BULLETIN
The chemistry of nickel electroplating solutions
J. Wang1, D. R. Gabe*1, A. C. Hart2 and P. C. Crouch2
This paper describes work to determine
the nature of the cationic species
present in the type of nickel solutions
used for commercial electroplating and
electroforming. The three nickel salts
examined – sulphate, chloride and
sulphamate – are the ones most
commonly used in these processes.
Despite the fact that nickel plating was
first invented in 1837 and has become
an extremely useful part of high
technology applications the nature of
the species in solution has never been
investigated.
The purpose of this study is to discover
if the differences in deposit properties –
particularly internal stress - produced
by the three types of nickel salt is
determined by the structure of the
cationic species and the effect, if any,
that the different anionic species have
upon the structure of the nickel ions in
aqueous solution.
Introduction and literature
survey
The first recorded claim for the
invention of nickel electroplating was
made by J. Bird1 in 1837; in 1840
another researcher, J. Shore,2 was
granted a UK Patent covering nickel
deposition. During the period from
1855 to 1878 there was a burst of
activity, no fewer than five patents
were granted related to nickel
electrodeposition in the USA alone.3–7
During the latter part of the 19th
century nickel salts used for this
process included sulphate, chloride and
ammonium sulphate double salt. A
major step forward took place in 1878
when Weston7 patented the use of
boric acid in nickel plating solutions. At
the time this was considered to act as a
1
Dept. Materials, Loughborough University,
LE11 3TU, UK
2 fully replaced sulphate based ones
Hart Materials Limited, Carrier House,
Wombourne, WV5 9DH, UK
*Author for correspondence: D.R.Gabe@
lboro.ac.uk
ß 2013 Institute of Metal Finishing
Published by Maney on behalf of the Institute
4 DOI 10.1179/0020296712Z.00000000079
pH buffer in the solution in close
proximity to the cathode surface where
nickel ions are reduced to nickel metal.
Recent work8,9 suggests that boric acid
may also have a complexing and/or
catalytic effect on the nickel ion.
However, what is arguably still the
most significant development in nickel
solution technology took place in 1916.
Oliver Watts, working at the behest of
a consortium of electroplaters in the
USA, published his results10 defining
the composition of a solution based on
nickel sulphate but also containing
nickel chloride and boric acid.
A typical Watts formulation is given
below.
NiSO4 :6H2 O 300 g L{1
NiCl2 :6H2 O 30 g L{1
H3 BO3 40 g L{1
The ‘Watts Solution’ - as it became
universally known - quickly became the
mainstay of the nickel electroplating
industry and has remained so until this
day. There have been many variations
on the basic composition such as high
and low chloride formulations and
chloride-free solutions. Some of these
have found specialist uses, for example
high chloride solutions are used when
increased deposition rates are required.
However, the most significant
modification of the Watts formulation
appeared during the 1950s and 1960s
when nickel sulphamate -
Ni(NH2SO3)2.4H2O - was introduced as
an alternative to nickel sulphate.
Sulphamate-based solutions have an
inherently higher electrical conductivity
than those based on nickel sulphate.
This allows high deposition rates, up to
60 A dm22, to be achieved which
provides much faster metal deposition.
In addition, nickel deposits produced by
sulphamate solutions inherently show
much lower levels of internal tensile
stress than those produced by either
sulphate or chloride formulations.
Despite their technical advantages
sulphamate based solutions have never
because of their higher cost.
In older literature the use of nickel
fluoborate solutions is recorded and in
Transactions of the Institute of Metal Finishing
recent years solutions based on nickel
methanesulphonate have appeared.
Neither of these types however have
ever established significant commercial
use. Consequently nickel
electrodeposition in the early 21st
century depends almost exclusively
based on the sulphate, sulphamate and
chloride salts.
Nickel electroplating and the
associated technology of nickel
electroforming have become extremely
important processes in a very wide
range of manufacturing operations
from the 19th century, throughout the
whole of the 20th century into the early
years of this century. The chemistry
employed does not differ basically from
that used in the early 20th century.
However, the immense sophistication
of the process technology that has
taken place has resulted in nickel
electroplating and electroforming
become absolutely essential for high
technology applications such as the
manufacture of CDs/DVDs/BRDs and
security holograms.
It has been estimated that in 2010
metal and metal salt consumption in
Europe for nickel electrodeposition
was around 28,000 tonnes p.a. At that
time approximately 3,000 companies
in the EU were calculated to be to be
involved in the business of nickel
plating. World consumption in 2010
was estimated at 133,000 tonnes p.a.,
due to massive market growth in China
and India (data courtesy of Heinz H.
Pariser, Alloy Metals & Steel Market
Research).
During the last 170 years there have
been innumerable papers, reviews and
books published on the subject of
nickel electrodeposition. Four
mainstream comprehensive reviews
are those by Dennis and Such,11
Lowenheim,12 Brugger13 and Bloom
and Hogaboom.14 Although these
many publications have covered
almost every practical aspect of nickel
electroplating a detailed literature
search revealed that there appears to
have been little, if any, work carried
out to define the chemical nature of
electrolytes involved in nickel
electrodeposition. As a consequence
2013 VOL 91 NO 1

