ORI GI NAL PAPER

Bacterial cellulose/triethanolamine based ion-conducting

membranes
Denise T. B. De Salvi

Hernane S. Barud

Agnieszka Pawlicka

Ritamara I. Mattos

Ellen Raphael

Younes Messaddeq

Sidney J. L. Ribeiro
Received: 1 October 2013 / Accepted: 20 February 2014 / Published online: 27 February 2014
Springer Science+Business Media Dordrecht 2014
Abstract New bacterial cellulose (BC)triethanola-
mine (TEA) ion-conducting membranes have been
prepared and characterized. The samples were
obtained by soaking BC membranes in triethanola-
mine aqueous solutions and drying. The scanning
electron microscopy pictures revealed that the incor-
poration of TEA in BC membranes covers the
cellulose microbrils. Raman spectra exhibited BC
and TEA characteristic group frequencies and thermal
analysis evidenced an inuence of TEA content on the
sample thermal stability. The ion-conductivity as a
function of the temperature showed an Arrhenius
behavior increasing from 1.8 9 10
-5
S/cm at room
temperature to 7.0 9 10
-4
S/cm at 80 C for the
BCTEA 1 M sample.
Keywords Bacterial cellulose
Ion-conduction Triethanolamine Membranes
Introduction
Gram-negative acetic-acid-producing bacteria of the
genus Acetobacter secrete bacterial cellulose (BC) as
ribbon-shaped brils, less than 100 nm wide (Iguchi
et al. 2000; Siro and Plackett 2010). These brils are
entangled in a 3-D network that, combined with the
hydroxyl groups present in bacterial cellulose struc-
ture ensure higher hydrophilicity, crystallinity,
mechanical resistance and purity in comparison with
cellulose extracted from plants (Barud et al. 2007,
D. T. B. De Salvi (&) H. S. Barud
Y. Messaddeq S. J. L. Ribeiro
Institute of Chemistry, Sao Paulo State Univ-UNESP,
CP 355, Araraquara, SP 14801-970, Brazil
e-mail: denisequimica@gmail.com
H. S. Barud
e-mail: hernane.barud@gmail.com
Y. Messaddeq
e-mail: younes.messaddeq@copl.ulaval.ca
A. Pawlicka R. I. Mattos E. Raphael
IQSC-USP, Sao Carlos, SP, Brazil
e-mail: agnieszka@iqsc.usp.br
R. I. Mattos
e-mail: cristal_br@yahoo.com.br
E. Raphael
e-mail: ellen.raphael@gmail.com
R. I. Mattos
FZEA-USP, Pirassununga, SP, Brazil
E. Raphael
DCNAT-UFSJ, Sao Joao Del Rei, MG, Brazil
Y. Messaddeq
Centre d
0
optique, photonique et laser (COPL), Universite
Laval, Quebec G1V 0A6, Canada
1 3
Cellulose (2014) 21:19751985
DOI 10.1007/s10570-014-0212-8
2008b). Other important features related to bacterial
cellulose are biocompatibility and the possibility of
production in membranes form with dened thickness
and size (Donini et al. 2010). BC is widely applied in
industry of food, paper, textile and headphone mem-
branes and its biocompatibility ensures biomedical
utilization as wound dressings, skin substitute and
implants (Juntaro et al. 2012; Klemm et al. 2005).
Most recently, BC was also investigated in the hybrid
and composite materials research eld (Barud et al.
2008a, 2011a, b; Perotti et al. 2011; Yang et al. 2012;
Salvi et al. 2012a).
Solid polymer electrolytes and conducting polymer
membranes are usually required for electrochromic
devices, batteries and fuel cell
0
s applications due to the
exibility of form, good adhesion to the other materials
and low weight. Among different polymeric materials,
membranes of poly(vinyl chloride)/poly(aniline)
(PVC/PANI) or poly(acrylonitrile) (PVC/PAN) (Ra-
jendran et al. 2008), poly(ethylene oxide) (PEO)
(Acosta and Morales 1998), peruorinated membranes
(Valenzuela et al. 2009) and SPEEK (Nagarale et al.
2010) are studied. Additionally, some of these mem-
branes are also industrially produced (Cohan 1975).
However, a new concept of Eco-friendly materials
which are biodegradable and obtained from renewable
sources has gained scientic attention (Lee et al. 2008).
Recently, natural macromolecules have been investi-
gated as electro-active materials and ion-conductive
matrices for electrolyte purposes. For example, such
applications cited are polymer electrolytes based on
hydroxyethyl cellulose (HEC) (Machado et al. 2007),
gelatin (Mattos et al. 2010), agar (Raphael et al. 2010,
2012), chitosan (Mattos et al. 2012), pectin (Andrade
et al. 2009), wood cellulose (Nystrom et al. 2010) and
bacterial cellulose (BC) (Legnani et al. 2008; Marins
et al. 2011; Salvi et al. 2012b).
Contrary to other polysaccharides cited above, BC
is produced as a highly hydrated membrane containing
99 % of water and only 1 % of polymer. The water
within the membrane may be simply removed under
soft compression or through drying by exposure to the
air (Numata et al. 2009). However, the presence of
water in membranes can be associated with ion-
conductive properties; thus, it is desirable to maintain
membranes
0
humidity (Kreuer 2001; Mahadeva et al.
2011; Valenzuela et al. 2009).
In our previous works regarding embedding of
silver nanoparticles (NP) in BC membranes, a
suggestion was made where the addition of TEA
contributed to maintenance of relatively high levels of
humidity (Barud et al. 2008b, 2011a, b). To explore
this property, the present paper reports on the utiliza-
tion of BCTEA as ion-conducting membranes. The
inuence of TEA and temperature on the ion-conduc-
tivity has been studied. The surface morphology of the
lms was examined by SEM, and the evaluation of
crystallinity was performed by X-ray diffraction
technique. Spectroscopic studies were performed
using Raman spectroscopy and thermal analysis was
used to determine thermal prole of these ion-
conducting samples.
Experimental
Materials
Analytical grade chemicals were used as received.
Bacterial cellulose membranes were obtained from
cultivation of the Gluconacetobacter hansenii strain
ATCC 23769. Culture media was held for 96 h at
28 C in trays of 30 9 50 cm
2
, containing the sterile
media composed of glucose (50 g/L), yeast extracts
(4 g/L), anhydrous disodium phosphate (2 g/L), hep-
tahydrated magnesium, sulphate (0.8 g/L) and ethanol
(20 g/L). After 96 h, 3 mm thick hydrated BC pelli-
cles containing up to 99 % of water and 1 % of
cellulose were obtained. These membranes were
several times washed rstly in water, then in 1wt %
aqueous NaOH at 70 C (in order to remove bacteria)
and again in water (until neutral pH). Next, 25 cm
2
BC
membranes were soaked in 25 mL of TEA (Synth)
aqueous solutions (0.01, 0.1 and 1 M) for 24 h at room
temperature. After that, samples were dried on petry
dishes at 37 C for 24 h. The ion-conducting mem-
branes prepared were named BCTEA 0.01 M,
BCTEA 0.1 M and BCTEA 1 M.
Characterization methods
XRD analysis
X-ray diffraction patterns (XRD) of the samples
(pellicles) were obtained by a Siemens Kristalloex
diffractometer using nickel ltered Cu K
a
radiation in
the range of 2h = 470, in steps of 0.02 and a step
time of 3 s.
1976 Cellulose (2014) 21:19751985
1 3
SEM characterization
Scanning electron microscopy (SEM) images were
obtained in a eld emission scanning electron micro-
scope JEOL JSM-7500F. Samples were coated with a
thin carbon layer.
Thermal behavior
Thermal gravimetric (TG) curves were obtained for
dried samples using SDT Q600 equipment from TA
Instruments. Samples were heated in open alumina
pans from 40 to 600 C, under nitrogen atmosphere
at ow rate of 70 mL/min and a heating rate of
10 C/min.
DSC curves were obtained from ambient temper-
ature to 300 C with TA Instruments DSC 2960, in
sealed aluminumpans under a 70 mL/min N
2
owrate
and a 10 C/min heating rate.
Raman spectroscopy
Raman spectra were recorded using a Raman HOR-
IBA JOBINYVON model LabRAM HR 800 spec-
trometer, operating with laser HeNe 632.81 nm with
a CCD camera model DU420A-OE-325.
Impedance measurements
The ion-conductivity measurements were performed
placing two cm round and 20400 lm thick mem-
branes between two mirror-polished stainless steel
electrodes xed in a Teon electrochemical cell. The
conductivity values were obtained between 25 and
80 C in vacuum by electrochemical impedance
spectroscopy using a SOLARTRON SI 1260 Imped-
ance/Gain Phase Analyzer coupled to a computer in
the 10
6
10 Hz frequency range with amplitude of
5 mV. All measurements were taken in triplicate.
Results and discussion
The main characteristic of BC is its tridimensional
structure, where the individual cellulose bers are
immersed in water forming a very soft membrane. To
prevent the water loss, triethanolamine (TEA) aqueous
solutions were successfully used here to substitute
water and also as an additive, due to good
compatibility with both, cellulose and water. Another
reason to use TEA is its high boiling point similarly to
poly(ethyleneglycol) (PEG) and glycerol, described as
useful plasticizers employed in polymer electrolytes
(Mattos et al. 2008; Numata et al. 2009).
SEM
The bacterial synthesis of BC ensures a different
structure from that of plant cellulose. During cultiva-
tion, the bacteria synthesize ne sub-elementary
cellulose brils, which are extruded from terminal
enzyme complexes into the culture medium. These
brils undergo a gradual transformation from initially
amorphous to a porous three-dimensional (3D) struc-
ture, i.e., crystalline cellulose I (Cai and Kim 2010).
The ribbon-shaped brils of BC, studied in present
work, can be observed in typical SEM images,
presented in Fig. 1a. The addition of TEA turns these
brils into a more dense and compact structure of the
membrane, as can be seen on image of BCTEA
0.01 M, showed in Fig. 1b. The large amount of TEA
incorporated into bulk and BC surface facilitates this
aggregation and is conrmed by the results showed by
Raman analysis and TG curves reported below.
XRD
Cellulose is composed of crystalline and very little
amorphous phases and cellulose crystallinity is
dened as the mass fraction of crystalline domains.
Figure 2 shows typical X-ray diffraction patterns
obtained for the BC and the BCTEA membranes.
The diffractograms of BC (Fig. 2a) and BCTEA
0.01 M (Fig. 2b) reveal two main principal diffraction
peaks at 14.4 and 22.5 (2h), characteristic of
cellulose I (French 2014). BCTEA 0.1 M and
BCTEA 1 M diffractograms show three diffraction
peaks at *15, *17 and *23. As stated by French
(2014), the three main peaks for the I
a
cellulose have
Miller indices of (100), (010) and (110), known as the
counterparts to the (110), (110) and (200) peaks of
the cellulose I
b
pattern.
Diffractograms of BCTEA (Fig. 2 c-d) show a
progressive decrease in relative intensity of the peak
centered near 15 associated with TEA addition. Takai
et al. (1975) attributed this modication to a decrease
in crystallinity. However, it was observed in this work
that large amounts of TEA and water in the samples
Cellulose (2014) 21:19751985 1977
1 3
BCTEA affect drastically the diffraction patterns (as
observed in Fig. 2bd) without affecting the crystal-
linity of the cellulose itself. The crystallinity of the
cellulose itself seems to be mostly retained, based on
the retention of fairly sharp diffraction peaks. BC
membranes containing a large amount of TEA will be
explored in TG curves results.
This progressive decrease in relative intensity of the
peak centered near 15 may be explained in terms of
the substitution of the water present in BC membrane
by TEA aqueous solutions, which causes a progressive
loss of preferred orientation of (100) plane at *15.
Takai et al. (1975) have studied the inuence of
substitution of water by polar and apolar solvents on
Fig. 1 SEM images of:
a BC and b BCTEA
0.01 M; 920,000
Fig. 2 XRD patterns of: a BC, b BCTEA 0.01 M, c BCTEA
0.1 M and d BCTEA 1 M
Fig. 3 Raman spectra of: a BC, b BCTEA 0.1 M and c TEA
1978 Cellulose (2014) 21:19751985
1 3
X-ray diffraction patterns. They have observed that
organic solvents contained in the swollen membranes
may inuence the preferential orientation of the (100)
plane upon BC membrane drying. In BCTEA
diffractograms (Fig. 2bd), the peak at *15 of
(100) plane becomes gradually less intense than the
Table 1 Assignment of
vibrational Raman bands
for bacterial cellulose and
triethanolamine (Barud
et al. 2008c; Jallapuram
et al. 2008; Schenzel and
Fischer 2001; Wiley and
Atalla 1987)
Frequency/
wavenumber
(cm
-1
)
Assignments
BC TEA
3,363 m(OH)
3,302
3,241
3,184 m(OH)
2,972 m(CH)
2,946 Asymmetric m(CH
2
)
2,894
2,835 Symmetric m(CH
2
)
1,6351,600 dOH
1,482 d(CH
2
)
1,465
1,445 d(CH
2
)
n
-
1,382 d(CH)
1,375 dCH def
1,340
1,335 d(OH), d(CH
2
) wagging
1,296 d(CH
2
)
a
twisting
1,295 dCH and dOH
1,1601,000 def mCO
1,157 mN(CH
2
)
3
1,155 m(CO) (Stretching vibrations of the
b-1,4-glycosidic ring linkages
between the D-glucose units
in cellulose d(OH)
1,127
1,060
1,037
1,030 m(CN)
968 Symmetric ring
960730 d-(CH) dCH
882 m(CNC) asymmetric
774 m(CN) asymmetric
735 d-(CH
2
)
2
- rocking
*534 d(CO), CH
2
OH d(CO), CH
2
OH
439 Skeletal deformation
383
332
550250 CCC, COC, OCC, OCO
Skeletal bending modes
CCH, OCH bending
CC, CO skeletal stretching
Cellulose (2014) 21:19751985 1979
1 3
peak at *23 of (110) plane. In addition, the
diffraction of (010) plane at *17 appeared sharply
as a result of the disorientation of (100) plane. These
results may indicate that the preferred orientation is
mainly controlled by the H-bonding ability of the
substituting liquids.
Raman spectroscopy
Figure 3 shows Raman spectra obtained for BC, TEA
and selected sample BCTEA 0.1 M (in the range
4,000100 cm
-1
).
The analysis of the BC Raman spectra, showed in
Fig. 3, reveals peaks in the frequency region below
1,500 cm
-1
, associated with deformations of the
internal coordinates of the BC anhydroglucopyranose
residues. Skeletal bending modes are seen in the region
250550 cm
-1
. Bands observed in 9501,180 cm
-1
region are assigned to CC and CO stretching, and
bending of HCC and HCO. Between 1,180 and
1,270 cm
-1
, the modes involve methane stretching
and bending, and 1,2701,500 cm
-1
region comprises
CCH, OCH, COH and HCH bending vibra-
tions. Raman bands at 1,455 and 1,479 cm
-1
are
related to bending vibration of HCHand COH. At
2,8003,000 cm
-1
region, bands observed are related
to CH and CH
2
stretching vibrations and from 3,100
to 3,500 cm
-1
, stretching vibrations of OH are
observed.
TEA molecule presents bands related to OH
stretching (3,3773,120 cm
-1
), CH
2
stretching
(2,946, 2,894 and 2,835 cm
-1
) and bending (1,445,
1,335, 1,296, 735 and 534 cm
-1
), CH bending
(1,382 cm
-1
) and CN stretching (1,157, 1,030, 882
and 774 cm
-1
), respectively. A summary of band
positions is shown in Table 1 and is similar to the
results presented by Socrates (Socrates 2001) and
Wiley and Atalla (Wiley and Atalla 1987).
Fig. 4 TGA/DTG curves for a BC and b BCTEA 1 M. DSC curves are shown in c for a BC and b BCTEA 1 M membranes samples
(inset)
1980 Cellulose (2014) 21:19751985
1 3
BCTEA 0.1 M, similarly to the BC and TEA
samples, shows a band at 3,1003,500 cm
-1
attributed
to stretching of hydroxyl groups. This band changes
shape after TEA addition (sample BCTEA 0.1 M;
Fig. 3b), which may be due to a decrease of free OH
groups content. At this point it should be stated that
signicant amounts of water are trapped within the
membrane due to hydrogen bonding with hydroxyl
groups of TEA, as reported by Dolenko et al. (2011).
Moreover, asymmetric and symmetric CH
2
stretch-
ing bands are seen for TEA (2,946, 2,894 and
2,835 cm
-1
), BC (2,894 cm
-1
) and BCTEA 0.1 M
(2,894 and 2,835 cm
-1
). The BCTEA 0.1 M band at
*1,461 cm
-1
is attributed to dCH
2
and has a
different shape when compared with the BC and
TEA spectra (Fig. 3, right), probably due to the
hydrogen bond interaction between TEA and BC.
The bands at *908, 879, 771 and 733 cm
-1
are also
related to TEA and BC bands (see Fig. 3a, c), as well
as the 520 cm
-1
BC band (overlapped with the
540 cm
-1
TEA Raman band).
TGA and DSC analysis
Figure 4a, b show TG/DTG curves for BC and
selected BCTEA 1 M sample. Two signicant mass
losses may be observed from room temperature to
200 C and from 200 to 400 C for pure BC
membrane (Fig. 4a). The rst one, of about 6.5 %, is
due to membrane dehydration, and is explained in
terms of physically adsorbed and linked by hydrogen
bond water lost; the second one, of about 65 % is due
to thermal degradation, comprising depolymerization
and decomposition of dehydrocellulose into gases as
water, carbon monoxide and carbon dioxide (Beall and
Eickner 1970).
Three thermal degradation steps are observed for
BCTEA 1 M sample (Fig. 4b), the rst one of about
*10.0 % occurred from ambient temperature to
150 C and was explained by dehydration process,
i.e., loss of adsorbed water. The second step comprises
the range of 150250 C and was associated with
evaporation and/or decomposition of TEA, providing
estimated 70 % of TEA in BCTEA 1 M membrane
(Wright et al. 2004). The third mass loss from 250 to
400 C is referred to pyrolysis of cellulose resulting in
carbon monoxide and carbon dioxide liberation
(Barud et al. 2007; Beall and Eickner 1970). The
remaining residues were *20 % for BC and *2 %
for BCTEA 1 M, comprising probably carbonaceous
materials.
DTG peaks on Fig. 4b revealed a slight decrease in
thermal stability of BCTEA 1 M, in comparison to
pure BC (Fig. 4a), from 350 C (BC) to 341 C
(BCTEA 1 M), these temperatures being referred to
onset values.
Figure 4c presents DSC curves for BC (a) and
BCTEA 1 M (b). An endothermic peak is observed
for BC in the range of 3076 C, with maximum at
56 C. This event is associated with water loss and
corroborates the TGA curve of BC. The DSC curve of
BCTEA1 Malso reveals an endothermic peak, in the
range of 103162 C (maximum at 122 C) and
associated with water loss observed in TGA results.
This shift in water loss maximum temperature, from
56 C for BC to 122 C for BCTEA 1 M, is due to
hydrogen bonds formed between OH groups from
BC and TEA, and water molecules as already
conrmed by Raman spectroscopy (Fig. 3). This
hydrogen bond system is responsible for water reten-
tion in these membranes, evidenced also by good
transparency of the BCTEA 1 M, when compared to
opaque dehydrates BC samples (inset of Fig. 4c).
As already mentioned, BC is produced as a highly
hydrated membrane, containing about 99 % of water
and only 1 % of cellulose. Due to the high percent of
membrane hydration, it is expected high ion-conduc-
tivity properties (Gelin et al. 2007). However, this
water is easily lost under pressure or temperature
rising, yielding an insulating membrane. The obtained
results by RAMAN, XRD and TG curves suggest that
TEA ensures higher water retention by BC (as
evidenced by DSC curve, shown in Fig. 3), since this
water is linked through hydrogen bonds (Salvi et al.
2012c), schematically represented in Fig. 5 for
BCTEA-H
2
O system. The hydrogen bonding
between TEA, BC and water provides water paths
and favors proton conduction.
Impedance measurements
The ion-conductivity of the polymeric membranes
depends on several factors, such as ion-conducting
species concentration, cationic or anionic types of
charge carriers, the charge carriers
0
mobility, and the
temperature (Raphael et al. 2010). Highly hydrated
bacterial cellulose membranes present ion-conductiv-
ity values of 1.0 9 10
-4
S/cm at room temperature
Cellulose (2014) 21:19751985 1981
1 3
(Gelin et al. 2007) while dried BC presents values of
6.5 9 10
-8
S/cm (Marins et al. 2011). Then, the loss
of water by evaporation or desorption, as a result of
drying process leads to insulating membranes. Con-
sequently, the humidity may be essential for promot-
ing conductivity in BC pellicles, as this is the case for
peruorinated membranes (Valenzuela et al. 2009).
