EP2468422B1 - Verfahren zur Herstellung einer polymerbeschichteten Kupfer-Zink-Legierungsstruktur mit besserer Haftung - Google Patents

Verfahren zur Herstellung einer polymerbeschichteten Kupfer-Zink-Legierungsstruktur mit besserer Haftung Download PDF

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Publication number
EP2468422B1
EP2468422B1 EP20100196553 EP10196553A EP2468422B1 EP 2468422 B1 EP2468422 B1 EP 2468422B1 EP 20100196553 EP20100196553 EP 20100196553 EP 10196553 A EP10196553 A EP 10196553A EP 2468422 B1 EP2468422 B1 EP 2468422B1
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Prior art keywords
alloy
inert gas
coating
treatment
plasma
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English (en)
French (fr)
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EP2468422A1 (de
Inventor
Süleyman Deveci
Yalcin Öksüz
Zafer Gemici
Mehmet Mutlu
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Mir Arastirma ve Gelistirme AS
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Mir Arastirma ve Gelistirme AS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0486—Operating the coating or treatment in a controlled atmosphere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/40—Metallic substrate based on other transition elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0406—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being air
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0433—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a reactive gas

Definitions

  • the present invention relates to a method for applying a polymeric material onto a substrate consisting substantially of copper and zinc, more particularly the invention relates to a method for applying polymeric materials onto a Cu-Zn alloy surface with improved interfacial adhesion between Cu-Zn alloy surface and said polymer, said polymer being grafted with maleic anhydride.
  • Treating of a metal surface with chemical agents in order to improve adherence quality is a well known way of increasing adhesion forces between metals and polymers as disclosed, for instance in GB-A-1161097 . Accordingly, it was reported that treating a metal surface with a chromium trioxide solution may improve adherence of an organic thermoplastic material upon the treated metal surface.
  • EP-A1-580944 discloses a method for producing metal/plastic composite structures, especially dental prostheses, which involves forming a mediator layer such as a silane adhesive layer for improving metal-plastic bonding structure by way of an electrochemical process.
  • WO 02/059391 discloses an ultrathin outer layer on a metallic substrate.
  • Process for coating of said metal comprises treatment of the metallic surface with a plasma containing water and/or carbon dioxide whereas oxygen may also be included into said plasma for depositing a polymer layer on the metallic substrate.
  • the polymer layer however, have very limited interaction with the oxide layers of the substrate.
  • EP 1 132 195 A2 describes use of a special plasmatron arrangement and a surface treatment method for coating metallic substrates involving a plasma treatment which may include an inert gas, an oxidant, polymerizing material or graft copolymer.
  • the arrangement and method is aiming at providing a homogenous treatment or coating rather than improving the adherence quality in between a metallic substrate and a polymer.
  • the specification neither discloses a specific metal-polymer arrangement that may result in an improved interaction layer having good adherence performance.
  • JP-A-2005007710 which involves treating a metal surface by dry plasma for degreasing and surface reforming on an aluminum substrate and forming a corrosion resistant and adhesion-promoted layer on the aluminum surface.
  • the present invention relates to a novel method for coating polymers on Cu-Zn alloy substrates with improved adhesion.
  • the alloy is treated in a plasma reactor with a two-step procedure in order to remove the impurities from the alloy surface and also to improve the surface oxide characteristics.
  • the first step is carried out under vacuum with an inert gas plasma wherein organic and inorganic contamination becomes volatile and is eventually removed.
  • the second step of the method involves treatment of the alloy with oxygen plasma for modifying and selectively oxidizing its surface.
  • carboxylic groups (-COOH) of the polymers behave as Lewis acid whereas the oxide layer on the metal behaves as Lewis base.
  • carboxylic group covalent bonding is constituted between polymers and metal surfaces. Therefore, formation of an oxide layer on the metal surface on which the polymer is to be coated is highly desirable.
  • Cu-Zn alloy substrates when carries out an oxidation, may contain a layer consisting mainly of oxides of zinc and copper.
  • oxidation of copper results in a biphasic oxide layer consisting of Cu 2 O and CuO.
  • oxidation of zinc produces mainly ZnO.
  • CuO is known as an oxidation state of copper which has higher stability as compared to Cu 2 O. Therefore, Cu 2 O may be regarded as more preferable for adhesion purposes ( Popova TV, Aksenova NV, Complexes of copper in unstable oxidation states, 2003, Russian Journal of Coordination Chemistry, Vol 29-11, 743-765 ).
  • ZnO provides the at most affinity for adhesion to maleic anhydride grafted polymeric materials such as the MAH grafted thermoplastics.
  • one of the objectives of the present invention appears in that providing a method for coating polymers onto a Cu-Zn alloy surface wherein said surface is treated with a selective oxidation for increasing the ZnO proportion as well as reducing the amount of CuO as much as possible.
  • the inventors surprisingly found that exposing the Cu-Zn alloy to a two-step plasma treatment provided rapid cleaning of the alloy surface and formation of the oxide layers CuO, Cu 2 O and ZnO.
