WO2021199956A1 - 溶融めっき鋼板 - Google Patents
溶融めっき鋼板 Download PDFInfo
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- WO2021199956A1 WO2021199956A1 PCT/JP2021/009271 JP2021009271W WO2021199956A1 WO 2021199956 A1 WO2021199956 A1 WO 2021199956A1 JP 2021009271 W JP2021009271 W JP 2021009271W WO 2021199956 A1 WO2021199956 A1 WO 2021199956A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
Definitions
- the present invention relates to a hot-dip galvanized steel sheet, and more particularly to a hot-dip galvanized steel sheet having good appearance pattern uniformity.
- the present application claims priority based on Japanese Patent Application No. 2020-061205 filed in Japan on March 30, 2020, the contents of which are incorporated herein by reference.
- Hot-dip galvanized steel sheet that is used as a steel sheet with good corrosion resistance.
- Hot-dip galvanized steel sheets which are typical examples of hot-dip galvanized steel sheets, are widely used in various manufacturing industries such as automobiles, home appliances, and building materials.
- a method for manufacturing a hot-dip galvanized steel sheet a method in which a cold-rolled steel sheet or a hot-rolled steel sheet is used as a base steel sheet and passed through a continuous hot-dip galvanized steel sheet (hereinafter referred to as CGL) is generally manufactured. ..
- the CGL process is a total reduction furnace method in which the base steel sheet is degreased by alkaline spray and then brush-cleaned in the cleaning section on the entry side, annealed in a reducing atmosphere in the annealing section, and then immersed in a hot-dip galvanizing bath. Is generally used.
- the Zendimia method in which a non-oxidizing furnace is provided in front of the annealing section, and the surface-cleaned base steel sheet is preheated in the non-oxidizing furnace, then reduced and annealed in the reduction furnace, and then immersed in a hot-dip galvanizing bath. It may be used.
- Patent Document 1 proposes a Zn—Al—Mg-based hot-dip galvanized steel sheet. Further, in Patent Document 1, by incorporating one or more of Ca, Be, Ti, Cu, Ni, Co, Cr, and Mn in a Zn—Al—Mg-based hot-dip galvanized steel sheet, melting with further excellent corrosion resistance is achieved. It is stated that a plated steel sheet can be obtained.
- [Al phase], [Zn phase], [MgZn 2- phase], [Al / MgZn 2 / Zn ternary eutectic structure] includes four main types of phases and tissues.
- Si is contained in the hot-dip plating layer in addition to Zn, Al, and Mg, mainly five types of phases and structures including [Mg 2 Si phase] are added to the above four types of phases and structures. Consists of organization.
- the [Al phase] exhibits a white color when it appears on the surface of the plating layer, and the [Al / MgZn 2 / Zn ternary eutectic structure] exhibits a metallic luster. Since [Al phase] and [Al / MgZn 2 / Zn ternary eutectic structure] coexist on the surface of the plating layer, the surface of the hot-dip plating layer has a satin-like appearance.
- the satin-like appearance of the hot-dip plating layer is affected by the size of the [Al phase] and the size of the [Al / MgZn 2 / Zn ternary eutectic structure]. If the sizes of these phases and structures are substantially uniform over the entire surface of the hot-dip plating layer, the overall appearance pattern uniformity is improved. However, the hot-dip plating layer of the conventional Zn-Al-Mg-based hot-dip galvanized steel sheet is not sufficient to satisfy the appearance pattern uniformity.
- Patent Document 2 describes that the surface appearance is improved by adding Ti, B, and Si to the molten Zn-Al-Mg plated steel sheet, but the appearance pattern uniformity is not sufficiently satisfactory. There wasn't.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a hot-dip galvanized steel sheet having good appearance pattern uniformity and excellent corrosion resistance.
- the present invention adopts the following configuration.
- a steel plate and a hot-dip plating layer formed on the surface of the steel plate are provided.
- the hot-dip plating layer contains Al: 2 to 22% by mass and Mg: 0.1 to 10% by mass in average composition, and the balance contains Zn and impurities.
- the intensity ratio A of each measurement region is determined by the following measurement method.
- the ratio (A / A ave ) of the intensity ratio A of each measurement region to the average value A ave is in the range of 0.70 or more and less than 1.40.
- each measurement area is extracted as gray scale 256-gradation image data having a size of 50 pixels ⁇ 50 pixels, and the 256-gradation image data is subjected to two-dimensional discrete Fourier transform to perform spatial frequency amplitude.
- a spectrum image is obtained, and in the obtained amplitude spectrum image, the sum of intensities S25 of spatial frequencies 1 to 25 and the sum of intensities S5 of spatial frequencies 1 to 5 are calculated, and the ratio of the sum of intensities S5 to the sum of intensities S25 (S5).
- S25 is a hot-dip plated steel plate, characterized in that the strength ratio is A.
- the hot-dip plating layer further contains 0.0001 to 2% by mass of any one or more of Ni, Ti, Zr, and Sr in total in an average composition [[4].
- the hot-dip plating layer further has an average composition of any one of Fe, Sb, Pb, Sn, Ca, Co, Mn, P, B, Bi, Cr, Sc, Y, REM, and Hf.
