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ABSTRACT: ellulose nanomaterials have a number of interesting and unique properties that make them well-suited
C
for use in electronics applications such as energy harvesting devices, actuators and sensors. Cellulose
nanofibrils and nanocrystals have good mechanical properties, high transparency, and low coefficient of
thermal expansion, among other properties that facilitate both active and inactive roles in electronics and
related devices. For example, these nanomaterials have been demonstrated to operate as substrates for
flexible electronics and displays, to improve the efficiency of photovoltaics, to work as a component of
magnetostrictive composites and to act as a suitable lithium ion battery separator membrane. A discussion
and overview of additional potential applications and of previously published research using cellulose
nanomaterials for these advanced applications is provided in this article. The concept of using cellulose
nanofibrils in stimuli-responsive materials is illustrated with highlights of preliminary results from
magnetostrictive nanocellulose membranes actuated using magnetic fields.
KEYWORDS: Cellulose nanofibrils, cellulose nanocrystals, flexible electronics, photovoltaics, batteries, magnetostrictive
composites
J. Renew. Mater., Vol. 4, No. 5, October 2016 © 2016 Scrivener Publishing LLC 297
Ronald Sabo et al.: Nanocellulose-Enabled Electronics, Energy Harvesting Devices, Sensors: A Review DOI: 10.7569/JRM.2016.634114
As cellulose is broken down into nanometer-scaled CNFs each bring unique properties and applications,
particles and fibers, the materials begin to exhibit and both have been explored for use in electronics and
some interesting and unique properties depending functional devices.
on their size, morphology, charge and other charac- Cellulose nanomaterials are often touted as poten-
teristics. Since these properties are important to their tial polymer reinforcements because of their high
application, a brief primer into their categorization strength and stiffness, and these good mechanical
and properties is warranted here. Typically, cellulose properties also lend these materials for use in func-
nanomaterials, especially from plant sources, can be tional devices such as electronics. The cellulose crystal
categorized as either cellulose nanocrystals (CNCs) or has been measured to have extremely high strength
cellulose nanofibrils (CNFs). CNCs are discrete, rod- and stiffness with values of about 10 GPa and up to
shaped cellulose particles (Figure 1) typically with about 200 GPa, respectively, but bulk materials, such
high crystallinity and are primarily produced through as films, made from nanocellulose have considerably
acid hydrolysis of native cellulose. Typically, CNCs lower mechanical properties [43–47]. Nonetheless,
have nanometer-scaled diameters with lengths of hun- cellulose nanomaterial films and composites have
dreds to thousands of nanometers, and they often con- mechanical properties that rival or exceed many poly-
tain surface charge groups and can thus be colloidally mers. The tensile strength and modulus of randomly
stable. Conversely, CNFs are typically network struc- oriented CNF films, for example, are commonly as
tured nanoscaled fibers (Figure 2) that can be produced high as 200 MPa and 20 GPa, respectively [47–49]. As a
from countless methods usually involving some kind comparison, polyethylene terephthalate (PET), which
of chemical treatment followed by mechanical refining. has been used as a substrate for flexible electronics,
The morphology of CNFs widely varies from process has tensile strength and modulus of approximately 55
to process, and they can often have a wide distribu- MPa and 3 GPa, respectively [50–52]. Typically, only
tion of diameters and lengths. Another type of cellu- the tensile properties of CNF or CNC films are mea-
lose nanomaterial is often called bacterial cellulose as sured or reported, but their tear and bending behav-
it is produced by a species of bacteria generally called iors are also important. The incorporation of polymers
Acetobacter xylinum [38]. The fibers produced by these and other modifiers can aid in improving flexibility
bacteria have cellulose I crystallinity with diameters and improving durability, but little data is available,
of tens to hundreds of nanometers [2, 39]. A number of especially pertaining to their application in electronics
reports have been made on using bacterial cellulose as and functional materials. Nonetheless, the mechanical
a substrate in electronic devices [40, 41]. Most of these properties of cellulose nanomaterials lend them to be
findings are likely transferrable to CNFs from plant- employed as components in a variety of devices.
based materials. In addition, nanofibers of regener-
ated cellulose can be created using the gel spinning
process, and such cellulose nanofibers have also been
employed in electronic applications [42]. CNCs and
200 nm 200 nm
Figure 1 Transmission electron micrograph of cellulose Figure 2 Transmission electron micrograph of cellulose
nanocrystals from wood; scale bar is 200 nm. nanofibrils from wood; scale bar is 200 nm.
