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The mechanism of electropolishing of titanium in methanol-sulfuric acid

electrolytes

Article  in  Journal of The Electrochemical Society · July 1998

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2362 J. Electrochem. Soc., Vol. 145, No.7, July 1998 The Electrochemical Society, Inc.

Pb02 is one of the most prominent anode materials, but REFERENCES

it has to be protected from chemical reduction by applying
an external trickle current. Platinum is also a good mate-
rial but does not have a high current efficiency for ozone
and is consumed due to a large wear rate. Carbon materi-
als are also good candidates for ozone evolution but are
easily corroded in acid solution. On the basis of these com-
parisons, it is also expected to be used as a special mater-
ial for an ozone generator that is suitable for the semicon-
ductor industry or medical field, where high purity of the
product would be required.
Acknowledgments
We express our gratitude to M. Koizumi (Permelec
Electrode, Ltd.) and Ri Songi (Tokai University) for help-
ing with this work.
Manuscript submitted August 5, 1997; revised manu-
script received March 27, 1998.
Permelec Electrode, assisted in meeting the publication
costs of this article.
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407 (1987).

The Mechanism of Electropolishing of Titanium in

Methanol-Sulfuric Acid Electrolytes
0. Piotrowski, C. Madore, and D. LandoIt
Laboratoire de metallurgic chimique, Département des matériaux, Ecole Polytechnique Fédérale de Lausanne,
MX-C Ecublens, CH-l015 Lausanne, Switzerland

ABSTRACT
The mechanism of electropolishing of titanium in methanol-sulfuric acid electrolytes is studied by steady-state meas-
urements and by ac-impedance spectroscopy using a rotating disk electrode. The effect of applied potential, electrode
rotation rate, temperature, and electrolyte composition on the response of the system is investigated at the mass-trans-
port-limited current plateau. Both steady-state measurements and impedance data suggest that the rate of reaction is
controlled by mass transport of tetravalent titanium species from the anode surface to the bulk electrolyte. The imped-
ance data confirm the presence of a compact film at the anode surface during titanium dissolution atthe limiting current.

Introduction The study of mass-transport mechanisms in polishing

Titanium and titanium alloys are lightweight structural
materials with good corrosion resistance. Due to their
chemical inertness, they find numerous applications in the
chemical process industry and for medical implants. In
recent years, there has been an increasing demand for
bright and polished titanium surfaces for ob)ects of often
complex shape. For such applications, electrochemical pol-
ishing processes are promising in view of their flexibility
and cost-effectiveness.'7 Electropolishing of titanium can
be carried out in acid media containing perchiorate ions, a
typical example being concentrated acetic acid—perchloric
acid solutions,45 where good electropolishing is obtained at
anode potentials of 20—30 V.5 The use of perchlorate-based
electrolytes for industrial applications, however, poses a
safety hazard. A few perchlorate-free electrolytes for elec-
tropolishing of titanium have been proposed.'2 They nor-
mally contain either fluoride or chloride ions in order to
facilitate attack of the passive oxide layer. An overview of
electrolyte formulations for electropolishing of titanium
proposed in the literature is given in Ref. 12. A common
feature of these electrolytes is their low water content. A
high water content tends to increase the chemical stability
of the passive oxide film formed on the titanium surface.
Anodic dissolution in such a case leads to pitting rather
than polishing.53
* Electrochemical Society Active Member.
systems is of scientific and technological interest for the
optimization of electrolyte formulations and of operating
parameters. The importance of mass-transport limitations
in electropolishing is supported by numerous experimental
observations; electropolishing conditions usually involve
anodic dissolution at the limiting current.'3 In some cases
mass-transport-controlled electropolishing of metals and
alloys takes place in the presence of a precipitated salt film,
which determines the surface concentration of the diffusing
metal cations.'4'5 In other cases, diffusion-limited transport
of an acceptor species necessary for solvation is observ-
ed.16'7 Several studies on the mechanism of electropolishing
of copper iron, and stainless steel were recently pub-
lished,'3 but relatively little is known about the phenom-
ena leading to electropolishing of valve metals which are
capable of forming thick oxide films. Beck,24'2' studying pit-
ting of titanium in different chloride and bromide elec-
trolytes, found brightening to occur at the bottom of pits,
and he attributed this behavior to the presence of a salt
film. Mathieu and Landolt4'5 investigated the anodic behav-
ior and anodic stoichiometry during electropolishing of
titanium in perchloric acid—acetic acid solution using a
rotating cylinder electrode. The onset of electropolishing
coincided with a current plateau in the potentiostatic
polarization curve, but solution-side mass-transport effects
were masked by the presence of a layer of reaction prod-
ucts. More recently, a perchlorate-free electropolishing
electrolyte has been developed by the present authors based
J. Electrochem. Soc., Vol. 145, No. 7, July 1998 The Electrochemical Society, Inc. 2363

