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    • 专利摘要:
    Heating device comprising a conductive sheet and metal electrodes and method of manufacturing thereof. Heating device comprising a conductive sheet, wherein said conductive sheet comprises carbon nanotubes, elastomers, and dispersing agents on a substrate and metal electrodes chemically adhered to the conductive sheet. Process for manufacturing a heating device, said method comprises coating the substrate with a conductive sheet by adding a conductive dispersion comprising carbon nanotubes, elastomers, and dispersing agents to the substrate where a sheet of varnish or acrylic resin is deposited on the conductive sheet as mask for a selective electrochemical deposition of the metal electrodes on the conductive film. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2574622A1
    申请号:ES201401049
    申请日:2014-12-18
    公开日:2016-06-21
    发明作者:Alberto TIELAS MACÍA；Miguel Ángel DE DIOS ÁLVAREZ；Carlos BANDRÉS DIÉGUEZ；Denise GARCÍA MURIAS；Vanessa VENTOSINOS LOUZAO；Raquel LEDO BAÑOBRE；Carmen Gloria PAJARÍN GONZÁLEZ
    申请人:Fundacion para la Promocion de la Innovacion Investigacion y Desarrollo Tecnologico en la Industria de Automocion de Galicia；
    IPC主号:
    专利说明:

    image 1
    image2
    image3 DESCRIPTION
    Heating device comprising a conductive sheet and metal electrodes and manufacturing process thereof. Field of the Invention
    The present invention is related to a heating device, comprising a conductive sheet on a substrate and metal electrodes. The substrate can be plastic film, textiles, paper, cardboard, wood, glass, foams and the heating device can be applied in the automotive sector, among others. Background of the invention
    There are different approaches to the problem of trying to develop a heating device that is flexible and at the same time emits heat homogeneously, across its entire surface. In this sense, WO 2007089118 A1 describes a heating element based on carbon nanotubes. This heating element is manufactured by applying a mixture comprising carbon nanotubes and an aqueous liquid to a heat resistant sheet, for example, poly (ethylene terephthalate), poly (ethylene nitrate) or amides. The application can be done by spraying. This sheet is preferably porous, so that the nanoparticles can be better introduced into the material. This element further comprises an electrically insulating layer that is disposed on the carbon nanotube coating and electrodes that are disposed between the insulating layer and the carbon nanotube coating, to which the power supply is connected.
    WO 02076805 discloses a heated steering wheel for automobiles formed by a base on which a layer of a synthetic conductive material is applied, preferably a polymer in which finely divided carbon particles have been dispersed, and on which a plurality are arranged of electrical contacts connected to a power supply. The base is a flexible fabric that is placed over the polyurethane padding, while its outer face is in contact with the conductive polymer. The electrical contacts are in contact with the inner face of the steering wheel lining.
    The IMAT project financed by the European Commission in the Seventh Framework Program addresses this problem by covering flexible substrates with conductive nanomaterials that are connected through multiple parallel electrodes.
    In ES 2402034 B1 there is another example of a radiant heat heating device, through an electrically conductive homogeneous surface on which different layers are arranged to ensure heat flow in the desired direction and encapsulate the conductive surface itself and the electrodes of Contact.
    There are more examples of heating devices from the coating of substrates with electrically conductive mixtures, although they all face the same challenge: effectively place the contact electrodes that will distribute the electric current through the conductive mixture. Ensuring good contact between the electrodes and the radiant layer is essential to maintain the electrical properties of the device. The existing solutions are based fundamentally on three approaches: the use of pressure by rolling the radiant layer and electrodes, the use of conductive glues or conductive paints to join the contacts to the radiant mixture or the use of metal tapes They incorporate electrically conductive glue. All of them have their drawbacks.
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    The laminate can be effective if the heating element is not going to be deformed. However, when the radiating device is subjected to different bending cycles, the electrode can slide over the conductive mixture due to the lack of chemical bond between them. This fact can cause wear of the conductive coating or contact problems between both layers.
    The use of electrically conductive glues or electrically conductive paints may limit the range of temperatures at which the device can operate. Very low temperatures can cause fractures or cracks in the joint by decreasing the flexibility of the glue or paint layer. Also, high temperatures can soften the glue or paint film causing changes in the contact resistance of the electrode-radiant layer joint.
    Finally, the use of metal tapes that incorporate conductive glue poses problems in ensuring the flexibility of the device. The different curvature of the different layers when flexing the heating element can cause wrinkles on the metal tape, producing hot spots on the heating surface.
