WO2024120990A1 - Procédé de production d'un élément métallique isolé et élément métallique isolé - Google Patents

Procédé de production d'un élément métallique isolé et élément métallique isolé Download PDF

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Publication number
WO2024120990A1
WO2024120990A1 PCT/EP2023/083899 EP2023083899W WO2024120990A1 WO 2024120990 A1 WO2024120990 A1 WO 2024120990A1 EP 2023083899 W EP2023083899 W EP 2023083899W WO 2024120990 A1 WO2024120990 A1 WO 2024120990A1
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WO
WIPO (PCT)
Prior art keywords
metal element
thermoplastic polymer
electrical properties
insulated
stable electrical
Prior art date
Application number
PCT/EP2023/083899
Other languages
English (en)
Inventor
Peter Persoone
Kris ROOMS
Maarten VIERSTRAETE
Philippe VANRANST
Original Assignee
Nv Bekaert Sa
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 Nv Bekaert Sa filed Critical Nv Bekaert Sa
Publication of WO2024120990A1 publication Critical patent/WO2024120990A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/307—Other macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/06—Insulating conductors or cables
    • H01B13/14—Insulating conductors or cables by extrusion
    • H01B13/145—Pretreatment or after-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
    • H01B3/427—Polyethers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
    • H01B7/2813—Protection against damage caused by electrical, chemical or water tree deterioration
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/292—Protection against damage caused by extremes of temperature or by flame using material resistant to heat

Definitions

  • the invention relates to a method to produce an insulated metal element having stable electrical properties, to an insulated metal element having stable electrical properties obtained with the said method, and the use of said insulated metal element as a magnet wire.
  • Insulated metal elements are used in several applications where a metal conductor needs to be insulated. For example it can design a cross-linked polyethylene (XLPE) insulated conductor for the medium- voltage lines and a XLPE insulated conductor or a polyvinyl chloride (PVC) insulated conductor for the low-voltage line.
  • XLPE cross-linked polyethylene
  • PVC polyvinyl chloride
  • Insulated metal elements are also used in the stator of electric motors, for both synchronous (permanent magnet) and asynchronous (induction) motors.
  • New challenges for automotive electric motors include:
  • insulated metal elements used as magnet wires in electrical motors need to be resistant at high voltage against partial discharges and hence exhibit a high partial discharge inception voltage (PDIV).
  • insulated metal elements used as magnet wires in electrical motors need to exhibit stable electrical properties with time. Stable electrical properties depend mainly on the type of insulation layer, its resistance to temperature variation and adhesion to the metal element.
  • an insulation layer acting as a barrier
  • the defect will display localized ionization when exposed to high voltage. This ionization starts at one voltage and stops at a lower voltage. These are called the inception and extinction voltages.
  • voltage will also build up across the void.
  • the inception voltage is reached, the void ionizes, shorting itself out.
  • the voltage across the void drops below the extinction voltage, ionization ceases. This action redistributes charge within the barrier and is known as partial discharge. If the barrier voltage continues to rise, another partial discharge cycle begins.
  • the barrier voltage is alternative current (AC) and is large enough, partial discharge cycles will repeat many times during the positive and negative peaks. If the ionization begins and continues, it can damage the barrier, leading to failure. If the discharge does not occur, the barrier receives no damage. The inception voltage of the individual voids tends to be constant. Therefore, the total charge redistributed within the barrier is a very good indicator of the number of the voids and their likelihood of becoming a failure. Setting a very low limit on the allowable current caused by partial discharges in testing gives a very high degree of confidence that high voltage failure will not occur.
  • AC alternative current
  • US 4471022A discloses a water-soluble polyimide, a coated wire and the method of coating.
  • the insulation layer consists of poly imide (PI), at least 6 layers are deposited with long curing time for each layer.
  • US 9324476B2 discloses an alternative insulated winding wire comprising at least two layers, the first one being an enamel polyamide-imide (PAI) layer, the second being polyether ether ketone (PEEK) or polyaryl-ether- ketone (PAEK).
