Classifications

• • 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
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1633—Process of electroless plating
  • C23C18/1655—Process features
  • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
• • 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
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1633—Process of electroless plating
  • C23C18/1646—Characteristics of the product obtained
  • C23C18/165—Multilayered product
  • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
• • 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
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
  • C23C18/2013—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by mechanical pretreatment, e.g. grinding, sanding
• • 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
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/22—Roughening, e.g. by etching
• • 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
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/28—Sensitising or activating
  • C23C18/285—Sensitising or activating with tin based compound or composition
• • 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
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/28—Sensitising or activating
  • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
• • 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
  • C25D5/10—Electroplating with more than one layer of the same or of different metals
  • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
  • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T50/00—Aeronautics or air transport
  • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft

Definitions

• the present invention relates to the use of an article whose surface exhibits a composite material in full or in parts, the composite material consisting of a polymer and a metallic layer present thereon, as moulding tool.
• the conventional way of manufacturing lost-wax casting models, spray, conversion or punching tools consists of manufacturing the tools and/or models according to drawings on cutting machines. Consequently, these conventional tools consist mainly of materials which can be worked yet exhibit the necessary properties with respect to hardness, low deformability and dimensional stability. Examples of such conventional materials are tool steel, case-hardened steels etc. Due to the need for the cutting manufacturing process, it is not possible to manufacture tool or models with very fine surface contours or corresponding moulded parts.
• Tools consisting of a metal/plastic composite material are little known.
• An example is a moulding tool which exhibits a shell of tool steel which is back-filled with polymeric materials such as fibre-reinforced epoxy resin or epoxy resin reinforced with metal particles in order to guarantee the rigidity of the mould.
• Articles with a surface exhibiting a metal/plastic composite consisting of a polymer and a metallic layer present thereon are otherwise known from other fields of application.
• a wide-spread field of application for this vapour deposition technique is coating of plastic films, e.g. for food packaging.
• DE 198 49 661 A1 discloses the vapour deposition of aluminium onto a special polyester film in such a way that it exhibits a strong oxygen barrier, a high gloss and a low coefficient of friction.
• the adhesive strengths of up to 3 N/mm indicated therein, however, are too low to withstand a functional application, subject to mechanical stress, of the metallised film.
• DE 42 11 712 A1 also describes the irradiation of the surface of a substrate in order to improve the adhesive strengths with an Eximer laser.
• a PET (polyethylene terephthalate) film is irradiated with this special laser in order to subsequently apply a ferromagnetic metal layer by vapour deposition within the framework of a PVD process.
• Such films are used as audio or video recording medium, among other things.
• a major disadvantage of this process is the considerable environmental pollution by the two chemical treatment agents such that this process cannot be used much longer for considerations of environmental politics.
• a disadvantage of this type of surface treatment which is based on a chemical reaction of the treatment solution with the substrate is that the swollen surfaces are highly sensitive to environmental influences such as e.g. dust embedments.
• the polyamide to be treated must be amorphous since partially crystalline or crystalline polyamides are not attacked by the method presented. Consequently, this method is a time-consuming, expensive process which has only limited use in order to achieve adhesive composite layers between the polymer substrate and metal layer.
• composite materials In order to avoid the problem of the complex and time-consuming manufacturing process in the case of PVD composite materials, composite materials have been developed in which the metal layer is produced by thermal spraying onto the plastic surface. During thermal spraying, metallic particles are heated and applied in an accelerated manner onto the substrate to be coated.
• the object of the present invention consists of the provision of a moulding tool whose surface exhibits in full or in parts a composite material of a plastic and a metal layer, which tool overcomes the disadvantages of the state of the art described above and can be manufactured on an industrial scale.
• the object is achieved according to the invention by the use of an article whose surface exhibits a composite material, in full or in parts, the composite material consisting of a non-metallic substrate containing at least one polymer, and a metallic layer present thereon and deposited without external current, having an adhesive strength of at least 4 N/mm 2 , as moulding tool.
• an object is used as electronic structural part whose surface exhibits a composite material, in full or in parts, the composite material exhibiting a first non-metallic layer and a second metallic layer applied thereon and
• Chemical pretreatment should be understood here and subsequently, as a delimitation to mechanical treatments, any treatment of a substrate surface which is carried out by pickling, etching, swelling, vapour deposition, plasma treatment or similar methods and in the case of which a change to the surface is caused by a chemical reaction.
