WO2002003759A1 - Multi-layer ceramic heater element and method of making same - Google Patents

Multi-layer ceramic heater element and method of making same Download PDF

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Publication number
WO2002003759A1
WO2002003759A1 PCT/CA2000/001147 CA0001147W WO0203759A1 WO 2002003759 A1 WO2002003759 A1 WO 2002003759A1 CA 0001147 W CA0001147 W CA 0001147W WO 0203759 A1 WO0203759 A1 WO 0203759A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
ceramic
resistive
conductive ceramic
heater
Prior art date
Application number
PCT/CA2000/001147
Other languages
English (en)
French (fr)
Inventor
Peter Leigh
Original Assignee
Le-Mark Patent International Limited
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 Le-Mark Patent International Limited filed Critical Le-Mark Patent International Limited
Priority to KR1020027017286A priority Critical patent/KR100750573B1/ko
Priority to AT00967456T priority patent/ATE270812T1/de
Priority to CA002414687A priority patent/CA2414687C/en
Priority to JP2002507031A priority patent/JP4849765B2/ja
Priority to US10/312,970 priority patent/US6884967B1/en
Priority to EP00967456A priority patent/EP1300052B1/en
Priority to AU2000277653A priority patent/AU2000277653A1/en
Priority to DE60012053T priority patent/DE60012053T2/de
Publication of WO2002003759A1 publication Critical patent/WO2002003759A1/en

Links

Classifications

    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00Ohmic-resistance heating
    • H05B3/10Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/141Conductive ceramics, e.g. metal oxides, metal carbides, barium titanate, ferrites, zirconia, vitrous compounds
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00Ohmic-resistance heating
    • H05B3/10Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23QIGNITION; EXTINGUISHING-DEVICES
    • F23Q7/00Incandescent ignition; Igniters using electrically-produced heat, e.g. lighters for cigarettes; Electrically-heated glowing plugs
    • F23Q7/001Glowing plugs for internal-combustion engines
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23QIGNITION; EXTINGUISHING-DEVICES
    • F23Q7/00Incandescent ignition; Igniters using electrically-produced heat, e.g. lighters for cigarettes; Electrically-heated glowing plugs
    • F23Q7/001Glowing plugs for internal-combustion engines
    • F23Q2007/004Manufacturing or assembling methods
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/027Heaters specially adapted for glow plug igniters

