EP1558779B1 - Verfahren und vorrichtung zum entzundern und/oder reinigen eines metallstrangs - Google Patents

Verfahren und vorrichtung zum entzundern und/oder reinigen eines metallstrangs Download PDF

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Publication number
EP1558779B1
EP1558779B1 EP03753485A EP03753485A EP1558779B1 EP 1558779 B1 EP1558779 B1 EP 1558779B1 EP 03753485 A EP03753485 A EP 03753485A EP 03753485 A EP03753485 A EP 03753485A EP 1558779 B1 EP1558779 B1 EP 1558779B1
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EP
European Patent Office
Prior art keywords
descaling
plasma
cleaning
metal strip
metal strand
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.)
Revoked
Application number
EP03753485A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1558779A1 (de
Inventor
Klaus Frommann
Bodo Block
Rolf Brisberger
Hans Georg Hartung
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.)
SMS Siemag AG
Original Assignee
SMS Demag AG
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
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Application filed by SMS Demag AG filed Critical SMS Demag AG
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • B08B7/0035—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by radiant energy, e.g. UV, laser, light beam or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/04—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for de-scaling, e.g. by brushing
    • B21B45/06—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for de-scaling, e.g. by brushing of strip material
    • 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
    • C23C2/003—Apparatus
    • C23C2/0038—Apparatus characterised by the pre-treatment chambers located immediately upstream of the bath or occurring locally before the dipping process
    • 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
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • 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
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • 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
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
    • B21B1/24—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length in a continuous or semi-continuous process
    • B21B1/28—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length in a continuous or semi-continuous process by cold-rolling, e.g. Steckel cold mill

