WO2012029632A1 - 冷延鋼板の製造方法、冷延鋼板および自動車部材 - Google Patents
冷延鋼板の製造方法、冷延鋼板および自動車部材 Download PDFInfo
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- WO2012029632A1 WO2012029632A1 PCT/JP2011/069193 JP2011069193W WO2012029632A1 WO 2012029632 A1 WO2012029632 A1 WO 2012029632A1 JP 2011069193 W JP2011069193 W JP 2011069193W WO 2012029632 A1 WO2012029632 A1 WO 2012029632A1
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- Prior art keywords
- steel sheet
- acid
- cold
- mass
- rolled steel
- Prior art date
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- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
Definitions
- the present invention relates to a method for producing a cold-rolled steel sheet, a cold-rolled steel sheet, and an automobile member. Specifically, it has excellent chemical conversion treatment properties and excellent post-coating corrosion resistance evaluated by a salt warm water immersion test or a combined cycle corrosion test.
- the present invention relates to a method for producing a cold rolled steel sheet, a cold rolled steel sheet produced by the method, and an automobile member using the cold rolled steel sheet.
- the cold-rolled steel sheet of the present invention can be suitably used for a high-strength cold-rolled steel sheet having a Si-containing tensile strength TS of 590 MPa or more.
- Patent Document 1 proposes a high-strength cold-rolled steel sheet in which the corrosion resistance is improved by setting the line width of a linear oxide containing Si observed at 1 to 10 ⁇ m from the steel sheet surface to 300 nm or less. .
- Patent Document 3 discloses that the Si-containing oxide concentrated on the surface of the steel sheet in the annealing process or the like is removed by pickling and further an S-based compound is added to the surface.
- Patent Document 4 discloses a technique for providing a P-based compound instead of an S-based compound in the above technique.
- JP 2004-204350 A JP 2004-244698 A JP 2007-217743 A JP 2007-246951 A
- Patent Documents 3 and 4 are effective for conventional plain steel sheets, but for high-strength cold-rolled steel sheets containing a large amount of Si, the low temperature of the chemical conversion treatment liquid It is not possible to expect a sufficient improvement effect that can cope with the development.
- the present invention has been made in view of the above-mentioned problems of cold-rolled steel sheets containing a large amount of Si, and its purpose is to provide chemical conversion treatment even when a low-temperature chemical conversion treatment liquid is used.
- the inventors conducted detailed analysis on the steel sheet surface characteristics after annealing, and conducted intensive studies on a method for increasing the reactivity between the steel sheet surface and the chemical conversion treatment liquid.
- the steel sheet surface that has been continuously annealed is strongly pickled, the Si-containing oxide layer formed on the steel sheet surface layer is removed during annealing, and the iron-based oxide produced on the steel sheet surface by the strong pickling.
- the present inventors have found that it is extremely important to reduce the steel sheet surface coverage by the present invention.
- the present invention proposes a method of manufacturing a cold-rolled steel sheet that is cold-rolled, pickled continuously annealed steel sheet, and then pickled again.
- a non-oxidizing acid different from the acid used for pickling before re-acid pickling is used.
- the non-oxidizing acid in the production method of the present invention is any one of hydrochloric acid, sulfuric acid, phosphoric acid, pyrophosphoric acid, formic acid, acetic acid, citric acid, hydrofluoric acid, oxalic acid, and an acid obtained by mixing two or more of these. It is characterized by.
- the non-oxidizing acid in the production method of the present invention includes hydrochloric acid having a concentration of 0.1 to 50 g / L, sulfuric acid having a concentration of 0.1 to 150 g / L, and hydrochloric acid having a concentration of 0.1 to 20 g / L. It is characterized by being one of acids mixed with 0.1 to 60 g / L sulfuric acid.
- the production method of the present invention is characterized in that the re-pickling is performed for 1 to 30 seconds at a re-pickling solution temperature of 20 to 70 ° C.
- the production method of the present invention is characterized in that the pickling is performed using any one of nitric acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, and an acid obtained by mixing two or more thereof.
- the pickling is performed with the nitric acid concentration exceeding 50 g / L and not more than 200 g / L, and the ratio of the hydrochloric acid concentration to the nitric acid concentration (HCl / HNO 3 ) is 0.01 to 1.0.
- the steel sheet in the production method of the present invention is characterized by containing 0.5 to 3.0 mass% of Si.
- the steel sheet in the production method of the present invention includes C: 0.01 to 0.30 mass%, Mn: 1.0 to 7.5 mass%, P: 0.05 mass% or less, and S: 0. .01 mass% or less and Al: 0.06 mass% or less, with the balance being a component composition of Fe and inevitable impurities.
- the steel sheet in the production method of the present invention further includes Nb: 0.3 mass% or less, Ti: 0.3 mass% or less, V: 0.3 mass% or less, Mo: 0.3 mass%.
- Nb 0.3 mass% or less
- Ti 0.3 mass% or less
- V 0.3 mass% or less
- Mo 0.3 mass%.
- one or more selected from Cr: 0.5 mass% or less, B: 0.006 mass% or less, and N: 0.008 mass% or less are contained.
- the steel sheet in the production method of the present invention further includes Ni: 2.0 mass% or less, Cu: 2.0 mass% or less, Ca: 0.1 mass% or less, and REM: 0.1 mass%. 1 type or 2 types or more chosen from the following are contained, It is characterized by the above-mentioned.
- the present invention is a cold-rolled steel sheet produced by any one of the methods described above, wherein the Si-containing oxide layer on the steel sheet surface layer is removed by pickling after continuous annealing, and re- pickling.
- the cold rolled steel sheet is characterized in that the surface coverage of the iron-based oxide existing on the surface of the subsequent steel sheet is 40% or less.
- the cold-rolled steel sheet of the present invention is characterized in that the maximum thickness of the iron-based oxide existing on the steel sheet surface after re-acid washing is 150 nm or less.
- the present invention is an automobile member characterized by using any one of the cold-rolled steel sheets described above.
- the present invention even when Si is contained in a large amount of 0.5 to 3.0 mass%, even when a low-temperature chemical conversion treatment liquid is used, it is excellent in chemical conversion treatment, and the salt warm water A cold-rolled steel sheet having excellent post-coating corrosion resistance can be provided even in a severe corrosive environment such as an immersion test or a combined cycle corrosion test. Therefore, according to the present invention, it becomes possible to greatly improve the chemical conversion property and the corrosion resistance after painting of a high-strength cold-rolled steel sheet containing a large amount of Si and having a tensile strength TS of 590 MPa or more. It can be suitably used for strength members and the like.
- FIG. 1 shows a cold rolled steel sheet standard sample No. 1 for determining the surface coverage of the iron-based oxide.
