EP1232511A1 - Isahode ray tube having an oxide cathode - Google Patents
Isahode ray tube having an oxide cathodeInfo
- Publication number
- EP1232511A1 EP1232511A1 EP01980367A EP01980367A EP1232511A1 EP 1232511 A1 EP1232511 A1 EP 1232511A1 EP 01980367 A EP01980367 A EP 01980367A EP 01980367 A EP01980367 A EP 01980367A EP 1232511 A1 EP1232511 A1 EP 1232511A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cathode
- oxide
- metal
- ray tube
- particles
- 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.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
- H01J29/02—Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
- H01J29/04—Cathodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
- H01J1/02—Main electrodes
- H01J1/13—Solid thermionic cathodes
- H01J1/14—Solid thermionic cathodes characterised by the material
Definitions
- the invention relates to a cathode ray tube equipped with at least one cathode, a cathode support with a cathode base made of a first cathode metal and a cathode coating made of an electron-emitting material, a second cathode metal and at least one alkaline earth oxide, selected from the group of oxides of calcium, strontium and Barium, contains, includes.
- a cathode ray tube consists of four functional groups:
- the function group of electron beam generation includes an electron emitting cathode which generates the electron current in the cathode ray tube and which is controlled by a control grid, e.g. a Wehnelt cylinder with a pinhole on the front.
- a control grid e.g. a Wehnelt cylinder with a pinhole on the front.
- An electron-emitting cathode for a cathode-ray tube is usually a point-like, heatable oxide cathode with an electron-emitting, oxide-containing cathode coating. If an oxide cathode is heated, electrons are evaporated from the emitting coating into the surrounding vacuum.
- the amount of electrons that can be emitted by the cathode coating depends on the work function of the electron-emitting material.
- Nickel which is usually used as the cathode base, itself has a relatively high work function. Therefore, the metal of the cathode base is usually coated with a material whose main task is to improve the electron-emitting properties of the cathode base. Characteristic of the
- Electron-emitting coating materials of oxide cathodes are that they contain an alkaline earth metal in the form of the alkaline earth metal oxide.
- an oxide cathode a correspondingly shaped sheet made of a nickel alloy is coated, for example, with the carbonates of the alkaline earth metals in a binder preparation.
- the carbonates are converted into the oxides at temperatures of approximately 1000 ° C.
- This cathode After this cathode has burned off, it already delivers a noticeable emission current, which, however, is not yet stable.
- An activation process follows. The activation process transforms the originally non-conductive ion lattice of the alkaline earth oxides into an electronic semiconductor by incorporating donor-type impurities in the crystal lattice of the oxides.
- the defects consist essentially of elemental alkaline earth metal, e.g.
- the electron emission from the oxide cathodes is based on the impurity mechanism.
- the purpose of the activation process is to create a sufficient amount of excess, elementary alkaline earth metal, through which the oxides in the electron-emitting coating can deliver the maximum emission current at a prescribed heating output.
- the reduction of the barium oxide to elemental barium by alloying components (“activators”) of the nickel from the cathode base makes an important contribution to the activation process.
- an oxide cathode with improved donor density and extended service life is known, which comprises a cup made of a nickel alloy, which is filled with a wire ball made of a nickel alloy and with an alkaline earth metal carbonate mixture.
- the object is achieved by a cathode ray tube equipped with at least one oxide cathode, which has a cathode support with a cathode base made of a first cathode metal with a cover layer consisting of ultrafine metal particles which contain nickel, and a cathode coating made of an electron-emitting material which is a particle -Particle composite material
- oxide particles and metal particles wherein the oxide particles an oxide selected from the oxides of scandium, yttrium and the lanthanides cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium and an alkaline earth oxide from the group of the oxides of calcium, strontium and barium, and the metal particles comprise a second cathode metal selected from the group comprising Ni, Co, Ir, Re, Pd, Rh and Pt.
