WO2009053470A1 - Composite polymère conducteur - Google Patents

Composite polymère conducteur Download PDF

Info

Publication number
WO2009053470A1
WO2009053470A1 PCT/EP2008/064460 EP2008064460W WO2009053470A1 WO 2009053470 A1 WO2009053470 A1 WO 2009053470A1 EP 2008064460 W EP2008064460 W EP 2008064460W WO 2009053470 A1 WO2009053470 A1 WO 2009053470A1
Authority
WO
WIPO (PCT)
Prior art keywords
conductive
component
annealing
polymer
tape
Prior art date
Application number
PCT/EP2008/064460
Other languages
English (en)
Inventor
Hua Deng
Antonius Andreas Johannes Maria Peijs
Original Assignee
Queen Mary And Westfield College, University Of London
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Queen Mary And Westfield College, University Of London filed Critical Queen Mary And Westfield College, University Of London
Publication of WO2009053470A1 publication Critical patent/WO2009053470A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/12—Articles with an irregular circumference when viewed in cross-section, e.g. window profiles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/91—Heating, e.g. for cross linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/88—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced
    • B29C70/882—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced partly or totally electrically conductive, e.g. for EMI shielding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/06—Rod-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/11—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels comprising two or more partially or fully enclosed cavities, e.g. honeycomb-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/304—Extrusion nozzles or dies specially adapted for bringing together components, e.g. melts within the die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/365—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using pumps, e.g. piston pumps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
    • B29C48/387—Plasticisers, homogenisers or feeders comprising two or more stages using a screw extruder and a gear pump
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/80—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the plasticising zone, e.g. by heating cylinders
    • B29C48/83—Heating or cooling the cylinders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0008—Anti-static agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/002—Agents changing electric characteristics
    • B29K2105/0023—Agents changing electric characteristics improving electric conduction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B29K2105/162—Nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
    • B29K2995/0005—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides

Definitions

  • the present invention relates to a method of preparing a conductive multi-component composite, a conductive multi-component composite and use of a conductive multi-component composite.
  • Conductive polymer composites can be made by adding conductive filler into an insulating polymer matrix, where it forms a conducting network.
  • Such composites are useful, for example, for antistatic, electrostatic discharge (ESD) , electrostatic painting and electromagnetic-radio frequency interference (EMI) protection purposes [1], particularly in the automotive and textile industries.
  • Applications include anti -static uniforms to avoid sparks caused by static electricity (for example, in chemical plants or petrol stations); anti-static carpets; anti-static conveyor belts in airports; and car parts (where the use of conducting material can save paint) .
  • Such composites are also useful as components in electrical circuits, for example in electric fences for animals .
  • Bin et al . [15, 16] showed that thermal annealing conducted by scanning temperatures ranging from room temperature to near melting temperature could increase the conductivity of highly oriented CPC fibre based on ultrahigh molecular weight polyethylene (UHMWPE) and MWNTs.
  • UHMWPE ultrahigh molecular weight polyethylene
  • Miaudet P. et al . [17] carried out an investigation on the effect of thermal treatment on the conductivity of CPC fibres containing polyvinyl alcohol (PVA) (a semi-crystalline polymer ⁇ and MWNTs. It was found that thermal annealing between the glass transition temperature (T g ) and melting temperature (T m ) of the polymer dramatically increased the conductivity of the fibre.
  • PVA polyvinyl alcohol
  • the present invention relates to a method of preparing a conductive multi-component material, comprising the steps of: preparing an initial multi -component material, the initial multi-component material including a continuous first polymeric component comprising conductive filler and a first polymer, and a second polymeric component comprising a second polymer, the first polymeric component having a lower melting temperature than the second polymeric component; subjecting the initial multi-component material to an orienting process; and annealing the oriented multi-component material to form the conductive multi-component material .
  • multi-component material includes or refers to a material wherein separate components do not form a continuous homogeneous phase. The materials are at least to some extent spatially separated within the material. They may be present as identifiable separate phases under SEM/TEM or as clearly demarcated layers.
  • continuous includes or refers to a component in which a path can be traced from one side of the material to another without moving without moving to another component.
  • melting temperature includes or refers to the temperature at start of the melting peak (or onset of the melting peak) in the case of semi-crystalline polymer as determined by differential scanning calorimetry (DSC) .
  • melting temperature includes or refers to the glass transition temperature as determined by DSC.
  • annealing refers to or includes treating material at elevated temperature for a certain period of time. Annealing is typically carried out above the melting temperature of the material. Annealing is used to mobilise the polymer chains and thus the conductive network.
  • the second polymeric layer is also continuous .
  • the multi-component may take various forms, for example film, tape, fibre or yarn (wherein the term “yarn” includes a collection of fibres) .
  • the multi -component material is a multilayer material, wherein the first polymeric component is a first polymeric layer and the second polymeric component is a second polymeric layer. Preferred dimensions for such materials and arrangements of layers are discussed further below.
  • the multi-component material may be a non-layered material.
  • the first polymeric component and second polymeric component may form a co-continuous blend.
  • Suitable dimensions for the multi -component material are as follows :
  • Width 1 mm to 10 m.
  • Thickness 1 ⁇ m to 10 mm
  • the width of the film is from 20 mm to 1 m, thickness is from 10 ⁇ m to 5 mm. Highly preferably, the width of the film is from 20 mm to 100 mm (it may be limited by the width of the die) . The highly preferred thickness of the film is from 10 Um to 3 mm (it may be limited by the thickness of the die and picking up speed of the roller) .
  • Width 1 mm to 1 m.
  • Thickness 1 ⁇ m to 10 mm
  • the width of the tape is from 1 mm to 500 mm, thickness is from 5 ⁇ m to 5 mm.
  • the width of the tape is from 1 mm to 100 mm (it may be limited by the width of the die and the draw ratio) .
  • the highly preferred thickness of the film is from 10 ⁇ m to 3 mm (it may be limited by the thickness of the die, picking up speed of the roller and draw ratio) .
  • the diameter of the yarn/ fibre is from 10 ⁇ m to 3 mm.
  • the diameter of the yarn/fibre is from 20 ⁇ m to 2 mm (it may be limited by the diameter of the die and draw ratio) .
  • the multi -component material may comprise two, three or more components.
  • a single first component and a single second component may be present (A: B structure) .
  • a single central second layer with a first layer on each side may be present (sandwich structure) , in which case the first layers may be the same (A:B:A structure) or different (A:B:C structure) .
  • Other examples of possible structures include A:B:A:B, A:B:C:D, A:A:B:D, A:C:C:D, B:C:D:D, A:B:C:D:E:F, etc., with one or more conductive components being present.
  • one or more core layers/ fibres and one or more sheath layers may be present, which may or may not be co-axial.
  • the core layer (s) /fibre (s) may have various cross-sectional shapes e.g. circular, elliptical, Y-shape, H-shape, X-shape. Alternatively or additionally, one or more segments may be present.
  • the conductive filler may have an aspect ratio of 1 or more. Aspect ratio is preferably determined by transmission electron microscopy (TEM) , scanning electron microscopy
  • the aspect ratio of the conductive filler is 10 or more. More preferably, the aspect ratio of the conductive filler is 30 or more.
  • the carbon black clusters used in this study have an average aspect ratio of 30 according to TEM study. Highly preferably, the aspect ratio of the conductive filler is 100 or more.
  • the MWNTs used in this study have an average aspect ratio of about 150.
  • the conductive filler is carbon nanotubes, carbon black, graphite, graphene, conductive nano-wires, carbon fibre, carbon nanofibre, metal powders or wires (such as copper, steel or silver) , conductive polymer, or a combination of any of these materials.
  • Carbon materials carbon black, carbon nanotubes, carbon fibre, carbon nanofibre, graphite, graphene, or a combination of any of these materials
  • Carbon nanotubes for example multi-wall nanotubes, double-wall nanotubes or single wall nanotubes are used in a preferred embodiment of the invention.
  • the nanotubes may be functionalised or coated with polymer or oxidised. Carbon black is used in another preferred embodiment of the invention.
  • the first polymeric component contains conductive filler in an amount of 0.0001 wt . % to 50 wt . % based on weight of the first polymeric component. More preferably, the first polymeric component contains conductive filler in an amount of 1 to 20 wt% based on weight of the first polymeric component. Highly preferably, the conductive filler is present in an amount of 1 wt . % to 6 wt . % for conductive filler with an aspect ratio of 100 or more (e.g. MWNTs), or in an amount of
  • the first polymer and second polymer may independently be crystalline or amorphous in nature. Typically the first polymer will have lower crystallinity or less complicated polymer chains than the second polymer.
  • the first polymer comprises polyolefin, polyester, polyamide, polycarbonate, poly(methyl methacrylate) (PMMA) and/or elastomer.
  • Preferred polymers include polypropylene co-polymer (co-PP) , polypropylene, polystyrene, polycarbonate, polybutylene terephthalate (PBT), polyethylene (PE, e.g.
  • the first polymer comprises polypropylene co-polymer (co-PP) , PA6 copolymer elastomer (co-PA6) , PET copolymer (co-PET) , LDPE or PMMA as demonstrated in example A and B.
  • the second polymer comprises polyolefin, polyester, polyamide, polycarbonate and/or elastomer.
  • Preferred polymers include polypropylene (PP) , polyethylene
  • the second polymer may optionally include conductive filler.
