WO2012101036A1 - Fibre composite polymer and production method therfor - Google Patents

Fibre composite polymer and production method therfor 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
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WIPO (PCT)
Prior art keywords
fiber
matrix
nano
fibers
bedding
Prior art date
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PCT/EP2012/050801
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German (de)
French (fr)
Inventor
Heinrich Kapitza
Christian Seidel
Heinrich Zeininger
Original Assignee
Siemens Aktiengesellschaft
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Publication of WO2012101036A1 publication Critical patent/WO2012101036A1/en

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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
    • C08J5/04—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

Abstract

The invention relates to a sheetlike fibre structure comprising fibres embedded in a matrix. The adhesion between the fibre and the embedding matrix is enhanced by filling of the matrix with nanomaterial.

Description

Beschreibung description
Faserverbundkunststoff sowie Herstellungsverfahren dazu Die Erfindung betrifft ein Faserflächengebilde, bei dem The invention relates to a fiber fabric in which
Fasern in eine Matrix eingebettet sind. Fibers are embedded in a matrix.
Faserverbundkunststoffe zeichnen sich im Vergleich zu Fiber composite plastics are characterized in comparison to
metallischen Konstruktionswerkstoffen durch ein deutlich geringeres spezifisches Gewicht und höhere spezifische metallic construction materials by a significantly lower specific gravity and higher specific
Eigenschaften aus. Properties off.
Es sind Faserverbundkunststoffe beispielsweise aus der They are fiber composite plastics, for example, from
DE 20 2004 008 122 bekannt, sie werden auch als „Organoblech" oder „Hybridgarngewebe" bezeichnet und im Flugzeug-, Schiffsoder Fahrzeugbau sowie in der Energieindustrie eingesetzt, generell bei Leichtbauanwendungen. DE 20 2004 008 122, they are also referred to as "organo sheet" or "hybrid yarn" and used in aircraft, ship or vehicle construction and in the energy industry, generally in lightweight applications.
Ein Faserverbundkunststoff (FVK) ist ein Mehrphasen- oder Mischwerkstoff aus mindestens zwei Hauptkomponenten, eine bettende Matrix und verstärkende Fasern. Als bettende Matrix wird ein Harz, als Faser beispielsweise eine Glas-, A composite fiber plastic (FRP) is a multiphase or mixed material of at least two main components, a bedding matrix and reinforcing fibers. As a bedding matrix, a resin, as a fiber, for example, a glass,
Kohlenstoff- und/oder Aramidfaser eingesetzt. FVK-Bauteile finden Anwendung in klassischen statischen Konstruktionen und zunehmend auch in dynamisch belasteten Bauteilen oder Carbon and / or aramid fiber used. FRP components are used in classical static designs and increasingly also in dynamically loaded components or
Komponenten, beispielsweise in Turbinenkomponenten für die Energieerzeugung inklusive Windräder, Bauteile für (Schienenfahrzeuge, Komponenten elektrotechnischer Geräte (Trafos, Generatoren, Motoren) oder in der Photovoltaik .  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.
Bei der Herstellung wird eine Faser mit dem Harz imprägniert oder infiltriert. Die Fasern tragen in der Regel zumindest teilweise eine Beschichtung, wie beispielsweise eine so genannte Schlichte an der Oberfläche, die zum einen eine glatte Faseroberfläche für die Webschritte gewährleistet zum anderen eine Kompatibilisierung mit der Matrix herstellt. Bei Faserverbunden werden die mechanischen Eigenschaften durch Auswahl der Fasern und Matrixharze bestimmt. Die mechanischen Eigenschaften in Faserrichtung sind vor allem durch die Eigenschaften der Fasern bestimmt, währen in During manufacture, 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. In fiber composites, 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
Querzugsrichtung insbesondere bei DU-Gelegen die Querzugsrichtung especially in DU-Located the
Eigenschaften der Matrix bestimmend sind. In Characteristics of the matrix are decisive. In
Faserverbundanwendungen für die Energietechnik;, wie Fiber composite applications for power engineering ;, such as
beispielsweise Windkraft und Medizintechnik beispielsweise Patientenliegen sollen Zug - und Querzugeigenschaften verbessert werden. Bei Glasfaserverbunden ist man auf das E- Glas beschränkt, so dass Eigenschaftsverbesserungen nur über die Matrix eingebracht werden können. Bei CFK-Verbunden stehen beispielsweise auch Hochmodul-Fasern zur Verfügung, durch deren gezielten Einbau die Steifigkeit des Verbundes erhöht wird. for example wind power and medical technology, for example patient couches, tensile and transverse tensile properties are to be improved. With glass fiber composites, one is limited to the E glass, so that property improvements can only be introduced via the matrix. With CFRP composites, for example, high-modulus fibers are also available, through the targeted installation of which the rigidity of the composite is increased.
