EP3809600A1 - Beheizbare platte und ihr herstellungsverfahren - Google Patents

Beheizbare platte und ihr herstellungsverfahren Download PDF

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Publication number
EP3809600A1
EP3809600A1 EP19823534.3A EP19823534A EP3809600A1 EP 3809600 A1 EP3809600 A1 EP 3809600A1 EP 19823534 A EP19823534 A EP 19823534A EP 3809600 A1 EP3809600 A1 EP 3809600A1
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EP
European Patent Office
Prior art keywords
sheet
thermoplastic material
heatable
conductive particles
additive
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
EP19823534.3A
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English (en)
French (fr)
Other versions
EP3809600B1 (de
EP3809600A4 (de
Inventor
Begoña Galindo Galiana
Vanessa GUTIÉRREZ ARAGONÉS
Vicent MARTÍNEZ SANZ
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.)
Asociacion de Investigacion de Materiales Plasticos y Conexas AIMPLAS
Original Assignee
Asociacion de Investigacion de Materiales Plasticos y Conexas AIMPLAS
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Publication of EP3809600A1 publication Critical patent/EP3809600A1/de
Publication of EP3809600A4 publication Critical patent/EP3809600A4/de
Application granted granted Critical
Publication of EP3809600B1 publication Critical patent/EP3809600B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/146—Conductive polymers, e.g. polyethylene, thermoplastics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/22—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible
    • H05B3/28—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor embedded in insulating material
    • H05B3/286—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor embedded in insulating material the insulating material being an organic material, e.g. plastic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/011—Heaters using laterally extending conductive material as connecting means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/017—Manufacturing methods or apparatus for heaters
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2214/00—Aspects relating to resistive heating, induction heating and heating using microwaves, covered by groups H05B3/00, H05B6/00
    • H05B2214/04—Heating means manufactured by using nanotechnology

