EP1115914B1 - Toles d'acier zingue revetues d'une couche prelubrifiante d'hydroxysulfate et procedes d'obtention de cette tole - Google Patents

Toles d'acier zingue revetues d'une couche prelubrifiante d'hydroxysulfate et procedes d'obtention de cette tole Download PDF

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Publication number
EP1115914B1
EP1115914B1 EP99941724A EP99941724A EP1115914B1 EP 1115914 B1 EP1115914 B1 EP 1115914B1 EP 99941724 A EP99941724 A EP 99941724A EP 99941724 A EP99941724 A EP 99941724A EP 1115914 B1 EP1115914 B1 EP 1115914B1
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EP
European Patent Office
Prior art keywords
zinc
treatment
ions
solution
coated
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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.)
Expired - Lifetime
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EP99941724A
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German (de)
English (en)
French (fr)
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EP1115914A1 (fr
Inventor
Alain Bello
Sylviane Wajda
Jacques Petitjean
Armand Rossi
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Sollac SA
Original Assignee
Sollac SA
Lorraine de Laminage Continu SA SOLLAC
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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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12583—Component contains compound of adjacent metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]

Definitions

  • the invention relates to the prelubrication of the galvanized surface of metal sheets coated with zinc or zinc-based alloy and the treatment of these sheets in aqueous solutions containing sulphates.
  • JP 61-60915, 63-46158, 63-46159 and EP 0 339 578 describe anodic treatments of galvanized steel sheets in solutions aqueous substances containing sulphates and the use of these treatments to color the galvanized surfaces of these sheets.
  • the concentration of electrolyte in the treatment solution is included between 70 and 200 g / l; the concentration of sodium sulphate is, for example, 150 g / l, ie about 1 mole / liter.
  • JP 63-274797 discloses the use of a treatment of the same type to improve the phosphatibility of coated steel sheets by electrodeposition of a nickel-based alloy containing nickel.
  • the treatment solution then contains, besides the sulphates (for example: magnesium, sodium or aluminum sulfate at 150 g / l), acids carboxylic acids (for example: citric, maleic, salicylic at 30 or 40 g / l).
  • sulphates for example: magnesium, sodium or aluminum sulfate at 150 g / l
  • acids carboxylic acids for example: citric, maleic, salicylic at 30 or 40 g / l.
  • the pH of the treatment solution is between 4 and 5.5.
  • the anodic treatment is conducted at a current density of between 30 and 200 A / dm 2 until the quantity of electricity consumed is between 50 and 500 C / dm 2 of surface to be treated.
  • this treatment improves phosphatibility because it results in the elimination of surface traces of zinc hydroxide Zn (OH) 2 - and improves the surface reactivity.
  • the conditions of application and drying are adapted to obtain a phosphate deposition of density of between 5 and 40 mg / m 2 .
  • the oil used can be a temporary protection oil against corrosion and / or lubricating oil for shaping, in particular stamping.
  • a first oiling can be carried out protection ; after destocking, we can carry out a second oiling of lubrication to prepare the shaping, especially by stamping.
  • the phosphating treatment, 5 prior to oiling can significantly improve the lubrication at the moment of formatting: this is therefore a prelubrication treatment.
  • the galvanized sheet obtained is provided with a pre-lubricating depot based on phosphate.
  • the object of the invention is to provide a pre-lubricated galvanized sheet more performing better than those obtained by phosphating and offering treatment pre-lubrication of galvanized sheets more efficient than a treatment of phosphating and more environmentally friendly at the level of effluents that it generates.
