EP1713148A1 - Procédé de fabrication de balais de charbon et balais de charbon faits par ce procédé - Google Patents

Procédé de fabrication de balais de charbon et balais de charbon faits par ce procédé Download PDF

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Publication number
EP1713148A1
EP1713148A1 EP05007934A EP05007934A EP1713148A1 EP 1713148 A1 EP1713148 A1 EP 1713148A1 EP 05007934 A EP05007934 A EP 05007934A EP 05007934 A EP05007934 A EP 05007934A EP 1713148 A1 EP1713148 A1 EP 1713148A1
Authority
EP
European Patent Office
Prior art keywords
thermoplastic binder
mixture
binder
carbon
carbon brushes
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
Application number
EP05007934A
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German (de)
English (en)
Other versions
EP1713148B1 (fr
Inventor
Christian Dr. Böttger
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.)
Schunk Kohlenstofftechnik GmbH
Original Assignee
Schunk Kohlenstofftechnik 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 Schunk Kohlenstofftechnik GmbH filed Critical Schunk Kohlenstofftechnik GmbH
Priority to EP05007934A priority Critical patent/EP1713148B1/fr
Priority to DE502005001969T priority patent/DE502005001969D1/de
Priority to AT05007934T priority patent/ATE378711T1/de
Priority to PCT/EP2006/003181 priority patent/WO2006108568A1/fr
Publication of EP1713148A1 publication Critical patent/EP1713148A1/fr
Application granted granted Critical
Publication of EP1713148B1 publication Critical patent/EP1713148B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01RELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R39/00Rotary current collectors, distributors or interrupters
    • H01R39/02Details for dynamo electric machines
    • H01R39/18Contacts for co-operation with commutator or slip-ring, e.g. contact brush
    • H01R39/26Solid sliding contacts, e.g. carbon brush
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01RELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R43/00Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
    • H01R43/12Manufacture of brushes

