EP0065618A1 - Metallised carbon fibres and laminated products containing these fibres - Google Patents

Metallised carbon fibres and laminated products containing these fibres Download PDF

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Publication number
EP0065618A1
EP0065618A1 EP82100896A EP82100896A EP0065618A1 EP 0065618 A1 EP0065618 A1 EP 0065618A1 EP 82100896 A EP82100896 A EP 82100896A EP 82100896 A EP82100896 A EP 82100896A EP 0065618 A1 EP0065618 A1 EP 0065618A1
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EP
European Patent Office
Prior art keywords
fibers
carbon
fibres
nickel
metal layer
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.)
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EP82100896A
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German (de)
French (fr)
Inventor
Harold Dr. Ebneth
Lothar Dr. Preis
Henning Dr. Giesecke
Gerhard Dieter Dr. Wolf
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Bayer AG
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Bayer AG
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Publication of EP0065618A1 publication Critical patent/EP0065618A1/en
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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D04H1/4242—Carbon fibres
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
    • D01F11/127—Metals
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D04H1/4234—Metal fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D04H1/43828—Composite fibres sheath-core
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/002—Inorganic yarns or filaments
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/902—High modulus filament or fiber
    • 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
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
    • Y10T428/249948—Fiber is precoated
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • 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
    • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
    • 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
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2958—Metal or metal compound in coating
    • 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
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31529—Next to metal

Definitions

  • a number of methods are known for chemically modifying reinforcing fibers for the production of fiber composite materials in such a way that an improvement in the adhesion between fiber and matrix materials is achieved.
  • the adhesion of the components to one another is essential for many usage properties of composite materials.
  • ILS interlaminar shear strength
  • the carbon fibers can come from various starting materials, e.g. from cellulose derivatives, special pitch types, for example bitumen or polyacrylonitrile.
  • the invention therefore relates to carbon threads, fibers or flat structures with an electrolessly applied metal layer.
  • Preferred metals are nickel, cobalt, copper, gold or silver or alloys of these metals with one another or with iron.
  • the thickness of the metal layer is between 0.05 and 10 ⁇ m, preferably 0.1 - 1 ⁇ m.
  • Preferred carbon fibers have a carbon content> 80% by weight. Fibers with a graphite-like structure and an elastic modulus> 300,000 MPa are particularly preferred.
  • Particularly preferred metals are cobalt and nickel or cobalt-nickel, cobalt-iron, nickel-iron and cobalt-nickel-iron alloys.
  • the invention further relates to composite materials made of electrolessly metallized carbon fibers with polymer matrices, which are characterized by improved fiber-matrix adhesion.
  • Preferred embodiments of these composite materials contain the carbon fibers marked as preferred.
  • the metal layer deposited on the fibers is firmly connected to the substrate.
  • the metallization produces electrically conductive substrates. Depending on the thickness of the metal layer, this can provide protection from electrostatic charge up to lightning protection. When using metals such as nickel or cobalt, shielding from electromagnetic radiation is obtained.
  • the improvement of the ILS is achieved with plastics from different starting points.
  • the metallized carbon fibers according to the invention e.g. the polymer classes listed below: epoxy resins, polyester resins, phenolic resins, aminoplasts, polyurethane resins, silicone resins, polyamides, polyimides, thermoplastic polyesters, polycarbonates and polyacrylates.
  • the reinforcing materials can be used in the form of fibers, fabrics, knitted fabrics or braids.
  • the metallization can be carried out both on the fibers and on the textile fabrics produced therefrom.
  • the metallization can be carried out according to the method described in DE-PS 2 743 768.
  • the activation is preferably carried out by a method which is characterized in that the surface to be metallized is wetted with an organometallic compound of elements of the 1st and 8th subgroups of the Periodic Table of the Elements which is homogeneously distributed in an organic solvent, the organic solvent is removed and the organometallic compound adhering to the surface to be metallized is reduced.
  • the metallization is then carried out approximately as in DE-PS 2 743 768.
  • a carbon filament yarn is activated for 10 seconds in a solution of 0.01 g butadiene palladium chloride, dried and then for 5 minutes in a metallization bath containing 30 g / 1 nickel chloride 6 H 2 O, 10 g / 1 citric acid and 3 g / 1 dimethylamine borane and pH 8.5, nickel-plated.
  • a molded body with 40% carbon content with a cross section of 4 x 10 mm is produced from the nickel-plated yarn in an epoxy resin.
  • a shear strength of 46.6 N / m 2 was determined on the molded body.
  • a comparatively produced molded body made of non-nickel-plated carbon yarn had a shear strength of 33.2 N / m 2 .
  • Carbon fibers with a modulus of elasticity of 415 00 MPa and a tensile strength of 2350 MPa were nickel-plated in accordance with Example 1.
  • Test specimens with 50% by volume unidirectionally oriented fibers were produced from these fibers using a commercially available epoxy resin based on bisphenol A (cold-curing).
  • the ILS was 58 MPa.
  • a test specimen which contained 50% by volume of untreated carbon fibers had an ILS of 29.5 MPa.
  • Test specimens with a commercially available polyester resin (isophthalic acid type) as a matrix were produced from carbon fibers according to Example 2.
  • the test specimens also contained 50% by volume of fibers, unidirectionally oriented.
  • a test specimen which contained the same polyester resin but contained 50% by volume of untreated carbon fibers gave an ILS value of 24 MPa.

