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 pH buffer in the solution in close recent years solutions based on nickel
the nature of the cationic species proximity to the cathode surface where methanesulphonate have appeared.
present in the type of nickel solutions nickel ions are reduced to nickel metal. Neither of these types however have
used for commercial electroplating and Recent work8,9 suggests that boric acid ever established significant commercial
electroforming. The three nickel salts may also have a complexing and/or use. Consequently nickel
examined – sulphate, chloride and catalytic effect on the nickel ion. electrodeposition in the early 21st
sulphamate – are the ones most However, what is arguably still the century depends almost exclusively
commonly used in these processes. most significant development in nickel based on the sulphate, sulphamate and
solution technology took place in 1916. chloride salts.
Despite the fact that nickel plating was Oliver Watts, working at the behest of Nickel electroplating and the
first invented in 1837 and has become a consortium of electroplaters in the associated technology of nickel
an extremely useful part of high USA, published his results10 defining electroforming have become extremely
technology applications the nature of the composition of a solution based on important processes in a very wide
the species in solution has never been nickel sulphate but also containing range of manufacturing operations
investigated. nickel chloride and boric acid. from the 19th century, throughout the
A typical Watts formulation is given whole of the 20th century into the early
The purpose of this study is to discover
below. years of this century. The chemistry
if the differences in deposit properties –
employed does not differ basically from
particularly internal stress - produced NiSO4 :6H2 O 300 g L{1 that used in the early 20th century.
by the three types of nickel salt is
NiCl2 :6H2 O 30 g L{1 However, the immense sophistication
determined by the structure of the
H3 BO3 40 g L{1 of the process technology that has
cationic species and the effect, if any,
taken place has resulted in nickel
that the different anionic species have The ‘Watts Solution’ - as it became electroplating and electroforming
upon the structure of the nickel ions in universally known - quickly became the become absolutely essential for high
aqueous solution. mainstay of the nickel electroplating technology applications such as the
industry and has remained so until this manufacture of CDs/DVDs/BRDs and
day. There have been many variations security holograms.
on the basic composition such as high It has been estimated that in 2010
Introduction and literature and low chloride formulations and metal and metal salt consumption in
survey chloride-free solutions. Some of these Europe for nickel electrodeposition
have found specialist uses, for example was around 28,000 tonnes p.a. At that
The first recorded claim for the high chloride solutions are used when time approximately 3,000 companies
invention of nickel electroplating was increased deposition rates are required. in the EU were calculated to be to be
made by J. Bird1 in 1837; in 1840
However, the most significant involved in the business of nickel
another researcher, J. Shore,2 was
modification of the Watts formulation plating. World consumption in 2010
granted a UK Patent covering nickel
appeared during the 1950s and 1960s was estimated at 133,000 tonnes p.a.,
deposition. During the period from
when nickel sulphamate - due to massive market growth in China
1855 to 1878 there was a burst of
Ni(NH2SO3)2.4H2O - was introduced as and India (data courtesy of Heinz H.
activity, no fewer than five patents
an alternative to nickel sulphate. Pariser, Alloy Metals & Steel Market
were granted related to nickel
Sulphamate-based solutions have an Research).
electrodeposition in the USA alone.3–7
inherently higher electrical conductivity During the last 170 years there have
During the latter part of the 19th than those based on nickel sulphate. been innumerable papers, reviews and
century nickel salts used for this This allows high deposition rates, up to books published on the subject of
process included sulphate, chloride and 60 A dm22, to be achieved which nickel electrodeposition. Four
ammonium sulphate double salt. A provides much faster metal deposition. mainstream comprehensive reviews
major step forward took place in 1878 In addition, nickel deposits produced by are those by Dennis and Such,11
when Weston7 patented the use of sulphamate solutions inherently show Lowenheim,12 Brugger13 and Bloom
boric acid in nickel plating solutions. At much lower levels of internal tensile and Hogaboom.14 Although these
the time this was considered to act as a stress than those produced by either many publications have covered
sulphate or chloride formulations. almost every practical aspect of nickel
Despite their technical advantages electroplating a detailed literature
1
Dept. Materials, Loughborough University, sulphamate based solutions have never search revealed that there appears to
LE11 3TU, UK
2 fully replaced sulphate based ones have been little, if any, work carried
Hart Materials Limited, Carrier House,
Wombourne, WV5 9DH, UK because of their higher cost. out to define the chemical nature of
*Author for correspondence: D.R.Gabe@ In older literature the use of nickel electrolytes involved in nickel
lboro.ac.uk fluoborate solutions is recorded and in electrodeposition. As a consequence

