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WO2006013115A1 - Mode de protection/coloration sélective d’un produit fini - Google Patents

Mode de protection/coloration sélective d’un produit fini Download PDF

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Publication number
WO2006013115A1
WO2006013115A1 PCT/EP2005/008750 EP2005008750W WO2006013115A1 WO 2006013115 A1 WO2006013115 A1 WO 2006013115A1 EP 2005008750 W EP2005008750 W EP 2005008750W WO 2006013115 A1 WO2006013115 A1 WO 2006013115A1
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WO
WIPO (PCT)
Prior art keywords
product
colouring
deposition
layer
protection
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/EP2005/008750
Other languages
English (en)
Inventor
Massimiliano Bestetti
Luca Magagnin
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.)
Politecnico di Milano
Original Assignee
Politecnico di Milano
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
Priority claimed from ITMI20041634 external-priority patent/ITMI20041634A1/it
Priority claimed from ITMI20050206 external-priority patent/ITMI20050206A1/it
Application filed by Politecnico di Milano filed Critical Politecnico di Milano
Priority to EP05772065A priority Critical patent/EP1784523A1/fr
Publication of WO2006013115A1 publication Critical patent/WO2006013115A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • C23C14/5853—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3689—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one oxide layer being obtained by oxidation of a metallic layer
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • C04B41/90—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being a metal
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0015—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23C8/02—Pretreatment of the material to be coated
    • 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
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/72—Decorative coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/31—Pre-treatment
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment
    • C03C2218/322—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/80—Optical properties, e.g. transparency or reflexibility
    • C04B2111/82—Coloured materials

Definitions

  • the present invention relates to a method for the protection/selective colouring of an end-product.
  • the invention relates to a method for the protection/selective colouring of an end-product made of steel and stainless steel, cast iron, copper and cop ⁇ per alloys, nickel and nickel alloys, magnesium and/or magnesium alloys, aluminum and/or aluminum alloys, cobalt and cobalt alloys, zinc and zinc alloys, composite mate ⁇ rials with a metallic matrix, polymers and composite ma ⁇ terials with a polymeric matrix, glass, ceramic, wood, leather, cellulose yarns, fabrics and materials.
  • the coating is directed at pro ⁇ viding a barrier against external attack. It must there- fore be uniform, well-adhering and free of porosity.
  • One of the problems associated with these materials or fields of application is, in fact, linked to the poor resistance of the material to the environment in which the end- product is used.
  • the purpose of the coating is to overcome these drawbacks by protecting the end-product .
  • a general objective of the present invention is con ⁇ sequently to provide a method for the protec ⁇ tion/selective colouring of an end-product.
  • a particular objective of the present invention is to provide a method for the protection/selective colour- ing of an end-product made of one or more of the follow ⁇ ing materials: steel, stainless steel, cast iron, copper, copper alloys, nickel, nickel alloys, magnesium and/or magnesium alloys, aluminum and/or aluminum alloys, co ⁇ balt, cobalt alloys, zinc, zinc alloys, composite materi- als with a metallic matrix, polymers and composite mate- rials with a polymeric matrix, glass, ceramic, wood, leather, cellulose yarns, fabrics and materials.
  • Another objective of the present invention is to provide an end-product made of one or more of the follow- ing materials: steel, stainless steel, cast iron, copper, copper alloys, nickel, nickel alloys, magnesium and/or magnesium alloys, aluminum and/or aluminum alloys, co ⁇ balt, cobalt alloys, zinc, zinc alloys, composite materi ⁇ als with a metallic matrix, polymers and composite mate- rials with a polymeric matrix, glass, ceramic, wood, leather, cellulose yarns, fabrics and materials, coated with thin uniform layers, well-adhering, free of porosity and such as to be able to be coloured without being dam ⁇ aged.
  • the method for the protection/selective colouring of an end-product com ⁇ prises the following phases: preparing an end-product; pretreating the end-product to prepare its surface for a coating treatment; coating the end-product with one or more thin layers; colouring the most external layer of the coating by the formation of an outer surface protec ⁇ tive oxide; possibly protecting the coloured layer by the application of a transparent layer.
  • figure 1 schematically represents the phases of the method according to the invention
  • figure 2 schematically represents a structure of the coating of the end-product according to the present in ⁇ vention
  • figures 3a, 3b schematically represent the structure of the coating of the end-product according to the pre ⁇ sent invention, made of a light alloy (Mg or Al)
  • figure 4 schematically represents the phases of the coating method of an end-product according to the inven- tion made of a light alloy
  • figure 5 schematically represents the pretreatment phases of the end-product made of a magnesium alloy or aluminum alloy
  • figures 6a and 6b schematically represent an appara- tus for the deposition and a colouring apparatus destined for a tape or yarn
  • figure 7 schematically represents the phases of a physical vapour deposition
  • these describe a method for the protection/selective colouring of an end- product comprising the following phases: preparing an end-product or base B, or LL; pretreating PRE said end-product B or LL for prepar ⁇ ing its surface for a coating treatment; - optionally applying a barrier layer SB which also acts as an adhesion layer for the metallic layer; coating said end-product with one or more thin lay ⁇ ers DEP; colouring said thin layer by the formation of an outer surface protective oxide; - possibly protecting the coloured layer with a trans ⁇ parent protective layer (RIV) .
  • the method is applied to an end- product made of one or more of the following materials: steel, stainless steel, cast iron, copper, copper alloys, nickel, nickel alloys, magnesium and/or magnesium alloys, aluminum and/or aluminum alloys, cobalt, cobalt alloys, zinc, zinc alloys, composite materials with a metallic matrix, polymers and composite materials with a polymeric matrix, glass, ceramic, wood, leather, cellulose yarns, fabrics and materials.
  • the method according to the invention can, in the case of the pro ⁇ duction of end-products with particular demands for re- sistance to corrosion, wear or the like, envisage a phase for the coating with a transparent protective layer RIV of said thin coloured layer COL following the formation of the outer surface protective oxide.
  • the surface of the material of which the end-product B is made, is pretreated to allow a better reception of the metallic coating.
  • the pretreatment can consist of various phases, de ⁇ pending on the type of material used as substrate .
  • the structure of the coating which is formed is in the most general case of the type shown in figure 2. Starting from the surface of the end-product B, this structure has a barrier layer SB overlaid by the deposi ⁇ tion layer DEP which is subdivided into a metallization layer ME and a coloured oxide layer COL on the surface of the former.
  • the deposition DEP or metallization is effected un ⁇ der vacuum with the PVD, physical vapour deposition, technique.
  • the colouring of the metallic layer ME depos ⁇ ited with the PVD technique is effected by oxidation in atmospheres containing oxygen (for example by heating in air) or by the direction deposition of titanium oxide (reactive PVD) , or, electrolytically (anodic oxidation) to obtain the oxidized layer COL.
  • the vacuum metallization phase is preceded by a preparation phase of the surface of the end-product B or deposition substrate.
  • the preparation of the surface B of the deposition substrate can comprise, in relation to the material to be treated, a chemical cleaning phase (with an organic or aqueous solvent) and/or mechanical phase
  • a basic organic film SB (which is advantageously applied typically in the metallization of plastics) can also be conveniently applied in the case of other materials, for example metals.
  • the organic layer SB offers further protection against corro- sion to the metallic substrate of the end-product B dur ⁇ ing the electrochemical colouring phase of the metalliza ⁇ tion layer deposited with the PVD technique (titanium and the like) and during the life of the end-product.
  • every possible outer protection layer, deposited on the titanium oxide or the like, should be effected so that it is transparent - so as not to hide the colouring - and this can be achieved by the application of a filmogenic organic material or a layer of quartz (SiOx) deposited by means of PECVD (Plasma Enhanced Chemical Vapour Deposition) .
