of Nb(C, N) precipitates having a diameter of 50 nm
-2 2
or more is controlled to 7.0X10 /m or less, and a zone
having a width of 0.2 to 2.4  m and an average area density
of NbC precipitates of 60 % or less of that of the central
portion of the ferrite grains is formed along grain
boundaries of the ferrite grains.
The Nb(C, N) precipitates having a diameter of 50 nm or
more are formed at hot rolling to have a diameter of
approximately 50 nm, do not become larger even at annealing
after cold rolling, and are uniformly dispersed in the
ferrite grains.
On the other hand, the NbC precipitates at the center
of the ferrite grains are formed at annealing, the diameter
of which is approximately 10 nm, and the NbC precipitates in
the PFZ are formed in such a way that fins precipitates
having a diameter of approximately 2 nm uniformly formed at
hot rolling are coarsened to have a diameter of
approximately 50 nm by the Ostwald-ripening.
The average area density of NbC and Nb(C, N)
- 8 -

precipitates was measured as described below using a
transmission electron microscope at a magnification of 5610
times and an accelerating voltage of 300 kV.
As to the Nb ran or more uniformly formed in the ferrite grains, arbitrary
50 portions therein were selected, the number of Nb(C, N)
precipitates existing in a circle of 2  m in diameter
centered at each of the portions was measured to calculate
the number per unit area (area density), and finally the
average was obtained therefrom.
The average area density of NbC precipitates in the
central portion of the ferrite grains was obtained in the
same manner as described above.
As to the NbC precipitates in the PFZ, arbitrary 50
precipitates coarsened by the Ostwald-ripening were selected.
For each of the NbC precipitates, a circle inscribed with
the NbC and the grain boundary adjacent to the NbC was
described, the number of NbC precipitates existing in the
circle was measured to obtain the area density, and the
average of the area density was then calculated.
The width of the PFZ was obtained as the average of the
diameters of the above 50 circles.
The high strength cold rolled steel sheet of the
present invention has the central portion of ferrite grain
in which fine NbC precipitates having the diameter of
- 9 -

approximately 10 nm are formed at a high density and the PFZ
along the grain boundary in which coarse NbC precipitates
having the diameter of approximately 50 nm are formed at a
low density. It is considered that a low YS and a high n
value can be obtained because the soft PFZ is deformed by a
low stress at the initial stage of the plastic deformation,
and that a high TS can be obtained due to the hard central
portion of ferrite grain.
As previously mentioned, the fine NbC precipitates
having a diameter of approximately 2 nm are uniformly formed
at the hot rolling and coarsen into the precipitates having
the diameter of approximately 50 nm on the grain boundary of
recrystallized ferrite grains at annealing in a continuous
annealing line (CAL) or a continuous galvanizing line (CGL)
after cold rolling. Therefore, the PFZ is believed to be
formed due to promotion of grain boundary migration.
In order not to make ferrite grains extremely coarse,
the recrystallized grains should be preferably as fine as
possible, and the PFZ can be more effectively formed.
2. Chemical Composition
As a high strength cold rolled steel sheet of the
present invention, for example, there may be mentioned a
cold rolled steel sheet consisting of 0.004 to 0.02 % of C,
1.5 % or less of Si, 3 % or less of Mn, 0.15 % or less of P,
0.02 % or less of S, 0.1 to 1.5 % of sol.Al, 0.001 to
- 10 -