298 J. Renew. Mater., Vol. 4, No. 5, October 2016 © 2016 Scrivener Publishing LLC
DOI: 10.7569/JRM.2016.634114 Ronald Sabo et al.: Nanocellulose-Enabled Electronics, Energy Harvesting Devices, Sensors: A Review
The optical properties of cellulose nanomaterials cellulose nanofibers was shown to be able to reduce
are also distinctive from bulk cellulose and can be the thermal expansion down to 1 ppm/K [62]. Nogi
favorable for electronic applications. Films and com- and Yano demonstrated that by adding only 5% of
posites made from cellulose nanomaterials, including bacterial cellulose nanofibers to an acrylic resin, ther-
CNCs, CNFs and bacterial cellulose, can be highly mal expansion of the film from 20 to 150 °C could be
transparent (Figure 3), depending on how they are reduced by more than a factor of 60 resulting in an
produced [41, 49, 53–58]. Fukuzumi et al. measured in-plane thermal expansion of 4 ppm/K [41]. Nogi
the light transmittance through a CNF film made from et al. measured the thermal expansion of “optically
softwood pulp to be up to 90% but only 78% when transparent nanofiber paper” from Douglas fir to be
made from hardwoods [53], and Nakagaito et al. com- 8.5 ppm/K over the range of 20 to 150 °C [55], and
pared the transparency of films made from a variety Yagyu et al. measured the CTE of CNF films from wood
of materials, including bacterial cellulose [54]. The to be 7–13 ppm/K [63]. These values are favorable
CNF films have also been measured to have high opti- compared to existing polymeric materials, which can
cal haze and strong scattering, which can potentially have CTE values up to hundreds of ppm/K [43, 56].
be exploited for photovoltaic applications [33, 34, 59]. Because low thermal expansion is important for elec-
Interestingly, CNC suspensions are also birefringent tronics printed or deposited onto flexible substrates,
and optically active and can be assembled in films such cellulose nanomaterials may offer favorable proper-
that they exhibit tailorable and even switchable optical ties and potentially improved performance over other
and color characteristics [18, 20, 46, 60]. These optical polymer films.
properties of cellulose nanomaterials offer enormous Because of all these properties, including sustain-
potential for use as electronic substrates, sensors, liq- ability, high strength, flexibility, transparency and
uid crystal devices and more. low thermal expansion, cellulose nanomaterials have
Cellulosic materials have low thermal expansion, been explored for their use in electronics and func-
which is desirable in electronic components that gen- tional devices. In some cases, cellulose nanomateri-
erate heat, and the coefficient of thermal expansion als can provide advantages over traditional materials.
(CTE) for cellulose nanomaterials and their compos- For example, cellulose-based nanocomposites can
ites has been measured and reported for various CNF overcome issues with piezoceramics such as brittle-
films. The thermal expansion of cellulose has been ness [64], high toxicity in lead zirconate titanate (PZT)
measured to be as low 0.1 ppm/K [61], and the CTE [64, 65], low energy conversion efficiency [66, 67],
for films and composites containing cellulose nano- inability to operate under long life cycles without the
materials has been reported to be as low as 1 ppm/K issues of depolarization [68–70], and the lack of flex-
[62]. Bacterial cellulose typically has a lower CTE than ibility to operate under strong ambient vibrations
plant-derived CNFs [54], and modification of bacterial [71, 72]. An overview of many of these applications is
provided here, but this account is not intended to be
comprehensive. Instead, this work aims to provide a
broad perspective of how cellulose nanomaterials may
play a role in electronics such as sensors, actuators,
displays and energy harvesting devices.
