EP1423559B1 - Procede de reformage de fibres composites et applications - Google Patents

Procede de reformage de fibres composites et applications Download PDF

Info

Publication number
EP1423559B1
EP1423559B1 EP02772485A EP02772485A EP1423559B1 EP 1423559 B1 EP1423559 B1 EP 1423559B1 EP 02772485 A EP02772485 A EP 02772485A EP 02772485 A EP02772485 A EP 02772485A EP 1423559 B1 EP1423559 B1 EP 1423559B1
Authority
EP
European Patent Office
Prior art keywords
polymer
process according
fibre
solvent
fiber
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
EP02772485A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1423559A1 (fr
Inventor
Philippe Poulin
Brigitte Vigolo
Pascale Launois
Patrick Bernier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Original Assignee
Centre National de la Recherche Scientifique CNRS
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 Centre National de la Recherche Scientifique CNRS filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP1423559A1 publication Critical patent/EP1423559A1/fr
Application granted granted Critical
Publication of EP1423559B1 publication Critical patent/EP1423559B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • 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
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/14—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2922—Nonlinear [e.g., crimped, coiled, etc.]
    • Y10T428/2924—Composite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
    • Y10T428/2931—Fibers or filaments nonconcentric [e.g., side-by-side or eccentric, etc.]