    Other approaches to the problem of trying to develop a heating device that is flexible and at the same time emits heat in a homogeneous way across its entire surface pose the use of electrodeposition to make contacts.
    US2005172950 refers to a garment that incorporates a flexible heating element. Said element is constituted by a polymeric material that contains conductive materials that increase its conductivity with the intention that an electric current passes through it and produces a heating. Such materials may be carbonaceous materials such as graphite. To facilitate contact, said material can be coated with a conductive copper-like metallic material, through different processes, such as electrolytic.
    Said polymeric material does not allow the impregnation of substrates, therefore it has a great disadvantage when it is integrated into any type of substrate or bearing material, such as a textile, since for this it is necessary to use an adhesive or some type of mechanical union.
    WO2009137725 refers to a heating element that is constituted by a sheet of carbon nanotubes made of carbon nanotube wires, an epoxy resin with graphite or other conductive materials. Said heating element may also comprise a connection with a conductive metal deposited by electrodeposition, for example, copper among others.
    The use of carbon nanotube wires provides good physicochemical properties, but this in turn leads to a number of major drawbacks. The process of making and weaving carbon nanotube threads requires high precision machinery and high cost. The conductivity of carbon nanotube wires (7 * 106 S / m) is similar to that of metals, which prevents the use of such a fabric to heat surfaces that must be in contact with the human body, since that even for very low voltages, temperatures exceeding 300ºC are reached very quickly. Similarly, when it is integrated into any type of substrate or bearing material, such as a textile, it is necessary to use an adhesive or some type of mechanical bond.
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    US2009011674 refers to the manufacture of metallized textiles or conductors in which heating elements can be incorporated. The incorporation of conductive materials in powder form refers to a polymer matrix. Such conductive materials are proposed to be metals whose dust particles are spherical. Special reference is made to what he calls "carbonyl iron" as the result of thermal decomposition of iron pentacarbonyl as the preferred conductive material. With said material and a polymeric material a paste is made that is applied on a textile to which it is then covered with a metal. Said coating with a metal can optionally be done by an electrolytic process.
    However, to fix the conductors in powder form to the polymer matrix, it is necessary to bake for five minutes at 150ºC. This thermal stress is something highly inadvisable when using natural tissues as a substrate, such as cotton, since it has its ignition point at 150ºC.
    Taking into account this problem, the present invention presents a different method for making the contact between the electrodes and the conductive mixture, consisting of impregnating the flexible substrate forming a conductive sheet and subsequent electrochemical deposition of a copper layer that will remain chemically bonded to the electrically conductive surface. In this way a surface is achieved in which the electrical conductivity has been improved in the areas where the electrodeposited contact electrodes are located. In this way, the problems mentioned above are avoided and the perfect union between the electrodes and the conductive layer of carbonaceous particles is achieved without the need to laminate different layers or the use of conductive adhesives or metal tapes. The nature of the conductive mixture that is also described in this invention favors the flexibility of the conductive surface in addition to allowing electrodeposition of the contact electrodes effectively. Description of the invention
    The present invention provides a heating device comprising a conductive sheet (3), wherein said conductive sheet (3) comprises 20-45% by weight of carbon nanotubes, 35-65% by weight of elastomers, and 30-50% in weight of dispersing agents on a substrate (1), where the heating device comprises electrodes (2) of metal chemically adhered to the conductive sheet (3).
    The present invention provides a heating device comprising a conductive sheet (3), wherein said conductive sheet (3) is obtained by applying a conductive mixture comprising 2-4% by weight of carbon nanotubes, 4-6.5% in weight of elastomers, and 3-5% by weight of dispersing agents on a substrate (1), wherein the heating device comprises metal electrodes (2) chemically adhered to the conductive sheet (3), hereinafter heated device of the invention.
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    Carbon nanotubes provide the ranges of electrical conductivity necessary to perform the electrodeposition of the metal and also, that the heating device has a low enough electrical resistance to operate at low voltage. In turn, carbon nanotubes also favor the adhesion of the metal during the electrodeposition process.
    Elastomers improve the fixation of the mixture to the substrate, prevent the appearance of cracks and improve the flexibility of the heating device.
    The dispersing agents are essential so that the nanotubes are not added in the mixture, which would result in a lower electrical conductivity of the mixture once applied.
    Another embodiment is the heated device of the invention, wherein said carbon nanotubes are multilayer carbon nanotubes.
    Another embodiment is the heating device of the invention, wherein said elastomers are aqueous-based acrylic elastomers.
