GB2306508A - Gold-iron alloy electroplating processes compositions and deposits - Google Patents
Gold-iron alloy electroplating processes compositions and deposits Download PDFInfo
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- GB2306508A GB2306508A GB9522997A GB9522997A GB2306508A GB 2306508 A GB2306508 A GB 2306508A GB 9522997 A GB9522997 A GB 9522997A GB 9522997 A GB9522997 A GB 9522997A GB 2306508 A GB2306508 A GB 2306508A
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- 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
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- 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
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Abstract
An electrodeposit free of cobalt, cadmium and nickel contains 1.25 to 1.55% w/w iron, 1 to 2 ppm zirconium; and 97.7 to 98.2% gold and has a pale yellow colour less than 3N on the NIHS scale. This deposit is produced from an electroplating bath, free of cobalt, cadmium and nickel comprising gold, as cyanide, iron as a soluble salt or complex, a soluble zirconium salt or complex, a citrate, a weak acid, and optionally a heterocyclic sulphonate, which in a preferred form comprises gold as cyanide in an amount of 2.5 to 3.5 g/l gold, iron as iron nitrate in an amount of 0.6 to 0.8 g/l, zirconium as zirconium nitrate in an amount of 0.2 to 0.5 g/l, diammonium hydrogen citrate in an amount of 75 to 125 g/l, citric acid in an amount of 40 to 80 g/l, and 3-(1-pyridino)-1-propane sulphonate in an amount of 1 to 3 g/l.
Description
ELECTROPLATING PROCESSES
COMPOSITIONS AND DEPOSITS
The present invention relates to gold-iron alloy electroplating processes, compositions for use therein and gold-iron alloy electrodeposits produced therefrom.
Gold alloy electrodeposits are extensively used for decorative and functional deposits. Gold alloys with copper, cadmium, cobalt, indium, zinc or tin or mixtures thereof are well known. Examples of patent literature giving details of such compositions revealed by searches by the applicants are JP 53-58023 (Matsushita), JP 5156241 (Citizen Watch), DE 1696087 (OMF), US 3926748 (AMP), GB 1445395 (Schering), GB 1375611 (Lea-Ronal), GB 1279141 (Degussa), GB 2151661 (LPW-Chemie) , EP 193848 (Emmenegger), US 4470886 (OMI), US 2724687 (Spreter), JP 57-120686 (Suwa Seikosha), JP 57-120685 (Suwa Seikosha), JP 56-136994 (Nippon Mining), JP 56-105494 (Nippon
Mining) and EP 140832 (H.E. Finishing).
An article in Galvanotechnik vol 83 (1992) pp 808817 and 1180-1184 by F. Simon mentions gold-iron electroplating using cyanide baths. It refers to gold cyanide complex baths containing cobalt, nickel, indium, iron (it is not clear whether these are present together or separately) in a weak acid bath at pH 3 - 6.
Gold-iron baths have the advantage of not inducing allergic reactions in contact with skin such as can be caused by gold alloys containing nickel or cobalt, and do not contain cadmium which is a toxic metal.
It is very desirable to use gold alloy electrodeposits which do not contain nickel or cobalt for skin contacting products, such as rings and spectacle frames.
Gold-iron alloy electrodeposits however are thought to be brittle and to be liable to crack damaging the corrosion resistance of the product. In addition they tend to be too warm a yellow for decorative uses and a paler colour is desired. Colour for gold alloy electrodeposits can be assessed on the (NIHS 03-50) standards scale. NIHS is Normes de l'industrie horlogere
Suisse or Swiss watch industry standards. This provides a colour scale ranging from 5N (red), via 4N (pink) to 3N, which is the too warm yellow colour of conventional gold-iron alloy electrodeposits, 2N-18 to 1N 14. The colours are made from gold-silver-copper alloys containing the following amounts for the relevant colours.
Colour SN 4N 3N 2N-18 1N-14 Ingredient gold 750 750 750 750 585 silver 45 90 125 100 265 copper 205 100 125 90 150
The NIHS 03-50 standard states that for gold articles the colour lN-14 is not obtainable for an alloy of more than 14 carats and for the colour 2N-18 for an alloy of more than 18 carats.
It is desired to produce a gold-iron alloy electrodeposit which has a colour of 2N-18 to lN-14 on the NIHS scale and which is free of cobalt, cadmium and nickel, and which has good corrosion resistance.
The applicants conducted extensive research to modify the colour of conventional gold-iron alloy deposits. These deposits contain 2.1W iron, 97.9k gold and have a colour of 3N(+).
Addition of zinc sulphate at from 50 - 200 mg/l gave a colour of 3N to 3N(+); at 300 mg/l the colour becomes too yellow-gray.
