ITFI20120103A1 - GALVANIC BATHROOMS FOR THE ACHIEVEMENT OF A LEAGUE OF LOW-CARATHED GOLD AND GALVANIC PROCESS THAT USES THESE BATHROOMS. - Google Patents
GALVANIC BATHROOMS FOR THE ACHIEVEMENT OF A LEAGUE OF LOW-CARATHED GOLD AND GALVANIC PROCESS THAT USES THESE BATHROOMS. Download PDFInfo
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- ITFI20120103A1 ITFI20120103A1 IT000103A ITFI20120103A ITFI20120103A1 IT FI20120103 A1 ITFI20120103 A1 IT FI20120103A1 IT 000103 A IT000103 A IT 000103A IT FI20120103 A ITFI20120103 A IT FI20120103A IT FI20120103 A1 ITFI20120103 A1 IT FI20120103A1
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- IT
- Italy
- Prior art keywords
- galvanic
- salts
- gold
- bath
- copper
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 9
- 239000010931 gold Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical class [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 17
- 229910052737 gold Inorganic materials 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Chemical class 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 229910052738 indium Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical class [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910001020 Au alloy Inorganic materials 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000003353 gold alloy Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 235000011180 diphosphates Nutrition 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 150000002343 gold Chemical class 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 claims description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- DPRMFUAMSRXGDE-UHFFFAOYSA-N ac1o530g Chemical compound NCCN.NCCN DPRMFUAMSRXGDE-UHFFFAOYSA-N 0.000 claims description 2
- IQXHAJSMTNDJGA-UHFFFAOYSA-O azanium;gold(1+);dicyanide Chemical compound [NH4+].[Au+].N#[C-].N#[C-] IQXHAJSMTNDJGA-UHFFFAOYSA-O 0.000 claims description 2
- 229940001468 citrate Drugs 0.000 claims description 2
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 2
- 229940050410 gluconate Drugs 0.000 claims description 2
- 150000002471 indium Chemical class 0.000 claims description 2
- 150000002688 maleic acid derivatives Chemical class 0.000 claims description 2
- 150000002690 malonic acid derivatives Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 150000003892 tartrate salts Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 238000007747 plating Methods 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical class N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 4
- 229960003975 potassium Drugs 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000005282 brightening Methods 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- -1 ethylenediamino Chemical group 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- MFIHOCAEOJNSOL-UHFFFAOYSA-N [Ag]C#N Chemical class [Ag]C#N MFIHOCAEOJNSOL-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 1
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- KZVLNAGYSAKYMG-UHFFFAOYSA-N pyridine-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=N1 KZVLNAGYSAKYMG-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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
- C25D3/62—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Paints Or Removers (AREA)
- Prevention Of Electric Corrosion (AREA)
Description
Bagni galvanici per l'ottenimento di una lega di oro a bassa caratura e processo galvanico che utilizza detti bagni. Galvanic baths for obtaining a low carat gold alloy and galvanic process using said baths.
Campo dell'invenzione Field of the invention
L'invenzione si riferisce al campo dei composti utilizzati nei processi galvanici, in particolare bagni galvanici per l'ottenimento di una lega di oro a bassa caratura ed al processo galvanico per ottenerla. The invention relates to the field of compounds used in galvanic processes, in particular galvanic baths for obtaining a low-carat gold alloy and to the galvanic process to obtain it.
Stato della tecnica State of the art
Per ottenere una lega di oro contenente con meno del 75% in peso di oro come metallo (corrispondente a una lega di oro 18 carati o meno) sono stati utilizzati per decenni bagni galvanici contenenti nella matrice (dove per matrice si intende una soluzione acquosa di acidi organici e inorganici e loro sali) quantità considerevoli sostanze tossiche, quali per esempio i cianuri, e metalli pesanti, anch’essi tossici e di difficile smaltimento, quali per esempio il cadmio. To obtain a gold alloy containing less than 75% by weight of gold as metal (corresponding to an alloy of 18 carat gold or less) galvanic baths containing in the matrix have been used for decades (where by matrix we mean an aqueous solution of organic and inorganic acids and their salts) considerable quantities of toxic substances, such as cyanides, and heavy metals, which are also toxic and difficult to dispose of, such as cadmium.