Es besteht immer der Bedarf, die Steifigkeit, Festigkeit, Reißfestigkeit, (Schlag) -Zähigkeit , die Verbesserung des Benetzungsverhaltens der Faser sowie die Schwingfestigkeit und Kompaktheit der FVKs zu optimieren. There is always a need to optimize the stiffness, strength, tear strength, (toughness) toughness, improvement of the wetting behavior of the fiber as well as the fatigue strength and compactness of the FRPs.
Aufgabe der vorliegenden Erfindung ist es daher, einen FVK zu schaffen, der gegenüber der Stand der Technik verbesserte mechanische Eigenschaften aufweist. The object of the present invention is therefore to provide an FRP which has improved mechanical properties compared to the prior art.
Die Lösung der Aufgabe und der Gegenstand der Erfindung sind in der Beschreibung, den Ansprüchen und der Figur offenbart. Allgemeine Erkenntnis der Erfindung ist es, dass durch den Einbau von Nano-Materialien, beispielsweise in Form The solution of the problem and the subject of the invention are disclosed in the description, the claims and the figure. General knowledge of the invention is that by the incorporation of nano-materials, for example in the form
nanopartikulärer Füllstoffe, Sole, Gele und/oder Kolloide, die mechanischen Eigenschaften sowohl in Faserrichtung als auch quer zur Faserrichtung deutlich verbessert werden können . Gegenstand der Erfindung ist daher ein nanoparticulate fillers, sols, gels and / or colloids, the mechanical properties both in the fiber direction and across the grain can be significantly improved. The invention is therefore a
Faserverbundkunststoff, Faser und eine bettende Matrix umfassend, wobei die bettende Matrix durch Nano-Materialien modifiziert ist. Außerdem ist Gegenstand der Erfindung ein Verfahren zur Herstellung eines Faserverbundkunststoffes, wobei die Matrix vor dem Einbetten der Faser durch Nano- Materialien modifiziert wird.  Comprising fiber composite plastic, fiber and a bedding matrix, wherein the bedding matrix is modified by nano-materials. In addition, 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.
Die Modifizierung der Polymermatrix durch Nano-Material findet im noch nicht vollständig und bevorzugt im The modification of the polymer matrix by nano-material is still not complete and is preferred in the
ungehärteten und/oder unvernetztem Zustand statt. unhardened and / or uncrosslinked state.
Zur Modifizierung der Polymermatrix durch Nano-Material werden bevorzugt Nano-Materialien in Form von nanoskaligen Partikel, beispielsweise als Füllstoffe, in Form von Solen, Kolloiden oder ähnlichem in die bettende Matrix For modifying the polymer matrix by nano-material, 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
eingearbeitet . incorporated.