Abstract

Kohlenstoff-Fäden und -Fasern sowie daraus hergestellte Flächengebilde mit vorzüglichen Hafteigenschaften gegenüber Kunststoffen ohne Beeinträchtigung ihrer Zugfestigkeit werden erhalten, wenn man die Kohlenstoff-Fäden und -Fasern mit Hilfe eines stromlosen Verfahrens mit einem metallischen Überzug versieht.Carbon filaments and fibers as well as sheet materials made therefrom with excellent adhesive properties to plastics without impairing their tensile strength are obtained if the carbon filaments and fibers are provided with a metallic coating using an electroless process.

Description

Es sind eine Reihe von Verfahren bekannt, Verstärkungsfasern zur Herstellung von Faserverbundwerkstoffen chemisch so zu modifizieren, daß eine Verbesserung der Haftung zwischen Faser- und Matrix-Materialien erreicht wird. Die Haftung der Komponenten untereinander ist wesentlich für viele Gebrauchseigenschaften von Verbundwerkstoffen.A number of methods are known for chemically modifying reinforcing fibers for the production of fiber composite materials in such a way that an improvement in the adhesion between fiber and matrix materials is achieved. The adhesion of the components to one another is essential for many usage properties of composite materials.

So sind z.B. eine Vielzahl von Methoden bekannt, die eine Verbesserung der Haftung von Kohlenstoffasern mit niedrigem und mittlerem E-Modul bewirken (z.B. GB-Patent 1 238 308, DE-OS 2 110 193, DE-AS 2 252 128).For example, a variety of methods are known which improve the adhesion of carbon fibers with low and medium modulus of elasticity (e.g. GB patent 1 238 308, DE-OS 2 110 193, DE-AS 2 252 128).

Jedoch gibt es bisher keine befriedigende Methode zur Mofifizierung von Kohlenstoffasern mit einem E- ' Modul > 300 000 MPa, die es erlaubt, die Verstärkungswirkung dieser Fasern im Verbundwerkstoff voll zu nutzen (Angew. Chem. 92, 375 (1980)).However, there has so far been no satisfactory method for the mofification of carbon fibers with an E modulus> 300,000 MPa, which allows the reinforcing effect of these fibers in the composite material to be fully utilized (Angew. Chem. 92, 375 (1980)).

Ein Maß für die Haftung der Komponenten eines Verbundsystems ist die interlaminare Scherfestigkeit (ILS). Ist die ILS groß, dann ist die Haftung der Komponenten gut..A measure of the adhesion of the components of a composite system is the interlaminar shear strength (ILS). If the ILS is large, the component liability is good.

Es hat sich in der Praxis gezeigt, daß die Mofifizierungsmittel, die zu Verbesserungen der Faser-Matrix-Verbundeigenschaften führen, sehr spezifisch, sowohl vom Faser-, als auch vom Matrixmaterial abhängen. So sind z.B. Produkte, die erhöhte ILS bei Glasfasern bewirken, für Kohlenstoffasern ungeeignet.It has been found in practice that the mofifying agents which lead to improvements in the fiber-matrix composite properties depend very specifically on both the fiber and the matrix material. For example, Products that cause increased ILS in glass fibers are unsuitable for carbon fibers.

Es wurde nun gefunden, daß man Kohlenstoff-Fäden oder -Fasern, sowie daraus hergestellte Flächengebilde mit vorzüglichen Hafteigenschaften gegenüber Kunststoffen ohne Beeinträchtigung ihrer Zugfestigkeit erhält, wenn man sie zuvor mit Hilfe eines stromlosen Verfahrens mit einem metallischen Überzug versieht.It has now been found that carbon threads or fibers, as well as fabrics made therefrom, having excellent adhesive properties to plastics without impairing their tensile strength, are obtained if they are previously provided with a metallic coating by means of an electroless process.

