EP2504167B1 - Element which is electrically conductive on at least one surface and comprises carbon nanotubes and a polymer, and method for the production thereof - Google Patents

Element which is electrically conductive on at least one surface and comprises carbon nanotubes and a polymer, and method for the production thereof Download PDF

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Publication number
EP2504167B1
EP2504167B1 EP10805677.1A EP10805677A EP2504167B1 EP 2504167 B1 EP2504167 B1 EP 2504167B1 EP 10805677 A EP10805677 A EP 10805677A EP 2504167 B1 EP2504167 B1 EP 2504167B1
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Prior art keywords
carbon nanotubes
polymer
substrate
moulding tool
coated
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German (de)
French (fr)
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EP2504167A2 (en
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Holger Althues
Stefan Kaskel
Christian Schrage
Jens Liebich
Erik Troschke
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Technische Universitaet Dresden
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Technische Universitaet Dresden
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    • 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

  • the invention relates to a method for producing an element, which is formed on at least one surface electrically conductive and with carbon nanotubes (CNTs) and a polymer and an element produced by the method.
  • 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. But there is a homogeneous distribution of soot particles difficult to reach within the polymer matrix. In addition, the optical transparency is significantly reduced.
  • WO 2007/024206 A2 It is known to apply a layer system to an optically transparent substrate. In this case, at least a very thin layer with carbon nanotubes and on this layer, a likewise thin polymer layer to be discharged. The layer thicknesses are in the nanometer range. It is also pointed out that the carbon nanotubes can also penetrate or diffuse into the polymer layer. The carbon nanotubes should cause an electrical conductivity. In this case, the polymer should essentially fulfill a protective function for these and the adhesion of the layers on the substrate, which should be a suitable optically transparent polymer or glass can guarantee.
  • the non-existent or too low electrical conductivity on the outer surface and the interface are not desirable in many applications, as well as the substrate is electrically non-conductive.
  • WO 2007/024206 describes transparent coatings with carbon nanotubes, which have a layer thickness in the range up to a maximum of 1000 nm.
  • a manufactured element according to the invention is formed with carbon nanotubes and a polymer. Different fabrics or materials are not required. However, electrical contacts, e.g. be made of a metal.
  • 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 at the respective surface is electrically conductive and at least in the interior of the total volume no electrical conductivity is given, since there is no or only an extremely small proportion of carbon nanotubes is / are.
  • the proportion of carbon nanotubes should decrease successively from the surface.
  • a graded distribution of carbon nanotubes in the inner volume of the element is possible.
  • the elements produced according to the invention should have a minimum thickness of 0.05 mm up to several millimeters.
  • the elements a surface is electrically conductive by means of the embedded carbon nanotubes and an oppositely arranged surface made entirely of the polymer is not electrically conductive.
  • Such elements can preferably be used for many applications, as is the case for example with a touch screen or even OLEDs. Further applications are possible as a heating element. But it can also be used an antistatic effect of the elements. In 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 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 introduced 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 mold.
  • the order of the carbon nanotubes can be in the form of an aqueous dispersion of the mold. After application, the liquid can be removed by drying. The dispersion may be added with a suitable emulsifier.
  • a suitable viscosity can be maintained by the use of the polymer in dissolved form, in the form of a melt or in dissolved or unpolymerized or partially polymerized form.
  • the hardening or solidification can be achieved by evaporation of a solvent or by an energy input, e.g. heating or irradiation can be achieved by means of suitable electromagnetic radiation.
  • Polymers used in the invention are selected from PMMA, PET, PC, PS and other polymers from the group of polyesters, polyolefins, polyurethanes, polyacrylates, polymethacrylates and copolymers and combinations of these polymers.
  • the filling of the polymer precursor is carried out in a mold, can be used with increased pressure. It can be a Pressing force has been exerted.
  • 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 the elements. 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 are at least partially enclosed by it.
  • an element can also take place in such a way that carbon nanotubes, preferably in a dispersion, are applied to at least one surface of a polymeric substrate.
  • a dispersion containing a surfactant it should be removed after application. This can be done by washing with a suitable Solvent for the surfactant, for example with ethanol. Afterwards a drying should be carried out.
  • the dried surface-adherent carbon nanotube substrate is reduced in viscosity, for example, by heating, on the coated surface, at least in the near surface area, so that it is softened in that 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. By 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 thereby. 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.
  • acetone, toluene, tetrahydrofuran or others for PMMA suitable solvents are used as a solvent for PMMA as a polymer.
  • 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 proportion of carbon nanotubes required for electrical conductivity 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 also changes accordingly, so that no refraction of electromagnetic radiation occurs at an interface, as in the prior art.
  • a dispersion was prepared using 12 mg carbon nanotubes and 12 g aqueous sodium dodecylsulfonic acid solution. The acid content was 1% by mass.
  • the dispersion was exposed to ultrasonic waves for better distribution of the carbon nanotubes.
  • Non-dispersible or insoluble components were centrifuged off.
  • the carbon nanotube dispersion was 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 sheet to a polymerization chamber.
  • the coated surface of the temporary substrate faced inside.
  • a spacer was inside the polymerization chamber, a cavity to be filled with a polymer.
  • MMA methyl methacrylate
  • BDMA butanediol monoacrylate
  • TMPTA trimethylolpropane 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 .
  • an electrical resistance of 10 kOhm was achieved.
  • an optical transparency of 75% was achieved.
  • aqueous dispersion containing 0.1% by mass of carbon nanotubes, 1% by mass of sodium dodecylbenzene sulfonate as surfactant was 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%.
  • the transparency of an element without embedded carbon nanotubes, in contrast, was 81.6%.
  • the element made of polyamide according to the invention had an optical transparency at a 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 k ⁇ for polycarbonate and 28.8 k ⁇ for polyamide as measured by the four-point method.
  • a dispersion was prepared and applied as in Example 2 .
  • a film of polyethylene terephthalate was appropriately coated with glycol (PET-G) having a thickness of 500 ⁇ m and an area of 250 mm * 200 mm.
  • PET-G glycol
  • the dry film was passed between two heated pressure rollers and the carbon nanotubes were pressed by the acting pressure forces 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 k ⁇ .