  • PAI enamel polyamide-imide
  • PEEK polyether ether ketone
  • PAEK polyaryl-ether- ketone
  • US 9224523B2 discloses an inverter surge-resistant insulated wire, also consisting of an enamel layer and extruded thermoplastic.
  • US 2019/0131037A1 describes an insulated electric conductor obtainable by a method in which the electric conductor is placed under a protective gas atmosphere and is bombarded with ions of the protective gas in a gas plasma in order to remove an oxide layer formed on a surface of the electric conductor and /or to increase the surface energy of the conductor.
  • the insulating coating layer either comprises at least one insulating layer made of thermoplastic material, or the insulating layer and a plasticcontaining intermediate layer.
  • W021041200A1 discloses an insulated electrical conductor comprising an electrical conductor comprising an oxide layer on at least part of a surface of the electrical conductor, and an insulating coating on at least a portion of the oxide layer. Good adhesion between the electrical conductor and the insulating coating is obtained by heat-treating the coated electrical conductor.
  • JPH02250206A discloses insulated electric wires having a PEEK insulating layer with crystallinity lower than 10% such that flexibility is obtained for winding, further subjected to a heat treatment to set the degree of crystallization of PEEK between 15 and 40% for improved hardness and chemical resistance.
  • US9691521 B2 discloses a conductor having a thermosetting resin layer and a plurality of thermoplastic layers, wherein the second thermoplastic layer has a relative crystallinity higher than the first thermoplastic layer, and the first thermoplastic layer has a relative crystallinity in the range of 20% to 50%.
  • US2018/005724A1 discloses a conductor wrapped in a PEEK tape layer having a crystallinity of at least 25%.
  • US5358786A discloses an insulated wire comprising a conductor, an inner insulation layer 0.1 -1 mm comprising a halogen-free polymer, an intermediate insulation layer 0.001 mm to 0.5mm having a melting point ⁇ 155°C, and an outer insulation layer 0.05mm to 1 mm having a melting point>155°C.
  • the metal element consists of pure metal or it can be a metallic alloy.
  • the metal element can be made of copper or copper-alloy.
  • the metal element can be made of aluminium or aluminium alloy.
  • the metal element can also comprise different metals.
  • a steel substrate can be coated with copper or a copper alloy.
  • a steel substrate coated with zinc or a zinc alloy is another example.
  • the polymer coating is preferably a thermoplastic, i.e. a substance that becomes plastic on heating and hardens on cooling, and is able to repeat these processes.
  • the polymer is selected in the family of poly(aryl ether ketone) (PAEK), for instance poly(ether ether ketone) (PEEK), or poly(ether ketone) (PEK), or poly(ether ketone ketone) (PEKK).
  • PAEK poly(aryl ether ketone)
  • PEEK poly(ether ether ketone)
  • PEK poly(ether ketone)
  • PEKK poly(ether ketone ketone)
  • the polymer consists of PEEK.
  • the polymer coating layer can be applied by any technique known in the art, for example by extrusion or powder coating.
  • the coating layer is an extruded coating layer, as can be identified by observing the polymer chain orientation in the coating layer.
  • the polymer coating layer has preferably a thickness in the range 20pm to 500pm, for example between 30pm and 400pm or between 40pm and 300pm.
  • the metal element has preferably a degreased surface.
  • Surface preparation is done by electrolytic cleaning, assisted chemical treatment (e.g. ultrasonic cleaning), plasma, laser ablation, or any combination thereof.
  • assisted chemical treatment e.g. ultrasonic cleaning
  • plasma e.g. laser ablation
  • Heating can be done by means of induction, resistive heating, gas oven, plasma, or any combination thereof.
  • thermoplastic polymer when the melting temperature Tm of said thermoplastic polymer is 340°C said metal element is heated at a temperature between 360°C and 400°C. [0045] Applying said thermoplastic polymer on the surface of said metal element
  • the polymer coating is applied on the hot metal element by means of extrusion or powder coating.