  • the method for the protec- tion/selective colouring of light alloys comprising the following phases: preparing an end-product made of a light alloy; pretreating said end- product to prepare its surface for a coating treatment; coating said end-product with one or more protective lay- ers; colouring the most external layer of said coating by the formation of an outer surface protective oxide.
  • the method is based on the use of light alloy coat ⁇ ing technologies (magnesium or aluminum) based on the physical vapour deposition of titanium and the like (Ti, Ta, Nb, Zr, Hf, W, V, Mo) and the subsequent colouring of the metal (Ti, Ta, Nb, Zr, Hf, W, V, Mo) by electrochemi ⁇ cal oxidation.
  • a variation of the technique consists in the physi ⁇ cal vapour deposition of a layer of titanium or the like (Ti, Ta, Nb, Zr, Hf, W, V, Mo) and the subsequent reac ⁇ tive physical deposition of a layer of TiO 2 (or similar oxide for the metals Ta, Nb, Zr, Hf, W, V, Mo) .
  • the pretreatment PR of the surface does in fact play an important part for allowing the development of a pro ⁇ tective coating R on magnesium and its alloys, or on alu- minum and alloys.
  • the most common pretreatment operations PR are me ⁇ chanical finishing, chemical cleaning and the deposition of a galvanic coating (typically zinc, copper and nickel) .
  • the mechanical finishing and chemical cleaning are indispensable for bringing the surface of the product to the optimal degree of roughness and decontamination, allowing it to receive a coating without problems of ad ⁇ hesion between the end-product, the substrate LL, and coating R (figure 3a) .
  • the use of an inter- mediate coating SB of a galvanic nature, which forms a barrier layer, (figure 3b) can be recommended for having a greater guarantee of protection of the substrate made of light alloy.
  • Magnesium or aluminum alloys are metals which are difficult to cover with humid methods. The layer of oxide which covers them must be removed before the deposition.
  • the coatings must have a very low po ⁇ rosity and the deposition solutions must not react vio ⁇ lently with the light alloy forming the substrate.
  • the quality of the coating depends on the quality of the preparation of the end-product made of magnesium or alu ⁇ minum alloy; pretreatment methods suitable for the type of base alloy are therefore necessary.
  • Figure 4 represents the sequence of operations starting from the end-product made of light alloy LL; the pretreatment PJ?; the coating R by the physical vapour deposition of a metal selected from titanium, tantalum, niobium, zirconium, vanadium, hafnium, molybdenum, rhe ⁇ nium, tungsten; and the colouring COL by oxidation ac ⁇ cording to the invention.
  • Table C summarizes the function of the pre- treatment operations which precede the galvanic deposi ⁇ tion whereas, with reference to figure 5, two pretreat- ment procedures of light magnesium or aluminum alloys are illustrated.
  • the acti ⁇ vation ZnA is effected followed by zincing in an alkaline solution of zinc Zn and the deposition of a copper Cu layer and a subsequent further coating R' is effected, if necessary.
  • the activation NiA is effected by means of fluorides followed by plating PL with chemical nickel (electroless) and a further coat ⁇ ing R' , if necessary.
  • the metallization and colouring process can also be ap ⁇ plied with a method of the "web coating" type.
  • a suitably pre-treated material for example: yarns, plastic films for packaging, galvanized sheet iron for cars, etc..
  • the tape 2 can be un ⁇ wound from the spool 1 following the direction of the ar ⁇ row F, coated with a metal layer of titanium, in a reac ⁇ tor PVD, by means of the ionic beam assisted deposition technique, and rewound on the reel as a bobbin 3.
  • the tape 6 coated with a titanium film is subsequently passed to the colouring step, for example electro-chemically.
  • the technique can be adopted for un ⁇ winding the bobbin 3 of metallized tape, sending it into the colouring tank 4 equipped with a cathode 5, making it to act as anode, and then rewinding it on a reel 7. Fi ⁇ nally the metallized and coloured tape (or yarn) is pos ⁇ sibly protected by a transparent protective layer.
  • the metallization can be effected by means of air- air systems, in which the tape enters the metallization reactor through low-medium-high vacuum zones, is metal ⁇ lized, and then exits passing through high-medium and low vacuum zones, until it returns into the atmosphere.
  • the operation can be effected by implementing the whole unwinding-winding system in the metallization reactor.
  • the electro-chemical colouring can be effected by means of brush methods.
  • a brush soaked with an electro ⁇ lytic solution is put in contact with the surface to be electrochemically oxidized.
  • a metal push-rod is present on the brush, which is connected to the negative pole (cathode) of a generator, the metal film is put in con ⁇ tact with the positive pole (anode) .
  • the an ⁇ odic oxidation region can be localized and the colouring is subsequently effected by anodic oxidation in the areas in which the brush is in contact with the metallized sur- face .
  • the deposited layer It is extremely important for the deposited layer to be sufficiently thick and adherent to the substrate, in order to electrochemically oxidize the surface of the metal deposited with the PVD technique.
  • the thickness of the film deposited plays an important role in the current distribution in the film during the anodic oxidation operation.
  • Colouring can be also effected directly in the met ⁇ allization reactor, for example by introducing in the magnetron sputtering reactor, at the end of the deposi- tion of the metal layer, an oxygen/argon mixture so that oxygen reacts with the metal (titanium and similar) form ⁇ ing a layer of coloured oxide.
  • the deposition of titanium (Ti, Ta, Nb, Zr, Hf, W, V, Mo and alloys thereof) in the form of a thin layer can be effected using several techniques.
  • the deposition technique and the operative parame ⁇ ters greatly influence the structure of the metallic films produced (dimensions, form and crystallographic orientation of the grains, defects, porosity, residual stress in the coating, and similar) .
  • the film structure influences the chemical and physical properties of the film itself.
  • the PVD deposition is the preferred technique for depositing metals such as titanium and similar (Ti, Ta, Nb, Zr, Hf, W, V, Mo and alloys thereof) .
  • the main physical vapour phase deposition techniques are listed hereunder: vacuum evaporation, wherein the material emitted from a thermal vaporization source, reaches the sub- strate without collisions with the gas molecules in the area between the source and the substrate; sputtering (cathodic ablation) in which the source of the vaporized material is the surface of one or more targets (cathode) , which are subjected to physical ablation (sputtering) .
  • arc deposition wherein a high current and low volt ⁇ age electric arc is shot in a low pressure gas, to erode the solid cathode or to melt and evaporate the anode; - ionic deposition which uses the bombardment of the developing film on the part of atomic particles hav ⁇ ing sufficient energy, to modify and control the composition and property of the film.
  • pressures can be reached by means of a pumping system equipped with a diffusion or turbo-molecular pump and a preliminary pump.
  • the conceptual scheme of a physical vapour deposi ⁇ tion process is shown in figure 7.
  • the atoms of the metal to be deposited are emitted EV from a liquid or solid source (target) T to form the gas Gl (due to the heating, as a result of collision with ions of inert gas, and similar) and with a transport mechanism TR, mediated by the gas G2 which is present at low pressure in the deposition reactor, CND are deposited on the substrate under the form of a film F.
  • the structure of the deposited layer is determined by the competition between the atomic mobility (which depends on the substrate tem ⁇ perature) and the arrival rate of the particles on the surface .
  • the ratio between the substrate temperature and the melting temperature of the metal deposited, Ts/Tf, is an extremely important parameter.
  • the problem of the porosity of the titanium (tanta ⁇ lum, niobium, etc..) metal coating is represented by the high melting point of the metal deposited.
  • the metal is vaporized and re-condensed on the sub ⁇ strate. If the conditions are not suitable, the film structure formed is porous.