2 SUBSTRATE MODIFICATION
Substrate quality is critical for the fabrication and
performance of electronics on cellulose substrates,
and methods for improving CNF substrates elec-
tronics have been explored and continue to be the
focus of both research and commercialization efforts
[30, 73–75]. Low surface roughness, strong water
resistance and robust mechanical properties are all
desirable properties for electronic substrates, and
in many cases, cellulose nanomaterials may require
modification or improvements to meet those needs.
Torvinen et al. evaluated the effects of composition
Figure 3 Cellulose nanofibril film overlaid on Forest Service and processing on the properties of composite films
logo. containing CNF inorganic filler [75]. They found that
J. Renew. Mater., Vol. 4, No. 5, October 2016 © 2016 Scrivener Publishing LLC 299
Ronald Sabo et al.: Nanocellulose-Enabled Electronics, Energy Harvesting Devices, Sensors: A Review DOI: 10.7569/JRM.2016.634114
calendering produced mechanically stable and flex- deposition techniques and transferring prefabricated
ible sheets with smooth surfaces on which silver nan- devices onto CNF substrates. The results from some
oparticle ink could be printed. The films had similar of these electronic devices on nanocellulose substrates
surface roughness and sheet resistance as those from are described below.
reference materials, including polyethylene tereph- Researchers at the University of Wisconsin and
thalate (PET), and they concluded that these CNF the USDA Forest Service Forest Products Laboratory
composite substrates would be suitable for use in recently demonstrated that high-speed transistors on
electronic applications, such as RFID sensors and tags. silicon nanomembranes can be fabricated onto CNF
For the case of transferring silicon nanomembrane films, as shown in Figures 4 and 5 [28, 30]. These
(Si NM) devices to cellulose substrates, both the sub- flexible electronics were built by first fabricating the
strate coating and adhesive layers were found to affect device on a special silicon wafer that allows thin sili-
the transferability to the substrate [30]. Thin, smooth con nanomembranes (Si NMs) to be released and then
epoxy layers resulted in better transfer to the substrate by transferring the Si NM to a CNF substrate. In the
and also p rovided enough protection to limit swell- first step (Figure 5i), the n+ wells for the source and
ing during subsequent wet cleaning steps. Couderc drain regions were formed using a spin-on-dopant dif-
et al. coated CNF sheets with thin polyimide layer, fusion process carried out in a nitrogen and oxygen
which improved the dielectric properties, reduced ambient furnace at 850 °C for 20 minutes. Next, the
the moisture uptake and decreased surface roughness thin silicon layer was released by wet etching with
[76]. Chinga-Carrasco et al. created CNF films modi- hydrofluoric acid (Figure 5ii), then the electrodes were
fied with hexamethyldisilazane to improve water
resistance and printability [73], and Shimaoka et al.
reported a proprietary modification process produc-
ing films with substantially reduced moisture uptake
and with low brittleness, such that they could be bent
and rolled tightly without cracking [74]. Therefore,
despite some of the drawbacks of pure CNF films,
such as large moisture absorption, modifications and
processing techniques have been demonstrated to
yield CNF films suitable for electronic applications.
3 FLEXIBLE ELECTRONICS
Because cellulose nanofibril films can be transparent,
have low CTE, are flexible and have good mechanical
properties, they are excellent candidates for substrates
for flexible electronics. A number of methods for cre-
ating electronics on cellulose nanomaterial substrates
have been demonstrated and include printing circuits Figure 4 Flexible electronics on cellulose nanofibril
directly onto the substrates, using coating and thermal substrate.