• the articles according to the present invention used exhibit a rough, sharp-edged boundary layer between the non-metallic layer and the metallic layer applied without external current.
• These sharp edged indentations and undercuts of the boundary layer are clearly recognisable as edged surface contours, e.g. in a microtome section analysis whose execution is described in the following.
• edged surface contours e.g. in a microtome section analysis whose execution is described in the following.
• edged surface contours e.g. in a microtome section analysis whose execution is described in the following.
• they can be distinguished from the rather roundish, and in any case rounded-off contours which are formed in an ABS plastic by a chemical pretreatment, e.g. by etching or by removing a 2 nd phase embedded for this purpose (FIG. 2).
• the adhesive strengths (indicated in N/mm 2 ) of the composite materials according to the invention are determined exclusively by way of the frontal tensile test according to DIN 50160:
• the frontal tensile test (vertical tensile test) according to DIN 50160 has been used for many years for testing semiconductors, the determination of the adhesive tensile strength of thermally sprayed layers and in various coating techniques.
• the standard deviation of the adhesive strength at six different measured value points distributed over the surface of the composite material is maximum 25% of the arithmetic mean.
• the indicated homogeneities of the adhesive strength allow the use according to the invention of articles with a composite material as moulding tools in a particular manner.
• manufacture tools which can be subjected to both high mechanical and thermal stress in a wide variety of forms, e.g. with complex surface contours.
• an article is used whose composite material exhibits a non-metallic substrate which is simultaneously the surface of the article.
• these surfaces are based on a polymeric material. Fibre-reinforced plastics, thermoplastics and other industrially used polymers are to be mentioned as being particularly preferred.
• the article used can consist of a metallic or ceramic material which is coated with a non-metallic substrate which contains at least one polymer.
• an articles with a composite material is used as moulding tool which exhibits a boundary present between the non-metallic substrate and the metallic layer with a roughness whose R z value does not exceed 35 ⁇ m.
• the R z value is a measure of the average vertical surface fragmentation.
• articles with a composite material are used as moulding tools, which exhibit a boundary present between the non-metallic substrate and the metallic layer with a roughness expressed by an R a value of maximum 5 ⁇ m.
• the R a value is a measure reproducible by measuring techniques of the roughness of surfaces, profile runaways (i.e. extreme troughs or elevations) being largely ignored in the surface integration.
• a specimen is taken from an article according to the invention and a microtome section is made according to the method detailed as follows.
• the specimen to be examined is placed into a transparent embedding mass (Epofix putty, obtainable from Struer).
• the embedded specimen is ground in a table grinding machine from Struer, type KNUTH-ROTOR-2.
• Different abrasive papers with silicon carbide and different granulations are used for this purpose.
• the exact sequence is as follows: Granulation Time First grinding treatment P800 approximately 1 min Second grinding treatment P1200 approximately 1 min Third grinding treatment P2400 approximately 30 sec Fourth grinding treatment P 4000 approximately 30 sec
• the specimen thus treated is polished with a motor-driven preparation device of the DAP-A type from Struer.
• a motor-driven preparation device of the DAP-A type from Struer.
• the specimen is instead polished exclusively by hand.
• a torque of between 40 to 60 rpm/min and an application force between 5 and 10 N is used.
• the microtome section is subsequently subjected to SEM micrography.
• the boundary line of the layer between the non-metallic substrate and the metallic surface is determined with a 10,000 fold magnification.
• the OPTIMAS program from Wilhelm Mikroelektronik is used. The result is determined in the form of the X-Y value pairs which describe the boundary line between the substrate and the layer.
• a distance of at least 100 ⁇ m is required.
• the course of the boundary layer needs to be determined with at least 10 measuring points per ⁇ m in this case.
• the boundary layer magnification is determined from the quotient of the true length by the geometric length.
• the geometric length corresponds to the distance of the measured distance, i.e. between the first and the last measuring point.
• the true length is the length of the line which passes through all the measuring points recorded.
• the surface roughness value R a is determined according to the standard DIN 4768/ISO 4287/1 again using the X-Y value pairs recorded before.
