Steel sheet having high young's modulus, hot-dip galvanized steel sheet using the same, alloyed hot-dip galvanized steel sheet, steel pipe having high young's modulus, and methods for manufacturing the same

Abstract
In an embodiment of a steel sheet having high Young's modulus, the steel can include in terms of mass %, e.g., C: 0.0005 to 0.30%, Si: 2.3% or less, Mn: 2.7 to 5.0%, P: 0.15% or less, 0.015% or less, Mo: 0.15 to 1.5%, B: 0.0006 to 0.01%, and Al: 0.15% or less, with the remainder being Fe and unavoidable impurities. One or both of {110}<223> pole density and {110}<111> pole density in the ⅛ sheet thickness layer can be 10 or more, and a Young's modulus in a rolling direction can be more than 230 GPa. Other embodiments can include, e.g., Mn: 0.1 to 5.0%, N: 0.01% or less, and one or more of Mo: 0.005 to 1.5%, Nb: 0.005 to 0.20%, Ti: at least 48/14×N (mass %) and 0.2% or less, and B: 0.0001 to 0.01%, at a total content of 0.015 to 1.91 mass %.
Description
TECHNICAL FIELD

The present invention relates to steel sheets having high. Young's modulus, hot-dip galvanized steel sheets using the same, alloyed hot-dip galvanized steel sheets, and steel pipes having high Young's modulus, and methods for manufacturing these.


This application claims priority from Japanese Patent Application No. 2004-218132 filed on Jul. 27, 2004, Japanese Patent Application No. 2004-330578 filed on Nov. 15, 2004, Japanese Patent Application No. 2005-019942 filed on Jan. 27, 2005, and Japanese Patent Application No, 2005-207043 filed on Jul. 15, 2005, the contents of which are incorporated herein by reference.


BACKGROUND ART

Many reports have been made on technologies for raising the Young's modulus. Most of those have pertained to technologies for increasing the Young's modulus in the rolling direction (RD) and in the transverse direction (TD) perpendicular to the rolling direction (RD).


Patent Documents 1 through 9, for example, each discloses a technology for increasing the Young's modulus in the TD direction by carrying out pressure rolling in the α+γ2 phase region.


Patent Document 10 discloses a technology for increasing the Young's modulus in the TD direction by subjecting the surface layer to pressure rolling in a temperature of less than the Ar3 transformation temperature.


On the other hand, technologies for increasing the Young's modulus in the transverse direction and simultaneously increasing the Young's modulus in the rolling direction also have been proposed. That is, Patent Document 11 proposes increasing both Young's moduli by carrying out rolling in a fixed direction as well as rolling in the transverse direction perpendicular to this direction. However, changing the rolling direction during the continuous hot-rolling processing of a thin-sheet noticeably compromises the productivity, and thus this is not practical.


Patent Document 12 discloses a technology related to cold-rolled steel sheets with a high Young's modulus, but in this case as well, the Young's modulus in the TD direction is high but the Young's modulus in the PD direction is not high.


Also, Patent Document 4 discloses a technology for increasing the Young's modulus by adding a composite of Mo, Nb, and B, but because the hot rolling conditions are completely different, the Young's Modulus in the TD direction is high but the Young's modulus in the RD direction is not high.


As illustrated above, although conventionally steel sheets having “high Young's modulus” have existed, all of these were steel sheets with high Young's moduli in the rolling direction (RD) and the transverse direction (TD). Incidentally, the maximum width of a steel sheet is about 2 m, and thus, if the direction with the largest Young's modulus is the lengthwise direction of the member, then the steel sheet could not be any longer than it is wide. Consequently, a demand has existed for steel sheets with a high Young's modulus in the rolling direction, that can serve as long members. Further, hot rolling in the α+γ region, in which fluctuations in the rolling reaction force readily occur, has been a prerequisite for the manufacturing methods, and this has caused a problem in the productivity.


When processing steel sheets into components for automobiles or construction, the ability of the steel sheet to fix into the proper shape is a major issue. For example, a steel sheet that has been bent tries to spring back to its original have when the load is removed, and this may lead to the problem that a desired shape cannot be obtained. This problem has become even more pronounced as steel sheets have become stronger, and is an obstacle when high-strength steel sheets are to be adopted as components.


Patent Document 1: Japanese Unexamined Patent Application, First Publication No. S5.9-83721


Patent Document 2: Japanese Unexamined Patent Application, First Publication No. H5-263191


Patent Document 3: Japanese Unexamined Patent Application, First Publication No. H8-283842


Patent Document 4: Japanese Unexamined Patent Application, First Publication No, H8-311541


Patent Document 5: Japanese Unexamined Patent Application, First Publication No. H9-53118


Patent Document 6: Japanese Unexamined Patent Application, First Publication No. H4-136120


Patent Document 77 Japanese Unexamined Patent Application, First Publication No. H4-141519


Patent Document 8: Japanese Unexamined Patent Application, First Publication No. H4-147916


Patent Document 9: Japanese Unexamined Patent Application, First Publication No. H4-293719


Patent Document 10: Japanese Unexamined Patent Application, First. Publication No. H4-143216


Patent Document 11: Japanese Unexamined Patent Application, First Publication No. H4-147917


Patent Document 12: Japanese Unexamined Patent Application, First Publication No. H5-255804


DISCLOSURE OF INVENTION
Problems to be Solved by the Invention

The present invention was arrived at in light of the foregoing matters, and it is an object thereof to provide a steel sheet having high Young's modulus that has an excellent Young's modulus in the rolling direction (RD direction), and a hot-dip galvanized steel sheet using the same, an alloyed hot-dip galvanized steel sheet, a steel pipe having high Young's modulus, and methods for manufacturing these.


Means for Solving the Problems

The keen research conducted by the inventors for the purpose of achieving the foregoing objects lead to the unconventional findings discussed below.


That is, by developing a predetermined texture near the surface of a steel that contains a predetermined amount of C, Si, Mn, P, S, Mo, B and Al, or C, Si, Mn, P, S, Mo, B, Al, N, Nb, and Ti, the inventors were successful in attaining a steel sheet with a high Young's modulus in the rolling direction.


The steel sheet that is obtained through the invention has a particularly high Young's modulus of 240 GPa or more near its surface and thus has noticeably improved bend formability, and for example, its shape fixability also is noticeably improved. The reason behind why the increase in strength results in more shape fix defects such as spring back is that there is a large rebound when the weight that is applied during press deformation has been removed. Consequently, increasing the Young's modulus keeps the rebound down, and it becomes possible to reduce spring back. Additionally, since the deformation behavior near the surface layer, where the bend moment is large during bending deformation, noticeably affects the shape fixability, a noticeable improvement becomes possible by increasing the Young's modulus in the surface layer only.


The present invention is a completely novel steel sheet, and a method for manufacturing the same, that has been conceived based on the above concepts and novel findings and that is not found in the conventional art, and the gist of the invention is as follows.


(1) A steel sheet having high Young's modulus, that includes, in terms of mass %, C: 0.0005 to 0.30%, Si: 2.5% or less, Mn: 2.7 to 50%, P: 0.15% or less, 0.015% or less, Mo: 0.15 to 1.5%, B: 0.0006 to 0.01%, and Al: 0.15% or less, with the remainder being Fe and unavoidable impurities, wherein one or both of {110}<223> pole density and {110}<111> pole density in the ⅛ sheet thickness layer is 10 or more, and a Young's modulus in a rolling direction is more than 230 GPa.


(2) The steel sheet having high Young's modulus as described in (1), wherein the {112}<110> pole density in the ½ sheet thickness layer is 6 or more.


(3) The steel sheet having high Young's modulus as described in (1), which further includes one or two of Ti: 0.001 to 0.20 mass % and Nb: 0.001 to 0.20 mass %.


(4) The steel sheet having high Young's modulus as described in (1), wherein a BH amount (MPa), which is evaluated by the value obtained by subtracting a flow stress when stretched 2% from an upper yield point when, after stretched 2%, the steel sheet is heat treated at 170° C. for 20 minutes and then a tensile test is performed again, is in a range from 5 MPa or more to 200 MPa or less.


(5) The steel sheet having high Young's modulus as described in (1), which further includes Ca at 0.0005 to 0.01 mass %.


(6) The steel sheet having high Young's modulus as described in (1), which further includes one or two or more of Sn, Co, Zn, W, Zr, V, Mg, and REM at a total content of 0.001 to 1.0 mass %.


(7) The steel sheet having high Young's modulus as described in (1), which further includes one or two or more of Ni, Cu, and Cr at a total content of 0.001 to 4.0 mass %.


(8) A hot-dip galvanized steel sheet includes: the steel sheet having high Young's modulus as described in (1); and hot-dip zinc plating that is applied to the steel sheet having high Young's modulus.


(9) An alloyed hot-dip galvanized steel sheet includes: the steel sheet having high Young's modulus as described in (1); and alloyed hot-dip zinc plating that is applied to the steel sheet having high Young's modulus.


(10) A steel pipe having high Young's modulus includes the steel sheet having high Young's modulus as described in (1), wherein the steel, sheet having high Young's modulus is curled in any direction.


(11) A method for manufacturing the steel sheet having high Young's modulus as described in (1), includes heating a slab containing, in terms of mass %, C: 0.0005 to 0.30%, Si: 2.5% or less, Mn: 2.7 to 5.0%, P: 0.15% or less, S: 0.015% or less, Mo: 0.15 to 1.5%, B: 0.0006 to 0.01%, and Al: 0.15% or less, with the remainder being Fe and unavoidable impurities, at a temperature of 950° C. or more and subjecting the slab to hot rolling so as to obtain a hot rolled steel sheet, wherein the hot rolling is carried out under conditions where rolling is performed at 800° C. or less in such a manner that a coefficient of friction between the pressure rollers and the steel sheet is greater than 0.2 and the total of the reduction rates is 50% or more, and the hot rolling is finished at a temperature in a range from the Ar3 transformation temperature or more to 750° C. or less.


(12) The method for manufacturing the steel sheet having high Young's modulus as described in (11), wherein in the hot rolling process, at least one pass of differential speed rolling at a different roll speeds ratio of 1% or more is conducted.


(13) The method for manufacturing die steel sheet having high Young's modulus as described in (11), wherein in the hot rolling process, pressure rollers whose roller diameter is 700 mm or less are used in one or more passes.


(14) The method for manufacturing the steel sheet having high Young's modulus as described in (11), which further includes annealing the hot roiled steel sheet after the hot rolling is finished, through a continuous annealing line or box annealing under the conditions in which a maximum attained temperature is in a range from 500° C. or more to 950° C. or less.


(15) The method for manufacturing the steel sheet having high Young's modulus as described in (11), which further includes: subjecting the hot rolled steel sheet after the hot rolling is finished to cold rolling at the reduction rate of less than 60%; and annealing after the cold rolling.


(16) The method for manufacturing the steel sheet having high Young's modulus as described in (11), which further includes: subjecting the hot rolled steel sheet to cold rolling at the reduction rate of less than 60%; annealing under the conditions in which a maximum attained temperature is in a range from 500° C. or more to 950° C. or less after the cold rolling; and cooling to 550° C. or less after the annealing and then performing thermal processing at 150 to 550° C.


(17) A method for manufacturing a hot-dip galvanized steel sheet, includes: manufacturing an annealed steel sheet having high Young's modulus by the method for manufacturing a steel sheet having high Young's modulus as described in (14); and subjecting the steel sheet having high Young's modulus to hot-dip galvanization.


(18) A method for manufacturing an alloyed hot-dip galvanized steel sheet, includes: manufacturing a hot-dip galvanized steel sheet by the method for manufacturing a hot-dip galvanized steel sheet as described in (17); and subjecting the hot-dip galvanized steel sheet to thermal processing in a temperature range of 450 to 600° C. for 1.0 seconds or more.


(19) A method for manufacturing a hot-dip galvanized steel sheet, includes manufacturing an annealed steel sheet having high Young's modulus by the method for manufacturing a steel sheet having high Young's modulus as described in (15); and subjecting the steel sheet having high Young's modulus to hot-dip galvanization.


(20) A method for manufacturing an alloyed hot-dip galvanized steel sheet, includes: manufacturing a hot-dip galvanized steel, sheet by the method for manufacturing a hot-dip galvanized steel sheet as described in (19); and subjecting the hot-dip galvanized steel sheet to thermal processing in a temperature range of 450 to 600° C. for 10 seconds or more.


(21) A method for manufacturing a steel pipe having high Young's modulus, includes: manufacturing a steel sheet having high Young's modulus by the method for manufacturing a steel sheet having high Young's modulus as described in (11); and curling the steel sheet having high Young's modulus in any direction so as to manufacture a steel pipe.


(22) A steel sheet having high Young's modulus, includes, in terms of mass %, C: 0.0005 to 0.30%, 2.5% or less, Mn: 0.1 to 5.0%, P: 0.15% or less, S: 0.015% or less, Al: 0.15% or less, N: 0.01% or less; and further includes one or two or more of Mo: 0.005 to 1.5%, Nb: 0.005 to 0.20%, Ti at least 48/14×N (mass %) and 0.2% or less, and B: 0.0001 to 0.01%, at a total content of 0.015 to 1.91 mass %, with the remainder being Fe and unavoidable impurities, wherein the {110}<223> pole density and/or the {110}<111> pole density in the ⅛ sheet thickness layer is 10 or more, and a Young's modulus in a rolling direction is more than 230 GPa.


(23) The steel sheet having high Young's modulus as described in (22), wherein the steel sheet includes all, of Mo, Nb, Ti, and B, the respective contents are Mo: 0.15 to 1.5%, Nb: 0.01 to 0.20%, Ti: at least 48/14×N (mass %) and 0.2% or less, and B: 0.0006 to 0.01%; and the {110}<001> pole density in the ⅛ sheet thickness layer is 3 or less.


(24) The steel sheet having high Young's modulus as described in (22), wherein the {110}<001> pole density in the ⅛ sheet thickness layer is 6 or less.


(25) The steel sheet having high Young's modulus as described in (22), wherein the Young's modulus in the rolling direction is 240 GPa or more in at least a range from the surface layer to the ⅛ sheet thickness layer.


(26) The steel sheet having high Young's modulus as described in (22), wherein the {211}<011> pole density in the ½ sheet thickness layer is 6 or more.


(27) The steel sheet having high Young's modulus as described in (22), wherein the {332}<113> pole density in the ½ sheet thickness layer is 6 or more.


(28) The steel sheet having high Young's modulus as described in (22), wherein the {100}<011> pole density in the ½ sheet thickness layer is 6 or less.


(29) The steel sheet having high Young's modulus as described in (22), wherein a BH amount (MPa), which is evaluated by the value obtained by subtracting the flow stress when stretched 2% from an upper yield point when, after stretched 2%, the steel sheet is heat treated at 170° C. for 20 minutes and then a tensile test is performed again, is in a range from 5 MPa or more to 200′MPa or less.


(20) The steel sheet having high Young's modulus as described in (22), which further includes Ca: 0.0005 to 0.01 mass %.


(31) The steel sheet having high Young's modulus as described in (22), which further includes one or two or more of Sn, Co, Zn, W, Zr, V, Mg, and REM at a total content of 0.001 to 1.0 mass %.


(32) The steel sheet having high Young's modulus as described in (22), which further includes one or two or more of Ni, Cu, and Cr at a total content of 0.001 to 4.0 mass %.


(33) A hot-dip galvanized steel sheet includes: the steel sheet having high Young's modulus as described in (22), and hot-dip zinc plating that is applied to the steel sheet having high Young's modulus.


(34) An alloyed hot-dip galvanized steel sheet includes: the steel sheet having high Young's modulus as described in (22); and alloyed hot-dip zinc plating that is applied to the steel sheet having high Young's modulus.


(35) A steel pipe having high. Young's modulus includes the steel sheet having high Young's modulus as described in (22), wherein the steel sheet having high Young's modulus is curled in any direction.


(36) A method for manufacturing the steel sheet having high. Young's modulus as described in (22), includes: heating a slab containing, in terms of mass %, C; 0.0005 to 0.30%, 2.5% or less, Mn: 0.1 to 5.0%, P: 0.15% or less, 0.015% or less, Al: 0.15% or less, N: 0.01% or less, and further containing one or two or more of Mo: 0.005 to 1.5%, Nb: 0.005 to 0.20%, Ti: at least 48/14×N (mass %) and 0.2% or less, and B: 0.0001 to 0.01%, at a total content of 0.015 to 1.91 mass %, with the remainder being Fe and unavoidable impurities, at a temperature of 1000° C. or more and subjecting the slab to hot rolling so as to obtain a of rolled steel sheet, wherein in the hot rolling, the rolling is carried out in such a manner that a coefficient of friction between the pressure rollers and the steel sheet is greater than 0.2, an effective strain amount ε* calculated by the following Formula [1] is 0.4 or more, and the total of the reduction rates is 5.0% or more, and the hot rolling is finished at a temperature in a range from the Ar3 transformation temperature or more to 900° C. or less,










ɛ
*

=





j
=
1


n
-
1





ɛ
j



exp


[

-




i
=
j


n
-
1





(


t
i


τ
i


)


2
/
3




]




+

ɛ
n






[
1
]







in which n is the number of rolling stands of the finishing hot rolling, is the strain added at the j-th stand, εn is the strain added at the n-th stand, is the travel time (seconds) between the i-th and the i+1-th stands, and τi can be calculated by the following Formula [2] using the can constant R (−1.987) and the rolling temperature Ti (K) of the i-th stand.

τi=8.46×10−9×exp{43800/R/Ti}  [2]


(37) The method for manufacturing a steel sheet having high Young's modulus as described in (36), wherein in the hot rolling, at least one pass of differential speed rolling at a different roll speeds ratio of 1% or more is conducted.


(38) The method for manufacturing a steel sheet having high Young's modulus as described in (36), wherein in the hot rolling process, pressure rollers whose roller diameter is 700 mm or less are used in one or more passes.


(39) The method for manufacturing a steel sheet having high Young's modulus as described in (36), which further includes annealing the hot rolled steel sheet after the hot rolling is finished, through a continuous annealing line or box annealing under the conditions in which a maximum attained temperature is in a range from 500° C. or more to 950° C. or less.


(40) The method for manufacturing a steel sheet having high Young's modulus as described in (36), which further includes: subjecting the hot rolled steel sheet after the hot rolling is finished to cold rolling at the reduction rate of less than 60%; and annealing after the cold rolling.


(41) The method for manufacturing a steel sheet having high. Young's modulus as described in (36), which further includes: subjecting the hot rolled steel sheet to cold rolling at the reduction rate of less than 60%; annealing under the conditions in which a maximum attained temperature is in a range from 500° C. or more to 950° C. or less after the cold rolling; and cooling to 550° C. or less after the annealing and then performing thermal processing at 150 to 550° C.


(42) A method for manufacturing a hot-dip galvanized steel sheet, includes: manufacturing an annealed steel sheet having high Young's modulus by the method for manufacturing a steel sheet having high Young's modulus as described in (39); and subjecting the steel sheet having high Young's modulus to hot-dip galvanization.