Definitions

  • the present invention relates to a manufacturing method for carbon brushes and carbon brushes available thereafter.
  • Carbon brushes are usually produced by compressing a powdery material, substantially carbon-based with a finely divided binder and for certain applications with the addition of metal powders in a mold and then the pressed material of a heat treatment for coking, curing or distribution of the binder or Sintering of the metal powder is subjected. The carbon brush thus obtained is then optionally subjected to mechanical finishing.
  • binders hitherto, e.g. Pitches and tars, synthetic thermosetting resins, such as phenolic resins, or thermoplastics.
  • thermosetting resin eg, a phenolic resin, or pitch as a binder in the manufacture of carbon brushes.
  • a synthetic powder resin in particular a duroplastic, for example an epoxy or phenolic resin, is used as a binder for producing a resin-bonded graphite material.
  • the binder is a dissolved in solvent powder resin or a solvent-free liquid resin.
  • GB-A-641.937 relates to the manufacture of electrical contact brushes and describes the use of a binder in a solution of a volatile solvent to disperse the binder well.
  • DE-A-24 44 957 discloses the production of carbon contact bodies by pressing together powder of graphite and a metal in a die and subsequent heat treatment.
  • the powder contains 0.5 to 50 parts by weight of a binder from the group of monovalent aromatic polymers, for example polyarylene sulfides, preferably polyphenylene sulfide in finely ground form.
  • thermoplastic binder examples include polyphenylene sulfides, polysulfones, polyphenyl sulfones, polyether ketones, polyethylene terephthalates, polyamides, polyimides, and copolymers derived therefrom.
  • DE-A-199 00 24 describes a method for producing a carbon brush from a powdery material, which is characterized by the use of an undissolved powdery binder of fine-grained thermoplastic powder having an average grain size of 5 .mu.m to 50 .mu.m and a very narrow particle size distribution.
  • Pitch-bonded materials for carbon brushes which also contain copper, silver or other metal powders and which are produced with pressed-in copper strand, have the disadvantage of sulfide formation on metal powders and stranded wire because of the sulfur content of the pitches. Similar problems arise with the use of polymers containing sulfur (eg polyphenylene sulfide) under the conditions of manufacture or application is at least partially set free. Many pitch-based binders are also carcinogenic.
  • thermoplastic or thermosetting polymers as a binder
  • soluble thermoplastics as binders lead to end products whose resistance to solvents and high application temperatures is comparatively low.
  • thermosetting polymers as binders, especially in combination with heat treatments leading to its partial or complete coking, leads to end products that fail to provide adequate dimensional stability (swelling) in high temperature and humidity applications, and significant resistance aging (increase in resistance). exhibit.
  • a process for the production of carbon brushes which avoids the above disadvantages.
  • good compressibility of the carbonaceous powder carbon brushes with good reproducibility of the material properties, high dimensional stability and resistance constancy associated with long life in use at high temperatures and low noise run.
  • the subject of the present invention is also a carbon brush obtainable by this process.
  • step (a) of the process according to the invention a composition is prepared which comprises a carbon powder and a powdery thermoplastic binder.
  • a suitable metal powder may be added to the composition already in step (a), which is further described below in detail.
  • carbon powder are, for example graphite (natural and artificial graphite), cokes and anthracites, and produced from these raw materials Intermediates and mixtures suitable.
  • Carbon brushes are preferably used for automotive applications natural graphite.
  • the carbon powder should in preferred embodiments, an average grain size (D 50 -Median the volume distribution (in volume percent) by means of laser granulometry) of 30 ⁇ m to 50 ⁇ m, more preferably about 40 ⁇ m have.
  • the maximum grain size should preferably not exceed 150 ⁇ m .
  • the required degree of purity of the carbon powder (ash) depends essentially on application requirements and can be easily determined by the person skilled in the art.
  • thermoplastic binders each in powder form, are: polyamides; polyimides; polyether ketones; Polyetheretherketones (PEEK); Polysulfones, in particular polyphenylene sulfones (PPSU); Polyphenylene sulfides (PPS); Polyethylene terephthalates and copolymers and mixtures of these polymers.
  • PEEK Polyetheretherketones
  • PPSU polyphenylene sulfones
  • PPS Polyphenylene sulfides
  • a preferred thermoplastic binder is polyamide, e.g. Polyamide-6, polyamide-11 and polyamide-12, as well as copolymers and blends of these polyamides.
  • thermoplastic binders other than PPS are preferably used. Sulfur-free thermoplastic binders are particularly preferably used. It is assumed that in the case of metal-containing carbon brushes, the sulfur from the binder can react with the metal particles or pressed-in copper strands and thus worsens the material properties of the carbon brushes.
