WO2012008373A1 - 電極形成用の導電微粒子及び金属ペースト並びに電極 - Google Patents
電極形成用の導電微粒子及び金属ペースト並びに電極 Download PDFInfo
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- WO2012008373A1 WO2012008373A1 PCT/JP2011/065673 JP2011065673W WO2012008373A1 WO 2012008373 A1 WO2012008373 A1 WO 2012008373A1 JP 2011065673 W JP2011065673 W JP 2011065673W WO 2012008373 A1 WO2012008373 A1 WO 2012008373A1
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4075—Composition or fabrication of the electrodes and coatings thereon, e.g. catalysts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
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- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Definitions
- the present invention relates to conductive fine particles for forming various electrodes such as a sensor electrode, a heater electrode, and a lead wire electrode, and further relates to a metal paste for electrode formation using the same.
- a metal paste containing conductive metal powder is applied to the substrate by various methods such as screen printing and fired. It is common to manufacture. In addition to being able to deal with complex electrode patterns, the form of metal paste can be used to simultaneously manufacture the substrate and the electrode by applying and baking the metal paste on the green sheet forming the ceramic substrate. This is because it is preferable from the viewpoint of manufacturing efficiency.
- a metal paste for electrode formation a mixture of conductive particles such as noble metal and ceramic powder such as Al 2 O 3 and ZrO 2 (YSZ) in a solvent is used.
- ceramic powder is mixed with metal paste, the difference in shrinkage between metal paste and green sheet is corrected when the substrate and electrode are manufactured by applying metal paste to green sheet and firing as described above. This is because the problem of warping or deformation of the substrate due to the difference in shrinkage rate is solved and the adhesion of the electrodes is improved.
- the conductive particles can be prevented from being oversintered during firing by mixing ceramic with the metal paste.
- a metal paste for electrode formation is naturally required to have a low electrical resistance value (specific resistance) because it is a precursor material for the electrode.
- specific resistance specific resistance
- mixing of the ceramic powder is an impediment, and the resistance value of the electrode film formed by firing the metal paste tends to be considerably higher than that of the bulk metal.
- the improvement in adhesion due to the mixing of the ceramic in the metal paste is contrary to the requirement for lowering the resistance of the electrode, but if the ceramic is not mixed or the mixing amount is too small, the formation of the electrode itself is not performed. It becomes impossible.
- the present invention has been made paying attention to the above-described problems, and provides conductive fine particles for producing a metal paste capable of producing a low-resistance electrode film, and a metal paste using the same. For the purpose.
- the inventors of the present invention conducted various studies on the above-mentioned problems, and firstly considered the cause of the high resistance value of the electrode film formed by the conventional metal paste.
- the conductive particles and ceramic particles are dispersed in a solvent, and by firing this, the conductive particles are sintered and bonded so as to be conductive as an electrode.
- the ceramic powder is also sintered.
- the unsintered ceramic particles present around the conductive particles gather so as to be extruded from the conductive particles that have started sintering. Then, when the sintering of the ceramic proceeds in such a non-uniform dispersion state of the conductive particles and the ceramic particles, the ceramic particles become coarse. According to the present inventors, the high resistance in the prior art was considered that this sintered ceramic powder is coarse, which affects the resistance of the electrode.
- the ceramic powder is necessary for electrode formation, and it is not a preferable measure to exclude this from the metal paste. Therefore, the present inventors have studied to find a metal paste in which fine ceramic particles can be dispersed in the firing process. As a result, it has been found that the conductive particles preferably have a core / shell structure in which the conductive particles are coated with ceramic.
- the present invention for solving the above-mentioned problems is a conductive particle for electrode formation, which is made of Pt or a Pt alloy, and is made of a core particle having a particle diameter of 10 to 200 nm and a ceramic containing Al 2 O 3 or ZrO 2 , A shell covering at least a part of the core particles, and the ceramic constituting the shell covers the core at an addition amount of 0.5 to 15% by weight with respect to the core particles. It is the electroconductive particle for electrode formation which has a shell structure.
- the conventional metal paste is obtained by dispersing conductive particles and ceramic powder separately in a solvent.