(iv)
(vi) (v)
Figure 5 Schematic of production process for flexible electronics on CNF substrate. (Reprinted with permission from [28];
Copyright 2015 AIP Publishing LLC)
300 J. Renew. Mater., Vol. 4, No. 5, October 2016 © 2016 Scrivener Publishing LLC
DOI: 10.7569/JRM.2016.634114 Ronald Sabo et al.: Nanocellulose-Enabled Electronics, Energy Harvesting Devices, Sensors: A Review
created (Figure 5iii). Next the Si NM was transferred to exhibited excellent properties as a field-effect transis-
a CNF substrate with an adhesive layer (Figure 5iv–v), tor substrate.
and finally the device was completed by photoresist Printed electronics are another application in which
patterning and dry etching steps (Figure 5vi). This cellulose nanomaterials have been demonstrated to be
thin-film transistor (TFT) built on the CNF substrates suitable as substrates [32, 63, 77, 78]. Printed electronics
was demonstrated to operate in the microwave range often employ inks consisting of nanometer-scale silver
with a transition frequency of 4.9 GHz while flat and particles in suspension, but carbon nanotube (CNT)-
3.8 GHz while bent [28]. The substrate was found to CNF mixtures have also been suggested as potential
have low gate leakage and field effect mobility values conductive inks with the CNFs acting as the dispersing
consistent with other Si NM transistors. The substrate agent [78]. Nge et al. demonstrated that silver nanopar-
was also shown to exhibit biodegradability, which ticle tracks printed on CNF substrates show lower elec-
could potentially offer opportunities to recover rare trical resistance than those printed on commonly used
metals used in electronics. Such high speed electronics plastics such as polyimide and poly(ethylene naphthal-
have numerous potential applications for communica- ate) (PEN) [77]. Those conductive tracks on CNF sub-
tion and computation devices, and preliminary inves- strates showed better electrical performance during
tigations show that cellulose nanomaterials perform and after folding than those on plastic substrates. In
satisfactorily. another example, flexible silver antennas were printed
In a more recent report from this group, various on crosslinked CNF films using gravure printing tech-
working electronic devices were fabricated on CNF niques [32]. The devices were demonstrated to have
substrates [31]. They reported an environmentally good radio frequency performance for application in
friendly method for creating gallium arsenide micro- radio frequency identification (RFID) antenna tags.
wave devices on CNF substrates with performances Although printed electronics do not typically match
comparable to those made on rigid devices. They the performance of typical silicon-based electronics,
also created Si-based complementary metal–oxide– there are a wide range of applications, including light-
semiconductor (CMOS) devices, including logic gates emitting diodes, sensors, medical devices, and radio
and a full adder, which worked at frequencies up to frequency identification (RFID) antennas, for which
5 kHz, as shown in Figure 6. The working character- CNF substrates can potentially be employed [79].
istics of these devices were clearly shown, indicating
that full circuits and working electronics can be cre-
ated on CNF substrates. 4 DISPLAYS AND LIGHT-EMITTING
In another example, flexible organic field-effect tran- DIODES
sistors (OFETs) were fabricated on flexible, transparent
cellulose “nanopaper,” which was created by oxida- Using CNFs as substrates for light-emitting diodes
tion and mechanical refining of bleached softwood and displays has received a great deal of attention,
Kraft pulp [29]. They created CNF films with surface including from electronics manufacturers, over the
roughness of about 5 nm, transparency of 90% and last several years. Okahisa et al. reported successful
coefficient of thermal expansion as low as 12 ppm/K. fabrication of an organic light-emitting diode (OLED)
A transparent, conductive carbon nanotube layer device on wood-based cellulose nanofibril composites
was then coated onto the CNF substrate, followed by [56] (Figure 7). They acetylated the CNFs, impreg-
spin-coating of a poly(methyl methacrylate) (PMMA) nated them with different acrylic resins and found the
dielectric layer. Next, they vacuum deposited an composite fabrication and formulation critical to the
n-type organic semiconductor NTCDI-F15, a naphtha- ability to fabricate a working device. The fabrication
lenetetracarboxylic diimide derivative. Finally, they of the device involved multiple steps adopted from
evaporated silver electrodes through shadow masks a device created on polymer substrates [80]. First, a
onto the semiconductor. The device was reported to smoothing layer was spin-coated on a CNF compos-
“exhibit good n-type transistor characteristics” and ite film, then a silicone oxynitride (SiON) barrier film
had effective carrier mobility of 4.3 × 10–3 cm2/(Vs) was sputter deposited. The anodes were created by
and Ion/Ioff ratio up to 200. The mobility only decreased sputter deposition and patterning; the organic layers
by about 10% when the device was bent either parallel were vacuum deposited, and the cathode was fabri-
or perpendicular to the conduction channel direction. cated by vacuum deposition. Finally, a passivation
They also noted that, unlike other organic semicon- film layer was created by chemical vapor deposition.
