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The influence of saccharin on the


electrodeposition and properties of CoNi alloy
thin films
DATASET OCTOBER 2015

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6 AUTHORS, INCLUDING:
Azizi Amor
Ferhat Abbas University of Setif (Algeria)
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The influence of saccharin on the


electrodeposition and properties of Co Ni
alloy thin films
S. Tebbakh1, Y. Messaoudi1, A. Azizi*1, N. Fenineche2, G. Schmerber3
and A. Dinia3
CoNi alloys thin films were electrodeposited on Ru substrates from a chloride-saccharin bath at
pH 3.8 and the effects of adding saccharin to the bath on the electrochemical deposition,
corrosion resistance, chemical composition, physical and magnetic properties of the deposits
were investigated. The analytical techniques of cyclic voltammetry (CV), potentiodynamic
polarisation, electrochemical impedance spectroscopy (EIS), atomic absorption spectroscopy
(AAS), atomic force microscopy (AFM), X-ray diffraction and hysteresis curves were applied to
assess the codeposition process, and determine corrosion resistance, composition, morphology,
nanocrystallinity and magnetic properties. Effectively, CV measurements revealed that the
addition of saccharin in the electrolytic bath modifies the deposition process and an anomalous
codeposition takes place; this enhanced the Co percentage in the CoNi deposits. Saccharin
addition also increases the double layer capacitance and decreases the charge transfer
resistance. On the other hand, the Tafel plots show a higher corrosion resistance for the deposits
obtained from a bath with saccharin than those obtained from a bath without it. Furthermore, the
presence of the saccharin in the bath also causes notable changes in the morphology and
structure characteristics of deposits. In addition, it was found that the additive influences the
magnetic properties of CoNi alloy thin films. The coercivity and magnetisation saturation are
diminished for CoNi films prepared from electrolytes with addition of saccharin.
Keywords: Electrodeposition, Co Ni, Anomalous co-deposition, Saccharin, Morphology, Corrosion

Introduction
Interest in the formation of CoNi alloy thin films by
electrochemical methods has been strong for many years
because of their excellent magnetic properties, hardness,
lightweight, wear, versatility, abrasion and corrosion
resistance.14 Owing to their exceptional magnetic properties, these characteristics are exploited and the films
used as magnetic recording media and as hard magnetic
materials for microelectromechanical systems (MEMS)
applications.1,5 The use of electrodeposition to produce
these alloys is attractive because of its lower cost, flexibility (e.g., deposition as single layer or multilayer coatings on planar and non-planar substrates), efficiency and
easy of high-volume production in contrast with other

1
Laboratoire de Chimie, Ingenierie Moleculaire et Nanostructures,
Universite Ferhat Abbas- Setif 1, 19000 Setif, Algeria
2
IRTES-LERMPS/FR FCLAB, Universite Technologique de BelfortMontbeliard (UTBM), 90010 Belfort, France
3
Institut de Physique et Chimie des Materiaux de Strasbourg (IPCMS),
UMR 7504 CNRS Universite de Strasbourg (UDS-ECPM), 23 rue du
Loess, BP 43, 67034 Strasbourg Cedex 2, France

*Corresponding author, email aziziamor@yahoo.fr

196

2015 Institute of Materials Finishing


Published by Maney on behalf of the Institute
Received 16 December 2014; accepted 12 April 2015
DOI 10.1179/0020296715Z.000000000247

methods such as sputtering and chemical vapour


deposition.68 Although electrodeposition has been one of
the methods using well-known processes for synthesising
nanocrystalline materials, properties of nanocrystalline
electrodeposits have been less evaluated, especially for
tribological application in nanoscale devices such as
MEMS and nano-electromechanical systems (NEMS).1,9
An important aspect of this system is that alloys of any
composition can be formed since the two metals form
solid solutions over the whole concentration range.10
Indeed, this feature enables their properties to be explored
over a wide range of compositions.
Additionally, the electrodeposition of CoNi alloys is a
codeposition of anomalous type,1015 where the less noble
metal (Co) deposits preferentially compared with the more
noble metal (Ni). The anomalous codeposition of CoNi
alloy thin film has been explained by the increase in
hydroxide concentration at the interface because of
the hydrogen evolution reaction (HER). Preferential
formation of cobalt hydroxide on the cathode surface
inhibits the rate of nickel deposition, while simultaneously
allowing the deposition of cobalt.1618 The functional
properties of electrodeposited CoNi alloy depend greatly
on their composition and structure,19,20 which should be

