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WO2003033778A1 - Production d'une zone superficielle a conduction metallique sur des alliages al-mg oxydes - Google Patents

Production d'une zone superficielle a conduction metallique sur des alliages al-mg oxydes Download PDF

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Publication number
WO2003033778A1
WO2003033778A1 PCT/EP2002/011298 EP0211298W WO03033778A1 WO 2003033778 A1 WO2003033778 A1 WO 2003033778A1 EP 0211298 W EP0211298 W EP 0211298W WO 03033778 A1 WO03033778 A1 WO 03033778A1
Authority
WO
WIPO (PCT)
Prior art keywords
laser
lacquer
substance
alloys
surface area
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2002/011298
Other languages
German (de)
English (en)
Inventor
Wolf-Dieter Franz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Franz Oberflaechentechnik GmbH and Co KG
Original Assignee
Franz Oberflaechentechnik GmbH and Co KG
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 Franz Oberflaechentechnik GmbH and Co KG filed Critical Franz Oberflaechentechnik GmbH and Co KG
Priority to US10/492,499 priority Critical patent/US20040244880A1/en
Publication of WO2003033778A1 publication Critical patent/WO2003033778A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/067—Metallic effect
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/20—Electrolytic after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/007—Processes for applying liquids or other fluent materials using an electrostatic field