  • the prelubricant obtained is greater than that provided by a treatment in a phosphate solution as described in EP 0 489 105.
  • this layer of zinc hydroxysulfate adheres to the treated surface: the conditions relating to the pH of the treatment solution and the drying step at the end of treatment are crucial for this purpose.
  • the layer deposited on the sheet After rinsing but before drying, the layer deposited on the sheet has the appearance of a gel still not adherent; drying is suitable for eliminate the residual liquid water from the deposit and makes it easier to adhere the layer on the sheet.
  • the prelubricating effect of the treatment is obtained only if the thickness of the deposited layer corresponds to more than 0.5 mg / m 2 in sulfur equivalent, preferably at least 3.5 mg / m 2 in sulfur equivalent.
  • the prelubricant effect of the hydroxysulphate layer decreased if the amount of sulfur deposited was well above 30 mg / m 2 , apparently due to the degradation of the adhesion of the hydroxysulfate layer. this layer; it was also found that if the amount of sulfur deposited exceeded 27 mg / m 2 , the phosphatability of the sheet obtained was degraded, the deposited phosphate crystals then being too large.
  • the amount of hydroxysulfates deposited should be greater than 0.5 mg / m 2 and less than or equal to 30 mg / m 2 in sulfur equivalent, preferably between 3.5 and 27 mg / m 2 in sulfur equivalent.
  • the applied charge density is adapted to this amount of hydroxysulfates capable of providing this significant prelubricant effect.
  • the charge density applied is preferably between 10 and 100 C / dm 2 of surface to be treated.
  • This first method of obtaining a sheet according to the invention therefore allows forming on a galvanized surface a layer based on hydroxysulphate, at the once thick enough and adherent.
  • the deposition efficiency is very low and the sulfur content of the deposited layer does not provide the optimum prelube effect.
  • the temperature of the treatment solution is generally understood between 20 ° C and 60 ° C; preferably, one proceeds to a higher temperature or equal to 40 ° C, so as to increase the conductivity of the solution and to reduce ohmic losses.
  • the speed of circulation of the solution on the surface of the sheet has not, here, of determining incidence on the treatment according to the invention.
  • the rinsing step is important to remove the reagents alkaline on the surface of the deposit, which would cause corrosion problems.
  • the sheet thus prelubricated by the treatment according to the invention has a homogeneous coloring, a little more sustained compared to that of a sheet metal untreated galvanized; this treatment, however, does not color the sheet, as in JP 61-60915, 63-46158, 63-46-159 and EP 0 339 578 already cited; observed under the microscope, the deposit resulting from the treatment according to the invention is in the form of sparse plates; it has been noticed that the density of plates increased with the amount of sulfur deposited per unit area.
  • the zinc necessary for the formation of the pre-lubricant deposit of zinc hydroxysulfate comes from the anodic dissolution of zinc under the effect polarization of the galvanized surface.
  • This first method of obtaining obviously has the disadvantage cost effective to require a polarization facility.
  • This second method of obtaining a sheet according to the invention does not require no polarization installation.
  • the pH of the treatment solution used for this second process is generally much less basic than that of the treatment solution used for the first method; the pH of the treatment solution corresponds preferably at the natural pH of the solution, without addition of base or acid; the value of this pH is generally between 5 and 7.
  • the treatment solution is applied to a galvanized sheet metal surface in a conventional manner, for example by dipping, spraying or coating.
  • the drying is adapted to remove residual liquid water from the deposit.
  • the sheet so as to eliminate the soluble part of the deposit obtained; the absence of rinsing and obtaining a partially solubilisable deposit with water which result are not very detrimental to the pre-lubricating effect, as long as the obtained deposit includes the prelubricating layer of insoluble hydroxysulfate with water in contact with the sheet.
