WO2022013138A1 - Conducteurs électriques pour transformateurs de puissance à haute conductivité électrique et thermique - Google Patents

Conducteurs électriques pour transformateurs de puissance à haute conductivité électrique et thermique Download PDF

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Publication number
WO2022013138A1
WO2022013138A1 PCT/EP2021/069298 EP2021069298W WO2022013138A1 WO 2022013138 A1 WO2022013138 A1 WO 2022013138A1 EP 2021069298 W EP2021069298 W EP 2021069298W WO 2022013138 A1 WO2022013138 A1 WO 2022013138A1
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WO
WIPO (PCT)
Prior art keywords
metal
phase
layer
copper
wire rod
Prior art date
Application number
PCT/EP2021/069298
Other languages
English (en)
Inventor
Vincenzo Tagliaferri
Nadia UCCIARDELLO
Silvio GENNA
Roberto Preda
Original Assignee
Company Trafil Production Srl
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Company Trafil Production Srl filed Critical Company Trafil Production Srl
Priority to EP21743453.9A priority Critical patent/EP4179554A1/fr
Publication of WO2022013138A1 publication Critical patent/WO2022013138A1/fr

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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/04Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing coils
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F27/00Details of transformers or inductances, in general
    • H01F27/28Coils; Windings; Conductive connections
    • H01F27/2847Sheets; Strips
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21CMANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/02Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of sheets

