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JES00K125

JES00K125

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Evaluation of Fluorine Ion Concentration in TiO
2
NTAnodization Process
Chien-Chon Chen
a
and Sheng-Jen Hsieh
b,z
a
Department of Energy and Resources, National United University, Lienda, Miaoli 36003, Taiwan
b
Department of Engineering Technology and Department of Mechanical Engineering, Texas A&M University,College Station, Texas 77843-3367, USA
Studies have shown that fluorine ions play a significant role in the initiation and growth of TiO
2
nanotubes. As fluorine is dopedin titanium nanotubes
TiO
2
NTs
, fluoride gases form during TiO
2
NT anodization. The concentration of fluorine in an electrolytedecreases as the anodization period increases. Maintaining a constant concentration of fluorine levels is a challenging task. In thispaper, we discuss and calculate the quantity of fluorine reduced in an electrolyte given various electrolyte temperatures, samplesizes, and anodization time effects. According to thermodynamic calculations, F, FO, and FO
2
have relatively low vapor pressuresbut HF, H
2
F
2
, H
3
F
3
, H
4
F
4
, H
5
F
5
, H
6
F
6
, and H
7
F
7
have relatively high vapor pressures during anodization. The effects of fluorinecontained in TiO
2
NT
12.2 wt %
and vaporized from the electrolyte can cause the fluorine concentration in the electrolyte todecrease.© 2010 The Electrochemical Society.
DOI: 10.1149/1.3374640
All rights reserved.Manuscript submitted December 1, 2009; revised manuscript received February 15, 2010. Published April 22, 2010.
The first TiO
2
nanotube
NT
arrays were formed by Zwilling etal.
1
More recently, as shown in TableI, short TiO
2
NTs have beenmade and studied in great detail.
Cai et al.’s
and Grimes’
groups fabricated TiO
2
NTs by the anodization process, and tubelengths were controlled by varying the amount of fluoride ions in theelectrolyte. For example, an aqueous HF-based electrolyte grew0.5
m long NTs, an aqueous NaF- or KF-based electrolyte grew6.8
m longNTs,
and anonaqueous F-ion-based electrolyte grew134
m NTs.
Mor et al.
fabricated TiO
2
NTs for use in a pho-tocleavage reaction, dye-sensitized solar cells
DSSC
, hydrogensensing, and self-cleaning sensor studies.With regard to DSSC power conversion efficiency, the freestand-ing TiO
2
NT film has better performance than the TiO
2
NT film ona Ti substrate due to the front side being illuminable and due to theabsence of a barrierlayer between theNT membrane and the Ti substrate. Mor et al.
and Paulose et al.
fabricated a TiO
2
NT filmon fluorine-doped tin oxideglass using sputter and anodization pro- cesses. Also, Albu et al.,
Chen et al.,
and Park et al.
describeda process by which NT array films can be transformed into free-standing membranes.Anodization of titanium foil in F
and minimizing water contentin a nonaqueous organic polar electrolyte form closely packed, ver-tically aligned NTs.This electrochemical processes may be de-scribed as follows
Ti
Ti
4+
+ 4e
1
H
2
O
2H
+
+ O
2−
2
Ti
4+
+ 2O
2−
TiO
2
3
Ti
4+
+ 2H
2
O
4H
+
+ TiO
2
4
6F
+ TiO
2
+ 4H
+
TiF
6
2−
+ 2H
2
O
5
TiF
6
2−
+
n
H
2
O
TiF
6−
n
OH
n
2−
+
n
H
+
+
n
F
6
TiF
6−
n
OH
n
2−
+
6
n
H
2
O
Ti
OH
6
2−
+
6
n
H
+
+
6
n
F
7
Ti
OH
6
2−
+ 2H
+
TiO
2
+ 4H
2
O
8
During anodization, oxidation reactions occur at the metal/ electrolyte. Reaction1is formed, and the water in the electrolyte isdecomposed
Reaction2
. TiO
2
then forms between the metal andthe electrolyte through ion migration
Reactions3and4
. Fluorineions etch TiO
2
, forming
TiF
6
2−
, and then combine with H
2
O toform
TiF
6−
n
OH
n
2−
Reactions5and6
. Because the fluorineions are doped in TiO
2
but do not form a compound, Reaction6canbe rewritten as Reaction7.Finally,
Ti
OH
6
2−
reacts to 2H
+
form-ing TiO
2
NTs
Reaction8
.Studies have shown that fluorine ions play a significant role inthe initiation and growth of TiO
2
NTs. The fluorine ions nucleatetitanium metal, generate interconnected pores, and allow current toflow within the oxide film. The dispersed pores align in the directionof the appliedelectric field to generate an array of tubes.
He et al.
studied the influence of fluorine on the structure andphotocatalytic activity of TiO
2
film in a tungstate electrolyte. Re-sults suggest that the porosity, element content, and phase composi-tion of TiO
2
films are affected by fluorine ion concentration in anelectrolyte. The number of pores, the content of tungsten, and thecontent of the anatase phase all increase when fluorine ions wereadded to the electrolyte.Grimes reported that relatively long TiO
2
NTs were fabricatedafter a period of anodization when Ti was in an organic solvent, andsolutes of H
2
O and NH
4
F were controlled in 2 vol % and 0.25–0.8wt %.
In anodization, good quality TiO
2
NT can be obtained bycarefully controlling fluorine concentrations. However, fluorine va-por gas has been observed during anodization, and fluorine is de-tected in the TiO
2
NT. In this paper, we calculate the fluorine con-sumption rate during a period of anodization based onelectrochemical and thermodynamic data.
Experimental
An ordered channel array of anodic titanium oxide was fabri-cated by anodizing titanium
Ti
foil
Aldrich, 99.7%
. Ti foilwas first fabricated using electropolishing
EP
. The EP conditionsinvolved a platinum sheet as a cathode, titanium plate as ananode, 5 vol % perchloric acid
HClO
4
+ 53 vol % ethyleneglycol monobutylether
HOCH
2
CH
2
OC
4
H
9
+ 42 vol % methanol
CH
3
OH
as an electrolyte at 15°C, 52 V for 1 min followed by 28V for 13 min at a constant stirring rate of 200 rpm. After EP, thesample was then etched in 5 vol % HF for 5 min to add an additionallayer of anodic film on the Ti substrate. TiO
2
NT growth wasachieved using electrolyte solutions
pH 6.8
of 0.15, 0.25, and 0.5wt % ammonium fluoride
NH
4
F,99.9%
+ 2 wt % H
2
O in ethyl-ene glycol
C
2
H
4
OH
2
solvent with anodization at a constant volt-age of 60 V for periods ranging from 0.5 to 12 h. The micromor-phology and composition of the TiO
2
NT were determined by usinga scanning electron microscope
SEM, JEOL 6500
and energy-dispersive spectroscopy
EDS
. The TiO
2
NT growth rate and the
z
E-mail: hsieh@tamu.edu
Journal of The Electrochemical Society,
157
6
K125-K130
2010
0013-4651/2010/157
6
/K125/6/$28.00 © The Electrochemical Society
K125
Downloaded 07 Mar 2011 to 202.170.51.232. Redistribution subject to ECS license or cop right; see http://www.ecsdl.org/terms_use.jsp
 
