Electrochimica Acta 50 (2005) 45574565

Phase structure of electrodeposited alloys

P.L. Cavallotti ,1 , L. Nobili, A. Vicenzo 1
Dipartimento di Chimica, Materiali, Ingegneria Chimica Giulio Natta, Politecnico di Milano, Via Mancinelli, 7-20131 Milano, Italy
Received 10 February 2005; received in revised form 8 March 2005; accepted 10 March 2005
Available online 20 June 2005

Abstract
By electrodeposition it is possible to obtain alloy phases of metastable structure; these phases may be different from those reported
for metallurgical equilibrium conditions or may have different compositions for the solubility limits, in some cases with very important
enlargement. Typical cases are examined, discussing published results and presenting new findings. To understand the general behaviour,
free energy versus composition g/x diagrams were calculated and are presented for the alloys examined in equilibrium conditions and after
modification to obtain composition limits for the electrodeposited phases in stable and metastable state.
The first reported case is NiSn alloy, where the well known metastable phase NiSn is obtained. The second case is the electrodeposition
of IBSn alloys from non-cyanide electrolytes. Phase structure of Zn-rich electrodeposited ZnNi alloys is also discussed as representative
of grain size effect on phase stability.
From the different cases examined, the occurrence of electrodeposited intermediate phases can be interpreted according to a local thermodynamic equilibrium, whilst long range order is difficult to observe in as-deposited layers. These phases depend on bath composition and
operation conditions (temperature, stirring, direct or pulse current density) giving phases of different grain size which in turn can influence
their stability.
2005 Elsevier Ltd. All rights reserved.
Keywords: Electrodeposition; ECD alloys; Phase structure; Metastable phases

1. Introduction
Electrodeposited ECD alloys may differ considerably in
their phase constitution from alloys of same chemical composition but obtained by metallurgical (thermal) methods.
Many examples are reported in the literature with some controversy on the phases obtained and their composition limits. The problem was examined by Brenner [1], Raub [2],
Fedotev [3] and Gorbunova and Polukarov [4], in the past,
and more recently by Povetkin et al. [5,6], Watanabe [7,8],
Stafford and Hussey [9], showing some important cases of
ECD alloys with phase structure differing from that of metallurgical alloys.
Depositing different metals at the same time the same voltage applies obtaining partial currents for each metal. The

Corresponding author. Tel.: +39 02 23993149; fax: +39 02 23993180.

E-mail address: pietro.cavallotti@polimi.it (P.L. Cavallotti).
ISE member.

0013-4686/$ see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2005.03.060

voltage value depends, according to Piontelli [10], on thermodynamic terms, related to metal nobility and metal and
metal ions activity, and kinetic terms, related to surface overpotential and concentration polarisation and an interaction
term that takes into account the depolarisation resulting from
codeposition. We can write for the discharge reaction of each
metal/cation couple Mz+ /M, in the transition from the liquid
phase to the solid phase , the following expression for the
single metal deposition voltage:
RT
RT

+
ln aM
ln aM
z+ M
zF
zF



b
cM
RT
z+

+ M

ln
s
zF
cM
z+

EM = EM

(1)

where the first three terms are the thermodynamic terms (standard electromotive force and activity contribution for the
solid and liquid phases), the 4th and 5th kinetic terms

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P.L. Cavallotti et al. / Electrochimica Acta 50 (2005) 45574565

(electrochemical activation overvoltage, which is given by

Tafels equation in term of partial current density for element
M, and concentration polarisation) and the last one a term
of mutual kinetic influence, taking into account the interaction between the alloy elements in the liquid and in the solid
phase.
In this paper we will propose an interpretation of the phase
behaviour of some important ECD alloy systems: NiSn,
with the metastable NiSn compound obtained only by electrodeposition; IBSn alloy systems, examining the structures
observed in electrodeposits of AgSn, CuSn and AuSn
alloys from thiourea acid electrolytes; ZnNi with electrodeposited phases from different solutions and in different conditions.
The starting point will be the comparison of the free
energy/composition curves at room temperature for the metallurgical phases, calculated using the CALPHAD method,
with the same curves for ECD alloys, derived from the curves
of equilibrium alloys with modifications, when needed, and
taking into account the possibility that some phases cannot
be obtained by electrodeposition.
The molar Gibbs free energy of a phase is calculated
from the sum of three terms:
g = g + gid + gxs

(2)