- the conductive particles and the ceramic powder are combined to form a core / shell structure before the paste is formed, and this is dispersed in a solvent to obtain a metal paste.
- the reason why the ceramic powder becomes finer by making the structure of the conductive particles into the core / shell structure in this way is to reduce the time lag of the start of sintering of the conductive particles and the ceramic particles. That is, in firing the paste containing the conductive particles having the core / shell structure, the shell (ceramic) is detached from the core particles before the core particles are sintered. This ceramic desorption temperature is relatively high, and is close to the sintering temperature of the ceramic. Therefore, the conductive particles cannot be sintered while being covered with the shell, and sintering is started at the stage where the shell is detached. The state can be maintained.
- the ceramic which covers this also becomes fine by making conductive particles fine.
- a fine ceramic in a uniform dispersed state can avoid the conventional coarsening even if sintered.
- the ceramic particles in the electrode are made finer and the resistance is reduced.
- the core particles are made of Pt or a Pt alloy. These metals have good conductivity and excellent heat resistance. Since various sensors are used at high temperatures, such as automobile exhaust sensors, they are suitable as their electrode materials.
- Pt or a Pt alloy as the core particle can be selected depending on its use and required characteristics.
- Pt has a lower resistance than a Pt alloy, and is suitable for applications in which lower resistance such as sensor electrodes and lead wire electrodes is first required.
- the Pt alloy has a higher resistance than Pt but has a low resistance temperature coefficient (TCR) and is suitable for applications such as heater electrodes.
- TCR resistance temperature coefficient
- Pd, Au, Ag, and Rh are preferable as the metal alloyed with Pt as the Pt alloy.
- a Pt—Pd alloy containing Pd is preferable from the viewpoint of good compatibility with the ceramic as a substrate and good wettability when used as a paste.
- the Pd content is preferably 30% by weight or less. This is because if the Pd content is excessive, the Pd oxide is likely to precipitate during the firing process, and the reliability of the electrode is lowered.
- the core particle Pt or Pt alloy may further contain 3% by weight or less of Al or Zr.
- the components Al and Zr are diffused and contained in the core particles.
- Al and Zr in the core particles are released from the core particles when the metal paste is fired, and are oxidized and finely dispersed in the electrode film as a ceramic like the shell. Therefore, there is no problem even if the core particles are an alloy containing Al and Zr, and the core particles must not contain Al and Zr.
- the shell covering the core particles is made of Al 2 O 3 or ZrO 2 ceramic. This is in consideration of the bondability to the ceramic substrate.
- the ceramic shell preferably covers the core particles uniformly, but all the conductive particles may not be covered entirely.
- the conductive particles may be included in a state where the ceramic is partially bonded to the core particles.
- the ceramic needs to be 0.5 to 15 wt% with respect to the core particles. This is because if it exceeds 15% by weight, the resistance value when the electrode is formed becomes excessive.
- the amount of ceramic is less than 0.5 weight, peeling and warping deformation are likely to occur when a paste is formed, applied and fired.
- the amount of ceramic is more preferably 1 to 15% by weight.
- the thickness of the ceramic shell is preferably in the range of 1 to 100 nm.
- ZrO 2 includes stabilized zirconia such as YSZ and partially stabilized zirconia such as P—YSZ.
- Examples of the method for producing the conductive particles having the core / shell structure described above include a method using a gas phase reaction in a high temperature atmosphere.
- the metal / alloy powder as the core particles and the ceramic powder as the shell are mixed, the mixed powder is discharged into a high-temperature atmosphere above the boiling points of both components, and the fine powder produced by cooling is obtained. It is to be collected.
- the high-temperature atmosphere for discharging the raw material powder is a plasma atmosphere.
- the particle diameter of the core particles can be adjusted by heat treatment.
- the core particles can be increased to 200 nm.
- the metal paste to which the conductive particles according to the present invention are applied is a mixture of the conductive particles and a solvent.
