EP1391530A1 - Alloy galvanized steel plate having excellent slidability - Google Patents
Alloy galvanized steel plate having excellent slidability Download PDFInfo
- Publication number
- EP1391530A1 EP1391530A1 EP01274269A EP01274269A EP1391530A1 EP 1391530 A1 EP1391530 A1 EP 1391530A1 EP 01274269 A EP01274269 A EP 01274269A EP 01274269 A EP01274269 A EP 01274269A EP 1391530 A1 EP1391530 A1 EP 1391530A1
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- European Patent Office
- Prior art keywords
- steel sheet
- dip galvanized
- alloyed hot
- galvanized steel
- potential
- Prior art date
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- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 39
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 39
- 229910045601 alloy Inorganic materials 0.000 title 1
- 239000000956 alloy Substances 0.000 title 1
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 230000005611 electricity Effects 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- FARSWWAYCLUQAG-UHFFFAOYSA-K [Cl-].[Na+].S(=O)(=O)([O-])[O-].[Zn+2] Chemical compound [Cl-].[Na+].S(=O)(=O)([O-])[O-].[Zn+2] FARSWWAYCLUQAG-UHFFFAOYSA-K 0.000 claims abstract description 11
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 10
- 230000001747 exhibiting effect Effects 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 abstract description 18
- 239000010959 steel Substances 0.000 abstract description 18
- 238000005275 alloying Methods 0.000 abstract description 8
- 238000007747 plating Methods 0.000 description 14
- 239000011701 zinc Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000011835 investigation Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910021362 Ti-Al intermetallic compound Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C23C2/26—After-treatment
-
- 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
- C23C2/26—After-treatment
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
Definitions
- the present invention relates to an alloyed hot-dip galvanized steel sheet with excellent sliding property which is suitable as an anti-corrosive steel sheet for use in car bodies.
- Alloyed hot-dip galvanized steel sheets are widely used as anti-corrosive steel sheets for use in car bodies.
- the alloyed hot-dip galvanized steel sheets are molded into car bodies by pressing and must therefore be excellent not only in anti-corrosive properties but also in sliding properties.
- Process steps for manufacturing an alloyed hot-dip galvanized steel sheet are broadly divided into the process step of immersing a material steel sheet in a plating bath to form a hot-dip galvanized layer on the surface of the steel sheet, and the step of subjecting the steel sheet carrying the hot-dip galvanized layer to alloying to thereby form an alloyed hot-dip galvanized layer.
- the hot-dip galvanized layer formed on the surface of the steel sheet in the plating bath comprises an intermetallic compound of Zn and Fe ( ⁇ , ⁇ 1, ⁇ ), and the sliding property of the alloyed hot-dip galvanized layer formed by alloying varies depending on the composition of the intermetallic compound.
- Various techniques have therefore been proposed in which the sliding property of an alloyed hot-dip galvanized steel sheet is improved by controlling the composition of such an intermetallic compound of the hot-dip galvanized layer formed prior to alloying.
- Japanese Unexamined Patent Application Publication No. 9-209106 discloses a steel sheet for use in alloyed hot-dip galvanized and an alloyed hot-dip galvanized steel sheet.
- This technique intends to form an alloyed hot-dip galvanized layer with satisfactory sliding property by controlling the composition of the base steel sheet.
- the composition of the hot-dip galvanized layer varies with changes in operating conditions of the plating process step and affects the sliding property of the resulting alloyed hot-dip galvanized layer. Accordingly, the technique disclosed in Japanese Unexamined Patent Application Publication No. 9-209106 cannot significantly yield satisfactory sliding property stably.
- Japanese Unexamined Patent Application Publication No. 11-200004 discloses an alloyed hot-dip galvanized steel sheet with excellent sliding property.
- This technique intends to manufacture an alloyed hot-dip galvanized steel sheet with high sliding property and resistance to plating adhesion failure by depositing a crystal mainly containing Ti and Al on the surface of the alloyed hot-dip galvanized layer.
- a plating bath must comprise Ti.
- the plating bath comprises Ti
- a Ti-Al intermetallic compound is formed and adheres to the hot-dip galvanized layer to cause problems in the surface appearance of the resulting galvanized steel sheet.
