Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
  • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
  • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
  • B27N3/02—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
  • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
  • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
  • B27N3/04—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from fibres

Definitions

• the invention relates to a method for manufacturing an eco-compatible solid material and an eco-compatible solid material.
• the term "eco-compatible material” means a material that satisfies the environmental principles of sustainable development, that is to say a material intended, for its manufacture, to limit emissions of pollutants for the environment - greenhouse gas emissions and to promote the use of renewable resources to the detriment of the use of fossil
• Such a process for manufacturing an eco-compatible solid material finds its applications in the field of the manufacture of recyclable materials, which do not produce, for their processing, by-products which are non-transformable waste and which require storage or appropriate reprocessing.
• Such a method of manufacturing an ecologically compatible solid material also finds its applications in the field of the diversified valorization of plant resources - in particular, but not exclusively, agricultural - and satisfies the arrangements made by the European Union to reconcile agricultural work and the preservation of the environment (Common Agricultural Policy, CAP).
• beech wood chips are treated with water vapor at a temperature of between 160 ° C. and 220 ° C for a period of 20 minutes.
• the beech wood chips thus obtained are then dried, then milled and selected to obtain a fraction of particles with a particle size of between 90 ⁇ and 250 ⁇ .
• the moisture content of the obtained beech wood flour is then adjusted to a value of 3% and said flour is compressed under a pressure of 30 MPa at a temperature of 180 ° C. for 10 min.
• Such a method is limited in its applications to the processing of beech wood chips.
• EP 0 987 089 describes a process for treating a sunflower or rapeseed cake having a weight content of hydration of between 5% and 55% in which a compression molding step is carried out at a pressure of between 15 and 25%. MPa and heating at a temperature between 130 ° C and 200 ° C. Such a compression molding treatment does not allow a reduction in the specific volume of the sunflower cake or rapeseed mass constant.
• a process for manufacturing a disposable biodegradable container in which a raw vegetable powder is mixed -particularly a powder with a particle size of between 70 and 120 mesh obtained by grinding a material chosen from the straw, sawdust, pulp, straw, starch, palm fibers, melamine-formaldehyde (MF) resin and water.
• MF melamine-formaldehyde
• the pouring mixture obtained is then poured into a mold and then the mixture is subjected to a succession of compression steps at a temperature of between 150 and 155 ° C.
• Such a process requires the addition of melamine which is a synthetic compound and which is therefore not a compound of plant origin.
• the invention aims to overcome the disadvantages mentioned above by proposing a method of manufacturing an eco-compatible solid material adapted to allow the development of plant resources - notably from agriculture -.
• the invention is aimed in particular at a process for manufacturing an eco-compatible solid material in which only raw materials of natural origin - in particular natural plant raw materials - are used, to the exclusion of any other non-natural material. -particularly of synthetic materials, in particular derived from fossil resources-.
• the invention is directed to such a process in which, in particular, a raw material obtained from agriculture is selected and the said raw material is subjected directly-that is to say without any prior step in the preparation of a feedstock. pourable composition containing said raw material at a compression adapted to form an eco-compatible material.
• the invention also aims at providing a method of manufacturing an eco-compatible material that does not require the use of compounds toxic to human health or the environment.
• the invention also aims to provide an eco-compatible material obtained by such a process which has improved mechanical properties compared to biodegradable materials of the state of the art.
• the invention also aims to achieve all these objectives at lower cost, by proposing a method of manufacturing an eco-compatible material of low cost.
• the invention also aims more particularly at providing such a solution that satisfies the criteria of sustainable development, environmental safety and economic development.
• the invention relates to a method for manufacturing a solid material, said eco-compatible material, wherein: selecting a solid organic material comprising at least one compound chosen from the group consisting of polysaccharides and polypeptides, said solid organic material having a moisture content of less than 12%, in particular between 5% and 10%;
• this solid organic material is subjected to a molding step in which said solid organic material is placed in a mold and the solid organic material is compressed at a predetermined temperature and at a predetermined pressure;
• the predetermined temperature and the predetermined pressure are adapted to allow a decrease in the specific volume of the solid organic material to substantially constant mass.