Definitions

  • the present invention generally relates to the after-treatment of composite fibers and in particular to a novel process for reforming composite fibers comprising colloidal particles and at least one binder and / or bridging polymer, the use of the process and the fibers reformed obtained by said process.
  • colloidal particles is intended to mean particles defined according to IUPAC international standards as being particles whose size is between a few nanometers and a few micrometers.
  • the entanglement can be modified by more or less twisting the fiber and, as in the case of conventional polymeric fibers, the orientation of the particles must be able to be modified by pulling on the fiber, which can be produced, for example, by an extrusion process.
  • these alignments or orientations are obtained hot. Indeed, at high temperature, the fiber becomes deformable and the more mobile polymer chains can then be oriented by the traction exerted on the fibers.
  • the invention therefore proposes to remedy these drawbacks by providing a process for reforming composite fibers comprising colloidal particles and at least one binder and / or bridging polymer of an implementation particularly simple, requiring little or no energy, preserving the integrity of all components of the fiber and not requiring the installation of a particular equipment.
  • these composite fibers comprising colloidal particles and at least one binder and / or bridging polymer could perfectly be treated "cold” or at room temperature or even slightly at room temperature by the use of simple means of deformation of said bridging polymer and / or binder.
  • cold reforming at ambient temperature or at a temperature slightly above ambient temperature, it is meant any treatment of the fibers applied in said process at a temperature ranging from 0 ° C. to a temperature slightly above ambient, this being generally considered as being of the order of 20 to 25 ° C. Higher temperatures are advantageously between 25 ° C and 50 ° C.
  • said means for deforming said polymer are constituted by a plasticizer addition.
  • Another possibility of deformation of these polymers consists of an immersion of said fiber in a solvent or a mixture of solvents such that the reciprocal solubility of said polymer in said solvent or said mixture of solvents determines the optimization of said applied mechanical stresses.
  • said solvent is chosen from among the solvents in which the polymer is soluble or partially soluble.
  • the fiber is then softened by partial solubilization of the polymer and thus becomes easily malleable and transformable.
  • said solvent is chosen from solvents in which the polymer is insoluble or practically insoluble.
  • one of the advantages of the process according to the invention is that the solvation of a composite fiber comprising particles and at least one binder and / or bridging polymer allows the particles to move relative to one another without destroying the cohesion of the binder and / or bridging polymer due to the bridging forces existing between the polymer and the particles.
  • a conventional fiber consisting of particles in a polymer matrix subjected to the process according to the invention would lead to the complete dissolution of the polymer and thus to destruction of the fiber.
  • the process may be carried out by selecting as solvent all volume and / or weight mixtures of at least one solvent in which the polymer is soluble or partially soluble and at least one solvent in which the polymer is insoluble. or practically insoluble.
  • said solvent may contain at least one crosslinking agent.
  • crosslinking agent since said polymer may be particularly soluble in certain solvents, the addition of a crosslinking agent will lead to the curing of said polymer while avoiding slipping without reorientation of said colloidal particles which may occur if said polymer is made too plastic since the polymer does not play the role of matrix here but is by definition binder and / or bridging between the particles. There is then a stiffening of said polymer which then allows a better transmission of the mechanical stresses applied to the fiber and by incidence to the colloidal particles whose reorientation is desired within said fiber.
  • crosslinking agents will, of course, be chosen according to the nature of said polymer and that of said solvent. They may for example be salts or organic compounds.
  • the solvents used for carrying out the process according to the invention will be chosen from water, acetone, ethers, dimethylformamide, tetrahydrofuran, chloroform, toluene and ethanol. and / or aqueous solutions whose pH and / or concentrations of any solutes are controlled.
  • said polymer will be chosen from the polymers adsorbing on said colloidal particles.
  • the binder and / or bridging polymers according to the invention will be chosen from polyvinylalcohol, the flocculant polymers commonly used in the liquid effluent depollution industry, such as polyacrylamides, which are neutral polymers, acrylamide copolymers and acrylic acid, which are negatively charged, copolymers of acrylamide and cationic monomer, which are positively charged, the inorganic polymers based on aluminum, and / or natural polymers such as chitosan, guar and / or starch.
  • polyacrylamides which are neutral polymers
  • acrylamide copolymers and acrylic acid which are negatively charged
  • copolymers of acrylamide and cationic monomer which are positively charged
  • the inorganic polymers based on aluminum and / or natural polymers such as chitosan, guar and / or starch.
  • said polymer is polyvinylalcohol (PVA), commonly used in the synthesis of composite fibers comprising particles and at least one binder and / or bridging polymer.
  • PVA polyvinylalcohol
  • said polymer is polyvinyl alcohol with a molar mass of between 10,000 and 200,000.
  • an example of a choice of solvents may be the following: water, in which the PVA is soluble, acetone in which the PVA is insoluble or a mixture of water and acetone in which the PVA will have a controlled solubility.
  • borates will be an example of crosslinking agents that can be used when the fiber is immersed in water.
  • the colloidal particles will be chosen from carbon nanotubes, sulphide of tungsten, boron nitride, clay platelets, cellulose whiskers and / or silicon carbide whiskers.
  • the method may comprise additional steps of extracting said fiber from the solvent and / or drying said fiber so as to obtain a fiber free of any plasticizer and / or any trace of solvent.
