EP4306678A1 - Verfahren zur herstellung eines schwarzen und selbstheilenden erscheinungsbildes mit edelmetallsubstrat und so hergestelltes teil - Google Patents

Verfahren zur herstellung eines schwarzen und selbstheilenden erscheinungsbildes mit edelmetallsubstrat und so hergestelltes teil Download PDF

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Publication number
EP4306678A1
EP4306678A1 EP23185064.5A EP23185064A EP4306678A1 EP 4306678 A1 EP4306678 A1 EP 4306678A1 EP 23185064 A EP23185064 A EP 23185064A EP 4306678 A1 EP4306678 A1 EP 4306678A1
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EP
European Patent Office
Prior art keywords
substrate
patina
copper
gold
anhydrous
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.)
Pending
Application number
EP23185064.5A
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English (en)
French (fr)
Inventor
Michel STUCKY
Miguel AGUADO
Stéphane MARCOTTE
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Hermes Sellier SAS
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Hermes Sellier SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hermes Sellier SAS filed Critical Hermes Sellier SAS
Publication of EP4306678A1 publication Critical patent/EP4306678A1/de
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces

Definitions

  • the invention relates to a method for producing a black-appearing, self-healing part having a precious metal substrate.
  • black bronzes is then found in other civilizations (Roman, Saxon, Chinese (Wu-tong), as well as in Japan, in the Middle Ages.
  • the “Niiro” coatings have a “purple” black. Furthermore, they are traditionally made using a Japanese radish (for example daikon) to prepare the surface and with the addition of traditional Japanese plum vinegar in the patina solution which is difficult to compatible with a industrial production.
  • a Japanese radish for example daikon
  • a black coating for example by dry deposition such as PVD (“physical vapor deposition”) or DLC (“diamond like carbon”), or again by application of a lacquer.
  • dry deposition such as PVD (“physical vapor deposition”) or DLC (“diamond like carbon”)
  • such a coating generally causes an adhesion problem, in particular on a relatively ductile substrate, which leads to chipping and/or delamination of the coating, particularly in the event of an impact.
  • An objective is to provide an alloy with a black appearance, at least on the surface, or even if possible a deep black, overcoming at least in part the aforementioned drawbacks.
  • a precious metal here means an alloy comprising at least one of gold, silver or platinum. Here, it is more particularly a gold-based alloy.
  • Such a process thus makes it possible to produce a part with a black appearance having self-repairing properties.
  • the black of the patina obtained after application of such a patina bath is for example characterized by colorimetry in the L*a*b* CIE 1976 color space with a value of “L” between 10 and 50, more particularly between 30 and 50, a value of “a” between -1.5 and 1; and a value of “b” between -8 and 1.
  • the contents can be measured by any method.
  • the gold content is measured by ICP-AES (atomic emission spectrometry - inductively coupled plasma), for example after dissolution in aqua regia (i.e. a mixture of nitric acid and hydrochloric acid, for example respectively in proportion 1:3), or by gravimetry (i.e. by attack of an alloy with nitric acid and weighing of the insolubles which are recovered on a filter which is weighed).
  • ICP-AES atomic emission spectrometry - inductively coupled plasma
  • the measured content values can vary up to 10% for example, and sometimes even more.
  • the method comprises a step of forming the substrate alloy.
  • the step of forming the substrate alloy comprises a step of mixing, in proportions, of at least 45 g to 55 g, for example 50 g, of gold (Au) with between 800 g and 1200 g, for example 1000 g, of pure copper (Cu).
  • the mixing step is configured to produce an alloy comprising between 4.5% and 4.8%, for example 4.76%, of gold (by mass).
  • the gold content obtained is for example 4.57wt.% when measured by ICP-AES and 4.66% when measured by gravimetry.
  • the method comprises a step of forming the substrate on a base.
  • the base is made of stainless steel, aluminum, bronze or brass or other, of any desired geometry or dimension.
  • the step of forming the substrate comprises a step of galvanic deposition or by spraying the alloy onto the base, in particular by techniques such as Cold Spray or Arc Spray. (arc projection).
  • This step is for example configured to form a thickness of the substrate of at least 100 ⁇ m.
  • the proportions given for the step of preparing a patina bath are for example for one liter of water, in particular distilled or permuted water.
  • the method comprises, prior to the step of applying the patina bath, a step of stripping, also called stripping, of the upper surface of the substrate.
  • the stripping step is for example configured to remove a possible oxide layer on the surface of the substrate.
  • the stripping step is for example carried out with a solution of sulfuric acid (H 2 SO 4 ) at a content between 0.5% and 10% diluted in water (H 2 O).
  • H 2 SO 4 sulfuric acid
  • the process can optionally include a degreasing step, for example by a solvent, or by ultrasound, for example in the presence of a surfactant.
  • a degreasing step for example by a solvent, or by ultrasound, for example in the presence of a surfactant.
  • the method comprises a step of rinsing the substrate, for example rinsing with water; this step is for example implemented after the stripping step.
  • the step of applying the patina bath comprises a step of immersing the substrate in the patina bath.