- a cathode ray tube with such an oxide cathode has a uniform beam current over a long period of time because the growth of high-resistance intermediate layers is locally distributed and reduced overall due to the homogeneous distribution of the reducing cathode metal and the activator metal in the material of the electron-emitting cathode coating.
- Elementary barium can be supplied for longer.
- the cover layer which consists of ultrafine metal particles containing nickel, has a particularly advantageous effect. It forms a resolved boundary between the cathode base and the cathode coating.
- the formation of a high-resistance deactivating separating layer between the cathode base and the cathode coating is discontinuous and the resistance of the high-resistance separating layer is reduced.
- Local delivery of activators and activator diffusion is promoted.
- the continuous barium tracking prevents the electron emission from being exhausted, as is known from conventional oxide cathodes. Much higher beam current densities can be achieved without endangering the cathode life. This can also be used to draw the necessary electron beam currents from smaller cathode areas.
- the spot size of the cathode spot is decisive for the quality of the beam focusing on the screen.
- the image sharpness over the entire screen is increased. Since the cathodes also age very slowly, image brightness and sharpness can be kept stable at a high level over the entire life of the tube.
- a metal from the group Ni, Co, Ir, Re, Pd, Rh and Pt is preferably selected as the first cathode metal.
- the first cathode metal is an alloy of a metal selected from the group Ni, Co, Ir, Re, Pd, Rh and Pt with a metal selected from the group Ni, Co, Ir, Re, Pd, Rh and Pt with a metal selected from the group Ni, Co, Ir, Re, Pd, Rh and Pt with a metal selected from the group Ni, Co, Ir, Re, Pd, Rh and Pt with a metal selected from the group Ni, Co, Ir, Re, Pd, Rh and Pt with a
- Activator metal selected from the group Mg, Mn, Fe, Si, W, Mo, Cr, Ti, Hf, Zr, Al contains.
- the cover layer additionally contains an activator metal, selected from the group Mg, Mn, Fe, Si, W, Mo, Cr, Ti, Hf, Zr, Al. This reduces the sensitivity to "poisoning" due to residual gases in the cathode tube vacuum.
- the metal particles contain a slow activator selected from the group Al, Mo, Ti and Si.
- the slow activators are preferably added in an amount of 1 to 4% by weight.
- the metal particles in the electron-emitting material are an alloy of a second cathode metal selected from the group Ni, Co, Ir, Re, Pd, Rh and Pt with an activator metal selected from the group Mg, Mn, Fe, Si, W, Mo, Cr, Ti, Hf, Zr, AI included.
- the oxide particles can be oxide particles of an alkaline earth oxide selected from the group of the oxides of calcium, strontium and barium, which with an oxide selected from the oxides of scandium, yttrium and the lanthanoids cerium, praseodymium, neodymium, Samarium, Europium, Gadolinium, Terbium, Dysprosium, Holmium, Erbium, Thulium, Ytterbium and Lutetium is included
- the oxide particles contain oxide particles of an alkaline earth oxide selected from the group of the oxides of calcium, strontium and barium, which is doped with one of the oxides of yttrium.
- yttrium oxide accelerates the sintering of the oxides during manufacture.
- Oxide particles Oxide particles of an oxide selected from the oxides of scandium, yttrium and the lanthanoids cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, and oxide particles of an alkaline earth oxide selected from the group the oxides of calcium, strontium and barium.
- the electron emitting material can contain 1 to 5% by weight of metal particles.
- % By weight contains nickel particles.
- the invention compared to the prior art if the metal particles have an ellipsoidal or spherical shape.
- the diffusion of the activator metals is controlled and the barium emission is more uniform in terms of location and time.
- Oxide cathodes with a higher DC current carrying capacity and a longer service life are obtained.
- the metal particles have an acicular shape, this can help to keep the diffusion of the activator metals uniform throughout the life of the oxide cathode.
