EP3251468A1 - Heating device, in particular a semi-transparent heating device - Google Patents
Heating device, in particular a semi-transparent heating deviceInfo
- Publication number
- EP3251468A1 EP3251468A1 EP16701766.4A EP16701766A EP3251468A1 EP 3251468 A1 EP3251468 A1 EP 3251468A1 EP 16701766 A EP16701766 A EP 16701766A EP 3251468 A1 EP3251468 A1 EP 3251468A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- heating
- layer
- equal
- transparent
- heating layer
- 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
Links
- 238000010438 heat treatment Methods 0.000 title claims abstract description 147
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000009792 diffusion process Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000002070 nanowire Substances 0.000 claims abstract description 9
- 239000010410 layer Substances 0.000 claims description 118
- 238000002834 transmittance Methods 0.000 claims description 26
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 20
- 238000001429 visible spectrum Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 13
- -1 polyolefms Polymers 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 5
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000005693 optoelectronics Effects 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002120 nanofilm Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000000020 Nitrocellulose Substances 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920002614 Polyether block amide Polymers 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001220 nitrocellulos Polymers 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001230 polyarylate Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 abstract description 3
- 229910017083 AlN Inorganic materials 0.000 abstract 1
- 239000010408 film Substances 0.000 description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- 239000002042 Silver nanowire Substances 0.000 description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001755 magnetron sputter deposition Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 101100222091 Arabidopsis thaliana CSP3 gene Proteins 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000000168 high power impulse magnetron sputter deposition Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001540 jet deposition Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000002663 nebulization Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
-
- 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
- H05B3/84—Heating arrangements specially adapted for transparent or reflecting areas, e.g. for demisting or de-icing windows, mirrors or vehicle windshields
-
- 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
- H05B2203/013—Heaters using resistive films or coatings
-
- 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
- H05B2203/034—Heater using resistive elements made of short fibbers of conductive material
-
- 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 a new multilayer heating device based on nanomaterials coated with aluminum nitride.
- such a device may have both good heating properties at low voltage and high transparency, making it advantageously suitable for its implementation as transparent conductive film for heating and / or demister systems for which is required a visibility requirement.
- Transparent conductive heating films are of growing interest for a wide range of applications, for example for display devices, automotive demisting or de-icing systems, heated windows, etc.
- TCOs transparent conductive oxide films
- ITO indium oxide doped with tin
- Zhang et al. [3] that propose a hybrid film architecture based on silver nanowires (AgNWs) and graphene oxide (rLGO), with good performance in terms of transparency and thermal conductivity.
- the present invention aims to propose a new multilayer heating device, allowing access to a rapid and homogeneous heating of a surface, while having properties of high transparency.
- the present invention relates, according to a first aspect, to a heating device comprising:
- an electroconductive layer carried by the substrate, and formed of at least one percolating network of nano-objects comprising metallic nanowires;
- thermal diffusion layer based on aluminum nitride, covering all or part of the heating layer.
- aluminum nitride is usually crystallized by molecular beam epitaxy (MBE) techniques or by vapor phase epitaxy (MOCVD for "Metal Organic Chemical Vapor Deposition” in the English language).
- MBE molecular beam epitaxy
- MOCVD vapor phase epitaxy
- the heating device according to the invention is advantageous in several ways. First, such a device has good low-voltage heating properties and allows to restore, in a uniform manner, the heat produced on the surface of the device.
- a heating device can combine both heating and optical transparency properties, which makes it suitable for the design of various heating systems and / or semi-transparent demister and transparent, for example for glazing, shower panels, spectacles, heating elements of optoelectronic devices, etc.
- a heating device may have an overall transmittance, over the entire visible spectrum, of at least 50%, advantageously at least 70% and more particularly at least 80%.
- the heating device according to the invention can be advantageously prepared by large-area and low-temperature printing techniques.
- the present invention relates, in another of its aspects, to a method for preparing a heating device, comprising at least the steps of:
- thermal diffusion layer based on aluminum nitride by magnetron cathode sputtering at high temperature or at a high power, at a temperature that is strictly less than 280 ° C.