• solid organic material means a solid biological material, that is to say a material that comes from living tissues or the transformation of products extracted from living organisms (plants or animals).
• a solid organic material can present cells by microscopic observation.
• such a solid organic material comprises at least one component of tissues and / or living cells such as a carbohydrate and / or a protide (amino acid, peptide, protein) and / or a lipid-in particular a phospholipid-and or a vitamin and / or a nucleic acid-in particular RNA and / or DNA-.
• such a solid organic material is not a material derived from a fossil resource - such as oil and / or natural gas - which is derived from the processing of a biological material but which does not include any constituent living cells.
• the solid organic material consists essentially - even exclusively - of such solid biological materials;
• moisture content of the solid organic material means the ratio multiplied by 100 between the mass of water contained in the solid organic material and the total mass of said solid organic material.
• moisture content of the solid organic material is determined by successively weighing the organic solid organic matter at equilibrium in atmospheric air at ambient pressure and temperature and weighing of the organic material, called dry organic matter, natural solid substantially dried at a temperature of the order of 103 ° C for a time necessary to obtain a substantially constant mass of said solid organic material.
• the solid organic material is placed in a mold in which the solid organic material is maintained during the molding step so as to have a substantially constant exposed surface area.
• the mold is a mold having a substantially flat pressing surface and adapted to allow the manufacture of plates of eco-compatible material in two dimensions. It is also possible that the mold is a mold adapted to allow the manufacture of non-planar shapes of eco-compatible material in three dimensions and / or in relief.
• the solid organic material is selected from the group consisting of fibrous solid organic materials and solid organic materials in the divided state.
• the solid organic material comprises at least one compound selected from the group consisting of vegetable proteins.
• the solid organic material comprises at least one compound selected from the group formed, as plant protein, cellulose, hemicelluloses, pectins, pectic substances, chitin and chitosan.
• the solid organic material comprises at least one compound selected from the group consisting of albumins, globulins, prolamines and glutelins.
• the solid organic material comprises at least one compound selected from the group consisting of casein, collagen and keratin.
• the solid organic material is an organic raw material.
• a raw material is a material that man is capable of extracting from nature - in particular to harvest - that is to say a natural resource. It can also be of a material produced in nature and used for the production of eco-compatible materials.
• the solid organic material may consist exclusively of organic molecules consisting of atoms chosen from the group consisting of the carbon atom, the hydrogen atom and the oxygen atom. , the majority nitrogen atom and, if appropriate, the sulfur atom and the minority phosphorus atom and of minerals in cationic or anionic form.
• the solid organic material is a material of natural origin, that is to say that is available in nature without requiring for its obtaining any chemical synthesis step or chemical transformation requiring human intervention.
• a solid organic material is a non-recovered waste from agriculture or livestock.
• the solid organic material is in the divided state.
• the solid organic material is a heterogeneous material formed of at least one polymeric compound selected from the group consisting of polysaccharides and polypeptides.
• a solid organic material having, in equilibrium with the surrounding atmosphere -particularly in a humidity atmosphere controlled at substantially 60% -a moisture content. between 0% and 6%.
• a solid organic material is especially chosen from the group consisting of organic materials formed essentially of cellulose.
• a solid organic material having, in equilibrium with the surrounding atmosphere -particularly in an atmosphere of humidity controlled at substantially 60% - a rate of humidity between 6% and 10%.
• a natural solid organic material is preferably chosen from the group consisting of lignocellulosic compounds consisting essentially of lignin, cellulose and hemicelluloses.
• a solid organic material having, in equilibrium with the surrounding atmosphere -particularly in an atmosphere of humidity controlled at substantially 60% - a humidity between 10% and 12%.
• a solid organic material is preferably selected from the group consisting of polysaccharide-rich materials with the exception of crystalline cellulose, especially cereal flours, beet pulp, proteinaceous flours (peas, faba beans) or other.
• the solid organic material may be a crop produced from agriculture, aquaculture - in particular seaweed farming - or forestry.
