WO2010037963A1 - Procede de fabrication d'un materiau poreux en sic - Google Patents
Procede de fabrication d'un materiau poreux en sic Download PDFInfo
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- WO2010037963A1 WO2010037963A1 PCT/FR2009/051845 FR2009051845W WO2010037963A1 WO 2010037963 A1 WO2010037963 A1 WO 2010037963A1 FR 2009051845 W FR2009051845 W FR 2009051845W WO 2010037963 A1 WO2010037963 A1 WO 2010037963A1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2068—Other inorganic materials, e.g. ceramics
- B01D39/2072—Other inorganic materials, e.g. ceramics the material being particulate or granular
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
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- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
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Definitions
- the present invention relates to the field of porous materials based on recrystallized silicon carbide. More particularly, the invention relates to a method of manufacturing a body or an element made of such a porous material and whose mechanical strength characteristics are improved. Such a body or element may in particular be used in the field of filtration or in the field of cooking supports or ceramic igniters.
- Porous ceramic or porous refractory materials based on silicon carbide (SiC) obtained by very high temperature sintering are increasingly used in applications where their high chemical inertness and high refractoriness enable them to withstand heavy mechanical stresses, in particular thermomechanical.
- Important but not limiting examples are typically applications such as the particulate filter in motor vehicle exhaust lines.
- the deposition of the coating catalytic within the porous material can be made possible by the fact that the material still has, after said deposition, sufficient porosity to allow the passage of gases without excessive pressure drop.
- the material is highly porous, that is to say when its open porosity is greater than 40%, even 45% or even 50%, and even more pronounced beyond 50%, the element achieved with such materials has too low mechanical strength and therefore thermomechanical, this weakness can be the cause of rapid deterioration of the material in use.
- the most conventional known means is to use additives in the starting composition to obtain the desired part or body.
- porogens of organic origin are used which decompose during an intermediate heating step or during the baking of the material. Such a process is described, for example, in application EP 1 403 231.
- the use of porogens or other organic materials nevertheless leads to the release of toxic gases and may also cause defects in the material such as microorganisms.
- EP 1 686 107 discloses for example a method of manufacturing a sintered ceramic body made from a mixture of at least two powders, a coarse grain powder and a fine grain SiC powder, in which the ratio between the average size of the coarse powder and the average size of the fine powder is between 8 and 250.
- EP 1 652 831 discloses sintered ceramic bodies obtained from a mixture of two powders of SiC particles having an average diameter respectively between 5 to 100 ⁇ m and between 0.1 to 10 ⁇ m.
- EP 1 839 720 discloses a method for preparing SiC filters with low dispersion around a target average pore diameter value.
- the two SiC powders initially used according to this teaching have a median diameter of 15 to 40 microns for the powder consisting of the largest particles and 0.5 microns for the powder consisting of the finest particles.
- the object of the present invention is to provide a process for preparing and synthesizing a porous silicon recrystallized ceramic material body having the best compromise between its porosity characteristics (open porosity volume, median pore diameter ) and its characteristics of mechanical and thermomechanical strength. More particularly, the object of the present invention is a process for producing a porous ceramic or refractory product based on SiC, sintered at a temperature greater than 1600 ° C., making it possible to obtain a material having an improved compromise. , compared to the methods known to date, between its porosity properties, in particular its open porosity and / or its median pore diameter and its mechanical and thermomechanical strength properties.
- the invention is based on the discovery made by the applicant, who found that at substantially equivalent porosity of the porous SiC material, some of the parameters of the process for obtaining said material could have a very significant effect on the mechanical strength characteristics of said material. .
- the experiments conducted by the applicant some of which are reported later in the present description, have shown that a very significant improvement in the mechanical properties of the material, with equivalent porosity, can be obtained by the strict and joint control: on the one hand, the size and distribution of the SiC grains present in the mixture of powders initially used in the process,
- the invention relates to a process for obtaining a porous material made of recrystallized SiC, in particular in the form of a filtering structure of a particulate-laden gas, comprising the following steps: a) preparation of a composition comprising at least two powders of SiC particles, a first powder of particles having a median diameter d 5 o less than 5 microns and a second powder of particles having a median diameter d 5 o of between 5 and 100 microns, the difference between the median diameter d 5 o of the second powder and the median diameter d 5 o of the first powder being greater than 5 microns, b) mixing of said composition with an organic material comprising an organic pore-forming agent and / or a binder, in proportions adapted and in the presence of a sufficient amount of a solvent such as water to allow the shaping of said mixture and shaping of the mixture obtained to obtain a green body, c) pr preferably drying and removal of the organic material, in particular by an intermediate heat treatment and / or by
- the difference between the percentile dgo of the second particle powder and the diole percentile of the first particulate powder multiplied by the volume of organic material in the initial mixture, in percent relative to the total volume of the SiC grains is between about 250 and about 1500, preferably between about 300 and about 1200.