- FIG. 1 shows a typical cross-sectional SEM observation of a hot-dip galvanized steel sheet having an average composition of Al: 11% by mass, Mg: 3% by mass, Si: 0.2% by mass, and a hot-dip plating layer containing Zn and impurities in the balance. It is a figure which shows the image.
- FIG. 2 is a diagram showing an example of grayscale 256-gradation image data in the measurement region and an example of a spatial frequency amplitude spectrum image obtained by a two-dimensional discrete Fourier transform on the gradation image data.
- FIG. 3 is a diagram showing the grayscale 256 gradation image data of the measurement region and the amplitude spectrum image of the spatial frequency obtained by the two-dimensional discrete Fourier transform on the gradation image data.
- FIG. 4 is a schematic view showing an example of the hot-dip plating equipment for the hot-dip galvanized steel sheet of the present embodiment.
- the melt-plated layer containing Al: 2 to 22% by mass and Mg: 0.1 to 10% by mass in average composition includes [Al phase], [MgZn 2 phase], [Zn phase], and [Al / MgZn].
- 2 / Zn ternary eutectic structure] is mainly composed of four types of phases and structures.
- the hot-dip plating layer contains Si in addition to Zn, Al, and Mg, there are mainly five types of phases and structures including [Mg 2 Si phase] in addition to the above four types of phases and structures. Consists of.
- the [Al phase] exhibits a white color when it appears on the surface of the plating layer, and the [Al / MgZn 2 / Zn ternary eutectic structure] exhibits a metallic luster. Since [Al phase] and [Al / MgZn 2 / Zn ternary eutectic structure] coexist on the surface of the plating layer, the surface of the hot-dip plating layer has a satin-like appearance. The satin-like appearance of the hot-dip plating layer is affected by the size of the [Al phase] and the size of the [Al / MgZn 2 / Zn ternary eutectic structure]. If the sizes of these phases and structures are substantially uniform over the entire surface of the hot-dip plating layer, the overall appearance pattern uniformity is improved.
- the appearance pattern uniformity means that the appearance pattern appearing on the plating surface is uniform.
- the appearance pattern may be a satin pattern, as long as the satin pattern is uniform.
- spots or the like are partially observed on the plating surface, the appearance pattern uniformity is not satisfied.
- the steel sheet pulled up after being immersed in the hot-dip plating bath is cooled by means such as forced air cooling after adjusting the adhesion amount of the plating layer by the wiping nozzle.
- forced air cooling after adjusting the adhesion amount of the plating layer by the wiping nozzle.
- the causes of the decrease in appearance pattern uniformity are the size of [Al phase], the size of [Al / MgZn 2 / Zn ternary eutectic structure], [Al phase] and [Al / MgZn 2 / Zn ternary both. It is conceivable that the abundance of each of [crystal structure] may change partially.
- a plurality of regions having a predetermined size are selected from the surface of the hot-dip plating layer, gray-scale image data is acquired for each region, and two-dimensional discrete Fourier transform is performed on these image data.
- the amplitude spectrum image of the obtained spatial frequency was analyzed, it was found that the analysis result of each amplitude spectrum image and the size of the satin pattern were correlated, and further, the variation of the analysis result of each amplitude spectrum image was evaluated. Therefore, it was found that a hot-dip plated steel plate having excellent appearance pattern uniformity can be specified.
- the hot-dip plated steel sheet of the present embodiment includes a steel sheet and a hot-dip plating layer formed on the surface of the steel sheet, and the hot-dip plating layer has an average composition of Al: 2 to 22% by mass and Mg: 0.1 to.
- Five square measurement regions containing 10% by mass, the balance containing Zn and impurities, and a side of 5 mm from the surface of the hot-dip plating layer were selected, and the intensity ratio A of each measurement region was determined by the following measurement method.
- the ratio (A / A ave ) of the strength ratio A of each measurement region to the average value A ave of the strength ratio A of the five measurement regions is in the range of 0.70 or more and less than 1.40. Is.
- the measurement method is to extract each measurement area as grayscale 256-gradation image data with a size of 50 pixels ⁇ 50 pixels, perform two-dimensional discrete Fourier transform on the 256-gradation image data, and perform a spatial frequency amplitude spectrum image.
- the sum of intensities S25 of spatial frequencies 1 to 25 and the sum of intensities S5 of spatial frequencies 1 to 5 are calculated, and the ratio of the sum of intensities S5 to the sum of intensities S25 (S5 / This is a method in which S25) is set to the strength ratio A.
- the material of the steel sheet used as the base of the hot-dip plating layer is not particularly limited.
- general steel or the like can be used without particular limitation, Al killed steel or some high alloy steel can also be applied, and the shape is not particularly limited.
- the hot-dip plating layer contains Al: 2 to 22% by mass and Mg: 0.1 to 10% by mass in average composition, and contains Zn and impurities as the balance. More preferably, the hot-dip plating layer contains Al: 2 to 22% by mass and Mg: 0.1 to 10% by mass in average composition, and is composed of Zn and impurities as the balance. Further, the hot-dip plating layer may contain Si: 0.0001 to 2% by mass in an average composition. Further, the hot-dip plating layer may contain 0.0001 to 2% by mass in total of any one or more of Ni, Ti, Zr, and Sr in an average composition.