• the solid organic material is derived directly or by transformation of a plant selected from the group formed by annual plants and biennial plants, that is to say plants whose development cycle (from the germination of a plant). seed to the formation of a "daughter" seed) extends over one or two years.
• the solid organic matter may be a plant specially grown for harvesting and used in a process for producing an environmentally friendly material. compatible. It can also be a by-product derived from agriculture, from a fraction usually not valued of a cultivated plant. In this case, said sub-product from agriculture can be harvested during the harvest of said crop or later harvesting the valued fraction of the crop.
• it may also be an agricultural by-product that can be collected during a subsequent stage of treatment and / or extraction of said valued fraction of the cultivated plant.
• the solid organic matter may be formed from all or part of the aerial part of at least one oleaginous plant chosen from the group consisting of rapeseed, sunflower, flax, soybean, castor oil and peanut. sesame, cotton, crambe, hemp, jatropha and neem (Azadirachta indica) or neem.
• the solid organic matter can be formed from all or part of a perennial plant, that is to say from a plant whose life cycle extends over more than two years.
• the solid organic matter may also comprise or consist of cores -including olive kernels (Olea europeana) -, nut shells (Juglans regia), cocoa beans (Theobroma cacao), apple seeds, kernels plums and fruit stones used in the manufacture of fruit juices, grape cakes.
• cores including olive kernels (Olea Europeana) -, nut shells (Juglans regia), cocoa beans (Theobroma cacao), apple seeds, kernels plums and fruit stones used in the manufacture of fruit juices, grape cakes.
• the solid organic material may be a lignocellulosic material.
• lignocellulosic material is meant any natural material comprising a proportion of cellulose, hemicellulose and lignin.
• the polymeric compound of the solid organic material may be cellulose, especially cotton.
• Solid organic material from silviculture can be a waste - especially wood shavings or sawdust from logging.
• the solid organic material may also be formed of cellulose suitable for use in the paper industry or paper waste for recycling.
• the solid organic material derived from forestry or agriculture can be selected from the group consisting of ligno-cellulosic materials in the divided state - particularly with an average particle size of the order of 5 mm - produced in particular, but not exclusively , the defibration of wood, hemp (chessevotte), flax (anas) or the grinding of corn stalks.
• Solid organic matter can also be a keratin-based animal product such as wool - especially raw wool or carded wool - eg sheep wool, goat wool (mohair), rabbit wool ( angora), llama wool, alpaca wool, guanaco wool, camel wool and yak wool.
• Solid organic matter can also be a keratin-based animal production such as chicken feathers, duck feathers, goose feathers or mammal hooves and horns.
• the solid organic material may also be formed of remains of the skin of an animal - particularly a mammal superior (bovine and pork) - from a pre-tanning stage of skins in the leather industry. It is also possible that the solid organic material is a fragment of a piece of leather obtained by tanning a skin of such an animal.
• Solid organic matter may also be selected from the group consisting of waste or by-products of the food industry - in particular organic waste from the fish industry.
• At least one solid organic material is selected and the latter is subjected directly to compression without the addition of water and the formation of a plastic paste.
• said compression of the solid organic material is carried out while substantially maintaining the mass of said solid organic material.
• substantially means that in a process according to the invention, the solid organic material is likely to lose a minimal amount of water.
• the invention therefore consists in proposing a process for transforming a solid organic material having a moisture content of less than 12% into a solid material having improved mechanical strength properties compared with solid materials obtained from a material solid state of the art.
• the solid organic material in such a method of manufacturing an eco-compatible solid material, it is not necessary to mix the solid organic material with water. Indeed, in such a method is directly subjected to the solid organic matter moisture content of less than 12% in a thermo-compression step for a predetermined time and adapted to form an eco-compatible material. However, in a method according to the invention, it is possible to humidify the solid organic material prior to the thermo-compression step so as to adjust the moisture content of the solid organic material to a suitable value to perform said thermo-compression.
• the solid organic material is free of synthetic binder - which is not in itself a solid organic material.
• said solid organic material is subjected directly to the molding step.
