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WO2021084074A1 - Compositions et films comprenant un polymère et des particules de tis2, leur préparation et leurs utilisations - Google Patents

Compositions et films comprenant un polymère et des particules de tis2, leur préparation et leurs utilisations Download PDF

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WO2021084074A1
WO2021084074A1 PCT/EP2020/080521 EP2020080521W WO2021084074A1 WO 2021084074 A1 WO2021084074 A1 WO 2021084074A1 EP 2020080521 W EP2020080521 W EP 2020080521W WO 2021084074 A1 WO2021084074 A1 WO 2021084074A1
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composition
polymer
film
particles
electrodes
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Olivier SANSEAU
Rabih AL RAHAL AL ORABI
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Solvay SA
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Solvay SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/14—Organic dielectrics
    • H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
    • H01G4/186—Organic dielectrics of synthetic material, e.g. derivatives of cellulose halogenated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/20—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06
    • H01G4/206—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06 inorganic and synthetic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/32—Wound capacitors

Definitions

  • compositions and films comprising a polymer and T1S 2 particles, and their preparation and uses Field
  • the present invention relates to the technical field of materials useful for the manufacture of electrical and electronic devices. More precisely, the invention provides a composition containing a polymer and T1S2 particles, which is suitable for forming a dielectric film, a film made with such a composition, a method for the manufacture of such a film and the electrical and electronic devices comprising such a film.
  • dielectric polymeric compositions suitable for capacitors, actuators and sensors applications in order to propose advanced devices with reduced weight, size, and cost.
  • a challenge for reducing the size of high-power devices is to develop materials with high dielectric permittivity (dielectric constant).
  • VDF vinylidene fluoride
  • dielectric permittivity values are very limited in some domains of frequency sweep; - WO 2019/073012 proposes a composition comprising at least one fluorinated polymer and silver nanowires coated with at least one metal oxide, for increasing the relative permittivity, with limited growth of dielectric losses.
  • the fluorinated polymer is chosen among vinylidene fluoride homopolymers or copolymers which provide advantageously high chemical resistance.
  • the dielectric losses of the composite also increase with the coated silver nanowire content.
  • nanocomposites composed of ceramic particles in a polymer matrix have been prepared as a mean of engineering dielectric property and energy storage capacity.
  • BaTiC>3 nanoparticles were introduced in a matrix of vinylidenefluoride, trifluoroethylene and chlorotrifluoroethylene copolymer P(VDF-TrFE-CTFE) or of vinylidenefluoride and chlorotrifluoroethylene copolymer P(VDF-CTFE) (J. Li et al. , supra and H. Tang et al.
  • compositions comprising:
  • the invention allows increasing the relative permittivity of the composition, or more precisely the real part e' of the relative permittivity by the addition of the T1S2 particles.
  • the present invention proposes a hybrid composition suitable for forming dielectric layers in applications such as in sensors, actuators and capacitors.
  • results obtained by the inventors show that, the introduction of T1S2, as inorganic filler into various polymers leads to an increase of the relative permittivity or, more precisely to an increase of the real part e' of the relative permittivity, with respect to the unmodified polymer.
  • results presented hereafter in the examples relative to P(VDF-TrFE-CTFE) terpolymer compositions show that the invention leads to a higher increase of the relative permittivity than the increase obtained by Li et al., with the use of BaTiC>3.
  • the obtained results show also that this increase of the e' value is obtained with low dielectric losses.
  • the dielectric losses are not greatly increased or of the same order of magnitude, with respect to the unmodified vinylidene fluoride (co)polymer and remain acceptable.
  • the invention also provides films composed of the composition according to the invention and carriers coated with the film of the invention.
  • the present invention also relates to a film comprising at least a composition according to the invention; as well as any carriers coated with the film of the invention.
  • the present invention also relates to a film obtained from the composition according to the invention, especially by crosslinking when the polymer in the composition is thermosetting, for instance when the polymer is an epoxy or a polyimide.
  • the present invention also concerns a method for the manufacture of the film according to the invention, said method comprising the following steps:
  • step (iv) drying the coating composition layer provided in step (iii) thereby providing the film.
  • the invention also provides electrical or electronic devices comprising the film according to the invention.
  • such devices are selected from the group consisting of capacitors, such as high voltage capacitors and pulse power capacitors, sensors and actuators.
  • the electrical or electronic devices according to the invention comprise at least:
  • the dielectric component consisting in a film according to the invention is disposed between the two electrodes and is bonded to the two electrodes, directly or by an adhesive layer.
  • the electrical or electronic device of the invention includes a set formed by the successive superposition of a substrate, one of the two electrodes, the dielectric component consisting in a film according to the invention and the other one of the two electrodes.
  • Devices including such a set are particularly suitable, as actuators or sensors.
  • the invention relates to the use of T1S2 particles in a composition or film comprising a polymer having a e' value corresponding to the real part of its relative permittivity measured at 23°C, IV and 1000 Hz, in the range from 1 to 50, for increasing the e' value of said composition or film, and preferably without increasing of more than 80% the dielectric losses measured at 23°C, IV and 1000 Hz.
  • the dielectric losses of said composition or film are increased from 10 to 60% only.
  • compositions, films, methods, devices, carriers and uses in accordance with the invention preferably exhibit one or more of the following features, or any combination of these features, or even all of the features below when they are not mutually exclusive:
  • the polymer is chosen among the list consisting in polycarbonates, polyethylenes, polypropylenes, epoxys, poly(methyl methacrylate)s, polyimides, silicones, styrene butadiene copolymers, polyethylene terephthalates (PET), polysulfones, polyphenylsulfides (PPS), polyamides, polyetherimides (PEI) and fluorinated polymers, such as vinylidene fluoride (co)polymers; the polymer is, preferably, a thermoplastic ; - very preferably, the polymer is a vinylidene fluoride (co)polymer comprising repeat units derived from vinylidene fluoride, in an amount of at least 50 mol.