- the reflected-electron image of the steel plate surface of a and b is shown.
- 2 shows a cold rolled steel sheet standard sample No.
- Fig. 5 shows a histogram of the number of pixels against the gray values of the reflected electron image photographs of a and b.
- FIG. 3 is a photograph of a cross section of the steel sheet surface coating after re-acid picking observed with a transmission electron microscope.
- FIG. 4 is a graph showing the result of energy dispersive X-ray (EDX) analysis of the iron-based oxide observed in FIG.
- FIG. 5 is a graph obtained by measuring the depth direction distribution of O, Si, Mn, and Fe on the test piece surfaces of Comparative Example (No. 1) and Invention Example (No. 9) of Example 1 by GDS.
- EDX energy dispersive X-ray
- Si-containing oxides such as Si oxide (SiO 2 ) and Si—Mn based complex oxide on the steel sheet surface.
- the structure of these oxides varies depending on the steel plate components and the annealing atmosphere, but generally both are often mixed.
- the Si-containing oxide is formed not only on the steel sheet surface but also inside the base iron, it inhibits the etching property of the steel sheet surface in the chemical conversion treatment (zinc phosphate treatment) that is performed as a base treatment for electrodeposition coating.
- the chemical conversion treatment zinc phosphate treatment
- the cold-rolled steel sheet surface after continuous annealing is strongly pickled using nitric acid or the like as the pickling solution, and the Si-containing oxide layer on the steel sheet surface layer formed by continuous annealing after cold rolling is removed.
- the Si-containing oxide is a SiO 2 or Si—Mn based composite oxide formed along the grain boundaries inside the steel sheet surface or inside the steel sheet during annealing after slab heating, hot rolling, or cold rolling.
- the thickness of the layer in which these Si-containing oxides are present varies depending on the steel plate components and annealing conditions (temperature, time, atmosphere), but is usually about 1 ⁇ m from the steel plate surface.
- the removal of the Si-containing oxide layer in the present invention means that pickling is performed to a level at which Si and O peaks do not appear when the steel sheet surface is analyzed in the depth direction by GDS (glow discharge emission spectroscopy). Removing the Si-containing oxide layer.
- the inventors set the coverage of the iron-based oxide formed on the steel plate surface by pickling to 40% or less, and when the maximum thickness of the iron-based oxide is 150 nm or less, It has been found that the processability is further improved, the corrosion resistance is further improved, and as a means for achieving this, it is effective to raise the concentration of the acid used for the re-pickling appropriately and re-pickling.
- the iron-based oxide in the present invention means an iron-based oxide having an atomic concentration ratio of iron of 30% or more among elements other than oxygen constituting the oxide. This iron-based oxide is present in a non-uniform thickness on the surface of the steel sheet, and is an oxide different from a natural oxide film that is uniform and layered with a thickness of several nm.
- the iron-based oxides formed on the surface of this cold-rolled steel sheet are found to be amorphous from observations with a transmission electron microscope (TEM) and analysis of diffraction patterns (diffraction patterns) by electron beam diffraction. ing.
- TEM transmission electron microscope
- diffraction patterns diffraction patterns
- Si 0.5 to 3.0 mass%
- Si is an effective element for achieving high strength of steel because it has a great effect on enhancing the strength of steel without significantly reducing workability (solid solution strengthening ability). It is also an element that adversely affects When Si is added as a means for achieving high strength, it is necessary to add 0.5 mass% or more. Moreover, if Si is less than 0.5 mass%, there is little influence by the deterioration of chemical conversion treatment conditions. On the other hand, when the Si content exceeds 3.0 mass%, the hot rollability and the cold rollability are greatly lowered, which adversely affects the productivity and causes the ductility of the steel sheet itself to be lowered. Therefore, Si is added in the range of 0.5 to 3.0 mass%. Preferably, it is in the range of 0.8 to 2.5 mass%.
- the cold-rolled steel sheet of the present invention must contain Si in the above range, but the other components can be allowed as long as they are in the composition range of a normal cold-rolled steel sheet, and are particularly limited. Is not to be done. However, when the cold-rolled steel sheet of the present invention is applied to a high-strength cold-rolled steel sheet having a tensile strength TS of 590 MPa or more used for an automobile body or the like, it preferably has the following component composition.
- C 0.01-0.30 mass%
- C is an element effective for increasing the strength of steel, and is also an element effective for generating retained austenite, bainite and martensite having a TRIP (Transformation Induced Plasticity) effect. is there. If C is 0.01 mass% or more, the above effect can be obtained. On the other hand, if C is 0.30 mass% or less, the weldability does not deteriorate. Therefore, C is preferably added in the range of 0.01 to 0.30 mass%, and more preferably in the range of 0.10 to 0.20 mass%.
- Mn 1.0 to 7.5 mass%
- Mn is an element having an effect of enhancing the hardenability by solid solution strengthening of steel, enhancing hardenability, and promoting the formation of retained austenite, bainite, and martensite. Such an effect is manifested by addition of 1.0 mass% or more.
- Mn is preferably added in the range of 1.0 to 7.5 mass%, and more preferably in the range of 2.0 to 5.0 mass%.
- P 0.05 mass% or less
- P is an element that does not impair the drawability for a large solid solution strengthening ability, and is an element effective for achieving high strength. Therefore, P should be contained in an amount of 0.005 mass% or more. Is preferred. However, although P is an element which impairs spot weldability, if it is 0.05 mass% or less, a problem will not arise. Therefore, P is preferably 0.05 mass% or less, and more preferably 0.02 mass% or less.
- S 0.01 mass% or less
- S is an impurity element that is inevitably mixed in, and is a harmful component that precipitates as MnS in steel and lowers the stretch flangeability of the steel sheet.
- S is preferably 0.01 mass% or less. More preferably, it is 0.005 mass% or less, More preferably, it is 0.003 mass% or less.
- Al 0.06 mass% or less
- Al is an element added as a deoxidizer in the steelmaking process, and is an element effective for separating non-metallic inclusions that reduce stretch flangeability as slag. It is preferable to contain 0.01 mass% or more. If Al is 0.06 mass% or less, the above effects can be obtained without increasing the raw material cost. Therefore, Al is preferably 0.06 mass% or less. More preferably, it is in the range of 0.02 to 0.06 mass%.
- the cold-rolled steel sheet of the present invention further includes Nb: 0.3 mass% or less, Ti: 0.3 mass% or less, V: 0.3 mass% or less, Mo: 0.3 mass% or less, One or more selected from Cr: 0.5 mass% or less, B: 0.006 mass% or less, and N: 0.008 mass% or less can be contained.
- Nb, Ti and V are elements that form carbides and nitrides, suppress the growth of ferrite in the heating stage during annealing, refine the structure, and improve formability, particularly stretch flangeability.