- substrate refers to a solid base structure on at least one of the faces of which are formed the heating layer and the thermal diffusion layer.
- the base substrate can be of various kinds.
- the substrate can be a flexible or rigid substrate.
- the substrate may be transparent, translucent, opaque or colored.
- the substrate is appropriately selected with respect to the intended application for the heating device.
- the substrate is chosen from semi-transparent or transparent substrates.
- semi-transparent is meant to qualify according to the invention a structure / layer having a transmittance, over the entire visible spectrum, greater than or equal to 50%.
- the transmittance of a given structure represents the light intensity passing through the structure on the visible spectrum. It can be measured by UV-Vis-IR spectrometry, for example using an integrating sphere on a Varian Carry 5000 type spectrometer.
- the transmittance on the visible spectrum corresponds to the transmittance for wavelengths between 350 and 800 nm.
- transparent means a structure / layer having a transmittance greater than or equal to 80%.
- the substrate may thus be a substrate made of glass or transparent polymers such as polycarbonate, polyolefins, polyethersulfone, polysulfone, phenolic resins, epoxy resins, polyester resins, polyimide resins, polyetherester resins, polyetheramide resins , polyvinyl (acetate), cellulose nitrate, cellulose acetate, polystyrene, polyurethanes, polyacrylonitrile, polytetrafluoroethylene, polyacrylates such as polymethyl methacrylate, polyarylate, polyetherimides, polyether ketones, polyethers ether ketones, polyvinylidene fluoride, polyesters such as polyethylene terephthalate or polyethylene naphthalate, polyamides, zirconia, or their derivatives.
- transparent polymers such as polycarbonate, polyolefins, polyethersulfone, polysulfone, phenolic resins, epoxy resins, polyester resins, polyimide resins, poly
- the base substrate may be glass or polyethylene naphthalate.
- the substrate may in particular have a thickness of between 500 nm and 1 cm, in particular between 200 ⁇ and 5 mm.
- the "heating layer”, carried by the base substrate refers to an electroconductive layer formed of at least one percolating network of nano-objects, the nano-objects including at least metal nanofilts .
- the metal nanofilas may be more particularly chosen from nanofilts of silver, gold and / or copper.
- the metal nanofilaments represent at least 40%, in particular at least 60%, of the total mass of the nano-objects of the heating layer.
- the heating layer may comprise, in addition to metallic nanofilts, carbon nanotubes and / or graphene, or their derivatives such as, for example, graphene oxides.
- the heating layer may be in the form of a single layer formed of a percolating network of nano-objects.
- the heating layer may be formed of a percolating network of metal nanofilts.
- the heating layer may have a multilayer percolating network.
- the percolating network of multilayer nano-objects is formed of at least two sub-layers of nano-objects of distinct compositions, in particular based on different nano-objects, at least one of the sub-layers comprising, even being formed of metal nanofil.
- At least one of the sub-layers, in particular the upper layer, is formed of metal nanofilas.
- a heating layer comprising at least two different types of nano-objects is hereafter designated as a "hybrid" heating layer.
- a hybrid heating layer may consist of a percolating network formed of a first layer of nano-objects, other than metallic nanofilts, for example carbon nanotubes, and a second layer of nanowires. metal.
- the heating layer has a transmittance, over the entire visible spectrum, greater than or equal to 50%, in particular greater than or equal to 70% and more particularly greater than or equal to 80%
- the nano-object density of the percolating network of the heating layer according to the invention is between 100 ⁇ g / m 2 and 500 mg / m 2 .
- the skilled person is able to adjust the density of nano-objects to implement to obtain a percolating and conductive network. Indeed, if the network of nano-objects is not dense enough, no conduction path is possible, and the layer will not be conductive. From a certain density of nano-objects, the network becomes percolating and the charge carriers can be transported over the entire surface of the heating layer.