  • the polymer is a vinylidene fluoride copolymer comprising repeat units derived from at least a floromonomer selected from the list consisting of vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, hexafluoroisobutylene, pentafluoropropene, fluoroalkyl vinyl ether, 3,3,3-trifluoropropene and perfluoromethylether ;
  • the polymer represents at least 40 wt. %, more preferably from 55 wt. % to 80 wt. %, preferentially from 65 to 80 wt. %, of the total weight of the composition ;
  • the T1S2 particles have a maximal size within the range from 2 nm to 10 pm, preferentially within the range from 1 pm to 10 pm ;
  • composition has e' value corresponding to the real part of its relative permittivity, measured at 23°C, IV and 1000 Hz, in the range from 2 to 150 ;
  • composition is free of any component other than the polymer and the T1S2 particles.
  • Figure 1 is a sectional view of a schematic representation of a film/electrodes assembly which can be included in the devices according to the invention. The thicknesses of the different elements are not respected.
  • Figure 2A is a sectional view of a schematic representation of elements of a transducer, one of the examples of the electrical and electronic devices according to the invention. The relative thicknesses of the different elements are not respected.
  • Figure 2B is a sectional view of a schematic representation of the transducer of Figure 2A, showing the bend obtained under an electrical field generated between the two electrodes.
  • Figure 2C is a sectional view of a schematic representation of an example of actuator according to the invention.
  • Figure 2D is a sectional view of a schematic representation of an example of sensor according to the invention.
  • the relative thicknesses of the different elements are not respected.
  • Figure 3 is a photography obtained by SEM of a film in a P(VDF-TrFE- CTFE) copolymer containing 24.2 wt.% of T1S2, according to the invention.
  • Figures 4 to 6 show respectively the evolution of the e' value
  • Figure 4 concerns films of P(VDF-TrFE-CTFE), Figure 5 films of PVDF-HFP, and Figure 6 films of polycarbonate (PC)), as a function of the frequency of the applied electrical field.
  • Figure 7 shows the e' value at 1000 Hz, of films of P(VDF-TrFE-CTFE) according to the invention modified with T1S2 particles, compared to films modified with another filler BaTiC>3, as a function of wt. % filler content.
  • Figures 8 and 9 show respectively the evolution of the dielectric losses of films of P(VDF-TrFE-CTFE) and PVDF-HFP, according to the invention, as a function of the frequency of the applied electrical field.
  • references to “a polymer” includes a single polymer, as well as two or more polymers; reference to “a VDF (co)polymer” includes a single VDF (co)polymer, as well as two or more VDF (co)polymers ; reference to “the disclosure” includes single or multiple aspects taught by the present disclosure. Aspects taught herein are encompassed by the term "invention”.
  • a polymer or "a VDF (co)polymer” includes single entities and combinations of two or more of such entities. Nevertheless, according to preferred embodiments, these terms designate a single entity.
  • Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub- ranges encompassed within that range as if each numerical value and sub ⁇ range is explicitly recited.
  • a temperature range of about 120°C to about 150°C should be interpreted to include not only the explicitly recited limits of about 120°C to about 150°C, but also to include sub-ranges, such as 125°C to 145°C, 130°C to 150°C, and so forth, as well as individual amounts, including fractional amounts, within the specified ranges, such as 122.2°C, 140.6°C, and 141.3°C, for example.
  • alkyl groups include saturated hydrocarbons having one or more carbon atoms, including straight-chain alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclic alkyl groups (or "cycloalkyl” or “alicyclic” or “carbocyclic” groups), such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, branched- chain alkyl groups, such as isopropyl, tert-butyl, sec-butyl, and isobutyl, and alkyl-substituted alkyl groups, such as alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups.
  • T1S2 particles are introduced, in a specific content, within a polymeric matrix.
  • particles is intended to mean a small piece of T1S2 of any form.
  • the particles can be spherical or non-spherical or in the form of platelets.
  • T1S2 particles are commercially available, for instance at Aldrich.
  • the particle size is not critical. Nevertheless, in general, the T1S2 particles which are present in the composition have a maximal size within the range from 2 nm to 10 pm, in particular within the range from 2 pm to 10 pm.
  • the maximal size of a particle means its highest dimension which can be measured, for instance by examining the composition by scanning electron microscopy (SEM).
  • the T1S2 particles have generally a lamellar structure (multi-layered particles), even if it is not excluded that the T1S2 particles may be totally exfoliated within the composition and so in a mono-layered structure. This will depend of the conditions used for the introduction of the T1S2 particles into the composition, and in particular if a high agitation is used.
  • compositions of the invention comprise a polymer.
  • This polymer forms the matrix of the composition.
  • This polymer is preferentially a thermoplastic polymer.
  • a thermoplastic polymer softens when heated, and solidifies upon cooling, its ability of physical changes being reversible.
  • the polymer of the composition is dielectric. Any polymer, and in particular, any thermoplastic polymer, having a e' value corresponding to the real part of the relative permittivity measured at 23°C, IV and 1000 Hz, in the range from 1 to 50, is suitable. The definition of the e' value corresponding to the real part of the relative permittivity and a reference method for its determination are given in the examples.
  • suitable dielectric polymers examples include silicones, styrene butadiene copolymers, epoxys, polyimides, poly(methyl methacrylate)s, polycarbonates, polyethylenes, polypropylenes, polysulfones, polyethylene terephthalates (PET), polyphenylsulfides (PPS), polyamides, polyetherimides (PEI) and fluorinated polymers, such as vinylidene fluoride (co)polymers. Mixtures of these polymers can be used in the compositions of the invention.
  • the polymer is preferably a thermoplastic, such as the poly(methyl methacrylate)s, polycarbonates, polyethylenes, polypropylenes, polysulfones, polyethylene terephthalates (PET), polyphenylsulfides (PPS), polyamides, polyetherimides (PEI) and fluorinated polymers, such as vinylidene fluoride (co)polymers.
  • a thermoplastic such as the poly(methyl methacrylate)s, polycarbonates, polyethylenes, polypropylenes, polysulfones, polyethylene terephthalates (PET), polyphenylsulfides (PPS), polyamides, polyetherimides (PEI) and fluorinated polymers, such as vinylidene fluoride (co)polymers.