- volume of organic material is meant in the sense of the present description the total volume of all organic materials incorporated in mixture with the grains of SiC, constituting the "mineral" part of the mixture. This total volume of organic matter is related to the total volume occupied by said grains of SiC in the mixture.
- the organic materials incorporated in the mixture include porogenic type functional agents, shaping agents such as binders, plasticizers, dispersants, lubricants, without this list being however exhaustive.
- the volume of organic material is between 5 and 150%, or even 20 to 110%, or even 30 to 100%, as a percentage of the total volume of the grains.
- SiC Preferably, the volume of porogen is between 0 and 120%, or even 10 to 95%, or even 15 to 80%, as a percentage relative to the total volume of SiC grains.
- binder is meant classically in the sense of the present invention a set of grains or particles characterized by a grain diameter distribution (also called grain size in the present description) generally centered and distributed around a median diameter.
- grain or “particle” is meant a solid product individualized in a powder or a mixture of powders.
- percentages such that a percentage of p% represents the fraction of the powder, by volume, comprising the p% of the grains having the largest diameters or sizes, and
- Such granulometric curve may in particular be conventionally carried out using a laser granulometer.
- D p is called in the sense of the present invention and conventionally, the grain diameter (abscissa on the abovementioned curve) corresponding to the percentage p% by volume.
- dio of a powder corresponds to a grain size for which 10% by volume of the grains of the powder have a size greater than or equal to dio (and consequently for which 90% of the grains, by volume, have a strictly smaller size to dio)
- Dgo of a powder is the size of grains for which 90% by volume of the grains of the powder have a size greater than or equal to dgo (and consequently for which 10% of the grains, in volume, have a size strictly less than dgo).
- the 5 o percentile is often called the median diameter of a powder.
- the process according to the invention consists, for example, in mixing powders of SiC particles to obtain the mixture of grains of size selected according to the invention and then to shape this mixture, and advantageously makes it possible to obtain, after firing and sintering at high temperature, a porous refractory ceramic product based on SiC whose combined characteristics of porosity and mechanical strength are improved and can be more easily controlled.
- the process according to the invention makes it possible to obtain a porous sintered body whose optimum mechanical strength is guaranteed.
- the difference between the dgo percentile of the second SiC particle powder and the dio percentile of the first SiC particle powder is greater than 1 micron, even more preferably greater than 3 micron. This difference reflects, according to the invention, the degree of particle size recovery between the two powders.
- the difference between the dgo percentile of the second SiC particle powder and the dio percentile of the first SiC particle powder is less than 20 microns, for example less than or equal to 15 microns or even less than or equal to 10 microns.
- the median diameter of the particles of the first SiC grain powder is less than 3 microns and preferably less than or equal to 1 micron.
- the median diameter of the particles of the first SiC powder could be of the order of a few tens of nanometers, or even of the order of a few nanometers.
- the median diameter of the particles constituting the second powder of SiC particles may be between 5 and 60 microns, preferably between 5 and 30 microns or even between 5 and 20 microns. Below 5 microns, no difference was observed significant compared to porous materials obtained by conventional methods. Above 60 microns, the mechanical strength of the porous body drops very strongly.
- the median diameter of the SiC particles of the second powder is at least five times greater than the median diameter of the SiC particles of the first powder and preferably at least ten times greater.
- the difference between the median diameter of the second powder and that of the first powder is between 8 and 30 microns.
- the ratio Ri between the difference of the di and dgo percentiles, and the median diameter d 5 o of the first powder: R 1 dso is between 0.1 and 10, preferably between 0.3 and 5 and very preferably between 0.5 and 5.
- the porous body has an open porosity of between 35 and 65%, and even more preferably between 40% and 60%.
- too low porosity leads to a too high pressure drop. Too high a porosity leads to a level of mechanical resistance that is too low.
- the median diameter dso, by volume, pores constituting the porosity of the material is between 5 and 30 microns, and preferably between 10 and 25 microns.
- too small pore diameter results in excessive pressure loss, whereas a median pore diameter too important causes poor filtration efficiency.
- the SiC powder may be SiC doped with a metal such as aluminum.
