EP1836244A1 - Verwendung von kohlenstoffnanoröhrchen zur herstellung einer leitfähigen organischen zusammensetzung und anwendung einer derartigen zusammensetzung - Google Patents

Verwendung von kohlenstoffnanoröhrchen zur herstellung einer leitfähigen organischen zusammensetzung und anwendung einer derartigen zusammensetzung

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Publication number
EP1836244A1
EP1836244A1 EP06709033A EP06709033A EP1836244A1 EP 1836244 A1 EP1836244 A1 EP 1836244A1 EP 06709033 A EP06709033 A EP 06709033A EP 06709033 A EP06709033 A EP 06709033A EP 1836244 A1 EP1836244 A1 EP 1836244A1
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EP
European Patent Office
Prior art keywords
poly
styrene
composition
carbon nanotubes
polymers
Prior art date
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Application number
EP06709033A
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English (en)
French (fr)
Inventor
Nour-Eddine El Bounia
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Arkema France SA
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Arkema France SA
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Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP1836244A1 publication Critical patent/EP1836244A1/de
Withdrawn legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio

Definitions

  • the present invention relates to the use of carbon nanotubes for the manufacture of an electrically conductive organic composition having a constant electrical resistivity as a function of temperature as well as the applications of these compositions.
  • Prior art and technical problem Prior art and technical problem.
  • Carbon nanotubes are known and used for their excellent properties of electrical and thermal conductivity as well as their mechanical properties. They are thus more and more used as additives to bring to materials including those of macromolecular type these electrical, thermal and / or mechanical properties (WO 91/03057, US5744235, US5445327, US54663230).
  • carbon nanotubes in many fields, in particular in electronics (depending on the temperature and their structure, they can be conductors, semiconductors or insulators), in mechanics, for example for the reinforcement of composite materials (nanotubes of carbon are one hundred times stronger and six times lighter than steel) and electromechanical (they can elongate or contract by charge injection).
  • carbon nanotubes in macromolecular compositions intended for the packaging of electronic components, for the manufacture of fuel lines (fuel oil), for antistatic coatings or coatings, in thermistors, electrodes for super-abilities, etc.
  • compositions which specifically exhibit effects of positive or negative variation of electrical resistance as a function of temperature (PTC or NTC effect) and their use in resistive devices (US Pat. No. 6,640,420) are well known. These compositions are generally formulations based on macromolecular substances of which at least one component is semi-crystalline in nature, for example polyethylene, and which contains conductive additives, the best known being carbon black (J. of PoI, Sci. Part B - Vol 41, 3094-3101 (2003)) or PVDF (US 20020094441 A1, US 6,640,420).
  • a PTC system can be used as a heating system by Joule effect or an electric limiter (voltage or current: circuit breaker) through a resistance that increases rapidly depending on the temperature through the Joule effect.
  • the PTC effect is used to shape thermistors, heat paints, heating systems for car seats, ...
  • the object of the invention is to propose the use of carbon nanotubes in other types of organic material in order to produce conductive organic compositions having a temperature insensitive electrical resistivity.
  • “Insensitive” means a relative variation of less than or equal to 80%, preferably less than or equal to 50%, more preferably less than or equal to 30% over the working temperature range (generally from -50 ° C to the melting temperature of the polymer when the formulation is based on a semi-crystalline or until the glass transition when the formulation is based on an amorphous polymer). In general, this temperature range is conditioned by the nature of the organic formulation used.
  • the organic materials used in the present invention are selected from a.
  • the group of thermoplastic resins consisting of resins: i. acrylonitrile-butadiene-styrene (ABS), ii. acrylonitrile-ethylene / propylene-styrene (AES), iii. methylmethacrylate-butadiene-styrene (MBS), iv. acrylonitrile-butadiene-methylmethacrylate-styrene (ABMS), ca. acrylonitrile-n-butylacrylate-styrene (AAS), b. modified polystyrene gums; vs. the resins of i.