• the solid organic material which is free of synthetic binder, in particular synthetic binder selected from the group consisting of thermoplastic synthetic binders and synthetic thermosetting binders is subjected directly to the molding stage without adding synthetic binder to said solid organic material.
• the solid organic material, in particular the solid organic material in the divided state is subjected to the molding step without the addition of synthetic binder, especially in the mold for molding said material. solid organic.
• the solid organic material being free of synthetic binder, said solid organic material is subjected directly to the molding step.
• the inventors have found that it is possible to transform a solid organic material into such an eco-compatible material without requiring the addition of a synthetic binder-especially a non-plant binder, in particular obtained from non-fossil resources. renewable resources.
• the inventors have found that it is possible to transform a composition comprising such a solid organic material into an eco-compatible material according to the invention.
• the inventors have observed that, in a totally surprising manner, the compression treatment of a solid organic material having a moisture content of less than 12% at a predetermined pressure and temperature leads, unlike compression treatments of humidity greater than 20%, densification of the solid organic matter without loss of mass (with the exception of a minimal amount of water) and formation of the eco-compatible material and having improved mechanical properties.
• the inventors assume that this densification of the solid organic material with a substantially constant mass results from a crushing of said solid organic material, conjugated with a molecular reorganization of the constituents -particularly of the polypeptide and polysaccharide constituents, in particular pectic and hemicellulosic components of said material. solid organic at predetermined temperature and pressure. Such simultaneous crushing and molecular reorganization would lead to the in situ formation of an endogenous binder of the solid material imparting to the solid material, after expansion and cooling, the mechanical properties of the eco-compatible material.
• an eco-compatible solid material in such a method of manufacturing an eco-compatible solid material according to the invention, it is possible to mix the solid organic material with at least one plant extract chosen from the group consisting of starch , plant-based fibers, protein isolates - in particular protein isolates extracted from oleaginous plants, in particular soybean, sunflower and rapeseed, or proteinaceous plants, in particular pea, fezpole or other-.
• plant extract chosen from the group consisting of starch , plant-based fibers, protein isolates - in particular protein isolates extracted from oleaginous plants, in particular soybean, sunflower and rapeseed, or proteinaceous plants, in particular pea, fezpole or other-.
• the solid organic material comprises a mass fraction of polysaccharides-especially holocellulose-greater than 50%.
• the mass fraction of polysaccharides contained in the solid organic material is measured by means known to those skilled in the art, in particular by the Van Soest detergent method (ISO 13906 2008 standard).
• the product of the mass fraction of polysaccharide and the mass fraction of lignin of the solid organic material is less than 0.125.
• the polysaccharide being cellulose
• the product of the cellulose mass fraction and the mass fraction of lignin of the solid organic material is less than 0.125.
• an organic material is used. solid having not undergone, between the harvesting of said organic resource and the thermo-molding step, no chemical treatment-especially no treatment by water vapor-. In such a process according to the invention, however, it is possible to carry out, where appropriate, a treatment for reducing the particle size of the organic resource-in particular a milling treatment-prior to the thermo-molding step.
• the eco-compatible material has a density greater than 1.28 g / cm 3 .
• the predetermined pressure is greater than 30 MPa, in particular between 35 MPa and 200 MPa, particularly between 40 MPa and 150 MPa, preferably between 50 MPa and 100 MPa.
• the predetermined temperature is between 160 ° C and 180 ° C.
• the predetermined temperature is between 120 ° C and 140 ° C.
• thermoforming of a solid organic material is carried out for the molding step.
• a quantity of solid organic material is placed between two molds of non-planar complementary shapes and said compression of the solid organic material is effected by exerting a relative approximation force of the two molds of complementary shapes adapted to crush the solid organic material and exert on it a predetermined pressure.
• the solid organic material is brought to a predetermined temperature.
• An object is made of eco-compatible material of complex shape extending in volume.
• the reduction in the specific volume of the solid organic material at the predetermined pressure and temperature is greater than 5%.
• the molding step is carried out directly from the solid organic material without any additional step of drying the solid organic material or voluntary addition of water to the solid organic material.
