Abs. 679, 204th Meeting, 2003 The Electrochemical Society, Inc.

Pulse Plating of Ni-W Alloys

S.Franz^, A.Marlot*, D.Landolt*
^Department of Chemistry, Materials & Chemical
Engineering G.Natta
Politecnico di Milano
20131 Milano, Italy
*Institute of Materials, Swiss Federal Institute of
Technology
CH-1015 Lausanne EPFL, Switzerland
The electrodeposition of Ni-W alloys is a typical
example of induced codeposition. In fact, according to
Brenner [1], tungsten cannot be electrodeposited from
either aqueous or organic electrolytes, but it can be
codeposited with iron-group metals such as nickel to form
an alloy. To the authors knowledge, a modelling of the
induced codeposition of tungsten with nickel is lacking.
Recently, the induced codeposition of molybdenum with
nickel in dc conditions on rotating electrodes has been
investigated and a reaction model was proposed [2-5].
According to the model, molybdenum is reduced only
with nickel while nickel deposition proceeds
independently of molybdenum. Depending on the relative
concentration, molybdenum deposition can be limited by
mass transport of either molybdenum or nickel. The
model predicts the effect of rotation rate and of imposed
potential on alloy composition and current efficiency both
for a molybdenum-rich and a nickel-rich electrolyte. Pulse
plating of Ni-Mo and similar alloys was also
comprehensively studied and a quantitative description of
the effect of the pulse variables on Ni-Mo alloys
composition was presented by A. Marlot et al.[6]. The
same authors observed a quite different behaviour in the
Ni-Mo system, related to which of the two species is mass
transport limited [7].
The aim of this study is to contribute to a
theoretical understanding of induced codeposition of
tungsten with nickel in pulse plating, both from nickelrich and tungsten-rich electrolyte.
Ni-W films were electrodeposited on a rotating
cylinder electrode using copper as a substrate. The
counter electrode and the reference electrode were a DSA
and a Mercurous Sulphate Electrode, respectively.
Cathodic and anodic compartments were separated by
glass frits. A charge of 53 C was supplied to the working
electrode in each experiment. A rectangular current wave
was supplied in intermittent potential conditions. During
the on-time tp and the off-time tp of the pulse, the current
density was 20 mA cm-2 and 0.02 mA cm-2. The duty
cycle =tp/(tp+tp) was 0.4. The pulse period tpp= tp+tp
ranged from 1 ms to 50 s. Ni-W films were
electrodeposited from two different electrolytes: the
nickel-rich electrolyte was 0.6 M NiSO4, 0.03 M
Na2WO4, 0.75 M Na3Cit, 0.3 M NH3, pH 8; the tungstenrich one was 0.03 M NiSO4, 0.6 M Na2WO4, 0.0375 M
Na3Cit, 0.3 M NH3, pH 11. The temperature was 25C.
At sufficiently low pulse periods (tpp < 10 s)
tungsten content in the alloy was around 5 at %, higher
than in dc plating (around 2 at %), while at higher tpp the
composition reached the steady state values in dc
conditions. The codeposition process was observed to
occur in quite different ways depending on the
composition of the electrolyte. Pulse plating of Ni-W
alloys from nickel-rich electrolyte could be adequately

described by the Viswanathan and Cheh model [2] further

developed by Podlaha and Landolt for Ni-Mo system [35]. Accordingly, tungsten deposition takes place via a
reaction intermediate with nickel, while the latter reacts
independently of tungsten:
NiCit + WO 42 + 2 H 2 O + 2e [NiCitWO 2 ]ads + 4OH

[NiCitWO 2 ]ads + 2 H 2 O + 4e Ws + NiCit

NiCit + 2e Ni s + Cit
Pulse plating of Ni-W alloys from tungsten-rich
electrolyte was modelled by assuming that the
codeposition process occurs mostly before the transition
time. The transition time was calculated by the
Rosebrugh and Miller equations [8]. For tp<2000 ms the
calculated transition time is longer than the pulse on-time
Therefore, the nickel never reaches limiting conditions
and the codeposition of tungsten is always proportional to
the nickel partial current density. When the pulse on-time
is longer than 2000 ms the codeposition of tungsten
occurs only for t<. The application of this simple model
gives a quite good preliminary description of the
experimental results.

Fig. 1: Pulse plating of Ni-W alloys from nickel-rich

electrolyte: tungsten content and current efficiency CE as
function of the pulse period tpp (ip=20 mAcm-2, 1000 rpm,
53 C, 25C, thickness 2 m); calculated composition
(line).
References:
1. A. Brenner, Electrodeposition od Alloys. Principles and
Practice. A. Press, Ed. (New York, NY, 1963).
2. K. Viswanathan, H. Y. Cheh, G. L. Standart,
J.Appl.Electrochem., 10, 37 (1980).
3. E. J. Podlaha, D. Landolt, J.Electrochem.Soc., 143 (3), 885
(1996).
4. E. J. Podlaha, D. Landolt, J.Electrochem.Soc., 143 (3), 893
(1996).
5. E. J. Podlaha, D. Landolt, J.Electrochem.Soc., 144, 1672
(1997).
6. A. Marlot, P. Kern, D. Landolt, Electrochim. Acta, 48, 29
(2002).
7. A. Marlot, D. Landolt, AESF SUR/FIN 2002 Proceedings,,
(2002).
8. T. R. Rosebrugh, W. L. Miller, Journal of Physical Chemistry,
14, 816 (1910).