on sulfuric acid—methanol mixtures.12 Good polishing per- Results

formance was obtained in a 3 M sulfuric acid—methanol
solution at an applied potential of 8 V against a saturated Effect of temperature—Figure 1 shows potentiodynam-
ic polarization curves measured in methanol-3 M sulfuric
mercurous sulfate reference electrode. Mass-transport-con- acid (96%) at 25, 0, and — 10°C, respectively All curves
trolled limiting current plateaus were observed for sulfuric exhibit a limiting current plateau extending from 2 to 8 V
acid concentrations between 2 and 4 M, but their origin was The limiting current density increases as the electrode
not identified. Sulfuric acid methanol electrolytes were also rotation rate and temperature are increased. The distinct
used for electrochemical micromachining of titanium.26 current minimum between 7 and 8 V results from the for-
The aim of this paper is to investigate the mechanism of mation and subsequent detachment of an anodic film
anodic polishing of titanium in methanol—sulfuric acid when sweeping from anodic to cathodic potentials. The
electrolytes using steady-state and impedance measure- time needed for the film to detach from the electrode sur-
ments. The effect of electrolyte composition, convection face (and hence the position of the minimum on the poten-
conditions, and temperature on the value of the limiting tiodynamic polarization curve) depended on the electrode
current is studied. Impedance measurements are per- rotation rate, a high rotation rate reducing the time need-
formed in the current-plateau region, and obtained results ed for film detachment. Figure 2 shows the reciprocal of
are interpreted in terms of existing theoretical models.
the limiting current density plotted against the reciprocal
of the square root of the rotation speed. Since the limiting
Experimental current plateaus exhibit a finite slope (probably due to
All experiments were performed with a rotating disk elec- Joule heating), the selection of the limiting current value
trode having a surface area of 0.2 cm2. The disk was made of used for comparison is important. In the present case val-
commercially pure titanium (Ti 99.6%, Goodfellow). It was ues at an ohmic (TB) corrected electrode potential of 2.5 V
embedded in an epoxy insulation of 10 mm diam. The disk were compared. The lB drop was determined from imped-
rotation rate was varied between 100 and 2500 rpm. Prior to ance measurements. The corresponding uncorrected
measurements, the electrode was mechanically polished potentials lie, roughly on a line parallel to the (ohmically
with 600 grit emery paper, rinsed with ethanol and doubly dominated) ascending part of the current-voltage curve
distilled water, and dried. A low-noise mercury contact con-
nected the disk to the potentiostat. A platinum wire
(Pt 99%) separated from the working electrode by a glass
sleeve was used as a counter electrode, and a saturated mer- 1.4
curous sulfate electrode (MSE) positioned about 3 cm from
the working electrode surface was used as a reference. All 1.2
potentials given in the present paper refer to this reference 1.0
electrode. A thin platinum wire was connected to the refer-
ence electrode through a capacitance of 0.1 p.E 14 This ar- E 0.8
rangement reduces phase shifts at high frequencies due to (a)
the internal resistance of the reference electrode. 0.6
Electrolytes were prepared from analytical grade 96% 0.4
sulfuric acid (95—97% according to manufacturer) and
methanol (pro analysi, Merck). In these solutions, the water 0.2
content increases with increasing sulfuric acid concentra-
tion. A 3 M sulfuric acid—methanol electrolyte prepared with 0.0
96% sulfuric acid contained 0.2% water as measured by
Karl Fischer titration. Some experiments were carried out
in electrolytes prepared with water-free sulfuric acid (ana- 0.7
lytical grade fuming sulfuric acid, 65% SO3, the sulfuric 0.6
acid content of 100 g fuming sulfuric acid is the equivalent
of 115 g pure H2S04) and dried methanol (pro analysi, 0.5
Merck). In these solutions, a water content of less than
0.02% (wt %) was measured for fuming sulfuric acid con- E 0.4 (b)
centrations up to 5 M. Due to their yellow color, the Karl 0.3
Fischer test could not be used in electrolytes containing
more than 5 M fuming sulfuric acid. The temperature was 0.2
maintained at 25, 0, or — 10°C by circulating a thermostated
mixture of water and glycerin through the jacketed electro- 0.1
chemical cell. Preliminary experiments showed that sparg- 0.0
ing the solution with dry nitrogen had no effect on the meas-
ured polarization behavior. For this reason, no gas sparging
was used for the experiments reported in this study The
kinematic viscosity of the electrolytes was measured at 25°C 0.7
with a viscometer (KPG Ubbelohde) following the ASTM
D2515 procedure. Conductivity measurements were per- 0.6
formed with a conductimeter (Tacussel, CD7N) at 25°C. 0.5
Anodic polarization curves were measured by sweeping
the potential from 8 to 0 V at a scan rate of —10 mV s- E 0.4
using a potentiostat (Tacussel, DEA 332) controlled by an
interface (Tacussel, IMT-101). It was found necessary to 0.3 (c)
sweep the potential from positive values in the cathodic 0.2
direction in order to obtain reproducible measurements and
to avoid pitting of the electrode surface. Impedance meas- 0.1
urements were performed with a frequency response ana- 0.0
lyzer (Solartron 1255) connected to a potentiostat (Sol- 0 2
artron 1286) and controlled with a commercial software 4 6 8
package (Zplot for Windows). The amplitude of potential V (vs MSE)
modulation was 10 mV rms. Starting with 65 kHz, the fre-
quency was swept automatically down to 0.1 Hz. A typical Fig. 1. Potentiostatic polarization curves determined in
run used an integration time of 10 s and a time delay of 1 s. methanol-3 M sulfuric acid 99.6% at (a) 25, (b) 0, and (c) —10°C.
2364 .1 Electrochem. Soc., Vol. 145, No. 7, July 1998 The Electrochemical Society, Inc.