0.007 % of N, 0.03 to 0.2 % of Nb, by mass, and the balance
of Fe and inevitable impurities. C, Nb., and sol.Al play a
very important role in the control of NbC and Nb(C, N)
precipitates, and the amounts of C, Nb, and sol.Al must be
controlled as follows.
C: Since C is combined with Nb, C plays an important
role in the control of NbC and Nb(C, N) precipitates. The
amount of C is set to 0.004 to 0.02 %, preferably 0.004 to
0.01 %.
Nb: In order to control the NbC and Nb{C, N)
precipitates, the amount of Nb is set to 0.03 % or more.
However, when the amount of Nb exceeds 0.2 %, the increase
in the rolling load at the hot rolling and the cold rolling
causes the decrease in productivity or the increase in cost.
Therefore, the amount of Nb is set to 0.2 % or less.
In order to increase r value, ([Nb]/ [C])X(12/93) preferably satisfied, and the ([Nb]/[C]) X (12/93) is more
preferably 1.5 to 3.0.
sol.Al: Even when the amount of C is controlled to
0.004 to 0.02 %, and the amount of Nb is controlled to 0.03
to 0.2 %, Ys of 270 MPa or less may not always be obtained
in some cases. It is considered to be due to coarse Nb(C,
N) precipitates formed at hot rolling. As the above-
mentioned, it is believed that the coarse Nb(C, N)
precipitates having the diameter of approximately 50 nm
- 11 -

which is formed at the hot rolling have difficulties to be
coarsened by the Ostwald-ripening at annealing because of
the large size and the smaller solubility in ferrite than
that of NbC precipitates, and the suppression of the PFZ
formation leads to the suppression of the decrease in YS.
Then, the inventors of the present invention
investigated a method for the formation of NbC precipitates
effective for forming PFZ by suppressing coarse Nb(C, N)
precipitates having a diameter of 50 nm or more, and found
that the addition of 0.1 % or more of sol.Al is effective.
It has been believed that-N is combined with Al to form
A1N. However, in steel containing 0.004 % or more of C and
0.03 % or more of Nb, precipitation of Nb(C, N) takes place
at finish rolling before A1N starts to precipitate. When
the amount of Al is increased to 0.1 % or more so that A1N
is precipitated before Nb(C, N) is precipitated, the
precipitation of NbC effective for forming the PFZ can be
proceeded.
Fig. 1 shows the relationship between the amount of
sol.Al and YS, n value and r value.
The results shown in Fig. 1 were obtained by
investigating YS, r value, and n value of cold rolled steel
sheets containing 0.0060 % of C, 0 to 0.45 % of Si, 1.5 to
2 % of Mn, 0.02 % of P, 0.002 % of S, 0.003 % of N, 0.0005 %
of B, 0.11 % of Nb, and 0.01 to 1.7 % of sol.Al, which are
- 12 -

heated at 1150 0C and 1250 0C, followed by the hot rolling to
3 mm thick in the y region and coiling at 560 0C, and
subsequently cold rolled to 0.8 mm thick, followed by
annealing at 820 0C for 80 seconds. Since the increases in
TS by the addition of one percent of Si, Mn, and sol.Al were
86 MPa, 33 MPa, and 32.5 MPa, respectively, the amounts of
Si, Mn, and Al were controlled so as to obtain a constant TS
of approximately 440 MPa. That is,
([Si]+[Mn]/2.6+[sol.Al]/2,6) was controlled to 1.25 %. Here,
[M] represents the amount of element M (mass%) .
YS, r value, and n value are also examined in a
conventional ultra low carbon cold rolled steel sheet
manufactured under the same conditions as described above
using a steel containing 0.0020 % of C, 0.75 % of Si, 2 % of
Mn, 0.02 % Of P, 0.002 % of S, 0.003 % of N, 0.0005 % of B,
0.015 % of Nb, and 0.03 % of Ti.
The cold rolled steel sheets containing 0.004 % or more
of C and 0.03 % or more of Nb have lower YS, higher n value,
and higher r values than the conventional ultra low carbon
cold rolled steel sheet. In particular, when the amount of
sol.Al is 0.1 to 1.5 %, YS becomes 270 MPa or less and n1-10
becomes 0.20 or more. In addition, when the amount of
sol.Al is 0.2 to 0.6 %, the YS is further decreased to 260
MPa or less in both cases of heating temperatures of 1250
and 1150 0C. The ferrite grains were sufficiently fine as
- 13 -