The first term in Eq. (2) is the Gibbs free energy of a mechanical mixture of the constituent pure elements. For a binary
alloy this is:

g = xA gA
+ xB gB
and g are the free energy change from the most
where gA
B
stable phase to the phase for the elements A and B, respectively. The second term in Eq. (2) is the entropic contribution
to the free energy of the phase for ideal mixing of elements
A and B:

gid = RT(xA ln xA + xB ln xB )
The third term in Eq. (2) is the excess free energy term,
described by a RedlichKister polynomial, where the values of the coefficient gi , taken from the literature, are optimised values correlating phase limits and thermochemical
data:
n
gxs = xA xB
gi (xA xB )i
i=0

In the following the optimised expressions of the free

energy/composition curve for the phases considered are
given, as well as the values of the free energy for the intermetallic compounds of fixed composition.

2. The NiSn system

The solid phases present in the NiSn system are the following [11]: the fcc solid solution (cF4) with solubility range
010.6 at.% Sn; a series of stoichiometric compounds of com-

position: Ni3 Sn, Ni3 Sn2 , Ni3 Sn4 ; the bct -Sn (tI4) phase
with no appreciable Ni solubility.
The low temperature LT crystal structure of Ni3 Sn is an
ordered hcp structure (hP8); its high temperature HT structure
is only tentatively reported as hexagonal; LT crystal structure
of Ni3 Sn2 is an ordered hexagonal structure of the NiAs type
(hP4); HT structure is a disordered modification of the Ni2 In
type (hP6) [12]; Ni3 Sn4 has a monoclinic structure of the
CoSn type (hP6).
NiSn phases obtained by electrodeposition show important differences with respect to equilibrium structure. The
following phases were observed: fcc solid solution with
reported values for Sn solubility ranging from 10 to 18 at.%
(see [13]); hexagonal NiSn with NiAs type structure, present
in a wide range of Ni composition with small lattice parameters change with respect to the near equiatomic composition
(a = 0.415 nm, c = 0.510 nm, c/a = 1.23 [14]); a phase identified with the equilibrium compound Ni3 Sn4 with tetragonal
lattice a = b = 0.511 nm and c = 0.488 nm [15], which, according to Watanabe [13], could be obtained as a single phase
in the composition range 6075 at.% Sn; a new metastable
phase, mainly observed in multiphase deposits, in the composition range 7590 at.% Sn [13] or 6697 at.% Sn [16], the
latter reported to have composition close to NiSn8 and crystal structure similar to Ni3 Sn4 ; bct Sn with practically no Ni
solubility.
Crystal structure and thermochemical properties of asplated NiSn alloy with 4060 at.% Sn were studied in details
due to its popularity as a most striking example of metastable
alloy formation. The identification of ECD NiSn as a single phase intermetallic compound with NiAs type crystal
structure was first reported by Rooksby [17], who suggested
that NiSn could be formed by filling a lattice site in the
Ni3 Sn2 cell with an extra Sn atom. Clarke and Dutta claimed
the ECD NiSn phase was a new compound that could be
obtained as stable phase at the temperature of deposition
[18]. This view was later criticised by Augis and Bennet
[19], who concluded, in agreement with Rooksby, that NiSn
was a metastable extension of the equilibrium phase Ni3 Sn2
over its homogeneity range; the formation of metastable
NiSn was explained as result of increased free energy of formation for the stable two-phase mixture with small grains
due to interface energy contribution. More recently Watanabe hypothesized that the enlargement of the composition
range for the metastable NiSn with respect to the stable
phase Ni3 Sn2 could be explained by a change of the lattice
occupancy probability by Ni atoms [13]. A different interpretation was put forward by Lo [20] who pointed out that
the ECD NiSn had basically the same crystal structure as
Ni3 Sn2 quenched from 1000 C; he explained the different
Sn to Ni ratio in the plated alloy by considering excess of
Sn atoms segregated at grain boundaries, as revealed by AES
measurements.
The molar Gibbs free energy of stable phases is calculated
from thermodynamic parameters proposed for phase diagram
evaluation [21]. Gibbs free energy functions are listed in the

P.L. Cavallotti et al. / Electrochimica Acta 50 (2005) 45574565

4559

The free energy of the NiSn metastable phase is estimated

by adding a term which is a linear interpolation of calorimetric data for ECD NiSn deposits, as reported by Augis and
Bennet [19]:
(5gNi3 Sn2 + 7gNi3 Sn4 )/12 + 1524
gNiSn
=
= 8.8941
RT
RT
The free energy-composition diagram at 298 K for the
NiSn system is shown in Fig. 1.