- the heating layer of a device according to the invention has a surface resistance of less than or equal to 500 ohm / square.
- the surface resistance also called “square resistance”
- square resistance can be defined by the following formula:
- e represents the thickness of the conductive layer (in cm)
- p represents the resistivity of the layer (in ⁇ ).
- the surface resistance can be measured by techniques known to those skilled in the art, for example by a 4-point resistivity meter, for example of the Loresta EP type.
- the heating layer of the device according to the invention has a surface resistance of less than or equal to 200 ohm / square, preferably less than or equal to 100 ohm / square and more preferably less than or equal to 60 ohm / square.
- a low electrical resistance improves the heating performance, the thermal power dissipated by the heating film being proportional to V 2 / R (Joule effect), V representing the voltage applied across the heating layer (DC DC) and R the resistance of the heating layer from one terminal to the other.
- a heating layer according to the invention thus has good low voltage heating properties. More particularly, it makes it possible to reach a temperature of at least 80 ° C. by applying low voltages, for example voltages of less than 12 V.
- the heating layer according to the invention also has high transparency properties.
- the heating layer advantageously has, over the entire visible spectrum, a transmittance greater than or equal to 50%.
- the heating layer has a transmittance, over the entire visible spectrum, greater than or equal to 70%, in particular greater than or equal to 80%.
- a heating layer according to the invention can advantageously combine properties of high electrical conductivity and optical transparency, allowing its implementation to form a semi-transparent or transparent heating device, as detailed in the following text.
- the thickness of the heating layer of a heating device according to the invention may be between 1 nm and 10 ⁇ m, in particular between 5 nm and 800 nm.
- the nano-objects may be previously prepared according to synthetic methods known to those skilled in the art.
- silver nanowires can be synthesized according to the synthesis method described in Nanotechnology, 2013, 24, 215501 [4].
- the copper nanowires can be obtained by the method described in the publication Nanoresearch 2014, pp 315-324 [5].
- the carbon nanotubes may be mono and / or multi-wall nanotubes, purified or unpurified, functionalized or non-functionalized nanotubes; they can be obtained according to known techniques, for example by laser ablation, CVD or arc discharge.
- the percolating network may be obtained by deposition on the surface of the base substrate of one or more suspensions of nano-objects in a solvent medium (water, methanol, isopropanol, etc.), followed by evaporation of the solvent (s).
- a solvent medium water, methanol, isopropanol, etc.
- the metal nano-objects can be dispersed beforehand in an easily evaporable organic solvent (for example methanol, isopropanol), or else dispersed in an aqueous medium in the presence of a surfactant.
- an easily evaporable organic solvent for example methanol, isopropanol
- the suspension of nano-objects can then be deposited on the surface of the substrate according to methods known to those skilled in the art, the most commonly used techniques being spray deposition ("spray-coating" in English), jet deposition. inks, dip coating, film coating, impregnation, doctoring, flexo-printing, etc.
- the heating layer is formed by nebulized deposition of one or more suspensions of the nano-objects in a solvent medium, followed by evaporation of the solvent or solvents.
- the solvent or solvents of the nano-object suspension are then evaporated to form a percolating network of nano-objects allowing the flow of current.
- the network of nano-objects for example nanowires, can be annealed at a temperature between 100 and 150 ° C.
- the percolating network of the heating layer of a device according to the invention may consist of several layers of nano-objects superimposed.
- the deposition steps of the suspension of nano-objects and solvent evaporation are repeated as many times as it is desired to obtain layers of nano-objects.
- the heating layer is coated in all or part of a layer of aluminum nitride (AIN), called “thermal diffusion layer”.
- AIN aluminum nitride
- Aluminum nitride films have particularly advantageous properties in terms of electrical insulation and thermal conductivity, which are dependent on their crystalline quality.
- the AlN layer covers the entire heating layer.
- a thermal diffusion layer according to the invention has a thermal conductivity greater than or equal to 20 WK .m -1 , in particular between 80 and 250 WK.