is the case in which the amount of sol.Al is 0.1 % or less.
When the amount of sol.Al is less than 0.1 %, a large
number of Nb(C, N) precipitates having a diameter of 50 nm
or more, which inhibit the formation of PFZ, are observed.
On the other hand, when the amount of sol.Al is 0.1 to 1.5 %,
the coarse Nb(C, N) precipitates are remarkably decreased to
an average area density of 0 to 7.0X10 /m , and the PFZ
is remarkably formed.
The reason why the r value is remarkably increased when
the amount of sol.Al is controlled to 0.1 % or more is not
clear. It is, however, inferred that Al has influences on
the formation of deformation band at cold rolling or on the
amount of solute C.
Si: Si is an element for the solid solution
strengthening, which may be added when it is necessary.
However, the amount of Si which exceeds 1.5 % deteriorates
the ductility and the anti-secondary work embrittlement, and
increases the YS. The amount of Si is set to 1.5 % or less.
In addition, since the addition of Si deteriorates the
conversion treatment properties of a cold rolled steel sheet
and appearance of a hot dip galvanized steel sheet, the
amount of Si is preferably set to 0.5 % or less. In order
to strengthen the steel sheet, the amount of Si is
preferably set to 0,003 % or more.
Mn: Since Mn is also an element for the solid solution
- 14 -

strengthening and an element for preventing the red
shortness, Mn may be added when it is necessary. However,
when the amount of Mn exceeds 3 %, the decrease in ductility
and the increase in YS occur. The amount of Mn is set to
3 % or less. In order to obtain the superior appearance of
the galvanized steel sheet, the amount of Mn is preferably
set to 2 % or less. The amount of Mn is preferably set to
0.1 % or more for the solid solution strengthening.
P: P is an effective element for strengthening the
steel. However, the excessive addition of P deteriorates
the anti-secondary work embrittlement and the ductility, and
causes the increase in YS. Therefore, the amount of P is
set to 0.15 % or less. In order to prevent the
deterioration of alloying treatment properties and adhesion
failure of coating of the galvanized steel sheet, the amount
of P is preferably set to 0.1 % or less. The amount of P is
preferably set to 0.01 % or more to increase the strength of
the steel sheet.
S: S exists as a sulfide in the steel sheet. Since the
excessive amount of S decreases the ductility, the amount of
S is set to 0.02 % or less. 0.004 % or more of S is
desirable for the descaling preferably set to, and 0.01 % or
less of S is favorable for the ductility.
N: Since N is necessary to precipitate as A1N with the
addition of 0.1 to 1.5 % of sol.Al, the amount of N is set
- 15 -

to 0.007 % or less. The amount of N is preferably decreased
as small as possible. However, since the amount of N can
not be decreased to less than 0.001 % by the steel smelting
process, the amount of N is set to 0.001 % or more.
The balance is Fe and inevitable impurities.
In addition to the elements described above, at least
one element selected from the group consisting of 0.0001 to
0.003 % of B, 0.5 % or less of Cu, 0.5 % or less of Ni,
0.3 % or less of Mo, 0.5 % or less of Cr, 0.04 % or less of
Ti, 0.2 % or less of Sb, and 0.2 % or less of Sn is
preferably added for the following reasons.
B: The amount of B is set to 0.0001 % or more in order
to improve the anti-secondary embrittlement. When the
amount of B exceeds 0.003 %, the effect saturates, and the
rolling load at hot rolling is increased. Therefore, the
amount of B is set to 0.0001 to 0.003 %.
Cu, Ni, Mo, and Cr: In order to increase the TS, the
anti-secondary work erabrittlement, and the r value, 0.5 % or
less of Cu, 0.5 % or less of Ni, 0.3 % or less of Mo, and
0.5 % or less of Cr may be added. Cu, Cr, and Ni are the
expensive elements, and when the amount of each element
exceeds 0.5 %, the surface appearance deteriorates.
Although Mo increases the TS without decreasing the anti-
secondary work embrittlement, the amount of Mo exceeding
0.3 % increases the YS. When Cu, Cr, and Ni are added, the
- 16 -

