WO2007096479A1 - Nouvelles compositions et procédés pour la production de celles-ci - Google Patents

Nouvelles compositions et procédés pour la production de celles-ci Download PDF

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WO2007096479A1
WO2007096479A1 PCT/FI2007/050100 FI2007050100W WO2007096479A1 WO 2007096479 A1 WO2007096479 A1 WO 2007096479A1 FI 2007050100 W FI2007050100 W FI 2007050100W WO 2007096479 A1 WO2007096479 A1 WO 2007096479A1
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composition according
electrically conductive
polymer
composition
group
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PCT/FI2007/050100
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English (en)
Inventor
Juha Hartikainen
Juha Repo
Kalle NÄTTINEN
Kirsi Immonen
Juha Sarlin
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Panipol Oy
Valtion Teknillinen Tutkimuskeskus
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Publication of WO2007096479A1 publication Critical patent/WO2007096479A1/fr

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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
    • 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
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • 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
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes

Definitions

  • the present invention relates to electrically conductive compositions.
  • the present invention concerns compositions comprising electrically conductive carbon particles having a high aspect ratio, which are mixed with a dispersing agent to provide an electrically conductive composition.
  • the present invention also concerns methods of producing such compositions and the use of the compositions in blends with thermoplastic polymers.
  • Carbon nanotubes are a new, third allotropic form of carbon in addition to graphite and diamond.
  • graphite lattices are rolled into perfect cylinders with a diameter of a few nanometers or less. Due to their structure, carbon nanotubes have exceptional properties of stability both with respect to air and temperature variations and excellent mechanical, electronic and structural properties, which provides for their use in a plurality of engineering and scientific applications.
  • One interesting application comprises composites of nanotubes and thermoplastic polymers, in which the nanotube component provides a three-dimensional conductive network within a matrix formed by the thermoplastic polymer. To achieve this aim, the nanotubes should be evenly distributed and dispersed within the matrix.
  • nanotubes have been dispersed in a host polymer by either lengthy sonication in a polymer solution or by in situ polymerization in the presence of the nanotubes. Lengthy sonication can damage the nanotubes and the in situ polymerization is useful only for specific polymers.
  • sodium dodecylsulphates or polysaccharides are used for dispersing the nanotubes which are then exfoliated in water.
  • the supernatant of the aqueous dispersion is recovered and mixed with latex particles obtained by emulsion polymerization to provide a composite consisting of evenly dispersed nanotubes in a polymer matrix.
  • novel conductive compositions comprise a mixture of carbon nanotubes or similar conductive carbon based particles and monomeric dispersants.
  • thermoplastic composition comprising a dispersed phase of conductive carbon nanotubes in a matrix of a thermoplastic polymer.
  • a novel method of producing a conductive composition comprising carbon nanotubes is provided.
  • the present invention is based on the finding that it is possible to efficiently disperse carbon nanotubes by mixing them with monomeric dispersants having an aromatic basic structure and capable of bonding to a polymeric structures comprising repeating units with aromatic structures.
  • An example of such polymeric structures is polyaniline, and it has surprisingly been found that compounds capable of acting as molecular recognition compounds with respect to polyaniline are also capable of acting as dispersing agents for carbon nanotubes as such or for carbon nanotubes coated with polymeric structures of the above kind.
  • the aromatic compounds of the above kind enter into non-covalent interaction which allows for their use as dispersing agents.
  • carbon nanotubes instead of carbon nanotubes, other carbon based materials having high aspect ratios can be used as conductive components in the conductive compositions according to the invention. Said conductive components are present in amounts sufficient for exceeding the percolation threshold of the composition.
  • conductive compositions of carbon based particles which comprise as dispersing agents compounds selected from the group of substituted aromatic compounds capable of bonding to a polyaniline structure by non-covalent interaction, to provide a dispersed, conductive composition having an electrical conductivity better than 10 ⁇ 8 S/cm.
  • the conductive compositions can be blended with thermoplastic polymers, such as polyolefins, polyesters, polyamides, polyimides, polyesterimides and polycarbonates to mention a few.
  • thermoplastic polymers such as polyolefins, polyesters, polyamides, polyimides, polyesterimides and polycarbonates to mention a few.