  • fluorinated polymer a polymer comprising repeat units derived from at least one fluorinated monomer.
  • fluorinated monomer is meant, in particular, ethylenically unsaturated monomer comprising at least one fluorine atom.
  • the polymer is a vinylidene fluoride (VDF) (co)polymer which provides advantageously high chemical resistance.
  • VDF vinylidene fluoride
  • a vinylidene fluoride (VDF) (co)polymer is also referred as polymer F or
  • VDF (co)polymer means a polymer based on vinylidene fluoride.
  • the VDF (co)polymer referred as polymer F, may be a homopolymer, i.e. a polyvinylidenefluoride (PVDF) or a copolymer of vinylidene fluoride with at least another recurring monomeric unit.
  • PVDF polyvinylidenefluoride
  • a copolymer includes vinylidene fluoride and two another recurring monomeric units, it is a terpolymer.
  • recurring unit "repeat unit” and
  • a copolymer comprises recurring units derived from vinylidene fluoride (VDF) and recurring units derived from at least another monomer or that a copolymer is a copolymer of vinylidene fluoride and at least another monomer, that means the polymer is obtained by copolymerisation of the corresponding monomers.
  • VDF vinylidene fluoride
  • Vinylidene fluoride copolymers comprise preferably at least 50 % by moles, very often at least 60 % by moles, more preferably at least 75 % by moles, in some embodiments at least 85 % by moles and possibly at least 95 % by moles, of repeat units derived from vinylidene fluoride, based on the total number of moles of recurring units which are present in the copolymer.
  • the other recurring unit may correspond to another fluoromonomer, in particular chosen among hexafluoropropylene (HFP), trifluoroethylene (TrFE), vinyl fluoride, tetrafluoroethylene, fluoroalkyl vinyl ether (such as fluoromethylvinylether), chlorotrifluoroethylene (CTFE), pentafluoropropene, hexafluoroisobutylene, 3,3,3-trifluoropropene, perfluoromethylether.
  • fluoromonomer(s) represent at most 15 mol.
  • recurring units corresponding to another fluoromonomer may represent at most 35 mol. % of the total number of moles of recurring units which are present in the copolymer.
  • suitable recurring monomeric unit are hydrophilic (meth)acrylic monomers, such as hydroxyethylacrylate FIEA, 2-hydroxypropyl acrylate FI PA, acrylic acid FIA.
  • the repeat units derived from the (meth)acrylic monomer represent at most 15 mol. %, preferably at least 10 mol. %, of the total number of moles of recurring units which are present in the copolymer.
  • the copolymer of vinylidene fluoride may comprise one or several, for instance one or two, recurring monomeric units chosen in the above mentioned list, in addition to the vinylidene fluoride recurring unit.
  • VDF-HFP copolymers VDF-TrFE copolymers
  • VDF-TrFE-CTFE terpolymers VDF-TrFE-CTFE terpolymers
  • VDF copolymers are commercially available, for instance under the references Solef® PVDF, in particular Solef® 21510, or Solvene® 200, Solvene® 250 and Solvene® 300 P(VDF-TrFE) copolymers, or
  • Solvene® T P(VDF-TrFE-CTFE) sold by SOLVAY sold by SOLVAY.
  • Polymers suitable as polymer F are also described in the applications WO 2019/073012, WO 2008/129041 and WO 2009/147030, which are incorporated herein by reference.
  • the polymer F is advantageously a linear polymer comprising linear sequences of recurring units derived from vinylidene fluoride (VDF) and at least one other monomer, in particular hexafluoropropylene (HFP).
  • VDF vinylidene fluoride
  • HFP hexafluoropropylene
  • the polymer F is advantageously a random copolymer comprising linear sequences of randomly distributed recurring units derived from vinylidene fluoride (VDF) and at least another monomer, in particular hexafluoropropylene (FIFP).
  • VDF vinylidene fluoride
  • FIFP hexafluoropropylene
  • the vinylidene fluoride (VDF) represents at least 75 mol. % (molar % that represents the number of moles of vinylidene fluoride units in %, with respect to the total number of moles of monomeric units in the copolymer), advantageously at least 80 mol. %, and preferably at least 84 mol. %, of the total number of moles of recurring units which are present in the copolymer.
  • the polymer F is a copolymer comprising at least 75 mol.
  • mol. % preferentially from 80 to 95 mol. %, and more preferentially from 84 to 92 mol. %, of recurring units derived from VDF and, up to 25 mol. %, preferentially from 5 to 20 mol. %, and more preferentially from 8 to 16 mol. %, of recurring units derived from at least one other suitable fluorinated monomer, e.g. hexafluoropropylene, chlorotrifluoroethylene, trifluoroethylene, and the like. These mol. % are given with respect to the total number of moles of recurring units which are present in the copolymer.
  • Copolymers of VDF and HFP and copolymers of VDF, CTFE and TrFE are preferred, and advantageously those with the above-mentioned mol. %, in particular those which do not include any monomer other than vinylidene fluoride (VDF) and hexafluoropropylene (HFP) or VDF, TrFE and CTFE, respectively.
  • Copolymers of HFP and VDF presents increased flexibility over PVDF homopolymer grades. Good results were obtained using, as the polymer, a VDF-FIFP copolymer referenced as Solef® or a VDF-TrFE-CTFE copolymer referenced as Solvene® T provided by SOLVAY.
  • compositions and method of preparation can be provided in the form of a liquid form, or, when the polymer is thermoplastic, in the form of a powder or pellets, or directly in the form of a film or sheet, or of a tubular- constructed product, depending of their final use.
  • the T1S2 particles are distributed within a matrix formed by at least one polymer, as defined in the invention.
  • the mixture of the polymer and T1S2 particles may be obtained according to any suitable method.
  • the maximal size of T1S2 particles which are mixed with the polymer is generally within the range from 2 nm to 10 pm, in particular within the range from 2 pm to 10 pm.