(43) A method for manufacturing an alloyed hot-dip galvanized steel sheet, includes: manufacturing a hot-dip galvanized steel sheet by the method for manufacturing a hot-dip galvanized steel sheet as described in (42); and subjecting the hot-dip galvanized steel sheet to thermal processing in a temperature range of 450 to 600° C. for 10 seconds or more.


(44) A method for manufacturing a hot-dip galvanized steel sheet, includes: manufacturing an annealed steel sheet having high Young's modulus by the method for manufacturing a steel sheet having high Young's modulus as described in (40); and subjecting the steel sheet having high Young's modulus to hot-dip galvanization.


(45) A method for manufacturing an alloyed hot-dip galvanized steel sheet, includes: manufacturing a hot-dip galvanized steel sheet by the method for manufacturing a hot-dip galvanized steel sheet as described in (44); and subjecting the hot-dip galvanized steel sheet to thermal processing in a temperature range of 450 to 600° C. for 10 seconds or more.


(45) A method for manufacturing a steel pipe having high Young's modulus, includes manufacturing a steel sheet having high Young's modulus by the method for manufacturing a steel sheet having high Young's modulus as described in (36); and curling the steel sheet having high Young's modulus in any direction so as to manufacture a steel pipe.


Advantageous Effects of the Invention

In accordance with the steel sheet having high Young's modulus of the present invention, it becomes possible to develop the shear texture near the surface layer in the low-temperature γ region by defining the composition set forth in (1) or in (22), Further, adopting the texture set forth in (1) or in (22) allows an excellent Young's modulus to be achieved in the rolling direction (RD direction) in particular.


In accordance with the method for manufacturing a steel sheet having high Young's modulus of the present invention, it becomes possible to develop the shear texture near the surface layer in the low-temperature γ region by using a slab having the composition set forth in (11) or in (36). Further, by hot rolling under the conditions described above, it is possible to achieve the texture set forth in (1) or in (22), and a steel sheet with an excellent Young's modulus in the rolling direction (RD direction) in particular can be obtained.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 is a cross-sectional view showing the test piece used in the hat shape bending test.





BEST MODE FOR CARRYING OUT THE INVENTION

The reasons for limiting the steel composition and the manufacturing conditions as described above in the invention are explained below.


First Embodiment

The steel sheet of the first embodiment contains, in percent by mass, C: 0.0005 to 0.30%, Si: 2.5% or less, Mn: 2.7 to 5.0%, P: 0.15% or less, S: 0.015% or less, Mo: 0.15 to 1.5%, B: 0.0006 to 0.01%, and Al: 0.15% or less, and the remainder is Fe and unavoidable impurities. One or both of the {110}<223> pole density and the {110}<111> pole density in the ⅛ sheet thickness layer is 10 or more, and the Young's modulus in the r ng direction is more than 230 GPa.


C is an inexpensive element that increases the tensile strength, and thus the amount of C that is added is adjusted in accordance with the target strength level. When C is less than 0.0005 mass %, not only does the production of steel become technically difficult and cost, most, but the fatigue properties of the welded sections become worse as well. Thus, 0.0005 mass % serves as the lower limit. On the other hand, a C amount above 030 mass % leads to a deterioration in moldability and adversely affects the weldability. Thus, 0.30 mass % serves as the upper limit.


Si not only acts to increase the strength as a solid solution strengthening element, but it also is effective for obtaining a structure that includes martensite or bainite as well as the residual γ, for example. The amount of Si that added is adjusted according to the target strength level. When the amount added is greater than 2.5 mass %, the press moldability becomes poor and leads to a drop in the chemical conversion. Thus, 2.5 mass % serves as the upper limit.


When hot-dip galvanization is conducted, Si causes problems such as lowering the plating adherence and lowering the productivity by delaying the alloying reaction, and thus it is preferable that Si is 1.2 mass % or less. Although no particular lower limits are set, production costs increase when the Si is 0.001 mass % or less, and thus the practical lower limit is above 0.001 mass %.


Mn is important in the present invention. That is to say, it is an element that is essential for obtaining a high Young's modulus. In the present invention, Mn can develop the Young's modulus in the rolling direction by developing the shear texture near the steel sheet surface layer in the low-temperature γ region. Mn stabilizes the γ phase and causes the γ region to expand down to low temperatures, thus facilitating low-temperature γ region rolling. Mn itself also may effectively act toward formation of the shear texture near the surface layer. From this standpoint, at least 2.7 mass % of Mn is added. On the other hand, when Mn is present at greater than 5.0 mass %, the strength becomes too high and lowers the ductility and hinders the ability of the zinc plating to adhere tightly. Thus, 5.0 mass % serves as the upper limit. Preferably this is 2.9 to 4.0 mass %.


P, like Si, is known to be an element that is inexpensive and increases strength, and in cases where it is necessary to increase the strength, additional P can be actively added. P also has the effect of achieving a finer hot rolled structure and improves the workability. However, when P is added at greater than 0.15 mass %, the fatigue strength after spot welding may become poor or the yield strength may increase too much and lead to surface shape defects when pressing. Further, when continuous hot-dip galvanization is performed, the alloying reaction becomes extremely slow, and this lowers the productivity. The secondary work embrittlement also becomes worse. Consequently, 0.15 mass % serves as the upper limit.


S, when present at greater than 0.015 mass %, becomes a cause of hot cracking and lowers the workability, and thus its upper limit is 0.015 mass %.


Mo and B are crucial to the present invention. It is not until these elements have been added that it becomes possible to increase the Young's modulus in the rolling direction. The reason for this is not absolutely clear, but it is believed that the effect of the combined addition of Mn, Mo and B changes the crystal rotation through shearing deformation that results from friction between the steel sheet and the hot roller. The result is that an extremely sharp texture is formed in the region from the surface layer of the hot rolling sheet down to about the ¼ sheet thickness layer, and this increases the Young's modulus in the rolling direction.


The lower limits of the amount of Mo and B are 0.15 mass % and 0.0006 mass %, respectively. This is because when added at amounts less than these, the effect of increasing the Young's modulus discussed above becomes small. On the other hand, when adding Mo and B more than 1.5 mass % and 0.01 mass %, respectively, it will not cause the effect of raising the Young's modulus to increase further and only increases costs, and thus 1.5 mass % and 0.01 mass % serve as the respective upper limits.


It should be noted that the effect of increasing the Young's modulus by simultaneously adding these elements can be further enhanced by combining them with C as well. Thus, it is preferable that the amount of C is 0.015 mass % or more.


Al can be used as a deoxidation regulator. However, since Al noticeably increases the transformation temperature and thus makes pressure rolling in the low-temperature γ region difficult, its upper limit is set to 0.15 mass %.


It is preferable that the steel sheet of the present embodiment contains Ti and Nb in addition to the components mentioned above. Ti and Nb have the effect of enhancing the effects of the Mn, Mo, and B discussed above to further increase the Young's modulus. They also are effective in improving the workability, increasing the strength, and making the structure finer and more uniform, and thus can be added as necessary. However, no effect is seen when these are added at less than 0.001 mass %, whereas the effects tend to plateau when these are added at more than 0.20 mass %, and thus this serves set as the upper limit. Preferably, these are present at 0.015 to 0.09 mass %.


Ca is useful as a deoxidizing element, and also exhibits an effect on the shape control of sulfides, and thus it can be added in a range of 0.0005 to 0.01 mass %. It does not have a sufficient effect when it is present at less than 0.0005 mass %, whereas it hampers the workability when it is added to greater than 0.01 mass %, and thus this range has been adopted.


A steel sheet that contains these as its primary components also may contain Sn, Co, Zn, W, Zr, Mg, and one or more REMs at a total content of 0.001 to 1 mass %. Here, REM refers to rare earth metal elements, and it is possible to select one or more from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.


However, Zr forms ZrN and thus reduces the amount of solid solution N, and for this reason it is preferable that Zr is present at 0.01 mass % or less.


Ni, Cu, and Cr are useful elements for performing low-temperature γ region rolling, and one or two or more of these can be added at a combined total of 0.001 to 4.0 mass %. No noticeable effect is obtained when this is less than 0.001 mass %, whereas adding more than 4.0 mass % adversely affects the workability.


N is a γ-stabilizing element, and thus is a useful element for conducting low-temperature γ region rolling. Thus, it can be added up to 0.02 mass %. 0.02 mass % serves as the practical upper limit because addition beyond that makes manufacturing difficult.


It is preferable that the amount of solid solution N and the solid solution C each is from 0.0005 to 0.004 mass %. When a steel sheet that contains these is processed as a member component, strain aging occurs even at room temperature and raises the Young's modulus. For example, when the steel sheet is adopted in automobile applications, executing paint firing after processing increases not only the yield strength but also the Young's modulus of the steel sheet.


The amount of solid solution N and solid solution C can be found by subtracting the amount of C and N present (measured quantity from chemical analysis of the extract residue) as the compounds with Fe, Al, Nb, Ti, and B, for example, from the total C and N content. The amount also may be found using an internal friction method or FIM (Field Ion Microscopy).


When the solid solution C and N content is less than 0.0005 mass %, a sufficient effect cannot be attained. When this is greater than 0.001 mass %, the BH properties tend to become saturated and thus 0.004 mass % serves as the upper limit.


The texture, Young's modulus, and the BH content of the steel sheet are described next.


The {110}<223> pole density and/or the {110}<111> pole density in the ⅛ sheet thickness layer of the steel plate of the first embodiment is 10 or more. As a result, it is possible to increase the Young's modulus in the rolling direction. When the pole density is less than 10, it is difficult to increase the Young's modulus in the rolling direction to above 230 GPa. The pole density is preferably 14 or more, and more preferably 20 or more.


The pole density (X-ray random strength ratio) in these orientations can be found from the three dimensional texture (ODF) calculated by a series expansion method based on a plurality of pole figures from among the {110}, {100}, {211}, and {310} pole figures measured by X-ray diffraction. In other words, the pole densities of the various crystal orientations is represented by the strength of (110)[2-23] and (110)[1-11] in the φ2=45° cross-section of the three-dimensional texture.


An example of how the pole density is measured is shown below.


The sample for X-ray diffraction was produced as follows.


A steel sheet was polished to a predetermined position in the sheet thickness direction through mechanical polishing or chemical polishing, for example. This polished surface was buffed into a mirror surface and then, while removing warping through electropolishing or chemical polishing, the thickness is adjusted so that the ⅛ layer thickness or the ½ layer thickness discussed later becomes the measured surface. For example, in the case of the ⅛ layer, when t serves as the thickness of the steel plate, then the steel plate surface is polished to a t/8 polishing thickness and the polished surface that is exposed serves as the measured surface. It should be noted that it is difficult to obtain a measured surface that is exactly ⅛ or ½ the sheet thickness, and thus it is sufficient to produce a sample whose measured surface is in a range of −3% to +3% the thickness of the target layer. Also, in cases where a segregation band is observed in the sheet thickness layer center layer of the steel sheet, it is possible to conduct measurement at a location where the segregation band does not exist, in a range of ⅜ to ⅝ sheet thickness. Further, in cases where X-ray measurement is difficult, it is possible to measure statistically significant values by EBSP or ECP.


The {hkl}<uvw> discussed above means that when the sample for X-ray is obtained as described above, the crystal orientation perpendicular to the sheet surface is <hkl> and the lengthwise direction of the steel sheet is <uvw>.


The characteristics of the texture of the steel sheet cannot be expressed by ordinary reverse pole figures or positive pole figures only, and for example, in a case where the reverse pole figure, which expresses the crystal orientation in the surface normal direction of the steel sheet, is measured near the ⅛ sheet thickness layer, then the surface strength ratio (X-ray random strength ratio) of the orientations is preferably <110>: 5 or more, and <112>: 2 or more. For the ½ sheet thickness layer, it is preferable that <112>: 4 or more, and <3.32>1.5 or more.


These limitations regarding the pole density are satisfied for at least the ⅛ sheet thickness layer, but it is preferable that these limitations are met not only for the ⅛ layer but also over a broad range up to the ¼ layer from the sheet thickness surface layer. Further, {110}<001> and {110}<110> are almost non-existent in the ⅛ sheet thickness layer, and their pole densities preferably are less than 1.5 and more preferably less than 1.0. In conventional, steel sheets this orientation was present to a certain extent in the surface layer, and thus it was not possible to increase the Young's modulus in the rolling direction.


In the first embodiment, it is further preferable that the {112}<110> ((112)[1-10] in the φ2=45° cross-section of the ODF) pole density in the ½ sheet thickness layer is 6 or more. When this orientation is developed, the <11.1> orientation builds up in the transverse direction (hereinafter, also referred to as the TD direction) perpendicular to the rolling direction, and the Young's modulus in the TD direction increases as a result. It is difficult for the Young's modulus in the TD direction to exceed 230 GPa when this pole density is less than 6, and thus this serves as the lower limit. Preferably the pole density is 8 or more, and more preferably is 10 or more.


The {554}<225> and {332}<113> ((554) [−2-25] and (332) [−1-13] in the φ2=45′ cross-section of the ODF) pole densities in the ½ sheet thickness layer can be expected to slightly contribute to the Young's modulus in the rolling direction, and thus preferably is 3 or more.


It should be noted that each of the crystal orientations discussed above permits variation within from −2.5° onward to within +2.5°.


By simultaneously meeting the criteria for the pole densities of the crystal orientations in the ⅛ sheet thickness layer and the ½ sheet thickness layer, it is possible to achieve a Young's modulus in both the rolling direction and the TD direction that exceeds 230 GPa.


The Young's modulus in the rolling direction of the steel sheet of the first embodiment is greater than 230 GPa. Measurement of the Young's modulus is performed by a lateral resonance method at room temperature in accordance with Japanese Industrial Standard JISZ2280 “High-Temperature Young's Modulus Measurement of Metal Materials”. In other words, vibrations are applied from an external transmitter to a sample that is not fastened and is allowed to float, and the number of vibrations of the transmitter is chanced gradually while the primary resonance frequency of the lateral resonance of the sample is measured, and from this the Young's modulus is calculated by Formula [3] below.

E=0.946×(l/h)3×m/w×f2  [3]


Here, E is the dynamic Young's modulus (N/m2), 1 is the length (m) of the test piece, h is thickness (m) of the test piece, m is the mass (kg), w is the width (m) of the test piece, and f is the primary resonance frequency (sec) of the lateral resonance method.


It is preferable that the BH amount of the steel sheet is 5 MPa or more That is, this is because the measured Young's modulus increases when mobile dislocations are fixed by paint firing. This effect becomes poor when the BH amount is less than 5 MPa, and a superior effect is not observed when the BH amount exceeds 200 MPa. Thus, the range for the BH amount is set to 5 to 200 MPa. The BH amount is more preferably 30 to 100 MPa.


It should be noted that the BH amount is expressed by Formula [4] below, in which σ2 (MPa) is the flow stress when the steel sheet has been stretched 2%, and σ1 (MPa) is the upper yield point when, after the steel sheet has been stretched 2%, it is treated with heat at 170° C. for 20 minutes and then stretched again.

BH=σ1−σ2(MPa)  [4]


It should be noted that Al-based plating or various types of electroplating may be conducted on the hot-rolled steel, sheets and the cold-rolled steel sheets. Depending on the objective, it is also possible to perform surface processing such as providing an organic film, an inorganic film, or various paints, on the hot-rolled steel sheets, the cold-rolled steel sheets, and the steel sheets obtained by subjecting these steel sheets to various types of plating.


The method for manufacturing the steel sheet of the first embodiment is described next.


The first embodiment includes heating a slab that contains, in percent by mass, C: 0.0005 to 0.30%, Si: 2.5% or less, Mn: 2.7 to 5.0%, P: 0.15% or less, S: 0.015% or less, Mo: 0.15 to 1.5%, B: 0.0006 to 0.01%, and Al: 0.15% or less, and the remainder being Fe and unavoidable impurities, at 950° C. or more and subjecting the slab to hot rolling to produce a hot-rolled steel sheet.


There are no particular limitations regarding the slab that is provided for this hot rolling. In other words, it is only necessary that it has been produced by a continuous casting slab or a thin slab caster, for example. The slab is also suited for a process such as continuous casting-direct rolling (CC-DR), in which hot rolling is performed immediately after casting.


To produce the hot-rolled steel sheet as a final product, it is necessary to limit the manufacturing conditions as follows.


The hot rolling heating temperature is set to 950° C. or more. This is the temperature required to set the hot-rolling finishing temperature mentioned later to the Ar3 transformation temperature or more.


Hot rolling is performed so that the total of the reduction rates per pass at 800° C. or less is 50% or more. The coefficient of friction between the pressure rollers and the steel sheet at this time is greater than 0.2. This is an essential condition for developing the shearing texture of the surface layer so as to increase the Young's modulus in the rolling direction.


It is preferable that the total of the reduction rates is 70% or more, and more preferably 100% or more. The total of the reduction rates is defined as R1+R2+ . . . +Rn, in the case of n passes of pressure rolling, where R1(%) through Rn(%) are the reduction rates from the first pass through the n-th pass Rn={sheet thickness after (n−1)-th pass−sheet thickness after n-th pass}/sheet thickness after (n−1)-th pass×100(%).


The finishing temperature of the hot rolling is et in a range from the Ar3 transformation temperature or more to 750° C. or less. When this is less than the Ar3 transformation temperature, the {110}<001> texture is developed, and this is not favorable for the Young's modulus in the rolling direction. When the finishing temperature is greater than 750° C., it is difficult to develop a favorable shearing texture in the rolling direction from the sheet thickness surface layer to near the ¼ sheet thickness layer.


There are no particular limitations regarding the curling temperature after the hot rolling, but since the Young's modulus increases when curling is performed at 400 to 600° C., it is preferable that curling is performed in this range.


When carrying out hot rolling, it is preferable that differential speed rolling in which the different roll speeds ratio between the pressure rollers is at least 1% is performed for at least one pass, Doing this promotes texture formation near the surface layer, and thus the Young's modulus can be increased more than in a case in which differential speed rolling is not performed. From this standpoint, it is preferable that differential speed rolling is performed at a different roll speeds ratio that is at least 1%, more preferably at least 5%, and most preferably at least 10%.


There are no particular restrictions regarding the upper limit for the different roll speeds ratio and the number of passes of differential speed rolling, but for the reasons mentioned above it goes without saying that when both of these is high, a large increase in the Young's modulus may be obtained. However, at the current time its is difficult to obtain a different roll speeds ratio greater than 50%, and ordinarily the number of finishing hot roll passes tops out at about 8 passes.


Here, the different roll speeds ratio in the present invention is the value obtained by dividing the difference in speed between the upper and lower pressure rollers by the speed of the slower roller, expressed as a percentage. As for the differential speed rolling of the present invention, there is no difference in the effect of increasing the Young's modulus regardless of whether it is the upper roller or the lower roller that has the greater speed.