- an object of the present invention is to solve the above problems and to provide an alloyed hot-dip galvanized steel sheet stably exhibiting excellent sliding property.
- the present inventors have made detailed investigations on alloyed hot-dip galvanized layers with excellent sliding property.
- the present inventors have made investigations on electrolytic behavior of alloyed hot-dip galvanized layers by electrolyzing them according to a constant potential electrolysis using various alloyed hot-dip galvanized steel sheets as an anode and an aqueous zinc sulfate-sodium chloride solution as an electrolyte. Furthermore, the present inventors have made investigations on the relationship between the quantity of electricity required by the constant potential electrolysis and the sliding property.
- alloyed hot-dip galvanized steel sheets exhibiting a potential of less than or equal to a specific level when they are immersed in the electrolyte, have satisfactory sliding property and that alloyed hot-dip galvanized steel sheets, in which the total quantity of electricity consumed until the completion of electrolysis is less than or equal to a specific level, have satisfactory sliding property.
- the present invention has been accomplished based on these findings and further investigations.
- the invention provides an alloyed hot-dip galvanized steel sheet with excellent processability and particularly with excellent sliding property, exhibiting a potential to a saturated calomel electrode of less than or equal to -850 mV when it is immersed in a zinc sulfate-sodium chloride electrolyte.
- the invention also provides an alloyed hot-dip galvanized steel sheet with excellent processability and particularly with excellent sliding property in which, when the alloyed hot-dip galvanized steel sheet is electrolyzed according to a constant potential electrolysis process in a zinc sulfate-sodium chloride electrolyte at a potential to a saturated calomel electrode of from -940 mV to -920 mV, the quantity of electricity consumed is less than or equal to 0.5 C/cm 2 .
- the resulting alloyed hot-dip galvanized steel sheet exhibits preferable sliding property.
- Figs. 1 and 2 are a vertical sectional view and a perspective view, respectively, schematically illustrating an example of constant-potential electrolysis devices.
- the alloyed hot-dip galvanized steel sheet of the present invention satisfies the following requirement.
- the alloyed hot-dip galvanized steel sheet is electrolyzed according to the constant potential electrolysis process in a zinc sulfate-sodium chloride electrolyte at a potential to a saturated calomel electrode in a range of from -940 mV to -920 mV, the quantity of electricity consumed is less than or equal to 0.5 C/cm 2 .
- the alloyed hot-dip galvanized steel sheet is immersed in the electrolyte, it exhibits a potential to a saturated calomel electrode of less than or equal to -850 mV.
- Base steel sheets having some textures or surface dimensions do not always satisfy the both requirements, but the objects can be achieved only if either of the two requirements is satisfied.
- the alloyed hot-dip galvanized steel sheet exhibits satisfactory properties in various tests for determining sliding property.
- the end point of constant potential electrolysis is set at the time when an electrolysis current density decreases and reaches 5 ⁇ A/cm 2 .
- An example of such tests for determining sliding property is a cylindrical flat-bottom cup drawing test.
- the constant potential electrolysis is performed in a zinc sulfate-sodium chloride electrolytic solution using an alloyed hot-dip galvanized steel sheet as an anode at a potential to a saturated calomel electrode in a range of from -940 mV to -920 mV.
- the potential is set at -940 mV to -920 mV.
- the electrolysis is performed in a zinc sulfate-sodium chloride electrolyte, because this type of electrolyte hardly dissolves the alloyed hot-dip galvanized layer chemically and is hardly affected by an oxide film formed on the surface of the alloyed hot-dip galvanized layer.
- the type of the electrolyte is changed, the potential at which portions of the alloyed hot-dip galvanized layer which significantly affect the sliding property are selectively electrolyzed changes, and the change of the potential must be verified by a preliminary test.
- Figs. 1 and 2 illustrate an example of a constant potential electrolytic apparatus 1.
- the electrolytic apparatus 1 uses an alloyed hot-dip galvanized steel sheet (a test sample) 2 as an anode and a platinum ring or platinum sheet, for example, as a counter electrode (a cathode) 3.
- a device 7 for setting the potential via a platinum wire 5.
- the potential is preferably set using a potentiostat with a reference electrode (RE) 4 such as a saturated calomel electrode or a silver-silver chloride electrode.