although it is well known that the
electrical conductivity of the solution
and the internal stress of the deposited
nickel are greatly influenced by the
anionic species in solution there has
been no work carried out to explain
how these properties are related to the
species in the solution.
It is accepted that nickel chloride
solutions have a higher electrical
conductivity than nickel sulphate and
sulphamate solutions of equivalent
concentration. Similarly it is accepted
that nickel sulphamate solutions have a
higher conductivity than nickel sulphate
based ones. For this reason they are
employed for high speed
electroforming using the Ni-Speed
solution developed by Watson and
Kendrick in the 1960s.15,16
The effect of the anionic species on
deposit stress is also well known.
Lowenheim12 quotes stress values of
125 MPa for a Watts solution whereas
for an all chloride solution much higher
values of 275 – 345 MPa are recorded.
A very low stress value of 3.5 MPa is,
however, reported for a nickel
sulphamate solution (without any
chloride addition).
This study therefore sets out to look
at two basic aspects of a number of
nickel plating solutions using the three
anionic species in common industrial
use to determine if these throw any light
on the hitherto unexplained differences
in behaviour of the different solutions.
The first aspect that has been
examined is the relative electrical
conductivity of the three types of
solution. Although some
measurements have been carried out in
the past there does not seem to be any
systematic study of this very simple
property in the public domain. Also, of
course, using modern instrumentation
much more accurate measurements
can currently be made. Secondly, the
absorption spectra from each solution
have been examined to check for
differences in the structure of the Ni
ions in the different solutions.
Experimental procedures
Solution compositions
Solutions of nickel sulphate and
chloride were prepared from analytical
grade crystals dissolved in de-ionised
water. Nickel sulphamate is not
normally available in crystalline form.
The experimental solutions were
therefore prepared from commercial
grade concentrated solution diluted
with de-ionised water. Currently
available nickel sulphamate concentrate
is of exceptional purity being
manufactured from ultra-high purity
carbonyl nickel powder. Relevant
molecular weights and nickel metal
contents are given below
NiSO4 :6H2 O MW 262:8 22:3% Ni
NiCL2 :6H2 O MW 237:6 24:7% Ni
Ni(NH2 SO3 )2 :4H2 O MW 322:9 18:2% Ni
The concentrations chosen are typical
of those used in commercial nickel
electroplating and electroforming. A
highly concentrated nickel sulphamate
solution was included in the
investigation since processes such as
Ni-Speed15 are operated at this level.
Conductivity Measurements
A model 4200 Jenway conductivity
meter, suitable for both industrial and
laboratory work, was employed for
these determinations. This has a
measurement range from 0 mS to
199.9 mS, and a temperature capability
from 210uC to 105uC.
Conductivity k is expressed normally
by the equation:
k~G:K
where G is conductance (S) and K is the
cell constant (cm21).
The instrument was calibrated
against a solution of 0.746 g of dried
A.R. Grade potassium chloride (KCl)
dissolved in 1 litre of deionised water.
The solutions were heated to 95uC with
magnetic stirring and then allowed to
cool naturally to just below 30uC the
conductivity being measured at
intervals of approximately 4uC.
Spectroscopic measurements
A Jenway type 6705 Series UV/Visible
single beam spectrometer with a
measuring range from 190 nm to
1100 nm was employed. The light
source has a 4 nm spectral bandwidth
and the instrument is accurate
between 15uC and 40uC. It would have
been preferable to have used a double
beam system to compensate for
background effects but this type of
instrument was not available.
A further problem occurred in relation
to the concentration of the solutions
used which were typical of those
employed commercially for nickel
plating. These concentrations are,
however, around two orders of
magnitude higher than those typically
examined in this type of spectroscopy.
Consequently, the absorbance peaks of
some of the spectra were off-scale as
far as the instrument was concerned.
Allowance had to be made for this in
the interpretation of the results.
Transactions of the Institute of Metal Finishing
BULLETIN
Results
Solution Conductivity
Measurements
Gabe and Chen17 examined the
conductivity of three nickel salt
solutions; sulphate, chloride and
sulphamate, at room temperature.
Fig. 1, using data from their work,
shows that the conductivity of each
solution increases with increasing
concentration up to a maximum, due to
increasing ion concentration, and then
decreases, due to decreasing ion
dissociation. The maximum
conductivity occurs at a higher
concentration for the chloride solution
than for either the sulphate or
sulphamate solutions.
Fig. 2 shows results from this study
for nickel sulphate and sulphamate
solutions at room temperature, with
the expected trend of increasing
conductivity with increasing
concentration. The measured
conductivities were higher than those
observed previously even though the
range of concentrations used was
considerably less.
The results obtained in the current
study for the three salts at two nickel
ion concentrations of 1.14 M and
1.70 M and at temperatures between
25uC and 75uC are shown in Fig. 3. At
the lower concentration the increase in
conductivity was less marked than at
the higher concentration. The chloride
solution shows much higher
conductivity than the other two
solutions and the sulphamate solution
somewhat higher conductivity than the
sulphate one. This is very much in line
with common practical experience with
nickel plating processes. However, the
conductivity difference between the
sulphate and sulphamate solutions is
perhaps less than might be expected.
In view of the importance of boric
acid in nickel plating solutions the
conductivity of each of the three nickel
salt solutions was examined with
additions of from 0 g L21 to 50 g L21
boric acid. (40 g L21 is the normal
concentration used in nickel plating
processes).
Figs. 4 and 5 show the results
observed with chloride and sulphamate
solutions where addition of boric acid
generally lowered the conductivity but
the expected increase in conductivity
with temperature accelerated markedly
at temperatures above 80uC. Fig. 6
shows the results for the nickel
sulphate solution which was not tested at
such high temperatures as for the other
2013 VOL 91 NO 1 5
BULLETIN

