WO2012101036A1 - Plastique composite renforcé par fibres et son procédé de fabrication - Google Patents

Plastique composite renforcé par fibres et son procédé de fabrication Download PDF

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Publication number
WO2012101036A1
WO2012101036A1 PCT/EP2012/050801 EP2012050801W WO2012101036A1 WO 2012101036 A1 WO2012101036 A1 WO 2012101036A1 EP 2012050801 W EP2012050801 W EP 2012050801W WO 2012101036 A1 WO2012101036 A1 WO 2012101036A1
Authority
WO
WIPO (PCT)
Prior art keywords
fiber
matrix
nano
fibers
bedding
Prior art date
Application number
PCT/EP2012/050801
Other languages
German (de)
English (en)
Inventor
Heinrich Kapitza
Christian Seidel
Heinrich Zeininger
Original Assignee
Siemens Aktiengesellschaft
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 Siemens Aktiengesellschaft filed Critical Siemens Aktiengesellschaft
Publication of WO2012101036A1 publication Critical patent/WO2012101036A1/fr

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Classifications

    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D06M10/025—Corona discharge or low temperature plasma
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts

Definitions

  • the invention relates to a fiber fabric in which
  • Fibers are embedded in a matrix.
  • Fiber composite plastics for example, from
  • a composite fiber plastic is a multiphase or mixed material of at least two main components, a bedding matrix and reinforcing fibers.
  • a bedding matrix a resin, as a fiber, for example, a glass,
  • FRP components are used in classical static designs and increasingly also in dynamically loaded components or
  • Components for example in turbine components for power generation including wind turbines, components for (rail vehicles, components of electrical equipment (transformers, generators, motors) or in photovoltaics.
  • a fiber is impregnated or infiltrated with the resin.
  • the fibers usually carry at least partially a coating, such as a so-called sizing on the surface, which on the one hand ensures a smooth fiber surface for the weaving, on the other hand makes a compatibilization with the matrix.
  • the mechanical properties are determined by selecting the fibers and matrix resins. The mechanical properties in the fiber direction are mainly determined by the properties of the fibers, while in
  • Fiber composite applications for power engineering such as
  • tensile and transverse tensile properties are to be improved.
  • glass fiber composites one is limited to the E glass, so that property improvements can only be introduced via the matrix.
  • CFRP composites for example, high-modulus fibers are also available, through the targeted installation of which the rigidity of the composite is increased.
  • the object of the present invention is therefore to provide an FRP which has improved mechanical properties compared to the prior art.
  • the invention is therefore a
  • the subject matter of the invention is a process for producing a fiber composite plastic, wherein the matrix is modified by nano-materials prior to embedding the fiber.
  • nano-materials in the form of nanoscale particles for example as fillers, in the form of sols, colloids or the like into the bed-end matrix are preferred.
  • Suitable nano-materials are, for example, SiO 2 , Al 2 O 3 , CNTs, metallic nano-materials, boron nitride (BN),
  • Silicon carbide (Sic), titanium oxide (Ti0 2 ), barium titanate
  • Transition metals in particular also of aluminum, titanium, chromium, vanadium, niobium and / or zirconium.
  • the nano-materials can further increase the thermal conductivity (for BN and Sic) of the FRP, in particular also perpendicular to the fiber orientation, ie in the thickness direction of the laminate.
  • the degree of filling of the nano-material in the bedding matrix is for example 0.05% to 70% by weight, depending on the effectiveness of the nano-material in the respective matrix. Depending on the nano material will be different
  • Percent ranges are preferred, for example, nano-Si0 2 in amounts of 7% to 40% by weight of nano-carbon nanotubes (CNT) in the range from 0.05 to 5% by weight and nano-Al 2 O 3 in amounts of from 30 to 50% by weight. Preferred ranges are then within these limits, that is, for example, for nano-Si0 2 at 10 to 25% by weight, at CNT from 0.1 to 3% by weight and at A1 2 0 3 at 30 to 40% by weight.
  • CNT nano-carbon nanotubes
  • the materials for the bedding matrix are then prepared and processed as usual. Accordingly comprises a
  • Matrix material for example, in addition to the actual polymer and the nano-material also depending on the embodiment
