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WO2018066007A1 - Procédé galvanique et thermique visant à obtenir la coloration de métaux, en particulier de métaux précieux - Google Patents

Procédé galvanique et thermique visant à obtenir la coloration de métaux, en particulier de métaux précieux Download PDF

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Publication number
WO2018066007A1
WO2018066007A1 PCT/IT2016/000230 IT2016000230W WO2018066007A1 WO 2018066007 A1 WO2018066007 A1 WO 2018066007A1 IT 2016000230 W IT2016000230 W IT 2016000230W WO 2018066007 A1 WO2018066007 A1 WO 2018066007A1
Authority
WO
WIPO (PCT)
Prior art keywords
per
galvanic
phase
metals
temperature
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/IT2016/000230
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English (en)
Other versions
WO2018066007A9 (fr
Inventor
Andrea TORRACCHI
Ester Falletta
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.)
Valmet Plating SRL
Original Assignee
Valmet Plating SRL
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 Valmet Plating SRL filed Critical Valmet Plating SRL
Priority to PCT/IT2016/000230 priority Critical patent/WO2018066007A1/fr
Publication of WO2018066007A1 publication Critical patent/WO2018066007A1/fr
Publication of WO2018066007A9 publication Critical patent/WO2018066007A9/fr
Anticipated expiration legal-status Critical
Ceased 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
    • 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
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • 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
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • 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
    • 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
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins

Definitions

  • the present invention refers to a technology with the purpose of obtaining particular colorations of objects, in particular on metal objects.
  • the invention refers to an innovative method which allows to obtain special color tones generally not obtainable with known techniques, in particular in metals and more particularly in precious metals for decorative purposes.
  • the creation of metallic objects can follow various known techniques depending on the object.
  • the production of precious objects can be processed by the known galvanic deposition process.
  • objects made of bronze or brass are processed by galvanic deposition in such a manner that mechanical and also technical characteristics are improved, especially if they are objects for the fashion industry or for jewelry industry in general.
  • colors such as orange, violet, red, blue and green cannot be obtained generally.
  • the method comprises a processing phase of the object by galvanic deposit, that is a standard electrolytic process and a heat treating phase which foresees the heating of the object to a predetermined temperature for a preset period.
  • said object is a metallic object; however, said object can also be an object with non-metallic base, for example, organic, organic-polymeric or mixed organic-metallic/organic- polymeric-metallic, which can be suitable to be undergone to a galvanic process and resist to high temperatures such as those temperatures used in the present method.
  • the galvanic processing phase has preferably to be made before the thermal processing phase. In this manner, the galvanic phase allows the deposit of the precious material which is subsequently colored with the thermal treatment. In this way, various different color shades are obtained.
  • the thermal-galvanic sequence is certainly possible but it has some problems due to the "cleaning" and “pre-treating", necessary to the good bond of the galvanic coating, that can actually damage the surface, modifying the final obtainable coloration and allowing hardly to obtain green-orange-blue-violet colorations. Instead, such colorations are obtainable by the preferred sequence "galvanic + firing (that is thermal treatment)". In that sense, the thermal-galvanic sequence is functional but it allows a more limited number of colorations in respect with the galvanic-thermal sequence, which represents the preferred configuration of the invention .
  • the present invention concerns a method to obtain the coloration of an object, preferably but not necessarily a metallic object.
  • the method comprising a phase of deposit of an external material on the object and a thermal treatment phase which foresees the heating of the object to a predetermined temperature for a preset period.
  • the two phases are not necessarily in said sequential order.
  • the obtaining of particular colorations, that is various shades of color, on metals has been surprisingly obtained by coupling a galvanic process and a subsequent thermal process.
  • the subsequent thermal process on the metal allows to modify the color of the previous galvanic phase, thus managing to obtain shades and colors obtainable generally by the use of painting treatments (with a resulting value impoverishment/reduction of the treated object) .
  • the "electroplating" process allows to cover an object of non-precious metallic material (of a suitable non-metallic material or of a composite non-metallic- metallic composite as well), with a thin layer or more layers of a more precious metal/s, by using the electrolytic plating.
  • a bath which constitutes the so-called galvanic bath, containing a water-based solution of salt of the metal to be deposited
  • two electrodes are immerged: the cathode is constituted by the object to be covered, while the anode can be constituted by the metal which has to be deposited, by another inert metal or by graphite.
  • a difference of potential is imposed to such electrodes by means of a power generator. In such conditions, the cations of the metal to be deposited will move towards the cathode (negatively charged) while anions will move towards the anode (positively charged) .
  • the thickness range of the depositing metal can be comprised from 0,001 (micron) ⁇ and 5 (micron) ⁇ and preferably from 0,05 to 1 micron ( ⁇ ) .
  • precious covering/plating metals generally Au, Pd, Ru, Rh, Pt, Ag, Ir
  • precious covering/plating metals are usually deposited as pure metals or in alloy with selected metals from the group comprising Cr, Fe, Co, Ni, Cu, Zn, Cd, In, Sn, Pb, Bi, V, Ga, Y, Zr, Mo, W; preferably Au, Pd, Ru, Rh, Pt, Ag, as pure metals or in alloy with Fe, Co, Ni, Cu, Zn, Cd, In, Sn, Pb, Bi; more preferably in alloy with Co, Ni, Cu, Zn, In, Sn, Bi .
  • Non-precious metals are usually selected from the group comprising Fe, Ni, In, Co, Sn, Cu, Zn, Cr, Bi, Al, V, Mn, Mo, Bi and their alloys; preferably comprising Fe, Ni, In, Co, Sn, Cu, Zn, Cr, Bi, Al; more preferably comprising Fe, Ni, In, Sn, Cu, Zn, Cr, Bi e Al .
  • the used underlying layers are preferably bright and/or glazed nickel (Ni) , bright and/or glazed copper (Cu) and white and/or yellow bronze, brass or other Cu, Sn and/or Zn alloys based; otherwise they are constituted by layers of overlapping precious metals (for example selected from the previous mentioned ones) , in order to create some diffusion barriers for the metal migration of the base material (for example but not only, selected from the previous mentioned ones, such as rhodium (Rh) , ruthenium (Ru) , tin (Sn) and/or their alloys) .
  • electrodes used for the electrolytic depositions of the desired metallic alloys are conveniently selected from those commonly used in background art, depending on the productive need. Only to exemplify and not to limit the aims of the present invention, electrodes can be selected from: soluble electrodes such as nickel or copper electrodes or inert electrodes such as graphite, mixed oxides and plated titanium electrodes.
  • electrolytic baths/electrolytes suitable to realize depositions of the desired galvanic layers are conveniently selected from those commonly used in background art, possibly by modifying them on necessity in order to obtain the desired alloy.
  • electrolytes can be selected from: electrolytes for the deposit of gold-iron alloys from citrate matrix, electrolytes for the deposit of palladium-iron alloys from alkaline ammoniac matrix, electrolytes for the deposit of palladium-iron alloys from acid matrix, electrolytes for the deposit of gold-copper-cadmium, gold-copper-zinc and gold-copper-zinc ternary alloys from acid matrix, acid electrolytes on sulphate and sulphammate base for the deposit of rhodium and ruthenium and their alloys.
  • Other saline matrices for the deposit can be matrix with base of phosphate, pyrophosphate, cyanide, thiocyanate, carb
  • the concentration of salts in solutions of said electrolytes is usually comprised between 1 and 500 g/L; preferably, between 10 and 400 g/L; more preferably, between 0,01 and 200 g/L.
  • the thickness of deposited layers is usually comprised between 0, 0001 ⁇ and 50 ⁇ for non-precious metals; preferably, between 0,001 and 10 ⁇ ; more preferably, between 0,01 and 5 ⁇ .
  • the thickness of deposited layers is equally comprised between 0, 0001 and 50 ⁇ for precious metals; preferably, between 0,001 and 10 ⁇ ; more preferably; between 0,01 and 5 ⁇ .
  • the heat treatment which foresees generally a temperature increase to reach an operative temperature, so-called set point, a maintenance for a determined period of the reached temperature and a subsequent cooling.
  • the cooling is fulfilled in suitable heating devices such as, for example, stoves or ovens.
  • the heating cycle can foresee the insertion of the object, which is at room temperature, inside a stove/oven at room temperature as well.
  • the stove/oven is turned on in order to bring it to the desired temperature (to the so-called set point temperature) , keeping it to such temperature for a predetermined period in order to cool it in calm air (but, possibly, also in moving air; for example, in forced air flow) , for example, simply turning off the stove/oven.
  • the firing cycle comprises first a heating phase of the stove/oven to the desired temperature followed by the insertion of the object, which is at room temperature. In this manner, the metal is subjected to a sort of initial thermal shock.
  • the treated object will have a more uniform coloration, while the insertion of the piece inside the stove/oven, already heated to the set point temperature for the treatment, allows to modulate soft colorations and depending on the layout of the objects themselves.
  • an oxidizing atmosphere for example, oxygen (0 2 ), air, air containing excess oxygen, nitric oxide (NOx) ;
  • a reducing atmosphere for example, hydrogen (H 2 ) , ammonia (NH 3 ) , carbon, carbon monoxide (CO) , molecular sulphur;
  • an inert atmosphere for example nitrogen (N 2 ), argon (Ar) , helium (He), vacuum.
  • the operative temperature (the so called "set- point" temperature for the thermal treatment, determined on the basis of the required coloration, of the base material and of the galvanic cycle to which the object is submitted) ;
  • the residence time of the specimen inside the stove/oven to the operative temperature (set-point) with stationing period of the specimen/product to such temperature preferably from 2 minutes (min) to 120 minutes (min) ;
  • the used preset temperature range, of set-point will be connected to the temperature possibly reachable by base materials and will generally vary from 150°C to 1000°C, preferably, from 250°C to 800°C.
  • the residence of the specimen and/or product inside the stove/oven will be less than 240 min, preferably, less than 120 min, more preferably less than 60 min.
  • Cooling cycles can vary from minimum 5 min to maximum 2 hours depending on objects size, by using forced air flow, if necessary.
  • Colors obtained with the above described two phases method of the present invention can be, for example, regulated from yellow to orange, red, brown, violet, from blue to green, by varying conveniently the alloy and/or deposited metal/s and their related thermal treatment.
  • a certain amount of preparations of products with different color shades is described, only as an example and not restrictively :
  • Example 1 It is described a procedure for the preparation of a gold- blue object.
  • Base material brass (a specimen for the test is a small brass plate of 5 x 3 cm with 0,3 cm thickness).
  • Electrolytic degreasing for 1 min
  • cyanide-free degreasing cathode treatment
  • Plating with white bronze (2 ⁇ ) alkaline bath with cyanide base, deposit of white lead-free bronze; deposited alloy: ternary alloy Cu-Sn-Zn. Operative conditions: 60°C, 1 A/dm 2 ;
  • Plating with gold-iron alloy (0,2 pm; alloy composition: Au 98%, Fe 2% in p/p) obtained by weakly acid electrolyte with citrate matrix pH 4,5, gold from gold salt (I), cyanide and iron, as iron sulphate; operative conditions: 40°C, 1 A/dm 2 .
  • Heat period at the above temperature 6 mini- Inserting of the specimen at the above heat point (without any pre-heating) .
  • the process of the present invention is applicable also to apt non-metallic objects, or not fully metallic, that are suitable to be subjected to the galvanic process of the present invention and resistant to expected high firing temperatures (set-point) and to the expected application period for themselves.
  • said non-metallic objects can be organic, organic-polymeric or mixed organic-metallic/organic-polymeric-metallic (such as a composite of an apt plastic material or a composite of an apt plastic material covered by one or more layers of metals or metallic alloys as those described above) , that can be subjected to the galvanic process of the invention and that are enough resistant to the high temperatures used in the thermal treatment of the present invention.
  • organic, organic-polymeric or mixed organic-metallic/organic-polymeric-metallic such as a composite of an apt plastic material or a composite of an apt plastic material covered by one or more layers of metals or metallic alloys as those described above