  • the conductive carbon based components with an inherently conductive polymer, such as polyaniline, conductivity of the composition can be further improved.
  • the coating of the carbon is preferably carried out by polymerization of the polymer in situ, in the presence of the carbon components.
  • the method according to the present invention for producing conductive compositions is characterized by what is stated in the characterizing part of claim 15 and the thermoplastic compositions according to the present invention by what is stated in the characterizing part of claim 20.
  • the use of the present monomeric dispersants allows for efficient dispersion of carbon nanotubes which considerably facilitates their dispersion in a thermoplastic polymer, such as polypropylene.
  • a thermoplastic polymer such as polypropylene.
  • the conductivity of the carbon nanotube and carbon fiber compositions are, as such, excellent and they are readily blended with thermoplastic polymers by conventional melt processing, for example in an extruder.
  • the production of the conductive composition is uncomplicated and requires merely a minimum of sonication, if any.
  • Figure 1 shows the percolation behaviour of Product 1 of the Examples with 20 % ethyl gallate in polypropylene.
  • the present invention provides novel conductive compositions of carbon based particles having high aspect ratio.
  • these particles comprise carbon nanotubes or carbon nanofibres.
  • the present invention is applicable to both single- wall nanotubes and multi-wall nanotubes.
  • single-wall nanotubes denote carbon nanotubes which consist of single layers of graphite lattice rolled into cylinders with a diameter in the range of, generally, about 0.1 to 5 nm, in particular about 0.5 to 3 nm, typically about 0.7 to 2 nm.
  • multi-wall nanotubes denotes carbon nanotubes which consist of sets of concentric cylindrical shell, each of which meets the definition used above for "single-wall nanotubes”.
  • aromatic compounds capable of bonding to a polyaniline structure by non-covalent interaction are used.
  • aromatic compounds can have, for example, the general formula (I)
  • A is a moiety selected from the group consisting of optionally substituted 3- to 7- membered rings, which rings may optionally include at least one nitrogen, sulfur or oxygen atom, and optionally substituted condensed ring systems thereof;
  • B is a moiety capable of hydrogen bonding with NH-groups and is selected from the group consisting of -OH, -COOH, -OCOO-Q 1 , -CO-Q 1 , -SO-Q 1 , -SO 2 -Q 1 , -
  • the dispersing agent comprises an aromatic residue which is coupled to the conductive carbon based particles via functional groups or aromatic rings present on the aromatic residue.
  • the dispersing agents used comprise substituted aromatic compounds which are capable of bonding to the polyaniline structure by strong physical forces, in particular by forces that can be characterized as being “non-covalent” and leading up to the forming of bonding due to van der Waals forces or a similar non-covalent interaction (said interaction can also be called “molecular recognition”). It should be pointed out that this interaction will not interfere with the mechanism of electric conductivity of the carbon nanotubes or fibres.
  • each A is independently selected from the group consisting of 5 or 6-membered aromatic rings, which rings may be optionally substituted and which may further include at least one nitrogen, sulfur or oxygen atom; and their substituted or unsubstituted condensed rings; and at least one B is -OH.
  • A can be the same on each occurrence or different on at least two occurrences.
  • Particularly preferred compounds for use as dispersing components are selected from the group of hydroxy- substituted benzoic acid derivatives, comprising 1 to 3 hydroxyl groups. Two or three hydroxyl groups are particularly preferred for compounds substituted with only hydroxy groups, and 1 to 3 hydroxyl groups are preferred for compounds which contain at least one other group B.
  • the dispersing component is selected from the group of hydroxyl-substituted benzoic acid derivatives containing a linear or branched alkyl chain having 1 to 24 carbon atoms.
  • examples of this kind of compounds are alkyl gallates, alkyl catechols and alkyl resorcinol, wherein each alkyl group is linear or branched and has 1 to 24 carbon atoms.
  • alkyl groups may contain one or more substituents selected from the group of moieties B above.
  • the electrically conductive composition consists essentially of the conductive component and the dispersing component, which means that there are essentially only two components in the composition, viz. the conductive carbon nanotubes or nanofibres and the dispersing agent.
  • the relative amounts are about 5 to 50 weight percent of the first component and about 95 to 50 of the other.
  • the dispersing component contacts directly with the conductive component, in particular with the surface of the component.