3. Alloys of IB group metals with Sn

Fig. 1. Gibbs free energy-composition diagram at 298 K for the NiSn system. Free energy of equilibrium phases is calculated from thermodynamic
parameters proposed for phase diagram evaluation [21]; free energy of ECD
NiSn phase is estimated by linear interpolation of calorimetric data for ECD
NiSn reported by Augis and Bennet [19]; it is also shown the estimated free
energy curve for the nanosize two-phase mixture of Ni3 Sn2 and Ni3 Sn4 .

following:
gfcc
= 1.8059xSn + xSn ln xSn + xNi ln xNi + +xSn xNi
RT

18.162 4.8433(1 2xSn ) 15.942


2
6xSn
6xSn + 1 + gm
with gm as magnetic contribution, assuming as a first
approximation gm = exp(23.67xSn )
gNi3 Sn
= 6.7826
RT
gNi3 Sn2
= 9.9588
RT
gNi3 Sn4
= 9.1880
RT
L g )
(bct gSn
Sn
= 1.1726
RT

bct g )
(fcc gSn
Sn
= 1.8059
RT

Many contradictory results were published on the structure of IBSn alloys electrodeposits. We studied the structure
of alloys obtained from cyanide free bath and we will refer
mainly to our results.
AgSn and AuSn alloy films were electrodeposited from
thiourea based plating baths. CuSn alloys were electrodeposited from acid solutions containing either cupric (sulphate) or cuprous (oxide) compounds: Cu(II) acid baths were
basically simple acidic sulphate or methansulfonate solutions; Cu(I) baths were prepared from acidic thiourea solutions. Table 1 reports baths composition and main operative
conditions for MeSn (Me = Cu, Ag, Au) alloys electrodeposition. Reducing and/or complexing agents were introduced
as Sn(II) cations stabilisers, either pyrocathecol (AgSn and
CuSn plating baths) or ascorbic acid (AuSn plating bath).
Electrodeposition was carried out under direct (CuSn and
AgSn) or pulsed (AuSn) current conditions, changing current density (cd) in the range from 0.5 to 6 A dm2 , at room
temperature (AgSn and CuSn from Cu(II) bath), at 40 C
(AuSn), and 50 C (CuSn from Cu(I) bath). Different materials were used as substrate: either brass or steel for CuSn;
brass sheets coated with a thin silver displacement film for
AgSn; Si\Ta\Au or Si\Cr\Ni\Au for ECD AuSn.
Deposits phase structure was determined by X-ray diffraction (XRD) with filtered Cu K radiation, using either the
standard powder or glancing angle technique. K1 diffraction lines were used for calculation of lattice parameters,
further refined by least-squares method. Deposits composition was determined by energy dispersion spectroscopy
(EDS).

Table 1
Composition of MeSn (Me = Cu, Ag, Au) alloy electrodeposition baths and operative conditions (chemicals and metal cations concentrations are given in
mol l1 )
Me

CS(NH2 )2

H2 SO4

Me(I)

Sn(II)

KI

T ( C)

cd (A dm2 )

Cu
Ag
Au

0.21.5
12
0.751

1
0.751
1

0.010.2
0.025 0.1
0.010.05

0.10.3
0.0250.05
0.040.08

1.8 103
0.61.2 103

2540
25
40

0.55
0.31.5
16a

Me

H2 SO4

CH3 SO3 H

Cu(II)

Sn(II)

C6 H11 O7 Na

T ( C)

ddc (A dm2 )

Cu
Cu

0.071

0.010.2
0.1

0.10.3
0.010.2

00.8

25
25

0.44
0.52.5

Low frequency pulse plating deposition with on time in the range 0.15 s and off time in the range 110 s.