Als Nano-Materialien eignen sich beispielsweise Si02, Al203, CNTs, metallische Nano-Materialien, Bornitrid (BN) , Suitable nano-materials are, for example, SiO 2 , Al 2 O 3 , CNTs, metallic nano-materials, boron nitride (BN),
Siliziumcarbid (Sic) , Titnoxid (Ti02) , Bariumtitanat Silicon carbide (Sic), titanium oxide (Ti0 2 ), barium titanate
(BaTi03) , Siliziumnitrid (SiN) , Magnesiumoxid (MgO) und (BaTi0 3 ), silicon nitride (SiN), magnesium oxide (MgO) and
allgemein Oxide, Nitride, Carbide aller Gruppen und in general, oxides, nitrides, carbides of all groups and
Übergangs-Metalle, insbesondere auch von Aluminium, Titan, Chrom, Vanadium, Niob und/oder Zirkon. Transition metals, in particular also of aluminum, titanium, chromium, vanadium, niobium and / or zirconium.
Die Nano-Materialien können weiterhin die Wärmeleitfähigkeit (für BN und Sic) des FVK erhöhen, insbesondere auch senkrecht zur Faserorientierung, also in Dickenrichtung des Laminats. 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.
Der Füllgrad des Nano-Materials in der bettenden Matrix beträgt beispielsweise 0,05 % bis 70 Gew%, abhängig von der Wirksamkeit des Nano-Materials in der jeweiligen Matrix. Abhängig vom Nano-Material werden verschiedene 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
Prozentbereiche bevorzugt, beispielsweise wird Nano-Si02 in Mengen von 7% bis 40 Gew%, Nano-CarbonNanoTubes (CNT) im Bereich von 0,05 bis 5 Gew% und Nano-Al203 in Mengen von 30 bis 50 Gewi eingearbeitet. Bevorzugte Bereiche liegen dann innerhalb dieser Grenzen, also beispielsweise für Nano-Si02 bei 10 bis 25 Gew%, bei CNT von 0,1 bis 3 Gew% und bei A1203 bei 30 bis 40 Gew%. 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.
Die Materialien für die bettende Matrix werden dann wie üblich hergestellt und verarbeitet. Demnach umfasst ein The materials for the bedding matrix are then prepared and processed as usual. Accordingly comprises a
Matrixmaterial beispielsweise neben dem eigentlichen Polymer und dem Nano-Material je nach Ausführungsform auch noch Matrix material, for example, in addition to the actual polymer and the nano-material also depending on the embodiment
Additive, Zusatzstoffe, Füllstoffe, Lösungsmittel etc. Additives, additives, fillers, solvents etc.
Die Verteilung des Nano-Materials innerhalb der bettenden Matrix ist bevorzugt homogen und/oder isotrop, es kann jedoch als Folge der Verarbeitung auch zu Inhomogenitäten in der Verteilung des Nano-Materials in der Matrix kommen. 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.
Beispiele für die bettende Matrix sind polymere Kunststoffe aller Art. Beispiele dafür sind Thermoplaste, Duroplaste,Examples of the bedding matrix are polymeric plastics of all kinds. Examples of these are thermoplastics, thermosets,
Harze auf Basis von Epoxid- , Polyurethan-, Acrylat . Es eignen sich außerdem ungesättigte Polyester (UP) -Harze, Vinylester (VE) -Harze, Duromere, Duroplaste, und/oder weitere Resins based on epoxy, polyurethane, acrylate. Also suitable are unsaturated polyester (UP) resins, vinyl ester (VE) resins, duromers, thermosets, and / or others
Kunstharze . Synthetic resins.
Beispiele für Thermoplasten sind Acrylnitril-Butadien-Styrol (ABS) , Polyamide (PA) , Polyactat (PLA) , Polymethylmethacrylat (PMMA) , Polycarbonat (PC) , Polyethylenterephtalat (PET) , Polyethylen (PE) , Polypropylen (PP) , Polystyrol (PS) , Examples of thermoplastics are acrylonitrile-butadiene-styrene (ABS), polyamides (PA), polyactate (PLA), polymethylmethacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polystyrene ( PS),
Polyetheretherketon (PEEK) , Polyvinylchlorid (PVC) . Polyetheretherketone (PEEK), polyvinylchloride (PVC).