  • the T1S2 particles can be introduced directly in the melted polymer.
  • the T1S2 particles may be introduced in a solution of the polymer dissolved in a solvent chosen for being a good solvent of the polymer.
  • the T1S2 particles may be introduced in the form of a dispersion in a solvent, in order to promote its dispersion into the polymer.
  • An ultrasonic treatment can be applied to such a dispersion, in order to deagglomerate the T1S2 particles, before their mixing with the polymer.
  • Such a dispersion of T1S2 particles can be introduced in a solution of the polymer or the polymer or a solution of the polymer may be directly introduced in the dispersion of T1S2 particles.
  • the solvent is eliminated, for example by simple evaporation, with or without heating. Examples of suitable solvents are given in the following part "Film and its method of manufacture".
  • the mixing of the components is generally carried out under agitation, for obtaining a good repartition.
  • a heating can be used.
  • the temperature of heating will depend on the polymer.
  • the conditions of mixing will be adapted by the man skilled in the art, considering the nature of polymer and the quantity of the constituents of the composition and in which form the composition is desired.
  • the composition comprises 20 to 45 wt. %, preferably from 20 wt. % to 35 wt. %, of T1S2 particles, based on the total weight of the composition.
  • This wt. % can be determined directly in the composition or in the film formed with such a composition, for instance by inductively coupled plasma optical emission spectrometry (ICP-OES) method.
  • ICP-AES Inductively coupled plasma atomic emission spectroscopy
  • ICP-OES inductively coupled plasma optical emission spectrometry
  • T1S2 particles which is present in the composition of the invention leads to an increase of the e' value corresponding to the real part of the relative permittivity of said composition of at least 100 %. According to the invention, the increase of the e' value corresponding to the real part of the relative permittivity of the composition is appreciated by comparison with the same composition which differs by the absence of T1S2 particles.
  • the composition comprises at least 40 wt. % of the polymer, preferably at least 50 wt. % of the polymer, based on the total weight of the composition.
  • An additive can be present in the composition in addition to the polymer and the T1S2 particles. When an additive is present in the composition of the invention, it preferably represents less than 40 wt. %, preferentially less than 5 wt. %, of the total weight of the composition.
  • the composition comprises from 55 wt. % to 80 wt. %, preferably from 65 wt. % to 80 wt. %, of the polymer based on the total weight of the composition, especially, when the composition does not comprise other compounds than the polymer and the T1S2 particles.
  • the addition of the wt. % of the polymer and the T1S2 particles is equal to 100 %.
  • compositions of the invention comprise:
  • TrFE and CTFE a copolymer of VDF, TrFE and CTFE, especially in which TrFE and CTFE represent at most 35 mol. % of the total number of moles of recurring units which are present in the copolymer, and in particular a copolymer of VDF, TrFE and CTFE which does not include any monomer other than VDF, TrFE and CTFE; or - a copolymer of VDF and HFP, especially in which HFP represents at most 15 mol.
  • the composition comprises a wt. % of said thermoplastic polymer equal or higher than 40 wt. %, more preferably from 55 wt. % to 80 wt. %, preferentially from 65 to 80 wt. %, based on the total weight of the composition.
  • the compositions according to the invention may also comprise an additive, in particular chosen among organic filler particles and inorganic filler particles, other than T1S2.
  • suitable filler particles that can be used as an additive may be chosen among the group consisting of metal particles, intrinsically conducting polymer particles, semi-conductive material particles, metal oxide particles and magnetic material particles.
  • the quantity of additive(s), in particular, when a conductive additive is present in the composition, will be adjusted for keeping the dielectric character of the composition.
  • the conductive additive(s), when present, is (are) in a limited quantity so as to maintain the e' value (corresponding to the real part of the relative permittivity of the composition, measured at 23°C, IV and 1000 Hz), below or equal to 150.
  • Filler particles can be selected among the group consisting of metal conductive metal filler particles, like copper, silver, gold, and zinc.
  • the conductive metal filler is silver or copper and more preferably is silver.
  • Conductive polymer particles are essentially composed or even composed of intrinsically conducting polymers (ICPs). They are organic polymers composed of macromolecules having fully conjugated sequences of double bonds along the chains. Such compounds may have metallic conductivity or can be semiconductors. Examples of intrinsically conducting polymers are polyacetylene, polythiophene, polypyrrole, or polyaniline. Among ICPs, polythiophene and polyaniline are preferably used.
  • ICPs intrinsically conducting polymers
  • Poly(3,4-ethylenedioxythiophene) or PEDOT and, in particular PEDOT-PSS, a polymer blend of poly(3,4-ethylenedioxythiophene) and polystyrene sulfonate) are used more preferably.
  • Semi-conductive fillers are essentially composed of, or composed of, a semi-conductive material.
  • the semi -conductive core comprises generally at least 95 wt. % of a semi -conductive material, preferably at least 97 wt. % and more preferably at least 99 wt. %.
  • the semi -conductive material is selected from the list consisting of Silicon (Si), Silicon-germanium (SiGe), Gallium arsenide (GaAs), Indium phosphide (InP), Gallium nitride (GaN), Silicon carbide (SiC), Zinc sulfide (ZnS), Zinc selenide (ZnSe), Cadmium selenide CdSe, and Cadmium sulfide (CdS), Barium titanate (BaTiOs), strontium titanate (SrTiC>3), barium lead titanate (Ba x Pbi- x TiC>3), barium strontium titanate (Ba x Sri- x TiC>3, barium neodymium titanate Ba6-3xNd8 + 2xTiis054 , aluminum trioxide (AI2O3), Calcium titanate (CaTi03), Strontium zirconium titanate (SrZr y Tiii
  • suitable filler particles are magnetic or ferromagnetic particles typically containing a magnetic or ferromagnetic metal or metal oxide or alloy thereof, such as magnetite (Fe3C>4), Cobalt (Co), Iron (Fe), Gadolinium (Gd), Dysporsium (Dy), Iron nickel alloy or permalloy (Fe x Nii_ x ), Awaruite (NbFe).