- the average particle diameter of the metal particles is preferably 0.2 to 5.0 ⁇ m. It can also be preferred that the metal particles are embedded in the particle-particle composite, in particular that the metal particles are embedded in the particle-particle composite vertically to the cathode base surface.
- the invention also relates to an oxide cathode, which has a cathode support with a cathode base made of a first cathode metal with a cover layer, which consists of ultrafine metal particles containing nickel, and a cathode coating made of an electron-emitting material, which is a particle-particle composite made of oxide particles and Contains metal particles, the oxide particles being an oxide selected from the oxides of scandium, yttrium and the lanthanoids cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium and an alkaline earth metal oxide selected from Group of the oxides of calcium, strontium and barium, and the metal particles comprises a second cathode metal selected from the group comprising Ni, Co, Ir, Re, Pd, Rh and Pt.
- Fig. 1 shows a schematic cross section through an embodiment of the oxide cathode according to the invention.
- a cathode ray tube is equipped with an electron gun, which typically includes an array with one or more oxide cathodes.
- An oxide cathode according to the invention comprises a cathode support with a cathode base and a cover layer, which consists of ultrafine metal particles which contain nickel, and a cathode coating.
- the cathode support contains the heater and the base with the top layer.
- the oxide cathode consists of a cathode support, i.e. a cylindrical tube 3, into which the heating wire 4 is inserted, a cap 2, which forms the cathode base, with the cover layer 7 and a cathode coating 1, which represents the actual cathode body.
- the material of the cathode base is preferably a metal selected from the
- the nickel alloys for the base of the oxide cathodes according to the invention can consist of nickel with an alloy portion from a reducing activator element, selected from the group consisting of magnesium, manganese, iron, silicon, tungsten, molybdenum, chromium, titanium, hafnium, zirconium and aluminum. Since the cathode coating also contains activator elements, the amount of activator elements in the material of the cathode base can be kept low. An alloy content of 0.05 to 0.8% activator metal in the material for the cathode base is preferred.
- the cathode base is coated with a top layer made of ultra-fine
- the ultrafine particles preferably contain an activator selected from the group Mg, Al, Mo, Ti, Si, Cr, Zr, Mg. It is particularly preferred if the metal particles selected a slow activator Group contains AI, Mo, Ti and Si.
- the slow activators are preferably added in an amount of 1 to 4% by weight.
- the cathode coating contains an electron-emissive material that consists of a particle-particle composite.
- the main component of the particle-particle composite in the electron-emitting material are oxide particles 6, which are an oxide selected from the oxides of scandium, yttrium and the lanthanoids cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, Thulium, ytterbium and lutetium; and an alkaline earth oxide selected from the group of oxides of calcium, strontium and barium.
- the oxide particles can contain oxide particles with oxides of the alkaline earth metal which are doped with the oxides of scandium, yttrium and the lanthanides cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
- the oxide particles contain oxide particles with oxides of the alkaline earth metal, and oxide particles with the oxides of scandium, yttrium and the lanthanoids cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
- alkaline earth oxide Barium oxide, together with calcium oxide and / or strontium oxide, is preferred as the alkaline earth oxide.
- the alkaline earth oxides are used as a physical mixture of alkaline earth oxides or as binary or ternary mixed crystals of the alkaline earth metal oxides. Preferred is a ternary alkaline earth mixed crystal oxide made from barium oxide,
- Strontium oxide and calcium oxide or a binary mixture of barium oxide and calcium oxide.
- the alkaline earth oxide can be doped from an oxide selected from the oxides of scandium, yttrium and the lanthanoids cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium,
- Ytterbium and lutetium e.g. B. in an amount of 10 to a maximum of 1000 ppm.
- the ions of scandium, yttrium and the lanthanoids occupy lattice sites or interlattice sites in the crystal lattice of the alkaline earth metal oxides.
- Yttrium is preferably used as the doping.
- the doped oxides are obtained by coprecipitation.