Definitions

  • the present invention relates to the remetallization of oxidized and / or phosphated surfaces on Al and Mg alloys. Since AI and Mg never appear as pure elements in technical practice, this application speaks basically of alloys. Of course, this also means alloys in which one of the two metals occurs practically exclusively.
  • Al, Mg and generally also their alloys are easily oxidizing materials on which a phosphate layer with embedded oxides quickly forms.
  • oxidation is understood in the chemical sense to mean any reaction by increasing the oxidation state by removing valence electrons, in particular the reaction with oxygen.
  • These can be oxidized surfaces which have been inadvertently formed by contact with air or other oxidizing substances - but the invention preferably relates to the remetallization of surfaces which have been deliberately oxidized and / or phosphated for technical reasons, as is known to the person skilled in the art various applications are known.
  • the invention also relates to the case in which the oxide / phosphate layer is to be removed down to the underlying metal alloy for reasons other than electrical, but a factually metallic conductive surface also arises.
  • the invention is therefore based on the technical problem of producing surface areas with good metallic conductivity on oxidized and / or phosphated surfaces of Al and / or Mg alloys.
  • this problem is solved by a method for producing a metallically conductive surface area in an oxidized and / or phosphated surface of an alloy which contains Al and / or Mg, in which the surface area is bombarded with a laser in order to remove the phosphate layer with embedded oxides and the area is then covered with a flowable metallic conductive substance.
  • oxide surface and “phosphated surface” here do not only mean surfaces with a covering of the pure oxides or phosphates of the alloy in question. Other substances may also be present in the layer, which have arisen in previous intended or unintentional reactions. In addition, the surface can also be covered with other layers that must also be removed. In particular, the invention is also directed to surfaces on which mixtures of oxides and phosphates are present, for example to surfaces with phosphate layers with embedded oxides.
  • a flowable substance is provided, which is applied in a flowable state and which adapts itself so well to the surface contour that complete installation and corresponding protection is possible.
  • a substance can be selected which hardens after application or at least becomes more viscous. At least in the final, ie if necessary hardened, state, the substance itself must have a metallic conductivity because it takes on the role of the metallic conductive surface instead of the actual alloy surface.
  • Overall, surprisingly good contact resistance values of, for example, 0.5-2.5 m ⁇ / mm 2 can be achieved with the method according to the invention.
  • the laser process has the advantage of being able to run even complex surface shapes or tracks on the surface in a very short time. Surfaces that are three-dimensionally complex can also be treated well. In particular, it has been found that the high throughput due to the short processing time in the case of larger quantities can ultimately result in much more cost-effective machining processes than in the case of mechanical removal processes.
  • the invention is preferably directed to technical oxide layers and / or phosphate layers on Al or Mg alloys.
  • Anodized surfaces are particularly suitable.
  • a special aspect of the invention is the additional application of a lacquer layer to the surface - with any additional layers in between - before the laser bombardment is carried out.
  • Organic materials and paints in particular, initially assumed that cracking and polymerization processes caused by the thermal energy coupling by the laser, which can lead to extremely resistant insulating coatings, cannot be avoided. In fact, very good results can be achieved with low contact resistances.
  • the lacquer layer has the primary advantage of stabilizing the layers during laser bombardment and in some cases preventing or at least covering inevitable cracks in the layers at the edges of the remetallized area. As a result, together with the sealing through the flowable material, it can be achieved that the Al or Mg alloy is finally completely encapsulated.
  • lacquer encompasses any adhesive material which is slightly elastic in the applied state and which fulfills the function described above.
  • KTL coating cathodic dip coating
  • electrophoretic coating layers are also possible.
  • the surface areas to be remetalized are bombarded twice or several times in succession with the laser, with some time in between in which, for example, other surface areas can be bombarded. This allows the energy input per shot to be kept low and thus prevents excessive heating, while ultimately it is possible to completely remove the layers.
  • the surface areas to be remetalized are preferably bombarded twice.
  • the laser type is basically open. However, infrared lasers and in particular Nd-activated yttrium aluminum garnet lasers (Nd: YAG) have proven successful. Typical power densities in laser bombardment are in the range from 8W / mm 2 to 20W / mm 2 , preferably between 8W / mm 2 and 40W / mm 2 .
  • a laser for example, is a commercial Nd: YAG of the Baasel "Star Mark" type. Typical feed speeds are between 100 and 500 mm / sec., Preferably between 200 and 400 mm / sec. Repetition frequencies of the flash lamp and thus of the laser pulses from 1 - 5 kHz, preferably 2 - 4 kHz can be achieved, with a flash lamp current of 10 - 30 A at 380 V being suitable.
  • a particularly important area of application of the invention is in housings and housing parts of electrical or electronic devices which, for weight reasons, have recently been increasingly produced from Al and in particular also from Mg alloys.
  • the conductive substance for example the silicone adhesive mentioned with silver-coated copper particles, can also be used as an adhesive or sealant.
  • the frame part 1 is coated with a commercial “ANOMAG” layer, namely an anodic oxidation / phosphotation layer of approximately 3-5 ⁇ m thick, which is offered commercially by the company Magnesium Technology Licensing Limited (Auckland, New Zealand) and its contractual partners Strictly speaking, it is a phosphate layer provided with embedded oxides on the magnesium alloy substrate.
  • ANOMAG anodic oxidation / phosphotation layer of approximately 3-5 ⁇ m thick
  • the ANOMAG layer is covered with an acrylic resin water-based paint before the laser treatment in order to improve the encapsulation of the surface and also its appearance.
  • the laser bombardment is also carried out at normal atmosphere and room temperature.
  • This surface is then treated on the drawn-in frame 2 and support domes 3 with a commercial Nd: YAG laser.
  • This laser is Q-switched.
  • the lines 2 and areas 3 shown in the figure are traced twice, with strictly speaking being set point to point.
  • the point spacing, the point size and the energy per point can be determined empirically in such a way that on the one hand there is a continuous path and on the other hand a sufficient path width.
  • the track width should not be too small to optimize the electrical contact resistance to the other housing part.
  • the web width should not be too large and should be completely covered by the adhesive bead applied later. It is 1 mm here.
  • the energy input per shot should not be set unnecessarily high in order to avoid excessive heating at greater depths.
  • the energy per shot can be reduced even further by double bombardment. 20 W / mm 2 are used here per shot. It is a "Baasel Star Mark" type laser that is set to a pulse repetition frequency of 3 kHz. The feed rate is around 300 mm / s, which enables very fast work.
  • the metallized areas are coated with a silicone adhesive with silver-coated copper particles. This should be done as soon as possible after the laser treatment in order to optimize the contact resistance.
  • This adhesive can also be used for sealing and connecting when gluing the shown frame part to other housing parts of the mobile phone.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Conductive Materials (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un procédé pour remétalliser des zones superficielles sur des alliages d'Al et/ou de Mg par bombardement laser puis par scellement avec une substance coulante électroconductrice.
PCT/EP2002/011298 2001-10-11 2002-10-09 Production d'une zone superficielle a conduction metallique sur des alliages al-mg oxydes Ceased WO2003033778A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/492,499 US20040244880A1 (en) 2001-10-11 2002-10-09 Production of a surface area with metallic conductivity on oxidised al-mg alloys

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP01124437A EP1302566B1 (fr) 2001-10-11 2001-10-11 Production d'une région de surface métalliquement conductive sur des alliages Al-Mg oxydés
EP01124437.3 2001-10-11

Publications (1)

Publication Number Publication Date
WO2003033778A1 true WO2003033778A1 (fr) 2003-04-24