  • These operations can advantageously be carried out in a known manner, such as, for example, drying in an oven at a temperature slightly below the boiling point of the solvent.
  • the method which is the subject of the invention may be used to manufacture fibers having an orientation of said particles composing said fiber mainly in the direction of the main axis of said fiber.
  • the method which is the subject of the invention may also be used to manufacture fibers having an increased length and / or a reduced diameter with respect to the original fiber.
  • the method which is the subject of the invention may be used to manufacture densified and / or refined fibers with respect to the original fiber.
  • carbon nanotube fibers are used so as to prove the efficiency and advantages of the process according to the invention.
  • This method comprises homogeneously dispersing nanotubes in a liquid medium.
  • the dispersion can be carried out in water using surfactants which adsorb at the interface of the nanotubes.
  • the nanotubes can be recondensed in the form of a ribbon or prefibre by injecting the dispersion into another liquid which causes the destabilization of the nanotubes.
  • This liquid may be for example a solution of polymers.
  • the flows involved can be modified to promote alignment of the nanotubes in the pre-fiber or ribbon. In addition, flow rates and flow rates also control the section of prefibers or ribbons.
  • pre-fibers or ribbons thus formed may then be washed or not by rinses which make it possible to desorb certain adsorbed species (in particular polymer or surfactants).
  • Pre-fibers or ribbons can be continuously produced and extracted from their solvent to be dried. We then obtain dry fibers and easily manipulated carbon nanotubes.
  • Drying in the initial manufacture of the fiber induces significant modifications that disturb the alignment of the carbon nanotubes and, regardless of the method for obtaining these fibers, they have little difference in orientation of the nanotubes of carbon.
  • the fiber is solvated in a given solvent to subject it to twists and / or pulls.
  • a polymer fiber can be oriented by simple extrusion or hot stretching. If the fiber contains particles such as carbon nanotubes or whiskers, they also orient themselves. The polymer then plays the role of matrix and it is the deformation of this support which causes the modifications of structures of the fiber.
  • the colloidal particles are directly connected to each other.
  • the cohesion of the structure no longer comes from the polymer itself, but directly from the particles which are bound by a bridging polymer.
  • the structure of the fiber can be modified by pulling or twisting, if the binder polymer is plastic, or made deformable by solvation.
  • such an implementation is carried out at ambient temperature by simply quenching the fiber in water or in another solvent having a certain affinity for the PVA.
  • the ribbon is then rinsed with pure water several times and extracted with water to form a dry thread.
  • water is qualified as a good solvent and acetone as a bad solvent.
  • the other important parameters correspond to the characteristics of the fibers and carbon nanotubes. As is known in the textile industry, for example, these parameters are critical for the final properties of a yarn composed of smaller fibers.
  • the problem here is identical insofar as the wire consists of carbon nanotubes.
  • the structural modifications are characterized by elongation measurements and by X-ray diffraction experiments which quantitatively give the average orientation of the carbon nanotubes.
  • the fibers thus obtained are then immersed in a solvent and subjected to tractions which are expressed in: kilogram (grams). Tractions are performed by hanging well defined masses to the fibers. The fibers are then extracted from the solvent and thus allowed to dry under tension. The dry fibers are recovered and their structure is characterized.
  • the carbon nanotubes in the fibers are organized into bundles and form a hexagonal network perpendicular to the axis of the fiber.
  • the alignment of the bundles of carbon nanotubes with respect to the axis of the fiber can be characterized by the total width at half height (FWHM) of the constant wave vector angular dispersion over a Bragg peak of the hexagonal network. (Gaussian adjustment) or by the value of the intensity diffracted along the axis of the fiber, that is to say by carbon nanotubes perpendicular to this axis.
  • the predominant role of the binder and / or bridging polymer is thus particularly emphasized in obtaining optimized mechanical properties for the solvated fiber.
  • it is the strong adsorption of the polymer on the particles and the important bridging which is carried out on the particles which is involved here.
  • the solvated fibers withstand strong twisting without breaking, up to more than a hundred turns per centimeter.
  • the carbon nanotube fibers are thus deformable and reformable by a simple cold treatment. These deformations, and the implementation of the method which is the subject of the invention make it possible to control the arrangement of the nanotubes by the combination of the numerous variable variable parameters such as torsion, tension, the quality of the solvent, the nature and the mass of the polymer. and the geometric characteristics of the fibers and ribbons used for reforming.
  • a fiber directly resulting from its manufacture will have a minimum FWHM of 80 °, whereas after reforming according to an implementation of the process according to the invention, the fiber will have a FWHM of less than 80 ° and thus an angular dispersion of between + 40 ° and -40 °.
  • the physical properties of the composite fibers comprising colloidal particles and at least one binder and / or bridging polymer are thus significantly improved. They become more efficient for all the applications they can be designed for, such as making high cables. resistance, light conductors, chemical detectors, force sensors and mechanical or sonic stress, electromechanical actuators and artificial muscles, the development of composite materials, nanocomposites, electrodes and microelectrodes for example.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
EP02772485A 2001-08-08 2002-08-05 Procede de reformage de fibres composites et applications Expired - Lifetime EP1423559B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0110611A FR2828500B1 (fr) 2001-08-08 2001-08-08 Procede de reformage de fibres composites et applications
FR0110611 2001-08-08
PCT/FR2002/002804 WO2003014431A1 (fr) 2001-08-08 2002-08-05 Procede de reformage de fibres composites et applications