Definitions

  • This invention relates to ceramic heater elements.
  • this invention relates to ceramic heater elements, and methods of manufacture therefor, such as ceramic heaters used in high-temperature a glow plugs for diesel engines.
  • Ceramic glow plugs having a multi-layered construction. Examples of such conventional glow plugs are described in United States Patent Nos. 4,742,209, 5,304,778 and 5,519,187.
  • these glow plugs have a ceramic heater with a conductive core enclosed by insulative and resistive ceramic layers, respectively. The layers are separately cast and fitted together. The resulting green body is then sintered to form a ceramic heater.
  • Such ceramic heaters suffer several drawbacks. Used in a glow plug, they experience cyclic heating and cooling, which results in high internal stresses at the interfacial junction between the ceramic layers, promoting eventual failure of the glow plugs. To reduce this failure rate, such ceramic heaters tend to be cycled at lower temperatures than would be optimal in a diesel engine.
  • the internal stresses of a layered glow plug are mainly the result of differences in the coefficients of tliermal expansion between the differently composed layers.
  • the different layers of the glow plug expand and contract at different rates. Further, residual stresses are the result of manufacture, particularly from uneven contraction in the cooling period which occurs below the plastic deformation state of the ceramic composition, and from non-uniform attachment between the layers.
  • the present invention provides a ceramic heater element and a glow plug incorporating a novel heater element.
  • the heater element has a base portion and a heater portion. Conductive, insulative and resistive layers extend through both the base and heater portions. An outer conductive layer is applied to the outside of the base portion to provide a highly conductive return path. This tends to limit the heating of the resistive layer in the base portion and results in better and more reliable heat concentration in the heater portion. A waterpro of non-conductive outer layer is provided over the outer surface of the heater element.
  • the heater element can be assembled to form a glow plug for a diesel engine.
  • the ceramic heater includes abase portion with a heater portion formed at one end.
  • the heater portion has a lesser diameter than the base portion.
  • the base portion and heater portion each having a conductive ceramic layer and a resistive ceramic layer, which are separated by an ins ⁇ lative ceramic layer except at a tip of the heater portion where they are electrically connected.
  • the base portion further has an outer conductive ceramic layer in electrical contact with the resistive ceramic layer.
  • a waterproof outer layer of non-electrically conductive ceramic extends over the base and the heater portions.
  • An optional central conductive core can be included in this heater, which extends substantially the length of the base portion.
  • a glow plug for a diesel engine employing the above-described heater element.
  • the glow plug has a metallic housing, including a barrel and a tapered sleeve.
  • a ceramic heater element having a base poition tapered to wedgingly fit within the sleeve, is mounted within the housing.
  • the heater element has a heater portion formed at an end of the base portion.
  • the heater portion has a lesser diameter than the base portion, and generally extends beyond the housing.
  • the base portion and heater portion each having a conductive ceramic layer and a resistive ceramic layer, which are separated by an insulative ceramic layer except at a tip of the heater portion where they are electrically connected.
  • the base portion further has an outer conductive ceramic layer in electrical contact with the resistive ceramic layer.
  • a waterproof non-electrically conductive outer layer extends over the base and the heater portions.
  • An optional central conductive core can be included in this heater, which extends substantially the length of the base portion.
  • Figure 1 is a schematic cross sectional view of a ceramic heater element according to an embodiment of the present invention, sectioned along its longitudinal axis;
  • Figure 2 is a schematic cross sectional view of the ceramic heater element according of Fig. 1, along the line A - A;
  • Figure 3 is a schematic cross sectional view of the ceramic heater element according to Fig. 1, along the line B - B;
  • Figure 4 is a cross section of a glow plug according to the present invention.
  • Figure 5 is a cross section of a further embodiment of the heater element of the present invention.
  • FIG. 1 A schematic view of a ceramic heater element according to a first embodiment of the present invention is shown in cross-section along its longitudinal axis in Fig. 1, and in cross-section along line A - A in Fig. 2.
  • the heater element is not shown to scale and is generally designated at reference numeral 10.
  • Element 10 consists of abase portion 20 and a heater portion 22.
  • Base portion 20 and heater tip portion 22 form a generally cylindrical heater element that is thicker in diameter through base portion 20 and tapers to a thinner diameter heater portion 22.
  • base portion 20 is typically sized to be received in a metal housing, including appropriate electrical contacts, to form a glow plug for a diesel engine. As described in U.S. Patent No.