  • first and second polymers respectively include co-PP/ PP, LDPE/HDPE, CO-PA6/PA6, co-PET/PET, LDPE/PP, and CO-PA6/PET.
  • preferred combinations are LDPE/PA6/co-PET, co-PET/PET/co-PA ⁇ , co-PP/PP/co-PP, co-PET/PA6/co-PA6 , co- PA6/PA6/CO-PA6, LDPE/PET/CO-PET, and LDPE/PET/CO-PA6.
  • the difference in melting temperature between the first polymeric component and the second polymer polymeric component is at least 5 a C.
  • the difference in melting temperature between the first polymeric component and the second polymer polymeric component is at least 10 2 C. Most preferably, the difference in melting temperature between the first polymeric component and the second polymer polymeric component is at least 30 2 C.
  • the first step of preparing a multi- component material is carried out by co-extrusion, hot pressing or spinning the first polymeric component and second polymeric component together, or filament winding the first polymeric component and second polymeric component and subsequently welding them together, or film stacking the first polymeric component and second polymeric component and then welding them together, or phase separation of different polymers during spinning.
  • the orienting process comprises one or more of drawing, extrusion and spinning.
  • drawing and “stretching” as used herein refer to or include applying tensile force to a material, optionally through a die.
  • solid drawing or “solid state drawing” as used herein refers to or includes drawing below the DSC melting temperature peak of the drawn material .
  • spinning refers to or includes drawing and/or simultaneously drawing and twisting a material, for example from a polymer in the melted state.
  • extruding refers to or includes forcing material through a die under pressure.
  • the orienting process may comprise one step or more than one step.
  • the draw ratio used in the orienting process may be 1 or more than 1, and may be up to the maximum achievable for the polymer (e.g. 500) .
  • the draw ratio is from 1 to 10 for film or tape; from 3 to 100 for solid state drawn yarn/fibre or tape; and from 100 to 500 for melt spun yarn/ fibre or tape (which are spun from polymers in their melt state and optionally subsequently further drawn in their solid state) .
  • the draw ratio is from 1 to 5 for as-extruded film or tape; from 3 to up to 50 for the yarn/ fibre or tape.
  • the draw ratio for film is 1, and the draw ratio for yarn/ fibre or tape is from 3 to 24.
  • draw ratio is a measure of the degree of stretch during the orientation of a sample, expressed as the ratio of the length of drawn material to that of undrawn material.
  • the overall draw ratio is the product of the draw ratios for each step.
  • the steps of preparing the multi- component material and subjecting the multi -component material to an orienting process are carried out simultaneously, for example by co-extrusion (which may be followed by one or more drawing steps) . These steps may alternatively be carried out separately.
  • Suitable annealing temperatures will depend on the melting temperature of the first polymer and the second polymer, since annealing is conducted near to or above the melting temperature (for semi-crystalline polymer) or glass transition temperature (for amorphous polymer) . The best results are obtained when the annealing temperature is as high as possible (close to the maximum temperature at which the whole multi -component material maintains its integrity during annealing) for a fixed amount of annealing time.
  • the annealing is conducted a temperature at least 30 0 C above the melting temperature of the first polymeric component.
  • an annealing temperature in the range of 120 0 C to 165 0 C has been found to be appropriate. Good results are obtained at long annealing times ⁇ such as 1 hour) . To achieve similar results, annealing time reduces with increasing temperature. Thus, suitable annealing temperatures could be as high as 400 0 C with a very short annealing time, for example 0.1 s, to maintain the integrity of the whole film, yarn/ fibre or tape. The cooling after annealing has been found to have negligible effect on the conductivity.
  • annealing can be conducted using one or more heated rollers, ovens or baths (for example water or oil baths) .
  • annealing takes place as part of a continuous process.
  • One or more annealing steps may be used.
  • the method is conducted in a continuous fashion. However, it may also be conducted in a batch fashion.
  • the invention relates to a conductive multi -component material prepared by the method described above.
  • the multi -component material has a conductivity (l/resistivity) of 1-E9 S/m to 10000 S/m. More preferably, the multi-component film, tape or yarn/fibre has a conductivity of 1-E9 S/m to 1000 S/m. Preferably, the multi -component material has a tensile strength of 20 MPa to 10 GPa and a Young's modulus of 100 MPa to 300 GPa.
  • a multi-component tape or yarn/fibre has a tensile strength of 100 MPa to 3 GPa and a Young's modulus of 1 GPa to 200 Gpa
  • a multi - component film ⁇ typically with a low draw ratio has a tensile strength of 20 MPa to 200 MPa and a Young's modulus of 100 MPa to 5 GPa.
  • a multi -component tape or yarn/ fibre has a tensile strength of 100 MPa to 3 GPa and a Young's modulus of 2 GPa to 150 GPa
  • a multi -component film has a tensile strength of 20 MPa to 100 MPa and a Young's modulus of 100 MPa to 2 GPa.
  • the Young's Modulus and/or tensile strength of the conductive multi-component material are at least twice as high as the Young's Modulus and/or tensile strength of the initial multi-component material, and/or the conductivity of the conductive multi-component material is at least 100 times as high as the conductivity of the oriented multi-component material before annealing.
  • the invention in a third aspect, relates to a multi- component material comprising: a first polymeric component comprising conductive filler in an amount of 1 to 20 wt% based on the weight of the first polymeric component and a first polymer,- and a second polymeric component comprising a second polymer; wherein the first polymeric component has a lower melting temperature than the second polymeric component; and the composite has a conductivity of at least 1-E9 S/m.
  • the invention in a fourth aspect, relates to an article made from the conductive multi-component material described above.
  • the article may for example be formed from a woven or non woven textile or a rigid material.
  • the multi -component material may be pressed or woven together in the article.
  • the article may for example be an article of clothing or a car component.
  • the article has anti-static properties .
  • the invention relates to use of an article described above to provide anti -static properties; electrostatic properties (for example for use in electrostatic discharge (ESD) , electrostatic painting or electromagnetic-radio frequency interference (EMI) protection) or as a component in an electrical circuit.
  • electrostatic properties for example for use in electrostatic discharge (ESD) , electrostatic painting or electromagnetic-radio frequency interference (EMI) protection
  • EMI electromagnetic-radio frequency interference
  • Fig. 1 shows a circuit used for measurement of resistivity
  • Fig. 2 shows schematically the arrangement of MWNTs within the first polymer layer (a) before drawing and annealing; (b) after drawing but before annealing; and (c) after drawing and annealing;
  • Fig. 3 is a sketch of the structures of various possible multi-component tapes of the invention.
  • Fig. 4 is a sketch of various possible multi -component yarns/fibres of the invention.
  • Nan ⁇ cyl ® 7000 MWNTs were provided by Nanocyl S. A.
  • the average aspect ratio of these MWNTs is 150 according to the data sheet.
  • the average diameter is 10 run.
  • DSC Differential Scanning Calorimetry
  • the polymer used in the skin layer (s) of the tape was PP copolymer (co-PP) Adsyl ® 5C39F from Basell. This is a random copolymer contain ethyl and polypropylene. Its melting temperature peak occurs at 114.6 0 C according to
  • DSC Differential Scanning Calorimetry
  • the conductive carbon black (CB) used was Printex ® XE-2 which was supplied by Grolman Ltd.
  • MWNTs or CB were melt blended with co-PP in a mini- extruder (DSM Micro 15) at 200 0 C, 200 rpm for 10 minutes.
  • the extruded strand was then hot pressed into film with a thickness of 150 ⁇ m at 200 0 C for 5 minutes.
  • the filler content of the CPC was measured by thermogravimetric analysis (TGA) .
  • TGA thermogravimetric analysis