- Mo, Cr and B are elements that improve the hardenability of the steel and promote the formation of bainite and martensite, and therefore can be added in the above range.
- N is an element that forms nitrides with Nb, Ti, and V or contributes to increasing the strength of the steel by forming a solid solution in the steel. If it is 0.008 mass% or less, a large amount of nitride is present. Since it is not formed, breakage due to void formation during press molding is suppressed, and the above effect can be obtained.
- the cold-rolled steel sheet of the present invention further includes Ni: 2.0 mass% or less, Cu: 2.0 mass% or less, Ca: 0.1 mass% or less, and REM: 0.1 mass% or less.
- Ni and Cu are effective in promoting the formation of a low temperature transformation phase and increasing the strength of the steel, and therefore can be added in the above range.
- Ca and REM are elements that control the form of sulfide inclusions and improve the stretch flangeability of the steel sheet, and therefore can be added in the above range.
- the balance other than the above components is Fe and inevitable impurities. However, addition of other components is not rejected as long as the effects of the present invention are not impaired.
- the cold-rolled steel sheet of the present invention has a steel sheet surface from which a Si-containing oxide layer such as SiO 2 or Si—Mn composite oxide formed on the steel sheet surface layer during annealing is removed. is necessary. For that purpose, it is necessary to perform strong pickling using an acid such as nitric acid and dissolve and remove the Si-containing oxide formed on the steel plate surface and the grain boundary portion near the surface together with the base iron.
- a Si-containing oxide layer such as SiO 2 or Si—Mn composite oxide formed on the steel sheet surface layer during annealing is removed.
- an acid such as nitric acid
- the cold-rolled steel sheet of the present invention further covers the steel sheet surface with an iron-based oxide that is generated on the steel sheet surface by strong pickling using nitric acid or the like in addition to removing the Si-containing oxide layer. It is necessary to reduce the rate to 85% or less as the area rate. If it exceeds 85%, the dissolution reaction of iron in the chemical conversion treatment is inhibited, and the growth of chemical crystals such as zinc phosphate is suppressed.
- the covering is 85% or less. The rate is insufficient, and it is necessary to reduce it to 40% or less, which is even lower. Preferably it is 35% or less.
- the surface coverage of the iron-based oxide is determined as follows. Using a scanning electron microscope (ULV-SEM) with ultra-low acceleration voltage that can detect extremely surface layer information, the steel plate surface after pickling is observed at an acceleration voltage of 2 kV, an operating distance of 3.0 mm, and a magnification of about 1000 times to observe about 5 fields of view. Then, spectral analysis is performed using an energy dispersive X-ray spectrometer (EDX) to obtain a reflected electron image. This reflected electron image is binarized using image analysis software, for example, Image J, the area ratio of the black portion is measured, and the surface coverage of the iron-based oxide is obtained by averaging the measured values of each field of view. Can be obtained.
- image analysis software for example, Image J
- Image J the area ratio of the black portion is measured
- the surface coverage of the iron-based oxide is obtained by averaging the measured values of each field of view. Can be obtained.
- the ultra-low acceleration voltage scanning electron microscope (ULV-SEM) is, for example, manufactured by SEISS; ULTRA 55, and the energy dispersive X-ray spectrometer (EDX) is, for example, manufactured by Thermo Fisher. NSS 312E may be mentioned.
- the steel slabs of steel code G shown in Table 3 of Examples described later are the same as No. 1 of Table 4 of Examples described later. 8 is hot-rolled, cold-rolled and continuously annealed to obtain a cold-rolled steel sheet having a thickness of 1.8 mm.
- Table 1 shows the cold-rolled steel sheet after the continuous annealing. Under conditions, pickling and re-acid pickling, washing with water and drying, then subjected to temper rolling of 0.7%, and the amount of iron-based oxide on the steel sheet surface is different. Two types of cold-rolled steel sheets a and b were obtained. Then, the above No.
- the cold rolled steel sheet a is a standard sample with a lot of iron-based oxides, No.
- the cold rolled steel sheet b was used as a standard sample with a small amount of iron-based oxides, and a reflected electron image was obtained for each steel sheet using the scanning electron microscope under the conditions described above.
- FIG. The reflection electron image photograph of the steel plates a and b is shown in FIG.
- the histogram of the pixel number with respect to the gray value of the said reflection electron image photograph of the steel plate of a and b is shown.
- a gray value (Y point) corresponding to the intersection (X point) of the histograms a and b was determined as a threshold value.
- No. When the surface coverage of the iron-based oxide of the steel sheets a and b was determined, No.
- the steel sheet of a is 85.3%
- No. As for the steel plate of b 25.8% was obtained.
- the cold-rolled steel sheet of the present invention in order to further improve the chemical conversion treatment and thus the corrosion resistance, in addition to the iron oxide coverage on the steel sheet surface after re-acid washing is 40% or less,
- the maximum thickness of the iron-based oxide is preferably 150 nm or less. If the maximum thickness of the iron-based oxide is 150 nm or less, the dissolution reaction of iron in the chemical conversion treatment is not locally inhibited, and precipitation of chemical crystals such as zinc phosphate is not locally suppressed. is there. More preferably, it is 130 nm or less.
- the maximum thickness of the iron-based oxide is determined as follows. First, ten extracted replicas capable of observing a cross section of about 8 ⁇ m in the width direction of the steel sheet are produced from the steel sheet surface after pickling by focused ion beam (FIB) processing. Next, using a transmission electron microscope (TEM) equipped with an energy dispersive X-ray spectrometer (EDX) capable of examining local information of the cross section, the cross section of each replica at an acceleration voltage of 200 kV and a magnification of 100,000 times Take 8 ⁇ m continuously. As an example, FIG. 3 shows a photograph of a cross-section of the coating layer formed by pickling existing on the steel plate surface, and FIG. 4 shows an EDX analysis result of the coating layer.
- TEM transmission electron microscope
- EDX energy dispersive X-ray spectrometer
- the coating layer is an iron-based iron-based oxide
- a line A indicating the steel plate iron shown in the cross-sectional photograph of FIG. 3
- a line B indicating the thickest part of the oxide layer Is measured for all ten replicas, and the maximum thickness among them is taken as the maximum thickness of the iron-based oxide.
- the size and number of replicas, the measurement conditions by TEM, and the like are merely examples, and it is needless to say that the replicas may be changed as appropriate.