F
, F
x
O
y
g
, and H
x
F
y
g
activities during anodization were evalu-ated using thermochemical data and thermodynamic calculations.
Results and Discussion
To calculate the rate of TiO
2
NT growth on the substrate, weused NH
4
F electrolyte in ethylene glycol at three concentrations toanodize Ti foil for various amounts of time. Figures1-3show side views of TiO
2
NT lengths as a function of time period of anodiza-tion; the length increases with increasing duration of anodizationand F
concentration. Figure4shows thickness curves of TiO
2
NTwith anodization times when the TiO
2
NT grows in electrolytescontaining 0.15, 0.25, and 0.5 wt % NH
4
F at a constant voltage of 60 V. The NT growth rates in electrolytes containing 0.15, 0.25, and0.5 wt % NH
4
F are about 1.8, 2.6, and 4.8
m h
−1
, respectively.Figure5shows the SEM images of the TiO
2
NT microstructuresand structure, including
a
the top view of TiO
2
NTs with a 120 nmpore diameter, a 150
5 nm pore distance, a 20
5 nm pore wall
Table I. Fabrication parameters for short TiO
2
NT.
ElectrolyteVoltage
V
Time
h
Temperature
°C
Pore size
nm
Length
m
Annealing Phase Reference1% HF 20 0.5 22 100
1 None Amorphous5KF
0.1 M
+ HNaSO
4
1 M
+ C
6
H
5
O
7
Na
3
+ 2H
2
O
0.2 M
, pH 5 25 17 22 110 6 600°C, 17 h Anatase6HF
1 vol %
20 0.75 22 76 0.4 280°C, 3 h Anatase7HF
0.5 vol %
+ H
3
PO
4
1 M
20 12 22 100 1.1 450°C, 3 h Anatase8HN
4
H
2
PO
4
1 M
+ NH
4
F
0.5 wt %
15 22 70 3 450°C, 3 h Anatase9HF
0.5 vol %
20 0.3 18 60 0.25 None Amorphous10H
2
SO
4
10 vol %
+ HF
1.2 vol %
20 0.025 25 100 0.17 None Amorphous11HN
4
SO
4
1 M
+ NH
4
F
0.5 wt %
20 2 22 100 2 450°C, 3 h Anatase12
Figure 1.
Side view SEM images of TiO
2
NT film showing various NTlengths
L
after anodization for
/
h
=
a
1,
b
2,
c
3,
d
4,
e
6,
9,
g
10, and
h
12; electrolyte: 0.15 wt % NH
4
F.
Figure 2.
Color online
Side view SEM images of TiO
2
NT film showingvarious NT lengths
L
after anodization for
/
h
=
a
0.5,
b
1,
c
2,
d
4,
e
5,
6,
g
8, and
h
10; electrolyte: 0.25 wt % NH
4
F.
K126
Journal of The Electrochemical Society
,
157
6
K125-K130
2010
K126
Downloaded 07 Mar 2011 to 202.170.51.232. Redistribution subject to ECS license or cop right; see http://www.ecsdl.org/terms_use.jsp
 