Definitions

  • the present invention relates to heatable panels produced by means of conventional plastic transformation processes based on conductive thermoplastic compounds.
  • the panel is heated as a result of Joule effect whereby an electrically conductive material is heated when an electric current is applied.
  • These panels can be used as a heating system in different sectors such as automotive, construction, aerospace, and packaging sectors.
  • the panels can be obtained by means of extrusion, injection, or compression molding and then shaped to enable adapting to different geometries.
  • Invention ES2574622 uses, as a heatable material, a thermosetting elastomer with a high percentage of carbon nanotubes (CNTs) (between 20 and 45% by weight) added as additive. This elastomer is used as a coating in different substrates.
  • the invention indicates the importance of copper electrodes which are deposited by means of electrochemical electrodeposition on the conductive material.
  • a highly conductive film that can be heated is obtained by spraying an aqueous solution of carbon nanotubes (CNTs) on a polymer sheet.
  • Invention DE102011086448(A1 ) is also based on the deposition of layers of an aqueous solution of carbon nanotubes (CNTs) for obtaining a heatable coating.
  • Invention WO2002076805 A1 describes a steering wheel that can be heated by means of applying carbon particle-based conductive coatings.
  • work is also performed with different layers of conductive coatings, and it also contemplates the encapsulation of heatable elements and electrodes.
  • conductive coatings are applied in heatable automobile elements, specifically in rear-view mirrors.
  • Claim 2 of patent DE102011003012 refers to a cross-linked polymer and the example specifies the use of a silicone. These materials are thermally stable and cannot be processed by extrusion. Thermoplastic polymers can be partially cross-linked to obtain an extruded sheet but, in that case, they cannot be melted again, leading to the inability to recycle same.
  • the materials are in no case cross-linked, with recyclability being a very novel feature of the panel. Furthermore, it relates to soft materials such as silicone, whereas the materials of the present invention are rigid panels.
  • the materials developed in the present invention have a much lower resistivity, being much more conductive than the materials specified in said German invention DE102011003012 .
  • the low conductivity conditions the design of the electrodes, resulting in said electrodes having to be relatively close and have a large size (similar to the geometry of the heatable sheet).
  • the process of obtaining a highly conductive film is very different from that developed in the present invention. It is based on annealing which is performed on the polymer after the extrusion of the film. This annealing can last up to 24 h.
  • the present invention does not contemplate this technology because good conductivity is achieved by properly dispersing the conductive charge and correctly processing the material to obtain the final film or part with the desired conductive properties. Therefore, a PTC plastic is obtained by means of conventional processes as a result of the good dispersion of the conductive particles which are achieved by applying certain specific processing conditions, which also allows producing larger geometries with a greater distance of the electrodes.
  • Invention CN201610317174 relates to solvent-based conductive pastes without being thermoplastic polymers.
  • the polymeric material produced by means of extrusion is the (non-conductive) substrate on which the conductive paste is applied. It is a functional ink printing process that is very different from thermoplastic processing.
  • the inventions that are found are based on the application of conductive paints or varnishes that finally form a conductive coating or on the extrusion of materials with worse electrical conductivities, which subsequently makes the configuration of the electrodes difficult and complicated.
  • the application of coatings is a manual process and the final behavior of the heating element depends on different factors, such as: the number of layers of the conductive solution or paint, the worker who applies the paint, the homogeneity of the solution, given that if the conductive particles decant over time, the first applied layer may have a much higher concentration of conductive particles than the last applied layer. Therefore, the heating homogeneity and the reproducibility of the heating elements produced are not stable.
  • the conductive particles are dispersed in the thermoplastic die in a co-rotating twin-screw extruder.
  • a homogeneous nanocompound with high electrical conductivity is obtained, allowing the electrodes to be positioned at a great distance.
  • this material is melted to obtain a conductive sheet.
  • Said process can be an extrusion, compression, or injection.
  • the obtained part will have a homogeneous concentration of conductive particles, ensuring a reproducible and homogeneous behavior.
  • the sheet can be ground and reprocessed, assuring recycling at the end of the product's service life. Recycling is not contemplated in the state of the art since different materials and thermosetting coatings that do not allow recycling are combined.
  • the materials developed and the manufacturing process carried out in the present invention provide a lower resistivity of the conductive sheet of 10 1 Ohm.cm, which is much lower with respect to patent DE102011003012A1 , which mentions resistances between 10 3 and 10 6 ohm.cm, implying a greater conduction by the developed panel.
  • the present invention has been devised as a heating panel which uses, as a power source, electrical energy that is to be converted into thermal energy.
  • the novelty lies in the type of material making up the heatable panel and in its manufacturing process.
  • the conceived solution is based on obtaining a sheet of recyclable, lightweight conductive polymer to be used in a wide variety of designs depending on the sizes and geometries required according to the application.
  • the polymer materials are usually insulating materials; however, as a result of the addition of conductive additives, they can change their thermal and electrical properties and replace heat-generating metallic resistors when this type of heating is required.
  • thermocouple sensor i.e., the thermocouple sensor, and the metallic electrodes. All these components forming the heatable panel, i.e., the sheet, the first insulating layer, the second insulating layer, the thermocouple sensor, and the metallic electrodes, are reusable to form part of another heatable panel or to form part of another system.
