EP1337681B1 - Installation de revetement par trempe d'une bande metallique - Google Patents

Installation de revetement par trempe d'une bande metallique Download PDF

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Publication number
EP1337681B1
EP1337681B1 EP01993714A EP01993714A EP1337681B1 EP 1337681 B1 EP1337681 B1 EP 1337681B1 EP 01993714 A EP01993714 A EP 01993714A EP 01993714 A EP01993714 A EP 01993714A EP 1337681 B1 EP1337681 B1 EP 1337681B1
Authority
EP
European Patent Office
Prior art keywords
sheath
bath
metal
strip
steel strip
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.)
Expired - Lifetime
Application number
EP01993714A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1337681A1 (fr
Inventor
Didier Dauchelle
Hugues Baudin
Patrice Lucas
Laurent Gacher
Yves Prigent
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.)
ArcelorMittal France SA
Original Assignee
Arcelor France SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Arcelor France SA filed Critical Arcelor France SA
Publication of EP1337681A1 publication Critical patent/EP1337681A1/fr
Application granted granted Critical
Publication of EP1337681B1 publication Critical patent/EP1337681B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34Hot-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
    • C23C2/36Elongated material
    • C23C2/40Plates; Strips
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/003Apparatus
    • C23C2/0034Details related to elements immersed in bath
    • C23C2/00342Moving elements, e.g. pumps or mixers
    • C23C2/00344Means for moving substrates, e.g. immersed rollers or immersed bearings
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06Zinc or cadmium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/14Removing excess of molten coatings; Controlling or regulating the coating thickness
    • C23C2/16Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives

Definitions

  • the present invention relates to a hot dipping coating plant and continuously a metal strip, including a steel strip.
  • steel sheets coated with a protective layer for example against corrosion and usually coated with a zinc layer are used.
  • This type of sheet is used in various industries to make all kinds of parts including appearance parts.
  • an Fe-Zn-Al intermetallic alloy is formed on the surface of said strip with a thickness of some ten nanometers.
  • the corrosion resistance of the parts thus coated is ensured by the zinc, the thickness of which is most often produced by pneumatic wringing.
  • the adhesion of the zinc on the metal strip is provided by the intermetallic alloy layer mentioned above.
  • this steel strip Before the passage of the steel strip in the bath of molten metal, this steel strip first circulates in a annealing furnace under a reducing atmosphere in order to recrystallize it after the important work hardening related to the rolling operation. cold, and prepare its chemical surface state to promote the chemical reactions necessary for the actual quenching operation.
  • the steel strip is brought to about 650 to 900 ° C depending on the grade for the time required for recrystallization and surface preparation. It is then cooled to a temperature close to that of the molten metal bath using exchangers.
  • the steel strip After passing through the annealing furnace, the steel strip passes through a sheath also called “bell drop” or “horn” under a protective atmosphere with respect to the steel and is immersed in the bath of molten metal.
  • a sheath also called "bell drop” or “horn” under a protective atmosphere with respect to the steel and is immersed in the bath of molten metal.
  • the lower end of the sheath is immersed in the metal bath to determine, with the surface of said bath and inside this sheath, a liquid seal which is traversed by the steel strip during its scrolling in said sheath.
  • the steel strip is deflected by a roll immersed in the metal bath and it emerges from the metal bath, then passes through the wiper means for regulating the thickness of the liquid metal coating on the steel strip.
  • the surface of the liquid gasket inside the sheath is generally covered with zinc oxide, resulting from the reaction between the atmosphere inside this sheath and the zinc liquid seal and intermetallic or solid matte compounds from the dissolution reaction of the steel strip.
  • These mattes or other particles, supersaturation in the zinc bath have a lower density than liquid zinc and go back to the surface of the bath and in particular to the surface of the liquid seal.
  • the coated steel strip has appearance defects which are amplified or even revealed during the zinc wringing operation.
  • the intruded particles are retained by the pneumatic wringing jets before being ejected or disintegrated, thus creating sub-thick streaks in the liquid zinc of a length of a few millimeters to a few centimeters.
  • a first solution to avoid these disadvantages consists in cleaning the surface of the liquid seal by pumping zinc oxides and mattes from the bath.
  • a second solution is to reduce the surface of the liquid seal at the point of passage of the steel strip by placing a plate of sheet metal or ceramic at this liquid seal to keep away from the band a portion of the particles present on the surface and get a self-cleaning of the liquid seal by this tape.
  • This arrangement does not allow to remove all the particles present on the surface of the liquid seal and the self-cleaning is all the more important that the surface of the liquid seal is reduced, which is incompatible with the industrial conditions of exploitation.
  • Another solution is to add a frame to the surface of the liquid seal in the sheath and surrounding the steel strip.
  • This arrangement does not completely eliminate the defects related to the entrainment of zinc oxides and mattes by the scrolling of the steel strip.
  • the zinc vapors at the liquid seal will condense on the walls of the frame and the slightest swirl caused by the vibrations or the thermal folds of the strip to immersion, the walls of the frame will become dirty and thus become areas for storing foreign bodies.
  • This solution can only work a few hours or even a day before becoming an additional source of defects.
  • this solution only partially processes the liquid seal and does not achieve a very low density of defects satisfying the requirements of customers wanting surfaces without appearance defects.
  • Renewal is achieved by introducing liquid zinc pumped into the bath in the vicinity of the immersion zone of the steel strip.
  • the piping ensuring the renewal of liquid zinc can cause scratches on the steel strip before immersion and is itself a source of defects by accumulation of condensed zinc vapor above the liquid seal.
  • a process is also known which is based on the renewal of zinc at the liquid seal and wherein this renewal is carried out using a stainless steel box surrounding the steel strip and opening on the surface of the liquid seal .
  • a pump sucks the particles entrained by the spill thus created and pushes them back into the volume of the bath.
  • This process also requires a very high pumping rate to maintain a permanent spill effect in that the box surrounding the strip in the bath volume above the bottom roller can not be hermetically sealed.
  • the object of the invention is to propose a continuous galvanizing installation of a metal strip which makes it possible to avoid the drawbacks previously mentioned and achieve the very low density of defects satisfying the requirements of customers desiring surfaces without appearance defects.
  • the subject of the invention is a continuous dipping coating installation of a metal strip according to claim 1.
  • the steel strip 1 passes into an annealing furnace, not shown, under a reducing atmosphere in order to recrystallize it after the cold-rolling-forming process, and prepare its chemical surface state to promote the chemical reactions necessary for the galvanizing operation.
  • the steel strip is brought to a temperature for example between 650 and 900 ° C.
  • the steel strip 1 passes into a galvanizing installation shown in FIG. 1 and designated by the general reference 10.
  • This installation 10 comprises a tank 11 containing a bath 12 of liquid zinc which contains chemical elements such as aluminum, iron and possible additives such as lead, antimony, in particular.
