Increased Metallic Character of Electrodeposited Mn Coatings Using

Metal Ion Additives

Jie Gong and Giovanni Zangari

Electrochem. Solid-State Lett. 2004, Volume 7, Issue 9, Pages C91-C94.

doi: 10.1149/1.1774972

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 Electrochemical and Solid-State Letters, 7 共9兲 C91-C94 共2004兲 C91
0013-4651/2004/7共9兲/C91/4/$7.00 © The Electrochemical Society, Inc.

Increased Metallic Character of Electrodeposited Mn Coatings

Using Metal Ion Additives
Jie Gong* and Giovanni Zangari**,a,z
Materials Science Program and Department of Metallurgical and Materials Engineering,
University of Alabama, Tuscaloosa, Alabama 35487-0209, USA

Small amounts of metal ions (Sn2⫹ or Cu2⫹) added to an electrolyte for Mn electrodeposition increase the metallic character of
amorphous Mn coatings grown at high current densities. The codeposited oxygen decreases from 54 atom % to less than 7 atom
%, while the codeposited Sn or Cu are below 1 and 3 atom %, respectively. The resulting amorphous coatings exhibit very
different mechanical properties and better corrosion resistance than those of amorphous manganese coatings electrodeposited
without metal ion additives.
© 2004 The Electrochemical Society. 关DOI: 10.1149/1.1774972兴 All rights reserved.

Manuscript submitted October 20, 2003; revised manuscript received January 20, 2004. Available electronically July 23, 2004.

The introduction of small amounts of additives to a solution for
aqueous electrodeposition of a metal can induce relevant changes in
the nature and properties of the films grown at the cathode. These
changes may include brightening of the deposit, leveling, as well as
variations in the mechanical and physical properties, reduction in the
internal stresses, and improvement in the corrosion resistance of the
coatings.1-3 Metal ions in particular may be added to act as grain
refiners. While studying the effect of small additions of Sn2⫹ or
Cu2⫹ on the Mn electroplating process, we found that small addi-
tions of metal ions may also have a profound influence on the
chemical state of the deposit and consequently on its mechanical and
corrosion resistance properties.
Electrodeposited coatings of manganese and its alloys have been
studied as a replacement for cadmium in the sacrificial protection of
steel, due to their environmentally friendly nature, potentially high
corrosion protection performance, good tribological behavior, and
suitable mechanical properties.3-8 Pure manganese has not been for-
merly considered as a protective coating for steel because of its high
chemical reactivity and brittle nature.8-11 Therefore, alloying of Mn
with other more noble metals, such as Sn,12 Zn9,13-18 or iron group
elements,19-23 has been attempted to reduce its reactivity. The brittle
nature of electrodeposited Mn originates from the room-temperature
phase transformation of as-deposited ductile ␥-Mn 共centered tetrag-
onal, ct兲, to the brittle ␣ form 共body-centered cubic, bcc兲. It has been
shown that this transformation may be prevented effectively by
codepositing Mn with face-centered cubic 共fcc兲 metals, such as Cu.8
In this work, the effect of the addition of small amounts of Sn2⫹ or
Cu2⫹ to Mn electroplating solutions on the resulting coatings was
studied. The structural, chemical, mechanical, and corrosion proper-
ties of these coatings were investigated. Significant differences in
the chemical state of the resulting coatings as well as on their prop-
erties were induced by the addition of Sn2⫹ or Cu2⫹ ions.
with analytical grade reagents 共Fisher Scientific兲 and triply distilled
water. Experiments were carried out at 25°C and under quiescent
conditions.
Surface morphology of the coatings was examined by scanning
electron microscopy 共SEM兲 using a Philips XL30 instrument.
Chemical analysis of the deposits was performed by an attached
energy-dispersive X-ray spectrometer 共EDX兲 with a CDU LEAP
detector. Incorporation of oxygen and the chemical states of each
element were further studied by X-ray photoelectron spectroscopy
共XPS兲, using a Kratos Axis 165 system with a monochromatic Al
K␣ (h␯ ⫽ 1486.6 eV) source 共for Mn and Sn-Mn coatings兲 and Mg
K␣ (h␯ ⫽ 1253.6 eV) source 共for Cu-Mn兲 at a pass energy of 160
eV 共survey scans兲 or 40 eV 共high-resolution scans兲. The use of Mg
K␣ radiation allowed us to distinguish between the Mn 2p3/2 and Cu
L3 M23M45 characteristic transitions,24 as well as between the Mn
L23M23M23 Auger peak and the shake-up peak of Cu共II兲 2p3/2 . The
Mn 2p peak was analyzed with the charge neutralizer on to avoid
surface charging effects.25,26 The atomic fraction of each element
was evaluated semiquantitatively by weighing the corresponding
signals after subtracting a Shirley-type background.25 Binding ener-
gies were calibrated using the adventitious C 1s peak at 285.0 eV as
a reference. Crystal structure was determined by X-ray diffraction
共XRD兲, using ␪-2␪ geometry with a Rigaku D/Max-2BX XRD sys-
tem with Cu K␣ radiation. A Nano Indenter II mechanical properties
microprobe 共Nano Instruments, Oak Ridge, TN兲 equipped with a
nanoscratch attachment was used to perform the constant load tribo-
logical experiments, using a Berkovich diamond tip. The nanoinden-
tation hardness and Young’s modulus were also measured using a
Hysitron Triboscope nanomechanical test instrument. Corrosion re-
sistance and possible passivation behavior of the coatings were mea-
sured by anodic polarization in 3% NaCl solution at pH 3.0. The
experimentally determined polarization curves were fitted using the
Stern-Geary equation to give the values of the corrosion potential
(E corr) and the corrosion current (I corr), using proprietary software.

Experimental Results and Discussion

Electrochemical and electrodeposition setups are described in de-
tail in Ref. 11. The solutions contained 0.59 M manganese sulfate
(MnSO4 ) and 1 M ammonium sulfate ((NH4 ) 2 SO4 ), with the addi-
tion of 0.001-0.01 M stannous sulfate (SnSO4 ) or 0.0025-0.02 M
cupric sulfate (CuSO4 ). pH was adjusted to 2.6-2.8 by adding sul-
furic acid. The Sn-Mn solutions were stable only up to these pH
values, and Cu-Mn solutions were well buffered and stable only in
this pH range and at pH 6.6-6.8. All solutions were freshly prepared
* Electrochemical Society Student Member.
** Electrochemical Society Active Member.
a
Present address: Department of Materials Science and Center for Electrochemical
Science and Engineering, University of Virginia, Charlottesville, VA 22904-4745.
z
E-mail: gz3e@virginia.edu
Morphological and structural characteristics.—Galvanostatic
electrodeposition of Mn,11 Sn-Mn,12 and Cu-Mn yielded two types
of sound coatings, crystalline 共type I兲 or amorphous 共type II兲, in
dependence of the applied current density. At high current density,
amorphous coatings were obtained in all cases. Under these elec-
trodeposition conditions, hydrogen evolution was very strong and
consequently stirring did not change the limiting current. The con-
tent of Sn in amorphous Sn-Mn coatings, and of Cu in amorphous
Cu-Mn coatings, was less than 1 and 3 atom %, respectively, almost
independent of current density. The conditions for the growth of
amorphous Cu-Mn coatings at pH 6.6-6.8 were similar to those at
pH 2.6-2.8, therefore we assumed that the effect of pH on the for-
mation of amorphous coatings was minimal. The morphology, com-
position 共by EDX, considering only the metallic elements兲, and
growth parameters of typical coatings are shown in Fig. 1. The grain

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C92 Electrochemical and Solid-State Letters, 7 共9兲 C91-C94 共2004兲
Figure 1. SEM secondary electron surface micrographs of type I and II
coatings electrodeposited at various current densities at pH 2.6-2.8. The elec-
trolytes contain MnSO4 共0.59 M兲, (NH4 ) 2 SO4 共1 M兲 and 共b兲 and 共e兲 SnSO4
共0.001 M兲; 共c兲 and 共f兲 CuSO4 共0.005 M兲.
size of type I Mn coatings systematically decreased upon codeposi-
tion of small amounts of Sn or Cu. A higher concentration of Sn2⫹
or Cu2⫹ tended to increase the minimum current density necessary
to obtain type II coatings.
XRD patterns of these films are compared in Fig. 2. As-deposited
type I coatings all exhibit the ␥共ct兲 structure, a metastable solid
solution in the bulk alloy. No solubility of Cu and little solubility of
Sn in Mn at room temperature has been reported in the correspond-
ing equilibrium phase diagrams.27 No separate peaks of Sn or Cu
phases were discerned in our experiments. Both Mn and Sn-Mn
crystalline coatings underwent phase transformation from ␥ to the
␣-phase 共bcc兲 in several weeks at room temperature. A small amount
of Cu 共3-4 atom %兲 on the contrary can stabilize the as-deposited ␥
form for over 18 months at room temperature. All type II amorphous
coatings exhibited a stable amorphous structure. No crystallization
was detected by XRD for these films after over 18 months aging at
room temperature.
Chemical states.—With the addition of Sn2⫹ and Cu2⫹ in the
electrolytes, the appearance of the amorphous coatings was bright
and glossy, in contrast with that of type II pure Mn coatings, which
is black and glossy.11 XPS was used to obtain detailed information
about the chemical composition of type II coatings.
Figure 3a-d shows high resolution 共HR兲 XPS scans of the Mn 2p
and O 1s regions for type II Sn-Mn and Cu-Mn coatings at the
surface and in the bulk, compared with type II Mn coatings. HR
XPS scans of the Sn 共Cu兲 regions were also collected but are not
shown. The standard peak position of each chemical state is shown
as dotted lines. In addition, the atomic percentage of Mn, Sn/Cu, and
O at different depths in the coatings is shown in Fig. 3e,f.
In amorphous 共type II兲 Mn coatings, the Mn:O atomic ratio re-
duced from 26:74 at the surface to 39:61 at 6 nm under the surface.
Below 6 nm, the composition and chemical states did not depend
much on depth 共Fig. 3e兲, Mn is predominantly in the ⫹2 and ⫹3
valence states 共Fig. 3a兲, and Mn共0兲 is only 6-8 atom % in the bulk.
The oxygen content in type II Sn-Mn coatings was greatly reduced,
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Figure 2. XRD patterns of as-deposited type 共a兲 I and 共b兲 II coatings ob-
tained at pH 2.6-2.8.
and the metal content increased to a relevant extent as a conse-
quence of the addition of a small amount of Sn2⫹ in the solution
共Fig. 3e兲. More precisely, the Mn:Sn:O atomic ratio changed from
55:3:42 at the surface 共about 2 nm deep兲 to 93:1:6 after 80 etching
cycles 共about 160 nm兲. The compositional gradient observed in type
II Sn-Mn coatings is different from that of pure Mn coatings. O
content reduced sharply in the first several nanometers of naturally
oxidized layer, and then decreased gradually. By deconvoluting the
O 1s peak using three components 共corresponding to H-O-H, Mn-
O-H, and Mn-O-Mn兲,25 most of the oxygen was found to exist in the
form of hydroxide 共66 atom %兲, though its overall content was very