  • a densification effect is observed in deposition processes wherein a beam of energy particles (ionic bom ⁇ bardment) hits the developing metal.
  • the deposition temperatures must be lower than the stability temperatures of the substrate B or the barrier layer SB, if present.
  • the high substrate temperature favours the formation of coatings having a compact structure. High temperatures of the substrate however are not practicable in the case of low-melting substrates.
  • IBAD ion beam assisted deposition
  • the film is struck, continuously or periodically, by highly energetic atoms of inert gas and by reactive particles which modify the development and properties of the film.
  • the technique allows the film adhesion and the cov ⁇ ering of the film on the substrate, to be improved; more ⁇ over, by controlling the ionic bombardment, it is possi ⁇ ble to operate on the film properties (density, morphol ⁇ ogy and residual stress) .
  • the light interference is due to the optical path difference between the lumi ⁇ nous rays reflected on the oxide surface A and those re ⁇ flected by the surface of the metal B. ' This phenomenon gives rise to interference colouring. The colour depends on the thickness of the oxide film.
  • Metals such as titanium, niobium, tantalum and simi ⁇ lar, oxidize in the air at room temperature, but the ox ⁇ ide film which is formed is too thin to provide interfer ⁇ ence colours.
  • the simplest thickening method of the oxide film consists of heating the metal in air.
  • the colouring of the metal layer, vapour deposited, can be effected by means of thermal or galvanic oxida ⁇ tion.
  • the colouring can also be obtained by reactive physical vapour deposition of the metal oxide.
  • argon/oxygen mixtures are used in the deposition reactor.
  • an oxide layer is obtained which creates interference colours.
  • the colours which are formed by heating the metal in air depend on the- time and temperature of the treatment-.
  • Table 1 of figure 9 indicates a chromatic scale example obtained by thermal oxidation of titanium in air.
  • the electrochemical colouring of titanium is a tech ⁇ nique which is effected at room temperature by dipping the piece to be oxidized in an electrolytic solution and connecting it to the positive pole of a current genera- tor.
  • a metal is connected to the negative pole, which acts as cathode (titanium, stainless steel and similar) .
  • the electric scheme is shown in figure 10 (anode: manufactured product coated with Ti and similar,- cathode: titanium, stainless steel and similar) .
  • the electrolytic solution can contain sulphuric acid (5%) or phosphoric acid (15%) or ammonium sulphate (10%) .
  • Other solutions are possible.
  • the oxidation active area can be delimited by shields, lacquers and the like so as to localize the formation of the coloured oxide.
  • the different colours are formed by varying the cell voltage. This method is extremely accurate as the elec- trie parameters, voltage and current, are easily con ⁇ trolled. In this way wide colour ranges can be obtained as shown as an example in table 2 of figure 11.
  • the electrochemical oxidation is generally effected by anodic polarization of the end-product covered by a cell voltage ranging from 5 to 300 volt, according to the desired colour.
  • the surface pre-treatment of massive titanium end- products plays an important role in the electrochemical development of the coloured titanium oxide.
  • the surface of the metal Ti, Ta, Nb, Zr, Hf, W, V, Mo and alloys thereof.
  • the preparation cycles of the metals which can be coloured by electrochemical oxidation are based on me- chanical finishing, cleaning and surface activation steps .
  • the acidic activation of titanium can be effected by immersion in 10% by weight solutions of nitric acid and 2.5% hydrofluoric acid, for various tens of seconds .
  • Tantalum can be attached by very aggressive acidic solutions: for example concentrated acids at boil ⁇ ing point.
  • Niobium can be attached in solutions of sul ⁇ phuric acid (20%) and hydrofluoric acid (10%) at a warm temperature. Other solutions can be used.
  • the preparation can be extremely simplified. The deposition of thin films is in fact effected under condi ⁇ tions of low oxygen concentration and if the target is extremely pure, the surface of the metal film which is deposited is also extremely pure. This makes the removal of the surface oxides before the electrochemical colour ⁇ ing less complex.
  • the deposition phase comprises the deposition of a layer of metal selected from titanium, tantalum, niobium, zirconium, vanadium, hafnium, molybdenum, rhenium, tung ⁇ sten and their alloys in thicknesses preferably ranging from 1 to 20 micrometers.
  • a very important problem which makes the electro ⁇ chemical oxidation of titanium (or similar) films with respect to massive titanium lies in the fact that in the anodic oxidation of titanium films, a correct current distribution must be obtained on the whole surface of the film.
  • This aspect is linked to problems of electric con ⁇ ductivity through a metallic film which can also have the thickness dl of a micrometer or even less .
  • the difficulty can be overcome by using massive con ⁇ ductor substrates on which the film is deposited, or by using barrier layers which contain metallic films depos ⁇ ited with the PVD or also galvanic technique, capable of sustaining the current in the anodization phase.
  • the me ⁇ tallic film, for example copper, beneath the titanium (or similar) film will act, together with the titanium film itself, as a conductor in the oxidation operation.
  • a good adhesion of the metallic film to the metal ⁇ lic substrate is typically obtained using surface prepa ⁇ ration techniques (with wet or vacuum methods) capable of removing the surface contamination and any possible layer which negatively influences the adhesion, and subse- quently depositing a material which easily binds with the base material .
  • High surface temperatures stimulate the diffusive phenomena and often allow a better adhesion.
  • Metal-metal pairs non-mutually soluble should be avoided, a good adhesion however can be obtained with non-mutually soluble metallic systems if the nucleation density during the PVD development is high.
  • the barrier layer must also act as an adhesion promoter, in the sense of attenuating all states of interfacial stress between the substrate and the film deposited. These states of interfacial stress can cause delamination and are due, for example, to different dila ⁇ tion coefficients of the materials or to differences in the crystalline or morphological structure.
  • nickel is often a good material as it binds with many metals and is ductile.
  • the metal oxide is removed during the outer cleaning process and the small quantities reformed after the cleaning are removed by activation in situ in the deposition reactor. If the natural oxides on the sur ⁇ face are not removed, then the metal deposited should have a high affinity for oxygen.
  • Ferrous metallic materials for the application of the present invention are: steels, cast irons, inox steels .
  • Non-ferrous metallic materials for the application of the present invention are: copper and copper alloys, nickel and nickel alloys, cobalt and cobalt alloys, zinc and zinc alloys.
  • the surface of the metallic materials used as sub ⁇ strate must be pretreated before the application of the barrier layer and metallization layer or the direct ap- plication of the metallization layer.
  • the pretreatment operations depend on the type of metallic material used.
  • the pretreatment op ⁇ erations can be of the mechanical type or chemical or electrochemical type.
  • mechanical type sandblasting and mass finishing can be mentioned in par ⁇ ticular.
  • Polymeric materials offer numerous possibilities from a metallization and colouring point of view.
  • the surface of the polymer In order to obtain a good adhesion, the surface of the polymer must be free of contaminants .
  • the adhesion of a metallic film to a polymeric sur- face can be obtained using metals which form organometal- lic bonds with the substrate.
  • metals which form organometal- lic bonds with the substrate.
  • main metals Al,
  • the surface of the polymer can be pretreated in plasma to make the surfaces more reactive with an increase in the nucleation density and of the bonds .
  • Oxygen or nitrogen plasmas are generally used to ac ⁇ tivate the surfaces.
  • Plastic materials which are industrially subjected to vacuum metallization are: acrylics, acrylonitrile- butadiene-styrene (ABS) , polyamide (PA) , polybuty- leneterephthalate (PBT) , polycarbonate (PC) , polyester, polyethersulfone (PES) , polyethylene (PE) , polyethyl- eneterephthalate (PET) , polyphenyleneoxide (PPO) , poly ⁇ propylene (PP) , polysulfone, polyvinylchloride (PVC) .