  • carbonaceous filler particles Another group of semiconductive or conductive filler particles that can be used are carbonaceous filler particles.
  • the term "carbonaceous filler” denotes fillers comprising more than at least 50 wt. % of elemental carbon, preferably at last 75 wt. % of elemental carbon, more preferably at least 90 wt. % of elemental carbon.
  • Especially preferred carbonaceous fillers comprise 99 wt. % or more of elemental carbon or consist of elemental carbon.
  • carbonaceous fillers are selected from carbon nanotubes, carbon nanohorns, graphite, graphene and carbon black. Particularly preferred for economical reasons is black carbon.
  • Suitable carbonaceous fillers are available from a variety of sources and suppliers and the skilled person will, based on his professional knowledge and the specific application case, select a suitable material for use in the composition of the present invention. Film and its method of manufacture
  • the present invention also concerns the films obtainable from the composition according to the invention.
  • These films comprise, preferably consist of, the composition according to the invention, in particular when the polymer is thermoplastic.
  • the film is preferably obtained after crosslinking the polymer.
  • film designates a flat piece of material having a thickness smaller than either its length or its width, generally than its length and its width.
  • the thickness of the film is chosen considering the required properties linked to its use, in particular its dielectric properties.
  • the film according to the present invention has a thickness of 1 to 2000 pm
  • the thickness may be measured using a digital micrometer onto the film.
  • the value can be the average value of at least ten different measurements made along the film and distanced of at least 1 cm.
  • the film may be manufactured by a method commonly used in the art, to which the invention belongs, except for using the composition of the invention.
  • the film may be manufactured by casting or melt molding a composition of the invention, for instance by using a hot press at a temperature which will be chosen in function of the melting point of the polymer.
  • the method of manufacturing the film is not limited thereto.
  • the invention relates to a method for the manufacture of a film, with the composition of the invention. As is known in the art, such a method may comprise the following steps:
  • step (iii) applying the composition in a liquid form CL provided in step (ii) onto at least one surface of the carrier provided in step (i), thereby providing a coating composition layer, and
  • step (iv) drying the coating composition layer provided in step (iii) thereby providing the film.
  • the method for the manufacture of the film may also comprise, after step (iv), a step (v) of annealing the film provided in step (iv) through the use of a thermal treatment.
  • the carrier may be a rigid or flexible carrier.
  • the carrier may be a support that is patterned or non- patterned.
  • a carrier according to the invention may be made of glass, quartz, ceramic, silicon, carbon, graphene, polymer or paper. It may notably be a membrane, a film, a wafer, in particular a composite wafer, a plate, a textile, a rubber sheet, or a semiconductor.
  • the surface of the carrier on which the film is formed is generally smooth.
  • the film is recovered by dipping the carrier into a water bath after step (iv) or (v), if an annealing step is implemented.
  • composition in a liquid form designates a composition in the liquid state, in particular at ambient temperature (23 °C) under atmospheric pressure (1013.25 hPa).
  • This composition is not totally liquid, as the T1S2 are only dispersed in the composition CL.
  • the composition CL typically comprises at least one organic solvent - solvent S - in which the polymer and the T1S2 particles are respectively dissolved and dispersed.
  • This composition in a liquid form may undergo a thermoreversible gelation at ambient temperature and under atmospheric pressure, thus becoming an elastic solid. This process is reversible by heating the elastic solid at a temperature higher than 40°C in order to recover a liquid state, before its application on the carrier.
  • Non-limitative examples of suitable solvent S include, notably, those capable of dissolving the polymer and dispersing the T1S2 particles.
  • the solvent S is, preferably, chosen among the polar aprotic solvents.
  • a polar aprotic solvent is a solvent with high dielectric constant and a sizable permanent dipole moment that cannot donate suitably labile hydrogen atoms to form strong hydrogen bonds.
  • Polar aprotic solvents suitable for the method according to the invention are solvents having a dielectric constant measured at 20°C generally over 5.
  • the dielectric constant of the polar aprotic solvent is preferably more than 10, more preferably more than 12 and even more preferably more than 15.
  • the dielectric constant of solvents can be determined using for example BI- 870 Dielectric Constant Meter available from Brookhaven Instruments Corporation, following the recommendations of the provider.
  • Suitable polar aprotic solvents are solvents having a dipole moment generally over 0.5 Debye, preferably more than 1.0 Debye, more preferably more than 1.5 Debye and even more preferably more than 2.0 Debye.
  • Suitable polar aprotic solvents are solvents having a normal boiling point preferably below 200°C, more preferably below 150°C and even more preferably below 100°C. Suitable polar aprotic solvents have a boiling point generally above
  • Normal boiling point is measured at atmospheric pressure by any method well known by the skilled person.
  • the solvent S suitable for implementing the method of manufacture according to the invention is generally chosen in the list consisting of ketones such as acetone, methylethylketone, diethyl ketone, cyclopentanone, cyclohexanone ; ethers such as 2-methyltetrahydrofuran and tetrahydrofuran (THF) ; esters such as ethylacetate and cyclohexyl acetate ; amides such as N,N-dimethylacetamide and dimethylformamide ; nitriles such as acetonitrile; sulfoxides such as dimethyl sulfoxide ; carbonates such as dimethylcarbonate, diethylcarbonate, dipropoylcarbonate, dibutylcarbonate, ethyl methy lea rbonate, ethylene carbonate, propylene carbonate, vinylene carbonate ; and mixtures thereof.
  • ketones such as acetone, methylethyl
  • Methylethyl ketone may be preferred, as solvent S.
  • solvent S may be a fluorinated polymer, such as vinylidene fluoride (co)polymers.
  • the composition CL contains a wt. % of the polymer (based on the total weight of the composition CL) from 10 to 30 wt. %.
  • step (iii) of the method of the invention the composition CL is applied onto at least one surface of the carrier provided in step (i), typically by using a processing technique selected from the group consisting of casting, spray coating, roll coating, doctor blading, slot die coating, gravure coating, ink jet printing, spin coating, screen printing, brush, squeegee, foam applicator, curtain coating and vacuum coating.