1 Conductivity of three nickel solutions at room tempera- 2 Conductivity of two nickel solutions at room temperature
ture, data from Gabe and Chen17

4 Conductivity of 1.28 M nickel chloride plus boric acid

3 Conductivity of three nickel solutions at two concentrations (g L21) solutions over a range of temperature
(1.14 M and 1.70 M) over a range of temperature

5 Conductivity of 1.02 M nickel sulphamate plus boric acid 6 Conductivity of 0.852 M nickel sulphate plus boric acid
(g L21) solutions over a range of temperature (g L21) solutions over a range of temperature

two solutions. They also show a small
increase in conductivity with addition of
boric acid at temperatures below 60uC.
The effect of temperature and boric
acid additions on the pH of chloride and
sulphamate solutions are shown in
Figs. 7 and 8, respectively. The results
for the sulphamate solution showed a
consistent decrease in pH with
increasing boric acid concentration and
temperature. The decrease in pH
became less as the temperature solutions containing nickel ions in the
increased. For the chloride solution the visible to UV region. Fig. 9, taken from
addition of boric acid did decrease the the Shigematsu work,18 shows the
pH but in not such a consistent manner following absorption peaks:-
as for the sulphamate solution. With
400 nm 25,000 cm{1
the exception of the results for 50 g
15,600 cm{1 (shoulder)
L21 boric acid the reduction in pH did 640 nm
not change greatly with temperature. 720 nm 13,900 cm{1
Solution Spectra 1150 nm 9,000 cm{1
The literature survey identified four The other studies showed similar results
papers18–21 that showed spectra of although with the Garcia-Urrutia19 work

6 Transactions of the Institute of Metal Finishing 2013 VOL 91 NO 1

 BULLETIN

7 pH value of 1.28 M nickel chloride plus boric acid (g L21) 8 pH value of 1.02 M nickel sulphamate plus boric acid
solutions over a range of temperature (g L21) solutions over a range of temperature

9 Spectra of 0.05 M nickel solutions, based on Fig. 1 from

Shigematsu et al.;18 media giving from highest to lowest
absorbance at low wavelength, (i) HCl (ii) acetic acid (iii) 10 Absorption spectra of nickel chloride in aqueous solu-
aquo, H2SO4 or HClO4 tion at three concentrations

12 Absorption spectra of nickel sulphamate in aqueous

11 Absorption spectra of nickel sulphate in aqueous solu-
tion at three concentrations solution at four concentrations

the peak at around 720 nm became a
shoulder on the side of the main
absorption band at 650 nm.
Figs. 10, 11 and 12 show
respectively the spectra observed for
three concentrations of nickel sulphate
and chloride and four of nickel
sulphamate, respectively. The spectra
of the three solutions at a concentration
of 0.76 M are compared in Fig. 13
plotted against wavelength and in
Fig. 14 against frequency. Above
290 nm (i.e. below 31,000 cm21) the
results are very similar although the
chloride solution seems to have a very
slightly higher absorption than the other
two.
The earlier studies18–21 employed a
wider range of anions and acidities and
much lower nickel ion concentrations
than those used in the current work. It
might therefore not have been totally
surprising if the absorption peaks
observed had been different. Despite
this most of the peaks observed in this
work, around 400 nm, 650 nm and
720 nm are in good agreement with the
earlier results.
(N.B. The peak observed in the earlier
studies at 1150 nm was not seen in the

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BULLETIN

13 Absorption spectra of three nickel salts in aqueous

solution (0.76 M) 14 Absorption spectra of three nickel salts in aqueous
solution (0.76 M)

15 Absorption spectra in high energy region of three

nickel salts in aqueous solution (0.76 M) 16 Absorption spectra of nickel sulphate (0.94 M) plus boric
acid (g L21) in aqueous solution

18 Absorption spectra of [Ni(OH2)6]2z (0.101 M) and

17 Absorption spectra of nickel sulphamate (1.02 M) plus [Ni(NH3)6]2z (0.315 M) in aqueous solution, based on Fig. 1
boric acid (g L21) in aqueous solution from Triest et al.21

present work because the range of the
instrument did not extend to this
wavelength).
A number of relatively low
absorbance peaks were observed
within the range 920 nm to 1090 nm.
Their wavelengths were consistent for
the three salts at all concentrations
examined. In addition a sharp
absorption peak was observed around
215 nm (45,000 to 48,000 cm-1), see
Fig. 14 and 15. The peak was strongest
for the chloride solution. This was not
evident in any of the previous18–21
investigations possibly due to limitations
of the instruments available at the time
the work was carried out.
The effect of boric acid
Boric acid has been used as a
constituent of nickel plating solutions
since 1878 and has been essential for
the long lasting Watts formulation.
Consequently it was a natural
extension of the work to examine its
influence on the spectra of the
solutions. As can be seen from Figs. 16
and 17 there is virtually no effect of
additions of boric acid up to 50 g L21 to
either sulphate or sulphamate
solutions.

