EP2726439A2 - Druckgussschlicker und daraus hergestellte feuerfestkeramik für gasturbinenanlagen - Google Patents
Druckgussschlicker und daraus hergestellte feuerfestkeramik für gasturbinenanlagenInfo
- Publication number
- EP2726439A2 EP2726439A2 EP12743142.7A EP12743142A EP2726439A2 EP 2726439 A2 EP2726439 A2 EP 2726439A2 EP 12743142 A EP12743142 A EP 12743142A EP 2726439 A2 EP2726439 A2 EP 2726439A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- refractory ceramic
- diameter
- size distribution
- gas turbine
- 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.)
- Withdrawn
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- B28—WORKING CEMENT, CLAY, OR STONE
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- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/26—Producing shaped prefabricated articles from the material by slip-casting, i.e. by casting a suspension or dispersion of the material in a liquid-absorbent or porous mould, the liquid being allowed to soak into or pass through the walls of the mould; Moulds therefor ; specially for manufacturing articles starting from a ceramic slip; Moulds therefor
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3241—Chromium oxides, chromates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5463—Particle size distributions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5463—Particle size distributions
- C04B2235/5472—Bimodal, multi-modal or multi-fraction
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6027—Slip casting
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23M—CASINGS, LININGS, WALLS OR DOORS SPECIALLY ADAPTED FOR COMBUSTION CHAMBERS, e.g. FIREBRIDGES; DEVICES FOR DEFLECTING AIR, FLAMES OR COMBUSTION PRODUCTS IN COMBUSTION CHAMBERS; SAFETY ARRANGEMENTS SPECIALLY ADAPTED FOR COMBUSTION APPARATUS; DETAILS OF COMBUSTION CHAMBERS, NOT OTHERWISE PROVIDED FOR
- F23M2900/00—Special features of, or arrangements for combustion chambers
- F23M2900/05004—Special materials for walls or lining
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23R—GENERATING COMBUSTION PRODUCTS OF HIGH PRESSURE OR HIGH VELOCITY, e.g. GAS-TURBINE COMBUSTION CHAMBERS
- F23R2900/00—Special features of, or arrangements for continuous combustion chambers; Combustion processes therefor
- F23R2900/00018—Manufacturing combustion chamber liners or subparts
Definitions
- the invention relates to a Druckgußschiicker for producing a refractory ceramic for use as a heat shield in the hot gas path of gas turbine plants according to the preamble of claim 1, and a refractory ceramic for use as a heat shield in the hot gas path of gas turbine plants according to the preamble of claim. 7
- Gas turbine plants consist essentially of a compressor, a burner and a gas turbine.
- In the compressor intake air is compressed before they are mixed in nachgeschalte ⁇ th and arranged in the compressor plenum burner in a combustion chamber with fuel and this mixture is burned ⁇ ver.
- the gas turbine downstream of the combustion chamber then removes thermal energy from the resulting combustion exhaust gases and converts them into mechanical energy.
- a generator connected to the gas turbine converts this mechanical energy for generating electricity into electrical energy.
- Today, gas turbine plants, like other power generating plants, must also have the lowest possible pollutant emissions with maximum efficiency in all load ranges. The height of the combustion temperature is limited by statutory prescribed NOx values.
- the temperature in the combustion chamber which forms the hot gas path between burner and gas turbine, is typically in the order of about 1300 to 1500 degrees Celsius.
- corresponding combustor liners must be provided against such hot gas attack to protect the hot gas path components enclosing and supporting structures so.
- Such heat shields can be carried out both metallic and ceramic.
- ceramic materials are be ⁇ vorzugt.
- refractory ceramics have a higher temperature and corrosion resistance, as well as a lower thermal conductivity.
- ⁇ plant material base for such ceramic heat shields are diveko- around containing refractory ceramics which are produced after the casting process, for example, described in DE 10 2008 011 820 AI Druckgußschlicker-.