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P.L. Cavallotti et al. / Electrochimica Acta 50 (2005) 45574565

Further details on preparation, electrochemical behaviour

and operative conditions of plating baths and on experimental techniques can be found in previously published papers:
CuSn [2225]; AgSn [2225]; AuSn [2527].
3.1. The CuSn system
The stable solid phases present in the CuSn system
are the following [28]: fcc (cF4) phase with solubility range 09.1 at.% Sn; bcc (cI2) phase, with solubility
range 13.116.5 at.% Sn; complex cubic (cF16) -phase,
formed by phase ordering; a -phase (cF416), identified
as an ordered -brass type superstructure; -phase, hexagonal superstructure (hP26) based on the -AgZn prototype
(hP9); orthorhombic (oC80) -phase, hcp lattice anti-phase
structure;  hexagonal superstructure based on an NiAs type
structure, transforming to the -phase, NiAs (hP4) structure,
between 186 and 189 C; bct (tI4) -Sn, with Cu solubility
about 0.01 at.%.
According to previously reported results [2225], ECD
CuSn alloys show the following sequence of phases with
increasing Sn content: the Cu rich terminal solid solution
with fcc structure and solubility limit about 11 at.% Sn; an
intermediate solid solution, not present in the equilibrium
phase diagram, with hcp structure and composition range
1218 at.% Sn (the axial ratio c/a of hcp structure deposits
changes from the ideal value 1.6331.622 as Sn content
increases from 12 to 18 at.%; no further change occurs when
Sn content increases above 18 at.%); a phase with bcc crystal
structure, related to the HT stable phase, as suggested by the
similarity between lattice parameters and the continuity of its
change with composition, appearing as a single phase in the
composition range 1825 at.% Sn; a phase with NiAs structure, without significant change of lattice parameters with
composition, corresponding to the HT stable phase. The
intermediate hcp phase was not reported in previous works
concerning CuSn alloy deposits from alkaline cyanide plating bath [4,2931]. Fedotev et al. reported the formation of
an hexagonal phase in a quite different composition range,
2025 at.% Sn content, seemingly related to the equilibrium
phase with hexagonal superstructure [30]. A phase with
hcp structure and composition close to the above reported
range for the ECD alloy was observed in deposits obtained
by vapour deposition [33]. Also results reported in Ref. [31]
can be reinterpreted according to this view, at variance with
authors conclusions.
The free energy of the stable phases at 298 K is calculated with the expressions given by Shim et al. derived
from thermodynamic optimization of the CuSn system
[32]. HT superstructure phases, , and phases, are not
considered.
gfcc
= 1.0495xSn + xSn ln xSn + xCu ln xCu
RT
+ xSn xCu [4.4857 5.3514(1 2xSn )]

Fig. 2. Gibbs free energy-composition diagram at 298 K for the CuSn

system. Free energy of stable phases is calculated from thermodynamic
parameters proposed for phase diagram evaluation [32]; free energy of the
metastable hcp phase is estimated by taking into account staking fault energy
contribution [33,34].

gbcc
RT

= 1.0542xSn + 1.4703xCu + xSn ln xSn + xCu ln xCu

+ xSn xCu [11.9302 9.5622(1 2xSn )]

g
g
= 3.3318
= 2.8387
RT
RT
Free energy of the solid solution with hexagonal structure,
not present in the equilibrium diagram, can be calculated
with respect to free energy of the fcc phase, taking into
account staking fault energy [33]. The following expression
is obtained, according to relations reported by Gallagher [34]
and using SGTE thermodynamic data for pure elements [35]:


2 

ghcp
gfcc
xSn
=
+ 0.3941 exp 6.98574
RT
RT
0.091 + xSn
0.0629 + 0.0571xSn 0.065xCu
The proposed free energy-composition diagram for ECD
CuSn alloys is presented in Fig. 2.
3.2. The AgSn system
The following phases are stable at room temperature in the
AgSn system [36]: fcc (cF4) solid solution with homogeneity range 011.5 at.% Sn; hcp (hP2) -phase with homogeneity range 1222 at.% Sn; ordered intermetallic compound
Ag3 Sn or -phase with deformed hexagonal structure of the
Cu3 Ti type (oP8) [37]; bct (tI4) -Sn, with very limited Ag
solubility.
We observed by electrodeposition the following phases
[2225]: fcc Ag rich solid solution with Sn content 09 at.%;
an intermediate phase, in the range 1223.5 at.% Sn, with
hcp structure, corresponding to the equilibrium phase; bct
-Sn phase with low Ag solubility. Lattice parameters of the

