EP2260117A1 - Matériau composite composé d'une matrice métallique dans laquelle sont répartis des filaments de nanotube de carbone et procédé de fabrication d'un tel matériau composite - Google Patents

Matériau composite composé d'une matrice métallique dans laquelle sont répartis des filaments de nanotube de carbone et procédé de fabrication d'un tel matériau composite

Info

Publication number
EP2260117A1
EP2260117A1 EP09730537A EP09730537A EP2260117A1 EP 2260117 A1 EP2260117 A1 EP 2260117A1 EP 09730537 A EP09730537 A EP 09730537A EP 09730537 A EP09730537 A EP 09730537A EP 2260117 A1 EP2260117 A1 EP 2260117A1
Authority
EP
European Patent Office
Prior art keywords
composite material
cnt
matrix
filaments
coating
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.)
Withdrawn
Application number
EP09730537A
Other languages
German (de)
English (en)
Inventor
Frank Heinrichsdorff
Jens Dahl Jensen
Manuela Schneider
Raymond Ullrich
Gabriele Winkler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
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 AG filed Critical Siemens AG
Publication of EP2260117A1 publication Critical patent/EP2260117A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/02—Pretreatment of the fibres or filaments
    • C22C47/025—Aligning or orienting the fibres
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/02—Pretreatment of the fibres or filaments
    • C22C47/06—Pretreatment of the fibres or filaments by forming the fibres or filaments into a preformed structure, e.g. using a temporary binder to form a mat-like element
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C22C2026/002—Carbon nanotubes
    • 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
    • Y10T428/249922—Embodying intertwined or helical component[s]
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2926—Coated or impregnated inorganic fiber fabric
    • Y10T442/2984—Coated or impregnated carbon or carbonaceous fiber fabric