It is preferable that at least one work roller whose roller diameter is 700 mm or less is used in the pressure rolling machine that is used for the finishing hot rolling. Doing this promotes texture formation near the surface layer and thus the Young's modulus can be increased more than in a case in which such a work roller is not used. From this standpoint, the work roller diameter is 700 mm or less, preferably 600 mm or less, and more preferably 500 mm or less. There are no particular restrictions regarding the lower limit of the work roller diameter, but the moving sheets cannot be controlled easily when this is below 300 mm. There are no restrictions regarding the upper limit to the number of passes in which a small diameter roller is used, but as mentioned previously, ordinarily the number of finishing hot roll passes is up to about 8 passes.


It is preferable that after the hot-rolled steel sheet that has been produced in this way is subjected to acid wash, it is subjected to thermal processing (annealing) at a maximum attained temperature in a range of 500 to 950° C. By doing this, the Young's modulus in the rolling direction is increased even further. The reason behind this is uncertain, but it is assumed that dislocations introduced by transformation after hot rolling are rearranged by the thermal processing.


When the maximum attained temperature is less than 500° C., the effect is not noticeable, whereas when it is greater than 950° C., an α→γ transformation occurs, and as a result, the accumulation of the texture is the same or weaker and the Young's modulus also tends to become worse. Thus, 500° C. and 950° C. serve as the lower limit and the upper limit, respectively.


The range of the maximum attained temperature preferably is 650° C. to 850° C. There are no particular limitations regarding the method of the thermal processing, and it is possible to perform thermal processing through an ordinary continuous annealing line, box annealing, or a continuous hot-dip galvanization line, which is discussed later, for example.


It is also possible to subject the hot-rolled steel sheet to cold-rolling and thermal processing (annealing). The cold rolling rate is set to less than 60%. This is because when the cold rolling rate is set to 60% or more, the texture for increasing the Young's modulus that has been formed in the hot-rolled steel sheet changes significantly and lowers the Young's modulus in the rolling direction.


The thermal processing is performed after cold rolling is finished. The range of the maximum attained temperature of the thermal processing is 500° C. to 950° C. When the maximum attained temperature is less than 500° C., the increase in the Young's modulus is small and the workability may become poor, and thus 500° C. serves as the lower limit.


On the other hand, when the thermal processing temperature exceeds 950° C., an α→γ transformation occurs, and as a result, the accumulation of texture is the same or weaker and the Young's modulus also tends to become worse. Thus, 500° C. and 950° C. serve as the lower limit and the upper limit, respectively. The preferable range of the maximum attained temperature is 600° C. to 850° C.


It is also possible to cool to 550° C. or less, preferably 450° C. or less, after the thermal processing and then to conduct further thermal processing at a temperature from 150 to 550° C. This can be carried out selecting appropriate conditions in accordance with various objectives, such as control of the solid solution C amount, tempering the martensite, and structural control such as promoting bainite transformation.


The structure of the steel sheet yielded by the method for manufacturing a steel sheet having high Young's modulus of this embodiment has ferrite or bainite as a primary phase, but both phases may be mixed together, and it is also possible for compounds such martensite, austenite, carbides, and nitrides to be present also. In other words, different structures can be created to meet the required characteristics.


Second Embodiment

The steel sheet of the second embodiment contains, in percent by mass, 0.0005 to 0.30%, Si: 2.5% or less, Mn: 0.1 to 5.0%, P: 0.15% or less, S: 0.015% or less, Al: 0.15% or less, N: 0.01% or less, and also contains one or two or more of Mo: 0.005 to 1.5%, Nb: 0.005 to 0.20%, Ti: 48/14×N (mass %) or more but less than 0.2%, and B: 0.0001 to 0.01%, at a total of 0.015 to 1.91 mass %, with the remainder being Fe and unavoidable impurities. The {110}<223> pole density and/or the {110}<111> pole density in the ⅛ sheet thickness layer is 10 or more. The Young's modulus in the rolling direction is greater than 230 GPa.


The reasons for limiting the steel composition as above are described here.


C is an inexpensive element that increases the tensile strength, and thus the amount of C that is added is adjusted in accordance with the target strength level. When C is less than 0.0005 mass %, not only does the production of steel become difficult and costs increase, but the fatigue properties of the welded sections become worse as well, and thus 0.0005 mass % serves as the lower limit. On the other hand, a C amount above 030 mass % leads to a deterioration in moldability and adversely affects the weldability, and thus 0.30 mass % serves as the upper limit.


Si not only acts to increase the strength as a solid solution strengthening element, but also is effective for obtaining a structure that includes martensite or bainite in addition to the residual γ, for example. The amount of Si that is added is adjusted according to the target strength level. When the amount added is greater than 2.5 mass %, the pressing moldability becomes poor and the chemical conversion is lowered, and thus 2.5 mass % serves as the upper limit. It should be noted that when hot-dip galvanization is conducted, Si causes problems such as lowering the ability of the zinc plating to adhere tightly and lowering the productivity by delaying the alloying reaction, and thus it is preferable that Si is not more than 1.2 mass %. Although no particular lower limit has been set, production costs increase when Si is 0.001 mass % or less, and thus in practical terms this is the lower limit.


Mn stabilizes the γ phase and causes the γ region to expand even down to low temperatures, thus facilitating low-temperature γ region rolling. Mn itself also may effectively act to form the shear texture near the surface layer. Taking this into account, the amount of Mn added is preferably at least 0.1 mass %, more preferably at least 0.5 mass %, and yet more preferably at least 1.5 mass % On the other hand, when Mn is present at greater than 5.0 mass %, the strength becomes too high and lowers the ductility and impairs the ability of the zinc plating to adhere closely, and thus 5.0 mass % serves as the upper limit. Thus, the amount of Mn added is preferably 2.9 to 4.0 mass %.


P, like Si, is known to be an inexpensive element that increases the strength, and in cases where increasing the strength is necessary, additional P can be actively added. P also has the effect of achieving a finer hot rolling structure and thereby improves the workability. However, when the amount added is greater than 0.15 mass %, the fatigue strength after spot welding is poor and the yield strength may increase too much and lead to surface shape defects when pressing. Further, when continuous hot-dip galvanization performed, the alloying reaction becomes extremely slow, and this lowers the productivity. The secondary work embrittlement also becomes worse. Consequently, 0.15 mass % serves as the upper limit.


S, when present at greater than 0.015 mass %, may become a cause of hot cracking or lower the workability, and thus its upper limit is 0.015 mass %.


Mo, Nb, Ti, and B are important for the present invention. It is not until one or two or more of these elements have been added that it becomes possible to increase the Young's modulus in the rolling direction. The reason for this is not absolutely clear, but recrystallization during hot rolling is inhibited and the processed texture of the γ-phase becomes sharp, and as a result, a change occurs in the shearing-deformed texture due to friction between the steel sheet and the hot rollers as well. The result is that an extremely sharp texture is formed in the region from the sheet thickness surface layer of the hot-rolled sheet down to about the ¼ sheet thickness layer, increasing the Young's modulus in the roll g direction. The lower limits of the amount of Mo, Nb, Ti, and B are 0.005 mass %, 0.005 mass %, 48/14×N mass %, 2.5 and 0.0001 mass %, respectively, preferably 0.03 mass 0.01 mass %, 0.0.3 mass %, and 0.0003 mass %, respectively, and more preferably 0.1 mass %, 0.03 mass %, 0.05 mass %, and 0.0006 mass %, respectively. This is because when added in smaller amounts, the effect of increasing the Young's modulus discussed above becomes small.


On the other hand, adding Mo, Nb, Ti, and B beyond 1.5 mass %, 0.2 mass %, 0.2 mass %, and 0.01 mass %, respectively, will not further increase the effect of raising the Young's modulus and only increases costs, and thus 1.5 mass %, 0.2 mass %, 0.2 mass %, and 0.01 mass % serve as the upper limits for the amount of Mo, Nb, Ti, and B, respectively, that is added.


When the total amount of these elements that has been added is less than 0.015 mass %, a sufficient Young's modulus increasing effect is not obtained, and thus 0.015 mass % serves as the lower limit of the total amount added. From this standpoint, it is preferable that the total amount added is at least 0.035 mass %, and more preferably at least 0.05 mass %. The upper limit of the total amount added is 1.91 mass %, which is the sum of the upper limits of the various added amounts.


Mo, Nb, Ti, and B interact with one another, and by adding these together, the texture becomes even stronger and the Young's modulus is increased further. From this, it is more preferable for at least two of these be added in combination. In particular, Ti forms nitrides with N in the γ high-temperature region, and inhibits the formation of BN. Thus, if B is to be added, it is preferable for Ti also to be added to at least 48/14×N mass %.


It is preferable that all of No, Nb, Ti, and B are present, and that these elements are added to at least 0.15 mass %, 0.01 mass %, 48/14×N mass %, and 0.0006 mass %, respectively. In this case, the texture becomes sharp, and in particular, {110}<001> of the surface layer, which lowers the Young's modulus, is reduced, effectively resulting in an increase in the Young's modulus. Thus, a high L-direction Young's modulus is attained.


It should be noted that the effect of increasing the Young's modulus that results from simultaneously adding these elements can be further enhanced by combining them with C as well. Thus, it is preferable that the amount of C is 0.015 mass % or more.


The lower limits for Mo, Nb, and B are 0.15 mass %, 0.01 mass %, and 0.0006 mass %, respectively. This is because adding these in an amount less than this reduces the effect of increasing the Young's modulus discussed above. However, if only the Young's modulus of the surface layer is to be controlled, then adding Mo to 0.1 mass % or more will allow a sufficient Young's modulus increasing effect to be obtained, and thus this serves as the lower limit. On the other hand, adding Mo, Nb, and B beyond 1.5 mass %, 0.2 mass %, and 0.01 mass %, respectively, will not result in a greater effect of raising the Young's modulus and only increases costs, and thus 1.5 mass %, 0.2 mass %, and 0.01 mass % serve as the respective upper limits.


It should be noted that the increase in the Young's modulus that results from simultaneously adding these elements can be further enhanced by combining them with C as well. Thus, it is preferable that the amount of C is 0.015 mass % or more.


Al can be used as a deoxidation regulator. However, since Al noticeably increases the transformation temperature and thus makes rolling in the low-temperature γ region difficult, its upper limit is set to 0.15 mass %. There are no particular limitations regarding the lower limit for Al, but from the standpoint of deoxidation, it is preferable that Al is present at 0.01 mass % or more.


N forms nitrides with B and lowers the effect of B in inhibiting recrystallization, and thus N is kept to 0.01 mass % or less. From this standpoint, preferably N is 0.005 mass % or less, and more preferably 0.002 mass % or less. No particular lower limit for N is set, but when less than 0.0005 mass % there is a diminished effect compared to the cost, and thus preferably the lower limit is 0.0005 mass % or more.


It is preferable that the amount of solid solution C is from 0.0005 to 0.004 mass %. When a steel sheet that contains C in solid solution is processed as a member component, strain aging occurs even at room temperature and raises the Young's modulus. For example, when the steel sheet is adopted for automobile applications, performing paint firing after processing increases not only the yield strength but also the Young's modulus of the steel sheet. The amount of solid solution C can be found by subtracting the amount of C present (measured quantity from chemical analysis of the extract residue) in the compounds with Fe, Al, Nb, Ti, and B, for example, from the total C content. The amount also may be found using an internal friction method or FIN (Field Ion Microscopy).


When the solid solution C is less than 0.0005 mass %, a sufficient effect cannot be attained. When greater than 0.004 mass %, the BH properties tend to saturate, and thus 0.004 mass % serves as the upper limit.


It is preferable that the steel sheet of the second embodiment includes Ca at 0.005 to 0.01 mass F in addition to the above composition.


Ca is useful as a deoxidizing element, and also has an effect on snare control of sulfides, and thus it can be added in a range of 0.005 to 0.01 mass %. It does not have a sufficient effect when it is present at less than 0.0005 mass %, whereas it decreases the workability when it is added to greater than 0.01 mass %, and thus this range has been chosen.


It is also possible for the steel sheet to contain Sn, Co, Zn, W, Zr, V, Mg, and one or more REMs for a total of 0.001 to 1% in percent by mass. In particular, W and V have the effect of inhibiting recrystallization of the γ region, and thus it is preferable that these are each added to at least 0.01 mass %. However, Zr forms ZrN and thus reduces the amount of solid solution N, and for this reason it is preferable that Zr is present at 0.01 mass % or less.


It is also possible to add one or two or more of Ni, Cu, and Cr for a combined total of 0.001 to 4.0% by mass.


When the total amount of Ni, Cu, and Cr added is less than 0.001 mass %, no noticeable effect is obtained, whereas the workability is adversely affected when these are added to greater than 4.0 mass %.


The texture, Young's modulus, and the BH content of the steel sheet are described next.


Regarding the texture of the steel sheet of the second embodiment, the {110}<223> pole density and/or the {110}<111> pole density in the ⅛ sheet thickness layer are 10 or more. As a result, it is possible to increase the Young's modulus in the rolling direction. When the pole density is less than 10, it is difficult to increase the Young's modulus in the rolling direction beyond 230 GPa. The pole density is preferably 14 or more, and more preferably 20 or more.


The pole density (X-ray random strength ratio) of these orientations can be found from the three dimensional texture (ODF) calculated by a series expansion method based on a plurality of pole figures from among the pole figures {110}, {100}, {211}, and {310} measured by X-ray diffraction. In other words, the pole density in these crystal orientations is expressed by the strength of (110) [2-23] and (110) [1-11] in the φ2=45° cross-section of the three-dimensional texture.


These pole densities are measured using the method that was described in the first embodiment.


The limitations regarding the pole density are satisfied for at least the ⅛ sheet thickness layer, but it is preferable that in practice these limitations are met not only for the ⅛ layer but also over a broad range from the sheet thickness surface layer up to the ¼ sheet thickness layer.


In the second embodiment, it is further preferable that the pole density in the {110}<110> orientation H110)[001] in the φ2=45° cross-section of the ODF) in the ⅛ sheet thickness layer is 3 or less Because this orientation noticeably lowers the Young's modulus in the rolling direction, when this orientation is greater than 3 it becomes difficult for the Young's modulus in the rolling direction to exceed 230 GPa. Factoring this into account, preferably the pole density is less than 3, and more preferably less than 1.5.


It is further preferable that the {211}<001> ((112)[1-10] in the φ2=45° cross-section of the ODE) pole density in the ½ sheet thickness layer is 6 or more. When this orientation is developed, the <111> orientation builds up in the transverse direction (TD direction), which is perpendicular to the rolling direction (RD direction), and thus the Young's modulus in the TD direction increases. It is difficult for the Young's modulus to exceed 230 GPa in the TD direction when this pole density is less than 6, and thus this serves as the lower limit. The preferable range for this pole density is 8 or more, and a more preferable range is 10 or more.


The (332)<113> ((332) [−1-13] in the φ2=45° cross-section of the ODF) pole density in the ½ sheet thickness layer can be expected to slightly contribute to the Young's modulus in the rolling direction. For this reason, it is preferable that the {332}<113> pole density in the ½ sheet thickness layer is 6 or more, more preferably 8 or more, and most preferably 10 or more.


The {110}<011> ((110)[1-10] in the φ2=45° cross-section of the ODF) pole density in the ½ sheet thickness layer noticeably lowers the Young's modulus in the 45° direction, and thus it is preferable that the pole density is set to 6 or less. The pole density of this orientation more preferably is 3 or less, and most preferably 1.5 or less.


It should be noted that each of the crystal orientations discussed above allows for variation within the range from −2.5° to +2.5°.


The characteristics of the texture of the steel sheet cannot be expressed by an ordinary reverse pole figure or a positive pole figure only, but, for example, in a case where the reverse pole figure, which expresses the crystal orientation in the surface normal direction of the steel sheet, has been measured near the ⅛ sheet thickness layer, the surface strength ratio (X-ray random strength ratio) of the various orientations is preferably <110>: 5 or more, and <112>: 2 or more. For the ½ layer, it is preferable that <112>: 4 or more, <332>: 4 or more, and <100>: 3 or less.


Regarding the Young's modulus of the steel sheet, by simultaneously satisfying the features for the pole density of the crystal orientation in the ⅛ sheet thickness layer and the ½ sheet thickness layer, it is possible to simultaneously achieve a Young's modulus that is beyond 230 GPa in not only the rolling direction (RD direction) but also in the direction perpendicular to the rolling direction, that is, the transverse (TD direction). For measurement of the Young's modulus, the method discussed in the first embodiment is adopted.


It is preferable that the lower limit value for the Young's modulus in the rolling direction in the ⅛ sheet thickness layer from the surface layer is 240 GPa. By doing this, a sufficient effect in improving the shape fixability is obtained. It is further preferable that the lower limit value for the Young's modulus in the rolling direction in the ⅛ layer from the surface layer is 245 GPa, and most preferably 250 GPa. There are no particular limitations regarding the upper limit value, but to exceed 300 GPa it is necessary to add a large quantity of other alloy elements, and other characteristics such as the workability become worse, and thus in practice the upper limit is 300 GPa or less. Even when the Young's modulus of the surface layer is greater than 240 GPa, a sufficient effect of improving the shape fixability is not attained when the thickness of this layer is less than ⅛ the sheet thickness. It should go without saying that the thicker a layer that has a high Young's modulus is, the higher the bend formability that is obtained.


It should be noted that the Young's modulus of the surface layer is measured by extracting a test piece at a thickness greater than ⅛ from the surface layer and performing the lateral resonance method discussed earlier.


There are no particular restrictions regarding the surface layer Young's modulus in the sheet transverse direction, but it should be apparent that a higher surface layer Young's modulus in the sheet transverse direction increases the bend formability in the transverse direction.


By adopting a composition that contains all of Mo, Nb, Ti, and B as discussed above at Mo: 0.15 to 1.5%, Nb: 0.01 to 0.20%, Ti: 48/14×N (mass %) or more and 0.2% or less, and B: 0.0006 to 0.01%, with a texture in which the {110}<223> pole density and/or the {110}<111> pole density in the ⅛ sheet thickness layer are 10 or more and the pole density of {110}<001> in the ⅛ sheet thickness layer is 3 or less, the surface layer Young's modulus in the transverse direction also exceeds 240 GPa like in the rolling direction.


It is preferable that the BH amount of the steel sheet is 5 MPa or more. That is, this is because the Young's modulus in the rolling direction (RD direction) increases when the mobile dislocation is fixed by paint firing. This effect becomes poor when the BH amount is less than 5 MPa, and a greater effect is not observed when the BH amount exceeds 200 MPa. Thus, the range for the BH amount is set to 5 to 200 MPa. The BR amount is more preferably in a range of 30 to 100 MPa.


The BH amount is expressed by Formula [4], which was discussed in the first embodiment.


The method for manufacturing the steel sheet of the second embodiment is described next.


The second embodiment includes heating a slab that contains, percent by mass, C: 0.0005 to 0.30%, Si: 2.5% or less, Mn: 0.1 to 5.0%, P: 0.15% or less, 0.015% or less, Mo: 0.15 to B: 0.0006 to 0.01%, 0.150 or less, Nb: 0.01 to 0.20%, N: 0.01% or less, and Ti: 48/14×N (mass %) or more and 0.2% or less, with the remainder being Fe and unavoidable impurities, at a temperature of 1000° C. or more and subjecting the slab to hot rolling to produce a hot-rolled steel sheet.