- the SiC powders used in the process according to the invention are preferably SiC in substantially alpha crystallographic form, preferably black SiC or green SiC according to the chemical purity of the powders used.
- porogens and / or binders and optionally plasticizers may be added.
- binding agents or plasticizers are for example chosen from the range of polysaccharides and cellulose derivatives, PVA, PEG, or even lignin derivatives or chemical setting agents such as phosphoric acid or sodium silicate as long as they are compatible with the cooking process. The applicant has observed that the rheology of the plastic mixture thus obtained can be easily controlled by routine experiments, including for substantial water additions.
- the grains of the first powder may be agglomerated with at least a part of the second powder or even without the latter, by means of a known method of agglomeration or formation of granules such as conventional methods of granulation or atomization.
- the binder for producing these granules may be, for example, a thermosetting resin chosen from epoxy resins, silicone resins, polyimide resins, polyester resins or, preferably, phenolic resins, a PVA optionally combined with inorganic or organo-mineral type binders, or acrylic resin preferably chosen for reasons of respect for the environment.
- the nature of the binder and its quantity are generally chosen as a function of the particle size of the starting SiC fine particle powders and the desired size of SiC granules obtained after agglomeration.
- the binder must make it possible to ensure sufficient mechanical strength so that the granules are not degraded before the possible debinding heat treatment (step c)) and especially during the shaping (step b)).
- the shaping of the porous product is preferably carried out so as to produce pieces of various shapes according to any known technique, for example by pressing, extrusion, vibration and / or molding, by casting under pressure or not by example in porous mold plaster or resin.
- the sizes of the granules resulting from the agglomeration of the fine particles of the first SiC powder and / or of the SiC particles constituting the second powder are adapted, according to the techniques in force, to the thickness of the part to achieve so as to ensure the properties of porosity, mechanical strength and appearance necessary for the desired application.
- the reduction of the fines content, agglomerated in the form of granules according to the invention made it possible to avoid clogging of the molds during casting or to reduce the delamination effects in the case of pressing.
- the removal of the solvent in step c) can be obtained by heat treatment or alternatively by the use of microwaves, for a time sufficient to bring the water content not chemically bound to less than 1%. mass.
- the removal of the binder or debinding (step c) is preferably carried out in air and at a temperature preferably below 700 ° C., so as to ensure sufficient mechanical strength before sintering and avoid uncontrolled oxidation of SiC.
- the cooking is carried out at high temperature, that is to say at a temperature above 1600 0 C, or even greater than 1800 0 C, preferably greater than 2000 0 C, more preferably greater than 2100 0 C but lower at 2400 ° C.
- said cooking is conducted under a non-oxidizing atmosphere, for example Argon.
- the invention furthermore relates to a porous SiC body recrystallized, preferably in essentially CC form, obtained by a process as previously described and to its use as a structure of a particulate filter in an exhaust line of a diesel engine or gasoline or as a ceramic firing support or igniter.
- the porous body produced according to FIG. method of the invention has a characteristic value of the mechanical strength, in particular
- the mixtures of Examples 1 to 3 according to the invention were carried out according to the mass compositions specified in Table 2 below from two SiC powders of different particle size, called fine and coarse, with reference to the respective size of the grains. the components.
- a binder is added methylcellulose type plasticizer, and a polyethylene type organic pore form in powder form with a median diameter of 15 microns.
- the mixtures were kneaded for 10 minutes in the presence of water in a kneader until a homogeneous paste was obtained.
- the dough is stretched for 30 minutes to make it plastic and allow the deaeration of the mixture.
- the open porosity is measured on the extruded honeycomb-like extruded monoliths according to ISO 5017.
- the median pore diameter is measured by mercury porometry.
- the breaking force is measured at room temperature for each example on 10 test pieces corresponding to unit elements (monoliths) of the same production batch of dimensions 25.4 cm in length and 36 mm in width.
- the 3-point flexural mounting according to standard NFB41-104 is carried out with a distance of 220 mm between the two lower supports and the speed of descent of the punch is constant and of the order of 5mm / min.
- Table 2 The main characteristics and results obtained for the filters according to Examples 1 to 3 are summarized in Table 2.
- Table 2 shows that the recrystallized SiC materials constituting the monoliths made according to Examples 1 to 3 and Comparative Example Ic have substantially the same porosity characteristics. (total pore volume and median pore diameter).
- the structures according to the invention of Examples 1 to 3, however, are characterized by a substantially higher mechanical strength than that of Comparative Example Ic, as indicated by the respective resistance values MOR obtained.
