EP2504167A2 - Élément électroconducteur au moins sur une surface et formé de nanotubes de carbone et d'un polymère et son procédé de production - Google Patents

Élément électroconducteur au moins sur une surface et formé de nanotubes de carbone et d'un polymère et son procédé de production

Info

Publication number
EP2504167A2
EP2504167A2 EP10805677A EP10805677A EP2504167A2 EP 2504167 A2 EP2504167 A2 EP 2504167A2 EP 10805677 A EP10805677 A EP 10805677A EP 10805677 A EP10805677 A EP 10805677A EP 2504167 A2 EP2504167 A2 EP 2504167A2
Authority
EP
European Patent Office
Prior art keywords
polymer
carbon nanotubes
substrate
mold
electrically conductive
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.)
Granted
Application number
EP10805677A
Other languages
German (de)
English (en)
Other versions
EP2504167B1 (fr
Inventor
Holger Althues
Stefan Kaskel
Christian Schrage
Jens Liebich
Erik Troschke
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.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Technische Universitaet Dresden
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Technische Universitaet Dresden
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 Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV, Technische Universitaet Dresden filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP2504167A2 publication Critical patent/EP2504167A2/fr
Application granted granted Critical
Publication of EP2504167B1 publication Critical patent/EP2504167B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon

Definitions

  • Element that is electrically conductive at least on one surface and formed with carbon nanotubes and a polymer, and method for its preparation
  • the invention relates to an element that is electrically conductive at least on one surface and formed with carbon nanotubes (CNTs) and a polymer and method for its preparation.
  • CNTs carbon nanotubes
  • Polymers are usually electrically non-conductive. This applies at least to the polymers available at low cost. However, since electrically conductive properties are desired for certain applications in combination with the use of such polymers, there are approaches to this end. For example, an admixture of electrically conductive substances, such as carbon in the form of soot is a possibility. However, a homogeneous distribution of the soot particles within the polymer matrix is difficult to achieve. In addition, the optical transparency is significantly reduced.
  • WO 2007/024206 A2 it is known to apply a coating system to an optically transparent substrate.
  • a coating system to an optically transparent substrate.
  • at least a very thin layer with carbon nanotubes and on this layer, a thin polymer layer is also applied.
  • the layer thicknesses are in the nanometer range.
  • the carbon nanotubes can also penetrate or diffuse into the polymer layer.
  • the carbon nanotubes should thereby produce an electrical conductivity.
  • the polymer should essentially fulfill a protective function for these and the
  • Adhesion of the layers on the substrate which is a suitable optically transparent polymer or glass can guarantee.
  • Interface are not desirable in many applications, as well as the substrate is electrically non-conductive.
  • An element according to the invention is formed with carbon nanotubes and a polymer. Other materials or materials are not required. It may be possible but electrical contacts, eg from a Metal be present.
  • Carbon nanotubes are embedded in the polymer starting from an electrically conductive surface.
  • the polymer is embedded in the polymer in a surface area starting from the surface which is at most 1000 nm, preferably at most 500 nm, particularly preferably at most 200 nm thick.
  • the carbon nanotubes are contained in a proportion of not more than 0.1% by mass. It can thereby be achieved that the element is electrically conductive at the respective surface and no electrical conductivity is present at least in the interior of the total volume since there is no or only an extremely small proportion of carbon nanotubes present there.
  • the proportion of carbon nanotubes should decrease successively from the surface. This is a graded distribution of carbon
  • Nanotubes in the inner volume of the element possible.
  • the elements according to the invention should have a minimum thickness of 0.05 mm up to several millimeters.
  • OLED's is the case. Other applications are as Heating element possible. But it can also be used an antistatic effect of the elements. For some applications, flexible deformability of the elements is advantageous.
  • the element may be an optically transparent substrate formed from a polymer, in particular a foil or plate.
  • a temporary substrate or a surface of a molding tool is coated with carbon nanotubes in a preferably homogeneous distribution over the surface.
  • carbon nanotubes in principle, all known types can be used.
  • a sufficiently viscous polymer or polymer precursor is to be applied to the carbon nanotube coated surface or filled into the mold.
  • the polymer or the polymer precursor is to be cured and in a final step, the element formed with the cured polymer and the carbon nanotube is removed from the temporary substrate or demolded from the mold.
  • the application of the carbon nanotubes can take place in the form of an aqueous dispersion on the surface of the temporary substrate or of the molding tool. After application, the liquid can be removed by drying.
  • the dispersion may be added with a suitable emulsifier.
  • a suitable viscosity may be maintained by the use of the polymer in dissolved form, as a melt, or in dissolved or unpolymerized or partially polymerized form.
  • the off ⁇ curing or solidification can then be achieved by evaporation of a solvent or by an energy input, such as heating or irradiation by means of suitable electromagnetic radiation.
  • Suitable usable in the invention are polymers selected from PMMA, PET, PC, PS and other polymers ⁇ from the group of polyester, Polyolelefine, polyurethanes, polyacrylates, polymethacrylates, and
  • Copolymers and combinations of these polymers.
  • a pressure be exercised. This can be achieved for example by means of at least one roller.
  • the filling of the polymer or the polymer precursor into a mold can be carried out analogously to plastic injection molding.
  • thermoplastic polymer should be selected. To cure then only a cooling is required.
  • a polymer precursor for the production of elements according to the invention. It is advantageous to fill the polymerizable liquid monomer and an initiator in a mold. A preliminary substrate provided with a layer of carbon nanotubes may form a wall of the molding tool. Thereafter, a thermal or radiation-initiated polymerization which leads to curing can be carried out.
  • the element After curing, the element can be detached or demolded from the temporary substrate. Surprisingly, the carbon nanotubes remain on the element and form an electrically conductive surface region, in which carbon nanotubes are embedded in the polymer matrix and at least partially enclosed by it.