  • the temperature of this liquid zinc bath is of the order of 460 ° C.
  • the steel strip 1 is cooled to a temperature close to that of the liquid zinc bath using exchangers and is then immersed in the bath 12 of liquid zinc.
  • an Fe-Zn-Al intermetallic alloy forming a zinc coating is formed on the surface of the steel strip 1, the thickness of which is a function of the residence time of the steel strip 1 in the bath 12 of liquid zinc.
  • the galvanizing installation 10 comprises a sheath 13 inside which the steel strip 1 passes under a protective atmosphere with respect to the steel.
  • This sheath 13 also known as "bell drop” or “horn” has, in the embodiment shown in the figures, a rectangular cross section.
  • the lower end of the sheath 13a is immersed in the zinc bath 12 so as to determine with the surface of said bath 12 and inside this sheath 13, a liquid seal 14.
  • the steel strip 1 is deflected by a roller 15 commonly called a bottom roller and placed in the zinc bath 12. At the outlet of this zinc bath 12, the coated steel strip 1 passes into spinning means 16 which are for example constituted by air jet nozzles 16a and which are directed towards each side of the steel strip 1 to regulate the thickness of the liquid zinc coating.
  • the lower end 13a of the sheath 13 is extended, on the opposite side of the face of the strip 1 located on the side of the deflector roll 15, by an inner wall 20 directed towards the surface of the liquid seal 14 and which is cleaning with the sheath 13, a spill compartment 21 liquid zinc to collect the particles of zinc oxides and intermetallic compounds that float on the surface of the liquid seal 14.
  • the upper edge 20a of the inner wall 20 is positioned below the surface of the liquid seal 14 and the compartment 21 is provided with means, not shown, for maintaining the level of liquid zinc in said compartment at a level below. below the surface of the liquid seal 14 to achieve a natural flow of liquid zinc from this surface of said seal 14 to this compartment 21.
  • the lower end 13a of the sheath 13 facing the face of the strip 1 placed opposite the deflector roll 15, is extended by an inner wall 22 directed towards the surface of the liquid seal 14 and leaving with sheath 13 a sealed compartment 23 for storing zinc oxide particles.
  • the upper edge 22a of the inner wall 22 is positioned above the surface of the liquid seal 14.
  • this compartment 23 serves as a receptacle for the zinc oxides that can come from the inclined bottom wall of the sheath and makes it possible to store these oxides in order to protect the steel strip 1.
  • the upper edge 22a of the inner wall 22 may be positioned below the surface of the liquid seal 14 and, in this case, the compartment 23 is a liquid zinc spill compartment, such as the compartment 21.
  • the steel strip 1 must enter the liquid zinc seal 14 without the risk of touching the walls 20 and 22 of the two compartments 21 and 23.
  • the line of passage of the steel strip 1 between the walls 20 and 22 of the two compartments 21 and 23 is determined by the diameter of the deflector roll 15 and by its position.
  • the sheath 13 comprises two parts, a fixed upper part 30 and a movable lower part 31, interconnected by a deformable element 32 so as to be able to modify the position of the movable lower part 31 of the sheath 13.
  • deformable element 32 is constituted by a bellows, for example stainless steel and the lower portion 31 of the sheath 13 is associated with means 35 for positioning the inner walls 20 and 22 relative to the steel strip 1.
  • the positioning means 35 comprise two actuating members, respectively 35a and 35b, constituted for example by hydraulic or pneumatic cylinders and connected to the lower part 31 of the sheath 13.
  • the movable lower portion 31 of the sheath 13 is displaced in translation parallel to the surface of the liquid metal bath 12 when the displacement stroke of the actuating rods of said cylinders is identical, as shown in FIG. 3, In this case, the lower movable portion 31 remains parallel to itself.
  • the lower movable portion 31 is pivotally displaced about the transverse virtual axis and in translation parallel to the surface liquid metal bath 12, as shown in FIG. 4.
  • This arrangement has the advantage of making it possible to adjust independently, on the one hand, the position of the movable portion 31 of the sheath 13 with respect to the steel strip 1 and, on the other hand, the horizontality of said portion mobile. This also makes it possible to balance the flow of liquid metal flowing into each compartment 21 and 23 and thereby increase the efficiency of the installation.
  • the position of the inner walls 20 and 22 of the compartments 21 and 23 is adjusted so that the steel strip 1 enters the liquid zinc seal 14 determined by said inner walls 20 and 22 without the risk of touching these walls.
  • the installation comprises means 40 for guiding the steel strip 1 inside the sheath 13.
  • These guide means 40 are formed by a deflector roll 41 or 42 placed in the sheath 13 to draw the line of passage of the steel strip 1 relative to the roll 15 and more easily adjust the passage of said steel strip 1 between the two walls 20 and 22 of the compartments 21 and 23.
  • the deflector roll 41 is disposed on the face of the strip 1 opposite that in contact with the roll 15, as shown in FIG. 5, and in the case of a thicker steel strip 1, the baffle roll 42 is disposed on the face of the web 1 in contact with the drive roller 15, as shown in FIG. 6.
  • the baffle roll 42 compensates for the bending of the steel strip 1 in the transverse direction which is related to the deformation gradient of the fibers of the steel strip, in its thickness, on the rolls of the furnace. upstream of the galvanizing tank.
  • the invention applies to any metal coating by dipping.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Coating Apparatus (AREA)
  • Laminated Bodies (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemical Treatment Of Metals (AREA)
EP01993714A 2000-11-10 2001-11-07 Installation de revetement par trempe d'une bande metallique Expired - Lifetime EP1337681B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0014482 2000-11-10
FR0014482A FR2816637B1 (fr) 2000-11-10 2000-11-10 Installation de revetement au trempe d'une bande metallique
PCT/FR2001/003454 WO2002038823A1 (fr) 2000-11-10 2001-11-07 Installation de revetement au trempe d'une bande metallique