Publications (2)

Publication Number Publication Date
EP1423559A1 EP1423559A1 (fr) 2004-06-02
EP1423559B1 true EP1423559B1 (fr) 2011-03-16

Family

ID=8866390

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02772485A Expired - Lifetime EP1423559B1 (fr) 2001-08-08 2002-08-05 Procede de reformage de fibres composites et applications

Country Status (16)

Country Link
US (1) US7288317B2 (no)
EP (1) EP1423559B1 (no)
JP (1) JP4518792B2 (no)
KR (1) KR100933537B1 (no)
CN (1) CN1309882C (no)
AT (1) ATE502139T1 (no)
AU (1) AU2002337253B2 (no)
BR (1) BR0211727B1 (no)
CA (1) CA2457367C (no)
DE (1) DE60239471D1 (no)
ES (1) ES2365726T3 (no)
FR (1) FR2828500B1 (no)
HU (1) HU229645B1 (no)
NO (1) NO333728B1 (no)
NZ (1) NZ530823A (no)
WO (1) WO2003014431A1 (no)

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1336672A1 (en) * 2002-02-15 2003-08-20 Dsm N.V. Method of producing high strength elongated products containing carbon nanotubes
FR2851260B1 (fr) * 2003-02-19 2005-07-01 Nanoledge Dispositif pour la fabrication de fibres et/ou de rubans, a partir de particules placees en suspension dans une solution
FR2854409B1 (fr) * 2003-04-30 2005-06-17 Centre Nat Rech Scient Procede d'obtention de fibres a haute teneur en particules colloidales et fibres composites obtenues
US20050061496A1 (en) * 2003-09-24 2005-03-24 Matabayas James Christopher Thermal interface material with aligned carbon nanotubes
FR2877351B1 (fr) 2004-10-29 2007-02-09 Centre Nat Rech Scient Cnrse Fibres composites comprenant au moins des nanotubes de carbone, leur procede d'obtention et leurs applications
FR2877262B1 (fr) 2004-10-29 2007-04-27 Centre Nat Rech Scient Cnrse Fibres composites et fibres dissymetriques a partir de nanotubes de carbonne et de particules colloidales
EP2570385A3 (en) * 2005-05-03 2013-10-16 Nanocomp Technologies, Inc. Carbon composite materials and methods of manufacturing same
CA2850951A1 (en) * 2005-07-28 2007-01-28 Nanocomp Technologies, Inc. Systems and methods for formation and harvesting of nanofibrous materials
NO20065147L (no) * 2006-11-08 2008-05-09 Ntnu Tech Transfer As Nanokompositter basert på cellulosewhiskers og celluloseplast
US9061913B2 (en) 2007-06-15 2015-06-23 Nanocomp Technologies, Inc. Injector apparatus and methods for production of nanostructures
WO2009029341A2 (en) * 2007-07-09 2009-03-05 Nanocomp Technologies, Inc. Chemically-assisted alignment of nanotubes within extensible structures
EP2176927A4 (en) 2007-08-07 2011-05-04 Nanocomp Technologies Inc ELECTRIC AND THERMALLY CONDUCTIVE NON-METAL ADAPTERS ON NANOSTRUCTURE BASE
US8308930B2 (en) * 2008-03-04 2012-11-13 Snu R&Db Foundation Manufacturing carbon nanotube ropes
CA2723619A1 (en) 2008-05-07 2009-11-12 Nanocomp Technologies, Inc. Nanostructure-based heating devices and method of use
WO2009137722A1 (en) * 2008-05-07 2009-11-12 Nanocomp Technologies, Inc. Carbon nanotube-based coaxial electrical cables and wiring harness
US8673258B2 (en) * 2008-08-14 2014-03-18 Snu R&Db Foundation Enhanced carbon nanotube
US8357346B2 (en) * 2008-08-20 2013-01-22 Snu R&Db Foundation Enhanced carbon nanotube wire
US8021640B2 (en) 2008-08-26 2011-09-20 Snu R&Db Foundation Manufacturing carbon nanotube paper
JP5257813B2 (ja) * 2009-03-13 2013-08-07 国立大学法人信州大学 ポリビニルアルコール系コンポジット繊維およびその製造方法
GB201007571D0 (en) 2010-05-06 2010-06-23 Q Flo Ltd Chemical treatment of of carbon nanotube fibres
JP5848878B2 (ja) * 2011-02-14 2016-01-27 ニッタ株式会社 Ｃｎｔ入り樹脂繊維およびこれを用いた不織布とその製造方法
US9303171B2 (en) 2011-03-18 2016-04-05 Tesla Nanocoatings, Inc. Self-healing polymer compositions
WO2013033562A2 (en) 2011-08-31 2013-03-07 Jorma Virtanen Composition for corrosion prevention
US10570296B2 (en) 2012-03-19 2020-02-25 Tesla Nanocoatings, Inc. Self-healing polymer compositions
WO2013155111A1 (en) 2012-04-09 2013-10-17 Nanocomp Technologies, Inc. Nanotube material having conductive deposits to increase conductivity
KR20140030975A (ko) * 2012-09-04 2014-03-12 삼성전자주식회사 신축성 전도성 나노섬유 및 그 제조방법
EP3010853B1 (en) 2013-06-17 2023-02-22 Nanocomp Technologies, Inc. Exfoliating-dispersing agents for nanotubes, bundles and fibers
US11434581B2 (en) 2015-02-03 2022-09-06 Nanocomp Technologies, Inc. Carbon nanotube structures and methods for production thereof
US10581082B2 (en) 2016-11-15 2020-03-03 Nanocomp Technologies, Inc. Systems and methods for making structures defined by CNT pulp networks
US11279836B2 (en) 2017-01-09 2022-03-22 Nanocomp Technologies, Inc. Intumescent nanostructured materials and methods of manufacturing same
RU2721501C1 (ru) 2017-07-28 2020-05-19 Кимберли-Кларк Ворлдвайд, Инк. Гигиеническое впитывающее изделие для женщин, содержащее нанопористые сверхвпитывающие частицы
BR112020023949B1 (pt) 2018-06-27 2023-01-31 Kimberly-Clark Worldwide, Inc. Partículas superabsorventes, e, método para formar as partículas superabsorventes