- the hot-dip plating layer has an average composition of any one or two of Fe, Sb, Pb, Sn, Ca, Co, Mn, P, B, Bi, Cr, Sc, Y, REM, and Hf.
- the above may be contained in a total of 0.0001 to 2% by mass.
- the Al content is in the range of 2 to 22% by mass in average composition. Al may be contained in order to ensure corrosion resistance. When the Al content in the hot-dip plating layer is 2% by mass or more, the effect of improving the corrosion resistance is further enhanced. When the Al content exceeds 22% by mass, the cause is unknown, but the corrosion resistance is lowered. From the viewpoint of corrosion resistance, the Al content is preferably 4 to 22% by mass, more preferably 5 to 18% by mass. The Al content is more preferably 6 to 16% by mass.
- the Mg content is in the range of 0.1 to 10% by mass in average composition. Mg is preferably contained in order to improve the corrosion resistance. When the Mg content in the hot-dip plating layer is 0.1% by mass or more, the effect of improving the corrosion resistance is further enhanced. If the Mg content exceeds 10% by mass, dross is significantly generated in the plating bath, and the adhesion of dross to the plating causes some parts where the plating is not normally formed, which may reduce the corrosion resistance. Therefore, the Mg content is set to 10% by mass or less. From the viewpoint of lowering the corrosion resistance due to the generation of dross, the Mg content is preferably 1.0 to 10% by mass, more preferably 1.5 to 6.0% by mass. The Mg content is more preferably in the range of 2.0 to 5.0% by mass.
- Si may or may not be contained because it may improve the adhesion of the hot-dip plating layer. Since the effect of improving the adhesion is exhibited by containing 0.0001% by mass or more of Si, it is preferable to contain 0.0001% by mass or more of Si. On the other hand, even if the content exceeds 2% by mass, the effect of improving the plating adhesion is saturated, so the Si content is set to 2% by mass or less. From the viewpoint of plating adhesion, the range may be 0.0001 to 1% by mass, or 0.01 to 0.8% by mass.
- the hot-dip plating layer may contain 0.0001 to 2% by mass in total of any one or more of Ni, Ti, Zr, and Sr in an average composition. Further, in the hot-dip plating layer, one or more of Fe, Sb, Pb, Sn, Ca, Co, Mn, P, B, Bi, Cr, Sc, Y, REM and Hf are contained in the average composition. It may contain 0.0001 to 2% by mass in total. By containing these elements, the corrosion resistance can be further improved.
- REM is one or more rare earth elements having atomic numbers 57 to 71 in the periodic table.
- the rest of the chemical composition of the hot-dip plating layer is zinc and impurities.
- Impurities include those that are inevitably contained in zinc and other bullions, and those that are contained by melting steel in a plating bath.
- the average composition of the hot-dip plating layer can be measured by the following method. First, the surface coating is removed with a coating remover that does not erode the plating (for example, Neo River SP-751 manufactured by Sansai Kako Co., Ltd.), and then the hot-dip plating layer is used with hydrochloric acid containing an inhibitor (for example, Hiviron manufactured by Sugimura Chemical Industrial Co., Ltd.). Can be obtained by dissolving the solution and subjecting the obtained solution to inductively coupled plasma (ICP) emission spectroscopic analysis. Further, when the surface layer coating film is not provided, the work of removing the surface layer coating film can be omitted.
- a coating remover that does not erode the plating for example, Neo River SP-751 manufactured by Sansai Kako Co., Ltd.
- hydrochloric acid containing an inhibitor for example, Hiviron manufactured by Sugimura Chemical Industrial Co., Ltd.
- ICP inductively coupled plasma
- the hot-dip plating layer containing Al, Mg and Zn contains [Al phase] and [ternary eutectic structure of Al / Zn / MgZn 2]. It has a form in which [Al phase] is included in the substrate of [Al / Zn / MgZn 2 ternary eutectic structure].
- [MgZn 2 phase] and [Zn phase] may be contained in the base material of [Al / Zn / MgZn 2 ternary eutectic structure].
- [Mg 2 Si phase] may be contained in the base material of [Al / Zn / MgZn 2 ternary eutectic structure].
- [Al / Zn / MgZn 2 ternary eutectic structure] is a portion represented by a white region, a gray region, and a fine white and black mixed region in the SEM image, as shown in FIG.
- [Al / Zn / MgZn 2 ternary eutectic structure] is a ternary eutectic structure of the Al phase, the Zn phase and the metal compound MgZn 2 phase, and the [Al / Zn / MgZn 2 ternary structure].
- the Al phase forming the [crystal structure] is, for example, the "Al" phase at a high temperature in the ternary equilibrium state diagram of Al-Zn-Mg (an solid Al solution that dissolves Zn and contains a small amount of Mg). Is equivalent to.
- the Al ′′ phase at high temperature usually appears as a fine Al phase and a fine Zn phase at room temperature. Further, the Zn phase in [Al / Zn / MgZn 2 ternary eutectic structure] is small. solid-solved Al, optionally a Zn solid solution solid solution a small amount of Mg is.