  • polystyrene polymethyl methacrylate, cellulose acetate, polyamide, polyester, polyacrylonitrile, polycarbonate, polyphenyleneoxide, polyketone, polysulphone, polyphenylenesulphide; d. the resins: i. halogenated, preferably fluorinated as polyvinylidene fluoride (PVDF) or chlorinated as polyvinyl chloride (PVC), silicone, polybenzimidazole; e.
  • PVDF polyvinylidene fluoride
  • PVC polyvinyl chloride
  • silicone silicone
  • polybenzimidazole polybenzimidazole
  • thermosetting resins consisting of resins based on phenol, urea, melamine, xylene, diallylphthalate, epoxy, aniline, furan, polyurethane; f.
  • thermoplastic elastomers consisting of styrene-type elastomers such as styrene-butadiene-styrene block co-polymers or styrene-isoprene-styrene block co-polymers or their hydrogenated form, elastomers of PVC, urethane, polyester, polyamide type, thermoplastic elastomers of polybutadiene type such as 1,2-polybutadiene or trans-1,4-polybutadiene resins; chlorinated polyethylene, fluoro-type thermoplastic elastomers, polyether esters and polyether amides; boy Wut.
  • the group of water soluble polymers consisting of cellulosic polymers, polyelectrolytes, ionic polymers, acrylate polymers, acrylic acid polymers, gum arabic, poly (vinyl pyrrolidone), poly (vinyl alcohol), poly (acrylic acid), poly
  • polyacrylic acid sodium polyacrylate
  • polyacrylamide poly (ethylene oxide), polyethylene glycol, poly (ethylene formamide), polyhydroxyether, poly (vinyl oxazolidinone), methyl cellulose, ethyl cellulose, carboxymethyl cellulose, ethyl (hydroxyethyl) cellulose, sodium polyacrylate , their copolymers, and mixtures thereof; h.
  • PSS polystyrene sulfonate
  • the present invention relates to the use of carbon nanotubes for the manufacture of a conductive organic composition having a temperature insensitive electrical resistivity.
  • the organic conductive composition in the aforementioned use, also has a thermal conductivity insensitive to temperature.
  • the composition comprises one or more electroconductive fillers of which at least one filler comprises carbon nanotubes having a ratio of form (L / D) greater than or equal to at 5 and preferably greater than or equal to 50 and advantageously greater than or equal to 100.
  • the percentage by weight of carbon nanotubes in the composition is less than 30%, preferably between 0.01 and 20%, and advantageously between 0.1 and 15%.
  • the carbon nanotubes have a diameter of between 0.4 and 50 nm and a length of 100 and 100,000 times their diameter.
  • the carbon nanotubes are in multi-wall form, their diameter being between 10 and 30 nm and their length being greater than 0.5 micron.
  • the organic composition has a percolation threshold ranging from 0.01 to 5%.
  • the organic composition further comprises one or more macromolecular materials chosen from liquids such as oils, greases such as those used for lubrication, liquid formulations. water based or solvents such as adhesives, paints and varnishes.
  • the organic composition comprises at least one semi-crystalline type polymer.
  • the invention finds a particularly noted application, in the context of the above-mentioned use, in the fields of the packaging of electronic components, the manufacture of fuel lines (fuel oil), antistatic coatings or coating, thermistors, electrodes for supercapacities, mechanical reinforcing fibers, textile fibers, rubber or elastomer formulations, seals, radiofrequency wave and electromagnetic wave screens.
  • the subject of the present invention is also, as a new industrial product, a conductive organic composition having a temperature-insensitive electrical resistivity comprising an amount up to 30% by weight, relative to the weight of the composition, of carbon nanotubes. whose diameter is between 0.4 and 50 nm, whose aspect ratio (L / D) is greater than 100.
  • the present composition comprises at least one polymeric material selected from a.