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strongly affected by deposition conditions (bath composition, applied potential/current density, pH, temperature,
substrate, organic additives, etc.).21 Thus, changes in any
of these experimental conditions may result in electrodeposition with different compositions, microstructures
or phases and magnetic properties.
In general, the use of additives in electrodeposition
solutions is extremely important because of their influence
on the nucleation growth mechanism, deposition kinetics
and microstructure of the resulting deposits.22 It is well
known that additives affect the physical and mechanical
properties of electrodeposits such as surface roughness,
grain size, texture, brightness, internal stress, current
efficiency (CE) and even chemical composition.23 It is
accepted that additives are generally understood to act as
catalysts or inhibitors in the electrodeposition process by
increasing the tendency of metal ions to form complexes
and/or increasing the activation polarisation of single ions
by blocking the active sites on the substrate.24 Among
these organic additives, saccharin has long been used in
electroplating to reduce the internal stress of deposits, to
refine the grain structure and to improve film quality.25
Effectively, saccharin molecules are adsorbed in a reversible way on active sites of the electrode surface, thereby
blocking active sites and reducing crystal growth. In the
literature, the additives as saccharin and 2-butin-1,4-diol
(BD) in small concentrations can be added to CoNi
plating baths to modify the process of electrocrystallisation for a variety of purposes, including obtaining a
mirror-like surface, increasing hardness and improving
corrosion resistance.24 The influences of additives on the
composition, morphology, microstructure and properties
of CoNi deposits have been investigated. It has been
established that the addition of saccharin resulted in a
slight reduction of cobalt content because of the increasing
deposition overpotential, which was in favour of activation-controlled nickel deposition.25 The electrodeposition from baths containing saccharin inevitably contains
certain amounts of sulphur impurities,17,26 which may lead
to poor ductility27 and corrosion resistance.28,29 Importantly, it is reported that nanocrystalline CoNi alloys
with a smooth surface deposited from a bath containing
saccharin had higher corrosion resistance in 10 wt.%
NaOH compared with the alloy thin films electrodeposited
from additive-free baths.30,31
Previous studies in the authors laboratory7 have shown
that the electroplating variables, such as cobalt ion concentration, applied potential/current density had different
effects on the electrochemical nucleation, growth and
properties of CoNi alloys deposited on a Ru substrate in
chloride baths. Consequently, the aim of this research is to
study the effect of saccharin addition on the mechanism of
deposition, corrosion, composition, morphology, structural and magnetic properties of CoNi electrodeposited
from a chloride bath, which generally shows higher electrical conductivity in the electrolyte, lower overpotential
for deposition of cobalt, lower anodic overpotentials and
higher cathodic CE, compared to sulphates.

Experimental procedures
CoNi alloy thin films were prepared by electrodeposition under potentiostatic conditions from chloride
plating bath with addition of saccharin with different
concentrations (0, 0.003, 0.004 and 0.005M). The CoNi