amount of each element is preferably set to 0.03 % or more.
When Mo is added, the amount of Mo is desirably set to
0.05 % or more. When Cu is added, Ni is preferably added
with the same amount as Cu.
Ti: In order to improve the r value, 0.04 % or less of
Ti may be added. The amount of Ti exceeding 0.04 %
increases the coarse precipitates containing Ti, which lead
to the decrease in the TS and the prevention of the decrease
in the YS by the suppression of A1N precipitation. When Ti
is added, the amount of Ti is preferably set to 0.005 % or
more.
Sb and Sn: In order to improve the surface appearance,
the coating adhesion, the fatigue resistance, and the
toughness of the galvanized steel sheet, 0.2 % or less of Sb
and 0.2 % or less of Sri are effectively added so that 0.002
[Sb]+1/2X [Sn]^0.2 is satisfied. Here, [Sb] and [Sn]
represent the amounts'1 of Sb and Sn (mass%) , respectively.
Since the addition of Sb and Sn prevents the surface
nitridation or oxidation at slab heating, at coiling after
hot rolling, at annealing in a CAL or a CGL, or at
additional intermediate annealing, the coating adhesion is
improved in addition to the suppression of the irregular
coating. Furthermore, since the adhesion of zinc oxides to
the steel sheet in a coating bath can be prevented, the
surface appearance of the galvanized steel sheet is also
- 17 -

improved. When the amounts of Sb and Sn exceed 0.2 %, they
deteriorate the coating adhesion and the toughness of the
galvanized steel sheet.
3. Manufacturing Method
The high strength cold rolled steel sheet can be
manufactured by a manufacturing method comprising the steps
of: hot rolling a steel slab having a chemical composition
within the range of the present invention into a hot rolled
steel sheet after heating the steel slab at a heating
temperature SRT which satisfies the following equations (3)
and (4); and pickling and cold rolling the hot rolled steel
sheet, followed by annealing within a temperature range of a
ferrite phase above the recrystallization temperature.
SRT 1050 0C^SRTS{770+([sol.Al]-0.0B5)°*24X820} 0C -(4),
where [sol.Al] represents the amount of sol. Al (mass%).
As shown in Fig. 1, when the amount of sol.Al is 0.1 to
0.6 %, the lower YS can be obtained at the heating
temperature SRT of 1150 0C as compared with that of 1250 0C.
The relation between the amount of sol.Al and SRT and
YS was investigated by using the cold rolled steel sheets
shown in Fig. 1.
As shown in Fig. 2, when the amount of sol.Al is 0.1 to
0.6 %, and SRT {770+([sol.Al]-0. 085) °'24X820} 0C is
satisfied, the low YS such as 260 MPa or less can be
- 18 -

obtained. It is believed to be caused by the suppression of
Nb(C, N) precipitation at hot rolling, accompanied by the
suppression of A1N dissolution at heating by controlling the
SRT. Fine ferrite grains having a grain diameter of 10  m
or less were obtained.
When the SRT is less than 1050 0C, the hot rolling load
is increased, so that the productivity is decreased, and
when the SRT is more than 1350 0C, the surface oxidation
apparently occurs, so that the surface quality deteriorates.
Therefore, SRT1350 0C, and 1050 t:SRT {770+ ([sol.Al] -
0.085)°"24X820} 0C must be satisfied.
In order to obtain the superior surface quality, the
scales formed at slab heating and at hot rolling should be
preferably sufficiently removed. The heating by the use of
a bar heater at hot rolling may also be performed.
The coiling temperature after hot rolling has
influences on the formation of PFZ and the r value. In
order to effectively form the PFZ, fine NbC must be
precipitated, and in order to obtain a high r value, the
amount of solute C must be sufficiently decreased. In view
of the effective formation of PFZ and the high r value, the
coiling temperature is preferably set to 480 to 700 0C, more
preferably 500 to 600 0C.
The high cold rolling reduction is desirable. However,
the cold rolling reduction which exceeds 85 % increases the
- 19 -