  • the group of thermoplastic resins consisting of resins: i. acrylonitrile-butadiene-styrene (ABS), ii. acrylonitrile-ethylene / propylene-styrene (AES), iii. methylmethacrylate-butadiene-styrene (MBS), iv. acrylonitrile-butadiene-methylmethacrylate-styrene (ABMS), ca. acrylonitrile-n-butylacrylate-styrene (AAS), b. modified polystyrene gums; vs. the resins of i.
  • polystyrene polymethyl methacrylate, cellulose acetate, polyamide, polyester, polyacrylonitrile, polycarbonate, polyphenyleneoxide, polyketone, polysulphone, polyphenylenesulphide; d. the resins: i. halogenated, preferably fluorinated as polyvinylidene fluoride (PVDF) or chlorinated as polyvinyl chloride (PVC), silicone, polybenzimidazole; e.
  • PVDF polyvinylidene fluoride
  • PVC polyvinyl chloride
  • silicone silicone
  • polybenzimidazole polybenzimidazole
  • thermosetting resins consisting of resins based on phenol, urea, melamine, xylene, diallylphthalate, epoxy, aniline, furan, polyurethane; f.
  • thermoplastic elastomers consisting of styrene-type elastomers such as styrene-butadiene-styrene block copolymers or styrene-isoprene-styrene block co-polymers or their hydrogenated form, elastomers of PVC, urethane, polyester, polyamide type, Thermoplastic elastomers of the polybutadiene type, such as resins
  • the group of water soluble polymers consisting of cellulosic polymers, polyelectrolytes, ionic polymers, acrylate polymers, acrylic acid polymers, gum arabic, poly (vinyl pyrrolidone), poly (vinyl alcohol), poly (acrylic acid), poly (methacrylic acid), sodium polyacrylate, polyacrylamide, poly (ethylene oxide), polyethylene glycol, poly (ethylene formamide), polyhydroxyether, poly (vinyl oxazolidinone), methyl cellulose, ethyl cellulose, carboxymethyl cellulose, ethyl (hydroxyethyl) cellulose, sodium polyacrylate, their copolymers, and mixtures thereof ; h.
  • polystyrene sulfonate PSS
  • polystyrene sulfonate PSS
  • poly (1-vinylpyrrolidone-co-vinyl acetate poly (1-vinylpyrrolidone-co-acrylic acid
  • poly (1-vinylpyrrolidone-co-dimethylaminoethyl methacrylate) polyvinyl sulfate
  • dextran dextran sulfate
  • gelatin bovine serum albumin
  • poly (methyl methacrylate-co-ethyl acrylate) polyallyl amino, and combinations thereof.
  • the carbon nanotubes in said composition have a diameter of between 10 and 30 nm and a length greater than 0.5 micron. According to one embodiment of the invention, said composition also has a temperature insensitive thermal conductivity.
  • the weight percentage of carbon nanotubes is between 0.1 and 20%, and preferably between 1 and 15%.
  • the composition has a percolation threshold ranging from 0.01 to 5% by weight of carbon nanotubes, preferably from 0.1 to 3%.
  • said composition further comprises one or more macromolecular materials chosen from liquids such as oils, greases such as those used for lubrication, liquid formulations based on water or solvents such as adhesives, paints and varnishes.
  • said composition comprises at least one semi-crystalline type polymer.
  • Figure 1 shows the percolation threshold of the organic composition used in the invention.
  • Figure 2 shows the effect of constant resistivity as a function of temperature, with a concentration of nanotubes below the percolation threshold.
  • Figure 3 shows the PTC effect of the reference example compared to the compositions used in the invention.
  • the composition comprises one or more electroconductive (and or thermally conductive) fillers of which at least one filler comprises carbon nanotubes having a shape ratio (LfD) greater than or equal to 5 and preferably greater than or equal to 50 and advantageously greater than or equal to
  • the carbon nanotubes used in the invention generally have a tubular structure with a diameter of less than 100 nm, preferably between 0.4 and 50 nm and / or in general of length greater than 5 times their diameter, preferably greater than 50 times their diameter and advantageously from 100 to 100000 or from 1000 to 10000 times their diameter.