Definitions

  • the present invention relates to a process for manufacturing electrical conductors for power transformers with high electrical and thermal conductivity, enhanced through the deposition of copper and graphene.
  • the present invention relates to an industrial process for the production of conductors having a rectangular section in copper and/or aluminium coated with GNP graphene (Graphene NanoPlatelets) with different thicknesses, in order to increase thermal and electrical conductivity of said conductors, which are then used in all the windings for electrical machines, transformers, generators, motors and, in particular, the power transformers.
  • GNP graphene Graphene NanoPlatelets
  • the transformer i a static electric machine powered by alternating current, based on the phenomenon of electromagnetic induction, intended to transform, between the primary circuit (input) and the secondary circuit (output) of the transformer, the voltage and current factors of the electric power.
  • the transformer therefore transfers the electric power from an electric circuit to another, which has a different voltage, coupling them inductively, without the transformer windings coming into contact with each other.
  • An electric current transformer in the primary winding generates a variable magnetic flux in the core of the transformer and consequently a variable magnetic field across the secondary winding (Faraday's law and Lenz's law).
  • This variable magnetic field induces an electromotive force, or voltage, in the secondary winding. This effect is called mutual induction.
  • the transformer is, therefore, a machine capable of operating essentially in alternating current, because it generally exploits the principles of electromagnetism linked to variable flows.
  • the efficiency of a transformer is very high and the losses are very low (in iron, due to the hysteresis and eddy currents, and in copper, due to the Joule effect).
  • a transformer To reduce the decrease in performance, a transformer must have the following characteristics: ⁇ Windings: o as few coils as possible o minimum length: the winding wire must be as short as possible; generally this depends on the section and shape of the core, square or (better still, where possible) circular. ⁇ Core: o a suitable section; o a length as short as possible; o in ferromagnetic material so as to have an electrical resistance as high as possible, to minimize losses due to the Joule effect and a coercive force as low as possible, in order to have a hysteresis cycle as tight as possible
  • Cooling the cooling is necessary to prevent the overheating of the transformer due to the dissipated power. It is particularly important in the transformers operating at high powers.
  • the cooling can be: o with air - typical solution of normal civil transformers and for small powers; o in oil bath - the transformers work in an oil bath in suitably shaped metal casings to facilitate heat dispersion; o in forced oil bath - compared to the oil bath system, there are also pumps for the forced circulation of the oil and a system of external fans to increase heat removal; o in resin - compared to the other systems, the windings are immersed in a special resin, which makes them dissipate the heat. This resin takes the place of oil. Size benefits can be gained from the resin transformer, since they are slightly smaller than an oil transformer.
  • transformers are recognized according to their cooling method.
  • the type of cooling is recognized by a code consisting of two or four letters (two, if the transformer has a single cooling; four, if the cooling is double).
  • the first letter shows what type of substance is being used for cooling (e.g. oil, resin, air)
  • the second letter shows the type of fluid circulation inside the transformer (natural or forced circulation).
  • transformer types are recognized:
  • WO20 14/ 141071 reports a method for the preparation of coated metal foams (through an electrodeposition process) with a metal matrix and graphene.
  • EP0859381A1 mentions an electrical conductor for the low voltage windings (and high currents), which allows greater heat exchange, maintaining the same performance as a transformer, which has, however, a much greater encumbrance. This allows the manufacturing of a power transformer having reduced dimensions, thus saving large quantities of copper during the construction of said transformer.
  • the present invention relates to a process for manufacturing electrical conductors for power transformers with high electrical and thermal conductivity, enhanced through the deposition of copper and graphene.
  • the present invention relates to an industrial process for the production of conductors having a rectangular section in copper and/or aluminium coated with GNP graphene (Graphene NanoPlatelets) with different thicknesses, in order to increase thermal and electrical conductivity of said conductors which are then used in all the windings for electrical machines, transformers, generators, motors and in particular the power transformers.
  • GNP graphene Graphene NanoPlatelets
  • a metal wire rod is drawn with special synthetic diamond and/or tungsten carbide dies, using an emulsion bath of water and oil. The drawing step is necessary to reduce the diameter of said metal wire rod until a circular section having a diameter of 1.8 mm is reached.
  • a metal wire rod is defined as a round object made of metallic material, which usually has a cylindrical shape. Said metal wire rod:
  • is made of a metal selected from the group comprising: aluminium, silver, nickel, gold, copper and/or their alloys; preferred are copper and aluminium.
  • Phase 2 - Laminating and edging The metal wire rod obtained at the end of phase 1 is shaped through a laminating and edging process to obtain a metal strip (having a rectangular section) that complies with the IEC (International Electrotechnical Commission) tolerance standards and has the following characteristics:
  • the metal strip obtained at the end of phase 2 is subjected to a thermal cooking cycle, optionally having the following temperatures and the following time intervals: cooking at a temperature of 550°C for a period of time of 4 hours (parameters usually used for copper strips), using an electric oven for static cooking in an inert atmosphere (nitrogen), to restore the metal to a soft and malleable physical state.
  • a thermal cooking cycle optionally having the following temperatures and the following time intervals: cooking at a temperature of 550°C for a period of time of 4 hours (parameters usually used for copper strips), using an electric oven for static cooking in an inert atmosphere (nitrogen), to restore the metal to a soft and malleable physical state.
  • Step 1 - the metal strip is coated with a “first metal layer”, deposited using a physical deposition technique (PVD/physical vapor deposition) or with a chemical deposition technique (CVD/ chemical vapor deposition), as described in Adv. Mater. 2000, 12, No. 9;
  • Step 2 - on the first metal layer of step 1 a “second metal layer (or its alloys) and graphene” is deposited/ stratified, using the electrodeposition described in W02014141071, wherein the metal associated with the graphene can be the same or different from the one used in step 1 ;
  • Step 3 - on the second “metal and graphene” layer of step 2 a “third metal layer” (or its alloys) is deposited/ stratified through a further electrodeposition process as described W02014141071, or a chemical or physical vapor deposition process using the PVD or CVD procedure as described in http:/ / www. mag- data. com/ dettaqli-tecnici/ introduuite-ai-film-polimerici/ ; Journal of Materials Chemistry C Volume 4 Number 37, 7 October 2016, Pages 8585-8830; and/or Adv. Mater. 2000, 12, No. 9.
  • the metal material of the first, the second and third layer is selected from the group comprising: aluminium, silver, nickel, gold, copper and/or their alloys; the metal of the first layer can be the same of different from the second layer, which can in turn be the same of different from the metal of the third layer.
  • the electrodeposited metal strip obtained at the end of phase 4 is insulated through a taping process, using a material selected from the group comprising: pure cellulose paper for oil impregnation, aramid paper, mica tape and/or polyamide tape. Phase 6 - Coupling the metal strips thus obtaining the power transformer.
  • the strips obtained at the end of phase 5 are grouped or coupled (depending on the transformer to be made) in helical windings, disc windings or other types of windings, thus obtaining the desired power transformer.
  • Said power transformer can be used in the industrial, industrial, energy, naval and / or aerospace field and having better characteristics of electrical and thermal conductivity, dissipated power and efficiency compared to current transformers on the market.
  • the metal strip obtained at the end of phase 5 which can be used for the construction of windings for electrical machines, transformers, generators and / or motors.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Coils Of Transformers For General Uses (AREA)
  • Insulated Conductors (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