thickness, and a 8
10
9
tubes
/
cm
2
pore density,
b
the lower viewof TiO
2
NT with 80 nm pore diameter,
c
the barrier layer on thebottom of the tubes,
d
the 95 nm pore diameter near the top of thetubes,
e
the 60 nm pore diameter near the bottom of the tubes, and
e
a schematic diagram of TiO
2
NT with radii
R
1
top pore
,
R
2
bottom pore
, and
R
3
outer column
and length
L
structure.Based on Fig.5a,bandd,TiO
2
NTs connect to one another withina localized area. Therefore, the electrolyte should be able to perme-ate into the tube interface, and the active surface area should includeboth the outer
A
o
and inner
A
i
tube surface areas. As shown inFig.5f ,the TiO
2
NT surface area can be represented by
A
o
+
A
i
P
, where
A
o
is the outer tube surface area,
A
i
is the inner tubesurface area, and
P
is the tube density. Furthermore,
A
o
= 2
R
3
L
and
A
i
=
R
1
L
+
R
2
L
+
R
2
R
2
. Therefore, when
R
1
= 120 nm,
R
2
= 50 nm, and
P
= 8
10
9
tubes
/
cm
2
, a curve of TiO
2
NT sur-face areas for various NT lengths can be drawn. In Fig.5f , TiO
2
NTwith 60
m NT length has a surface area of 3580 cm
2
on a 1 cm
2
substrate. In other words, in a 1 cm
3
sample of a TiO
2
NT structure,the total surface area of all the NTs is 596,600 cm
2
, and in a com-pact cube with a surface area of 6 cm
2
, the total surface area for allthe NTs increases by a factor of 99,433. The weight of the TiO
2
NTcan be calculated as
o
i
+
b
, where
o
is the outer tubevolume
column
,
i
is the inner tube volume
cone
,
b
is thevolume of the barrier layer, and
is the TiO
2
density
4.32 g cm
−3
. Therefore, the weight of each TiO
2
NT can be cal-culated as followsweight
TiO
2
NT
=
4.32 g cm
−3
R
12
L
1
3
R
12
L
+
1
3
R
22
9
where
is the barrier layer thickness
100 nm
. Therefore, theweight of each TiO
2
NT and the total TiO
2
NTs with various NTlengths can be calculated. For example, Fig.6shows a curve of TiO
2
NTs with various NT lengths,
a
the weight of a single TiO
2
Figure 3.
Color online
Side view SEM images of TiO
2
NT film showingvarious NT lengths
L
after anodization for
/
h
=
a
0.5,
b
1,
c
2,
d
3,
e
4,
5,
g
6, and
h
8; electrolyte: 0.50 wt % NH
4
F.
Figure 4.
Color online
Thickness curves of TiO
2
NT with anodization timewhen the TiO
2
NTs are grown in an electrolyte with various NH
4
F concen-trations.
Figure 5.
SEM images show TiO
2
NT microstructures.
a
Top view of TiO
2
NTs with 120 nm pore diameter,
b
lower view of TiO
2
NTs with 80 nmpore diameter,
c
barrier layer on the bottom of the tubes,
d
95 nm poresdiameter near the top tube,
e
60 nm pore diameter near the bottom tube,
schematic diagram of TiO
2
NT with radii of 
R
1
top pore
,
R
2
bottom pore
,and
R
3
outer column
, and length
L
structure, and
NT length withsurface area curve.
K127
Journal of The Electrochemical Society
,
157
6
K125-K130
2010
K127
Downloaded 07 Mar 2011 to 202.170.51.232. Redistribution subject to ECS license or cop right; see http://www.ecsdl.org/terms_use.jsp

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