There are no particular limitations regarding the slab that is supplied for this hot rolling. In other words, it is only necessary that it is a continuous casting slab or has been produced by a thin slab caster, for example. The slab is also suited for a process such as continuous casting-direct rolling (CC-DR), in which hot rolling is performed immediately after casting.


In this hot-rolling process, the hot rolling heating temperature is set to 1000° C. or more. The hot rolling heating temperature is set to 1000° C. or more. This is the temperature required to set the hot-rolling finishing temperature mentioned later to the Ar3 transformation temperature or more.


Hot rolling is performed under the conditions in which a coefficient of friction is greater than 0.2 between the pressure rollers and the steel sheet, an effective strain amount ε* calculated by Formula [5] below is 0.4 or more, and the total of the reduction rates is 5.0% or more. The above conditions are the essential conditions for developing the shear texture of the surface layer so as to increase the Young's modulus in the rolling direction.










ɛ
*

=





j
=
1


n
-
1





ɛ
j



exp


[

-




i
=
j


n
-
1





(


t
i


τ
i


)


2
/
3




]




+

ɛ
n






[
5
]







Here, n is the rolling stand number of the finishing hot rolling, εj is the strain added at the j-th stand, εn is the strain added at the n-th stand, ti is the travel time (seconds) between the i-th and the (i+1)-th stands, and τi can be calculated by Formula [6] below using the gas constant R (=1.987) and the roll rig temperature Ti (K) of the i-th stand.

τi=8.46×10−9×exp{43800/R/Ti}  [6]


The total of the reduction rates RT can be calculated by Formula [7] below, where, in the case of n-number of passes of pressure rolling, R1(%) through Rn(%) are the reduction rates from the first pass through the n-th pass.

RT=R1+R2+ . . . +Rn  [7]


However, it also can be expressed by Rn={sheet thickness after (n−1)-th pass−sheet thickness after n-th pass}/sheet thickness after (n−1)-th pass×100(%).


The effective strain amount ε* is 0.4 or more, preferably 0.5 or more, and more preferably 0.6 or more. The total of the reduction rates is 50% or more, preferably 70% or more, and more preferably 100% or more.


The finishing temperature of the hot-rolling is set to a range from the Ar3 transformation temperature or more to 900° C. or less.


When the finishing temperature is less than the Ar3 transformation temperature, the {110}<001> texture is developed, and this is not favorable for the Young's modulus in the rolling direction. When the finishing temperature is greater than 900° C., it is difficult to develop a favorable shearing texture in the rolling direction from the sheet thickness surface layer to near the ¼ sheet thickness layer. From this standpoint, the finishing temperature for the hot rolling preferably is 850° C. or less, and more preferably 800° C. or less.


There are no particular limitations regarding the curling temperature after the hot rolling, but since the Young's modulus increases when curling is performed at 400 to 600° C., it is preferable that curling is performed in this range.


When carrying out hot rolling, it is preferable that differential, speed rolling in which the different roll speeds ratio between the pressure rollers is at least 1% is performed for at least one pass. Doing this promotes texture formation near the surface layer, and thus the Young's modulus can be increased more than in a case in which differential speed rolling is not performed. From this standpoint, it is preferable that differential speed rolling is performed at a different roll speeds ratio that is at least 1%, more preferably at least 5%, and most preferably at least 10%.


There are no particular restrictions regarding the upper limit for the different roll speeds ratio and the number of passes of differential speed rolling, but for the reasons mentioned above it goes without saying that when both of these is high, the effect of a large increase in the Young's modulus is obtained. However, at the current time it is difficult to obtain a different roll speeds ratio greater than 50%, and ordinarily the number of finishing hot roll passes is up to about 8 passes.


Here, the different roll speeds ratio in the invention is the value obtained by dividing the difference in speed between the upper and lower pressure rollers by the speed of the slower roller, expressed as a percentage. As for the differential speed rolling of the present invention, there is no difference in the effect of increasing the Young's modulus regardless of whether it is the upper roller or the lower roller that has the greater speed.


It is preferable that at least one work roller whose roller diameter is 700 mm or less is used in the pressure rolling machine that is used for the finishing hot rolling. By doing this, texture formation near the surface layer is promoted, and thus the Young's modulus can be increased more than in a case in which such a work roller is not used. From this standpoint, the work roller diameter is 700 mm or less, preferably 600 mm or less, and more preferably 500 mm or less. There are no particular restrictions regarding the lower limit of the work roller diameter, but when it is below 300 mm it becomes difficult to control the moving sheets. There are no particular restrictions regarding the maximum number of passes in which the small diameter roller is used, but as mentioned above, ordinarily the number of finishing hot roll passes is up to about 3 passes.


It is preferable that once the hot-rolled steel sheet that has been manufactured in this way is subjected to acid wash, it is then subjected to thermal processing (annealing) with a maximum attained temperature in a range of 500 to 950° C. Thus, the Young's modulus in the rolling direction is increased even further. The reason behind this is unclear, but it is likely that dislocations introduced due to transformation after hot rolling are rearranged by thermal processing.


When the maximum attained temperature is less than 500° C., the effect is not noticeable, whereas an α→γ transformation occurs when this is greater than 950° C., and as a result, the accumulation of texture is the same or worse and the Young's modulus tends to become worse as well. Thus, 50.0° C. and 950° C. serve as the lower limit and the upper limit, respectively.


The range of the maximum attained temperature preferably is 650° C. to 850° C.


There are no particular limitations regarding the method of the thermal processing, and it is possible to perform thermal processing through an ordinary continuous annealing line, box annealing, or a continuous hot-dip galvanization line, which is discussed later, for example.


It is also possible to perform cold-rolling and thermal processing (annealing) on the hot-rolled steel sheet after acid wash. The cold rolling rate is set to less than 60%. This is because when a cold rolling rate is set to 60% or more, the texture for increasing the Young's modulus that has been formed in the hot-rolled steel sheet is significantly altered and lowers the Young's modulus in the rolling direction.


The thermal processing is performed after cold rolling is finished. The maximum attained temperature of the thermal processing is in a range of 500° C. to 950° C. When the maximum attained temperature is less than 500° C., the increase in the Young's modulus is small and the workability may become poor, and thus 500° C. serves as the lower limit.


On the other hand, an α→γ transformation occurs when the thermal processing temperature exceeds 950° C., and as a result, the accumulation of texture is the same or weaker and the Young's modulus tends to become worse as well. Thus, 500° C. and 950° C. serve as the lower limit and the upper limit, respectively.


The preferable range of the maximum attained temperature is 600° C. to 850° C.


There is no particular limitation to the heating up rate towards the maximum attained temperature, but preferably this is in a range of 3 to 70° C./second. When the heating speed is under 3° C./second, recrystallization proceeds during heating and disrupts the texture that is effective in increasing the Young's modulus, Setting the heating up rate in excess of 70° C./second does not lead to a change in the superior material properties, and thus it is preferable that this value serves as the upper.


It is also possible to cool cc 550° C. or less, preferably 450° C. or less, after the thermal processing and then to conduct thermal processing again at a temperature from 150 to 550° C. This can be carried out selecting appropriate conditions in accordance with various objectives, such as control of the solid solution C amount, tempering of the martensite, and structural control such as promoting bainite transformation.


The structure of the steel sheet that is produced by the method for manufacturing a steel sheet having high Young's modulus of this embodiment has ferrite or bainite as a primary phase, but both phases may be mixed together, and it is also possible for compounds such martensite, austenite, carbides, and nitrides to be present as well. In other words, different structures can be created to meet the required characteristics.


Third Embodiment

In the third embodiment, examples of a hot-dip galvanized steel sheet, an alloyed hot-dip galvanized steel sheet, and a steel pipe having high Young's modulus, that contain the steel sheets having high Young's modulus of the first and the second embodiments, and methods for manufacturing these, are described.


The hot-dip galvanized steel sheet has the steel sheet having high Young's modulus according to the first or the second embodiment, and hot-dip zinc plating that is conducted on that steel sheet having high Young's modulus. This hot-dip galvanized steel sheet is produced by subjecting the hot-rolled steel sheet after annealing that is obtained in the first and second embodiments, or a cold-rolled steel sheet obtained by performing cold rolling, to hot-dip galvanization.


There are no particular limitations regarding the composition of the zinc plating, and in addition to zinc it may also include Fe, Al, Mn, Cr, Mg, Pb, Sn, or Ni, for example, as necessary.


It should be noted that it is also possible to conduct thermal processing and zinc plating through a continuous hot-dip galvanization line after cold rolling.


The annealed hot-dip galvanized steel sheet has the steel sheet having high Young's modulus according to the first or the second embodiment, and the annealed hot-dip zinc plating that is applied to that steel sheet having high Young's modulus. This annealed hot-dip galvanized steel sheet is produced by annealing the hot-dip galvanized steel sheet.


The alloying is carried, out by thermal processing within in a range of 450 to 600° C. The alloying does not proceed sufficiently when this is less than 450° C., whereas on the other hand, the alloying proceeds too much and the plating layer becomes brittle when this is greater than 600° C. This consequently leads to problems such as the plating peeling off due to pressing or other processing. Alloying is carried out for at least 10 seconds Less than 10 seconds, alloying does not proceed sufficiently. If an alloyed hot-dip galvanized steel sheet is to be produced, it is also possible to perform acid wash as necessary after hot rolling and then conduct a skin pass of the reduction rate of 10% or less in-line or off-line.


The steel pipe having high Young's modulus is a steel pipe that contains a steel sheet having high Young's modulus according to the first or second embodiment, in which the steel sheet having high Young's modulus is curled in any direction. For example, the steel pipe having high Young's modulus may be produced by curling the steel sheet having high Young's modulus of the first or the second embodiment discussed above in such a manner that the rolling direction is a 0 to 3.0° angle with respect to the lengthwise direction of the steel pipe. By doing this, it is possible to produce a steel pipe having high Young's modulus in which the Young's modulus of the steel pipe in the lengthwise direction is high.


Since curling parallel to the rolling direction results in the highest Young's modulus, it is preferable that this angle is as small as possible. From this standpoint, it is particularly preferable that the sheet is curled at an angle that is 15° or less. As long as this relationship between the rolling direction and the lengthwise direction of the steel pipe is satisfied, any method may be employed to produce the pipe, including UO piping, seam welding, and spiraling. Of course, it is not necessary to limit the direction having the high Young's modulus to the direction parallel to the lengthwise direction of the steel pipe, and there is absolutely no problem with producing a steel pipe that has a high Young's modulus in a desired direction in accordance with the application.


It should be noted that it is also possible to subject the steel pipe having high Young's modulus to Al-based plating or various types of electrical plating. It is also possible to carry out surface processing, including forming an organic film, an inorganic film, or using various paints, on the hot-dip galvanized steel sheet, the alloyed hot-dip galvanized steel sheet, and the steel pipe having high young's modulus, based on the objective to be achieved.


EXAMPLES

Next, the present invention is explained by examples.


Examples of the first and third embodiments are described below.


Example 1

Steel having the composition shown in Tables 1 and 2 was subjected to casting and hot rolling was performed under the conditions shown in Tables 3 and 4. The heating temperature at this time was 1250° C. in all cases. The final three stages in the finishing rolling stand, which had a total of seven stages, had a coefficient of friction between the rollers and the steel sheet in a range of 0.21 to 0.24, and the total of the reduction rates of the final three stages was 70%. In all cases, the skinpass rolling reduction rate was 0.3%.


The Young's modulus was measured by the lateral resonance method discussed earlier, A JIS 5 tension test piece was sampled, and the tension characteristics in the TD direction were evaluated. The texture in the ⅛ sheet thickness layer was also measured.


The results are shown in Tables 3 and 4. From these results, it is clear that by subjecting the steel that had the chemical composition of the present invention to hot rolling under the appropriate conditions, at was possible to achieve a Young's modulus greater than 230 GPa in the rolling direction.


Here, in the tables of the working examples, FT is the final finishing output temperature of the hot rolling, CT is the curling temperature, TS is the tensile strength, YS is the yield strength, El is the elongation, E(RD) is the Young's modulus in the RD direction, E(D) is the Young's modulus in a direction inclined at 45 relative to the RD direction, and E(TD) is the Young's modulus in the TD direction. I.E. represents inventive example, and C.E. represents comparative example. These indices are the same in the descriptions of subsequent tables as well.
















TABLE 1





Steel









No.
C
Si
Mn
P
S
Al
N






















A
0.0040
0.01
3.01
0.010
0.0019
0.031
0.0024


B
0.0044
0.01
2.44
0.011
0.0022
0.028
0.0026


C
0.0036
0.01
1.95
0.008
0.0019
0.033
0.0031


D
0.0047
0.01
4.34
0.007
0.0025
0.029
0.0029


E
0.050
0.02
3.26
0.005
0.0034
0.022
0.0033


F
0.051
0.02
3.33
0.005
0.0037
0.027
0.0032


G
0.050
0.01
2.27
0.006
0.0034
0.030
0.0030


H
0.055
0.55
3.58
0.007
0.0016
0.024
0.0025


I
0.103
0.09
3.04
0.011
0.0020
0.035
0.0027


J
0.112
0.84
3.00
0.010
0.0020
1.660
0.0034


K
0.100
0.08
3.04
0.009
0.0018
0.032
0.0028


L
0.010
0.22
3.63
0.005
0.0027
0.037
0.0026


M
0.009
0.04
3.50
0.009
0.0031
0.031
0.0034


N
0.011
0.01
0.52
0.022
0.0053
0.033
0.0019























TABLE 2





Steel





Ar3



No.
Mo
B
Ti
Nb
Others
(° C.)
Remarks






















A
0.28
0.0025



630
Inventive steel


B
0.25
0.0016
0.011
0.008

690
Comparative









steel


C
0.17
0.0033
0.022


712
Comparative









steel


D
0.29
0.0022
0.009
0.013

526
Inventive steel


E
0.52
0.0020
0.030
0.040

582
Inventive steel


F


0.029
0.038

649
Comparative









steel


G
0.53
0.0024
0.025
0.041

656
Comparative









steel


H
0.36
0.0037
0.014
0.022
Cr = 0.40
560
Inventive steel


I
0.40
0.0019
0.018
0.019

599
Inventive steel


J
0.39
0.0020
0.020
0.019

949
Comparative









steel


K
0.41

0.021
0.044
V = 0.010
627
Comparative









steel


L
0.33
0.0041

0.028

558
Inventive steel


M
0.42
0.0030


Cu = 0.42
571
Inventive steel


N





887
Comparative









steel




























TABLE 3





Sample
Steel
FT
CT
TS
YS
El
E(RD)
E(D)
E(TD)
{110}
{110}



No.
No.
(° C.)
(° C.)
(MPa)
(MPa)
(%)
(GPa)
(GPa)
(GPa)
<223>
<111>
Remarks



























1
A
840
500
525
377
29
216
195
228
5
3
C.E.


2

770
500
568
424
26
225
196
229
9
5
C.E.


3

700
500
607
459
23
234
192
231
13
10
I.E.


4
B
880
400
491
354
30
220
202
226
5
4
C.E.


5

700
400
563
495
13
209
190
229
8
5
C.E.


6

580
400
722
683
7
198
195
218
2
3
C.E.


7
C
900
550
476
321
32
219
208
222
4
3
C.E.


8

800
550
495
338
30
223
201
225
6
4
C.E.


9

700
550
544
504
11
190
220
225
4
2
C.E.


10
D
800
650
550
412
26
223
197
240
8
5
C.E.


11

740
600
572
429
25
242
194
236
16
15
I.E.


12

680
500
609
460
21
242
189
243
23
19
I.E.


13
E
730
580
988
746
12
236
192
240
19
14
I.E.


14

700
550
1003
728
11
242
195
240
22
16
I.E.


15

550
400
1110
650
13
208
203
237
6
6
C.E.


16
F
790
600
925
688
12
215
204
230
4
3
C.E.


17

710
550
977
651
13
224
199
232
6
4
C.E.


18

600
400
1046
622
14
195
193
229
4
3
C.E.


19
G
850
550
910
763
14
221
211
228
5
3
C.E.


20

760
550
934
779
13
217
212
224
4
3
C.E.


21

720
550
951
807
13
220
204
222
4
3
C.E.


22
H
800
650
1243
1089
9
228
196
241
8
6
C.E.


23

690
550
1286
1101
8
248
191
243
26
22
I.E.


24

650
500
1355
1162
7
251
186
245
30
23
I.E.




























TABLE 4





Sample
Steel
FT
CT
TS
YS
El
E(RD)
E(D)
E(TD)
{110}
{110}



No.
No.
(° C.)
(° C.)
(MPa)
(MPa)
(%)
(GPa)
(GPa)
(GPa)
<223>
<111>
Remarks



























25
I
850
500
1093
879
12
227
203
229
8
7
C.E.


26

700
500
1152
926
11
242
194
239
20
15
I.E.


27

650
500
1189
947
11
244
192
240
22
14
I.E.


28
J
950
700
774
478
19
218
213
223
4
3
C.E.


29

800
650
881
595
17
197
195
231
3
2
C.E.


30

700
550
1198
720
9
199
189
225
3
2
C.E.


31
K
850
550
1042
823
13
220
205
220
7
5
C.E.


32

700
550
1090
901
12
226
199
235
7
6
C.E.


33

650
550
1177
923
11
228
203
235
9
6
C.E.


34
L
740
600
754
627
17
239
197
236
16
11
I.E.


35

700
550
772
652
16
243
192
241
21
18
I.E.


36

650
500
806
679
15
250
182
239
29
19
I.E.


37
M
780
630
721
597
19
228
210
233
8
4
C.E.


38

700
550
756
635
17
238
199
234
17
14
I.E.


39

650
500
779
658
16
244
192
246
24
22
I.E.


40
N
910
700
334
188
48
215
211
224
4
4
C.E.


41

800
650
329
165
50
218
207
225
3
3
C.E.


42

700
550
378
276
41
207
198
238
4
3
C.E.









Example 2

The hot-roiled steel sheets E and L of Example 1 were subjected to continuous annealing (held at 700° C. for 90 seconds), box annealing (held at 700° C. for 6 hr), and continuous hot-dip galvanisation (maximum attained temperature of 750° C.; alloying was performed at 550° C. for 20 seconds after immersion in a galvanization bath), and the tension characteristics and the Young's modulus were measured.


The results are shown in Table 5. From these results, it is clear that by subjecting steel that had the chemical composition of the present invention to hot rolling under suitable conditions, and then performing appropriate thermal processing, the Young's modulus was increased.