- Gas turbine systems must now be able to be adapted to the respective load conditions in a very short time.
- Highest loads on the components and supporting structures of the gas turbine system, including the heat shields, are created during rapid shutdown of base load.
- the thus induced in the heat shields requires thermal shock for the refractory ceramic material properties, the high strength at gleichzeiti ⁇ ger high thermal conductivity and allow at temperatures of up to about 1500 degrees Celsius and more.
- the refractory ceramics must have a high resistance to cracking.
- Refractory ceramics are known from EP 1 327 108 A1 which fulfill the abovementioned properties, with the refractory ceramic on the particularly stressed hot gas side having on average a different particle size distribution than on the opposite colder combustion chamber wall side.
- a particle size distribution has the disadvantage that additional internal stresses can be induced at the interfaces of the different pore size distributions, which can have a negative effect on the passive safety of the heat shields.
- Ceramics with optimized homogeneous particle size distribution have a positive effect on the passive safety of the overall system.
- the object of the invention is to provide a Druckgußschiicker and a refractory ceramic made therefrom, which has a high thermal shock resistance and is therefore particularly well suited for use as a heat shield in the hot gas path of gas turbines. This object is achieved with the Druckgußschiicker with the Merkma ⁇ len of claim 1.
- the Druckgußschiicker a granular mixture of at least two materials with different coefficients of thermal expansion, and organic and / or inorganic binding and adjusting agent comprises, wherein the multimodal Korn ⁇ size distribution of the mixture is divided to 10-20 Ge ⁇ weight percent coarse grain in the size range 1-5 mm in diameter, 10-20% by weight of medium grain in the size range of 0.5-1 mm diameter, and 60-80% by weight of fine grain in the size range up to 0.5 mm in diameter, the weight distribution must be proportionally chosen so that together 100 percent by weight of the granular mixture results in a particularly preferred for use in gas turbine plants total porosity of the resulting Feuerfestkera ⁇ mik with a particularly high thermal shock resistance.
- Sol ⁇ che produced according to the invention refractory ceramics thus have a material behavior that can safely withstand the rapid thermal cycles resulting from rapid shutdown or generally when starting and stopping the gas turbine plant.
- the middle grain fraction itself consists of at least 20 percent by weight of the material with the lower coefficient of thermal expansion. This causes internal stresses to arise in the structure during the firing of the die cast strip, which leads to an increase in the strength of the refractory ceramic produced therefrom and thus to an improvement in the thermal shock behavior of the heat shield.
- xanthan insbeson ⁇ particular xanthan in a concentration of more than 0.05 overall percent by weight of the die casting slip.
- the use of xanthan leads to a stabilization of the multimodal particle size distribution in Druckgußschiicker. This stability is necessary in order to achieve the desired uniform pore size distribution and a homogeneous porosity over the GESAM ⁇ te prepared therefrom refractory ceramic, in particular for complex heat shield geometries.
- the figure shows schematically a Elektronenrastermikroskop- annähme an exemplary section through a fiction, ⁇ produced refractory ceramic, which is designed as Hitzeschildkera ⁇ mik for use in gas turbine plants.
- Schematically indicated in the sectional view is the uniform Ver ⁇ distribution of the coarse, medium and fine grains HO- like that runs through the entire refractory ceramic, thus causing a targeted virtually uniformly distributed porosity of about 18- 20% over the entire ceramic.
- the setting of a uniform as possible porosity is not insignificantly influenced by the binder used.
- the binder provided is a silicate binder or a combination of silicate binders, it is possible to achieve a die casting slurry which can be modulated particularly well.
- AI cement-containing, phosphate-containing, aluminum hydroxide-containing binders binds a silicate binder only during sintering of Druckgußschiickers.