P.L. Cavallotti et al. / Electrochimica Acta 50 (2005) 45574565

ECD phases with close packed structure [25] are in close

agreement with those for metallurgical alloys, reported by
Owen and Roberts for the fcc phase [38] and by King and
Massalski for the hcp phase [39]. When Sn content in the
alloy is above 24 at.%, electrodeposits show a biphasic + Sn structure.
The stoichiometric intermetallic compound Ag3 Sn or
phase with orthorhombic lattice structure was not observed
in ECD alloys, contrary to early reports by Leidheiser and
Ghuman [40] and Kubota and Sato [41] and recently by Arai
and Watanabe [42,43]. Actually, these authors did not provide
unambiguous evidence of direct intermetallic formation by
electrodeposition, since their claims were mainly based on
the observation that deposits composition was preferentially
at an Ag to Sn ratio close to 3:1.
Gibbs free energy curves for terminal solid solutions
and intermediate phases are calculated from thermodynamic
parameters proposed for phase diagram evaluation [44]. The
Gibbs free energy expressions for the stable LT phases are
reported:
gfcc
= 1.0495xSn + xSn ln xSn + xAg ln xAg
RT
+ xSn xAg [4.7915 18.057(1 2xSn )]
hcp

g
= 0.6544xSn + 0.1572xAg + xSn ln xSn + xAg ln xAg
RT
+ xSn xAg [3.0192 17.38(1 2xSn )]
gbct
= 1.6887xAg + xSn ln xSn + xAg ln xAg + 7.7074xSn xAg
RT
g
= 1.5912
RT
The proposed free energy-composition diagram for ECD
AgSn alloys is reported in Fig. 3.

Fig. 3. Gibbs free energy-composition diagram at 298 K for the AgSn

system. Free energy of stable phases is calculated from thermodynamic
parameters proposed for phase diagram evaluation [44].

4561

4. The AuSn system

According to the AuSn phase diagram assessed by
Okamoto and Massalski [45], the stable solid phases are the
following: fcc (cF4) solid solution with homogeneity range
06.8 at.% Sn; phase or Au10 Sn (9.1 at.% Sn) with complex
hexagonal structure (hP16) of the Ni3 Ti prototype; hexagonal phase (hP2) with homogeneity range 1018.5 at.% Sn; a
 or Au5 Sn ordered intermetallic compound (16.7 at.% Sn),
whose structure presents hexagonal symmetry; or AuSn
(5050.5 at.% Sn) with hP4 structure of the NiAs prototype;
ordered intermetallic compound or AuSn2 (66.7 at.% Sn),
with orthorhombic symmetry; ordered intermetallic compound or AuSn4 (80 at.% Sn), with orthorhombic symmetry
(oC20) of the PtSn4 prototype; a bct (tI4) -Sn with 0.2 at.%
Au solubility.
AuSn alloys electrodeposits obtained from acidic
thiourea baths show the presence of three phases in the composition range 050 at.% Sn [2527]. The fcc phase with
Sn content up to about 7 at.%; an hcp intermediate solid
solution for Sn content in the range 918 at.%, which was
also observed depositing from a Au(III) cyanide bath in a
similar composition range [46,47]; in the composition range
79 at.%, corresponding, in the equilibrium diagram, to the
stability field of the phase and to the adjoining regions of
two-phase equilibria, ECD alloy deposits are either hcp single
phase or mixed fcc + hcp; a phase with NiAs type structure,
i.e. the structure of the equilibrium phase, obtained as a single phase in a composition range about 50 at.%. Long range
ordered phases occurring in the equilibrium system, either
with fixed composition ( phase) or in a limited homogeneity field ( phase) were not observed in ECD AuSn alloys.
The observed maximum Sn content of the electrocrystallised phase roughly corresponds to the solubility limit
of Sn in fcc Au, i.e. 6.6 at.% at 532 C [48]. Lattice spacings for the ECD fcc structure are in agreement with those of
metallurgical phase, as reported by Owen and Roberts [49]
and by Nuding and Ellner [50]. Lattice spacings for ECD hcp
phase are slightly lower than those of metallurgical phase
(homogenised at 275 C), as reported by Massalski and King
[51] and by Henderson and Raynor [52]. Lattice parameters
of phase, which appears as single phase in a limited composition range, are close to those of equilibrium phase and
do not show any appreciable change with composition [27].
Gibbs free energy curves for fcc solid solution and intermediate phases existing in electrodeposits are calculated from
thermodynamic parameters proposed by Chevalier for phase
diagram evaluation [53]. The thermodynamic description of
the AuSn system presented by Chevalier was largely based
on the first assessment of AuSn phase diagram by Okamoto
and Massalski [45], later reexamined by the same authors
[54]; more recently, the Au rich side of AuSn system was
redetermined by Ciulik and Notis [48], clarifying that the
and phases could be stable down to room temperature.
Therefore, the Gibbs free energy expressions for the stable LT
phases reported below are not optimised based on the most

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P.L. Cavallotti et al. / Electrochimica Acta 50 (2005) 45574565

Fig. 4. Free energy-composition diagram at 298 K for the AuSn system.