- Thermal conductivity gives the ability of a material to dissipate heat. It can be measured by a transient hot-band type technique.
- Such a thermal diffusion layer makes it possible to restore the heat produced by the underlying heating layer uniformly over the entire exposed surface of the heating device.
- the superposition according to the invention of a heating layer having a low surface resistance and a thermal diffusion layer with a high thermal conductivity allows access, in a very short time, to a uniform heating of the entire surface of the heating device.
- Such a device is particularly advantageous for applications for heating systems, for example automotive demisting / defrosting, for which it is desired to obtain a rapid effect of starting the heating system.
- the thermal diffusion layer has a thickness of between 50 nm and 5 ⁇ , in particular between 80 nm and 800 nm.
- the AlN layer according to the invention advantageously has a high transparency.
- the AlN layer has a transmittance, over the entire visible spectrum, greater than or equal to 50%, in particular greater than or equal to 70%, and more particularly greater than or equal to 80%.
- the inventors take advantage of the recent optimizations of magnetron sputtering deposition techniques to access, at low temperature, a thin film of AlN of good quality crystalline and having good thermal conductivity.
- the thermal diffusion layer of a device according to the invention may be formed, on the surface of the percolating network of nano-objects, by magnetron cathode sputtering in continuous DC mode or pulsed at high power HiPIMS (for "High Power Impulse Magnetron Sputtering "in the English language).
- the technique of depositing a thin film on a substrate by magnetron cathode sputtering generally consists in bombarding a target, which forms the cathode of a magnetron reactor and which is made of the material to be deposited, with ions from an electrical discharge (plasma). This ion bombardment causes the sputtering of the target in the form of a "vapor" of atoms or molecules which are deposited in the form of a thin layer on the substrate placed near the target of the magnetron.
- the HiPIMS technology advantageously makes it possible to generate very high instantaneous currents while maintaining reduced heating of the target due to the use of pulses of short duration.
- a thin layer of AlN of good crystallinity can be more particularly achieved by magnetron sputtering from an aluminum target and an argon / nitrogen reactive mixture.
- it is formed at a temperature of less than or equal to 250 ° C, and more particularly less than or equal to 200 ° C.
- the multilayer heating device according to the invention can, advantageously, have both good heating performance and high transparency.
- the invention relates to a semitransparent or transparent heating device, comprising:
- a semitransparent or transparent base substrate in particular as defined above, for example made of glass or transparent polymer
- a heating layer having a transmittance, over the entire visible spectrum, greater than or equal to 50%, in particular greater than or equal to 70% and more particularly greater than or equal to 80%;
- thermal diffusion layer based on aluminum nitride covering all or part of the heating layer.
- a heating device may have an overall transmittance over the entire visible spectrum of at least 50%, in particular greater than or equal to 70% and more particularly greater than or equal to 80%.
- Global transmittance means the transmittance of the entire structure formed by the substrate stack, heating layer and thermal diffusion layer according to the invention.
- a heating device can be implemented as a thin transparent heating film for various applications, in particular in heating and / or defogging systems.
- the skilled person is able to adapt the shape and dimensions of the heating device according to the invention to integrate it into the desired heating system.
- the heating device according to the invention can be used by applying a voltage between two opposite edges of the heating layer.
- two non-transparent conductive strips may be deposited on the base substrate, in contact with two opposite edges of the heating layer, as shown in FIG.
- These strips called “contact pickups”, can be, for example, made from metal paste or silver lacquer, to allow a better connection with external power supply systems.
- the power supply of the system incorporating a heating device can be fixed or mobile, for example a battery, a battery or a photovoltaic cell, and fed continuously or discontinuously.
- the present invention thus relates to a heating and / or defogging system comprising a heating device as described above, in particular a semi-transparent or transparent heating device.
- the heating and / or defogging system may concern all types of systems known in the state of the art requiring the implementation of a heating film, in particular with high transparency.