Definitions

  • the invention relates to a method for descaling and / or cleaning a metal strand, in particular a hot-rolled strip of mild steel or stainless steel, in which the metal strand is guided in a conveying direction through a device in which it a plasma descaling and / or Plasma cleaning is subjected. Furthermore, the invention relates to a device for descaling and / or cleaning of such a metal strand.
  • JP 03207518 A known A method of the generic type is known from JP 03207518 A known.
  • the pickling of steel strip is carried out in continuous lines, the process part of which can have a very long length depending on the strip speed. Such systems therefore require very high investments.
  • the pickling process also requires a great deal of energy and wastewater disposal and regeneration of hydrochloric acid, which is commonly used in mild steel.
  • the cited prior art is primarily based on the descaling of wire and pipes. This results in the advantage that due to the geometry of the material to be inflamed a relatively simple guidance of the electrodes is possible, so that the descaling can be done efficiently.
  • JP 07 275920 A a generic method in which a set of bending rollers is arranged in front of the plasma descaling, with which the incoming into the chamber belt is treated.
  • the achievable strip flatness is therefore not sufficient to achieve the desired quality of descaling.
  • the invention is therefore an object of the invention to provide a method and an associated device for descaling and / or cleaning a metal strand, with which or with which it is possible, even wide metal strands over their entire width extension in a consistent quality efficiently and effectively by means descaling plasma technology, with both the economic and environmental benefits of this process being exploitable.
  • This object is achieved by the method according to the invention in that the metal strand is subjected in the conveying direction before the apparatus for plasma descaling and / or plasma cleaning a stretch straightening process or a stretch bending straightening process, which gives the metal strand a high degree of planarity.
  • the result of the descaling or cleaning is thereby significantly improved, so that the finished metal strip has a high quality.
  • the tensile force in the straightening process is selected so that a tensile stress occurs in the metal strand, which corresponds to at least 10% of the yield strength of the material of the metal strand.
  • the process can be operated with continuously passing metal strand; but it is also just as possible to perform the strand discontinuously, ie at a non-constant speed, through the descaling or cleaning system.
  • the latter case is especially interesting for small plants.
  • a particularly high quality of the manufactured metal strand can be achieved if, according to the device for plasma descaling and / or plasma cleaning, a test of the surface of the metal strand is carried out; it is then envisaged that the rate at which the metal strand is passed through the apparatus for plasma descaling and / or plasma cleaning, so depending on the test in a closed loop is specified that a desired Entzu concernings considerably or cleaning quality is achieved.
  • a coating of the strand with liquid metal in particular a hot dip galvanizing.
  • the known coating methods are used.
  • One possibility is to pass the metal strand through a vessel filled with the liquid coating metal, with a redirection of the metal strand in the vessel.
  • the CVGL method Continuous Vertical Galvanizing Line
  • the metal rod is preferably heated, preferably by induction heating.
  • cold rolling of the metal strand can advantageously take place.
  • the device for descaling and / or cleaning the metal strand has an arrangement through which the metal strand is guided in the conveying direction and in which the metal strand is subjected to plasma descaling and / or plasma cleaning.
  • the device is characterized according to the invention by means of which a high degree of flatness can be imparted to the metal strand in the conveying direction before the arrangement for plasma descaling and / or plasma cleaning, wherein at least one clamping device for generating a tensile force in the metal strand is arranged in front of and / or behind the means , These means consist of at least one stretch straightening or stretch bending machine. As tensioning device, the S-roller stand has proven itself.
  • a particularly good guidance of the metal strand by the device for plasma descaling and / or plasma cleaning can be achieved if, in the conveying direction behind the device for plasma descaling and / or plasma cleaning, a tensioning device for generating a tensile force in the metal strand is arranged, whereby also here preferably is thought of an S-roll stand.
  • a tensioning device for generating a tensile force in the metal strand is arranged, whereby also here preferably is thought of an S-roll stand.
  • the device for plasma descaling and / or plasma cleaning can have a treatment chamber under vacuum, in which a number of modularly constructed electrodes are arranged in the conveying direction of the metal strand. It can be provided that the individual electrodes depending on the degree of scaling and / or the degree of contamination of the surface of the metal strand and in dependence on the speed at which the metal strand passes through the plasma device, independently switched on and off , In particular, it is possible to switch on just as many electrodes during descaling or cleaning that a desired result is achieved.
  • control means which control means dictate the rate at which the metal strand is passed through the device in response to the test so as to achieve a desired descaling quality or cleaning quality of the metal strand.
  • the descaling or cleaning system according to the invention is advantageously used in combination with further treatment devices for the metal strand.
  • means for coating the metal strand with liquid metal in particular for hot dip galvanizing
  • these means may comprise a liquid metal kettle and at least one pulley integrated therein.
  • the coating means may comprise a liquid metal kettle and, under the kettle, electromagnetic means for retaining the liquid Metal in the boiler.
  • in the conveying direction behind the device for plasma descaling and / or plasma cleaning and in the conveying direction before the means for coating the metal strand means for heating the metal strand, in particular induction heating, may be arranged.
  • means for rolling the metal strand can be arranged in the conveying direction behind the device for plasma descaling and / or plasma cleaning; These may be a multi-stand cold rolling tandem mill.
  • a continuous operation of the entire system is facilitated by the fact that a tape storage is arranged in the conveying direction before the device for plasma descaling and / or plasma cleaning.
  • the productivity of the plant is further improved by arranging means for oiling the metal strand in the conveying direction behind the device for plasma descaling and / or plasma cleaning.