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1174959A (en) * 1966-09-16 1969-12-17 Carborundum Co Whisker Orientation and Shaped Bodies containing Uniaxially Oriented Whiskers
US3660556A (en) * 1968-07-26 1972-05-02 Kurashiki Rayon Co Process for producing polyvinyl alcohol filaments
FR2088130A7 (en) * 1970-05-21 1972-01-07 Sfec Alumina threads - drawn from aluminium hydroxide gel
DE3889230T2 (de) * 1987-01-23 1994-08-11 Fuji Photo Film Co Ltd Verpackungsmaterial für lichtempfindliches Material.
US4898761A (en) * 1987-09-11 1990-02-06 Reemay, Inc. Barrier fabric and method
CN1003872B (zh) * 1987-10-30 1989-04-12 北京维尼纶厂 6-30万袋聚乙烯醇长丝束生产工艺
JP2578873B2 (ja) * 1988-01-19 1997-02-05 昭和電工株式会社 微細繊維含有熱可塑性樹脂成形物の製造方法
JPH03260109A (ja) * 1990-03-05 1991-11-20 Nkk Corp 気相成長炭素繊維混入有機繊維
US5759462A (en) * 1994-10-14 1998-06-02 Amoco Corporaiton Electrically conductive tapes and process
JPH08284021A (ja) * 1995-02-10 1996-10-29 Kuraray Co Ltd ポリビニルアルコールとセルロース系ポリマーよりなる易フィブリル化繊維
DE69607586D1 (de) * 1995-09-05 2000-05-11 Kuraray Co Polyvinylalkoholfasern mit hervorragender beständigkeit genenüber kochendem wasser und verfahren zu ihrer herstellung
JPH09282938A (ja) * 1996-04-17 1997-10-31 Yazaki Corp 導電性多孔質材料、及びその製造方法
US6124058A (en) * 1996-05-20 2000-09-26 Kuraray Co., Ltd. Separator for a battery comprising a fibrillatable fiber
CN1081686C (zh) * 1998-04-14 2002-03-27 中国石油化工总公司 聚乙烯醇湿法交联纺丝工艺
CA2349946C (en) * 1998-11-06 2007-10-30 Patrick Muller Method and device for preparing a mixture of substances containing organic components
EP1054036A1 (en) 1999-05-18 2000-11-22 Fina Research S.A. Reinforced polymers
SG91279A1 (en) * 1999-06-09 2002-09-17 Kuraray Co Polyvinyl alcohol polymer production method and polyvinyl alcohol polymer
US6299812B1 (en) * 1999-08-16 2001-10-09 The Board Of Regents Of The University Of Oklahoma Method for forming a fibers/composite material having an anisotropic structure
FR2805179B1 (fr) * 2000-02-23 2002-09-27 Centre Nat Rech Scient Procede d'obtention de fibres et de rubans macroscopiques a partir de particules colloidales, et notamment de nanotubes de carbone
JP3656732B2 (ja) * 2000-04-21 2005-06-08 日産自動車株式会社 エネルギー変換繊維体および吸音材
JP4581181B2 (ja) * 2000-05-23 2010-11-17 東レ株式会社 炭素繊維強化樹脂複合体および成形品、ならびに炭素繊維の回収方法