12 . furic acid electrolytes are shown in Fig. 4 for fuming sulfu-

nc acid concentrations of 3 and 6 M, respectively. The lim-
-10 iting current density increases with decreasing sulfuric acid
10 - C concentration. Figure 5 shows the relationship between the
reciprocal of the limiting current density and the reciprocal
8- . of the square root of the rotation speed for several fuming
"0°C sulfuric acid concentrations. Similarly to the results of Fig.
C 2, titanium dissolution in the limiting current region is mass
6- . , -, transport controlled for all sulfuric acid concentrations
E
C
'C 9' - ---
--
- ..-- studied. In Fig. 6 the limiting current density is plotted
4. - against the product of the kinematic viscosity to the nega-
6/ -'
- ..
a -' tive sixth power and the sulfuric acid concentration. The
limiting currents were determined on the current plateau at
2 ;Ø -' - -- - 2SC - a potential of 3 V, corrected for ohmic drop. The figure

-- - as shows a linear decrease. The kinematic viscosities measured

0 I I I
0.0 0.1 0.2 0.3
i / Q°
Fig. 2. Reciprocal of the limiting current density plotted against
the reciprocal of the square root of the rotation speed determined
for methanol-3 M sulfuric acid 99.6%.
corresponding to active dissolution. For a mass-transport-
limited reaction at a rotating disk electrode, a plot of 1/i1
vs. l/ 11 should yield straight lines going through the ori-
gin)4 The results of Fig. 2 confirm that the reaction rate at
the limiting current is mass transport controlled at all
temperatures studied.
Effect of water concentration—Electrolytes with differ-
ent water contents ranging from 0.02 to 10% were made by
adding doubly distilled water to a methanol-3 M fuming
sulfuric acid electrolyte. Figure 3 shows the effect of water
concentration on the anodic polarization curves measured
at 25°C for an electrode rotation rate of 400 rpm. The lim-
iting current density decreases with increasing water con-
centration. At 5% water the plateau becomes less well de-
fined, and at 10% added water the anode becomes passive
over the whole range of potentials studied. It was previ-
ously observed that when electrolytes were prepared with
96% sulfuric acid the titanium anode passivated at sulf u-
nc acid concentrations of 5 M or more.12 The results of
Fig. 3 suggest that this behavior was due to the presence of
water added when preparing electrolytes with 96% sulfu-
ric acid. Mansfeld27 found that in 0.1 N H2S04-methanol
electrolytes passivation of titanium occurs upon addition
of as little as 1% water.
Effect of H2S04 concentration.—Potentiodynamic polar-
ization curves measured at 0°C in water-free methanol—sul-
for each sulfuric acid concentration are reported in Table I.
I
A linear decrease in the rate of dissolution with increasing
0.4 0.5 sulfuric acid concentration has been reported for nickel in
aqueous electropolishing electrolytes by Alanis and
Schiffrin.19
Effect of Ti4t concentration.—In a previous study, the
apparent valence for dissolution of titanium under elec-
tropolishing conditions was determined by weight loss
experiments showing that titanium at the limiting plateau
dissolves in the tetravalent state.12 In order to test whether
transport of anodically produced tetravalent titanium
species is rate limiting a series of experiments was per-
formed in electrolytes containing different amounts of
Ti4t. The electrolytes were prepared by dissolving
Ti(0C2H5)4 in a methanol-3 M 112S04 (96%) solution. In
Fig. 7, the limiting current density measured at 25°C and
400 rpm is plotted as a function of the product of the kine-
matic viscosity to the negative one-sixth power and the
1.2
1.0
0.8
E 0.6 (a)
0.4
0.2
0.0