- Comparative Example 2c differs from that of the present invention in that the parameter Y is too low, mainly because of the proximity between the dgo of the larger diameter grain powder and the dio of the grain powder of smaller diameter.
- the negative value of the process parameter Y for Example 2c is thus explained by a partial overlap between the two particle size curves of the powders.
- Another mixture is made using the same steps and the same experimental protocol as previously described, for obtaining monoliths having the same dimensions (see Table 1).
- the composition of the mixtures of large and fine SiC powders, as well as the level of organic material added to the initial mixture have been adjusted so as to further increase the porosity characteristics of the target porous material and in particular the diameter of the pores of the porous structure.
- Table 4 for details of the preparation of the mixture, its composition and the porous characteristics of the material finally obtained after cooking.
- Comparative Example 3c another mixture (Comparative Example 3c) was produced using the same steps and the same experimental protocol as that previously described, but so as to obtain porosity characteristics substantially equivalent to those of Example 7 according to US Pat. 'invention.
- the method according to Comparative Example 3c differs from that subject of the present invention in that the parameter Y is too important, due in part to the great difference between the dgo of the grain powder of more large diameter and the dio of the powder of grains of smaller diameter and secondly the very important addition of porogenic agent necessary to obtain the porosity target parameters (see Table 4).
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Chemical & Material Sciences (AREA)
- Ceramic Products (AREA)
- Filtering Materials (AREA)
- Catalysts (AREA)
- Spark Plugs (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200980138587XA CN102171163A (zh) | 2008-09-30 | 2009-09-29 | 制造SiC多孔材料的方法 |
EP09752427A EP2334617A1 (fr) | 2008-09-30 | 2009-09-29 | Procede de fabrication d'un materiau poreux en sic |
MX2011002827A MX2011002827A (es) | 2008-09-30 | 2009-09-29 | Proceso para elaborar un material sic poroso. |
JP2011528406A JP2012504092A (ja) | 2008-09-30 | 2009-09-29 | 多孔質SiC材料の製造方法 |
US13/063,766 US20110171099A1 (en) | 2008-09-30 | 2009-09-29 | Process for manufacturing a porous sic material |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0856563 | 2008-09-30 | ||
FR0856563A FR2936512B1 (fr) | 2008-09-30 | 2008-09-30 | Procede de fabrication d'un materiau poreux en sic. |
Publications (1)
Publication Number | Publication Date |
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WO2010037963A1 true WO2010037963A1 (fr) | 2010-04-08 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2009/051845 WO2010037963A1 (fr) | 2008-09-30 | 2009-09-29 | Procede de fabrication d'un materiau poreux en sic |
Country Status (7)
Country | Link |
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US (1) | US20110171099A1 (fr) |
EP (1) | EP2334617A1 (fr) |
JP (1) | JP2012504092A (fr) |
CN (1) | CN102171163A (fr) |
FR (1) | FR2936512B1 (fr) |
MX (1) | MX2011002827A (fr) |
WO (1) | WO2010037963A1 (fr) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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KR101854731B1 (ko) * | 2011-07-28 | 2018-05-04 | 엘지이노텍 주식회사 | 잉곳 제조 방법 |
JP6046989B2 (ja) * | 2012-11-20 | 2016-12-21 | 東京窯業株式会社 | 炭化ケイ素焼結体の製造方法 |
US10093587B2 (en) * | 2013-06-18 | 2018-10-09 | Robin Crawford | Processes for the manufacture of lightweight ceramic materials and articles produced thereby |
CN105523765B (zh) * | 2014-11-27 | 2017-06-06 | 比亚迪股份有限公司 | 多孔SiC预制体及其制备方法和陶瓷金属复合材料 |
RU2605257C1 (ru) * | 2015-09-11 | 2016-12-20 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский технологический университет" | Полимерная композиция для получения карбида кремния |
CN108017409B (zh) * | 2016-11-04 | 2020-09-15 | 云南菲尔特环保科技股份有限公司 | 一种低温烧结的碳化硅蜂窝陶瓷材料及制备方法 |