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  • 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)
  • Manufacturing Of Electric Cables (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Description

Die Erfindung betrifft ein Verfahren zur Herstellung eines Elements, das zumindest an einer Oberfläche elektrisch leitend und mit Kohlenstoff-Nanoröhrchen (CNT's) und einem Polymer gebildet ist und ein mit: dem Verfahren hergestelltes Element.The invention relates to a method for producing an element, which is formed on at least one surface electrically conductive and with carbon nanotubes (CNTs) and a polymer and an element produced by the method.

Polymere sind in der Regel elektrisch nicht leitend. Dies trifft zumindest auf die kostengünstig erhältlichen Polymere zu. Da aber elektrisch leitende Eigenschaften für bestimmte Applikationen in Kombination mit dem Einsatz solcher Polymere gewünscht werden, gibt es hierfür Lösungsansätze. So ist beispielsweise eine Beimischung elektrisch leitender Stoffe, wie z.B. Kohlenstoff in Form von Russ eine Möglichkeit. Dabei ist aber eine homogene Verteilung der Russpartikel innerhalb der Polymermatrix nur schwer erreichbar. Außerdem wird die optische Transparenz erheblich verringert.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. But there is a homogeneous distribution of soot particles difficult to reach within the polymer matrix. In addition, the optical transparency is significantly reduced.

Bei metallischen Deckschichten, die auf die Oberfläche von Polymeren aufgebracht werden können, ist ebenfalls die optische Transparenz beeinträchtigt außeradem kann es zu Haftungsproblemen kommen. Letzteres trifft auch auf Schichten, die mit elektrisch leitenden Oxiden, wie z.B. ITO gebildet sind, ebenfalls zu.In the case of metallic cover layers which can be applied to the surface of polymers, the optical transparency is also impaired, otherwise adhesion problems can arise. The latter also applies to layers coated with electrically conductive oxides, e.g. ITO are formed, too.

Es hat daher Versuche gegeben Polymere im Verbund mit Kohlenstoff-Nanoröhrchen einzusetzen. Dabei wird in US 2003/0158323 A1 vorgeschlagen Kohlenstoff-Nanoröhrchen in Polymere zu dispergieren und anschließend das jeweilige Polymer auszuhärten. wegen der schwierigen Oberflächenspannungsverhältnisse ist es daher nicht oder nur sehr aufwändig möglich eine homogene oder andere gezielte Verteilung der Kohlenstoff-Nanoröhrchen innerhalb des polymervolumens einhalten zu können.It has therefore been attempts to use polymers in combination with carbon nanotubes. It will be in US 2003/0158323 A1 proposed to disperse carbon nanotubes in polymers and then to cure the respective polymer. Because of the difficult surface tension conditions, it is therefore not possible or only with great difficulty to be able to observe a homogeneous or other targeted distribution of the carbon nanotubes within the polymer volume.

Aus WO 2007/024206 A2 ist es bekannt, ein Schichtsystem auf ein optisch transparentes Substrat aufzubringen. Dabei soll zumindest eine sehr dünne Schicht mit Kohlenstoff-Nanoröhrchen und auf dieser Schicht eine ebenfalls dünne Polymerschicht ausgetragen werden. Die Schichtdicken liegen dabei im Nanometerbereich. Es wird außerdem darauf hingewiesen, dass die Kohlenstoff-Nanoröhrchen auch in die Polymerschicht penetrieren bzw. eindiffundieren können. Die KohlenstoffNanoröhrchen sollen dabei eine elektrische Leitfähigkeit hervorrufen. Dabei soll das Polymer im Wesentlichen eine Schutzfunktion für diese erfüllen und die Haftung der Schichten auf dem Substrat, das ein geeignetes optisch transparentes Polymer oder Glas sein kann, gewährleisten.Out WO 2007/024206 A2 It is known to apply a layer system to an optically transparent substrate. In this case, at least a very thin layer with carbon nanotubes and on this layer, a likewise thin polymer layer to be discharged. The layer thicknesses are in the nanometer range. It is also pointed out that the carbon nanotubes can also penetrate or diffuse into the polymer layer. The carbon nanotubes should cause an electrical conductivity. In this case, the polymer should essentially fulfill a protective function for these and the adhesion of the layers on the substrate, which should be a suitable optically transparent polymer or glass can guarantee.