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

La présente invention concerne un procédé visant à obtenir la coloration sur un objet, le procédé comprenant une phase de traitement de l'objet par dépôt galvanique et une phase suivante de traitement thermique qui prévoit le chauffage de l'objet à une température prédéterminée pendant une durée prédéfinie.
PCT/IT2016/000230 2016-10-06 2016-10-06 Procédé galvanique et thermique visant à obtenir la coloration de métaux, en particulier de métaux précieux Ceased WO2018066007A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/IT2016/000230 WO2018066007A1 (fr) 2016-10-06 2016-10-06 Procédé galvanique et thermique visant à obtenir la coloration de métaux, en particulier de métaux précieux

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IT2016/000230 WO2018066007A1 (fr) 2016-10-06 2016-10-06 Procédé galvanique et thermique visant à obtenir la coloration de métaux, en particulier de métaux précieux

Publications (2)

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WO2018066007A1 true WO2018066007A1 (fr) 2018-04-12
WO2018066007A9 WO2018066007A9 (fr) 2018-08-23

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT202300000294A1 (it) * 2023-01-12 2024-07-12 Galvanica Gmp Srl Metodo di rivestimento in lega d’oro di un corpo metallico

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1712244A (en) * 1924-12-11 1929-05-07 Bek Process of finishing metal articles and the product thereof
GB1395146A (en) * 1970-10-21 1975-05-21 Corillium Corp Gold-plating
US20130277225A1 (en) * 2010-12-10 2013-10-24 Royal Canadian Mint Method to Produce Golden Bronze by Diffusion of Tin Into Copper Under Controlled Conditions
US20150027898A1 (en) * 2009-10-15 2015-01-29 The Swatch Group Research And Development Ltd Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1712244A (en) * 1924-12-11 1929-05-07 Bek Process of finishing metal articles and the product thereof
GB1395146A (en) * 1970-10-21 1975-05-21 Corillium Corp Gold-plating
US20150027898A1 (en) * 2009-10-15 2015-01-29 The Swatch Group Research And Development Ltd Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials
US20130277225A1 (en) * 2010-12-10 2013-10-24 Royal Canadian Mint Method to Produce Golden Bronze by Diffusion of Tin Into Copper Under Controlled Conditions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KURTZ O ET AL: "Gold-Eisen-Hochleistungselektrolyt als leistungsfähige Alternative zu Kobalt- und Nickel-Hartgoldelektrolyten", GALVANOTECHNIK, LEUZE VERLAG, vol. 102, no. 3, 31 March 2011 (2011-03-31), pages 529 - 534, XP001561876, ISSN: 0016-4232 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT202300000294A1 (it) * 2023-01-12 2024-07-12 Galvanica Gmp Srl Metodo di rivestimento in lega d’oro di un corpo metallico

Also Published As

Publication number Publication date
WO2018066007A9 (fr) 2018-08-23

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