CN111533572B (zh) * | 2020-05-08 | 2022-03-15 | 武汉工程大学 | 一种多孔碳化硅陶瓷支撑体的制备方法 |
CN117682865B (zh) * | 2024-01-30 | 2024-04-12 | 山东奥福环保科技股份有限公司 | 一种碳化硅蜂窝陶瓷及其制备方法与应用 |
Citations (7)
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WO2002081054A1 (fr) * | 2001-04-09 | 2002-10-17 | Corning Incorporated | Corps de filtre poreux et procede |
US20050161849A1 (en) * | 2004-01-13 | 2005-07-28 | Ibiden Co., Ltd. | Honeycomb structure, porous body, pore forming material for the porous body, and methods for manufacturing the pore forming material, the porous body and the honeycomb structure |
US20060051556A1 (en) * | 2003-09-12 | 2006-03-09 | Ibiden Co., Ltd. | Sintered ceramic compact and ceramic filter |
EP1652831A1 (fr) * | 2004-06-25 | 2006-05-03 | Ibiden Co., Ltd. | Procédé de production de corps poreux, corps poreux, et corps structurel alvéolaire |
EP1808228A1 (fr) * | 2004-09-02 | 2007-07-18 | Ibiden Co., Ltd. | Structure en nid d abeilles, procédé de production et dispositif de purification de gaz d échappement |
EP1839720A1 (fr) * | 2006-03-31 | 2007-10-03 | Ibiden Co., Ltd. | Corps structurel en nid d'abeille et procédé pour la fabrication d'un corps structurel en nid d'abeille |
EP1900709A1 (fr) * | 2006-09-14 | 2008-03-19 | Ibiden Co., Ltd. | Procédé pour la préparation de structures en nid d'abeille et composition pour structures en nid d'abeille frittées |
Family Cites Families (3)
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KR100899952B1 (ko) * | 2004-05-28 | 2009-05-28 | 생-고뱅 세라믹스 앤드 플라스틱스, 인코포레이티드 | 점화기 시스템 |
US20080142149A1 (en) * | 2004-09-27 | 2008-06-19 | Ngk Insulators, Ltd. | Setter Used in Firing and Method for Firing of Formed Honeycomb Body Using the Setter |
WO2006082938A1 (fr) * | 2005-02-04 | 2006-08-10 | Ibiden Co., Ltd. | Structure en nid d’abeille ceramique et procede de fabrication de celle-ci |
-
2008
- 2008-09-30 FR FR0856563A patent/FR2936512B1/fr not_active Expired - Fee Related
-
2009
- 2009-09-29 EP EP09752427A patent/EP2334617A1/fr not_active Withdrawn
- 2009-09-29 CN CN200980138587XA patent/CN102171163A/zh active Pending
- 2009-09-29 US US13/063,766 patent/US20110171099A1/en not_active Abandoned
- 2009-09-29 JP JP2011528406A patent/JP2012504092A/ja active Pending
- 2009-09-29 WO PCT/FR2009/051845 patent/WO2010037963A1/fr active Application Filing
- 2009-09-29 MX MX2011002827A patent/MX2011002827A/es not_active Application Discontinuation
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002081054A1 (fr) * | 2001-04-09 | 2002-10-17 | Corning Incorporated | Corps de filtre poreux et procede |
US20060051556A1 (en) * | 2003-09-12 | 2006-03-09 | Ibiden Co., Ltd. | Sintered ceramic compact and ceramic filter |
US20050161849A1 (en) * | 2004-01-13 | 2005-07-28 | Ibiden Co., Ltd. | Honeycomb structure, porous body, pore forming material for the porous body, and methods for manufacturing the pore forming material, the porous body and the honeycomb structure |
EP1652831A1 (fr) * | 2004-06-25 | 2006-05-03 | Ibiden Co., Ltd. | Procédé de production de corps poreux, corps poreux, et corps structurel alvéolaire |
EP1808228A1 (fr) * | 2004-09-02 | 2007-07-18 | Ibiden Co., Ltd. | Structure en nid d abeilles, procédé de production et dispositif de purification de gaz d échappement |
EP1839720A1 (fr) * | 2006-03-31 | 2007-10-03 | Ibiden Co., Ltd. | Corps structurel en nid d'abeille et procédé pour la fabrication d'un corps structurel en nid d'abeille |
EP1900709A1 (fr) * | 2006-09-14 | 2008-03-19 | Ibiden Co., Ltd. | Procédé pour la préparation de structures en nid d'abeille et composition pour structures en nid d'abeille frittées |
Also Published As
Publication number | Publication date |
---|---|
FR2936512B1 (fr) | 2010-09-17 |
CN102171163A (zh) | 2011-08-31 |
EP2334617A1 (fr) | 2011-06-22 |
JP2012504092A (ja) | 2012-02-16 |
US20110171099A1 (en) | 2011-07-14 |
MX2011002827A (es) | 2011-04-05 |
FR2936512A1 (fr) | 2010-04-02 |
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