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WO2012160229A1 - Composition de matière carbonée pouvant être obtenue par carbonisation d'un biopolymère supporté sur de l'argile - Google Patents

Composition de matière carbonée pouvant être obtenue par carbonisation d'un biopolymère supporté sur de l'argile Download PDF

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Publication number
WO2012160229A1
WO2012160229A1 PCT/ES2012/070362 ES2012070362W WO2012160229A1 WO 2012160229 A1 WO2012160229 A1 WO 2012160229A1 ES 2012070362 W ES2012070362 W ES 2012070362W WO 2012160229 A1 WO2012160229 A1 WO 2012160229A1
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Prior art keywords
carbonaceous material
clay
biopolymer
preparing
composition according
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Ceased
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English (en)
Spanish (es)
Inventor
Eduardo Ruiz Hitzky
Francisco Miguel Moreira Martins Fernandes
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Consejo Superior de Investigaciones Cientificas CSIC
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Consejo Superior de Investigaciones Cientificas CSIC
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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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/04—Clay; Kaolin
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
    • C04B35/532—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components containing a carbonisable binder
    • 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00853—Uses not provided for elsewhere in C04B2111/00 in electrochemical cells or batteries, e.g. fuel cells
    • 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
    • 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
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances

Definitions

  • the present invention relates to carbonaceous materials supported on clays provided with electrical conductivity using clays and polymers of natural origin or biopolymers as precursors.
  • the present invention relates to the process of obtaining said materials by carbonization of the biopolymer previously associated with clay by heat treatments.
  • the present invention also makes reference to the use of said materials as a polymer matrix charge, providing them with electrical conductivity, to their forming as conductive foams, as elements of electrical and electrochemical devices such as supercapacitors, electrocatalysts and biosensors.
  • a strategy applied to the preparation of high specific surface carbonaceous materials is to associate the precursor organic material to porous solids such as silica, either synthetic (Wang, H. C, L, B. L, L, JT , Lin, P., Bian, XB, L ⁇ , J., Zhang, B. and Wan, ZX "Direct synthesis of mesoporous carbon from the carbonized of hydroxypropyl- [beta] - cyclodextrin / silica composite and its catalytic performance. "Applied Surface Science 257, 4325) or of biogenic origin (Liu, D., Yuan, P., Tan, D., Liu, H., Fan, M., Yuan, A ., Zhu, J.
  • clays as a support material for carbonaceous compounds has been developed mainly with laminar-type clays such as Montmorillonite (Santos, C, Andrade, M., Vieira, A. L, Martins, A., Pires, J., Freiré, C. and Carvalho, AP (2010) "Templated synthesis of carbon matenals mediated by porous clay heterostructures.” Carbon 48, 4049; Montilla, F., Morallón, E., Vázquez, J. L, Alca ⁇ iz-Monge, J., Cazorla-Amorós, D. and Linares-Solano, A. (2002).
  • Montmorillonite Suddenos, C, Andrade, M., Vieira, A. L, Martins, A., Pires, J., Freiré, C. and Carvalho, AP (2010) "Templated synthesis of carbon matenals mediated by porous clay heterostructures.” Carbon 48, 4049; Montilla,
  • Carbon-ceramic composites from coal tar pitch and clays application as electrocatalyst support. Carbon 40, 2193) and to a lesser extent with fibrous clays such as palygorskite (Bispo, TS, Ba n, GB, Giménez, IF and Barreto, LS (201 1) "Semiconductor carbon composite from coir dust and sepiolite.” Materials Characte zation 62, 143) and sepiolite (Fernandez-Saavedra, R ., Darder, M., Gomez-Aviles, A., Aranda, P. and Ruiz- Hitzky, E. (2008).
  • fibrous clays such as palygorskite (Bispo, TS, Ba n, GB, Giménez, IF and Barreto, LS (201 1) "Semiconductor carbon composite from coir dust and sepiolite.” Materials Characte zation 62, 143) and
  • biopolymers such as gelatin or collagen containing said element
  • biopolymers are per se precursors of carbonaceous compounds that can provide electrical conductivity. This is the case of gelatin (Larsen, EC and Walton, JH (1940). "Activated Carbon as a Catalyst in Certain Oxidation-Reduction Reactions.” The Journal of Physical Chemistry 44, 70) that has recently been used for the preparation and application of carbonaceous materials for electrochemical devices (C ⁇ , Y., Ge, J., Wang, XF, Chen, WH, Guo, YC and Chen, LJ (2007).
  • a first aspect of the present invention relates to a carbonaceous material comprising a clay and carbon generated by heat treatment of carbonization of biopolymers. Therefore, precursor materials in the present invention are understood as the clay and biopolymer assembly.
  • the present invention relates firstly to a composition of carbonaceous material characterized in that it comprises carbonaceous material supported on clay and which is obtainable by a carbonization treatment of at least one biopolymer associated with at least one clay.
  • clay in the present invention are those silicates of natural or synthetic origin of laminar or smectitic type such as montmorillonite, hectorite, saponite, stevensite, Hita, beidelite and combinations of the above, or microfibrous type such as sepiolite or palygorskita, also known as attapulgita, and combinations of them.
