EP2468422A1 - Procédé de production d'une structure en alliage de cuivre/zinc revêtu de polymère doté d'une adhérence améliorée - Google Patents

Procédé de production d'une structure en alliage de cuivre/zinc revêtu de polymère doté d'une adhérence améliorée Download PDF

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Publication number
EP2468422A1
EP2468422A1 EP10196553A EP10196553A EP2468422A1 EP 2468422 A1 EP2468422 A1 EP 2468422A1 EP 10196553 A EP10196553 A EP 10196553A EP 10196553 A EP10196553 A EP 10196553A EP 2468422 A1 EP2468422 A1 EP 2468422A1
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EP
European Patent Office
Prior art keywords
alloy
coating
inert gas
plasma
polymers
Prior art date
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EP10196553A
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German (de)
English (en)
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EP2468422B1 (fr
Inventor
Süleyman Deveci
Yalcin Öksüz
Zafer Gemici
Mehmet Mutlu
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MIR ARASTIRMA VE GELISTIRME ANONIM SIRKETI
Original Assignee
Dizayn Grup Teknoloji Arastirma ve Gelistirme San Tic 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.
  • 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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EP20100196553 2010-12-22 2010-12-22 Procédé de production d'une structure en alliage de cuivre/zinc revêtu de polymère doté d'une adhérence améliorée Active EP2468422B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20100196553 EP2468422B1 (fr) 2010-12-22 2010-12-22 Procédé de production d'une structure en alliage de cuivre/zinc revêtu de polymère doté d'une adhérence améliorée

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Application Number Priority Date Filing Date Title
EP20100196553 EP2468422B1 (fr) 2010-12-22 2010-12-22 Procédé de production d'une structure en alliage de cuivre/zinc revêtu de polymère doté d'une adhérence améliorée

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EP2468422A1 true EP2468422A1 (fr) 2012-06-27
EP2468422B1 EP2468422B1 (fr) 2013-05-29

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017182646A1 (fr) * 2016-04-22 2017-10-26 Schaeffer Ag Procédé d'application d'un apprêt, en particulier d'un apprêt pour systèmes de revêtement uv, sur la surface d'un substrat conducteur d'électricité
US11471964B2 (en) 2018-08-09 2022-10-18 MTU Aero Engines AG Method for the production of drill holes in difficult to machine materials

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1161097A (en) 1966-11-01 1969-08-13 Dow Chemical Co Treatment of Metals for Promoting Adhesion of Thermoplastic Materials.
EP0580944A1 (fr) 1992-07-30 1994-02-02 Heraeus Kulzer Gmbh Procédé et dispositif pour la fabrication d'un composite métal-plastique
EP1132195A2 (fr) * 2000-03-08 2001-09-12 Wolff Walsrode AG Traitement de surface ou revêtement de bandes utilisant un plasmatron atmosphérique à arc non transféré
WO2002059391A1 (fr) * 2001-01-25 2002-08-01 Friedrich-Alexander-Universität Erlangen-Nürnberg Couches de couverture ultrafines sur substrats metalliques, leur procede de fabrication et leur utilisation
JP2005007710A (ja) 2003-06-18 2005-01-13 Osaka Industrial Promotion Organization 表面処理された金属材およびそ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

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1161097A (en) 1966-11-01 1969-08-13 Dow Chemical Co Treatment of Metals for Promoting Adhesion of Thermoplastic Materials.
EP0580944A1 (fr) 1992-07-30 1994-02-02 Heraeus Kulzer Gmbh Procédé et dispositif pour la fabrication d'un composite métal-plastique
EP1132195A2 (fr) * 2000-03-08 2001-09-12 Wolff Walsrode AG Traitement de surface ou revêtement de bandes utilisant un plasmatron atmosphérique à arc non transféré
WO2002059391A1 (fr) * 2001-01-25 2002-08-01 Friedrich-Alexander-Universität Erlangen-Nürnberg Couches de couverture ultrafines sur substrats metalliques, leur procede de fabrication et leur utilisation
JP2005007710A (ja) 2003-06-18 2005-01-13 Osaka Industrial Promotion Organization 表面処理された金属材およびそ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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY, vol. 29, no. 11, 2003, pages 743 - 765

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017182646A1 (fr) * 2016-04-22 2017-10-26 Schaeffer Ag Procédé d'application d'un apprêt, en particulier d'un apprêt pour systèmes de revêtement uv, sur la surface d'un substrat conducteur d'électricité
US11471964B2 (en) 2018-08-09 2022-10-18 MTU Aero Engines AG Method for the production of drill holes in difficult to machine materials

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