    Another embodiment is the heating device of the invention, wherein said dispersing agents are anionic surfactants.
    Another embodiment is the heating device of the invention, wherein said anionic surfactants are sodium dodecyl sulfate (SDS) or sodium dodecylbenzenesulfate (SDBS).
    Another embodiment is the heating device of the invention, wherein said metal is selected from the group consisting of gold, silver, copper, zinc, nickel and chromium.
    Another embodiment is the heating device of the invention, which comprises a sheet of varnish or acrylic resin on the conductive sheet (3).
    The invention also provides a method of manufacturing a heating device, which comprises coating the substrate (1) with a conductive sheet (3) by adding a conductive dispersion comprising 2-4% by weight of carbon nanotubes, 4-6.5% in weight of elastomers, and 3-5% by weight of dispersing agents to the substrate (1) and drying said conductive dispersion, characterized in that a varnish sheet or acrylic resin is deposited on the conductive sheet (3) as a mask for electrochemical deposition Selective of the metal electrodes (2) on the conductive sheet (3), hereinafter the method of the invention. This mask made by varnish or acrylic resin does not need to be removed after performing the electrodeposition process since it fulfills the dual function of mask and definitive encapsulant of the heating device.
    This double function of the varnish or acrylic resin sheet has advantages over the processes currently in place for the electrochemical deposition. The no need to remove the mask reduces the amount of total manufacturing hours and the amount of waste produced, typically the masks are removed by peeling or burning. At older, the subsequent application of an insulating layer is not necessary to encapsulate the heating device, thus reducing the amount of materials used and total manufacturing hours.
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    The object of the invention is to manufacture a flexible, homogeneous heat radiating device consisting of a conductive sheet (3) in which the conductivity of the areas where the contact electrodes should be placed has been improved
    (2) by a process of selective electrodeposition of metal. One of the major drawbacks in the manufacture of flexible heating devices is to place and fix the electrical contacts that feed said elements. Thus, some solutions are based on the use of conductive metal tapes bonded with some type of conductive adhesive or by means of pressure, metallic threads of copper or aluminum, conductive paints of silver, copper or nickel, etc. The problem lies in the progressive increase in contact resistance as the device flexes, almost losing its heating power in not too many deformation cycles of the material. In addition, the use of conductive adhesives or paints with metallic loads makes the manufacture of such devices more expensive and even limits the range of temperatures between which the heating element can operate, since the joints, between the contacts and the radiant heat substance , they crack at low temperatures and decompose at high temperatures.
    The electrodes (2) are zones of controlled geometry in which the electrical conductivity has been improved by electrodeposition of a metal, all without using adhesives, metal tapes or any type of pressure bonding between layers, maintaining flexibility and structural stability and electrical permanently.
    A conductive dispersion is used to make the aforementioned heating device. The special composition of the same based on carbon nanotubes, elastomers and mixture of dispersing agents in aqueous base allows its application in a wide variety of substrates, even in those that must maintain their flexibility without losing their electrical properties. Thus, the choice of the substrate (1) will depend on the type of application and may be, for example: different plastic films, natural and synthetic textiles or a mixture of both paper, cardboard, wood, glass, foams, etc.
    Once the type of substrate (1) has been chosen, it is then coated with the electrically conductive mixture, and can be applied by spraying, roller printing, brush, etc., with the only requirement that the mixture be evenly distributed through the entire surface of the substrate (1).
    After a drying process that can be carried out by applying hot air or infrared light lamps, the conductive sheet (3) is completely adhered to the substrate (1) giving it the electrical properties necessary to use it as a heating element.
    Subsequently, a sheet of varnish or acrylic resin is deposited on the conductive sheet (3) as a mask for a selective electrochemical deposition of the metal electrodes (2) on the conductive sheet (3). This mask made by varnish or acrylic resin does not need to be removed after performing the electrodeposition process since it fulfills the dual function of mask and definitive encapsulant of the heating device.
    Its function as encapsulant allows to protect the conductive surface (3) from scratches or scratches as well as moisture and corrosion. This layer will also allow the use of the heating device outdoors or areas of high humidity, even submerged.
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    Once there is a conductive sheet (3) covered with a sheet of varnish or acrylic resin as a mask, the electrical contacts that will feed the heating device are made. For this, a method of reduction and electrochemical deposition is used in order to reduce metal cations directly on the surface of the carbon nanotubes contained in the conductive mixture previously applied. In this way, controlled extension and shape zones are achieved in which there is chemically bonded metal to the surface of the carbon nanotubes, which will serve as contact electrodes (2) to uniformly transmit the low-voltage electric current from the source supply to the heating element.
    Another embodiment is the process of the invention, where the electrochemical deposition is performed by a galvanic bath or by an electrochemical electrodeposition by a electroplating brush.
    In the galvanic bath, the substrate (1), previously coated with the conductive mixture, connected to a power source as a cathode, is introduced into a slightly acidic metal solution in which an electrode of the metal also connected to the source is submerged That will act as an anode. Applying in this way a sufficient potential difference, the metal begins to deposit in the desired area. The potential difference to be applied depends on the type of substrate (1), the concentration of carbon nanotubes contained in the conductive mixture, as well as the area to be coated. As an example, for a cotton and polyester textile substrate, and an electrode of rectangular dimensions of 10 mm x 100 mm it is necessary to apply an approximate potential of 6.5 volts, the fabric resistance being 70 ohm / sq. Once the reduction and electrochemical deposition have been completed, the assembly is washed with distilled water to remove the remains of acid from the galvanic bath. Subsequently, it is dried.
    In the electrochemical electrodeposition by means of a electroplating brush, the substrate (1) previously coated with the conductive mixture, connected to the source as a cathode, is arranged. The difference with respect to the galvanic bath is in the way of positioning the metal anode. In this case a sheet of metal is introduced into a piece of absorbent foam that is impregnated with a solution. The foil inserted in the foam is connected to the power supply as an anode. As the foam is pressed on the area of the conductive sheet (3) where the contact electrode is to be deposited, the reduction of the metal cations takes place being adhered thereto.
    By means of the described procedures a flexible heating device is obtained in which the contacts are chemically bonded to the conductive sheet itself (3) providing this last characteristic, all the mentioned advantages: absence of adhesives that limit the operating temperature range, absence of union between different layers, absence of wires or metal contact tapes, and improvement of the resistance to bending while maintaining its electrical properties. The contact electrodes (2) are integrated into the conductive surface itself (3).
    Another embodiment is the process of the invention, wherein said carbon nanotubes are multilayer carbon nanotubes.
    Another embodiment is the process of the invention, wherein said elastomers are aqueous-based acrylic elastomers.
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    Another embodiment is the process of the invention, wherein said dispersing agents are anionic surfactants.
    Another embodiment is the process of the invention, wherein said anionic surfactants are sodium dodecyl sulfate or sodium dodecylbenzenesulfate.
    Another embodiment is the process of the invention, wherein said metal is selected from the group consisting of gold, silver, copper, zinc, nickel and chromium. Brief description of the figures
    The attached drawings show an exemplary embodiment, not limiting, which will allow a better understanding of the characteristics of the heating device of the invention and of the manufacturing method of said heating device.
    Figure 1 schematically shows the arrangement of the conductive surface (3), the contact electrodes (2) chemically attached to it, on the substrate (1) and a flexible acrylic varnish or resin (4) that encapsulates the heating device.
    Figure 2 schematically shows the galvanic bath, in which an immersion of the desired contact area is performed in a galvanic bath. The metal sheets and the heating element are arranged as anode and cathode respectively.
    Figure 3 schematically shows electrochemical deposition by electroplating brush. The brush is formed by a metallic sheet covered with absorbent foam and connected as an anode, and the heating element connected as a cathode to the power supply.
    Figures 4 and 5 show, in a non-limiting manner, contact electrodes of different geometries produced by selective electrodeposition. Preferred Modes
    A heating device is shown schematically in Figure 1.
    A rectangular heated device has been made, following the procedure of the invention, of dimensions 145 mm x 200 mm, using as a substrate a fabric composed of 70% synthetic fibers and 30% natural fibers.
    The substrate was coated with a conductive sheet, adding the following conductive dispersion to the substrate:
    -  3% by weight multilayer carbon nanotubes (multi-wall carbon nanotubes), produced by chemical vapor deposition (CVD).
    -  4-6.5% by weight water-based acrylic elastomers and
    -  3-5% by weight sodium dodecyl sulfate (dispersing agent).
    The multilayer carbon nanotubes had the following characteristics: - average diameter: 9.5 gauges (determined by transmission electron microscopy)
    image18
    -  average length: 1.5 microns (determined by transmission electron microscopy)
    -  % carbon: 90% (determined by gravimetric thermal analysis (TGA))
    -% metal oxide: 10%
    - surface area: 250-300 m2 / g (determined by BET)
    The BET area analysis provides the surface area value calculated by the Stephen Brunauer, Paul Hugh Emmett, and Edward Teller method. The information obtained from the adsorbed volume allows to determine the area, the porous distribution, the size and volume of pores in the sample.