Die bettende Matrix kann auch als Blend von mehreren The bedding matrix can also be used as a blend of several
polymeren Kunststoffen vorliegen. Als Faser können alle Arten von Fasern, insbesondere polymeric plastics. As a fiber, all types of fibers, in particular
Hochleistungsfasern eingesetzt werden, beispielsweise High performance fibers are used, for example
ausgewählt aus der Gruppe folgender Fasern: Kohlenstofffasern, Glasfaser, Aramidfaser, polymere Fasern wie Polyethylenfaser, Polypropylenfaser, Polystyrolfaser, Polyethylenterephtalatfaser , Keramikfaser wie 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
Siliziumcarbidfaser, Aluminiumoxidfasern oder sonstige verstärkende Fasern. Silicon carbide fiber, alumina fibers or other reinforcing fibers.
Die Fasern können auch als Gemisch von Fasern vorliegen. The fibers may also be present as a mixture of fibers.
Die Fasern können in Form von einem Gewebe, Gewirke, Gelege, Geflecht, Faservlies vorliegen. The fibers may be in the form of a woven, knitted, scrim, braid, non-woven fabric.
Nach einer bevorzugten Ausführungsform sind die Fasern beschichtet, so dass beispielsweise nasschemisch eine According to a preferred embodiment, the fibers are coated so that, for example, wet-chemically
Schlichte auf die Faser aufgebracht wurde und/oder diese ummantelt. Plain was applied to the fiber and / or these sheathed.
Nach einer weiteren bevorzugten Ausführungsform haben die Fasern eine aktivierte Oberfläche, das heißt, die Oberfläche der Fasern, unabhängig davon ob die Faser beschichtet ist oder nicht, ist chemisch und/oder physikalisch aktiviert.According to another preferred embodiment, the fibers have an activated surface, that is, the surface of the fibers, whether coated or not, is chemically and / or physically activated.
Eine derartige physikalische Aktivierung ist beispielsweise über eine Plasmabehandlung, eine chemische beispielsweise über Säure- /Basebehandlung zu erreichen. Die Fasern mit der aktivierten Oberfläche haben eine wesentlich bessere Adhäsion zu der bettenden Matrix als die Fasern ohne Aktivierung. 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.
Zur Herstellung des FVKs werden die Fasern entweder mit dem unvernetzten Polymer imprägniert, also mit dem unvernetzten Polymer überzogen oder die Fasern werden durch ein Tauchbad mit dem unvernetzten Polymer gezogen. Die FVKs können auch durch einen Tripreg Prozess hergestellt werden. To produce the FRP, 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.
Durch die Modifizierung mit Nano-Material wird eine The modification with nano-material becomes a
wesentlich stärkere Adhäsion zwischen der bettenden Matrix und der Faser erreicht, unabhängig davon, ob die Faser beschichtet ist oder nicht. Die Fasern liegen beispielsweise in Form von Gewebe, Gewirke, Gelege, Geflecht und/oder Faservlies vor. much greater adhesion between the bedding matrix and the fiber, regardless of whether the fiber is coated or not. The fibers are, for example, in the form of woven, knitted fabric, scrim, braid and / or non-woven fabric.
Die Faser wird zur Bildung des FVKs beispielsweise durch ein Bad mit dem modifizierten, noch nicht vernetzten Harz The fiber is used to form the FRP, for example, by bathing with the modified, uncrosslinked resin
gezogen. Damit wird das Harz in einer dünnen Schicht auf die Faser aufgebracht . drawn. Thus, the resin is applied in a thin layer on the fiber.
Im Folgenden wird noch anhand eines Diagramms eines The following is still based on a diagram of a
Ausführungsbeispiels gezeigt, welche durchschlagende Embodiment shown which resounding
Verbesserung im Bezug auf die Faser-Matrix-Adhäsion eine Modifizierung mit Nano-Material bringen kann.  Improvement in fiber-matrix adhesion can bring about modification with nano-material.
Die Figur 1 zeigt einen Vergleich zwischen der ungefüllten bettenden Matrix links im Diagramm und der mit 0,8Gew% CNT (CarboNanoTubes) gefüllten Matrix rechts davon. Gemessen wurde die Spaltfestigkeit in MPa, die ein direktes Maß für die Adhäsion zwischen der Faser und der bettenden Matrix in einem FVK darstellt. 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.