  • the pulverulent thermoplastic binder has an average particle size (D 50 -Median the volume distribution (in volume percent) by means of laser granulometry) of 5 ⁇ m to 70 ⁇ m, more preferably from 10 ⁇ m to 50 ⁇ m, and most preferably from 20 ⁇ m to 30 ⁇ m .
  • the proportions of the powdery thermoplastic binder in the composition of the step (a) are preferably 2 to 20% by weight, more preferably 3 to 18% by weight, based on the total weight of the carbon powder and the powdered thermoplastic binder.
  • carbon brushes for use in automobiles (electrical system 12 V to 42 V) or electrical appliances and tools on battery 3 to 8 wt .-% powdered thermoplastic binder are particularly preferred, depending on the particular application 3 to 6 wt .-% (target position low-noise operation of the corresponding electric motors, eg air conditioning and fan heaters or modulating motors) or 6 to 8 wt .-% (objective stability at high application temperatures and high humidity) powdered thermoplastic binder are preferred, each based on the total weight of carbon powder and powdered thermoplastic binder.
  • thermoplastic binder In carbon brushes for use in power tools and household appliances (mains voltage 110 V / 230 V) 8 to 15 wt .-% powdered thermoplastic binder are particularly preferred, most preferred for this purpose 10 to 12 wt .-% powdered thermoplastic binder, each based on the total weight of carbon powder and powdered thermoplastic binder.
  • step (a) of the process according to the invention the individual components, ie the carbon powder, the powdered thermoplastic binder and optionally metal powder, simply dry mixed together to produce a powdered, preferably homogeneous composition.
  • the mixing can be done in a suitable mixing device carried out, such as a plowshare mixer or a simplex mixer.
  • step (a) The powdered composition of step (a) is then processed in step (b) at a temperature above the melting point of the thermoplastic binder.
  • a mixture is obtained which contains the carbon powder, optionally metal powder, and the molten thermoplastic binder.
  • the composition usually has a coarse to feinkrümelige consistency.
  • the diameter of the bonded grains is often in the range of 40 ⁇ m to 2 mm.
  • the thermoplastic binder wets and coats the particles of the carbon powder and optionally the metal powder.
  • the processing temperature in step (b) is above the melting point of the thermoplastic binder and depends on a number of factors, such as the type, amount and grain size distribution of the carbon powder, the thermoplastic binder and optionally the metal powder. It can be readily determined by one skilled in the art and is preferably 10K to 40K, more preferably 10K to 25K, and most preferably 15K to 20K above the melting point of the thermoplastic binder. Of course, the maximum processing temperature in step (b) is below the decomposition temperature of the binder and is chosen to be as low as technically possible for economic reasons.
  • step (b) The processing of the powdery composition from step (a) in step (b) takes place in a suitable device with mixing and kneading action.
  • a suitable device with mixing and kneading action.
  • a twin-screw extruder works with two parallel metal screws, which are divided into various transport and kneading areas.
  • the arrangement of these transport and Knet Schemee, the rotational speeds of the screw, as well as the exact temperature distribution in the heating zones of the extruder are not essential to the invention and can be easily optimized by a person skilled in the art by preliminary experiments.
  • the mixture obtained from step (b) is either directly ground and screened (step (c)) or optionally first pre-pressed for reasons of better processability, then ground and screened.
  • the grinding process can be done in any suitable mill; can be used, for example Hammer mills, cross beater mills, disc mills, pin mills, toothed disk mills, roll mills and air jet mills.
  • the milled mixture is preferably sieved at 0.4 mm to 0.8 mm, more preferably at 0.5 mm, so that a granule is obtained.
  • the milling and sieving in step (c) serves to produce an optimum grain size, but is not essential to the practice of the present invention.
  • this prepressing step is preferably carried out on a plate press, preferably at pressures of 500 to 1500 bar.
  • step (b) If the mixture of step (b) does not contain any metal powder and if a metal-containing carbon brush is to be produced, the metal powder is added before step (d), the subsequent pressing.
  • Metal powders are commonly added to reduce material resistance and contact resistance between carbon brush and commutator in formulations for carbon brushes operating in areas of low voltages, such as on-board automotive or material handling equipment, and electrical appliances and tools on battery power.
  • metal powder for example, powders of copper, copper alloys, silver or iron can be used, copper powder is preferred. It can also be different Metal powder can be used in mixture. The proportion of the metal powder in the mixture depends on the later application of the carbon brush produced therefrom.
  • Preferred quantitative ranges of metal powders in the mixture in the following applications of the finished carbon brushes are: Automotive electrical system 12 V: 30 to 60 wt.%, Automotive on-board 24 V: 15 to 35 wt.%, Automotive vehicle electrical system 42 V: 5 up to 25% by weight, fixed networks 110 V / 230 V: max. 15% by weight.