  • Plastic materials require an adequate pretreatment before metallization.
  • the primary purpose is to remove the contaminants which can cause poor adhesion, a low- quality finishing, etc.
  • the cleaning is effected by means of organic or wa ⁇ ter-based solvents.
  • a base layer this is an organic coating, also called base-coat, whose main function is to produce a smooth surface so that the metal deposited is shiny; it is also used for improving adhesion between the metallic coating and the substrate.
  • the base layer also acts as a seal of the substrate surface for the gases which are released from the plastic material during the vacuum set-up of the deposition reactor.
  • Many plastic materials can be metal ⁇ lized directly but the results are generally unsatisfac- tory, except for acrylic materials and polycarbonates. In the case of thin films, all surface edges and faults are faithfully reproduced. For this reason, the surfaces are generally prepared by the application of an organic base layer (SB) . This layers allows a satisfactory adhesion, it fills small defects or holes in the surface of the substrate and provides a smooth surface for the metalli ⁇ zation.
  • SB organic base layer
  • PVD vacuum techniques
  • top-coat A coating layer applied on the metallic oxide which produces interference colours,- this layers is also called top-coat and its main function is to protect the metal and metal oxide. In some cases, the top-coat is not ap- plied.
  • the top-coat can be deposited directly in the re ⁇ actor (quartz layer deposited with the PECVD technique) .
  • the top-coat can be an organic material which hardens due to UV or thermal action.
  • the maximum thermal treatment temperatures of the organic layers, used as barrier layer (SB) and protective layer (RIV) of the metallization, should be selected in relation to the type of plastic material.
  • the type of plastic material to be metallized is the determinant factor in selecting the composition of the organic layers.
  • nitrocellulose resin modified in a solvent (sys- tern of ketones, alcohols, glycol ether and aromatic hy ⁇ drocarbons) which easily evaporate in air;
  • epoxy-acrylate resins unsaturated acrylate, ac- rylate esters in a solvent based on methylisobutylketone and isopropyl alcohol, with photo-setting agents which, when exposed to UV radiation, begin the setting process;
  • protective layer Epoxy modified acrylic resin in n-butanol and xylol, sometimes with the addition of 2-ethoxyethanol .
  • the formulations for the base layer can have a non ⁇ volatile content ranging from 30% to 50% by weight, whereas the formulations for the protective layer can have a non-volatile content ranging from 20% to 30% by weight .
  • the application of the organic layers can be ef ⁇ fected automatically or manually by: a) immersion; b) flow or shower; c) spraying.
  • the setting of the organic layers is extremely im ⁇ portant, it must in fact be complete, especially in the case of the base layer.
  • the plastic surfaces up ⁇ stream of the coating treatment with organic film, using, for example, water-based or organic-based solvents.
  • organic solvent can have a good capacity of eliminat- ing the organic contaminants, it can, on the other hand, damage the plastic material on which the metallic layer is to be deposited.
  • Environmental problems relating to the release of solvents into the atmosphere should also be taken into consideration.
  • the cleaning can be effected in solvent vapours, by- immersion in liquid phase - or a combination of both.
  • the stirring of the plastic components in ultrasounds can help to remove the contamination from recesses, blind holes, etc.
  • the cleaning can be effected in the vacuum deposition chamber, by adding a plasma assisted activa ⁇ tion station and subsequently eliminating the cleaning as a separate process step. In this way, excellent adhesion of the metallic film to the plastic can be obtained.
  • the vacuum metallization of plastic materials offers many openings for engineering and design, as it can be used for the substitution of components previously made with other materials.
  • the plastics to be metallized must have a uniform composition and should not release vola ⁇ tile substances under vacuum.
  • plastic materials are good insulators, they have the disadvantage of becoming electrostatically charged, attracting dust. This necessi ⁇ tates cleaning and preparation treatment. Non-removed volatile substances can contaminate the metallization system and ruin the work.
  • plastics unlike glass and metals desorb gases with va ⁇ pours extremely slowly. In many cases the metallization plants are generously equipped with adequately powerful vacuum systems.
  • pretreatment of plastic materials before metallization are based on chemical activation in tetra- chloromethylene, or in concentrated sulphuric acid and subsequent washing in water.
  • a further example is represented by activation with oxygen or ionic bombardment treatment .
  • One of the most common types of pretreatment consist in surface roughening by means of sandblasting.
  • the mi ⁇ cropores act as nucleation and anchoring sites of the me- tallic film.
  • One of the problems of chemical pretreatment is that the use of additives, which increase the thermal and me- chanical resistance of the polymer, requires more aggres ⁇ sive chemical agents, and this can be a limitation.
  • the surfaces can be treated in the plasma of inert gases.
  • the activation in this case is probably " due " to " the UV radiation from the plasma.
  • the treatment of polymers in plasma can cause tex ⁇ tures and improves the adhesion strength with a mechani ⁇ cal interlocking mechanism.
  • the texture can be accompa ⁇ nied by a variation in the chemistry of the surface due to the variation in the terminal species.
  • an optimum surface treatment for Kapton has proved to be a detergent washing followed by caustic attack to roughen the surface and subsequently UV treatment under partial oxygen pressure which oxidizes the surface.
  • the activation of the polymeric surfaces can be ef- fected by the deposition of an additional polymer layer which is more subject to the formation of bonds.
  • Mechanical brushing of the surface is a technique which destroys the oxide and exposes the metal producing an improved adhesion of the coatings deposited under vac ⁇ uum on a steel tape.
  • the sensitisation consists in the addition of small particles of material on the surface which act as nuclea- tion sites. Ionic implanting can also be used for introducing foreign elements into the material and improving adhe ⁇ sion.
  • the pre- and post-me ' tallization varnishes can be of the traditional type: with solvent, water, hardenable with UV rays.
  • the premetallization varnishes can be applied for example to polymeric materials (PP, Nylon, ABS, etc.) , metals, glass, etc.
  • the UV hardening varnishes require short hardening times .
  • Wood, leather and natural fibres of an animal or vegetable origin and cellulose materials can be protected and decorated with the application by means of PVD tech- niques of one or more metallic layers and an oxide layer which creates interference colours.
  • soft wood fir, pinewood, sequoia, etc.
  • hard wood birch, cherry, beech, nut, oak, etc.
  • ex ⁇ otic hard wood ebony, mahogany, teak, etc.
  • the metallization of these materials should take into account the fact that they degas under vacuum.
  • the metallization can be preceded by the application of a base layer, for example of a photo-polymerizable fil- mogenic material with UV radiation, suitable for sealing the material to prevent the release of gas and to promote the uniformity and " adhesion of the metallic coating.
  • the sealing phase of the pores with a base layer which can consist, for example but not exclusively, of a thermosetting polymeric material, UV setting, or metallic material (for example nickel deposited with a wet auto- catalytic method), is extremely important.
  • a layer of titanium is then deposited with PVD proc- esses on the metallized wood material.
  • the metallization treatment and colouring can be ap ⁇ plied to glass and ceramic.
  • silica glass 96% silica (VycorTM) , sodium-calcium glass, lead silicate, high lead silicate, borosilicate, aluminum- boro-silicate, aluminumsilicate .
  • the mobile species segregate on the surface and form nod- ules which, if not removed in the pretreatment phase, cause dotting in the metallization film.
  • Float glass is the type which is most commonly metallized with the PVD technique.
  • the side of the glass which has been in contact with the molten tin can be con- taminated by a tin oxide.
  • the tin oxide can be removed with a light attack with a solu ⁇ tion of ammonium bifluoride.
  • a further cause of the surface contamination of glass is represented by the packaging and storage phases.