Addition of ammonium monovanadate at from 100 mg/l to 1500 mg/l only gave a colour of 3N.
Addition of cadmium acetate on its own or with diethylene triamine penta-acetic acid (DTPA) chelate only gave a colour of 3N.
Lead acted as a metallic impurity, only brown and matt deposits being produced.
Addition of vanadium (IV) oxidesulphate in amounts up to 150 mg/l only gave a colour of 3N to 3N(+).
Addition of ammonium bismuth citrate with DTPA only gave a colour of 3N to 3N(+).
Addition of sodium tungstate dihydrate at from 0.55 to 4.45 g/l of tungsten at current densities of 1 to 4
A/dm2 and at pH values from 3.5 to 4.45 only gave a colour of 3N.
Addition of 5 g/l of nicotinic acid allowed one to increase the current density to 4 A/dm2 without burnt deposits but the colour remained at 3N(+).
Bismuth and lead both acted as a metallic impurity and only brown and matt deposits were produced. Lead was added as lead nitrate. Bismuth was added as bismuth III nitrate pentahydrate.
Addition of potassium stannate 1 g/l at current densities of 1 to 3 A/dm2 only gave a colour of 3N(+).
Addition of cerium (III) nitrate hexahydrate at 1 g/l gave a colour of between 3N and 2N-18. Cerium (III) sulphate, cesium nitrate and cesium sulphate all had no effect on the colour of the deposit.
The applicants then tried addition of zirconium sulphate at 1 g/l at a current density of 1 A/dm2 at 320C and a pH of 3.14. This gave a deposit with a colour near 2N-18 but very slightly more grey.
EP-A-0193848 is concerned with gold-copper-cadmium zinc cyanide baths and refers to a number of inorganic brighteners. Baths B1 to B5 show the use of selenium as sodium selenite, arsenic as sodium arsenite and zirconium as the sodium zirconium hydroxy ethyl-imino-diacetate, as inorganic brighteners in B2-B5, no brighteners being used in B1.
Col. 13 1. 38-42 of EP-A-0193848 states that all these deposits are pale yellow and give a colour of approximately 1N-14. There is no teaching of any effect on colour produced by the presence of zirconium. Bath B2 contains zirconium as the inorganic brightener, bath B1 does not contain an inorganic brightener.
In addition it is extremely difficult to obtain a constant colour in the range lN-14 to 2N-18 with goldcopper-cadmium or gold-copper-cadmium-zinc systems.
According to the present invention an electrodeposit is provided which contains 1.25 to 1.55 k w/w iron, 1 to 2 ppm zirconium; and 97.7 to 98.2% gold and has a pale yellow colour less yellow than 3N on the NIHS scale, and preferably at or near 2N-18.
It will be recognised that such a deposit is also of high carat. It is preferred that the deposit be of 2323.6 carat.
The gold-iron-zirconium deposits of the present invention are free of toxic and allergy causing ingredients, have high carat values and corrosion resistance and at the same time a desirable pale yellow colour.
The invention also extends to an electroplating bath, desirably free of cobalt, cadmium or nickel comprising gold, as cyanide, iron as a soluble salt or complex, a soluble zirconium salt or complex, a citrate, a weak acid, and optionally a heterocyclic sulphonate such as PPS. The function of the PPS is to allow higher cathodic current densities and to improve the macrodistribution a little.
The gold is preferably present as gold potassium cyanide preferably in an amount of 1.0 to 10 g/l especially 2.5 to 3.5 g/l of gold.
The iron is preferably present as a nitrate which may be hydrated. It is preferably present in an amount up to 5 g/l of iron e.g. 0.1 to 5 g/l preferably 0.2 to 3 g/l especially 0.6 to 0.8 g/l. Different contents of iron in the plating bath do not affect the colour of the deposit significantly, but the more iron there is in the bath the more there is in the deposit. However at a currently density of 0.5 A/dm2 as the iron content of the bath increases from 0.25 g/l, at which the cathodic efficiency is 25 mg/A.min, to 2.0 g/l the cathodic efficiency falls to 7 mg/A.min.
Examples of other salts which may be used instead of iron nitrate are iron sulphate, iron (III) chloride, iron (III) citrate and iron (III) phosphate.
The zirconium is preferably present as the nitrate, which may be hydrated, or less conveniently as the sulphate or as ammonium zirconium citrate complex. The zirconium is preferably present in an amount of 0.01 to 2 g/l of zirconium e.g. 0.04 to 1.5 g/l or 0.1 to 1 g/l, especially 0.2 to 0.5 g/l.
The citrate is preferably diammonium hydrogen citrate (C6H14N207) or (NH4)2C6H607 and is preferably present in an amount of 10 to 500 g/l e.g. 50 to 200 g/l especially 75 to 125 g/l. Diammonium hydrogen citrate is preferred to sodium or potassium citrate because it gives much higher macrodistribution of the gold layer e.g. as high as 90% as shown by tests in a Haring cell, as compared with about 50% when sodium or potassium citrate is used.
The weak acid is preferably a hydroxy carboxylic acid such as citric acid (HO(COOH) (CH2COOH)2.H20, though other carboxylic acids such as oxalic, lactic, formic, thiomalic, gluconic, tartaric, acetic or malic acid could be used. Phosphoric acid could also be used instead of citric acid.
The weak acid is preferably present in an amount of 1 to 500 g/l e.g. 10 to 200 g/l e.g. 20 to 100 g/l especially 40 to 80 g/l.
The PPS is 3-(1-pyridino)-1-propane sulphonate (C8H11NO3S). It is preferably present in an amount of 0.1 to 10 g/l e.g. 0.5 to 5 g/l especially 1 to 3 g/l.
Materials which can be used instead of PPS include for example pyridine-4-ethanesulphonic acid.
The bath can be used to plate gold-iron-zirconium deposits directly on a range of substrates such as nickel undercoat, or one of the following when provided with a flash of pure gold, namely copper, palladium, palladiumnickel, palladium-cobalt, gold-silver or gold-coppercadmium.
The invention can be put into practice in various ways and a number of specific embodiments will be described to illustrate the invention with reference to the accompanying examples.
Example 1A, 1B and 1C
Examples 1A and 1B are comparison examples of a gold-iron acid plating bath which does not contain zirconium; Example 1C is in accordance with the invention. Details are given in Table 1 below.
Table 1
Example 1A 1B 1C
Ingredient
Gold g/l 3 3 4
as gold potassium 4.39 4.39 5.85
cyanide (1)
Iron g/l 0.72 0.72 0.72
as iron (III) nitrate 5.2 5.2 5.2
nonahydrate
Additional metal g/l
zirconium as zirconyl silicate - - < 0.5 (ZrSiO4)
as zirconyl nitrate
hydrate
Citrate g/l
diammonium hydrogen
citrate
sodium citrate dihydrate 40 40 49
potassium citrate
Weak Acid g/l
citric acid 60 60 60
Additive g/l
PPS (2)
Table 1 (cont'd)
Example 1A 1B
Bath properties
pH 3.5 3.5 3.5
density OBe (Baume) 8 8 8
Plating conditions
Temperature C 32 32 32
rack/barrel (3) R R R
current density A/dm2 1 0.5 2
plating time min 9 21 6
number of A/litre 0.2 0.2 0.4
anode - cathode ratio 4/1 4/1 4/1
agitation solution (4) 4A 4A 4A
agitation cathode (5) 7 7 7
cathode (6) brass brass brass
anode (7) PT PT PT
Plating performance
efficiency mg/A.min 19.5 16.2 14
plating rate mins/ 9 21 6
micrometer thick
ness of deposit
macrodistribution W (8) - - 38
DePosit characteristics
colour (NIHS) 3N+ 3N 2N18
thickness 1.0 1.0 1.0
Carat 23.5 23.5
hardness (Knoop) 140 140
Notes on Table 1 (1) Gold potassium cyanide is KAu(CN)2 (3) Rack plating is signified by R, barrel plating by B.
(2) PPS is 3- (1-pyridino) -1-propane-sulphonate (C8H1lNO3S).
(4) Agitation of the solution by vigorous stirring with a magnetic stirrer is signified by 4A.
(5) Agitation of the cathode by revolution of the cathode is given by the number of rpm of the cathode e.g. 7.
(6) The cathode is brass.
(7) The anode is platinized titanium.
(8) The term macrodistribution is concerned with the extent to which different samples on different parts of a plating jig or rack are coated to the same thickness using a current density of 1 A/dm2.
The Haring cell gives an indication of the macrodistribution. If the t value obtained is low (20-30% in this case) this means that there will be a large range of different deposit thicknesses for the different articles being plated. If the value is 80-90W this means that the deposit thickness on the articles will be more or less the same wherever they are on the jig.
The Haring cell consists of a rectangular plating cell having opposed end walls affording cathodes and a planar anode placed between them parallel to the cathode and dividing the cell unequally. The extent to which the cathodes are plated the same amount is assessed as the macrodistribution. If they are equally plated the macrodistribution is 100%.
Example 1C demonstrates that even a relatively insoluble zirconium salt can be used as a vehicle for introducing zirconium into the system. However more soluble salts are easier to work with and are preferred.
Example 2
This is in accordance with the present invention, details are given in Table 2 and give results at different current densities.