The influence of saccharin

electrolyte was prepared from analytical grade cobalt


chloride (CoCl2, 6H2O), nickel chloride (NiCl2, 6H2O),
potassium chloride (KCl) and boric acid (H3BO3).
Saccharin (C7H5NO3S) was chosen as an additive in the
initially free bath and in controlled concentrations was
added to the electroplating baths. The compositions of
the initial additive-free CoNi bath and saccharin-added
CoNi bath are given in Table 1. The pH value of the
bath was adjusted to 3.8 with addition of HCl and
NaOH. Electrochemical experiments were carried out in
a conventional three-electrodes cell using a VoltaLab 40
potentiostat/galvanostat controlled by a personal computer. The counter and reference electrodes were a
platinum wire and a saturated calomel electrode (SCE),
respectively. The working electrode was an approximately 50 nm-thick ruthenium layer deposited by sputtering onto Si(100) pieces at low temperature. The
electrodes were held parallel to each other with an interelectrode gap of 20 mm. The preferred orientation of
electrodeposited metals depends mainly on the crystal
structure of the substrate and the bath conditions. The
choice of the ruthenium substrate is based on the lattice
parameter misfit between the substrate lattice and thin
film lattice. In the case of CoNi, the misfit is lower than
15% which means that the electrocrystallisation of the
CoNi lattice follows the substrate orientation. The
deposits were produced at room temperature *20uC
(see Table 1). To see the additive effect on film properties, deposits must have the same thickness, and for this
reason the charge quantity was fixed at 1.31 C cm22
during the deposition of films.
Before the deposition, the substrates were cleaned
ultrasonically in acetone and ethanol followed by distilled
and deionised water cleaning for 10 min. All the experiments were performed in unstirred solutions. The baths
were purged with nitrogen. Distilled water and analytical
grade chemicals were used for the preparation of the
solution for the electrodeposition of CoNi thin films.
To verify the influence of different conditions on the deposition process, cyclic voltammetry (CV) measurements
were used. Polarisation and electrochemical impedance
spectroscopy (EIS) were performed to obtain the corrosion resistance of deposits. Ecorr and icorr values were
obtained from the plot of E versus log i curve by the Tafel
extrapolation method using an electrochemical analyser
Model IM6 with Thales software. The same threeelectrodes cell assembly and instrument was used for the
AC impedance measurements. The CoNi plated samples
in the absence and presence of additive were used as
working electrode and 3.5 wt.% NaCl solution was used
as the test solution. The electrochemical impedance
measurements were carried out at open circuit potential
(463 mV versus SCE) in the frequency range from
60 kHz to 5 MHz. The values of double layer capacitance
(Cdl) and charge transfer resistance (Rct) were obtained
from the Nyquist plots of the real (Zr) versus imaginary
(2Zi) components of the impedance. The corrosion
potential and the corrosion current density were obtained
with the Tafel extrapolation method from potentiodynamic polarisation curves. The polarisation resistance
(Rp) of CoNi alloy was determined using the Stern
Geary equation32 as follows
RP

ba bc
1
2:303ba bc icorr

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Table 1 Composition of plating bath and plating conditions


Conventional bath

Saccharin-added bath

Composition

Concentration/M

Composition

Concentration/M

CoCl2, 6H2O
NiCl2, 6H2O
H3BO3
KCl

0.1
0.02
0.5
1

CoCl2, 6H2O
NiCl2, 6H2O
H3BO3
KCl
C7H5NO3S

0.1
0.02
0.5
1
(0.00, 0.003, 0.004
and 0.005)

where ba, bc are anodic and cathodic Tafel slopes,


respectively, extracted from potentiodynamic polarisation
curves. The inhibition efficiency gz was calculated using
the polarisation resistance as follows33

RP 2 R0P
gz
100
RP

where Rp and R0p are the polarisation resistances of


solutions with and without saccharin, respectively.
Film thicknesses were measured using a profilometer
KLA Tencor, P15 model. The compositional analysis of
the films was carried out by atomic absorption spectroscopy (AAS) using a spectrometer Shimadzu AAS6000. The deposit layer was dissolved in 20 cm3 of 3 M
HNO3, the solution then diluted up to 100 cm3 with doubly
distilled water in 100 cm3 measuring flask. A suitable
diluted solution was then analysed to ascertain the Co and
Ni contents in the deposited alloy using the AAS technique.
The surface morphology was observed by atomic force
microscopy (AFM) technique (Nano-Re model). The
crystalline structure of the electrochemically deposited
films were identified by X-ray diffraction (XRD) with
CuKa1 incident radiation (l 0.154056 nm) using a
RIGAKU SmartLab diffractometer in the symmetrical
geometry h2h. The magnetic properties were investigated
using an alternating gradient force magnetometer
(AGFM) device, made by MicroMage 2900 Series from
Lakeshore Cryotronics in an applied magnetic field
sweeping between /2 13 kOe. at room temperature. The
hysteresis loops of the CoNi coatings were obtained using
a magnetic field parallel to the films plane.