- the method for producing a cold-rolled steel sheet according to the present invention comprises heating a steel material (slab) containing 0.5 to 3.0 mass% of Si, followed by hot rolling, cold rolling, continuous annealing, and then nitric acid or the like. After removing the Si-containing oxide layer on the steel sheet surface layer by strong pickling using iron, the surface coverage of the iron-based oxide generated on the steel sheet surface by further pickling is 40% or less. It is necessary to be a method capable of reducing the maximum thickness of the iron-based oxide to 150 nm or less. Therefore, although it can manufacture in accordance with a conventional method from the steelmaking process to the continuous annealing process after cold rolling, it is preferable that the pickling after continuous annealing is made into the following conditions.
- the Si—Mn composite oxide is easily dissolved in an acid, but SiO 2 is hardly soluble in an acid. Therefore, in order to remove Si-containing oxides including SiO 2 , it is necessary to perform strong pickling and remove the oxide layer together with the base iron of the steel sheet.
- an acid that can be used for the strong pickling nitric acid, which is a strong oxidizing acid, can be preferably used, but hydrofluoric acid, hydrochloric acid, sulfuric acid, etc. may be used as long as the Si-containing oxide layer can be removed.
- the type of acid is not particularly limited. In addition, it is also effective to promote the dissolution of base iron by adding a pickling accelerator to the acid or using an electrolytic treatment in combination.
- the concentration of nitric acid is set in the range of more than 50 g / L to 200 g / L, and hydrochloric acid having an effect of destroying the oxide film is added to the ratio R ( HCl / HNO 3 ) is mixed so as to be in the range of 0.01 to 1.0, or the ratio of hydrofluoric acid concentration to nitric acid concentration (HF / HNO 3 ) is 0.01 to 1
- R HCl / HNO 3
- the ratio of hydrofluoric acid concentration to nitric acid concentration (HF / HNO 3 ) is 0.01 to 1
- the temperature of the pickling solution is 20 to 70 ° C. and the pickling time is 3 to 30 seconds.
- the surface coating of iron-based oxides formed on the steel sheet surface can be achieved by simply pickling using nitric acid and hydrochloric acid or a pickling solution in which nitric acid and hydrofluoric acid are mixed. It is difficult to stably control the rate to 40% or less. Therefore, in the present invention, as a method of more reliably reducing the iron-based oxides generated on the steel sheet surface by the strong pickling, the steel sheet pickled after the continuous annealing is further re-pickled with a non-oxidizing acid. It was decided to dissolve and remove the iron-based oxide.
- non-oxidizing acid examples include hydrochloric acid, sulfuric acid, phosphoric acid, pyrophosphoric acid, formic acid, acetic acid, citric acid, hydrofluoric acid, oxalic acid, or an acid obtained by mixing two or more of these. Yes, any of them may be used, but hydrochloric acid or sulfuric acid generally used in the steel industry can be preferably used.
- hydrochloric acid is a volatile acid, so that it is difficult for residues such as sulfate radicals to remain on the surface of the steel sheet after washing like sulfuric acid, and because the oxide destruction effect by chloride ions is large, Is preferred.
- the hydrochloric acid concentration is 0.1 to 50 g / L
- sulfuric acid when used, the sulfuric acid concentration is 0.1 to 150 g / L.
- an acid mixed with hydrochloric acid and sulfuric acid is used for re-acid washing, an acid mixed with a hydrochloric acid concentration of 0.1 to 20 g / L and a sulfuric acid concentration of 0.1 to 60 g / L is used. Is preferred.
- the re-pickling in the present invention is preferably carried out at a temperature of the re-pickling solution in the range of 20 to 70 ° C.
- the concentration of the re-pickling solution is not less than the above lower limit, the solution temperature is not less than 20 ° C., and the treatment time is not less than 1 second, removal of the iron-based oxide remaining on the steel sheet surface is sufficient, If the concentration of the washing liquid is not more than the above upper limit concentration, the temperature is not more than 70 ° C., and the treatment time is not more than 30 seconds, the dissolution of the steel sheet surface does not become excessive and a new surface oxide film is not generated. Because.
- the concentration of the pickling solution used in the re-pickling appropriately.
- the concentration of hydrochloric acid is preferably 3 to 50 g / L
- sulfuric acid is used for re-pickling
- the concentration of sulfuric acid is preferably 8 to 150 g / L.
- the cold rolled steel sheet with the iron oxide coverage on the steel sheet surface of 40% or less, or further the maximum thickness of the iron oxide is used as a product sheet through a normal processing step such as temper rolling.
- these hot-rolled steel sheets are pickled, scales are removed, and cold-rolled to obtain cold-rolled steel sheets having a thickness of 1.8 mm. Then, these cold-rolled steel sheets are averaged at 750 to 780 ° C. After heating to the heat temperature and holding for 40 to 50 seconds, the temperature from the above soaking temperature to the cooling stop temperature of 350 to 400 ° C is cooled at 20 to 30 ° C / second and held in the above cooling stop temperature range for 100 to 120 seconds. After performing continuous annealing, the steel sheet surface is pickled under the conditions shown in Table 2, further re- pickled, washed with water, dried, subjected to temper rolling with an elongation of 0.7%, No. 2 shown in FIG. 1 to 85 cold-rolled steel sheets were obtained.
- Specimens were collected from each of the above cold-rolled steel sheets, and the surface of the steel sheet was accelerated using an ultra-low acceleration voltage scanning electron microscope (ULV-SEM; manufactured by SEISS; ULTRA55) at an acceleration voltage of 2 kV, a working distance of 3.0 mm, and a magnification.
- UUV-SEM ultra-low acceleration voltage scanning electron microscope
- Five fields of view were observed at 1000 times, and a reflection electron image was obtained by spectroscopic analysis using an energy dispersive X-ray spectrometer (EDX; manufactured by Thermo Fisher, Inc .; NSS312E). This reflected electron image was obtained by using the image analysis software (Image J) and the standard sample No. described above.
- the gray value (Y point) corresponding to the intersection (X point) of the histograms a and b is set as a threshold value, binarization processing is performed, the area ratio of the black portion is measured, the average value of the five fields of view is obtained, and iron The surface coverage of the system oxide was used.
- specimens are collected from each of the above cold-rolled steel sheets, subjected to chemical conversion treatment and coating treatment under the following conditions, and then subjected to three types of corrosion tests: a salt warm water immersion test, a salt spray test, and a combined cycle corrosion test.
- the corrosion resistance after coating was evaluated.
- the depth direction distribution of O, Si, Mn, and Fe on the surface of the test piece collected from each cold-rolled steel sheet was measured using GDS.
- Chemical conversion treatment conditions The test pieces collected from each of the above cold-rolled steel sheets were degreased by Nippon Parkerizing Co., Ltd .: FC-E2011, surface conditioner: PL-X, and chemical conversion treatment agent: Palbond PB-L3065.
- Chemical conversion treatment was performed so that the amount of chemical conversion coating film deposited was 1.7 to 3.0 g / m 2 under the following two conditions: standard conditions and comparative conditions in which the temperature of the chemical conversion liquid was lowered to lower the temperature.