  • the sheet Since the sheet has a PTC thermistor behavior, when an electrical current is applied to the metallic electrodes, the sheet works by increasing the electrical resistance with the increase of temperature. In other words, once the desired temperature is reached, it stabilizes and no temperature peaks are generated, making it a safe heating system. This feature gives it the particularity of being self-regulating, dispensing with the need for thermostats that are necessary in other heating systems.
  • the conductive particles added as additive to the thermoplastic material of the sheet have directly proportional percentages in the mixture with the thermoplastic material, depending on the final temperature required by the heatable panel and on the type of conductive particles used. Once the material has been formulated, the temperature of the panels can be regulated by adapting the input voltage or cutting off the current supply, without having to adapt the formulation to each of the applications.
  • These temperature conducting particles of the sheet can be carbon black, graphite, graphene, carbon nanotubes, or a combination of the foregoing.
  • the conductive particles added as additive to the thermoplastic material of the sheet are carbon nanotubes and have a concentration comprised between 5 and 10% with respect to the total weight of the sheet.
  • the concentration is comprised between 20 and 40%, when they are of carbon black, the concentration is between 10 and 30%, when they are of graphene, between 3 and 10%, all these percentages being with respect to the total weight of the mixture forming the sheet.
  • thermoplastic materials of the sheet can be polyolefins, polyesters, polyamides, thermoplastic elastomers, polysulfones, polyetherimides, or a combination of all the foregoing, since all of them allow mixing with the temperature conducting particles and have structural and mechanical characteristics suitable for the use of the heatable panel, although a type of polyolefin, i.e., polypropylene, is preferably used.
  • the composite layer can adopt several forms by means of thermoforming, obtaining a lightweight final compound, allowing the use thereof for spaces with special geometries. Furthermore, machining operations can be applied thereto to make the adjustment with other elements.
  • the heatable panel also comprises a coating fabric partially or completely covering the panel, said coating fabric being an electrically insulating material that is resistant to temperature changes and selected depending on the characteristics of the installation of the panel.
  • the conductive materials of the metallic electrodes can be copper or silver, although other metallic materials that can be mechanically attached to the sheet to be reused can be selected.
  • the manufacturing process for manufacturing the sheet made of thermoplastic material with temperature conducting particles added as additive is carried out by means of plastic and thermoplastic transformation processes.
  • the conductive particles in the form of powder and the thermoplastic material in the form of pellets are first introduced in a heated container of a co-rotating twin-screw extruder.
  • thermoplastic material Once the conductive particles and the thermoplastic material have been introduced in the container, they are hot mixed, melting the thermoplastic material in the extruder, to achieve a homogeneous mixture, applying a specific mechanical energy of at least 0.5 kWh/kg while melting the thermoplastic material.
  • the purpose of this process is to disperse the conductive charge in the polymer die to achieve optimal electrical properties homogeneously throughout the volume of the sheet.
  • thermoplastic material is melted at a temperature of 210°C, for the preferred case of a polypropylene die, and the screws rotate at a speed greater than 600 rpm, for a material input of 10 kilograms per hour in the co-rotating extruder measuring 25 mm diameter and with a length to diameter ratio equal to 40.
  • said mixture of molten plastic with the conductive particles is passed through an extruder head configured for generating filaments of thermoplastic material with conductive particles added as additive.
  • these filaments of thermoplastic material with added additive are cut using a shear to obtain pellets of said material.
  • processing In order not to lose electrical conductivity, processing must be optimized, assuring slow cooling of the material at the head outlet.
  • the calender rollers must be at a high temperature, assuring that the carbon nanotubes have enough time to be distributed into the polymer die and form the conductive network.
  • said pellets are melted to obtain the sheet of heatable panel by means of a new extrusion, drawing, roller lamination, or a combination of these manufacturing processes, all these processes being hot processes to facilitate the molding of the sheet, although it can also be performed by means of injection into plastic dies or compression molding.
  • the geometry of the sheet can be adaptable to any geometry depending on the shape and size requirements.
  • thermoplastic material conductive sheet with conductive particles added as additive can be obtained in a single step, coupling a co-rotating extruder to a flat sheet head.
  • the panel is therefore more cost-effective and faster to manufacture.
  • the sheet can be ground to obtain pellets again, and reprocessed, assuring recycling at the end of the product's service life. This recycling is not contemplated in the prior art found since different embedded materials and thermosetting coatings that do not allow recycling are combined.
  • the conductive particles do not coat any material, but are dispersed in the die of the co-rotating twin-screw extruder with the thermoplastic material, unlike these inventions mentioned in the prior art, so the materials developed in the present invention obtain the mentioned resistivity of 10 1 Ohm.cm, and a greater thermal conduction.
  • This good conductivity is only achieved by properly dispersing the conductive charge and correctly processing the conductive particles to obtain the sheet with the desired conductive properties.
  • a PTC plastic sheet is achieved by means of manufacturing processes as a result of the dispersion of the conductive particles, which are achieved by applying certain specific processing conditions. This also allows producing geometries having a larger size than those found and a greater distance between the electrodes.