rolling load, so that the productivity decreases. Therefore,
the cold rolling reduction is preferably 85 % or less.
The high annealing temperature promotes the
precipitation of coarser NbC existing in the vicinity of
grain boundary, which causes the low YS and the high n value.
Therefore, the annealing temperature is preferably set* to
820 °C or more. When the annealing temperature is lower
than the recrystallization temperature, the sufficiently low
YS and the high n value can not be obtained. Therefore, the
annealing temperature must be at least not less than the
recrystallization temperature. However, when the annealing
temperature exceeds the Ac1 transformation temperature,
ferrite grains become very fine by the ferrite
transformation from the austenite, which leads to increase
the YR. Therefore, the annealing temperature must be the
temperature of the AC1 transformation temperature or less.
When the annealing time is increased, grain boundary
migration occurs more significantly to promote the formation
of PFZ. Therefore, the soaking time is preferably set to 4 0
seconds or more.
A cold rolled steel sheet after annealing may be
galvanized by electrogalvanizing or hot dip galvanizing.
The excellent press formability can also be obtained in the
galvanized steel sheet where pure zinc coating, alloy zinc
coating, and zinc-nickel alloy coating may be applied. Even
- 20 -

when the organic film is deposited after the coating, the
superior press can also be obtained.
Example 1
Several types of steel A to V having the chemical
compositions listed in Table 1 were smelt and continuously
cast into the slabs having a thickness of 230 mm. These
slabs were heated to 1090 to 1325 °C and hot rolled to 3.2
mm thick under the hot rolling conditions listed in Table 2.
These hot rolled steel sheets were cold rolled to 0.8 mm
thick, followed by annealing in a continuous annealing line
(CAL), a hot dip galvanizing line (CGL), or a box annealing
furnace (BAF) under the annealing conditions shown in Table
2, and subsequently, temper rolling with the elongation of
0.5 %.
The hot dip zinc coating was performed at 4 60 °C in the
CGL, followed by the alloying treatment of the coated layer
at 500 °C in an in-line alloying furnace. The amount of the
coating per one surface was 45 g/m2 .
The tensile tests were performed using JIS No. 5 test
pieces cut from the direction of 0° , the direction of 45° ,
and the direction of 90° to the rolling direction,
respectively. The averages of YS, n10, r value, and TS
were obtained by the following equation, respectively.
The average V=([V0]+2[V45]+[V90])/4,
- 21 -

where [V0], [V45] and [V90] show the value of the properties
obtained in the direction of 0° , 45° and 90° to the
rolling direction, respectively.
The ferrite grain diameter was measured by the point-
counting method in the rolling direction, the thickness
direction, and the direction of 45° to the rolling
direction at the cross section parallel to the rolling
direction, and the average of the ferrite grain sizes was
obtained. The sizes of NbC and Nb(C, N) and the average
area density thereof were obtained by the method previously
mentioned.
The results are shown in Table 2.
Samples Nos. 1 to 19 of the present invention have the
YS of 27 0 MPa or less, the n1-10 of 0.20 or more, and the
high r value of 1.8 or more. In particular, the samples Nos.
2 to 6, 9 to 11, 15 to 17, and 19 have the YS of 260 MPa.or
less because the amounts of sol.Al are 0.1 to 0.6 % and the
temperature are within the present invention. In case of
samples of the present invention, the average area density
of coarse Nb(C, N) precipitates having a diameter of 50 nm
or more, which prevents the formation of PFZ, is 7.0X10 /
m2 or less, and the PFZ having a width of 0.2 to 2.4  m
was formed in the vicinity of the ferrite grain boundary.
On the other hand, samples Nos. 20 to 27 of the
comparative examples have the high YS and the low n value
- 22 -