- RE reference electrode
- an aqueous zinc sulfate-sodium chloride solution is used as an electrolyte 6.
- This type of electrolytes hardly dissolves the alloyed hot-dip galvanized layer chemically and is hardly affected by an oxide film formed on the surface of the alloyed hot-dip galvanized layer.
- the concentrations of zinc sulfate and of sodium chloride are preferably controlled to within ranges from 1 to 50 mass % and 1 to 30 mass %, respectively.
- the alloyed hot-dip galvanized steel sheet of the present invention is not specified by its manufacturing process, but can be manufactured, for example, by controlling alloying conditions according to procedures disclosed in Japanese Unexamined Patent Application Publications No. 7-41925 and No. 10-130802 and by further exactly controlling plating and alloying conditions. Particularly, the alloying operation should preferably be performed at temperatures higher than those in ordinary cases, by controlling the Al content in the zinc-coated layer at a high level.
- an alloyed hot-dip galvanized layer having characteristics of the alloyed hot-dip galvanized steel sheet of the present invention
- the following conditions are preferred: quantity of plating on a single side: 40 to 60 g/m 2 , Fe content in the zinc-coated layer: 9 to 13 mass %, Al content: 0.20 to 0.30 mass %, Pb content: 0.002 to 0.2 mass %, Mn content: 0.001 to 0.1 mass %, Si content: 0.0001 to 0.01 mass %, and P content: 0.0001 to 0.01 mass %.
- Mn, Si and P are not necessarily incorporated concurrently.
- the steel is not specifically limited in its grade, but is preferably a ultra low carbon steel (e.g., C 0.0020-Si 0.01-Mn 0.10-P 0.01-Al 0.030-Ti 0.025-Nb 0.010 mass %).
- a ultra low carbon steel e.g., C 0.0020-Si 0.01-Mn 0.10-P 0.01-Al 0.030-Ti 0.025-Nb 0.010 mass %.
- a test piece of a ultra low carbon steel having the composition shown in Table 1 was processed into an ingot in a converter, was then continuously cast and thereby yielded a slab.
- the slab was subjected to hot-rolling process at a slab heating temperature of 1150°C to 1250°C and a finished temperature in hot-rolling process of 920°C, was rolled at 550°C and thereby yielded a hot-rolled sheet coil 3.2 mm thick.
- the coil was subjected to acid pickling to remove mill scale, was subjected to cold rolling and thereby yielded a cold rolled steel sheet 0.8 mm thick.
- the cold rolled steel sheet was subjected to a continuous hot-dip galvanized line at an annealing temperature of 790°C to 830°C, a temperature of incoming sheet into the plating bath of 460°C to 470°C, a bath temperature of the plating bath of 460°C to 470°C, and an alloying temperature of 490°C to 530°C and thereby yielded an alloyed hot-dip galvanized steel sheet.
- the quantity of plating on a single side was set at 40 to 50 g/m 2 , and the quantity of plating a single on both sides were controlled to be equal to each other.
- the alloyed hot-dip galvanized steel sheet was stamped into a disc shape 15 mm in diameter and was subjected to constant potential electrolysis at a potential to a saturated calomel electrode of -930 mV using 20 mass % zinc sulfate-10 mass % sodium chloride aqueous solution as an electrolyte.
- the electrolysis was performed until a current density became 5 ⁇ A/cm 2 or below, and the quantity of electricity consumed from the beginning of electrolysis was determined. It took about 10 to 20 minutes for electrolysis.
- the end point of constant potential electrolysis was set at the time when an electrolysis current density decreased to 5 ⁇ A/cm 2 . However, sice the current is low in the vicinity of the end point, even if a current density level somewhat lower than the above specified current density would be employed, since there is not influence upon determination of quantity of electricity, and accordingly accurate estimation can be made.
- the immersing potential of the test piece to a saturated calomel electrode in the aforementioned electrolyte was determined.
- a conventional rust preventive oil was applied to the alloyed hot-dip galvanized steel sheet in an amount of 1.5 g/m 2 , the alloyed hot-dip galvanized steel sheet was then subjected to a drawing test using a cylindrical flat-bottom cup 33 mm in diameter to determine a limiting drawing ratio.