- oxide particles of the alkaline earth oxides and oxide particles of the oxides of scandium, yttrium and the lanthanoids cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium can also be produced separately and used as a physical mixture become.
- the particle-particle composite material of the electron-emitting material contains as a second component metal particles 5 which contain the second cathode metal.
- the material for the second component is an alloy of a second Cathode metal selected from the group Ni, Co, Ir, Re, Pd, Rh and Pt with an activator metal selected from the group Mg, Mn, Fe, Si, W, Mo, Cr, Ti, Hf, Zr, Al.
- Metal particles with a spherical or ellipsoidal grain shape can preferably be used for the particle-particle composite material of the present invention.
- the mean grain diameter is preferably 0.2 to 5 ⁇ m. It is also possible to use needle-shaped metal particles with a maximum grain diameter of 10 to 15 ⁇ m. Such needle-shaped particles can be aligned vertically to the cathode base by means of suitable deposition processes.
- the slowly diffusing activator metals such as Mo and W in a concentration of 2 to 10% by weight in the alloy are particularly suitable for particles with a small grain diameter.
- the faster diffusing activator metals such as Zr and M * g & are suitable for particles with a larger grain diameter.
- the ultrafine particles which contain nickel or another cathode metal, can be produced from the corresponding targets by a laser ablation process.
- These targets contain cathode nickel, which can be alloyed with activators such as Mg. Al, Ti, Zr, Si, Cr, Zr and Mg.
- the ultrafine particles for the cover layer can be produced separately and applied to the cathode base by a conventional coating process. It is also possible to deposit the ultrafine particles for the cover layer directly on the cathode base by laser ablation. It is also possible to use wet chemical or sol-gel preparation methods to make the ultrafine particles.
- the carbonates of the alkaline earth metals calcium, strontium and barium are ground and mixed with one another.
- the weight ratio of calcium carbonate: strontium carbonate: barium carbonate: zirconium is 25.2: 31.5: 40.3: 3 or 1: 1.25: 6 or 1:12:22 or 1: 1.5: 2.5 or 1: 4: 6
- the carbonates are one or more oxides of
- Scandiums, yttriums and the lanthanoids cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium were added.
- Y 2 O 3 is preferably added in an amount of 130 ppm.
- Carbonates, oxides and metal particles are mixed to the raw mass.
- a binder preparation can also be added to the raw material.
- the binder preparation can contain water, ethanol, ethyl nitrate, ethyl acetate or diethyl acetate as the solvent.
- the raw material for the cathode coating is then applied to the cathode base by brushing, dipping, cataphoretic deposition or spraying.
- the thickness of the cathode coating is preferably 30 to 80 ⁇ m.
- the coated oxide cathodes are installed in the cathode ray tube.
- the cathodes are formed while the cathode ray tube is being evacuated. To do this, they are heated to a temperature of 1000 ° C to 1200 ° C. At this temperature, the alkaline earth carbonates are converted to the alkaline earth oxides with the release of CO and CO 2 and then form a porous sintered body. After this "burning off" of the cathodes, the activation takes place, the purpose of which is to supply excess elemental alkaline earth metal embedded in the oxides. The excess alkaline earth metal is created by the reduction of alkaline earth metal oxide. During the actual reduction activation, the alkaline earth oxide is reduced by the released CO or activator metal. In addition, there is a current activation, which generates the formation of the required free alkaline earth metal through electrolytic processes at high temperatures.
- the fully formed, electron-emitting material can preferably contain 1 to 5% by weight of metal particles.
- a cathode for a cathode tube has a cap-shaped cathode base which is made of an alloy of nickel with 0.12% by weight of Mg, 0.06% by weight of Al and 2.0% by weight of W assures on.
- the cathode base is located at the top of a cylindrical cathode support (sleeve) in which the heater is mounted.
- the cover layer which consists of ultrafine metal particles that contain nickel, the cathode base is placed in the ablation chamber of a laser ablation system.