• thermo-pressing mold is chosen formed of two parts complementary to one another and co-adapted to each other, then;
• the solid organic material is placed in said mold between the two complementary parts, then;
• the pressing time is less than 15 min, especially between 1 min and 10 min, particularly between 1 min and 5 min.
• a reduction step is carried out-particularly by mechanical grinding-of the particle size of the solid organic material.
• a densification step of the solid organic material adapted to allow easy filling of the mold is carried out prior to the heat-compression treatment.
• This densification step is carried out with any means known to those skilled in the art, in particular with a pellet press or a pelletizer.
• the invention also aims at a solid material, said eco-compatible material, characterized in that it has:
• the invention extends also to an eco-compatible material obtained by a process according to the invention and having:
• the eco-compatible material is free of synthetic binder, in particular chosen from the group formed by thermoplastic synthetic binders and synthetic thermosetting binders - in particular non-vegetal binders.
• such an eco-compatible material is free of melamine.
• the invention also extends to a solid material, said eco-compatible material, of natural origin, characterized in that it has at least one of the following characteristics:
• a mass fraction of lignin of less than 0.25, in particular less than 0.20%;
• a flexural breaking strength substantially greater than 30 MPa, in particular between 30 MPa and 60 MPa, preferably between 50 MPa and 55 MPa.
• the eco-compatible material has:
• Flexural modulus and tensile strength measurements are carried out under the conditions defined in the NF EN ISO 178 standard.
• the invention also extends to such an eco-compatible material obtained by a method according to the invention.
• the eco-compatible material has a mass fraction of polysaccharide greater than 0.50.
• the product of the mass fraction of polysaccharide and the mass fraction of lignin of said eco-compatible material is less than 0.125.
• the polysaccharide being cellulose
• the product of the cellulose mass fraction and the mass fraction of lignin of said eco-compatible material is less than 0.125.
• the eco-material compatible is free of non-plant synthetic thermoplastic binder.
• the eco-compatible material has a color substantially identical to the initial solid organic material.
• the invention also relates to a method and an eco-compatible material characterized in combination by all or some of the characteristics mentioned above or below.
• FIG. 1 is a representation of the change in the mass volume (cm 3 / g) of three samples representing a rate of 100%, 92% and 80% of dry matter as a function of the temperature (° C.) during implementation of a method according to the invention;
• FIG. 2 is a representation of the change in the mass volume (cm 3 / g) of three samples subjected to a pressure of the order of 500 bar (50 MPa), of the order of 1000 bar (100 MPa) and of the order of 1600 bar (160 MPa) depending on the temperature (T, ° C) during the implementation of a method according to the invention.
• EXAMPLE 1 Thermo-molding of Sunflower Proteins 5.2 g of a powdered sunflower seed protein extract having a solids content of 90% are placed in three of the four imprints of a rigid mold of a thermo-press (MAPA 50, PEI, Pinette Emidecau Industries, Chalon sur Saone, France) adapted for the production of specimens.
• the dimensions (L xi) of each imprint are 80 mm x 10 mm.
• the heat press plates are heated to a predetermined temperature value of 162 ° C. When the temperature of the plates of the thermo-press has reached the predetermined temperature, pressure is applied to the press plates so as to reach a stable value of 41 MPa. This pressure is maintained for a period of 12 minutes and then released progressively the pressure up to atmospheric pressure under conditions adapted to not cause the explosion of the molded object in the rigid mold.
• the mold is extracted from the thermo-press and the test pieces are demolded.
• test pieces thus formed are placed in a thermostatically controlled chamber maintained at a temperature of 25 ° C. and at an atmospheric humidity level of 60% for 14 days.
• the thickness of the test pieces obtained is 4 mm.
• the test pieces of solid material according to the invention have a density of 1.287 g / cm 3 , a three-point flexural modulus (measured according to the NF EN ISO 178 standard) of 4.23 GPa and a flexural tensile strength ( measured according to standard NF EN ISO 178) of 37.4 MPa.
