United States Patent [19] [11] Patent Number: 4,502,927

Barclay et a1. [45] Date of Patent: Mar. 5, 1985

[54] ELECTRODEPOSITION OF CHROMIUM 3,238,112 3/1966 Haslam ........................... .. 204/43 R

AND ITS ALLOYS 4,062,737 12/1977 Barclay et a1. 204/51 X
4,161,432 7/1979 Barclay et a1. .... .. 204/51
[75] Inventors: Donald J. Barclay, Winchester; 4,256,548 3/1981 Barclay et a1. . 204/51 X
William M. Morgan, Chandlers Ford; 4,278,512 7/1981 Barclay et a1. ...... .. 204/51 X
James M. Vigar, Winchester, all of
England FOREIGN PATENT DOCUMENTS
[73] Assignee: International Business Machines 1488381 10/1977
1591051 6/1981
United Kingdom ................ .. 204/51
United Kingdom ..
Corporation, Armonk, NY. 2071151 9/1981 Un?od Kingdom ..
[21] Appl. No.: 437,989 1602404 11/1981 United Kingdom ................ .. 204/51

[22] Filed: Nov. 1, 1982 Primary ExaminerG. L. Kaplan

[30] Foreign Application Priority Data Assistant ExaminerNam X. Nguyen
Attorney, Agent, or FirmFrancis A. Sirr
Nov. 18, 1981 [GB] United Kingdom ............... .. 8134776
[57] ABSTRACT
[51] Int. Cl.3 .............................................. .. C25D 3/06
[52] US. Cl. .......... .. A trivalent chromium electroplating solution contain
[58] Field of Search .............................. .. 204/43 R, 51 ing trivalent chromium ions, a complexant, a buffer and
an organic compound having a C=S group or a
[56] References Cited -C-S- group. The complexant is selected to give the
U.S. PATENT DOCUMENTS chromium complex a stability constant, K1, in the range
2,822,326 2/1958 Safranek .............................. .. 204/51 108<K1<1O12M1.
2,849,351 8/1958 Giindel et a1. ..
3,203,878 8/1965 Willmund et a1. .................. .. 204/51 20 Claims, No Drawings
 4,502,927
1 2
was greatly simpli?ed and, secondly, the color of the
ELECTRODEPOSITION OF CHROMIUM AND ITS chromium deposit was much lighter.
ALLOYS Oxidation of chromium and other constituents of the
electrolyte at the anode are known to progressively and
TECHNICAL FIELD rapidly inhibit plating. Additionally some electrolytes
This invention relates to electrodeposition of chro result in anodic evolution of toxic gases. An electroplat
mium and its alloys from electrolytes containing triva ing bath having an anolyte separated from a catholyte
lent chromium ions. by a perfluorinated cation exchange membrane, de
scribed in United Kingdom patent speci?cation No.
BACKGROUND OF THE INVENTION 1,602,404, successfully overcomes these problems. Al
Chromium is commercially electroplated from elec ternatively an additive, which undergoes oxidation at
trolytes containing hexavalent chromium, but many the anode in preference to chromium or other constitu
attempts over the last ?fty years have been made to ents, can be made to the electrolyte. A suitable additive
develop a commercially acceptable process for electro is described in U.S. Pat. No. 4,256,548. The disadvan
plating chromium using electrolytes containing triva tage of using an additive is the ongoing expense.
lent chromium salts. The incentive to use electrolytes United Kingdom patent speci?cation No. 1,488,381
containing trivalent chromium salts arises because hexa describes an electrolyte for electroplating chromium in
valent chromium presents serious health and environ which thiourea is suggested as a complexant either sin
mental hazards-it is known to cause ulcers and is be 20 gly or in combination with other compounds for stabi
lieved to cause cancer, and, in addition, has technical lizing trivalent chromium ions, but no speci?c example
limitations including the cost of disposing of plating or experimental results were given.
baths and rinse water. THE INVENTION
The problems associated with electroplating chro
mium from solutions containing trivalent chromium 25 'Three related factors are responsible for many of the
ions are primarily concerned with reactions at both the problems associated with attempts to plate chromium
anode and cathode. Other factors which are important from trivalent electrolytes. These are: a negative plating
for commercial processes are the material, equipment potential which results in hydrogen evolution accompa
and operational costs. nying the plating reaction, slow electrode kinetics and
In order to achieve a commercial process, the precip the propensity of chromium (III) to precipitate as hy
itation of chromium hydroxy species at the cathode droxy species in the high pH environment which exists
surface must be minimized to the extent that there is a at the electrode surface. The formulation of the plating
suf?cient supply of dissolved, i.e., solution-free, chro electrolytes of the present invention are based on an
mium (III) complexes at the plating surface; and the understanding of how these factors could be contained.
reduction of chromium ions is promoted. U.S. Pat. No. Cr (III) ions can form a number of complexes with
4,062,737 describes a trivalent chromium electroplating ligands, L, characterized by a series of reactions which
process in which the electrolyte comprises aquo chro may be summarized as:
mium (III) thiocyanato complexes. The thiocyanate
ligand stabilizes the chromium ions, inhibiting the for Cr + L = CrL K1
mation of precipitated chromium (III) salts at the cath CrL + L = CrL;
ode surface during plating, and also promotes the re
duction ofchromium (III) ions. United Kingdom patent BIC.
speci?cation No. 1,591,051 described an electrolyte
comprising chromium thiocyanato complexes in which 45
the source of chromium was a cheap and readily avail where charges are omitted for convenience and
able chromium (III) salt such as chromium sulphate. K1, K2, . . . etc. are the stability constants and are
Improvements in performance, i.e., ef?ciency or plat calculated from:
ing rate, plating range and temperature range, were
achieved by the addition of a complexant which pro
vided one of the ligands for the chromium thiocyanato
complex. These complexants, described in U.S. Pat. No.
4,161,432, comprised amino acids such as glycine and
etc.
aspartic acid, formates, acetates or hypophosphites. The
improvement in performance depended on the com 55
plexant ligand used. The complexant ligand was effec where the square brackets represent concentrations.
tive at the cathode surface, to further inhibit the forma Numerical values may be obtained from (1) Stability
tion of precipitated chromium (III) species. In U.S. Pat. Constants of Metal-Ion Complexes, Special Publica
No. 4,161,432 it was noticed that the improvement in _ tion No. 17, The Chemical Society, London 1964--L.
performance permitted a substantial reduction in the 60 G. Sillen and A. E. Martell; (2) Stability Constants of
concentration of chromium ions in the electrolyte with Metal-Ion Complexes, Supplement No. 1, Special Pub
out ceasing to be a commercially viable process. In U.S. lication No. 25, The Chemical Society, London
Pat. No. 4,278,512 practical electrolytes comprising 1971L. G. Sillen and A. E. Martell; (3) Critical Sta
chromium thiocyanato complexes were described bility Constants, Vol. 1 and 2, Plenum Press, New
which contained less than 30 mM chromium--the thio York 1975-R. M. Smith and A. E. Martell. The ranges
cyanate and complexant being reduced in proportion. for K given in the above references should be recog
The reduction in chromium concentration had two nised as being semi-quantative, especially in view of the
desirable effects, ?rstly, the treatment of rinse waters spread of reported results for a given system and the
 4,502,927
3 l 4
in?uence of the ionic composition of the electrolyte. Organic compound: 10-5 to 10-2M
Herein K values as taken at 25 C. , A practical chromium/complexant ligand ratio is ap
During the plating process, the surface pH can rise to proximately l:l. - ,
a value determined by the current density and the acid Above a minimum concentration necessary for ac
ity constant, pKa, and concentration of the buffer agent ceptable plating rates, it is unnecessary to increase the
(e.g. boric acid). This pH will be signi?cantly higher amount of the organic compound in proportion to the
than the pH in the bulk of the electrolyte and under concentration of chromium in the electrolyte. Excess of
these conditions chromium-hydroxy species may pre the organic compound may not be harmful to the plat
cipitate. The value of K1, K2, . . . etc. and the total ing process, but can result in an increased amount of
concentrations of chromium (III) and the complexant sulphur being co-deposited with the chromium metal.
ligand determine the extent to which precipitation oc This has two affects, firstly, to produce a progressively
curs; the higher the values of K1, K2, . . . etc. the less darker deposit and, secondly, to produce a more ductile
precipitation will occur at a given surface pH. As plat deposit.
ing will occur from solution-free (i.e., non-precipitated) The preferred source of trivalent chromium is chro
chromium species, higher plating ef?ciencies may be 15 mium sulphate which can be in the form of a commer
expected from ligands with high K values. cially available mixture of chromium and sodium sul
However, a second consideration is related to the phates known as tanning liquor or chrometan. Other
electrode potential adopted during the plating process. trivalent chromium salts, which are more expensive
If the K values are too high, plating will be inhibited than the sulphate, can be used, and include chromium
because of the thermodynamic stability of the chro 20 chloride, carbonate and perchlorate.
mium complexes. Thus, selection of the optimum range The preferred buffer agent used to maintain the pH of
for the stability constants, and of the concentrations of the bulk electrolyte comprises boric acid in high con
chromium and the ligand, is a compromise between centrations, i.e., near saturation. Typical pH range for
these two opposing affects: a weak complexant results the electrolyte is in-the range 2.5 to 4.5.
in precipitation at the interface, giving low efficiency 25 The conductivity of the electrolyte should be as high
(or even blocking of plating by hydroxy species), as possible to minimize both voltage and power con
whereas too strong a complexant inhibits plating for sumption. Voltage is often critical in practical plating
reasons of excessive stability. environments since recti?ers are often limited to a low
A third consideration is concerned with the electro voltage, e.g., 8 volts. In an electrolyte in which chro
chemical kinetics of the hydrogen evolution reaction mium sulphate is the source of the trivalent chromium
(H.E.R.) and of chromium reduction. Plating will be ions a mixture of sodium and potassium sulphate is the
favored by fast kinetics for the latter reaction and slow optimum. Such a mixture is described in United King
kinetics for the H.E.R. Thus, additives which enhance dom patent speci?cation No. 2,071,151.
the chromium reduction process or retard the H.E.R. A wetting agent is desirable and a suitable wetting
will be bene?cial with respect to ef?cient plating rates. 35 agent is FC98, a product of the 3M Corporation." How
It has been found that many sulphur containing species ever, other wetting agents such as sulphosuccinates or
having -C=S or CS groups favour the reduc alcohol sulphates may be used.
tion of chromium (III) to chromium metal. It is preferred to use a per?uorinated cation exchange
The present invention provides a chromium electro~ membrane to separate the anode from the plating elec
plating electrolyte containing a source of trivalent chro trolyte as described in United Kingdom patent speci?
mium ions, at complexant, a buffer agent and organic cation No. 1,602,404. A suitable per?uorinated cation
compound having a --C.._S group or a C-S exchange membrane is Na?on (trademark), a product of
group within the molecule for promoting chromium the E. I. du Pont de Nemours & Co.- It is particularly
deposition, the complexant being selected so that the advantageous to employ an anolyte which has sulphate
stability constant K1 of the chromium complex as de 45 ions when the catholyte uses chromium sulphate as the
?ned herein is in the range l08<K1<l012M_1. source of chromium, since inexpensive lead or lead
By way of example complexant ligands having K1 alloy anodes can be used. In a sulphate anolyte, a thin
values within the range l03<K1< l012M-1 include conducting layer of lead oxide is formed on the anode.
aspartic acid, iminodiacetic acid, nitrilotriacetic acid Chloride salts in the catholyte should be avoided since
and S-sulphosalicylic acid. 50 the chloride anions are small enough to pass through the
The organic compound having -C:S group can be membrane in sufficient amount to cause both the evolu
selected from thiourea, N-monoallyl thiourea, N-mono tion of chlorine at the anode and the formation of a
p-tolyl thiourea, thioacetamide, tetramethyl thiuram highly resistive ?lm of lead chloride on lead or lead
monosulphide, tetraethyl thiuram disulphide and dieth alloy anodes. Cation exchange membranes have the
yldithiocarbamate. The organic compound having a 55 additional advantage in sulphate electrolytes that the
C-S- group can be selected from mercaptoacetic pH of the catholyte can be stabilized by adjusting the
acid and mercaptopropionic acid. pH of the anolyte to allow hydrogen ion transport
Very low concentrations of the organic compound through the membrane to compensate for the increase
are needed to promote reduction of the trivalent chro in pH of the catholyte by hydrogen evolution at the
mium ions. Also, since the plating ef?ciency of the cathode. Using the combination of a membrane, and
electrolyte is relatively high, a commercial trivalent sulphate based anolyte and catholyte, a plating bath has
chromium electrolyte can have as low as 5 mM chro been operated for over 40 Amphours/liter without pH
mium. This removes the need for expensive rinse water adjustment.
treatment since the chromium content of the drag~out The invention will now be described with reference
from the plating electrolyte is extremely low. 65 to detailed Examples. In each Example a bath consisting
In general the concentration of the constituents in the of anolyte separated from a catholyte by a Na?on cation
electrolyte are as follows: . exchange membrane is used. The anolyte comprises an
Chromium (III) ions: 10-3 to 0.1M aqueous solution of sulphuric acid in 2% by volume
 5
4,502,927
concentration (pH 1.6). The anode is a ?at bar of a lead
alloy of the type conventionally used in hexavalent
chromium plating processes.
The catholyte for each Example was prepared by
making up a base electrolyte and adding appropriate
amounts of chromium (III), complexant and the organic
compound.
The base electrolyte consisted of the following con
stituents dissolved in 1 liter of water:
Potassium sulphate: 1M
Sodium sulphate: 0.5M
Boric acid: 1M
Wetting agent FC98: 0.1 gram
EXAMPLE 1
The following constituents were dissolved in the base
electrolyte:
Chromium (III): 10 mM (from chrometan)
DL aspartic acid: 10 mM
Thiourea: 1 mM
at pH: 3.5
Although equilibration will occur quickly in normal
use, initially the electrolyte is preferably equilibrated
until no spectroscopic changes can be detected. The
bath was found to operate over a temperature range of 25 source of chromium is chromium sulphate and includ
25 to 60 C. Good bright deposits of chromium were
obtained over a current density range of 5 to 80
mA/cmz.
EXAMPLE 2
30
The following constituents were dissolved in the base
electrolyte:
' Chromium (III): 10 mM (from chrometan)
Iminodiacetic acid: 10 mM
Thiourea: 1 mM
at pH: 3.5
The electrolyte is preferably equilibrated until there are
no spectroscopic changes. The bath was found to oper
ate over a temperature range of 25 to 60 C. Good
bright deposits of chromium were obtained.
EXAMPLE 3
The following constituents were dissolved in the base
electrolyte: \ the chromium ions and the complexant is in the range
Chromium (III): 100 mM (from chrometan)
DL Aspartic acid: 100 mM
Mercaptoacetic acid: 1 mM
at pH: 3.5
The electrolyte is preferably equilibrated until there are
no spectroscopic changes. The bath was found to oper
ate over a temperature range of 25 to 60 C. Good
bright deposits were obtained.
EXAMPLE 4
The following constituents were dissolved in the base
electrolyte:
Chromium (III): 100 mM (from chrometan)
DL Aspartic acid: 100 mM
Thiourea: 1 mM
at pH: 3.5
The electrolyte is preferably equilibrated until there are
no spectroscopic changes. The bath was found_to oper
ate over a temperature range of 25 to 60 C. Good
bright deposits were obtained over a current density
range of 10 to 800 mA/cmz.
By way of comparison, when the complexant aspartic
acid in this Example is replaced with citric acid, the or a -SS group within the molecule for promoting
stability constant K1 of which is less than 103, the plat
6
ing ef?ciency is less than one-half that with aspartic
acid.
While the invention has been particularly shown and
described with reference to preferred embodiments
thereof, it will be understood by those skilled in the art
that various changes in form and details may be made
therein without departing from the spirit and scope of
the invention.