  • a highly productive plant for processing a metal strand preferably for hot rolled strip of mild steel or stainless steel, which can ensure an economical and ecological descaling and / or cleaning of the metal strand and which has proven especially in combination with downstream treatment facilities ,
  • FIG. 1 is schematically outlined a device with which a metal strand 1 is first descaled and then hot-dip galvanized.
  • the metal strand 1 enters the system at a predetermined conveying speed v in the conveying direction R and is initially guided between two S-roll stands 5 and 6, which exert a tensile force F on the metal strand 1.
  • a means 4 for straightening the metal strand 1 is arranged. This means 4 is a stretch bending straightening machine.
  • the metal strand 1 in the stretch bending straightening machine 4 is bent or set by adjustable rollers under high tension by the tensile force F so that the metal strand 1 has a high degree of flatness after leaving the stretch bending straightening machine 4 Has.
  • the metal strand 1 is fed to the device 2 for plasma descaling or cleaning.
  • This device 2 has a treatment chamber 8, which is kept under a vacuum.
  • a respective lock 19 and 20 is provided at the inlet or outlet of the metal strand 1 into or out of the treatment chamber 8.
  • an S-roller stand 7 is also arranged; in cooperation with the S-roller stand 6, it is thus possible to keep the metal strand 1 in pulling the device 2 under train (tensile force F), so that in synergy with the stretch bending straightening machine 4 ensures that the metal strand 1, the device. 2 goes through with an extremely high degree of flatness. This is necessary to achieve a good result of the descaling or cleaning.
  • a number of electrodes 9 are arranged, which are required to generate the plasma, with which the surface of the metal strand 1 is descaled or cleaned. Details can be found in the aforementioned literature.
  • FIG. 1 In conveying direction R are - like it FIG. 1 can be removed - several electrodes 9 arranged one behind the other. These can all be activated simultaneously for descaling or cleaning, d. h be supplied with electrical energy. However, it is also possible to selectively switch the individual module-shaped electrodes 9 in such a way that only a number of electrodes is activated as required to achieve a desired descaling or cleaning result.
  • a test means 10 is arranged, which is able to inspect the surface of the metal strand 1 and pass the result of the test to a control means 11.
  • the control means 11 acts on the drive of the overall device, not shown, in such a way that the conveying speed v of the metal strand 1 is influenced such that the result of the descaling or cleaning of a desired specification equivalent.
  • the control means 11 can reduce the conveying speed v; As a result, the surface of the metal strand 1 is exposed to a longer exposure time of the plasma, which improves the Entzu matters- or cleaning result. However, if there is already an excessively large, unneeded quality, the control means 11 can provide an increase in the conveying speed v, so that although the quality of the descaling or cleaning is reduced, the productivity of the overall system is increased.
  • FIG. 1 can be further removed, located in the conveying direction R behind the device 2 for plasma descaling or cleaning an induction heating 14, which can heat the metal strand 1.
  • This may in particular be an inductively heated annealing furnace with a protective gas atmosphere, with which it is possible to heat the metal strand 1 to a temperature of about 500 ° C. in a very short time.
  • the metal strand 1 is conducted under protective gas and via a proboscis, not shown, into a vessel 3 with liquid coating metal.
  • a guide roller 13 is arranged, which deflects the metal strand 1 after coating with liquid coating metal vertically upwards.
  • the induction heating means 14, the boiler 3 and the deflection roller 13 form the schematically illustrated means 12 for coating the metal strand 1.
  • FIG. 2 An alternative embodiment of the system is in FIG. 2 to see.
  • the difference to FIG. 1 is that in FIG. 2
  • the device 2 for plasma descaling or cleaning means 15 for rolling the descaled or cleaned metal strand 1 are connected downstream. These means are a multi-stand cold rolling tandem mill on which the metal strand 1 is rolled to the desired final thickness.
  • FIG. 3 an apparatus is sketched, which serves only the descaling of the metal strand 1, but in the manner of the in the FIGS. 1 and 2 shown solutions can also be combined with subsequent facilities.
  • the metal strand 1 is fed in wound form from a reel 21 of a welding machine 22, where the metal strand 1 is welded together with the preceding metal strand. Before welding, the tape ends are cut with scissors 23 to allow a perfect weld.
  • the metal strand 1 is then fed to the stretch straightening machine 4, in which the strand 1 can be directed by bending and applying a tensile force so that it has an optimum flatness, before it enters the device 2 for plasma descaling or plasma cleaning enters.
  • the metal strand 1 passes through the lock 19, whereupon it is in the treatment chamber 8, in which there is a vacuum.
  • the vacuum is generated by the vacuum pump 24.
  • descaling or cleaning is carried out by the located between the electrodes 9 and the metal strand 1 plasma.
  • the number of electrodes 9 depends on the belt speed v to ensure the required residence time of the metal strand 1 in the plasma.
  • the exact width of the metal strand 1 is achieved. If necessary, the metal strand 1 is then electrostatically oiled with the oiling machine 18 to protect the surface of the metal strand 1 from corrosion. With a pair of scissors 26, the metal strand 1 is divided before pushing off the finished federal. It can also be used with two reels 21 and 27 be worked in the inlet and the outlet to achieve the shortest possible exchange times.
  • Cold-rolled, oiled steel strip for example, has to pass through special alkaline and electrolytic cleaning tanks, followed by rinsing and sometimes also brushing, in front of a metallic coating in order to achieve the required metallically bright surface.
  • Previous systems also use this chemical means in which pose the aforementioned environmental problems.
  • the use of the plasma technology for the cleaning of the metal strand brings here also great advantages.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Metal Rolling (AREA)
  • Coating With Molten Metal (AREA)
  • Cleaning In General (AREA)
  • Arc Welding In General (AREA)
  • Heat Treatment Of Strip Materials And Filament Materials (AREA)
  • Physical Vapour Deposition (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Catalysts (AREA)
EP03753485A 2002-11-09 2003-09-30 Verfahren und vorrichtung zum entzundern und/oder reinigen eines metallstrangs Revoked EP1558779B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10252178 2002-11-09
DE10252178A DE10252178A1 (de) 2002-11-09 2002-11-09 Verfahren und Vorrichtung zum Entzundern und/oder Reinigen eines Metallstrangs
PCT/EP2003/010852 WO2004044257A1 (de) 2002-11-09 2003-09-30 Verfahren und vorrichtung zum entzundern und/oder reinigen eines metallstrangs