  • these parameters are optimized in a manner known per se to obtain a deposition of hydroxysulfate according to the invention, ie containing a quantity of sulfur greater than 0.5 mg / m 2 .
  • the treatment solution contains an oxidizing agent for zinc, such as hydrogen peroxide; this oxidizing agent can have a very marked hydroxysulfation accelerating effect at low concentration; it was found that the addition of only 0.03%, ie 8 10 -3 mole / liter of hydrogen peroxide, or 2 ⁇ 10 -4 mole / liter of potassium permanganate in the solution allowed to double (approximately) the deposit rate; it has been found, on the contrary, that concentrations 100 times higher no longer made it possible to obtain this improvement in the rate of deposition.
  • an oxidizing agent for zinc such as hydrogen peroxide
  • the invention has Finally, a method of forming a steel sheet coated with a zinc-based metal layer comprising the steps of treating the surface of said coated sheet according to the first or second method described above, applying a film of lubricating oil to said treated treated surface and to shape strictly said sheet.
  • the sulphate used for the second process according to the invention is zinc sulphate heptahydrate ZnSO 4 , 7 H 2 O.
  • stamping press adapted to realize buckets 50 mm inner diameter from sheet blanks diameter 90 mm; a punch having a diameter of 50 mm and having at the end a radius of curvature of 3 mm, a matrix of diameter 52.6 mm having a inner rim of radius of curvature 3.5 mm.
  • the stamping speed is set at 12 cm / min. ; the maximum force of blank is 150 kN.
  • the press is equipped with means of continuous control of the parameters stamping, in particular the blanking pressure, the stamping force and the punch race.
  • a weak slope corresponds to low friction, that is to say to well-lubricated sheets on both sides.
  • This stamping test protocol therefore makes it possible to evaluate the level of lubrication of the surface of a sheet for stamping; to evaluate this level on one side, we affix on the other side a film of Teflon ® (punch side) so as to obtain on this other face a friction always constant with regard to the one exercising on the surface to be evaluated.
  • this protocol is applied to prelubricated sheets by pretreatment and oiled in a standard manner (with Teflon ® film on the untreated side ); the standard oiling consists here of applying, on the treated surface, the oil referenced 6130 of the QUAKER Company so as to obtain a layer of 1 g / m 2 approximately.
  • the sheet samples are phosphated according to a predetermined protocol corresponding to conventional methods practiced in the automotive industry, using several conventional baths of surface treatment adapted to form a layer of phosphates of zinc, manganese and nickel; we can use the baths marketed for this purpose by the PARKER Companies or CFPI; so we generally use and successively: one or two alkaline degreasing baths, a refining bath, then a phosphating bath; each step is followed by rinsing with water.
  • deposited phosphates layer in particular in terms of morphology and chemical composition; for this purpose, electron microscopy is used for scanning and atomic absorption spectroscopy.
  • Sheet metal sample processing is carried out in a "cell to electrolyte circulation "where they are immersed in this solution brought to 40 ° C, and where they are polarized anodically with respect to a titanium cathode ; the "electrolyte circulation cell” is set so that the speed of the electrolyte in the vicinity and along the surface of the sheet to be treated is 100 m / min.
  • the surface of the samples is then analyzed in order to measure the amount of sulfur deposited on the surface; we also measure the amount of sodium on the surface; the results are reported in Table I.