  • the coating composition layer provided in step (iii) is dried, typically at a temperature from 10°C to 100°C, preferably at a temperature in the range from 15°C to 40°C and advantageously at room temperature (23°C).
  • this drying may be completed or replaced by a heating treatment at a temperature closed to or higher than the boiling temperature of the solvent S but below the melting temperature of the polymer.
  • This heating treatment may be carried out under reduced pressure, typically at a reduced pressure from 10 to 1.10 4 Pa, preferably at a pressure from 100 to 1000 Pa.
  • the film provided in step (iv) may be annealed typically at a temperature from 60°C to 120°C, preferably at a temperature in the range from 80 to 100°C, under reduced pressure, typically at a reduced pressure from 10 to 1.10 4 Pa, preferably at a pressure from 100 to 1000 Pa.
  • a heating at a suitable temperature for obtaining the crosslinking of the polymer is used in step (iv) and/or in step (v), if such a step is present.
  • the invention proposes to use T1S2 particles in a composition or film comprising a polymer, for increasing the e' value of said composition or film.
  • the e' value (corresponding to the real part of the relative permittivity) of the unmodified polymer is in the range from 1 to 50, when measured at 23°C, IV and 1000 Hz.
  • the T1S2 particles are introduced within the composition.
  • the increase of the e' value of said composition is appreciated by comparison with the same composition which differs by the absence of T1S2 particles.
  • An increase of at least 100 % is preferentially obtained. So, according to the invention, a composition or film including T1S2 particles and having a e' value measured at 23°C, IV and 1000 Hz in the range from 2 to 150, and preferentially in the range from 10 to 150, is obtained.
  • the content of used T1S2 particles is from 20 to 45 wt. %, preferably from 20 wt. % to 35 wt. %, of the total weight of the composition.
  • the T1S2 particles are used in said composition or film for increasing the e' value of said composition or film, but without increasing of more than 80% the dielectric losses measured at 23°C, IV and 1000 Hz.
  • all the characteristics of the composition, of the T1S2 particles and of the polymer, and in particular of the VDF (co)polymer, which are specifically described or preferred in the previous disclosure are preferentially used.
  • compositions and films of the invention in an electrical or electronic device.
  • the present invention provides an electrical or electronic device including a composition, in particular in the form of a film, according to the invention.
  • a device may be:
  • a capacitor comprising a film according to the invention ; in particular a high voltage capacitor or a pulse power capacitor ;
  • the film of the invention is present in combination with two electrodes and acts as a dielectric layer.
  • the film according to the invention is generally placed between the two electrodes.
  • the electrodes are disposed on the opposite sides of the film.
  • each electrode located on a side of the film according to the invention exhibits at least one overlapping portion with the other electrode located on the other side of the film.
  • the electrodes can recover only a part of the surface of the film or the totallity of the surface of the film.
  • the electrodes are made of a material commonly used in the art, in the manufacture of capacitors, actuators or sensors.
  • the two electrodes may be composed of the same material or of different materials.
  • the electrodes may be made of or include an electrically conductive material chosen among the conductive metals, conductive metal oxides, carbon compounds, conductive polymers or the like, and they are preferably made of or include one or more materials selected from the group consisting of gold (Au), silver (Ag), aluminum (Al), platinum (Pt), nickel (Ni), palladium (Pd), copper (Cu), molybdenum (Mo), titanium (Ti), chromium (Cr), tungsten (W), Al-Cu alloy, ITO (Indium Tin Oxide), carbon (C), carbon based materials like carbon nanotube, carbon nanohorns, graphite, graphene, carbon black, conductive polymers like PEDOT (poly-3, 4-ethylenedioxythiophene), PEDOT-PSS (poly-3, 4- ethylened
  • An electrode may comprise an electrically conductive agent, preferably based on carbon, dispersed in a polymer or an electrically conductive polymer.
  • the electrically conductive agent may, for example, be carbon nanotubes, carbon black, carbide derived carbon, activated carbon nanofibers or vapor grown carbon fibers.
  • the preparation of such electrodes is, for example, described in US 7,315,106, the content of which is incorporated herein by reference. More generally, the electrodes may be formed by a method commonly used in the art. In particular, the electrodes are disposed and attached on both surfaces of the film according to the invention by various methods. In particular, the two electrodes are, each, directly deposited on the opposite sides of the film according to the invention.
  • the electrodes may be deposited on both sides of the film by a method such as sputtering, printing or slit coating.
  • a conductive metal layer or a conductive metal oxide layer may be formed on each side of the film according to the invention, for instance by a sputtering method, for forming the electrode.
  • the two electrodes may be disposed at the same time, particularly when they are composed of the same material.
  • the electrodes in the devices according to the present invention usually have an average thickness not exceeding 100 pm, and in general in the range from 2 to 100 pm, and preferentially not exceeding 50 pm, and more preferentially not exceeding 10 pm.
  • the thickness of the electrodes depends on the thickness of the film according to the invention.
  • the shape and size of the film of the invention can vary considerably and will generally depend on the application for which the invention is used. For example, it may be employed in a variety of applications, including without limitation, grippers, three-dimensional membrane actuators, composite wing-flaps, robotic swimming structures, robotic fish, resonant flying machines, surgical tools, valves, pumps, micropumps, microelectromechanical systems, electromechanical relay switches, artificial smooth muscle actuators, artificial sphincter and ocular muscles, artificial ventricular or cardiac arrest muscles, optical units, imaging apparatus, continuous variable aperture mirrors and antenna dishes, linear actuators, haptic devices to get a touch feedback for example in Braille Displays or virtual reality equipments, slithering devices, soft part orientators, incontinence assist devices, displacement sensor devices, pressure transducers for joints, and blood pressure, pulse rate and rhythm measurement devices.
  • the film of the invention acts as a dielectric component and, according to common practice, can simply be disposed and sandwiched between two conductive plates positioned parallel to each other and acting as electrodes, and presented on Figure 1, under references 21 and 22.
