U.S. patent number 3,878,066 [Application Number 05/394,959] was granted by the patent office on 1975-04-15 for bath for galvanic deposition of gold and gold alloys.
Invention is credited to Manfred Dettke, Karl-Hans Fuchs, Rolf Ludwig.
United States Patent |
3,878,066 |
Dettke , et al. |
April 15, 1975 |
Bath for galvanic deposition of gold and gold alloys
Abstract
Galvanic baths are provided for the deposition of gold or gold
alloy coatings, such baths containing in combination aldehyde and
nitrogen compounds with arsenic compounds.
Inventors: |
Dettke; Manfred (1 Berlin 19,
DT), Fuchs; Karl-Hans (7015 Korntal, DT),
Ludwig; Rolf (1 Berlin 19, DT) |
Family
ID: |
5855965 |
Appl.
No.: |
05/394,959 |
Filed: |
August 29, 1973 |
Foreign Application Priority Data
Current U.S.
Class: |
205/240; 205/242;
205/241; 205/247; 205/250; 205/251; 205/267; 205/268 |
Current CPC
Class: |
C25D
3/48 (20130101); C25D 3/62 (20130101) |
Current International
Class: |
C25D
3/48 (20060101); C25D 3/62 (20060101); C25D
3/56 (20060101); C25D 3/02 (20060101); C23b
005/28 (); C23b 005/42 (); C23b 005/46 () |
Field of
Search: |
;204/46G,43G,44
;106/1 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Kaplan; G. L.
Attorney, Agent or Firm: Padlon; Joseph F.
Claims
1. An aqueous bath for the electrodeposition of gold or gold alloys
having a high gloss, said bath having a pH of from about 5 to 10
and an amount of components, A, B and C to provide a coating having
high gloss and extraordinary adhesion, said bath comprising
A. from about 0.005 to 50 grams per liter of at least one compound
of the general formula RCHO wherein R is selected from the group
consisting of hydrogen, methyl, and the group - CHO, and an
aldehyde bisulfite addition compound thereof, and
B. from about 0.1 to 50 grams per liter of at least one compound of
the general formula R.sub.2 N--(R'--NR).sub.m --(R').sub.n --NR in
which each R is selected from the group consisting of hydrogen,
alkyl having from 1 to 5 carbon atoms and hydroxy-substituted alkyl
having from 1 to 5 carbon atoms, m and n is 0 or an integer from 1
to 3, and
C. from about 0.001 to 5 grams per liter of at least one alkali
metal salt of a member of the group consisting of arsenic acid and
arsenious acid, and
D. a water soluble gold compound in an amount of about 1 to 50
grams per
2. A bath adding to claim 1 which contains about 10 to 200 grams
per liter of boric acid and about 10 to 200 grams per liter of a
polyvalent alcohol, the ratio of boric acid to polyvalent alcohol
being from about 1:1 to
3. A bath according to claim 2 wherein the polyvalent alcohol is
ethylene
4. A bath according to claim 1 wherein component A is selected from
the group consisting of formaldehyde, acetaldehyde and glyoxal and
component B is selected from the group consisting of hydrazine,
methyl hydrazine, N-(3-propyl-1,2-diol)-diethylene triamine,
triethylene tetramine and salts
5. A bath according to claim 1 for electrodeposition of gold alloy
containing at least one alloy metal selected from the group
consisting of silver, copper, zinc, cadmium, cobalt, nickel,
palladium, indium, manganese, antimony and tin wherein the
alloy-metals are added to the bath in the form of water-soluble
compounds in amounts of about 0.01 to 200 grams per liter.
Description
The invention relates to a bath for the galvanic deposition of gold
coatings and gold alloy coatings, containing a combination of
organic compounds on a base of aldehydes and nitrogen compounds
with arsenic compounds.
The use of nitrogen-containing compounds, such as hydrazine and
derivatives thereof, in gold electrolytes for reducing the internal
stresses of the coatings deposited therefrom is known, cf., German
Pat. Nos. 1,215,467, 1,218,248 and 1,222,347.
It is further known that soluble arsenic compounds are added to
gold electrolytes in order thereby to achieve an improved luster of
the gold coatings. Cf., German Nos. 2,042,127, 1,621,172 and
1,621,068.
An essential disadvantage of these electrolytes, however, is that
their smoothing or leveling action is not satisfactory.
It is, therefore, an object of the present invention to avoid the
disadvantages of the known electrolytes and to provide galvanic
baths from which smooth coatings of gold and the alloys can be
deposited.
This is achieved according to the present invention by providing a
bath which is characterized by a content of
A. at least one compound of the general formula R -- CHO
in which R signifies hydrogen, methyl or the group --CHO, or one of
its addition compounds and
B. at least one compound of the general formula R.sub.2
N--(R'--NR).sub.m --(R').sub.n --NR.sub.2
in which the radicals R are identical or different and represent
hydrogen, possibly alkyl substituted by hydroxy groups with
preferably 1 to 4 carbon atoms or aryl and R' alkylidene radicals
with preferably 1 to 5 carbon atoms, m and n being 0 or
representing integers from 1 to 3, or one of their salts and
C. at least one alkali salt of arsenic or arsenous acid, such as
sodium and potassium arsenite or sodium and potassium arsenate.
In the general formula under (B) above, the radicals R signify for
example methyl, ethyl, propyl, butyl or isobutyl, and the radicals
R', signify methylene, ethylidene, propylidene, butylidene,
pentylidene and the like, the alkyl radicals being preferably
substituted with up to 2 hydroxy groups.
The components (A), (B) and (C) seem to influence each other
synergistically in the bath, for when used alone they are
completely ineffective.
The concentrations required for a high-gloss gold deposition or a
chromatic gold alloy deposition are, for the aldehydes, i.e.,
component A, about 0.005 to 50 g/liter, for the nitrogen compounds,
i.e., component B, about 0.1 to 50 g/liter, and for the arsenic
compounds, i.e., component C, about 0.001 to 5 g/liter.
As aldehyde components there are suitable preferably formaldehyde,
acetaldehyde and glyoxal, which can be used per se or in the form
of their addition compounds, i.e., as bisulfites.
Nitrogen compounds that are especially suitable, are hydrazine or
methyl hydrazine, which are to be used according to invention
either by themselves or in the form of their salts, such as the
chlorides or sulfates, or alone or in a mixture with one another.
In addition, prropyl hydrazine as well as phenyl hydrazine and the
substitution products thereof and their salts have proved to be
suitable.
Further nitrogen compounds that may be used according to the
invention are, for example, N-(3-propyl-1,2-diol)-diethylene
triamine, triethylene tetramine, ethylene diamine, diethylene
triamine, triethylenetetramine and tetraethylene pentamine, of
which the first two in particular have been found to be very
favorable with respect to their smoothing action.
Also, these compounds can be used by themselves as such, as well as
in the form of their salts, for example, the chlorides or
acetates.
Suitable arsenic compounds that are effective are the alkali salts
of arsenic and arsenous acid, such as sodium and potassium arsenate
or arsenite.
It is understood that the components (A), (B) and (C) may be used
either by themselves alone, or in the form of their mixtures.
As a bath, there is generally used an aqueous solution which
contains a water-soluble gold salt, preferably a complex compound
of gold, in particular potassium dicyanoaurate (I), in
concentrations of about 1 to 50 g/liter.
If gold alloy coatings are to be deposited, there are added to the
bath the alloy metals silver, copper, zinc, cadmium, manganese,
cobalt, nickel, palladium, indium, antimony or tin, in the form of
their water-soluble compounds, preferably in the form of the
complex compounds, such as the chelate or the cyano complexes, in
total concentrations of about 0.01 to 200 g/liter. Depending on
whether binary, ternary or quaternary alloy coatings are intended,
corresponding mixtures of the metal compounds are used.
It has been found particularly appropriate if the bath contains
boric acid and a polyvalent alcohol, preferably ethylene glycol,
namely more particularly in a ratio by weight of about 1:1 to 1:2
and in a concentration of about 10 to 200 g/liter of boric acid or
of about 10 to 2000 g/liter of alcohol.
