Advanced Materials Research Vols.

418-420 (2012) pp 237-241

Online available since 2011/Dec/06 at www.scientific.net
© (2012) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.418-420.237

Fabrication and characterization of regenerated cellulose /TiO2

nanocomposite hybrid fibers
Shunxin Shu Chaorong Li*
(Department of Physics ,and Key Laboratory of Advanced Textile Material and Manufacturing
Technology Ministry of Education of China, Zhejiang Sci-Tech University ,Hangzhou 310018,
People’s Republic of China )
E-mail: [email protected]

Keywords: Electrospinning, Composite nanofiber, Regenerated cellulose, Cellulose acetate,

Titanium dioxide sol.
Abstract. Nanocomposite fibers are one of the most fascinating materials with broad applications. In
the present work，nanocomposite fibers were prepared by a low-cost, simple, and “green” process.
The nanocomposite of regenerated cellulose/TiO2 was realized by combining the functional oxide
material TiO2 with the regenerating electrospun cellulose acetate fibers. The structural features were
characterized by scan electron microcopy, transmission electron microscopy and infrared spectrum.
The compositing mechanism was proposed. The surface functionalized hydroxyl by the regenerating
process plays an important role for the formation of hybrid material.

Introduction
Polymer nanocomposite fibers have attracted much attention in the past decade because of their
unique properties, such as mechanical, thermal, electrical, and magnetic properties, as well as
antibacterial activities, and so forth. There are various viable methods for fabricating hybrid organic
inorganic fibers, such as blending, coating and electrospinning. Electrospinning has been attracted
considerable attention recently since it is the most convenient technique for preparing ultra-fine fibers
with diameters ranging from nanometer to micrometer scale [1-2]. Electrospun nanofibers have a
number of important characteristics such as high surface volume value and small fiber diameter [3-5].
Particularly, it is fairly easy to improve the functionality of nanofibers by incorporating additives
during the electrospinning process [6].
Metal oxide nanomaterials have received much attention due to their unique physical properties
and potential applications in nanoelectronics, catalysts, sensors, and optical devices. Among oxide
metals, TiO2 nanomaterials have shown promising physical properties for various applications in
photoelectronic activity, solar energy conversion, and photocatalysis for self-cleaning surface, air, and
water purification [7-10]. TiO2 has been proved to be the most excellent photocatalyst for the
oxidative degradation of organic compounds under ultraviolet (UV) irradiation[11-13]. Cellulose
acetate (CA), an acetylated derivative of cellulose, is widely used due to its nanotoxicity and good
processability.
In this paper, we utilize a simple method for the preparation of nanocomposite fibers with a coating
layer of TiO2 nanoparticles via sol-gel method. It is worthy to note that the regenerated cellulose fiber
films from electrosping possess a porous structure and hydroxyl groups on the fiber surface, and
consequently should be useful for the combination of inorganic nanoparticles in the cellulose matrix.
On the basis of the porous structure and hydroxyl groups of regenerated cellulose fibers, titanium
dioxide nanoparticle coating have been fabricated in the cellulose matrix surface.

Experimental Section
Reagents: All chemical reagents, including cellulose acetate(CA; white powder; Mw=30,000;
acetyl content 40wt%, from Aladdin Co.), acetone and N, N-Dimetthylacetamide(DMAC, Shanghai
chemical reagents), absolute ethanol (C2H5OH, Tianjin Yongda chemical reagent Co.), Tetrabutyl
titanate (Ti(OC4H9)4, Tianjin Kemiou chemical reagent Co.), Nitric acid(HNO3, Zhejiang Zhongxin
chemical reagent Co.) are analytical grade and used without further purification.

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www.ttp.net. (ID: 130.113.86.233, McMaster University, Hamilton, Canada-23/03/15,18:04:18)
238 Materials Processing Technology, ICAMMP2011

Preparation of cellulose acetate fibers: The process of preparing cellulose acetate solutions for
electrospinning is as following : 1.400g CA was dissolved in 12ml of DMAC/acetone (1:2, v/v)
mixed solvent through stiring until the CA was completely dissolved, and finally a transparent and
clarification solution for electrospinning was obtained. Electrospinning was done by a self-made
apparatus that consists of a high voltage supply (Glassman high voltage, FC60P2), a peristaltic pump
(USA KDS Scientific Inc, KDS100), a syringe with metal needle (inner diameter, ID=0.84mm) and a
collector. In the typical electrospinning process, the cellulose acetate precursor was electrospun at
18KV voltage, 14cm working distance (the distance between the needle tip and the collector), and
0.6ml/h flow rate at room temperature. The as-collected CA nanofiber nonwoven mats were dried for
24h at 60℃ under vacuum prior to the subsequent further treatment.
(a) (b)