  • the conductivity and electrical contact between the individual nanotubes or fibres is improved by coating them with a conductive polymer, preferably an inherently electrically conductive polymer, which can be doped to generate charge carriers.
  • a conductive polymer preferably an inherently electrically conductive polymer, which can be doped to generate charge carriers.
  • the inherently conductive polymer coats at least a majority, i.e. at least 50 %, in particular about 70 to 100 %, of the surface of the conductive component.
  • the proportion of conductive polymer can amount, for example, to about 7 - 50 %, in particular to about 10 - 35 %, depending on the thickness of the conductive coat.
  • the tubes or fibres are coated with a thin polyaniline layer and then the coated nanotubes or fibres are mixed with a thermoplastic polymer in an extrusion process or by another melt processing method.
  • a layer of polyaniline or another inherently conductive polymer
  • reduction of surface resistivity may also take place, thus having positive impact on the electric conductivity of the nanotubes in some applications.
  • Electrode conductive polymer or “Conductive polymer” means inherently conductive polymers (ICP), which are “doped” (furnished, processed) in order to generate charge carriers (holes and electrons).
  • ICP inherently conductive polymers
  • Common to all electrically conductive polymers are the conjugated double bonds of the backbone chain (alternate single and double bonds, delocalized silicon electron system), which enable the movement of the charge carriers.
  • Electrically conductive polymers have both ionic and electronic conductivity, which can be utilized in various applications. The conductivity of electrically conductive polymers can fluctuate and be regulated within the whole conductivity range, from an insulating material to a near- metallic conductor. Generally, a polymer is considered to be electrically conductive if its maximum surface resistance is 10 11 ohm.
  • electrically conductive polymer can be bound in fibres both in an electrically conductive and in an electrically non-conductive form. Consequently, the term "electrically conductive polymer” in the claims presented below also means a polymer that is non- conductive at the time of reference, but which, however, can be brought to an electrically conductive state, for instance by using a suitable doping agent treatment.
  • Polyaniline, polypyrrole, polyacetylene, polyparaphenyl or polytiophene, or derivatives or mixtures of them are used as electrically conductive polymers.
  • the derivatives especially the alkyl and aryl derivatives and the chlorine and bromine- substituted derivatives of the polymers mentioned above, are worth mentioning.
  • Polyaniline is particularly preferred in the present invention.
  • the monomer in the aniline polymer is aniline or its derivative, the nitrogen atom of which is in most cases bonded to the para-position carbon of the benzene ring of the next unit.
  • the unsubstituted polyaniline can be in different forms, among which the emeraldine form, which is characterized by a clear, emerald-green colour, which stands for its name, is generally used for conductive polymer applications
  • the electrically neutral polyaniline can be converted into a conductive polyaniline-complex.
  • the doping agents used in the present invention can vary widely and they are generally employed when doping conjugated polymers into an electrically conductive or semiconductive form.
  • the dopant is selected from the group of inorganic acids and organic acids and derivatives thereof, including mineral acids, sulphonic acids, picric acid, n-nitrobenzene acid, dichloric acetic acid and polymer acids and mixtures thereof. And the salt of the dopant and the monomer is soluble in water.
  • Protonic acids are known doping agents in the field of inherently conductive polymers, as will appear from the references by J.-C. Chiang and Alan G. MacDiarmid and in the W. R. Salaneck citation: o Chiang et al., Synth. Metals (1986) 13:193-205 o MacDiarmid et al., Papers from the 6th European Physical Society Industrial
  • Such doping agents comprise organic acids, and their derivatives, among which sulphonic acids, picric acid, n-nitrobenzene acid, dichloric acetic acid and polymer acids are typical examples. If desired, more than one doping acid can be used.
  • a functional acid is used for doping, such as sulphonic acid, particularly aromatic sulphonic acid, which comprises one aromatic ring, or two merged rings, in which case at least one ring may have a polar or a non-polar cyclic substituent, such as a functional group (for instance a hydroxyl group) or a hydrocarbon chain, such as an alkyl chain with 1-20 carbons.
  • a functional group for instance a hydroxyl group
  • hydrocarbon chain such as an alkyl chain with 1-20 carbons.