- An excimer laser beam is directed at a pressure of a few mbar onto a rotating cylindrical target made of cathode nickel, which contains a suitable amount of activators, and ablates this.
- a plasma torch with leached ultrafine particles forms over the target.
- These leached-out ultrafine particles are transported to the cathode base by means of a carrier gas stream of Ar / H 2 and are deposited there.
- the Ar / H carrier gas prevents oxidation of the particles during transport.
- Other inert gases can also be suitable for this.
- the cathode has a cathode coating on the top of the cathode base.
- the cathode base is first cleaned. Then a 2.0% by weight metal particle and 98% by weight powder of a starting compound for the oxide particles are suspended with 130 ppm yttrium oxide in a solution of ethanol, butyl acetate and nitrocellulose.
- the metal particles consist of an alloy of nickel with 0.02 wt .-% Al, 3.0 wt .-% W and 6.0 wt .-% Mo.
- the metal particles have a needle-like grain shape with an average needle length of 3 + 2 ⁇ m.
- the powder with the starting compounds for the oxide particles consists of barium strontium carbonate with 130 ppm yttrium oxide. This suspension is sprayed onto the cathode base.
- the layer is formed at a temperature of 650 to 1100 ° C to effect alloying and diffusion between the cathode metal of the metal base and the metal particles.
- the cathode thus formed has a DC current carrying capacity of 4 A / cm 2 with a lifespan of 20,000 h and an internal tube pressure of 2 * 10 "9 bar.
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01980367A EP1232511B1 (en) | 2000-09-19 | 2001-09-11 | Oxide cathode |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00308164 | 2000-09-19 | ||
EP00308164 | 2000-09-19 | ||
EP01201836 | 2001-05-02 | ||
EP01201836 | 2001-05-02 | ||
EP01980367A EP1232511B1 (en) | 2000-09-19 | 2001-09-11 | Oxide cathode |
PCT/EP2001/010453 WO2002025681A1 (en) | 2000-09-19 | 2001-09-11 | Isahode ray tube having an oxide cathode |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1232511A1 true EP1232511A1 (en) | 2002-08-21 |
EP1232511B1 EP1232511B1 (en) | 2007-08-15 |
Family
ID=26073313
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01980367A Expired - Lifetime EP1232511B1 (en) | 2000-09-19 | 2001-09-11 | Oxide cathode |
Country Status (8)
Country | Link |
---|---|
US (1) | US7019450B2 (en) |
EP (1) | EP1232511B1 (en) |
JP (1) | JP5048907B2 (en) |
KR (1) | KR100867149B1 (en) |
CN (1) | CN100336154C (en) |
AT (1) | ATE370515T1 (en) |
DE (1) | DE50112861D1 (en) |
WO (1) | WO2002025681A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100449759B1 (en) * | 2002-03-21 | 2004-09-22 | 삼성에스디아이 주식회사 | Cathode for electron tube and preparing method thereof |
GB0230125D0 (en) * | 2002-12-24 | 2003-01-29 | Lg Philips Displays Netherland | Oxide cathode |
US20060068196A1 (en) * | 2004-09-24 | 2006-03-30 | Kabushiki Kaisha Toshiba | High-frequency magnetic material, producing method for the same and high-frequency magnetic device |
DE102008020164A1 (en) * | 2008-04-22 | 2009-10-29 | Siemens Aktiengesellschaft | Cathode with a flat emitter |