Table 2
Example 2A 2B 2C
Ingredient
Gold g/l 3.0 3.0 3.0
as gold potassium 4.39 4.39 4.39
cyanide
Iron g/l 0.72 0.72 0.72
as iron (III) nitrate 5.2 5.2 5.2
nonahydrate
Additional metal g/l
zirconium 0.27 0.27 0.27
as zirconyl silicate
(ZrSiO4)
as zirconyl nitrate 1.0 1.0 1.0
hydrate
Citrate g/l
diammonium hydrogen 100 100 100
citrate
sodium citrate
potassium citrate
Weak Acid g/l
citric acid 60 60 60
Additive g/l
PPS 2 2 2
Table 2 (cont'd)
Example 2A 2B 2C
Bath properties
pH 3.4 3.4 3.4
density OBe (Baume) 9 9 9
Plating conditions
Temperature OC 40 40 40
rack/barrel (3) R R R
current density A/dm2 2 1 3
plating time min 4'10" 6'10" 3'15"
number of A/litre 0.4 0.2 0.6
anode - cathode ratio 4/1 4/1 4/1
agitation solution (4) 4A 4A 4A
agitation cathode (5) 7 7 7
cathode (6) brass brass brass
anode (7) PT PT PT
Plating Performance
efficiency mg/A.min 21 29.0 18.2
plating rate mins/ 4'10" 6'10" 3'15"
micrometer thick
ness of deposit
macrodistribution % (8B) 90 59
(at 2A/dm2)
Deposit characteristics
colour (NIHS) 2N-18+/3N 3N 2N-18+
thickness
Carat 23.5 23.5 23.5
hardness (Knoop)
% iron 1.25 -
Table 2 (cont'd)
Example 2D 2E 2F
Inaredient
Gold g/l 3.0 3.0 2.0
as gold potassium 4.39 4.39 2.92
cyanide
Iron g/l 0.72 0.72 0.72
as iron (III) nitrate 5.2 5.2 5.2
nonahydrate
Additional metal g/l
zirconium 0.27 0.27 0.27
as zirconyl silicate - - (ZrSiO4)
as zirconyl nitrate 1.0 1.0 1.0
hydrate
Citrate g/l
diammonium hydrogen 100 100 100
citrate
sodium citrate
potassium citrate
Weak Acid g/l
citric acid 60 60 60
Additive g/l
PPS 2 2 2
Table 2 (cont'd)
Example 2D 2E 2F
Bath properties
pH 3.4 3.4 3.4
density OBe (Baume) 9 9 9
Plating conditions
Temperature OC 40 40 40
rack/barrel (3) R R R
current density A/dm2 4 5 2
plating time min 3'13" 3'13" 5'20"
number of A/litre 0.8 1.0 0.4
anode - cathode ratio 4/1 4/1 4/1
agitation solution (4) 4A 4A 4A
agitation cathode (5) 7 7 7
cathode (6) brass brass brass
anode (7) PT PT PT
Plating Derformance efficiency mg/A.min 12.6 11.1 16.8
plating rate min/ 3'13" 3'13" 5'20"
micrometer thick
ness of deposit
macrodistribution % (8B) - -
Deposit characteristics
colour (NIHS) 2N-18+ - 2N-18+/3N thickness
Carat 23.5 23.5 23.5
hardness (Knoop) k iron - - 1.25 Notes on Table 2
The anode/cathode ratio, solution agitation (4), cathode agitation (5), cathode material (6) and anode material (7) were as in Table 1.
(8B) The current density used for testing macrodistribution in Examples 2A to 2F was 2 A/dm2.
Heating a brass panel carrying the gold-iron-zirconium deposit (98.78 Au, 1.25% Fe, 2 ppm Zr) of Example 2A of the present invention for 2 hours at 2000C produced no detectable change in appearance, neither discolouration nor change incolour, and no cracking.
Example 3
Details are given in Table 3.