1.0

0.8

r E
0.6
a
C,
(b)
a:
0.4

0.2

0.0 2 4 6 8
0 2 4 6 8
V (V vs MSE)
V (V vs SME)
Fig. 4. Potentiostatic polarization curves determined at 0°C in
Fig. 3. Potentiostatic polarization curves determined in methanol electrolytes containing (a) 3 and (b) 6 M sulfuric acid
methanal-3 M sulfuric acid fuming at 25°C and 400 rpm for sever-
al water contents. fuming.
J. Electrochem. Soc., Vol. 145, No. 7, July 1998 The Electrochemical Society, Inc. 2365

20 I I
/ 0.7:'I'''I''I''I''I'' H
0.6 -
JD6M
15 - -
0.5

E 10 - / 5M E
0.4

0.3 - --I
4M
5. /cA-- --' 0 -,
3M
0.2 -

0.1
/---n---
-- Er

0.0 — _ S
0.0 0.1 0.2 0.3 0.4 0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
3
v-1/6C- (xlO mole cm-1 s.1
1/005
Fig. 5. Reciprocal of the limiting current density plotted against Fig. 7. Relation between the limiting current density measured at
the reciprocal of the square root of the rotation speed determined 6 V and the product of the kinematic viscosity to the negative sixth
in methanol—sulfuric acid fuming electrolytes at 0°C. power and the concentration of Ti4.

1.2 I I
0.30 -
1.0 -
0.25 -
0.8 -
0.20
0.6 - 0.15 -

0.4 - 0.10 -
I
0.2 - 0.05 -
0.00 - I I

0.0 0 200 400 600 800 1000

0 2 4 6 8 10
-1/6 -3
v CH(x10 mole cm-1s-1
Fig. 6. Relation between the limiting current density measured at
6 V and the product of the kinematic viscosity to the negative sixth
power and sulfuric acid fuming concentration.
concentration of Ti4t The limiting currents were deter-
mined on the current plateau at a potential of 3 V, correct-
ed for ohmic drop. The figure shows a linear decrease in
current density with increasing Ti" concentration.
Impedance experiments—Impedance experiments were
performed in the methanol-3 M sulfuric acid (96%) elec-
trolyte under steady-state conditions. In Fig. 8, a typical
current transient observed in potentiostatic experiments is
12
t (s)
Fig. 8. Current transient measured at 8 V in methanol—3 M sul-
furic acid 96% at —10°C and 400 rpm.
200 s, the time at which a steady-state current is attained.
Figure 9 shows the influence of applied potential on the
impedance diagrams determined at 0°C for an electrode
rotation rate of 400 rpm. The applied potential was varied
from 2 to 8 V within the limiting-current region. The
diameter of the high-frequency loop increases with in-
creasing applied potential, but the high-frequency limit of
-8 —
I I I —

shown for an applied potential of 8 V. Initially, upon appli- 1kHz

cation of a constant anodic potential, the current density
decreases due to the formation of an anodic film. After -
about 100 s it increases abruptly, indicating that the anod-
ic film has become unstable and can be removed by the .
U
fluid flow. Impedance measurements were started after E 65kHz
. .. -
\. . • •• • •
C.,
-4

:•:•/•••
U..
Table I. Measured kinematic viscosities and calculated apparent
N U. L
. fS
surface concentrations for water-free methanol—sulfuric
acid electrolytes.

Kinematic viscosity
Apparent surface
concentration of Ti
-2 - ..
f&.J/
4V 6V
/
A

8V
/ 1OV
1-
Solution 0 —
I I I —
(cm2 s') (mol L') 4 6 8 10 12 14
3 M H2S04 0.018 2.9 Zr (0cm2)
4 M H2S04 0.026 2.1
5.2 M H2S04 0.037 1.3 Fig. 9. Impedance diagram determined at 0°C and 400 rpm in
6 M H2S04 0.051 0.9 methanol—3 M sulfuric acid 99.6%.
2366 J Electrochem. Soc., Vol. 145, No. 7, July 1998 The Electrochemical Society, Inc.