  • a first electrode 21 and a second electrode 22 are directly bonded to both surfaces of the film 20 according to the invention.
  • the bonding of the two electrodes on each side of the film according to the invention may be obtained by an adhesive layer.
  • This kind of device architecture including a superposition electrode/film/electrode is detailed hereafter, for transducers.
  • a transducer is a device that converts electrical energy into mechanical energy or mechanical energy into electrical energy. If the transducer converts electrical into mechanical energy, it acts as an actuator. If the transducer converts mechanical into electrical energy, it acts as a sensor.
  • the electrical device according to the invention can be a transducer, and so a sensor or an actuator.
  • the transducers of the invention use the bending behavior of the film according to the invention, as dielectric component, placed between two electrodes.
  • this kind of film/electrodes assembly is subjected to an applied electrical field (which corresponds to the actuator working)
  • attraction between the two electrodes due to Maxwell stress leads to a contraction of the film in the direction of the electrical field and an elongation in the direction perpendicular to the electrical field.
  • Various movements can be obtained thanks to this basic element.
  • the film of the invention carrying an electrode on both sides is associated to a substrate.
  • This stack composed by the superposition of the substrate 23, the electrode 21, the film 20 and the electrode 22, which are linked to each other, forms a unitary set.
  • a substrate is bonded to one of the electrodes as illustrated on Figure 2A.
  • a film 20 according to the invention is disposed between two electrodes 21 and 22.
  • One of the electrodes 21 is bonded to a substrate 23.
  • the electrode 21 and the substrate 23 are directly attached but they can be indirectly bonded, for instance by an adhesive layer.
  • Such a substrate 23 may be made of or include a polymer, and in particular a thermoplastic polymer, for example selected among polyethylene terephthalate (PET), the polycarbonates, polyethylenes, polypropylenes, epoxys, poly(methyl methacrylate)s, polyimides, silicones, styrene butadiene copolymers, polysulfones, polyphenylsulfides (PPS), polyamides, polyetherimides (PEI) and fluorinated polymers.
  • PET polyethylene terephthalate
  • PPS polyphenylsulfides
  • PPS polyamides
  • PEI polyetherimides
  • fluorinated polymers for example selected among polyethylene terephthalate (PET), the polycarbonates, polyethylenes, polypropylenes, epoxys, poly(methyl methacrylate)s, polyimides, silicones, styrene butadiene copolymers, polysulfones, polyphenylsulf
  • the substrate may have an average thickness not exceeding 100 pm, and in general in the range from 2 to 100 pm, and preferentially not exceeding 50 pm, and more preferentially not exceeding 10 pm.
  • the thickness of the substrate will be adjusted considering the thicknesses of the film according to the invention and of the electrodes.
  • the subtrate 23 can recover only a part of the surface of the electrode 21 on which it is disposed or, more generally, the totallity of the surface of the electrode 21.
  • an actuator of the present invention comprises a voltage generator which forms with the two electrodes, an electric field generator for applying an electric field to the opposite sides of the film of the invention and to cause said film to deform and flex.
  • the first electrode 21 and the second electrode 22 form an electric field when a voltage is applied from the outside.
  • the two electrodes 21 and 22 are connected to a voltage generator (not illustrated) which generates an electric voltage across the thickness of the film 20.
  • Voltages having varying strengths or voltages having opposite electrical properties may be applied to the first electrode 21 and the second electrode 22, respectively, in order to form an electric field between the two electrodes.
  • the voltage applied to the electrodes may be an alternating current voltage or a direct current voltage. When an alternating current voltage is applied, the stack and so the film 20 is periodically displaced, whereas when a direct current voltage is applied, the film 20 can be maintained in a bent stage.
  • the film flexes and creates a strain D as illustrated on Figure 2B.
  • This strain D can, for example, be measured using a suitable device (not represented), like a laser vibrometer or a camera.
  • the generalized configuration illustrated on Figure 2A functions as a sensor
  • a force like a pressure
  • This force leads to the flexing of the stack and so of the film 20.
  • the two electrodes 21 and 22 are connected to a voltage generator, when the applied voltage is constant, the dielectric film 20 is characterized by a given capacitance. The bending caused by the applied force generates a change of the capacitance in the film 20 that can be detected or measured.
  • the sensor of the present invention may include a suitable electrical circuit, not illustrated, connected to the electrodes 21 and 22.
  • This electrical circuit will include a suitable device for measuring the capacitance or detecting the change of capacitance generated between the two electrodes 21 and 22 or a corresponding generated excitation signal.
  • the change of capacitance is proportional to the applied force, for instance to the applied pressure.
  • Figure 2C illustrates another embodiment of an actuator according to the invention.
  • the transducer includes a stack formed by the superposition of a substrate 33, an electrode 31, a film 30 and an electrode 32. They are all bonded to each other.
  • the substrate 33 is not directly bonded on the electrode 31, but by the intermediary of an adhesive layer 34 which does not change the monomorph character of the stack.
  • Figure 2C illustrates an embodiment in which the bending corresponds to a concave flexing of the stack.
  • the electrodes 31 and 32 are connected to an electrical circuit, which includes a voltage generator 35.
  • the actuator also includes a device for measuring the displacement or the flexion of the film (not represented on the figure) caused by the applied voltage on the electrodes.
  • the illustrated transducer works as a sensor: it also includes a stack formed by the superposition of a substrate 33, an electrode 31, a film 30 and an electrode 32 and a voltage generator 35 connected to the electrodes 31 and 32 by an electrical circuit. It includes a device (not represented) for applying a force (for instance a pressure) on the film 30, or more generally on the stack formed by the substrate 33, the electrode 31, the film 30 and the electrode 32. It also comprises a suitable device 36 for measuring the capacitance or detecting the change of capacitance between the two electrodes 31 and 32. The device 36 is connected by an electrical circuit to the electrodes 31 and 32.
  • the voltage generator 35 delivers a constant voltage and the change of capacitance is proportional to the applied force. When the force is a pressure, such sensors are called pressure capacitive sensors.
