US20050170116A1 - Continuous chromate-free fluidized-bed pipe coating - Google Patents

Continuous chromate-free fluidized-bed pipe coating Download PDF

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Publication number
US20050170116A1
US20050170116A1 US10/624,590 US62459003A US2005170116A1 US 20050170116 A1 US20050170116 A1 US 20050170116A1 US 62459003 A US62459003 A US 62459003A US 2005170116 A1 US2005170116 A1 US 2005170116A1
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United States
Prior art keywords
pipe
coating
fluidized
thickness
coated
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.)
Abandoned
Application number
US10/624,590
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English (en)
Inventor
Dirk Heinrich
Heinz Scholten
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.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
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 Degussa GmbH filed Critical Degussa GmbH
Assigned to DEGUSSA AG reassignment DEGUSSA AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HEINRICH, DIRK, SCHOLTEN, HEINZ
Publication of US20050170116A1 publication Critical patent/US20050170116A1/en
Assigned to EVONIK DEGUSSA GMBH reassignment EVONIK DEGUSSA GMBH CHANGE ADDRESS Assignors: EVONIK DEGUSSA GMBH
Assigned to DEGUSSA GMBH reassignment DEGUSSA GMBH CHANGE OF ENTITY Assignors: DEGUSSA AG
Assigned to EVONIK DEGUSSA GMBH reassignment EVONIK DEGUSSA GMBH CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: DEGUSSA GMBH
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C09D5/031—Powdery paints characterised by particle size or shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B05D1/22—Processes for applying liquids or other fluent materials performed by dipping using fluidised-bed technique
    • B05D1/24—Applying particulate materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2254/00—Tubes
    • B05D2254/02—Applying the material on the exterior of the tube
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2505/00—Polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B05D3/0281—After-treatment with induction heating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • 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
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
    • Y10T428/1393—Multilayer [continuous layer]
    • 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
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/254—Polymeric or resinous material
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]

Definitions

  • the invention relates to a process which permits the continuous chromium-free coating of pipe.
  • Coated pipes for the automotive industry have hitherto been produced by coating processes that include the use of chromium VI compounds (chromates). Chromates are used in order to achieve very good adhesion values in the extrusion process employed to manufacture such pipes. Chromate-treated pipes as well as chromate-treated aluminum pipes and steel pipes that are first aluminum-treated and then chromate-treated have been manufactured in this manner. However, the automotive industry recently began a switch to chromium-free pipes.
  • FIG. 1 shows a schematic diagram of the pipe coating process
  • the system preferably operates automatically and continuously to externally coat pipes by fluidized-bed coating.
  • the process may also coat any pipe surface including internal, external or both.
  • the process includes:
  • the induction coils (II), (III) and (IV) may be operated in various combinations and with varying power including
  • the pipes are heated by medium-frequency induction.
  • Formulae for the electrical energy required, the coating rate of the process, and the powder usage are provided herein.
  • Suitable coating materials are fusible polymers capable of fluidization, and mixtures of these.
  • Polyamide powders are particularly suitable, especially those based on nylon-11 or nylon-12. Powders which give particularly good processing are described in DE 29 06 647 (Hüls AG), the trade name for which is VESTOSINT (Degussa AG). These powders have a particularly round granular shape due to preparation by a precipitation process.
  • a commercially available adhesion promoter (e.g. VESTOSINT adhesion promoter WS 5) is first applied to the pipe surface.
  • Suitable primers here include any of the familiar grades for polymers, in particular those for polyamides. They may be applied in solution, suspension, or in powder form. Particularly suitable adhesion promoters for VESTOSINT are those specifically adapted to VESTOSINT.
  • the layer thickness of the primer after air-drying is typically from 5 to 8 ⁇ m. If a solvent-containing adhesion promoter is used the solids content is generally about 8%. If use is made of a solvent-containing adhesion promoter whose solids content is about 8%, the layer thickness of the primer after air-drying is from 5 to 8 ⁇ m.
  • the process of the invention can achieve uniform layer thicknesses of from 50 to 1000 ⁇ m. Preferred coating layer thicknesses are from 50 to 300 ⁇ m. The process of the invention can achieve tolerances of +30% in the coating layer thickness.
  • Pipes produced by the process of the invention are particularly suitable as hydraulic piping and brake piping, e.g. for the automotive industry.
  • Medium-frequency induction heating provides a heating method which is readily controllable but nevertheless very fast, and gives the further advantage that the induction coil which heats the pipe as it passes through the system can be placed directly within the fluidized powder, with the result that there are no heat losses.
  • heating by 300° C. takes 1 s.
  • the greater penetration depth makes the heating process even faster, and at 2000 Hz the time would be only 0.73 s under the same conditions.
  • the induction coil takes the form of coiled tubing and is cooled by passage of water.
  • the induction coil remains cold, as does the powder.
  • the generator system is composed of a machine generator which generates the high frequency, a control cabinet with a control desk, a capacitor battery, and an induction coil.
  • the system may simply be regarded as a transformer with high-frequency electrical energy fed into its primary side and with the workpiece forming its secondary side composed of just one winding. The resultant very high current density in the secondary circuit results in fast heating.
  • Workpieces passing through the system preferably have uniform cross section and uniform wall thickness, including articles with rotational symmetry, such as wires, pipes, rods, and the like.
  • the throughput rate (advance rate) of the pipes depends on pipe diameter and wall thickness, i.e. on the weight of the pipe per unit length, and also on the generator power.
  • the generator efficiency and the required degree of heating of the pipe also play a role in throughput rate.
  • these latter variables can initially be regarded as constant or at least not subject to great variation, appropriate average numerical values can be assumed.
  • N G ⁇ c p ⁇ ⁇ ⁇ ⁇ t 860 ⁇ ⁇ ( 1 )
  • N the generator power in kW
  • G the pipe weight in kg/h passing through the system
  • c p the specific heat of steel ( ⁇ 0.12 kcal/kg degree)
  • ⁇ t the required pipe temperature increase
  • ⁇ the overall efficiency of the generator system (approximately from 0.6 to 0.75).
  • an approximate guideline value for power required is: N ⁇ 50 ⁇ ⁇ W kg ⁇ / ⁇ h ( 3 )
  • the throughput rate v max has to be inserted here in m/min, the generator power N in kW, the external pipe diameter d e in mm, and the pipe wall thickness s likewise in mm.
  • a pipe-coating process was used to prepare coated pipes.
  • the process includes:
  • German Application 1023345.9 filed on Jul. 23, 2002 is incorporated herein by reference in its entirety.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Polyamides (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
US10/624,590 2002-07-23 2003-07-23 Continuous chromate-free fluidized-bed pipe coating Abandoned US20050170116A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1023345.9 2002-07-23
DE2002133344 DE10233344A1 (de) 2002-07-23 2002-07-23 Polyamid-Wirbelsinterpulver für das Dünnschichtwirbelsintern

Publications (1)

Publication Number Publication Date
US20050170116A1 true US20050170116A1 (en) 2005-08-04

Family

ID=30128257

Family Applications (4)

Application Number Title Priority Date Filing Date
US10/624,528 Abandoned US20050244630A1 (en) 2002-07-23 2003-07-23 Polyamide fluidized-bed-coating powder for thin-layer fluidized-bed coating
US10/624,590 Abandoned US20050170116A1 (en) 2002-07-23 2003-07-23 Continuous chromate-free fluidized-bed pipe coating
US11/693,966 Abandoned US20070166451A1 (en) 2002-07-23 2007-03-30 Polyamide fluidized-bed-coating powder for thin-layer fluidized-bed coating
US12/182,522 Expired - Lifetime US7951416B2 (en) 2002-07-23 2008-07-30 Polyamide fluidized-bed-coating powder for thin-layer fluidized-bed coating

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US10/624,528 Abandoned US20050244630A1 (en) 2002-07-23 2003-07-23 Polyamide fluidized-bed-coating powder for thin-layer fluidized-bed coating

Family Applications After (2)

Application Number Title Priority Date Filing Date
US11/693,966 Abandoned US20070166451A1 (en) 2002-07-23 2007-03-30 Polyamide fluidized-bed-coating powder for thin-layer fluidized-bed coating
US12/182,522 Expired - Lifetime US7951416B2 (en) 2002-07-23 2008-07-30 Polyamide fluidized-bed-coating powder for thin-layer fluidized-bed coating

Country Status (12)

Country Link
US (4) US20050244630A1 (ja)
EP (1) EP1384759B1 (ja)
JP (1) JP2004051989A (ja)
KR (1) KR20040030239A (ja)
CN (1) CN1328341C (ja)
AT (1) ATE355337T1 (ja)
AU (1) AU2003220709B2 (ja)
CA (1) CA2435689A1 (ja)
DE (2) DE10233344A1 (ja)
ES (1) ES2282543T3 (ja)
NZ (1) NZ527065A (ja)
TW (1) TW200404872A (ja)

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CN103480547A (zh) * 2013-09-06 2014-01-01 浙江巨龙涂装设备有限公司 一种多管内外壁同时涂塑连续式生产工艺
CN103480545A (zh) * 2013-09-06 2014-01-01 浙江巨龙涂装设备有限公司 一种多管内外壁同时涂塑连续式生产设备
US20190132908A1 (en) * 2017-10-31 2019-05-02 Trinity Bay Equipment Holdings, LLC System and method for heating and re-rounding spoolable pipe
CN111121519A (zh) * 2018-10-31 2020-05-08 青岛海尔特种电冰柜有限公司 金属管制造方法及采用该方法的制冷设备
CN116213224A (zh) * 2023-02-20 2023-06-06 郑茂颂 一种耐腐蚀护套管及其制备方法

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WO2005097475A1 (en) * 2004-03-30 2005-10-20 Valspar Sourcing, Inc. Selective laser sintering process and polymers used therein
DE102004020453A1 (de) * 2004-04-27 2005-11-24 Degussa Ag Polymerpulver mit Polyamid, Verwendung in einem formgebenden Verfahren und Formkörper, hergestellt aus diesem Polymerpulver
DE102004047876A1 (de) * 2004-10-01 2006-04-06 Degussa Ag Pulver mit verbesserten Recyclingeigenschaften, Verfahren zu dessen Herstellung und Verwendung des Pulvers in einem Verfahren zur Herstellung dreidimensionaler Objekte
DE202004018390U1 (de) * 2004-11-27 2005-02-17 Degussa Ag Thermoplastische Kunststoffpulverformulierung für Beschichtungen mit einem metallischen, insbesondere edelstahlähnlichen Farbeindruck
ATE495227T1 (de) 2008-06-02 2011-01-15 Deceuninck Nv Lack oder farbe
WO2015023438A1 (en) 2013-08-12 2015-02-19 United Technologies Corporation Powder spheroidizing via fluidized bed
EP3239214A4 (en) * 2014-12-24 2018-07-25 Toray Industries, Inc. Polyamide microparticles
CN111361072A (zh) * 2020-03-04 2020-07-03 上海交通大学 非接触加热式微米级内径柔性聚合物管制备装置及方法
FR3115042B1 (fr) * 2020-10-09 2023-01-06 Arkema France Procédé de préparation d’une composition de poudre de polyamides avec rendement optimisé

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US3108022A (en) * 1960-05-09 1963-10-22 Polymer Processes Inc Apparatus for coating an elongate body with fluidized coating material
US3560239A (en) * 1964-03-25 1971-02-02 United States Steel Corp Method of coating an elongated body
US3616983A (en) * 1967-12-27 1971-11-02 Matsushita Electric Works Ltd Apparatus for continuously forming plastic-coated metallic tubings
US3887728A (en) * 1969-09-15 1975-06-03 Dynamit Nobel Ag Vinylchloride-alkylene copolymer and uses therefor
US3982050A (en) * 1973-05-21 1976-09-21 Dai Nippon Co., Ltd. Method for coating inner faces of metal pipes of small diameter
US3965551A (en) * 1975-08-14 1976-06-29 Allied Tube & Conduit Corporation Production of polymer-coated steel tubing
US4358887A (en) * 1980-04-04 1982-11-16 Creps John A Method for galvanizing and plastic coating steel
US4385081A (en) * 1981-04-27 1983-05-24 International Standard Electric Corporation Process of coating an electric component with a setting artificial resin
US4685985A (en) * 1982-12-20 1987-08-11 Mannesmann Ag Method of enveloping metal hollows with polyethylene
US4621399A (en) * 1985-12-18 1986-11-11 Allied Tube & Conduit Corporation Tube-coating method and apparatus therefor
US4771523A (en) * 1987-10-05 1988-09-20 Allied Tube & Conduit Corporation Method of applying low gloss nylon coatings
US5176755A (en) * 1990-02-14 1993-01-05 Armco Inc. Plastic powder coated metal strip

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CN103480545A (zh) * 2013-09-06 2014-01-01 浙江巨龙涂装设备有限公司 一种多管内外壁同时涂塑连续式生产设备
US20190132908A1 (en) * 2017-10-31 2019-05-02 Trinity Bay Equipment Holdings, LLC System and method for heating and re-rounding spoolable pipe
US10694591B2 (en) * 2017-10-31 2020-06-23 Trinity Bay E Quipment Holdings, Llc System and method for heating and re-rounding spoolable pipe
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CN116213224A (zh) * 2023-02-20 2023-06-06 郑茂颂 一种耐腐蚀护套管及其制备方法

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US20080286567A1 (en) 2008-11-20
AU2003220709A1 (en) 2004-02-12
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EP1384759B1 (de) 2007-02-28
EP1384759A1 (de) 2004-01-28
NZ527065A (en) 2005-02-25
JP2004051989A (ja) 2004-02-19
KR20040030239A (ko) 2004-04-09
US7951416B2 (en) 2011-05-31
ATE355337T1 (de) 2006-03-15
TW200404872A (en) 2004-04-01
CN1495240A (zh) 2004-05-12
CN1328341C (zh) 2007-07-25
AU2003220709B2 (en) 2006-04-13
US20070166451A1 (en) 2007-07-19
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CA2435689A1 (en) 2004-01-23
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