Working conditions
pH
Agitation
T (8C)
Anode
Cathode

3.8
No
,20
Pt
Si(100)/Cr/Ru (0.5 cm2)

the cobalt percentage in the alloy increases. Furthermore, in the curves, it is possible to note the presence of
cross-overs of the cathodic and anodic branches, typical
of the formation of a new phase, involving a nucleation
followed by diffusion limited growth process.35
The CE is an important aspect in metal electrodeposition. In this case, the parallel reaction corresponding
to HER has a great influence in the electrodeposition.
To help explain the role of additives, the CE during the
co-deposition process was determined. In most cases studied, the CE of CoNi alloys co-deposited from chloride
baths is v100% denoting simultaneous HER. The deposition CE was calculated from the stripping/deposition
charge ratio using equation36,37
CE

Qanod
100
Qcath

Results and discussion


In order to investigate the effect of saccharin addition on
the mechanism of the electrodeposition of CoNi thin
films, CV was used as an in situ technique to study
single-metal and alloy electrodeposition and dissolution
in all baths. The CVs obtained in supporting electrolyte
(0.5 M H3BO3 1 M KCl) with and without the presence of saccharin as an additive for a solution containing 0.1 M CoCl2, 6H2O 0.02 M NiCl2, 6H2O
concentration of metal salts are shown in Fig. 1. The
potential scan was started from 0.2 V versus SCE,
reversed to 21.4 V and terminated at 0.2 V at a scan
rate of 20 mV s21. The obtained voltammograms have
the same general form and show the presence of one
cathodic peak associated with the ion deposition, which
increases with increasing of the saccharin concentration
in the bath. On the anodic part, only one oxidation peak
appears and its position is a function of the alloy composition.7,34 It shifts to more negative potentials when

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1 Cyclic voltammograms of 0.1 M CoCl2 1 0.02 M NiCl2 with


different concentrations of saccharin: a 0, b 0.003, c 0.004
and d 0.005 M. Supporting electrolyte 1 M KCl 1 0.5 M
H3BO3, pH 3.8. The sweep rate was 20 mV s21

Tebbakh et al.

Qanod and Qcath are total (integrated) anodic and cathodic


charges, respectively. The amount of charge used for electrodeposition (Qc) and for dissolution (Qa) were estimated
by integrating the area under cathodic and anodic peaks,
respectively. The CE for CoNi electrodeposition from
different baths as a function of concentration of saccharin
is shown in Fig. 2. It can be seen in this latter figure that the
increasing of the saccharin amount in the bath causes the
CE to decrease, because the saccharin present in solution
can be adsorbed on the electrodes surface and consequently
blocks the nucleation sites. This occurs because in the
presence of saccharin deposition is accompanied by
adsorbed hydroxide at high concentrations of H caused
by complexation; part of the charge is used for promoting
the HER.
The elemental compositions of Co in the films
according to Co ion concentration in the electrolyte with
a fixed concentration of Ni ions were obtained using the
AAS measurements and are presented in Fig. 3. The Co
content of the coatings was always higher than expected
from the bath composition reference line. Also, the results
revealed that the Co percentage in the films obtained with
addition of saccharin is higher than films produced
without saccharin additive. From Fig. 3, the increasing of
Co2 ions concentration in the solution is accompanied
by an increase in the fraction of this metal in the deposit.
It was found that the percentage of Co/(Co Ni) ratio in
the films was higher than that in the Co2/(Co2 Ni2)
ratio in the electrolyte for all films deposited, in agreement with the literature.38,39 This trend can be attributed
to an anomalous co-deposition reaction, which favours
the deposition of less noble metal; in the anomalous
character of CoNi alloy deposition, the less noble
constituent (Co) is deposited preferentially.3,1416 This
reaction is a consequence of the side reaction of metal
reduction, which involves the evolution of hydrogen. This
process depletes protons and increases the local concentration of hydroxyl ions. The enhancement of the
hydroxyl ions results in the formation and adsorption of
metal monohydroxide ions or metal hydroxides on the
deposit. This scenario can be proposed in the following
sequence40

2 Effect of saccharin concentration on cathodic current


efficiency for CoNi alloy thin film deposition

The influence of saccharin

3 Effects of the saccharin concentration on the cobalt


content of CoNi alloy thin films as a function of the bath
cobalt content

2H2 O 2e 2 ! H2 2OH2

4a

M2 OH2 ! MOH

4b

MOH !

