ORIGINAL PAPER

Bacterial cellulose/triethanolamine based ion-conductingmembranes

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 microfibrils. Raman spectra exhibited BC

and TEA characteristic group frequencies and thermal

analysis evidenced an influence 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

BC–TEA 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 fibrils, less than 100 nm wide (Iguchi

et al. 2000; Siro and Plackett 2010). These fibrils 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 d0optique, photonique et laser (COPL), Universite

Laval, Quebec G1V 0A6, Canada

123

Cellulose (2014) 21:1975–1985

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 defined 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 field (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 cell0s applications due to the

flexibility 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), perfluorinated 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 scientific 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

membranes0 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 BC–TEA as ion-conducting membranes. The

influence of TEA and temperature on the ion-conduc-

tivity has been studied. The surface morphology of the

films 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 profile 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 cm2, 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 firstly in water, then in 1wt %

aqueous NaOH at 70 �C (in order to remove bacteria)

and again in water (until neutral pH). Next, 25 cm2 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 BC–TEA 0.01 M,

BC–TEA 0.1 M and BC–TEA 1 M.

Characterization methods

XRD analysis

X-ray diffraction patterns (XRD) of the samples

(pellicles) were obtained by a Siemens Kristalloflex

diffractometer using nickel filtered Cu Ka radiation in

the range of 2h = 4–70�, in steps of 0.02� and a step

time of 3 s.

1976 Cellulose (2014) 21:1975–1985

123

SEM characterization

Scanning electron microscopy (SEM) images were

obtained in a field 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 flow 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 aluminum pans under a 70 mL/min N2 flow rate

and a 10 �C/min heating rate.

Raman spectroscopy

Raman spectra were recorded using a Raman HOR-

IBA JOBIN–YVON model LabRAM HR 800 spec-

trometer, operating with laser He–Ne 632.81 nm with

a CCD camera model DU420A-OE-325.

Impedance measurements

The ion-conductivity measurements were performed

placing two cm round and 20–400 lm thick mem-

branes between two mirror-polished stainless steel

electrodes fixed in a Teflon 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 106–10 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 fibers 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 fine sub-elementary

cellulose fibrils, which are extruded from terminal

enzyme complexes into the culture medium. These

fibrils 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 fibrils of BC, studied in present

work, can be observed in typical SEM images,

presented in Fig. 1a. The addition of TEA turns these

fibrils into a more dense and compact structure of the

membrane, as can be seen on image of BC–TEA

0.01 M, showed in Fig. 1b. The large amount of TEA

incorporated into bulk and BC surface facilitates this

aggregation and is confirmed 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

defined as the mass fraction of crystalline domains.

Figure 2 shows typical X-ray diffraction patterns

obtained for the BC and the BC–TEA membranes.

The diffractograms of BC (Fig. 2a) and BC–TEA

0.01 M (Fig. 2b) reveal two main principal diffraction

peaks at 14.4� and 22.5� (2h), characteristic of

cellulose I (French 2014). BC–TEA 0.1 M and

BC–TEA 1 M diffractograms show three diffraction

peaks at *15�, *17� and *23�. As stated by French

(2014), the three main peaks for the Ia cellulose have

Miller indices of (100), (010) and (110), known as the

counterparts to the (1–10), (110) and (200) peaks of

the cellulose Ib pattern.

Diffractograms of BC–TEA (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 modification to a decrease

in crystallinity. However, it was observed in this work

that large amounts of TEA and water in the samples

Cellulose (2014) 21:1975–1985 1977

123

BC–TEA affect drastically the diffraction patterns (as

observed in Fig. 2b–d) 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 influence of

substitution of water by polar and apolar solvents on

Fig. 1 SEM images of:

a BC and b BC–TEA

0.01 M; 920,000

Fig. 2 XRD patterns of: a BC, b BC–TEA 0.01 M, c BC–TEA

0.1 M and d BC–TEA 1 MFig. 3 Raman spectra of: a BC, b BC–TEA 0.1 M and c TEA

1978 Cellulose (2014) 21:1975–1985

123

X-ray diffraction patterns. They have observed that

organic solvents contained in the swollen membranes

may influence the preferential orientation of the (100)

plane upon BC membrane drying. In BC–TEA

diffractograms (Fig. 2b–d), 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(CH2)

2,894

2,835 Symmetric m(CH2)

1,635–1,600 dO–H

1,482 d(CH2)

1,465

1,445 d–(CH2)n-

1,382 d–(CH)

1,375 dC–H def

1,340

1,335 d(OH), d(CH2) wagging

1,296 d(CH2)a twisting

1,295 dC–H and dO–H

1,160–1,000 def mC–O

1,157 mN(CH2)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

960–730 d-(CH) dC–H

882 m(CNC) asymmetric

774 m(CN) asymmetric

735 d-(CH2)2- rocking

*534 d(CO), –CH2OH d(CO), –CH2OH

439 Skeletal deformation

383

332

550–250 C–C–C, C–O–C, O–C–C, O–C–O

Skeletal bending modes

C–C–H, O–C–H bending

C–C, C–O skeletal stretching

Cellulose (2014) 21:1975–1985 1979

123

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 BC–TEA 0.1 M (in the range

4,000–100 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

250–550 cm-1. Bands observed in 950–1,180 cm-1

region are assigned to C–C and C–O stretching, and

bending of H–C–C and H–C–O. Between 1,180 and

1,270 cm-1, the modes involve methane stretching

and bending, and 1,270–1,500 cm-1 region comprises

C–C–H, O–C–H, C–O–H and H–C–H bending vibra-

tions. Raman bands at 1,455 and 1,479 cm-1 are

related to bending vibration of H–C–H and C–O–H. At

2,800–3,000 cm-1 region, bands observed are related

to C–H and C–H2 stretching vibrations and from 3,100

to 3,500 cm-1, stretching vibrations of O–H are

observed.

TEA molecule presents bands related to O–H

stretching (3,377–3,120 cm-1), C–H2 stretching

(2,946, 2,894 and 2,835 cm-1) and bending (1,445,

1,335, 1,296, 735 and 534 cm-1), C–H bending

(1,382 cm-1) and C–N 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 BC–TEA 1 M. DSC curves are shown in c for a BC and b BC–TEA 1 M membranes samples

(inset)

1980 Cellulose (2014) 21:1975–1985

123

BC–TEA 0.1 M, similarly to the BC and TEA

samples, shows a band at 3,100–3,500 cm-1 attributed

to stretching of hydroxyl groups. This band changes

shape after TEA addition (sample BC–TEA 0.1 M;

Fig. 3b), which may be due to a decrease of free O–H

groups content. At this point it should be stated that

significant 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 C–H2 stretch-

ing bands are seen for TEA (2,946, 2,894 and

2,835 cm-1), BC (2,894 cm-1) and BC–TEA 0.1 M

(2,894 and 2,835 cm-1). The BC–TEA 0.1 M band at

*1,461 cm-1 is attributed to dC–H2 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 BC–TEA 1 M sample. Two significant mass

losses may be observed from room temperature to

200 �C and from 200 to 400 �C for pure BC

membrane (Fig. 4a). The first 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

BC–TEA 1 M sample (Fig. 4b), the first 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 150–250 �C and was associated with

evaporation and/or decomposition of TEA, providing

estimated 70 % of TEA in BC–TEA 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 BC–TEA 1 M, comprising probably carbonaceous

materials.

DTG peaks on Fig. 4b revealed a slight decrease in

thermal stability of BC–TEA 1 M, in comparison to

pure BC (Fig. 4a), from 350 �C (BC) to 341 �C

(BC–TEA 1 M), these temperatures being referred to

onset values.

Figure 4c presents DSC curves for BC (a) and

BC–TEA 1 M (b). An endothermic peak is observed

for BC in the range of 30–76 �C, with maximum at

56 �C. This event is associated with water loss and

corroborates the TGA curve of BC. The DSC curve of

BC–TEA 1 M also reveals an endothermic peak, in the

range of 103–162 �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 BC–TEA 1 M, is due to

hydrogen bonds formed between OH groups from

BC and TEA, and water molecules as already

confirmed 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 BC–TEA 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

BC–TEA-H2O 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 carriers0 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) 21:1975–1985 1981

123

(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

perfluorinated membranes (Valenzuela et al. 2009).

Figure 6 shows the impedance plots for BC–TEA

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 (Rb) 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/RbA, where l is the thickness of

the electrolyte sample (20 lm for BC and 400 lm for

BC–TEA 1 M) and A is the contact area between the

electrolyte and the electrode (Raphael et al. 2010). The

BC–TEA 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 BC–TEA 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., BC–TEA 1 M (Fig. 7a) and

BC–TEA 0.1 M (Fig. 7b) in the temperature range

Fig. 5 Schematic

representation of hydrogen

bonds formed in BC–TEA

1 M

Fig. 6 Complex plane diagram of: BC–TEA 1 M in temper-

ature range from 20 to 80 �C

Fig. 7 Arrhenius plots of: a BC–TEA 1 M and b BC–TEA

0.1 M samples

1982 Cellulose (2014) 21:1975–1985

123

from room temperature to 80 �C. The linear increase

in the ion-conductivity as a function of temperature is

similar to that observed for Nafion� samples (Valen-

zuela et al. 2009) and means that hopping mechanism

is responsible for ion transport (Ueki and Watanabe

2008). Moreover, these results confirm 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 confirm this conductivity enhancement when

comparing BC–TEA samples and dried BC (Marins

et al. 2011). After immersion of BC membranes in

TEA aqueous solution, TEA impregnates through

cellulose chains/fibrils (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 BC–TEA membranes were success-

fully obtained by soaking BC hydrated membranes

into aqueous TEA solutions. 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 BC–TEA

1 M sample. It was confirmed 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 nanofi-

brils evidenced by SEM pictures. Moreover, the XRD

analyses evidenced the XRD patterns of cellulose.

Additionally, Raman spectra showed BC, TEA and

BC–TEA characteristic group frequencies. These

membranes also show transparency. All these results

suggest applications of BC–TEA membranes in bat-

teries and electrochemical devices (e.g., electrochro-

mic windows).

Acknowledgments The financial 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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