Publications (2)

Publication Number Publication Date
EP1337681A1 EP1337681A1 (fr) 2003-08-27
EP1337681B1 true EP1337681B1 (fr) 2008-01-02

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EP01993714A Expired - Lifetime EP1337681B1 (fr) 2000-11-10 2001-11-07 Installation de revetement par trempe d'une bande metallique

Country Status (32)

Country Link
US (1) US6923864B2 (pt)
EP (1) EP1337681B1 (pt)
JP (1) JP3779272B2 (pt)
KR (1) KR101144757B1 (pt)
CN (1) CN1220787C (pt)
AR (1) AR034182A1 (pt)
AT (1) ATE382719T1 (pt)
AU (2) AU2002223776B2 (pt)
BG (1) BG65317B1 (pt)
BR (1) BR0100007B1 (pt)
CA (1) CA2428486C (pt)
CZ (1) CZ298884B6 (pt)
DE (1) DE60132240T2 (pt)
DK (1) DK1337681T5 (pt)
EA (1) EA004334B1 (pt)
EC (1) ECSP034592A (pt)
EE (1) EE04821B1 (pt)
ES (1) ES2296830T3 (pt)
FR (1) FR2816637B1 (pt)
HR (1) HRP20030364B1 (pt)
HU (1) HUP0303550A2 (pt)
MA (1) MA25854A1 (pt)
ME (1) ME00793B (pt)
MX (1) MXPA03004075A (pt)
NO (1) NO20032088L (pt)
PL (1) PL201515B1 (pt)
PT (1) PT1337681E (pt)
SK (1) SK286934B6 (pt)
TW (1) TW554072B (pt)
UA (1) UA74225C2 (pt)
WO (1) WO2002038823A1 (pt)
ZA (1) ZA200303501B (pt)

