TECHNlqLLY

speal\.lng
BY . PROTSENKO .", V.O. GORDIiENKoa, F.I. DANILOVa AND S.c. KWON b
aDepartment of Physical Chemistry,
Ukrainian State University of Chemical Technology,
Gagarin Av. 8, Dnepropetrovsk 49005, Ukraine
bSurface Engineering Department,
Korea Institute of Machinery and Materials,
66 Sangnam-dong, Changwon, Gyeongnam 641-010, Republic of Korea

Thick Chromium Electrodeposition

from Trivalent Chromium
Bath Containing Carbamide
and Formic Acid
An investigation into current efficiency, electrodeposition
rate and surface morphology.
ABSTRACT
Effect of bath composition and
electrolysis conditions on the current efficiency, electroplating rate
and surface morphology of Cr-coatings was studied using a trivalent
chromium bath containing chromium sulfate, sodium sulfate, aluminium sulfate, boric acid, formic
acid, carbamide and surfactant. The
optimal concentrations of Cr(II1)ions, carbamide and formic acid
were stated to be 1.0, 0.5 and 0.5 M,
respectively. At optimal bath composition and electrolysis conditions, the deposition rate does not
appreciably diminish during electrolysis time and reaches -1-1.5 J.l.m
min'l. The value of current efficiency of chromium electrodeposition
process is close to -30-40%. The
thick chromium coatings deposited
from the bath under consideration
are bright and smooth; they exhibit
nodular rype of surface structure.
1. INTRODUCTION
Hard chromium electroplating plays
an imponant role in modem industry due to unique properties of
chromium deposits. Hard chromium
www.metalfinishing.com

coatings are currently produced

from chromic acid solutions containing highly toxic compounds of
hexavalent
chromium.
Environmental considerations are
responsible for the increased interest
in less toxic trivalent chromium
baths as an eco-friendly alternative to
hexavalent chromium baths l -15
However, it is not easy to obtain
thick deposits from trivalent chromium baths. The rate of chromium
deposition was stated to be
decreased rapidly with deposition
time, and after 10 minutes of elec-

trolysis no mass gain was observable 16. The principal problem seems
to be formation of Cr(IIl) hydroxocomplexes in the near-electrode layer
during Cr-deposition. The electrode
surface may be blocked by poorly soluble adsorbed hydroxide compounds of Cr(III) 17. 18. Therefore, the
rate of chromium plating diminishes. In addition, the particles of the
Cr(III) hydroxide solution are incorporated into coating structure,
which causes cracking and darkening ofdeposits.
In order to avoid these undesirable phenomena, some special complexing agents and buffers should
be used 1. In recent years, the trivalent Cr-baths which contain carbamide and formate (or formic
acid) as such complexing agents
and buffers were investigated in a
number of papers 4-7.
However, the effect of bath composition and electrodeposition conditions on the current densiry, electroplating rate and surface morphology

36.5

36.5

0.05

33.5

21.3

0.1

29.0

20.1

0.15

29.0

20.1

0.2

29.0

19.7

Table 1
Deposition time 1S min; 1.5; temperature 35C; current density 35 A dm,2

June 2011 I rMtalfinlshlncl33

TECHNlqLLY
spea~lng

of Cr-coatings obtained from trivalent chromium bath which contains

carbamide and formic acid (formate)
has been studied insufficiently.
2. EXPERIMENTAL
Chromium electrodeposition was
carried out in a usual thermostated
glass cell (V = 1 L). Chromium was
deposited at a steady value ofcurrent
density on the disc electrode of copper foil (5 = 1.77 cm2) ftxed in a plastic holder.
The electrolysis was carried out
using titanium-manganese dioxide
anodes (TMDA). On the TMDA
the electrooxidation of Cr(III) ions
occurs with a rather small rate 19 .
Therefore, chromium electroplating can be performed without separation of anodic and cathodic
compartments.
The current efficiency was calculated by comparing the weight gain of
the cathodes placed in the chromeplating bath with that of a copper
coulometer connected in series.
The surface morphology of
deposits was investigated by scanning electron microscopy (EVO
40XVP). The samples used in SEMstudy were electroplated on the electropolished Cu-substrate, the thickness ofdeposits being about 20llm.
3. RESULTS AND DISCUSSION