- the limiting drawing ratio was rated as follows: the limiting drawing ratio of equal to or more than 2.0%: Rating 1, from 1.9% to 2.0%: Rating 2, from 1.8% to 1.9%: Rating 3, from 1.7% to 1.8%: Rating 4, and less than or equal to 1.7%: Rating 5. The results are shown in Table 2.
- the present invention can provide an alloyed hot-dip galvanized steel sheet stably exhibiting excellent sliding property.
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Abstract
Description
- The present invention relates to an alloyed hot-dip galvanized steel sheet with excellent sliding property which is suitable as an anti-corrosive steel sheet for use in car bodies.
- Alloyed hot-dip galvanized steel sheets are widely used as anti-corrosive steel sheets for use in car bodies. The alloyed hot-dip galvanized steel sheets are molded into car bodies by pressing and must therefore be excellent not only in anti-corrosive properties but also in sliding properties.
- Process steps for manufacturing an alloyed hot-dip galvanized steel sheet are broadly divided into the process step of immersing a material steel sheet in a plating bath to form a hot-dip galvanized layer on the surface of the steel sheet, and the step of subjecting the steel sheet carrying the hot-dip galvanized layer to alloying to thereby form an alloyed hot-dip galvanized layer.
- The hot-dip galvanized layer formed on the surface of the steel sheet in the plating bath comprises an intermetallic compound of Zn and Fe (ζ, δ1, Γ), and the sliding property of the alloyed hot-dip galvanized layer formed by alloying varies depending on the composition of the intermetallic compound. Various techniques have therefore been proposed in which the sliding property of an alloyed hot-dip galvanized steel sheet is improved by controlling the composition of such an intermetallic compound of the hot-dip galvanized layer formed prior to alloying.
- For example, Japanese Unexamined Patent Application Publication No. 9-209106 discloses a steel sheet for use in alloyed hot-dip galvanized and an alloyed hot-dip galvanized steel sheet. This technique intends to form an alloyed hot-dip galvanized layer with satisfactory sliding property by controlling the composition of the base steel sheet. However, the composition of the hot-dip galvanized layer varies with changes in operating conditions of the plating process step and affects the sliding property of the resulting alloyed hot-dip galvanized layer. Accordingly, the technique disclosed in Japanese Unexamined Patent Application Publication No. 9-209106 cannot significantly yield satisfactory sliding property stably.
- Japanese Unexamined Patent Application Publication No. 11-200004 discloses an alloyed hot-dip galvanized steel sheet with excellent sliding property. This technique intends to manufacture an alloyed hot-dip galvanized steel sheet with high sliding property and resistance to plating adhesion failure by depositing a crystal mainly containing Ti and Al on the surface of the alloyed hot-dip galvanized layer. To deposit a crystal mainly containing Ti and Al, a plating bath must comprise Ti. However, when the plating bath comprises Ti, a Ti-Al intermetallic compound (so-called "dross") is formed and adheres to the hot-dip galvanized layer to cause problems in the surface appearance of the resulting galvanized steel sheet.
- Accordingly, an object of the present invention is to solve the above problems and to provide an alloyed hot-dip galvanized steel sheet stably exhibiting excellent sliding property.
- The present inventors have made detailed investigations on alloyed hot-dip galvanized layers with excellent sliding property.
- Specifically, the present inventors have made investigations on electrolytic behavior of alloyed hot-dip galvanized layers by electrolyzing them according to a constant potential electrolysis using various alloyed hot-dip galvanized steel sheets as an anode and an aqueous zinc sulfate-sodium chloride solution as an electrolyte. Furthermore, the present inventors have made investigations on the relationship between the quantity of electricity required by the constant potential electrolysis and the sliding property. As a result, they have found that alloyed hot-dip galvanized steel sheets exhibiting a potential of less than or equal to a specific level, when they are immersed in the electrolyte, have satisfactory sliding property and that alloyed hot-dip galvanized steel sheets, in which the total quantity of electricity consumed until the completion of electrolysis is less than or equal to a specific level, have satisfactory sliding property.
- The present invention has been accomplished based on these findings and further investigations.