  • the preparation of an element according to the invention can in an alternative but also be such that, are preferably applied in a Dispersion ⁇ at least one surface of a polymeric substrate carbon nanotubes.
  • a dispersion containing a surfactant it should be be removed. This can be achieved by washing with a suitable solvent for the surfactant, for example with ethanol. Afterwards, drying should be carried out. The dried with those adhering to the surface
  • Carbon Nanotube Substrate is reduced in its viscosity, for example by heating, at the coated surface, at least in the area near the surface, so that it is softened in this area. Simultaneously or subsequently, compressive forces are to be exerted in order to embed the carbon nanotubes in the surface-near region of the substrate. As a result of the cooling, the carbon nanotubes are permanently fixed in the polymer surface.
  • the compressive forces can be applied with a press or with at least one roller.
  • the press or roller (s) can be heated. However, heating can also be achieved by suitable irradiation.
  • a coated substrate in the form of a film or a plate can also be moved between two pressure rollers.
  • This process is similar to lamination.
  • the viscosity at the surface in the area close to the surface can be reduced by applying a suitable solvent for the respective polymer and this area can be sufficiently softened.
  • a solvent can be sprayed in sufficient amount, for example, on the respective surface.
  • the carbon nanotubes may already have been applied to the surface.
  • a solvent for PMMA as a solvent for PMMA as polymer Acetone, toluene, tetrahydrofuran or other solvents suitable for PMMA can be used.
  • the embedding of the carbon nanotubes can also be achieved or at least supported in this form by pressure forces exerted.
  • the solvent used can be evaporated after embedding. The required for the electrical conductivity
  • Proportion of carbon nanotubes is very small.
  • the optical transparency is thus only slightly reduced.
  • the mechanical, chemical and thermal properties of the polymeric base material are not or only very slightly changed.
  • the optical refractive index likewise changes accordingly, so that no refraction of electromagnetic radiation occurs at an interface, as in the prior art.
  • Example 1 With 12 mg carbon nanotubes and 12 g aqueous
  • Sodium dodecylsulfonic acid solution became a dispersion produced.
  • the acid content was 1% by mass.
  • the dispersion was applied for better distribution of Koh ⁇ lenstoff nanotubes with ultrasonic waves. Non-dispersible or insoluble components were centrifuged off. The supernatant obtained was applied as a layer on a temporary sub ⁇ strat. After drying this
  • Layer which had a layer thickness of about 50 nm, was carried out an order of a polymer solution.
  • PMMA molding compound 7N
  • 20 g of PMMA (molding compound 7N) were dissolved in 27.5 g of toluene. After application of the polymer solution, it was dried to evaporate the solvent. Drying may take place at elevated but also at room temperature ⁇ .
  • the element which had been provided with carbon nanotubes embedded in the polymer at the surface facing the temporary substrate in advance could be easily peeled off from the temporary substrate by peeling.
  • the element had a total thickness of 0.29 mm and an area of 864 mm 2 .
  • an electrical resistance of 100 kOhm was achieved.
  • an optical transparency of 81% was achieved.
  • a carbon nanotube dispersion was prepared as in Example 1 and sprayed and dried on a surface of a temporary glass substrate in the form of a glass sheet.
  • the thus coated temporary substrate was mounted by means of a spacer (polymer seal) and another uncoated glass pane to a polymerization chamber.
  • the coated surface of the temporary substrate faced inside. Through the spacer was inside the
  • Polymerization chamber a cavity to be filled with a polymer.
  • MMA methyl methacrylate
  • BDMA butanediol monoacrylate
  • TMPTA Trimethylpropane triacrylate
  • TPO 2,4,6-trimethylbenzylphosphine oxide
  • the polymerization chamber was dismantled, thereby demolding the finished element.
  • the element had a total thickness of 1.58 mm and an area of 1848 mm 2 . Im by means of the carbon
  • Nanotube electrically conductive region has reached an electrical resistance of 10 kOhm. At a wavelength of electromagnetic radiation of 600 nm, an optical transparency of 75% was still achieved.
  • aqueous dispersion containing 0.1% by mass of carbon nanotubes and 1% by mass of sodium dodecylbenzene sulfonate as surfactant was included prepared and dispersed by means of ultrasound at 20 kHz over a period of about 0.5 hours. Subsequently, the dispersion was centrifuged at 2600 g for a period of 12 minutes.
  • the upper 80% of the dispersion obtained after centrifuging was applied for application in a mold suitable for plastic injection molding with an airbrush nozzle at a pressure of 4 bar and at a flow rate of 0.1 ml / min.
  • the thus coated surface was washed with ethanol to remove the surfactant. This was followed by drying to remove the liquid residues.
  • the mold was then closed and a polymer in the form of a melt injected. A holding and curing time of 20 s was maintained until removal from the mold.
  • the element to be produced had dimensions of 150 mm * 150 mm * 5 mm.
  • Two polymers, namely polyamide 11 and polycarbonate were used for the production of an element according to the invention under otherwise identical conditions.
  • the element made of polycarbonate according to the invention had an optical transparency at a wavelength of 600 nm of 74.2%. In contrast, the transparency of an element without embedded carbon nanotubes was 81.6%.
  • the element made of polyamide according to the invention had an optical transparency at one wavelength of 600 nm of 79.1%. In contrast, the transparency of an element without embedded carbon nanotubes was 84.4%. The transparency was therefore only slightly reduced.
  • the elements achieved a surface electrical resistance of 12.3 kQ for polycarbonate and 28.8 kQ for polyamide as measured by the four-point method.
  • a dispersion was prepared and applied as in Example 3.
  • PET-G polyethylene terephthalate with glycol
  • the dry film was passed between two heated pressure rollers, whereby the carbon nanotubes were pressed by the compressive forces acting in the heat softened polymer so that they were embedded in the surface near area.
  • the carbon nanotube-modified PET film had an optical transparency of 79.8% at a wavelength of 600 nm.
  • a carbon nanotube-free PET film had a transparency of 85.5% by comparison.
  • the film obtained according to the invention had a surface electrical resistance of 110 kü.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Laminated Bodies (AREA)
  • Moulding By Coating Moulds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