Table 3 Example 3A 3B
Ingredient
Gold g/l 4.0 4.0
as gold potassium 5.85 5.85
cyanide
Iron g/l 0.72 0.72
as iron (III) nitrate 5.2 5.2
nonahydrate
Additional metal g/l
zirconium
as zirconyl silicate
(ZrSiO4)
as zirconyl nitrate 0.2 1.0
hydrate
Citrate g/l
diammonium hydrogen
citrate
sodium citrate 48.75 48.75
potassium citrate
Weak Acid g/l
citric acid 60 60
Additive g/l
PPS
Table 3 (cont'd)
Example 3A 3B
Bath properties
pH 3.4 3.4
density OBe (Baume)
Plating conditions
Temperature OC 32 32
rack/barrel (3) R R
current density A/dm2 2 2
plating time min 435W 4'35"
number of A/litre 0.4 0.4
anode - cathode ratio 4/1 4/1
agitation solution (4) 4A 4A
agitation cathode (5) 7 7
cathode (6) brass brass
anode (7) PT PT
Plating performance
efficiency mg/A.min 19.10 19.10
plating rate mins/ 4'35" 4'35"
micrometer thick
ness of deposit
macrodistribution k (8) 38.5
Deposit characteristics
colour (NIHS) 2N18(+) 2N18(+)
thickness
Carat
hardness (Knoop)
Table 3 (con't)
Example 3C 3D 3E
Ingredient
Gold g/l 4.0 4.0 4.0
as gold potassium 5.85 5.85 5.85
cyanide
Iron g/l 0.72 0.72 0.72
as iron (III) nitrate 5.2 5.2 5.2 nonahydrat e Additional metal g/l
zirconium
as zirconyl silicate
(ZrSiO4)
as zirconyl nitrate 0.2 0.2 0.2
hydrate
Citrate g/l
diammonium hydrogen
citrate
sodium citrate 48.75 48.75 48.75
potassium citrate
Weak Acid g/l
citric acid 60 60 60
Additive g/l
PPS
Table 3 (cont'd)
Example 3C 3D 3E
Bath properties
pH 3.4 3.4 3.4
density OBe (Baume)
Platina conditions
Temperature OC 31 31 31
rack/barrel (3) R R R
current density A/dm2 0.5 1 2
plating time min 22' 9'50" 4'35"
number of A/litre 0.1 0.2 0.4
anode - cathode ratio 4/1 4/1 4/1
agitation solution (4) 4A 4A 4A
agitation cathode (5) 7 7 7
cathode (6) brass brass brass
anode (7) PT PT PT
Plating Derformance efficiency mg/A.min 15.7 17.9 19.1
plating rate mins/ 22' 9'50" 4'35 micrometer thick
ness of deposit
macrodistribution % (8) 38.5 38.5 38.5
Deposit characteristics
colour (NIHS) 2N18+ 2N18+ 2N18+
thickness
Carat
hardness (Knoop)
Notes on Table 3
The anode/cathode ratio, solution agitation (4), cathode agitation (5), cathode material (6) and anode material (7) were as in Table 1.
Example 4
In these examples the effects of varying the additive and the citrate was tested. Details are given in Table 4. The tests were done in a Haring cell.
In addition the tests were done on 7 nickel plated rings and 8 palladium plated rings which were rack plated.
Table 4
Example 4A 4B
Ingredient
Gold g/l 4 4
as gold potassium 5.85 5.85
cyanide
Iron g/l 0.72 0.72
as iron (III) nitrate 5.2 5.2
nonahydrate
Additional metal g/l
zirconium 0.054 0.054
as zirconyl silicate
(ZrSiO4)
as zirconyl nitrate 0.2 0.2
hydrate
Citrate g/l
diammonium hydrogen
citrate
sodium citrate 48.75 48.75
potassium citrate
Weak Acid g/l
citric acid 60 60
Additive g/l
PPS - 2
nicotinic acid
Table 4 (cont'd)
Example 4A 4B
Bath properties
pH 3.4 3.4
density OBe (Baume)
Plating conditions
Temperature OC 31 31
rack/barrel (3) R R
current density A/dm2 1 1
plating time min 10 10
number of A/litre 2.85 2.85
anode - cathode ratio 3/1 3/1
agitation solution (4) 4A 4A
agitation cathode (5) 0 0
cathode (6) brass brass
anode (7) PT PT
Plating serformance efficiency mg/A.min 19.6 20.6
plating rate mins/
micrometer thick
ness of deposit
macrodistribution % (8) 38.6 34.5
Table 4 (con't)
Example 4C 4D
Ingredient
Gold g/l 4 4
as gold potassium 5.85 5.85
cyanide
Iron g/l 0.72 0.72
as iron (III) nitrate 5.2 5.2
nonahydrate
Additional metal g/l
zirconium
as zirconyl silicate
(ZrSiO4)
as zirconyl nitrate 0.2 0.2
hydrate
Citrate g/l
diammonium hydrogen - 100
citrate
sodium citrate 48.75 48.75
potassium citrate
Weak Acid g/l
citric acid 60 60
Additive g/l
PPS 2 2
nicotinic acid 5 5
Table 4 (cont'd) Example 4C 4D
Bath properties
pH 3.4 3.9
density OBe (Baume)
Plating conditions
Temperature OC 31 31
rack/barrel (3) R R
current density A/dm2 1 1
plating time min 10 10
number of A/litre 0.285 0.285
anode - cathode ratio 3/1 3/1
agitation solution (4) 4A 4A
agitation cathode (5) 0 0
cathode (6) brass brass
anode (7) PT PT
Plating performance
efficiency mg/A.min 9.8 14.7
plating rate mins/
micrometer thick
ness of deposit
macrodistribution % (8) 52.2 82.2
Examples 5A to 5F Examples A to F were carried out in a Haring cell.