TABLE 5









Processing












Sample
Steel
FT
CT
after hot
TS
YS
El
BH
E(RD)
E(D)
E(TD)
{110}
{110}


No.
No.
(° C.)
(° C.)
rolling
(MPa)
(MPa)
(%)
(MPa)
(GPa)
(GPa)
(GPa)
<223>
<111>
Remarks





























43
E
700
550
None
1003
728
11
68
242
195
240
22
16
I.E.


44
E
700
550
Continuous
980
751
11
95
245
196
242
20
17
I.E.






annealing


45
E
700
550
Box annealing
943
777
12
56
250
197
242
16
11
I.E.


46
E
700
550
Continuous
966
722
12
74
244
196
243
19
15
I.E.






alloyed hot-dip






galvanization


47
L
700
550
None
772
652
16
60
243
192
241
21
18
I.E.


48
L
700
550
Continuous
745
614
18
89
248
193
243
19
16
I.E.






annealing


49
L
700
550
Box annealing
712
633
20
47
252
195
246
17
12
I.E.


50
L
700
550
Continuous
739
620
19
66
249
195
242
18
15
I.E.






alloyed hot-dip






galvanization









Example 3

The hot-rolled steel sheets E and L of Example 1 were subjected to cold rolling at the reduction rate of 30% and then were subjected to continuous hot-dip galvanization (the maximum attained temperature was variously changed, and after immersion in a galvanization bath, alloying was performed at 550° C. for 20 seconds), and the tension characteristics and the Young's modulus were measured.


The results are shown in Table 6. From these results, it is clear that by subjecting the steel that has the chemical composition of the present invention to hot rolling and cold rolling under suitable conditions, and then subjecting the steel to appropriate thermal processing, it is possible to obtain a cold-rolled steel sheet with excellent Young's moduli in both the RD direction and the TD direction. However, in cases where the maximum attained temperature was particularly high, there was a minor drop in the Young's modulus.
























TABLE 6









Cold
Maximum












Sample
Steel
FT
CT
rolling
temperature
TS
YS
El
BH
E(RD)
E(D)
E(TD)
{110}
{110}


No.
No.
(° C.)
(° C.)
rate (%)
(° C.)
(MPa)
(MPa)
(%)
(Mpa)
(GPa)
(GPa)
(GPa)
<223>
<111>
Remarks






























51
E
700
550
30
960
1058
784
10
53
231
194
233
11
8
I.E.


52
E
700
550
30
800
1181
695
13
94
237
198
235
14
10
I.E.


53
E
700
550
30
700
964
665
13
69
239
197
237
19
15
I.E.


54
L
700
550
30
970
810
679
15
57
231
199
232
11
7
I.E.


55
L
700
550
30
800
774
519
18
71
238
195
240
15
9
I.E.


56
L
700
550
30
700
711
536
18
65
240
194
239
16
11
I.E.









Example 4

The hot-rolled steel sheets E and L of Example 1 were subjected to the following processing.


The steel sheet was heated to 650° C. through a continuous hot-dip galvanization line and then cooled to approximately 470° C., thereafter it was immersed in a 460° C. hot-dip galvanization bath. The thickness of plate of the zinc on average was 40 g/m2 one side. Subsequent to the hot-dip galvanization, the steel sheet surface was subjected to (1) organic film coating or (2) painting as described below, and the tension characteristics and the Young's modulus were measured.


The results are shown in Table 7. From these results, it can be clearly understood that the steel sheets that are subjected to hot-dip galvanization and the steel sheets that are subjected to hot-dip galvanization and have an organic film or paint applied to their surface have a good Young's modulus.


(1) Organic Film


4 mass % corrosion inhibitor and 12% colloidal silica were added to a water-borne resin in which the solid resin portion was 27.6 mass %, the dispersion liquid viscosity was 1400 mPa·s (25° C.), the pH was 8.8, the content of carboxyl group ammonium salts (—COONH4) was 9.5 mass % of the total solid resin portion, the carboxyl group content was 2.5 mass % of the total solid resin portion, and the mean dispersion particle diameter was approximately 0.030 μm, so as to produce a rustproofing liquid. This rustproofing liquid was applied to the above steel sheet by a roll coater and dried to a 120° C. attained surface temperature of the steel sheet, so as to form an approximately 1-μm thick film.


(2) Paint


As a chemical treatment, a roll coater was used to apply “ZM1300AN” made by Nihon Parkerizing Co., Ltd. onto the above steel sheet after it had been degreased. Hot-air drying was performed so that the reached temperature of the steel sheet was 60° C. The amount of deposit of the chemical treatment was 50 mg/m by Cr deposit. A primer paint, was applied to one side of this chemically treated steel sheet, and a rear surface paint was applied to the other surface, using a roll coater. These were dried and hardened by an induction heater that includes the use of hot air. The temperature reached at this time was 210° C.


A top paint, was then applied by a roller curtain coater to the surface on which the primer paint had been applied. This was dried and hardened by an induction heater that involves the use of hot air at a reached temperature of 230° C. It should be noted that the primer paint was applied at a dry film thickness of 5 μm using “FL640EU Primer” made by Japan Fine Coatings Co., Ltd. The rear surface paint was applied at a dry film thickness of 5 μm using “FL100HQ” made by Japan Fine Coatings Co., Ltd. The top paint was applied at a dry film thickness of 15 μm using “FL100HQ” made by Japan Fine Coatings Co., Ltd.






















TABLE 7





Sample
Steel
FT
CT
Surface
TS
YS
El
E(RD)
E(D)
E(TD)
{110}
{110}



No.
No.
(° C.)
(° C.)
processing
(MPa)
(MPa)
(%)
(GPa)
(GPa)
(GPa)
<223>
<111>
Remarks




























57
E
700
550
Hot-dip
1010
775
11
237
194
239
18
15
I.E.






galvanization






only


58
E
700
550
Organic film
1016
763
11
240
196
240
19
14
I.E.


59
E
700
550
Paint
1042
822
10
245
200
243
18
15
I.E.


60
L
700
550
Hot-dip
781
654
15
238
192
238
16
12
I.E.






galvanization






only


61
L
700
550
Organic film
789
679
14
239
194
240
16
11
I.E.


62
L
700
550
Paint
838
707
13
247
203
246
17
12
I.E.









Example 5

The steels E and L shown in Table 1 were subjected to differential speed rolling. The different roll speeds rate was changed over the last three stages of the finishing rolling stand, which was constituted by a total of seven stages. The hot rolling conditions and the results of measuring the tension characteristics and the Young's modulus are shown in Table 8. It should be noted that the hot rolling conditions that are not shown in Table 8 are the same as those in Example 1.


It is clear from the results that the formation of texture near the surface layer is facilitated in the case in which one or more passes of differential speed rolling at 1% or more are added when hot rolling the steel having the chemical composition of the present invention under appropriate conditions, and this further increases the Young's modulus.












TABLE 8









Different roll




speeds ratio (%)






















Sample
Steel
FT
CT
5th
6th
7th
TS
YS
El
E(RD)
E(D)
E(TD)
{110}
{110}



No.
No.
(° C.)
(° C.)
pass
pass
pass
(MPa)
(MPa)
(%)
(GPa)
(GPa)
(GPa)
<223>
<111>
Remarks

























63
E
700
550
0
0
0
1003
728
11
242
195
240
22
16
I.E.


64
E
700
550
0
0
3
1005
733
11
245
193
240
24
18
I.E.


65
E
700
550
1
2
3
1011
729
10
247
188
242
25
19
I.E.


66
E
700
550
10
5
5
1009
731
12
253
186
246
31
25
I.E.


67
L
700
550
0
0
0
772
652
16
243
192
241
21
18
I.E.


68
L
700
550
3
3
3
773
655
15
245
189
242
24
18
I.E.


69
L
700
550
0
0
10
775
650
15
249
190
244
26
19
I.E.


70
L
700
550
0
20
20
772
653
15
256
186
248
31
26
I.E.









Example 6

The steels E and L shown in Table 1 were subjected to pressure rolling with small-diameter rollers. The roller diameter was changed in the last three stages of the finishing rolling stand, which is composed of seven stages in total. The hot rolling conditions and the results of measuring the tension characteristics and the Young's modulus are shown in Table 9. It should be noted that the hot rolling conditions that are not shown in Table 9 are all the same as those Example 1.


It is clear from the results that the formation of texture near the surface layer is facilitated in the case in which rollers with a roller diameter of 700 mm or less are used in one or more passes when hot rolling the steel having the chemical composition of the present invention under appropriate conditions, and this further increases the Young's modulus.












TABLE 9









Roller




diameter(mm)






















Sample
Steel
FT
CT
5th
6th
7th
TS
YS
El
E(RD)
E(D)
E(TD)
{110}
{110}



No.
No.
(° C.)
(° C.)
pass
pass
pass
(MPa)
(MPa)
(%)
(GPa)
(GPa)
(GPa)
<223>
<111>
Remarks

























71
E
700
550
800
800
800
1003
728
11
242
195
240
22
16
I.E.


72
E
700
550
800
800
600
1011
736
10
246
190
242
24
19
I.E.


73
E
700
550
600
600
600
1009
725
11
251
187
244
28
21
I.E.


74
E
700
550
500
500
500
998
733
10
255
186
243
33
24
I.E.


75
L
700
550
800
800
800
772
652
16
243
192
241
21
19
I.E.


76
L
700
550
800
800
600
783
658
14
247
189
243
25
17
I.E.


77
L
700
550
600
600
600
779
655
15
250
188
242
27
20
I.E.


78
L
700
550
500
500
500
768
649
16
253
186
245
30
25
I.E.









Example 7

Next, examples pertaining to the second and the third embodiments are discussed below.


Steel having the compositions shown in Tables 10 to 13 are subjected to casting and hot roll a is performed under the conditions of Tables 14 to 19, in all cases, the heating temperature at this time was 230° C. The coefficient of friction between the rollers and the steel sheet in the last three stages of the finishing rolling stand, which is composed of seven stages in total, was in a range of 0.21 to 0.24, and the total of the reduction rates of the last three stages was 55%. In all cases, the skinpass rolling reduction rate was 0.3%.


The Young's modulus was measured by the lateral resonance method discussed earlier. A JIS 5 tension test piece was sampled and the tension characteristics in the TD direction were evaluated. The texture in the ⅛ sheet thickness layer and the 7/16 sheet thickness layer was also measured.


The results are shown in Tables 14 through 19. It should be noted that Table 15 is a continuation of Table 14, and that Table 17 is a continuation of Table 16. Also Table 19 is continuation of Table 18. In one table and the table that is a continuation of that table, values in the same row indicate values for the same sample. The same applies for subsequent tables in the specification as well. Values that are underlined indicate values that are outside the range of the invention. This applies in the description of the subsequent tables as well.


From Tables 14 through 19 it can be understood that when the steel having the chemical composition of the present invention has been hot rolled under appropriate conditions, it is possible to achieve a Young's modulus in the rolling direction that is more than 230 GPa.


















TABLE 10





Steel











No.
C
Si
Mn
P
S
Al
N
Mo
B
























A
0.0010
0.01
1.82
0.010
0.0023
0.036
0.0025
0.200
0.0010


B
0.0036
0.01

0.07

0.011
0.0019
0.042
0.0031
0.150
0.0008


C
0.038
0.01
2.98
0.007
0.0022
0.038
0.0042
0.300
0.0012


D
0.025

2.90

1.23
0.006
0.0035
0.035
0.0045
0.180
0.0001


E
0.050
0.02
0.52
0.007
0.0042
0.028
0.0036
0.250
0.0023


F
0.120
0.02
1.29
0.005
0.0023

1.050

0.0038
0.420
0.0016


G
0.055
0.01
2.30
0.006
0.0011
0.039
0.0038
0.010
0.0020


H
0.061
0.43

0.05

0.007
0.0016
0.045
0.0030
0.000
0.0002


I
0.011
0.42
0.51
0.012
0.0023
0.026
0.0045
0.004
0.0016


J
0.087
0.77
1.13
0.001
0.0025
0.035
0.0035
0.000
0.0000


K
0.102
0.03
2.35
0.021
0.0011
0.036
0.0036
0.320
0.0031


L
0.092
0.03
3.26
0.008
0.0016
0.036
0.0033
0.530
0.0018


M
0.053
0.22
2.05
0.009
0.0037
0.042
0.0042
0.000
0.0008


N
0.076
0.01
4.33
0.012
0.0025
0.038
0.0023
0.620
0.0016


O
0.032
0.06
3.50
0.010
0.0045
0.032
0.0021
0.000
0.0008


P
0.021
0.03
2.30
0.007
0.0036
0.033
0.0022
0.000
0.0012


Q
0.050
1.20
1.32
0.012
0.0087
0.042
0.0023
0.000
0.0011























TABLE 11









Mo +





Steel


Ti − 48/
Nb +

Ar3


No.
Nb
Ti
14 × N
B + Ti
Others
(° C.)
Remarks






















A
0.015
0.04 
0.031
0.2560

756
Inventive steel


B
0.023
0.025
0.014
0.1988

903
Comparative









steel


C
0.042
0.031
0.017
0.3742
Cr: 0.2
641
Inventive steel


D
0.031
0.023
0.008
0.2341

906
Comparative









steel


E
0.023
0.023
0.011
0.2983

820
Inventive steel


F
0.028
0.018
0.005
0.4676
V: 0.04
995
Comparative









steel


G
0.025
0.023
0.010
0.0600
Cu: 0.3
701
Inventive steel


H
0.006
0.000
−0.010

0.0062


922
Comparative









steel


I
0.006

0.230

0.215
0.2416

876
Comparative









steel


J
0.000
0.000
−0.012

0.0000


840
Comparative









steel


K
0.044
0.042
0.030
0.4091

688
Inventive steel


L
0.025
0.053
0.042
0.6098

574
Inventive steel


M
0.004
0.004
−0.010

0.0088

Ca:
748
Comparative







0.003

steel


N
0.014
0.029
0.021
0.6646

563
Inventive steel


O
0.020
0.015
0.008
0.0358
W: 0.03
643
Inventive steel


P
0.038
0.023
0.015
0.0622

742
Inventive steel


Q
0.095
0.019
0.011
0.1151

852
Inventive steel

























TABLE 12





Steel











No.
C
Si
Mn
P
S
Al
N
Mo
B
























R
0.032
0.80
3.20
0.008
0.0042
0.031
0.0021
0.012
0.0006


S
0.048
0.30
1.57
0.010
0.0110
0.035
0.0018
0.036
0.0008


T
0.027
0.02
1.10
0.013
0.0078
0.042
0.0013
0.105
0.0003


U
0.036
0.50
2.05
0.008
0.0032
0.044
0.0023
0.520
0.0006


V
0.042
0.02
1.52
0.011
0.0051
0.023
0.0025
0.080
0.0021


W
0.033
0.60
0.97
0.006
0.0066
0.033
0.0020
0.020
0.0025


X
0.030
0.03
1.83
0.023
0.0035
0.035
0.0019
0.120
0.0016


Y
0.043
0.02
2.70
0.021
0.0022
0.032
0.0022
0.140
0.0027


Z
0.038
0.70
2.10
0.008
0.0067
0.040
0.0021
0.070
0.0009


AA
0.049
0.02
0.98
0.010
0.0050
0.026
0.0013
0.000
0.0027


AB
0.047
0.03
1.23
0.009
0.0042
0.032
0.0019
0.100
0.0030


AC
0.030
0.02
1.92
0.013
0.0023
0.036
0.0021
0.000
0.0000


AD
0.028
0.03
1.63
0.006
0.0033
0.042
0.0024
0.000
0.0000


AE
0.049
0.40
2.48
0.009
0.0054
0.031
0.0019
0.500
0.0000


AF
0.035
0.02
1.20
0.012
0.0063
0.033
0.0023
0.000
0.0000























TABLE 13









Mo +





Steel


Ti − 48/
Nb +

Ar3


No.
Nb
Ti
14 × N
B + Ti
Others
(° C.)
Remarks






















R
0.000
0.009
0.002
0.0216

692
Inventive steel


S
0.000
0.011
0.005
0.0478

801
Inventive steel


T
0.000
0.030
0.026
0.1353

838
Inventive steel


U
0.000
0.025
0.017
0.5456

775
Inventive steel


V
0.042
0.015
0.006
0.1391

796
Inventive steel


W
0.065
0.020
0.013
0.1075

864
Inventive steel


X
0.030
0.012
0.005
0.1636
V: 0.02
777
Inventive steel


Y
0.012
0.019
0.011
0.1737

703
Inventive steel


Z
0.032
0.120
0.113
0.2229

776
Inventive steel


AA
0.035
0.000
−0.004
0.0377

837
Inventive steel


AB
0.000
0.000
−0.007
0.1030

819
Inventive steel


AC
0.042
0.000
−0.007
0.0420

770
Inventive steel


AD
0.000
0.096
0.088
0.0960

795
Inventive steel


AE
0.000
0.000
−0.007
0.5000

731
Inventive steel


AF
0.040
0.045
0.037
0.0850

825
Inventive steel



























TABLE 14





Sample
Steel
Ar3

FT
CT
TS
YS
El
E(RD)
E(D)
E(TD)


No.
No.
(° C.)
ε*
(° C.)
(° C.)
(MPa)
(MPa)
(%)
(GPa)
(GPa)
(GPa)


























79
A
756
0.52
870
600
408
306
33
233
205
234


80


0.48
860
500
398
299
35
234
210
233


81



0.33

890
550
411
303
32

218

210
225


82
B
903
0.46

930

600
342
250
41

200

209
212


83


0.55

872

500
339
244
41

198

195
210


84
C
641
0.51
870
500
585
489
20
245
201
242


85


0.51
780
550
579
472
19
247
196
240


86


0.55

920

550
575
468
20

202

203
205


87
D
906
0.49

830

550
383
295
34

210

212
217


88



0.31


880

550
394
297
33

208

200
205


89
E
820
0.62
850
600
415
319
30
232
193
229


90


0.58
860
500
432
325
31
232
195
230


91



0.34


800

550
428
321
32

200

197
208


92
F
995
0.56

870

350
615
463
25

205

202
206


93


0.57

860

350
598
455
25

208

203
203


94
G
701
0.45
780
500
781
599
14
245
204
238


95


0.44
850
500
792
608
14
236
210
236


96



0.35

810
500
788
600
16

225

212
231



















TABLE 15








Texture in the ⅛
Texture in the sheet



Sam-
sheet thickness layer
thickness center layer














ple
{110}
{110}
{110}
{211}
{332}
{100}
Re-


No.
<223>
<111>
<001>
<011>
<113>
<011>
marks





79
13 
13 
1
9
10 
4
I.E.


80
12 
12 
1
11 
11 
3
I.E.


81

6


7

2

5


4

2
C.E.


82

6


6


7


4


5

4
C.E.


83

7


8


9

6

5

5
C.E.


84
16 
17 
4
11 
13 
1
I.E.


85
18 
18 
2
10 
11 
1
I.E.


86

8


7


8

8
7
5
C.E.


87

8


8


7

7

5

2
C.E.


88

7


6

5
6

5

3
C.E.


89
12 
12 
1
8
11 
1
I.E.


90
11 
12 
1
10 
10 
3
I.E.


91

6


6

5

5


5

6
C.E.


92

4


4

5
6

5

5
C.E.


93

4


4

3
6
6
6
C.E.


94
15 
14 
0
13 
11 
1
I.E.


95
11 
13 
1
10 
8
1
I.E.