  • base portion 20 of heater element 10 can be so formed, but the present invention can be employed advantageously with any ceramic heater element, regardless of its particular shape and dimensions.
  • heater portion 22 has a lesser diameter than base portion 20. This results in a higher resistance in heater portion 22, and, consequently, a higher heat output. Thus, heating of element 10 is ideally concentrated in heater portion 22.
  • base portion 20 is formed of six layers of ceramic material. As is well known, the composition of the layers differs, particularly in the amount of conductive ceramic component such as MoSi 2 , such that the electrical conductivity of the different layers can be controlled. Beginning at the centre, base portion 20 consists of an inner electrically conductive core 24, an electrically conductive layer 26, an electrically insulative layer 28, an electrically resistive layer 30, an outer electrically conductive layer 32 and an outer insulative waterproof layer 38. Generally, base portion 20 also includes hole 34 that permits connection to an electrical lead (not shown) when element 10 is assembled as a glow plug. For the purposes of description, conductive layer 26 and resistive layer 30 are differentiated. However, as will be further- described below, these two layers have similar characteristics, and any heating ascribed to resistive layer 30 can be equally well accomplished in conductive layer 26.
  • heater portion 22 is formed of four layers of ceramic material. Beginning again at the innermost layer, heater portion 22 consists of conductive layer 26, insulative layer 28, resistive layer 30 and an outer insulative waterproof layer 38. The distal end of heater portion 22 is formed into a tip 36 that forms an electrical connection between conductive layer 26 and resistive layer 30.
  • the ceramic material forming the various layers is selected from the group comprising Si 3 N , Y 2 O 3 , silicon carbide, aluminum nitride, alumina, silica and zirconia. These non- conductive ceramic materials are then doped with one or more conductive components selected from the group comprising MoSi 2 , TiN, ZrN, TiCN and TiB 2 . The percent concentration of the conductive component, in conjunction with the layer thickness, determines the resulting conductivity of the ceramic material.
  • a sintering additive from about 10 to about 0 percent by volume can also be included. The sintering additive includes yttrium, magnesia, calcium, hafnia and others of the Lanthanide group of elements.
  • the conductive and non-conductive components are supplied as finely ground particles. Optimally, the particles can range in size from about 0.2 to about 0.8 microns.
  • the finely ground components are mixed and suspended in a solvent, such as water, to form a slurry.
  • a suitable defiocculant, such as ammonium polyacrylate. known commercially as DARVAN CTM can also be added.
  • the non-conductive ceramic material is Si 3 N 4 and the conductive component is MoSi 2 .
  • Inner core 24 can have 41 - 80 vol. % MoSi 2
  • conductive layer 26 can have 30 - 45 vol. % MoSi 2
  • insulative layer 28 and waterproof outer layer 38 can have 0 - 28 vol. % MoSi 25
  • resistive layer 30 can have 30 - 45 vol. % MoSi 2
  • outer layer 32 can have 41 - 80 vol. % MoSi,.
  • heater element 10 can be formed of five layers, without a core. In this case, conductive la ⁇ 'er 26 also occupies the volume of conductive core 24.
  • core 24 is presently believed to provide to heater element 10 is an improved conduction of electricity tlirough base portion 20 to concentrate heat development in heater portion
  • heater element 10 can include a core that extends beyond the length of base portion 20. For example, for certain applications it can be desirable to have core 24 extend nearly to tip 36.
  • Ceramic heater element 10 is preferably manufactured by slip casting, such as is described in U.S Patent Application No. 08/882,306, the contents of which are incorporated herein by reference. The method described therein is modified somewhat to incorporate the additional layers: inner core 24 and outer layer 32.
  • An absorbent, tubular mold, open at both ends, is provided.
  • the mold can be fabricated from plaster of Paris or any other suitable absorbent material.
  • the mold is provided with a smaller inner diameter step to produce element
  • successive layers of element 10 are added to the mold from the tip 36 end.
  • the method commences by laying down outer waterproof insulative layer 38, then outer electrically conductive layer 32, and then forming resistive layer 30.
  • insulative layer 28 is formed in the mold. It has been found, in a standard sized heater element, that insulative layer 28 needs to be at least 0.3 mm to provide an effective electrically insulative barrier between resistive layer 30 and conductive layer 26.
  • conductive layer 26 is formed in a well known manner.
  • Inner core 24 is then injected into the mold from the opposite end of the mold such that it extends substantially the length of base portion 20. Connecting hole 34 can be formed in inner core 24 at this time.
  • tip 36 of the green body is reformed by, for example, applying low intensity vibrations from an ultrasonic wand to tip 36 before the green body is removed from the mold, The low intensity vibrations cause the particles at the tip to be blended into an electrically conductive tip joining the inner and outer volumes. Once the liquid phase has been substantially absorbed through the walls of the mold, the green body with a reformed tip is removed from the mold and allowed to air dry.
  • the ceramic heater element 10 can be formed by commencing with resistive layer 30, and continuing as described above. Then prior to sintering the green bod ⁇ ', it is dipped into a conductive ceramic slurry to form outer layer 32. This results in very thin coating of conductive material that covers base portion 20. Next, the green body is dipped into an insulative ceramic body to form outer waterproof insulative layer. As is well known, the green ceramic body is then sintered and polished to produce element 10. Casting outer layer 32 is presently preferred, as greater control of the layer 32 thickness is achieved.
  • element 10 can then be assembled to form a glow plug assembly 40, as described in the aforementioned U.S. Patent No. 5,880,432.
  • Element 10 is inserted into a metallic housing 42 consistmg of a barrel 44 and a sleeve 46.
  • Sleeve 46 is tapered to match the outer taper of base portion 20 such that element 10 is wedgingly held in place within housing 42.
  • a conductive wire 48 is inserted into hole 34 of element 10. and element 10 and wire 48 are secured in place by filling barrel 44 with an epoxy, or other fixant suitable for operation in a corrosive, high temperature atmosphere. Barrel 44 is then sealed with connector cap 50.
  • sleeve 46, and hence housing 42 is in electrical contact with ouler layer 32, while wire 48 is in electrical contact with inner core 24.
  • an electrical potential is applied across housing 42 and conductive wire 48. This causes an electrical current to flow from conductive wire 48 tlirough conductive inner core 24 to conductive layer 26.
  • the current then flows through resistive layer 30 at the exterior of heater portion 22, and returns along outer layer 32 to housing 42. As the current flows through resistive layer 30 in the region of heater portion 22, it heats heater portion 22 to a temperature sufficient for diesel fuel ignition.
  • Experimental testing of element 10 has resulted in repeated cycling to heater temperatures in the range of 1500°C without failure of the element 24.
  • the high conductivity of outer layer 32 results in little current flow tlirough the resistive layer 30 in the base portion 20, thus limiting the heating of the base portion, and improving the concentration of heat in the resistive layer 30 of heater portion 22.
  • a ceramic heater element of the present invention is shown, and generally designated at reference numeral 60.
  • This embodiment differs from the first embodiment in that it has no inner core. Instead conductive layer 26 fills the interior volume of element 10 and forms the inner core. Generally, this four layer ceramic heater element 60 relies on the conductive layer 26 to carry the electrical current to heater portion 22.
  • the slightly less efficient resistivity of layer 26 results in slightly lower operating temperatures, typically in the range of 1300°C, but has the benefit of lowering the production costs of the ceramic heater elements.
  • the ceramic heater element of the present invention has a number of advantages over the prior art.
  • the four or five layer structure and and outer layer 32 result in a more efficient concentration of heat at heater portion 22, and enhances the stability and uniformity of the ceramic heater elements.
  • the non-conductive waterproof outer layer 38 further enhances performance by protecting the heater element and minimizing the effects of atmospheric moisture on the electrical properties of the heater element. Consequently, this results in the manufacture of fewer rej ected pieces, thereby lowering production costs and increasing profit.
  • the concentration of heat also results in a heater element that can be repeatedly cycled to approximately 1300 - 1500°C, which is a significant improvement over prior art ceramic heater elements which typically operate at 900 - 1100°C.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Resistance Heating (AREA)
  • Ceramic Capacitors (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Ceramic Products (AREA)
PCT/CA2000/001147 1999-06-16 2000-10-06 Multi-layer ceramic heater element and method of making same WO2002003759A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
KR1020027017286A KR100750573B1 (ko) 2000-07-03 2000-10-06 다층형 세라믹제 히터 소자 및 그 제조 방법
AT00967456T ATE270812T1 (de) 2000-07-03 2000-10-06 Mehrschichtiges keramisches heizelement und verfahren zu dessen herstellung
CA002414687A CA2414687C (en) 2000-07-03 2000-10-06 Multi-layer ceramic heater element and method of making same
JP2002507031A JP4849765B2 (ja) 2000-07-03 2000-10-06 多層セラミックヒータ素子及びその製造方法
US10/312,970 US6884967B1 (en) 1999-06-16 2000-10-06 Multi-layer ceramic heater element and method of making same
EP00967456A EP1300052B1 (en) 2000-07-03 2000-10-06 Multi-layer ceramic heater element and method of making same
AU2000277653A AU2000277653A1 (en) 2000-07-03 2000-10-06 Multi-layer ceramic heater element and method of making same
DE60012053T DE60012053T2 (de) 2000-07-03 2000-10-06 Mehrschichtiges keramisches heizelement und verfahren zu dessen herstellung

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US60966900A 2000-07-03 2000-07-03
US09/609,669 2000-07-03

Publications (1)

Publication Number Publication Date
WO2002003759A1 true WO2002003759A1 (en) 2002-01-10

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA2000/001147 WO2002003759A1 (en) 1999-06-16 2000-10-06 Multi-layer ceramic heater element and method of making same

Country Status (8)

Country Link
EP (1) EP1300052B1 (ko)
JP (1) JP4849765B2 (ko)
KR (1) KR100750573B1 (ko)
AT (1) ATE270812T1 (ko)
AU (1) AU2000277653A1 (ko)
CA (1) CA2414687C (ko)
DE (1) DE60012053T2 (ko)
WO (1) WO2002003759A1 (ko)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006016566A1 (de) * 2005-09-22 2007-03-29 Beru Ag Zusammengesetzter Leiter, insbesondere für Glühkerzen für Dieselmotoren

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007035856B8 (de) * 2007-07-31 2009-04-16 Sintec Keramik Gmbh Widerstandsheizer und Verfahren zum Herstellen desselben
JP5438961B2 (ja) * 2008-02-20 2014-03-12 日本特殊陶業株式会社 セラミックヒータ及びグロープラグ
DE102009015536B4 (de) * 2009-04-01 2011-01-13 Beru Ag Keramischer Glühstift und Glühkerze
JP5414381B2 (ja) * 2009-06-24 2014-02-12 ボッシュ株式会社 グロープラグ及びグロープラグの製造方法
JP2011017504A (ja) * 2009-07-10 2011-01-27 Bosch Corp グロープラグ
DE102011055283B4 (de) 2011-11-11 2016-06-23 Borgwarner Ludwigsburg Gmbh Glühkerze und Verfahren zum Herstellen eines Glühstifts
CN106912120A (zh) * 2015-08-21 2017-06-30 重庆利迈陶瓷技术有限公司 一种陶瓷电热体

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US882306A (en) 1907-12-13 1908-03-17 Gustafva Fredrickson Fly-trap.
DE3318458A1 (de) * 1983-05-20 1984-11-22 Robert Bosch Gmbh, 7000 Stuttgart Gluehkerze fuer brennkraftmaschinen
US4742209A (en) 1985-06-27 1988-05-03 Jidosha Kiki Co., Ltd. Glow plug for diesel engine
US5304778A (en) 1992-11-23 1994-04-19 Electrofuel Manufacturing Co. Glow plug with improved composite sintered silicon nitride ceramic heater
US5519187A (en) 1993-10-15 1996-05-21 Detroit Diesel Corporation Electrically conductive ceramic glow plug with axially extending pocket and terminal received therein
US5880432A (en) * 1996-12-23 1999-03-09 Le-Mark International Ltd. Electric heating device with ceramic heater wedgingly received within a metalic body
US5993722A (en) * 1997-06-25 1999-11-30 Le-Mark International Ltd. Method for making ceramic heater having reduced internal stress
US6084212A (en) * 1999-06-16 2000-07-04 Le-Mark International Ltd Multi-layer ceramic heater element and method of making same

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JPS57199762A (en) * 1981-06-02 1982-12-07 Koutsu Seisakusho:Kk Suction valve operation controller in automatic winder
JPS57199762U (ko) * 1981-06-15 1982-12-18
JPS61217624A (ja) * 1985-03-22 1986-09-27 Jidosha Kiki Co Ltd 自己温度制御型グロ−プラグ
JPS62141424A (ja) * 1985-12-13 1987-06-24 Jidosha Kiki Co Ltd デイ−ゼルエンジン用グロ−プラグ

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US882306A (en) 1907-12-13 1908-03-17 Gustafva Fredrickson Fly-trap.
DE3318458A1 (de) * 1983-05-20 1984-11-22 Robert Bosch Gmbh, 7000 Stuttgart Gluehkerze fuer brennkraftmaschinen
US4742209A (en) 1985-06-27 1988-05-03 Jidosha Kiki Co., Ltd. Glow plug for diesel engine
US5304778A (en) 1992-11-23 1994-04-19 Electrofuel Manufacturing Co. Glow plug with improved composite sintered silicon nitride ceramic heater
US5519187A (en) 1993-10-15 1996-05-21 Detroit Diesel Corporation Electrically conductive ceramic glow plug with axially extending pocket and terminal received therein
US5880432A (en) * 1996-12-23 1999-03-09 Le-Mark International Ltd. Electric heating device with ceramic heater wedgingly received within a metalic body
US5993722A (en) * 1997-06-25 1999-11-30 Le-Mark International Ltd. Method for making ceramic heater having reduced internal stress
US6084212A (en) * 1999-06-16 2000-07-04 Le-Mark International Ltd Multi-layer ceramic heater element and method of making same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006016566A1 (de) * 2005-09-22 2007-03-29 Beru Ag Zusammengesetzter Leiter, insbesondere für Glühkerzen für Dieselmotoren
DE102006016566B4 (de) * 2005-09-22 2008-06-12 Beru Ag Zusammengesetzter Leiter, insbesondere für Glühkerzen für Dieselmotoren

Also Published As

Publication number Publication date
DE60012053D1 (de) 2004-08-12
CA2414687C (en) 2010-03-09
EP1300052A1 (en) 2003-04-09
AU2000277653A1 (en) 2002-01-14
KR20030045683A (ko) 2003-06-11
EP1300052B1 (en) 2004-07-07
ATE270812T1 (de) 2004-07-15
JP4849765B2 (ja) 2012-01-11
KR100750573B1 (ko) 2007-08-21
CA2414687A1 (en) 2002-01-10
JP2004524648A (ja) 2004-08-12
DE60012053T2 (de) 2005-05-25

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