  • auxiliaries may be added to the mixture of step (b) or (c), if appropriate, before the final pressing in step (d), optionally in addition to metal powder as already explained above.
  • the auxiliaries may also be added at an earlier stage in the process, for example during the preparation of the powdered composition in step (a). If several adjuvants are added, the separate addition of the individual excipients at different times in the process is possible.
  • auxiliaries which can be used in the process according to the invention for producing carbon brushes are solid lubricants, such as MoS 2 and WS 2 , and cleaning agents, such as silicates, oxides and carbides, in particular silicon carbide.
  • step (d) If at least one further component (ie, metal powder and / or adjuvant (s)) is added to the powdered composition of step (b) or (c), if done, prior to final pressing in step (d), all of the constituents are preferably in one homogenized suitable mixing device before pressing. In this case, similar mixing devices can be used as in step (a).
  • the pressing in step (d) takes place in a suitable mold consisting of die and stamping, so that the resulting body has the shape of the desired carbon brush.
  • the transmission of the pressing force on punch and / or die occurs via mechanical (eg eccentric) or hydraulic presses.
  • the pressing tools used can have one or more cavities (single or multiple dies).
  • Metal-free carbon brushes are preferably pressed at pressures of 1000 bar to 2000 bar.
  • Metal-containing carbon brushes are preferably pressed at pressures of 2500 bar to 4000 bar, with metal-containing carbon brushes often simultaneously a metal strand (eg copper wire) is pressed with.
  • the pressed carbon brushes thus obtained are thermally treated in step (e) at a temperature above the melting point of the thermoplastic binder but below its decomposition temperature.
  • This treatment leads to an even more uniform distribution of the binder in the form of thin polymer films between the carbon and optionally metal grains, which in particular improves the strength properties of the carbon brushes.
  • metal-containing carbon brushes there is also a sintering of the metal grains, which leads to a further increase in the strength, but in particular to a reduction in the specific electrical resistance.
  • the thermal treatment is preferably carried out in continuous or discontinuous industrial furnaces, e.g. Strip or retort ovens. In preferred embodiments, the thermal treatment is carried out in a reducing atmosphere, such as in a mixture of nitrogen and hydrogen.
  • the thermally treated carbon brushes can be mechanically reworked.
  • the post-processing serves to maintain the required dimensional tolerances or to promote the running-in behavior and is preferably carried out by grinding, in particular in the pressing direction or on the tread.
  • the invention Carbon brushes in particular by comparatively low hardness, but high bending strength and thus good damping and sliding properties, which require increased service life, higher speeds, better speed stability and low-noise operation in use.
  • the carbon brushes according to the invention are widely used, for example in the automotive industry in vehicle electrical systems of 12 V to 42 V (for example 12 V, 24 V and 42 V) for power tools in battery mode or at mains voltages (110 V / 230 V), for home appliances and industrial engines.
  • Step 1 Preparation of the graphite binder base mixtures (granules)
  • Graphite and polyamide are dry-homogenized according to Example A or B in a Lödige mixer (ploughshare mixer). This homogenized powder is fed continuously to a heatable twin-screw extruder and processed at 170 rpm. Setting the temperature zones in the conveying direction: 170 ° C to 220 ° C. As a result of the mixing and kneading process, a mixture consisting of graphite grains coated with polyamide is obtained and, by bonding to each other, has a coarse to fine crumbly consistency (particle size: 40 ⁇ m to 2 mm).
  • This mixture is pressed at 1500 bar into plates, ground on a hammer mill and sieved at 0.5 mm, so that a granule with a typical grain distribution is produced as follows: 10%> 400 ⁇ m, 60%> 125 ⁇ m, 90% > 63 ⁇ m
  • Step 2 Preparation of a metal-containing powder for pressing carbon brushes
  • step 1 produced granules according to Example A or B. 50.0% copper powder 1.5% molybdenum disulfide 0.3% silicon carbide as a cleaning agent
  • the above ingredients are placed in a Lödige mixer (ploughshare mixer) and homogenized for 10-15 minutes.
  • the powders produced in step 2 are pressed on a bench press in multiple dies with pressures of about 3500 bar while simultaneously pressing in a copper strand.
  • the pressed carbon brushes are subjected in a belt furnace to a thermal treatment at temperatures of 330 ° C under a reducing atmosphere under a nitrogen-hydrogen mixture.
  • Example A Carbon brushes for use at temperatures above 100 ° C and high humidity
  • Example B Carbon brushes for use in low-noise demand
  • example B carbon brush A 473 from Schunk Kohlenstoff-Technik GmbH, phenolic resin binder, coked
  • the airborne sound measurements were carried out with a "Pulse Analyzer” from Brüel & Kjaer in a noise measurement booth, the microphone being located at a distance of 10 cm from the brush holder opening of the motor housing.
  • Table 2 ⁇ u> Table 2 ⁇ / u>
  • Example B Comparative example Airborne sound (0 to 20kHz) (dB (A)) 45.2 49.6