  • Sulfur is measured by X-ray fluorescence ("SFX"); the depth taken into account by this method of analysis is several microns; as the galvanized steel substrate does not contain sulfur (except quantities corresponding to unavoidable impurities), the signal given by this method of dosing then corresponds effectively to deposited sulfur during treatment; the amount of sulfur deposited is calculated from the signal measured, according to a pre-established law.
  • SFX X-ray fluorescence
  • AAS Atomic Absorption Spectroscopy
  • the amount of sodium observed at the surface of the reference sample is quite conventional for an electrogalvanized steel; quantities Approximately identical readings from treated samples indicate that the sodium from the treatment solution does not incorporate the deposit-based hydroxysulphate.
  • Example 1 On the same sheet samples as in Example 1, a comparative treatment under anodic polarization (charge density: 12 C / dm 2 - current density: 9.8 A / dm 2 ) was carried out in a solution at room temperature. Same temperature and at the same pH as in Example 1, but not containing sulphates; this comparative treatment therefore consists in depositing a layer of zinc hydroxides in the place of the hydroxysulfates of Example 1.
  • the low level of current density used comes from the low level of conductivity of the electrolyte used which contains only sodium hydroxide.
  • Example 1 the treatments are carried out in a "Rotating electrode cell"; the circular-shaped sample is plunged in this cell and is animated by a rotation movement; the speed of electrolyte flow in the vicinity of the sample therefore depends on the rotation speed.
  • Example 1 Each treatment is performed under a different current density; after treatment, the amount of sulfur deposited by a method is measured different from that described in Example 1, which involves the use of a Silicon-Lithium diode ("Si-Li") adapted for this purpose on an installation of scanning microscopy.
  • Si-Li Silicon-Lithium diode
  • Example 1 A series of treatments are performed on the same samples as in Example 1 and using a solution analogous to that of Example 1, at pH value close; the treatment facility is the same as in the example 2 ("rotating electrode cell").
  • All the treatments are carried out under the same charge density 20 C / dm 2 and under the same current density 200 A / dm 2 .
  • Each treatment is performed using a different pH solution; after treatment, the amount of sulfur deposited by the same method as in Example 2.
  • the amount of sulfur deposited does not become significant, ie greater than 0.5 mg / m 2 only if, approximately, 12 ⁇ pH ⁇ 13.
  • a solution of treatment by dissolution of sulfate of zinc heptahydrate in water is used at its natural pH, without addition of acid or base; the natural pH obtained is close to 7.
  • the treated samples are rinsed twice with water demineralized: first at 20 ° C for about 8 seconds, then at 50 ° C for about 5 seconds.
  • the rinsed samples are then dried.
  • a homogeneous film of coating treatment solution is applied sheet samples; the solution is applied at room temperature.
  • the sample is dried.
  • the deposits obtained on the dried samples then all present the same thickness and the same amount of sulfur.
  • solubilizable part of the deposit depends on the delay (5 to 60 seconds) between application and drying, during which the hydroxysulfation reaction could develop.
  • the amount of sulfur corresponding to the solubilizable part of the deposit and that corresponding to the insolubilizable part, that is, hydroxysulfate is, hydroxysulfate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)
  • Lubricants (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Paper (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP99941724A 1998-09-15 1999-09-09 Toles d'acier zingue revetues d'une couche prelubrifiante d'hydroxysulfate et procedes d'obtention de cette tole Expired - Lifetime EP1115914B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9811441A FR2783256B1 (fr) 1998-09-15 1998-09-15 Traitement anodique de toles d'acier zingue dans des solutions aqueuses contenant des sulfates
FR9811441 1998-09-15
PCT/FR1999/002141 WO2000015878A1 (fr) 1998-09-15 1999-09-09 Toles d'acier zingue revetues d'une couche prelubrifiante d'hydroxysulfate et procedes d'obtention de cette tole