Im Folgenden wird die Erfindung noch anhand eines In the following, the invention is still based on a
Ausführungsbeispiels näher erläutert: Embodiment explained in more detail:
Herstellung eines FVK Production of a FRP
Zum einen kann ein entsprechendes Laminat über einen RTM- Prozess (z.B. Infusion) und/oder über Vakuuminfusion First, a corresponding laminate may be via an RTM process (e.g., infusion) and / or via vacuum infusion
folgendermaßen hergestellt werden. Etliche Lagen CarbonFaser- UniDirektional (CF-DU) -Fasergelege werden in eine Form eingebracht. Nach dem Schließen und Verschrauben des be prepared as follows. Several layers of carbon fiber unidirectional (CF-DU) fiber webs are placed in a mold. After closing and screwing the
Werkzeuges wird die Form in einem Vakuumschrank auf 80 °C erwärmt und evakuiert. Über eine Öffnung, versehen mit einem Schlauch, wird die Harzmatrix in die Form durch Belüften des Schrankes reingezogen. Das CF-Fasergelege wird dabei  Tool 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
vollständig überflutet. Der Inhalt der Form (CF + Matrix) wird mit einem für die Matrix definierten Temperaturprofil ausgehärtet . Danach wird die Form auf Raumtemperatur completely flooded. The content of the mold (CF + matrix) is cured with a temperature profile defined for the matrix. Thereafter, the mold is at room temperature
abgekühlt und das fertige FVK in Form eines CFK-Laminats entnommen . cooled and removed the finished FRP in the form of a CFRP laminate.
Weiterhin kann auch eine Imprägnierung der einzelnen Furthermore, an impregnation of the individual
Faserlagen mit dem entsprechend modifizierten Harz Fiber layers with the appropriately modified resin
durchgeführt werden (Prepreg-Technologie) . In diesem Fall erfolgt die Herstellung des Verbund-Laminats durch ein be carried out (prepreg technology). In this case, the production of the composite laminate by a
Verpressen imprägnierten Faserlagen unter Temperatur und Druck . Pressing impregnated fiber layers under temperature and pressure.
Die Viskosität liegt bei den Verarbeitungstemperaturen für den Infusionsprozess < 600 mPas und für den Prepregprozess bei < 3000 mPas, so dass im Prepregprozess auch höhere Nano- Material-Konzentrationen verarbeitet werden können. 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.
Die Si02-Nanopartikel sind beispielsweise gut dispergierbar, bis zu Konzentrationen 40% sind keine Agglomerationen For example, the SiO 2 nanoparticles are readily dispersible, up to concentrations of 40% are not agglomerations
festzustellen. Der AL-Wert wird durch das Nano-Material nicht wesentlich beeinflusst. Der AL-Wert von 10% Si02 liegt innerhalb der Messgenauigkeit bei 0,158 im Vergleich zum unmodifizierten Matrixsystem bei 0,150. Als Ausführungsbeispiele seine folgende Materialien genannt, die jedoch beliebig erweitert werden können mit weiteren Nano-Materialien und ebenso für weitere, beispielsweise auch kommerziell verfügbare, polymere Komponenten auf Basis von Epoxidharzen sowie UP- und PU-Harzen: determine. 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. As examples of its following materials mentioned, but which can be arbitrarily extended with other nano-materials and also for other, for example, commercially available, polymeric components based on epoxy resins and UP and PU resins:
Harze resins
Araldite LY556 / Aradur 917 / DY070 Fa. Huntsman (Harzbasis: DGBA)  Araldite LY556 / Aradur 917 / DY070 from Huntsman (resin base: DGBA)
Araldite CY179 / Aradur 917 / DY070 Fa. Huntsman (Harzbasis: Cycloaliphatisches Epoxidharz) Araldite CY179 / Aradur 917 / DY070 from Huntsman (resin base: cycloaliphatic epoxy resin)
Nanopox E 470 mit 40% kolloidalen Si02 Partikeln von 20 nm (Harzbasis: DGBA)  Nanopox E 470 with 40% colloidal SiO 2 particles of 20 nm (resin base: DGBA)
Nanopox C 620 mit 40% kolloidalen Si02 Partikeln von 20 nm (Harzbasis: Cycloaliphatisches Epoxidharz)  Nanopox C 620 with 40% colloidal SiO 2 particles of 20 nm (resin base: cycloaliphatic epoxy resin)
Nano-Materialien: Nano-materials:
Carbon Nanotubes (CNT) : MWCNT, Typ Baytubes C 150P, MWCNT, Typ Nanocyl 7000  Carbon nanotubes (CNT): MWCNT, type Baytubes C 150P, MWCNT, type Nanocyl 7000
Aluminiumoxid: Disperal HP 14 Alumina: Disperal HP 14
Siliziumoxid: Si02, Nanopox E 470, Nanopox C 620, kolloidal in Epoxidharz eingearbeitet  Silica: SiO 2, Nanopox E 470, Nanopox C 620, colloidally incorporated in epoxy resin
Alle Typen von kommerziell verfügbaren Kohlenstoff -Fasern in Form von Gelegen und Geweben, insbesondere basierend auf Glas- und Kohlenstofffaser, können eingesetzt werden. All types of commercially available carbon fibers in the form of loops and fabrics, especially based on glass and carbon fiber, can be used.
Folgende Teste und/oder Messungen zeigen die Verbesserung der mechanischen Eigenschaften der FVKs (Figur2) The following tests and / or measurements show the improvement of the mechanical properties of the FRPs (FIG. 2)
Die Tabellen zeigen, dass im Imprägnierverfahren durch Zusatz von 10% Nano-Si02 eine Steigerung des E-Moduls in The tables show that in the impregnation process by adding 10% nano-Si0 2 an increase in the modulus of elasticity in
Querzugsrichtung von ca. 20% erzielt werden kann; in Traverse direction of about 20% can be achieved; in
Hauptbiegerichtung senkrecht zur Faser wird trotz der Hauptbiegerichtung perpendicular to the fiber is despite the
Faserdominanz eine Verbesserung des E-Moduls von 10 % erreicht. Durch höhere nano-Si02 Zugaben werden die Fiber dominance achieved an improvement in the modulus of 10%. By higher nano-Si02 additions are the
mechanischen Eigenschaften weiter verbessert. Ähnliche Verbesserungen werden bei der gleichen 10%igen mechanical properties further improved. Similar improvements will be at the same 10%
Zugaben von nano-Si02 mit einem Kohlefaser-Gewebe erhalten. Sowohl der E-Modul als auch die Biegefestigkeit nehmen um über 10% zu. Additions of nano-Si0 2 obtained with a carbon fiber fabric. Both the modulus of elasticity and the flexural strength increase by more than 10%.
Verbesserung Faser-Matrix Haftung Improvement fiber matrix adhesion
Es wurde festgestellt, dass in einem Glasfaser verstärkten Material durch die Einarbeitung von CNT in einer It was found that in a glass fiber reinforced material by the incorporation of CNT in one
Konzentration von 0,3% die Faser-Matrix-Adhäsion im  Concentration of 0.3% of the fiber matrix adhesion in the
Transverse Fiber Bündle Test von 23 N/mm2 für das ungefüllte Harz auf 33 N/mm2 für das modifizierte Harz gesteigert werden kann. Dies entspricht einer Steigerung > 42 %. 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%.