• the non-metallic substrate contains at least one fibre-reinforced polymer, in particular a polymer reinforced with carbon fibres, and the diameter of the fibres is less than 10 ⁇ m.
• the non-metallic substrate may contain at least one fibre-reinforced polymer, in particular a polymer reinforced with glass fibre, the diameter of the fibre amounting to more than 10 ⁇ m.
• reinforced plastics in particular plastics reinforced with carbon fibre (CRP), plastics reinforced with glass fibre (GFP) and also plastics reinforced with aramite fibres or plastics reinforced with mineral fibres are used particularly preferably.
• CRP carbon fibre
• GFP glass fibre
• aramite fibres or plastics reinforced with mineral fibres are used particularly preferably.
• the fibre diameter has a strong influence on the roughness values such that, in the case of such materials according to the present invention, a roughness value R a of maximum 10 ⁇ m is achieved.
• R a roughness value
• the articles used according to the invention have a high homogeneity of adhesion. This makes it possible for the first time to substantially increase the service life of the moulding tool since even a local delamination of the layer composite leads to failure of the moulding tool as a whole.
• Of particular weight is the advantage in the case of moulding tools with a surface covered by the layer composite of more than 10 dm 2 , i.e. in the case of large structural parts or moulding tools with a large surface area.
• the article described above exhibits a boundary between the non-metallic substrate and the metallic layer which exhibits a roughness with an R z value of maximum 100 ⁇ m.
• the polymer of the non-metallic substrate is selected from the group of polyamide, polyvinyl chloride, polystyrene, epoxy resins, polyether ether ketone, polyoxymethylene, polyformaldehyde, polyacetal, polyurethane, polyether imide, polyphenyl sulphone, polyphenylene sulphide, polyarylamide, polycarbonate and polyimide.
• the metallic layer may exhibit an adhesive strength of at least 12 N/mm 2 .
• the polymer of the non-metallic metallic substrate may similarly also be selected from polypropylene or polytetrafluoroethylene.
• the non-metallic layer contains either polypropylene and/or polytetrafluoroethylene
• adhesive strengths of at least 4 N/mm 2 are achieved. This represents an excellent value, in particular in combination with the high homogeneity of the adhesive strength which could not be achieved previously.
• Embodiments according to the invention are particularly preferred which exhibit a standard deviation of the adhesive strength of six different measured value points distributed over the surface of the layer composite of maximum 25%, in particular maximum 15%, of the arithmetic mean.
• the metal layer deposited without electric current is a metal alloy or metal dispersion layer.
• articles with a composite material can be used as moulding tools for the first time which exhibit an excellent adhesion of the metallic layer to the non-metallic substrate.
• the homogeneity of the adhesion of the metallic layer also plays an important part for the suitability of these articles as structural parts subjected to high stress.
• a controlled selection of the non-metallic substrate and the metallic layer present thereon allows an accurate adjustment of the property profile to the conditions of the field of use.
• a copper, nickel or gold layer is applied onto the non-metallic layer of the article used according to the invention as a metal layer deposited without external current.
• a metal alloy or metal dispersion layer deposited without external current can also be applied, preferably a copper, nickel or gold layer with embedded non-metallic particles.
• the non-metallic particles may exhibit a hardness of more than 1,500 HV and may be selected from the group of silicon carbide, corundum, diamond and tetraboron carbide.
• These dispersion layers consequently have other functions, apart from the properties described above; for example, the resistance to wear and tear or surface wetting of the articles used can be improved.
• the non-metallic particles may exhibit friction-reducing properties and be selected from the group of polytetrafluoroethylene, molybdenum sulphide, cubic boron nitride and tin sulphide.
• the articles according to the present invention to be used as moulding tools exhibit, as composite material, first of all a non-metallic substrate which contains at least one polymer.
• the surface of the non-metallic substrate is microstructured in a first step by means of a blasting treatment.
• the process used is described in DE 197 29 891 A1, for example.
• Inorganic particles resistant to wear and tear, in particular, are used as blasting agent.
• these consist of copper-aluminium oxide or silicon carbide. It has proven advantageous in this respect that the blasting agent has a particle size of between 30 and 300 ⁇ m. It is further described therein that a metal layer can be applied by means of metal deposition without external current onto surfaces roughened in this way.
• the activation of the substrate surface takes place in two steps.