L'invention concerne un élément, qui est électroconducteur au moins sur une surface et formé de nanotubes de carbone et d'un polymère, ainsi que son procédé de production. L'objectif de l'invention est de créer des éléments qui sont constitués en majeure partie d'un polymère non électroconducteur et qui présentent, au moins dans des zones superficielles, des propriétés électroconductrices, lesdits éléments devant être produits de manière simple et économique. À cet effet, des nanotubes de carbone sont incorporés, à partir d'une surface électroconductrice, dans le polymère dans une zone présentant une épaisseur de couche maximale de 1000 nm et la proportion maximale de nanotubes de carbone dans l'élément est de 0,1 % en masse.
EP10805677.1A 2009-11-23 2010-11-19 Élément électroconducteur au moins sur une surface et formé de nanotubes de carbone et d'un polymère et son procédé de production Active EP2504167B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009056583.3A DE102009056583B4 (de) 2009-11-23 2009-11-23 Verfahren zur Herstellung eines Elements, das zumindest an einer Oberfläche elektrisch leitend und mit Kohlenstoff-Nanoröhrchen und einem Polymer gebildet ist, sowie ein mit diesem Verfahren hergestelltes Element
PCT/DE2010/001388 WO2011060774A2 (fr) 2009-11-23 2010-11-19 Élément électroconducteur au moins sur une surface et formé de nanotubes de carbone et d'un polymère et son procédé de production