96

8


8

6
11 
8

7

C.E.



























TABLE 16





Sample
Steel
Ar3

FT
CT
TS
YS
El
E (RD)
E (D)
E (TD)


No.
No.
(° C.)
ε*
(° C.)
(° C.)
(MPa)
(MPa)
(%)
(GPa)
(GPa)
(GPa)


























97
H
922
0.45

860

550
635
502
20

195

198
221


98


0.52

700

550
662
508
18

203

203
215


99
I
876
0.56
850
600
720
550
16

212

205
217


100



0.28

800
600
742
552
15

218

200
221


101
J
840
0.43
780
450
715
521
25

210

202
223


102


0.44

910

450
698
516
24

215

212
218


103
K
688
0.56
750
500
890
688
14
247
198
243


104


0.49
850
550
875
670
15
245
203
240


105



0.3

880
500
865
670
13

206

203
209


106
L
574
0.5 
700
550
942
730
12
251
212
240


107


0.5 
850
550
925
712
10
248
210
240


108



0.29

830
550
899
689
9

220

195
225


109
M
748
0.51
820
600
860
660
11

223

211
235


110



0.37


930

600
851
653
11

210

206
221


111
N
563
0.46
780
500
1121
889
8
253
201
248


112


0.43
850
500
1101
895
6
250
207
241


113



0.38


920

500
1098
882
5

225

205
223



















TABLE 17








Texture in the ⅛
Texture in the sheet



Sam-
sheet thickness layer
thickness center layer














ple
{110}
{110}
{110}
{211}
{332}
{100}
Re-


No.
<223>
<111>
<001>
<011>
<113>
<011>
marks

















97

5


5

4

4


4

2
C.E.


98

8


8


10

7
6

8

C.E.


99

7


7

6
9

4


7

C.E.


100

8


8


6

7

5


8

C.E.


101

7


7

5
8

5


8

C.E.


102

6


6

4

5


4

5
C.E.


103
15 
16 
5
13 
11 
4
I.E.


104
15 
15 
3
13 
12 
5
I.E.


105

5


5

5

5


3


7

C.E.


106
18 
19 
0
17 
15 
0
I.E.


107
17 
17 
0
15 
14 
0
I.E.


108

9


8


7


7

8

10

C.E.


109

9


9

5
10 
7
2
C.E.


110

5


5

3

8


4


9

C.E.


111
21 
22 
0
15 
18 
0
I.E.


112
18 
18 
0
13 
15 
0
I.E.


113

6


5

2

7


4

6
C.E.



























TABLE 18





Sample
Steel
Ar3

FT
CT
TS
YS
El
E(RD)
E(D)
E(TD)


No.
No.
(° C.)
ε*
(° C.)
(° C.)
(MPa)
(MPa)
(%)
(GPa)
(GPa)
(GPa)


























114
O
643
0.42
880
650
892
743
10
233
200
239


115
P
742
0.45
870
600
598
445
22
238
197
235


116
Q
852
0.5
880
550
785
695
18
245
203
241


117
R
692
0.43
830
550
859
773
12
232
205
239


118
S
801
0.41
850
500
594
475
25
235
208
235


119
T
838
0.44
880
600
481
385
30
240
199
240


120
U
775
0.49
790
500
696
556
23
243
202
239


121
V
796
0.56
810
550
719
559
20
241
205
239


122
W
864
0.51
890
600
762
553
21.04
245
208
241


123
X
777
0.42
830
600
592
474
20
239
193
235


124
Y
703
0.43
860
500
721
577
17
247
190
242


125
Z
776
0.49
880
550
779
657
15
243
200
243


126
AA
837
0.44
870
500
463
298
26
239
203
237


127
AB
819
0.42
840
450
502
402
24
237
201
237


128
AC
770
0.44
830
550
604
522
25
233
194
239


129
AD
795
0.52
800
250
562
326
26
237
203
239


130
AE
731
0.48
820
450
745
596
20
239
208
239


131
AF
825
0.5
890
550
652
495
15
241
200
237



















TABLE 19








Texture in the ⅛
Texture in the sheet



Sam-
sheet thickness layer
thickness center layer














ple
{110}
{110}
{110}
{211}
{332}
{100}
Re-


No.
<223>
<111>
<001>
<011>
<113>
<011>
marks

















114
17
17
6
8
8
5
I.E.


115
15
16
5
11
11
4
I.E.


116
15
16
2
10
13
2
I.E.


117
13
14
6
8
10
6
I.E.


118
18
16
4
9
7
3
I.E.


119
12
12
1
12
9
1
I.E.


120
15
15
2
13
11
4
I.E.


121
16
15
1
10
13
2
I.E.


122
13
14
0
10
15
1
I.E.


123
14
13
1
9
11
3
I.E.


124
18
19
1
12
10
1
I.E.


125
17
16
0
9
8
1
I.E.


126
14
15
3
10
11
2
I.E.


127
13
13
3
8
8
4
I.E.


128
16
16
4
11
11
6
I.E.


129
15
14
3
13
13
5
I.E.


130
11
11
3
11
11
4
I.E.


131
13
13
2
15
14
2
I.E.









Example 8

Steel slabs having the composition of steels No. C and L in Tables 10 and 11 were subjected to casting and hot rolling under the conditions shown in Table 20. In all cases, the slabs were heated to a temperature of 1230° C. As for the other rolling conditions, the coefficient of friction between the rollers and the steel sheet in the last three stages of the finishing rolling stand, which was made of a total of seven stages, was in a range of 0-21 to 0.24, and the total of the reduction rates of the last three stages was 55%. In all cases, the skinpass rolling reduction rate was 0.3%. The Ar3 was the same as in Tables 14 and 16.


After rolling, any one of continuous annealing (held at 700° C. for 90 seconds), box annealing (held at 700° C. for 6 hr), and continuous hot-dip galvanization (maximum attained temperature of 750° C.; alloying performed at 500° C. for 20 seconds after immersion in a galvanization bath), was performed, and the tension characteristics and the Young's modulus were measured.


The results are shown in Tables 20 and 21. It should be noted that Table 21 is a continuation of Table 20. It is clear from these results that the Young's modulus is increased by subjecting the steel that has the chemical composition of the present invention to hot rolling under suitable conditions and then appropriate thermal, processing.





















TABLE 20





Sample
Steel

FT
CT
Processing after
TS
YS
El
BH
E(RD)
E(D)
E(TD)


No.
No.
ε*
(° C.)
(° C.)
hot rolling
(MPa)
(MPa)
(%)
(MPa)
(GPa)
(GPa)
(GPa)



























132
C
0.51
870
500
None
585
489
20
47
245
201
242


133
C
0.51
870
500
Continuous
556
442
23
65
243
203
240







annealing


134
C
0.51
870
500
Box annealing
530
418
25
48
248
201
243


135
C
0.51
870
500
Continuous
549
418
22
62
241
201
240







alloyed hot-dip







galvanization


136
L
0.5
850
550
None
925
712
10
62
248
210
240


137
L
0.5
850
550
Continuous
898
716
14
79
245
211
242







annealing


138
L
0.5
850
550
Box annealing
867
694
15
52
251
208
247


139
L
0.5
850
550
Continuous
882
694
12
60
245
208
246







alloyed hot-dip







galvanization



















TABLE 21








Texture in the ⅛
Texture in the sheet



Sam-
sheet thickness layer
thickness center layer














ple
{110}
{110}
{110}
{211}
{332}
{100}
Re-


No.
<223>
<111>
<001>
<011>
<113>
<011>
marks

















132
16
17
0
11
13
1
I.E.


133
17
16
0
11
10
1
I.E.


134
17
18
0
13
12
0
I.E.


135
16
16
0
11
11
0
I.E.


136
17
17
0
15
14
0
I.E.


137
18
17
0
14
13
0
I.E.


138
19
18
0
14
15
0
I.E.


139
17
19
0
15
13
0
I.E.









Example 9

Steel slabs having the composition of steels No. C and in Tables 10 and 11 were subjected to casting and hot rolling under the conditions shown in Table 22. In all cases, the slabs were heated to a temperature of 1230° C. As for the other rolling conditions, the coefficient of friction between the rollers and the steel sheet in the last three stages of the finishing rolling stand, which was made of a total of seven sages, was in a range of 0.21 to 0.24, and the total of the reduction rates of the last three stages was 55%. In all cases, the skinpass rolling reduction rate was 0.3%. The Ar3 was the same as in Tables 14 and 16.


Cold rolling was conducted after the hot rolling, and then continuous hot-dip galvanization (the maximum attained temperature was variously changed, and alloying was performed at 500° C. for 20 seconds after immersion in a galvanization bath) was performed. The tension characteristics and the Young's modulus were then measured.


The results are shown in Tables 22 and 23. It should be noted that Table 23 is a continuation of Table 22, it is clear from these results that by subjecting the steel that has the chemical composition of the invention to hot rolling and cold rolling, and then subjecting the steel to suitable thermal processing, it is possible to obtain a cold rolled steel sheet that has excellent Young's moduli in both the RD direction and the TD direction. However, in cases where the maximum attained temperature was noticeably high, there was a slight drop in the Young's modulus.






















TABLE 22










Cold
Maximum









Sample
Steel

FT
CT
rolling
temperature
TS
YS
El
BH
E(RD)
E(D)
E(TD)


No.
No.
ε*
(° C.)
(° C.)
rate (%)
(° C.)
(MPa)
(MPa)
(%)
(MPa)
(GPa)
(GPa)
(GPa)




























140
C
0.51
870
500
52
970
613
492
17
53
239
211
238


141
C
0.51
870
500
52
830
600
478
20
82
244
203
243


142
C
0.51
870
500
52
750
589
469
21
65
245
201
203


143
L
0.5
850
550
30
970
1008
789
8
62
239
211
241


144
L
0.5
850
550
30
830
976
761
10
78
242
207
238


145
L
0.5
850
550
30
750
949
736
11
61
240
203
242



















TABLE 23








Texture in the ⅛
Texture in the sheet



Sam-
sheet thickness layer
thickness center layer














ple
{110}
{110}
{110}
{211}
{332}
{100}
Re-


No.
<223>
<111>
<001>
<011>
<113>
<011>
marks

















140
15
14
0
10
10
2
I.E.


141
17
17
0
11
12
2
I.E.


142
16
17
1
10
11
1
I.E.


143
13
15
1
13
12
2
I.E.


144
16
17
0
15
15
1
I.E.


145
16
15
0
14
15
1
I.E.









Example 10

Steel slabs having the composition of steels No. C and L in Tables 10 and 11 were subjected to casting and hot rolling under the conditions shown in Table 24. In all cases, the slabs were heated to a temperature of 1230° C. As for the other rolling conditions, the coefficient of friction between the rollers and the steel sheet in the last three stages of the finishing rolling stand, which was made of a total of seven stages, was in a range of 0.21 to 0.24, and the total of the reduction rates of the last three stages was 55%. In all cases, the skinpass rolling reduction rate was 0.3%. The Mm was the same as in Tables 14 and 16.


After hot rolling, the steel sheet was heated to 650° C. through a continuous hot-dip galvanization line and then cooled to approximately 470° C., thereafter it was immersed in a 460° C. hot-dip galvanization bath. The thickness of plate of the zinc was 40 g/m2 one side on average. Subsequent to the hot-dip galvanization, the steel sheet surface was subjected to (1) organic film coating or (2) painting as described below, and the tension characteristics and the Young's modulus were measured.


(1) Organic Film


4 mass % corrosion inhibitor and 12% colloidal silica were added to a water-borne resin in which the solid resin portion was 27.6 mass %, the dispersion liquid viscosity was 1400 mPa·s (25° C.), the pH was 8.8, the content of carboxyl group ammonium salts (—COONH4) was 9.5 mass % of the total solid resin portion, the carboxyl group content was 2.5 mass % of the total solid resin portion, and the mean dispersion particle diameter was approximately 0.030 μm, as to produce a rustproofing liquid, and this rustproofing was then applied to the above steel sheet by a roll coater and dried so that the surface of the steel sheet reached a temperature of 120° C., so as to form an approximately 1-μm thick film.


(2) Paint


As a chemical treatment, a roll coater was used to apply “ZM1300AN” made by Nihon Parkerizing Co., Ltd. onto the steel sheet after it had been degreased, and was hot-air dried so that the reached temperature of the steel sheet was 60° C. The amount of deposit of the chemical treatment was 50 mg/m2 of Cr deposit. A primer paint was applied to one side of this chemically treated steel sheet, and a rear surface paint was applied to the other surface, using a roll coater. These were dried and hardened by an induction heater that also employs hot air. The temperature reached at this time was 210° C.


A top paint was then applied by a roller curtain coater to the surface on which the primer paint had been applied, and was dried and hardened by an induction heater that involves the use of hot air at a reached temperature of 230° C. It should be noted that the primer paint was applied at a dry film thickness of 5 μm using “FL640EU Primer” made by Japan Fine Coatings Co., Ltd. The rear surface paint was applied at a dry film thickness of 5 μm using “FL100HQ” made by Japan Fine Coatings Co., Ltd. The top paint was applied at a dry film thickness of 15 μm using “FL100HQ” made by Japan Fine Coatings Co., Ltd.


The results are shown in Tables 24 and 25. It should be noted that Table 25 is a continuation of Table 24. From these results it can be clearly understood that the steel sheets that are subjected to hot-dip galvanization and the steel sheets that are subjected to hot-dip galvanization and have an organic film or paint applied to their surface have a good Young's modulus.




















TABLE 24





Sample
Steel

FT
CT
Surface
TS
YS
El
E(RD)
E(D)
E(TD)


No.
No.
ε*
(° C.)
(° C.)
processing
(MPa)
(MPa)
(%)
(GPa)
(GPa)
(GPa)


























146
C
0.51
870
500
Hot-dip
559
418
22
243
201
242







galvanization







only


147
C
0.51
870
500
Organic film
582
421
22
245
208
243


148
C
0.51
870
500
Paint
590
421
20
247
206
245


149
L
0.5
850
550
Hot-dip
889
678
10
246
210
240







galvanization







only


150
L
0.5
850
550
Organic film
912
687
9
249
210
243


151
L
0.5
850
550
Paint
932
691
11
251
207
245



















TABLE 25








Texture in the ⅛
Texture in the sheet



Sam-
sheet thickness layer
thickness center layer














ple
{110}
{110}
{110}
{211}
{332}
{100}
Re-


No.
<223>
<111>
<001>
<011>
<113>
<011>
marks

















146
16
17
0
11
13
1
I.E.


147
17
15
0
13
13
1
I.E.


148
19
16
1
12
14
0
I.E.


149
17
17
0
15
14
0
I.E.


150
19
18
0
15
14
1
I.E.


151
19
17
0
16
15
0
I.E.









Example 11

The steels C and L shown in Tables 10 and 11 were subjected to differential speed rolling. The different roll speeds rate was changed over the last three stages of the finishing rolling stand, which was made of a total of seven stages. The hot rolling conditions, and the results of measuring the tension characteristics and the Young's modulus are shown in Table 26. It should be noted that all hot rolling conditions that are not shown in Table 26 are the same as those in Example 7.


The results that were obtained are shown in Tables 26 and 27. It should be noted that Table 27 is a continuation of Table 22. It is clear from the results that the formation of texture near the surface layer is facilitated in the case in which one or more passes of differential speed rolling at 1% or more are added when hot rolling the steel having the chemical composition of the present invention under appropriate conditions, and this further increases the Young's modulus.












TABLE 26









Different roll




speeds ratio (%)




















Sample
Steel

FT
CT
5th
6th
7th
TS
YS
El
E(RD)
E(D)
E(TD)


No.
No.
ε*
(° C.)
(° C.)
pass
pass
pass
(MPa)
(MPa)
(%)
(GPa)
(GPa)
(GPa)























152
C
0.51
870
500
0
0
0
585
489
20
245
201
242


153
C
0.49
868
500
0
0
3
591
446
20
247
203
242


154
C
0.5
872
500
1
2
3
589
445
20
248
202
240


155
C
0.51
875
500
10
5
5
597
451
21
251
202
243


156
L
0.5
850
550
0
0
0
925
712
10
248
210
240


157
L
0.51
853
550
3
3
3
931
721
11
250
211
242


158
L
0.49
855
550
0
0
10
924
715
11
252
211
242


159
L
0.5
850
550
0
20
20
925
716
11
254
209
243



















TABLE 27








Texture in the ⅛
Texture in the sheet



Sam-
sheet thickness layer
thickness center layer














ple
{110}
{110}
{110}
{211}
{332}
{100}
Re-


No.
<223>
<111>
<001>
<011>
<113>
<011>
marks

















152
16
17
0
11
13
1
I.E.


153
17
17
0
10
13
1
I.E.


154
18
16
0
10
14
0
I.E.


155
20
16
1
10
15
0
I.E.


156
17
17
0
15
14
0
I.E.


157
18
17
0
14
14
0
I.E.


158
20
16
1
15
15
0
I.E.


159
22
16
0
13
16
0
I.E.









Example 12

The steel C and L shown in Tables 10 and 11 were subjected to pressure rolling with small-diameter rollers. The roller diameter was changed in the last three stages of the finishing rolling stand, which was made of a total of seven stages. The hot rolling conditions, and the results of measuring the tension characteristics and the Young's modulus are shown in Table 28. It should be noted that all hot rolling conditions that are not shown in Table 28 are the same as those in Example 7.


The results that were obtained are shown in Tables 28 and 29. It should be noted that Table 29 is a continuation of Table 28. It is clear from the results that the formation of texture near the surface is facilitated in the case in which rollers with a roller diameter of 700 mm or less are used in one or more passes when hot rolling the steel having the chemical composition of the present invention under appropriate conditions, and this further increases the Young's modulus.












TABLE 28









Roller diameter (mm)





















Sample
Steel

FT
CT
5th
6th
7th
TS
YS
El
E(RD)
E(D)
E(TD)


No.
No.
ε*
(° C.)
(° C.)
pass
pass
pass
(MPa)
(MPa)
(%)
(GPa)
(GPa)
(GPa)























160
C
0.51
870
500
800
800
800
585
489
20
245
201
242


161
C
0.51
873
500
800
800
600
583
440
22
246
202
243


162
C
0.53
870
500
600
600
600
585
442
20
249
203
243


163
C
0.53
867
500
500
500
500
589
445
19
253
203
243


164
L
0.5
850
550
800
800
800
925
712
10
248
210
243


165
L
0.51
855
550
800
800
600
927
718
11
251
210
245


166
L
0.52
853
550
600
600
600
931
721
11
253
210
246


167
L
0.52
852
550
500
500
500
933
723
10
256
212
243



















TABLE 29








Texture in the ⅛
Texture in the sheet



Sam-
sheet thickness layer
thickness center layer














ple
{110}
{110}
{110}
{211}
{332}
{100}
Re-


No.
<223>
<111>
<001>
<011>
<113>
<011>
marks

















160
16
17
0
11
13
1
I.E.


161
18
16
0
10
14
0
I.E.


162
20
16
1
11
15
2
I.E.