• the structural part is immersed into a colloidal solution (activator bath).
• the palladium seeds necessary for the metallisation and already present in the activator solution are adsorbed to the plastic surface.
• the tin(II) and/or tin(IV) oxide hydrate which is additionally formed on immersion into the colloidal solution is dissolved by rinsing in an alkaline aqueous solution (conditioning) and the palladium seed is exposed as a result.
• nickel coating or copper coating can take place using chemical reduction baths.
• the baths for the nickel and/or copper deposition have the characteristic of reducing the metal ions dissolved therein at the seeds and to deposit elementary nickel or copper.
• the two reactants must approach the noble metal seeds on the plastic surface.
• the conductive layer is formed, the noble metal seeds absorbing the electrons of the reducing agents in this case and releasing them again when a metal ion approaches. In this reaction, hydrogen is liberated.
• the layer applied takes on the catalytic effect. This means that the layer grows together starting out from the palladium seeds until it is completely closed.
• the deposition of nickel will be discussed in further detail here.
• the seeded and conditioned plastic surface is immersed into a nickel metal salt bath which permits a chemical reaction to take place within a temperature range of between 82° C. and 94° C.
• the electrolyte is a weak acid with a pH of between 4.4 and 4.9.
• the thin nickel coatings applied can be strengthened with an electrolytically deposited metal layer. Coating of structural parts with layer thicknesses of >25 ⁇ m is not economical because of the low rate of deposition of chemical deposition processes. Moreover, only a few coating materials can be deposited using the chemical deposition processes such that it is advantageous to make use of electrolytic processes for further industrially important layer materials.
• a further essential aspect consists of the different properties of layers chemically and electrolytically deposited with layer thicknesses of >25 ⁇ m, e.g. levelling, hardness and gloss.
• the bases of electrolytic metal deposition have been described e.g. in B. Gaida, “Einrance in die Galvanotechnik” (Introduction into electroplating) “E. G. Leuze-Verlag, Saulgau, 1988 or in H. Simon, M. Thoma, “Angewandte gamblentechnik für metallische Werkstoffe” (Applied surface technology for metallic materials) “C. Hanser-Verlag, Kunststoff (1985).
• Plastic parts which exhibit an electrically conductive layer as a result of a coating processes applied without electric current differ with respect to electrolytic metallisation only slightly from those of the metals. Nevertheless, a few aspects should not be disregarded in the case of the electrolytic metallisation of metallised polymers. As a result of the usually low conductive layer thickness, the current density must be reduced at the beginning of electrolytic deposition. If this aspect is ignored, a detachment and combustion of the conductive layer may occur. Moreover, care should be taken to ensure that undesirable layers of tarnish are removed by pickling baths particularly adapted for this purpose. Moreover, inherent stresses may lead to the destruction of the layer.
• tensile stresses of the order of 400 to 500 MPa, for example, may occur.
• additives such as saccharin and butine diols
• a change to the structure of the nickel coating in the form of a modified grain size and the formation of microdeformations may promote the decrease in internal stresses which may have a positive effect on a possible premature failure of the coating.
• one or several further layers, in particular metallic, ceramic and crosslinked or cured polymer layers can be arranged on the metallic layer.
• the articles used according to the present invention can also exhibit a nickel layer as metallic layer onto which a further nickel layer is applied. It is possible in this way to achieve a high rigidity of the resulting plastic parts, thus guaranteeing an application for components subject to high mechanical stress.
• metallic layers can be applied onto an article with a metallic layer according to the invention not only electrolytically but also by means of other processes such as CVD/PVD.
• a layer of aluminium, titanium or their alloys is applied onto the metallic layer, deposited without electric current, of the article used according to the invention, the surface of the layer being anodically oxidised or ceramic coated.
• Such layers of aluminium, titanium or their alloys oxidised or ceramic-coated by the anodic route are known on metallic articles and are marketed under the trade name Hart-Coat® or Kepla-Coat®, for example, by AHC fatiguentechnik GmbH & Co. OHG. These layers are characterised by a particularly high hardness and a high operating resistance and resistance to mechanical stresses.
• one or several further metallic layers can be arranged.
• the further metallic layers ranged between the layer deposited without electric current and the aluminium layer are selected according to the purpose of use.