- standard conditions standard conditions and comparative conditions in which the temperature of the chemical conversion liquid was lowered to lower the temperature.
- ⁇ Standard conditions> ⁇ Degreasing process: treatment temperature 40 ° C., treatment time 120 seconds ⁇ Spray degreasing, surface adjustment step: pH 9.5, treatment temperature room temperature, treatment time 20 seconds ⁇ Chemical conversion treatment process: temperature of chemical treatment liquid 35 ° C., treatment time 120 seconds ⁇ temperature reduction conditions> Conditions under which the temperature of the chemical conversion treatment liquid was lowered to 33 ° C.
- FIG. 5 shows the profile in the depth direction of O, Si, Mn, and Fe when the surface analysis was performed on the 9 test pieces by GDS.
- Steels A to Z having the composition shown in Table 3 were melted by a normal refining process through a converter, degassing treatment, etc., and continuously cast into a steel slab. These steel slabs are hot-rolled under the hot-rolling conditions shown in Table 4 to form hot-rolled steel sheets with a thickness of 3 to 4 mm, pickled to remove the scale on the steel sheet surface, and then cold-rolled to plate A cold-rolled steel sheet having a thickness of 1.8 mm was used. Next, these cold-rolled steel sheets were continuously annealed under the conditions shown in Table 4 and then pickled under the conditions shown in Table 5, re- pickled, then washed with water, dried, and an elongation of 0.7%. The temper rolling of No. 1 to 39 cold-rolled steel sheets were obtained.
- a specimen was collected from each of the cold-rolled steel sheets thus obtained, and after measuring the surface coverage of the iron-based oxide on the steel sheet surface after re-acid washing in the same manner as in Example 1, the following tension was applied.
- the test and post-coating corrosion resistance test were used.
- collected from each cold-rolled steel plate was measured using GDS.
- these cold-rolled steel sheets are heated to a soaking temperature of 750 to 780 ° C. and held for 40 to 50 seconds, and then, from the soaking temperature to a cooling stop temperature of 350 to 400 ° C., 20 to 30 ° C./sec.
- the steel sheet surface was subjected to continuous annealing that was maintained for 100 to 120 seconds within the above-mentioned cooling stop temperature range, and then the steel plate surface was pickled under the conditions shown in Table 6, re-acid pickled, washed with water, dried, No. 1 shown in Table 6 after temper rolling with an elongation of 0.7%. 1 to 61 cold-rolled steel sheets were obtained.
- Specimens were collected from each of the above cold-rolled steel plates, and the surface coverage and the maximum thickness of the iron-based oxide produced on the steel plate surface by pickling were measured using the method described above.
- Chemical conversion treatment was performed so that the amount of chemical conversion coating film deposited was 1.7 to 3.0 g / m 2 under the following two conditions: standard conditions and comparative conditions in which the temperature of the chemical conversion liquid was lowered to lower the temperature.
- standard conditions standard conditions and comparative conditions in which the temperature of the chemical conversion liquid was lowered to lower the temperature.
- ⁇ Standard conditions> ⁇ Degreasing process: treatment temperature 40 ° C., treatment time 120 seconds ⁇ Spray degreasing, surface adjustment step: pH 9.5, treatment temperature room temperature, treatment time 20 seconds ⁇ Chemical conversion treatment process: temperature of chemical treatment liquid 35 ° C., treatment time 120 seconds ⁇ temperature reduction conditions> Conditions under which the temperature of the chemical conversion treatment liquid was lowered to 33 ° C.
- Corrosion test A film was formed on the surface of the test piece subjected to the chemical conversion treatment using an electrodeposition paint: V-50 made by Nippon Paint Co., Ltd. Electrodeposition coating was applied so that the thickness was 25 ⁇ m, and the samples were subjected to the following three types of corrosion tests under more severe conditions as compared with Example 1.
- ⁇ Salt warm water immersion test> The surface of the above-mentioned test piece (n 1) subjected to chemical conversion treatment and electrodeposition coating was applied with a 45 mm long crosscut wrinkle with a cutter, and then the test piece was put into a 5 mass% NaCl solution (60 ° C.) at 480.
- the results of the above test are shown in Table 6. From this result, the steel plate surface after annealing was acidified under the conditions that the surface coverage of the iron-based oxide on the steel plate surface after re-acid washing was 40% or less and the maximum thickness of the iron-based oxide was 150 nm or less.
- the steel sheet of the present invention that was washed and re-acid-washed had a maximum peel width in all of the salt warm water immersion test, salt spray test, and combined cycle corrosion test that was conducted under long and severe conditions compared to Example 1. Is small and shows very good corrosion resistance after coating.
- the steel plate pickled under conditions suitable for the present invention does not show any Si or O peak, and Si-containing oxidation It was confirmed that the material layer was sufficiently removed.
- the cold-rolled steel sheet produced according to the present invention not only has excellent post-painting corrosion resistance, but also has high strength and excellent workability, so that it is not only used as a material for automobile body parts, It can also be suitably used as a material for applications that require similar characteristics in the field of building materials and the like.