163
22
17
1
11
16
0
I.E.


164
17
17
0
15
14
0
I.E.


165
18
18
1
14
15
0
I.E.


166
20
17
0
15
15
0
I.E.


167
23
16
0
13
17
0
I.E.









Example 13

The steels shown in Tables 30 through 33 were heated from 1200° C. to 1270° C. and hot rolled under the hot rolling conditions shown in Tables 34, 36, 38, and 40, so as to produce hot rolled steel sheets of 2 mm thick. Here, “present” is entered in the column for hot rolled sheet annealing (3*) for those hot rolled steel sheets that have been annealed, and “none” is entered for those hot rolled steel sheets that have not been annealed. This annealing was performed at 600 to 700° C. for 60 minutes. This notation applies in the description for subsequent tables.


As for measuring the Young's modulus of the surface layer, a sample was obtained from the ⅙ sheet thickness layer from the surface layer, and the Young's modulus was measured using the lateral resonance method discussed above. A JIS 5 tension to piece was sampled and the tension characteristics in the transverse direction were evaluated.


The shape fixability was evaluated using a strip-shaped sample 260 mm long×50 mm wide×sheet thickness, molded into a hat-shape with various creasing pressing thicknesses at a punch width of 78 mm, a punch shoulder R of 5 mm, and a die shoulder R of 4 mm, and measuring the shape of the central portion in the sheet width by a three-dimensional shape measuring device. As shown in FIG. 1, the shape fixability was measured by adopting the mean value left and right of the value obtained by subtracting 90° from the angle of the intersection between the line connecting point A and point B and the line connecting point C and point D as the spring back amount, and adopting the value obtained by multiplying the value obtained by left-right averaging the reciprocal of the radius of curvature ρ [mm] between point C and point E by 1000 as the wall camber amount. The smaller 1000/ρ is, the better the shape fixability. It should be noted that bending was performed in such a manner that a fold line appeared perpendicular to the rolling direction.


In general, it is known that when the strength of a steel sheet increases, its shape fixability becomes worse. The inventors actually molded components, and found that in a case where the spring back amount and 1000/ρ at a blank holding force of 70 kN as measured by the method above are (0.015×TS-6) (°) or less, and (0.01×TS-3) (mm−1) or less, respective, with respect to the tensile strength [MPa] of the steel sheet, the shape fixability is remarkably good. Thus, the evaluation was conducted taking the fulfilling of these two criteria simultaneously as the condition for good shape fixability.


The results that were obtained are shown in Tables 34 to 41. It should be noted that Table 35 is a continuation of Table 34, and Table 37 is a continuation of Table 36. Also, Table 39 is a continuation of Table 38, and Table 41 is a continuation of Table 40. Here, for the rolling rate (1*), “suitable” is entered if the total rolling rate of the hot rolling is 50% or more, and “unsuitable” is entered if this is less than 50%. For the coefficient of friction (2*), “suitable” is entered if the mean coefficient of friction during hot rolling is greater than 0.2, and “unsuitable” is entered if this is 0.2 or less. The shape fixability is listed as “good” if the two criteria are met, and “poor” if they are not met. These entries are the same in the subsequent descriptions of the tables.


When the blank holding force is increased, 1000/ρ tends to become smaller. However, regardless of the blank holding force that is chosen, the dominance order of the shape fixability of the steel sheet does not change. Consequently, the evaluation at 70 kN of blank holding force accurately represents the shape fixability of the steel sheet.


















TABLE 30





Steel











No.
C
Si
Mn
P
S
Al
N
Mo
B
























P1
0.003
0.01
1.50
0.080
0.0012
0.036
0.0025
0.200
0.0010


P2
0.031
0.75
0.50
0.013
0.0009
0.029
0.0027
0.420
0.0020


P3
0.023
0.02
0.60
0.009
0.0034
0.029
0.0025
0.350
0.0020


P4
0.042
0.36
0.32
0.008
0.0026
0.031
0.0036
0.430
0.0020


P5
0.020
0.09
1.45
0.015
0.0006
0.032
0.0024
0.180
0.0010


P6
0.045
0.53
1.85
0.010
0.0045
0.037
0.0041
0.170
0.0009


P7
0.080
1.30
1.70
0.028
0.0062
0.034
0.0031
0.210
0.0013


P8
0.160
0.07
0.98
0.013
0.0053
0.044
0.0024
0.300
0.0015


P9
0.110
0.05
2.12
0.010
0.0036
0.680
0.0024
0.290
0.0020


P10
0.150
1.80
1.95
0.018
0.0028
0.019
0.0031
0.320
0.0022


P11
0.007
0.08
1.22
0.030
0.0035
0.023
0.0021
0.070
0.0030


P12
0.130
0.11
1.52
0.009
0.0065
0.034
0.0022
0.000
0.0000


P13
0.020
0.06
0.98
0.012
0.0033
0.070
0.0033
0.000
0.0025


P14
0.079
0.06
0.73
0.013
0.0045
0.032
0.0028
0.300
0.0000


P15
0.060
0.20
0.77
0.040
0.0052
0.029
0.0022
0.140
0.0028























TABLE 31









Mo +





Steel


Ti − 48/
Nb +

Ar3


No.
Nb
Ti
14 × N
Ti + B
Others
(° C.)
Remarks






















P1
0.030
0.018
0.0094
0.249

781
Inventive steel


P2
0.028
0.018
0.0087
0.468

842
Inventive steel


P3
0.018
0.020
0.0114
0.390

818
Inventive steel


P4
0.03
0.031
0.0187
0.493

840
Inventive steel


P5
0.042
0.010
0.0018
0.233

783
Inventive steel


P6
0.022
0.023
0.0089
0.216
Cr: 0.5
761
Inventive steel


P7
0.021
0.013
0.0024
0.245

778
Inventive steel


P8
0.033
0.021
0.0128
0.356
Ca:
762
Inventive steel







0.0015


P9
0.035
0.012
0.0038
0.339
V: 0.02
806
Inventive steel


P10
0.035
0.015
0.0044
0.372

727
Inventive steel


P11
0.022
0.021
0.0138
0.116

782
Inventive steel


P12
0.080
0.000
−0.0075
0.080

774
Inventive steel


P13
0.052
0.000
−0.0113
0.055

819
Inventive steel


P14
0.000
0.000
−0.0096
0.300

826
Inventive steel


P15
0.000
0.000
−0.0075
0.143

804
Inventive steel

























TABLE 32





Steel











No.
C
Si
Mn
P
S
Al
N
Mo
B







P16
0.062
0.23
1.20
0.006
0.0066
0.042
0.0025
0.000
0.0000


P17
0.062
0.06
2.35
0.012
0.0003
0.033
0.0026
0.000
0.0000


P18
0.067
0.24
1.52
0.008
0.0045
0.035
0.0023
0.080
0.0011


P19
0.043
0.53
1.98
0.010
0.0036
0.042
0.0022
0.130
0.0020


C1
0.020
0.01
1.50
0.012
0.0017
0.032
0.0035
0.000
0.0001


C2
0.010
0.37
1.20
0.010
0.0003
0.023
0.0033
0.005
0.0023


C3
0.051
0.57

0.05

0.009
0.0026
0.026
0.0029
0.230
0.0001


C4
0.045

2.60

1.80
0.014
0.0042
0.027
0.0024
0.000
0.0010


C5
0.100
1.30
1.70
0.062
0.0056

1.200

0.0030
0.600
0.0008


C6
0.120
1.80
0.10
0.007
0.0029
0.620
0.0032
0.330
0.0004























TABLE 33









Mo +





Steel


Ti − 48/
Nb +

Ar3


No.
Nb
Ti
14 × N
Ti + B
Others
(° C.)
Remarks






















P16
0.040
0.080
0.0714
0.120
W: 0.01
826
Inventive steel


P17
0.000
0.110
0.1011
0.110

726
Inventive steel


P18
0.024
0.015
0.0071
0.120

775
Inventive steel


P19
0.033
0.020
0.0125
0.185

739
Inventive steel


C1
0.001
0.009
−0.0030

0.010


804
Comparative









steel


C2
0.002
0.000
−0.0113

0.009


808
Comparative









steel


C3
0.040
0.023
0.0131
0.293

909
Comparative









steel


C4
0.000
0.005
−0.0032

0.006

Cu: 0.2
843
Comparative









steel


C5
0.024
0.021
0.0107
0.646

981
Comparative









steel


C6
0.031
0.007
−0.0040
0.368

1031
Comparative









steel






























TABLE 34


















Surface layer
Surface layer







Coef-


Hot rolled




Young's
Young's


Sam-



Rolling
ficient of


sheet




modulus
modulus


ple
Steel
Ar3

rate
friction
FT
CT
annealing
TS
E(RD)
E(D)
E(TD)
in rolling
in transverse


No.
No.
(° C.)
ε*
(1*)
(2*)
(° C.)
(° C.)
(3*)
(MPa)
(GPa)
(GPa)
(GPa)
direction (GPa)
direction (GPa)





























168
P1
781
0.65
Suitable
Suitable
835
500
None
469
246
205
240
255
255


169


0.57
Suitable
Suitable
830
600
None
460
243
206
239
253
256


170



0.37

Suitable
Suitable
850
550
None
467

212

205
235

221

239


171
P2
842
0.72
Suitable
Suitable
860
400
None
500
245
199
239
259
263


172


0.59
Suitable
Suitable
875
600
None
498
250
200
245
262
257


173


0.49

Unsuitable

Suitable
880
600
None
503

204

205
218

218

229


174
P3
818
0.67
Suitable
Suitable
840
450
None
446
242
203
238
253
255


175


0.82
Suitable
Suitable
870
450
Present
450
241
202
240
254
254


176


0.48
Suitable

Unsuitable

850
450
None
449

213

206
239

225

235


177
P4
840
0.52
Suitable
Suitable
860
500
Present
479
246
198
40
256
261


178


0.59
Suitable
Suitable
875
500
None
482
239
197
238
248
253


179


0.57
Suitable
Suitable

750

500
None
485

214

200
230

223

223























TABLE 35









Texture in the ⅛
Texture in the sheet







sheet thickness layer
thickness center layer
Spring
Wall

















Sample
{110}
{110}
{110}
{211}
{332}
{100}
back
camber
Shape



No.
<223>
<111>
<001>
<011>
<113>
<011>
(°)
(1000/ρ)
fixability
Remarks





168
13
13
3
10 
10 
2
0.0
0.4
Good
I.E.


169
13
12
2
9
9
1
0.5
0.4
Good
I.E.


170
4
5
6

5


3

5
1.4
2.2

Poor

C.E.


171
13
12
3
11 
10 
2
0.1
0.7
Good
I.E.


172
16
15
3
10 
12 
3
0.3
0.8
Good
I.E.


173
5
4
3

4


3

4
2.2
3.2

Poor

C.E.


174
12
12
0
9
10 
3
0.1
0.9
Good
I.E.


175
13
13
0
8
9
2
0.0
0.9
Good
I.E.


176
5
6
4

5


3

5
1.4
1.9

Poor

C.E.


177
14
15
1
10 
10 
2
0.0
0.8
Good
I.E.


178
12
11
2
9
8
4
0.1
1.5
Good
I.E.


179
6
5
6

5


3

5
1.3
2.8

Poor

C.E.






























TABLE 36


















Surface layer
Surface layer







Coef-


Hot rolled




Young's
Young's


Sam-



Rolling
ficient of


sheet




modulus
modulus


ple
Steel
Ar3

rate
friction
FT
CT
annealing
TS
E(RD)
E(D)
E(TD)
in rolling
in transverse


No.
No.
(° C.)
ε*
(1*)
(2*)
(° C.)
(° C.)
(3*)
(MPa)
(GPa)
(GPa)
(GPa)
direction (GPa)
direction (GPa)





























180
P5
783
0.64
Suitable
Suitable
820
600
None
590
239
206
237
245
241


181


0.63
Suitable
Suitable
880
600
None
553
248
203
245
259
255


182


0.72
Suitable
Suitable

920

600
None
567

209

200
218

231

253


183
P6
788
0.65
Suitable
Suitable
880
350
None
632
248
197
243
268
257


184


0.52
Suitable
Suitable
870
500
None
609
246
195
239
262
263


185


0.57
Suitable
Suitable
860

730

None
578

216

201
229

225

229


186
P7
778
0.61
Suitable
Suitable
830
450
None
782
246
203
238
255
255


187


0.76
Suitable
Suitable
850
250
None
779
247
195
244
262
255


188


0.72
Suitable
Suitable

930

400
None
749

203

199
213

209

219


189
P8
762
0.59
Suitable
Suitable
830
350
None
792
235
200
239
249
238


190


0.54
Suitable
Suitable
850
500
Present
800
240
205
238
253
255


191



0.25

Suitable

Unsuitable

850
400
None
803

210

203
220

219

220























TABLE 37









Texture in the ⅛
Texture in the sheet







sheet thickness layer
thickness center layer
Spring
Wall

















Sample
{110}
{110}
{110}
{211}
{332}
{100}
back
camber
Shape



No.
<223>
<111>
<001>
<011>
<113>
<011>
(°)
(1000/ρ)
fixability
Remarks





180
11
10
1
9
8
1
1.0
2.1
Good
I.E.


181
14
13
3
11 
11 
0
0.6
1.5
Good
I.E.


182
4
5
5

4


3

6
3.0
3.0

Poor

C.E.


183
14
13
0
10 
11 
2
0.6
1.9
Good
I.E.


184
14
14
1
11 
10 
4
1.0
1.4
Good
I.E.


185
6
5
6

5


4

6
3.4
3.0

Poor

C.E.


186
14
15
0
10 
10 
2
4.6
4.0
Good
I.E.


187
13
14
2
12 
11 
3
4.0
3.5
Good
I.E.


188
5
4
2

5


3

7
6.5
5.8

Poor

C.E.


189
10
11
1
8
9
2
5.1
4.1
Good
I.E.


190
11
12
0
7
8
4
4.4
3.6
Good
I.E.


191
5
5
5
4
4
6
6.8
5.7

Poor

C.E.






























TABLE 38


















Surface layer
Surface layer







Coef-


Hot rolled




Young's
Young's


Sam-



Rolling
ficient of


sheet




modulus
modulus


ple
Steel
Ar3

rate
friction
FT
CT
annealing
TS
E(RD)
E(D)
E(TD)
in rolling
in transverse


No.
No.
(° C.)
ε*
(1*)
(2*)
(° C.)
(° C.)
(3*)
(MPa)
(GPa)
(GPa)
(GPa)
direction (GPa)
direction (GPa)





























192
P9
806
0.67
Suitable
Suitable
860
500
None
980
241
198
236
252
259


193


0.72
Suitable
Suitable
870
400
None
997
239
209
235
250
253


194


0.71

Unsuitable

Suitable
850
350
None
1029

213

210
219

225

245


195
P10
727
0.47
Suitable
Suitable
780
300
None
1008
245
211
237
256
260


196


0.5
Suitable
Suitable
830
350
None
1102
247
208
237
261
255


197


0.52
Suitable

Unsuitable

850
500
None
904

206

203
230

215

219


198
P11
782
0.41
Suitable
Suitable
840
500
None
498
241
211
236
250
249


199
P12
774
0.44
Suitable
Suitable
860
550
None
605.8
240
206
236
253
243


200
P13
819
0.62
Suitable
Suitable
830
500
None
652
239
209
239
249
246


201
P14
826
0.42
Suitable
Suitable
860
600
None
723
242
196
238
256
247


202
P15
804
0.53
Suitable
Suitable
850
500
None
525.7
239
200
236
262
249


203
P16
826
0.56
Suitable
Suitable
880
550
None
581.5
237
202
238
246
242


204
P17
726
0.59
Suitable
Suitable
800
450
None
700.5
245
200
237
253
253























TABLE 39









Texture in the ⅛
Texture in the sheet







sheet thickness layer
thickness center layer
Spring
Wall

















Sample
{110}
{110}
{110}
{211}
{332}
{100}
back
camber
Shape



No.
<223>
<111>
<001>
<011>
<113>
<011>
(°)
(1000/ρ)
fixability
Remarks




















192
12
12
3
9
9
3
7.9
5.8
Good
I.E.


193
11
10
1
10 
8
1
8.0
6.4
Good
I.E.


194
5
5
4

4


3

5
10.0
7.9

Poor

C.E.


195
13
12
2
10 
10 
2
7.8
6.2
Good
I.E.


196
14
13
0
11 
11 
3
8.7
6.8
Good
I.E.


197
4
4
3

5


3

5
9.2
6.7

Poor

C.E.


198
12
12
6
10 
9
5
0.5
0.0
Good
I.E.


199
13
12
4
9
8
4
1.9
2.0
Good
I.E.


200
11
12
3
9
8
3
2.5
3.0
Good
I.E.


201
11
12
2
8
9
2
3.2
3.0
Good
I.E.


202
11
10
0
10 
8
4
0.9
1.2
Good
I.E.


203
15
14
6
9
8
4
1.2
1.8
Good
I.E.


204
14
14
5
9
10 
1
3.1
3.0
Good
I.E.






























TABLE 40


















Surface layer
Surface layer







Coef-


Hot rolled




Young's
Young's


Sam-



Rolling
ficient of


sheet




modulus
modulus


ple
Steel
Ar3

rate
friction
FT
CT
annealing
TS
E(RD)
E(D)
E(TD)
in rolling
in transverse


No.
No.
(° C.)
ε*
(1*)
(2*)
(° C.)
(° C.)
(3*)
(MPa)
(GPa)
(GPa)
(GPa)
direction (GPa)
direction (GPa)





























205
P18
775
0.44
Suitable
Suitable
880
400
None
621.6
249
199
239
260
255


206
P19
739
0.48
Suitable
Suitable
860
500
None
712.7
243
200
235
256
250


207
C1
804
0.65
Suitable
Suitable
880
400
Present
439

204

205
205

210

225


208


0.68

Unsuitable

Suitable
850
450
None
419

196

203
209

205

226


209
C2
808
0.78
Suitable
Suitable
840
500
Present
439

201

207
205

223

249


210


0.88
Suitable
Suitable
850

750

None
447

200

205
203

209

231


211
C3
909
0.57
Suitable
Suitable

820

600
None
567

208

207
219

227

246


212


0.67
Suitable
Suitable

840

500
None
557

212

205
220

225

245


213
C4
843
0.95
Suitable
Suitable
850
550
None
529

199

206
218

208

222


214


0.77
Suitable
Suitable
880
550
Present
549

200

206
223

203

220


215
C5
981
0.65
Suitable
Suitable

870

450
None
780

205

199
209

198

221


216



0.32

Suitable
Suitable

830

300
None
770

195

200
230

204

219


217
C6
1031
0.44
Suitable
Suitable

850

300
None
790

222

205
207

231

237


218


0.7 

Unsuitable

Suitable

800

250
None
834

196

203
220

205

223























TABLE 41









Texture in the ⅛
Texture in the sheet







sheet thickness layer
thickness center layer
Spring
Wall

















Sample
{110}
{110}
{110}
{211}
{332}
{100}
back
camber
Shape



No.
<223>
<111>
<001>
<011>
<113>
<011>
(°)
(1000/ρ)
fixability
Remarks





205
15 
14 
2
12 
11 
2
2.0
2.2
Good
I.E.