- the [Al phase] looks like an island with a clear boundary in the substrate of [Al / Zn / MgZn 2 ternary eutectic structure] in the SEM image, and the white and black colors are fine. It is the part represented by the mixed state color.
- the [Al phase] corresponds to, for example, the "Al" phase at a high temperature in the ternary equilibrium diagram of Al-Zn-Mg (an Al solid solution that dissolves Zn and contains a small amount of Mg). be.
- the amount of Zn and Mg that dissolve in the Al "phase at high temperature differs depending on the concentration of Al and Mg in the plating bath.
- the Al" phase at this high temperature is usually fine Al phase and fine Zn at room temperature.
- the island-like shape seen at room temperature can be seen as retaining the skeleton of the Al ′′ phase at high temperature.
- other additive elements are dissolved in this phase.
- the retained phase is referred to as [Al phase] in the present specification.
- This [Al phase] is clearly different from the Al phase forming [Al / Zn / MgZn 2 ternary eutectic structure] by microscopic observation. Can be distinguished.
- the [Zn phase] is a white portion that looks like an island with a clear boundary in the base material of [Al / Zn / MgZn 2 ternary eutectic structure] in the SEM image.
- the [Zn phase] may actually be a solid solution of a small amount of Al or even a small amount of Mg.
- the region having a diameter equivalent to a circle of 2.5 ⁇ m or more is defined as the Zn phase.
- the phase diagram it is considered that other additive elements are not solid-solved in this phase, or even if they are solid-solved, the amount is extremely small.
- This [Zn phase] can be clearly distinguished from the Zn phase forming [Al / Zn / MgZn 2 ternary eutectic structure] by microscopic observation.
- the plating layer of the present invention may contain [Zn phase] depending on the plating composition and manufacturing conditions, but since the experiment showed almost no effect on the improvement of the corrosion resistance of the processed portion, the [Zn phase] was found in the plating layer. ] Is included, there is no particular problem.
- [MgZn 2- phase] is represented in gray, which looks like an island with a clear boundary in the base material of [Al / Zn / MgZn 2 ternary eutectic structure] in the SEM image. It is a part.
- [MgZn 2- phase] may actually be a solid solution of a small amount of Al. As far as the phase diagram is concerned, it is considered that other additive elements are not solid-solved in this phase, or even if they are solid-solved, the amount is extremely small.
- This [MgZn 2 phase] can be clearly distinguished from the MgZn 2 phase forming [Al / Zn / MgZn 2 ternary eutectic structure] by microscopic observation.
- the plating layer of the present invention may not contain [MgZn 2- phase] depending on the plating composition and production conditions, but it is contained in the plating layer under most production conditions.
- [Mg 2 Si phase] is a black portion that looks like an island with clear boundaries in the solidified structure of the hot-dip plating layer when Si is contained in the SEM image, as shown in FIG. ..
- the phase diagram it is considered that Zn, Al, and other additive elements are not solid-solved in [Mg 2 Si phase], or even if they are solid-solved, the amount is extremely small.
- This [Mg 2 Si phase] can be clearly distinguished by microscopic observation during plating.
- the hot-dip plating layer For the hot-dip plating layer according to the present embodiment, five square measurement regions having a side of 5 mm are selected from the surface of the hot-dip plating layer, and the strength ratio A of each measurement region is obtained by the following measurement method.
- the ratio of the intensity ratio A of each measurement region (A / A ave ) to the average value A ave of the intensity ratio A of the measurement region of is in the range of 0.70 or more and less than 1.40.
- the five measurement areas may be arbitrarily selected, but the distance between the measurement areas is preferably 10 cm or less, for example. If the distance between the measurement areas is more than 10 cm, it becomes difficult to properly judge the uniformity of the appearance pattern such as the satin pattern, and there is a possibility that there may be a discrepancy with the visual judgment result of the uniformity of the appearance pattern. be.
- the interval between measurement areas is set. It shall be 10 cm or less.
- a square area having a side of 10 cm is selected, and the four corners of the square and the intersection of the two diagonal lines of the square are located at a total of five positions. , It is advisable to select a square measurement area with a side of 5 mm.
- a sample including the selected measurement area and its surroundings is cut out from the hot-dip galvanized steel sheet, and the image data of the measurement area is extracted using this sample.
- the image data of the measurement area is extracted by scanning the surface of the hot-dip plating layer of the sample with a scanner connected to a computer.
- the measurement area is extracted as grayscale 256-gradation image data having a size of 50 pixels ⁇ 50 pixels.
- the scanner to be used is, for example, a flatbed type scanner.
- image correction is performed for each acquisition. Therefore, it is preferable to extract the measurement area by trimming after acquiring the image data of the entire sample at once.
- image data is acquired with a large number of pixels of 50 pixels or more with respect to 5 mm, so it is preferable to resize the image data to 50 pixels ⁇ 50 pixels using computer software.
- image data can be extracted by taking a picture, but in the case of taking a picture, it is difficult to irradiate the entire hot-dip plating layer, which is the subject, with the illumination light at the time of taking a picture completely evenly, and the appearance pattern is evaluated. Extraction with a scanner is preferable because it may not be possible to accurately perform the above.
- the image data is grayscale 256-gradation image data.