  • the adhesion of the metallic film to the surface of glass increases with time after the depo ⁇ sition, as reactions in the solid state take place at the interface, which can proceed very slowly after deposi ⁇ tion. This can be due to the diffusion of reactive spe- cies such as oxygen at the interface or by the release of the film stress with time.
  • the cleaning with plasma of a glass surface before deposition of the metallic film has proved, for example, to improve the adhesion of the film with time.
  • Metals having a strong affinity for oxygen generally form well-adhering coatings on glass.
  • Adhesion to the surface of glass is generally ob ⁇ tained by preparing a decontaminated surface and using a material having a high affinity for oxygen, such as for example, Ti and similar products. Furthermore, in order to reduce internal stress of the film, the thickness of the titanium film should be limited and the desired prop ⁇ erties generated using a multilayer structure.
  • a su-r-face chemist-r-y or- conductive deposition can be used which forms a high density of nu- clei .
  • the nucleation density can be in ⁇ creased by initiating the deposition with oxygen, resid ⁇ ual in the environment or adsorbed on the surface of the substrate, which has a strong affinity with the film of material which is deposited.
  • a high initial deposition rate in ⁇ creases the nucleation density on the surface.
  • the sur ⁇ face chemistry of the oxides can be altered with selec ⁇ tive treatment which modifies the composition and nuclea ⁇ tion of the ad-atoms on the surface.
  • good adhesion can be obtained by generating an interface with a composition gradient and being certain that a minimum residual stress is exerted.
  • Ceramic materials can also be subjected to metalii- zation and colouring.
  • Traditional ceramic materials are classified as follows: traditional ceramics, brickwork, tiles, sanitary products, technical porcelains, refrac ⁇ tory materials.
  • Ceramics for traditional use can be subdivided ac- cording to their structure into porous or greified, de ⁇ pending on the surface state into glazed or unglazed, and in relation to the colour into white or coloured.
  • End-products made of magnesium or aluminum alloys do not tolerate high temperatures and consequently the ther ⁇ mal oxidation of the titanium (or similar) film which covers the light alloy end-product must be carried out at sufficiently low temperatures for longer times, depending on the type of light alloy used.
  • the electrochemical colouring of tita ⁇ nium is a technique which is effected at room temperature by immersing the piece to be oxidized into an electro ⁇ lytic solution and connecting it to the positive pole of a current generator.
  • a metal which acts as cathode (titanium, stainless steel, etc.) is connected to the negative pole.
  • the electric scheme is shown in figure 7 (anode: light alloy coated with Ti and similar products; cathode: titanium, stainless steel, and the like) .
  • the electrolytic solution can contain sulphuric " acid (5%) or phosphoric acid (15%) or also ammonium sulfate (10%) .
  • Other solutions are possible.
  • the active oxidation area can be delimited by shields, lacquers, and the like so as to localize the formation of coloured ox- ide.
  • Electrochemical oxidation is generally effected by anodically polarizing the coated end-product at a cell voltage ranging from 5 to 300 volts, in relation to the desired colour.
  • the preparation of the titanium surface plays an itn- portant role.
  • the mechanical resistance of anodic films made of titanium and similar metals (Ti, Ta, Nb, Zr, Hf, W, V, Mo) is greatly conditioned by the state of the sur ⁇ face downstream of the physical vapour deposition.
  • the surface of the metal (Ti, Ta, Nb, Zr, Hf, W, V, Mo) must be suitably prepared.
  • the preparation cycles of metals which can be col ⁇ oured by means of electrochemical oxrdation are base ' d on mechanical finishing, cleaning and acid activation stages.
  • the acid activation of titanium for example, can be effected by immersion in solutions of nitric acid 10% by weight and hydrofluoric acid 2.5%, for tens of sec ⁇ onds.
  • Tantalum can be attacked with very aggressive acid solutions: for example, acids concentrated at boiling point.
  • Niobium can be attacked in solutions of sulphuric acid (20%) and hydrofluoric acid (10%) at a warm tempera ⁇ ture. Other solutions can be used.
  • the preparation can be extremely simplified.
  • the deposition of thin films takes place under conditions of low oxygen concentration, and if the target is very pure, the surface of the metal film which is de ⁇ posited is just as pure. This makes the removal of the surface oxides before the electrochemical colouring less complex.
  • the deposition phase comprises the deposition of a metal layer selected from titanium, tantalum, niobium, zirconium, vanadium, hafnium, molybdenum, rhenium, tung ⁇ sten in thicknesses preferably ranging from 0.5 to 50 mi- crometers, and even more preferably ranging from 1 mi ⁇ crometer to 10 micrometers. Deposition and colouring tests
  • the experimental tests were carried out using sam ⁇ ples made of magnesium alloy AM60B.
  • Metal plates (10 cm x 10 cm x 0.5 cm) , were cut from ingots of magnesium alloy AM60B, using a belt saw.
  • the surface finishing was im ⁇ proved, by smoothing the surface of the samples with sandpaper (up to 1200 grits) .
  • the samples were washed in acetone, abundantly rinsed with distilled water, pickled in diluted nitric acid, rinsed again in distilled water. At this point, the samples were subjected to coating treatment with titanium by means of the physical vapour deposition technique.
  • the deposition reactor is of the sputtering magne- tron type and is equipped with an ionic source.
  • the ionic source was used to clean and activate the surface of the sample before deposition, effected with the sputtering magnetron technique.
  • Both the activation and cleaning phase with the ionic source and the sputtering magnetron deposition phase were carried out in an argon atmosphere at a low pressure (in the order of mTorr) .
  • the electrochemical colouring was effected by ano ⁇ dizing the titanium film having a thickness of a few mi ⁇ crometers and deposited on magnesium alloy.
  • An electro ⁇ lyte based on sulphuric acid (at 5%) was used, exerting cell voltages in the order of tens of volts.
  • the magnesium alloy substrate was uniformly coated on the whole surface .
  • the thickness of the coating is a few microns.
  • the porosity is extremely low: upon placing a drop of acid on the titanium surface, no hydrogen development due to the attack of the magnesium, was observed, even after prolonged exposure.
  • the colouring of the titanium film on magnesium al ⁇ loy was effected electrochemically.
  • the coating is compact and uniform. It does not de- laminate from the substrate and with the drop of sul ⁇ phuric acid test, it proves to be non-porous.
  • a coating and colouring test of a sample made of aluminum alloy 6060 was effected.
  • the aluminum sample (10 cm x 5 cm x 0.2 cm) was smoothed with paper (up to 1200 grits) , was washed in acetone and subsequently with de- ionized water. This pretreatment phase was followed by the ionic cleaning phase in the deposition reactor. A ti ⁇ tanium layer was then deposited.
  • the coating is compact and uniform. A tear test was effected with adhesive tape. There were no delaminations of the titanium film from the substrate.
  • the aluminum alloy sample coated with titanium was electrochemically coloured with a light blue colour, un ⁇ der identical voltage conditions to those of test 2.
  • a flat UNS 316 stainless steel sample was subjected to titanium coating followed by electrochemical colour ⁇ ing.
  • the surface of the sample was degreased with isopro- pylic alcohol.
  • the deposition cycle of the titanium layer envisaged an initial activation phase with the use of an ionic source: the activation treatment lasted 5 minutes at 1.9 mTorr of argon pressure at a voltage of 1.4 kV.
  • This was followed by a coating phase using the physical deposition technique of the magnetron sputtering type: the coating treatment lasted 20 minutes at 1.9 mTorr of argon pressure; the sputtering current was 6.6 A.
  • the re ⁇ sult was a deposit in the order of a micrometer with a dark grey shiny appearance.
  • a flat CZ 121 M brass sample was subjected to coat ⁇ ing with a barrier layer of the metallic type followed by titanium coating and finally electrochemical colour ⁇ ing.