As additional additives, the bath may contain common conducting
salts, for example ammonium sulfate or alkali salts of sulfuric
acid, nitric acid or hydrochloric acid, pH-regulating substances,
appropriately the organic and/or inorganic buffer mixtures commonly
used for this purpose such as, mixtures of citric acid and
potassium citrate or sodium hydrophosphate and sodium
dihydrophosphate as well as surface-active substances, such as
ethylhexylsulfate and N-ethoxyhexylamine.
The pH value of the bath may be from about 5 to 10, preferably 6.8
to 7.5. It is operated appropriately at temperatures of about
20.degree. to 70.degree. C, preferably at temperatures between
25.degree. to 30.degree. C, current densities from about 0.1 to 5
amp.dm.sup.2 being used.
The bath according to the invention is suitable in particular for
the galvanic deposition of high-gloss gold coatings and chromatic
gold alloy coatings with excellent smoothing appearance.
Another advantage of the invention consists in the extraordinary
adhesion of the coatings, which, surprisingly, far exceeds that of
the coatings produced by the usual, known methods. Thus, for
example, even the lead containing brass alloy, which is very
difficult to galvanize or plate, can be gold plated directly
without the previous deposition of an intermediate layer by means
of the bath according to this invention resulting in a substantial
saving of material and time.
It should be stressed further that the bath of the invention
permits the use of high current densities and at good current
efficiency shorter exposure times, whence special advantages result
for the practice.
The following examples will illustrate the invention, without
limitation thereof.
EXAMPLE 1
g/liter ______________________________________ Potassium
dicyanoaurate (I), K(Au(CN).sub.2) 18.0 Ammonium sulfate,
(NH.sub.4).sub.2 SO.sub.4 60.0 Boric acid, H.sub.3 BO.sub.3 40.0
Ethylene glycol, HO--CH.sub.2 --CH.sub.2 --OH 80.0 Formaldehyde,
CH.sub.2 O 5.0 Hydrazine hydrate, N.sub.2 H.sub.4.sup.. H.sub.2 O
15.0 Sodium arsenite Na.sub.3 AsO.sub.3 0.07 pH value: 6.8 which is
adjusted with sulfuric acid Applicable current density: from 0.1 to
maximum 2.0 amp.dm.sup.2 Temperature: 20 to 70.degree. C The rate
of deposition at 1 amp/dm.sup.2 : 1 micron in 4
______________________________________ minutes.
This electrolyte composition according to the invention is suitable
for the deposition of nearly 24 carat gold. The coatings deposited
from this electrolyte are of high luster, saturated gold color, and
have a hardness of about 170 microvickers.
With the electrolyte, lead containing brass can be proviced,
without an intermediate layer, with a gold coating which is of high
luster from about 8 micron on.
EXAMPLE 2
g/liter ______________________________________ Potassium
dicyanoaurate (I), K(Au(CN).sub.2) 12.0 Ammonium sulfate,
(NH.sub.4).sub.2 SO.sub.4 70.0 Boric acid, H.sub.3 BO.sub.3 40.0
Ethylene glycol, HO--CH.sub.2 --CH.sub.2 --OH 80.0< Copper
sulfate, CuSO.sub.4.sup.. 5H.sub.2 O 8.0 Ethylene diamine
tetraceticacid dipotassium salt 9.5 Formaldehyde, CH.sub.2 O 5.0
Hydrazine hydrate N.sub.2 H.sub.4.sup.. H.sub.2 O 12.0 Sodium
arsenite, Na.sub.3 ASO.sub.3 0.045
______________________________________
By means of this electrolyte, about 18 carat coatings can be
deposited, which have the color of rolled gold. The coatings are of
high gloss and tarnish resistant.