- Solvents applicable to the metal paste include ethylene glycol, propylene glycol, ethyl cellosolve, butyl cellosolve, ethylene glycol monophenyl ether, ethylene glycol monomethyl ether acetate, benzyl alcohol, kerosene, paraffin, toluene, cyclohexanone, ⁇ -butyrolactone, methyl ethyl ketone, General materials such as N-methylpyrrolidone, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, butyl carbitol, turpentine oil, ⁇ -terpineol, terpineol, etc. can be applied, especially ⁇ -terpineol Such a thing is suitable.
- the amount of conductive particles mixed is preferably 50 to 90% by weight with respect to the entire paste. If it is less than 50% by weight, the electrode film becomes too thin, and if it exceeds 90% by weight, it becomes difficult to form a paste.
- a resin usually used for imparting viscosity and thixotropy to the metal paste may be added.
- this resin natural resins, amino resins, alkyd resins and the like are common. Particularly preferred is ethyl cellulose.
- the firing temperature is preferably 1300 to 1600 ° C. This is because a sufficiently low sintered product can be obtained.
- the electrode film thus formed is in a state in which fine ceramic particles (Al 2 O 3 particles, ZrO 2 particles) are uniformly dispersed. Specifically, more than half of the ceramic particles are 300 nm or less. It has become.
- the conductive particles according to the present invention can be applied to a metal paste and fired to form a low-resistance electrode film in which fine ceramic particles are dispersed. Making it possible to form a low-resistance electrode film makes it possible to reduce the film thickness of the electrode film, leading to a reduction in the amount of noble metal such as Pt and the cost of the apparatus.
- conductive particles coated with Al 2 O 3 using Pt and Pt—Pd alloys as core particles were manufactured to produce a metal paste, and the resistance value of an electrode obtained by firing the metal paste was measured.
- the core particles made of the Pt—Pd alloy the characteristics of the paste due to the change in the Pd content were evaluated.
- FIG. 1 A TEM image of the produced conductive particle powder having a core / shell structure is shown in FIG.
- this conductive particle powder was subjected to composition analysis by EDX analysis, it was confirmed that it contained 0.93% by weight of Al.
- This Al is considered that Al of the Al 2 O 3 powder diffused into the Pt particles released into the plasma atmosphere in the above manufacturing process.
- conductive particles to which a Pt—Pd alloy (Pd 25 wt%) was applied as core particles were also produced (Examples 3 and 4).
- Pt powder having an average particle diameter of 10 nm, Al 2 O 3 powder having an average particle diameter of 10 nm, and Pd powder having an average particle diameter of 40 nm were used as the raw material powder.
- Other manufacturing conditions were the same as above.
- the particle size of the core particle at this time was 20 nm.
- the conductive particles applying the Pt—Pd alloy to the core particles manufactured in the same manner as in Examples 3 and 4 were heat-treated at 900 ° C. for 1 hour, and granulated (particle size adjustment) to manufacture conductive particles. (Examples 5 and 6).
- the particle size of the core particles at this time was 200 nm.
- a TEM image of the produced conductive particle powder having a core / shell structure is shown in FIG.
- fine particles of Pt and Pt—Pd alloys without coating of Al 2 O 3 were also produced (Comparative Examples 1 to 4).
- the fine particles were produced by releasing Pt powder and Pd powder as raw materials into the plasma gas phase.
- the effect of the present invention is not exhibited simply by refining the metal particles. That is, a powder composed only of Pt or a Pt—Pd alloy cannot form an electrode film without blending ceramic, and the resistance value of the electrode is remarkably increased even when ceramic is mixed. As described above, the reason why there is no effect only by miniaturization of the conductive particles is that the conductive particles are likely to aggregate due to the miniaturization, and the sintering start temperature is lowered. 1, 3) On the other hand, it is considered that even when the ceramic mixing amount is increased, the dispersion state of the ceramic particles is not improved and the resistance value is increased.
- FIG. 2 is a cross-sectional photograph of the electrodes manufactured in Example 1 and Conventional Example 1. From Figure 2, Al 2 O 3 particles in the electrodes prepared in Examples are fine, which are uniformly dispersed. On the other hand, in the conventional example, the presence of coarse ceramic particles is confirmed.