    Sodium dodecyl sulfate (SDS) was used as dispersing agent.
    The acrylic elastomer was an acrylic resin obtained from copolymerization of acrylic acid or any of its esters (methyl acrylate, ethyl acrylate, butyl acrylate ...) with one
    or more of its comonomers (acrylic acid, acrylamide, N-methylol-acrylamide, ...).
    Subsequently, the conductive dispersion was dried by infrared lamp.
    Once dry, an acrylic elastomer was applied, which fulfills a double function of mask for electrochemical deposition and encapsulating element of the heating device.
    The acrylic elastomer was an acrylic resin obtained from copolymerization of acrylic acid or any of its esters (methyl acrylate, ethyl acrylate, butyl acrylate ...) with one
    or more of its comonomers (acrylic acid, acrylamide, N-methylol-acrylamide, ...).
    Subsequently, the acrylic elastomer was dried by infrared lamp.
    Once dry, an electrochemical deposition of two copper electrodes made by means of a galvanic bath located longitudinally on its major sides was carried out, characterized by having a surface resistance of 16.5 Ohm and applying a voltage of 12 V. 30 ° C thermal jump over the entire surface of the device. After being subjected to 10,000 bending cycles, the variation of the electrical resistance of the heating device is not more than 1%.
    权利要求:
    Claims (14)
    [1]
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    one.  Heating device comprising a conductive sheet (3), characterized in that said conductive sheet (3) comprises 20-45% by weight of carbon nanotubes, 35-65% by weight of elastomers, and 30-50% by weight of agents dispersants on a substrate (1), where the heating device comprises electrodes (2) of metal chemically adhered to the conductive sheet (3).
    [2]
    2.  Heating device according to claim 1, characterized in that said carbon nanotubes are multilayer carbon nanotubes.
    [3]
    3.  Heating device according to claim 1 or 2, characterized in that said elastomers are aqueous-based acrylic elastomers.
    [4]
    Four.  Heating device according to any one of claims 1 to 3, characterized in that said dispersing agents are anionic surfactants.
    [5]
    5.  Heating device according to claim 4, characterized in that said anionic surfactants are sodium dodecyl sulfate or sodium dodecylbenzenesulfate.
    [6]
    6.  Heating device according to any one of claims 1 to 5, characterized in that said metal is selected from the group consisting of gold, silver, copper, zinc, nickel and chromium.
    [7]
    7.  Heating device according to any one of claims 1 to 6, characterized in that it comprises a sheet of varnish or acrylic resin on the conductive sheet (3).
    [8]
    8.  Method of manufacturing a heating device according to any one of claims 1 to 7, characterized in that it comprises coating the substrate (1) with a conductive sheet (3) by adding a conductive dispersion comprising 2-4% by weight of carbon nanotubes, 4-6.5% by weight of elastomers, and 3-5% by weight of dispersing agents to the substrate (1) and drying said conductive dispersion, characterized in that a varnish sheet or acrylic resin is deposited on the conductive sheet (3) as mask for a selective electrochemical deposition of metal electrodes
    (2) on the conductive sheet (3).
    [9]
    9.  Method according to claim 8, characterized in that said carbon nanotubes are multilayer carbon nanotubes.
    [10]
    10.  Method according to any one of claims 8 or 9, characterized in that said elastomers are aqueous-based acrylic elastomers.
    [11]
    eleven.  Process according to any of claims 8 to 10, characterized in that said dispersing agents are anionic surfactants.
    [12]
    12.  Process according to claim 11, characterized in that said anionic surfactants are sodium dodecyl sulfate or sodium dodecylbenzenesulfate.
    [13]
    13.  Process according to any of claims 8 to 12, characterized in that said metal is selected from the group consisting of gold, silver, copper, zinc, nickel and chromium.
    [14]
    14.  Method according to any one of claims 8 to 13, characterized in that the electrochemical deposition is carried out by a galvanic bath or by an electrochemical electrodeposition by a electroplating brush.
    10
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    eleven
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    法律状态:
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    优先权:
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    ES201401049A|ES2574622B1|2014-12-18|2014-12-18|Heating device comprising a conductive sheet and metal electrodes and manufacturing process thereof|ES201401049A| ES2574622B1|2014-12-18|2014-12-18|Heating device comprising a conductive sheet and metal electrodes and manufacturing process thereof|
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