  • the immersion stage has a duration of between 45 minutes and 120 minutes, for example 60 minutes.
  • the patina bath has a temperature between 80°C and 100°C.
  • the process may include a drying step, for example in the open air, and/or in an oven.
  • the process may possibly include a step of polishing the patina.
  • the process can also include a finishing step.
  • the finishing step may include a step of applying a non-volatile organic substance, for example a protection, for example an organic material, such as for example a gum arabic, a wax, a resin or other .
  • This non-volatile organic substance by impregnating it, allows the patina to go from an overall anthracite-looking patina to a deeper black.
  • the finish thus helps to provide a deep black appearance to the room.
  • This deeper black obtained after finishing can be characterized by colorimetry in the L*a*b* CIE 1976 color space with a value of “L” between 10 and 40, a value of “a” between -1.5 and 1; and a value of “b” between -4 and 1.
  • the finishing step is, for example, also configured to protect the patina and/or provide it with a glossy, satin or matte finish.
  • the finish application step can for example be carried out by dipping, spraying, dabbing, application with a cloth or brush.
  • the substrate addition element has a content of between 0% and 1%, or even between 0% and 0.01%.
  • the substrate addition element comprises at least one of: silver (Ag); arsenic (As), zinc (Zn), lead (Pb), iron (Fe), or tin (Sn).
  • the silver content is for example less than 1%, for example between 0% and 1%.
  • the substrate alloy comprises 95.24% copper (Cu) and 4.76% gold (Au), particularly when the gold content is measured by ICP-AES. Such an alloy is then devoid of addition element (which corresponds to a content of 0%).
  • the patina further comprises at least one element in trace form, for example at a content of between 0% and 0.01%.
  • the element in trace form comprises for example at least one of: carbon, oxygen, chlorine, potassium, calcium, or iron.
  • the patina has a gold content of between 5% and 15%, for example 13%.
  • the gold content in the patina is for example measured by EDX.
  • the part according to an implementation example thus presents a “deep black”.
  • the black of the patina obtained after application of such a patina bath is for example characterized by colorimetry in the L*a*b* CIE 1976 color space with a value of “L” between 10 and 50, more particularly between 30 and 50, a value of “a” between -1.5 and 1; and a value of “b” between -8 and 1.
  • this black can be characterized in the L*a*b* CIE 1976 color space with a value of “L” comprised more particularly between approximately 10 and 40, a value of “a” comprised approximately between -1.5 and 1; and a value of “b” approximately between -4 and 1.
  • the total is 100%.
  • Gold content can be measured by any method; preferably, it is measured by ICP-AES (atomic emission spectrometry - inductively coupled plasma), for example after dissolution in aqua regia (i.e. a mixture of nitric acid and hydrochloric acid, for example respectively in proportion 1: 3), or by gravimetry (i.e. by attacking an alloy with nitric acid and weighing the insolubles which are recovered on a filter which is weighed; here, only gold is insoluble).
  • ICP-AES atomic emission spectrometry - inductively coupled plasma
  • the measured content values can vary up to 10% for example, and sometimes even more.
  • the process may include a step of forming the alloy of the substrate comprising a step of mixing at least 45 g to 55 g, for example 50 g, of gold (Au) with between 800 g and 1200 g, for example 1000 g, of pure copper (Cu).
  • a step of forming the alloy of the substrate comprising a step of mixing at least 45 g to 55 g, for example 50 g, of gold (Au) with between 800 g and 1200 g, for example 1000 g, of pure copper (Cu).
  • the mixing step is for example configured to produce an alloy comprising between 4.5% and 4.8%, for example 4.76%, of gold (by mass).
  • the gold content obtained is for example 4.57wt.% when measured by ICP-AES and 4.66% when measured by gravimetry.
  • the substrate 10 is formed of an alloy comprising 95.24% copper (Cu) and 4.76% gold (Au).
  • the alloy does not have any addition element; but it could nevertheless contain at least one, preferably in a content between 0% and 4%.
  • Such a substrate 10 is for example represented figure 1 .
  • This is for example a substrate configured to form a ring.
  • the substrate having a surface 11, called upper surface 11, to which a patina 20, described below, is subsequently applied.
  • the substrate preferably has a thickness of at least 100 ⁇ m from the upper surface 11.
  • a thickness of at least 100 ⁇ m of the substrate makes it possible to better guarantee sufficient depth for anchoring the patina 20.
  • the substrate 10 is here formed of a curved armature, for example a curved wire with a circular or truncated circular section, here having a diameter 12 of approximately 3 mm.
  • the substrate here is a massive element.
  • the substrate could be a coating layer (in the aforementioned copper-gold alloy), at least 100 ⁇ m thick, applied to a base of another material, for example stainless steel, aluminum, bronze or brass. or other, of any desired geometry or dimension.
  • the method can for example include a step of forming the substrate comprising a step of galvanic deposition or by projection on the base, in particular by techniques such as Cold Spray or Arc Spray, of the alloy as described previously, this step being configured to form a substrate thickness of at least 100 ⁇ m.