- Example 1 Al 2 O 3 Pt / Al 2 O 3 mixed powder mixing amount was adjusted powder to produce the release conductively particles in plasma vapor to prepare a metal paste, electrode A membrane was produced. And resistance value was measured like Example 1,2. The results are shown in Table 2.
- the amount of Al 2 O 3 added up to 13% by weight does not have a great adverse effect on the resistance value.
- the resistance value could be measured up to 15% by weight, but the resistance value could not be measured beyond this. Therefore, it can be said that the upper limit of the amount of Al 2 O 3 added is preferably 15% by weight.
- the Pt—Pd alloy has a smaller wetting angle than that of Pt, and is better suited to ceramic than Pt. This effect is considered to be effective even when the powder is made into a paste.
- the decrease in the wetting angle with respect to the substrate indicates the ease of application of the metal paste to the substrate and the ease of application, and improves the adhesion of the electrode. Connected. It can be seen that the wetting angle tends to decrease by increasing the amount of Pd. Therefore, when the Pt—Pd alloy is applied to the present invention, the Pd content may be increased. However, as described above, when Pd exceeds 30% by weight, Pd oxide tends to precipitate, Reduces electrode reliability.
- the core / shell structure conductive particles of the first embodiment were manufactured by applying ZrO 2 (YSZ) as a shell.
- ZrO 2 (YSZ) As a shell.
- YSZ ZrO 2
- the metal paste was manufactured similarly to 1st Embodiment, it apply
- the characteristics of the electrode film of a metal paste in which Pt powder and ZrO 2 (YSZ) powder were separately mixed were also evaluated. The results are shown in Table 4.
- the conductive particles were produced by discharging a mixed powder of Pt powder and Al 2 O 3 powder into the plasma gas phase to obtain conductive particles having a core / shell structure.
- the coating amount of the shell was adjusted by adjusting the amount of Al 2 O 3 powder in the mixed powder.
- a metal paste is manufactured in the same manner as in the first embodiment, and 0.5 ⁇ 20 mm (three at 1 mm intervals), 0.1 ⁇ 5.0 mm (at 0.1 to 0.5 mm intervals) on an alumina substrate. 11) It was applied and baked in three patterns of 5 ⁇ 5 mm. After firing, the electrode film was peeled off and checked for warpage. The results are shown in Table 5.
- a metal paste for forming an electrode capable of forming a low-resistance electrode can be provided.
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Abstract
Description
平均粒径10nmのPt粉末と、平均粒径10nmのAl2O3粉末とを、V型混合機で混合して均一な混合粉末を用意した。このときの混合比は、Al2O3シェルの添加量に相当する。そして、これを高周波誘導熱プラズマ装置にてアルゴン雰囲気でプラズマ雰囲気中に放出した。発生した微粉末をフィルターにて回収した。以上の工程により、Ptをコア粒子とするコア/シェル構造の導電粒子粉末を得た(実施例1、2)。このとき導電粒子粉末について、TEM写真から粒子の寸法(最大寸法)を読み取ったところ、コア粒子の粒径は、20nmであり、粒子全体の粒径は、40nmであった。
上記で製造した導電性粒子を、有機溶剤であるエステルアルコールに投入し、更に、ジアミン系界面活性剤及びエチルセルロースを混合して、3本ロールミルにて混合・混練してペースト化した。導電性粒子の混合量は、70%とした。また、このペースト作製においては、従来の金属ペーストとして粒径0.7μmの金属粉末と、粒径0.3μmのAl2O3粉末を混合したものを用意した(従来例1~4))。更に、Al2O3の被覆のないコア粒子のみからなる粒径20nmの粒子(比較例1~4)については、導電粒子に粒径10nmのAl2O3粉末を混合して金属ペーストとした。