8 Transactions of the Institute of Metal Finishing 2013 VOL 91 NO 1


Discussion
Solution Conductivity
Measurements
The conductivity measurements
provide useful quantitative confirmation
of the properties expected of the three
solutions based on long experience.
This is in itself useful since, despite the
widespread use of these solutions,
quantitative measurements of the basic
property of electrical conductivity do
not seem to have been published.
Unfortunately, however, the results
do not show any consistent differences
that might indicate some difference in
the structure of the nickel cation as a
result of interaction with the different
anions examined.
Solution Spectra
The spectra of the three solutions are
very similar in relation to the general
position and shape of the absorption
curves and peaks. These observations
were consistent over the concentration
range studied and with earlier results in
the presence of similar anions in solution.
With all three salts the absorbance
increased, as expected, with increasing
nickel ion concentration.
A theoretical treatment of the absor-
ption spectrum of a transition metal ion
with a d8 configuration such as Ni2z 22
predicts three peaks due to transitions
from the 3A2g ground state to the 3T2g,
3
T1g(F) and 3T1g(P) excited states.
The assignment of two lowest
energy peaks observed in this work are
as follows:-
N ca. 14,000 cm21, assigned to 3A2g R
3
T1g(F) transition
N ca. 25,000 cm21, assigned to 3A2g R
3
T1g(P) transition
The splitting of the 14,000 cm21 peak
is attributed to spin-orbit coupling. This
mixes the 3T1g and 1Eg states which are
very close together in the electronic
environment provided by six water
molecules in an octahedral arrangement
around the nickel ions.22 An alternative
explanation of the splitting has been put
forward more recently.20
The 3A2g R3T2g transition is normally
assigned to a peak observed at around
9,000 cm21 or 1100 nm; this is
unfortunately just outside the range of
the current measurements.
However there is an area of rapid
absorption fluctuation observed
between about 960 and 1090 nm The
trend of these fluctuations is upwards
and so might be the start of a peak
outside the range of the
spectrophotometer.
Although the sulphamate and sulphate
spectra showed almost identical
absorbance values a slightly stronger
absorbance was noted with the chloride
solutions at 0.76 M. This is not
unexpected since the sulphate or
sulphamate anions are less likely to
replace the water molecules surrounding
the nickel ions and influence the
electronic environment of the metal ion
than the smaller chloride ion.
The peak(s) at around 46,000 cm21
(around 215 nm) have not been
allocated to any specific electronic
transition in the way that the lower
energy peaks have since their source
does not seem to have been identified.
Further work is currently in progress to
investigate the origin and possible
relevance of these absorption peaks.
Relevance to electroplating
behaviour
The close similarity of the spectra of
each of the three salts at the longer
wavelength (lower frequency) part of
the range investigated indicates that
the nickel ions exist in the same form in
these types of highly concentrated
solutions irrespective of the anionic
species. It is therefore reasonable to
conclude that they are surrounded by a
coordination shell of a very similar
nature; this is almost certainly six water