  • Two outer layers of CPC film with co- PP/MWNTs (or carbon black) and one central layer of PP film were then pressed into a sandwich structure at 155 0 C.
  • the sandwich tape was then hot drawn into tapes at different draw ratios at 12O 0 C on a tensile test machine Instron 5584 equipped with an environmental chamber.
  • Thermal annealing was conducted on mechanically constrained tape at 155 0 C for 15 minutes in the same environmental chamber.
  • the thickness of the solid state drawn tapes, or solid state drawn and annealed tapes ranges from 30 ⁇ m to 100 ⁇ m as they have different draw ratios.
  • the width of the tape can range from 1 mm to 50 mm for different draw ratios or different starting width for the initial film.
  • DSC Differential scanning calorimetry
  • the automated online electrical measurement set up is schematically shown in Fig. 1.
  • the voltage scan was chosen to be 1 V to avoid a strong electric current through the sample.
  • 300 ms internal voltage (0 Volt) was applied for every 700 ms at 1 Volt.
  • Silver paint was applied on both ends of the sample to ensure good contact.
  • High temperature resistant polymer coated copper wire was used in the oven to connect the sample with electrodes and wires outside the oven. The oven was heated to a targeted temperature and kept there until a relative stable current value was obtained. Then the heating was stopped and the oven cooled down to room temperature by air cooling (effectively by opening the door of the oven) . Therefore, the total annealing time was different for different type of specimens. The temperature was recorded during heating and cooling and at the same time the current data was recorded in order to calculate the resistivity.
  • Morphology studies were carried out by scanning electron microscopy (SEM) using a JEOL JSM-6300F SEM apparatus in order to investigate the form of the conductive network during tape fabrication and after annealing.
  • SEM scanning electron microscopy
  • a high accelerating voltage ⁇ 25 kv) was applied for the SEM study, which is known to be contrast mode [18] .
  • TEM Transmission electron microscopy
  • Tensile tests were performed on an Instron 5566 apparatus equipped with a video extensometer .
  • the gage length and cross-head speed used for drawn or un-drawn film, tapes or yarn/ fibres were 30 mm and 30 mm/min respectively.
  • At least five specimens were tested to obtain the average value .
  • the melting temperature for co- PP starts (onset) at 70 0 C (the same value for different content of MWNTs in co-PP ⁇ , and the melting temperature peak occurs at 134.6 0 C (146 0 C for different content of MWNTs in co-PP) .
  • the melting temperature peak for PP starts (onset) at 140 0 C and its peak occur at 168 0 C.
  • the I-V curves were noticed to be linear.
  • the drawn and annealed sample had resistivity at least 3 orders of magnitude below that of the drawn sample.
  • Table 1 shows the resistivity results for MWNTs/co- PP.
  • Hot pressed film network of randomly isotropic Isotropic CB network dispersed MWNTs bundles solid state highly orientated MWNTs Orientated CB structure drawing bundles, and highly oriented
  • Solid state hairy orientated bundles Isotropic CB network drawing and highly oriented bundles, but annealing locally random oriented MWNTs inside the bundles
  • the oriented MWNT bundles in a solid state drawn tape can be considered as aligned cylinders in such a system, where the radius is the half of the diameter of the MWNT bundles. After annealing, the diameter of the MWNT bundles increases dramatically. Approximately, their diameter increase from 70-190 nm to 500-1000 nm. With the MWNTs bundles becoming "hairy" ⁇ as shown in Figure 2) . This is believed to be due to the largely random orientation of MWNTs within the bundles, which remain largely oriented at a mesoscopic scale. These oriented "hairy" bundles not only allow for more MWNTs being effectively aligned in a particular direction, but also provides the MWNT bundles with lateral inter-bundle connections through individual nanotubes to reduce tunnelling resistance.
  • Carbon black is used as a conductive filler for comparison because it has much a smaller aspect ratio than MWNTs.
  • the aspect ratio of the filler plays an important role during the drawing process, as shown in the literature [4, 10] .
  • the resistivity of drawn and annealed tape is similar to that of hot pressed film. This can be understood as the orientated CPC having returned to isotropic state, with no difference between a hot pressed film and a drawn and annealed sample because of the smaller aspect ratio of carbon black which results in less physical interaction between the filler clusters, giving an isotropic conductive network after annealing.
  • the MWNTs bundles are believed to be under strain (possibly different strain for different parts of the bundle) after solid state drawing as they were deformed during stretching.
  • the constrained MWNT bundles tend to return to their original state as the polymer around them allows them more mobility during annealing. Therefore, they become locally random oriented, but in large scale they are still oriented to give exceptional electrical properties in the drawing direction.
  • Resistivity was measured for MWNT/co-PP composites with a draw ratio of 8 over a variety of filler contents .
  • the annealing conditions were 155 0 C for 15 mins .
  • the results are shown in Table 4:
  • Resistivity was measured for 5.3 MWNT/co-PP tape and 10 wt.%, 15 wt. % and 20 wt . % CB/co-PP tapes over a variety of draw ratios. Samples were thermally annealed at 155 0 C for 15 mins. Results are shown in Tables 5 and 6:
  • Resistivity was measured for 2.3 wt . % MWNT/co-PP tape with a draw ratio of 24 and an annealing time of 15 mins at different annealing temperatures. Results are shown in Table 7: TABLE 7
  • Resistivity was measured for a 5.3 wt . % MWNT/co-PP tape with a draw ratio of 21. Samples were thermally annealed. Electrical properties were monitored online during annealing. Results are shown in Table 7a:
  • Annealing can be conducted at a relative low- temperature (above than the melting temperature of the first polymeric material) for a relatively long period of time; or, alternatively, annealing can be conducted at a higher temperature for a relatively short period of time.
  • Anisotropy index (RT/RL) is defined as:
  • RT/RL after drawing and annealing for CPC loaded with MWNTs only dropped from 100 to 10 at draw ratio 6, showing that some anisotropy remains in the network after annealing.
  • the electrical anisotropy study confirmed the morphological study (Example Al) : the network constructed by carbon black showed some anisotropy after solid drawing, but decreased to nearly isotropic after annealing; the network formed by MWNTs showed significant anisotropy in solid drawn tape, and some anisotropy was kept after annealing due to orientated MWNT bundles in large scale being maintained.
  • the percolation threshold is increased from between 1.44 wt . % and 1.82 wt . % to between 3.1 wt% and 5 wt% after solid drawing, but is decreased to between 1.15 wt% to 1.44 wt . % after the drawn tape is annealed, as a sudden drop of resistivity is observed between these filler contents.
  • the resistivity of drawn and annealed tape is even lower than the resistivity of isotropic CPC.
  • the percolation threshold of the carbon black/co-PP system increases from near 3 wt% to 10 wt% by solid drawing, and thermal annealing brings the percolation threshold back to 3 wt%.
  • the resistivity of the drawn and annealed tape is the same as isotropic film. However, in both the cases shown in Table 10 and 11, a significant drop in resistivity is observed for solid state drawn tapes after annealing.
  • the mechanical properties of the co-extruded tape are mainly contributed by the middle neat polymer layer.
  • the outer CPC layers are expected to have very low mechanical properties comparing with the highly orientated PP tape, because they have been annealed above their melting temperature, so that the orientation of the polymer chain is reduced significantly.
  • a 10 wt% MWNT/co-PP master batch was provided by Nanocyl S. A.
  • the master batch was prepared by mixing co-PP
  • NC 7000 MWNTs (as above) in a twin-screw extruder at 70 rpm and 220 0 C. 2 wt% MWNT/co-PP and 5 wt%
  • MWNT/co-PP were diluted at 100 rpm and 220 0 C from the master batch.
  • NC 7000 MWNTs (as above) were mixed with LDPE, co-PET, CO-PA6 and PMMA in a twin-screw extruder at an initial content of 10 wt . % to make respective master batches.