Die Kohlenstoffasern können dabei aus verschiedenen Ausgangsmaterialien stammen, z.B. aus Cellulosederivaten, spezielle Pechsorten, beispielsweise Bitumen oder Polyacrylnitril.The carbon fibers can come from various starting materials, e.g. from cellulose derivatives, special pitch types, for example bitumen or polyacrylonitrile.

Gegenstand der Erfindung sind daher Kohlenstoff-Fäden, -Fasern oder Flächengebilde mit einer stromlos aufgebrachten Metallschicht. Bevorzugte Metalle sind Nickel, Cobalt, Kupfer, Gold oder Silber bzw. Legierungen dieser Metalle untereinander oder mit Eisen. Die Dicke der Metallschicht liegt zwischen 0,05 und 10 µm, vorzugsweise 0,1 - 1 µm. Bevorzugte Kohlenstoffasern haben einen Kohlenstoffanteil >80 Gew.-%. Besonders bevorzugt sind Fasern mit graphit- ähnlicher Struktur und einem E-Modul > 300 000 MPa.The invention therefore relates to carbon threads, fibers or flat structures with an electrolessly applied metal layer. Preferred metals are nickel, cobalt, copper, gold or silver or alloys of these metals with one another or with iron. The thickness of the metal layer is between 0.05 and 10 µm, preferably 0.1 - 1 µm. Preferred carbon fibers have a carbon content> 80% by weight. Fibers with a graphite-like structure and an elastic modulus> 300,000 MPa are particularly preferred.

Besonders bevorzugte Metalle sind Cobalt und Nickel bzw. Cobalt-Nickel-, Cobalt-Eisen-, Nickel-Eisen- und Cobalt-Nickel-Eisen-Legierungen.Particularly preferred metals are cobalt and nickel or cobalt-nickel, cobalt-iron, nickel-iron and cobalt-nickel-iron alloys.

Die Erfindung betrifft weiterhin Verbundwerkstoffe aus stromlos metallisierten Kohlenstoffasern mit Polymermatrices, die sich durch verbesserte Faser-Matrixhaftung auszeichnen.The invention further relates to composite materials made of electrolessly metallized carbon fibers with polymer matrices, which are characterized by improved fiber-matrix adhesion.

Bevorzugte Ausführungsformen dieser Verbundwerkstoffe enthalten die als bevorzugt gekennzeichneten Kohlenstoffasern.Preferred embodiments of these composite materials contain the carbon fibers marked as preferred.

Die auf den Fasern abgeschiedene Metallschicht ist mit dem Substrat fest verbunden.The metal layer deposited on the fibers is firmly connected to the substrate.

Vergleichende Untersuchungen zwischen metallisierten und nicht metallisierten Kohlenstoffasern zeigen, daß die Zugfestigkeit und der E-Modul der Fasern durch die Metallisierung nicht beeinträchtigt wird und die ILS von aus metallisierten Kohlenstoffasern hergestellten Verbundwerkstoffen gegenüber Vergleichsmaterialien aus nicht ausgerüsteten Fasern um bis zu 100 % erhöht wird.Comparative studies between metallized and non-metallized carbon fibers show that the tensile strength and the modulus of elasticity of the fibers are not impaired by the metallization and the ILS of composite materials made from metallized carbon fibers is increased by up to 100% compared to comparison materials made from non-finished fibers.

Für die mit metallisierten Kohlenstoffasern verstärkten Verbundwerkstoffe ist es ferner von Vorteil, daß durch die Metallisierung elektrisch leitfähige Substrate entstehen. Dadurch kann je nach Metallschichtdicke ein Schutz vor elektrostatischer Aufladung bis hin zum Blitzschutz erreicht werden. Bei Verwendung von Metallen wie beispielsweise Nickel oder Cobalt erhält man eine Abschirmung von elektromagnetischer Strahlung.For the composite materials reinforced with metallized carbon fibers, it is also advantageous that the metallization produces electrically conductive substrates. Depending on the thickness of the metal layer, this can provide protection from electrostatic charge up to lightning protection. When using metals such as nickel or cobalt, shielding from electromagnetic radiation is obtained.