Zr
the impedance is relatively insensitive to potential. The
effect of rotation rate on the shape of the impedance dia-
grams measured at 0°C is shown in Fig. 10 for a potential
of 8 V The high-frequency limit of the impedance remains CdlRp l/COmax
constant while the diameter of the high-frequency ioop
increases with increasing rotation speed. The effect of
temperature is reported in Fig. 11 for an electrode poten-
tial of 8 V and a rotation rate of 400 rpm. The diameter of
the high-frequency ioop increases with decreasing temper- RQ+Rp
ature while the high-frequency limit of the impedance
increases due to a decreasing electrolyte conductivity.
Discussion
Impedance experiments.—Impedance spectroscopy has
been used in the past to distinguish the salt-film mechan-
isms14"5 and the acceptor mechanisms'6'7 of electropolish-
ing. The ability to distinguish transport mechanisms in
electropolishing by impedance has been reviewed by
Matlosz.'5 Assuming that the high-frequency portion of the
impedance spectrum can be described by a semicircle, any
of the following three observations can suggest the exis-
tence of a salt film: (i) the measured ohmic resistance varies Cdl
with applied potential or rotation speed; (ii) the interface Fig. 2. Schematic Nyquist plot and equivalent circuit corre-
capacitance changes with applied potential or rotation sponding to the high-frequency part of the impedance diagram.
speed; or (iii) the polarization resistance changes with ap-
plied potential. For a porous salt film in which ionic trans-
port occurs in the electrolyte filling the pores of the film, steady-state current density, should decrease with the in-
condition (0 is fulfilled, while for a thin, compact film in verse of the square root of rotation rate.
which a solid-state conduction process occurs in parallel to Figure 12 shows a schematic diagram, indicating the
capacitive charging of the film, conditions (ii) and (iii) hold. ohmic resistance, R,, (the left intercept of the semicircle),
Grimm et al.,'4 studying dissolution of iron in concentrated the capacitance, Cdl, determined from the frequency at the
chloride media, found that all three conditions were ful- top of the circle, and the polarization resistance, R5, deter-
filled. They interpreted their data by postulating the exis- mined from the diameter of the semicircle. The low-fre-
tence of an anodic salt film with a duplex structure con- quency phenomena, which for a salt film should yield a
sisting of an outer porous and an inner compact layer. In the vertical line on the Nyquist plot, are not discussed here.'4
case of an adsorbate-acceptor mechanism, none of these The measured high-frequency data between 1 and 65 kllz
conditions should apply, but the system is expected to ex- were fitted to a semicircle to estimate R,,, R5, and Cdl.
hibit a Warburg—Nernst impedance. In addition, the polar- Tables II—IV summarize the results for T = 25, 0, and
ization resistance, which is inversely proportional to the — 10°C. At 25°C the measured ohmic resistance is roughly

the same, independent of the applied potential and rota-

tion rate, having an average value of 3.0 11 cm2. The elec-
trolyte resistance calculated for a rotating disk under pri-
mary current distribution conditions is given by
= [1]
C 4K
C)
a
where r is the radius of the rotating disk electrode and K
RI
is the conductivity. The conductivity for the 3 M sulfuric
acid (96%) containing electrolyte at 25°C was measured
separately, and a value of K = 0.049 fY' cm' was found.
5 10 15 20 25 According to Eq. 1, this value corresponds to a theoretical
resistance to the disk of R,, = 3.98 fi cm2, in good agree-
Zr (0cm2) ment with that determined from impedance. It is conclud-
Fig. 10. Impedance diagram determined at 0°C and 8 V in ed that no additional ohmic resistance due to a porous
methanol-3 M sulfuric acid 99.6%. anodic film contributed to the measured impedance.
The polarization resistance, R5, determined as the diam-
eter of the high-frequency part of the impedance diagram,
-12 - increases with the applied potential, suggesting the pres-
ence of an anodic film. With increasing rotation rate, R5
-10 - decreases in all cases. The decrease is larger than what

-8
1kHz
E
0
4 Table II. Parameters estimated from the high-frequency
-6 65kHz impedance spectra at 25°C.
a £
N
.4 S ..•.n.••.• £
Vanode [1 R,, F5 C41

-
sat! ii (V vs. MSE) (rpm) (mA cm 2) (11 cm') (11 cm2) (pF cm
-2
7SSsij 0°C -10°C 4 400 520 4.1 2.1 1.22
0.82
25°C 6 400 590 3.9 3.3
0: 15 20
8 400
400
650
750
4.0
3.7
4.1
4.1
0.61
0.43
5 10 10
8 100 305 4.6 9.2 0.39
Zr(D cm2) 8 400 650 4.0 4.1 0.61
8 900 900 3.8 2.0 0.82
Fig. 11. Impedance diagram determined at 8 V and 400 rpm in 8 1.600 1250 3.5 1.3 0.97
8 2500 1550 3.5 0.8 1.58
methanol-3 M sulfuric acid 99.6%.
 J. Electrochem. Soc., Vol. 145, No. 7, July 1998 The Electrochemical Society, Inc. 2367

Table Ill. Parameters estimated from the high-frequency 3.0 F I I I

impedance spectra at 0°C.
2.5 -
V anode (1 R R Cd]
(V vs. MSE) (rpm) (mA cm2) cm2) ([1 cm2) (F cm2)

Yz
(11
20- A .'o Y -
4 400 312 6.1 3.4 1.17 a. . -.
6
8
10
400
400
400
322
340
390
6.2
6.1
6.1
4.6
6.1
7.1
0.82
0.61
0.46
E 1.5- . -n
-
8 100 175 7.4 15.3 0.48
8 400 340 6.1 5.9 0.61 1.0 -
8 900 510 5.4 3.6 0.77 i/c
8
8
1600
2500
660
795
5.2
4.9
2.4
2.0
0.84
0.97 0.5 - ,.' / -

0.0 - - -- I I I -l
Table IV. Parameters estimated from the high-frequency 0 2 4 6 8
impedance spectra at —10°C.
_________________________________________________________ V .4 A0 (V)