  • the conditions used were 70 rpm and 200 0 C for LDPE, 70 rpm and 160 0 C for co-PET, 70 rpm and 230 0 C for co-PA6, 70 rpm and 240 0 C for PMMA. These materials were diluted to lowered concentrations at 100 rpm at the same temperatures (as described above), respectively.
  • the polymers used here are oven dried for 24 h before processing or compounding at 50 0 C for 5 wt. % MWNT/LDPE, 5 wt . % MWNT/co-PET, 5 wt . % MWNT/co- PA6; 80 0 C for PET, PA6 , PC and PMMA.
  • HDPE was HDPE VL4580 produced by Borealis A/S.
  • LDPE was LDPE 352E produced by The DOW Chemical Company.
  • Co-PET was Griltex D1616E, a co-polyester hotmelt adhesive.
  • C0-PA6 Pebax 5533 SA 01, a thermoplastic elastomer made of flexible polyether and rigid polyamide.
  • PET was Futura PET resin- 1.1 lv.
  • PA6 was Ultramid B33L from BASF.
  • the polycarbonate (PC) was Calibre 201-10 from The DOW Chemical Company.
  • PMMA was Altuglas V825T 101 produced by Altuglas International of Arkema Inc.
  • a set of extruders and co-extrusion tape die (with a width of 100 mm and thickness of 3 mm) produced by Dr. Collin GmbH were used to make A:B, A:B:A and A:B:C type tapes.
  • Three single-screw extruders (2 TEACH-LINE E20T SCD15 and 1 SCDl5 equipped with a melt pump) were connected to the co-extrusion die directly through three heated melt pipes. Temperature control was realised by adding thermal couples to monitor the temperature for different heating zones through the extruders.
  • a melt pump was used between one of the single-screw extruder and the co-extrusion die to control the melt pressure in the die as well as to have more thermal couples available.
  • a temperature controlled pick up roller (TEACH-LINE CR72T) was used to collect the as-spun film or tapes .
  • Co-extrusion was conducted under different temperatures for different polymers. As these three single extruders were the input for the co-extrusion die, they were set at suitable temperatures for different polymers or compound, but the co-extrusion die was set to a temperature which allows the polymer with the highest melting temperature to flow smoothly (for example in the A:B:A tape of MWNT/co- PA6 :PA6 :MWNT/CO-PA6, the temperature of the die was set to 240 0 C to allow good flow of PA6, so the temperature of the die was much higher than the melting temperature peak of the MWNT/CO-PA6 which is 165 0 C according to DSC measurement) .
  • the as-extruded tapes had relatively low resistivity because they were already annealed to some extent by the high temperature die during extrusion.
  • the thickness ratio of the co-extruded tape was controlled by the adjusting the extrusion speed of the single screw extruders or the melt pump output. The component of the tape was changed by simply changing input materials in the extruders .
  • the as extruded film or tape was produced by collecting film or tapes from the co-extrusion die to a pick up roller, which typically consisted of several temperature controlled rollers. The film or tape collected here was considered as extruded film or tape with a draw ratio of 1. In the case of polymer blends between 5 wt .
  • Annealing was conducted in an environmental chamber equipment with the Instron machine 5584 as described before.
  • the specimens were typically mechanically constrained and annealed for 20-30 mins in the oven at different suitable temperatures for different polymers as stated below.
  • the melting temperature was studied by DSC for different polymers, with results as follows:
  • LDPE 70 0 C for MWNT/LDPE
  • 60 0 C for co-PET and MWNT/co-PET 60 0 C for co-PA6 and MWNT/co-PA6, 100 0 C for HDPE, 220 0 C for PET, 200 0 C for PA6.
  • the glass transition temperature (T g ) is 104 0 C and 170 0C for the PMMA and PC, respectively, according to DSC study.
  • Example B2 The results from different polymers combinations (example B2 ) show that annealing reduces the resistivity of oriented tapes consisting of a wide range of polymers, including polyester, polyamide, polyolefin and amorphous polymers. Tapes including two or three polymers coming from different polymer types have been tested. The mechanical properties of the whole tape are largely retained after annealing, indicating that the polymer orientation in the middle layer is not significantly reduced. Therefore, it is expected that the results would be applicable to any polymer type.
  • the tapes or yarns /fibres of the Examples have the following advantages: good mechanical properties; - good electrical properties,- ease of production; good recyclability.
  • the material can potentially be produced on a large scale, as demonstrated by Example B.
  • a continuous process using co-extrusion and inline annealing could potentially be used.
  • the core layer is of a single polymer material.
  • the polymers of the core and CPC layer are sufficiently similar that the tape qualifies as a mono-component material (such as co-PP/PP, LDPE/HDPE, co-PET/PET, CO-PA6/PA6) , which is an advantage in recycling because the material can be simply re-melted and reused again.
  • the small amount of conductive filler remaining in the co-polymer layer, leading to even smaller amounts of conductive filler in the overall tape, has no significant effect on recyclability .
  • the CPC components are capable of welding multiple tapes together to make composites.
  • Miaudet P Bartholome C, Derre A, Maugey M, Sigaud G, Zakri C, and Poulin P. Polymer 2007 ; 48 : 4068-4074.
  • This study describes a method fabricating mechanically strong and conductive polymer/MWNTs tape, which consists of melt compounding, drawing and annealing process.
  • Highly oriented carbon nanotube structure is observed in highly drawn composites tape, the annealing process after drawing has relaxed the structure into orientated hairy MWNTs bundle. This structure is even more conductive than the random dispersed isotropic film from the concentration.
  • the percolation threshold in conductive polymer tape is decreased from near 5.03 wt% to 1.51 wt% without sacrifice the mechanical properties by annealing. It is the lowest in literature for highly orientated polymer tape according to our knowledge. This method has solved the problem of losing conductive network when polymer/MWNTs undergo deformation during fibre/ tape processing. It is expected to be useful for conductive nanotube composites tape application.
  • CPC Conductive polymer composites
  • CPC can be made by adding conductive filler into insulating polymer matrix. It has been demonstrated that a sudden jump of conductivity can be reached when a critical loading of conductive filler is added into the matrix [1] . This phenomenon is described as percolation threshold.
  • the percolation threshold of fibre reinforced CPC have been shown both experimentally and theoretically that decrease with the filler aspect ratio [2, 3] . Carbon nanotubes have been extensively investigated since 1991 [4-8]. It has been shown that CPC based on MWNTs can reach percolation threshold as low as 0.0025 wt% in epoxy matrix [9] . Though, melt compounding polymer with MWNTs have only reached percolation threshold of 1.44 wt% [10] . It is still relatively low comparing with conventional conductive filler where the percolation threshold is between 20 wt% to 30 wt%.
  • CPC In order to process CPC containing carbon nanotubes into desired shape, CPC has to undergo processing, such as: injection moulding, spinning or stretching.
  • the conducting network is deformed to different extent during these processing methods.
  • Some work have been carried out to investigate the influence of deformed conducting network on the conductivity [11-13] .
  • Inhomogeneous conductive network was observed for injection molded sample, it is due to shear flow during processing [13] .
  • Alig I., et al . [11, 12] has performed study to investigate the influence of shear on the conductivity of CPC in the melt.
  • thermo annealing near the glass transition temperature of the polymer have dramatically increased the conductivity of the fibre.
  • XRD study has shown that the increased conductivity might due to the increased mobility of polymer chain, it can leads to mobility of carbon nanotube which could increase the quality and the density of nanotube contacts.
  • the percolation threshold was decreased due to the orientated hairy bundles structure MWNTs have formed.
  • Anisotropy of the highly orientated bundle and hairy bundle conductive network has been studied.
  • CPC contains carbon black is investigated for comparison.
  • mechanical properties of highly orientated neat PP tape are studied before and after the annealing, no significant decrease is found. It is expected to be useful for conductive nanotube composites tape application.