- Specifically, the invention provides an alloyed hot-dip galvanized steel sheet with excellent processability and particularly with excellent sliding property, exhibiting a potential to a saturated calomel electrode of less than or equal to -850 mV when it is immersed in a zinc sulfate-sodium chloride electrolyte. The invention also provides an alloyed hot-dip galvanized steel sheet with excellent processability and particularly with excellent sliding property in which, when the alloyed hot-dip galvanized steel sheet is electrolyzed according to a constant potential electrolysis process in a zinc sulfate-sodium chloride electrolyte at a potential to a saturated calomel electrode of from -940 mV to -920 mV, the quantity of electricity consumed is less than or equal to 0.5 C/cm2.
- When the quantity of the electricity is less than or equal to 0.3 C/cm2, the resulting alloyed hot-dip galvanized steel sheet exhibits preferable sliding property.
- Figs. 1 and 2 are a vertical sectional view and a perspective view, respectively, schematically illustrating an example of constant-potential electrolysis devices.
- The alloyed hot-dip galvanized steel sheet of the present invention satisfies the following requirement. When the alloyed hot-dip galvanized steel sheet is electrolyzed according to the constant potential electrolysis process in a zinc sulfate-sodium chloride electrolyte at a potential to a saturated calomel electrode in a range of from -940 mV to -920 mV, the quantity of electricity consumed is less than or equal to 0.5 C/cm2. Alternatively, when the alloyed hot-dip galvanized steel sheet is immersed in the electrolyte, it exhibits a potential to a saturated calomel electrode of less than or equal to -850 mV. Base steel sheets having some textures or surface dimensions do not always satisfy the both requirements, but the objects can be achieved only if either of the two requirements is satisfied.
- When the quantity of electricity consumed during constant potential electrolysis is less than or equal to 0.5 C/cm2, the alloyed hot-dip galvanized steel sheet exhibits satisfactory properties in various tests for determining sliding property. The end point of constant potential electrolysis is set at the time when an electrolysis current density decreases and reaches 5 µA/cm2. An example of such tests for determining sliding property is a cylindrical flat-bottom cup drawing test. The constant potential electrolysis is performed in a zinc sulfate-sodium chloride electrolytic solution using an alloyed hot-dip galvanized steel sheet as an anode at a potential to a saturated calomel electrode in a range of from -940 mV to -920 mV. To electrolyze portions of the alloyed hot-dip galvanized layer which significantly affect the sliding property selectively, the potential is set at -940 mV to -920 mV. The electrolysis is performed in a zinc sulfate-sodium chloride electrolyte, because this type of electrolyte hardly dissolves the alloyed hot-dip galvanized layer chemically and is hardly affected by an oxide film formed on the surface of the alloyed hot-dip galvanized layer. When the type of the electrolyte is changed, the potential at which portions of the alloyed hot-dip galvanized layer which significantly affect the sliding property are selectively electrolyzed changes, and the change of the potential must be verified by a preliminary test.
- In general, the lower is the potential of the alloyed hot-dip galvanized steel sheet when it is immersed in the electrolyte, the lower is the quantity of electricity consumed during constant potential electrolysis. Figs. 1 and 2 illustrate an example of a constant potential electrolytic apparatus 1. The electrolytic apparatus 1 uses an alloyed hot-dip galvanized steel sheet (a test sample) 2 as an anode and a platinum ring or platinum sheet, for example, as a counter electrode (a cathode) 3. Each of these components is connected to a device 7 for setting the potential via a
platinum wire 5. The potential is preferably set using a potentiostat with a reference electrode (RE) 4 such as a saturated calomel electrode or a silver-silver chloride electrode. - As an
electrolyte 6, an aqueous zinc sulfate-sodium chloride solution is used. This type of electrolytes hardly dissolves the alloyed hot-dip galvanized layer chemically and is hardly affected by an oxide film formed on the surface of the alloyed hot-dip galvanized layer. The concentrations of zinc sulfate and of sodium chloride are preferably controlled to within ranges from 1 to 50 mass % and 1 to 30 mass %, respectively. The alloyed hot-dip galvanized steel sheet of the present invention is not specified by its manufacturing process, but can be manufactured, for example, by controlling alloying conditions according to procedures disclosed in Japanese Unexamined Patent Application Publications No. 7-41925 and No. 10-130802 and by further exactly controlling plating and alloying conditions. Particularly, the alloying operation should preferably be performed at temperatures higher than those in ordinary cases, by controlling the Al content in the zinc-coated layer at a high level. - To form an alloyed hot-dip galvanized layer having characteristics of the alloyed hot-dip galvanized steel sheet of the present invention, the following conditions are preferred: quantity of plating on a single side: 40 to 60 g/m2, Fe content in the zinc-coated layer: 9 to 13 mass %, Al content: 0.20 to 0.30 mass %, Pb content: 0.002 to 0.2 mass %, Mn content: 0.001 to 0.1 mass %, Si content: 0.0001 to 0.01 mass %, and P content: 0.0001 to 0.01 mass %. Mn, Si and P are not necessarily incorporated concurrently.