  • Carbon nanotubes consist of an allotropic variety of carbon in a sp 2 configuration consisting of a long single, double or multi-walled tube of aromatic rings con
  • the nanotube When the nanotube consists of a single tube, we speak of mono-wall, two tubes we speak of double walls. Beyond that, we will talk about multi walls.
  • the outer surface of the nanotubes may be uniform or textured.
  • nanotubes can be chemically or physically treated to purify or functionalize them in order to give them new properties of dispersion, and interaction with the components of the formulation such as polymer matrices, elastomers, thermosetting resins, oils, greases, water-based or solvent-based formulations such as paints, adhesives, varnishes.
  • the carbon nanotubes can be prepared by various methods, such as the Electric Arc method (C. Journet et al in Nature (London), 388 (1997) 756, the CVD gas phase method, Hipco (P. Shinv et al. in Chem Phys Lett, 1999, 313, 91), the Laser process (AG Rinzler et al in Appl Phys., A, 1998, 67, 29), or any method giving tubular shapes that are empty or filled with carbonaceous substances. or other than carbon We can refer for example more particularly to WO 86/03455, WO 03/002456 for the preparation of separate or non-aggregated multi-wall carbon nanotubes.
  • the organic composition comprises one or more macromolecular materials.
  • These materials are generally liquids or solids such as oils or greases such as those used for lubrication, water-based liquid formulations or solvents such as adhesives, paints and varnishes, polymers and the like. copolymers, in particular thermoplastic or thermosetting, water-soluble polymers, elastomers and their formulations in bulk, or in suspension or in dispersion ....
  • thermoplastic resins examples include: acrylonitrile-butadiene-styrene (AB S), acrylonitrile-ethylene / propylene-styrene (AES), methylmethacrylate-butadiene-styrene (MBS), acrylonitrile-butadiene-methylmethacrylate-styrene (ABMS ), acrylonitrile-n-butylacrylate-styrene (AAS) 5 gums polystyrene modified resins: polystyrene, polymethyl methacrylate, polyvinyl chloride, cellulose acetate, polyamide, polyester, polyacrylonitrile, polycarbonate, polyphenyleneoxide, polyketone, polysulphone, polyphenylenesulphide, resins: halogenated, preferably fluorinated as PVDF or chlorinated as the
  • thermosetting resins examples include resins based on phenol, urea, melamine, xylene, diallylphthalate, epoxy, aniline, furan, polyurethane, etc.
  • thermoplastic elastomers examples include elastomer of the polyolefin type, of the styrene type, such as styrene-butadiene-styrene block co-polymers or styrene-isoprene-styrene block copolymers, or their hydrogenated form, the elastomers of the PVC, urethane, polyester, polyamide type, thermoplastic elastomers of the polybutadiene type, for example 1,2-polybutadiene or trans-1,4-polybutadiene resins; chlorinated polyethylene, fluoro-type thermoplastic elastomers, polyether esters and polyether amides etc.,
  • water-soluble polymers examples include amphiphilic polymers, also referred to as surfactant polymers, which contain both hydrophobic and hydrophilic segments, cellulosic polymers, polyelectrolytes, ionic polymers, acrylate polymers, polymer polymers and the like. acrylic acid, copolymers thereof and mixtures thereof.
  • amphiphilic polymers also referred to as surfactant polymers, which contain both hydrophobic and hydrophilic segments
  • cellulosic polymers polyelectrolytes, ionic polymers, acrylate polymers, polymer polymers and the like.
  • acrylic acid copolymers thereof and mixtures thereof.
  • polyethylene glycol poly (ethylene formamide), polyhydroxyether, poly (vinyl oxazolidinone), methyl cellulose, ethyl cellulose, carboxymethyl cellulose, ethyl (hydroxyethyl) cellulose, sodium polyacrylate, their copolymers, and mixtures thereof.
