WO2012175327A1 - Plastique composite renforcé par fibres contenant des nanoparticules et procédé de préparation - Google Patents

Plastique composite renforcé par fibres contenant des nanoparticules et procédé de préparation Download PDF

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Publication number
WO2012175327A1
WO2012175327A1 PCT/EP2012/060563 EP2012060563W WO2012175327A1 WO 2012175327 A1 WO2012175327 A1 WO 2012175327A1 EP 2012060563 W EP2012060563 W EP 2012060563W WO 2012175327 A1 WO2012175327 A1 WO 2012175327A1
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WO
WIPO (PCT)
Prior art keywords
fiber
matrix
nano
composite plastic
prepreg
Prior art date
Application number
PCT/EP2012/060563
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 WO2012175327A1 publication Critical patent/WO2012175327A1/fr

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Classifications

    • 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
    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • 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

Definitions

  • the invention relates to a fiber composite plastic (FRP) comprising a bedding matrix and reinforcing fibers.
  • FRP fiber composite plastic
  • the invention relates to a FRP with improved mechanical properties in the transverse direction.
  • Fiber composite 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 elektrotechni ⁇ shear devices (transformers, generators, motors) or in the Pho - Voltaics.
  • the prepreg ge ⁇ introduced in its final form; Rather, the fiber composite material is formed itself currencies ⁇ rend component production. Therefore, the prepreg production is of decisive importance for the FRP components.
  • prepreg semi-finished products are referred to, for example, who called ⁇ the pre-impregnated fibers as a prepreg.
  • Prepreg preparation is aimed at a uniform distribution of the matrix material around the fibers.
  • nanoparticle-modified prepregs were prepared, whereby the desired breakthrough could not be achieved, on the one hand due to filtration effects and, on the other hand, due to inadequate contact of the reinforcing particles with the surface of the long fiber reinforcement.
  • Filtration effect is, for example, an enrichment or a percentage filtration / depletion of solids within a matrix. It is therefore an object of the present invention to provide a nomodifizerten prepreg and a manufacturing method thereto, which shows improved mechanical properties compared to non-nanomodified same systems.
  • a solution of the object and subject of the invention is therefore a nanomodified fiber composite plastic for a prepreg, a fiber and a bedding matrix comprising, wherein the bet ⁇ tende matrix is nanomodified.
  • the invention likewise provides a process for the production of a prepreg in which the matrix is nanomodified before embedding the fiber.
  • the mechanical properties are determined by selecting the fibers and matrix resins.
  • the mechanical properties in the fiber direction are primarily determined by the properties of the fibers, while in the transverse direction, especially in the case of unidirectional layers, the properties of the matrix are decisive.
  • fiber composite applications for power engineering, such as wind power and in medical technology, such as Pati ⁇ entenlie tensile and transverse tensile properties are to be improved.
  • glass fiber composites one is limited to the E glass, so that property improvements can be introduced only over the matrix.
  • CFRP carbon fiber composites
  • high-modulus fibers are also available, through the targeted installation of which the stiffness of the composite is increased.
  • nano-modified is referred to herein a matrix, are dispersed in the nanoparticles.
  • the distribution of Na no-material within the bed matrix is preferably ho ⁇ Mogen and / or isotropic.
  • Encompassed by the invention is of course also the shape of the nano-modification a matrix, at the inhomogeneities in the distribution of nano-material in the matrix occur.
  • the degree of filling of the nano-material in the bedding matrix is, for example, 0.05% to 70% by weight, in the case of carbon nanotubes, for example, preferably 0.1 to 20% by weight and, likewise, in the case of carbon nanotubes as a nano-material - particularly preferably 0.1 to 10 wt .-%.
  • the degree of filling depends on the effectiveness of the nano-material in the respective matrix.
  • ⁇ for metal oxides filler contents 3 to 60 wt .-%, in particular from 7 to 50 wt .-% and particularly preferably 10 to 40 wt .-%.
  • these values then shift, in particular also depending on the bedding matrix.
  • Silicon oxide again has slightly different filling degree optimum of 10 to 25 wt .-%.
  • nano-materials are generally metal compounds and / or metals or their alloys alone or in mixtures, wherein the nano-materials may be modified by suitable side chains for better solubility in the matrix.
  • metal compounds S 1O 2 , Al 2 O 3 , CNTs, graphenes and nanographites metal ⁇ nische nano-materials, boron nitride (BN), silicon carbide are examples.
  • SiC titanium oxide
  • TiO 2 titanium oxide
  • BaTiO 3 barium titanate
  • SiN silicon nitride
  • MgO magnesium oxide
  • Suitable metals and / or metal alloys are all known metals.
  • the materials for the bedding matrix are then prepared and processed as usual. Accordingly, a matrix ⁇ material includes, for example, in addition to the actual polymer and the nano-material, depending on the embodiment, even additives, additives, fillers, solvents, etc.
  • nano material nano-materials in the form of nanoscale Par Tikel are preferred, for example, as fillers, in the form of sols, Col. ⁇ colloids or the like incorporated into the matrix bed.
  • nano-Si02 in amounts of 7% to 40 wt .-%
  • nano-carbon nanotubes (CNT) in the range of 0.05 to 5 wt .-%
  • nano- Al 2 03 in quantities of 30 to
  • bedding matrix examples include polymeric plastics of all kinds. Examples of these are thermosets, resins based on epoxy, polyurethane, acrylate. Also suitable are unsaturated polyester (UP) resins, Vinylester (VE) resins, you ⁇ centromere, thermosets, and / or other synthetic resins.
  • thermosets resins based on epoxy, polyurethane, acrylate.
  • unsaturated polyester (UP) resins vinylester (VE) resins, you ⁇ centromere, thermosets, and / or other synthetic resins.
  • UP unsaturated polyester
  • VE Vinylester
  • filtration effects can be avoided because the fibers are completely wetted by a specific press-fitting process of the fiber webs into the sclerped resin bed by improved singulation.
  • a very good separation of the nanoparticles and a production process of the prepreg is achieved, which is a direct contact of the fiber reinforcement with the nanoparticle-modified resin ("press-in process").
  • press-in process a layer of the liquid prepreg resin is applied to a release film via a doctor blade / nozzle or Walzen descendantss- process.
  • the gene can be suppressed Faserverstärkun ⁇ set by means of a pressure roller or platen in the resin bed.
  • the advantage of this procedure in comparison with a classic ⁇ rectangular infusion process for producing the FRP that the particle-modified resin wetted only the fibers and kei ⁇ ne long flow paths are formed by the fiber fabric.
  • the method is performed so that the
  • the dispersion can take place, for example, using the three-roll technology.
  • the dispersion takes place by shearing the coarsely pre-dispersed nanoparticles in two columns at different speeds of rotating rolls. As a result, a good separation of nanoparticles is achieved in resins.
  • CNTs can be any organic radicals.
  • CNTs can be any organic radicals.
  • CNTs can be any organic radicals.
  • NC 7000 Multiwall CNTs from Nanocyl; NC 3101: Nanocyl multiwall CNTs, acid group functionalized)
  • the resin for example, the known as Araldite LY 556 epoxy resin from Huntsmann can be used.
  • Step 2 mixing with hardener and / or accelerator as the curing agent can be used, for example, the dicyandiamide curing agent and as accelerator (Aradur® 1571 * / 1573 * Accelerator Hardener XB 3403), the mixture is ⁇ example, via a Standard stirrer.
  • Step 3 Preparation of the prepregs formed by coating a release film (thickness: 800 .mu.m) and subsequently Eindrü ⁇ CKEN of the carbon fiber fabric (basis weight: 200 g / m 2, 0/90 ° twill weave) In a fourth process step of the prepreg the fiber ⁇ composite plastic are produced.
  • the FIGURE shows the flexural modulus of 3 nano-modified FRPs according to the invention compared to an identical non-nanomodified FRP sample.
  • the standardized 3-point bending test according to ISO 14125 was carried out. It can be seen that the flexural modulus can be increased by up to 25% compared to the reference sample.
  • the invention relates to a fiber composite plastic (FRP) comprising a bedding matrix and reinforcing fibers.
  • the invention relates to a FRP with improved mechanical properties in the transverse direction.
  • First significantly increased mechanical properties are gemes ⁇ sen because the bedding matrix of the fibers is nano-modifizert prior to embedding of the fibers. This is particularly because not only before the introduction of the fiber, the resin is nanomodified, but by the method specified here for nanomodification of the resin matrix, an improved singulation of the nanoparticles takes place.