  • This group also includes derivatives of clays subjected to heat treatments to dehydrate or dehydroxylate them.
  • biopolymer in the present invention are those polymers of natural origin of the polysaccharide type such as chitosan, alginate, pectin, guar gum, cellulose and their derivatives; proteins such as gelatin, collagen, zein; nucleic acids such as DNA, and combinations of the above.
  • the use of clays is an advantage in the present invention over the use of other inorganic solids because of its colloidal stability in aqueous medium, its high specific surface area, its reduced cost and its non-toxic or contaminating character since they are considered inert from the point of environmental view
  • the clay that is selected is sepiolite, palygorskite, bentonite or montmorillonite.
  • the clay that is selected is sepiolite.
  • sepiolite is considered advantageous because its aspect ratio and in general its fibrous morphology is maintained in the supported carbonaceous material of the invention.
  • sepiolite of rheological grade is used, that is to say with the ability to flow, with which very stable gels are obtained in polar liquid media, facilitating the preparation of dispersions of filamentous carbon materials object of the present invention.
  • sepiolite of lesser degree of purity or different granulometry implies the prior preparation of a gel or dispersion by means of prior wet grinding and ultrasonic application.
  • biopolymers in the present invention represent an advantage over the use of other organic precursors in their solubility, ability to form stable gels, because of their affinity towards the surface of clay-like silicates by strongly associating with them, because of their biodegradable, biocompatible nature, Non-toxic and with very little polluting power.
  • biopolymer that is selected is gelatin.
  • gelatin is considered advantageous because it allows a good reversible control of its gelation state by varying the temperature of the medium, which is an advantage when it comes to forming materials as foams. Other advantages are its high water solubility, its relatively low cost and its high nitrogen content of great convenience in the preparation of conductive carbonaceous materials.
  • gelatin that is selected is gelatin type A, of porcine origin.
  • the precursor materials are associated with each other in a liquid medium.
  • the liquid medium is selected in a preferred embodiment from the list comprising water, alcohols, carbonyl compounds, combinations of carbonyl compounds or any combination of the foregoing.
  • the present invention also relates to a process for obtaining supported carbonaceous materials provided with electrical conductivity using biopolymer precursors associated with clays.
  • the present invention relates to the process of obtaining said materials by carbonization of the biopolymer previously associated with clay by heat treatments.
  • the present invention relates to a method of obtaining the composition as described above, comprising the steps: a. adding the precursors to a polar liquid medium as described above, b. homogenization of the composition obtained in step (a) by mechanical agitation c. recovery of the solid resulting from step (b) by elimination of the liquid medium d. heat treatment of the material generated in stage (c)
  • the precursor materials are initially in the clay / biopolymer mass ratio between 10: 1 and 1: 1. In another more preferred embodiment the precursor materials are initially in the 1: 1 mass ratio clay / biopolymer.
  • the precursor materials are mixed with the liquid medium in a mass ratio between 1: 1000 and 1: 10. In another more preferred embodiment, the precursor materials are mixed with the liquid medium in a proportion of 5%. by mass (50 g of precursor per kg of liquid medium).
  • step (b) the homogenization mentioned in step (b) is carried out in periods of 15 minutes to 3 hours. In a more preferred embodiment the homogenization is carried out in a period of 30 minutes.
  • the homogenization is carried out at the most favorable temperature so that the biopolymer is in the form of the sun.
  • the homogenization of the gelatin-containing precursor is carried out at a temperature of 60 ° C.
  • step (c) the removal of the liquid medium mentioned in step (c) is carried out by filtration.
  • the removal of the liquid medium mentioned in step (c) is carried out by centrifugation. In another more preferred embodiment, the removal of the liquid medium mentioned in step (c) is carried out by forced evaporation under reduced pressure and at a temperature above 25 ° C.
  • the removal of the liquid medium mentioned in step (c) is carried out by supercritical drying. In another more preferred embodiment the removal of the liquid medium mentioned in step (c) is carried out by lyophilization in a temperature range between 77K and 273K. In another preferred embodiment the heat treatment mentioned in step (d) is carried out under a non-oxidizing atmosphere.
  • the heat treatment mentioned in step (d) is carried out under a nitrogen atmosphere in flux.
  • the heat treatment mentioned in step (d) the nitrogen flow is set at 5 ml / minute.
  • step (d) the heat treatment mentioned in step (d) is carried out at temperatures between 550 and 1200 ° C.
  • the heat treatment mentioned in step (d) is carried out at a temperature of 800 ° C.
  • Another aspect of the present invention relates to a product that is a composition of carbonaceous material characterized in that it comprises a charred mixture of at least one biopolymer supported on at least one clay.