- the flowable and pumpable Druckgußschiicker from the inventive particle mixture consisting of oxides on the basis of A1 2 0 3, MgO, MgAl 2 0 4, CaO, Zr0 2, Cr 2 0 3, Ce0 2, Y 2 0 3, Ti0 2 , bauxite, andalusite, dolomite, pubic Motte, spinels, mullite and / or non-oxides based SiC, C and / or those containing raw materials ⁇ mixed with an aqueous dispersion medium and the binder system.
- kaolin or clay or bentonite or combinations of these three silicates is added as a silicate binder system before the pressure casting slip is then pressurized into a liquid or liquid permeable casting mold of a diecasting system. is introduced so that the molded part is formed from the granular mixture on an inside surface of a casting chamber of the casting mold by discharging liquid contained in the slurry through the casting mold.
- binder systems of xanthan gum and guar gum solution or alternatively based on xanthan or locust bean gum or carrageenan or agar or tragacanth or karaya or gum arabic or tara gum or konj ak-mannan or cassia gum are used as the first polysaccharide with a second polysaccharide.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Dispersion Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Composite Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Mold Materials And Core Materials (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12743142.7A EP2726439A2 (de) | 2011-08-16 | 2012-08-01 | Druckgussschlicker und daraus hergestellte feuerfestkeramik für gasturbinenanlagen |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11177668A EP2559678A1 (de) | 2011-08-16 | 2011-08-16 | Druckgußschlicker und daraus hergestellte Feuerfestkeramik für Gasturbinenanlagen |
PCT/EP2012/065002 WO2013023913A2 (de) | 2011-08-16 | 2012-08-01 | Druckgussschlicker und daraus hergestellte feuerfestkeramik für gasturbinenanlagen |
EP12743142.7A EP2726439A2 (de) | 2011-08-16 | 2012-08-01 | Druckgussschlicker und daraus hergestellte feuerfestkeramik für gasturbinenanlagen |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2726439A2 true EP2726439A2 (de) | 2014-05-07 |
Family
ID=46604312
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP11177668A Ceased EP2559678A1 (de) | 2011-08-16 | 2011-08-16 | Druckgußschlicker und daraus hergestellte Feuerfestkeramik für Gasturbinenanlagen |
EP12743142.7A Withdrawn EP2726439A2 (de) | 2011-08-16 | 2012-08-01 | Druckgussschlicker und daraus hergestellte feuerfestkeramik für gasturbinenanlagen |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP11177668A Ceased EP2559678A1 (de) | 2011-08-16 | 2011-08-16 | Druckgußschlicker und daraus hergestellte Feuerfestkeramik für Gasturbinenanlagen |
Country Status (5)
Country | Link |
---|---|
US (1) | US9221718B2 (de) |
EP (2) | EP2559678A1 (de) |
CN (1) | CN103732560A (de) |
RU (1) | RU2606739C2 (de) |
WO (1) | WO2013023913A2 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014197246A1 (en) * | 2013-06-04 | 2014-12-11 | H.C. Starck Inc. | Slip and pressure casting of refractory metal bodies |
RU2742265C1 (ru) * | 2020-07-29 | 2021-02-04 | Акционерное общество «Обнинское научно-производственное предприятие «Технология» им. А.Г.Ромашина» | Сырьевая смесь для изготовления огнеупорных изделий |
CN113135751A (zh) * | 2021-05-20 | 2021-07-20 | 宜兴市九荣特种陶瓷有限公司 | 防静电氧化钛陶瓷及其制备方法 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1299546B (de) | 1967-01-13 | 1969-07-17 | Dorst Keramikmaschb Inh Otto D | Verfahren zum Druckgiessen keramischer Gegenstaende |