Free energy of stable phases is calculated from thermodynamic parameters
proposed for phase diagram evaluation [53].

recent assessment of the AuSn phase diagram:

gfcc
= 1.0495xSn + xSn ln xSn + xAu ln xAu
RT
+ xSn xAu [5.9110 4.9851(1 2xSn )]
hcp

g
= 1.045xSn + 0.258xAu + xSn ln xSn + xAu ln xAu
RT
+ xSn xAu [5.6907 25.2469(1 2xSn )

Zn(Ni) solid solution , possibly with solute supersaturation, and a phase with structure of cubic symmetry identified
with the equilibrium phase, without or with low intensity
superstructure reflections [59,60,6266]. The intermetallic
phase was detected in ZnNi coatings only after heat treatment at 250 C [59]; when its formation in as-plated deposits
was claimed, e.g. [58] its identification appears controversial. There is no agreement on the occurrence of the hcp
phase as single phase: either single phase or two-phase
coatings (Zn + ) were obtained increasing Ni content, with
single phase deposits showing the hcp Zn(Ni) supersaturated
solution up to 8 at.% Ni [57,59] and two-phase deposits of
composition ranging from 5 to 16 at.% Ni [59,67]. The composition range over which the formation of single -phase
deposits was claimed change accordingly: a safe indication
is from about 12% to 25 at.% Ni. On the other hand, deposits
with Ni content up to 40 at.% were also reported to be single
-phase [67,68].
Gibbs free energy curves for terminal solid solution of
zinc () and intermetallic phases (, ) are calculated from
thermodynamic parameters proposed for phase diagram evaluation [69].
The phase is described by a three sublattice model with
composition (Ni,Zn)4 Ni4 Zn18 :
g
= yNi (7.1457) + yZn (5.4755) + yZn ln yZn
RT
+ yNi ln yNi 1.4033yZn yNi

+ 18.0424(1 2xSn ))2 ]

g
= 6.029
RT
g
= 2.182
RT

g
= 5.167
RT
g
= 3.010
RT

g
= 1.140
RT

yNi =

26
xNi 1
4

yZn = 2

26
xNi
4

The hcp phase is described by an ordinary substitutional

solution model with excess free energy expressed in the form

The resulting free energy-composition diagram for the

AuSn binary system at room T is shown in Fig. 4.

5. The NiZn system

In the zinc rich side of the NiZn system, in the composition range from 0 to 25 at.% Ni, the following stable solid
phases are present [55]: hcp Zn-based solid solution (hP2,
Mg prototype), with very low Ni solubility; phase, at about
89 at.% Zn and a small homogeneity range, with a mC6 crystal structure related to the CoZn13 prototype [56]; phase,
an electron phase of -brass type Cu5 Zn8 (cI52), with homogeneity range from 74 to 85 at.% Zn.
The phase structure of ECD ZnNi alloy deposits was
studied with special interest for Zn-rich alloy deposits
[5766], owing to its use as protective coatings, and over
the whole composition range by Imai et al. [8]. Two phases
are observed over the composition range up to 25 at.% Ni;

Fig. 5. Gibbs free energy curves for terminal solid solution of zinc () and
intermetallic phases (, ) calculated from thermodynamic parameters proposed for phase diagram evaluation [69]. The free energy curves of the
two-phase system + for bulk (dotted line) and 10 nm crystal size alloy
(dashed line) are also reported.

P.L. Cavallotti et al. / Electrochimica Acta 50 (2005) 45574565

of a standard RedlichKister polynomial:

ghcp
RT

= 0.573 ln xNi + xZn ln xZn + xNi ln xNi

26.222xZn xNi

the phase is treated as a stoichiometric compound of

Ni2 Zn15 composition:
g
= 4.3837
RT
Fig. 5 shows the free energy-composition diagram for the
NiZn binary systems at room T.