MOH
ads

4c

2
2
MOH
ads 2e ! M OH

4d

where M indicates Ni and Co atoms. The deposition of


Co is promoted by the surface enrichment of its corresponding adsorbed metal hydroxide ions CoOH
ads :
It is well known that the Co content has a significant
influence on corrosion resistance, surface morphology
and phase structure (see next section). As the adsorption
ability of Ni(OH) is lower than Co(OH), the formation of a Co(OH)-enriched film on the substrate
surface inhibits the adsorption of Ni(OH) and consequently the reduction of cobalt is promoted.30
In order to investigate the electrochemical process for
CoNi deposition, EIS measurements were performed
for deposits prepared at 21.1 V versus SCE in baths
with and without saccharin. The impedance diagrams
obtained in 3.5 wt.% NaCl solution are shown in Fig. 4.
Deviations from perfect circular shape are often referred
to the frequency dispersion of interfacial impedance,
which arises because of surface roughness, impurities,
dislocations, grain boundaries and formation of porous
layers and inhomogenates of the electrode surface.
Figure 4a shows the EIS diagram for CoNi deposits
without any additive and Fig. 4bd show the EIS for
CoNi deposits from 0.003, 0.004 and 0.005 M of saccharin addition, respectively. From those curves, in all
baths, two time constants can be distinguished. The first
time constant, which appears as a capacitive loop at high
frequencies, belong to double layer capacitance parallel
to charge transfer resistance.41 The second time constants, which appear as inductive loops at lower

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The influence of saccharin

4 Nyquist plots of NiCo alloy thin films deposited at pH 3.8


in 3.5 wt.% NaCl solutions in the presence of different
concentrations of saccharin: a 0, b 0.003, c 0.004 and
d 0.005M. The range of frequencies is between 60 kHz
and 5 MHz

frequencies, are most probably created because of the


adsorption of hydrogen and intermediate complexes.42,43
The charge transfer resistance and the double layer capacitance values were extracted from the Nyquist plots
and are presented in Table 2. As seen from this table, the
charge transfer resistance is reduced and the double
layer capacitance increases with increasing of the saccharin concentration in the bath. This may be related to
the reversible adsorption of saccharin molecules. Thus,
saccharin can act as an obstacle to prevent surface diffusion of adions towards the active sites of growth.
Therefore, the growth rate is decreased and finer grains
are obtained. By applying equivalent circuit models
where physicochemical processes occurring within the
CoNi thin films are represented by a network of resistors, capacitors and inductors, meaningful qualitative
and quantitative information regarding the sources of
impedance within the thin films can be extracted.
It is established that the CoNi electrodeposits have the
potential to be used in aerospace, automobile and general
industries as an alternative to hard chromium coatings
because of their high hardness, anti-wear and anticorrosion resistance properties.9,30,39,44,45 For this, the
corrosion resistance for the deposits obtained from a bath
with saccharin and those obtained from a bath without
saccharin are determined. In effect, the Tafel plots of log j
versus E or potentiodynamic polarisation curve in logarithmic scale for CoNi in 3.5 wt.% NaCl solution are
shown in Fig. 5. Corrosion characteristics such as corrosion potential (Ecorr), anodic and cathodic Tafel slopes
(ba), (bc), respectively, and corrosion current (icorr),
obtained from the intersection of anodic Tafel curve
tangent and corrosion potential line are given. Polarisation resistances (Rp) and corrosion rates (rcorr) were also
calculated from these data. Table 2 summarises the corrosion characteristics obtained from polarisation curves.
It is obvious that the corrosion potential versus SCE
positively increased from 20.586 to 20.474 V as the

saccharin concentration addition in electrolyte increased


from 0 to 0.005 M. The corrosion current density of
deposits obtained from saccharin-containing solution had
the lowest corrosion current among the CoNi alloys.
The results indicate that the deposits obtained from
saccharin baths have a very good corrosion resistance
compared to the deposit obtained from a saccharin-free
bath. This is in agreement with the work of Hassani
et al.,31 who reported that the nanocrystalline CoNi
alloys deposited from a bath containing saccharin had
higher corrosion resistance in 10 wt.% NaOH compared
with the coatings with the same composition plated from
additive-free baths. In addition, the polarisation resistance Rp and the inhibition efficiency gz of CoNi alloy
thin films increase upon increasing the saccharin concentration in the bath. However, the polarisation resistance of CoNi alloy thin films decreases when decreasing
the saccharin concentration in the bath.
The corrosion of the alloys involves the following
reactions46
Ni ! Ni2 2e 2

5a

Co ! Co2 2e 2

5b

O2 2H2 O 4e 2 ! 4OH2

5c

The electrode was anodically polarised to a more


positive potential whereas the corresponding current
remained limited. In the present research, the four
coatings exhibited activepassive polarisation behaviour
in 3.5% NaCl solution. The formation of the passive film
on the electrode surface includes the following steps4749
M H2 O ! MH2 Oads