Hierbei ist keine oder nur eine sehr geringe elektrische Leitfähigkeit an der äußeren Oberfläche gegeben, da dort entweder nur Polymer vorhanden ist oder Kohlenstoff-Nanoröhrchen mit sehr kleinem Anteil vorhanden sind. Außerdem ist zwischen den beiden Schichten und dem Substrat eine Grenzfläche vorhanden, bei der ein abrupter Wechsel des optischen Brechungsindex auftritt.Here, no or only a very low electrical conductivity is given on the outer surface, since there either only polymer is present or carbon nanotubes with a very small proportion are present. In addition, there is an interface between the two layers and the substrate in which an abrupt change in the optical refractive index occurs.

Die nicht vorhandene oder zu geringe elektrische Leitfähigkeit an der äußeren Oberfläche und die Grenzfläche sind aber bei vielen Applikationen nicht erwünscht, da ja auch das Substrat elektrisch nicht leitend ist.However, the non-existent or too low electrical conductivity on the outer surface and the interface are not desirable in many applications, as well as the substrate is electrically non-conductive.

In WO 2007/024206 sind tranparente Beschichtungen mit Kohlenstoff-Nanoröhren beschrieben, die eine Schicht-dicke im Bereich bis zu maximal 1000 nm aufweisen.In WO 2007/024206 describes transparent coatings with carbon nanotubes, which have a layer thickness in the range up to a maximum of 1000 nm.

Ein Mehrschichtaufbau mit Kohlenstoff-Nanoröhrchen ist aus US 2006/0274049 bekannt.A multi-layer construction with carbon nanotubes is out US 2006/0274049 known.

Von O'Connor et al. ist in "Development of transparent conducting composites by surface infiltrationof nanotubes into commercial polymer films"; CARBON ELSEVIER, OXFORD, GB, Bd, 47, Nr. 8, 1. Juli 2009, Seiten 1983-1988, XP026104602, ISSN; 0008-6223 , DOI:DOI:10.1016/J.Carbon.2009.03.048 ist ein Verfahren, bei dem CNT's in Poren eines gequollenen Polymers eingebettet werden sollen, beschrieben. Dabei soll mit Ultraschallwellen gearbeitet werden. By O'Connor et al. is in "Development of transparent conducting composites by surface infiltration of nanotubes into commercial polymer films"; CARBON ELSEVIER, OXFORD, GB, Bd, 47, No. 8, 1 July 2009, pages 1983-1988, XP026104602, ISSN; 0008-6223 , DOI: DOI: 10.1016 / J.Carbon.2009.03.048 is a process in which CNTs are to be embedded in pores of a swollen polymer. It should be worked with ultrasonic waves.

Yu et al. beschreiben in "Fabrication of carbon nanotube based transparentconductive thin films using layer-by-layer technology", SURFACE AND COATINGS TECHNOLOGY, ELSEVIER, AMSTERDAM, NL, Bd. 202, Nr. 10, 14. Januar 2008, Seiten 2002-2007, XP022419838, ISSN: 0257-8972, DOI:DOI:10.1016/J.SURFCOAT.2008.12.012 die Zugabe von CNT's in eine Polymermatrix. Yu et al. describe in "Fabrication of carbon nanotube based transparent conductive thin film using Layer-by-layer technology, SURFACE AND COATINGS TECHNOLOGY, ELSEVIER, AMSTERDAM, NL, Vol. 202, No. 10, 14 January 2008, pages 2002-2007, XP022419838, ISSN: 0257-8972, DOI: DOI: 10.1016 /J.SURFCOAT.2008.12.012 the addition of CNTs into a polymer matrix.

Möglichkeiten für die Herstellung transparenter Kompositfilmen mit Kohlenstoff-Nanoröhrchen in Polyurethan sind von Ki, H. S. et al. in "Fabrication of transparent conductive carbon nanotubes/polyurethaneurea composite films by solvent evaporation-induced self assembly (EISA)", COMPOSITE SCIENCE AND TECHNOLOGY, ELSEVIER, uk; Bd: 69, Nr. 5, 1. April 2009, Seiten 645-650, XPO25947105, ISSN: 0266-3539, DOI:DOI:10.1016/J.COMPSCITECH.2008.12.012 beschrieben.Possibilities for the production of transparent composite films with carbon nanotubes in polyurethane are of Ki, HS et al. in "Fabrication of transparent conductive nanotubes / polyurethaneurea composite films by solvent evaporation-induced self assembly (EISA)", COMPOSITE SCIENCE AND TECHNOLOGY, ELSEVIER, uk; Vol. 69, No. 5, 1 April 2009, pages 645-650, XPO25947105, ISSN: 0266-3539, DOI: DOI: 10.1016 / J.COMPSCITECH.2008.12.012 described.

Eine Begrenzung des CNT-Anteils in elektrsich leitenden transparenten Filmen auf 1 Masse-% ist von L. Valentini et al. in "Electrodeposited carbon nanotubes as template for preparation of semitransparent conductive thin films by in situ polymerization of methyl methacrylate"; CARBON, ELSEVIER, OXFORD, GB, Bd. 45, Nr. 13, 20. Oktober 2007), Seiten 2685-2691, XP022308256, ISSN: 0008-6223 erwähnt .A limitation of the CNT content in electroconductive transparent films to 1 mass% is of L. Valentini et al. in "Electrodeposited carbon nanotubes as template for the preparation of semitransparent conductive thin films by in situ polymerization of methyl methacrylate"; CARBON, ELSEVIER, OXFORD, GB, Vol. 45, No. 13, Oct. 20, 2007), pages 2685-2691, XP022308256, ISSN: 0008-6223 ,

Es ist daher Aufgabe der Erfindung, Elemente, die zum größten Teil aus einem elektrisch nicht leitenden Polymer gebildet sind, zumindest in oberflächenbereichen mit elektrisch leitenden Eigenschaften zur Verfügung zu stellen; wobei die Elemente mit geringem Aufwand kostengünstig hergestellt werden können.It is therefore an object of the invention to provide elements which are formed for the most part of an electrically non-conductive polymer, at least in surface areas with electrically conductive properties available; wherein the elements can be produced inexpensively with little effort.