  • Particular embodiments refer to the clay being selected from a laminar type clay, a fibrous clay and combinations thereof.
  • the laminar clay is selected from montmorillonite, saponite, beidellite, estevensite, Hita, and combinations thereof, or the arciall is fibrous and is selected from sepiolite, palygorskite and combinations thereof.
  • the biopolymer can be chitosan, alginate, pectin, guar cellulose gum, gelatin, collagen, zein, DNA and any combination thereof.
  • Said product is a composite or composite material consisting of carbonaceous compounds supported on clays, which has the advantage over non-supported carbonaceous materials of having a greater specific surface and showing a controllable morphology, also presenting electrical conductivity.
  • the present invention relates to the use of said materials as a polymer matrix charge to confer electrical conductivity, to its conformation as conductive foams, to its use as elements of electrical and electrochemical devices such as supercapacitors, electrocatalysts and biosensors.
  • the present invention relates to the use of the product described above, as a polymer charge to provide them with electrical and thermoelectric properties, as a collector component of sensors and electrocatalysts, as a component of supercapacitors and battery electrodes, electromagnetic radiation sealant.
  • the product of the invention formed as foams its use refers to the development of conductive composites by filling the porous structure of the foam with polymers of different nature.
  • Figure (a) is a scanning electron microscopy (FE-SEM) image of the carbonaceous material supported on clay of the invention prepared using gelatin and sepiolite.
  • Figure (b) is a scanning electron microscopy image of the carbonaceous material prepared using gelatin without the presence of a clay.
  • Figure (c) is a transmission electron microscopy image of the carbonaceous material supported on clay of the invention prepared using gelatin and sepiolite where the morphology of the carbonaceous material influenced by the morphology of the clay can be observed.
  • FIG. 2 Photographic image of the foams obtained from the previous lyophilization of the precursors of the carbonaceous material before (figure c) and after heat treatment (figure b).
  • Figure (a) corresponds to the conductive foam shown in Figure (b) after filling and curing process with an epoxy resin.
  • Example 1 Preparation of a sepiolite supported carbonaceous material from this clay and gelatin in a 1: 1 ratio
  • the material obtained is dried in an oven at a temperature of 40 ° C for 12 hours and charred in a tubular oven under a flow of nitrogen of 5 ml / minute for 2 hours.
  • the oven temperature increases by 5 ° C / minute to reach 800 ° C, at which temperature it is maintained for 2 hours.
  • the material obtained is characterized by scanning electron microscopy with field effect (FE-SEM) and the nanoparticulate nature of the carbonaceous solid generated can be observed (Figure 1 a).
  • FE-SEM scanning electron microscopy with field effect
  • Figure 1b The same procedure applied to a material without the presence of sepiolite generates carbonaceous particles of mass appearance
  • Example 3 Preparation of a conductive composite by filling carbonaceous foam with epoxy resin.
  • a conductive foam is prepared according to the procedure described in Example 2. Subsequently, 13.7 grams of a stoichiometric mixture of epoxy resin (diglycidyl ester of bisphenol A) and a diamino compound (polypropyleneglycol (bis-2-aminoeter)) are added before Cure occurs. Dynamic vacuum is applied to the foam assembly with the formulation of the epoxy resin and the diamino compound until the pores of the carbonaceous foam are filled with polymeric material. Finally, the resin is cured at 60 ° C for 12 hours followed by a post-cure of 2 hours at 120 ° C. The final material can be easily machined to expose its conductive faces.
  • epoxy resin diglycidyl ester of bisphenol A
  • a diamino compound polypropyleneglycol (bis-2-aminoeter)
  • the volumetric conductivity of the material measured after the deposition of a layer of gold by sputtering as a contact element is 0.01 S.cm "1.
  • the macroscopic appearance of the conductive carbonaceous foam - epoxy resin composites is presented in Figure 2a .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne une composition de matière carbonée caractérisée en ce qu'elle comprend une matière carbonée supportée sur de l'argile, ladite argile étant de préférence de type laminaire comme la montmonrillonite, la saponite, la beidellite, l'estévensite, l'illite, et des combinaisons de celles-ci, ou de l'argile fibreuse telle que la sépiolite, la palygorskite et des combinaisons de celles-ci, ladite composition pouvant être obtenue par un traitement de carbonisation d'au moins un biopolymère, tel que du chitosane, de l'alginate, de la pectine, de la gomme de guar, de la cellulose, de la gélatine, du collagène, de la zéine, de l'ADN et n'importe laquelle de leurs combinaisons, ledit biopolymère étant associé à au moins une argile. L'invention concerne un procédé d'obtention de ladite composition et son utilisation en tant qu'additif de matrices polymères pour les doter de propriétés électriques, thermoélectriques, en tant que composant dans des supracondensateurs et des électrodes de batteries, en tant que composant de panneaux écrans contre le rayonnement électromagnétique, pour la préparation de composites conducteurs électriques et thermiques par remplissage de la structure poreuse de la mousse à l'aide de polymères.
PCT/ES2012/070362 2011-05-23 2012-05-22 Composition de matière carbonée pouvant être obtenue par carbonisation d'un biopolymère supporté sur de l'argile Ceased WO2012160229A1 (fr)