- the image data includes a binarized image, a gradation image, a color image, and the like, but the binarized image is represented by two values of light and dark, and the amount of information is insufficient. Further, in a color image, since the pixels have color information, the amount of information becomes excessive. Since the surface appearance of the hot-dip plating layer of the present embodiment has low saturation, grayscale gradation image data is sufficient as the amount of information. Therefore, in the present embodiment, a grayscale 256-gradation image having an appropriate amount of information and a gradation of 0 to 255 steps that is easy to handle by a computer is preferable.
- the gradation image data becomes data including 2500 pixels.
- Each pixel has brightness data in a square region having a side of 0.1 mm, which reflects an appearance pattern such as a satin pattern. Theoretically, even if the size of the measurement area and the number of pixels are increased, the same tendency of measurement results can be obtained, but in order to reduce the calculation load, the minimum sizes of 5 mm and 50 pixels, which are practically acceptable, are set as the measurement area. bottom.
- the gradation image data in the obtained measurement area is subjected to a two-dimensional discrete Fourier transform to obtain an amplitude spectrum image of the spatial frequency.
- the two-dimensional discrete Fourier transform may be performed by a computer in which a program is incorporated in advance.
- the two-dimensional discrete Fourier transform is performed using the following (Equation 1).
- f (x, y) is a pixel value at the (x, y) position
- F (u, v) is a complex number indicating a sine wave at the (u, v) position of the spatial frequency.
- u is the frequency of the x component
- v is the frequency of the y component.
- An amplitude spectrum image is obtained by obtaining the absolute value of a complex number indicating a sine wave. For the obtained amplitude spectrum image, an operation of exchanging the first quadrant and the third quadrant and the second quadrant and the fourth quadrant is performed for the purpose of improving the ease of handling the data.
- the pattern on the plating surface is a rough satin pattern
- the two-dimensional discrete Fourier transform when the two-dimensional discrete Fourier transform is performed, many sine waves with relatively small frequency components are included.
- the pattern on the plating surface is a fine satin pattern
- the two-dimensional discrete Fourier transform when the two-dimensional discrete Fourier transform is performed, a large number of sine waves having a relatively large frequency component are included. The result of such a two-dimensional discrete Fourier transform is reflected in the spatial frequency amplitude spectrum image after the two-dimensional discrete Fourier transform is performed.
- FIG. 2 shows an example of the gradation image data and an example of the amplitude spectrum image of the spatial frequency obtained by the two-dimensional discrete Fourier transform on the gradation image data.
- the amplitude spectrum image shows the amplitude of a sine wave having a low frequency component as it approaches the center of the image, and shows the amplitude of a sine wave having a higher frequency component as it moves concentrically from the center.
- the magnitude (intensity) of the amplitude of the sine wave is represented by shading. The darker the sine wave, the higher the intensity, and the whiter the sine wave, the lower the intensity. That is, the spatial spectrum image shown in FIG. 2 shows that the intensity of the sine wave having a low frequency component is high among the sine waves of all frequencies.
- the sum of intensities S25 of the spatial frequencies 1 to 25 and the sum of the intensities S5 of the spatial frequencies 1 to 5 can be calculated.
- the sum of intensities S25 having a spatial frequency of 1 to 25 or more is the sum of the intensities in the region surrounded by the outer circle in FIG. 2
- the sum of intensities S5 of the spatial frequencies 1 to 5 is the sum of the intensities in FIG. Is the sum of the intensities in the area surrounded by the circle.
- the intensity of the spatial frequency 0 at the center of the amplitude spectrum image is excluded. From the sum of strengths S25 and sum of strengths S5, the strength ratio A, which is the ratio of the sum of strengths S5 to the sum of strengths S25 (S5 / S25), can be obtained.
- the intensity ratio A is a parameter that can objectively evaluate the fineness of the pattern.
- FIG. 3 shows various gradation image data and an example of the amplitude spectrum image of the spatial frequency obtained from the gradation image data.
- the upper image is the gradation image data
- the lower image is the amplitude spectrum image
- FIG. 3 shows five sets of image data.
- the satin pattern becomes rougher from the left side to the right side in FIG. It can be seen that as the satin pattern becomes coarser, the intensity at the center of the spatial frequency spectrum image increases and the intensity ratio A increases.
- the intensity ratio A is obtained by performing a two-dimensional discrete Fourier transform on the gradation image data extracted from any five positions of the hot-dip plating layer. Further, the average value A ave of the obtained five intensity ratios A is obtained.
- the hot-dip plating layer of the present embodiment needs to have the ratio (A / A ave ) of the intensity ratio A of each of the five measurement regions to the average value A ave in the range of 0.70 or more and less than 1.40, respectively. .. If the ratio (A / A ave ) of the intensity ratio A is less than 0.70 or 1.40 or more among the five measurement regions, the uniformity of the appearance pattern is lowered.
- the ratio (A / A ave ) may be 0.80 or more, or 0.85 or more. Further, the ratio (A / A ave ) may be 1.30 or less, or 1.20 or less. The closer the ratio (A / A ave ) in the five measurement regions is to 1.00, the better the appearance pattern uniformity becomes.