  • the surface of the brass sample was degreased with acetone and deoxidized by immersion for 5 minutes in a sulphuric acid solution (20% by weight) at room tempera ⁇ ture.
  • the brass substrate was activated with a commercial solution of Sn/Pd by immersion at room temperature for 2 minutes. This was followed by metallization by the auto- catalytic deposition of Ni-P alloy in a bath having the following composition and characteristics: nickel acetate 0.12 M, sodium hypophosphite 0.32 M, lactic acid 0.5 M, pH 4.7, operating temperature 85°C.
  • the deposition of nickel-phosphorous was carried out for 30 minutes produc- ing a deposit having a thickness of 10 ⁇ m.
  • the deposition cycle of the titanium layer was based on an initial acti ⁇ vation phase with the use of an ionic source: the activa ⁇ tion treatment lasted 5 minutes at 1.9 mTorr of argon pressure at a voltage of 1.4 kV. This was followed by the coating phase by means of the magnetron sputtering tech ⁇ nique: the coating treatment lasted 20 minutes at 1.9 mTorr of argon pressure; the sputtering current was 6.6 A.
  • a deposit was formed in the order of a micrometer with a dark grey shiny appearance. There was an extremely good adhesion of the titanium to the stainless steel.
  • the ti ⁇ tanium layer was coloured by anodic oxidation in a solu ⁇ tion of phosphoric acid, at a voltage of 20 V, obtaining a vrolet-blue-coloured " layer of ⁇ titan ⁇ um ⁇ oxrde "
  • Example 3 A sample made of copper-tin alloy (white bronze) was coated with a layer of tantalum by means of the magnetron sputtering technique. The layer was deposited after cleaning the surface of the sample with acetone and acti ⁇ vation in sulfamic acid. The tantalum deposition was ef- fected for a period of 10 minutes at an argon pressure of 1.9 mTorr and a sputtering current of 6.4 A. The deposit was electrochemically coloured in a solution of sulfuric acid.
  • Example 4 A product made of ABS plastic material was subjected to coating with zirconium and subsequently electrochemi ⁇ cal colouring.
  • the metallization was effected with the magnetron sputtering technique: 15 minutes at 1.9 mTorr of argon pressure, a sputtering current of 6.6 A.
  • a thin deposit was formed which was subjected to electrochemical colouring by means of anodic oxidation in a solution of phosphoric acid.
  • the result was an object made of ABS plastic coated with a coloured layer of zirconium oxide.
  • Example 5 A product made of ABS plastic material premetallized with a copper layer, was subjected to coating with tita ⁇ nium and subsequently electrochemical colouring.
  • the ti ⁇ tanium deposition - was- effected with the magnetron--sput ⁇ tering technique: 15 minutes at 1.9 mTorr of argon pres- sure, a sputtering current of 6.6 A.
  • a thin deposit was formed (less than a micrometer) which was subjected to electrochemical colouring by means of anodic oxidation in a solution of phosphoric acid.
  • the result was an object made of ABS plastic coated with a coloured layer of tita- nium oxide.
  • the metallic copper barrier layer acted as an adhesion layer for the titanium and also as a current- carrier in the electrochemical colouring phase.
  • ABS plastic material was subjected to coating with titanium with the magnetron sputtering technique and then colouring with the reactive magnetron sputtering technique.
  • the surface of the ABS plastic ob ⁇ ject was subjected first to the deposition cycle, with activation in oxygen plasma (2.20 mTorr) for 5 minutes.
  • the metallization was effected with the magnetron sputtering deposition technique: 2 minutes at 1.6 mTorr of argon pressure. At 6.6-6.7 A of sputtering current.
  • the colouring of the ABS plastic object was effected with the reactive magnetron sputtering technique: the deposition was effected for 3 minutes and 30 seconds at
  • the titanium deposition was effected using a reactor of the magnetron sputtering type.
  • the glass sheets were degreased in acetone.
  • a quartz glass ball was metallized and coloured with the technique described above.
  • the metallization was car ⁇ ried out with the magnetron sputtering technique preceded by ionic activation with argon.
  • the colouring was ef ⁇ fected " electrochemically in a solution of ⁇ sulfuric ⁇ acid7
  • a bulb was produced with a blue-coloured outer layer.
  • a ceramic tile (glazed stoneware) , having dimensions of 10 cm x 10 cm x 1 cm, was subjected to a coating cycle with titanium and subsequent electrochemical colouring.
  • the titanium deposition was effected using a reactor of the magnetron sputtering type.
  • the surface of the tile was degreased with acetone.
  • the deposition cycle envisaged an initial activation phase using an ionic source: the activation treatment lasted 5 minutes at 1.9 mTorr of argon pressure at a voltage of 1.4 kV.
  • the result was a deposit in the order of a few micrometers with a dark grey shine appearance.
  • the titanium adhesion was extremely good.
  • the ceramic tile coated with the thin layer of titanium was subjected to an electrochemical colouring test, by means of anodic oxidation in a solution of phosphoric acid. The result was a ceramic tile metallized with a blue-coloured layer of titanium oxide.
  • a ceramic tile (glazed stoneware) having dimen ⁇ sions- of 10 "-cm- x 10 cm- x 1 cm, was -subjected-to a coating cycle with titanium with the evaporation technique and subsequent electrochemical colouring.
  • the evaporation was carried out under a vacuum of 0.1-10 mPa.
  • a titanium layer of about 1.5 micrometers was deposited.
  • the titanium layer was electrochemically coloured, with a similar technique to that described in the previ ⁇ ous examples.
  • a ceramic tile (glazed stoneware) , having dimensions of 10 cm x 10 cm x 1 cm, was subjected to a coating cycle with titanium with the cathodic arc technique and subse- quent electrochemical colouring.
  • Example 12 The evaporation was carried out under a vacuum of 0.001-0.1 Pa. A titanium layer of about 2 micrometers was deposited, which was well adhered to the substrate. The titanium layer was electrochemically coloured, with a similar technique to that described in the previ ⁇ ous examples .
  • Example 12
  • a ceramic tile (glazed stoneware) , having dimensions of 10 cm x 10 cm x 1 cm, was subjected to a coating cycle with titanium with the magnetron sputtering technique and subsequent electrochemical colouring.
  • the deposition cycle envisaged an initial activation phase using an ionic source: the activation treatment lasted 5 minutes at 1.9 mTorr of argon pressure at a voltage of 1.4 kV.
  • the result was a deposit in the order of a few micrometers with a dark grey shine appearance.
  • the adhesion of the titanium to the tile was extremely good.
  • Example 13 A ceramic tile (glazed stoneware) , having dimensions of 10 cm x 10 cm x 1 cm, was subjected to a coating cycle with titanium with the magnetron sputtering technique and subsequent electrochemical colouring.
  • the surface of the tile was degreased with acetone.
  • the deposition cycle envisaged an initial activation phase using an ionic source: the activation treatment lasted 5 minutes at 1.9 mTorr of argon pressure at a voltage' " Of " l.4" ⁇ kV ⁇ .
  • a coating phase followed " , " ⁇ by ⁇ means ⁇ of magnetron sputtering: the coating treatment lasted 1 min- ute at 1.7 mTorr of argon pressure; the sputtering cur ⁇ rent was 6.6 A.
  • the deposi ⁇ tion of titanium oxide was effected with the reactive magnetron sputtering technique by introducing an argon- oxygen mixture (total pressure of 2.6 mTorr) for a time of 3 minutes at 6.7-6.8 A.
  • an argon- oxygen mixture total pressure of 2.6 mTorr
  • a col ⁇ oured surface of titanium oxide was produced.
  • Example 15 A sample of beech-wood was sealed with a thermoset ⁇ ting organic layer. It was then metallized by thermal evaporation. A metallic titanium layer was formed, having a thickness of 1 micrometer. The titanium layer was elec- trochemically coloured.