6. Discussion and conclusions

In electrocrystallisation of alloys phase selection and formation is the result of non-equilibrium processes, responsible
for the suppression of an equilibrium phase or for the formation of a metastable phase. A possible interpretation of this
behaviour can still rely on thermodynamic analysis, if kinetic
constraints are introduced and excess energy contributions
are taken into account, in order to characterise in a simple
way the irreversibility ruling the crystallisation process.
This approach is discussed in the following with reference
to the ECD alloys presented in the previous section.
The ECD NiSn phase is a model case of metastability
which has prompted different interpretations, that can be led
back to the following views: NiSn is actually a new phase,
according to Clarke and Dutta [18]; or it is rather a modification or extension of the Ni3 Sn2 equilibrium phase, following
Augis and Bennet [19], which is made possible either by the
nanometer sized crystal structure of the alloy and the segregation of excess Sn at grain boundaries [20] or by insertion
of extra Sn atoms into vacant lattice sites [17].
In fact, NiSn is obtained in the composition range where,
based on equilibrium thermodynamics, a two-phase alloy
consisting of Ni3 Sn2 and Ni3 Sn4 is expected. If we accept
either the view that ECD NiSn is a new phase or that it is a
metastable extension of Ni3 Sn2 , its formation requires that
the free energy of the two-phase system be shifted above the
free energy of ECD NiSn. In the two-phase system consisting of small grains of Ni3 Sn2 and Ni3 Sn4 , Gibbs free energy
increase may result from interfacial energy contribution. By
assuming that the grains are randomly distributed, the following expression for molar free energy of the two-phase system
is derived:
Vm
g = x g + x g + 3 [2x x ( ) + ]
(3)
d
where x , x and g , g are molar fractions and molar Gibbs
free energies of phases and , respectively, Vm is the molar
volume; d is the grain size (cubic shape with equal dimension
assumed for all grains); is the surface energy for /
interface; is the similar term for / and / interfaces,
supposed to have equal surface energy.

4563

This line of reasoning is exemplified in the free energycomposition diagram for the NiSn system shown in Fig. 1,
where the free energy curve of the two-phase system, i.e.
the line connecting the points representative of Ni3 Sn2 and
Ni3 Sn4 phases, is also drawn. By setting the following values for the interface and surface energy: = 1 J m2 and
= 0.02 J m2 , it is found that the Gibbs free energy of the
mixture is higher than that of NiSn when the grain size is
smaller than 11 nm; if we assume that the grains of the two
phases are alternating (ordered distribution), the grain size
for which the Ni3 Sn2 and Ni3 Sn4 mixture becomes unstable
with respect to NiSn is larger than that (19 nm). Therefore,
assuming that formation of Ni3 Sn2 and Ni3 Sn4 is prevented
and that formation of the ordered intermetallic Ni3 Sn is forbidden in the ECD conditions of crystallization, the observed
phase structure of ECD NiSn alloys on the Ni rich side of the
system (fcc solid solution for Sn content up to about 20 at.%;
NiSn in the range 4060 at.%) can be at least qualitatively
explained.
ECD alloys of Sn with IB group metals provide a model
case for phase structure investigation. In fact, the binary
systems IB group metals-Sn are characterised by the presence of stoichiometric compounds and/or phases with small
homogeneity range and long-range order structure along with
terminal and intermediate substitutional solid solutions.
The reported free energy diagrams for CuSn, AgSn and
AuSn systems are briefly discussed in the following and
shown to be a valuable tool for the description of the phase
constitution of ECD alloys if the peculiarities of the electrocrystallisation process are taken into account: suppression
of long range order interaction and formation of disordered
phases with favourable free energy effect.
The proposed free energy-composition diagram for ECD
CuSn alloys (Fig. 2) shows that the fcc and hcp phases
present the lowest free energy in the composition range
06 Sn and 615 at.% Sn, respectively. The phase boundary derived from the modified diagram, i.e. in the absence of
, , and phases, are the following: 4.6 at.% Sn for the fcc
phase; 7.79.2 at.% Sn for the hcp phase; 20.934.3 at.%
Sn for the phase with bcc structure. The sequence of phases
predicted by the modified diagram is in agreement with the
experimental findings for ECD alloys; phase boundaries are
in reasonable agreement with those experimentally observed,
except for the primary solid solution.
The phase limits derived from the free energy-composition
diagram for AgSn alloys, presented in Fig. 3, in the absence
of the phase, are in good agreement with the observed composition range for the ECD and phases. The stability limit
of the primary solid solution is about 9 at.% Sn, very close to
observed phase boundary of ECD phase; phase boundaries are 11 and 23 at.% Sn, in close agreement with the phase
boundaries of ECD hcp structure.
The free energy-composition diagram of the AuSn system, reported in Fig. 4, is modified by suppressing the and
 phases. The resulting phase limits are somewhat different from those observed in ECD alloys [27]. In particular,