Abstract
Description
冷間圧延した冷延鋼板を再結晶させ、所望の組織と強度、加工性を付与するために行われる連続焼鈍炉を用いた焼鈍工程では、通常、雰囲気ガスとして非酸化性または還元性のガスが用いられており、露点も厳格に管理されている。そのため、合金添加量の少ない普通の一般冷延鋼板では、鋼板表面の酸化は抑制されている。しかし、0.5mass%以上のSiや、Mnを含有する鋼板では、焼鈍時の雰囲気ガスの成分や露点を厳格に管理しても、Feと比較して易酸化性であるSiやMn等が酸化して、鋼板表面にSi酸化物(SiO2)やSi-Mn系複合酸化物などのSi含有酸化物を形成することが避けられない。これら酸化物の構成は、鋼板成分や焼鈍雰囲気などによっても変化するが、一般的には、両者が混在していることが多い。そして、上記Si含有酸化物は、鋼板表面だけでなく、地鉄内部にまで形成されるため、電着塗装の下地処理としてなされる化成処理(リン酸亜鉛処理)における鋼板表面のエッチング性を阻害し、健全な化成処理皮膜の形成に悪影響を及ぼすことが知られている。
なお、本発明における鉄系酸化物とは、酸化物を構成する酸素以外の元素のうちで鉄の原子濃度比が30%以上である鉄主体の酸化物のことをいう。この鉄系酸化物は、鋼板表面上に不均一な厚さで存在しており、数nmの厚さで均一かつ層状に存在する自然酸化皮膜とは異なる酸化物である。なお、この冷延鋼板の表面に生成した鉄系酸化物は、透過型電子顕微鏡(TEM)による観察や電子線回折によるディフラクションパターン(回折図形)の解析結果から非晶質であることがわかっている。
本発明は、上記新規な知見に、さらに検討を加えて完成したものである。
Si:0.5~3.0mass%
Siは、加工性を大きく損なうことなく鋼の強度を高める効果(固溶強化能)が大きいため、鋼の高強度化を達成するのに有効な元素であるが、化成処理性や塗装後耐食性に悪影響を及ぼす元素でもある。Siを高強度達成手段として添加する場合には、0.5mass%以上の添加が必要である。また、Siが0.5mass%未満では、化成処理条件の悪化による影響は少ない。一方、Siの含有量が3.0mass%を超えると、熱間圧延性や冷間圧延性が大きく低下し、生産性に悪影響を及ぼしたり、鋼板自体の延性の低下を招いたりする。よって、Siは0.5~3.0mass%の範囲で添加する。好ましくは0.8~2.5mass%の範囲である。
Cは、鋼を高強度化するのに有効な元素であり、さらに、TRIP(変態誘起塑性:Transformation Induced Plasticity)効果を有する残留オーステナイトや、ベイナイト、マルテンサイトを生成させるのにも有効な元素である。Cが0.01mass%以上であれば上記効果が得られ、一方、Cが0.30mass%以下であれば、溶接性の低下が生じない。よって、Cは0.01~0.30mass%の範囲で添加するのが好ましく、0.10~0.20mass%の範囲で添加するのがより好ましい。
Mnは、鋼を固溶強化して高強度化するとともに、焼入性を高め、残留オーステナイトやベイナイト、マルテンサイトの生成を促進する作用を有する元素である。このような効果は、1.0mass%以上の添加で発現する。一方、Mnが7.5mass%以下であれば、コストの上昇を招かずに上記効果が得られる。よって、Mnは1.0~7.5mass%の範囲で添加するのが好ましく、2.0~5.0mass%の範囲で添加するのがより好ましい。
Pは、固溶強化能の大きい割に絞り性を害さない元素であり、高強度化を達成するのに有効な元素であるため、0.005mass%以上含有させることが好ましい。ただし、Pは、スポット溶接性を害する元素であるが、0.05mass%以下であれば問題は生じない。よって、Pは0.05mass%以下が好ましく、0.02mass%以下とするのがより好ましい。
Sは、不可避的に混入してくる不純物元素であり、鋼中にMnSとして析出し、鋼板の伸びフランジ性を低下させる有害な成分である。伸びフランジ性を低下させないためには、Sは0.01mass%以下が好ましい。より好ましくは0.005mass%以下、さらに好ましくは0.003mass%以下である。
Alは、製鋼工程で脱酸剤として添加される元素であり、また、伸びフランジ性を低下させる非金属介在物をスラグとして分離するのに有効な元素であるので、0.01mass%以上含有させるのが好ましい。Alが0.06mass%以下であれば、原料コストの上昇を招かず、上記効果を得ることができる。よって、Alは0.06mass%以下とするのが好ましい。より好ましくは0.02~0.06mass%の範囲である。
Nb,TiおよびVは、炭化物や窒化物を形成し、焼鈍時の加熱段階でフェライトの成長を抑制して組織を微細化させ、成形性、特に伸びフランジ性を向上させる元素であるため、また、Mo,CrおよびBは、鋼の焼入性を向上し、ベイナイトやマルテンサイトの生成を促進する元素であるため、上記範囲で添加することができる。また、Nは、Nb,TiおよびVと窒化物を形成しあるいは鋼中に固溶して鋼の高強度化に寄与する元素であり、0.008mass%以下であれば、窒化物が多量に形成されないので、プレス成形時のボイド形成による破断が抑制され、上記効果を得ることができる。
NiおよびCuは、低温変態相の生成を促進し、鋼を高強度化する効果があるので、上記範囲で添加することができる。また、CaおよびREMは、硫化物系介在物の形態を制御し、鋼板の伸びフランジ性を向上させる元素であるので、上記範囲で添加することができる。
本発明の冷延鋼板は、上記成分以外の残部はFeおよび不可避的不純物である。ただし、本発明の作用効果を害しない範囲であれば、その他の成分の添加を拒むものではない。
前述したように、本発明の冷延鋼板は、焼鈍時に鋼板表層に形成されるSiO2やSi-Mn系複合酸化物等のSi含有酸化物層を除去した鋼板表面を有するものであることが必要である。そのためには、硝酸等の酸を用いて強酸洗し、鋼板表面や表面近傍の粒界部分に形成されたSi含有酸化物を地鉄ごと溶解、除去したものであることが必要である。
極表層情報を検出できる極低加速電圧の走査型電子顕微鏡(ULV-SEM)を用いて酸洗後の鋼板表面を加速電圧2kV、作動距離3.0mm、倍率1000倍程度で5視野程度を観察し、エネルギー分散型X線分光器(EDX)を用いて分光分析し、反射電子像を得る。この反射電子像を画像解析ソフト、例えば、Image Jを用いて2値化処理して黒色部の面積率を測定し、各視野の測定値を平均化することで鉄系酸化物の表面被覆率を得ることができる。なお、上記極低加速電圧の走査型電子顕微鏡(ULV-SEM)としては、例えば、SEISS社製;ULTRA55を、また、エネルギー分散型X線分光器(EDX)としては、例えば、Thermo Fisher社製;NSS312Eを挙げることができる。