V anode £1 i,, R11 Cd]

R11 Fig. 13. Properties of the compact salt film as a functian of the
(V vs. MSE) (rpm) (mA cm°) ((1 cm2) (ii cm2) (F cm2)
___________________________________________________ potential drop across the film.
4 400 237 7.0 4.7 1.12
6 400 250 7.1 6.2 0.82
8 400 262 7.4 6.9 0.66 i0 = 153 mA/cm2. The slope of the capacitance data gives
10 400 275 6.9 8.4 0.53 a/cpen,i = 1.11. Assuming a reasonable value a = 0.3 nm and
8 100 132 8.8 18.6 0.48 with z = 4 for titanium cations, one gets a = 5.1 X
8 400 262 7.4 6.9 0.66
8 900 395 6.5 4.7 0.71 10 cm/V and a film thickness of X, = 82 nm at 6 V and
8 1600 505 6.3 3.3 0.76 0°C. Similarly, a film thickness of A = 91 nm is calculated
8 2500 595 6.2 2.5 0.82 at 6 V and 25°C.
Mass transport limiting species—Results obtained in
should be expected from the corresponding variation in the this study confirm that high-rate dissolution of titanium
current density with rotation rate for an acceptor model. in concentrated methanol—sulfuric acid electrolytes is
The product Ri and the capacitance are largely indepen- mass-transport controlled. Possible mass transport limit-
dent of temperature. The product Ri is of the order of a few ing species taking part directly or indirectly in the disso-
volts, which is typical for transport of ions by high-field lution reaction are Ti", S0, MeOW, and 1120. MeOW
conduction.14 The capacitance Cd] increases by more than ions should not directly affect the dissolution other than to
300% with increasing rotation speed and decreasing poten- influence the conductivity. Diffusion of the water molecule
tial. The absolute values of C,11 are at least an order of mag- has been suggested to be rate limiting in electropolishing
nitude lower than the typical value of the double-layer of stainless steel in concentrated sulfuric acid—phosphoric
capacitance for a smooth surface. A similar behavior has acid electrolytes.26'17 In the present experiments, diffusion
previously been observed for iron dissolving in chloride of 1120 cannot be the rate-limiting process because accord-
solution at the limiting current. 14 The data in Tables 11—IV ing to the data of Fig. 3, increasing the water content from
are generally consistent with a compact—film model. 0.02 to 1% decreases rather than increases the value of the
In a compact salt film, ions migrate by high-field con- limiting current. Water plays an important role for passi-
duction. In addition, current is used for the capacitive vation; a water concentration as low as 5% in the elec-
charging of the film trolyte leads to passivation of the titanium electrode. The
data of Fig. 4 show that increasing the sulfuric acid con-.
a(V -
4) + C1 _________
______
(V— o) centration in water-free (0.02%) electrolytes from 3 to 6 M
= zF/RT i0 exp_________ [2]
) leads to a decrease in the magnitude of the plateau current
by almost a factor of four. This excludes a mechanism
Here V is the electrode potential at the metal surface, & is based on rate-limiting transport of sulfuric acid acceptor
the potential at the film surface, a is an atomic jump dis- species. The data of Fig. 7 suggest that transport of tetra-
tance, i is a parameter independent of potential, and X,2 is valent titanium species away from the anode is limiting.
the film thickness. The capacity of the film, C1, is given by Such a mechanism is in agreement with the impedance
C1 = €perm/Xc
data, which suggest the presence of a compact salt film at
[3] the surface.
where €,,,, is the electrical permittivity of the film. For a Upon anodic dissolution, a concentration gradient builds
compact salt film it was shown by Grimm et al.14 that up near the anode, and the local concentration of Ti" near
the electrode surface increases with increasing current den-
= X,,, = (V i1?)
—
[4] sity. (The chemical nature of the solvated tetravalent titani-
a ln , um species in the present solutions is not kno; for sim-
plicity they are designated as Ti".) The Ti" concentration
1
— a (V — i,,!?0) at the surface cannot increase indefinitely, however, be-
[5] cause precipitation of a titanium salt occurs when the sol-
C1 in ,,
perm
ubility limit is reached. It was impossible to isolate and
where X is the steady-state compact-film thickness and analyze the anodic film formed under limiting current con-
i,, the steady-state current density The constant a charac- ditions, and its stoichiometric composition is therefore
terizes the lattice spacing of the film and is defined by unknown. It may be reasonably assumed, however, that the
zF tetravalent titanium compound formed at the anode is tita-
a = a— [6] nium sulfate or a methanolic titanium sulfate complex. The
RT
mass-transport-limited dissolution current at a rotating
Figure 13 shows a plot of i,,!?11 and of 1/C1 against (V — disk electrode (neglecting migration) is given by
i,,R) at 0°C. A linear behavior is expected when i0 is inde- = 0.624FD213v 1161W2 (c, — c6) [7]
pendent of potential. The experimental data support the
high-field conduction model. Using a value of i,, = where v is the kinematic viscosity [1 is the electrode ro-
340 mA/cm2 measured at 400 rpm, Eq. 5 yields a value of tation rate, c, and c, are the surface and the bulk concen-
2368
trations, respectively, D is the diffusion coefficient of the
limiting species, Ti". The maximum possible Ti" concen-
tration at the anode surface, which corresponds to the sat-
uration concentration of Ti", is reached at the limiting
current. Figure 7 can be used to estimate the apparent sur-
face concentration of Ti" at the limiting current. Extra-
polation to zero current yields an intercept with the X-axis
of v c4 = 2.6. For a kinematic viscosity of v = 0.25 cm2