ß 2013 Institute of Metal Finishing

Published by Maney on behalf of the Institute
4 DOI 10.1179/0020296712Z.00000000079 Transactions of the Institute of Metal Finishing 2013 VOL 91 NO 1
 BULLETIN

although it is well known that the is of exceptional purity being Results

electrical conductivity of the solution manufactured from ultra-high purity
and the internal stress of the deposited carbonyl nickel powder. Relevant Solution Conductivity
nickel are greatly influenced by the molecular weights and nickel metal Measurements
anionic species in solution there has contents are given below Gabe and Chen17 examined the
been no work carried out to explain conductivity of three nickel salt
NiSO4 :6H2 O MW 262:8 22:3% Ni
how these properties are related to the solutions; sulphate, chloride and
species in the solution. NiCL2 :6H2 O MW 237:6 24:7% Ni sulphamate, at room temperature.
It is accepted that nickel chloride Ni(NH2 SO3 )2 :4H2 O MW 322:9 18:2% Ni Fig. 1, using data from their work,
solutions have a higher electrical The concentrations chosen are typical shows that the conductivity of each
conductivity than nickel sulphate and of those used in commercial nickel solution increases with increasing
sulphamate solutions of equivalent electroplating and electroforming. A concentration up to a maximum, due to
concentration. Similarly it is accepted highly concentrated nickel sulphamate increasing ion concentration, and then
that nickel sulphamate solutions have a solution was included in the decreases, due to decreasing ion
higher conductivity than nickel sulphate investigation since processes such as dissociation. The maximum
based ones. For this reason they are Ni-Speed15 are operated at this level. conductivity occurs at a higher
employed for high speed concentration for the chloride solution
electroforming using the Ni-Speed Conductivity Measurements than for either the sulphate or
solution developed by Watson and A model 4200 Jenway conductivity sulphamate solutions.
Kendrick in the 1960s.15,16 meter, suitable for both industrial and Fig. 2 shows results from this study
The effect of the anionic species on laboratory work, was employed for for nickel sulphate and sulphamate
deposit stress is also well known. these determinations. This has a solutions at room temperature, with
Lowenheim12 quotes stress values of measurement range from 0 mS to the expected trend of increasing
125 MPa for a Watts solution whereas 199.9 mS, and a temperature capability conductivity with increasing
for an all chloride solution much higher from 210uC to 105uC. concentration. The measured
values of 275 – 345 MPa are recorded. Conductivity k is expressed normally conductivities were higher than those
A very low stress value of 3.5 MPa is, by the equation: observed previously even though the
however, reported for a nickel range of concentrations used was
k~G:K
sulphamate solution (without any considerably less.
chloride addition). where G is conductance (S) and K is the The results obtained in the current
This study therefore sets out to look cell constant (cm21). study for the three salts at two nickel
at two basic aspects of a number of The instrument was calibrated ion concentrations of 1.14 M and
nickel plating solutions using the three against a solution of 0.746 g of dried 1.70 M and at temperatures between
anionic species in common industrial A.R. Grade potassium chloride (KCl) 25uC and 75uC are shown in Fig. 3. At
use to determine if these throw any light dissolved in 1 litre of deionised water. the lower concentration the increase in
on the hitherto unexplained differences The solutions were heated to 95uC with conductivity was less marked than at
in behaviour of the different solutions. magnetic stirring and then allowed to the higher concentration. The chloride
The first aspect that has been cool naturally to just below 30uC the solution shows much higher
examined is the relative electrical conductivity being measured at conductivity than the other two
conductivity of the three types of intervals of approximately 4uC. solutions and the sulphamate solution
solution. Although some somewhat higher conductivity than the
Spectroscopic measurements
measurements have been carried out in sulphate one. This is very much in line
the past there does not seem to be any A Jenway type 6705 Series UV/Visible
single beam spectrometer with a with common practical experience with
systematic study of this very simple nickel plating processes. However, the
property in the public domain. Also, of measuring range from 190 nm to
1100 nm was employed. The light conductivity difference between the
course, using modern instrumentation sulphate and sulphamate solutions is
much more accurate measurements source has a 4 nm spectral bandwidth
and the instrument is accurate perhaps less than might be expected.
can currently be made. Secondly, the
between 15uC and 40uC. It would have In view of the importance of boric
absorption spectra from each solution
been preferable to have used a double acid in nickel plating solutions the
have been examined to check for
beam system to compensate for conductivity of each of the three nickel
differences in the structure of the Ni
background effects but this type of salt solutions was examined with
ions in the different solutions.
instrument was not available. additions of from 0 g L21 to 50 g L21
A further problem occurred in relation boric acid. (40 g L21 is the normal
Experimental procedures concentration used in nickel plating
to the concentration of the solutions
Solution compositions used which were typical of those processes).
Solutions of nickel sulphate and employed commercially for nickel Figs. 4 and 5 show the results
chloride were prepared from analytical plating. These concentrations are, observed with chloride and sulphamate
grade crystals dissolved in de-ionised however, around two orders of solutions where addition of boric acid
water. Nickel sulphamate is not magnitude higher than those typically generally lowered the conductivity but
normally available in crystalline form. examined in this type of spectroscopy. the expected increase in conductivity
The experimental solutions were Consequently, the absorbance peaks of with temperature accelerated markedly
therefore prepared from commercial some of the spectra were off-scale as at temperatures above 80uC. Fig. 6
grade concentrated solution diluted far as the instrument was concerned. shows the results for the nickel
with de-ionised water. Currently Allowance had to be made for this in sulphate solution which was not tested at
available nickel sulphamate concentrate the interpretation of the results. such high temperatures as for the other

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

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 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

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

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

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

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BULLETIN

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

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