206
12 
13 
4
10 
9
3
3.4
3.1
Good
I.E.


207

4


5

3

5


4

3
1.5
2.8

Poor

C.E.


208

8


9

7

4


3

6
2.0
2.8

Poor

C.E.


209

4


3

4

4


5

5
1.2
1.7

Poor

C.E.


210

4


5

3

5


3

6
2.5
3.2

Poor

C.E.


211

6


7

5

3


5

4
2.9
3.2

Poor

C.E.


212

5


4

4

5


2

3
2.9
3.0

Poor

C.E.


213

5


6

4

6


3

5
3.4
3.5

Poor

C.E.


214

7


8

5

4


5

4
4.0
4.3

Poor

C.E.


215

7


6

6

5


3

5
7.9
6.4

Poor

C.E.


216

5


4

3

5


3

7
7.7
6.5

Poor

C.E.


217

8


7

7

6


4

5
5.8
5.2

Poor

C.E.


218

5


6

5

3


6

5
8.4
6.5

Poor

C.E.









Example 14

The steels P5 and P8 shown in Tables 30 and 31 were subjected to differential speed rolling. The different roll speeds rate was changed in the last three stages of the finishing rolling stand, which was constituted by a total of seven stages. The hot rolling conditions, the results of measuring the tension characteristics and the Young's modulus, and the results of evaluating the shape fixability, are shown in Table 42. It should be noted that manufacturing conditions that are not listed in the table are the same as those in Example 13.


The results that were obtained are shown in Table's 42 and 43. It should be noted that Table 43 is a continuation of Table 42. It is clear from the results that in the case in which one or more passes of differential speed rolling at or more are added when hot rolling the steel that has the chemical composition of the present invention under appropriate conditions, the Young's modulus near the surface layer is increased even further and the shape fixability is good.


















TABLE 42















Different roll







Rolling
Coefficient of


speeds ratio (%)
Hot rolled


















Sample
Steel
Ar3

rate
friction
FT
CT
5th
6th
7th
sheet annealing


No.
No.
(° C.)
ε*
(1*)
(2*)
(° C.)
(° C.)
pass
pass
pass
(3*)





219
P5
783
0.65
Suitable
Suitable
870
500
0
0
0
None


220


0.67
Suitable
Suitable
880
500
0
0
3
Present


221


0.67
Suitable
Suitable
860
500
1
2
3
None


222


0.66
Suitable
Suitable
870
500
10
5
5
None


223
P8
762
0.65
Suitable
Suitable
850
500
0
0
0
None


224


0.65
Suitable
Suitable
860
500
3
3
3
Present


225


0.67
Suitable
Suitable
850
500
0
0
10
None


226


0.65
Suitable
Suitable
850
500
0
20
20
None























Surface layer Young's
Surface layer Young's



Sample
TS
E(RD)
E(D)
E(TD)
modulus in rolling
modulus in transverse



No.
(MPa)
(GPa)
(GPa)
(GPa)
direction (GPa)
direction (GPa)







219
582
239
205
236
245
247



220
590
242
205
238
259
250



221
598
244
202
240
252
252



222
584
248
200
242
266
259



223
793
240
195
235
249
248



224
775
241
198
237
257
249



225
780
243
196
238
255
250



226
789
246
197
240
263
252
























TABLE 43









Texture in the ⅛
Texture in the sheet







sheet thickness layer
thickness center layer
Spring
Wall

















Sample
{110}
{110}
{110}
{211}
{332}
{100}
back
camber
Shape



No.
<223>
<111>
<001>
<011>
<113>
<011>
(°)
(1000/ρ)
fixability
Remarks




















219
13
12
2
9
8
4
1.7
2.1
Good
I.E.


220
12
11
1
9
9
3
1.1
1.8
Good
I.E.


221
12
13
0
10
10
3
0.6
1.6
Good
I.E.


222
14
15
0
11
12
1
0.1
1.3
Good
I.E.


223
11
12
2
10
9
3
5.2
4.1
Good
I.E.


224
12
11
0
9
8
2
4.7
3.6
Good
I.E.


225
12
13
0
11
9
2
4.2
3.3
Good
I.E.


226
15
14
0
10
10
1
3.9
3
Good
I.E.









Example 15

The steels P5 and P8 shown in Tables 30 and 31 were subjected to pressure rolling with small-diameter rollers. The roller diameter was changed in the last three stages of the finishing rolling stand, which was constituted by a total of six stages. The hot rolling conditions, the results of measuring the tension characteristics and the Young's modulus, and the results of evaluating the shape fixability, are shown in Table 44. It should be noted that manufacturing conditions that are not listed in the table are the same as those in Example 13.


The results that were obtained are shown in Tables 44 and 45. It should be noted that Table 45 is a continuation of Table 44. It is clear from the results that in the case in which rollers with a roller diameter of 700 mm or less are used in one or more passes when hot rolling the steel that has the chemical composition of the present invention under appropriate conditions, the Young's modulus near the surface layer is increased even further and the shape fixability is good.














TABLE 44









Rolling
Coefficient of
Roller diameter (mm)
Hot rolled


















Sample
Steel
Ar3

rate
friction
FT
CT
4th
5th
6th
sheet annealing


No.
No.
(° C.)
ε*
(1*)
(2*)
(° C.)
(° C.)
pass
pass
pass
(3*)





227
P5
783
0.62
Suitable
Suitable
850
550
800
800
800
None


228


0.67
Suitable
Suitable
855
550
800
800
600
None


229


0.6
Suitable
Suitable
860
550
600
600
600
None


230


0.73
Suitable
Suitable
845
550
500
500
500
None


231
P8
762
0.65
Suitable
Suitable
870
550
800
800
800
None


232


0.63
Suitable
Suitable
860
550
800
800
600
Present


233


0.67
Suitable
Suitable
860
550
600
600
600
None


234


0.6
Suitable
Suitable
865
550
500
500
500
None























Surface layer Young's
Surface layer Young's



Sample
TS
E(RD)
E(D)
E(TD)
modulus in rolling
modulus in transverse



No.
(MPa
(GPa)
(GPa)
(GPa)
direction (GPa)
direction (GPa)







227
579
238
205
239
246
249



228
577
241
202
240
247
251



229
592
245
205
240
253
253



230
585
249
198
246
257
256



231
792
241
199
237
249
250



232
783
245
200
239
255
249



233
801
247
198
240
260
251



234
803
251
202
241
265
260
























TABLE 45









Texture in the ⅛
Texture in the sheet







sheet thickness layer
thickness center layer
Spring
Wall

















Sample
{110}
{110}
{110}
{211}
{332}
{100}
back
camber
Shape



No.
<223>
<111>
<001>
<011>
<113>
<011>
(°)
(1000/ρ)
fixability
Remarks




















227
11
11
2
9
7
3
1.9
2.1
Good
I.E.


228
12
12
1
9
8
0
1.2
1.8
Good
I.E.


229
13
12
0
10
10
2
0.6
1.6
Good
I.E.


230
14
15
0
11
12
3
0.1
1.3
Good
I.E.


231
12
11
3
9
8
6
5.2
4.1
Good
I.E.


232
13
12
2
10
10
4
4.7
3.6
Good
I.E.


233
14
15
1
11
10
4
4.2
3.3
Good
I.E.


234
15
16
0
12
12
3
3.9
3
Good
I.E.









Example 16

A cold-roiled, annealed sheets were manufactured using the steels P5 and P8 shown in Tables 30 and 31. The hot rolling, cold rolling, and annealing conditions, the tension characteristics, the results of measuring the Young's modulus, and the results of evaluating the shape fixability, are shown in Table 46. It should be noted that the manufacturing conditions that are not listed in the table are the same as those in Example 13.


The results that were obtained are shown in Tables 46 and 47. It should be noted that Table 47 is a continuation of Table 46. It is clear from the results that in the case in which the steel having the chemical composition of the present invention is hot rolled, cold rolled, and annealed under appropriate conditions, the Young's modulus of the surface layer exceeds 245 GPa and the shape fixability is increased.


















TABLE 46











Rolling
Coefficient of


Cold
Maximum


Sample
Steel
Ar3

rate
friction
FT
CT
rolling
temperature


No.
No.
(° C.)
ε*
(1*)
(2*)
(° C.)
(° C.)
rate (%)
(° C.)





235
P5
783
0.65
Suitable
Suitable
850
550
30
800


236


0.68
Suitable
Suitable
850
550
60
780


237


0.72
Suitable
Suitable
860
550

95

800


238


0.53
Suitable
Suitable
870
550
40

960



239


0.59
Suitable
Suitable
870
550
70

450



240
P8
762
0.55
Suitable
Suitable
840
550
50
770


241


0.68
Suitable
Suitable
860
550
60
780


242


0.67
Suitable
Suitable
860
550

90

800


243


0.69
Suitable
Suitable
850
550
40

980






















Surface layer Young's
Surface layer Young's


Sample
TS
E(RD)
E(D)
E(TD)
modulus in rolling
modulus in transverse


No.
(MPa)
(GPa)
(GPa)
(GPa)
direction (GPa)
direction (GPa)





235
590
239
205
236
249
247


236
585
242
205
238
257
255


237
580
205
195
234

204


223



238
598

205

210
216

205


210



239
976

219

200
230

230


225



240
789
239
196
234
250
253


241
820
242
205
237
253
249


242
826
205
189
235

218


230



243
795
205
205
209

208


216
























TABLE 47









Texture in the ⅛
Texture in the sheet







sheet thickness layer
thickness center layer
Spring
Wall

















Sample
{110}
{110}
{110}
{211}
{332}
{100}
back
camber
Shape



No.
<223>
<111>
<001>
<011>
<113>
<011>
(°)
(1000/ρ)
fixability
Remarks





235
10 
11 
1
9
8
4
2.6
2.6
Good
I.E.


236
11 
12 
2
9
9
3
2.5
2.5
Good
I.E.


237
2
3
0
8
7
11 
4.5
4.1

Poor

C.E.


238

4


4

3
5
6
6
4.5
3.8

Poor

C.E.


239

5


6

3
6
4
8
*
*

Poor

C.E.


240
12 
11 
3
9
8
2
5.4
3.5
Good
I.E.


241
13 
12 
1
9
9
6
5.8
3.7
Good
I.E.


242

4


4


0


5


3


4

8.5
6.3

Poor

C.E.


243

1


1


3


5


3


2

7.9
5.8

Poor

C.E.









INDUSTRIAL APPLICABILITY

The steel sheet having high Young's modulus according to the present invention may be used in automobiles, household electronic devices, and construction materials, for example. The steel sheet having high Young's modulus according to the present invention includes narrowly defined hot rolled steel sheets and cold roiled steel sheets that are not subjected to surface processing, as well as broadly defined hot rolled steel sheets and cold rolled steel sheets that are subjected to surface processing such as hot-dip galvanization, alloyed hot-dip galvanization, and electroplating, for example, for the purpose of preventing rust, Aluminum-based plating is also included. Steel sheets in which an organic film, an inorganic film, or paint, for example, is present on the surface of a hot rolled steel sheet, a cold rolled steel sheet, or various types of plated steel sheets, as well as steel sheets that combine a plurality of these, are also included.


Because the steel sheet having high Young's modulus of the invention is a steel sheet that has a high Young's modulus, its thickness can be reduced compared to that of the steel sheets to date, and as a result, it can be made lighter. Consequently, it can contribute to protection of the global environmental.


The steel sheet having high Young's modulus of the present invention has improved shape fixability, and can easily be adopted as a high-strength steel sheet for pressed components such as automobile components. Additionally, the steel sheet of the present invention has an excellent ability to absorb collision energy, and thus it also contributes to improving automobile safety.

Claims
  • 1. A steel sheet having high Young's modulus, which has a composition comprising, in terms of mass %, C: 0.0005 to 0.30%, Si: 2.5% or less, Mn: 0.1 to 5.0%, P: 0.15% or less, S: 0.015% or less, Al: 0.15% or less, N: 0.0005 to 0.01%; and further comprising all of Mo: 0.005 to 1.5%, Nb: 0.005 to 0.20%, Ti: at least 48/14×N (mass %) and 0.2% or less, and B: 0.0001 to 0.01%, at a total content of 0.015 to 1.91 mass %,with the remainder being Fe and unavoidable impurities,wherein the {110}<223> pole density and/or the {110}<111> pole density in the ⅛ sheet thickness layer is 10 or more,the {211}<011> pole density in the ½ sheet thickness layer is 6 or more, anda Young's modulus in a rolling direction is more than 230 GPa.
  • 2. The steel sheet having high Young's modulus according to claim 1, wherein the respective contents of Mo, Nb, Ti, and B are Mo: 0.15 to 1.5%, Nb: 0.01 to 0.20%, Ti: at least 48/14×N (mass %) and 0.2% or less, and B: 0.0006 to 0.01%; andthe {110}<001> pole density in the ⅛ sheet thickness layer is 3 or less.
  • 3. The steel sheet having high Young's modulus according to claim 1, wherein the {110}<001> pole density in the ⅛ sheet thickness layer is 6 or less.
  • 4. The steel sheet having high Young's modulus according to claim 1, wherein the Young's modulus in the rolling direction is 240 GPa or more in at least a range from the surface layer to the ⅛ sheet thickness layer.
  • 5. The steel sheet having high Young's modulus according to claim 1, wherein the {332}<113> pole density in the ½ sheet thickness layer is 6 or more.
  • 6. The steel sheet having high Young's modulus according to claim 1, wherein the {100}<011> pole density in the ½ sheet thickness layer is 6 or less.
  • 7. The steel sheet having high Young's modulus according to claim 1, wherein a BH amount (MPa) is in a range from 5 MPa or more to 200 MPa or less, and the BH amount is expressed by the following formula, BH=σ1−σ2 (MPa), wherein σ2 (MPa) is the flow stress when the steel sheet has been stretched 2%, and σ1 (MPa) is an upper yield point when, after the steel sheet has been stretched 2%, it is treated with heat at 170° C. for 20 minutes and then stretched again.
  • 8. The steel sheet having high Young's modulus according to claim 1, which further comprises Ca: 0.0005 to 0.01 mass %.
  • 9. The steel sheet having high Young's modulus according to claim 1, which further comprises one or two or more of Sn, Co, Zn, W, Zr, V, Mg, and REM at a total content of 0.001 to 1.0 mass %.
  • 10. The steel sheet having high Young's modulus according to claim 1, which further comprises one or two or more of Ni, Cu, and Cr at a total content of 0.001 to 4.0 mass %.
  • 11. A hot-dip galvanized steel sheet comprising: the steel sheet having high Young's modulus according to claim 1, andhot-dip zinc plating that is applied to the steel sheet having high Young's modulus.
  • 12. An alloyed hot-dip galvanized steel sheet comprising: the steel sheet having high Young's modulus according to claim 1; andalloyed hot-dip zinc plating that is applied to the steel sheet having high Young's modulus.
  • 13. A steel pipe having high Young's modulus comprising the steel sheet having high Young's modulus according to claim 1, wherein the steel sheet having high Young's modulus is curled in any direction.
  • 14. The steel sheet having high Young's modulus according to claim 1, wherein the steel sheet is manufactured by a method which comprises heating a slab having the composition at a temperature of 1000° C. or more and subjecting the slab to hot rolling so as to obtain a hot rolled steel sheet, andin the hot rolling, the rolling is carried out in such a manner that a coefficient of friction between the pressure rollers and the steel sheet is greater than 0.2, an effective strain amount ε* calculated by the following formula [1] is 0.4 or more, and the total of the reduction rates is 50% or more, and the hot rolling is finished at a temperature in a range from the Ar3 transformation temperature or more to 900° C. or less,
Priority Claims (4)
Number Date Country Kind
2004-218132 Jul 2004 JP national
2004-330578 Nov 2004 JP national
2005-019942 Jan 2005 JP national
2005-207043 Jul 2005 JP national
CROSS-REFERENCE TO RELATED APPLICATION(S)

The present application is a divisional application of U.S. application Ser. No. 11/572,693 filed on Jan. 25, 2007, which is a U.S. national phase application of International Application No. PCT/JP2005/013717 filed on Jul. 27, 2005, which claims the benefit of Japanese Application Nos. 2004-218132, 2004-330578, 2005-019942, and 2005-207043, filed on Jul. 27, 2004, Nov. 15, 2004, Jan. 27, 2005 and Jul. 15, 2005, respectively. Further, the present application relates to Japanese Application Nos. 2004-002622 and 2004-045729, filed on Jan. 8, 2004 and Feb. 23, 2004, respectively. The entire disclosures of the above-identified applications are hereby incorporated by reference in their entireties.

US Referenced Citations (2)
Number Name Date Kind
5461770 Kumura Oct 1995 A
20030196735 Sugiura et al. Oct 2003 A1
Foreign Referenced Citations (35)
Number Date Country
1840723 Oct 2006 CN
1327695 Jul 2003 EP
1362930 Nov 2003 EP
1 568 791 Aug 2005 EP
1681363 Jul 2006 EP
59083721 May 1984 JP
64-15319 Jan 1989 JP
04136120 May 1992 JP
04141519 May 1992 JP
04143216 May 1992 JP
04147916 May 1992 JP
04147917 May 1992 JP
04293719 Oct 1992 JP
04301060 Oct 1992 JP
04314823 Nov 1992 JP
05255804 Oct 1993 JP
05263191 Oct 1993 JP
06-11503 Jan 1994 JP
06269808 Sep 1994 JP
08283842 Oct 1996 JP
08311541 Nov 1996 JP
09053118 Feb 1997 JP
09-316619 Dec 1997 JP
2002363695 Dec 2002 JP
20031312 Jan 2003 JP
200355739 Feb 2003 JP
2003-166035 Jun 2003 JP
2003-253385 Sep 2003 JP
2004-137565 May 2004 JP
2005-314793 Nov 2005 JP
2006-183130 Jul 2006 JP
2006-183131 Jul 2006 JP
2007-146275 Jun 2007 JP
03031669 Apr 2003 WO
WO 2006011503 Feb 2006 WO
Non-Patent Literature Citations (7)
Entry
Corresponding European Search Report dated Jan. 8, 2008 of application No. 05767035.8-2122.
Office Action issued in Japanese Patent Application No. 2004-218132 mailed on Oct. 20, 2009 with an English translation.
International Search Report for PCT/JP2005/013717, Oct. 2005.
Canadian Office Action dated Apr. 13, 2011, issued in Canadian Patent Application 2,668,987.
Chinese Office Action dated Jun. 12, 2010, issued in Chinese Patent Application 200780041422.1.
European Search Report dated Feb. 28, 2013, issued in European Patent Application 07831772.4.
International Search Report issued in PCT/JP2007/072042 on Feb. 19, 2008.
Related Publications (1)
Number Date Country
20120077051 A1 Mar 2012 US
Divisions (1)
Number Date Country
Parent 11572693 US
Child 13245295 US