GB2195660A - Process for galvanic deposition of low-carat gold/copper/zinc alloys - Google Patents
Process for galvanic deposition of low-carat gold/copper/zinc alloys Download PDFInfo
- Publication number
- GB2195660A GB2195660A GB08717937A GB8717937A GB2195660A GB 2195660 A GB2195660 A GB 2195660A GB 08717937 A GB08717937 A GB 08717937A GB 8717937 A GB8717937 A GB 8717937A GB 2195660 A GB2195660 A GB 2195660A
- Authority
- GB
- United Kingdom
- Prior art keywords
- zinc
- alkali
- electrolyte
- acids
- copper
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000010949 copper Substances 0.000 title claims abstract description 17
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 15
- 239000010931 gold Substances 0.000 title claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 230000008021 deposition Effects 0.000 title claims abstract description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 6
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 52
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 52
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 239000013522 chelant Substances 0.000 claims abstract description 22
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 19
- 239000000956 alloy Substances 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000002585 base Substances 0.000 claims abstract description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000007792 addition Methods 0.000 claims abstract description 3
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 238000007127 saponification reaction Methods 0.000 claims description 4
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 description 1
- DDHUNHGZUHZNKB-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diamine Chemical compound NCC(C)(C)CN DDHUNHGZUHZNKB-UHFFFAOYSA-N 0.000 description 1
- SNDGSXYUWAVQDK-UHFFFAOYSA-N 3-azaniumylpropylazanium;diacetate Chemical compound CC(O)=O.CC(O)=O.NCCCN SNDGSXYUWAVQDK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000337 buffer salt Substances 0.000 description 1
- RGTXVXDNHPWPHH-UHFFFAOYSA-N butane-1,3-diamine Chemical compound CC(N)CCN RGTXVXDNHPWPHH-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- -1 zinc salt compounds Chemical class 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
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)
Abstract
A process for the galvanic deposition of low-carat gold/copper/zinc alloys from an electrolyte, which contains gold as alkali-gold cyanide, copper as alkali-copper cyanide, zinc as alkali-zinc chelate together with additional alkali cyanide, but is free from any complex alkali-zinc cyanide. Additions are made to the electrolyte, in at least stoichiometric proportions relative to zinc, of zinc chelate formers based on substituted or unsubstituted aliphatic single- or multi-base aminocarboxylic acids and/or based on substituted or unsubstituted aliphatic single- or multi-base aminophosphonic acids and/or salts thereof. Use is made of an electrolyte containing at least one zinc chelate former having two functional amino- groups, at least one of which is not alkylated up to the tertiary amine state. An intrinsically bright alloy deposit is obtained without additional brighteners.
Description
SPECIFICATION
Process for galvanic deposition of low-carat gold/copper/zinc alloys
This invention relates generically to a process for the galvanic deposition of low-carat gold/copper/zinc alloys from an electrolyte, which contains gold as alkali-gold cyanide, copper as alkalicopper cyanide, zinc as alkali-zinc chelate together with additional alkali cyanide, but is free from any complex alkali-zinc cyanide, in which additions are made to the electrolyte, in at least stoichiometric proportions relative to zinc, of zinc chelate formers based on substituted or unsubstituted aliphatic single- or multi-base aminocarboxylic acids and/or based on substituted or unsubstituted aliphatic single- or multi-base aminophosphonic acids and/or salts thereof.
In a known process of this type (DE-OS 33 45 795), the amino-groups of the zinc chelate formers are alkylated up to the tertiary amine state. In this way, it is possible to deposit galvanically alloys with usually very low zinc concentrations barely reaching about 0.5 wt.%. To obtain a bright deposit, it is necessary within the known process features to provide additional brighteners.
Consequently, at substantial deposit thicknesses the deposit develops stresses which can lead to damaging tearing and exfoliation.lts ductility is unsatisfactory.
The object of the invention is to modify the generic process so that an intrinsically bright deposit can be obtained without additional brighteners.