Publications (2)

Publication Number Publication Date
EP1115914A1 EP1115914A1 (fr) 2001-07-18
EP1115914B1 true EP1115914B1 (fr) 2003-04-02

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EP99941724A Expired - Lifetime EP1115914B1 (fr) 1998-09-15 1999-09-09 Toles d'acier zingue revetues d'une couche prelubrifiante d'hydroxysulfate et procedes d'obtention de cette tole

Country Status (10)

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US (1) US6528182B1 (es)
EP (1) EP1115914B1 (es)
AT (1) ATE236279T1 (es)
BR (1) BR9913743B1 (es)
CA (1) CA2343016C (es)
DE (1) DE69906555T2 (es)
ES (1) ES2196847T3 (es)
FR (1) FR2783256B1 (es)
PT (1) PT1115914E (es)
WO (1) WO2000015878A1 (es)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10287665B2 (en) 2014-06-27 2019-05-14 Henkel Ag & Co. Kgaa Dry lubricant for zinc coated steel

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2864552B1 (fr) * 2003-12-24 2006-07-21 Usinor Traitement de surface par hydroxysulfate
JP5239570B2 (ja) 2007-09-04 2013-07-17 Ｊｆｅスチール株式会社 亜鉛系めっき鋼板
KR20110073573A (ko) * 2008-12-16 2011-06-29 제이에프이 스틸 가부시키가이샤 아연계 도금 강판 및 그 제조 방법
CN104040027A (zh) 2012-01-10 2014-09-10 安赛乐米塔尔研发有限公司 含硫酸根离子的溶液用于减少金属板在其存储期间的黑化或锈蚀的用途以及用所述溶液处理的金属板
US9363857B2 (en) 2012-01-17 2016-06-07 Koninklijke Philips N.V. Modulation of light emitted by a lighting device, using plurality of different modulation periods
EP2937411A1 (de) 2014-04-25 2015-10-28 Voestalpine Stahl GmbH Blech und Verfahren zur Verbesserung der Umformbarkeit eines Blechs
EP2995674B1 (de) 2014-09-11 2020-07-15 thyssenkrupp AG Verwendung eines Sulfats sowie Verfahren zum Herstellen eines Stahlbauteils durch Umformen in einer Umformmaschine
WO2016120669A1 (fr) 2015-01-30 2016-08-04 Arcelormittal Procédé de préparation d'une tôle revêtue comprenant l'application d'une solution aqueuse comprenant un aminoacide et utilisation associée pour améliorer la résistance à la corrosion
WO2016120671A1 (fr) 2015-01-30 2016-08-04 Arcelormittal Procédé de préparation d'une tôle revêtue comprenant l'application d'une solution aqueuse comprenant un aminoacide et utilisation associée pour améliorer les propriétés tribologiques
US11078573B2 (en) * 2016-01-19 2021-08-03 Thyssenkrupp Ag Method for producing a steel product with a Zn coating and a tribologically active layer deposited on the coating, and a steel product produced according to said method
WO2019073273A1 (en) * 2017-10-12 2019-04-18 Arcelormittal PROCESS FOR PROCESSING METAL SHEET AND METAL SHEET TREATED WITH THIS METHOD
WO2019073274A1 (en) 2017-10-12 2019-04-18 Arcelormittal PROCESS FOR PROCESSING METAL SHEET AND METAL SHEET TREATED USING THE SAME
DE102018209737A1 (de) 2018-06-18 2019-12-19 Thyssenkrupp Ag Trennschicht für die Warmumformung
WO2021074672A1 (en) 2019-10-16 2021-04-22 Arcelormittal Metal sheet treatment method and metal sheet treated with this method
WO2024105887A1 (ja) * 2022-11-18 2024-05-23 日本電信電話株式会社 保護被膜形成方法および保護被膜形成装置

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JPS6160915A (ja) * 1984-09-01 1986-03-28 Kyoei:Kk 水面自走式油分離機
JPH0663113B2 (ja) * 1987-05-01 1994-08-17 川崎製鉄株式会社 化成処理性の優れたＺｎ系電気めっき鋼板の製造方法
JPH0230795A (ja) * 1988-04-28 1990-02-01 Kawasaki Steel Corp 黒色鋼板の製造方法
FR2651700B1 (fr) * 1989-09-11 1994-10-14 Lorraine Laminage Procede d'emboutissage d'un flan de tole metallique.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10287665B2 (en) 2014-06-27 2019-05-14 Henkel Ag & Co. Kgaa Dry lubricant for zinc coated steel

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Publication number Publication date
CA2343016C (fr) 2011-06-28
FR2783256A1 (fr) 2000-03-17
FR2783256B1 (fr) 2000-10-27
ES2196847T3 (es) 2003-12-16
BR9913743B1 (pt) 2009-05-05
ATE236279T1 (de) 2003-04-15
DE69906555D1 (de) 2003-05-08
EP1115914A1 (fr) 2001-07-18
PT1115914E (pt) 2003-08-29
BR9913743A (pt) 2001-06-05
DE69906555T2 (de) 2004-03-04
US6528182B1 (en) 2003-03-04
WO2000015878A1 (fr) 2000-03-23
CA2343016A1 (fr) 2000-03-23

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