6a

MH2 Oads ! MOH H 2e 2

6b

MOH H2 O 4e 2 ! MOH2 H

6c

where M represents Ni and Co. The dissolved oxygen in


equation (5c) can accelerate the formation of the M(OH)2
passive film. As the potential increases in the active
region, the anodic current density increases because of the
dissolution of the adsorbed species M(H2O)ads:49
MH2 Oads 2Cl2 ! MCl2 H2 O 2e 2

As the adsorbed species dissolve, new active sites on


the working electrode surface appear which leads to the
breakdown of the passive film.
It has been established that the corrosion resistance of
deposited alloys may be correlated to several important
factors such as chemical composition, phase composition,
texture or preferred orientation, grain size, residual
stresses, defects, surface morphology, and roughness.37

Table 2 Electrochemical parameters obtained from the Tafel plots

200

Saccharin
concentration

Rct/V cm22 Cdl/mF cm21 2Ecorr/V

rcorr/
icorr/mA cm22 ba/V dec21 2bc/V dec21 Rp/V cm22 mm year21 gz

0
0.003
0.004
0.005

437
362
214
168

70.0
64.4
60.3
53.6

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0.099
0.107
0.107
0.111

0.250
0.274
0.307
0.312

439.90
534.98
554.11
663.25

9.38
7.25
5.52
4.81

17.77
2061
33.67

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5 Potentiodynamic polarisation curve of CoNi alloy thin


films in 3.5 wt.% NaCl solution with different concentrations of saccharin: a 0, b 0.003, c 0.004 and d 0.005 M

Figure 6 shows AFM images of CoNi thin films


obtained at different concentrations of saccharin. From
the images, it is seen that all the film surfaces are well
covered with the variably distributed forms of grains.
It is clearly seen that presence of saccharin changes the

The influence of saccharin

topography of films from clusters into well-defined


triangular grains. Surface roughness is one of the
important properties of the CoNi thin films for many
MEMS and NEMS applications, and also in Fig. 6 is
shown the root mean square (RMS) roughness of
deposits obtained at various concentrations of saccharin:
0, 0.003, 0.004 and 0.005 M. It is found that the surface
roughness is strongly dependent on concentration of
additive. From this figure, when saccharin concentration
increased from 0 to 0.005 M, the RMS roughness
decreases from 88 down to 14 nm. It has to be noted that
the thickness of the CoNi thin films obtained without
saccharin is only slightly lower than that with saccharin
(Table 3), thus the clear differences in roughness shown in
Fig. 6 depend on the concentration of saccharin and not
on the thickness of the layers. It seems clear that the
surface morphologies of CoNi alloys strongly depend on
saccharin concentration and consequently on cobalt
content.39 The morphological aspects are also influenced
by a parallel reaction of hydrogen evolution.50
The structural state of the electrodeposited CoNi thin
films was characterised by XRD technique. Figure 7 shows
the XRD patterns of CoNi thin films deposited from
the electrolytes with different saccharin concentrations.
As seen in these patterns, only two peaks show at 2h 428
and 44.308, which are consistent with the (100)hcp
and (111)fcc/(002)hcp planes for Co lattice, respectively.
By increasing the concentration of saccharin content, there
is no obvious change in the texture orientation while a
sensitive reduction in the intensity is observed for highsaccharin concentration. Indeed, the peaks for deposits
obtained from 0.005 M of saccharin are considerably
smaller because of the higher concentration of saccharin,

6 Atomic force microscopy (AFM) images of CoNi thin films obtained at different concentrations of saccharin:
a 0, b 0.003, c 0.004 and d 0.005 M

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Table 3 Evolution of structural and magnetic parameters (Hc and Ms) as a function of the saccharin content in the
deposited alloy
x Saccharin/M

Thickness/nm

Co/at.%

D/nm

Hc/Oe

Ms/emu cm23

0
0.003
0.004
0.005

661
742
732
764

91.98
94.52
95.14
95.77

50.53
44.04
43.85
43.75

56.01
6.05
3.63
1.40

1394.26
493.36
572.43
1034.01

comparable with the additive-free electrolytes. Therefore,


this pattern exhibits for all samples the presence of a mixed
hcp and fcc structures.
Average crystallite size of the deposits was calculated
from the diffraction peak broadening after subtracting the
instrumental line broadening (estimated using Si single
crystal data as the standard), using the Scherrer equation 51
D