  • Example 15 A sample of beech-wood was sealed with a thermoset ⁇ ting organic layer. It was then metallized by thermal evaporation. A metallic titanium layer was formed, having a thickness of 1 micrometer. The titanium layer was elec- trochemically coloured. Example 15
  • a 5 cm x 5 cm sample of cotton fabric was subjected to titanium deposition by means of vacuum evaporation.
  • the thermal evaporation was effected in a reactor at a pressure of 0.1-10 mPa for a few minutes.
  • the titanate fabric was subjected to electrochemical colouring.
  • Example 16 A 20 cm x 20 cm sample of cotton fabric was sub ⁇ jected to the deposition of titanium by means of magne ⁇ tron sputtering and titanium oxide by means of reactive magnetron sputtering.
  • the titanium- deposition-- was —ef ⁇ fected in an argon atmosphere (1.7 mTorr) for 30 seconds.
  • an argon/oxygen mixture was introduced into the reactor, regulating the total pressure at a value of 2.13 to 2.7 mTorr for a pe ⁇ riod of 4 minutes.
  • a sample of cotton fabric was pro ⁇ quizged, coloured (purple-brown) on the side exposed to the target.
  • a polyethylene sheet was subjected to metallization with titanium using the thermal evaporation technique.
  • the thermal evaporation was effected in a reactor at a pressure of 0.1-10 mPa for a few minutes.
  • the titanate fabric was subjected to electrochemical colouring.
  • the metallization and colouring of various glass containers were cleaned in acetone and in isopropylic alcohol. They were placed inside the deposition reactor under vacuum.
  • the magnetron sputtering deposition was preceded by an acti ⁇ vation phase with argon plasma (1.85 mTorr at 1.6 kV and 0.3 A) which lasted 5 minutes.
  • the titanium deposition via magnetron sputtering lasted 20 minutes at 1.70-1.80 mTorr of argon pressure, at a sputtering current of 6.6-6.9 A and a voltage of 365- ⁇ 385- ⁇ V.
  • the- bottles- were uniformly coated by a titanium layer.
  • the titanium layer is compact, shiny and adherent. There are no signs of de ⁇ tachment .
  • a pyramid-shaped glass bottle (used for food) was metallized adopting the deposition parameters of the pre ⁇ vious test.
  • the metallization with titanium was effected via magnetron sputtering with a correct result.
  • the tita- nium layer is uniform and adherent on the whole layer.
  • the electrochemical colouring was effected in a solution of phosphoric acid at room temperature and produced a uniform dark-yellow-coloured titanium oxide.
  • a glass container (such as a sugar bowl) was sub ⁇ jected to metallization with titanium by means of the magnetron sputtering technique and colouring by the depo ⁇ sition of titanium oxide using the reactive magnetron sputtering technique.
  • the basic vacuum in the deposition reactor was 3 x 10 "3 Pa.
  • the titanium deposition was pre ⁇ ceded by an ionic activation phase (Kauffman-type source) in argon plasma at 1.80 mTorr of pressure for 5 minutes at 1.4 kV and 0.22 A.
  • the titanium deposition via magnetron sputtering lasted 4 minutes, at 6.7-6.8 A, with pressure values of 1.69-1.93 mTorr of argon.
  • the deposition of titanium oxide was effected with the reactive magnetron sputtering technique introducing an argon-oxygen mixture (total pressure of 2.50-2,80 mTorr) for a time of 4 minutes at 6.7-6.9 A.
  • an argon-oxygen mixture total pressure of 2.50-2,80 mTorr
  • a glass container was produced, uniformly coated by a layer of titanium and coloured titanium oxide with typical interference colours.
  • a C70 carbon steel sheet with a thin perlite struc ⁇ ture was metallized and coloured using the parameters of the previous test.
  • the dimension of the sheet was 15 cm x 20 cm with a thickness of 0.5 mm.
  • the titanium deposition was effected in a magnetron sputtering reactor, starting from a basic pressure of
  • the sample was subjected to ionic activation in argon at 1.76 mTorr, 16 kV and 0.26 A for a period of 5 minutes.
  • the steel sheet was then coated with a layer of ti ⁇ tanium by means of the magnetron sputtering technique, at an argon pressure of 1.5-1.7 mTorr and a sputtering cur ⁇ rent of 6.8 A and a voltage of 375 V.
  • the sheet coated with titanium was then coated with titanium oxide by means of the reactive magnetron sput ⁇ tering technique, using an argon-oxygen mixture at a pressure of 2.2-2.5 mTorr, for 4 minutes at 6.5-6.8 A.
  • a steel sheet was produced coated by a layer of ti- tanium and a layer of titanium oxide with the typical colours of light interference phenomena.
  • a glass bottle (of the type used for food) was sub ⁇ jected to metallization with titanium (magnetron sputter ⁇ ing) and colouring with titanium oxide (reactive magne- tron sputtering) .
  • the bottle was cleaned in acetone and isopropylic alcohol. The bottle was then placed in the deposition and ionic activation reactor.
  • the ionic activation took place with an argon pressure of 1.84 mTorr and a voltage of 1.4 kV and 0.22 A.
  • the titanium deposition (magnetron sputtering DC) was effected" for 3 minutes at 1.-7-1.8 mTorr - of argon pressure at 6.8 A of sputtering current .
  • the deposition of titanium oxide (reactive magnetron sputtering DC) was effected for 6 minutes in an argon- oxygen mixture at a total pressure of 2.4-2.6 mTorr and 6.8 of sputtering current .
  • a cardboard sheet (of the type used for food) was subjected to metallization with titanium (magnetron sput ⁇ tering) and colouring with titanium oxide (reactive mag- netron sputtering) .
  • the titanium deposition (magnetron sputtering DC) was effected for 1 minute at 1.6 mTorr of argon pressure at 6.7 A of sputtering current.
  • titanium oxide reactive magnetron sputtering DC
  • a glazed stoneware tile was coated with a layer of titanium by means of the cathodic arc deposition tech ⁇ nique.
  • the coated tile was treated in an air oven for colouring by thermal oxidation. After about ten minutes at 370 0 C, a yellow-coloured layered was obtained.
  • Example 26 A hollow ball, having a diameter of 12 cm, consist ⁇ ing of a mixture of polyester resin and alabaster powder was coated with a layer of titanium by means of the mag ⁇ netron sputtering technique. The deposition lasted 1 min- ute at 1.72 mTorr of argon pressure. At the end of the titanium deposition a layer of titanium oxide was depos ⁇ ited with the reactive magnetron sputtering technique, using an argon/oxygen mixture at 2.5-2.7 mTorr of total pressure. The deposition lasted 3 minutes: the result was a surface coated with titanium oxide and characterized by typical interference colours .
  • a flat chromium-plated sample (10 cm x 10 cm x 0.5 cm) was degreased with acetone and activated in diluted sulfuric acid at 3% for a few minutes at room tempera ⁇ ture.
  • the surface was coated with an organic layer hard ⁇ ened with UV rays.
  • a metallic nickel layer was deposited on this organic layer using the procedure of Example 1.
  • a titanium layer was deposited on the composite barrier layer (organic + nickel) with the magnetron sputtering technique. Titanium oxide was deposited on this layer by reactive sputtering.
  • a sample with a coloured surface was produced.
  • a sample of polyacrylonitrile organic fibre was sub ⁇ jected to coating with a barrier layer of the metallic type, followed by coating with titanium and finally elec- trochemical colouring.
  • the surface of the fibre was acti ⁇ vated with a commercial solution of Sn/Pd by immersion at room temperature for 2 minutes.
  • Metallization was then effected by the autocatalytic deposition of copper in a bath based on formaldehyde at room temperature for 10 minutes.