measured in the solution containing 2 M Ti" , this
= 2.1 mol L1. According to Eq. 7, zero
yields a value of Cb
current corresponds to the condition cb = c,; therefore, c, =
2.1mol L' is obtained. Replacing c, in Eq. 7, a diffusion
coefficient of D = 1.2 x 10" crn2/s is calculated for Ti"
species in the methanol—3 M (96%) sulfuric acid electrolyte
at 25°C. By a similar procedure Heinrich and Feller20'21
determined a value of c, = 2.5 mol U' for nickel dissolu-
tion in a methanol—2 M H2S04 electrolyte.
The value of c. can also be estimated from the tempera-
ture dependence of the limiting currents. In Fig. 2, the
Levich behavior is shown to be sensitive to changes in
temperature. The solution viscosity, the diffusion coeffi-
cient, and the concentration difference c, — Cb for the rate-
controlling species may all depend on temperature. The
variation of the limiting current density with temperature
can be fitted to the Arrhenius equation, Eq. 8
Iim = Ic,, exp(_..)Qh/2
Here k5 is a constant independent of temperature, and E5
is the activation energy. Figure 14 shows Arrhenius plots
of the limiting current density at different rotation speeds.
The average slope of the curves gives an activation energy
of E5 = 21.6 kJ mol. Combining Eq. 7 and 8 gives
D213(c, c4) = Ic,, exp(—E,,/RT)
0.624Fof"
where c,, = 0 in the absence of Ti44 in the electrolyte.
Substitution of the calculated value of E,,, D, and the
measured value of v at 25°C into Eq. 9 yields for the sur-
face concentration c, = 2.2 M. This value is in good agree-
ment with that estimated from the experiment in which
the Ti" concentration was varied.
The surface concentration of Ti" at the limiting current
was estimated for different sulfuric acid concentrations
using Eq. 7 assuming an ionic diffusion coefficient of D =
1.2 X 10" cm2/s and setting c, = 0. The results are given in
Table I. They suggest that the observed decrease in the
magnitude of the limiting currents with increasing sulfu-
ric acid concentration is due to a corresponding decrease
in the solubility of Ti".
0 Ic,,
2 - -1600
F
400
- V
-
A.
- Z real part of the impedance
100rpm -7-
0.1
3.7
3.3 3.4 3.5 3.6
1/T(1 /°K)
Fig. 14. Arrhenius plots of the limiting current density at differ-
ent rotation speeds and temperatures in methanol-3 M sulfuric
acid 99.6%.
J. Electrochem. Soc., Vol. 145, No. 7, July 1998 The Electrochemical Society, Inc.
Effect of water—The passivating effect of water on tita-
nium in methanol-based electrolytes at water contents
exceeding a few percent has been reported by several
authors.2923 Passivation is due to the overall reaction
Ti + 2H,,O - Ti02 + 4W + 4E
which in methanol—sulfuric acid electrolytes is in competi-
tion with the dissolution reaction yielding solvated Ti44. In
the present study, at a water content smaller than 5% tita-
nium did not passivate during potential-sweep measure-
ments starting from high potentials in the cathodic direc-
tion. On the other hand, starting the potential sweep from
low potentials and going anodically led to unreproducible
results and interference from passivation. This suggests that
not only the electrolyte composition but also the previous
exposure history of the electrode plays a role in the forma-
tion and stability of the passive films. Once formed, passive
oxide films tend to block parts of the surface from dissolu-
tion. On the other hand, if polarization conditions are cho-
sen such that a salt film forms first, uniform dissolution and
polishing are maintained. To understand better the role of
polarization conditions and water content on the formation
and properties of anodic films on titanium in methanol—sul-
furic acid electropolishing electrolytes, additional studies
employing transient techniques are necessary.
[81
Conclusions
The present data show that electropolishing of titanium
in methanol—sulfuric acid electrolytes is mass transport
controlled. The observed variation of the limiting current
density with electrolyte composition suggests that the
transport of dissolved tetravalent titanium species from
the anode surface to the bulk solution is rate limiting.
High-frequency impedance data are in agreement wrth
this mechanism, and they provide strong evidence of the
[91 presence of a compact salt film at the anode surface under
limiting current conditions. Water at a concentration in
excess of a few percent leads to passivation of the surface
and suppresses polishing.
Acknowledgments
This work was financially supported by the Swiss
Priority Program on Materials Research.
Manuscript received November 10, 1997.
Ecole Polytechnique assisted in meeting the publication
costs of this article.
LIST OF SYMBOLS
a atomic jump distance, cm
c salt concentration, mol cm'
C4, double-layer capacitance, F cm2
C, capacitance of compact film, F cm2
D diffusion coefficient, cm2 s'
E,, activation energy, kJ mol"
F Faraday's constant, 96i487 C equiv'
i current density, A cm
i, parameter used in high-field conduction model in
Eq. 2, A cm"
constant independent of potential in Eq. 8, A cm"
r,, disk electrode radius, cm
R universal gas constant, 8.314 J mol" K-'
R polarization resistance, (1 cm2
R,, ohmic resistance, U cm2
0 T electrolyte temperature, °C
electrode potential, V
--
z
Z
charge number
imaginary part of the impedance
-----V Greek
a parameter used in high-field conduction model in
Eq. 2, cm
3.gxlO pesTh permittivity ,
F cm"
potential used in Eq. 2, V
ic electrolyte conductivity, rnt cm"
K film thickness, cm
v kinematic viscosity, cm2 s"
w frequency of modulation, s'
U disk rotation rate, s"
J. Electrochem. Soc., Vol. 145, No. 7, Ju'y 1998 1 The Electrochemical Society, Inc. 2369