• EXAMPLE 2 Thermo-Molding of a Sunflower Cake
• 5.2 g of sunflower cake the average particle size of which was adjusted by grinding to a value of 2 mm and having a solids content of 93% in three of the four imprints of a rigid mold of the thermo-press.
• the predetermined temperature of the platens of the press is 160 ° C. and the equilibrium pressure exerted is 35 MPa. This pressure is maintained at equilibrium for a period of 12 minutes.
• test pieces 4 mm thick After conditioning the test pieces at a temperature of 25 ° C. and at an atmospheric moisture content of 60% for 14 days, specimens 4 mm thick are obtained.
• the test pieces of solid material according to the invention have a density of 1.297 g / cm 3 , a three-point flexural modulus of 3.31 GPa and a measured flexural rupture strength of 29.4 MPa.
• thermo-press 12 g of -cellulose (Sigma-Aldrich, Lyon, France), previously conditioned, are placed in an enclosure containing a controlled humidity atmosphere (45%, 60% and 85%) in a square mold of 50 mm ⁇ 50 mm diameter. a thermo-press.
• the plates of the thermo-press are heated from a value of 50 ° C. to a predetermined temperature value of 150 ° C. according to a gradient temperature of 5 ° C / min under a pressure of 49 MPa.
• the pressure is gradually released (1 MPa / sec) to atmospheric pressure.
• the mold is extracted from the thermo-press and the mold is removed from the mold.
• the plates are placed in a thermostatically controlled chamber maintained at a temperature of 25 ° C. and at an atmospheric moisture content of 60% for 14 days.
• the plates are cut into specimen shapes 10 mm wide.
• the mechanical properties of the materials obtained are given in Table 1 below.
• the solid material obtained has a density of 1.40 g / cm 3 , a three-point flexural modulus of 6.1 GPa and a bending strength of 49.8 MPa.
• the three powders are successively placed in the piston of a PVT analyzer (PVT 100, Thermo Electron, Düsseldorf, Germany). Constant compression is applied to said powder at a value of 500 bar and the temperature is increased from an initial value of 50 ° C. to final value of the order of 200 ° C.
• the mass volume (V, in cm 3 / g) of the sample is measured during this thermal increase.
• FIG. 1 The results are given in FIG. 1 in which the solid circle series ( ⁇ ) represents the extract at 100% dry mass, the solid square series ( ⁇ ) represents the extract at 92% dry mass and the series of solid triangle (A) represents the extract at 80% dry mass.
• the 100% solids content sample shows a transition from a high mass volume state (1.07 cm 3 / g) between 50 ° C and 100 ° C and a compacted state of decreased mass volume (0, 8 cm 3 / g) for temperature values above 170 ° C. This transition is carried out at constant mass, that is to say without significant loss of water.
• the dry matter sample of 92% shows a transition between a state of high mass volume (0.95 cm 3 / g around 50 ° C) and a compacted state of reduced specific volume (0.75 cm 3 / g) for temperature values above 90 ° C. This transition is carried out at constant mass, that is to say without significant loss of water.
• a powdered sunflower seed protein extract having a solids content of 94% is prepared as described in Example 1.
• a PVT analysis of a sample of this powder is carried out at a constant pressure value of 500 bars, then analysis of a second sample at 1000 bars and analysis of a third sample at 1600 bars.
• the initial temperature of the compression chamber is 50 ° C.
• the mass volume (V, in cm 3 / g) of the sample is measured during this thermal increase for these three pressures. The results are given in Figure 2.

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• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Wood Science & Technology (AREA)
• Forests & Forestry (AREA)
• Casting Or Compression Moulding Of Plastics Or The Like (AREA)
• Dry Formation Of Fiberboard And The Like (AREA)

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• 2010
  • 2010-11-23 FR FR1004556A patent/FR2967690B1/fr not_active Expired - Fee Related
• 2011
  • 2011-11-16 WO PCT/FR2011/052668 patent/WO2012069736A1/fr active Application Filing
  • 2011-11-16 EP EP11794558.4A patent/EP2643132A1/de not_active Withdrawn

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