Details are given in Table 5.
Table 5 Example 5A 5B 5C Ingredient
Gold g/l 4 4 4
as gold potassium 5.85 5.85 5.85
cyanide
Iron g/l 0.72 0.72 0.72
as iron (III) nitrate 5.2 5.2 5.2
nonahydrate
Additional metal g/l
zirconium 0.081 0.081 0.081
as zirconyl silicate - - (ZrSiO4)
as zirconyl nitrate 0.3 0.3 0.3
hydrate
Citrate g/l
diammonium hydrogen 70 100 100
citrate
sodium citrate
potassium citrate
Weak Acid g/l
citric acid 60 60 60
Additive g/l
PPS - - 2
nicotinic acid
Table 5 (cont'd) Example 5A SB 5C Bath properties
pH 3.24 3.39 3.39
density OBe (Baume)
Plating conditions
Temperature OC 30 30 30
rack/barrel (3) R R R
current density A/dm2 1 1 1
plating time min 10 10 10
number of A/litre 0.285 0.285 0.285
anode - cathode ratio 3/1 3/1 3/1
agitation solution (4) 4A 4A 4A
agitation cathode (5) 0 0 0
cathode (6) brass brass brass
anode (7) PT PT PT
Plating serformance efficiency mg/A.min 23.7 25.4 27.8
plating rate mins/
micrometer thick
ness of deposit
macrodistribution (8) 43.6 56.4 56.6
Table 5 (con't)
Example 5D 5E 5F Ingredient
Gold g/l 4 4 3
as gold potassium 5.85 5.85 4.39
cyanide
Iron g/l 0.72 0.72 0.72
as iron (III) nitrate 5.2 5.2 5.2
nonahydrate
Additional metal g/l
zirconium 0.081 0.081 0.27
as zirconyl silicate
(ZrSiO4)
as zirconyl nitrate 0.3 0.3 1
hydrate
Citrate g/l
diammonium hydrogen 100 100 100
citrate
sodium citrate
potassium citrate
Weak Acid g/l
citric acid 60 60 60
Additive g/l
PPS 2 2 2
nicotinic acid
Table 5 (cont'd)
Example 5D 5E 5F Bath properties
pH 3.5 3.5 3.5
density OBe (Baume)
Plating conditions
Temperature OC 40 40 40
rack/barrel (3) R R R
current density A/dm2 1 2 2
plating time min 10 10 10
number of A/litre 0.285 0.57 0.57
anode - cathode ratio 3/1 3/1 3/1
agitation solution (4) 4A 4A 4A
agitation cathode (5) 0 0 0
cathode (6) brass brass brass
anode (7) PT PT PT
Plating Derformance efficiency mg/A.min 30.2 19.6 17.1
plating rate mins/
micrometer thick
ness of deposit
macrodistribution % 59.2(8) 90.1(8B) 91.6(8B)
The bath compositions of the present invention are made up in conventional manner.
The pH of the bath (at 400C) is adjusted to 3.35 to 3.7 electromeric. The final volume is made up with distilled or deionized water and the bath temperature is then controlled to the desired use temperature for the specific example.
During use of the bath the gold metal content should be maintained at the recommended range of 2.5 to 3.5 g/l by periodic additions of gold potassium cyanide.
The gold will be consumed at a rate of about 100 g per 4500 ampere minutes, working at 2A/dm2, or for every 8330 ampere minute, working at 4A/dm2. A replenisher solution will also be used as is conventional to replace the other ingredients which are consumed during use of the bath
When rack plating is being used as in the examples given above the current density is typically 2-4 A/dm2 preferably 3 with the formulation of Example 2C.
The ratio of the anode area to the cathode area is preferably 3:1 or 4:1 or higher. The solution density is preferably at least 90 Baume.
Claims (18)
1. An electrodeposit free of cobalt, cadmium and nickel which contains 1.25 to 1.55% w/w iron, 1 to 2 ppm zirconium; and 97.7 to 98.2W gold and has a pale yellow colour less than 3N on the NIHS scale.
2. An electrodeposit as claimed in claim 1, in which the colour is in the range 3N to 2N-18.
3. An electrodeposit as claimed in claim 1 or claim 2 in which the deposit is of 23-23.6 carat.
4. An electroplating bath, free of cobalt, cadmium and nickel comprising gold, as cyanide, iron as a soluble salt or complex, a soluble zirconium salt or complex, a citrate, a weak acid, and optionally a heterocyclic sulphonate.