Questi bagni permettono effettivamente di ottenere depositi di oro alla caratura voluta e a spessori notevoli ma la presenza in essi di elementi altamente nocivi ne rende ormai improponibile l’utilizzo pratico. These baths actually make it possible to obtain deposits of gold at the desired carat weight and at considerable thicknesses, but the presence in them of highly harmful elements makes their practical use impossible by now.
Per ovviare agli inconvenienti suddetti sono state ricercate alternative alle formulazioni che prevedessero in particolare la sostituzione del cianuro, come complessante, e del cadmio come legante in combinazione col rame. To obviate the aforementioned drawbacks, alternatives have been sought to formulations which envisage in particular the substitution of cyanide, as a complexing agent, and of cadmium as a binder in combination with copper.
Le alternative a tutt'oggi in uso utilizzano però prodotti che hanno solo parzialmente risolto le problematiche connesse all’utilizzo dei bagni galvanici precedenti ed inoltre non presentano la stessa praticità d'utilizzo e la stessa qualità dei risultati: infatti si tratta in generale di formulazioni che eliminano solo in parte i prodotti tossici utilizzati o che hanno intervalli di utilizzo ristretto o con le quali si ottiene una lega avente caratteristiche di caratura, spessore o aspetto non del tutto corrispondenti alle necessità applicative: in particolare si ottengono depositi non del tutto uniformi, o con colorazioni troppo tendenti al rosa e al rosso per gli scopi estetici per i quali sono impiegati. However, the alternatives still in use today use products that have only partially solved the problems associated with the use of previous galvanic baths and also do not have the same practicality of use and the same quality of results: in fact, it is generally a matter of formulations that only partially eliminate the toxic products used or that have restricted ranges of use or with which an alloy is obtained having characteristics of carat weight, thickness or appearance that do not entirely correspond to the application needs: in particular, deposits that are not completely uniform are obtained , or with colors that tend to be too pink and red for the aesthetic purposes for which they are used.
Tra i bagni di questo tipo si ritrovano anche bagni che utilizzano comunque cianuro in matrice, o che, pur non contenendo cianuro in matrice, contengono altri elementi dotati di una certa tossicità . Among the baths of this type there are also baths which in any case use cyanide in the matrix, or which, although not containing cyanide in the matrix, contain other elements with a certain toxicity.
Per esempio, US4358351descrive un bagno contenente oro, rame, zinco, cianuro libero e arsenico come brillantante; US4487664 descrive un bagno contenente oro Argento e cianuro libero; US5085744 descrive un bagno contenente oro, rame, zinco, cianuro libero e antimonio come brillantante; US4687557 descrive un bagno contenente oro, rame, cadmio privo di cianuro libero in soluzione. For example, US4358351 describes a bath containing gold, copper, zinc, free cyanide and arsenic as a rinse aid; US4487664 discloses a bath containing gold, silver and free cyanide; US5085744 discloses a bath containing gold, copper, zinc, free cyanide and antimony as a rinse aid; US4687557 describes a bath containing gold, copper, cadmium free of free cyanide in solution.
E' ovvio quindi alla luce di quanto suddetto quanto sia industrialmente desiderabile poter disporre di bagni galvanici che siano praticamente esenti dalle sostanze tossiche sopra citate, pratici nell'utilizzo e che consentano di ottenere una caratura precisa nell'intervallo 12 – 18 carati, spessori adeguati, deposito uniforme e colore tendente al giallo tipico di un deposito di oro. It is therefore obvious in the light of the above how industrially desirable it is to have galvanic baths that are practically free from the toxic substances mentioned above, practical in use and that allow to obtain a precise carat in the 12 - 18 carat range, adequate thicknesses, uniform deposit and yellowish color typical of a gold deposit.
Descrizione dettagliata dell’invenzione Detailed description of the invention
La presente invenzione consente di rispondere alle esigenze suddette grazie a bagni galvanici alcalini contenenti: sali di Oro, Rame e Indio, sali di acidi organici policarbossilici, ammine organiche ed eventualmente complessanti, tensioattivi ed altri metalli in quantità secondarie come brillantanti e raffinatori del deposito. The present invention allows to meet the above requirements thanks to alkaline galvanic baths containing: salts of Gold, Copper and Indium, salts of polycarboxylic organic acids, organic amines and possibly complexing agents, surfactants and other metals in secondary quantities as brighteners and refiners of the deposit.