Erfindungsgemäß wird diese Aufgabe mit Verfahren, die die Merkmale der Ansprüche 1 oder 2 aufweisen, gelöst. Vorteilhafte Ausgestaltungen und Weiterbildungen der Erfindung sind mit in untergeordneten Ansprüchen bezeichneten Merkmalen realisierbar.According to the invention, this object is achieved by methods having the features of claims 1 or 2. Advantageous embodiments and further developments of the invention can be realized with features designated in subordinate claims.

Ein erfindungsgemäße hergestelltes Element ist mit Kohlenstoff-Nanoröhrchen und einem Polymer gebildet. Anders Stoffe oder Materialien sind nicht erforderlich. Es können ggf. aber elektrische Kontakte, z.B. aus einem Metall vorhanden sein.A manufactured element according to the invention is formed with carbon nanotubes and a polymer. Different fabrics or materials are not required. However, electrical contacts, e.g. be made of a metal.

Dabei sind Kohlenstoff-Nanoröhrchen ausgehend von einer elektrisch leitenden Oberfläche in das Polymer eingebettet. Das Polymer ist dabei in einem Oberflächenbereich ausgehend von der Oberfläche, der maximal 1000 nm, bevorzugt maximal 500 nm, besonders bevorzugt maximal 200 nm dick ist, in das Polymer eingebettet. Die Kohlenstoff-Nanoröhrchen sind mit einem Anteil von maximal 0,1 Masse-% enthalten. Dadurch kann erreicht werden, dass das Element an der jeweiligen Oberfläche elektrisch leitend und zumindest im Inneren des Gesamtvolumens keine elektrische Leitfähigkeit gegeben ist, da dort keine bzw. nur ein äußerst kleiner Anteil an Kohlenstoff-Nanoröhrchen vorhanden ist/sind.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 at the respective surface is electrically conductive and at least in the interior of the total volume no electrical conductivity is given, since there is no or only an extremely small proportion of carbon nanotubes is / are.

Der Anteil an Kohlenstoff-Nanoröhrchen sollte sich ausgehend von der Oberfläche sukzessive verringern. Damit ist eine gradierte Verteilung der Kohlenstoff-Nanoröhrchen in das innere Volumen des Elements möglich.The proportion of carbon nanotubes should decrease successively from the surface. Thus, a graded distribution of carbon nanotubes in the inner volume of the element is possible.

Die erfindungsgemäß hergestellten Elemente sollten eine Mindestdicke von 0,05 mm bis hin zu mehreren Millimetern aufweisen.The elements produced according to the invention should have a minimum thickness of 0.05 mm up to several millimeters.

Es besteht die Möglichkeit, die Elemente so herzustellen, dass eine oberfläche mittels der eingebetteten Kohlenstoff-Nanoröhrchen elektrisch leitend und eine gegenüberliegend angeordnete vollständig aus dem Polymer gebildete Oberfläche elektrisch nicht leitend ist. Solche Elemente können bevorzugt für viele Anwendungen genutzt werden, wie dies beispielsweise bei einem Touch screen oder auch OLED's der Fall ist. Weitere Anwendungen sind als Heizelement möglich. Es kann aber auch eine antistatische Wirkung der Elemente genutzt werden. Bei einigen Applikationen ist eine flexible Verformbarkeit der Elemente von Vorteil.It is possible to make the elements a surface is electrically conductive by means of the embedded carbon nanotubes and an oppositely arranged surface made entirely of the polymer is not electrically conductive. Such elements can preferably be used for many applications, as is the case for example with a touch screen or even OLEDs. Further applications are possible as a heating element. But it can also be used an antistatic effect of the elements. In some applications, flexible deformability of the elements is advantageous.

Das Element kann ein optisch transparentes aus einem Polymer gebildetes Substrat, insbesondere eine Folie oder Platte sein.The element may be an optically transparent substrate formed from a polymer, in particular a foil or plate.

Die Herstellung erfindungsgemäßer Elemente kann mit einfach und kostengünstig durchführbaren Verfahren erfolgen, bei dem wenige Verfahrensschritte auszuführen sind.The production of elements according to the invention can be carried out by simple and cost-effective methods in which a few process steps are to be carried out.

So wird in einem ersten Schritt eine Oberfläche eines Formwerkzeuges mit Kohlenstoff-Nanoröhrchen in bevorzugt homogener Verteilung über die Fläche beschichtet. Dabei können prinzipiell alle bekannten Arten an Kohlenstoff-Nanoröhrchen eingesetzt werden.Thus, in a first step, a surface of a molding tool is coated with carbon nanotubes in a preferably homogeneous distribution over the surface. In principle, all known types of carbon nanotubes can be used.

In einem nachfolgenden Schritt soll ein ausreichend viskoses Polymer oder eine Polymervorstufe in das Formwerkzeug eingefüllt werden.In a subsequent step, a sufficiently viscous polymer or polymer precursor is to be introduced into the mold.

In einem dritten Schritt soll das Polymer oder die Polymervorstufe ausgehärtet werden und in einem letzten Schritt wird das mit dem ausgehärteten Polymer und den Kohlenstoff-Nanoröhrchen gebildete Element aus dem Formwerkzeug entformt.In a third step, 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 mold.

Es ist also kein dem aus WO 2007/024206 vergleichbares Substrat mehr vorhanden. Vielmehr wird dieses durch das Polymer im Verbundmaterial vollständig ersetzt. Die Kohlenstoff-Nanoröhrchen werden ohne weiteres zu tun in das Polymer eingebettet. Die Eindringtiefe kann durch die Dicke der im ersten Verfahrensschritt mit den Kohlenstoff-Nanoröhrchen ausgebildeten Schicht beeinflusst werden.So it's not like that WO 2007/024206 comparable substrate more available. Rather, this is completely replaced by the polymer in the composite material. The carbon nanotubes are readily embedded in the polymer. The penetration depth can be influenced by the thickness of the layer formed in the first process step with the carbon nanotubes.

Der Auftrag der Kohlenstoff-Nanoröhrchen kann in Form einer wässrigen Dispersion des Formwerkzeugs erfolgen. Nach dem Auftrag kann die Flüssigkeit durch Trocknen entfernt werden. Der Dispersion kann ein geeigneter Emulgator zugegeben werden.The order of the carbon nanotubes can be in the form of an aqueous dispersion of the mold. After application, the liquid can be removed by drying. The dispersion may be added with a suitable emulsifier.

Beim Auftragen des Polymers oder der Polymervorstufe auf die Oberfläche eines Formwerkzeugs kann eine geeignete Viskosität durch den Einsatz des Polymers in gelöster Form, als Schmelze oder in gelöster bzw. in nicht oder teilweise polymerisierter Form, eingehalten werden. Die Aushärtung bzw. Verfestigung kann dabei durch Verdampfen eines Lösungsmittels oder durch einen Energieeintrag, z.B. eine Erwärmung oder Bestrahlung mittels geeigneter elektromagnetischer Strahlung erreicht werden.When applying the polymer or the polymer precursor to the surface of a mold, a suitable viscosity can be maintained by the use of the polymer in dissolved form, in the form of a melt or in dissolved or unpolymerized or partially polymerized form. The hardening or solidification can be achieved by evaporation of a solvent or by an energy input, e.g. heating or irradiation can be achieved by means of suitable electromagnetic radiation.

Bei der Erfindung eingesetzte Polymere sind ausgewählt aus PMMA, PET, PC, PS und weitere Polymere aus der Gruppe der Polyester, Polyolelefine, Polyurethane, Polyacrylate, Polymethacrylate sowie Copolymere und Kombinationen dieser Polymere.Polymers used in the invention are selected from PMMA, PET, PC, PS and other polymers from the group of polyesters, polyolefins, polyurethanes, polyacrylates, polymethacrylates and copolymers and combinations of these polymers.

Beim Verfahrensschritt, das Einfüllen der Polymervorstufe in ein Formwerkzeug erfolgt, kann mit erhöhtem Druck gearbeitet werden. Dabei kann eine Druckkraft ausgeübt worden.In the process step, the filling of the polymer precursor is carried out in a mold, can be used with increased pressure. It can be a Pressing force has been exerted.

Das Einfüllen des Polymers oder der Polymervorstufe in ein Formwerkzeug kann analog zum Kunststoffspritzgießen durchgeführt werden.The filling of the polymer or the polymer precursor into a mold can be carried out analogously to plastic injection molding.

Wird das Polymer als Schmelze zum Auftragen oder Einfüllen eingesetzt, sollte ein thermoplastisches Polymer gewählt werden. Zur Aushärtung ist dann lediglich eine Abkühlung erforderlich.If the polymer is used as a melt for application or filling, a thermoplastic polymer should be selected. To cure then only a cooling is required.

Es kann auch eine Polymervorstufe für die Herstellung der Elemente eingesetzt werden. Dabei ist es günstig das polymerisierbare flüssige Monomer und einen Initiator in ein Formwerkzeug zu füllen. Ein vorab mit einer Schicht von Kohlenstoff-Nanoröhrchen versehenes temporäres Substrat kann eine Wand des Formwerkzeuges bilden. Danach kann eine thermische oder strahlungsinitiierte Polymerisation, die zur Aushärtung führt, durchgeführt werden.It is also possible to use a polymer precursor for the production of the elements. 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.

Nach dem Aushärten kann das Element vom temporären Substrat abgelöst oder entformt werden. überraschenderweise verbleiben dabei die Kohlenstoff-Nanoröhrchen am Element und bilden einen elektrisch leitenden Oberflächenbereich, in dem Kohlenstoff-Nanoröhrchen in der Polymermatrix eingebettet und von diesem zumindest teilweise umschlossen sind.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 are at least partially enclosed by it.