500nm 500nm

(c) (d)

500nm

(e) (f)

Fig. 1 SEM images of (a) CA, (b) regenerated cellulose at the CA nanofibers after deacetylating, (c)
regenerated cellulose/TiO2 nanocomposite fibers, (d) EDS spectrum of regenerated cellulose/TiO2
nanocomposite fibers, (e) TEM image of regenerated cellulose/TiO2 nanocomposite fibers, (f)
HRTEM image of regenerated cellulose/TiO2 nanocomposite fibers.
Regeneration to cellulose: In order to remove acetyl group via alkali catalyzed saponification, the
dried CA nanofiber was immersed into 0.5M NaOH solution in ethanol for 6h at room temperature.
The regenerated cellulose mats were thoroughly rinsed and kept in deionized water for further
treatment.
Preparation of regenerated cellulose/TiO2 nanocomposite fibers ： TiO2 sol solution was
prepared using the method as Zeng et al [14], by adding 8ml of tetrabutyl titanate (Ti(OBu)4) into 20
ml of anhydrous ethanol under stirring, and then 20 ml of 1 M HNO3 solution was added by dropping
under vigorous stirring for 1h to obtain the TiO2 sol solution at room temperature. Finally a pale
 Advanced Materials Research Vols. 418-420 239

yellow, transparent solution was obtained. The regenerated cellulose fiber mats were immersed into
anhydrous ethanol for 1h and then immersed into TiO2 sol solution for 5 h. The resultant
TiO2/cellulose composite fibers were washed by deionized water for 24 h. Finally, the composite
fibers were naturally dried at ambient condition.
Characterization: The morphologies and composition of electrospun nanofibers were studied by
the filed-emission scanning electron microscope (FESEM, HitachiS-4800) equipped with an
Energy-dispersive X-ray spectroscopy (EDS), and transmission electron microscope (JEM2100,
200KV). The structural property of composite nanofibers was characterized by FTIR（Thermo Nicolet
avatar 370）.

Results and discussion

Characterization of structure and morphology.
The SEM micrographs of CA and regenerated cellulose/TiO2 nanocomposite fibers are shown in Fig.
1. It can be seen that the fibers are random oriented. From Fig.1(a), one can see that the surface of CA
electrospun fiber was quite smooth and the diameter was from 200 nm to 300nm. However, the
regenerated cellulose, obtained by treating the CA nanofiber with 0.5M NaOH/ethanol solution for
6h, exhibits a similar smooth surface structure but with a little swollen morphology, as shown in Fig.1
(b). Fig.1 (c) and (d) are the morphology and composition of the cellulose/TiO2 composite. Though
the morphology has no obvious variation, the TiO2 was successfully combined with the CA fiber from
EDS spectrum (for detail locations see the TEM images). This demonstrated that the hydroxyl on the
regenerated cellulose nanofiber surface plays an important role in the hybrid process (without
regenerating process, the Ti element can hardly be found in the fibers). Therefore, the TiO2/cellulose
composite fibers are successfully fabricated by in situ synthesis in the regenerated cellulose matrix.

CA
regenerated cellulose from CA
regenerated cellulose/TiO2
Rlative Absorbance

1370

3400

1750 1040
1230

4000 3500 3000 2500 2000 1500 1000 500

-1

Fig. 2 FT-IR spectra of the CA fibers (solid line), regenerated cellulose fibers (dashed line) and
regenerated cellulose /TiO2 nanocomposite fibers (dotted line).