  • Controlled cooling can be obtained by means of spraying a gas, e.g. N2 or compressed air on the surface of the coated metal element.
  • a gas e.g. N2 or compressed air
  • controlled cooling is done by immersion in water or by spraying water on the surface of the coated metal element.
  • Other controlled cooling techniques mixing gas and water may also be used.
  • the duration and intensity of the cooling should be adjusted such that the surface of the coated metal element reaches a temperature higher than [(Tm+Tg)/2 - 40°C] and lower than [(Tm+Tg)/2 + 40°C]. No reheating above (Tm+Tg)/2 + 40°C should occur after the first cooling step.
  • a temperature holding zone may be used.
  • Said temperature holding zone may comprise insulation elements and heating elements or hot air.
  • the temperature holding time between 2s and 10s determines the crystallinity rate, ensures good adhesion and stable electrical properties of the insulated metal element. In particular, holding times lower than 2s cause low crystallinity, and bad adhesion of the coating.
  • the final cooling step can be obtained by means of spraying a gas, e.g. N2 or compressed air on the surface of the coated metal element.
  • a gas e.g. N2 or compressed air
  • quenching is done by immersion in water or by spraying water on the surface of the coated metal element.
  • Other controlled cooling techniques mixing gas and water may also be used.
  • steps c) to h) are executed in a production line wherewith said metal element is running at a linear velocity higher than 40m/min, e.g. 50m/min, e.g. 100m/min.
  • the temperature range and temperature holding time at the end of the first cooling step are independent from the linear velocity of said metal element.
  • a metal element is coated with a thermoplastic polymer coating. There is no intermediate layer between the polymer and the metal element and the polymer coating is in semi-crystalline state.
  • Conductors from prior art always contain an adhesion layer between the metal element and the polymer coating because there is usually no adhesion between polymer and metal.
  • the method to produce the insulated element of the invention allows the suppression of an intermediate or bonding layer.
  • the insulated element of the present invention therefore only contains a core metal element, the conductor and a polymer coating.
  • the adhesion between the polymer coating and the metal element is obtained by the control of the process parameters, in particular the speed of polymer deposition by e.g. extrusion, and the control of the cooling.
  • the controlled cooling leads to a polymer coating with a desired range of crystallinity, which is characteristic for the present invention.
  • the rate of crystallinity is between 10% and 40%, more preferably between 15% and 35%, even more preferably between 20% and 35%.
  • the metal element having a polymer coating of the invention has a partial discharge inception voltage at 20°C above 800Vrms, preferably above 900Vrms, more preferably above lOOOVrms.
  • the polymer coating is applied on the hot metal element by means of extrusion or powder coating.
  • the insulated metal element of the invention obtained with the described method, is resistant at high voltage against partial discharges, has stable electrical properties in use, and is easier and cheaper to produce than insulated metal elements of the prior art.
  • a preferred use for an insulated metal element having stable electrical properties according to the invention is as hairpin wire for rotating or static parts of an electric motor.
  • said insulated metal element comprises Cu or a Cu-alloy as metal element and PEEK or a thermoplastic polymer from the family of PAEK.
  • FIG. 1 Is a schematic cooling curve
  • FIG. 2. Is a plot of PEEK crystallinity as a function of the temperature holding time
  • Different insulated metal elements were produced according to the disclosed method: a) rectangular shaped copper with section dimensions 3.7mm x 2mm and >0.3mm corner radius were provided as metal element on a carrier b) PEEK was provided as thermoplastic polymer. The commercial PEEK was obtained from e.g. Solvay or Victrex. Both melting temperature Tm and glass transition temperature Tg were measured by DSC and were found to be 340°C and 150°C, respectively. c) The rectangular shaped copper wire was unwound from the carrier at a linear velocity of 40m/min, cleaned and heated in line by means of plasma.
