Materials Letters 309 (2022) 131385

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Hydrophilic, transparent, and stretchable film using unmodified

cellulose fibers
Jee Eun Oh a, Nae-Man Park a, b, *
a
ICT Creative Research Laboratory, Electronics and Telecommunications Research Institute (ETRI), Daejeon 34129, Republic of Korea
b
ETRI School, University of Science and Technology, Daejeon 34113, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Keywords: As interest in wearable devices increases, much research has focused on stretchable polymers. However, most
Cellulose film semiconductor materials used in such devices are hydrophilic and stretchable polymers are hydrophobic, which
Stretchable arises an adhesion problem at their interfaces. In addition, most of these polymers are not biodegradable, which
Hydrophilic
creates environmental problems. In this study, in order to avoid these two problems, we used cellulose, the most
Transparent
abundant natural polymer on earth, as a framework, and chemically cross-linked cellulose chains with
epichlorohydrin to provide elasticity to the film. As a result, this hydrophilic film stretched to 196% and was
insoluble in solvents. It also had the optical transmittance of 90% in the visible region.

1. Introduction hydrophobic and semiconductor materials are mostly hydrophilic.

Polymers have several advantages: good plasticity, light weight, and
durability. Their properties can also be adjusted through molecular
weight control, blending, or co-polymerization. Therefore, polymers are
commercially used in various areas, such as containers, packaging, au­
tomobiles, building materials, and electronic devices. However, non-
degradable synthetic polymers based on petroleum have various prob­
lems, among which environmental problems are caused by non-
hydrolysis in nature. This has motivated the development of biode­
gradable polymers. Biodegradable polymers were first introduced in the
1980s [1]. Biodegradable polymers can be derived from petrochemicals,
for example, polycaprolactone and polyglycolide [2], but they are syn­
thesized in non-economical and non-environmentally friendly processes
using various solvents and catalysts. There are also natural biodegrad­
able polymers including cellulose, starch, chitosan, hyaluronic acid, and
protein. Among them, cellulose has a high tensile strength [3] and
properties such as hydrophilicity, low coefficient of thermal expansion
of 0.1 ppm/K, high dimensional stability, bio-friendliness, and biode­
gradability [4]. Due to these characteristics, cellulose is used in various
applications including super capacitors, sensors, conductive film and
substrates [5].
As interest in wearable devices increases, studies on stretchable
materials are also growing [6]. For example, polydimethylsiloxane
(PDMS) films are widely used as stretchable substrates, but they are
Therefore, there is a problem of poor interface adhesion. Methods
modifying the surface of PDMS to be a little hydrophilic have been tried
by chemical or plasma treatment, but they are not a solution because it
becomes hydrophobic again over time [7,8]. However, cellulose film is
hydrophilic due to a large number of hydroxyl groups, which can give us
a perfect solution for a biodegradable and stretchable material. The
previously studied stretchable cellulose film was prepared by adding
urea and glucose as plasticizers based on the cellulose derivative hy­
droxyl ethyl cellulose (HEC) [9]. Although it stretched up to 184%, the
film is easily soluble in water because the chains are simply entangled.
Thus, a stretchable HEC film is not practical. Chemical crosslinking is
absolutely necessary to make a stretchable film insoluble in the solvent
[10]. Therefore, we hereby homogeneously cross-linked unmodified
cellulose with epichlorohydrin (ECH) to make a stretchable cellulose
film. ECH has been used to make hydrogels or composites [11,12], but
this is the first work to make a pure film rather than a hydrogel or
composite. The obtained stretchable cellulose film was visibly trans­
parent and naturally hydrophilic.
2. Experimental
Details of experiment including materials and the method of a
nanocellulose paper are described in the supplementary information.
When LiOH and urea were dissolved in water, the solution with

* Corresponding author at: 218 Gajeong-no, Yuseong-gu, Daejeon 34129, Republic of Korea.
E-mail address: nmpark@etri.re.kr (N.-M. Park).