上記の金属ペーストを、96%アルミナ基板上にスクリーン印刷にて塗布形成した。その後120℃で10分乾燥し、1500℃で1時間焼成処理し、電極膜を作製した。
Claims (7)
- 電極形成用の導電性粒子であって、
Pt又はPt合金からなり、粒径10~200nmのコア粒子と、
Al2O3又はZrO2を含むセラミックからなり、前記コア粒子の少なくとも一部を覆うシェルと、からなり、
前記シェルを構成する前記セラミックは、コア粒子に対して0.5~15重量%の添加量でコアを被覆するものである、コア/シェル構造を有する電極形成用の導電性粒子。 - コア粒子は、Ptである請求項1記載の電極形成用の導電性粒子。
- コア粒子は、30重量%以下のPdを含むPt-Pd合金である請求項1記載の電極形成用の導電性粒子。
- コア粒子は、更に、3重量%以下のAl又はZrを含むPt又はPt合金である請求項1~請求項3のいずれかに記載の電極形成用の導電性粒子。
- 電極形成用の金属ペーストにおいて、
請求項1~請求項4のいずれかに記載の電極形成用の導電性粒子と溶剤とからなることを特徴とする金属ペースト。 - 導電性粒子の混合量は、ペースト全体に対して50~90重量%である請求項5記載の電極形成用の金属ペースト。
- 請求項5又は請求項6記載の電極形成用の金属ペーストを焼成してなる電極。
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KR1020127002915A KR101313982B1 (ko) | 2010-07-12 | 2011-07-08 | 전극 형성용의 도전 미립자, 금속 페이스트 및 전극 |
CN201180004459.3A CN102714072B (zh) | 2010-07-12 | 2011-07-08 | 电极形成用的导电粒子及金属糊料以及电极 |
US13/387,976 US8771553B2 (en) | 2010-07-12 | 2011-07-08 | Conductive fine particle and metal paste for electrode formation, and electrode |
DE112011100135T DE112011100135T5 (de) | 2010-07-12 | 2011-07-08 | Leitendes feines Partikel und Metallpaste zur Bildung von Elektroden und eine Elektrode |
US14/252,762 US9556343B2 (en) | 2010-07-12 | 2014-04-14 | Conductive fine particle and metal paste for electrode formation and electrode |
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JP2010157801A JP4834170B1 (ja) | 2010-07-12 | 2010-07-12 | 電極形成用の導電微粒子及び金属ペースト並びに電極 |
JP2010-157801 | 2010-07-12 |
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US13/387,976 A-371-Of-International US8771553B2 (en) | 2010-07-12 | 2011-07-08 | Conductive fine particle and metal paste for electrode formation, and electrode |
US14/252,762 Division US9556343B2 (en) | 2010-07-12 | 2014-04-14 | Conductive fine particle and metal paste for electrode formation and electrode |
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CN (1) | CN102714072B (ja) |
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GB2504957A (en) * | 2012-08-14 | 2014-02-19 | Henkel Ag & Co Kgaa | Curable compositions comprising composite particles |
TWI499775B (zh) | 2013-01-28 | 2015-09-11 | Tanaka Precious Metal Ind | 氣體感測電極形成用之金屬膏 |
JP6212328B2 (ja) * | 2013-08-28 | 2017-10-11 | 田中貴金属工業株式会社 | ガスセンサー電極形成用の金属ペースト |
KR101440728B1 (ko) * | 2013-06-13 | 2014-09-18 | 서울대학교산학협력단 | 실리카/이산화티타늄 코어/셀 나노입자를 포함하는 염료감응형 태양전지의 산화전극 페이스트 제조법 |
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JP6889083B2 (ja) * | 2017-10-06 | 2021-06-18 | 日本特殊陶業株式会社 | センサ及びセンサの製造方法 |
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CN102714072A (zh) | 2012-10-03 |
US20150123045A1 (en) | 2015-05-07 |
DE112011100135T5 (de) | 2012-09-20 |
CN102714072B (zh) | 2015-08-12 |
US8771553B2 (en) | 2014-07-08 |
JP4834170B1 (ja) | 2011-12-14 |
KR101313982B1 (ko) | 2013-10-01 |
JP2012022799A (ja) | 2012-02-02 |
US9556343B2 (en) | 2017-01-31 |
KR20120034222A (ko) | 2012-04-10 |
US20120126183A1 (en) | 2012-05-24 |
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