  • FIG. 1 Is a schematic cooling curve illustrating steps f) g) and h) of the method.
  • the letter C indicates the end of step g), i.e. the start of the quenching step after 2 to 10s temperature holding time.
  • the letter D indicates the end of the quenching step when the insulated metal element reaches a temperature below 50°C.
  • the percent crystallinity of the thermoplastic polymer was determined from the heats of melting and cold crystallization as measured via DSC and the reference heat of melting of the 100% crystalline thermoplastic polymer according to ASTM D3418-15. Approximately 10mg of thermoplastic polymer was removed from the insulated metal element by e.g. scraping or grating. Heating and cooling rates of 10°C/min were used to produce the heat flow curves. The heats of melting, AHm and cold crystallisation, AHc were determined by integrating the areas (J/g) under the peaks.
  • %Crystallinity 100*[AHm- AHc]/ AHm° where AHm° is the heat of melting of a fully crystalline polymer, which is 130 J/g for PEEK.
  • FIG. 2 is a plot of crystallinity as a function of the stop cooling time.
  • a too short temperature holding time between the first cooling step and the quenching step leads to low crystallinity or a completely amorphous polymer coating, causing bad adhesion between the polymer and the metal element, and unstable electrical properties.
  • Very long stop cooling times lead to the highest crystallinity value.
  • too long stop cooling time may cause variations of the coating thickness and unstable electrical properties.
  • insulated metal elements were produced according to the disclosed method and compared to 2 insulated metal elements from prior art.
  • Two reference samples from prior art, namely REF.1 and REF.2 were selected. In both samples the metal element consisted of copper with 99.9% purity and containing less than 400ppm O2.
  • the metal element had a rectangular shape with 3.7mm width and 2mm height, and corner radius > 0.3mm.
  • REF. 1 was coated with a 103pm thick enamel layer consisting of PAI, obtained by several deposition and curing cycles.
  • REF. 2 was coated with a first enamel layer consisting of PAI, with a thickness of 38pm, and a second polymer layer consisting of PEEK, with a thickness of 112pm.
  • the total insulation layer thickness was 150pm.
  • Samples INV.1 to INV.3 were obtained with the same starting metal element, i.e. rectangular shaped copper with section dimensions 3.7mm x 2mm and >0.3mm corner radius.
  • the 3 samples produced according to the disclosed method had a PEEK coating thickness ranging between 40pm and 300pm.
  • adhesion was tested according to IEC60317 standards, by means of elongation tests with incision through the polymer coating.
  • the PDIV of the different samples was measured according to the standards IEC 60664-1 and 61800-5-1.
  • test voltage AC 50Hz, RMS
  • the test voltage was gradually increased until partial discharge was registered with the measuring capacitor above a level of 10pC.
  • the coating thickness, t indicated in the table needs to be doubled in the formula as pairs of samples are tested.