Subscripts 15. R. D. Grimm and D. Landolt, Corros. Sci., 36, 1847

b bulk (1994).
c compact 16. S. Magaino, M. Matlosz, and D. Landolt, J. Elec-
ss steady state trochem. Soc., 140, 1365 (1993).
sat saturated 17. M. Matlosz, S. Magaino, and D. Landolt, J. Elec-
trochem. Soc., 141, 410 (1994).
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Electrochemkal Behavior and Surface Morphologk

Changes of Copper Substrates in the Presence of
2,5-Dimercapto- 1 ,3,4-thiadiazole
In Situ EQCM and Phase Measurement Interferometric Microscopy

Qijin Chi7 Tetsu Tatsuma,*,a Masahide Ozoki7 Tadashi Sotomura,*b and Noboru Oyama*0
Department of Applied Chemistry, Faculty of Technology, Tokyo University of Agriculture and Technology,
Naka-cho, Koganei, Tokyo 184, Japan
bMatsushita Electric Industrial Company Limited, Corporate Research Division, 3-1 Yagumo-nakamachi,
Moriguch.i, Osaka 570, Japan

ABSTRACT
Interaction between copper and 2,5-dimercapto-1,3,4-thiadiazole (DMcT) plays a crucial role in the performance of
the DMcT-based polymer composite cathode with a copper current collector. In order to understand this interaction, we
employed voltammetry combined with in situ electrochemical quartz crystal microgravimetry (EQCM) and in situ phase
measurement interferometric microscope (PMIM), and investigated electrochemical behavior and surface morphologic
changes of a copper substrate in nonaqueous solutions without and with DMcT. Voltammetric results show that DMcT
inhibits electrodissolution of copper at potentials negative of 1.0 V vs. SSCE. EQCM results suggest that Cumay dissolve
chiefly as Cut, which may be stabilized by DMcT by forming a complex, at more positive potentials than 1.0 V. The PMIM
images and corresponding data demonstrate that copper dissolution is a nonuniform process and results in a roughness
increase of surface in the absence of DMcT, while the presence of DMcT makes the substrate surface remain relatively
smooth. Scanning electron micrographs further support the PMIM observations.

Infroduction rate at room temperature, which limits their practical

The search for cathode materials suitable for recharge-
able lithium batteries with high power high energy densi-
ty, low weight, and low cost has been extensively attempt-
ed by a lot of researchers. Among various materials,
organosulfur compounds containing two or more SH
groups have become one of the most promising cathodes
since they were introduced first by Visco and his cowork-
ers'3 However, mercaptans such as 2,5-dimercapto-1,3,4-
thiadiazole (DMcT) usually exhibit a low redox reaction
* ity and a wide operating voltage range when a carbon sub-
Electrochemical Society Active Member.
application as cathode materials. An effective way for
accelerating the reaction rate of organosulfur compounds
has been found in our group by mixing them with a con-
ducting polymer (e.g., polyaniline),48 which can exchange
electrons rapidly with organosulfur compounds.9'° Our
previous studies demonstrated that polymer composite
cathodes consisting of DMcT and polyaniline for lithium
batteries have a high energy density.67 Unfortunately,
these cathodes exhibited a relatively low current capabil-
strate was used as a current collector. As a great improve-

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