5. An electroplating bath as claimed in claim 4 in which the gold is present as gold potassium cyanide in an amount of 1.0 to 10 g/l.
6. An electroplating bath as claimed in claim 4 or claim 5 in which there is 2.5 to 3.5 g/l of gold.
7. An electroplating bath as claimed in claim 4, 5 or 6 in which the iron is present as a nitrate which may be hydrated, iron sulphate, iron (III) chloride, iron (III) citrate or iron (III) phosphate.
8. An electroplating bath as claimed in claim 7 in which the iron content is in the range from 0.25 g/l to 5.0 g/l.
9. An electroplating bath as claimed in any one of claims 4 to 8 in which the zirconium is present as the nitrate, which may be hydrated, as the sulphate or as ammonium zirconium citrate complex.
10. An electroplating bath as claimed in claim 9 in which the zirconium is present in an amount of 0.01 to 2 g/l of zirconium.
11. An electroplating bath as claimed in any one of claims 4 to 9 in which the citrate is diammonium hydrogen citrate.
12. An electroplating bath as claimed in claim 11 in which the citrate is present in an amount of 10 to 500 g/l.
13. An electroplating bath as claimed in any one of claims 4 to 12 in which the weak acid is a hydroxy carboxylic acid or phosphoric acid.
14. An electroplating bath as claimed claim 13 in which the weak acid is citric acid (HO(COOH)(CH2COOH)2.H2O, oxalic, lactic, formic, thiomalic, gluconic, tartaric, acetic or maleic acid.
15. An electroplating bath as claimed in claim 13 or claim 14 in which the weak acid is present in an amount of 1 to 500 g/l.
16. An electroplating bath as claimed in any one of claims 4 to 15 in which the heterocyclic sulphonate is 3 (1-pyridino) -1-propane sulphonate or pyridine-4ethanesulphonic acid.
17. An electroplating bath as claimed in claim 16 in which the heterocyclic sulphonate is present in an amount of 0.1 to 10 g/l.
18. An electroplating bath, free of cobalt, cadmium and nickel comprising gold as cyanide in an amount of 2.5 to 3.5 gold, iron as iron nitrate in an amount of 0.6 to 0.8 g/l, zirconium as zirconium nitrate in an amount of 0.2 to 0.5 g/l, diammonium hydrogen citrate in an amount of 75 to 125 g/l, citric acid in an amount of 40 to 80 g/l, and 3- (1-pyridino) -1-propane sulphonate in an amount of 1 to 3 g/l.
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES96935123T ES2179952T3 (en) | 1995-11-03 | 1996-10-31 | COMPOSITIONS AND DEPOSITS OF ELECTRODEPOSITION PROCEDURES. |
AU73209/96A AU7320996A (en) | 1995-11-03 | 1996-10-31 | Electroplating processes compositions and deposits |
AT96935123T ATE220736T1 (en) | 1995-11-03 | 1996-10-31 | ELECTROPLATTING METHODS, COMPOSITIONS AND COATINGS |
CN96197909A CN1200774A (en) | 1995-11-03 | 1996-10-31 | Electroplating processes compositions and deposits |
PCT/GB1996/002652 WO1997017482A1 (en) | 1995-11-03 | 1996-10-31 | Electroplating processes compositions and deposits |
EP96935123A EP0871801B1 (en) | 1995-11-03 | 1996-10-31 | Electroplating processes compositions and deposits |
CA002235408A CA2235408A1 (en) | 1995-11-03 | 1996-10-31 | Electroplating processes compositions and deposits |
DE69622431T DE69622431T2 (en) | 1995-11-03 | 1996-10-31 | ELECTROPLATING METHODS, COMPOSITIONS AND COATINGS |
KR1019980703274A KR19990067295A (en) | 1995-11-03 | 1996-10-31 | Electroplating Process Compositions and Deposits |
TW085113426A TW446760B (en) | 1995-11-03 | 1996-11-04 | Electroplating processes compositions and deposits |
US09/069,442 US6576114B1 (en) | 1995-11-03 | 1998-04-29 | Electroplating composition bath |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9522591.8A GB9522591D0 (en) | 1995-11-03 | 1995-11-03 | Electroplating processes compositions and deposits |
Publications (3)
Publication Number | Publication Date |
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GB9522997D0 GB9522997D0 (en) | 1996-01-10 |
GB2306508A true GB2306508A (en) | 1997-05-07 |
GB2306508B GB2306508B (en) | 1999-04-28 |
Family
ID=10783366
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GBGB9522591.8A Pending GB9522591D0 (en) | 1995-11-03 | 1995-11-03 | Electroplating processes compositions and deposits |