  • the relative permittivity, s r is depending on the type of coating and was estimated to be 3.9 for Enamel (PAI), and 3.1 for PEEK
  • the metal element having a polymer coating of the present invention is particularly suitable for use in hairpin wire for rotating or static parts of an electric motor.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un nouveau procédé de production d'un élément métallique isolé ayant des propriétés électriques stables comprend les étapes consistant à : a) fournir un élément métallique ; b) fournir un polymère thermoplastique ; c) nettoyer la surface dudit élément métallique ; d) chauffer ledit élément métallique à une température comprise entre Tm + 20°C et Tm + 60°C, Tm étant la température de fusion dudit polymère thermoplastique ; e) appliquer ledit polymère thermoplastique sur la surface dudit élément métallique ; f) refroidir l'élément métallique revêtu à une température supérieure à [(Tm+Tg)/2 – 40°C] et inférieure à [(Tm+Tg)/2 + 40°C], avec Tm la température de fusion dudit polymère thermoplastique et Tg la température de transition vitreuse dudit polymère thermoplastique ; g) arrêt du refroidissement pendant 2s à moins de 10s ; h) trempe de l'élément métallique revêtu à une température inférieure à 50°C
PCT/EP2023/083899 2022-12-05 2023-12-01 Procédé de production d'un élément métallique isolé et élément métallique isolé WO2024120990A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP22211403 2022-12-05
EP22211403.5 2022-12-05

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WO2024120990A1 true WO2024120990A1 (fr) 2024-06-13

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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4471022A (en) 1981-04-17 1984-09-11 Essex Group, Inc. Water soluble polyimide, coated wire and method of coating
JPH02250206A (ja) * 1989-03-22 1990-10-08 Fujikura Ltd 絶縁電線およびこれを巻回したコイル
US5358786A (en) 1990-01-31 1994-10-25 Fujikura Ltd. Electric insulated wire and cable using the same
JP2015138626A (ja) * 2014-01-21 2015-07-30 日立金属株式会社 絶縁電線とその製造方法、及び電気機器のコイルとその製造方法
US9224523B2 (en) 2013-02-05 2015-12-29 Furukawa Electric Co., Ltd. Inverter surge-resistant insulated wire
US9324476B2 (en) 2014-02-05 2016-04-26 Essex Group, Inc. Insulated winding wire
US9691521B2 (en) 2014-01-10 2017-06-27 Furukawa Electric Co., Ltd. Rectangular insulated wire and electric generator coil
US20180005724A1 (en) 2015-01-30 2018-01-04 Victrex Manufacturing Limited Insulated conductors
US20180268962A1 (en) * 2015-11-20 2018-09-20 Furukawa Electric Co., Ltd. Assembled wire, method of producing the same, and electrical equipment using the same
US20190131037A1 (en) 2016-04-01 2019-05-02 Gebauer & Griller Metallwerk Gmbh Insulated electric conductor
US20200047379A1 (en) 2018-08-09 2020-02-13 Canon Kabushiki Kaisha Flexible mask modulation for controlling atmosphere between mask and substrate and methods of using the same
WO2021041200A1 (fr) 2019-08-23 2021-03-04 Zeus Industrial Products, Inc. Fils revêtus de polymère

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4471022A (en) 1981-04-17 1984-09-11 Essex Group, Inc. Water soluble polyimide, coated wire and method of coating
JPH02250206A (ja) * 1989-03-22 1990-10-08 Fujikura Ltd 絶縁電線およびこれを巻回したコイル
US5358786A (en) 1990-01-31 1994-10-25 Fujikura Ltd. Electric insulated wire and cable using the same
US9224523B2 (en) 2013-02-05 2015-12-29 Furukawa Electric Co., Ltd. Inverter surge-resistant insulated wire
US9691521B2 (en) 2014-01-10 2017-06-27 Furukawa Electric Co., Ltd. Rectangular insulated wire and electric generator coil
JP2015138626A (ja) * 2014-01-21 2015-07-30 日立金属株式会社 絶縁電線とその製造方法、及び電気機器のコイルとその製造方法
US9324476B2 (en) 2014-02-05 2016-04-26 Essex Group, Inc. Insulated winding wire
US20180005724A1 (en) 2015-01-30 2018-01-04 Victrex Manufacturing Limited Insulated conductors
US20180268962A1 (en) * 2015-11-20 2018-09-20 Furukawa Electric Co., Ltd. Assembled wire, method of producing the same, and electrical equipment using the same
US20190131037A1 (en) 2016-04-01 2019-05-02 Gebauer & Griller Metallwerk Gmbh Insulated electric conductor
US20200047379A1 (en) 2018-08-09 2020-02-13 Canon Kabushiki Kaisha Flexible mask modulation for controlling atmosphere between mask and substrate and methods of using the same
WO2021041200A1 (fr) 2019-08-23 2021-03-04 Zeus Industrial Products, Inc. Fils revêtus de polymère

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