後述する実施例の表3に示した鋼符号Gの鋼スラブを、同じく後述する実施例の表4のNo.8に示した条件で、熱間圧延し、冷間圧延し、連続焼鈍して板厚が1.8mmの冷延鋼板とし、次いで、上記連続焼鈍後の冷延鋼板を、表1に示した条件で、酸洗と再酸洗し、水洗し、乾燥した後、0.7%の調質圧延を施して、鋼板表面の鉄系酸化物量が異なるNo.aおよびbの2種類の冷延鋼板を得た。次いで、上記No.aの冷延鋼板を鉄系酸化物の多い標準サンプル、No.bの冷延鋼板を鉄系酸化物の少ない標準サンプルとし、それぞれの鋼板について、走査型電子顕微鏡を用いて前述した条件で反射電子像を得た。図1は、No.a,bの鋼板の反射電子像写真を、また、図2は、No.a,bの鋼板の上記反射電子像写真のグレー値に対するピクセル数のヒストグラムを示す。本発明では、上記図2に示したNo.a,bのヒストグラムの交点(X点)に対応するグレー値(Y点)を閾値として定めた。因みに、上記閾値を用いて、No.a,bの鋼板の鉄系酸化物の表面被覆率を求めたところ、No.aの鋼板は85.3%、No.bの鋼板は25.8%が得られた。
まず、酸洗後の鋼板表面から、集束イオンビーム(FIB)加工により、鋼板の幅方向に対して8μm程度の断面を観察できる抽出レプリカを10個作製する。次いで、断面の局所情報を調べることができるエネルギー分散型X線分光器(EDX)を備えた透過型電子顕微鏡(TEM)を用いて、加速電圧200kV、倍率10万倍にて、各レプリカの断面8μmを連続して撮影する。一例として、図3には、鋼板表面に存在する酸洗で生成した被覆層の断面をTEMで観察した写真を、図4には、その被覆層のEDX分析結果を示した。図4から、上記被覆層は鉄主体の鉄系酸化物であることがわかるので、図3の断面写真に示した鋼板地鉄を示す線Aと酸化物層の最も厚い部分を示す線Bとの間隔を10個のレプリカ全てについて測定し、その中の最大厚さを鉄系酸化物の最大厚さとする。なお、上記レプリカのサイズや個数、TEMによる測定条件等は一つの例示であり、適宜変更してよいことは勿論である。
本発明の冷延鋼板の製造方法は、Siを0.5~3.0mass%含有した鋼素材(スラブ)を加熱後、熱間圧延し、冷間圧延し、連続焼鈍し、その後、硝酸等を用いて強酸洗して鋼板表層部分のSi含有酸化物層を除去した後、さらに、再酸洗して、上記強酸洗により鋼板表面に生成した鉄系酸化物の表面被覆率を40%以下にできる方法であることが必要であり、さらに、上記鉄系酸化物の最大厚さが150nm以下にできる方法であることが好ましい。したがって、製鋼工程から冷間圧延後の連続焼鈍工程までは、常法に従って製造することができるが、連続焼鈍後の酸洗は、以下の条件とするのが好ましい。
上記連続焼鈍後の鋼板表層には、SiO2やSi-Mn系複合酸化物等のSi含有酸化物が多量に生成されており、このままでは化成処理性や塗装後耐食性が著しく低下する。そこで、本発明の製造方法では、焼鈍後の冷延鋼板を、硝酸等を用いて強酸洗し、鋼板表面のSi含有酸化物層を地鉄ごと除去してやることが必要である。
しかしながら、上記のような硝酸と塩酸、あるいは硝酸と弗酸を混合した酸洗液を用いて強酸洗するだけでは、鋼板表面に生成する鉄系酸化物の表面被覆率を安定して40%以下に制御することは難しい。そこで、本発明では、上記強酸洗によって鋼板表面に生成した鉄系酸化物をより確実に低減する方法として、上記連続焼鈍後に酸洗した鋼板を、さらに非酸化性の酸で再酸洗して鉄系酸化物を溶解・除去することとした。
(1)化成処理条件
上記各冷延鋼板から採取した試験片に、日本パーカライジング社製の脱脂剤:FC-E2011、表面調整剤:PL-Xおよび化成処理剤:パルボンドPB-L3065を用いて、下記の標準条件および化成処理液の温度を下げて低温度化した比較条件の2条件で、化成処理皮膜付着量が1.7~3.0g/m2となるよう化成処理を施した。
<標準条件>
・脱脂工程:処理温度 40°C、処理時間 120秒
・スプレー脱脂、表面調整工程:pH 9.5、処理温度室温、処理時間 20秒
・化成処理工程:化成処理液の温度 35℃、処理時間 120秒
<低温度化条件>
上記標準条件における化成処理液の温度を33℃に低下した条件
(2)腐食試験
上記化成処理を施した試験片の表面に、日本ペイント社製の電着塗料:V-50を用いて、膜厚が25μmとなるように電着塗装を施し、下記3種類の腐食試験に供した。
<塩温水浸漬試験>
化成処理および電着塗装を施した上記試験片(n=1)の表面に、カッターで長さ45mmのクロスカット疵を付与した後、この試験片を、5mass%NaCl溶液(60℃)に360時間浸漬し、その後、水洗し、乾燥し、カット疵部に粘着テープを貼り付けた後、引き剥がすテープ剥離試験を行い、カット疵部左右を合わせた最大剥離全幅を測定した。この最大剥離全幅が5.0mm以下であれば、耐塩温水浸漬試験における耐食性は良好と評価することができる。
<塩水噴霧試験(SST)>
化成処理、電着塗装を施した上記試験片(n=1)の表面に、カッターで長さ45mmのクロスカット疵を付与した後、この試験片を、5mass%NaCl水溶液を使用して、JIS Z2371:2000に規定される中性塩水噴霧試験に準拠して1200時間の塩水噴霧試験を行った後、クロスカット疵部についてテープ剥離試験し、カット疵部左右を合わせた最大剥離全幅を測定した。この最大剥離全幅が4.0mm以下であれば、塩水噴霧試験における耐食性は良好と評価することができる。
<複合サイクル腐食試験(CCT)>
化成処理、電着塗装を施した上記試験片(n=1)の表面に、カッターで長さ45mmのクロスカット疵を付与した後、この試験片を、塩水噴霧(5mass%NaCl水溶液:35℃、相対湿度:98%)×2時間→乾燥(60℃、相対湿度:30%)×2時間→湿潤(50℃、相対湿度:95%)×2時間、を1サイクルとして、これを120サイクル繰り返す腐食試験後、水洗し、乾燥した後、カット疵部についてテープ剥離試験し、カット疵部左右を合わせた最大剥離全幅を測定した。この最大剥離全幅が6.0mm以下であれば、複合サイクル腐食試験での耐食性は良好と評価できる。
圧延方向に直角方向(C方向)から採取したJIS Z2201:1998に規定のJIS5号引張試験片(n=1)を用いて、JIS Z2241:1998の規定に準拠して引張試験を行い、引張強さTSを測定した。
(2)塗装後耐食性
各冷延鋼板から採取した試験片に、実施例1と同じ条件で、化成処理し、電着塗装を施した試験片を作製し、実施例1と同様にして、塩温水浸漬試験、塩水噴霧試験(SST)および複合サイクル腐食試験(CCT)の3種類の腐食試験に供して、塗装後耐食性を評価した。
(1)化成処理条件
上記各冷延鋼板から採取した試験片に、日本パーカライジング社製の脱脂剤:FC-E2011、表面調整剤:PL-Xおよび化成処理剤:パルボンドPB-L3065を用いて、下記の標準条件および化成処理液の温度を下げて低温度化した比較条件の2条件で、化成処理皮膜付着量が1.7~3.0g/m2となるよう化成処理を施した。
<標準条件>
・脱脂工程:処理温度 40°C、処理時間 120秒
・スプレー脱脂、表面調整工程:pH 9.5、処理温度室温、処理時間 20秒