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ESP201130835 2011-05-23
ES201130835A ES2393474B1 (es) 2011-05-23 2011-05-23 Composición de material carbonoso obtenible por carbonización de un biopolímero soportado sobre arcilla.

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015150676A1 (fr) 2014-03-31 2015-10-08 Institut Français Des Sciences Et Technologies Des Transports, De L'aménagement Et Des Réseaux Dispositif d'acquisition, procede de fabrication de celui-ci, procede de mesure de force.
WO2019122475A1 (fr) * 2017-12-19 2019-06-27 Narbon, S.L. Composition émotionnelle à base d'argile destinée à une utilisation en tant que reliquaire

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CN117904894B (zh) * 2023-04-07 2025-08-01 冠宏化工（扬州）有限公司 一种表面活化聚合的填料制备工艺

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WO2006110137A1 (fr) * 2005-04-08 2006-10-19 Dow Global Technologies, Inc. Composite d’argile expanse dans la suite et son procede de preparation

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DE3826452A1 (de) * 1988-08-04 1990-02-08 Bitzer Diethelm Tone
WO2005087854A2 (fr) * 2003-10-10 2005-09-22 Dow Global Technologies Inc. Composite d'argile expansee dans la suie et son procede de preparation
WO2006110137A1 (fr) * 2005-04-08 2006-10-19 Dow Global Technologies, Inc. Composite d’argile expanse dans la suite et son procede de preparation

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GOMEZ-AVILES, A. ET AL.: "Multifunctional materials based on graphene- like sepiolite nanocomposites.", APPLIED CLAY SCIENCE, vol. 47, 2010, pages 203 - 211 *
SANTOS BISPO, T. ET AL.: "Semiconductor carbon composite from coir dust and sepiolite.", MATERIALS CHARACTERIZATION, vol. 62, January 2011 (2011-01-01), pages 143 - 147 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015150676A1 (fr) 2014-03-31 2015-10-08 Institut Français Des Sciences Et Technologies Des Transports, De L'aménagement Et Des Réseaux Dispositif d'acquisition, procede de fabrication de celui-ci, procede de mesure de force.
US10989612B2 (en) 2014-03-31 2021-04-27 Institut Francais Des Sciences Et Technologies Des Transport, De L'amenagement Et Des Reseaux Sensor with a plurality of acquisition devices that measure force using impedance
WO2019122475A1 (fr) * 2017-12-19 2019-06-27 Narbon, S.L. Composition émotionnelle à base d'argile destinée à une utilisation en tant que reliquaire

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ES2393474A1 (es) 2012-12-21

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