Definitions

  • Composite material consisting of a metallic matrix in which CNT filaments are distributed, as well as methods for producing such a composite material
  • the invention relates to a composite material consisting of a metallic matrix in which CNT filaments are distributed. Furthermore, the invention relates to a method for creating a composite material, which consists of a metallic matrix, are distributed in the CNT filaments.
  • a composite material of the type mentioned can be prepared for example according to US 2007/0036978 Al.
  • CNT are dispersed in an electrolyte and a component to be coated is electroplated in this electrolyte.
  • a layer separates, which results in the aforementioned material composite.
  • the dispersed CNTs are incorporated in this layer. These are present in the material composite in a stoichiometric distribution with any orientation.
  • a fiber-reinforced composite material with a metal matrix is described.
  • the filaments used for application may be, for example, carbon fibers themselves coated with a metal. These are mixed with the matrix material and processed as part of a so-called rapid prototyping process.
  • the rate of incorporation of CNT filaments into the matrix is limited by the manufacturing process. Namely, a dispersion of the CNT in the electrolyte must be stabilized with wetting agents, the concentration of dispersed CNTs being dependent on the efficiency of these wetting agents. depends, but is limited. This is also the limiting factor to see if the CNT to be incorporated during the galvanic formation of the layer in the matrix material. This is because a stationary state sets in which determines the limited incorporation rate of CNT in the deposited matrix material.
  • the object of the invention is to provide a method for producing a composite material with CNT filaments contained therein, with which the incorporation rate of CNT filaments can be increased in comparison to the prior art.
  • CNT semifinished product consisting of a knitted fabric, a woven fabric, a net, a fleece or a paper, with which the material of the metallic matrix is coated.
  • the degree of filling of CNT filaments in the metallic matrix can be set almost arbitrarily.
  • the carrier for the composite material is much more the semifinished product itself containing the CNT filaments. This can be purchased in advance from suitable manufacturers, with the finishing deciding on the degree of filling of CNT in the material composite to be produced.
  • a different degree of filling of CNT filaments in the finished composite material is also obtained.
  • a significantly higher degree of filling of CNT filaments can be set by the use of said semifinished products, than by an electrochemical deposition of dispersed CNT.
  • the material of the metallic matrix is applied to the CNT semifinished product electrochemically, preferably galvanically, that is to say when a deposition potential is applied.
  • This is advantageously a method in which larger layer thicknesses can be achieved with little effort.
  • the ratio of matrix material to the material of the CNT filaments can be adjusted to a comparatively large extent.
  • CNT filaments are basically electrically conductive.
  • the semifinished product which is immersed, for example, on one side in an electrochemical coating bath and pulled out on the other side (continuous coating process), can be subjected to an electrical potential.
  • the coating result can be improved and the coating can be accelerated if, prior to the electrochemical coating, a pretreatment of the CNT semifinished product is carried out in order to improve the electrical conductivity and / or the adhesion properties for the material of the metallic matrix.
  • a pretreatment of the CNT semifinished product is carried out in order to improve the electrical conductivity and / or the adhesion properties for the material of the metallic matrix.
  • Such pretreatment can be carried out, for example, by coating by means of PVD coating technologies.
  • metallic bridges can be produced at the contact points of the CNT in the semifinished product.
  • An electrochemical coating can therefore take place under higher separation flows, whereby higher deposition rates can be achieved.
  • the matrix material is conditioned in particular when heated above the recrystallization temperature in order subsequently to perform a deformation which proceeds according to the principle of cold working.
  • This can be, for example, an extension of the composite material, whereby the already mentioned preferential orientation of the CNT filaments is favored.
  • a special embodiment of the method according to the invention thus also results if the composite of materials after the coating is folded and / or layered and / or twisted. This makes it possible, for example, to produce the already mentioned stranded electrical conductors.
  • the CNT semifinished product is of strand-shaped design and the method steps of the method are carried out continuously in each case on a section of the CNT semifinished product or of the starting material. Henden strand-shaped composite material are performed.
  • the strand-like semi-finished product thus passes through the stations of the manufacturing process one after the other, wherein the respective manufacturing step does not have to be stopped or started up only rarely.
  • the object of the invention is further to provide a composite material with a metallic matrix and CNT filaments distributed therein, which allows comparatively high incorporation rates of CNT.
  • This object is achieved according to the invention by virtue of the fact that, in the case of a composite material in which the CNT filaments in the matrix are intertwined or interwoven or linked together, the matrix is present in a work-hardened state.
  • This has the advantage that the material properties of the matrix can be adapted to the high-strength material properties of the embedded CNT in this. This allows a more homogeneous behavior of the composite material with regard to its mechanical properties. Cold working is made possible by embedding the CNT filaments by electrochemical means rather than by casting or rapid prototyping. This makes it possible to produce a ductile structure in comparison to cast structures.
  • the strain hardening can be carried out, for example, by stretching the composite material, which can advantageously simultaneously achieve a preferred orientation of the CNT filaments in the matrix material. Therefore, it is particularly advantageous also possible that the composite material is formed strand-shaped. This strand can be solidified by stretching, in particular, a material is formed which is suitable for the already mentioned application of an electrical conductor. According to the invention, a self-supporting framework of CNT filaments is formed in the matrix, which can advantageously greatly increase the incorporation rates of CNT in the metallic matrix.
  • the incorporation rate is no longer determined by the setting of a stationary state (diffusion process in the electrolyte), but is determined by the manner of constructing a used CNT semifinished with CNT filaments, which are intertwined or interwoven or linked together.
  • the mentioned semifinished products can for example be obtained from the company FutureCarbon. For example, on February 13, 2008, they offered 2D and 3D networks consisting of CNT on their website www.future-carbon.de, which can be processed as semi-finished products in the production process according to the invention (more on this in the following). Also, it is for example from Xiaobo Zhang et al. "Spinning and Processing Continuous Yarns from 4-inch Wafer Scale Super-Aligned Carbon Nanotube Arrays", Adv. Mater.
  • a particular embodiment of the invention is obtained when the intertwined or interwoven CNT filaments are arranged in several mutually adjacent layers in the matrix.
  • a composite of materials are used with CNT semi-finished products, which alone would not fill the required cross-sectional area. These could be, for example, strips of a CNT nonwoven. These are then layered in the manufacturing process, wherein formed between the individual layers parts of the metallic matrix, which are not interspersed by CNT filaments. Overall, a composite material with Sandwichartigem structure.
  • FIG. 1 shows a perspective view of an embodiment of the composite material according to the invention with illustrated sectional area through the cross section
  • Figure 2 shows an embodiment of the inventive method for producing the composite material
  • Figures 3 and 4 variants of a further processing of the composite material according to further embodiments of the inventive method.
  • a composite material 11 is shown, which is constructed as a sandwich of a plurality of layers 12 of a CNT semifinished product. These layers 12 have, as can be seen from the enlarged detail in FIG. 1, CNT filaments 13, which are intertwined. The cut-out enlargement can also be deduced that the layers 12 of CNT filaments 13 have a preferred orientation 14, which is oriented at the longitudinal extent of the strand-shaped composite material 11.
  • the CNT semifinished product can consist, for example, of strips of a CNT flow which are not shown in detail.
  • the individual layers are completely surrounded by the material of the matrix 15. This can be achieved, for example, by an electrochemical coating of the layers 12, which also ensures complete closure of the edges of the layers 12.
  • FIG. 2 shows a continuous production method for producing, for example, a composite material according to FIG.
  • a semifinished product 16 with CNT filaments not shown in more detail is unrolled from a supply roll 17 and provided on both sides with a starting layer of copper in a PVD coating installation 18 by means of two tags 19. Thereafter, the pretreated semifinished product 16 is guided via deflecting rollers through an electrochemical bath 21, this being acted upon via a not-shown electrode arrangement with a separating stream. In this case, the semifinished product 16 is connected as a cathode, so that a further coating with copper can take place.
  • a heat treatment device 22 After discharge of the semifinished product 16 from the bath 21, this is introduced into a heat treatment device 22. There is a heater 23, which on the one hand causes drying of the semi-finished product 16 of the electrolyte and secondly, for example, allows heating of the metallic matrix material above the recrystallization temperature.
  • a further processing of the thus treated semi-finished product, which already represents the composite material 11, can take place in different ways, wherein in the figures 3 and 4, two variants are shown.
  • the material composite according to FIG. cut strips which may for example have the dimensions of Figure 1.
  • a twist not shown 25 of the individual strands which are subsequently pulled out via a generating device 26 to a CNT wire 27.
  • the generating device 26 has a funnel-shaped hole 31 which on one side has the diameter of the CNT wire 27 to be produced.
  • the composite material 11 When passing through the generating device 26, the composite material 11 undergoes an elongation while reducing its diameter, which on the one hand leads to work hardening of the matrix material (copper) and on the other hand causes a preferential orientation of CNT filaments in the matrix material, which takes place at the longitudinal orientation of the produced CNT wire 27 oriented (similar to that shown in Figure 1).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Abstract

