EP1336669B1 - Verfahren zum Bereitstellen eines schildkrötenpanzerartigen Farbeffekts auf Metalloberflächen - Google Patents

Verfahren zum Bereitstellen eines schildkrötenpanzerartigen Farbeffekts auf Metalloberflächen Download PDF

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Publication number
EP1336669B1
EP1336669B1 EP03075332A EP03075332A EP1336669B1 EP 1336669 B1 EP1336669 B1 EP 1336669B1 EP 03075332 A EP03075332 A EP 03075332A EP 03075332 A EP03075332 A EP 03075332A EP 1336669 B1 EP1336669 B1 EP 1336669B1
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EP
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Prior art keywords
process according
temperature
substrate
acid
metallic substrate
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Expired - Lifetime
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EP03075332A
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English (en)
French (fr)
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EP1336669B9 (de
EP1336669A3 (de
EP1336669A2 (de
Inventor
Ugo Gussalli Beretta
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Beretta SpA
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Fabbrica dArmi Pietro Beretta SpA
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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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F1/00—Designs or pictures characterised by special or unusual light effects
    • B44F1/08—Designs or pictures characterised by special or unusual light effects characterised by colour effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F9/00—Designs imitating natural patterns
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50—Treatment of iron or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/52—Treatment of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/58—Treatment of other metallic material
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer

Definitions

  • the present invention relates to a process for providing a tortoise-shell chromatic effect to metallic substrates.
  • the present invention relates to a process for providing a tortoise-shell chromatic effect to nickelated components of fire-arms.
  • tortoise-shell effect is a particular spotted chromatic effect conferred for ornamental purposes to tools or metallic parts of devices of varying origins.
  • the tortoise-shell effect is particularly requested for providing an aesthetically pleasant chromatic effect to the action body or other metallic parts of shotguns.
  • a tortoising process of metallic substrates which requires high operating temperatures and also a low temperature chemical process capable of providing a simple uniform colouring to metallic substrates, are currently known.
  • the high temperature tortoising process consists in the thermal treatment of a steel matrix which comprises heating to a temperature of about 700°C and quenching the steel in an aqueous solution of oxidizing salts.
  • the spotted colouring is created by the different surface oxidation degree of the steel and by the different thickness of the oxide layer formed.
  • the thermal treatment required for obtaining the particular aesthetic tortoise-shell effect has a negative influence on the hardness and mechanical performance in general of the metallic component treated.
  • FR-A-2 735 075 discloses a process for providing a coloring effect to substrates wherein the contact between the coloring solution and the substrate can be done by immersion at ambient temperature and wherein the coloring solution comprises sodium thiosulphate, lead or copper acetate and potassium acid tartrate.
  • GB-A-1 229 502 discloses a process for making designs on metal surfaces including a step of coating the colored metal surface with a heat and corrosion resistant transparent coating.
  • WO 97/35046 discloses a process for providing a a cloring metallic effect to metallic substrates wherein the substrate is contacted with sodium hyposulfite lead and copper acetate by immersion at a temperature of 50 to 100°C.
  • a first aspect of the present invention relates to a process for providing a tortoise-shell chromatic effect to substrates as claimed in the appended claims
  • the metallic substrate to be treated is heated to a suitable temperature for providing a chromatic effect, said temperature being a non-high temperature at which there are no thermal distortions caused in the substrate which can jeopardize its use in high-precision applications.
  • the oxidizing solution of the invention is typically a solution based on sodium thiosulfate containing a reagent metal conveniently in the form of an acetate, preferably consisting of copper or lead acetate or their mixtures.
  • the term acidifying compound includes compounds with acid hydrolysis or however compounds which when added to an aqueous solution are capable of reducing its pH.
  • Suitable acidifying compounds comprise organic acids such as carboxylic acids, for example, acetic acid, citric acid; oxalic acid, salicylic acid and potassium acid tartrate; inorganic acids such as hypochlorous acid and hypophosphorous acid.
  • organic acids such as carboxylic acids, for example, acetic acid, citric acid; oxalic acid, salicylic acid and potassium acid tartrate; inorganic acids such as hypochlorous acid and hypophosphorous acid.
  • Substrates suitable for being subjected to the tortoising process of the invention comprise metallic matrixes, provided they have at least one surface portion with a metallic layer, galvanically deposited or with another technology.
  • Steel matrixes, nickelated steels, metal alloys such as aluminum, copper, nickel alloys and super-alloys, can be used, for example.
  • Nickelated details or components of end-products and articles for varying uses can be appropriately treated with the process of the invention.
  • the application of said oxidizing solution advantageously takes place by means of buffering on localized portions of the metallic substrate to be treated so as to cause oxidation and consequently a chromatic variation, limited to the buffered areas.
  • the surface metal layer undergoes a more intense oxidation process the greater the residence time of the oxidizing solution. process the greater the residence time of the oxidizing solution.
  • An embodiment of the process of the invention comprises the direct development of the chromatic effect on the metallic substrate using a solution based on thiosulfate containing copper acetate as reagent metal.
  • a metallic substrate is heated to a temperature conveniently within the range of 100 to 110°C and subsequently buffered with a chromatically effective quantity of an aqueous solution containing sodium thiosulfate, copper acetate and potassium acid tartrate, at a temperature advantageously within the range of 40-110°C, preferably 60-80°C, until the development of the desired chromatic variation.
  • the buffering phase can be repeated once or several times, until the desired tonality or chromatic effect is obtained.
  • the tortoise-shell chromatic effect is caused by the oxidizing action of the solution on the surface of the metallic substrate.
  • the coloured oxidized layer formed is firmly anchored to the metallic surface producing a long-lasting chromatic effect.
  • the Applicant has discovered that the direct development of a long-lasting chromatic variation which is particularly appreciable from an aesthetic point of view, is obtained using an oxidizing aqueous solution containing 220-240 g/l of sodium thiosulfate, 30-40 g/l of copper acetate and 30-40 g/l of potassium acid tartrate.
  • This further embodiment of the invention therefore includes:
  • This oxidizing solution contains a strong oxidizing agent, preferably consisting of ammonium persulfate, preferably present in a quantity ranging from 150-180 g/l.
  • the process of the invention allows a variety of chromatic effects and different colourings to be obtained, by simply increasing the contact time of the oxidizing solutions on the surface of the metallic substrates. It is thus possible to produce yellow-gold, red, blue and grey colourings and shades in different tonalities.
  • a nickelated steel action body for a shotgun was initially heated to a temperature of 100°C and subsequently subjected to localized buffering at a temperature of 70°C with an oxidizing aqueous solution containing 230 g/l of sodium thiosulfate, 35 g/l of copper acetate and 35 g/l of potassium acid tartrate, until a spotted colouring, of the tortoise-shell type, is formed.
  • aqueous solution containing 230 g/l of sodium thiosulfate, 22 g/l of lead acetate and 25 g/l of potassium acid tartrate was applied with a buffer on a nickel alloy article heated to a temperature of 140°C.
  • the article was immersed or buffered, without rinsing, at a temperature of 60°C, with an aqueous solution containing 160 g/l of ammonium persulfate. After a few minutes, a chromatic variation, with a typical tortoise-shell effect, is formed in the buffered areas.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Chemically Coating (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Farming Of Fish And Shellfish (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Claims (11)