  • T1S2 were obtained from Sigma-Aldrich and used as received. Their median size given by Aldrich is 50 pm. Analysis by Scanning Electron Microscopy (SEM) confirmed their 2D platelet structure.
  • VDF vinylidenefluoride
  • HFP hexafluoropropylene copolymer
  • Solef® 21510, SOLVAY commercially available
  • the copolymer of vinylidenefluoride (VDF), trifluoroethylene (TrFE) and chlorotrifluoroethylene (CTFE) copolymer comprising 28.3 mol. % of TrFE and 5.1 mol. % of CTFE, was commercially available (Solvene® T 445/32, SOLVAY).
  • the polycarbonate (PC) was commercially available and was obtained from LG chemicals (ref: PC Lupoy 1300).
  • the solvent methylethyl ketone or MEK
  • MEK methylethyl ketone
  • a dispersion of the required quantity of particles of T1S2 (required quantity for 3g of the selected polymer) in 20g of MEK was prepared and placed in a glass bottle. The bottle was then placed in a crystallizer filled with dry ice and maintained under N2. An ultrasonic treatment at 50 watts was carried out for 30 minutes, three times, making sure the temperature did not exceed 0°C. After, 3g of the selected polymer were added under agitation and heating at 60°C and the MEK was partially evaporated at 60°C, in order to obtained in the final liquid composition a content of polymer representing 25 wt. % and 20 wt. % for Solvene® T and Solef®, respectively.
  • Elcometer 4340 Motorised film applicator.
  • a glass plate previously cleaned was positioned on the 4340 automatic table from Elcometer and cleaned with acetone.
  • the adjustable applicator was also cleaned with acetone, as well as the knife setting corresponding to the chosen thickness (knife of 500pm for a final film around 50pm under these conditions).
  • the applicator was positioned on the glass plate, against the mobile cart of the Elcometer table.
  • the solution to cast was then placed as close as possible to the applicator and the carrier of the Elcometer table movement was triggered (at speed 2) at room temperature (23°C).
  • the recovered glass plate was then put in an oven at 70°C under reduced pressure for 2 hours. Once dry and cooled, the film was removed from the substrate by dipping the glass plate in demineralized water. It was then stored between two sheets of paper. Size of the TiS? particles
  • the size of the T1S2 particles into the film can be checked by scanning electron microscopy (SEM).
  • SEM scanning electron microscopy
  • the Figure 3 shows a photography obtained by SEM of the film prepared with the copolymer (P(VDF-TrFE-CTFE) and containing 24.2 wt.% of T1S2.
  • the particles of T1S2 appear in white: their maximal size can be measured and is inferior to 10 pm, which is lower than the median size announced by Aldrich. This reduction is due to the ultrasonic treatment of the particles, before their introduction into the polymer, which leads to the fragmentation of the particles or agglomerates. Dielectric spectroscopy
  • the dielectric spectroscopy on the different obtained films was used to determine the relative permittivity (also referred as dielectric constant) and the dielectric losses of the obtained films.
  • the relative permittivity e is the ratio of the capacitance of a capacitor using that material as a dielectric, on the capacitance of a similar capacitor that has vacuum as its dielectric, expressed as
  • Capacitance eheO.A / D wherein er is relative permittivity of the material, eq is void permittivity, A is electrode area (in m 2 ) and D is the distance between electrodes (in m), for a plane capacitor.
  • the tests were carried out at room temperature (23°C). A first side of the film was completely metallized with gold using the sputtering coater Q150R S available from Quorum.
  • the metallization was performed with the same apparatus on a central disk of 20 mm diameter in order to preserve an insulating ring. It ensures the insulation between the 2 sides of the film.
  • the metallization was made during twice 60 seconds, on each face with a current of 60 mA.
  • the dielectric spectroscopy (Modulab XM MTS equipment from Solartron analytical at a voltage of 1 V from 1 Hz to 1 MHz through 10 measures by decades, at room temperature (23°C)) was performed on the obtained thin film sandwiched between two stainless steel electrodes of 20 mm in diameter deposited by a sputtering method, on both sides of the studied thin film.
  • Figures 4, 5 and 6 also present the e' value for the films made with P(VDF-TrFE-CTFE), PVDF-HFP and PC, respectively, as a function of frequency.
  • FIGS 8 and 9 show the tan6 for the films made with P(VDF-TrFE- CTFE) and PVDF-HFP, respectively, as a function of frequency. It appears that the addition of a quantity of T1S2, even above 20 wt. % does not greatly affect dielectric losses. In conclusion, by introducing T1S2 particles at a content of 20 wt. % or higher, in the different tested polymeric matrices, the e' value was greatly increased. For P(VDF-TrFE-CTFE) and PVDF-HFP, the dielectric losses were similar, with respect to the polymer alone. The mechanical properties of modified P(VDF-TrFE-CTFE) films were also tested and were improved.

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Abstract

L'invention concerne une composition comprenant : - un polymère ayant une valeur ε' correspondant à la partie réelle de sa permittivité relative, mesurée à 23 °C, 1 V et 1 000 Hz, dans la plage de 1 à 50 et - des particules de TiS2, la teneur en particules de TiS2 représentant de 20 à 45 % en poids du poids total de la composition. Un film composé de cette composition ou comprenant cette composition, son procédé de fabrication et des dispositifs électriques ou électroniques comprenant un tel film sont d'autres aspects de l'invention.
PCT/EP2020/080521 2019-10-30 2020-10-30 Compositions et films comprenant un polymère et des particules de tis2, leur préparation et leurs utilisations Ceased WO2021084074A1 (fr)

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WO2023238043A1 (fr) * 2022-06-08 2023-12-14 Poweron Limited Capteur souple

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Cited By (2)

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WO2023238043A1 (fr) * 2022-06-08 2023-12-14 Poweron Limited Capteur souple
CN115101661A (zh) * 2022-06-15 2022-09-23 电子科技大学 一种压电薄膜及其制备方法

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