CN101447376B (en) * | 2008-12-31 | 2010-09-01 | 北京工业大学 | Y2O3-Lu2O3 system composite rare earth-molybdenum electron emission material and preparation method thereof |
CN103050347A (en) * | 2011-10-13 | 2013-04-17 | 中国科学院电子学研究所 | Method for preparing nickel-scandium (Ni-Sc) sponge oxide cathode |
CN103700557B (en) * | 2013-12-24 | 2016-03-30 | 北京工业大学 | A kind of carbonization rare-earth oxidation lutetium doping molybdenum cathode material and preparation method thereof |
JP6285254B2 (en) * | 2014-04-02 | 2018-02-28 | 大学共同利用機関法人 高エネルギー加速器研究機構 | Electron beam generating cathode member and manufacturing method thereof |
CN110690085B (en) * | 2019-10-24 | 2022-03-11 | 成都国光电气股份有限公司 | Method for preparing six-membered cathode emission material |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1270890A (en) * | 1985-07-19 | 1990-06-26 | Keiji Watanabe | Cathode for electron tube |
JPS62165832A (en) * | 1986-01-18 | 1987-07-22 | Mitsubishi Electric Corp | Cathode for electron tube |
KR910009660B1 (en) * | 1988-02-23 | 1991-11-25 | 미쓰비시전기 주식회사 | Cathode for electron tube |
JP2758244B2 (en) * | 1990-03-07 | 1998-05-28 | 三菱電機株式会社 | Cathode for electron tube |
DE4207220A1 (en) * | 1992-03-07 | 1993-09-09 | Philips Patentverwaltung | SOLID ELEMENT FOR A THERMIONIC CATHODE |
EP0639848B1 (en) * | 1993-08-20 | 1997-09-10 | Samsung Display Devices Co., Ltd. | Oxide cathode for electron tube |
DE19527723A1 (en) * | 1995-07-31 | 1997-02-06 | Philips Patentverwaltung | Electric discharge tube or discharge lamp and Scandat supply cathode |
JP2876591B2 (en) * | 1996-11-29 | 1999-03-31 | 三菱電機株式会社 | Cathode for electron tube |
KR100249714B1 (en) * | 1997-12-30 | 2000-03-15 | 손욱 | Cathode used in an electron gun |
KR100268243B1 (en) * | 1997-12-30 | 2000-10-16 | 김순택 | Cathod used in an electron gun |
JPH11204019A (en) | 1998-01-09 | 1999-07-30 | Sony Corp | Oxide cathode |
KR20000038644A (en) * | 1998-12-08 | 2000-07-05 | 김순택 | Cathode for electric gun |
JP2001345041A (en) * | 2000-06-01 | 2001-12-14 | Mitsubishi Electric Corp | Cathode for electron tube |
-
2001
- 2001-09-11 AT AT01980367T patent/ATE370515T1/en not_active IP Right Cessation
- 2001-09-11 JP JP2002529794A patent/JP5048907B2/en not_active Expired - Fee Related
- 2001-09-11 EP EP01980367A patent/EP1232511B1/en not_active Expired - Lifetime
- 2001-09-11 US US10/130,338 patent/US7019450B2/en not_active Expired - Lifetime
- 2001-09-11 KR KR1020027006342A patent/KR100867149B1/en not_active IP Right Cessation
- 2001-09-11 WO PCT/EP2001/010453 patent/WO2002025681A1/en active IP Right Grant
- 2001-09-11 CN CNB018038999A patent/CN100336154C/en not_active Expired - Fee Related
- 2001-09-11 DE DE50112861T patent/DE50112861D1/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO0225681A1 * |
Also Published As
Publication number | Publication date |
---|---|
US7019450B2 (en) | 2006-03-28 |
JP5048907B2 (en) | 2012-10-17 |
ATE370515T1 (en) | 2007-09-15 |
CN1395737A (en) | 2003-02-05 |
KR100867149B1 (en) | 2008-11-06 |
KR20020053863A (en) | 2002-07-05 |
US20020163308A1 (en) | 2002-11-07 |
JP2004510291A (en) | 2004-04-02 |
DE50112861D1 (en) | 2007-09-27 |
EP1232511B1 (en) | 2007-08-15 |
CN100336154C (en) | 2007-09-05 |
WO2002025681A1 (en) | 2002-03-28 |
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