Secondo la presente invenzione per “bagno galvanico†si intendono le soluzioni acquose in cui vengono immersi le superfici da trattare con il processo galvanico. According to the present invention, “galvanic bath” means the aqueous solutions in which the surfaces to be treated with the galvanic process are immersed.
Secondo la presente invenzione i sali di oro sono preferibilmente scelti fra: potassio dicianoaurato, potassio tetracianoaurato, ammonio cianoaurato, o una combinazione di questi. According to the present invention, the gold salts are preferably selected from: potassium dicianoaurate, potassium tetracyanoaurate, ammonium cyanoaurate, or a combination of these.
Si noti che, a differenza dello stato dell'arte sopra citato, nella presente invenzione il cianuro non à ̈ presente nella matrice del bagno ed il suo contenuto nella soluzione galvanica à ̈ dovuto alla sua funzione di contro-ione nei sali di oro, ed à ̈ quindi praticamente irrilevante anche se necessario per la stabilità dei metalli stessi in soluzione. It should be noted that, unlike the aforementioned state of the art, in the present invention cyanide is not present in the bath matrix and its content in the galvanic solution is due to its counter-ion function in the gold salts, and It is therefore practically irrelevant even if necessary for the stability of the metals themselves in solution.
La quantità di Oro, calcolata sui rispettivi sali, à ̈ compresa tra 0,7 e 4 g/L, preferibilmente tra 1,5 e 3 g/L per ottenere l'efficienza e gli spessori desiderati. The quantity of Gold, calculated on the respective salts, is between 0.7 and 4 g / L, preferably between 1.5 and 3 g / L to obtain the desired efficiency and thickness.
Per sali di Rame secondo l'invenzione si intendono ad esempio: solfato, fosfato, pirofosfato, cloruro, o altri sali stabili nelle condizioni di lavoro del bagno stesso. By copper salts according to the invention we mean for example: sulphate, phosphate, pyrophosphate, chloride, or other stable salts under the working conditions of the bath itself.
Il Rame, calcolato sui rispettivi sali, à ̈ presente in quantità compresa fra 0,3 a 2,5 g/L, preferibilmente tra 0,5 e 2 g/L, in relazione alla caratura che si vuole ottenere nell'intervallo 12 – 18 carati. Copper, calculated on the respective salts, is present in quantities ranging from 0.3 to 2.5 g / L, preferably between 0.5 and 2 g / L, in relation to the desired carat weight in the range 12 â € “18 carat.
Sali di Indio utili secondo l'invenzione sono, ad esempio: cloruro, solfato, citrato, tartrato, gluconato, od altro complesso organico o amminico compatibile con le condizioni di lavoro del bagno. Useful indium salts according to the invention are, for example: chloride, sulphate, citrate, tartrate, gluconate, or other organic or amino complex compatible with the working conditions of the bath.
La concentrazione di Indio, calcolata sui rispettivi sali, va da 0,1 a 2 g/L, preferibilmente da 0,5 a 1,5 g/L in relazione alla caratura desiderata nell'intervallo 12 – 18 carati. The concentration of Indium, calculated on the respective salts, ranges from 0.1 to 2 g / L, preferably from 0.5 to 1.5 g / L in relation to the desired carat in the range of 12 - 18 carats.
La matrice del bagno à ̈ costituita da sali di acidi carbossilici o minerali avente sia caratteristiche di tampone sia potere complessante, quali ad esempio citrati, pirofosfati, tartrati, gluconati, maleati, malonati, eventualmente in combinazione con gli acidi corrispondenti per la creazione dell'opportuno tampone, ed eventualmente in miscela tra di sé per raggiungere l'opportuno potere complessante. The bath matrix consists of salts of carboxylic or mineral acids having both buffer characteristics and complexing power, such as citrates, pyrophosphates, tartrates, gluconates, maleates, malonates, possibly in combination with the corresponding acids for the creation of appropriate buffer, and possibly mixed with each other to achieve the appropriate complexing power.
Questi acidi ed i rispettivi sali vengono usati ciascuno in quantità comprese tra i 30 e i 150 g/L, e più comunemente tra i 50 ed i 100 g/L. These acids and their respective salts are each used in quantities between 30 and 150 g / L, and more commonly between 50 and 100 g / L.