  • PSS polystyrene sulfonate
  • polystyrene sulfonate poly (1-vinylpyrrolidone-co-vinyl acetate), poly (1-vinylpyrrolidone-co-acrylic acid), poly (1-vinylpyrrolidone-co-dimethylaminoethyl methacrylate), polyvinyl sulfate, poly (sodium styrene sulfonic acid co-maleic acid), dextran, dextran sulfate, gelatin, bovine serum albumin, poly (methyl methacrylate-co-ethyl acrylate), polyallyl amino, and combinations thereof.
  • PSS polystyrene sulfonate
  • poly (1-vinylpyrrolidone-co-vinyl acetate poly (1-vinylpyrrolidone-co-acrylic acid
  • the formulations of the organic compositions with constant resistivity are defined as a function of the desired Joule heat energy and of the electrical power used (voltage or imposed current).
  • the percentage by weight of carbon nanotubes in the composition is less than 30%, preferably between 0.01 and 20%, more preferably the percentage of nanotubes will be between 0. , 1 and 15%.
  • composition with constant resistivity as a function of temperature can be obtained by any method known to those skilled in the art such as dry mixing, concentrated in a polymer matrix or resin, suspended, etc.
  • the mixing process can use different technologies such as those used for rubbers, polymers, liquids, etc. Internal mixers, single or twin screw extruders, buses, ultraturax mixers, ultrasonic mixers or any type of mixing tool known to those skilled in the art.
  • compositions can be obtained directly or by dilution via the use of a master batch as described in WO 91/03057 or US 5646990, EP 692136 or US 5591382 US 5643502 or US 5651922, US 6221283.
  • These compositions can also be obtained by direct synthesis of the organic material in the presence of carbon nanotubes.
  • a physical interaction between the polymer or copolymer and the carbon nanotubes is generated or a covalent bond which is sought when the aim is to significantly improve the mechanical properties (good transfer of the mechanical forces between the matrix and the carbon nanotubes.
  • composition has a percolation threshold in the range of 0.01 to 5%, preferably 0.1 to 3% by weight of carbon nanotubes.
  • the percolation threshold corresponds to the amount of conductive filler in the macromolecular substance to change the composition of a conductive regime to an insulating regime and vice versa.
  • the percolation threshold depends on the state of dispersion and therefore the tool and the mixing parameters.
  • this threshold is proportional to the L / D form ratio.
  • One of the relations giving this threshold is (L / D) .Fv ⁇ 3 where Fv is the volume fraction in carbon nanotube.
  • Fv is the volume fraction in carbon nanotube.
  • the volume fraction at the percolation threshold will be 3% and 0.3% for L / D ⁇ 1000.
  • compositions may have the same uses as known macromolecular compositions containing carbon nanotubes as cited in the following references: US 6 689835 - US6746627 - US 6491789- Carbon, 2002,40 (10) 1741/1749 - US2003 / 0130061-WO97 / 15934-JP 2004-244490-WO2004 / 097853 - Science 2000, 290 (5495), 1331/1334 - J.Mater.Chem., 2994,14, 1/3 .
  • the compositions according to the invention also have the mechanical advantages related to the use of nanotubes.
  • compositions with constant temperature resistivity can be used in the final applications described above in different forms: liquid, solid or elastomeric solid, powder, film, fiber, gel ... Examples The following examples illustrate the present invention without however, limit its scope.
  • Carbon nanotubes obtained according to the method described in PCT patent WO 03/002456 A2 are used. These nanotubes have a diameter of between 10 and 30 nm and a length> 0.4 ⁇ m. They are presented in the final composition, in multi-wall form in whole or in more than 98% in distinct form, ie not aggregated.
  • a polymer formulation, additive of graphite and carbon black marketed by Timcal under the name ENSACO 250 for the reference formulation is used a polymer formulation, additive of graphite and carbon black marketed by Timcal under the name ENSACO 250.
  • Fluorinated or chlorinated halogenated polymers such as PVDF or PVC are used in the formulations.
  • the polymer used is a thermoplastic polymer of the PVDF type marketed by Arkema under the name Kynar 720. Unless otherwise indicated, the amounts are expressed by weight.