- the system can be implemented for example for a glazing unit, a shower panel, a mirroring element, a visor, a mask, glasses, a radiator, a heating element of an optoelectronic device, a transparent food container, by example a bottle.
- a heating device made with a flexible and transparent base substrate, can be implemented for a transparent heating element (transparent electrode) in an optoelectronic device, for example a display screen. .
- a heating and semi-transparent device according to the invention can also be implemented for a heated windshield, the heating device being intended to heat the windshield in order to demist or defrost.
- the performance of the heating device according to the invention in terms of heating and high transparency allow quick access, in the context of an application for an automobile windshield, to a clear vision, after activation of the heating device.
- Figure 1 Schematic representation, in a vertical sectional plane, of the structure of a heating device (1) according to the invention.
- FIG. 2 Diagrammatic view of the application of a voltage by means of a voltage generator (22), on the resumption of contact of a device (1) according to the invention, as operated in the examples 1 to 4.
- Total transmittance is measured using an integrating sphere on a Varian Carry 5000 spectrometer.
- the transmittance on the visible spectrum corresponds to the transmittance for wavelengths between 350 and 800 nm.
- the transmittance is measured every 2 nm.
- silver nanofilaments are synthesized and purified according to the process described in Nanotechnology, 2013, 24, 215501 [4].
- nanowires are deposited on Eagle XG TM glass (Corning) (substrate (11)) according to a spraying method ("spray-coating" in English).
- the material thus deposited, constituting the heating layer (12), has a square resistance of 28 ohm / square. Repetitions of electrical contacts (21) are performed on two opposite edges by using a silver lacquer or a metal film deposit, for example by CVD or PVD. Formation of the thermal diffusion layer (13)
- Aluminum nitride (AlN) is deposited on this heating layer (12) by DC magnetron sputtering. During this deposition, the electrical contact times are protected for use thereafter to apply a potential on the device.
- the power used is 175 W.
- the ratio of quantities of nitrogen and argon QN 2 / (QN 2 + QAr) is 25%.
- the deposition rate is about 40 nm / min, which allows precise control of the thickness of the deposited AlN layer.
- the deposition is carried out for 5 minutes, which makes it possible to obtain a layer (13) of 200 nm.
- This heating device (1) has a global transmittance, measured using an integrating sphere on a Varian Carry 5000 spectrometer, of 85% minimum over the entire visible spectrum.
- carbon nanotubes (type CSP3 of Carbon solution) are dispersed in NMP (N-methylpyrrolidone) and deposited on Eagle XG TM glass (Corning) according to a nebulization deposition method ("spray coating"). In the English language). The transmittance of the deposited layer, over the entire visible spectrum, is 99.2%.
- Silver nanowires are synthesized and purified according to the process described in Nanotechnology, 2013, 24, 215501. These nanowires are deposited on the carbon nanotube layer.
- Repeats of electrical contacts (21) are performed on two opposite edges by using a silver lacquer or a metal film deposit, for example by CVD.
- Aluminum nitride (AlN) is deposited on this heating layer as described in Example 1.
- This device (1) has an overall transmittance of 88% minimum over the entire visible spectrum.
- a heating device (1) similar to that described in Example 1 is produced, by implementing instead of silver nanowires, copper nanofilts manufactured according to the method described in the publication Nanoresearch 2014, pp 315-324 [ 5].
- the heating layer (12) thus produced has a square resistance of 53 ohm / square.
- the AIN deposition is carried out as described in Example 1. By applying a voltage of 9 V on the resumption of contact, a temperature of 63 ° C is reached in less than one minute, homogeneously over the entire surface of the heating device.
- This device has an overall transmittance of 82% minimum over the entire visible spectrum.
- a heating device (1) similar to that described in Example 1 is produced, by implementing instead of the glass substrate, a substrate (11) made of polyethylene naphthalate 125 ⁇ thick.
- the heating layer (12) thus produced has a square resistance of 19 ohm / square.
- This device has an overall transmittance of 90% minimum over the entire visible spectrum.