According to the present invention the electrolyte contains at least one zinc chelate former having two functional amino-groups, at least one of which is not alkylated up to the tertiary amine state, the amounts of this zinc cheiate former and of zinc ions in the electrolyte being selected so that the amount of zinc deposited produces a bright alloy deposit.
The zinc content incorporated in the galvanic deposit is preferably between 0.5 and 6 wt.%, and the electrolyte preferably contains at least one zinc chelate former having two functional amino-groups, in at least stoichiometric proportions relative to the zinc content of the electrolyte, neither of which is alkylated up to the tertiary amine state. "Incorporated" means "dissolved in the alloy", since at extreme zinc contents grey giitter can otherwise develop in the galvanic deposit. In general, the process of the invention requires chelate-bonded zinc concentrations lower than 6 g/l, when working at cathode current densities of about 1 A/dm2.In spite of these low zinc concentrations in the electrolyte, zinc is surprisingly incorporated in the deposit in amounts exceeding 0.5 and up to 10 wt.%, i.e., the zinc is dissolved in the alloy without producing a grey glitter of merely deposited but not dissolved zinc. These zinc concentrations suffice to produce an intrinsically bright alloy without the use of additional brighteners, provided that the articles on which the alloy is deposited are vigorously agitated. The deposit does not develop the damaging internal streeses to which the brighteners used in the known process contribute. It is highly ductile. The gold in the alloy can be very extensively replaced by copper.
Even extremely low-carat alloys can be deposited by the process of the invention. The copper and zinc contents naturally influence the colour of the deposit.
The process of the invention can be refined and optimised by a variety of detailed means. The process can be carried out at very high deposition rates when the zinc chelate former and the zinc together form a 6-member coordination ring complex and a 5-member, or better another 6member, salt ring complex.
The deposition rate in this case can attain, for example, 75 to 80 mg of 18-ct alloy per ampere-minute (A-min.). If lower deposition rates are acceptable, use can be made of an electrolyte in which the zinc chelate former and the zinc together form a 5-member coordination ring complex and a 5- or 6-member salt ring complex. Since larger amounts of free alkali cyanide are needed to form intrinsically bright deposits, the maximum deposition rate is only, for example, 55 to 65 mg of 20-ct alloy per A-min. It is self-evident that within the scope of the invention one could alternatively form the zinc chelate former by the complicated method of saponification within the electrolyte. Zinc chelate formers which are particularly suited to the process of the invention are specified in Claim 6 and will now be discussed in more detail.For the sake of clarity, the substances will be split up into a group of specific unsubstituted or substituted aliphatic amino-groups and separately into a group of specific unsubstituted and substituted functional aliphatic acid-groups.
6-member zinc coordination compounds as examples
al) 1, 3 propanedi3Fn N ~ CH2 - CH2 - CK2; N a2) 1 ,3-butanediamine-@ to be understood as:
(1-methyl) - 1,3-propanediamine-...
CH2-CH2-CH-CH3 \zn2+ a3) propanoldiamine-... to be understood as:
(2-hydroxy) - 1,3 - propanediamine I I - CH2 - CHOH Zinc Example al) is preferred since it is readily available. It is self-evident that the substitutions on the C-atoms can be many and varied, such as for example 2,2-dimethyl-1,3-propanediamine-..
and so on.