because the average area density of coarse Nb{C, N)
precipitates having a diameter of 50 run or more or the width
of the PFZ is out of the invention. Sample No. 20 in which
the amount of sol.Al is small has the YS of more than 27 0
MPa, the n value of less than 0.20, ant the r value of less
than 1.8. Sample No. 21 in which the amount of sol.Al is
excessive has the YS of more than 270 MPa and the n value of
less than 0.20. Samples Nos. 23, 24, 25, and 26 in which C,
Si, Mn, and P are out of the range of the present invention
have the YS of excessively larger than 270 MPa. Sample No.
27 in which the amount of Nb is small has the n value of
less than 0.20 and the excessively low r value.
Sample No. 22 as the conventional ultra low carbon high
strength cold rolled steel sheet has the YS of much larger
than 270 MPa, and the n value of less than 0.20.
In each of samples Nos. 1 to 19 of the present
invention, the ferrite grains are fine having a diameter of
less than 10  m as compared with that of sample No. 22 of
the conventional example, 11.4 m. Therefore, each of
samples Nos. 1 to 19 of the present invention has the
superior resistance to the occurrence of the orange peel and
the anti-secondary work embrittlement.
- 23 -

- 24 -

- 25 -

We claim :-
1. A high strength cold rolled steel sheet composed of
ferrite grains having an average grain diameter of 10  m or
less, in which the average number per unit area (hereinafter
referred to as "average area density") of Nb{C, N)
precipitates having a diameter of 50 nm or more is 7.0X10 /
 m or less, and a zone having a width of 0.2 to 2.4  m
and an average area density of NbC precipitates of 60 % or
less of that of the central portion of the ferrite grains is
formed along grain boundaries of the ferrite grains.
2. The high strength cold rolled steel sheet according to
Claim 1 consisting of 0-004 to 0.02 % of C, 1.5 % or less of
Si, 3 % or less of Mn, 0.15 % or less of P, 0.02 % or less
of S, 0.1 to 1.5 % of sol.Al, 0.001 to 0.007 % of N, 0.03 to
0.2 % of Nb, by mass, and the balance of Fe and inevitable
impurities.
3. The high strength cold rolled steel sheet according to
Claim 2, wherein the amount of sol.Al is 0.2 to 0.6 %.
4. The high strength cold rolled steel sheet according to
Claim 2, wherein the following equation (1) is satisfied;
([Nb]/[C])X (12/93)^1 -{1),
- 26 -

where [Nb] and [C] represent the amounts of Nb and C (mass%),
respectively.
5. The high strength cold rolled steel sheet according to
Claim 3, wherein the following equation (1) is satisfied;
([Nb]/[C]) X (12/93) >1 -(1),
where [Nb] and [C] represent the amounts of Nb and C (mass%),
respectively.
6. The high strength cold rolled steel sheet according to
Claim 2 further containing 0.0001 to 0.003 % of B.
7. The high strength cold rolled steel sheet according to
Claim 5 further containing .0.0001 to 0.003 % of B.
8. The high strength cold rolled steel sheet according to
Claim 2 further containing at least one element selected
from the group consisting of 0.5 % or less of Cu, 0.5 % or
less of Ni, 0.3 % or less of Mo, 0.5 % or less of Cr, and
0.04 % or less of Ti.
9. The high strength cold rolled steel sheet according to
Claim 7 further containing at least one element selected
from the group consisting of 0.5 % or less of Cu, 0.5 % or
less of Ni, 0.3 % or less of Mo, 0.5 % or less of Cr, and
- 27 -