Die Herstellung eines Elements kann in einer Alternative aber auch so erfolgen, dass auf mindestens eine Oberfläche eines polymeren Substrats Kohlenstoff-Nanoröhrchen, bevorzugt in einer Dispersion aufgetragen werden. Bei einer Dispersion in der ein Tensid enthalten ist, sollte dieses nach dem Auftrag entfernt werden. Dies kann durch Waschen mit einem geeigneten Lösungsmittel für das Tensid, beispielsweise mit Ethanol, erreicht werden. Im Anschluss sollte eine Trocknung durchgeführt werden.Alternatively, the production of an element can also take place in such a way that carbon nanotubes, preferably in a dispersion, are applied to at least one surface of a polymeric substrate. For a dispersion containing a surfactant, it should be removed after application. This can be done by washing with a suitable Solvent for the surfactant, for example with ethanol. Afterwards a drying should be carried out.

Das getrocknete mit den an der Oberfläche anhaftenden Kohlenstoff-Nanoröhrchen Substrat wird, beispielsweise durch eine Erwärmung, an der beschichteten Oberfläche in seiner Viskosität zumindest im Oberflächen nahen Bereich verringert, so dass es in diesem Bereich erweicht ist. Gleichzeitig oder nachfolgend dazu sollen Druckkräfte ausgeübt werden, um die Kohlenstoff-Nanoröhrchen im Oberflächen nahen Bereich des Substrats einzubetten. Durch die Abkühlung sind dann die Kohlenstoff-Nanoröhrchen dauerhaft in der Polymeroberfläche fixiert. Die Druckkräfte können mit einer Presse oder mit mindestens einer Walze aufgebracht werden. Die Presse oder walze(n) können dabei beheizbar sein. Eine Erwärmung kann aber auch durch eine geeignete Bestrahlung erreicht werden. Ein beschichtetes in Form einer Folie oder einer Platte ausgebildetes Substrat kann auch zwischen zwei Druckwalzen hindurch bewegt werden.The dried surface-adherent carbon nanotube substrate is reduced in viscosity, for example, by heating, on the coated surface, at least in the near surface area, so that it is softened in that 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. By 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 thereby. 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.

Dieses Verfahren ist mit dem Laminieren vergleichbar.This process is similar to lamination.

Allein oder zusätzlich zum Erwärmen kann die Viskosität an der Oberfläche im Oberflächen nahen Bereich durch den Auftrag eines für das jeweilige Polymer geeigneten Lösungsmittels reduziert und dieser Bereich ausreichend erweicht werden. Ein Lösungsmittel kann in hierfür ausreichender Menge beispielsweise auf die jeweilige Oberfläche aufgesprüht werden. Die Kohlenstoff-Nanoröhrchen können dabei bereits auf die Oberfläche appliziert worden sein.On its own or in addition to heating, 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.

So können als Lösungsmittel z.B. für PMMA als Polymer Aceton, Toluoul, Tetrahydrofuran oder andere für PMMA geeignete Lösungsmittel eingesetzt werden.For example, as a solvent for PMMA as a polymer, acetone, toluene, tetrahydrofuran or others for PMMA suitable solvents are used.

Die Einbettung der Kohlenstoff-Nanoröhrchen kann auch in dieser Form durch ausgeübte Druckkräfte erreicht oder zumindest unterstützt werden. Das eingesetzte Lösungsmittel kann nach der Einbettung verdampft werden.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.

Der für die elektrische Leitfähigkeit erforderliche Anteil an Kohlenstoff-Nanoröhrchen ist sehr klein. Die optische Transparenz wird somit nur geringfügig reduziert. Die mechanischen, chemischen und thermischen Eigenschaften des polymeren Basiswerkstoffs werden nicht oder nur sehr geringfügig verändert.The proportion of carbon nanotubes required for electrical conductivity 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.

Durch den gradierten Übergang des Anteils an Kohlenstoff-Nanoröhrchen ausgehend von der jeweiligen Oberfläche in das Innere des Elements ändert sich der optische Brechungsindex ebenfalls entsprechend, so dass keine Brechung elektromagnetischer Strahlung an einer Grenzfläche, wie beim Stand der Technik, auftritt.Due to the graded transition of the proportion of carbon nanotubes from the respective surface into the interior of the element, the optical refractive index also changes accordingly, so that no refraction of electromagnetic radiation occurs at an interface, as in the prior art.

Für die Herstellung können an sich bekannte Technologien, wie sie bei der Verarbeitung von Polymeren eingesetzt werden, genutzt werden. Es ist kein Unterdruck oder gar Vakuumbedingungen erforderlich.For the production of known technologies, such as those used in the processing of polymers can be used. There is no vacuum or even vacuum conditions required.

Nachfolgend soll die Erfindung an Hand von Beispielen näher erläutert werden.The invention will be explained in more detail with reference to examples.

Beispiel 1:Example 1:

Mit 12 mg Kohlenstoff-Nanoröhrchen und 12 g wässriger Natriumdodecylsulfonsaurelösung wurde eine Dispersion hergestellt. Der Säureanteil lag dabei bei 1 Masse-%.A dispersion was prepared using 12 mg carbon nanotubes and 12 g aqueous sodium dodecylsulfonic acid solution. The acid content was 1% by mass.

Die Dispersion wurde zur besseren Verteilung der Kohlenstoff-Nanoröhrchen mit Ultraschallwellen beaufschlagt. Nicht dispergierbare oder unlösliche Bestandteile wurden abzentrifugiert.The dispersion was exposed to ultrasonic waves for better distribution of the carbon nanotubes. Non-dispersible or insoluble components were centrifuged off.

Die Dispersion, mit Kohlenstoff-Nanoröhrchen wurde auf eine Oberfläche eines temporären Glassubstrats, in Form einer Glasscheibe, gesprüht und getrocknet.The carbon nanotube dispersion was sprayed and dried on a surface of a temporary glass substrate in the form of a glass sheet.