ductor devices, the good bonding between CNF and The device was able to illuminate lettering expressing
carbon nanotubes (CNTs) diminished the problem of the researcher’s affiliations. Legnani et al. produced
protruding CNTs, which can cause an electrical short OLEDs on bacterial cellulose membranes by deposit-
circuit. The highly transparent, flexible CNF substrate ing indium tin oxide thin films using radio frequency
J. Renew. Mater., Vol. 4, No. 5, October 2016 © 2016 Scrivener Publishing LLC 301
Ronald Sabo et al.: Nanocellulose-Enabled Electronics, Energy Harvesting Devices, Sensors: A Review DOI: 10.7569/JRM.2016.634114
–0.8 1.6
–0.7 1.4
–0.6 1.2
–0.5 1.0
ID (mA)
–0.4 0.8
–0.3 0.6
–0.2 0.4
–0.1 0.2
–0.0 0.0
–6 –5 –4 –3 –2 –1 0 1 2 3 4 5 6
(a) (b) VD (V)
Voltage (V)
Voltage (V)
0 0
0
–2 –2
–2 –4 –4
–6 –6
–4 Input Input A Input A
–8 Input B –8 Input B
Output Output Output
–6 –10 –10
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.1 0.2 0.3 0.4 0.00 0.05 0.10 0.15 0.20 0.25 0.30
(d) Time (ms) (f) Time (ms) (h) Time (ms)
Full adder 4
0 Input A
–4
4
0 Input B
–4
Voltage (V)
4
0 Carry in
–4
4
0 Sum
–4
4
0 Carry out
–4
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
(i) (j)
Time (ms)
Figure 6 Digital electronics on CNF. (Reprinted under Creative Commons license from [31])
302 J. Renew. Mater., Vol. 4, No. 5, October 2016 © 2016 Scrivener Publishing LLC
DOI: 10.7569/JRM.2016.634114 Ronald Sabo et al.: Nanocellulose-Enabled Electronics, Energy Harvesting Devices, Sensors: A Review
Ag (150 nm)
MoO3 (15 nm)
PBDTTT-C:PCBM (90 nm)
PEIE (10 nm)
Ag (20 nm)
CNC substrate
(a) (b)
J. Renew. Mater., Vol. 4, No. 5, October 2016 © 2016 Scrivener Publishing LLC 303
Ronald Sabo et al.: Nanocellulose-Enabled Electronics, Energy Harvesting Devices, Sensors: A Review DOI: 10.7569/JRM.2016.634114
the photoactive layers. The device reached a power Cellulose nanofibrils also have the potential to
conversion efficiency of 2.7% and demonstrated a replace thermoplastic polymer films as membrane
potential approach for using sustainable cellulose separators for Li-ion batteries [85, 88, 91]. For example,
nanomaterials as a component in recyclable electronic Chun et al. compared the performance of separators
components. made from CNFs created by high-pressure homog-
Cellulose-based materials have been widely enization to a commercially available tri-layer poly-
explored for use in batteries, and using cellulose nano- propylene/polyethylene/polypropylene (PP/PE/PP)
materials is a natural extension for battery applica- separator and found that the CNF separator showed
tions [85, 94]. Flexible electrodes for batteries and other comparable electrochemical performance to the com-
applications have been created using cellulose nano- mercial one. Furthermore, they concluded that the
materials as binders, templates, etc., in conjunction CNF separator offered some potential advantages
with conductive materials [84, 87, 88, 90]. For example, over the PP/PE/PP separator, including improved
Jabbour et al. used graphite and cellulose nanofibrils, ionic conductivity, electrolyte wettability, and thermal
which they referred to as microfibrillated cellulose, to shrinkage. The thermal shrinkage of the CNF separa-
create flexible electrodes for batteries [84]. They found tor was judged to be negligible as compared to 36%
the electrodes had a conductivity of about 0.3 S/cm for the PP/PE/PP one, which could lead to improved
even as they were rolled around hoses with radii electrode isolation and safety of Li-ion batteries.
ranging from 3 to 32 mm, but this conductivity was Leijonmarck et al. reported a process in which the
significantly lower than reference electrodes. The elec- electrodes and separator were created from cellulose
trode had specific discharge capacity close to the theo- nanofibrils in a sequential filtration process as shown
retical specific capacity of graphite and good cycling in Figure 9 [88]. The result of the sequential filtration
performances, and they expressed high optimism for process was a flexible, single-paper Li-ion battery cell,
cellulose nanomaterials to play a role as electrodes in as shown in Figure 10. The anode consisted of CNFs,
electronic devices. In another example, flexible silicon- graphite and Super-P carbon; the cathode consisted of
conductive cellulose nanopaper was demonstrated as CNFs, LiFePO4, and Super-P carbon; and the separa-
a functional Li-ion battery electrode [87]. This electrode tor contained CNFs and SiO2. The paper batter was
was fabricated by first creating a CNF-carbon nano- soaked in electrolyte, then copper and aluminum foil
tube (CNT) aerogel, followed by plasma-enhanced charge collector were placed on the negative and posi-
chemical vapor deposition (PECVD) of a thin silicon tive sides of the battery, respectively, and the battery
layer in the porous aerogel channels. The electrode cells were sealed in a pouch. They tested the electro-
performance was evaluated in coin-type Li-ion battery chemical performance of the battery cells and found
for up to 100 charge/discharge cycles, and they con- that they could be used for hundreds of charge cycles
cluded that the electrode performed quite well with while maintaining a large part of their capacity. They
the discharge capacity remaining above 1200 mA h/g, also found that the battery could work while being
which is more than three times the theoretical capacity bent, indicating their applicability in flexible devices.
of conventional graphite anodes. Such examples dem- Therefore, in addition to potentially improving the
onstrate the role that cellulose nanomaterials can play sustainability and environmental impact of battery
in electrodes for batteries and other applications and components, cellulose nanomaterials could offer
how they can be incorporated with other nanotechnol- improvements over conventional Li-ion battery sepa-
ogy for advanced applications. rator properties.
NFC + LiFePO4
NFC + SiO2 NFC + SiO2
NFC + Graphite NFC + Graphite NFC + Graphite
Filter paper Filter paper Filter paper Filter paper
Figure 9 An illustration of the sequential filtration steps during the production of a paper battery cell. (Reproduced with
permission from [88]; The Royal Society of Chemistry)
304 J. Renew. Mater., Vol. 4, No. 5, October 2016 © 2016 Scrivener Publishing LLC
DOI: 10.7569/JRM.2016.634114 Ronald Sabo et al.: Nanocellulose-Enabled Electronics, Energy Harvesting Devices, Sensors: A Review
J. Renew. Mater., Vol. 4, No. 5, October 2016 © 2016 Scrivener Publishing LLC 305
Ronald Sabo et al.: Nanocellulose-Enabled Electronics, Energy Harvesting Devices, Sensors: A Review DOI: 10.7569/JRM.2016.634114
fully functional electronic sensing devices for use in incorporate magnetic particles with cellulose materi-
biomedical or chemical analysis applications. als by coprecipitation methods [113–115]. Cobalt ferrite
nanotubes with an average diameter of 217 nm were
synthesized by coprecipitation using freeze-dried
8
PIEZOELECTRIC AND bacterial nanocellulose as template [116]. The metal
ELECTROACTIVE EFFECTS IN precursors (Fe3+ and Co2+ ions) bind to cellulose nanofi-
CELLULOSE NANOMATERIALS brils via e lectrostatic interactions between the hydroxyl
groups (electron-rich oxygen atoms) of the nanocellu-
Cellulose nanomaterials have also been demonstrated lose and electropositive transition metal c ations. The
to display piezoelectric and electroactive effects, authors were able to show magnetic behavior at room
which potentially can be exploited for use as actua- temperature that they attributed to the fraction of nan-
tors and sensors in a wide range of devices, including oparticles in superparamagnetic state.
microelectromechanical systems, robotics, speakers,
micropumps and more [107–110]. For example, Csoka
et al. demonstrated that thin CNC films demonstrated 10
MAGNETOSTRICTIVE CELLULOSE
a piezoelectric effect with an effective shear piezo- NANOCOMPOSITES FOR
electric constant of 2.1 Å/V, which is comparable to a ACTUATION AND SENSING
reference ZnO film [109]. Jeon et al. demonstrated that
bacterial cellulose films exhibited electrically driven In ferromagnetic materials, magnetostriction leads to
bending deformation, which could be enhanced by the variation of their physical geometries according to
chemical modification [110]. Nanocellulose-based an external magnetic field. The magnetostrictive effect
actuators and electroactive devices have enormous is usually negligible for regular materials like nickel.
potential, but there exists a fairly wide gap in fun- The advent of rare earth iron alloys, such as Terfenol-D,
damental understanding of these effects as well as a that exhibit giant magnetostrictive effect has led to the
lack of effective demonstration of these materials in promising development of sensors and energy har-
devices compared to existing materials. vesting devices requiring higher energy density, faster
response and better precision. Additionally, the magne-
tostrictive effect has been used in transducers for appli-
9 MAGNETIC CELLULOSE cations in sonars [117–119], energy harvesting [120–123],
NANOCOMPOSITES IN AEROGELS active vibration control [124–126] and position control
AND NANOPAPER systems [127, 128]. However, the monolithic Terfenol-D
materials are heavy and not easily moldable into desir-
Composite materials offer a unique opportunity of able shapes for sensor and actuator fabrication; they
combining two or more materials that retain their indi- are still relatively brittle and can only withstand small
vidual properties but when combined can produce strains to failure [129]. A potential remedy is to take
new features. An example of this composite approach advantage of the superb mechanical properties of the
is the efforts to integrate magnetic particles within nanocellulose matrix to form a magnetostrictive com-
cellulose materials. A hydrophobic cellulose aerogel posite with magnetostrictive particles. The structure of
composite was previously prepared with magnetic the cellulose nanofibers provides a layered substrate for
nanoparticles for oil absorption applications [111]. The magnetostrictive materials. Since the resulting compos-
principle of this composite is that the cellulose would ite is in the form of film and inherit magnetic properties
absorb the oil from a spill and then be magnetically from magnetostrictive particles, it is known as magne-
retrieved. The aerogel produced was able to absorb oil tostrictive nanocellulose membrane (MNM).
up to about 28 times of its own weight within 10 min- For magnetostriction, the Joule effect describes the
utes and could be easily removed and recovered from change in length due to a change in the magnetization
the water surface by an external magnet. Olsson et al. state of the material. Consequently, the magnetic field
were able to make magnetic aerogels and nanopaper can be used to actuate or morph the flexible MNM.
using cellulose nanofibrils as templates by facilitat- Whereas through the inverse magnetostrictive effect
ing the growth of ferromagnetic cobalt ferrite nano- (also known as the Villari effect), the mechanical stress
particles [112]. The nanocellulose is then compacted will change the magnetic susceptibility of a material.