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P.L. Cavallotti et al. / Electrochimica Acta 50 (2005) 45574565

Sn solubility in the fcc solid solution from the modified diagram is about 3 at.%, against the observed value of 7 at.%;
besides, the stability field of the phase obtained from the
diagram is 1214 at.%, contrary to the observed composition
range for the ECD phase 1218 at.% Sn. In the case of the
AuSn system, it should be emphasized that the phase diagram is still controversial in the low temperature region of
the Au-rich side and the thermodynamic optimisation cannot
be considered satisfactory.
The phase diagram for NiZn alloys is presented in Fig. 5,
where contribution from grain boundaries is included, by
evaluating the interface free energy of nanosized systems.
Similarly to NiSn alloys, molar Gibbs free energy of the
two-phase system consisting of nanosized and phases
is assessed from Eq. (3) where and stand for and ,
respectively, assuming the following values for the interface
and surface energy: = 1 J m2 and = 0.02 J m2 . The
resulting g/x curve of the two-phase system for crystal size
value of 10 nm is reported as the dashed line curve connecting
equilibrium compositions in Fig. 5. As shown by the diagram,
the increase of Ni solubility in the hcp -phase could be produced by the positive shift of the Gibbs free energy curve
of the nanosized + system. The -phase could be stable
up to about 6 at.% Ni compared with a reported maximum
value of about 8 at.% Ni solubility. For proper comparison,
free energy curves of nanosized single phases were also calculated for the same values of surface and interface energy;
however, these curves can hardly be distinguished from those
of bulk alloys.
The ECD phase is not the same phase as obtained by metallurgical methods; it is a bcc superstructure, but with very
low superlattice reflections (in some cases absent), showing
that long range order in the ECD phase is strongly reduced.
Also this effect can increase, though to a small extent, the
phase free energy, perhaps changing its shape and thus giving
reason to the possibility of a distorted phase of low nickel
content [59]. The structural differences reported in different
papers on ZnNi ECD alloys can be mainly related to the
bath composition, and less to the operative conditions. Different structures are obtained at similar deposition potentials
[65]. According to us the possibility of obtaining different
structures at same potential could be ascribed to a different
ratio between accumulation and dissipation free energy, with
possible variation of the surface energy effect.
The ability to tailor or even foresight the phase structure of
alloy deposits based on known equilibrium structure would
be an important achievement both for the theory and practice
of alloy electrodeposition.
The starting point must be a reasonably reliable knowledge of the equilibrium phase constitution of the alloy of
interest, which is not always the case; then, appropriate
constraints expressing the actual conditions of crystallization can be introduced to account for phases competition
and metastability. The observed metastable phases have
usually a higher free energy than the stable metallurgical
structures and the presence of defects, in particular surface

effects, can give only an increase of the free energy of the

phases.
In this frame, the inherent thermodynamic properties of
the alloy phases must be first considered. When the free
enthalpy of formation for the alloy examined is negative,
there may be a tendency towards formation of intermetallics.
Experimentally it is found that by electrodeposition phases
with long range ordered structures are difficult to obtain,
suggesting that long range interactions do not come into
play during electrocrystallisation. On the other hand, structure types that can be interpreted as a consequence of short
range order interaction, such as HT structures of the NiAs
and CsCl type, the later for instance in ECD equiatomic
AuCd alloy [70], can be found in as-plated layers and may
be related to electrodeposition proceeding with strong depolarization effects or in underpotential deposition UPD range
[71].
Different is the case of alloys with positive free energy of
formation obtained in metastable state as supersaturated solid
solution; in this case it is possible to speculate that crystalline
ordering occurs at the growing surface, as a consequence of
UPD. This view provides an explanation for the solid solubility of Pb, Sb and Bi in ECD binary copper alloys [7275];
however, in this case, not only the stability of the Cu fcc
structure with dissolved elements but also nucleation and dispersion of the new phase should be taken into account.
In conclusion, a thermodynamic approach to the examination of phase structure peculiarities in electrochemical
phase formation is proposed and applied to model cases of
alloys electrodeposition. It is shown that the phase structure of ECD alloys can be interpreted by modified free
energy-composition diagrams accounting for the experimental observation of long range order structures suppression and
by adding appropriate excess free energy terms to the total
free energy of the system; in particular, interfacial energy
contribution may easily arise in alloys electrocrystallisation
because of the tendency towards formation of nanocrystals
in condition of high supersaturation.
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