Das so beschichtete temporäre Substrat wurde mittels eines Abstandshalters (Polymerdichtung) und einer weiteren unbeschichteten Glasscheibe zu einer Polymerisationskammer montiert. Die beschichtete Oberfläche des temporären Substrats wies in deren Inneres. Durch den Abstandshalter befand sich im Inneren der Polymerisationskammer ein Hohlraum, der mit einem Polymer befüllt werden soll.The thus-coated temporary substrate was mounted by means of a spacer (polymer seal) and another uncoated glass sheet 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.

Hierfür wurden 5 g Methylmetacrylat (MMA) mit 1,5 g Butandiolmonoacrylat (BDMA), 1,5 g Trimethylpropanetriacrylat (TMPTA) und 0,08 g 2,4,6-trimethylbenzylphosphinoxid (TPO) vermischt. Diese Monomermischung wurde dann in das Innere der Pölymerisationskammer gefüllt, bis der Hohlraum vollständig ausgefüllt war. Die Aufhärtung erfolgte über einen Zeitraum von 25 min. Dabei wurde UV-Strahlung eingesetzt.For this purpose, 5 g of methyl methacrylate (MMA) were mixed with 1.5 g of butanediol monoacrylate (BDMA), 1.5 g of trimethylolpropane triacrylate (TMPTA) and 0.08 g of 2,4,6-trimethylbenzylphosphine oxide (TPO). This monomer mixture was then filled into the interior of the polymerization chamber until the cavity was completely filled. The hardening took place over a period of 25 min. In this case, UV radiation was used.

Im Anschluss daran wurde die Polymersisationskammer demontiert und dabei das fertige Element entformt.Following this, the polymerization chamber was dismantled, thereby demolding the finished element.

Das Element hatte eine Gesamtdicke von 1.58 mm und eine Fläche von 1848 mm2. Im mittels der Kohlenstoff-Nanoröhrchen elektrisch leitenden Bereich wurde ein elektrischer Widerstand von 10 kOhm erreicht. Bei einer Wellenlänge elektromagnetischer Strahlung von 600 nm wurde noch eine optische Transparenz von 75 % erreicht.The element had a total thickness of 1.58 mm and an area of 1848 mm 2 . In the electrically conductive region by means of the carbon nanotubes, an electrical resistance of 10 kOhm was achieved. At a wavelength of electromagnetic radiation of 600 nm, an optical transparency of 75% was achieved.

Beispiel 2:Example 2:

Es wurde eine wässrige Dispersion in der 0,1 Masse-% Kohlenstoff-Nanoröhrchen, 1 Masse-% Natrium-Dodecylbenzen-Sulfonat als Tensid enthalten waren hergestellt und mittels Ultraschall bei 20 kHz über einen Zeitraum von ca. 0,5 Stunden dispergiert. Im Anschluss wurde die Dispersion mit 2600 g über einen Zeitraum von 12 min zentrifugiert.An aqueous dispersion containing 0.1% by mass of carbon nanotubes, 1% by mass of sodium dodecylbenzene sulfonate as surfactant was 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.

Die nach dem Zentrifugieren erhaltenen oberen 80 % der Dispersion wurden für den Auftrag in ein Formwerkzeug, das zum Kunststoffspritsgießen geeignete ist, mit einer Airbrushdüse bei einem Druck von 4 bar und mit einem Volumenstrom von 0,1 ml/min aufgebracht.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.

Die so beschichtete Oberfläche wurde mit Ethanol gewaschen, um das Tensid zu entfernen. Anschließend erfolgte eine Trocknung zur Entfernung der Flüssigkeitsrückstande.The thus coated surface was washed with ethanol to remove the surfactant. This was followed by drying to remove the liquid residues.

Das Formwerkzeug wurde dann geschlossen und ein in Form einer Schmelze vorliegendes Polymer eingespritzt. Es wurde dabei eine Halte- und Aushärtezeit von 20 s bis zum Entformen eingehalten.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.

Das herzustellende Element hatte dabei Abmaße von 150 mm * 150 mm * 5 mm. Es wurden zwei Polymere, nämlich Polyamid 11 und Polycarbonat für die Herstellung eines erfindungsgemäßen Elements unter ansonsten gleichen Bedingungen eingesetzt.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.

Das erfindungsgemäß aus Polycarbonat hergestellte Element hatte eine optische Transparenz bei einer Wellenlänge von 600 nm von 74,2 %. Die Transparenz eines Elements ohne eingebettete Kohlenstoff-Nanoröhrchen lag im Gegensatz dazu bei 81.6 %.The element made of polycarbonate according to the invention had an optical transparency at a wavelength of 600 nm of 74.2%. The transparency of an element without embedded carbon nanotubes, in contrast, was 81.6%.

Das erfindungsgemäß aus Polyamid hergestellte Element hatte eine optische Transparenz bei einer Wellenlänge von 600 nm von 79,1 %. Die Transparenz eines Elements ohne eingebettete Kohlenstoff-Nanoröhrchen lag im Gegensatz dazu bei 84,4 %. Die Transparenz wurde also nur geringfügig reduziert.The element made of polyamide according to the invention had an optical transparency at a 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.