Figure 6 shows the impedance plots for BCTEA
1 M membranes measured at different temperatures.
The impedance diagram in the complex plane exhibits
two features: (1) in the high frequency range, a
semicircle which can be related to a charge transfer
process, and (2) in the low frequency range, a straight
line that is characteristic of a diffusion process. From
these plots, one can observe a decrease in the
semicircle with the increase of temperature from 25
to 80 C, indicating a decrease of resistance of the
samples and an increase of the ion-conductivity. The
electrolyte bulk resistance (R
b
) is obtained by the
intercept of the semicircle with the real axis and is
used for deducing the ion-conductivity values employ-
ing the formula r = l/R
b
A, where l is the thickness of
the electrolyte sample (20 lm for BC and 400 lm for
BCTEA 1 M) and A is the contact area between the
electrolyte and the electrode (Raphael et al. 2010). The
BCTEA 1 M ion-conductivity is found to increase
from 1.8 9 10
-5
S/cm at room temperature to
7.0 9 10
-4
S/cm at 80 C. For BCTEA 0.1 M and
0.01 M, the ion-conductivity was found to be
8.3 9 10
-6
S/cm and 2.1 9 10
-8
S/cm, respectively.
The temperature-dependent ion-conductivity mea-
surements were then considered in order to analyze the
possible mechanism of ion-conduction in these sys-
tems. Figure 7 reveals Arrhenius plots for two more
conductive samples, i.e., BCTEA 1 M (Fig. 7a) and
BCTEA 0.1 M (Fig. 7b) in the temperature range
Fig. 5 Schematic
representation of hydrogen
bonds formed in BCTEA
1 M
Fig. 6 Complex plane diagram of: BCTEA 1 M in temper-
ature range from 20 to 80 C
Fig. 7 Arrhenius plots of: a BCTEA 1 M and b BCTEA
0.1 M samples
1982 Cellulose (2014) 21:19751985
1 3
from room temperature to 80 C. The linear increase
in the ion-conductivity as a function of temperature is
similar to that observed for Naon

samples (Valen-
zuela et al. 2009) and means that hopping mechanism
is responsible for ion transport (Ueki and Watanabe
2008). Moreover, these results conrm the presence of
water being effective for increasing absolute values of
proton conductivity in these systems as in the case of
agar-based membranes (Raphael et al. 2010). It was
also observed for other cellulose samples, as in ionic
liquid loaded pristine cellulose, ion-conduction is
facilitated and seems to be dependent on water content
(Mahadeva et al. 2011).
It is observed for electrolytes that conductivity is
facilitated through additives addition (Gray 1991). We
may conrm this conductivity enhancement when
comparing BCTEA samples and dried BC (Marins
et al. 2011). After immersion of BC membranes in
TEA aqueous solution, TEA impregnates through
cellulose chains/brils (observed in SEM results,
Fig. 1b), due to BC and TEA hydrophilic properties.
After drying, some water remains in the membrane
since TEA avoids its elimination (DSC curve, shown
in Fig. 4c, exhibits the water loss maximum temper-
ature shifted to 122 C) favoring the formation of
internal water paths. Studies evaluated in cellulose
materials, e.g., in cellophane, suggest the conduction
occurs by proton exchange. This takes place between
hydrogen-bonded water molecules from these water
paths, and occurs when protons jump between adja-
cent water molecules (Arrhenius and/or Grotthuss
model), followed by rotation of the water molecules
for transference of hydrogen atoms (Kreuer 1996).
Adsorbed water molecules and the cellulose hydroxyl
groups participate in the conduction process, but
conduction is dominated by the adsorbed water
(Christie and Woodhead 2002).
Conclusions
Ion-conducting BCTEA membranes were success-
fully obtained by soaking BC hydrated membranes
into aqueous TEAsolutions. The best ion-conductivity
values of 1.8 9 10
-5
S/cm at 25 C and
7.0 9 10
-4
S/cm at 80 C were found for BCTEA
1 Msample. It was conrmed that the addition of TEA
avoids completely dryness of BC membranes, ensur-
ing humidity necessary for maintaining high ion-
conductivity, and promoting covering of BC nano-
brils evidenced by SEM pictures. Moreover, the XRD
analyses evidenced the XRD patterns of cellulose.
Additionally, Raman spectra showed BC, TEA and
BCTEA characteristic group frequencies. These
membranes also show transparency. All these results
suggest applications of BCTEA membranes in bat-
teries and electrochemical devices (e.g., electrochro-
mic windows).
Acknowledgments The nancial support of the Brazilian
agencies CAPES, CNPq and FAPESP are gratefully
acknowledged. FEG-SEM facilities were provided by LMA-
IQ and English spelling was performed by Brian Elias from
WCC, MI, USA, and Michael Floros from Trent University,
Ontario, Canada.
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