3.1. Selection ofsome bath constituents

In present work, chromium sulfate
and chrome alum were proofed as a
source of Cr(III)-ions. Several buffer
agents (boric acid and aluminium
sulfate) as well as conducting salts
(sodium sulfate, ammonium sulfate
and potassium sulfate) were used for
bath preparation.
The results obtained in preliminary investigations allow us to draw
the conclusions as follows:
i) The additive of carbamide
favorably affected the chromium
electroplating process if solutiori
is acid enough-the coatings
become visually bright when pH
tends to a value of-1.5 and
34 I metalflnlshlng I June 2011

Crz(S04h 6HzO
HCOOH

--

0.5

0.5

CO(NHzlz

0.5

pH 1.5

Al z(S04h 18H zO

0.15

Temperature 35C

Na ZS0 4

0.3

Current density
30 - 35 A dm- z

H3 B0 3

0.5

Sodium dodecyl sulfate

0.05 - 0.1 gL- 1

Table 2. Optimal Basic Bath Composition and Electrodeposition Conditions.

lower;
ii) An increase in the Cr(II1)-ions
content improves surface appearance and results in an increase in
the current efficiency and
chromium deposition rate;
iii) When the current density is
rather high, the pitting appears
on the coating surface. In order
to remove pitting, it is necessary
to use some wetting agents, for
example, sodium dodecyl sulfate
(sodium lauryl sulfate);
iv) In electrolytes with a rather
high chromium (III) content (0.9
M and greater), the restricted
mutual solubility of constituents
may be reached even at room
temperature and salts precipitate
partly at the bottom of the bath.
The last phenomenon is especially
exhibited when ammonium ions are
present in the solution (in the form
of (NHJ2S0J or the electrolyte is
prepared on the base ofchrome alum
(KCr(S04hx12H20). The chemical
analysis showed that the sediment
was either potassium alum or ammonium alum; it did not contain
chromium (III) ions.
The phenomenon concerned may
be related with a sufficiently smaller
solubility of the alums containing
potassium or ammonium in comparison with those containing sodium. For example, reference data on
the solubility of waterless salts
NaAI(S04)2 x 12H 2 0,
KAI(S04)2x12H20
and
NH4Al(S04hx12H20 are 39.72, 5.9
and 7.17, respectively (in g in 100 g

H 20 at 20C)20.
Formation of sediment at the bottom of the bath containing chrome
alum can create obvious complications in commercial operation. Thus,
it is reasonable to prepare chromium
electrolytes on the base ofchromium
sulfate. The Cr(III)-ions content in
the bath containing Crz<S04h may
be brought up to 1 M.
Concerning conducting salts, sodium sulfate, but not potassium or
ammonium compounds, seems
rationally to utilize because ofa larger solubility of sodium salts as compared with potassium and ammonium compounds.
The current efficiency of chromium electrodeposition reaction and
the quality of deposits proved to
depend signiftcantly on the presence
of buffer agents in the bath.
When the bath does not contain
boric acid, the current efficiency is
rather high but dull chromium
deposits are obtained.
If aluminum sulfate is absent in
the bath, the current efficiency grows
appreciably (up to 40-50%). However,
gray and extremely rough coatings
deposit in this case.
Thus, the high-quality deposits can
be obtained only when both boric
acid and aluminum sulfate are present in the trivalent chromium bath.
The optimal contents of these additives are close to 0.15 and 0.5 M for
Al2(SOJ3 and H3B03, respectively.
As stated above, using some wetting agents proved to be necessary to
remove pitting formation on the
deposits' surface. A whole number of
www.metaltinishing.com

TECHNlqLLY
speal\.lng

43%
(2.26 Jim mm")

50

tf!. 40
~
c: 30
Ol

'u

50

C 20
~
u" 10

... ~~~~~~~.. 1

--

>u

..

lii 30

Tj

,~

,~

'

lE

"

... 3
,,~~:::: __----_. 2

g30
~"

20 '0

"

'0

25

::

"c

10 is

:E

15

10

1.2

1.5

oI

35

Current density I A dm-2

Fig. 1 - Dependencies of current efficiency on
current density at different concentration of
formic acid.
(1) 0.3 M HCOOH; (2) 0.5 M HCOOH; (3) 0.7
MHCOOH
Bath composition (M): 1.0 Cr(III). 0.5
CO(NHzh, 0.5 H3B0 3 0.15 Alz(SOJ3xlSHzO.
0.3 NazSO., and 0.1 g L-1 sodium dodecyl sulfate
Deposition time 15 min; pH 1.5; temperature
35C