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Motor Or Generator Current Collectors (AREA)
  • Carbon And Carbon Compounds (AREA)
EP05007934A 2005-04-12 2005-04-12 Procédé de fabrication de balais de charbon et balais de charbon faits par ce procédé Not-in-force EP1713148B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP05007934A EP1713148B1 (fr) 2005-04-12 2005-04-12 Procédé de fabrication de balais de charbon et balais de charbon faits par ce procédé
DE502005001969T DE502005001969D1 (de) 2005-04-12 2005-04-12 Verfahren zur Herstellung von Kohlebürsten und nach diesem Verfahren hergestellte Kohlebürsten
AT05007934T ATE378711T1 (de) 2005-04-12 2005-04-12 Verfahren zur herstellung von kohlebürsten und nach diesem verfahren hergestellte kohlebürsten
PCT/EP2006/003181 WO2006108568A1 (fr) 2005-04-12 2006-04-07 Procede de production de balais de charbon, et balais de charbon produits a l'aide dudit procede

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP05007934A EP1713148B1 (fr) 2005-04-12 2005-04-12 Procédé de fabrication de balais de charbon et balais de charbon faits par ce procédé

Publications (2)

Publication Number Publication Date
EP1713148A1 true EP1713148A1 (fr) 2006-10-18
EP1713148B1 EP1713148B1 (fr) 2007-11-14

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EP05007934A Not-in-force EP1713148B1 (fr) 2005-04-12 2005-04-12 Procédé de fabrication de balais de charbon et balais de charbon faits par ce procédé

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EP (1) EP1713148B1 (fr)
AT (1) ATE378711T1 (fr)
DE (1) DE502005001969D1 (fr)
WO (1) WO2006108568A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2927626A1 (fr) * 2008-02-15 2009-08-21 Arkema France Poudre fine de polyamide issu de matieres renouvelables et procede de fabrication d'une telle poudre.
WO2011107378A1 (fr) * 2010-03-03 2011-09-09 Robert Bosch Gmbh Procédé de fabrication d'un balai de charbon d'un collecteur
EP2681812A1 (fr) * 2011-02-28 2014-01-08 Mersen France Amiens SAS Balai de contact
WO2016156112A1 (fr) 2015-03-30 2016-10-06 Schunk Hoffmann Carbon Technology Ag Utilisation d'un matériau composite à base de carbone pour fabriquer des corps de contact électriques pour une pompe à carburant, et corps de contact ainsi obtenus
DE102017131340A1 (de) 2017-12-27 2019-06-27 Schunk Carbon Technology Gmbh Kohlebürste und Verfahren zur Herstellung