Publications (2)

Publication Number Publication Date
EP1558779A1 EP1558779A1 (de) 2005-08-03
EP1558779B1 true EP1558779B1 (de) 2008-12-31

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ID=32185405

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Application Number Title Priority Date Filing Date
EP03753485A Revoked EP1558779B1 (de) 2002-11-09 2003-09-30 Verfahren und vorrichtung zum entzundern und/oder reinigen eines metallstrangs

Country Status (17)

Country Link
US (1) US20060108034A1 (ja)
EP (1) EP1558779B1 (ja)
JP (1) JP4431045B2 (ja)
KR (1) KR101010580B1 (ja)
CN (1) CN100471981C (ja)
AT (1) ATE419407T1 (ja)
AU (1) AU2003271666B2 (ja)
BR (1) BR0315719A (ja)
CA (1) CA2505152C (ja)
DE (2) DE10252178A1 (ja)
ES (1) ES2316798T3 (ja)
MX (1) MXPA05004995A (ja)
MY (1) MY138080A (ja)
PL (1) PL207871B1 (ja)
RU (1) RU2325965C2 (ja)
TW (1) TWI316002B (ja)
WO (1) WO2004044257A1 (ja)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102020202722A1 (de) 2020-03-03 2021-09-09 Trumpf Laser- Und Systemtechnik Gmbh Verfahren zum Bearbeiten eines Werkstücks und Bearbeitungssystem
WO2021175726A1 (de) 2020-03-03 2021-09-10 Trumpf Laser- Und Systemtechnik Gmbh Verfahren zum bearbeiten eines werkstücks und bearbeitungssystem

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DE50311018D1 (de) 2009-02-12
DE10252178A1 (de) 2004-05-27
MY138080A (en) 2009-04-30
CN100471981C (zh) 2009-03-25
CN1694975A (zh) 2005-11-09
AU2003271666A1 (en) 2004-06-03
CA2505152C (en) 2011-03-22
US20060108034A1 (en) 2006-05-25
MXPA05004995A (es) 2005-08-02
PL207871B1 (pl) 2011-02-28
ATE419407T1 (de) 2009-01-15
JP2006505411A (ja) 2006-02-16
TWI316002B (en) 2009-10-21
TW200408466A (en) 2004-06-01
RU2325965C2 (ru) 2008-06-10
EP1558779A1 (de) 2005-08-03
CA2505152A1 (en) 2004-05-27
ES2316798T3 (es) 2009-04-16
KR20050084976A (ko) 2005-08-29
BR0315719A (pt) 2005-09-06
JP4431045B2 (ja) 2010-03-10
PL374974A1 (en) 2005-11-14
KR101010580B1 (ko) 2011-01-24
WO2004044257A1 (de) 2004-05-27
AU2003271666B2 (en) 2009-03-12

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