  • the inventors further noted that the two-step plasma treatment as envisaged in the scope of the invention permits selective oxidation of Cu and Zn causing concentration of ZnO to increase relatively more than CuO and Cu 2 O. It was even observable that Cu content in the uppermost surface of the alloy underwent an oxidation state with Cu 2 O relatively more than CuO. This clearly implicate one of the advantages of the invention with excellent selectivity in providing an oxide layer predominantly comprising ZnO which has crucial benefits in terms of the adherence properties as stated supra.
  • the plasma treatment equipment that can be used in the present invention may include a compartment for establishing a sealed low pressure medium and electrodes positioned around said compartment.
  • the equipment may further comprise a reactor, power supplier and a vacuum pump as conventionally used in many applications.
  • the power supplier may be in the form of a RF, LF or MW supply as well known by the specialists in the field.
  • metallic samples such as brass
  • interior pressure of the reactor is decreased by applying vacuum.
  • said pressure is reduced to a value between 0.05 and 0.30 mbar, more preferably to a value between 0.10 and 0.12 mbar.
  • the internal pressure of the reactor is increased to a value between 0.10 and 0.50 mbar, more preferably to 0.20-0.30 mbar by injecting an inert gas into the reactor.
  • Argon is the preferred inert gas for use in the present invention.
  • the inert gas, preferably argon plasma is applied onto the samples for at least 5 minutes, more preferably at least 10 minutes, and most preferably for 15 minutes.
  • the duration of the plasma treatment may be more or less than the above stated treatment times depending on the amount of impurities and contamination on the surface.
  • the power applied in this term may be in the range of 50-2000 W depending on the volume of the reactor.
  • the inert gas is disconnected and synchronously, oxygen is started to be injected into the reactor, and the oxygen plasma is applied onto the samples for at least 10 minutes, more preferably for 20 minutes by applying a power approximately in the range of 50-2000 W depending on the volume of the reactor.
  • the medium pressure during the oxygen treatment is adjusted to a value between 0.10 and 0.20 mbar. Later on, the internal pressure of the reactor is increased to the atmospheric pressure and the samples whose surfaces are covered with a layer substantially of zinc oxide are obtained as ready for a coating process.
  • the first step of the disclosed method according to the present invention that is carried out under vacuum with exposure to inert gas provides effective removal of the impurities and surface activation of the copper-zinc alloy.
  • the effect of the inert plasma physical ablation of the impurities on the sample surface is achieved in a rapid and efficient manner.
  • the in situ surface cleaning continues during oxygen plasma treatment since the impurities are forced to undergo an oxidation reaction which results in an additional cleansing effect. Therefore, the invention is advantageous especially in the event that excessive amount of contamination exist on the sample surface.
  • Electron Spectroscopy for Chemical Analysis was sequentially performed on a sample before and after plasma treatment.
  • carbon, oxygen, copper and zinc contents were investigated by using Mg-K alpha source.
  • Depth analyses are carried out for all of the samples by bombarding with argon ions.
  • ion bombardment treatment parameters of energy (1000eV) and time (3 min.) are stabilized for each cycle.
  • excellent oxidation of the alloy is attained in a selective manner.
  • relative amount of the zinc oxide is considerably increased while the copper oxides undergo dramatic decrease by virtue of the plasma conditions.
  • the analysis confirms the envisaged advantages with respect to selective oxidation (promoting ZnO) and cleansing of the surface without any need of additional cleaning agents.
  • the inventors report that effect of the plasma treatment is improved when the sample is closer to the electrodes.
  • the subsequent step of the method according to the present invention involves coating of a polymer onto the zinc-copper alloy as treated in the above procedure.
  • the polymer as referred herein is preferably of a thermoplastic nature, and is more preferably polypropylene, polyethylene or a blend thereof.
  • the inventors noted that when the said polymer is grafted with maleic anhydride, the objective adhesion performance is further increased. Excellent results were obtained when maleic anhydride grafted polypropylene (PP-g-MAH) or maleic anhydride grafted polyethylene (PE-g-MAH) is applied on the surface of a Zn-Cu alloy.
  • the coating procedure may include, but not limited to, lamination, electrostatic powder coating, dip coating and fluidized bed powder coating.
  • Non-polar main chain and grafted polar chains are thermodynamically incompatible. As a consequence, polar branched chains are situated actively on the surface of polymer which is thought to contribute the desired adhesion effect.
  • Maleic anhydrite (C 4 H 2 O 3 ) is known per se and is generally used in the production of polymers, agricultural chemicals, pharmaceutical products, surfactants and plasticizers.
  • the inventors attribute the good performance of maleic anhydride grafted polymers, especially of MA grafted polypropylene and MA grafted polyethylene, in the method of the present invention further to the fact that MA undergoes hydrogenation to succinic anhydride which has higher affinity to ZnO than the other copper oxides.
  • MA grafted polymers may be coated on Zn-Cu alloys by any conventional method such as thermal coating and electrolytic coating. Therefore, the method of the present invention eliminates the necessities for additional chemical treatment steps for cleaning and adherence purposes while providing excellent adhesion performance inbetween polymers and Cu-Zn alloys.
  • the method is applicable with any kind of alloy system having predominant Cu-Zn content such as brass which may find large application areas, for instance boilers, piping systems, electronics, bearings and ornamentals.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
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Claims (12)