Family

ID=8178945

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/011298 Ceased WO2003033778A1 (fr) 2001-10-11 2002-10-09 Production d'une zone superficielle a conduction metallique sur des alliages al-mg oxydes

Country Status (5)

Country Link
US (1) US20040244880A1 (fr)
EP (1) EP1302566B1 (fr)
AT (1) ATE259005T1 (fr)
DE (1) DE50101451D1 (fr)
WO (1) WO2003033778A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014218595A1 (de) 2014-09-16 2016-03-17 Volkswagen Aktiengesellschaft Verfahren zum zumindest teilweisen Entfernen einer Mischoxid- bzw. Oxidschicht von einer Oberfläche eines intermetallischen Aluminid und/oder Aluminiumlegierung umfassenden Körpers

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2087928A (en) * 1980-11-26 1982-06-03 Gen Electric Co Ltd Methods of Marking Metal Surfaces
US4519876A (en) * 1984-06-28 1985-05-28 Thermo Electron Corporation Electrolytic deposition of metals on laser-conditioned surfaces
JPH05317924A (ja) * 1992-05-18 1993-12-03 Nippon Steel Corp 圧延用ダルロールの製造方法
JPH0741992A (ja) * 1993-07-29 1995-02-10 Pentel Kk アルミニウム又はその合金の表面処理方法
US5792335A (en) * 1995-03-13 1998-08-11 Magnesium Technology Limited Anodization of magnesium and magnesium based alloys
WO1999002759A1 (fr) * 1997-07-11 1999-01-21 Magnesium Technology Limited Procede de scellement pour substrats en metal et/ou en metal anodise
DE19851278A1 (de) * 1997-06-06 2000-05-11 Alfred R Franz Fa Verfahren zur Herstellung elektrisch leitfähiger und optimal haftfähiger Oberflächenbereiche auf chemisch u. o. galvanisch beschichteten u. o. lackierten Spritzgußteilen aus Magnesium

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4861407A (en) * 1985-06-18 1989-08-29 The Dow Chemical Company Method for adhesive bonding articles via pretreatment with energy beams
US4647346A (en) * 1985-10-10 1987-03-03 Eastman Kodak Company Anodized aluminum support, method for the preparation thereof and lithographic printing plate containing same
DE59502118D1 (de) * 1994-05-27 1998-06-10 Herberts Gmbh Verfahren zur beschichtung phosphatierter metallsubstrate

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2087928A (en) * 1980-11-26 1982-06-03 Gen Electric Co Ltd Methods of Marking Metal Surfaces
US4519876A (en) * 1984-06-28 1985-05-28 Thermo Electron Corporation Electrolytic deposition of metals on laser-conditioned surfaces
JPH05317924A (ja) * 1992-05-18 1993-12-03 Nippon Steel Corp 圧延用ダルロールの製造方法
JPH0741992A (ja) * 1993-07-29 1995-02-10 Pentel Kk アルミニウム又はその合金の表面処理方法
US5792335A (en) * 1995-03-13 1998-08-11 Magnesium Technology Limited Anodization of magnesium and magnesium based alloys
DE19851278A1 (de) * 1997-06-06 2000-05-11 Alfred R Franz Fa Verfahren zur Herstellung elektrisch leitfähiger und optimal haftfähiger Oberflächenbereiche auf chemisch u. o. galvanisch beschichteten u. o. lackierten Spritzgußteilen aus Magnesium
WO1999002759A1 (fr) * 1997-07-11 1999-01-21 Magnesium Technology Limited Procede de scellement pour substrats en metal et/ou en metal anodise

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199402, Derwent World Patents Index; Class A88, AN 1994-011371, XP002191354 *
DATABASE WPI Section Ch Week 199516, Derwent World Patents Index; Class A35, AN 1995-119137, XP002191355 *
W. MACHU: "Elektrotauchlackierungen", 1974, VERLAG CHEMIE, WEINHEIM, XP002191185 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014218595A1 (de) 2014-09-16 2016-03-17 Volkswagen Aktiengesellschaft Verfahren zum zumindest teilweisen Entfernen einer Mischoxid- bzw. Oxidschicht von einer Oberfläche eines intermetallischen Aluminid und/oder Aluminiumlegierung umfassenden Körpers

Also Published As

Publication number Publication date
US20040244880A1 (en) 2004-12-09
ATE259005T1 (de) 2004-02-15
DE50101451D1 (de) 2004-03-11
EP1302566B1 (fr) 2004-02-04
EP1302566A1 (fr) 2003-04-16

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