- The steel is not specifically limited in its grade, but is preferably a ultra low carbon steel (e.g., C 0.0020-Si 0.01-Mn 0.10-P 0.01-Al 0.030-Ti 0.025-Nb 0.010 mass %). In particular, by satisfying either or both requirements of B content of 0.0002 to 0.015 mass % and Sb content of 0.002 to 0.015 mass %, a steel sheet having a significantly highly slidable galvanized layer can be manufactured.
- A test piece of a ultra low carbon steel having the composition shown in Table 1 was processed into an ingot in a converter, was then continuously cast and thereby yielded a slab. The slab was subjected to hot-rolling process at a slab heating temperature of 1150°C to 1250°C and a finished temperature in hot-rolling process of 920°C, was rolled at 550°C and thereby yielded a hot-rolled sheet coil 3.2 mm thick. The coil was subjected to acid pickling to remove mill scale, was subjected to cold rolling and thereby yielded a cold rolled steel sheet 0.8 mm thick.
C
(mass %)Si
(mass %)Mn
(mass %)P
(mass %)Al
(mass %)Ti
(mass %)Nb
(mass %)Sb
(mass %)B
(mass %)0.0020 0.01 0.10 0.01 0.030 0.025 0.010 0.007 0.0005 - The cold rolled steel sheet was subjected to a continuous hot-dip galvanized line at an annealing temperature of 790°C to 830°C, a temperature of incoming sheet into the plating bath of 460°C to 470°C, a bath temperature of the plating bath of 460°C to 470°C, and an alloying temperature of 490°C to 530°C and thereby yielded an alloyed hot-dip galvanized steel sheet. The quantity of plating on a single side was set at 40 to 50 g/m2, and the quantity of plating a single on both sides were controlled to be equal to each other.
- The alloyed hot-dip galvanized steel sheet was stamped into a disc shape 15 mm in diameter and was subjected to constant potential electrolysis at a potential to a saturated calomel electrode of -930 mV using 20 mass % zinc sulfate-10 mass % sodium chloride aqueous solution as an electrolyte. The electrolysis was performed until a current density became 5 µA/cm2 or below, and the quantity of electricity consumed from the beginning of electrolysis was determined. It took about 10 to 20 minutes for electrolysis. The end point of constant potential electrolysis was set at the time when an electrolysis current density decreased to 5 µA/cm2. However, sice the current is low in the vicinity of the end point, even if a current density level somewhat lower than the above specified current density would be employed, since there is not influence upon determination of quantity of electricity, and accordingly accurate estimation can be made.
- Separately, using the steel sheet stamped into the disc shape as a test piece, the immersing potential of the test piece to a saturated calomel electrode in the aforementioned electrolyte was determined.