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RU2344197C2 (ru) * 2003-02-27 2009-01-20 Смс Демаг Акциенгезелльшафт Способ и устройство для нанесения покрытий погружением в расплав на металлические ленты, в частности на стальные ленты
KR100695948B1 (ko) * 2006-02-03 2007-03-16 문일호 구이용 팬
KR101353197B1 (ko) * 2011-10-25 2014-01-17 주식회사 포스코 강판 도금라인의 스나우트 장치
DE102013101131A1 (de) * 2013-02-05 2014-08-07 Thyssenkrupp Steel Europe Ag Vorrichtung zum Schmelztauchbeschichten von Metallband
DE102013104267B3 (de) 2013-04-26 2014-02-27 Thyssenkrupp Steel Europe Ag Vorrichtung zum kontinuierlichen Schmelztauchbeschichten von Metallband
KR101533212B1 (ko) * 2015-03-17 2015-07-01 최경철 스나우트의 댐 레벨 유지장치
WO2017187225A1 (fr) 2016-04-26 2017-11-02 Arcelormittal Installation de revêtement au trempé à chaud et en continu d'une bande métallique et procédé associé
WO2017187226A1 (fr) 2016-04-26 2017-11-02 Arcelormittal Installation de revêtement au trempé à chaud et en continu d'une bande métallique et procédé associé
WO2018228661A1 (de) * 2017-06-12 2018-12-20 Thyssenkrupp Steel Europe Ag Rüssel für eine schmelztauchbeschichtungsanlage sowie verfahren für dessen betrieb
KR101999029B1 (ko) * 2017-12-26 2019-07-10 주식회사 포스코 도금 스나우트
WO2019224584A1 (en) * 2018-05-25 2019-11-28 Arcelormittal Method for dip-coating a metal strip
FR3105796B1 (fr) * 2019-12-26 2022-06-10 Fives Stein Dispositif pour l’evacuation de mattes de la surface d’un bain de metal liquide a l’interieur d’une descente de cloche d’une ligne de revetement en continu d’une bande metallique
US11898251B2 (en) * 2020-05-22 2024-02-13 Cleveland-Cliffs Steel Properties Inc. Snout for use in a hot dip coating line
MX2022014521A (es) 2020-05-22 2022-12-13 Cleveland Cliffs Steel Properties Inc Pico de vertido para usarse en una linea de inmersion en caliente.
CN114107863B (zh) * 2021-11-19 2023-08-18 武汉钢铁有限公司 一种能减少锌液挂渣的炉鼻子装置
CN118321091B (zh) * 2024-06-17 2024-09-17 江苏荣明不锈钢有限公司 一种钢丝浸涂机

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KR100244646B1 (ko) 1995-12-30 2000-03-02 이구택 용융아연 도금욕의 씽크롤 교환주기 연장장치

Also Published As

Publication number Publication date
HUP0303550A2 (en) 2004-03-01
SK286934B6 (sk) 2009-07-06
MA25854A1 (fr) 2003-07-01
NO20032088D0 (no) 2003-05-09
CA2428486A1 (fr) 2002-05-16
KR20030048121A (ko) 2003-06-18
ECSP034592A (es) 2003-09-24
AU2002223776B2 (en) 2006-01-05
KR101144757B1 (ko) 2012-05-21
FR2816637A1 (fr) 2002-05-17
ZA200303501B (en) 2003-11-13
CZ298884B6 (cs) 2008-03-05
EP1337681A1 (fr) 2003-08-27
PT1337681E (pt) 2008-02-21
DE60132240D1 (de) 2008-02-14
SK5102003A3 (en) 2003-12-02
FR2816637B1 (fr) 2003-10-24
AU2377602A (en) 2002-05-21
DK1337681T5 (da) 2008-05-13
PL201515B1 (pl) 2009-04-30
JP2004513237A (ja) 2004-04-30
EA004334B1 (ru) 2004-04-29
CN1220787C (zh) 2005-09-28
BR0100007A (pt) 2002-07-09
CN1473205A (zh) 2004-02-04
BG107777A (en) 2004-01-30
AR034182A1 (es) 2004-02-04
DE60132240T2 (de) 2009-04-16
ME00793B (me) 2012-03-20
PL362471A1 (en) 2004-11-02
HRP20030364A2 (en) 2003-06-30
CZ20031292A3 (cs) 2004-01-14
US20040028832A1 (en) 2004-02-12
UA74225C2 (uk) 2005-11-15
US6923864B2 (en) 2005-08-02
DK1337681T3 (da) 2008-03-17
WO2002038823A1 (fr) 2002-05-16
HRP20030364B1 (en) 2008-11-30
BR0100007B1 (pt) 2012-10-02
EE200300210A (et) 2003-08-15
ES2296830T3 (es) 2008-05-01
MXPA03004075A (es) 2004-04-20
BG65317B1 (bg) 2008-01-31
ATE382719T1 (de) 2008-01-15
EA200300551A1 (ru) 2003-10-30
JP3779272B2 (ja) 2006-05-24
TW554072B (en) 2003-09-21
CA2428486C (fr) 2009-04-07
EE04821B1 (et) 2007-04-16
NO20032088L (no) 2003-07-08

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