Vorteile ergeben sind in der Auslegung der Faserverbund- Bauteile, beispielsweise bei Rotorblattern. Durch die verbesserten mechanischen Eigenschaften kann die Konstruktion material- und gewichtssparender durchgeführt werden. Die Verbesserung der Faser-Matrix Haftung ergeben sich Vorteile bei dynamischen Belastungsf llen, da eine Delamination bei Wechselbelastungen bei höheren Belastungskräften bzw. -Zyklen auftritt. Damit erhöht sich auch die Lebensdauer der Benefits arise in the design of fiber composite components, such as rotor blades. Due to the improved mechanical properties, the construction can be carried out with less material and weight. The improvement in fiber-matrix adhesion provides advantages in dynamic load cases, as delamination occurs at alternating loads at higher loading forces or cycles. This also increases the life of the
Bauteile . Components.
Durch die Erfindung wird erstmals gezeigt, wie durch einfache Modifizierung einer bettenden Matrix mit Nano-Material in einem FVK eine Steigerung der Adhäsion zwischen Faser und bettender Matrix von beachtlichem Wert, beispielsweise von 50% erreicht werden kann. 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.
Additiv und alternativ zu diesem Effekt kann die Adhäsion zwischen bettender Matrix und Faser noch durch die As an additive and as an alternative to this effect, the adhesion between the bedding matrix and the fiber can still be influenced by the
Oberflächenaktivierung der Faser deutlich erhöht werden. Surface activation of the fiber can be significantly increased.

Claims

Patentansprüche claims
1. Faserverbundkunststoff, Faser und bettende Matrix um¬ fassend, wobei die bettende Matrix durch Nano-Material modi- fiziert ist. 1. Fiber-reinforced plastic, fiber and bedding matrix to ¬ collectively, the bed matrix is modi- fied by nano-material.
2. Faserverbundkunststoff nach Anspruch 1, wobei der Füll¬ grad der bettenden Matrix mit Nano-Material zwischen 0,05 und 70 Gew% liegt. 2. fiber composite plastic according to claim 1, wherein the filling ¬ degree of the bedding matrix with nano-material between 0.05 and 70% by weight.
3. Faserverbundkunststoff nach einem der vorstehenden Ansprüche, wobei die Faser in Form von einem Gewebe, Gewirke, Gelege, Geflecht und/oder als Faservlies vorliegt. 3. Fiber-reinforced plastic according to one of the preceding claims, wherein the fiber is in the form of a woven, knitted fabric, scrim, braid and / or non-woven fabric.
4. Faserverbundkunststoff nach einem der vorstehenden Ansprüche, wobei die Oberfläche der Faser beschichtet ist. 4. fiber composite plastic according to any one of the preceding claims, wherein the surface of the fiber is coated.
5. Faserverbundkunststoff nach einem de vorstehenden Ansprüche, wobei die Oberfläche der Faser chemisch und/oder physikalisch aktiviert ist. 5. fiber composite plastic according to one of the preceding claims, wherein the surface of the fiber is chemically and / or physically activated.
6. Verfahren zur Herstellung eines Faserverbundkunststof¬ fes, wobei die Matrix vor dem Einbetten der Faser durch Nano- Material modifiziert wird. 6. A method for producing a Faserverbundkunststof ¬ fes, wherein the matrix is modified by the embedding of the fiber by nano-material.
7. Verfahren zur Herstellung eines Faserverbundkunststof¬ fes nach Anspruch 6, wobei die Faseroberfläche vor dem Ein¬ betten der Faser in die Matrix chemisch und/oder physikalisch aktiviert wird. 7. A method for producing a Faserverbundkunststof ¬ fes according to claim 6, wherein the fiber surface is chemically and / or physically activated before Ein¬ betten the fiber in the matrix.
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DE202004008122U1 (en) 2004-05-22 2005-10-20 C. Cramer, Weberei, Heek-Nienborg, Gmbh & Co. Kg Prepreg for organo-sheet material used for the construction of load bearing e.g. carbon fibre structures
EP1734069A1 (en) * 2005-06-18 2006-12-20 Hexcel Composites Limited Composite material
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DE202004008122U1 (en) 2004-05-22 2005-10-20 C. Cramer, Weberei, Heek-Nienborg, Gmbh & Co. Kg Prepreg for organo-sheet material used for the construction of load bearing e.g. carbon fibre structures
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