0:9l
b cos h

where D is the crystallite size, l is the wavelength of the


CuKa1 radiation (0.154056 nm), b is the full-width at halfmaximum (FWHM) of the diffraction peak, and h is the
Bragg angle. Table 3 shows the size of the crystallites
obtained from XRD for [100] planes for hcp phase for
alloys electrodeposited at four concentrations of saccharin.
The crystallite size was typically 4350 nm. The alloy
deposits therefore possess a nanocrystalline structure.
Saccharin has a significant effect on the reduction of crystallite size. Effectively, the average size of crystallites
decreases with increasing saccharin additive concentration
in the chloride baths. It can be suggested that adsorption of
saccharin molecules can block the active growth centres
during electrodeposition and acts as a grain refiner. This
result agrees with those obtained in the literature.52,53 This
observation indicates clearly that the refinement effect of
saccharin in the electrodeposition process. In agreement

with the literature, the organic additives can act as a grain


refiner by absorbing on the deposit surface and modifying
electrocrystallisation.54
In addition, it is well known that the electrocrystallisation can be strongly influenced by the presence
of adsorbed molecules and ions at the surface of the
electrode.55 The preferential orientation in the electrodeposition process is known to occur and is related to the
growth conditions. The change in the texture degrees of
films deposited from the electrolytes based on Ni has been
usually attributed to the presence of inhibiting species
such as hydrogen and nickel hydroxide, which can slow
down propagation steps, block growth site, and/or modify
the activity of emerging structural defects.56,57 Such
species can be formed depending on the electrolyte composition and deposition parameters and can be adsorbed
partially on the cathode surface. The amount of inhibiting
species can be changed with the electrolyte pH.58
The magnetic behaviour of the CoNi alloys thin films
is also very sensitive to the concentration of saccharin
additive. Representative examples of the magnetisation
curves obtained from the studied CoNi films are shown
in Fig. 8. Magnetic measurements showed that all the
coatings have an in plane easy magnetisation axis and a
soft magnetic character with coercivity lower than
60 Oe. But clearly, changes in magnetic properties are
observed with the addition of saccharin to the deposition
bath. Indeed, because of the presence of saccharin the

7 X-ray diffraction (XRD) patterns of CoNi alloy thin films co-deposited from solution with different concentrations of
saccharin: a 0, b 0.003, c 0.004 and d 0.005 M

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8 Alternating gradient force magnetometer (AGFM) hysteresis loop for CoNi alloy thin films electrodeposited at 21.1 V from
chloride bath with different concentrations of saccharin: a 0, b 0.003, c 0.004 and d 0.005 M

deposits exhibit lower values of coercivity and magnetisation saturation compared to those without saccharin.
The coercivity values decrease to 1.4 Oe and magnetisation saturation decreases in comparison to the film
without saccharin (Table 3), although the decrease in Ms
is considerably lower at the highest saccharin content of
0.00 M. The magnetic properties of the deposits can be
related to the grain refinement and the internal stress
and under a critical crystallites size we can observed
a superparamagnetic behaviour.59 Such behaviour
(decrease of the coercivity with the decrease of the
crystallites size) was observed by other studies for CoNi
and FeNi alloys obtained by mechanical alloying.60

Conclusion
In this study, the effect of saccharin additive in the mechanism of CoNi co-deposition and alloy properties is

presented. From the experimental results, it could be


concluded that the presence of saccharin in chloride solutions inhibits the Ni deposition and accelerates the rate of
Co deposition. Also, the presence of the saccharin content
in the bath increases the percentage of Co in the electrodeposits. The electrodeposition of CoNi produced with
and without saccharin is confirmed by the anomalous
character of the alloy deposition, where the less noble (Co)
constituent is deposited preferentially. Moreover, the
addition of saccharin to the bath leads to a cobalt-rich
deposit, to an increase of the corrosion resistance of the
electrodeposited layers and consequently to an increase
of the life of the material, which is important for technological applications. From XRD analysis, it can be
suggested that the saccharin acts as a grain refiner.
Therefore, the saccharin concentration represents an
important factor for the coercivity of electrodeposited
CoNi alloys thin films. It is clear that the magnetisation

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curves show low values of the coercivity for alloys deposited from saccharin-containing baths indicating that the
produced films are suitable for magnetic applications.

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