- To estimate sliding property for comparison, a conventional rust preventive oil was applied to the alloyed hot-dip galvanized steel sheet in an amount of 1.5 g/m2, the alloyed hot-dip galvanized steel sheet was then subjected to a drawing test using a cylindrical flat-bottom cup 33 mm in diameter to determine a limiting drawing ratio. The lower the rating of the limiting drawing ratio is, the higher the sliding property is. The limiting drawing ratio was rated as follows: the limiting drawing ratio of equal to or more than 2.0%: Rating 1, from 1.9% to 2.0%:
Rating 2, from 1.8% to 1.9%:Rating 3, from 1.7% to 1.8%: Rating 4, and less than or equal to 1.7%:Rating 5. The results are shown in Table 2.Quantity of Plating on single side
(g/m2)Content in plating layer Potential upon immersing
(mV vs SCE)Quantity of electricity during constant potential electrolysis
(C/cm2)Sliding property rating Zn
(mass %)Fe
(mass %)Inventive Example 1 40 90.4 9.6 -900 0.13 1 Inventive Example 2 47 88.3 11.6 -880 0.16 1 Inventive Example 3 40 88.5 11.5 -886 0.21 1 Inventive Example 4 45 89.6 10.4 -870 0.30 1 Inventive Example 5 43 90.1 9.9 -852 0.47 3 Inventive Example 6 45 90.8 9.2 -845 0.47 3 Inventive Example 7 47 91.0 9.0 -854 0.52 3 Comp. Ex. 42 90.0 10.0 -825 0.55 5 - The zinc-coated steel sheet according to Comparative Example in which the quantity of electricity exceeds 0.5 C/cm2 exhibits deteriorated sliding property of "
Rating 5". In contrast, the galvanized steel sheets in which the quantity of electricity is less than or equal to 0.5 C/cm2 exhibit satisfactory sliding property of "Rating 3" or below. Particularly, all the galvanized steel sheets in which the quantity of electricity is less than or equal to 0.3 C/cm2 exhibit significantly satisfactory sliding property of "Rating 1". - In addition, all the steel sheets exhibiting an immersing potential of less than or equal to -850 mV exhibit satisfactory sliding property of "
Rating 3" or below. - The present invention can provide an alloyed hot-dip galvanized steel sheet stably exhibiting excellent sliding property.
Claims (2)
- An alloyed hot-dip galvanized steel sheet with excellent processability and particularly with excellent sliding property, wherein, when the alloyed hot-dip galvanized steel sheet is electrolyzed according to a constant potential electrolysis process in a zinc sulfate-sodium chloride electrolyte at a potential to a saturated calomel electrode in a range of from -940 mV to -920 mV, the quantity of electricity passing therethrough is less than or equal to 0.5 C/cm2.
- An alloyed hot-dip galvanized steel sheet with excellent processability and particularly with excellent sliding property, exhibiting a potential to a saturated calomel electrode of less than or equal to -850 mV when the alloyed hot-dip galvanized steel sheet is immersed in a zinc sulfate-sodium chloride electrolyte.
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JP2001158364 | 2001-05-28 | ||
JP2001158364 | 2001-05-28 | ||
PCT/JP2001/010612 WO2002097151A1 (en) | 2001-05-28 | 2001-12-05 | Alloy galvanized steel plate having excellent slidability |
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EP1391530A1 true EP1391530A1 (en) | 2004-02-25 |
EP1391530A4 EP1391530A4 (en) | 2005-11-23 |
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EP01274269A Withdrawn EP1391530A4 (en) | 2001-05-28 | 2001-12-05 | Alloy galvanized steel plate having excellent slidability |
Country Status (6)
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EP (1) | EP1391530A4 (en) |
KR (1) | KR20030023635A (en) |
CN (1) | CN1443251A (en) |
CA (1) | CA2411879A1 (en) |
TW (1) | TWI245080B (en) |
WO (1) | WO2002097151A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2864552A1 (en) * | 2003-12-24 | 2005-07-01 | Usinor | Utilisation of an aqueous treatment solution containing sulphate ions for treating the surface of galvanised steel sheet to provide temporary corrosion protection and lubrication during shaping |
Families Citing this family (1)