  • the distribution of the nano-material within the bedding matrix is preferably homogeneous and / or isotropic, however, as a result of the processing, inhomogeneities may also occur in the distribution of the nano-material in the matrix.
  • bedding matrix examples are polymeric plastics of all kinds. Examples of these are thermoplastics, thermosets, and
  • Resins based on epoxy, polyurethane, acrylate are also suitable.
  • thermoplastics examples include acrylonitrile-butadiene-styrene (ABS), polyamides (PA), polyactate (PLA), polymethylmethacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polystyrene ( PS),
  • ABS acrylonitrile-butadiene-styrene
  • PA polyamides
  • PLA polyactate
  • PMMA polymethylmethacrylate
  • PC polycarbonate
  • PET polyethylene terephthalate
  • PE polyethylene
  • PE polypropylene
  • PS polystyrene
  • Polyetheretherketone PEEK
  • polyvinylchloride PVC
  • the bedding matrix can also be used as a blend of several materials
  • High performance fibers are used, for example
  • Fibers selected from the group of the following fibers: Carbon fibers, glass fiber, aramid fiber, polymeric fibers such as polyethylene fiber, polypropylene fiber, polystyrene fiber, polyethylene terephthalate fiber, ceramic fiber such as
  • Silicon carbide fiber Silicon carbide fiber, alumina fibers or other reinforcing fibers.
  • the fibers may also be present as a mixture of fibers.
  • the fibers may be in the form of a woven, knitted, scrim, braid, non-woven fabric.
  • the fibers are coated so that, for example, wet-chemically
  • Plain was applied to the fiber and / or these sheathed.
  • the fibers have an activated surface, that is, the surface of the fibers, whether coated or not, is chemically and / or physically activated.
  • Such a physical activation can be achieved for example via a plasma treatment, a chemical, for example via acid / base treatment.
  • the fibers with the activated surface have a much better adhesion to the bedding matrix than the fibers without activation.
  • the fibers are either impregnated with the uncrosslinked polymer, ie coated with the uncrosslinked polymer, or the fibers are drawn through an immersion bath with the uncrosslinked polymer.
  • the FRPs can also be made by a Tripreg process.
  • the modification with nano-material becomes a
  • the fibers are, for example, in the form of woven, knitted fabric, scrim, braid and / or non-woven fabric.
  • the fiber is used to form the FRP, for example, by bathing with the modified, uncrosslinked resin
  • the resin is applied in a thin layer on the fiber.
  • Improvement in fiber-matrix adhesion can bring about modification with nano-material.
  • FIG. 1 shows a comparison between the unfilled bedding matrix on the left in the diagram and the matrix filled with 0.8% by weight CNT (CarboNanoTubes) to the right.
  • the split strength was measured in MPa, which is a direct measure of the adhesion between the fiber and the bedding matrix in a FRP.
  • a corresponding laminate may be via an RTM process (e.g., infusion) and / or via vacuum infusion
  • CF-DU carbon fiber unidirectional
  • the mold is heated in a vacuum oven to 80 ° C and evacuated. Through an opening provided with a hose, the resin matrix is drawn into the mold by aerating the cabinet.
  • the CF fiber fabric is included
  • the content of the mold (CF + matrix) is cured with a temperature profile defined for the matrix. Thereafter, the mold is at room temperature
  • the viscosity is ⁇ 600 mPas at the processing temperatures for the infusion process and ⁇ 3000 mPas for the prepreg process, so that even higher nano-material concentrations can be processed in the prepreg process.
  • the SiO 2 nanoparticles are readily dispersible, up to concentrations of 40% are not agglomerations
  • the AL value is not significantly affected by the nano-material.
  • the AL value of 10% Si0 2 is within the measurement accuracy at 0.158 compared to the unmodified matrix system at 0.150.
  • Araldite CY179 / Aradur 917 / DY070 from Huntsman (resin base: cycloaliphatic epoxy resin)
  • Nanopox E 470 with 40% colloidal SiO 2 particles of 20 nm (resin base: DGBA)
  • Nanopox C 620 with 40% colloidal SiO 2 particles of 20 nm (resin base: cycloaliphatic epoxy resin)
  • Fiber dominance achieved an improvement in the modulus of 10%.
  • Transverse Fiber Bundle Test can be increased from 23 N / mm 2 for the unfilled resin to 33 N / mm 2 for the modified resin. This corresponds to an increase of> 42%.
  • the invention shows for the first time how, by simple modification of a bedding matrix with nano-material in an FRP, an increase in the adhesion between the fiber and the bedding matrix of considerable value, for example of 50%, can be achieved.
  • the adhesion between the bedding matrix and the fiber can still be influenced by the