GB9522997A Expired - Fee Related GB2306508B (en) | 1995-11-03 | 1995-11-09 | Electroplating processes compositions and deposits |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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GBGB9522591.8A Pending GB9522591D0 (en) | 1995-11-03 | 1995-11-03 | Electroplating processes compositions and deposits |
Country Status (2)
Country | Link |
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KR (1) | KR19990067295A (en) |
GB (2) | GB9522591D0 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2323853A (en) * | 1997-03-25 | 1998-10-07 | Enthone Omi | An electrodeposit free of cobalt, cadmium and nickel |
ITFI20130057A1 (en) * | 2013-03-18 | 2014-09-19 | Bluclad S R L | SOLUTION FOR THE ELECTRODEPTITION OF A GOLDEN LEAGUE AND THE LEAGUE THEREOF DERIVING. |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1426849A (en) * | 1973-11-07 | 1976-03-03 | Degussa | Electroplating bath for depositing coatings of brilliant gold |
US4075065A (en) * | 1975-07-07 | 1978-02-21 | Handy & Harman | Gold plating bath and process |
EP0037534A2 (en) * | 1980-04-03 | 1981-10-14 | Degussa Aktiengesellschaft | Plating bath and its use for depositing very lustrous coatings of white gold |
US4358351A (en) * | 1980-05-31 | 1982-11-09 | Degussa Aktiengesellschaft | Alkaline bath for the electrolytic deposition of low carat yellow colored gold alloy layers |
US4687557A (en) * | 1985-03-01 | 1987-08-18 | Heinz Emmenegger | Gold alloys and galvanic bath for the electrolytic deposit thereof |
GB2242200A (en) * | 1990-02-20 | 1991-09-25 | Omi International | Plating compositions and processes |
EP0480876A2 (en) * | 1990-10-08 | 1992-04-15 | Metaux Precieux Sa Metalor | Electrodeposition of a gold alloy containing copper and zinc and its method of production |
JPH0718484A (en) * | 1992-07-28 | 1995-01-20 | Bikutoria:Kk | Gold alloy plating solution |
-
1995
- 1995-11-03 GB GBGB9522591.8A patent/GB9522591D0/en active Pending
- 1995-11-09 GB GB9522997A patent/GB2306508B/en not_active Expired - Fee Related
-
1996
- 1996-10-31 KR KR1019980703274A patent/KR19990067295A/en not_active Application Discontinuation
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1426849A (en) * | 1973-11-07 | 1976-03-03 | Degussa | Electroplating bath for depositing coatings of brilliant gold |
US4075065A (en) * | 1975-07-07 | 1978-02-21 | Handy & Harman | Gold plating bath and process |
EP0037534A2 (en) * | 1980-04-03 | 1981-10-14 | Degussa Aktiengesellschaft | Plating bath and its use for depositing very lustrous coatings of white gold |
US4358351A (en) * | 1980-05-31 | 1982-11-09 | Degussa Aktiengesellschaft | Alkaline bath for the electrolytic deposition of low carat yellow colored gold alloy layers |
US4687557A (en) * | 1985-03-01 | 1987-08-18 | Heinz Emmenegger | Gold alloys and galvanic bath for the electrolytic deposit thereof |
GB2242200A (en) * | 1990-02-20 | 1991-09-25 | Omi International | Plating compositions and processes |
EP0480876A2 (en) * | 1990-10-08 | 1992-04-15 | Metaux Precieux Sa Metalor | Electrodeposition of a gold alloy containing copper and zinc and its method of production |
JPH0718484A (en) * | 1992-07-28 | 1995-01-20 | Bikutoria:Kk | Gold alloy plating solution |
Non-Patent Citations (1)
Title |
---|
WPI Accession no 95-094271/13 & JP 07 018 484 A * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2323853A (en) * | 1997-03-25 | 1998-10-07 | Enthone Omi | An electrodeposit free of cobalt, cadmium and nickel |
GB2323853B (en) * | 1997-03-25 | 2002-04-24 | Enthone Omi | Electroplating processes compositions and deposits |
ITFI20130057A1 (en) * | 2013-03-18 | 2014-09-19 | Bluclad S R L | SOLUTION FOR THE ELECTRODEPTITION OF A GOLDEN LEAGUE AND THE LEAGUE THEREOF DERIVING. |
EP2781629A1 (en) * | 2013-03-18 | 2014-09-24 | Bluclad S.R.L. | Solution for the electrodeposition of a gold alloy and the alloy derived therefrom |
Also Published As
Publication number | Publication date |
---|---|
KR19990067295A (en) | 1999-08-16 |
GB9522997D0 (en) | 1996-01-10 |
GB2306508B (en) | 1999-04-28 |
GB9522591D0 (en) | 1996-01-03 |
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PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20101109 |