  • PSAs phenol sulphonic acids or hydroxybenzene sulphonic acids
  • PPA phenyl phosphine acids
  • Polystyrene (PSSA), polyolefins, polyethylene oxide, polyvinyls], as well as sulphonated polyparaphenylenes and sulphonated aromatic polyamides and alike substances, can be mentioned as examples of polymeric acids.
  • Preferred acids are dodecylbenzene sulpfonic acid (DBSA), camphor sulphonic acid, para- toluene sulphonic acid and phenol sulphonic acid.
  • DBSA dodecylbenzene sulpfonic acid
  • camphor sulphonic acid camphor sulphonic acid
  • para- toluene sulphonic acid para- toluene sulphonic acid
  • phenol sulphonic acid phenol sulphonic acid
  • the polymerization of the electrically conductive polymer is carried out "in situ" on the carbon nanotubes or fibres. This is achieved first by mixing both the monomer to be polymerized and a doping agent of the conductive polymer, allowing these to form a salt. Next, the nanotubes or fibres are added to this mixture. Thereafter, a catalyst or an oxidative agent enabling a polymerization reaction is added resulting in polymerization of the doped monomer inside the nanotubes or fibres and on the top of the tubes or fibres.
  • Oxidizing agents are generally used in polymerization of a monomeric compound into a corresponding electrically conductive polymer.
  • Preferred oxidizing agents are polyatomic metallic salts such as iron(III) salts and per-compounds like peroxides, peracids, persulphates, perborates, permanganates, perchlorates and chlorates, nitrates and quinones.
  • the amount of an oxidizing agent in relation to the monomer is generally from 10:1 to 1:1, most preferably from about 5:1 to 2:1 (parts by weight) or from 4:1 to 1:1 as mole fractions (oxidative/monomer).
  • Polyaniline is preferably coated on the nanotubes or fibres in electrically conductive form.
  • Polyaniline has to be doped by a counter-ion for converting it into a conductive form. It is particularly preferred to coat with polyaniline in an electrically conductive form because it can be assumed that the binding of polyaniline happens, at least partially, with the aid of the doping agent.
  • the electrical resistivity of the coated nanotube or fibre composition built up in accordance with the invention is generally about 10 - 10 8 ohm.
  • the product can be produced by bringing the nanotubes or fibres into intimate contact with a monomer that forms an electrically conductive polymer, in a suitable medium, in particular in an aqueous medium.
  • a suitable medium in particular in an aqueous medium.
  • Organic, polar and nonpolar solvents can be used in addition to water and aqueous solutions.
  • intimate contact it is meant that the nanotubes or fibres and a monomeric precursor of polymer and/or a doping agent of polymer is mixed vigorously to have the monomer and/or doping agent efficiently distributed in the carbon material.
  • aqueous medium stands for both water and water solutions in which nanotubes or fibres are slurried.
  • the consistency of the aqueous slurry is from 0.1 to 50 % (weight/weight), preferably from about 0.5 to 30 %, and particularly from about 0.7 to 20 %.
  • the counter-ion or the monomer of the electrically conductive agent to be polymerized, respectively can be dissolved in the aqueous phase.
  • the amount of the doping agent varies depending on the amount of a monomer.
  • the amount of monomer is from about 0.1 to 200 % of the amount of carbon nanotubes or fibres, typically about 1 to 150 w-%, preferably about 5 to 120 w-%, and particularly about 10 to 100 w-%.
  • the amount of a counter-ion can be equimolar with the amount of monomer but it can also be approximately the amount of moles of the monomer +30 %.
  • the temperature is generally above 0 0 C but below room temperature. Typically, the temperature is from about 1 to 18 ° C, preferably from about 2 to 15 0 C.
  • an acidic counter-ion is used and the pH of the aqueous phase, used in pairing of tubes or fibres and a polymer/monomer, is most suitably clearly acidic, preferably the pH is below 5 but above 1. Too high pH values can affect disadvantageously to the polymerization of the monomer and too low pH values can cause degradation of the conductive particles. This is why the preferred pH environment is from about 1 to 5 and, most suitably, from 1 to 3.
  • an aggregate (a complex or a salt) formed by the monomer and the doping agent is first introduced among the nanotubes or fibres and, thereafter, the monomer is polymerized in order to coat the polymer on the tubes or fibres in such a way that it is not washed out at demanding conditions.