  • the deposition cycle of the titanium layer on the copper-coated fibre was based on an initial activa ⁇ tion phase with the use of an ionic source: the activa ⁇ tion- treatment- lasted 5 minutes -at 1.-9 -mTorr of—-argon pressure at a voltage of 1.4 kV.
  • the coating phase was followed by the coating phase by means of the magnetron sputtering tech ⁇ nique: the coating treatment lasted 20 minutes at an ar ⁇ gon pressure of 1.9 mTorr; the sputtering current was 6.6 A. The result was a deposit in the order of a micrometer with a dark grey shiny appearance.
  • the titanium layer was coloured by means of anodic oxidation in a solution of phosphoric acid.
  • a sample of polyacrylonitrile organic fibre was sub- jected to coating with a barrier layer of the metallic type, followed by coating with titanium and finally elec ⁇ trochemical colouring.
  • the surface of the fibre was acti ⁇ vated by immersion at room temperature for 2 minutes in a commercial solution of Sn/Pd.
  • Metallization was then ef- fected by the autocatalytic deposition of copper in a bath based on formaldehyde at room temperature for 10 minutes.
  • a second activation of the copper base was sub ⁇ sequently effected with a commercial solution of Sn/Pd by immersion at room temperature for 2 minutes.
  • Metalliza- tion was then effected by the autocatalytic deposition of an Ni-P alloy in the composition bath with the following characteristics: nickel acetate 0.12 M, sodium hypo- phosphite 0.32- M, lactic acid--0.5- M, pH 4 ⁇ 7, -opera-ting- temperature 85 0 C.
  • the nickel-phosphorous deposition was carried out for 30 minutes, producing a deposit having a thickness of 10 micrometers.
  • the deposition cycle of the titanium layer was based on an initial activation phase with the use of an ionic source: the activation treatment lasted 5 minutes at 1.9 mTorr of argon pressure, at a voltage of 1.4 kV.
  • the coating phase by means of the magnetron .sputtering technique: the coat ⁇ ing treatment lasted 20 minutes at an argon pressure of 1.9 mTorr; the sputtering current was 6.6 A. The result was a deposit in the order of a micrometer with a dark grey shiny appearance.
  • the titanium layer was coloured by means of anodic oxidation in a solution of phosphoric acid, at a voltage of 20 V, obtaining a violet/blue- coloured layer of titanium oxide.

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Abstract

Le mode de protection et de coloration sélective d’un produit fini présente les étapes suivantes: préparation du produit fini, prétraitement du produit fini afin de préparer sa surface pour un revêtement d’enduit, revêtement du produit fini en une ou plusieurs couches fines, coloration de la surface extérieure du revêtement par la formation d’un oxyde protecteur de la surface extérieure.
PCT/EP2005/008750 2004-08-06 2005-08-04 Mode de protection/coloration sélective d’un produit fini Ceased WO2006013115A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05772065A EP1784523A1 (fr) 2004-08-06 2005-08-04 Mode de protection/coloration sélective d"un produit fini

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
ITMI2004A001634 2004-08-06
ITMI20041634 ITMI20041634A1 (it) 2004-08-06 2004-08-06 Metodo per la protezione-colorazione selettiva di manufatti in lega leggera
ITMI2005A000206 2005-02-14
ITMI20050206 ITMI20050206A1 (it) 2005-02-14 2005-02-14 Metodo per la protezione-colorazione selettiva di un manufatto

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WO2006013115A1 true WO2006013115A1 (fr) 2006-02-09

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007113240A1 (fr) * 2006-03-31 2007-10-11 Technische Universität Clausthal Materiau organique dont la surface comporte un revetement catalytique
ITTO20090234A1 (it) * 2009-03-27 2009-06-26 Fonderie A Doglione & C S P A Procedimento per il rivestimento di particolari in lega di alluminio, in particolare in lega di alluminio pressocolata, e particolari realizzati tramite tale procedimento
WO2009083772A1 (fr) * 2007-12-21 2009-07-09 Gianpaolo Girardello Procédé de dépôt
WO2010109506A2 (fr) 2009-03-27 2010-09-30 Fonderie A. Doglione & C. S.P.A. Modules et éléments de mobilier autoporteurs en métal, en particulier en alliage d'aluminium moulé sous pression et procédé de finition possible de leur surface
CN102582339A (zh) * 2012-01-18 2012-07-18 厦门建霖工业有限公司 一种在铝合金表面双色拉丝镀膜的方法
EP2305880A3 (fr) * 2009-10-01 2014-04-16 Taiwan Textile Research Institute Textile de couleur
CN109182962A (zh) * 2018-08-28 2019-01-11 江苏塞恩斯金属新材料科技有限公司 新型圆柱型金属表面处理工艺
CN110139508A (zh) * 2018-02-09 2019-08-16 华为技术有限公司 复合材料、加工复合材料的方法、壳体以及终端
CN115668494A (zh) * 2020-05-21 2023-01-31 兰克森控股公司 用于制造具有彩色触片的电子芯片卡模块电路的方法和由该方法生产的电路
CN115821261A (zh) * 2022-07-19 2023-03-21 得利钟表制品厂有限公司 表面改性和颜色改变方法以及物品
CN116479404A (zh) * 2023-04-25 2023-07-25 曼德电子电器有限公司 一种用于车灯装饰件的镀膜方法、复合膜层及其应用

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007113240A1 (fr) * 2006-03-31 2007-10-11 Technische Universität Clausthal Materiau organique dont la surface comporte un revetement catalytique
WO2009083772A1 (fr) * 2007-12-21 2009-07-09 Gianpaolo Girardello Procédé de dépôt
ITTO20090234A1 (it) * 2009-03-27 2009-06-26 Fonderie A Doglione & C S P A Procedimento per il rivestimento di particolari in lega di alluminio, in particolare in lega di alluminio pressocolata, e particolari realizzati tramite tale procedimento
WO2010109505A1 (fr) 2009-03-27 2010-09-30 Politecnico Di Torino Processus de revêtement de parties faites d'alliage d'aluminium, et parties obtenues ainsi
WO2010109506A2 (fr) 2009-03-27 2010-09-30 Fonderie A. Doglione & C. S.P.A. Modules et éléments de mobilier autoporteurs en métal, en particulier en alliage d'aluminium moulé sous pression et procédé de finition possible de leur surface
EP2305880A3 (fr) * 2009-10-01 2014-04-16 Taiwan Textile Research Institute Textile de couleur
CN102582339A (zh) * 2012-01-18 2012-07-18 厦门建霖工业有限公司 一种在铝合金表面双色拉丝镀膜的方法
CN110139508A (zh) * 2018-02-09 2019-08-16 华为技术有限公司 复合材料、加工复合材料的方法、壳体以及终端
CN109182962A (zh) * 2018-08-28 2019-01-11 江苏塞恩斯金属新材料科技有限公司 新型圆柱型金属表面处理工艺
CN115668494A (zh) * 2020-05-21 2023-01-31 兰克森控股公司 用于制造具有彩色触片的电子芯片卡模块电路的方法和由该方法生产的电路
US20230281421A1 (en) * 2020-05-21 2023-09-07 Linxens Holding Electric Circuit for an Electronic Chip Card Module with Colored Contacts and Method for Producing Same
CN115821261A (zh) * 2022-07-19 2023-03-21 得利钟表制品厂有限公司 表面改性和颜色改变方法以及物品
CN115821261B (zh) * 2022-07-19 2024-01-23 得利钟表制品厂有限公司 表面改性和颜色改变方法以及物品
CN116479404A (zh) * 2023-04-25 2023-07-25 曼德电子电器有限公司 一种用于车灯装饰件的镀膜方法、复合膜层及其应用

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