Landscapes
- Surface Heating Bodies (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1550666A FR3032084B1 (en) | 2015-01-28 | 2015-01-28 | HEATING DEVICE, PARTICULARLY SEMI-TRANSPARENT |
PCT/EP2016/051648 WO2016120302A1 (en) | 2015-01-28 | 2016-01-27 | Heating device, in particular a semi-transparent heating device |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3251468A1 true EP3251468A1 (en) | 2017-12-06 |
EP3251468B1 EP3251468B1 (en) | 2020-11-18 |
Family
ID=53269652
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16701766.4A Active EP3251468B1 (en) | 2015-01-28 | 2016-01-27 | Heating device, especially semi-transparent |
Country Status (4)
Country | Link |
---|---|
US (1) | US20180014359A1 (en) |
EP (1) | EP3251468B1 (en) |
FR (1) | FR3032084B1 (en) |
WO (1) | WO2016120302A1 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101637920B1 (en) * | 2015-01-06 | 2016-07-08 | 연세대학교 산학협력단 | Transparent film heater and manufacturing method thereof |
KR101812024B1 (en) * | 2016-06-10 | 2017-12-27 | 한국기계연구원 | A Heating Wire and A PLANAR HEATING SHEET comprising THE SAME |
FR3056070B1 (en) * | 2016-09-13 | 2018-10-05 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | NANOWIL PERCOLATING NETWORK FOR LOCALIZED HEATING. |
FR3066349B1 (en) * | 2017-05-12 | 2021-06-04 | Valeo Vision | CONDUCTIVE COATING WITH SILVER PARTICLES FOR PROJECTOR GLASS WITH DEFROST FUNCTION |
FR3066644B1 (en) * | 2017-05-19 | 2019-07-05 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | ELECTRICALLY CONDUCTIVE, TRANSPARENT OR SEMI-TRANSPARENT DEVICE BASED ON METALLIC NANOWIRES AND POROUS SILICA NANOPARTICLES |
DE102017121039A1 (en) * | 2017-05-24 | 2018-11-29 | Webasto SE | air heater |
FR3070973B1 (en) * | 2017-09-11 | 2022-02-04 | Commissariat Energie Atomique | METHOD FOR PREPARING AN ELECTRICALLY AND THERMALLY CONDUCTIVE METALLIC AEROGEL |
FR3087991B1 (en) | 2018-10-29 | 2022-12-09 | Commissariat Energie Atomique | PREPARATION OF A HEATING SYSTEM FROM A HEAT-SHRINK SUBSTRATE |
CN113631367B (en) | 2019-04-03 | 2023-10-31 | 3M创新有限公司 | Optical film and glass laminate |
CN110670411A (en) * | 2019-09-10 | 2020-01-10 | 衢州五洲特种纸业股份有限公司 | Food paperboard with heat preservation and heating functions and preparation method thereof |
CN110685186A (en) * | 2019-09-10 | 2020-01-14 | 衢州五洲特种纸业股份有限公司 | Modified graphene/nano-cellulose conductive functional coating and preparation method and application thereof |
FR3106204B1 (en) * | 2020-01-10 | 2022-01-21 | Commissariat Energie Atomique | METHOD FOR MEASURING THE TEMPERATURE OF A PERCOLATING NETWORK OF METALLIC NANOWIRE |
CN112009694B (en) * | 2020-09-03 | 2021-12-03 | 北京航空航天大学 | Preparation method of electric heating anti-icing coating for three-dimensional complex curved surface |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW250618B (en) * | 1993-01-27 | 1995-07-01 | Mitsui Toatsu Chemicals | |
WO2004010737A1 (en) * | 2002-07-18 | 2004-01-29 | Glaverbel | Heated glass pane |
JP5409094B2 (en) * | 2008-07-17 | 2014-02-05 | 富士フイルム株式会社 | Curved molded body and manufacturing method thereof, front cover for vehicle lamp and manufacturing method thereof |
-
2015
- 2015-01-28 FR FR1550666A patent/FR3032084B1/en active Active
-
2016
- 2016-01-27 WO PCT/EP2016/051648 patent/WO2016120302A1/en active Application Filing
- 2016-01-27 EP EP16701766.4A patent/EP3251468B1/en active Active
- 2016-01-27 US US15/545,151 patent/US20180014359A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
FR3032084A1 (en) | 2016-07-29 |
WO2016120302A1 (en) | 2016-08-04 |
EP3251468B1 (en) | 2020-11-18 |
FR3032084B1 (en) | 2017-02-10 |
US20180014359A1 (en) | 2018-01-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3251468B1 (en) | Heating device, especially semi-transparent | |
CA2115320A1 (en) | Glass with multiple thin-film coatings having properties pertaining to the infrared and/or visible spectrum | |