10

15

20

1.8

w ....",,'"
yo'"

0
25

ElectrodopositJon time I min

pH

30

:l.

~~~

25

30

u"

,," ,,'"

~
20
c
~
<3 10

40

35

"
~ 20

IE
Ol

eft. 40

40
~

Fig. 3 - Dependencies of current efficiency

and electrodeposition rate upon pH
Bath composition (M): 1.0 Cr(III). 0.5 HCOOH.
0.5 CO(NHzlz. 0.5 H3B03. 0.15
AI2(SOJ3xlSHzO. 0.3 NazSO and 0.1 g L-1
sodium dodecyl sulfate
Deposition time 15 min; temperature 35C;
current density 35 A dm-z

Fig. 5 - Effect of eleetrodeposition time on

current efficiency and chromium electrodeposition rate
Bath composition (M): 1.0 Cr(III), 0.5 HCOOH.
0.5 CO(NHzh. 0.5 H3B03 0.15
Alz(SOJ3xlSHzO, 0.3 Na2S004. and 0.05 g L- 1
sodium dodecyl sulfate
Temperature 35 C; pH 1.5; current density 35
Adm- z

50

~ 40
~
c
.~

30

!i:
Q)

~ 20
t::

2:::
?/40'C

Fig. 6 - Photo of steel cylinder for air compressor in air-conditioning with Cr-deposits
from the bath under consideration
Thickness of Cr layer is about 30 11m

OJ

50

~~~

eft. 40

--

>u

..' " "

c
.!!1 30
u
lE
Q)

..

C 20

:l

.;'

~~ ..

e"

"

",'" "

'"

25

30

35

Fig. 4 - Effect of current density and temperature on current efficiency of chromium electrodeposition
Bath composition (M): 1.0 Cr(III). 0.5 HCOOH.
0.5 CO(NHzh. 0.5 H3B03 0.15

",""

30

Current density I A dm-2

10

10
25

.~ .... 3
e~~~~---" 2

'

35

Alz(SOJ3x18HzO. 0.3 NazSO and 0.05 g L-1

sodium dodecyl sulfate
Deposition time 15 min; pH 1.5

Current density I A dm-2

Fig. 2 - Dependencies of current efficiency on
current density at different concentration of
CO{NHz>z
(1) 0.3 M CO(NHz>z; (2) 0.5 M CO(NHz>z; (3)
0.7 M CO(NHz)z
Bath composition (M): 1.0 Cr(lll). 0.5 HCOOH.
0.5 H3B03, 0.15 Alz(SOJ3x 18HzO. 0.3
NazSO and 0.1 g L-1 sodium dodecyl sulfate
Deposition time 15 min; pH 1.5; temperature
35C

different wetting agents may be used

thereto. Introduction of the surfactant into the chromium bath results
in a decrease in current efficiency
and deposition rate (Table 1). We
chose sodium dodecyl sulfate as a
surfactant for further investigations

www.metalfinishing.com

because a decrease in the current efficiency is not very appreciable in the

presence of this substance. The optimal concentration of the sodium
dodecyl sulfate lies in the range from
0.05 to 0.1 g L-1. There is an intensive
foam formation when the content of
sodium dodecyl sulfate is more than
-0.1 g L-1.

3.2. Effect of formic add and car

bamide content on current eJfldency
and surfe appearance ofCr-coatings
As shown in Figure 1, when formic
acid concentration changes from 0.3
to 0.5 M, the current efficiency of
chromium
electrodeposition

decreases
appreciably;
while
HCOOH concentration is 0.7 M and
over, the current efficiency slightly
grows. It should be noted that the
deposits readily crack and exfoliate
from the substrate at the HCOOH
concentration of 0.3 M. At a greater
content of formic acid (~0.5 M), the
coatings are smooth, bright;' they
adhere firmly to the substrate.
The dependencies of the current
efficiency on carbamide concentration are similar to the foregoing
ones (Figure 2). Namely, the current
efficiency has a minimum at a "middle" carbamide concentration (0.5
M). When the CO(NHzh content
increases or decreases, the current
efficiency grows at any cathodic current density. However, while the carbamide concentration is relatively
small (0.3 M), the deposits are bright
but somewhat strained and there is a
large number ofwide cracks on their
surface. Note that the deposits
become rather dull if CO(NHzh
concentration is equal to 0.7 M.
Taking into account all these
facts, we assume that the optimal
content of both formic acid and

June 2011 I metalftnlshlng I 35

TECHNlqLLY
speal\.lng

7b

7a

7c

.
'.