La présente invention concerne un matériau composite (11) composé d'une matrice métallique (15) dans laquelle sont répartis des filaments de nanotube de carbone (13). Selon l'invention, ces filaments de nanotube de carbone sont entrelacés, tissés ensemble ou combinés et la matrice (15) est écrouie. On obtient ainsi un taux de remplissage supérieur de filaments de nanotube de carbone dans le matériau de la matrice que par exemple dans le cas d'un dépôt électrochimique de nanotubes de carbone dispersés. L'invention concerne également un procédé de fabrication d'un tel matériau composite (11). Selon le procédé, des produits semi-finis adaptés, tels que des articles tricotés, des tissus, des articles à mailles, des non-tissés ou des papiers en filaments de nanotube de carbone sont recouverts de la matrice métallique (de préférence par voie électrochimique).
EP09730537A 2008-04-10 2009-04-01 Matériau composite composé d'une matrice métallique dans laquelle sont répartis des filaments de nanotube de carbone et procédé de fabrication d'un tel matériau composite Withdrawn EP2260117A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200810018695 DE102008018695A1 (de) 2008-04-10 2008-04-10 Materialverbund, bestehend aus einer metallischen Matrix, in der CNT-Filamente verteilt sind, sowie Verfahren zur Herstellung eines solchen Materialverbundes
PCT/EP2009/053843 WO2009124862A1 (fr) 2008-04-10 2009-04-01 Matériau composite composé d'une matrice métallique dans laquelle sont répartis des filaments de nanotube de carbone et procédé de fabrication d'un tel matériau composite

Publications (1)

Publication Number Publication Date
EP2260117A1 true EP2260117A1 (fr) 2010-12-15

Family

ID=40937351

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09730537A Withdrawn EP2260117A1 (fr) 2008-04-10 2009-04-01 Matériau composite composé d'une matrice métallique dans laquelle sont répartis des filaments de nanotube de carbone et procédé de fabrication d'un tel matériau composite

Country Status (4)

Country Link
US (1) US20110033692A1 (fr)
EP (1) EP2260117A1 (fr)
DE (1) DE102008018695A1 (fr)
WO (1) WO2009124862A1 (fr)

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Publication number Priority date Publication date Assignee Title
BR112012012525A2 (pt) * 2009-12-01 2019-09-24 Applied Nanostructured Sols materiais compósitos de matriz elétrica contendo materiais de fibra infundidos com nanotubos de carbono e métodos para produção dos mesmos
CA2785803A1 (fr) 2010-02-02 2011-11-24 Applied Nanostructured Solutions, Llc Matieres fibreuses a infusion de nanotubes de carbone contenant des nanotubes de carbone a alignement parallele, leurs procedes de production, et materiaux composites derives
US20120031644A1 (en) * 2010-04-15 2012-02-09 Los Alamos National Security, Llc Ultraconducting articles
US9017854B2 (en) 2010-08-30 2015-04-28 Applied Nanostructured Solutions, Llc Structural energy storage assemblies and methods for production thereof
EP2511393A1 (fr) * 2011-04-11 2012-10-17 Siemens Aktiengesellschaft Matrice dotée de nanotubes
CN108866369B (zh) * 2017-05-08 2020-03-17 清华大学 三维多孔复合材料
CN108866412B (zh) * 2017-05-08 2020-09-29 清华大学 三维多孔复合材料的制备方法

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US6080504A (en) * 1998-11-02 2000-06-27 Faraday Technology, Inc. Electrodeposition of catalytic metals using pulsed electric fields
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DE10215101A1 (de) * 2002-04-05 2003-10-16 Bayerische Motoren Werke Ag Verbundkörper aus einem Leichtmetallgrundwerkstoff
US8216956B2 (en) * 2003-10-10 2012-07-10 Ohio University Layered electrocatalyst for oxidation of ammonia and ethanol
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Also Published As

Publication number Publication date
WO2009124862A1 (fr) 2009-10-15
DE102008018695A1 (de) 2009-10-15
US20110033692A1 (en) 2011-02-10

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