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* Cited by examiner, † Cited by third party
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RU2613245C1 (ru) * 2015-10-27 2017-03-15 федеральное государственное автономное образовательное учреждение высшего образования "Южно-Уральский государственный университет" (национальный исследовательский университет)" (ФГАОУ ВО "ЮУрГУ" (НИУ)") Способ изготовления графитопластовых изделий
EP3170877B1 (fr) 2015-11-19 2020-11-18 3M Innovative Properties Company Adhésif structurel avec amélioration de mode de défaillance
JP2017118620A (ja) * 2015-12-22 2017-06-29 日立化成株式会社 摺動部材形成材料及び摺動部材
RU2656375C1 (ru) * 2017-09-05 2018-06-05 федеральное государственное автономное образовательное учреждение высшего образования "Южно-Уральский государственный университет (национальный исследовательский университет)" Композиция для изготовления электротехнических изделий
RU2708291C1 (ru) * 2018-11-15 2019-12-05 Общество с ограниченной ответственностью "ТрансТрибоЛогик" (ООО "ТрансТрибоЛогик") Способ изготовления материала на основе графита для скользящих электрических контактов и материал
CN113603391B (zh) * 2021-08-11 2022-08-16 摩根新材料(上海)有限公司 一种碳刷填充材料的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3716609A (en) * 1970-10-05 1973-02-13 United Aircraft Corp Process for preparing molded structure from polyphenylene sulfide resin and filler
DE2836045A1 (de) * 1978-08-17 1980-02-28 Bosch Gmbh Robert Kontaktkoerper fuer elektrischen stromkreis
DE19900024A1 (de) * 1999-01-02 2000-07-06 Carbone Ag Verfahren zur Herstellung einer Kohlebürste sowie nach diesem Verfahren hergestellte Kohlebürste
EP1280217A2 (fr) * 2001-07-26 2003-01-29 Matsushita Electric Industrial Co., Ltd. Séparateur pour pile à combustible, son procédé de fabrication, et pile à combustible

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3716609A (en) * 1970-10-05 1973-02-13 United Aircraft Corp Process for preparing molded structure from polyphenylene sulfide resin and filler
DE2836045A1 (de) * 1978-08-17 1980-02-28 Bosch Gmbh Robert Kontaktkoerper fuer elektrischen stromkreis
DE19900024A1 (de) * 1999-01-02 2000-07-06 Carbone Ag Verfahren zur Herstellung einer Kohlebürste sowie nach diesem Verfahren hergestellte Kohlebürste
EP1280217A2 (fr) * 2001-07-26 2003-01-29 Matsushita Electric Industrial Co., Ltd. Séparateur pour pile à combustible, son procédé de fabrication, et pile à combustible

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2927626A1 (fr) * 2008-02-15 2009-08-21 Arkema France Poudre fine de polyamide issu de matieres renouvelables et procede de fabrication d'une telle poudre.
WO2011107378A1 (fr) * 2010-03-03 2011-09-09 Robert Bosch Gmbh Procédé de fabrication d'un balai de charbon d'un collecteur
EP2681812A1 (fr) * 2011-02-28 2014-01-08 Mersen France Amiens SAS Balai de contact
EP2681812B1 (fr) * 2011-02-28 2016-04-27 Mersen France Amiens SAS Balai de contact
US9525258B2 (en) 2011-02-28 2016-12-20 Mersen France Amiens Sas Contact brush
WO2016156112A1 (fr) 2015-03-30 2016-10-06 Schunk Hoffmann Carbon Technology Ag Utilisation d'un matériau composite à base de carbone pour fabriquer des corps de contact électriques pour une pompe à carburant, et corps de contact ainsi obtenus
DE102015205735A1 (de) 2015-03-30 2016-10-06 Schunk Hoffmann Carbon Technology Ag Verwendung eines Kohlenstoffverbundmaterials zur Herstellung von elektrischen Kontaktkörpern für eine Kraftstoffpumpe sowie Kontaktkörper
CN107431323A (zh) * 2015-03-30 2017-12-01 申克霍夫曼碳科技股份公司 碳复合材料用于制造用于燃料泵的电气接触元件的用途和接触元件的用途
DE102017131340A1 (de) 2017-12-27 2019-06-27 Schunk Carbon Technology Gmbh Kohlebürste und Verfahren zur Herstellung
WO2019129628A1 (fr) 2017-12-27 2019-07-04 Schunk Carbon Technology Gmbh Balai à charbon et son procédé de fabrication

Also Published As

Publication number Publication date
EP1713148B1 (fr) 2007-11-14
DE502005001969D1 (de) 2007-12-27
ATE378711T1 (de) 2007-11-15
WO2006108568A1 (fr) 2006-10-19

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