SU749816A1 (ru) * | 1978-04-21 | 1980-07-23 | Предприятие П/Я А-7840 | Огнеупорна масса |
US4363199A (en) * | 1980-05-05 | 1982-12-14 | Kennecott Corporation | Fire resistant sealing system for holes in fire resistant building partitions |
JPH01282148A (ja) * | 1988-05-06 | 1989-11-14 | Shinagawa Refract Co Ltd | 耐塩素ガス用溶融シリカ質耐火煉瓦 |
US5252248A (en) * | 1990-07-24 | 1993-10-12 | Eaton Corporation | Process for preparing a base nitridable silicon-containing material |
NL9201483A (nl) * | 1992-08-20 | 1994-03-16 | Hoogovens Ind Ceramics | Werkwijze voor het vervaardigen van een keramisch membraan voor microfiltratie. |
RU2122534C1 (ru) * | 1997-07-24 | 1998-11-27 | Юрий Ефимович Пивинский | Способ изготовления литого сталеразливочного огнеупора |
DE19745232C1 (de) | 1997-10-13 | 1998-12-24 | Thuringia Netzsch Feinkeramik | Anlage zum Druckgießen keramischer Artikel |
EP1199520A1 (de) | 2000-10-16 | 2002-04-24 | Siemens Aktiengesellschaft | Hitzeschildstein zur Auskleidung einer Brennkammerwand, Brennkammer sowie Gasturbine |
NO316509B1 (no) * | 2002-06-17 | 2004-02-02 | Elkem As | Silisiumoksidslurry og fremgangsmåte for fremstilling av slik slurry |
RU2267469C1 (ru) * | 2004-05-11 | 2006-01-10 | Федеральное государственное унитарное предприятие "Обнинское научно-производственное предприятие "Технология" | Сырьевая смесь для изготовления огнеупорных изделий |
FR2873685B1 (fr) * | 2004-07-28 | 2007-06-22 | Saint Gobain Ct Recherches | Procede d'obtention de ceramiques poreuses |
DE102008011820A1 (de) | 2008-02-29 | 2009-09-03 | Dorst Technologies Gmbh & Co. Kg | Druckschlicker-Gießvorrichtung bzw. Verfahren zum Gießen eines Formteils |
EP2138474B1 (de) * | 2008-06-23 | 2018-08-08 | Imerys Kiln Furniture Hungary Ltd. | Sic-material |
EP2169311A1 (de) * | 2008-09-29 | 2010-03-31 | Siemens Aktiengesellschaft | Materialmischung zur Herstellung eines Feuerfestwerkstoffes, Feuerfestformkörper und Verfahren zu seiner Herstellung |
EP2168935A1 (de) * | 2008-09-29 | 2010-03-31 | Siemens Aktiengesellschaft | Materialzusammensetzung zur Herstellung eines Feuerfestwerkstoffes sowie ihre Verwendung und Feuerfestformkörper sowie Verfahren zu seiner Herstellung |
US8327778B2 (en) * | 2009-10-28 | 2012-12-11 | Dellorusso Jr Anthony J | Light weight portable fire resistant containment system |
-
2011
- 2011-08-16 EP EP11177668A patent/EP2559678A1/de not_active Ceased
-
2012
- 2012-08-01 US US14/239,032 patent/US9221718B2/en not_active Expired - Fee Related
- 2012-08-01 WO PCT/EP2012/065002 patent/WO2013023913A2/de active Application Filing
- 2012-08-01 CN CN201280039569.8A patent/CN103732560A/zh active Pending
- 2012-08-01 EP EP12743142.7A patent/EP2726439A2/de not_active Withdrawn
- 2012-08-01 RU RU2014109925A patent/RU2606739C2/ru not_active IP Right Cessation
Non-Patent Citations (2)
Title |
---|
None * |
See also references of WO2013023913A2 * |
Also Published As
Publication number | Publication date |
---|---|
RU2606739C2 (ru) | 2017-01-10 |
US9221718B2 (en) | 2015-12-29 |
WO2013023913A3 (de) | 2013-05-16 |
WO2013023913A2 (de) | 2013-02-21 |
CN103732560A (zh) | 2014-04-16 |
EP2559678A1 (de) | 2013-02-20 |
RU2014109925A (ru) | 2015-09-27 |
US20140228198A1 (en) | 2014-08-14 |
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