5- and 6-member zinc salt compounds as examples
bi) .,.,..-acetic ac[d N Cm2 \ C#2 I N \ zn2+ b2)
.0... .-2-propionic acid H C - CH \ V I n b3)
--butyrIc acid I H5C2-CH C=O O ~ ~ b4)
0O .-2-valerianic acid N H7 C3- C1H\ C- zt2+ b5)
... . .-2-chlor0acetic acid N Ct - CH c=o b Xz"2+ b6)
....'-2,2-chlorpropionic acid NN H3C - I - Cts c=o b7)
....metl1ylenephosphonsc acid I CH I 2 \\ P\=O Z zn2+2+ ,c' HO O' b8)
.... 3-propionic acid I CH2 CH2 C=O o b9)
g ....-3- butyric acid I-DULY H, - CH CIH2 I, 0 b10)
....-3-velerianle acid I Hscz rH Zn2+ 0H2 C=O ,' ~0, b11)
... .3- (2-rnethyl)-propionic acid 7112+ CH2 o' I H30-tH C= 0/ OZ b12)
;...-ethylenephosphonlc the enephosphonic acid Ns C1H2 CH2 ',,"Zn2+ p=o HO The scope for substitutions at the acid groups can clearly be widened still further. Thus for example chlorine atoms can be replaced by bromine or iodine atoms. Moreover, polymerisation across halogen atoms cannot be excluded. Diamines can be simultaneously alkylated with different acid groups, though naturally this is very complicated. It is further obvious that during the production of these partially alkylated chelate formers statistical distributions of -mono-, -di- and -tri- acids can occur.However, the target in every case is the -di- acid, for example like:
1,3-propanediaminediacetic acid
1,3-propanediaminebis-(2-propionic acid)
1,3-propanediamine bis-(3-propionic acid) or, as an example of two different acid groups, 1 ,3-propanediamine-monoacetic acid-mono-(2propionic acid), or their respective alkali salts or mixtures of different substances. The number of varients is increased still further by the numerous isomerisation possibilities.
Also within the scope of the invention are substances which upon saponification with alkali are converted to the above-mentioned compounds or their alkali salts, since they are finally used in an alkaline electrolyte. In this connection, mention can be made of substances having acid amide-, acid imide-, acid halide-, acid ester- or nitrile residues, such for example as 1,3propanediaminediacetonitrile. Their use would be very costly, however, since saponification in electrolytes is very time-consuming, but must reach completion to ensure stable conditions in the electrolyte.
It is further advantageous to add conduction and/or buffer salts to the electrolyte, phosphates being particularly preferred because of the working pH range.
The following examples will illustrate the invention:
1) 11 g nitrilotriacetic acid
12 g 1 ,3-propanediamine diacetic acid
30 g dipotassium hydrogen phosphate.3H20
2.5 g zinc oxide, 80 % Zn
20 g copper cyanide, 70 % Cu
42-43 g potassium cyanide
8.2 g potassium-gold cyanide, 67 % Au
1 ml wetting agent (phosphoric acid ester)
potassium hydroxide to obtain a pH value of
9.92 at a working temperature of 65"C water
to obtain 1 litre of electrolyte
cathode current density 1 A/dm2
platinised titanium anodes
work agitated
A polished brass plate attains a bright yellowish, slightly green-flecked alloy deposit. The deposition rate was found to be about 75.8 mg of alloy per A-min.. The deposit analysed:
86 % Au, 9.6 % Cu, 4.4 % Zn (20.64 carat).
2) 11 g nitrilotriacetic acid
12 g propanediaminebis-(3-propionic acid)
30 g dipotassium hydrogen phosphate.3H20
2.5 g zinc oxide, 80 % Zn
34.3 g copper cyanide, 70 % Cu
62-63 g potassium cyanide
7.9 g potassium-gold cyanide, 67 % Au
1 ml wetting agent (phosphoric acid ester)
potassium hydroxide to obtain a pH value of
9.76 at a working temperature of 70"C
otherwise as Example 1.
A polished brass plate acquires a bright and ductile deposit of pinkish colour. The deposition rate was found to be about 60.5 mg of alloy per A-min.. The deposit analysed: 52.5 % Au, 45.2 % Cu, 2.3 % Zn (12.6 carat).
A comparison of Examples 1 and 2 brings out the influence of the various acid residues from the partially aikylated zinc chelate former on the alloy composition. At the same zinc concentration in the electrolyte, the zinc content of the alloy is almost halved. By providing a higher copper concentration in the electrolyte, gold is extensively replaced by copper to obtain very low-carat alloys.