  • the electrically conductive carbon particles are selected from the group consisting of carbon nanotubes and carbon nanofibres, having an aspect ratio of at least 100, preferably about 150 to 5000, in particular about 200 to 3000. They may comprise single- wall or multi-wall carbon nanotubes or carbon fibres having a purity of at least 85 %. In view of the above-explained conditions of the polymerization, it is required that the electrically conductive carbon particles are chemically stable at a pH below 4, in particular at pH of 1 or higher.
  • the preferred novel compositions comprise - 1 to 50 parts by weight of electrically conductive carbon particles,
  • the amount of dispersing agent (in parts per weight) is equal to or greater than the amount of the conductive material.
  • the weight ratio between the dispersive agent and the conductive material is about 0.8 to 10, preferably about 1 to 5, in particular about 1.1 to 4.
  • the "conductive material” includes the carbon based material which optionally is coated with an inherently conducting polymer.
  • the conductive carbon based particles should always be present in an amount exceeding the percolation threshold to allow for the formation of a conductive pathway through the composition.
  • An economically dictated upper limit can be set at about 50 % of the composition.
  • the percolation threshold can be more readily exceeded with smaller concentrations of the particles, thus, typically the amount of the particles will be on the order of about 1 to 25 wt-%, in particular about 2 to 20 wt-%, e.g. about 3 to 18 wt-%.
  • the composition according to the invention is mixed and/or blended with thermoplastic polymers to provide modified and conductive thermoplastic compositions.
  • Such compositions typically contain about 1 to 30 % by weight of a composition described above and 70 to 99 % by weight of a thermoplastic polymer, although typically there is 1 to 20 wt-% of a conductive composition and 80 to 99 wt-% of the thermoplastic.
  • thermoplastic polymer can also constitute a carrier of a conductive composition of the above kind.
  • a carrier can be present in an amount of 1 to 50 wt-% of the total composition.
  • the carrier is used for binding together the composition.
  • thermoplastic polymer is typically selected from the group of polyolefins, polyesters, polyethers, polyesterimides, polyamides, polycarbonates and mixtures thereof.
  • the thermoplastic polymer can also be a thermoplastic elastomer (TPE) or a mixture or a TPE and one or several of the above thermoplastics.
  • TPE thermoplastic elastomer
  • the thermoplastic elastomer can be selected from the group consisting of styrene based block-copolymers, polyolefin based elastomers, polyurethane based elastomers and polyester based elastomers and mixtures thereof.
  • Multiwalled carbon nanotubes (MWCNT, purity > 87 %) were supplied by Nanocyl S.A.
  • carbon nanofibres CNF
  • CB carbon black Printex XE2
  • PSA phenol sulphonic acid
  • APS ammonium persulphate
  • the surface resistivity of Product 1 was 6 Ohms measured with multimeter.
  • Aniline was polymerized by chemical polymerisation in the presence of carbon black (CB) in a 1 1 round bottle flask equipped with a semi-circular adjustable speed mixer and ice bath.
  • CB carbon black
  • 9 g of CB was dispersed in 500 ml water containing 100 ⁇ l of a dispersing agent and using ultrasonic for 20 minutes (mixture A) and overnight mixing.
  • 8.63 g of PSA-solution was added to 350 ml of deionised water and mixed for 30 minutes.
  • 3.0 g of Aniline was added to the reaction mixture and mixed for 30 minutes. After that the reaction mixture was cooled to 5 0 C and mixture A was added.
  • Aniline was polymerized by chemical polymerisation in the presence of nanosized alumina in a 3 1 round bottle flask equipped with a semi-circular adjustable speed mixer and ice bath.
  • 35 g of dodecylbenzene sulphonic acid was dissolved in 2 1 of water and mixed for 30 minutes.
  • 10 g of aniline was added to the reaction mixture and mixing was continued for 45 minutes while cooling the reaction mixture at the same time.
  • 100 g of nanosized alumina was added to the mixture and it was cooled.
  • reaction temperature 8 0 C
  • 24.5 g of APS in a 20 w-% aqueous solution was added during one hour.
  • the reaction was allowed to proceeding under agitation at the reaction temperature for 1 h and overnight at room temperature.
  • the product comprising dark green particles was washed three times with water using a centrifuge.
  • the product was dried at temperature below 4O 0 C and ground to fine powder.
  • the surface resistivity of Product 4 was 200 kOhms measured with a multimeter.
  • a 6.00 g blend of electrically conductive PANI-Nanoparticle-hybrid, selected substituted aromatic compound, and polypropylene (PP Domolen 2600 M, MFI 7.5) was mixed in a miniature, co-rotating conical twin-screw extruder at a temperature of 200 0 C for 1 minute at a screw rotation speed of 100 rpm.
  • the resulting blend was discharged in a miniature injection moulding machine and further moulded into rectangular 1 x 10 x 60 mm samples at 220 0 C with a mould temperature of 40 0 C, injection pressure 350 bar (3 seconds), and post pressure of 160 bar (5 seconds).
  • the electrical conductivity of the resulting samples was measured with a four-point probe method according to ISO 3915 which was adapted to suit the sample dimensions.
  • EXAMPLE 1 A blend was prepared from 0.60 g Product 1, 1.2O g ethyl gallate (Sigma- Aldrich) and 4.20 g polypropylene (Domolen 2600M) according to Method A. The electrical conductivity was determined to be 26 S/cm.
  • Example 1 was repeated; blends were prepared according to Method A of Products 1 - 3, multiwall carbon nanotubes and carbon nanofibres, selected substituted aromatic compounds and polypropylene.
  • the aromatic compounds are selected from those mentioned in U.S. Patent No. 5,783,111.
  • the blend compositions, and conductivities are collected in Table 1.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition conductrice et procédé de production d'une telle composition. La composition comprend des particules à base de carbone électriquement conductrices ayant un rapport d'allongement élevé, telles que des nanotubes de carbone, les particules étant présentes en quantité dépassant le seuil de percolation de la composition, et au moins un composant dispersant sélectionné dans le groupe constitué de composés aromatiques substitués capables de se fixer à une structure de polyaniline par une interaction non covalente, le composant dispersant étant présent en quantité suffisante pour obtenir une composition conductrice dispersée ayant une conductivité électrique meilleure que 10-8 S/cm. De préférence, les particules sont recouvertes d'un polymère qui est conducteur par nature. Grâce à l'invention, il est possible de mélanger en phase fondue efficacement des nanotubes de carbone avec des thermoplastiques pour obtenir des compositions hautement conductrices avec de faibles concentrations des nanotubes.
PCT/FI2007/050100 2006-02-23 2007-02-23 Nouvelles compositions et procédés pour la production de celles-ci WO2007096479A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012160288A1 (fr) 2011-05-23 2012-11-29 Arkema France Fibres composites conductrices comprenant des charges conductrices carbonees et un polymere conducteur
WO2013164488A1 (fr) * 2012-05-04 2013-11-07 Universite Catholique De Louvain Nanocomposite électroconducteur
US9115271B2 (en) 2011-09-14 2015-08-25 Industrial Technology Research Institute Carbon nanotube powders and methods for manufacturing the same and composite materials
WO2018220083A1 (fr) 2017-06-01 2018-12-06 Albis Plastic Gmbh Composite
JP7485279B2 (ja) 2020-04-10 2024-05-16 丸尾カルシウム株式会社 導電性表面処理粉体填料およびその製造方法、ならびに該填料を含有する導電性組成物

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012160288A1 (fr) 2011-05-23 2012-11-29 Arkema France Fibres composites conductrices comprenant des charges conductrices carbonees et un polymere conducteur
US9115271B2 (en) 2011-09-14 2015-08-25 Industrial Technology Research Institute Carbon nanotube powders and methods for manufacturing the same and composite materials
WO2013164488A1 (fr) * 2012-05-04 2013-11-07 Universite Catholique De Louvain Nanocomposite électroconducteur
WO2018220083A1 (fr) 2017-06-01 2018-12-06 Albis Plastic Gmbh Composite
DE102017209357A1 (de) * 2017-06-01 2018-12-06 Albis Plastic Gmbh Compound
JP7485279B2 (ja) 2020-04-10 2024-05-16 丸尾カルシウム株式会社 導電性表面処理粉体填料およびその製造方法、ならびに該填料を含有する導電性組成物

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