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

Abstract

L'invention concerne un plastique composite renforcé par fibres contenant une matrice d'intégration et des fibres de renforcement. L'invention concerne en particulier un plastique composite renforcé par fibres présentant des propriétés mécaniques améliorées dans la direction de contraction transversale. Pour la première fois, des propriétés mécaniques nettement améliorées sont mesurées du fait que la matrice d'intégration des fibres est nano-modifiée avant intégration des fibres.
PCT/EP2012/060563 2011-06-24 2012-06-05 Plastique composite renforcé par fibres contenant des nanoparticules et procédé de préparation WO2012175327A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011078040A DE102011078040A1 (de) 2011-06-24 2011-06-24 Faserverbundkunststoff mit Nanopartikel und Herstellungsverfahren dazu
DE102011078040.8 2011-06-24

Publications (1)

Publication Number Publication Date
WO2012175327A1 true WO2012175327A1 (fr) 2012-12-27

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Country Status (2)

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DE (1) DE102011078040A1 (fr)
WO (1) WO2012175327A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014218226A1 (de) 2014-09-11 2016-03-17 Audi Ag Bauteil aus einem Faserverbundwerkstoff, Fahrzeug mit einem derartigen Bauteil sowie Verfahren zur Herstellung des Bauteils

Citations (2)

* 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
US20100143701A1 (en) * 2003-06-16 2010-06-10 Jiang Zhu Fiber-Reinforced Polymer Composites Containing Functionalized Carbon Nanotubes

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10334856B4 (de) * 2003-07-29 2007-06-06 Deutsches Zentrum für Luft- und Raumfahrt e.V. Verbundformteil und Verfahren zu seiner Herstellung
DE102006048920B3 (de) * 2006-10-10 2008-05-21 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Elektrisch leitendes Leichtbauteil und Verfahren zu seiner Herstellung
DE102007009124B4 (de) * 2007-02-24 2011-11-03 Evonik Degussa Gmbh Induktionsgestützte Fertigungsverfahren
BRPI0919688B1 (pt) * 2008-10-22 2019-04-02 Cytec Technology Corp. Método para formar prepregs conformados com componentes voláteis reduzidos

Patent Citations (2)

* 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
US20100143701A1 (en) * 2003-06-16 2010-06-10 Jiang Zhu Fiber-Reinforced Polymer Composites Containing Functionalized Carbon Nanotubes

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