  • Nanocyl ® 7000 is kindly provided by Nanocyl S. A. (Belgium) .
  • the surface area of MWNTs is 250-300 m 2 /g according the data sheet.
  • the polymer used in outer layer is PP copolymer ( co-PP ⁇ Adsyl ® 5C39F from Basell .
  • the conductive carbon black (CB) used is Printex ® XE-2 which is supplied by Grolman Ltd. Characterization study of several carbon blacks including Printex ® XE-2 was carried out by Pantea D. et al .
  • Printex ® XE-2 has comprehensive conductivity comparing with others. It has surface area of 910 m 2 /g. MWNTs or CB is melt blended with co-PP in mini- extruder ⁇ DSM Micro 15) at 200 0 C 7 200 rpm for 10 minutes. The extruded rod is then hot pressed into film in the thickness of 150 ⁇ m at 200 0 C for 5 minutes. The filler content of the CPC is measured by TGA (Thermo gravimetric analysis) . Two layers of CPC film with co-PP/MWNTs ⁇ or carbon black) and one layer of PP film are then pressed into sandwich structure at 155°C with PP film in the middle.
  • TGA Thermo gravimetric analysis
  • Morphology studies are carried out on JEOL JSM-6300F SEM in order to investigate the informing of conductive network during tape fabrication and after annealing.
  • High accelerating voltage is applied for SEM study, MWNTs or CB in the polymer matrix material is charged and give an enriched secondary-electron as demonstrated by Loos J. et al. in [30] .
  • TEM imaging of cross-sectional cut samples was performed.
  • the as-prepared nanocomposite samples were sectioned at room temperature using an ultra-microtome (Reichert-Jung Ultracut E) .
  • the TEM was operated in bright-field mode at 80 kv to increase the contrast between MWNTs and the surrounding polymer matrix.
  • DC electrical resistivity is measured for the composites at different stage of processing. Two points method with voltage scan from 1 volt to 10 volt is conducted in resistivity measurement, silver paint is applied on both ends of the sample to ensure contact. Thus, contact resistance is much smaller comparing with sample resistance.
  • the dimension of the sample is not uniform in this study due to the thickness and width varies with draw ratio.
  • the resistances are measured by an Agilent 6614C programmable voltage source in combination with a Keithley 6485 picoammeter. All the equipments are interfaced with a computer to record the I -V curve in order to calculate the resistivity. The I-V curves are noticed to be linear in this study.
  • the electrodes are applied on the top and bottle surface of the film instead of on the ends to obtain measurable resistance.
  • the sandwich tape used in this study is shown in Figure 1.
  • CPC is applied on the surface layer of the tape.
  • Neat PP in the middle part has higher melting temperature than CPC. This allows three different processes to be conducted: anneal the isotropic CPC in the melt, draw the CPC in the melt, draw the CPC in the solid state and anneal it in the melt.
  • Table 1-3 have shown the resistivity results of the tapes have undergone three different processes respectively. Dramatic resistivity decrease is observed after the isotropic tape is annealed in the melt as shown in Table 1. This could be explained by re-aggregation of MiAfMTs in the melt as demonstrated by Alig I. et al . [12] .
  • Table 2 has shown the resistivity of the tape before and after melt drawing in which the CPC is drawn in the melt with PP substrate in the middle layer of the tape.
  • the CPC specimens have become insulate after melt drawing. Morphological study have found rough surface on the tape ( Figure 2a) , and randomly distributed MWNTs under SEM ( Figure 3b) .
  • the melt drawn CPC could be considered as similar system as the case investigated in [12] .
  • the CPC have lost its conductivity after deformation is applied on it in the melt.
  • the isotropic CPC specimens have lost their conductivity after solid drawing, but the annealing after solid drawing has made them even more conductive than the original isotropic film. This could solve the problem reported in literature [13, 16, 17, 19], where resistivity is decreased dramatically when MWNTs is orientated by injection molding or drawing. The annealing process has brought back the conductive network after large deformation.
  • Orienting MWNTs has been considered as a method to increase the mechanical reinforcing efficiency in polymer composites [5] . It is thought that orientated MWNTs should be able to increasing the conductivity along its deformation direction, because more MWNTs should be contributing the network after the deformation.
  • Theoretical study on percolation in anisotropic network has been done by Munson-McGee S. H. in
  • cylinder shape like filler is considered in 3D system, planar system and orientated system.
  • the radius of the cylinder is shown to be very important, (when the length of the filler is fixed) to the probability of two cylinders intersecting in a unit volume.
  • the probability could be considered as the ability of fillers forming conductive network.
  • the probability increases linearly with increasing radius in aligned system.
  • the aligned MWNTs bundles in solid drawn tape (as shown in
  • Figure 3c can be considered as aligned cylinders in the system, where the radius is close to the diameter of MWNTs bundles. The diameter of bundles has increased dramatically
  • the hot pressed film obtained randomly isotropic dispersed MWWTs bundles network as shown in Figure 5b. Highly orientated MWNTs bundles are achieved by drawn isotropic film at solid state, and hairy orientated bundles are observed in drawn and annealed tape ( Figure 5 c and d) .
  • DC resistivity study on different specimens from stated processing stages are presented in Figure 6. Drawn and annealed sample has the lowest resistivity among all. The annealing procedure has dropped the resistivity more than 3 orders of magnitude.
  • Figure 7 and 8 have shown the morphological study and resistivity study on the CPC loaded with carbon black to compare with the CPC with MWNTs.
  • RT/RL is defined aS : R-Transverse/R-Longitudinal / where R-Transverse ⁇ d R-Longi tudmal are the resistivity of the CPC at transverse and longitudinal direction to the drawing direction respectively. It is considered as an index to describe the anisotropy of the network.
  • RT/RL is approaching 1 after anneal indicating that the composites is nearly isotropic as shown in Figure 9a.
  • the percolation threshold of carbon black/co-PP system has increased from near 3 wt% to 10 wt% by solid drawing, and the thermal annealing has brought the percolation threshold back to 3 wt%.
  • the resistivity of the drawn and annealed tape has reached the same value as isotropic film. Due to their low aspect ratio, the network form by carbon black is not showing any significant orientation after solid drawing and annealing.
  • the deformation of the conductive network has dramatically increased the percolation threshold.
  • the percolation threshold and exponent t is 1.51 wt% and 3 respectively for isotropic MWNTs /co-PP system as shown in Figure 12a.
  • the t value is higher than the one calculated by [1] for 3D random network, but it is still within mean filed theory [31] .
  • the percolation threshold and exponent t values are 1.51 wt% and 1.3 respectively.
  • the t value fits with the universal scaling value for 2D conductive network as shown in Figure 12b. It has confirmed the SEM, TEM observation and anisotropy study shown in Figure 3d, Figure 4 and Figure 9: 2D conductive network in large scale, but it remains random locally to ensure good contact between MWNTs bundles.
  • outer layers are not taking into account regarding to the mechanical properties because the thickness of outer layers have not been optimized in this study in order to maximize the mechanical properties and keep the electrical conductivity of the three layer structure. Large scale experiment is being carried out to study the industrial feasibility of conductive polymer tape.
  • CPC contains carbon black is investigated for comparison, they have shown similar recovery of conductive network after drawing, but no orientated structure was found after annealing.
  • mechanical properties of highly orientated neat PP tape are studied before and after the annealing, no significant decrease is found.
  • large scale experiment is being carried out to study the industrial feasibility of conductive polymer tape.
  • the effect of dispersion quality on the forming of orientated hairy MWNTs structure is also under investigation to minimize the percolation threshold in 2D conductive network.
  • Table 3 The effect of solid drawn and annealing on isotropic MWNTs/co-PP film