low in the bulk. By deconvoluting the Mn 2p peak using three
components 共corresponding to Mn共0兲, Mn共II兲, and Mn共III/IV兲兲,25
near the surface 共in the naturally oxidized layer兲 the coating was rich
in Mn共II-IV兲, while the bulk was rich in Mn共0兲 共⬎60 atom %兲 共Fig.
3a兲. Sn was in an oxidized form at the surface12 and ‘‘quasi-
metallic’’ form28,29 in the bulk 共⬎20 nm deep兲. The relative concen-
tration of Sn was kept under 1 atom % below 10 nm depth and
throughout the coating.
The addition of Cu2⫹ had a similar effect on the coating chemi-
cal composition. For type II Cu-Mn films, the Mn:Cu:O atomic ratio
changed from 61:3:36 at 10 nm depth to 90:3:7 at 120 nm depth
共Fig. 3f兲. However, the compositional gradient for the Cu-Mn coat-
ing was different from the others; a relatively thick oxide layer was
observed, with a nonmonotonous variation of oxygen content with
thickness. As in Sn-Mn, the bulk content of O in amorphous Cu-Mn
coatings was much lower than in type II Mn coatings, and even
lower than that in metallic, crystalline type I Cu-Mn coatings. De-
 Electrochemical and Solid-State Letters, 7 共9兲 C91-C94 共2004兲
Figure 3. High resolution XPS spectra of type II alloy coatings 共see Fig. 4 in
Ref. 11 for Mn兲: 共a兲 Sn-Mn, Mn 2p, 共b兲 Cu-Mn, Mn 2p, 共c兲 Sn-Mn, O 1s; 共d兲
Cu-Mn, O 1s, 共e兲 Mn-O-Sn compositional depth profiles, and 共f兲 Mn-O-Cu
compositional depth profiles. 共a兲, 共b兲 and 共f兲 also include for comparison the
XPS spectrum and the compositional depth profile of type II Mn 共from Ref.
11兲. Sn-Mn coatings are obtained from an electrolyte containing SnSO4 共0.01
M兲, MnSO4 共0.59 M兲, and (NH4 ) 2 SO4 共1 M兲 at 600 mA/cm2. Cu-Mn coat-
ings are obtained from an electrolyte containing CuSO4 共0.005 M兲, MnSO4
共0.59 M兲, and (NH4 ) 2 SO4 共1 M兲 at 600 mA/cm2. pH is 2.6-2.8.
tailed investigation of O 1s spectra indicated that the small amount
of oxygen inclusions was in the form of MnOx (OH) 2⫺x •nH2 O,
where x increases and n decreases with depth. In addition, an obvi-
ous Mn共0兲 peak 共Fig. 3b兲 showed that Mn共0兲 is the main form of Mn
共over 60% of total Mn兲. Cu was in the metallic form throughout and
was distributed uniformly.
Summarizing, at high current density electrodeposited manga-
nese coatings grew predominantly as Mn oxyhydroxides, probably
due to a local pH increase at the interface caused by strong hydrogen
evolution, which led to metal hydrolysis 共Eq. 1兲 and then to the
further oxidation of metal hydroxides 共Eq. 2兲
Mn2⫹ ⫹ H2 O → Mn共 OH兲 2 ⫹ H⫹ 共 at pH ⬎ 7.5兲
2Mn共 OH兲 2 ⫹ O2 → 2MnO共 OH兲 2
These reactions and consequently the inclusion of oxygen in
amorphous Mn coatings seem to be inhibited by the addition of
Table I. Mechanical and tribological properties of Mn, Sn-Mn, and Cu-Mn coatings.
ECD Type I
Cd Mn
Friction 0.8 — 0.5
Coefficient
Nanohardness H 共GPa兲 0.3 0.4
Reduced modulus E r 共GPa兲 151.9 31.1
H/E 2 (⫻10⫺4 ) 0.13 4.1
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C93
Sn2⫹ or Cu2⫹ ions, perhaps due to the presence of different species
that adsorb on the electrode preferentially to Mn(OH) ads , avoiding
Mn-oxyhydroxide incorporation, and/or to the possibility of differ-
ent chemical equilibria in the electrolyte bulk. These phenomena
result in a dramatic change in the chemical states of amorphous Mn
coatings, and hence in the production of essentially metallic amor-
phous Mn 共O content below 7 atom %, other metals below 1 共Sn兲
and 3 共Cu兲 atom %兲. The crystalline to amorphous transition in Mn
and Mn alloys is due to the extremely high nucleation rate induced