2O)IFIl
~

7e

7d

.,.' <,g1.;:t~ :",';'"

~~-r",f':f ~~ .Y.~~;~

i_

'.'.. "K .'

f&t~~'~i~'" -:

eo..~
H

..,.uow
WO-IIO_

...."
",-

,
*1i

III ]

7f

"""
_

7g

7h

carbamide is 0.5 M.
It is noticeable that the current
efficiency of chromium deposition
dramatically decreases and deposits
readily exfoliate from the substrate if
the electrolyte does not contain
either formic acid or carbamide.

value is equal to -1.8 and more. The

pH value being decreased, the surface appearance of chromium coatings improves but the values of current efficiency and deposition rate
diminish essentially. Therefore, we
think that the optimal value of pH
is about 1.5.
There is an increase in the current
efficiency when increasing cathodic
current density and decreasing electrolyte temperature (Figure 4).
It should be stressed that growing
the bath temperature results in deterioration of deposits-the deposits
are not bright enough for the temperature of 30C and lower.
Therefore, the optimal value of bath

3.3. Effect ofelectrolysis conditions on

current effICiency, electrodeposition
rate and surface appearance of Crcoatings
The current efficiency and the rate of
chromium
electrodeposition
increase with an increase in bath pH
(Figure 3). However, the dark and
striped deposits with poor adhesion
to the substrate are formed when pH
36 I metalfinishing I june 2011

hKl

Fig. 7 - SEM image of coating from the optimal basic chromium bath without (a) and
with surfactant ((b)-(h
(a) and (b) - at current density 35 A dm-2;
temperature 35C and pH 1.5;
(c) pH 1.3. (d) pH 1.7 - at current density 3S
A dm-2 and temperature 35 C;
(e) 30 A dm-2 (f) 40 A dm-2 - at temperature
35C and pH 1.5;
(g) 30 C. (h) 40 C - at current density 35 A
dm" and pH 1.5

~~,,' ,:J;,

--ir-~"

.....
, w
wo ..._

temperature is about 35C.

When the current density of
chromium deposition is equal to -40
A dm-2 and higher, the deposits surface becomes rough and not bright
enough. Additionally, the "burnings"
occur on the deposits surface with an
increase in the current density. Thus,
the most favorable value of current
density is close to 30-35 A dm-z.
The current efficiency and the
velocity of chromium electroplating process from the bath under
consideration diminish slightly
with deposition time (Figure 5). It
is very important and favorable that
even after 10 minutes of electrolysis
the plating rate remains high and
www.metalfinishing.com

TECHNlqLLY

speal\lng

large and thick chromium layers

can be obtained during relatively
short time.
The optimal basic bath composition and electrodeposition conditions are summarized in Table 2.
Figure 6 shows a sample with Cr
coating deposited from the trivalent
chromium bath under consideration.
3.4. SEM characteriZAtion ofcoatings

surface
As shown in Figure 7(a), when the
bath does not contain surfactant, the
surface ofcoating is rough and irregular with a great number of spheroids ofdifferent size. The surface of
coatings deposited from electrolytes
containing sodium dodecyl sulfate is
more uniformly and smoother
(Figure 7(b; the number of spheroids diminishes substantially.
The surface morphology changes
by variation of pH. For pH 1.3,
there are no cracks on the surface of
Cr-layers (Figure 7(c). The number
of nodules is not large; these spheroids seem to have a small size. An
increase in bath pH results in deterioration of the coating surface
(Figure 7(d). The cracks appear and
the number of nodules rises. The
surface morphology becomes not
uniform and defective.
The current density of chromium
electrodeposition affects the surface
morphology (Figs. 7(e) and (t). For
30 A dm 2, the surface is rather
smooth and uniform; some spheroids of small size are observed. The
cracks are practically absent at this
value of cathodic current density.
The current density being increased
up to 40 A dm'2, the cracks appear on
the chromium surface.
By decreasing the temperature to
30C, a great number of small
spherical nodules occur and some