  • the heating panel is constructed by means of custom machining according to the desired geometry of the final panel or by means of thermoforming, connecting the electrodes to the sheet and placing the insulation layers on the sides of said sheet.
  • the assembly is covered by means of the coating fabric customized according to the design and the final application, with fabrics that are resistant to temperature changes or possible iterations that they may have with the exterior to provide a finish suitable for use.
  • the heatable panel of the present invention is formed by a sheet (1), manufactured from a thermoplastic material, metallic electrodes (6) mechanically connected on the sides to the sheet (1), a first insulating layer (3) located on one side of the sheet (1), preventing the sheet from losing temperature on the side opposite the desired side and also preventing the passage of electric current on that side, a second electricity-insulating layer (2) for limiting the passage of electric current on the opposite side of the sheet (1) where heat is emitted, and a thermocouple sensor (5) attached to the sheet (1) measuring the internal temperature of the heatable panel.
  • said heatable panel is partially or completely coated by a coating fabric (4) made of an electrically insulating material for two purposes. Preventing a user who is close to the panel from coming into unwanted contact with the electrically conductive heatable sheet (1) and providing a finish according to the panel installation location.
  • This coating fabric (4) can be of many types, but a natural fabric is preferably selected.
  • the sheet (1) is capable of emitting heat because electrically conductive particles are added as additive, providing the sheet (1) with PTC behavior.
  • These temperature conducting particles of the sheet (1) can be of different types such as carbon black, graphite, graphene, carbon nanotubes, and a combination of the foregoing, carbon nanotubes (CNTs) preferably being used due to their heat conduction properties.
  • the percentage of these carbon nanotube particles is comprised between 5 and 10% with respect to the total weight of the sheet, which is completed with thermoplastic materials selected from polyolefins, polyesters, polyamides, thermoplastic elastomers, polysulfone, polyetherimide, or a combination of all of the foregoing, although polypropylene, a compound from the groups of polyolefins, is preferably used.
  • FIG 2 shows the temperature that the heatable panel can reach using carbon nanotubes (CNTs) in different percentages and different sizes as additive particle, so that the higher the percentage of nanotubes, the higher the temperature reached by the panel.
  • CNTs carbon nanotubes
  • thermoplastic material used in this case is a polypropylene in which different percentages of carbon nanotubes (CNTs) from 3% to 10% by weight have been mixed. Different temperatures in degree Celsius are generated by applying a voltage of 48 V to the heatable panel, reaching up to 100°C if the panel has a smaller surface with sides measuring 15 x 15 cm.
  • CNTs carbon nanotubes
  • the energy consumption of said heatable panel is 120 W for a rectangular geometry measuring 350 cm on one side by 250 cm on the other side and by 2 cm wide, applying 48 V and 64 W, for the same geometry, applying 24 V.
  • the energy consumption is 20 W at 48 V and 5 W at 24 V.
  • the sheet (1) is formed by a thermoplastic material and particles added as additive, firstly the mixing of both components is performed, so that they are blended together in the state of pellets and powder, and heated to melt the plastic material, where it is stirred inside an extruder applying a specific mechanical energy of at least 0.5 kWh/kg.
  • thermoplastic material is melted at a temperature of at least 210°C when polypropylene is used and the screws rotate at a speed of at least 600 rpm for a material input of 10 kilograms per hour in a co-rotating extruder measuring 25 mm in diameter and with a length to diameter ratio equal to 40.
  • the material is extruded to obtain filaments that are cooled and solidified in rollers, to be subsequently cut using a shear and to obtain new pellets but from the mixture of components.
  • Said pellets are used to obtain the sheet (1) following one or different plastic transformation processes, such as extrusion, drawing, compression molding, roller lamination, or die injection.
  • the sheet (1) is attached to the rest of the components forming the heatable panel and is ready for use.
  • Example 1 Polypropylene- and carbon nanotube (CNT)-based heatable panel
  • the present example refers to a sheet made of polypropylene and carbon nanotubes obtained by means of flat sheet extrusion.
  • the plastic material is melted by means of heat and shear in an extruder and is forced to pass through a head, giving it the shape of a sheet.
  • the sheet is passed through a roller system or calender.
  • the cooling of the material is controlled by varying the temperature of these rollers.
  • Table 1 The key parameters for processing the sheet with high electrical conductivity by means of extrusion are shown in Table 1.
  • Table 1 Optional extrusion parameters Parameter Value Area 1 (°C) 180 Area 2 (°C) 185 Area 3 (°C) 195 Area 4 (°C) 200 Area 5 (°C) 210 Head (°C) 220 Melt temperature (°C) 211 Pressure (bar) 57 Speed (rpm) 60 Torque (N/m2) 4.5 - 23% Drawing (%) 1.0 Die Gap ( ⁇ m) (Nozzle opening) 900 Roller temperature (°C) 80 Film thickness ( ⁇ m) 900
  • the percentage of carbon nanotubes is determined according to the temperature of use required by the application. The optimal range being between 5 and 10% of nanotubes to reach temperatures between 25 and 100°C.
  • Example 2 Polypropylene- and graphite-based heatable panel
  • the sheet is obtained by means of compression molding.
  • the main parameters involved in the process are the pressure exerted on the mold, the cycle time, and the temperature during processing.
  • Table 2 shows the processing conditions to achieve optimum electrical conductivity in the graphite plates.
  • Table 2 Compression molding processing parameters Units BIPOLAR Min E1 E2 E3 E4 E5 4 2 2 4 15 bar P1 P2 P3 P4 P5 4 40 75 150 70 °C T1 T2 Dry samples for 2 h at 80°C 190 190
  • Table 3 shows the temperatures reached in three areas of the heatable panel when a certain voltage is applied.
  • the panels have a geometry of 15 x 15 cm and they were obtained by means of compression molding.
  • Table 3 Thermal behavior of panels containing polypropylene and graphite PP+20%graphite PP+30%graphite PP+40%graphite T1 45.9 96.6 102 T2 45.7 100 86.9 T3 46.3 80.6 60.7 V 48 48 38 Current (A) 0.24 5.12 5.11 Power (W) 11.52 245 195