The TEM and HRTEM images of the regenerated cellulose /TiO2 nanocomposite fibers are shown
in Fig.1 (e) and (f) respectively. The TEM results indicate that TiO2 nanoparticles with a mean
diameter of 1nm are uniformly dispersed on the cellulose matrix surface as shown in Fig.1 (e). That
hints the surface hydroxyl by the regenerating process plays an important role for the formation of
hybrid material. The observed lattice structure in the high-resolution TEM (HRTEM) image reveals
(Fig.1 (f)) that the TiO2 nanoparticles on the surface cellulose fibers have been crystallized, but with
defects. The results have confirmed that the TiO2 nanoparticles have been combined successfully with
the regenerated cellulose fibers surface through in situ synthesizing process.
240 Materials Processing Technology, ICAMMP2011

The FTIR spectrum of CA nanofibers (Fig.2 solid line) has absorption peaks for carbonyl
stretching at 1750 cm-1 (νC=O), alkoxyl stretch of the ester at 1230 cm-1 (νC-O-C), and methyl
bending at 1370 cm-1 (δC-CH3), for groups of the acetate substituent. The acetal linkages of the
cellulose backbone can be observed around 1040cm-1 and the broad hydroxyl group absorption at
approximate 3400cm-1. Compared the intensity of the regenerated cellulose fibers (Fig.2 dashed line)
in the FTIR profile with the spectrum of CA nanofibers, the absorption peaks at 1750, 1370, and 1230
cm-1 related to the acetyl group content drastically decreased after treated with NaOH/ethanol
solution. However, the intensity related to the hydroxyl absorption increased after treatment. This
change illustrates the substitution of acetyl groups with hydroxyl groups on the fiber surface. As for
the regenerated cellulose /TiO2 nanocomposite fibers (Fig.2 dotted line), absorption peaks for
stretching vibrations of the hydroxyl groups shifted to a lower wavenumber, and its intensity
obviously decreased. This indicates that there is a strong interaction between the hydroxyl groups of
regenerated cellulose and the TiO2 particles through hydrogen bonding interactions. This strong
interfacial interaction led to a strong attachment of the TiO2 nanoparticles on the regenerated cellulose
surface.
The formation process of titanium dioxide coatings on the electrospun regenerated cellulose
fibers

Deacetylation Hydrolysis

(a) (b)

Surface Hydrolysis Hydrolysis Synthesis

(c) (d)

Fig. 3 Schematic illustration of the formation process of titanium dioxide coatings on the electrospun
regenerated cellulose fibers. (a) surface structure of the electrospun CA fiber. (b) surface structure of
the regenerated cellulose from CA fiber treated with NaOH/ethanol solution. (c) adsorption of
titanium dioxide sol molecules on the surface of regenerated cellulose fibers. (d) titanium dioxide
nanoparticles synthesis in situ on the surface of regenerated cellulose fibers.

Based on the electron microscope morphologies and FTIR spectra, the formation process for the
regenerated cellulose/ TiO2 composite nanofibers is deduced, as shown in Fig.3. The procedure is
closely related to the variation of surface structures. On the surface of CA fibers, it contains acetyl
groups in addition to the hydroxyl group (Fig.1 a). After treated with NaOH/ethanol solution, the
acetyl groups converted to hydroxyl groups through hydrolysis (Fig.3 b). When the regenerated
cellulose nanofibers were immersed into TiO2 sol solution, the Ti(OBu)4 hydrolyzes to Ti4+
surrounded by the OH- to produce an active hydroxyl of titanium acid. The hydroxyl of regenerated
 Advanced Materials Research Vols. 418-420 241

nanofibers interacts with the titanium acid through the hydrogen bonding (Fig.3 c). After dehydrating
Ti(OH)4, TiO2 nanoparticles are produced in situ on the surface of regenerated cellulose fibers
(Fig3 d).

Conclusion
CA regeneration can be carried out by NaOH ethanol solution with minimal degradation of the
cellulose while retaining the original fiber structure of the electrospun mat. We have successfully
fabricated regenerated cellulose/TiO2 composite fibers through electrostatic spinning technology
combined with sol-gel method by in situ synthesis of TiO2 nanoparticles on the cellulose fibers
surface. A strong interfacial interaction between the hydroxyl groups of the regenerated cellulose and
hydrated Ti(OBu)4 led to the formation of TiO2 nanoparticles on the cellulose surface. Moreover, the
interactions between TiO2 nanoparticles and the cellulose matrix are strong and could prevent TiO2
nanoparticles from being removed from cellulose fibers. This facile method can be expanded to
fabrication of wide range of functional hybrid materials based on cellulose fibers and functional
inorganic particles and may open new applications for cellulose.

Acknowledgments
This work was supported by NSF of China (Nos. 51172209, 91122022 and10874153).

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Materials Processing Technology, ICAMMP2011
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Fabrication and Characterization of Regenerated Cellulose/TiO2 Nanocomposite Hybrid Fibers

10.4028/www.scientific.net/AMR.418-420.237