https://doi.org/10.1016/j.matlet.2021.131385
Received 23 September 2021; Received in revised form 8 November 2021; Accepted 25 November 2021
Available online 1 December 2021
0167-577X/© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
J.E. Oh and N.-M. Park
Fig. 1. SEM images of a) cellulose paper and b) stretchable cellulose film. c) Optical transmittances of straight light for a cellulose paper and a stretchable cellulose
film. d) Images of a cellulose paper(left) and a stretchable cellulose film(right).
cellulose fibers was cooled to below − 8 ℃, which promoted the cellu­
lose to be easily dissolved. ECH was added to the cellulose solution as a
cross-linking agent to make cellulose molecules entangled to form a film.
ECH reactivity changes according to the pH [12]. Since the cellulose
solution is basic due to LiOH, the ring of ECH opens and reacts with the
hydroxyl group of the cellulose chain, which cross-links uniformly be­
tween cellulose chains. As shown in Fig. S1, the best condition for a
stretchable cellulose film was when ECH was added to a 2 wt% cellulose
solution with a mass ratio of 1:5. When it reacted for 90 min at 300
revolutions per minute at room temperature, it became a transparent
solution. The solution was transferred to a glass petri dish for 3 h at room
temperature for a cross-linking reaction. Subsequently, the jelly-like
solution was transferred on a hydrophobic film for drying at 80 ◦ C to
obtain a stretchable cellulose film.
The scanning electron microscope (SEM) images were obtained using
a FEI Sirion 400 operating at 10 keV. Optical transmittance was obtained
using a DH-2000-BAL. Fourier Transform Infra-Red (FT-IR) analysis was
performed with a Nicolet iS50 Spectrometer. X-ray photoelectron
spectroscopy (XPS) analysis (K-alpha, Thermo Scientific Inc.) was per­
formed to determine the chemical composition of the stretchable cel­
lulose film. The contact angle of water was also measured using 4 μl of
water on the film to confirm the hydrophilicity.
3. Results and discussion
The surfaces of the cellulose paper and stretchable film were
analyzed with SEM. Their thicknesses were 24㎛ and 50㎛, respectively.
Fig. 1a and 1b are SEM images of the cellulose paper and stretchable
cellulose film, respectively. The cellulose paper had a rough surface and
many pores because the shapes of the nanofiber were maintained. As a
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Materials Letters 309 (2022) 131385
result, the cellulose paper was very hazy due to light scattering [13]. On
the other hand, the stretchable cellulose film did not have the shape of
fiber and pores. Therefore, the stretchable cellulose film looks very clear
as shown in Fig. 1c and 1d.
Fig. 2a shows the mechanical strength of the cellulose paper and
stretchable cellulose film. The tensile strength of the cellulose paper was
35 MPa and the elongation at break was about 10%. Because the cel­
lulose chains were strongly bonded between chains due to hydrogen
bonds and the fibers were aggregated, the cellulose paper was not
stretchable. However, if the cellulose fibers can be dissolved to reduce
the effect of hydrogen bonding between the molecules and the polymer
chains be homogeneously cross-linked, a cellulose film can be stretch­
able. We dissolved the cellulose nanofibers in LiOH/urea solution [14]
and used ECH as a cross-linking agent between the cellulose molecules.
Urea additionally played as a proper plasticizer. These two factors
played important roles in providing elasticity and resulted in a low
tensile strength of 1.6 MPa and a high elongation at break of 196% in a
stretchable cellulose film. As a similar result, David Boon used urea as a
plasticizer to prepare a stretchable film of hydroxyethyl cellulose and a
cellulose derivative [9], but the film was easily soluble in water because
the chains were simply entangled. However, our film is not soluble in
common solvents such as water, acetone, or ethanol.
FT-IR analysis was performed to confirm the presence of urea as a
plasticizer in the stretchable cellulose film. Fig. 2b shows the results of
the FT-IR analysis. Absorption bands at 3330, 2696, 1371, 1030, and
894 cm− 1 were assigned respectively to O–H stretching, C–H stretching,
C–H deformation, –C–O– stretching, and β-glycosidic linkage of the
glucose units. Most of the peaks were similar. However, there were three
more peaks at 1658, 1618, and 1454 cm− 1 in the stretchable cellulose
film, which were respectively assigned to C– – O, N–H, and C-N. These
J.E. Oh and N.-M. Park Materials Letters 309 (2022) 131385

Fig. 2. A) Tensile strength of a cellulose paper and a stretchable cellulose film. B) FT-IR spectra of a cellulose paper and a stretchable Cellulose film. C) XPS analysis
of a stretchable cellulose film.

peaks were considered to be related to the urea remaining in the film

[15].
To confirm the FT-IR analysis, we performed XPS analysis. Fig. 2c
shows XPS results for the stretchable cellulose film. Urea is the nitrogen
compound and has both C-N and C– – O bonds. The C1s graph shows a
C–C peak at 285 eV, a C-O peak at 286.7 eV, and a C– – O peak at 288.3
eV. The C– – O peak does not exist in cellulose and originates from the
urea. The C-N peak overlaps the energy domain of C-O, so it is not visible
separately. In the O1s graph, a peak at 532.9 eV represents O-C bonds
from cellulose, and a peak at 531.6 eV represents O–– C-N bonds from the Fig. 3. Water contact angle of a stretchable cellulose film.
urea. The N1s graph shows the N–(C– – O) bond from urea [16]. The XPS
analysis confirmed again that urea was present in the stretchable cel­ stretchable cellulose film was 44◦ (Fig. 3), which shows that our
lulose film. stretchable cellulose film is hydrophilic and means the good adhesion
Synthetic stretchable polymers are mostly hydrophobic such as with hydrophilic semiconductor materials.
PDMS which has a high water contact angle of more than 100◦ [17].
Plasma or chemical treatment is required to make the surface of PDMS 4. Conclusion
hydrophilic [8,18]. which is not a perfect solution due to a short
continuance. On the other hand, cellulose has hydrophilicity due to a Cellulose nanofibers were dissolved in an aqueous LiOH/urea solu­
large number of hydroxyl groups in the chain. The contact angle is a tion and ECH was used as a crosslinking agent, which made it possible to
quantitative measure of the wettability of a surface of material. In the prepare a stretchable, visibly transparent, and hydrophilic cellulose
case of water as testing liquid, substrates with a contact angle of < 90◦ film. The resulting cellulose film stretched to over 190%. It had a rela­
are considered to be hydrophilic. In terms of energetics, this implies that tively even surface with a transmittance over 90% in the visible range.
the forces associated with the interaction of water with the surface are This film used as a substrate is under studying for applications of energy
greater than the cohesive forces associated with bulk liquid water. Good storage devices, sensors array, or light emitting devices.
wetting is generally related to good adhesion. The contact angle of our

3
J.E. Oh and N.-M. Park
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was supported by Electronics and Telecommunications
Research Institute (ETRI) grant funded by the korean government
(18ZB1500) and Korea Institute for Advancement of Technology (KIAT)
grant (P0011390) funded by the Korean government.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.matlet.2021.131385.
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