Beruflich Dokumente
Kultur Dokumente
discussions, stats, and author profiles for this publication at: http://www.researchgate.net/publication/282665202
READS
6 AUTHORS, INCLUDING:
Azizi Amor
Ferhat Abbas University of Setif (Algeria)
46 PUBLICATIONS 160 CITATIONS
SEE PROFILE
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
196
2015
VOL
93
NO
Tebbakh et al.
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
ba bc
1
2:303ba bc icorr
2015
VOL
93
NO
197
Tebbakh et al.
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)
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
198
2015
VOL
93
NO
Tebbakh et al.
2H2 O 2e 2 ! H2 2OH2
4a
M2 OH2 ! MOH
4b
MOH !
MOH
ads
4c
2
2
MOH
ads 2e ! M OH
4d
2015
VOL
93
NO
199
Tebbakh et al.
5a
Co ! Co2 2e 2
5b
O2 2H2 O 4e 2 ! 4OH2
5c
6a
6b
MOH H2 O 4e 2 ! MOH2 H
6c
200
Saccharin
concentration
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
260
266
296
336
2015
0.586
0.492
0.481
0.474
VOL
93
NO
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
Tebbakh et al.
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
2015
VOL
93
NO
201
Tebbakh et al.
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
0:9l
b cos h
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
202
2015
VOL
93
NO
Tebbakh et al.
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
2015
VOL
93
NO
203
Tebbakh et al.
curves show low values of the coercivity for alloys deposited from saccharin-containing baths indicating that the
produced films are suitable for magnetic applications.
References
1. M. Duch, J. Esteve, E. Gomez, R. Perez-Castillejos and E. Valles:
J. Micromech. Microeng., 2002, 12, 400405.
2. D. Kim, D. Y. Park, B. Y. Yoo, P. T. A. Sumodjo and
N. V. Myung: Electrochim. Acta, 2003, 48, 819830.
3. B. Chi, J. Li, X. Yang, Y. Gong and N. Wang: Int. J. Hydrogen
Energy, 2005, 30, 2934.
4. C. Ma, S. C. Wang and F. C. Walsh: Trans. IMF, 2015, 93, 817.
5. D. Y. Park, K. S. Park, J. M. Ko, D. H. Cho, S. H. Lim,
W. Y. Kim, B. Y. Yoo and N. V. Myung: J. Electrochem. Soc.,
2006, 153, C814C821.
6. D. Landolt: Electrochim. Acta, 1994, 39, 10751090.
7. S. Tebbakh, A. Azizi, N. Fenineche, G. Schmerber and A. Dinia:
Trans. IMF, 2013, 91, 1723.
8. L. Mentar, M. R. Khelladi, A. Azizi, G. Schmerber and A. Dinia:
Trans. IMF, 2011, 89, 143150.
9. C. Ma, S. C. Wang, R. J. K. Wood, Q. Luo, C. T. J. Low and
F. C. Walsh: Metals Mater. Int., 2013, 19, 11871192.
10. P. Crook: ASM handbookVol. 2, , 446; 1990, Ohio, ASM
International.
11. D. Golodnitsky, Y. Rosenberg and A. Ulus: Electrochim. Acta,
2002, 47, 27072714.
12. L. Burzynska and E. Rudnik: Hydrometallurgy, 2000, 54, 133149.
13. D. Golodnitsky, N. V. Gudin and G. A. Volyanuk: J. Electrochem.
Soc., 2000, 147, 41564163.
14. N. Zech, E. J. Podlaha and D. Landolt: J. Electrochem. Soc., 1999,
146, 28862891.
15. S. Gadad and T. M. Harris: J. Electrochem. Soc., 1998, 145,
36993703.
16. S. Goldbach, R. de Kermadec and F. Lapicque: J. Appl.
Electrochem., 2000, 30, 277284.
17. Y. Li, H. Jiang, D. Wang and H. Ge: Surf. Coat. Technol., 2008,
202, 49524956.
18. A. Brenner: Electrodeposition of alloys, 1963, New York,
Academic Press.
19. T. Osaka: Electrochim. Acta, 1999, 44, 38853890.
20. E. Gomez, R. Pollina and E. Valles: J. Electroanal. Chem., 1995,
397, 111118.
21. L. Mentar, M. R. Khelladi, A. Azizi and A. Kahoul: Trans. IMF,
2012, 90, 98104.
22. W. H. Safranek: The properties of electrodeposited metals and
alloys, 1986, Orlando FL, AESF.
23. J. W. Dini: Electrodeposition the materials science of coatings and
substrates, 1995, Park Ridge NJ, Noyes Publications.
24. H. Natter and R. Hempelmann: J. Phys. Chem., 1996, 100,
1952519532.
25. K. Marikkannu, G. P. Kalaignan and T. Vasudevan: J. Alloys
Compd., 2007, 438, 332336.
26. G. Qiao, T. Jing, N. Wang, Y. Gao, X. Zhao, J. Zhou and
W. Wang: Electrochim. Acta, 2005a, 51, 8592.
27. A. El-Sherik and U. Erb: J. Mater. Sci., 1995, 30, 57435749.
28. W. Yin, S. Whang and R. Mirshams: Acta Mater., 2005, 53, 383392.
29. R. Mishra and R. Balasubramaniam: Corros. Sci., 2004, 46, 30193029.
204
2015
VOL
93
NO