  • the method according to an example of implementation of the invention also comprises a step of preparing a patina bath 21.
  • distilled or permutated water is heated to 90°C (+/-10°C).
  • the copper acetate and half of the copper sulfate i.e. 5 g are added to the distilled or permutated water.
  • This first mixture is stirred for one hour, then one gram (1 g) of salt is added as well as the rest of copper sulfate (i.e. 5 g).
  • This second mixture is then stirred for about an hour as well.
  • the method then includes a step of applying the patina bath 21 to the upper surface 11 of the substrate 10.
  • the process includes for example a step of stripping, also called stripping, of the upper surface 11 of the substrate.
  • the stripping step is for example configured to remove a possible oxide layer on the surface 11 of the substrate.
  • the stripping step is for example carried out with a solution of sulfuric acid (H 2 SO 4 ) at a content between 0.5% and 10% diluted in water (H 2 O).
  • H 2 SO 4 sulfuric acid
  • the process can optionally include a degreasing step, for example by a solvent, or by ultrasound, for example in the presence of a surfactant.
  • a degreasing step for example by a solvent, or by ultrasound, for example in the presence of a surfactant.
  • the process can optionally include a step of rinsing the substrate, for example rinsing with water.
  • the substrate 10 is for example immersed in the patina bath 21, as illustrated figure 2 .
  • the patina bath 21 is for example brought to a temperature between 80°C and 100°C.
  • the substrate 10 is immersed in the patina bath 21 for a period of between 45 minutes and 120 minutes, for example 60 minutes.
  • the process may include a drying step, for example in the open air, and/or in an oven.
  • the process may possibly include a polishing step.
  • the process can also include a finishing step.
  • the finishing step may include a step of applying a protection, for example an organic material, such as a gum arabic, a wax, a resin or the like.
  • This organic, non-volatile substance can possibly intensify the black of the patina.
  • the black of the patina obtained after application of such a patina bath is for example characterized by colorimetry in the L*a*b* CIE 1976 color space with a value of “L” between 10 and 50, more particularly between 30 and 50, a value of “a” between -1.5 and 1; and a value of “b” between -8 and 1.
  • this black can be characterized in the L*a*b* CIE 1976 color space with a value of “L” comprised more particularly between approximately 10 and 40, a value of “a” comprised approximately between -1.5 and 1; and a value of “b” approximately between -4 and 1.
  • the finish thus helps to provide a deep black appearance to the room.
  • the finishing step is, for example, configured to protect the patina and/or provide it with a glossy, satin or matte finish.
  • the finish application step can for example be carried out by dipping, spraying, dabbing, application with a cloth or brush.
  • Cuprite is naturally red, but it appears that such a patina leads to a black tint thanks to the presence of gold (and/or silver) coming from the substrate.
  • Such a part 30 thus presents a “deep black”.
  • the black of the patina obtained after application of such a patina bath is for example characterized by colorimetry in the L*a*b* CIE 1976 color space with a value of “L” between 10 and 50, more particularly between 30 and 50, a value of “a” between -1.5 and 1; and a value of “b” between -8 and 1.
  • this black can be characterized in the L*a*b* CIE 1976 color space with a value of “L” comprised more particularly between approximately 10 and 40, a value of “a” comprised approximately between -1.5 and 1; and a value of “b” approximately between -4 and 1.
  • Such a part 30 also has a self-repairing property.
  • the part 30 has been scratched to damage the apparent surface of the part 30 and form a “cut” 31.
  • the cut 31 After exposure to open air and/or light, natural or artificial, for example for a few days or even a few weeks, the cut 31 has attenuated and forms a trace 32, illustrated figure 4B) .
  • the patina 20 may optionally comprise at least one of: carbon, oxygen, chlorine, potassium, calcium, or even iron.
  • the patina is for example present between 0% and 0.01% of the patina, i.e. at most in the form of a trace, but ideally, the patina is devoid of it. More generally, if the substrate includes an addition element, the addition element has a content of between 0% and 1%, or even between 0% and 0.01%.
  • the addition element comprises for example at least one of: silver (Ag), arsenic (As), zinc (Zn), lead (Pb), iron (Fe), or even tin (Sn).
  • the spectrum has peaks that represent primarily copper and gold, as well as carbon and oxygen.
  • patina 20 is therefore enriched in gold.
  • the relatively low presence of carbon in the present example can be explained for example by the use of gum arabic for a finishing step of the part 30, and/or by pollution.
  • the spectral resolution is in a range between 9 cm -1 and 15 cm -1 .
  • patina 20 is mainly made up of cuprite.
  • the invention thus makes it possible to provide a precious metal part with a black and self-healing appearance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Adornments (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
EP23185064.5A 2022-07-13 2023-07-12 Verfahren zur herstellung eines schwarzen und selbstheilenden erscheinungsbildes mit edelmetallsubstrat und so hergestelltes teil Pending EP4306678A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR2207267A FR3137924A1 (fr) 2022-07-13 2022-07-13 Procédé de réalisation d’une pièce d’apparence noire et auto-cicatrisante ayant un substrat en métal précieux, et pièce obtenue

Publications (1)

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EP4306678A1 true EP4306678A1 (de) 2024-01-17

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EP23185064.5A Pending EP4306678A1 (de) 2022-07-13 2023-07-12 Verfahren zur herstellung eines schwarzen und selbstheilenden erscheinungsbildes mit edelmetallsubstrat und so hergestelltes teil

Country Status (4)

Country Link
US (1) US20240018677A1 (de)
EP (1) EP4306678A1 (de)
CN (1) CN117403216A (de)
FR (1) FR3137924A1 (de)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5160381A (en) * 1991-06-26 1992-11-03 Fumigation Maritime Ltee Method for forming artificially and rapidly patina on copper, products thereof and solutions therefor
JP2002191421A (ja) * 2000-12-25 2002-07-09 National Institute Of Advanced Industrial & Technology 緑色の金合金宝飾品の製造方法とその製品
CN103199072A (zh) * 2013-03-14 2013-07-10 江西蓝微电子科技有限公司 镀金铜钯合金单晶键合丝及其制造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5160381A (en) * 1991-06-26 1992-11-03 Fumigation Maritime Ltee Method for forming artificially and rapidly patina on copper, products thereof and solutions therefor
JP2002191421A (ja) * 2000-12-25 2002-07-09 National Institute Of Advanced Industrial & Technology 緑色の金合金宝飾品の製造方法とその製品
CN103199072A (zh) * 2013-03-14 2013-07-10 江西蓝微电子科技有限公司 镀金铜钯合金单晶键合丝及其制造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MATHIS F ET AL: "HMTY-KM (black copper) and the Egyptian bronzes' collection of the Musee du Louvre", JOURNAL OF CULTURAL HERITAGE, EDITIONS SCIENTIFIQUES ET MEDICALES ELSEVIER, AMSTERDAM, NL, vol. 10, no. 1, 1 January 2009 (2009-01-01), pages 63 - 72, XP025977258, ISSN: 1296-2074, [retrieved on 20090313], DOI: 10.1016/J.CULHER.2008.03.006 *

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CN117403216A (zh) 2024-01-16
FR3137924A1 (fr) 2024-01-19

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