molecules in an octahedral
arrangement. This is not surprising
since the concentration of each of the
three anionic species studied are in the
order of 1 M whereas for water
molecules it is around 50 M.
The spectrum of the Ni(NH3)62z in
relation to that of the nickel hexaquo
ion is shown in Fig. 18 (taken from
reference 21). This clearly
demonstrates that while more strongly
complexing ligands can influence the
spectra the minor changes observed
here suggest that like the chloride ion
the sulphamate and sulphate ions are
only weak complexants.
As a consequence it can reasonably
be concluded that the nickel ions in
sulphate, chloride and sulphamate
solutions are very similar in the bulk
solution and are present as hexaquo
ions. This seems to indicate that the
differences in behaviour of these
solutions, particularly in respect of
deposit stress, cannot be explained by
differences in the form of the nickel
ions in the bulk solution.
It can also be concluded from the
current results that the addition of boric
acid to the solutions has no observable
effect on the structure of the nickel ions.
Transactions of the Institute of Metal Finishing
BULLETIN
The question of why the three types
of solution produce deposits with such
significantly different levels of internal
tensile stress therefore remains open.
One of the obvious limitations of the
work is that the cationic species were
only studied in the bulk of the solution.
It might be that the three different salts
behave differently when they are in the
electrochemical reduction zone – the
Helmholtz layer – in close proximity to
the cathode surface. It would,
however, be difficult to determine the
spectra in this region.
Further work is in progress to extend
the scope of this work in order to develop
a better understanding of the spectra
obtained to determine if these reveal
information relevant to the nature of the
ionic species present in these solutions
in order to explain their electrodeposition
behaviour. In addition other nickel salts
commonly used in electrodeposition
processes are currently being
investigated to determine if their
behaviour is consistent with the three
included in this present investigation.
Conclusions
This current study demonstrates that in
nickel sulphate, chloride and
sulphamate solutions at concentrations
used in commercial electrodeposition
processes the cationic species in the
bulk solution is very probably the nickel
hexaquo ion. Consequently this
hypothesis does not explain the
difference in behaviour of these
solutions, particularly in relation to
deposit stress. Equally well the
conductivity measurements do not
throw any light on this question.
Given the commercial importance of
the nickel electrodeposition process in
21st century society this phenomenon
deserves further investigation in the hope
that some light might be shed on the
situation to clarify the electrodeposition
mechanism of nickel metal.
References
1. G. Bird, Phil. Trans., 1837, 127, 37.
2. J. Shore, UK Patent 8407 (1840).
3. I. Adams, US Patent 52271 (1866).
4. W. H. Remington, U.S. Patent
82877 (1868).
5. I. Adams, US Patent 93157 (1869).
6. I. Adams, US Patent 137734 (1874).
7. E. Weston, US Patent 211071 (1878).
8. J. P. Hoare, J. Electrochem. Soc.,
1987, 134, (12), 3102.
9. Y. Wu, D. Chang, D. Kim and S-C.
Kwon, Surf. Coat. Technol., 2003,
173, 259.
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BULLETIN

