Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
  • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
  • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
  • H01M8/023—Porous and characterised by the material
  • H01M8/0232—Metals or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
  • C25B9/70—Assemblies comprising two or more cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
  • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
  • H01M8/023—Porous and characterised by the material
  • H01M8/0241—Composites
  • H01M8/0245—Composites in the form of layered or coated products
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
  • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
  • H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
  • H01M8/0254—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form corrugated or undulated
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
  • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
  • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
  • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
  • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
  • H01M8/026—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant characterised by grooves, e.g. their pitch or depth
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
  • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
  • H01M8/0276—Sealing means characterised by their form
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
  • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
  • H01M8/028—Sealing means characterised by their material
  • H01M8/0282—Inorganic material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
  • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
  • H01M8/0286—Processes for forming seals
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
  • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
  • H01M8/242—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes comprising framed electrodes or intermediary frame-like gaskets
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
  • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
  • H01M8/2425—High-temperature cells with solid electrolytes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
  • H01M8/2465—Details of groupings of fuel cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
  • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
  • H01M8/04197—Preventing means for fuel crossover
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the present invention relates to a device forming a seal between two spaces each capable of being occupied by a gas, the two gases being reactive with one another to form a fluid.
• reactive gases between them two gases which in the presence of each other react to form a fluid in the form of gas or vapor.
• hydrogen reacts with oxygen to form water as a vapor.
• the invention finds particular application in the electrolysis of high temperature water vapor (EVHT), typically between 600 ° C and 1000 ° C, where there is currently no satisfactory sealing at the same time the constraints medium (high temperature, redox atmosphere %) and the system (thermal transients).
• EVHT high temperature water vapor
• the invention can also be applied to other fields, such as the SOFC fuel cell, or for chemical industry reactors, and for systems operating in other temperature ranges where V sealing is difficult to achieve.
• the object of the invention is to propose another sealing solution between two spaces occupied by reactive gases with one another.
• a particular object of the invention is to propose an alternative sealing solution capable of completing and securing an existing sealing solution in a high temperature water electrolysis (EHT) reactor or in a reactor constituting a fuel cell, in particular of the SOFC type.
• the subject of the invention is a device forming a seal for separating two spaces each capable of being occupied by a gas, the two gases being reactive with one another to form a fluid, the device comprising at least one plate and a chamber, called buffer chamber, separating the two spaces, the buffer chamber being adapted to be occupied by the same fluid as that formed by reaction of the two reactive gases with each other.
• One of the two spaces is separated from the chamber by a first support portion and a plate portion facing;
• Each of the first and second support portions form with the plate portion facing a bearing zone defining a microchannel; the microchannels being porous volumes delimited by the surface roughness of the support portions and plate portions;
• the flow of reactive gases in the microchannels is mainly molecular.
• microchannel is understood to mean a fluid channel of micrometric height defined by the surface roughness of the support and plate portions, that is to say typically a channel. whose height or in other words the depth is of the order a few tens of microns (microns).
• a microchannel defined by the surface roughness of the support and plate portions has a width of the order of from fifty to a hundred ⁇ (micrometers).
• the inventors have defined a new type of seal: unlike state-of-the-art gaskets for which it is desired to give them a perfect barrier function, here an imperfect sealing zone controlled by 1 is defined.
• one of the two surfaces is very rough or even porous, which makes this kind of barrier solution according to the state of the art even more utopian.
• the seal device according to the invention is a pneumatic seal which consists in slowing the displacement of at least one of the two reactive gases, ie the one which has the smallest molar mass, by effect steric.
• a barrier of molecules of greater molar mass and in greater quantity In front of the molecule of the reactive gas in question is interposed a barrier of molecules of greater molar mass and in greater quantity.
• the fluid resulting from the reaction between the two reactive gases, and present inside the buffer chamber, has a collision cross section much larger than that of each of the two reactive gases.
• the molecular diffusion of the gases is necessarily reduced. reagents inside the microchannels.
• a buffer chamber occupied by water vapor having a much larger cross section requires molecular diffusion of H 2 and less 0 2 in the microchannels.