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur un procédé de préparation d'un matériau à composants multiples conducteur. Le procédé consiste à préparer un matériau à composants multiples initial qui renferme un premier composant polymère continu comprenant une charge conductrice et un premier polymère, et un deuxième composant polymère comprenant un deuxième polymère, le premier composant polymère ayant une température de fusion inférieure à celle du deuxième composant polymère; à soumettre le matériau à composants multiples initial à un traitement d'orientation; et à recuire le matériau à composants multiples orienté pour obtenir le matériau à composants multiples conducteur.
PCT/EP2008/064460 2007-10-24 2008-10-24 Composite polymère conducteur WO2009053470A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US98228107P 2007-10-24 2007-10-24
US60/982,281 2007-10-24

Publications (1)

Publication Number Publication Date
WO2009053470A1 true WO2009053470A1 (fr) 2009-04-30

Family

ID=40292431

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/064460 WO2009053470A1 (fr) 2007-10-24 2008-10-24 Composite polymère conducteur

Country Status (1)

Country Link
WO (1) WO2009053470A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010136729A1 (fr) 2009-05-27 2010-12-02 Arkema France Fibre conductrice multicouche et son procede d'obtention par co-extrusion
WO2010151141A1 (fr) 2009-06-22 2010-12-29 Institutt For Energiteknikk Dispositif de décharge électrostatique et procédé de fabrication de celui-ci
JP2013245271A (ja) * 2012-05-25 2013-12-09 Jsr Corp 導電性樹脂組成物および導電性樹脂フィルム
WO2014074397A1 (fr) * 2012-11-07 2014-05-15 Bayer Materialscience Llc Procédé d'incorporation d'un polymère conducteur ionique dans un article en polymère pour obtenir un comportement anti-statique
DE202013009479U1 (de) * 2013-10-28 2015-01-29 Jörn von Bornstädt Folie mit einer leitfähigen Deckschicht für den Einsatz in Behältern
WO2016039695A1 (fr) * 2014-09-11 2016-03-17 Agency For Science, Technology And Research Fibres de carbone conductrices électrofilées
WO2019224397A1 (fr) * 2018-05-25 2019-11-28 Carbonx B.V. Utilisation de nanofibres de carbone comprenant des réseaux de carbone

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4265789A (en) * 1979-10-22 1981-05-05 Polymer Cencentrates, Inc. Conductive polymer processable as a thermoplastic
US4818439A (en) * 1986-01-30 1989-04-04 Sunbeam Corporation PTC compositions containing low molecular weight polymer molecules for reduced annealing
EP0399397A2 (fr) * 1989-05-22 1990-11-28 E.I. Du Pont De Nemours And Company Filage de filaments "âme-gaine" à section multilobée ayant une âme conductrice
EP1219734A1 (fr) * 1999-09-17 2002-07-03 Kanebo Limited Fibre conductive a composite coeur-gaine
US6750284B1 (en) * 1999-05-13 2004-06-15 Exxonmobil Chemical Patents Inc. Thermoplastic filled membranes of propylene copolymers
EP1452304A1 (fr) * 2001-12-06 2004-09-01 Toray Industries, Inc. Film en couches et procede de production associe
US20040211942A1 (en) * 2003-04-28 2004-10-28 Clark Darren Cameron Electrically conductive compositions and method of manufacture thereof
WO2005034144A1 (fr) * 2003-09-29 2005-04-14 General Electric Company Compositions thermoplastiques conductrices, procedes de fabrication et articles derives desdites compositions
EP1712592A1 (fr) * 2004-01-29 2006-10-18 Teijin Dupont Films Japan Limited Film bi-oriente
WO2007100573A2 (fr) * 2006-02-22 2007-09-07 Entegris, Inc. Compositions composites de nanotubes et de polymère et leurs méthodes de fabrication