Die Verbesserung der ILS wird mit Kunststoffen unterschiedlicher Ausgangsbasis erreicht. Für die erfindungsgemäßen metallisierten Kohlenstoffasern eignen sich z.B. die nachstehend aufgeführten Polymerklassen: Epoxidharze, Polyesterharze, Phenolharze, Aminoplaste, Polyurethanharze, Siliconharze, Polyamide, Polyimide, thermoplastische Polyester, Polycarbonate und Polyacrylate.The improvement of the ILS is achieved with plastics from different starting points. For the metallized carbon fibers according to the invention, e.g. the polymer classes listed below: epoxy resins, polyester resins, phenolic resins, aminoplasts, polyurethane resins, silicone resins, polyamides, polyimides, thermoplastic polyesters, polycarbonates and polyacrylates.

Die Verstärkungsmaterialien können in Form von Fasern, Geweben, Gewirken oder Geflechten eingesetzt werden. Die Metallisierung kann sowohl an den Fasern als auch an den daraus hergestellten textilen Flächengebilden durchgeführt werden.The reinforcing materials can be used in the form of fibers, fabrics, knitted fabrics or braids. The metallization can be carried out both on the fibers and on the textile fabrics produced therefrom.

Die Metallisierung kann nach dem in der DE-PS 2 743 768 geschilderten Verfahren erfolgen.The metallization can be carried out according to the method described in DE-PS 2 743 768.

Vorzugsweise wird die Aktivierung nach einem Verfahren durchgeführt das dadurch gekennzeichnet ist, daß die zu metallisierende Oberfläche mit einer in einem organischen Lösungsmittel homogen verteilten organometallischen Verbindung von Elementen der 1 und 8. Nebengruppe des Periodensystems der Elemente benetzt, das organische Lösungsmittel entfernt und die an der zu metallisierenden Oberfläche haftende organometallische Verbindung reduziert wird. Anschließend wird die Metallisierung etwa wie in DE-PS 2 743 768 durchgeführt.The activation is preferably carried out by a method which is characterized in that the surface to be metallized is wetted with an organometallic compound of elements of the 1st and 8th subgroups of the Periodic Table of the Elements which is homogeneously distributed in an organic solvent, the organic solvent is removed and the organometallic compound adhering to the surface to be metallized is reduced. The metallization is then carried out approximately as in DE-PS 2 743 768.

Beispiel 1example 1

Ein Kohlenstoffilamentgarn wird 10 Sekunden in einer Lösung von 0,01 g Butadienpalladiumchlorid aktiviert, getrocknet und anschließend 5 Minuten in einem Metallisierungsbad, das 30 g/1 Nickelchlorid 6 H20, 10 g/1 Citronensäure und 3 g/1 Dimethylaminboran enthält und pH 8,5 hat, vernickelt.A carbon filament yarn is activated for 10 seconds in a solution of 0.01 g butadiene palladium chloride, dried and then for 5 minutes in a metallization bath containing 30 g / 1 nickel chloride 6 H 2 O, 10 g / 1 citric acid and 3 g / 1 dimethylamine borane and pH 8.5, nickel-plated.

Aus dem vernickelten Garn wird ein Formkörper mit 40 % Kohlenstoffgehalt vom Querschnitt 4 x 10 mm in einem Epoxidharz hergestellt. An dem Formkörper wurde eine Scherfestigkeit von 46,6 N/m2 bestimmt.A molded body with 40% carbon content with a cross section of 4 x 10 mm is produced from the nickel-plated yarn in an epoxy resin. A shear strength of 46.6 N / m 2 was determined on the molded body.

Ein vergleichsweise hergestellter Formkörper aus nicht vernickeltem Kohlenstoffgarn hatte eine Scherfestigkeit von 33,2 N/m2.A comparatively produced molded body made of non-nickel-plated carbon yarn had a shear strength of 33.2 N / m 2 .

Beispiel 2Example 2

Kohlenstoffasern mit einem E-Modul von 415 00 MPa und einer Zugfestigkeit von 2350 MPa wurden gemäß Beispiel 1 vernickelt.Carbon fibers with a modulus of elasticity of 415 00 MPa and a tensile strength of 2350 MPa were nickel-plated in accordance with Example 1.

Aus diesen Fasern wurden mit einem handelsüblichen Epoxidharz auf Basis Bisphenol A (kalthärtend) Prüfkörper mit 50 Vol-% unidirektional orientiertern Fasern hergestellt.Test specimens with 50% by volume unidirectionally oriented fibers were produced from these fibers using a commercially available epoxy resin based on bisphenol A (cold-curing).