by the high applied overvoltage and by the strong hydrogen evolu-
tion and probable incorporation, that cannot be detected by XPS.
Although the mechanism for the observed change in chemical states
is not clear at this time, we believe that this effect may be important
for other codeposition systems, as well as for the electrodeposition
of other active metals.
The increase in the metallic character of amorphous Mn elec-
trodeposits induces also relevant changes in their properties, as dis-
cussed in the following.
Tribological and mechanical properties.—The friction coeffi-
cients extracted from nanoscratch experiments, as well as nanohard-
ness and reduced modulus as deduced from Hysitron experiments
for type II Mn, Sn-Mn, and Cu-Mn coatings are shown in Table I,
where they are compared with reference electrodeposited Cd and
crystalline 共type I兲 Mn coatings. All coatings exhibit a friction co-
efficient lower than Cd, which is desirable in practical uses. Type II
Sn-Mn coatings exhibit higher nanohardness than both Cd and Mn,
and in addition possess high modulus. Incorporation of Cu into the
Mn lattice on the contrary decreases both hardness and modulus.
The resistance to plastic penetration, H/E 2 , 30 is also shown in Table
I, showing that Cu-Mn alloys in particular present outstanding me-
chanical properties for use as protective coatings of steel.
Corrosion resistance.—Anodic potentiodynamic corrosion ex-
periments were performed for type II Mn, Sn-Mn, and Cu-Mn coat-
ings, as shown in Fig. 4. In contrast with Mn, coatings containing
small amounts of Sn or Cu show a pseudopassive region at anodic
potentials in 3% NaCl solution at pH 3.0. In addition, the open-
circuit potential 共OCP兲 of Cu-Mn is slightly higher than Sn-Mn,
probably as a consequence of the higher redox potential of Cu and
the higher Cu content with respect to Sn. The OCP of these coatings
共around ⫺1.25 VSCE) is more active than that of low carbon steels.
It is thus anticipated that these coatings may provide sacrificial pro-
tection while presenting low chemical reactivity and thus slow dis-
solution in corrosive media.
Conclusions
The addition of a small amount of Sn2⫹ or Cu2⫹ to an electrolyte
for Mn electrodeposition induced profound changes in the appear-
ance, composition, and properties of amorphous coatings obtained at
关1兴
high current density. In particular, essentially metallic Mn films con-
关2兴 taining small amounts of the metal additives were obtained in amor-
phous form. The coating mechanical and tribological properties, as
well as the corrosion resistance, may be improved by addition of Sn
or Cu in the electrolyte. The possibility of influencing the chemical
Type II Type II Type I Type II
Mn Sn-Mn Cu-Mn Cu-Mn
0.35 0.7 0.5
4.0 7.3 0.1 0.5
95.3 162 10.5 32.9
4.4 2.8 9.1 4.6
C94 Electrochemical and Solid-State Letters, 7 共9兲 C91-C94 共2004兲
Figure 4. Typical anodic potentiodynamic behavior of type II Mn, Sn-Mn,
and Cu-Mn coatings in 3% NaCl solution 共pH 3.0兲. Scan rate is 2 mV/s.
state of electrodeposited reactive metals by use of small amounts of
metal ions may in principle be observed in other electrodeposition
systems and possibly have important applications.
Acknowledgments
This work was supported by DOD-SERDP under contract
DACA72-99-P-0201, and by grant no. NSF-DMR-0093154. The use
of MRSEC shared facilities was supported by NSF-DMR 9809423.
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