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  • Compositions Of Macromolecular Compounds (AREA)
  • Surface Heating Bodies (AREA)
EP19823534.3A 2018-06-18 2019-04-23 Beheizbare platte und ihr herstellungsverfahren Active EP3809600B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES201830593A ES2735428B2 (es) 2018-06-18 2018-06-18 Panel calefactable y procedimiento de fabricacion del mismo
PCT/ES2019/070276 WO2019243644A1 (es) 2018-06-18 2019-04-23 Panel calefactable y procedimiento de fabricación del mismo

Publications (3)

Publication Number Publication Date
EP3809600A1 true EP3809600A1 (de) 2021-04-21
EP3809600A4 EP3809600A4 (de) 2021-08-18
EP3809600B1 EP3809600B1 (de) 2023-03-08

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EP19823534.3A Active EP3809600B1 (de) 2018-06-18 2019-04-23 Beheizbare platte und ihr herstellungsverfahren

Country Status (4)

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EP (1) EP3809600B1 (de)
ES (2) ES2735428B2 (de)
PT (1) PT3809600T (de)
WO (1) WO2019243644A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH717849B1 (fr) * 2020-09-15 2024-06-14 Graphenaton Tech Sa Dispositif de chauffage d'un bâtiment.
CN112822803B (zh) * 2020-12-31 2023-08-04 泰安市中研复合材料科技有限公司 一种胶带结构的可弯折的加热装置及其制备方法

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JPH0688350B2 (ja) * 1990-01-12 1994-11-09 出光興産株式会社 正温度係数特性成形体の製造方法
US20050172950A1 (en) 2001-02-15 2005-08-11 Integral Technologies, Inc. Low cost heated clothing manufactured from conductive loaded resin-based materials
WO2002076805A1 (es) 2001-03-27 2002-10-03 Dalphi Metal España, S.A. Volante calefactable para automoviles
KR100749886B1 (ko) 2006-02-03 2007-08-21 (주) 나노텍 탄소나노튜브를 이용한 발열체
DE102007004953A1 (de) 2007-01-26 2008-07-31 Tesa Ag Heizelement
US20100112545A1 (en) 2007-07-13 2010-05-06 Subra Muralidharan Trans-1,2-diphenylethlene derivatives and nanosensors made therefrom
US8003016B2 (en) * 2007-09-28 2011-08-23 Sabic Innovative Plastics Ip B.V. Thermoplastic composition with improved positive temperature coefficient behavior and method for making thereof
DE102009010437A1 (de) * 2009-02-26 2010-09-02 Tesa Se Beheiztes Flächenelement
DE102011003012A1 (de) 2011-01-23 2012-07-26 Jürgen Schaeffer Sitzheizung auf Basis einer Heizfolie
ES2402034B1 (es) 2011-10-13 2014-02-25 Fundación Para La Promoción De La Innov., Inv. Y Desarrollo Tecnológico En La Industria De Automoción De Galicia Procedimiento de fabricación de un recubrimiento radiante de calor.
DE102011086448A1 (de) 2011-11-16 2013-05-16 Margarete Franziska Althaus Verfahren zum Herstellen eines Heizelements
ES2537400B1 (es) 2013-12-04 2016-01-22 Seat, S.A. Procedimiento para la obtención de un calefactor en un automóvil
ES2574622B1 (es) 2014-12-18 2017-04-05 Fundación Para La Promoción De La Innovación, Invest. Y Desarrollo Tecnológico En La Industria De Automoción De Galicia Dispositivo calefactable que comprende una lámina conductora y electrodos de metal y procedimiento de fabricación del mismo
CN104788818B (zh) * 2015-04-09 2017-05-31 郑州大学 Ptc强度可调控的ptc聚合物基导电复合材料及其制备方法
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US9668301B2 (en) * 2015-07-03 2017-05-30 Ndt Engineering & Aerospace Co., Ltd. Wet-use plane heater using PTC constant heater-ink polymer

Also Published As

Publication number Publication date
PT3809600T (pt) 2023-03-22
EP3809600B1 (de) 2023-03-08
ES2735428B2 (es) 2022-10-26
ES2735428A1 (es) 2019-12-18
WO2019243644A1 (es) 2019-12-26
EP3809600A4 (de) 2021-08-18
ES2940748T3 (es) 2023-05-11

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