Claims (7)
1. A process for the galvanic deposition of low-carat gold/copper/zinc alloys from an electrolyte, which contains gold as alkali-gold cyanide, copper as alkali-copper cyanide, zinc as alkalizinc chelate together with additional alkali cyanide, but is free from any complex alkali-zinc cyanide, in which additions are made to the electrolyte, in at least stoichiometric proportions relative to zinc, of zinc chelate formers based on substituted or unsubstituted single- or multibase aminocarboxylic acids and/or based on substituted or unsubstituted aliphatic single- or multi-base aminophosphonic acids and/or salts thereof, and in which the electrolyte contains at least one zinc chelate former having two functional amino-groups, at least one of which is not alkylated up to the tertiary amine state, the amounts of this zinc chelate former and of zinc ions in the electrolyte being selected so that the amount of zinc deposited products a bright alloy deposit.
2. A process as in Claim 1, wherein the zinc content incorpoated in the galvanic deposit is between 0.5 and 10 wt.%.
3. A process as in Claim 1 or Claim 2, wherein the electrolyte contains at least one zinc chelate former in which neither amino-group is alkylated up to the tertiary amine state.
4. A process as in any one of Claims 1 to 3, wherein the zinc chelate former and the zinc together form a 6-member coordination ring complex and a 5-member, or 6-member, salt ring complex.
5. A process as in any one of Claims 1 to 4, wherein the zinc chelate former is formed in the electrolyte by saponification.
6. A process as in any one of Claims 1 to 5, wherein the zinc chelate former is a member of the group comprising substituted and unsubstituted propandiaminemonocarboxylic acids, propanediaminedicarboxylic acids, propanediaminetricarboxylic acids, substituted and unsubstituted propandiaminemonophosphonic acids, propanediaminediphosphonic acids, propanediaminetriphosphonic alloys, corresponding substituted and unsubstituted propandiaminecarboxyphosphonic acids, alkali salts of the abovementioned substances, isomeric forms of the abovementioned substances, and mixtures of the abovementioned substances.
7. A process for the galvanic deposition of low-carat gold/copper/zinc alloys substantially as hereinbefore described with reference to the examples.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19863633529 DE3633529A1 (en) | 1986-10-02 | 1986-10-02 | METHOD FOR GALVANICALLY DEPOSITING LOW CARA GOLD / COPPER / ZINC ALLOYS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8717937D0 GB8717937D0 (en) | 1987-09-03 |
| GB2195660A true GB2195660A (en) | 1988-04-13 |
Family
ID=6310882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08717937A Withdrawn GB2195660A (en) | 1986-10-02 | 1987-07-29 | Process for galvanic deposition of low-carat gold/copper/zinc alloys |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS6389694A (en) |
| DE (1) | DE3633529A1 (en) |
| FR (1) | FR2604730A1 (en) |
| GB (1) | GB2195660A (en) |
| IT (1) | IT1222608B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5085744A (en) * | 1990-11-06 | 1992-02-04 | Learonal, Inc. | Electroplated gold-copper-zinc alloys |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH714243B1 (en) * | 2006-10-03 | 2019-04-15 | Swatch Group Res & Dev Ltd | Electroforming process and part or layer obtained by this method. |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3345795A1 (en) * | 1983-12-17 | 1985-07-04 | LPW-Chemie GmbH, 4040 Neuss | ELECTROLYTE FOR GALVANIC DEPOSITION OF LOW-CARAE GOLD-COPPER-ZINC ALLOYS |
-
1986
- 1986-10-02 DE DE19863633529 patent/DE3633529A1/en not_active Withdrawn
-
1987
- 1987-07-29 GB GB08717937A patent/GB2195660A/en not_active Withdrawn
- 1987-09-04 FR FR8712324A patent/FR2604730A1/en not_active Withdrawn
- 1987-09-07 IT IT21821/87A patent/IT1222608B/en active
- 1987-10-02 JP JP62248206A patent/JPS6389694A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5085744A (en) * | 1990-11-06 | 1992-02-04 | Learonal, Inc. | Electroplated gold-copper-zinc alloys |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3633529A1 (en) | 1988-05-19 |
| IT8721821A0 (en) | 1987-09-07 |
| GB8717937D0 (en) | 1987-09-03 |
| JPS6389694A (en) | 1988-04-20 |
| IT1222608B (en) | 1990-09-05 |
| FR2604730A1 (en) | 1988-04-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |