4202 Macromolecules 2006, 39, 4202-4206

Discovery of Cellulose as a Smart Material

Jaehwan Kim* and Sungryul Yun
Center for EAPap Actuator and Department of Mechanical Engineering,
Inha UniVersity, Incheon 402-751, Korea
Zoubeida Ounaies
Department of Aerospace Engineering, Texas A&M UniVersity, College Station, Texas 77843
ReceiVed February 3, 2006; ReVised Manuscript ReceiVed April 11, 2006

ABSTRACT: The past 10 years has witnessed a renewed interest in cellulose research and application, sparked
mostly by technological interests in renewable raw materials and more environmentally friendly and sustainable
resources. In this paper, we further expand the current knowledge in cellulose applications and technologies by
reporting our discovery of cellulose as a smart material that can be used for biomimetic sensor/actuator devices
and micro-electromechanical systems. This smart cellulose is termed electroactive paper (EAPap). It can produce
a large bending displacement with low actuation voltage and low power consumption. The actuation phenomenon
and its characteristics are illustrated in this paper. Because cellulose EAPap is ultra-lightweight, inexpensive, and
biodegradable, it is advantageous for many applications such as micro-insect robots, micro-flying objects, micro-
electromechanical systems, biosensors, and flexible electrical displays.

1. Introduction
Cellulose is the most abundant natural polymer on earth,
consisting of glucose-glucose linkages arranged in linear chains,
where every other glucose residue is rotated in the opposite
direction.1 It has been estimated that the yearly biomass
production of cellulose is 1.5 trillion tons, making it an
inexhaustible source of raw material for environmentally friendly Figure 1. Regenerated cellulose process with xanthate cellulose
and biocompatible products.2 Cellulose derivatives are used for solution.
coatings, laminates, optical films, pharmaceuticals, foods, and As a naturally occurring biopolymer, cellulose is a type of
textiles. Numerous new applications of cellulose take advantage electroactive polymer (EAP).6-10 EAPs, also termed artificial
of its biocompatibility and chirality for the immobilization of muscles due to their operational similarity to biological muscles,
proteins and antibodies and for the separation of enantiomeric refer to a class of materials that has received much attention in
molecules as well as the formation of cellulose composites with the past 10 years, owing to the unique set of promising
synthetic polymers and biopolymers. Wood pulp remains the characteristics such as large strains in response to an electric
most important source in cellulose processing used for papers stimulus, low density, ease of processing, and good mechanical
and cardboards. The discovery of an electromechanical coupling properties. To demonstrate the applicability of cellulose as a
effect in wood dates back to 1950 when Bazhenov reported a smart EAP, a bending actuator is processed, fabricated, and
piezoelectric response in wood.3 In 1955, Fukada experimentally tested in our laboratory using cellulose paper. The fabrication
verified the piezoelectric coefficients of wood and demonstrated process, actuation phenomenon, and the test results are ex-
that oriented cellulose crystallites were responsible for the plained.
observed shear piezoelectricity.4 Piezoelectricity, a linear cou-
pling between electrical and mechanical properties, is displayed 2. Experimental Section
by crystal structures that lack a center of symmetry (non- Preparation of Cellulose EAPap Actuator. Cellulose EAPap
centrosymmetric). Most biopolymers, such as hair, wool, bone, is made with a cellulose film. Cellulose film can be made by
collagen, DNA, protein, and wood,4,5 are naturally oriented and dissolving cellulose fibers into a solution and cast it. Cellophane
is a well-known cellulose film made with cellulose xanthate
exhibit shear piezoelectricity due to the internal rotation of polar
solution. Commercial cellophane made from Weifang Co., China,
atomic groups associated with asymmetric carbon atoms. Oak, was used as a cellulose film for EAPap actuator. Figure 1 shows
pine, spruce, birch, alpha cellulose, and wood pulp are all the chemical reaction for cellulose xanthate process. Cotton pulps
cellulose-based biopolymers that exhibit shear piezoelectric are saturated with sodium hydroxide and allowed to steep for
constants comparable to that of quartz crystal.3 Shear piezo- enough time for the caustic solution to penetrate the cellulose and
electricity in woods varies depending on the type of wood, convert it into sodium cellulose. After pressing, shredding, and aging
orientation of wood samples, moisture, and temperature. Despite process, the solution is treated with gaseous carbon disulfide to
these early studies, however, the potential of cellulose as a smart form xanthate ester groups. Then the solution is allowed to stand
lightweight material that can be used as a sensor and an actuator for a period of time to ripen. After the solution is made, it is
has not been fully explored. extruded through a nozzle into two sulfuric acid baths, followed
by drying process. Once the solution is coagulated in the acid bath,
it is converted back to pure while cellulose. A roller system is
* Corresponding author: Tel +82-32-860-7326, Fax +82-32-868-1716, conveying the film via these baths, and washing and drying
e-mail [email protected]. processes are followed by a reel system.
10.1021/ma060261e CCC: $33.50 © 2006 American Chemical Society
Published on Web 05/19/2006
Macromolecules, Vol. 39, No. 12, 2006 Cellulose Smart Material 4203

Figure 2. Concept of electroactive paper actuator: (a) cellulose microfibril has ordered crystalline regions and disordered regions; (b) EAPap is
made from cellulose paper on which gold electrodes are deposited on both sides; (c) water molecules are bonded with hydroxyls on the cellulose
surface (bound water) or clustered in free (free water).

Figure 3. Schematic diagram of the force measurement system.

Figure 2a shows the cellulose electroactive paper (EAPap) as a actuator, and it produced a bending deformation. The tip displace-
bending actuator. Gold electrodes are deposited on both sides of ment of the EAPap actuator was measured by the high-precision
the cellophane by means of physical vapor deposition. The thickness laser Doppler vibrometer (Ometron VS100) mounted on an optical
of gold electrodes was extremely thin, so that its stiffness was table, and the signal was converted to the displacement through
negligible compared to that of the cellophane. The size of sample the Labview software in the computer. Simultaneously, the current
was 30 mm × 10 mm, and the thickness was 0.03 mm. In nature, probe (Tektronix TCPA300) measured the input current supplied
cellulose never occurs as a single chain but exists from the moment from the function generator.
of its synthesis as a crystalline array of many parallel, oriented Force Measurement. The measurement of output force of
chainssmicrofibrilsswhich are its fundamental structural units. A EAPap actuator is important for the performance evaluation. To
microfibril of cellulose has both crystalline and amorphous domains simultaneously acquire the tip blocked force, a microbalance was
(Figure 2b). used. Figure 3 shows the schematic diagram of the force measure-
To understand the fundamental behaviors of the material, physical ment system. An EAPap actuator was fixed vertically in the
and chemical characterization is necessary. The Young’s modulus environmental chamber by using tongs and the microbalance
of the material was measured using the material testing system (Precisa XT220A, micronewton resolution) was mounted on an
(Instron 5542). Since cellulose film has different mechanical optical table. A vertical fixture was placed on the balance, and the
properties in the machine direction (0°) and transverse direction tip of the actuator was contacted with the fixture. Since the tip of
(90°), samples were cut into three orientations, 0°, 45°, and 90°. EAPap actuator was contacted by the top of the fixture, a horizontal
Three samples in each orientation were pulled with slow speed, pushing force on the fixture was converted to the vertical force
and strain and stress were recorded in the computer of the testing due to the moment equilibrium of the fixture structure. The pure
system. To investigate the ion concentration in the cellulose films, vertical force was measured by the balance after nullifying the initial
a chemical analysis was performed by using inductively coupled weight of the vertical fixture.
plasma mass spectrometer (ICP-MS). The dielectric constant of the XRD Test and TSC Test. To understand the actuation phe-
cellulose film was measured using the LCR meter (HP 4284A). nomenon, X-ray diffraction (XRD) and thermally stimulated current
Bending Displacement Measurement. To measure the tip (TSC) measurement were performed. XRD was measured with the
displacement of EAPap actuators, a computerized displacement X-ray diffractometer (D/MAX-2500, Rigaku). XRD patterns with
measurement system was made. An EAPap actuator was supported Cu KR radiation at 40 kV and 30 mA were recorded 2θ ) 5-80°.
vertically in an environment chamber that can be controlled the TSC was used to characterize cellulose-based EAPap under electric
humidity and temperature. Function generator (Agilent 33220A) field and temperature conditions. TSC analysis is a more sensitive
controlled by a computer sent out the excitation voltage to the tool to detect the relaxation phenomena for the material composing
4204 Kim et al. Macromolecules, Vol. 39, No. 12, 2006

Table 1. Ion Contents in the Cellulose Film (in ppm)

element amount element amount
Na 1693.08 S 2867.59
Al 391.95 Cu 89.47
Cr 97.81 Pb 117.08
Co 1.281 Zn 179.13

of molecular chains with dipolar nature such as cellulose. From

this analysis, the relaxation phenomena can be inferred, which is
associated with orientation polarization of permanent or induced
dipoles and real charge injection. The classical procedure in TSC
includes (1) heating the sample to a given temperature (200 °C),
(2) applying the electric field at this temperature for a time t, (3)
cooling the sample down to room temperature with the field on to Figure 4. Tip displacement of EAPap bending actuator with different
freeze-in any dipolar alignment, (4) reheating the sample at a slow relative humidity (%): room temperature (23 °C) and 4 Hz actuation
rate while monitoring the current to quantify any dipolar alignment frequency.
that took place in step 2 (350 °C), and (5) the sample is reheated
one last time while current is monitored once again (350 °C). This modulus of cellulose EAPap material, compared with that of
last step may differentiate between current discharge due to dipolar other ionic EAP materials, can allow the possibility of enhancing
alignment and real charge injection (space charge); real charge the storable energy density.
injection may not fully escape the material in one heating. Before The electrical power consumption was 18 mW, which
testing the TSC, the sample was kept at 80 °C in the vacuum oven corresponds to 5 mW/cm2. This low electrical power consump-
for a day to remove the free water in the cellulose paper sample. tion is promising for achieving a microwave-driven actuator.
The glass transition temperature of the cellulose film was 203 °C.
Cellulose EAPap can be integrated with a microstrip antenna,
3. Results and Discussion so-called rectenna (rectifying antenna). When microwave arrives
at the rectenna, it converts the microwave power into dc power,
Characterization of Cellulose EAPap Material. Before and this power is distributed to the EAPap actuator via power
testing the performance of the cellulose EAPap actuator, its allocation device (PAD) circuit. Since rectenna and PAD are
physical and chemical properties were tested. When the material thin film based, they can be integrated onto cellulose EAPap,
was tested, the Young’s modulus ranged from 4.3 to 7.1 GPa, which comprise a remotely driven EAPap actuator. This means
depending on the orientation. The Young’s modulus in me- that EAPap actuators can be remotely driven using microwaves,
chanical direction was higher, and the transverse direction was making them attractive candidates for ultra-lightweight multi-
lower; meanwhile, the 45° direction was 5 GPa. The density of functional applications such as micro-insect robots, flapping
the cellulose film was 0.77. The ion concentration in the wings for flying objects, smart wallpaper, MEMS, and so on.
cellulose film was analyzed using ICP-MS (Table 1). Large Actuation Phenomenon. To successfully transit cellulose
amounts of sodium and sulfur were observed. Notice that the EAPap actuators into these applications, it is crucial to ascertain
amount of sulfur is almost twice that of sodium, which is the actuation mechanism responsible for the performance
expected from the xanthate reaction. Also, some other metallic parameters mentioned above. On the basis of the cellulose
ions such as aluminum and chrome were observed. These ions structure and our processing of the cellulose-based EAPap, we
might be observed from the bathing and washing processes. The believe that the actuation is due to a combination of two
relative dielectric constant was measured at 20 Hz, and it was mechanisms: ion migration and dipolar orientation. In the rest
between 40 and 20, depending on the orientation. The mechan- of the paper, we present experimental evidence of both.
ical direction exhibited a higher dielectric constant. This Cellulose EAPap material is a sheet of regenerated cellulose.
dielectric constant value is larger than ordinary papers. Morphologically, regenerated cellulose has ordered and disor-
Performance of Cellulose EAPap Actuator. When an dered regions, in which the ordered domains are mostly
electric field was applied across the thickness direction of the crystalline. The disordered molecules retain preferential direction
paper, it produced a large bending deformation. For a 30 mm parallel to the chains in the microfibrils, and they form surface
long EAPap sample, a maximum tip displacement of 4.2 mm disorder on the microfibrils. Figure 2b shows the concept of
and the maximum force of 12.7 mN were obtained under the microfibril. The EAPap material has large regions of disordered
applied voltage of 0.23 V/µm, at 7 Hz, 95% relative humidity cellulose chains, where water molecules can be found attached
and in room temperature (Figure 4). The corresponding electric to hydroxyl groups (Figure 2c). During the paper making
field required to reach displacement saturation is 1-2 orders process, sodium ions were injected in the paper fiber.11 When
of magnitude lower than that of other electronic EAPs.8 The an external electric field is applied, these ions can be mobile
humidity affects the displacement, where a high relative and migrate to the anode. In addition, the molecular motion of
humidity leads to a large displacement. The displacement free water in disordered region cannot be restricted by the
increases by as much as 2 orders of magnitude when the cellulose molecules, and the water molecules can be interacted
humidity is increased from 50% to 95%. with ions in the cellulose. In the presence of electric field, the
According to Prof. Zhang’s paper,9 the elastic energy density sodium ions surrounded with free water molecules will move
can be found as E ) (1/2)Y2 ) (1/2)9 × 109(3.8 × 10-4)2 ) to the anode. Selective ionic and water transport across the
650 J/m3 ) 0.84 J/kg. Here, the bending strain  was found by polymer under electric field results in volumetric changes, which
 ) h/2F, where h is the thickness and F the radius of curvature. in turn lead to bending. When a dc electric field was applied,
The radius of curvature can be found from the maximum tip the cellulose EAPap actuator was bent to the positive electrode,
displacement, 4.2 mm. According to ref 6 (p 82), the required which confirmed the above explanation. The ambient humidity
net energy density for biological muscles is 0.2-40 J/kg. Thus, effect on the EAPap actuator performance is a further evidence
the specific energy density of EAPap is marginally within the of this, where ion transport is facilitated when humidity intake
requirement for artificial muscle actuators. The high Young’s is higher.
Macromolecules, Vol. 39, No. 12, 2006 Cellulose Smart Material 4205

poling electric fields, and Figure 5b shows the peak current

values as a function of the poling electric field. The depolar-
ization current increases linearly as the poling electric field
increases. This behavior is usually indicative of dipole orienta-
tion.13 Generally, the polarizability of dielectric materials may
be separated into several parts. An electronic contribution arises
from a displacement of the electron shell relative to a nucleus
and an ionic contribution from the displacement of a charged
ion with respect to other ions. In cellulose material that possesses
molecular groups having permanent molecular dipole moments
such as water or the hydroxyl and carboxyl groups will also
make a contribution.11 At low frequency all of these parts
contribute to the polarizability, as will any free ions (space
charges) in the material. As the frequency increases, the space
charges and permanent dipoles relax out. Space charges are
usually the first to relax out, followed by the permanent dipole
groups. In the cellulose EAPap, the presence of disordered
region gives rise to localized states associated with hydrogen
bonding of cellulose chains. Since there are many localized
states, the release or excitation of the carriers in these states
may dominate the charge transfer process. Thus, the disordered
region mainly contributes to the dipolar orientation, by stabiliz-
ing dipoles and leading to a permanent polarization, resulting
in a piezoelectric behavior.
Further investigating the actuation behavior of EAPap mate-
rial, XRD was done on an EAPap sample before and after the
electrical actuation. Figure 6 shows the XRD results. Table 2
summarizes the X-ray diffraction peaks before and after the
actuation. After actuation, the (110) peak at 2θ ) 12.26°
Figure 5. TSC results of cellulose EAPap: (a) the depolarized current decreases to 12.08° while the (200) peak at 2θ ) 21.64°
with temperature with different poling electric fields; (b) the peak increases slightly to 22.02°. Quality factors were found on these
current values as a function of the poling electric field. The straight peaks. A large quality factor indicates sharp peak. It is cleat
line shows the linear relationship between the electric field and the
depolarization current. that the (110) peak sharpened after the actuation while the (200)
peak was changed to blunt. This confirms that the first peak
Cellulose EAPap material is composed of molecular chains was increased, and the second peak was decreased. Notice that
with a dipolar nature. In particular, the crystal structure of the small peak at 2θ ) 16.78° only appears after the electrical
cellulose II is monoclinic, which is non-centrosymmetric and activation. This means that some structural change have
exhibits piezoelectric and pyroelectric properties. To investigate happened during the electrical actuation, which may be associ-
the dipole effects in EAPap, TSC analysis12 was used. Figure ated with the crystallization of amorphous region. In other
5a shows the depolarized current with temperature with different words, crystallization of amorphous cellulose of EAPap sample

Figure 6. XRD result: the (110) peak at 12.26° was decreased to 12.08°, and the (200) peak at 21.64° was increased slightly to 22.02°, while the
small peak at 16.78° was started to appear after the electrical activation.
4206 Kim et al. Macromolecules, Vol. 39, No. 12, 2006

Figure 7. Cellulose paper applications: (A) micro-flying object; (B) micro-insect robots; (C) biodegradable MEMS.

Table 2. X-ray Peaks of Cellulose EAPap Material before and after inexpensive and lightweight biomimetic actuators and MEMS
Electrical Actuation (Last Two Columns Show the Peaks for devices. Cellulose-based EAPap material is also promising as
Cellulose I and II for Comparison)
biosensors since it is biodegradable, biocompatible, sustainable,
before after and capable of broad chemical modification and has high
peak Q peak Q cellulose cellulose mechanical stiffness and strength. Control of disordered region,
location factor location factor I II recrystallization, and orientation of cellulose are all issues that
(110) 12.26 67.7 12.08 87.9 14.80 12.10 need to be addressed in order for cellulose EAPap to fulfill its
(1ıj0) 16.78 16.74 16.30 19.8 promise as a smart material.16,17
(200) 21.46 22.6 22.02 12.9 22.60 22.0
Acknowledgment. This work was supported by the Creative
is accelerated by molecular rearrangement during the electrical Research Initiatives Program of Korea Science and Engineering
activation, leading to a structure closer to that of cellulose II Foundation (KOSEF).
allomorph. Structural changes of native cellulose crystals have
been made by annealing in aqueous alkaline and acid solutions References and Notes
in high temperature.14 However, there has not been any report
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that the cellulose polymorphs can be changed in the presence (2) Klemm, D.; Heublein, B.; Fink, H.-P.; Bohn, A. Angew. Chem., Int.
of electric fields. Our observation may be the first report on Ed. 2005, 44, 3358.
the structural change of cellulose by applying electric field. (3) Bazhenov, V. A. Piezoelectric Properties of Woods; Consultants
PVDF is a phase transformation example: alpha phase is Bureau: New York, 1961.
(4) Fukada, E. IEEE Trans. Ultrason. Ferro. Freq. Contr. 2000, 47, 1277.
transformed into beta phase in the presence of electric field. (5) Lang, S. B. Nature (London) 1996, 212, 704.
Moisture content may cause crystal growth in regenerated (6) Bar-Cohen, Y. ElectroactiVe Polymer (EAP) Actuators as Artificial
cellulose material accompanied by molecular rearrangement due Muscles: Reality, Potential, and Challenges; SPIE Press: Bellingham,
to sorbed water.15 The electrical activation is believed to enhance 2004.
(7) Shahinpoor, M.; Bar-Cohen, Y.; Simpson, J. O.; Smith, J. Smart Mater.
the recrystallization. This enhanced crystallization may improve Struct. 1998, 7, R15.
the piezoelectricity of EAPap material. (8) Pelrine, R.; Kornbluh, R.; Joseph, J. Sens. Actuators, A 1998, 64, 77.
(9) Zhang, Q. M.; Li, H.; Poh, M.; Xia, F.; Cheng, Z.-Y.; Xu, H.; Huang,
4. Summary and Conclusions C. Nature (London) 2002, 419, 284.
(10) Kim, J.; Seo, Y.-B. Smart Mater. Struct. 2002, 11, 355.
We reported the discovery of cellulose paper as a smart (11) Mark, R. E. Handbook of Physical and Mechanical Testing of Paper
material by demonstrating a EAPap bending actuator that and Paperboard; Marcel Dekker: New York, 1989.
exhibted a large displacement, low actuation voltage, and low (12) Pissis, P. J. Phys. D: Appl. Phys. 1985, 18, 1897.
(13) Sessler, G. M. Electrets, 3rd ed.; Laplacian Press: Morgan Hill, CA,
electrical power consumption. We note that the cellulose-based 1999; Vol. I.
EAPap material has recrystallized in the presence of electric (14) Yamamoto, H.; Horii, F.; Odani, H. Macromolecules 1989, 22, 4130.
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