Publications (2)

Publication Number Publication Date
EP2504167A2 true EP2504167A2 (fr) 2012-10-03
EP2504167B1 EP2504167B1 (fr) 2017-01-11

Family

ID=43927220

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10805677.1A Active EP2504167B1 (fr) 2009-11-23 2010-11-19 Élément électroconducteur au moins sur une surface et formé de nanotubes de carbone et d'un polymère et son procédé de production

Country Status (4)

Country Link
EP (1) EP2504167B1 (fr)
DE (1) DE102009056583B4 (fr)
ES (1) ES2615283T3 (fr)
WO (1) WO2011060774A2 (fr)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4306990B2 (ja) * 2001-10-18 2009-08-05 独立行政法人産業技術総合研究所 非線形光学素子
US7588699B2 (en) 2001-11-02 2009-09-15 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Electrically conductive, optically transparent polymer/carbon nanotube composites and process for preparation thereof
JP2007512658A (ja) * 2003-08-08 2007-05-17 ゼネラル・エレクトリック・カンパニイ 導電性組成物及びその製造方法
KR100832259B1 (ko) * 2004-04-20 2008-05-28 타키론 가부시기가이샤 터치 패널용 투명 전기전도 성형체 및 터치 패널
DE102004032152A1 (de) * 2004-07-02 2006-01-26 Ticona Gmbh Verbund umfassend mindestens eine harte Komponente und mindestens eine weiche Komponente
WO2007024206A2 (fr) 2004-08-11 2007-03-01 Eikos, Inc. Liant fluoropolymere pour revetements conducteurs transparents a base de nanotubes de carbone
US7645497B2 (en) * 2005-06-02 2010-01-12 Eastman Kodak Company Multi-layer conductor with carbon nanotubes
DE502007000060D1 (de) * 2006-02-09 2008-09-18 Innovent Ev Technologieentwicklung Modifiziertes polymeres Substrat, insbesondere kunststoff, Verfahren zu dessen Herstellung und dessen Verwendung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011060774A2 *

Also Published As

Publication number Publication date
DE102009056583B4 (de) 2015-08-20
EP2504167B1 (fr) 2017-01-11
ES2615283T3 (es) 2017-06-06
DE102009056583A1 (de) 2011-06-01
WO2011060774A3 (fr) 2011-07-28
WO2011060774A2 (fr) 2011-05-26

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