- FIG. 4 shows a hot-dip plating facility suitable for manufacturing the hot-dip galvanized steel sheet of the present embodiment.
- the hot-dip plating equipment shown in FIG. 4 includes a hot-dip plating bath 2, a sink roll 3 arranged in the hot-dip plating bath 2, a wiping nozzle 4 placed above the hot-dip plating bath 2, and a wiping nozzle 4 above the wiping nozzle 4. It includes an arranged electromagnetic vibration control device 5, a cooling device 6 arranged above the electromagnetic vibration control device 5, and a top roll 7 arranged above the cooling device 6.
- the hot-dip plating bath 2 preferably contains Al: 2 to 22% by mass and Mg: 0.1 to 10% by mass, and contains Zn and impurities as the balance. Further, the hot-dip plating bath may contain Si: 0.0001 to 2% by mass. Furthermore, the hot-dip plating bath may contain any one or more of Ni, Ti, Zr, and Sr in a total amount of 0.0001 to 2% by mass. In addition, the hot-dip plating bath contains any one or more of Sb, Pb, Sn, Ca, Co, Mn, P, B, Bi, Cr, Sc, Y, REM, and Hf, for a total of 0.0001. It may contain up to 2% by mass.
- the average composition of the hot-dip plating layer of this embodiment is almost the same as the composition of the hot-dip plating bath 2.
- the temperature of the hot-dip plating bath 2 varies depending on the composition, but is preferably in the range of 400 to 500 ° C., for example. This is because if the temperature of the hot-dip plating bath 2 is within this range, a desired hot-dip plating layer can be formed.
- the electromagnetic vibration control device 5 prevents the vibration of the steel plate, and a generally known device can be used.
- the electromagnetic vibration control device 5 includes, for example, a pair of electromagnets symmetrically arranged on both sides of a traveling steel plate 1 at a predetermined interval (for example, 20 to 30 mm), and more preferably two or more electromagnets on one side in the plate width direction.
- An electromagnet and a non-contact type steel strip position detector are provided, and undulations are removed in the plate width direction by controlling the attractive force of each electromagnet by a controller based on the detection signal of the steel strip position detector. As described above, it has a function of preventing vibration of the steel plate.
- the electromagnetic vibration damping device 5 extends from the cooling start position of the cooling device 6 (when the refrigerant is injected toward the steel plate, the center position where the refrigerant hits the steel plate) to 1 m along the direction opposite to the traveling direction of the steel plate 1. It is desirable that it is installed within the range of. That is, it is preferable that the cooling device 6 is installed near the entrance side. It is desirable that the amplitude of the steel sheet (maximum amplitude of the steel sheet in the cooling device) after leaving the electromagnetic vibration damping device is 40 mm or less. Further, it is desirable that the electromagnetic vibration damping device is operated in the range of 0.03 to 0.06T.
- a method for manufacturing a hot-dip galvanized steel sheet using the manufacturing equipment shown in FIG. 4 will be described.
- a hot-rolled steel sheet is manufactured, and if necessary, hot-rolled sheet is annealed. After pickling, cold rolling is performed to obtain a cold rolled plate. After degreasing and washing the cold-rolled board with water, it is annealed (annealed cold-rolled board).
- the annealed steel sheet 1 is immersed in the hot-dip galvanizing bath 2, and then the sink roll 3 changes the traveling direction and pulls it up in the vertical direction.
- the excess amount of hot-dip plating adhering to the surface of the steel sheet 1 by blowing a high-pressure gas such as air or nitrogen from the wiping nozzle 4 arranged above the hot-dip galvanizing bath 2 onto the surface of the pulled steel sheet 1.
- a high-pressure gas such as air or nitrogen
- the amount of adhesion of the hot-dip plating layer is preferably adjusted so that the total amount of adhesion on both sides of the steel sheet is in the range of 30 to 600 g / m 2. If the adhesion amount is less than 30 g / m 2 , the corrosion resistance of the hot-dip galvanized steel sheet is lowered, which is not preferable. If the amount of adhesion exceeds 600 g / m 2, the molten metal adhering to the steel sheet will hang down and the surface of the hot-dip plating layer cannot be smoothed, which is not preferable.
- the steel plate 1 is introduced into the cooling device 6 while suppressing the vibration of the steel plate 1 by the electromagnetic vibration control device 5.
- the steel plate 1 is introduced into the cooling device 6 in a state where vibration is suppressed by the electromagnetic vibration control device 5.
- the cooling device 6 has a built-in injection nozzle that injects a refrigerant toward the steel sheet, and the injection nozzle injects a refrigerant such as a non-oxidizing gas or a non-oxidizing gas containing mist toward the steel sheet 1.
- NS non-oxidizing gas
- an electromagnetic vibration damping device may be arranged near the wiping nozzle 4 in order to suppress the variation in the amount of plating adhered, but the electromagnetic vibration placed near the winding nozzle 4 is provided. Since the vibration damping device is separated from the cooling device 6, the effect of suppressing the vibration of the plate during cooling cannot be obtained.
- the ratio of the strength ratio A of each measurement region to the average value A ave of the strength ratio A of the five measurement regions selected from the surface of the hot-dip plating layer (A / A ave ).