• the selection of such intermediate layers is well known to the expert and described e.g. in the book “Die AHC-Ober Design—Handbuch für Konstrutation undtechnik (The AHC surface—Handbook for construction and manufacture”) 4 th enlarged edition 1999.
• the surface of such an article prefferably be a ceramic oxide layer of aluminium, titanium or their alloys which is coloured black by foreign ion embedment.
• the ceramic oxide layer of aluminium, titanium or their alloys which is coloured black by foreign ions is of particular interest for high value optical elements, in particular in the aircraft and aerospace industry.
• an article according to the present invention can be used as punching, casting or conversion tool.
• the surface pretreatment is carried out with a modified pressure blasting device from Straaltechnik International.
• the blasting device is operated at a pressure of 4 bar.
• a boron carbide nozzle with a diameter of 8 mm is used as jet nozzle.
• the blasting period is 4.6 s.
• SiC with the granulation P80 with an average grain diameter of 200 to 300 ⁇ m is used as blasting agent.
• a stream of compressed air transports the blasting agent with a pressure as low as possible to the nozzle.
• the flow conditions guarantee a low wear and tear of the unit and the blasting agent as a result of a high volume stream of the blasting agent and a low proportion of compressed air.
• Only at the end of the conveying hose in front of the mixing nozzle is the cross section reduced in order to adjust the desired volume stream.
• a constant volume flow of 1 l/min was set.
• compressed air volume stream 1 flows to the nozzle which can be adjusted steplessly within a pressure range of 0.2-7 bar.
• the blasting agent which is conveyed into the mixing nozzle at a very low flow rate is then accelerated by the high flow rate of the compressed air stream.
• the panel roughened in this way is treated in an ultrasonic bath with a mixture of deionised water and 3% by vol. of butyl glycol for five minutes.
• the series of baths used for the metal deposition of the conductive layer are based on the known colloidal palladium activation in association with a final catalysed metal reduction. All bath sequences required for this purpose were purchased from Max Schlötter. The immersion sequences, treatment times and treatment temperatures indicated by the manufacturer were maintained in all the process steps of nickel deposition:
• the specimen was cooled in distilled water from approximately 90° C. to approximately 60° C. in order to be then coated further electrolytically with nickel at 55° C.
• This intermediate step had the purpose of avoiding the formation of reaction layers and excluding inherent stresses caused by rapid cooling.
• the specimens which were coated exclusively with a conductive nickel layer cooled slowly to 25° C. in a distilled water bath.
• microtome section investigations by SEM (1,500 fold and 3,000 fold) are represented in the following figures (FIG. 3).
• the example according to the invention is repeated; however, after the blasting treatment, the panel is treated in an ultrasonic bath, in a suspension of 5% by weight of CaCO 3 in 96% ethanol for 5 minutes.
• the panel is treated in a further ultrasonic bath with pure 96% ethanol for a further five minutes.
• FIG. 4 The micro section investigations by SEM (1,500 fold and 3,000 fold) are shown in the following figures (FIG. 4).
• the resutls clearly show a signficant difference between the standard deviation of the adhesive strength of the different measured valued points distributed over the surface of the composite material.

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• Chemical & Material Sciences (AREA)
• Metallurgy (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Laminated Bodies (AREA)
• Moulds For Moulding Plastics Or The Like (AREA)
• Physical Vapour Deposition (AREA)
• Chemically Coating (AREA)
• Other Surface Treatments For Metallic Materials (AREA)
• Molds, Cores, And Manufacturing Methods Thereof (AREA)

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• 2004
  • 2004-04-15 US US10/553,242 patent/US20060260780A1/en not_active Abandoned
  • 2004-04-15 EP EP04727640A patent/EP1615766B1/de not_active Expired - Lifetime
  • 2004-04-15 CA CA002523009A patent/CA2523009A1/en not_active Abandoned
  • 2004-04-15 AT AT04727640T patent/ATE339303T1/de not_active IP Right Cessation
  • 2004-04-15 DE DE502004001493T patent/DE502004001493D1/de not_active Expired - Lifetime
  • 2004-04-15 WO PCT/IB2004/050462 patent/WO2004091906A2/de active IP Right Grant
  • 2004-04-15 JP JP2006506862A patent/JP2006523774A/ja not_active Withdrawn

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