  1. Verfahren zum Versehen einer Metallummantelung eines Substrats mit einem schildpattartigen Farbeffekt, wobei das Verfahren umfasst:
    Erhitzen des metallischen Substrats auf eine geeignete Temperatur zum Aufbringen eines Farbeffekts, wobei die Temperatur eine Nicht-Hochtemperatur ist, bei der keine thermischen Verwerfungen im Substrat bewirkt werden,
    Anwenden einer Oxidationslösung, die Natrium- oder Kaliumthiosulfat, ein aus Kupferazetat und Bleiazetat und Mischungen davon ausgewähltes Reagensmetall und eine säurebildende Verbindung aufweist, unter Wärme, bei einer Temperatur innerhalb eines Bereichs von 40 bis 110°C, auf einem Abschnitt des metallischen Substrats.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Reagensmetall aus Kupferazetat, Bleiazetat oder deren Mischungen ausgewählt wird.
  3. Verfahren nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, dass die säurebildende Verbindung aus Kaliumsäuretartrat, Zitronensäure, hypophosphoriger Säure, Oxalsäure, Salizylsäure, Essigsäure, unterchloriger Säure und deren Mischungen ausgewählt wird.
  4. Verfahren nach einem der vorhergehenden Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Oxidationslösung durch Puffern auf der Metallummantelung des Substrats angewendet wird.
  5. Verfahren nach einem der vorhergehenden Ansprüche 1 bis 4, wobei eine direkte Entwicklung eines schildpattartigen Farbeffekts durch Erhitzen des Metallsubstrats auf eine Temperatur innerhalb des Bereichs von 100-110°C und Puffern bei einer Temperatur innerhalb des Bereichs von 40-110°C mit einer Oxidationslösung stattfindet, die umfasst: Natriumthiosulfat 220-240 g/l Kupferazetat 30-40 g/l Kaliumsäuretartrat 30-40 g/l
    bis der Farbeffekt erhalten wird.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass das Puffern des Metallsubstrats bei einer Temperatur im Bereich von 60-80°C stattfindet.
  7. Verfahren nach einem der vorhergehenden Ansprüche 1 bis 4, wobei ein schildpattartiger Farbeffekt in zwei Phasen entwickelt wird, das Verfahren umfassend:
    eine Anwendungsphase mittels Puffern einer Lösung, die Natriumthiosulfat 220-240 g/l Bleiazetat 30-40 g/l Kaliumsäuretartrat 30-40 g/l
    aufweist, auf ein auf eine Temperatur im Bereich von 140-150°C erhitztes metallisches Substrat und
    eine zweite Anwendungsphase einer Oxidationslösung auf dem Substrat bei einer Temperatur im Bereich von 40-80°C.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass in der zweiten Phase die Anwendung der Oxidationslösung mittels Puffern oder mittels Eintauchen des metallischen Substrats stattfindet.
  9. Verfahren nach Anspruch 7 oder 8, dadurch gekennzeichnet, dass die Oxidationslösung eine Ammoniumpersulfatlösung ist.
  10. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Ummantelungsmetall aus Nickel, Nickellegierungen, Stählen, Nickelatstählen, Kupfer, Superlegierungen ausgewählt wird.
  11. Verfahren nach einem der vorhergehenden Ansprüche 1 bis 10, dadurch gekennzeichnet, dass das metallische Substrat ein Aktionskörper einer Schusswaffe ist.
EP03075332A 2002-02-15 2003-02-04 Verfahren zum Bereitstellen eines schildkrötenpanzerartigen Farbeffekts auf Metalloberflächen Expired - Lifetime EP1336669B9 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT2002MI000307A ITMI20020307A1 (it) 2002-02-15 2002-02-15 Procedimento per conferire un effetto cromatico a tartaruga a substrati metallici
ITMI20020307 2002-02-15

Publications (4)

Publication Number Publication Date
EP1336669A2 EP1336669A2 (de) 2003-08-20
EP1336669A3 EP1336669A3 (de) 2004-06-30
EP1336669B1 true EP1336669B1 (de) 2007-03-28
EP1336669B9 EP1336669B9 (de) 2007-10-03

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EP03075332A Expired - Lifetime EP1336669B9 (de) 2002-02-15 2003-02-04 Verfahren zum Bereitstellen eines schildkrötenpanzerartigen Farbeffekts auf Metalloberflächen

Country Status (7)

Country Link
US (1) US20030159762A1 (de)
EP (1) EP1336669B9 (de)
JP (1) JP2003277946A (de)
AT (1) ATE358193T1 (de)
DE (1) DE60312752D1 (de)
ES (1) ES2285035T4 (de)
IT (1) ITMI20020307A1 (de)

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Publication number Priority date Publication date Assignee Title
GB2464700B (en) * 2008-10-22 2012-11-28 Univ Plymouth A method of colouring tin and tin-containing articles

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ES2285035T3 (es) 2007-11-16
ES2285035T4 (es) 2008-05-16
EP1336669B9 (de) 2007-10-03
JP2003277946A (ja) 2003-10-02
DE60312752D1 (de) 2007-05-10
ITMI20020307A0 (it) 2002-02-15
EP1336669A3 (de) 2004-06-30
ATE358193T1 (de) 2007-04-15
US20030159762A1 (en) 2003-08-28
ITMI20020307A1 (it) 2003-08-18
EP1336669A2 (de) 2003-08-20

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