Complessanti che può essere opportuno utilizzare per migliorare la stabilità dei metalli in soluzione e per modularne l'andamento in lega sono, ad esempio, acido etilendiamminotetraacetico e suoi sali, acido editronico e suoi sali, acido etilendiammino tetrametil fosfonico e suoi sali, acido nitrilotrifosfonico e suoi sali, acido nitrilotriacetico e suoi sali; questi complessanti vengono normalmente utilizzati in quantità comprese tra 1 e 50 g/L in funzione del potere complessante di ciascuno di essi e ogni esperto del settore saprà riconoscere quale complessante à ̈ più opportuno usare e in quali quantità e combinazioni, in funzione della caratura desiderata nell'intervallo 12 – 18 carati. Complexing agents that may be appropriate to use to improve the stability of the metals in solution and to modulate their performance in the alloy are, for example, ethylenediaminetetraacetic acid and its salts, editronic acid and its salts, ethylenediamino tetramethyl phosphonic acid and its salts, nitrilotrifosphonic acid and its salts, nitrilotriacetic acid and its salts; these complexing agents are normally used in quantities between 1 and 50 g / L depending on the complexing power of each of them and every expert in the sector will be able to recognize which complexing agent is more appropriate to use and in what quantities and combinations, depending on the desired weight. in the range 12 - 18 carats.
Un'azione sia complessante che di regolazione dei metalli in lega à ̈ svolta dalla componente amminica del bagno. A complexing and regulating action of the alloying metals is performed by the amine component of the bath.
In particolare si à ̈ trovato che alcuni tipi di ammine consentono una più fine regolazione della percentuale di Indio in lega. In particular, it has been found that some types of amines allow a finer regulation of the percentage of Indium in the alloy.
In particolare, le ammine utili a questo scopo sono la trietilentetrammina e la dietilentetrammina ma possono assolvere allo stesso ruolo anche altre ammine organiche quali la etilendiammina, la tetraetilenpentaammina e altre ammine con struttura similare. L'ammina in questione viene usata in quantità che variano dai 0,05 a 1 g/L, e più proficuamente da 0,1 a 0,7 g/L, a seconda della percentuale di Indio in lega desiderata, all'interno dell'intervallo di caratura 12 – 18 carati. In particular, the amines useful for this purpose are triethylenetetramine and diethylenetetramine but other organic amines such as ethylenediamine, tetraethylenepentaamine and other amines with similar structure can also perform the same role. The amine in question is used in quantities ranging from 0.05 to 1 g / L, and more profitably from 0.1 to 0.7 g / L, depending on the percentage of Indium in the alloy desired, within the 'carat range 12 - 18 carats.
Il bagno può inoltre ovviamente contenere altri componenti abitualmente utilizzati nei processi galvanici per la loro azione brillantante e tensioattiva. The bathroom can also obviously contain other components usually used in galvanic processes for their brightening and surfactant action.
In particolare, per l'azione brillantante risulta opportuno aggiungere elementi quali argento, cobalto, tellurio, selenio, bismuto, nella forma tale da risultare solubile e stabile nella condizioni di lavoro; le quantità da impiegare sono comprese tra 0,005 a 0,2 g/L di elemento come tale, e più in particolare tra 0,010 a 0,1 g/L. In particular, for the brightening action it is appropriate to add elements such as silver, cobalt, tellurium, selenium, bismuth, in such a form as to be soluble and stable in the working conditions; the quantities to be used are between 0.005 and 0.2 g / L of element as such, and more particularly between 0.010 and 0.1 g / L.
I tensioattivi hanno azione sia brillantante sia surfattante, e sono impiegati in questa invenzione quelli normalmente utilizzati nell'ambito galvanico in bagni aventi matrici di questo tipo: la persona esperta dell'arte saprà individuare la tipologia più opportuna da impiegare; comunque le quantità utilizzate non sono mai superiori a 0,005 L/L di una loro soluzione acquosa al 10% p/v: dosi superiori abbassano l'efficienza del bagno e creano interferenza con l'andamento regolare dei metalli in lega. The surfactants have both a brightening and a surfactant action, and those normally used in the galvanic field in baths having matrices of this type are used in this invention: the person skilled in the art will be able to identify the most suitable type to be used; however, the quantities used are never higher than 0.005 L / L of their aqueous solution at 10% w / v: higher doses lower the efficiency of the bath and create interference with the regular trend of the alloying metals.