  1. Ein Verfahren zum Beschichten von Polymeren auf einem Substrat aus einer Cu-Zn - Legierung, welches folgende Schritte aufweist:
    Behandeln der Cu-Zn - Legierung in einem Plasmareaktor unter Vakuum und Liefern eines Inertgases zum Konditionieren und Reinigen der Legierungsoberfläche,
    Entfernen der Inertgaszufuhr, Einführen von Sauerstoff in die Reaktorkammer und Behandeln der Legierung unter Sauerstoffplasma zum Modifizieren und selektiven Oxidieren ihrer Oberfläche,
    Erhöhen des internen Drucks des Reaktors auf den Atmosphärendruck und Erhalten der behandelten Legierung, und
    Beschichten der Oberfläche der behandelten Legierung durch mit Maleinsäureanhydrid aufpolymerisierten Polymeren.
  2. Ein Verfahren gemäß Anspruch 1, wobei das Inertgas Argon ist.
  3. Ein Verfahren gemäß Anspruch 1, wobei die Beschichtung durch ein Verfahren ausgeführt wird, welches aus der Gruppe ausgewählt ist, welche aus Laminieren, elektrostatische Pulverbeschichtung, Tauchbeschichtung und Pulverbeschichtung im Wirbelschichtbett besteht.
  4. Ein Verfahren gemäß Anspruch 1, wobei die Polymere aus Thermoplasten gebildet sind.
  5. Ein Verfahren gemäß Anspruch 4, wobei die Thermoplaste Polypropylen, Polyethylen oder eine Mischung davon sind.
  6. Ein Verfahren gemäß Anspruch 1, wobei die Behandlung mit Inertgasplasma unter Vakuum bei einem Druck zwischen 0,05 und 0,30 mbar ausgeführt wird.
  7. Ein Verfahren gemäß Anspruch 6, wobei die Behandlung mit Inertgasplasma unter Vakuum bei einem Druck zwischen 0,10 und 0,12 mbar ausgeführt wird.
  8. Ein Verfahren gemäß Anspruch 1, wobei die Leistung, welche zu der Reaktorkammer während der Inertgasplasma-Behandlung geliefert wird, zwischen 50 und 2000 W beträgt.
  9. Ein Verfahren gemäß Anspruch 1, wobei das Sauerstoffplasma während mindestens 20 Minuten angewendet wird.
  10. Ein Verfahren gemäß Anspruch 1, wobei der mittlere Druck während der Sauerstoffplasma-Behandlung auf einen Wert zwischen 0,10 und 0,20 mbar eingestellt wird.
  11. Ein Verfahren gemäß Anspruch 1, wobei die Leistung, welche zu der Reaktorkammer während der Sauerstoffplasma-Behandlung geliefert wird, zwischen 50 und 2000 W beträgt.
  12. Ein Verfahren gemäß Anspruch 1, wobei die Legierung Messing ist.
EP20100196553 2010-12-22 2010-12-22 Verfahren zur Herstellung einer polymerbeschichteten Kupfer-Zink-Legierungsstruktur mit besserer Haftung Active EP2468422B1 (de)

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EP20100196553 EP2468422B1 (de) 2010-12-22 2010-12-22 Verfahren zur Herstellung einer polymerbeschichteten Kupfer-Zink-Legierungsstruktur mit besserer Haftung

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EP3235575A1 (de) * 2016-04-22 2017-10-25 Schaeffer AG Verfahren zum aufbringen eines primers, insbesondere eines primers für uv-beschichtungssysteme, auf der oberfläche eines elektrisch leitfähigen substrats
DE102018213392A1 (de) 2018-08-09 2020-02-13 MTU Aero Engines AG Verfahren zur Herstellung von Bohrungen in schwer zu zerspanenden Werkstoffen

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GB1161097A (en) 1966-11-01 1969-08-13 Dow Chemical Co Treatment of Metals for Promoting Adhesion of Thermoplastic Materials.
DE4225106C2 (de) 1992-07-30 1995-10-05 Heraeus Kulzer Gmbh Verfahren und Vorrichtung zur Herstellung eines Metall-Kunststoff-Verbundes
DE10011276A1 (de) * 2000-03-08 2001-09-13 Wolff Walsrode Ag Verwendung eines indirrekten atomosphärischen Plasmatrons zur Oberflächenbehandlung oder Beschichtung bahnförmiger Werkstoffe sowie ein Verfahren zur Behandlung oder Beschichtung bahnförmiger Werkstoffe
DE10103463B4 (de) * 2001-01-25 2009-10-08 Thyssenkrupp Steel Ag Verbundmaterial aus metallischen Substraten und Verfahren zur Herstellung und dessen Verwendung
JP4215200B2 (ja) 2003-06-18 2009-01-28 財団法人大阪産業振興機構 表面処理された金属材の製造方法と製造装置
US20090069790A1 (en) * 2007-09-07 2009-03-12 Edward Maxwell Yokley Surface properties of polymeric materials with nanoscale functional coating

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