Die Elemente erreichten einen elektrischen Oberflächenwiderstand von 12,3 kΩ für Polycarbonat und 28,8 kΩ für Polyamid, gemessen mit der Vier-Punkt-Methode.The elements achieved a surface electrical resistance of 12.3 kΩ for polycarbonate and 28.8 kΩ for polyamide as measured by the four-point method.

Beispiel 3Example 3

Es wurde eine Dispersion, wie beim Beispiel 2 hergestellt und aufgetragen.A dispersion was prepared and applied as in Example 2 .

Es wurde eine Folie aus Polyethylenterephtalat mit Glycol (PET-G) mit einer Dicke von 500 µm und einer Fläche von 250 mm * 200 mm entsprechend beschichtet.A film of polyethylene terephthalate was appropriately coated with glycol (PET-G) having a thickness of 500 μm and an area of 250 mm * 200 mm.

Tensid und Wasser wurden ebenfalls, wie beim Beispiel 2 entfernt.Surfactant and water were also removed as in Example 2.

Die trockenen Folie wurde zwischen zwei beheizten Druckwalzen geführt und dabei die Kohlenstoff-Nanoröhrchen durch die wirkenden Druckkräfte in das durch Erwärmen erweichte Polymer eingedrückt, so dass sie im Oberflächen nahen Bereich eingebettet waren.The dry film was passed between two heated pressure rollers and the carbon nanotubes were pressed by the acting pressure forces in the heat softened polymer so that they were embedded in the surface near area.

Dabei wurde eine Temperatur von 120 °C an den Druckwalzen eingehalten.In this case, a temperature of 120 ° C at the pressure rollers respected.

Die mit den Kohlenstoff-Nanoröhrchen modifizierte PET-Folie hatte eine optische Transparenz von 79,8 % bei einer Wellenlänge von 600 nm. Eine von Kohlenstoff-Nanoröhrchen freie PET-Folie hatte im Vergleich eine Transparenz von 85,5 %.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.

Die erfindungsgemäß erhaltene Folie hatte einen elektrischen Oberflächenwiderstand von 110 kΩ.The film obtained according to the invention had a surface electrical resistance of 110 kΩ.

Claims (8)

  1. A method for producing an element which is electrically conductive at least at one surface thereof and is formed with carbon nanotubes and a polymer, characterized in that in a method step
    (i) a surface of a moulding tool is coated with carbon nanotubes;
    in a subsequent step
    (ii) a sufficiently viscous polymer or a polymer precursor is filled in the moulding tool in dissolved form, in the form of a melt or in a partially polymerised form as a monomer, wherein the polymer is selected from PMMA, PET, PC, PS, polymers of the group of polyesters, polyolefins, polyurethanes, polyacrylates and PMA as well as copolymers or combinations thereof;
    in step
    (iii) the polymer or the polymer precursor is hardened and
    in step
    (iv) the element which is formed with the hardened polymer and the carbon nanotubes is demoulded from the moulding tool; wherein
    carbon nanotubes are embedded in the polymer of the element in a proportion of 0.1 % by mass at a maximum.
  2. A method for producing an element which is electrically conductive at least at one surface thereof and is formed with carbon nanotubes and a polymer, characterized in that
    carbon nanotubes are applied to at least one surface of a polymeric substrate, subsequently viscosity of the polymeric substrate is reduced at least in the area near the surface by heating the surface which is coated with carbon nanotubes and/or by partially dissolving an area near the surface using a solvent for the polymer, and the carbon nanotubes are thereby simultaneously or subsequently embedded in the area near the surface in a proportion of 0.1 % by mass at a maximum by application of compressive forces; wherein the polymer is selected from PMMA, PET, PC, PS, polymers of the group of polyesters, polyolefins, polyurethanes, polyacrylates and PMA as well as copolymers or combinations thereof.
  3. A method according to claim 1, characterized in that the carbon nanotubes are applied to the surface of the moulding tool in the form of an aqueous dispersion and are subsequently dried.
  4. A method according to claim 1 or 3, characterized in that a surface of a temporary substrate which forms a wall of a moulding tool is coated with carbon nanotubes.
  5. A method according to one of claims 1 or 2, characterized in that in step (iii) solvent is evaporated or the monomer is hardened or polymerised by application of energy.
  6. A method according to one of claims 1 or 3 to 6, characterized in that in step (ii) the polymer, the polymer precursor or the monomer is injected into the moulding tool with increased pressure.
  7. A method according to claim 2, characterized in that the carbon nanotubes of a polymeric substrate which is coated with carbon nanotubes is embedded in the area near the surface of the substrate in a press or using at least one roller exerting compressive forces onto the surface of the substrate.
  8. A method according to one of the preceding claims, characterized in that the proportion of carbon nanotubes is successively reduced starting from the surface.
EP10805677.1A 2009-11-23 2010-11-19 Element which is electrically conductive on at least one surface and comprises carbon nanotubes and a polymer, and method for the production thereof Active EP2504167B1 (en)

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PCT/DE2010/001388 WO2011060774A2 (en) 2009-11-23 2010-11-19 Element which is electrically conductive on at least one surface and comprises carbon nanotubes and a polymer, and method for the production thereof

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WO2007024206A2 (en) 2004-08-11 2007-03-01 Eikos, Inc. Fluoropolymer binders for carbon nanotube-based transparent conductive coatings
US7645497B2 (en) * 2005-06-02 2010-01-12 Eastman Kodak Company Multi-layer conductor with carbon nanotubes
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