0.04 % or less of Ti.
10. The high strength cold rolled steel sheet according
to Claim 2 further containing at least one element selected
from the group consisting of 0.2 % or less of Sb and 0.2 %
or less of Sn, wherein the following equation (2) is
satisfied;
0.002 where [Sb] and [Sn] represent the amounts of Sb and Sn
(mass%), respectively.
11. The high strength cold rolled steel sheet according
to Claim 9 further containing at least one element selected
from the group consisting of 0.2 % or less of Sb and 0.2 %
or less of Sn, wherein the following equation (2) is
satisfied;
0.002 where [Sb] and [Sn] represent the amounts of Sb and Sn
mass%), respectively.
12. A method for manufacturing a high strength cold
rolled steel sheet comprising the steps of:
hot rolling a steel slab having the chemical
composition according to any one of Claims 2 to 11 into a
hot rolled steel sheet after heating the steel slab at a
- 28 -

heating temperature SRT which satisfies the following
equations (3) and (4); and
pickling and cold rolling the hot rolled steel sheet,
followed by annealing within a temperature range of a
ferrite phase above the recrystallization temperature,
SRT - 29 -
1050 °C where [sol.Al] represents the amount of sol. Al (mass%).

The present invention relates to a high strength cold
rolled steel sheet composed of ferrite grains having an
average grain diemeter of 10 m or less, in which the
average number per unit area of Nb(C, N) precipitates having
a diemeter of 50 cm or more is 7.0x 10-2/ um2 or less, and a
zone having a width of 0.2 to 2.4 um and an average area
density of NbC precipitates of 60% or less of that of the
cenral portion of the ferrite grains is formed along grain
boundaries of the ferrite grains, for example, the steel
sheet consisting of 0.004 to 0.02% of c, 1.5 % or less of
si, 3% or less of mn, 0.15% or less of p, 0.02 & or less
of s, 0.1 to 1.5 % of sol.Al, 0.001 to 0.007 % of N, 0.03 to
0.2 % of Nb, by mess, and the balance of fe and invitable
impurities. The steel sheet of the present invention is
most preferably used for automobile panel parts since it has
the Ts of 340 MPa or more and superior surface strain
resistance and press formability.

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Patent Number

219927

Indian Patent Application Number

01795/KOLNP/2005

PG Journal Number

20/2008

Publication Date

16-May-2008

Grant Date

14-May-2008

Date of Filing

09-Sep-2005

Name of Patentee

JEE STEEL CORPORATION

Applicant Address

2-3, UCHISAIWAI-CHO 2-CHOME, CHIYODA-KU, TOKYO 100-0011 JAPAN

Inventors:

#	Inventor's Name	Inventor's Address
1	ONO, YOSHIHIKO	C/O INTELLECTUAL PROPERTY DEPT., JFE STEEL CORPORATION, 2-3, UCHISAIWAI-CHO 2-CHOME, CHIYODA-KU, TOKYO 100-0011 JAPAN
2	NAGATAKI, YASUNOBU	C/O INTELLECTUAL PROPERTY DEPT., JFE STEEL CORPORATION, 2-3, UCHISAIWAI-CHO 2-CHOME, CHIYODA-KU, TOKYO 100-0011 JAPAN
3	TANAKA, YASUSHI	C/O INTELLECTUAL PROPERTY DEPT., JFE STEEL CORPORATION, 2-3, UCHISAIWAI-CHO 2-CHOME, CHIYODA-KU, TOKYO 100-0011 JAPAN
4	HARADA, KOZO	C/O INTELLECTUAL PROPERTY DEPT., JFE STEEL CORPORATION, 2-3, UCHISAIWAI-CHO 2-CHOME, CHIYODA-KU, TOKYO 100-0011 JAPAN
5	ANDO, HISANORI	C/O INTELLECTUAL PROPERTY DEPT., JFE STEEL CORPORATION, 2-3, UCHISAIWAI-CHO 2-CHOME, CHIYODA-KU, TOKYO 100-0011 JAPAN

PCT International Classification Number

C21D 9/46 ;C22C 38/00

PCT International Application Number

PCT/JP2004/017990

PCT International Filing date

2004-11-26

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2003-407 124	2003-12-05	Japan