Il bagno lavora preferibilmente in un intervallo di pH compreso tra 7 e 12, e più opportunamente tra 8 e 10; il pH à ̈ regolato con gli acidi organici appartenenti alla coppia tampone scelta, o con acidi minerali come l'acido solforico, fosforico, solfammico, metansolfonico, piridinsolfonico, oppure con idrossidi di metalli alcalini, come potassio e sodio. The bath preferably works in a pH range between 7 and 12, and more conveniently between 8 and 10; the pH is regulated with organic acids belonging to the chosen buffer pair, or with mineral acids such as sulfuric, phosphoric, sulfamic, methanesulfonic, pyridin sulphonic acid, or with alkali metal hydroxides, such as potassium and sodium.
Il pH non à ̈ un parametro critico in questa formulazione per l'ottenimento di una caratura precisa, ma à ̈ fondamentale che il pH sia alcalino per la stabilità dei componenti in soluzione. The pH is not a critical parameter in this formulation for obtaining a precise carat, but it is essential that the pH is alkaline for the stability of the components in solution.
La temperatura di lavoro del bagno galvanico in questione à ̈ preferibilmente tra 50°C e 70°C; pur non essendo un parametro critico per l'ottenimento di una caratura precisa. The working temperature of the galvanic bath in question is preferably between 50 ° C and 70 ° C; although it is not a critical parameter for obtaining a precise carat weight.
La corrente da applicare al bagno galvanico secondo l'invenzione à ̈ normalmente compresa fra 0,3 - 2 A/dmq, preferibilmente 0,5 - 1,5 A/dmq. The current to be applied to the galvanic bath according to the invention is normally between 0.3 - 2 A / dmq, preferably 0.5 - 1.5 A / dmq.
I tempi di applicazione variano in base all'amperaggio imposto e dello spessore desiderato: con il bagno secondo l'invenzione à ̈ possibile ottenere depositi aventi spessore fino a 500 micron. The application times vary according to the amperage imposed and the desired thickness: with the bath according to the invention it is possible to obtain deposits having a thickness of up to 500 microns.
Variando opportunamente la corrente applicata si possono ottenere leghe di diversa caratura e colore in quanto aumenti di corrente applicata provocano la diminuzione dell'Oro in lega e aumento del Rame, quindi carature più basse e colori più tendenti al rosso, viceversa diminuzioni della corrente applicata provocano l'aumento dell'Oro in lega e quindi carature più alte e colori più tendenti al giallo. By suitably varying the applied current, alloys of different carats and colors can be obtained as increases in applied current cause a decrease in the gold in the alloy and an increase in copper, therefore lower carats and colors more tending to red, vice versa decreases in the applied current cause the increase of gold in alloy and therefore higher carats and more yellowish colors.
E' quindi possibile ottenere ogni percentuale intermedia nell'intervallo 12 – 18 carati in modo preciso impostando la corrente opportuna. It is therefore possible to obtain every intermediate percentage in the 12 - 18 carat range precisely by setting the appropriate current.
Utilizzando i bagni come sopra descritti si ottengono per deposito al catodo della cella galvanica leghe di oro in cui l'oro varia dal 50% al 75% (percentuali espresse in peso). Esempio Using the baths as described above, gold alloys are obtained by depositing at the cathode of the galvanic cell in which the gold varies from 50% to 75% (percentages expressed by weight). Example
Fu preparato un bagno avente la seguente composizione: A bath was prepared having the following composition:
Acido citrico: 50 g/ Citric acid: 50 g /
Potassio Citrato: 120 g/L Potassium Citrate: 120 g / L
EDTA tetrasodico: 30 g/L Tetrasodium EDTA: 30 g / L
Oro: 1,2 g/L come metallo, immesso come potassio dicianoaurato Gold: 1.2 g / L as metal, entered as potassium dicyanoaurate
Rame: 0,7 g/L come metallo, immesso come rame solfato Copper: 0.7 g / L as metal, entered as copper sulphate
Indio: 0,3 g/L come metallo, immesso come indio solfato Indium: 0.3 g / L as metal, entered as indium sulfate
Etilendiammina 0,2 mL/L come sostanza pura, immessa come soluzione acquosa 50% p/v Argento 0,05 g/L come metallo, immesso come sale argento cianuro 80,6% Ethylenediamine 0.2 mL / L as pure substance, entered as aqueous solution 50% w / v Silver 0.05 g / L as metal, entered as 80.6% silver cyanide salt
Il bagno fu portato a pH 8,5 con potassio idrossido, e scaldato a 60°C. The bath was brought to pH 8.5 with potassium hydroxide, and heated to 60 ° C.