  • compositions are generally made by melt blending a polymer with carbon nanotubes or the reference additive.
  • the mixture is produced using an internal mixer, for example of the Haak type.
  • the temperature of the mixture is generally about 230 ° C.
  • the mixing time is conditioned by the stability of the torque of the mixer. In general, it is less than 7 minutes.
  • the ingredients are introduced into the mixer in the following manner: 50% of the polymer is first introduced. When the polymer begins to melt, the conductive filler is added and then the remaining portion of polymer is added.
  • the evaluation of the PTC effect is done using a dielectric spectrometer at the frequency 50.02 Hz.
  • the sample in the form of a compression molded plate is covered on both sides by a layer of silver.
  • compositions on either side of this threshold namely 0.5, 1 and 2% of nanotubes. These compositions are referenced IA, IB and IC.
  • composition according to the prior art is prepared according to the following composition: 70.4% of an organic composition based on PVDF 720 17.6% graphite 12% carbon black
  • Figure 2 shows the effect of constant resistivity as a function of temperature, with a concentration of nanotubes below the percolation threshold.
  • Figure 3 shows the PTC effect of the reference example compared to the compositions used in the invention.
  • compositions of the invention have no PTC effect and what is before or after the percolation threshold.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)
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EP06709033A 2005-01-05 2006-01-05 Verwendung von kohlenstoffnanoröhrchen zur herstellung einer leitfähigen organischen zusammensetzung und anwendung einer derartigen zusammensetzung Withdrawn EP1836244A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0500075A FR2880353B1 (fr) 2005-01-05 2005-01-05 Utilisation de nanotubes de carbone pour la fabrication d'une composition organique conductrice et applications d'une telle composition
PCT/FR2006/000016 WO2006072741A1 (fr) 2005-01-05 2006-01-05 Utilisation de nanotubes de carbone pour la fabrication d'une composition organique conductrice et applications d'une telle composition.

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EP1836244A1 true EP1836244A1 (de) 2007-09-26

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EP06709033A Withdrawn EP1836244A1 (de) 2005-01-05 2006-01-05 Verwendung von kohlenstoffnanoröhrchen zur herstellung einer leitfähigen organischen zusammensetzung und anwendung einer derartigen zusammensetzung

Country Status (8)

Country Link
US (1) US20090121196A1 (de)
EP (1) EP1836244A1 (de)
JP (1) JP2008527064A (de)
KR (1) KR20070092725A (de)
CN (1) CN101098921A (de)
CA (1) CA2593476A1 (de)
FR (1) FR2880353B1 (de)
WO (1) WO2006072741A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
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US20140087185A1 (en) * 2008-07-17 2014-03-27 Katholieke Universiteit Leuven Method for the preparation of a reinforced thermoset polymer composite

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* Cited by examiner, † Cited by third party
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JP4528223B2 (ja) * 2005-07-25 2010-08-18 本田技研工業株式会社 熱輸送流体
JP4878832B2 (ja) * 2005-12-26 2012-02-15 株式会社プライムポリマー 成形体及びその製造方法
WO2008034939A1 (en) * 2006-09-04 2008-03-27 Natucell Ay Functionalized cellulose - carbon nanotube nanocomposites and hybride materials
WO2008046165A2 (fr) * 2006-10-18 2008-04-24 Nanocyl S.A. Composition anti-adhesive et antistatique
FR2907442B1 (fr) * 2006-10-19 2008-12-05 Arkema France Materiau composite conducteur a base de polymere thermoplastique et de nanotube de carbone
JP4528324B2 (ja) * 2007-01-11 2010-08-18 本田技研工業株式会社 熱輸送流体およびその製造方法
FR2907443B1 (fr) * 2007-02-20 2012-04-20 Arkema France Materiau composite conducteur a base de polymere thermoplastique et de nanotube de carbone
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KR20070092725A (ko) 2007-09-13
CA2593476A1 (fr) 2006-07-13
CN101098921A (zh) 2008-01-02
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