Gemäß ASTM D 2344 ergab sich für die ILS ein Wert von 58 MPa. Ein Prüfkörper, der 50 Vol-% unbehandelte Kohlenstoffasern enthielt, hatte eine ILS von 29,5 MPa.According to ASTM D 2344, the ILS was 58 MPa. A test specimen which contained 50% by volume of untreated carbon fibers had an ILS of 29.5 MPa.

Beispiel 3Example 3

Aus Kohlenstoffasern gemäß Beispiel 2 wurden Prüfkörper mit einem handelsüblichen Polyesterharz (Isophthalsäuretyp) als Matrix hergestellt. Die Prüfkörper enthielten ebenfalls 50 Vol-% Fasern, unidirektional orientiert.Test specimens with a commercially available polyester resin (isophthalic acid type) as a matrix were produced from carbon fibers according to Example 2. The test specimens also contained 50% by volume of fibers, unidirectionally oriented.

Nach ASTM D 2344 wurde eine ILS von 46,4 MPa gemessen.According to ASTM D 2344, an ILS of 46.4 MPa was measured.

Ein Prüfkörper, der das gleiche Polyesterharz, aber 50 Vol-% unbehandelte Kohlenstoffasern enthielt, brachte einen ILS-Wert von 24 MPa.A test specimen which contained the same polyester resin but contained 50% by volume of untreated carbon fibers gave an ILS value of 24 MPa.

Claims (6)

1. Kohlenstoff-Fäden, -Fasern oder -Flächengebilde mit einer stromlos aufgebrachten Metallschicht.1. Carbon threads, fibers or fabrics with an electrolessly applied metal layer. 2. Kohlenstoff-Fäden, -Fasern und -Flächengebilde nach Anspruch 1, mit einer Metallschicht aus Nickel, Cobalt, Kupfer, Gold, Silber, Legierungen dieser Metalle untereinander oder mit Eisen.2. Carbon threads, fibers and fabrics according to claim 1, with a metal layer of nickel, cobalt, copper, gold, silver, alloys of these metals with each other or with iron. 3. Kohlenstoff-Fäden, -Fasern und -Flächengebilde nach Anspruch 1, mit einer Metallschichtstärke zwischen 0,05 und 10 µm.3. carbon threads, fibers and fabrics according to claim 1, with a metal layer thickness between 0.05 and 10 microns. 4. Kohlenstoff-Fäden, -Fasern und -Flächengebilde nach Anspruch 1 mit einem Kohlenstoffanteil > 80 Gew.-%.4. carbon threads, fibers and fabrics according to claim 1 with a carbon content> 80 wt .-%. 5. Kohlenstoff-Fäden, -Fasern und -Flächengebilde nach Anspruch 1 mit einer graphitähnlichen Struktur und einem E-Modul > 300 000 MPa.5. Carbon threads, fibers and fabrics according to claim 1 with a graphite-like structure and an elastic modulus> 300,000 MPa. 6. Verbundwerkstoffe aus Kohlenstoffasern nach den Ansprüchen 1 - 5 und polymeren Matrices.6. Composites made of carbon fibers according to claims 1-5 and polymer matrices.
EP82100896A 1981-02-21 1982-02-08 Metallised carbon fibres and laminated products containing these fibres Ceased EP0065618A1 (en)

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DE19813106506 DE3106506A1 (en) 1981-02-21 1981-02-21 METALIZED CARBON FIBERS AND COMPOSITES THAT CONTAIN THESE FIBERS
DE3106506 1981-02-21

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EP0419882A1 (en) * 1989-08-30 1991-04-03 The Furukawa Electric Co., Ltd. Optical fiber cable coated with conductive metal coating and process therefor
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EP0419882A1 (en) * 1989-08-30 1991-04-03 The Furukawa Electric Co., Ltd. Optical fiber cable coated with conductive metal coating and process therefor
US5093880A (en) * 1989-08-30 1992-03-03 Furukawa Electric Co., Ltd. Optical fiber cable coated with conductive metal coating and process therefor
GB2248620A (en) * 1990-10-12 1992-04-15 Kitagawa Ind Co Ltd Plastic material for wrapping over and carrying food
GB2248620B (en) * 1990-10-12 1994-06-08 Kitagawa Ind Co Ltd Plastic material for wrapping over and carrying food

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US4481249A (en) 1984-11-06
JPS57149551A (en) 1982-09-16
DE3106506A1 (en) 1982-10-07

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