・化成処理工程:化成処理液の温度 35℃、処理時間 120秒
<低温度化条件>
上記標準条件における化成処理液の温度を33℃に低下した条件
(2)腐食試験
上記化成処理を施した試験片の表面に、日本ペイント社製の電着塗料:V-50を用いて、膜厚が25μmとなるように電着塗装を施し、実施例1と比較してより厳しい条件の下記3種類の腐食試験に供した。
<塩温水浸漬試験>
化成処理および電着塗装を施した上記試験片(n=1)の表面に、カッターで長さ45mmのクロスカット疵を付与した後、この試験片を、5mass%NaCl溶液(60℃)に480時間浸漬し、その後、水洗し、乾燥し、カット疵部に粘着テープを貼り付けた後、引き剥がすテープ剥離試験を行い、カット疵部左右を合わせた最大剥離全幅を測定した。この最大剥離全幅が5.0mm以下であれば、耐塩温水浸漬試験における耐食性は良好と評価することができる。
<塩水噴霧試験(SST)>
化成処理、電着塗装を施した上記試験片(n=1)の表面に、カッターで長さ45mmのクロスカット疵を付与した後、この試験片を、5mass%NaCl水溶液を使用して、JIS Z2371:2000に規定される中性塩水噴霧試験に準拠して1400時間の塩水噴霧試験を行った後、クロスカット疵部についてテープ剥離試験し、カット疵部左右を合わせた最大剥離全幅を測定した。この最大剥離全幅が4.0mm以下であれば、塩水噴霧試験における耐食性は良好と評価することができる。
<複合サイクル腐食試験(CCT)>
化成処理、電着塗装を施した上記試験片(n=1)の表面に、カッターで長さ45mmのクロスカット疵を付与した後、この試験片を、塩水噴霧(5mass%NaCl水溶液:35℃、相対湿度:98%)×2時間→乾燥(60℃、相対湿度:30%)×2時間→湿潤(50℃、相対湿度:95%)×2時間、を1サイクルとして、これを150サイクル繰り返す腐食試験後、水洗し、乾燥した後、カット疵部についてテープ剥離試験し、カット疵部左右を合わせた最大剥離全幅を測定した。この最大剥離全幅が6.0mm以下であれば、複合サイクル腐食試験での耐食性は良好と評価できる。
Claims (14)
- 冷間圧延後、連続焼鈍した鋼板を酸洗した後、さらに再酸洗する冷延鋼板の製造方法。
- 上記再酸洗には、再酸洗前の酸洗に用いる酸とは異なる、非酸化性の酸を用いることを特徴とする請求項1に記載の冷延鋼板の製造方法。
- 上記非酸化性の酸は、塩酸、硫酸、リン酸、ピロリン酸、ギ酸、酢酸、クエン酸、弗酸、シュウ酸およびこれらの2種以上を混合した酸のいずれかであることを特徴とする請求項2に記載の冷延鋼板の製造方法。
- 上記非酸化性の酸は、濃度が0.1~50g/Lの塩酸、0.1~150g/Lの硫酸、および、0.1~20g/Lの塩酸と0.1~60g/Lの硫酸を混合した酸のいずれかであることを特徴とする請求項2に記載の冷延鋼板の製造方法。
- 上記再酸洗を、再酸洗液の温度を20~70℃として1~30秒間行うことを特徴とする請求項1~4のいずれか1項に記載の冷延鋼板の製造方法。
- 上記酸洗を、硝酸、塩酸、弗酸、硫酸およびそれらを2種以上混合した酸のいずれかを用いて行うことを特徴とする請求項1~5のいずれか1項に記載の冷延鋼板の製造方法。
- 上記酸洗を、硝酸濃度が50g/L超え200g/L以下で、硝酸濃度に対する塩酸濃度の比(HCl/HNO3)が0.01~1.0である硝酸と塩酸を混合した酸、または、硝酸濃度が50g/L超え200g/L以下で、硝酸濃度に対する弗酸濃度の比(HF/HNO3)が0.01~1.0である硝酸と弗酸を混合した酸のいずれかを用いて行うことを特徴とする請求項1~6のいずれか1項に記載の冷延鋼板の製造方法。
- 上記鋼板は、Siを0.5~3.0mass%含有することを特徴とする請求項1~7のいずれか1項に記載の冷延鋼板の製造方法。
- 上記鋼板は、Siの他に、C:0.01~0.30mass%、Mn:1.0~7.5mass%、P:0.05mass%以下、S:0.01mass%以下およびAl:0.06mass%以下を含有し、残部がFeおよび不可避的不純物からなる成分組成を有することを特徴とする請求項8に記載の冷延鋼板の製造方法。
- 上記鋼板は、上記成分組成に加えてさらに、Nb:0.3mass%以下、Ti:0.3mass%以下、V:0.3mass%以下、Mo:0.3mass%以下、Cr:0.5mass%以下、B:0.006mass%以下およびN:0.008mass%以下のうちから選ばれる1種または2種以上を含有することを特徴とする請求項8または9に記載の冷延鋼板の製造方法。
- 上記鋼板は、上記成分組成に加えてさらに、Ni:2.0mass%以下、Cu:2.0mass%以下、Ca:0.1mass%以下およびREM:0.1mass%以下のうちから選ばれる1種または2種以上を含有することを特徴とする請求項8~10のいずれか1項に記載の冷延鋼板の製造方法。
- 請求項1~11のいずれか1項に記載の方法で製造された冷延鋼板であって、連続焼鈍後の酸洗で鋼板表層のSi含有酸化物層が除去されてなり、かつ再酸洗後の鋼板表面に存在する鉄系酸化物の表面被覆率が40%以下であることを特徴とする冷延鋼板。
- 上記冷延鋼板は、再酸洗後の鋼板表面に存在する鉄系酸化物の最大厚さが150nm以下であることを特徴とする請求項12に記載の冷延鋼板。
- 請求項12または13に記載の冷延鋼板を用いてなることを特徴とする自動車部材。
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EP11821649.8A EP2612957B1 (en) | 2010-08-31 | 2011-08-25 | Method for producing cold-rolled steel sheet as well as cold-rolled steel sheet and members for automobile |
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MX2013000619A (es) | 2013-05-28 |
US20130149526A1 (en) | 2013-06-13 |
KR20130031285A (ko) | 2013-03-28 |
BR112013004853A2 (pt) | 2016-06-07 |
JP5729211B2 (ja) | 2015-06-03 |
KR101502213B1 (ko) | 2015-03-12 |
TW201224216A (en) | 2012-06-16 |
JP2012132092A (ja) | 2012-07-12 |
MX348689B (es) | 2017-06-26 |
EP2612957A4 (en) | 2015-04-08 |
EP2612957B1 (en) | 2021-04-14 |
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