EXAMPLE 3
g/liter ______________________________________ Potassium
dicyanoaurate, (I), K(Au(CN).sub.2) 12.0 Ammonium sulfate,
(NH.sub.4).sub.2 SO.sub.4 30.0 Boric acid, H.sub.3 BO.sub.3
60.0< Ethylene glycol, HO--CH.sub.2 --CH.sub.2 --OH 60.0 Cadmium
sulfate CdSO.sub.4.sup.. 8/3 H.sub.2 O 3.5 Ethylene diamine
tetracetic acid dipotassium salt 4.0 Formaldehyde, CH.sub.2 O 10.0
Hydrazine sulfate, N.sub.2 H.sub.4.sup.. H.sub.2 SO.sub.4 30.0
Sodium arsenite, Na.sub.3 ASO.sub.3 0.5 pH value: 8.0 Applicable
current density: From 0.1 to 1.5 amp/dm.sup.2 Temperature: 20 to
60.degree. C Rate of deposition at 1 amp.dm.sup.2 : 1 micron in 4
minutes. Intensive agitation of electrolyte or cathode is effected.
______________________________________
This electrolyte furnishes light yellow, about 20 carat coatings.
The coatings deposited from this electrolyte are high gloss and
tarnish resistant.
EXAMPLE 4
g/liter ______________________________________ Potassium
dicyanoaurate (I) K(Au(CN).sub.2) 10.0 Ammonium sulfate
(NH.sub.4).sub.2 SO.sub.4 50.0 Boric acid H.sub.3 BO.sub.3 30.0<
Ethylene glycol, HO--CH.sub.2 --CH.sub.2 --OH 60.0 Palladium
cyanide, Pd(CN).sub.2 4.5 Nickel sulfate NiSO.sub.4.sup.. 7H.sub.2
O 10.0 Ethylene diamine tetracetic acid dipotassium salt 12.0
N-(3-propyl-1,2-diole)-diethylene triamine, (CH.sub.2
--OH--CHOH--CH.sub.2 NH--CH.sub.2 --CH.sub.2 --NH--CH.sub.2
--CH.sub.2 --NH.sub.2 1.0 Sodium arsenate, Na.sub.3 AsO.sub.4 0.2
Formaldehyde, CH.sub.2 O 7.5 pH value: 6.5 Applicable current
density: from 0.2 to 1.0 amp/dm.sup.2 Temperature: 20 to 70.degree.
C The rate of deposition at 1 amp/dm.sup.2 is 1 micron in 8
______________________________________ minutes.
This electrolyte furnishes almost white, high-gloss coatings. The
deposited alloy is approximately 16 carat.
EXAMPLE 5
g/liter ______________________________________ Potassium
dicyanoaurate (I), K(Au(CN.sub.2) 15.0 Ammonium sulfate,
(NH.sub.4).sub.2 SO.sub.4 80.0 Boric acid, H.sub.3 BO.sub.3 50.0
Ethylene glycol, HO--CH.sub.2 --CH.sub.2 --OH 100.0 Cobalt sulfate,
CoSo.sub.4.sup.. 7H.sub.2 O 3.0 Nickel sulfate NiSO.sub.4.sup..
7H.sub.2 O 2.0 Indium sulfate, In.sub.2 (SO.sub.4).sub.3 0.5 Methyl
hydrazine CH.sub.3 --NH--NH.sub.2 0.1 Ethylene diamine tetracetic
acid dipotassium salt 6.0 Formaldehyde, CH.sub.2 O 3.0 Sodium
arsenite, Na.sub.3 AsO.sub.3 0.3 pH value: 5.0 Applicable current
density: from 0.1 to 2.5 amp/dm.sup.2 Temperature: 20 to 35.degree.
C Rate of deposition at 2 amp/dm.sup.2 : 1 micron in 2 minutes
______________________________________
According to the invention an alloy of good electrical properties
and excellent abrasive strength can be deposited with this
bath.
The coatings are of high gloss and have a fineness of 23 carat. The
current efficiency is 40 to 60%. The content of alloy metals can be
greatly influenced by varying the current density and the speed of
goods or by electrolyte agitation. From a layer thickness of about
5 micron on, a smoothing effect can already be observed.
* * * * *