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4265789A (en) * 1979-10-22 1981-05-05 Polymer Cencentrates, Inc. Conductive polymer processable as a thermoplastic
US4818439A (en) * 1986-01-30 1989-04-04 Sunbeam Corporation PTC compositions containing low molecular weight polymer molecules for reduced annealing
EP0399397A2 (fr) * 1989-05-22 1990-11-28 E.I. Du Pont De Nemours And Company Filage de filaments "âme-gaine" à section multilobée ayant une âme conductrice
US6750284B1 (en) * 1999-05-13 2004-06-15 Exxonmobil Chemical Patents Inc. Thermoplastic filled membranes of propylene copolymers
EP1219734A1 (fr) * 1999-09-17 2002-07-03 Kanebo Limited Fibre conductive a composite coeur-gaine
EP1452304A1 (fr) * 2001-12-06 2004-09-01 Toray Industries, Inc. Film en couches et procede de production associe
US20040211942A1 (en) * 2003-04-28 2004-10-28 Clark Darren Cameron Electrically conductive compositions and method of manufacture thereof
WO2005034144A1 (fr) * 2003-09-29 2005-04-14 General Electric Company Compositions thermoplastiques conductrices, procedes de fabrication et articles derives desdites compositions
EP1712592A1 (fr) * 2004-01-29 2006-10-18 Teijin Dupont Films Japan Limited Film bi-oriente
WO2007100573A2 (fr) * 2006-02-22 2007-09-07 Entegris, Inc. Compositions composites de nanotubes et de polymère et leurs méthodes de fabrication

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010136729A1 (fr) 2009-05-27 2010-12-02 Arkema France Fibre conductrice multicouche et son procede d'obtention par co-extrusion
FR2946176A1 (fr) * 2009-05-27 2010-12-03 Arkema France Fibre conductrice multicouche et son procede d'obtention par co-extrusion.
AU2010263367B2 (en) * 2009-06-22 2015-08-06 Condalign As Electrostatic discharge device and method for manufacturing the same
EP2446447A1 (fr) * 2009-06-22 2012-05-02 Condalign AS Dispositif de décharge électrostatique et procédé de fabrication de celui-ci
EP2446447A4 (fr) * 2009-06-22 2013-04-24 Condalign As Dispositif de décharge électrostatique et procédé de fabrication de celui-ci
WO2010151141A1 (fr) 2009-06-22 2010-12-29 Institutt For Energiteknikk Dispositif de décharge électrostatique et procédé de fabrication de celui-ci
US9437347B2 (en) 2009-06-22 2016-09-06 Condalign As Method for manufacturing an electrostatic discharge device
JP2013245271A (ja) * 2012-05-25 2013-12-09 Jsr Corp 導電性樹脂組成物および導電性樹脂フィルム
WO2014074397A1 (fr) * 2012-11-07 2014-05-15 Bayer Materialscience Llc Procédé d'incorporation d'un polymère conducteur ionique dans un article en polymère pour obtenir un comportement anti-statique
US8758860B1 (en) 2012-11-07 2014-06-24 Bayer Materialscience Llc Process for incorporating an ion-conducting polymer into a polymeric article to achieve anti-static behavior
US9388324B2 (en) 2012-11-07 2016-07-12 Covestro Llc Process for incorporating an ion-conducting polymer into a polymeric article to achieve anti-static behavior
DE202013009479U1 (de) * 2013-10-28 2015-01-29 Jörn von Bornstädt Folie mit einer leitfähigen Deckschicht für den Einsatz in Behältern
WO2016039695A1 (fr) * 2014-09-11 2016-03-17 Agency For Science, Technology And Research Fibres de carbone conductrices électrofilées
WO2019224397A1 (fr) * 2018-05-25 2019-11-28 Carbonx B.V. Utilisation de nanofibres de carbone comprenant des réseaux de carbone
CN112424272A (zh) * 2018-05-25 2021-02-26 卡波恩科斯Ip5私人有限公司 包含纳米碳纤维的碳网状物的用途

Similar Documents

Publication Publication Date Title
WO2009053470A1 (fr) Composite polymère conducteur
JP5770962B2 (ja) ポリマーマトリックス中に埋封された配向ナノ繊維
Du et al. The present status and key problems of carbon nanotube based polymer composites
EP2734580B1 (fr) Compositions à base de nanotubes et de composés polymères de fibre de carbone finement broyée et leur procédé de fabrication
Wen et al. The electrical conductivity of carbon nanotube/carbon black/polypropylene composites prepared through multistage stretching extrusion
Deng et al. Effect of thermal annealing on the electrical conductivity of high-strength bicomponent polymer tapes containing carbon nanofillers
US20110147673A1 (en) Method of manufacturing composite conducting fibres, fibres obtained by the method, and use of such fibres
Deng et al. Effect of melting and crystallization on the conductive network in conductive polymer composites
Krause et al. Comparative study of singlewalled, multiwalled, and branched carbon nanotubes melt mixed in different thermoplastic matrices
Jimenez et al. Electrically conductive polymer nanocomposites of polymethylmethacrylate and carbon nanofibers prepared by chaotic mixing
Mishra et al. Manipulation of thermo-mechanical, morphological and electrical properties of PP/PET polymer blend using MWCNT as nano compatibilizer: a comprehensive study of hybrid nanocomposites
Gordeyev et al. A promising conductive material: highly oriented polypropylene filled with short vapour-grown carbon fibres
JP2003534955A5 (fr)
JP5485293B2 (ja) Ｐｅｋｋ複合繊維と、この繊維の製造方法と、その使用
Deng et al. A novel concept for highly oriented carbon nanotube composite tapes or fibres with high strength and electrical conductivity
EP2195369A2 (fr) Procédé de préparation d'une composition polymère conductrice
Zhang et al. Static and dynamic percolation of phenoxy/carbon nanotube nanocomposites
JP2012528253A (ja) 多層伝導性繊維と、共押出によるその製造
Araujo et al. Conductive composites of polyamide-6 with polyaniline coated vegetal fiber
WO2010102731A1 (fr) Corps moulés à partir de mélanges de polymères et de nanoparticules de carbone avec propriété de gradient de la conductibilité électrique
Latko et al. Non-woven veils manufactured from polyamides doped with carbon nanotubes
Wang et al. Preparation and characterization of CNTs/PE micro‐nanofibers
Cecci et al. Effect of graphene nanoplatelets presence on the thermal and mechanical properties of polypropylene fibers produced by melt spinning
EP1803763B1 (fr) Nanofibres orientées intégrées dans une matrice polymère
WO2009069565A1 (fr) Articles moulés, procédé de fabrication des articles moulés et utilisation des articles moulés

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08842251

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08842251

Country of ref document: EP

Kind code of ref document: A1