Also Published As

Publication number Publication date
CN1309882C (zh) 2007-04-11
KR100933537B1 (ko) 2009-12-23
FR2828500A1 (fr) 2003-02-14
US20040177451A1 (en) 2004-09-16
NO333728B1 (no) 2013-09-02
HUP0501027A2 (en) 2006-01-30
HU229645B1 (hu) 2014-03-28
WO2003014431A1 (fr) 2003-02-20
CN1589340A (zh) 2005-03-02
AU2002337253B2 (en) 2007-04-26
US7288317B2 (en) 2007-10-30
HUP0501027A3 (en) 2007-08-28
DE60239471D1 (de) 2011-04-28
CA2457367A1 (fr) 2003-02-20
ES2365726T3 (es) 2011-10-10
EP1423559A1 (fr) 2004-06-02
KR20040026706A (ko) 2004-03-31
JP2005526186A (ja) 2005-09-02
BR0211727B1 (pt) 2013-09-10
NO20040548L (no) 2004-03-26
FR2828500B1 (fr) 2004-08-27
ATE502139T1 (de) 2011-04-15
NZ530823A (en) 2008-03-28
CA2457367C (fr) 2011-01-11
BR0211727A (pt) 2004-09-21
JP4518792B2 (ja) 2010-08-04

Similar Documents

Publication Publication Date Title
EP1423559B1 (fr) Procede de reformage de fibres composites et applications
EP1618233B1 (fr) Procede d obtention de fibres a haute teneur en particules c olloidales et fibres composites obtenues
EP1268894B1 (fr) Procede d'obtention de fibres et de rubans macroscopiques a partir de particules collo dales, et notamment de nanotubes de carbone
EP2099849B1 (fr) Procede pour ameliorer l'adherence de fibres de carbone vis-a-vis d'une matrice organique
FR3024873B1 (fr) Fibre optique et procede de production de celle-ci
EP2256236A1 (fr) Procédé de fabrication de fibres composites conductrices à haute teneur en nanotubes
Ahn et al. In-situ synthesis of carbon dot at cellulose nanofiber for durable water treatment membrane with high selectivity
WO2009047456A2 (fr) Procede continu d ' obtention de fibres composites a base de particules colloïdales et fibre obtenue par ce procede
EP1917702A2 (fr) Guide optique comprenant des nanoparticules et procede de fabrication d'une preforme destinee a former un tel guide optique
EP2480630A1 (fr) Materiau composite utilisant un elastomere mesomorphe et son procede de fabrication
FR3058166A1 (fr) Procede de fabrication de fibres de carbone a partir de precurseurs biosources et fibres de carbone obtenues
CN110540734A (zh) 碳纳米管复合纤维及其制备方法
FR2713647A1 (fr) Procédé de fabrication d'un matériau composite et matériau en résultant.
FR2975708A1 (fr) Fibres composites conductrices comprenant des charges conductrices carbonees et un polymere conducteur
WO2014001699A1 (fr) Procede de fabrication d'une poudre de cellulose fibrillee adaptee a etre dispersee en milieu aqueux
EP1362936A1 (fr) Procédé pour produits façonnés en fibres-ciment et fibres de renforcement pour de tels produits.
EP2028236B1 (fr) Ensemble comportant des agrégats J
WO2019102141A1 (fr) Dispersion aqueuse de polymere thermoplastique, applications pour l'impregnation de fibres de renforts
FR2680525A1 (fr) Fibres a base de melanges pvc/pvc chlore possedant des proprietes mecaniques ameliorees et files de fibres de tenacite amelioree obtenus a partir de ces fibres.
FR2890075A1 (fr) Procede d'hydrosilylation
JPH04209740A (ja) 炭素繊維複合材

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040211

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RIN1 Information on inventor provided before grant (corrected)

Inventor name: POULIN, PHILIPPE

Inventor name: BERNIER, PATRICK

Inventor name: LAUNOIS, PASCALE

Inventor name: VIGOLO, BRIGITTE

17Q First examination report despatched

Effective date: 20090812

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60239471

Country of ref document: DE

Date of ref document: 20110428

Kind code of ref document: P

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60239471

Country of ref document: DE

Effective date: 20110428

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20110316

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110316

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110617

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110316

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110316

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110316

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110616

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2365726

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20111010

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110718

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110316

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110316

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110316

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110316

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110316

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20111219

BERE Be: lapsed

Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (CNR

Effective date: 20110831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110316

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110831

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 60239471

Country of ref document: DE

Effective date: 20111219

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110831

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110831

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110316

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110805

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110316

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20180920

Year of fee payment: 17

Ref country code: FR

Payment date: 20180830

Year of fee payment: 17

Ref country code: DE

Payment date: 20180813

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20180821

Year of fee payment: 17

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60239471

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20190805

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190831

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200303

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190805

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20210105

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190806