defects and cracks are observed on

the deposit surface (Figure 7(g).
When the bath temperature
increases up to 40C, the number
of nodules formed on the surface
diminishes, but simultaneously the
quantity of microcracks seems to
become larger (Figure 7(h).
CONCLUSIONS
Trivalent chromium electrodeposition from a sulfate trivalent chromium bath which contains both formic
acid and carbamide as the complexing agents was considered. Using
chromium sulfate but not chrome
alum is reasonable for preparation of
high-concentrated trivalent chromium bath. Some wetting agents
should be used in order to remove
pitting formation.
The value of current efficiency of
chromium electrodeposition process
reaches -30-40%. The chromium
electroplating rate does not decrease
dramatically during electrolysis time;
it is close to -1-1.5 mm min,1.
The thick Cr-coatings with a nodular type of surface structure deposit
from the trivalent chromium bath
under consideration.

REFERENCES
1. G. Hong, K.S. Siow, G. Zhiqiang,
AX Hsieh, Plat. Surf. Finish. 88
(3) (2001) 69.
2. AA Edigaryan, Yu.M. Polukarov,
Zashch. Met. 34 (1998) 117.
3. A.A. Edigaryan, Yu.M. Polukarov,
Zashch. Met. 35 (1999) 5.
4. V.N. Kudryavtsev, E.G.
Vinokurov, V.V, Kuznetsov,
Gal'vanotekhn. Obrab. Poverkhn.
6 (1998) 24.
5. V.v. Kuznetsov, E.G. Vinokurov,
V.N. Kudryavtsev, Russ.].
Electrochem. 37 (2001) 699.
6. S. Survilene, O. Nivinskiene, A
Cesuniene, A Selskis, J. App!.
Electrochem. 36 (2006) 649.

7. S. Surviliene, V. Jasulaitiene, O.
Nivinskiene, A Cesuniene, Appl.
Surf. Sci. 253 (2007) 6738.
8. S.c. Kwon, M. Kim, S.U. Park,
D.Y Kim, D. Kim, K.S. Nam, Y
Choi, Surf. Coat. Technol. 183
(2004) 151.
9. YB. Song, D.-T. Chin,
Electrochim. Acta 48 (2002) 349.
10. F.I. Danilov, V.S. Protsenko, T.E.
Butyrina, E.A Vasil'eva, AS.
Baskevich, Prot. Met. 42 (2006)
560.
11. B.S. Li, A Lin, Key Eng. Mater.
373-374 (2008) 200.
12. G. Saravanan, S. Mohan, J. App!.
Electrochem. 40 (2010) 1.
13. S. Mohan, J. Vijayakumar, G.
Saravanan, Surf. Eng. 25 (2009)
570.
14. AA Edigaryan, V.A. Safonov,
E.N. Lubnin, L.N. Vykhodtseva,
G.E. Chusova, Yu.M. Polukarov,
Electrochim. Acta 47 (2002)
2775.
15. O.V. Safonova, L.N.
Vykhodtseva, N.A. Polyakov,].C.
Swarbrick, M. Sikora, P. Glatzel,
V.A Safonov, Electrochim. Acta
56 (2010) 145.
16. I. Drela,]. Szynkarczuk, J.
Kubicki, J. Appl. Electrochem. 19
(1989) 933.
17. M.N. Ben-Ali, F.I. Danilov,
Elektrokhimiya 25 (1989) 1537.
18. V. Protsenko, F. Danilov,
Electrochim. Acta 54 (2009)
5666.
19. F.I. Danilov, AB. Velichenko,
Electrochim. Acta 38 (1993) 437.
20. I.L. Knuniantz (ed.),
Khimicheskaja entsiklopedia
(Encyclopedia on Chemistry, in
Russian), voL 2, Soviet
Encyclopedia, Moscow, 1990, p.
730.

* Corresponding author. Tel. (fax):

+380-5~2-474586.

E-mail address:Vprotsenko@smtp.ru

WW'N.metalfinishing.com
'N'N'N.organicfinishing.com
www.meralfinishing.com

June 2011 I nwtalflnishing I37