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KR100961371B1 (en) * | 2007-12-28 | 2010-06-07 | 주식회사 포스코 | ZINC ALLOY COATED STEEL SHEET HAVING GOOD SEALER ADHESION and CORROSION RESISTANCE AND PROCESS OF MANUFACTURING THE SAME |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1025597A (en) * | 1996-07-12 | 1998-01-27 | Nkk Corp | Production of galvanized steel sheet |
JPH1088309A (en) * | 1996-09-17 | 1998-04-07 | Kawasaki Steel Corp | Galvannealed steel sheet excellent in slidability and cratering resistance in electrodeposition coating and its production |
JPH11200004A (en) * | 1998-01-21 | 1999-07-27 | Kobe Steel Ltd | Galvannealed steel sheet excellent in slidability |
JP2000017417A (en) * | 1998-07-03 | 2000-01-18 | Kawasaki Steel Corp | Hot dip galvannealed steel sheet |
EP1273912A1 (en) * | 2000-12-05 | 2003-01-08 | Kawasaki Steel Corporation | Method for determining alloy phase in plating layer and method for evaluating sliding property of alloy galvanized steel plate |
Family Cites Families (1)
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JP2000192209A (en) * | 1998-12-25 | 2000-07-11 | Nippon Steel Corp | Aluminum-containing plated steel sheet excellent in corrosion resistance after coating |
-
2001
- 2001-12-05 KR KR1020027016608A patent/KR20030023635A/en not_active Application Discontinuation
- 2001-12-05 EP EP01274269A patent/EP1391530A4/en not_active Withdrawn
- 2001-12-05 CN CN01813079A patent/CN1443251A/en active Pending
- 2001-12-05 WO PCT/JP2001/010612 patent/WO2002097151A1/en not_active Application Discontinuation
- 2001-12-05 TW TW090130128A patent/TWI245080B/en not_active IP Right Cessation
- 2001-12-05 CA CA002411879A patent/CA2411879A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1025597A (en) * | 1996-07-12 | 1998-01-27 | Nkk Corp | Production of galvanized steel sheet |
JPH1088309A (en) * | 1996-09-17 | 1998-04-07 | Kawasaki Steel Corp | Galvannealed steel sheet excellent in slidability and cratering resistance in electrodeposition coating and its production |
JPH11200004A (en) * | 1998-01-21 | 1999-07-27 | Kobe Steel Ltd | Galvannealed steel sheet excellent in slidability |
JP2000017417A (en) * | 1998-07-03 | 2000-01-18 | Kawasaki Steel Corp | Hot dip galvannealed steel sheet |
EP1273912A1 (en) * | 2000-12-05 | 2003-01-08 | Kawasaki Steel Corporation | Method for determining alloy phase in plating layer and method for evaluating sliding property of alloy galvanized steel plate |
Non-Patent Citations (6)
Title |
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PATENT ABSTRACTS OF JAPAN vol. 1998, no. 05, 30 April 1998 (1998-04-30) -& JP 10 025597 A (NKK CORP), 27 January 1998 (1998-01-27) * |
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 09, 31 July 1998 (1998-07-31) -& JP 10 088309 A (KAWASAKI STEEL CORP), 7 April 1998 (1998-04-07) * |
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 12, 29 October 1999 (1999-10-29) -& JP 11 200004 A (KOBE STEEL LTD), 27 July 1999 (1999-07-27) * |
PATENT ABSTRACTS OF JAPAN vol. 2000, no. 04, 31 August 2000 (2000-08-31) -& JP 2000 017417 A (KAWASAKI STEEL CORP), 18 January 2000 (2000-01-18) * |
See also references of WO02097151A1 * |
YUTAKA TSURU ET AL: "Study on determing the composition of copper-zinc alloy deposits by anodic chronoamperometry" HYOMEN GIJUTSU - JOURNAL OF THE SURFACE FINISHING SOCIETY OF JAPAN, HYOMEN GIJUTSU KYOKAI, TOKYO, JP, vol. 40, no. 9, 1989, pages 1026-1030, XP002907932 ISSN: 0915-1869 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2864552A1 (en) * | 2003-12-24 | 2005-07-01 | Usinor | Utilisation of an aqueous treatment solution containing sulphate ions for treating the surface of galvanised steel sheet to provide temporary corrosion protection and lubrication during shaping |
WO2005071140A1 (en) * | 2003-12-24 | 2005-08-04 | Usinor | Hydroxysulfate surface treatment |
EP2450470A1 (en) * | 2003-12-24 | 2012-05-09 | Arcelormittal France | Surface treatment by hydroxysulphate |
Also Published As
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CN1443251A (en) | 2003-09-17 |
KR20030023635A (en) | 2003-03-19 |
EP1391530A4 (en) | 2005-11-23 |
CA2411879A1 (en) | 2002-12-04 |
WO2002097151A1 (en) | 2002-12-05 |
TWI245080B (en) | 2005-12-11 |
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