EP1391530A1 - Galvanisierte stahlplatte mit ausgezeichneter gleiteigenschaft - Google Patents

Galvanisierte stahlplatte mit ausgezeichneter gleiteigenschaft Download PDF

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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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EP
European Patent Office
Prior art keywords
steel sheet
dip galvanized
alloyed hot
galvanized steel
potential
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01274269A
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English (en)
French (fr)
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EP1391530A4 (de
Inventor
Kyoko c/o Kawasaki Steel Corporation FUJIMOTO
Makoto c/o Kawasaki Steel Corporation SHIMURA
Susumu c/o Kawasaki Steel Corporation Satoh
Yoichi c/o Kawasaki Steel Corporation TOBIYAMA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Steel Corp
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JFE Steel Corp
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Filing date
Publication date
Application filed by JFE Steel Corp filed Critical JFE Steel Corp
Publication of EP1391530A1 publication Critical patent/EP1391530A1/de
Publication of EP1391530A4 publication Critical patent/EP1391530A4/de
Withdrawn legal-status Critical Current

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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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Thermal Sciences (AREA)
  • Electrochemistry (AREA)
  • Coating With Molten Metal (AREA)
EP01274269A 2001-05-28 2001-12-05 Galvanisierte stahlplatte mit ausgezeichneter gleiteigenschaft Withdrawn EP1391530A4 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2001158364 2001-05-28
JP2001158364 2001-05-28
PCT/JP2001/010612 WO2002097151A1 (fr) 2001-05-28 2001-12-05 Plaque d'acier galvanise par alliage, presentant d'excellentes proprietes de glissement

Publications (2)

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EP1391530A1 true EP1391530A1 (de) 2004-02-25
EP1391530A4 EP1391530A4 (de) 2005-11-23

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EP01274269A Withdrawn EP1391530A4 (de) 2001-05-28 2001-12-05 Galvanisierte stahlplatte mit ausgezeichneter gleiteigenschaft

Country Status (6)

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EP (1) EP1391530A4 (de)
KR (1) KR20030023635A (de)
CN (1) CN1443251A (de)
CA (1) CA2411879A1 (de)
TW (1) TWI245080B (de)
WO (1) WO2002097151A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2864552A1 (fr) * 2003-12-24 2005-07-01 Usinor Traitement de surface par hydroxysulfate

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100961371B1 (ko) * 2007-12-28 2010-06-07 주식회사 포스코 실러 접착성 및 내식성이 우수한 아연계 합금도금강판과 그제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1025597A (ja) * 1996-07-12 1998-01-27 Nkk Corp 亜鉛系メッキ鋼板の製造方法
JPH1088309A (ja) * 1996-09-17 1998-04-07 Kawasaki Steel Corp 摺動性及び電着塗装時の耐クレータリング性に優れた合金化溶融亜鉛めっき鋼板及びその製造方法
JPH11200004A (ja) * 1998-01-21 1999-07-27 Kobe Steel Ltd 摺動性に優れた合金化溶融亜鉛めっき鋼板
JP2000017417A (ja) * 1998-07-03 2000-01-18 Kawasaki Steel Corp 合金化溶融亜鉛めっき鋼板
EP1273912A1 (de) * 2000-12-05 2003-01-08 Kawasaki Steel Corporation Verfahren zur feststellung der legierungsphase in plattierungsschichten und verfahren zur feststellung der gleitfähigkeit von hochfesten galvanisierten stahlplatten

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000192209A (ja) * 1998-12-25 2000-07-11 Nippon Steel Corp 塗装後耐食性に優れたアルミ含有めっき鋼板

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1025597A (ja) * 1996-07-12 1998-01-27 Nkk Corp 亜鉛系メッキ鋼板の製造方法
JPH1088309A (ja) * 1996-09-17 1998-04-07 Kawasaki Steel Corp 摺動性及び電着塗装時の耐クレータリング性に優れた合金化溶融亜鉛めっき鋼板及びその製造方法
JPH11200004A (ja) * 1998-01-21 1999-07-27 Kobe Steel Ltd 摺動性に優れた合金化溶融亜鉛めっき鋼板
JP2000017417A (ja) * 1998-07-03 2000-01-18 Kawasaki Steel Corp 合金化溶融亜鉛めっき鋼板
EP1273912A1 (de) * 2000-12-05 2003-01-08 Kawasaki Steel Corporation Verfahren zur feststellung der legierungsphase in plattierungsschichten und verfahren zur feststellung der gleitfähigkeit von hochfesten galvanisierten stahlplatten

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2864552A1 (fr) * 2003-12-24 2005-07-01 Usinor Traitement de surface par hydroxysulfate
WO2005071140A1 (fr) * 2003-12-24 2005-08-04 Usinor Traitement de surface par hydroxysulfate
EP2450470A1 (de) * 2003-12-24 2012-05-09 Arcelormittal France Hydroxysulfat-Oberflächenbehandlung

Also Published As

Publication number Publication date
EP1391530A4 (de) 2005-11-23
WO2002097151A1 (fr) 2002-12-05
KR20030023635A (ko) 2003-03-19
CN1443251A (zh) 2003-09-17
TWI245080B (en) 2005-12-11
CA2411879A1 (en) 2002-12-04

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