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Plasma & Fusion (AREA)
  • Materials Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne une structure fibreuse plane dans laquelle des fibres sont incorporées dans une matrice. L'adhésion entre les fibres et la matrice d'incorporation est améliorée par remplissage de la matrice avec des nano-matériaux.
PCT/EP2012/050801 2011-01-28 2012-01-19 Plastique composite renforcé par fibres et son procédé de fabrication WO2012101036A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201110003313 DE102011003313A1 (de) 2011-01-28 2011-01-28 Faserverbundkunststoff sowie Herstellungsverfahren dazu
DE102011003313.0 2011-01-28

Publications (1)

Publication Number Publication Date
WO2012101036A1 true WO2012101036A1 (fr) 2012-08-02

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ID=45509511

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/050801 WO2012101036A1 (fr) 2011-01-28 2012-01-19 Plastique composite renforcé par fibres et son procédé de fabrication

Country Status (2)

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DE (1) DE102011003313A1 (fr)
WO (1) WO2012101036A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013219765A1 (de) * 2013-09-30 2015-04-02 Siemens Aktiengesellschaft Wärmeleitfähiger, faserverstärkter Kunststoff für Elektromotorengehäuse sowie Verfahren zur Herstellung und Verwendung dazu

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005028174A2 (fr) * 2003-06-16 2005-03-31 William Marsh Rice University Fabrication de composites de polymeres epoxydes renforces par des nanotubes de carbone a l'aide de nanotubes de carbone fonctionnalises
DE202004008122U1 (de) 2004-05-22 2005-10-20 C. Cramer, Weberei, Heek-Nienborg, Gmbh & Co. Kg Prepreg für Organoblech
EP1734069A1 (fr) * 2005-06-18 2006-12-20 Hexcel Composites Limited Matériau composite
WO2009076499A1 (fr) * 2007-12-12 2009-06-18 Kubota Research, Inc. Article composite et son procédé de fabrication
GB2467409A (en) * 2010-01-05 2010-08-04 Univ Bolton Noble/inert gas treatment of a material to increase its resistance to flash fire exposure

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1770115A1 (fr) * 2005-09-30 2007-04-04 Quadrant Plastic Composites AG Produit semi-fini de forme plane renforcé de fibres
WO2008012196A1 (fr) * 2006-07-22 2008-01-31 Sineurop Nanotech Gmbh Composite

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005028174A2 (fr) * 2003-06-16 2005-03-31 William Marsh Rice University Fabrication de composites de polymeres epoxydes renforces par des nanotubes de carbone a l'aide de nanotubes de carbone fonctionnalises
DE202004008122U1 (de) 2004-05-22 2005-10-20 C. Cramer, Weberei, Heek-Nienborg, Gmbh & Co. Kg Prepreg für Organoblech
EP1734069A1 (fr) * 2005-06-18 2006-12-20 Hexcel Composites Limited Matériau composite
WO2009076499A1 (fr) * 2007-12-12 2009-06-18 Kubota Research, Inc. Article composite et son procédé de fabrication
GB2467409A (en) * 2010-01-05 2010-08-04 Univ Bolton Noble/inert gas treatment of a material to increase its resistance to flash fire exposure

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Publication number Publication date
DE102011003313A1 (de) 2012-08-02

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