Ad una piastrina di ottone nichelato avente superficie 0,5 dmq, opportunamente sgrassata e risciascquata con acqua deionizzata, fu applicata una corrente di 0,7 A/dmq per 3 minuti. Al termine del tempo, la lastrina fu sciacquata con acqua deionizzata ed asciugata con aria compressa. A current of 0.7 A / dmq for 3 minutes was applied to a nickel-plated brass plate having a surface of 0.5 dmq, suitably degreased and rinsed with deionized water. At the end of the time, the plate was rinsed with deionized water and dried with compressed air.
Le coordinate di colore misurate secondo i parametri CIELab furono i seguenti: L= 79,2 a= 1,8 b= 13,6 The color coordinates measured according to the CIELab parameters were the following: L = 79.2 a = 1.8 b = 13.6
La lega fu analizzata superficialmente tramite microscopio a scansione elettronica; furono trovate le seguenti percentuali: The alloy was superficially analyzed by means of a scanning electron microscope; the following percentages were found:
Au: 58% In: 8% Cu: 34% Au: 58% In: 8% Cu: 34%
Corrispondenti ad una lega definibile 14 carati. Corresponding to a definable 14 carat alloy.
Claims (8)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT000103A ITFI20120103A1 (en) | 2012-06-01 | 2012-06-01 | GALVANIC BATHROOMS FOR THE ACHIEVEMENT OF A LEAGUE OF LOW-CARATHED GOLD AND GALVANIC PROCESS THAT USES THESE BATHROOMS. |
| EP13170067.6A EP2669407B1 (en) | 2012-06-01 | 2013-05-31 | Galvanic baths for obtaining a low-carat gold alloy, and galvanic process that uses said baths |
| ES13170067T ES2918576T3 (en) | 2012-06-01 | 2013-05-31 | Galvanic baths to obtain a low-carat gold alloy and galvanic process that uses said baths |
| PT131700676T PT2669407T (en) | 2012-06-01 | 2013-05-31 | Galvanic baths for obtaining a low-carat gold alloy, and galvanic process that uses said baths |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT000103A ITFI20120103A1 (en) | 2012-06-01 | 2012-06-01 | GALVANIC BATHROOMS FOR THE ACHIEVEMENT OF A LEAGUE OF LOW-CARATHED GOLD AND GALVANIC PROCESS THAT USES THESE BATHROOMS. |
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| Publication Number | Publication Date |
|---|---|
| ITFI20120103A1 true ITFI20120103A1 (en) | 2013-12-02 |
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| IT000103A ITFI20120103A1 (en) | 2012-06-01 | 2012-06-01 | GALVANIC BATHROOMS FOR THE ACHIEVEMENT OF A LEAGUE OF LOW-CARATHED GOLD AND GALVANIC PROCESS THAT USES THESE BATHROOMS. |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2669407B1 (en) |
| ES (1) | ES2918576T3 (en) |
| IT (1) | ITFI20120103A1 (en) |
| PT (1) | PT2669407T (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016020812A1 (en) * | 2014-08-04 | 2016-02-11 | Nutec International Srl | Electrolytic bath, electrolytic deposition method and item obtained with said method |
| EP2990507A1 (en) * | 2014-08-25 | 2016-03-02 | ATOTECH Deutschland GmbH | Composition, use thereof and method for electrodepositing gold containing layers |
| US20160145756A1 (en) * | 2014-11-21 | 2016-05-26 | Rohm And Haas Electronic Materials Llc | Environmentally friendly gold electroplating compositions and methods |
| CN109504991B (en) * | 2019-01-21 | 2020-08-07 | 南京市产品质量监督检验院 | Cyanide-free 18k gold electroforming solution, and preparation method and application thereof |
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| US3174918A (en) * | 1961-01-24 | 1965-03-23 | Sel Rex Corp | Bright gold electroplating |