L'invention concerne un procédé de fabrication de conducteurs électriques pour transformateurs de puissance ayant une conductivité électrique et thermique élevée, amélioré par le dépôt de cuivre et de graphène. En particulier, l'invention concerne un procédé industriel pour la production de conducteurs dans du cuivre et/ou de l'aluminium ayant une section rectangulaire (bandes) revêtue de graphène, afin d'augmenter la conductivité thermique et électrique desdits conducteurs, qui sont ensuite utilisés dans tous les enroulements pour transformateurs de puissance.
PCT/EP2021/069298 2020-07-13 2021-07-12 Conducteurs électriques pour transformateurs de puissance à haute conductivité électrique et thermique WO2022013138A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP21743453.9A EP4179554A1 (fr) 2020-07-13 2021-07-12 Conducteurs électriques pour transformateurs de puissance à haute conductivité électrique et thermique

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT102020000016903A IT202000016903A1 (it) 2020-07-13 2020-07-13 Conduttori elettrici per trasformatori di potenza ad elevata conducibilità elettrica e termica.
IT102020000016903 2020-07-13

Publications (1)

Publication Number Publication Date
WO2022013138A1 true WO2022013138A1 (fr) 2022-01-20

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EP (1) EP4179554A1 (fr)
IT (1) IT202000016903A1 (fr)
WO (1) WO2022013138A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4318509A3 (fr) * 2022-08-03 2024-05-01 Infineon Technologies Austria AG Graphène dans des systèmes électromagnétiques

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1217703A (en) * 1967-03-29 1970-12-31 Westinghouse Electric Corp Electrical winding structures
EP0859381A1 (fr) 1997-02-13 1998-08-19 Invex Fili Isolati Speciali S.p.A. Câble torsadé pour la fabrication d'enroulements de machines électriques, son procédé de fabrication, et procédé de fabrication d'un enroulement avec un tel câble torsadé
US20070234542A1 (en) * 2003-08-25 2007-10-11 Joerg Eickemeyer Method for Producing Metallic Flat Wires or Strips with a Cube Texture
CN103943226A (zh) * 2014-05-09 2014-07-23 浙江大学 一种具有镍-石墨烯复相护层的电线电缆及其制备方法
WO2014141071A1 (fr) 2013-03-12 2014-09-18 Jaber Innovation S.R.L. Électrodéposition sur des mousses métalliques
US20160228964A1 (en) * 2015-02-06 2016-08-11 Agie Charmilles Sa Graphene electrode
WO2018167041A1 (fr) * 2017-03-14 2018-09-20 Vincenzo Tagliaferri Câbles électriques ou de transmission de données à conductivité électrique élevée et/ou à vitesse de transmission de données élevée

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1217703A (en) * 1967-03-29 1970-12-31 Westinghouse Electric Corp Electrical winding structures
EP0859381A1 (fr) 1997-02-13 1998-08-19 Invex Fili Isolati Speciali S.p.A. Câble torsadé pour la fabrication d'enroulements de machines électriques, son procédé de fabrication, et procédé de fabrication d'un enroulement avec un tel câble torsadé
US20070234542A1 (en) * 2003-08-25 2007-10-11 Joerg Eickemeyer Method for Producing Metallic Flat Wires or Strips with a Cube Texture
WO2014141071A1 (fr) 2013-03-12 2014-09-18 Jaber Innovation S.R.L. Électrodéposition sur des mousses métalliques
CN103943226A (zh) * 2014-05-09 2014-07-23 浙江大学 一种具有镍-石墨烯复相护层的电线电缆及其制备方法
US20160228964A1 (en) * 2015-02-06 2016-08-11 Agie Charmilles Sa Graphene electrode
WO2018167041A1 (fr) * 2017-03-14 2018-09-20 Vincenzo Tagliaferri Câbles électriques ou de transmission de données à conductivité électrique élevée et/ou à vitesse de transmission de données élevée

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Metals Fabrication: Understanding the Basics", 1 November 2013, ASM INTERNATIONAL, ISBN: 978-1-62708-018-7, article CAMPBELL FLAKE C.: "Metal Fabrication: Understanding the Basics", pages: 157 - 161, XP055846603 *
ADV. MATER., vol. 12, no. 9, 2000
JOURNAL OF MATERIALS CHEMISTRY C, vol. 4, no. 37, 7 October 2016 (2016-10-07), pages 8585 - 8830, Retrieved from the Internet <URL:littp:llwww.magdata.com/dettagi-tecnici/introduzione-ai-film-polimerici/>

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4318509A3 (fr) * 2022-08-03 2024-05-01 Infineon Technologies Austria AG Graphène dans des systèmes électromagnétiques

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EP4179554A1 (fr) 2023-05-17
IT202000016903A1 (it) 2022-01-13

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