What is claimed is:
1. A chromium electroplating electrolyte containing
trivalent chromium ions, a complexant, a buffer agent
and an organic compound having a -C-:S group or a
CS group within the molecule for promoting
chromium deposition, the complexant being selected so
that the stability constant K1 of the reaction between
the chromium ions and the complexant is in the range
l08<K1<1O191M-1 at about 25 C.
2. An electrolyte as claimed in claim 1 in which the
complexant is selected from aspartic acid, iminodiacetic
acid, nitrilotriacetic acid and S-sulphosalicylic acid.
3. An electrolyte as claimed in claim 2 in which the
organic compound is selected from mercaptoacetic and
mercaptopropianic acid.
4. An electrolyte as claimed in claim 3 in which the
ing conductivity ions selected from sulphate salts.
5. An electrolyte as claimed in claim 4 in which the
sulphate salts are a mixture of sodium and potassium
sulphate.
6. An electrolyte as claimed in claim 1 in which the
organic compound is selected from thiourea, N-monoal
lyl thiourea, N-mono-p-tolyl thiourea, thioacetamide,
tetramethyl thiuram monosulphide, tetraethyl thiuram _
disulphide and diethyldithiocarbamate.
35 7. An electrolyte as claimed in claim 1 in which the
organic compound is selected from mercaptoacetic and
mercaptopropianic acid.
8. A chromium electroplating electrolyte containing
trivalent chromium ions, a complexant, a buffer agent
and an organic compound having a C:S group or a
CS- group within the molecule for promoting
chromium deposition, the complexant being selected so
that the stability constant K1 of the reaction between
45 lO3<K1<lO12M-1 at about 25 C., the complexant
being selected from aspartic acid, iminodiacetic acid,
nitrilotriacetic acid or S-sulphosalicylic acid, and the
organic compound being selected from thiourea, N
monoallyl thiourea, N-mono-p-tolyl thiourea, thi
oacetamide, tetramethy] thiuram monosulphide, tetra
ethyl thiuram disulphide, diethyldithiocarbonate, mer
captoacetic or mercaptopropianic acid.
9. An electrolyte as claimed in claim 8 in which the
buffer agent is boric acid.
10. An electrolyte as claimed in claim 8 in which the
source of chromium is chromium sulphate and includ
ing conductivity ions selected from sulphate salts.
11. An electrolyte as claimed in claim 10 in which the
sulphate salts are a mixture of sodium and potassium
60 sulphate.
12. A bath for electroplating chromium comprising
an anolyte separated from a chromium electroplating
catholyte by a perfluorinated cation exchange mem
brane, the catholyte comprising an electrolyte contain
65 ing trivalent chromium ions, a complexant, a buffer
agent and an organic compound having a ~C=S group
chromium deposition, the complexant being selected so
 4,502,927
7 8
that the stability constant K; of the reaction between 16. A bath as claimed in claim 12 in which the organic
the chromium ions and the complexant is in the range compound is selected from mercaptoacetic and mercap
l08<K|< IOlZM-l at about 25" C. topropianic acid.
13. A bath as claimed in claimv 12 in which the com 17. A bath as claimed in claim 12 in which the anolyte
plexant is selected from aspartic acid, iminodiacetic comprises sulphate ions.
18. A bath as claimed in claim 17 including a lead or
acid, nitrilotriacetic acid and S-sulphosalicylic acid.
14. A bath as claimed in claim 13 in which the organic
lead alloy anode immersed therein.
19. A bath as claimed in claim 12 including a lead or
compound is selected from thiourea, N-monoallyl thio lead alloy anode immersed therein.
urea, N-mono-p-tolyl thiourea, thioacetamide, tetra 10 20. A bath as claimed in claim 12 in which the buffer
methyl thiuram monosulphide, tetraethyl thiuram disul agent is boric acid, the source of chromium is chromium
phide and diethyldithiocarbonate. sulphate, including conductivity ions provided by a
15. A bath as claimed in claim 13 in which the organic mixture of sodium and potassium sulfate, and including
compound is selected from mercaptoacetic and mercap a lead or lead alloy anode.
topropianic acid. 15 =1! 1R * * *

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