- the average composition of the hot-dip plating layer contains Al: 2 to 22% by mass and Mg: 0.1 to 10% by mass, and the balance contains Zn and impurities. Has excellent corrosion resistance.
- the steel sheet after cold rolling was degreased and washed with water. Then, the steel sheet was annealed by cold rolling.
- the steel sheet after annealing the cold-rolled sheet was introduced into the hot-dip plating facility shown in FIG. 4, immersed in a hot-dip plating bath, and then pulled up. Then, the amount of adhesion was adjusted by gas wiping, and further cooling was performed.
- the cooling was performed by blowing a non-oxidizing gas in the cooling device while suppressing the vibration of the steel sheet by the electromagnetic vibration damping device.
- the electromagnetic vibration damping device changed its position from the cooling start position (the center position where the non-oxidizing gas hits the steel sheet) along the direction opposite to the traveling direction of the steel sheet.
- the vibration damping device is within a range of 1 m from the cooling start position along the direction opposite to the traveling direction of the steel plate 1" immediately below the cooling device in the column of the damping device position. Show that.
- the maximum amplitude of the steel sheet in the cooling device is shown in Tables 1A and 1B. In this way, No. 1 shown in Tables 1A and 1B. 1 to 52 hot-dip galvanized steel sheets were manufactured.
- the measurement area was selected as follows. A square area with a side of 10 cm is selected at an arbitrary position on the surface of the plating layer, and a square with a side of 5 mm is selected at a total of 5 positions at the four corners of the square and the intersection of the two diagonal lines of the square. The measurement area of was selected.
- the image data of the measurement area was extracted by scanning the surface of the hot-dip plating layer of the sample with a flatbed scanner connected to a computer.
- the image data was grayscale 256-gradation image data.
- a two-dimensional discrete Fourier transform was performed on the gradation image data to obtain an amplitude spectrum image of the spatial frequency.
- the amplitude spectrum image of the spatial frequency for each gradation image data the sum of intensities S25 of the spatial frequencies 1 to 25 and the sum of the intensities S5 of the spatial frequencies 1 to 5 are calculated, and the ratio of the sum of intensities S5 to the total sum of intensities S25 (S5 / S25) was determined as the strength ratio A. Further, the average value A ave of the obtained five intensity ratio ratios A was obtained. Then, the ratio (A / A ave ) of the intensity ratio A of each of the five measurement regions to the average value A ave was determined.
- the appearance pattern uniformity was visually evaluated.
- the appearance of the plating was visually evaluated.
- the case where the pattern unevenness was not visible from 1 m ahead was evaluated as F as having good appearance pattern uniformity, and the case where the pattern unevenness was visible was evaluated as P because the appearance pattern uniformity was insufficient. F was accepted and P was rejected.
- Tables 2A and 2B The results are shown in Tables 2A and 2B.
- the corrosion resistance of the hot-dip galvanized steel sheet was evaluated by the corrosion weight loss after the CCT test.
- the plated steel sheet was cut to 150 ⁇ 70 mm, and the corrosion weight loss after 30 cycles of CCT was investigated using a CCT compliant with JASO-M609.
- the evaluation is as follows: Corrosion weight loss of 30 g / m 2 or less is F, corrosion weight loss of 30 g / m 2 or more and less than 50 g / m 2 is G, corrosion weight loss of 50 g / m 2 or more and less than 60 g / m 2 is P, and corrosion weight loss of 60 g / m 2
- Corrosion weight loss of 30 g / m 2 or less is F
- corrosion weight loss of 30 g / m 2 or more and less than 50 g / m 2 is G
- corrosion weight loss of 50 g / m 2 or more and less than 60 g / m 2 is P
- corrosion weight loss of 60 g / m 2 The above was regarded as X, F, G and P were regarded as acceptable, and X was regarded as rejected.
- Tables 2A and 2B The results are shown in Tables 2A and 2B.
- the hot-dip galvanized steel sheet of 46 examples of the present invention was excellent in both the uniformity of the appearance pattern and the corrosion resistance.
- the hot-dip galvanized steel sheet of the comparative example of 54 was inferior in the uniformity of the appearance pattern or inferior in the corrosion resistance.
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Abstract
Description
[1] 鋼板と、前記鋼板の表面に形成された溶融めっき層と、を備え、
前記溶融めっき層は、平均組成で、Al:2~22質量%、Mg:0.1~10質量%を含有し、残部がZnおよび不純物を含み、
前記溶融めっき層の表面から一辺が5mmの正方形の測定領域を5箇所選定し、下記の測定方法によって各測定領域の強度比率Aをそれぞれ求めた場合に、5箇所の測定領域の強度比率Aの平均値Aaveに対する各測定領域の強度比率Aの比(A/Aave)が、0.70以上1.40未満の範囲であり、
前記測定方法は、各測定領域を50ピクセル×50ピクセルのサイズのグレースケールの256階調画像データとして抽出し、前記256階調画像データに対して二次元離散フーリエ変換を行って空間周波数の振幅スペクトル像を得て、得られた前記振幅スペクトル像において、空間周波数1~25の強度和S25と、空間周波数1~5の強度和S5を算出し、強度和S25に対する強度和S5の比率(S5/S25)を強度比率Aとする方法であることを特徴とする、溶融めっき鋼板。
[2] 前記溶融めっき層が、平均組成で、Al:4~22質量%、Mg:1.0~10質量%を含有することを特徴とする[1]に記載の溶融めっき鋼板。
[3] 前記溶融めっき層が、更に、平均組成で、Si:0.0001~2質量%を含有することを特徴とする[1]または[2]に記載の溶融めっき鋼板。
[4] 前記溶融めっき層が、更に、平均組成で、Ni、Ti、Zr、Srのいずれか1種または2種以上を、合計で0.0001~2質量%含有することを特徴とする[1]乃至[3]のいずれか一項に記載の溶融めっき鋼板。
[5] 前記溶融めっき層が、更に、平均組成で、Fe、Sb、Pb、Sn、Ca、Co、Mn、P、B、Bi、Cr、Sc、Y、REM、Hfのいずれか1種または2種以上を、合計で0.0001~2質量%含有することを特徴とする[1]乃至[4]のいずれか一項に記載の溶融めっき鋼板。
[6] 前記溶融めっき層の付着量が前記鋼板両面合計で30~600g/m2であることを特徴とする[1]乃至[5]のいずれか一項に記載の溶融めっき鋼板。
本実施形態に係る溶融めっき層は、溶融めっき層の表面から一辺が5mmの正方形の測定領域を5箇所選定し、下記の測定方法によって各測定領域の強度比率Aを求めた場合に、5箇所の測定領域の強度比率Aの平均値Aaveに対する各測定領域の強度比率Aの比(A/Aave)が、0.70以上1.40未満の範囲になる必要がある。
Claims (6)
- 鋼板と、前記鋼板の表面に形成された溶融めっき層と、を備え、
前記溶融めっき層は、平均組成で、Al:2~22質量%、Mg:0.1~10質量%を含有し、残部がZnおよび不純物を含み、
前記溶融めっき層の表面から一辺が5mmの正方形の測定領域を5箇所選定し、下記の測定方法によって各測定領域の強度比率Aをそれぞれ求めた場合に、5箇所の測定領域の強度比率Aの平均値Aaveに対する各測定領域の強度比率Aの比(A/Aave)が、0.70以上1.40未満の範囲であり、
前記測定方法は、各測定領域を50ピクセル×50ピクセルのサイズのグレースケールの256階調画像データとして抽出し、前記256階調画像データに対して二次元離散フーリエ変換を行って空間周波数の振幅スペクトル像を得て、得られた前記振幅スペクトル像において、空間周波数1~25の強度和S25と、空間周波数1~5の強度和S5を算出し、強度和S25に対する強度和S5の比率(S5/S25)を強度比率Aとする方法であることを特徴とする溶融めっき鋼板。 - 前記溶融めっき層が、平均組成で、Al:4~22質量%、Mg:1~10質量%を含有することを特徴とする請求項1に記載の溶融めっき鋼板。
- 前記溶融めっき層が、更に、平均組成で、Si:0.0001~2質量%を含有することを特徴とする請求項1または請求項2に記載の溶融めっき鋼板。
- 前記溶融めっき層が、更に、平均組成で、Ni、Ti、Zr、Srのいずれか1種または2種以上を、合計で0.0001~2質量%含有することを特徴とする請求項1乃至請求項3のいずれか1項に記載の溶融めっき鋼板。
- 前記溶融めっき層が、更に、平均組成で、Fe、Sb、Pb、Sn、Ca、Co、Mn、P、B、Bi、Cr、Sc、Y、REM、Hfのいずれか1種または2種以上を、合計で0.0001~2質量%含有することを特徴とする請求項1乃至請求項4のいずれか一項に記載の溶融めっき鋼板。
- 前記溶融めっき層の付着量が前記鋼板両面合計で30~600g/m2であることを特徴とする請求項1乃至請求項5のいずれか一項に記載の溶融めっき鋼板。
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JP2004269930A (ja) * | 2003-03-06 | 2004-09-30 | Jfe Steel Kk | 溶融金属めっき鋼板の製造方法 |
JP2013014794A (ja) * | 2011-06-30 | 2013-01-24 | Nippon Steel & Sumitomo Metal Corp | 外観均一性に優れた高耐食性溶融亜鉛めっき鋼板 |
KR20130074269A (ko) * | 2011-12-26 | 2013-07-04 | 주식회사 포스코 | 노즐 복합형 강판 냉각장치 |
JP2020153004A (ja) * | 2019-03-22 | 2020-09-24 | Jfeスチール株式会社 | 溶融Zn−Al系めっき鋼板、およびその製造方法 |
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US6465114B1 (en) | 1999-05-24 | 2002-10-15 | Nippon Steel Corporation | -Zn coated steel material, ZN coated steel sheet and painted steel sheet excellent in corrosion resistance, and method of producing the same |
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JP2013014794A (ja) * | 2011-06-30 | 2013-01-24 | Nippon Steel & Sumitomo Metal Corp | 外観均一性に優れた高耐食性溶融亜鉛めっき鋼板 |
KR20130074269A (ko) * | 2011-12-26 | 2013-07-04 | 주식회사 포스코 | 노즐 복합형 강판 냉각장치 |
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