| US3878066A (en) * | 1972-09-06 | 1975-04-15 | Manfred Dettke | Bath for galvanic deposition of gold and gold alloys |
| US3883409A (en) * | 1972-07-10 | 1975-05-13 | Degussa | Gold alloy electroplating bath |
| GB2028873A (en) * | 1978-08-31 | 1980-03-12 | Lea Ronal Uk Ltd | Gold Alloy Electroplating Bath and Method |
| JP2000319794A (en) * | 1999-04-28 | 2000-11-21 | Seiko Corp | Plating film, ornaments having the same and production of plating film |
| US6165342A (en) * | 1996-07-23 | 2000-12-26 | Degussa Huls Aktiengesellschaft | Cyanide-free electroplating bath for the deposition of gold and gold alloys |
| WO2009037180A1 (en) * | 2007-09-21 | 2009-03-26 | G. Aliprandini | Method of obtaining a yellow gold alloy coating by electroplating without the use of toxic metals or metalloids |
| EP2135972A1 (en) * | 2007-03-02 | 2009-12-23 | Citizen Tohoku Co., Ltd. | Gold alloy coating, gold alloy coating clad laminate and gold alloy coating clad member |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4088549A (en) * | 1976-04-13 | 1978-05-09 | Oxy Metal Industries Corporation | Bright low karat silver gold electroplating |
| DE3020765A1 (en) | 1980-05-31 | 1981-12-10 | Degussa Ag, 6000 Frankfurt | ALKALINE BATH FOR GALVANIC DEPOSITION OF LOW-CARAINE PINK TO YELLOW-COLORED GOLD ALLOY LAYERS |
| DE3309397A1 (en) | 1983-03-16 | 1984-09-20 | Degussa Ag, 6000 Frankfurt | ELECTROLYTIC BATH FOR DEPOSITING LOW-CARAE, GLOSSY GOLD-SILVER ALLOY COATINGS |
| GB8501245D0 (en) * | 1985-01-18 | 1985-02-20 | Engelhard Corp | Gold electroplating bath |
| CH662583A5 (en) | 1985-03-01 | 1987-10-15 | Heinz Emmenegger | GALVANIC BATH FOR THE ELECTROLYTIC DEPOSITION OF GOLD-COPPER-CADMIUM-ZINC ALLOYS. |
| US5085744A (en) | 1990-11-06 | 1992-02-04 | Learonal, Inc. | Electroplated gold-copper-zinc alloys |
| SG127854A1 (en) * | 2005-06-02 | 2006-12-29 | Rohm & Haas Elect Mat | Improved gold electrolytes |
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2012
- 2012-06-01 IT IT000103A patent/ITFI20120103A1/en unknown
-
2013
- 2013-05-31 ES ES13170067T patent/ES2918576T3/en active Active
- 2013-05-31 EP EP13170067.6A patent/EP2669407B1/en active Active
- 2013-05-31 PT PT131700676T patent/PT2669407T/en unknown
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3174918A (en) * | 1961-01-24 | 1965-03-23 | Sel Rex Corp | Bright gold electroplating |
| US3883409A (en) * | 1972-07-10 | 1975-05-13 | Degussa | Gold alloy electroplating bath |
| US3878066A (en) * | 1972-09-06 | 1975-04-15 | Manfred Dettke | Bath for galvanic deposition of gold and gold alloys |
| GB2028873A (en) * | 1978-08-31 | 1980-03-12 | Lea Ronal Uk Ltd | Gold Alloy Electroplating Bath and Method |
| US6165342A (en) * | 1996-07-23 | 2000-12-26 | Degussa Huls Aktiengesellschaft | Cyanide-free electroplating bath for the deposition of gold and gold alloys |
| JP2000319794A (en) * | 1999-04-28 | 2000-11-21 | Seiko Corp | Plating film, ornaments having the same and production of plating film |
| EP2135972A1 (en) * | 2007-03-02 | 2009-12-23 | Citizen Tohoku Co., Ltd. | Gold alloy coating, gold alloy coating clad laminate and gold alloy coating clad member |
| WO2009037180A1 (en) * | 2007-09-21 | 2009-03-26 | G. Aliprandini | Method of obtaining a yellow gold alloy coating by electroplating without the use of toxic metals or metalloids |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2669407B1 (en) | 2022-03-30 |
| ES2918576T3 (en) | 2022-07-19 |
| PT2669407T (en) | 2022-06-28 |
| EP2669407A1 (en) | 2013-12-04 |
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