• the buffer chamber according to the invention makes it possible to stabilize the exchanges of reactive gases between the two spaces, that is to say to reduce at most the gradient between these two spaces.
• the buffer fluid in the chamber decreases the reaction rate between the two reactive gases.
• the water vapor in the chamber decreases the reaction rate between H 2 and O 2 from each of one of the spaces on either side of the chamber.
• the collision cross section is evaluated respectively at:
• the dimensioning (height and width) of the buffer chamber is preferably made according to the constraints of use of the seal. The lower the pressure and the higher the temperature, the larger the buffer chamber will be to allow the transformation of the reactive gases between them.
• the volume of gas must also make it possible to absorb the heat resulting from the reaction.
• the structure of the seal is made at the support portions with the same technology and the same processes as the rest of the parts used, such as the plates.
• the walls of the chamber and the support portions are formed in the same separating element interposed between said two spaces.
• the separating element consists of a stamped sheet.
• a separation element manufactured by stamping has the advantages of being mass-produced and low-cost.
• care is taken to choose a thickness of sheet sufficiently thin to allow easy stamping, but large enough so that the reserve of minor elements of the alloy (typically Al or Cr) is sufficient to allow protection against oxidation throughout its life.
• the stamped sheet may advantageously be made of nickel base alloy, such as Inconel 600, Inconel 718, Haynes 230. It may also be made of stainless steel, such as AISI 310S, AISI 316L, AISI 430.
• the invention also relates to an electrochemical reactor comprising at least one gasket device as described above, in which the spaces on either side separated by the gasket are the circulation spaces for the reactive gases. inside the reactor.
• the reactor comprises a stack of elementary electrochemical cells each formed of a cathode, an anode and an electrolyte interposed between the cathode and the anode, at least one interconnecting plate being arranged between two adjacent elementary cells and in electrical contact with an electrode of one of the two elementary cells and an electrode of the other of the two elementary cells, the interconnecting plate delimiting at least one cathode compartment and at least one anode compartment for the circulation of gases respectively at the cathode and the anode, it is expected that the cathode compartment or the anode compartment is advantageously one of two spaces separated by the seal device.
• it may be a reactor for electrolysis of water at high temperatures, intended to operate at temperatures above 450 ° C., typically between 600 ° C. and 1000 ° C.
• reactor constituting a SOFC fuel cell, intended to operate at temperatures between 600 ° C and 800 ° C.
• the buffer chamber has the following dimensions: height between 100 and 500 ⁇ m, the height being defined as the distance between the bottom of the chamber and the support surface;
• width at least equal to 500 ⁇ m, width being defined as being the minimum distance between the two support portions of the separating element.
• the force of support between the support portions and the plate portions is between 0.1 N / mm and 10 N / mm.
• the buffer chamber is preferably annular in shape around a space for recovering hydrogen produced.
• a buffer chamber height of between 100 and 500 ⁇ and a width of at least 500 ⁇ m are adapted.
• FIG. 1 is a schematic view showing the operation of a seal forming device according to the invention
• FIG. 2 is a perspective view of an element of a device according to a first embodiment of the invention
• FIG. 3 is a semi-perspective view of a device according to a second embodiment according to the invention.
• FIG. 4 is a partial sectional view of FIG. 3;
• FIG. 5 is a schematic view showing a device forming a seal according to the invention according to another embodiment
• FIG. 6 is a schematic view showing a device forming a seal according to the invention according to another embodiment
• FIGS. 7A to 7C show the curves of the average free path respectively of air, of hydrogen H 2, and of water vapor H 2 0 as a function of pressure and temperature, the mean free path to define a desired molecularly desired flow with a seal according to the invention
• FIG. 8 is a schematic representation of different types of flow as a function of the Knudsen number to define a predominantly molecular flow from the mean free range.
• the seal device is described below with reference to electrolysis of water (EHT) or a SOFC fuel cell.
• the sealing device according to the invention comprises a first space 1 occupied by hydrogen H 2 and a second space 2 occupied by oxygen O 2 .
• separating element 4 comprising two support portions 40, 41 held in abutment against a single support plate 5 with a given compression force which makes it possible to obtain a predominantly molecular type flow of the reactive gas molecules in the microchannels defined 60, 61 (see arrows).
• the microchannels 60, 61 are porous volumes delimited by the surface roughness of the bearing portions 40, 41 and portions of the plate 5.
• a buffer chamber 7 is delimited by the support portions 40, 41 where, in order for this characteristic to persist, the pressure difference between the oxygen and hydrogen chambers must not be too high (a few bars) so that the buffer chamber 7 remains the reaction place of the gases.
• the dimensions (height H and width L as shown in FIG. 4) of the buffer chamber 7 are determined in such a way as to allow a reaction of the two reactive gases O 2 , H 2 therebetween.
• the physical phenomenon obtained with the device according to the invention is a recombination reaction - geometrically controlled - of two constituents are typically the production of water vapor by the recombination of molecules of hydrogen and oxygen (see Figure 1). Once this water vapor has been obtained, it has advantageous characteristics such as:
• Each of the microchannels 60, 61, or in other words leakage zones, defined between a bearing portion 40, 41 and the support plate 5 passes two gases which do not react but which are counter-controlled at the level of the flow.
• the buffer chamber 7 is in overpressure with respect to two spaces 1, 2 to isolate.