EP3347945B1 (en) | Radome provided with a resistive heating system formed from strips of metal nanoelements | |
WO2008037658A2 (en) | Method of producing a photovoltaic cell with a heterojunction on the rear face | |
EP3615485B1 (en) | Coloured glazing and method for obtaining same | |
WO2021130461A1 (en) | Photovoltaic module | |
FR3066644B1 (en) | ELECTRICALLY CONDUCTIVE, TRANSPARENT OR SEMI-TRANSPARENT DEVICE BASED ON METALLIC NANOWIRES AND POROUS SILICA NANOPARTICLES | |
FR3070973A1 (en) | PROCESS FOR PREPARING AN ELECTRICALLY AND THERMALLY CONDUCTIVE METAL AEROGEL | |
FR2629222A1 (en) | VARIABLE TRANSMISSION GLAZING OF THE ELECTROCHROME TYPE | |
FR3065737B1 (en) | TARGET FOR OBTAINING A COLORED GLAZING | |
FR3066499A1 (en) | ELECTRICALLY CONDUCTIVE, TRANSPARENT OR SEMI-TRANSPARENT DEVICE BASED ON POLY (THIO- OR SELENO-) PHENIC POLYMERS AND POROUS SILICA NANOPARTICLES | |
EP2676296A2 (en) | Conductive transparent glass substrate for photovoltaic cell | |
EP0092452A1 (en) | Coating for photothermal conversion | |
Rasheed et al. | The effect of the annealing on the properties of ZnO/Cu/ZnO multilayer structures | |
WO2018069286A1 (en) | Use, as a heating element, of a transparent conductive polymeric film composed of thiophenic or selenophenic polymers | |
FR2932611A1 (en) | PHOTOVOLTAIC CELL AND PHOTOVOLTAIC CELL SUBSTRATE | |
FR3057710A1 (en) | RADOME EQUIPPED WITH A HEATING SYSTEM BASED ON POLY (THIO- OR SELENO-) PHENIC POLYMERS | |
EP3849769B1 (en) | Method for manufacturing an opto-electronic component substrate and associated devices | |
EP3328806B1 (en) | Electrostatic doping of a layer of a conductive or non-conductive material | |
EP3364461A1 (en) | Method for doping graphene | |
EP2576866B1 (en) | Method for diffusing metal particles within a composite layer | |
WO2020002832A1 (en) | Conductive polymer composition and method for producing same | |
Bornholdt et al. | Investigations on the energy balance of the substrate during ZnO magnetron sputtering | |
EP1208067A1 (en) | Transparent conductor and means for making same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20170828 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20190710 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20200610 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: FRENCH |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602016048003 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1337158 Country of ref document: AT Kind code of ref document: T Effective date: 20201215 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1337158 Country of ref document: AT Kind code of ref document: T Effective date: 20201118 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20201118 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210318 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210218 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210219 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210218 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210318 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602016048003 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210127 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20210131 |
|
26N | No opposition filed |
Effective date: 20210819 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210131 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210131 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210127 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210318 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20160127 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201118 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240228 Year of fee payment: 9 Ref country code: GB Payment date: 20240131 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20240130 Year of fee payment: 9 |