10. O. P. Watts, Trans. Amer. Electro-
chem. Soc., 1916, 39, 395.
11. J. K.Dennis and T. E.Such, ‘Nickel
and Chromium plating’, 3rd Ed.,
1993, Woodhead Publishing Ltd, UK.
12. F. A. Lowenheim, ‘Modern Electro-
plating’, 3rd Ed., 1974, London,
John Wiley & Sons.
13. R. Brugger, ‘Nickel Plating’, 1970,
Teddington, Robert Draper Ltd.
14. Bloom and Hogaboom, ‘Principles of
Electroplating and Electroforming’,
3rd Ed., 1949, New York, McGraw-
Hill Inc.
15. R. J. Kendrick, Trans. Inst. Met.
Fin., 1964, 42, 235.
16. R. J. Kendrick and S. A. Watson, Elec-
trochemical Mettalorum, 1966, May.
17. D. R. Gabe and L. Chen, Trans.
Inst. Met. Fin., 2009, 87, 8.
18. T. Shigematsu, Y. Yamamoto,
M. Tabushi and T. Kitagawa, Bull.
Inst. Chem. Res., Kyoto University,
1960, 38, 307.
19. I. Garcia-Urrutia, L. A. Jones, J. A.
Diez and C. Muller, Trans. Inst.
Met. Fin., 2011, 89, 132.
20. O. G. Holmes and D. S. McClure,
J. Chem. Phys., 1957, 26, 1686.
21. M. Triest, G. Bussiere, H. Belisle and
C. Reber, J. Chem. Ed., 2000, 77,
670.
22. F. A. Cotton and G. Wilkinson,
‘Advanced Inorganic Chemistry’,
5th ed., 1988, New York, John
Wiley & Sons.

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