• This method makes it possible to overcome a supply of a buffer gas and therefore an additional complexity.
• the buffer chamber 7 can be made easily from stamped shapes (FIG. 2).
• FIGS. 3 and 4 there is illustrated a device forming a seal according to the invention which constitutes what is usually referred to as a "stand alone" seal.
• the seal forming device according to the invention is a sort of dynamic seal which consists in controlling leakage by molecular flow (Knudsen type). It is thus perfectly suited to electrochemical applications with high operating temperatures because it makes it possible to let two pieces slide in contact (separating element and support plate), which allows large differential expansions.
• the invention can be applied in other electrochemical reactors for which it is sought to find a high performance seal.
• the device according to the invention when integrated directly into a reactor, the device according to the invention requires only a single buffer chamber.
• the support plate 5 on which the separating element 4 shown in FIGS. 2 to 4 is supported is flat: it goes without saying that it can have any other shape that bears with two bearing portions 40, 41 of the separating element.
• An example of another form is shown in Figure 5.
• FIGS. 2 to 4 a single separating element 4 is shown in FIGS. 2 to 4: according to the invention, it is of course possible to integrate another separating element 4 'in the same buffer chamber 7 as represented in FIG. 6.
• This other separation element 4 ' can for example be an additional piece of stamped sheet.
• the initial roughness of the surfaces of the materials constituting the gasket (separating element 4 supporting ortions 40, 41) and the bearing surface (bearing plate 5) vis-à- vis will typically have an arithmetic average deviation of Ra ⁇ 0.4 ⁇ m, obtained by polishing, or even by the care given to the surfaces during the elaboration.
• a linear force of 0.5 N per mm of joint makes it possible to obtain a molecular flow regime of the Knudsen type, provided that the material of the seal used (metal separating element 4) is sufficiently soft at the temperature of use, for example ferritic steel of type AISI 430 at 600 ° C, and that its initial roughness is low (Ra ⁇ 0.4 ⁇ m) and that pressures in spaces 1, 2 and 7 are around the atmospheric pressure. Under these conditions, the greater the linear support force is and the more one tends to obtain a molecular flow regime.
• the first method consists of comparing the value of the mean free path of the reactive gases, here respectively H2 and O2, and of the fluid formed by the reaction, in this case water vapor, with the dimensions of the microchannels defined by the roughness states of the portions. support and support plate.
• the mean free path ⁇ of a fluid can be expressed by the following equation:
• ⁇ denotes the average free path in m
• ⁇ denotes the dynamic viscosity in Pa s
• R denotes the universal constant of perfect gases (8,314) in J.mo-1.k-1; ;
• T denotes the temperature in Kelvin degree
• M denotes the molar mass of the fluid in g / mol.
• the average free path of the fluid therefore increases as a function of the temperature and the dynamic viscosity of the fluid, but decreases as a function of the pressure and the molar mass.
• FIGS. 7A, 7B and 7C are shown for the three gases of the preferred application, namely respectively air, hydrogen and water vapor, the representative curve of the average free path as a function of temperature and the pressure they are subjected to. We see that for the three gases the average free path increases with temperature and decreases very significantly with the pressure.
• the average free path is about the same level as the air (towards 0.5 ⁇ m at atmospheric pressure and at 700 ° C).
• the average free path is more important. This corroborates the relative collision cross section values, that of hydrogen being lower than those of substantially equal oxygen and water vapor.
• the Knudsen Kn number defined by the ratio between the mean free path and the characteristic length of the channel where the flow takes place, for example the diameter of a capillary.
• A denotes a free molecular flow
• D denotes a continuous flow.
• the seal according to the invention. invention can be considered as starting to be effective. Gasket is the most efficient from a characteristic microchannel length less than 0.1 times the mean free path.
• the second method consists in measuring the mass flow rate of a leak as a function of the overpressure on both sides of a seal. If the relation is of quadratic form, then one considers that it is rather a flow of type of Darcy. If the relation is linear, then we consider that it is rather a molecular flow.
• ⁇ H2 and ⁇ air respectively denote the effective collision diameter of H2 and air in nanometers (nm);
• MH2 and Mair respectively denote the molar mass of H2 and air in g / mol.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Electrochemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Sustainable Energy (AREA)
• Sustainable Development (AREA)
• Manufacturing & Machinery (AREA)
• Life Sciences & Earth Sciences (AREA)
• Inorganic Chemistry (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Composite Materials (AREA)
• Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
• Fuel Cell (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=44115678

Family Applications (1)

Country Status (10)

Families Citing this family (4)

Family Cites Families (12)

• 2010
  • 2010-11-23 FR FR1059639A patent/FR2967695B1/fr not_active Expired - Fee Related
• 2011
  • 2011-11-23 US US13/989,301 patent/US20130244136A1/en not_active Abandoned
  • 2011-11-23 CA CA2818620A patent/CA2818620A1/fr not_active Abandoned
  • 2011-11-23 EP EP11785455.4A patent/EP2643878A1/de not_active Withdrawn
  • 2011-11-23 CN CN2011800656918A patent/CN103339778A/zh active Pending
  • 2011-11-23 BR BR112013012662A patent/BR112013012662A2/pt not_active IP Right Cessation
  • 2011-11-23 KR KR1020137015531A patent/KR20140009255A/ko not_active Application Discontinuation
  • 2011-11-23 JP JP2013540347A patent/JP2013545896A/ja active Pending
  • 2011-11-23 WO PCT/EP2011/070828 patent/WO2012069543A1/fr active Application Filing
• 2013
  • 2013-05-27 ZA ZA2013/03830A patent/ZA201303830B/en unknown

Also Published As

Similar Documents

Legal Events