to make stiff magnetic nanopaper. The nanofibrils Since the film is expected to respond to changes in the
act as templates for the ferromagnetic nanoparticles. external mechanical stresses by changing its magnetic
Their flexibility, high porosity and surface area make state, these changes in the magnetic state can induce
them attractive for use in microfluidics or electronic voltage in coil(s) in accordance with Faraday’s law,
actuators. Researchers have also shown the ability to which can then be readily used to deliver power to an
306 J. Renew. Mater., Vol. 4, No. 5, October 2016 © 2016 Scrivener Publishing LLC
DOI: 10.7569/JRM.2016.634114 Ronald Sabo et al.: Nanocellulose-Enabled Electronics, Energy Harvesting Devices, Sensors: A Review
electrical load. Moreover, a magnetic field can be used to Testing of the composite was performed via a video
optimize magnetostrictive properties of the composite extensometry method, using DC magnetic fields inside
by favorably aligning particles [130–133] during the pro- a laboratory electromagnet to actuate the sample. The
cessing stage (Figure 11). Figure 12 shows a unimorph magnet was placed atop a damped optics table to
nanocellulose composite that is actuated by a magnetic eliminate random vibrations from the environment.
field and the Joule effect. The magnetic field is cycled An optical microscope (Stemi 2000-C, Carl Zeiss AG,
from 0 to 2 kOe and back down in 200 Oe increments. Germany) equipped with a digital camera (AxioCam
The composite material fabrication procedure gen- ICc 1, Carl Zeiss AG, Germany) was mounted to the
erally followed the CNF preparation procedure dis- electromagnet for the purpose of non-contact displace-
cussed in earlier literature [134], with additional steps ment measurement. A black and white grating pattern
for introducing Terfenol-D particles. Filtration was was painted at the tip of both edges of the particle-
carried out until approximately 80% of the water by containing sample. The sample was then cantilevered
volume was removed from the composite. An identi- within the center of the electromagnet air gap, with
cal volume of CNF slurry was then added atop the par- length direction along the central axis of the pole
tially filtered layer, this time without any Terfenol-D pieces. Ten cycles of a low frequency AC magnetic
particles. This was done to create a unimorph struc- field were applied to the sample in order to relax any
ture which would allow the material to bend instead residual stresses introduced during the mounting pro-
of linearly deforming under an applied magnetic field. cedure. DC current was supplied to the electromagnet
Filtration was again carried out until approximately such that the magnetic field strength incremented by
80% water was removed from the material. At this 200 Oe, completing a full loop between −2 kOe and
point, the sample was removed from the filtration ves- 2 kOe. An optical microscope image of the sample
sel, and sandwiched between two sheets of wax paper was captured at each increment. The image sequence
with absorptive pads on either side. The stack was obtained was then converted to a video file, and the
then pressed at 100 N for 24 hours while sitting atop a angular displacement of the sample as a function of
layer of silica gel desiccant which drew out remaining magnetic field strength was extracted by tracking the
water. painted-on grating with open source video analysis
software (Tracker). The process was repeated with the
sample flipped over in its holder, and its other edge
in view of the microscope. A total of five trials were
performed for each sample at each orientation. Images
of a sample with grating being analyzed in Tracker can
be seen in Figure 12.
Figure 13 shows the angular deflection data for a
30% volume fraction Terfenol-D/CNF unimorph com-
posite film compared with a control sample contain-
ing an equal volume of non-magnetostrictive grade
10 mm
68 ferrite particles. In addition to lacking appreciable
magnetostrictive properties, the 68 ferrite has com-
Figure 11 Nanocelllulose membranes with magnetostrictive parable initial DC magnetic permeability to that of
materials (top: random and bottom: aligned). Terfenol-D. As such, the control sample experiences
Figure 12 Angular deflection data being extracted from microscope images of samples during testing.
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0.1
cal haze, low thermal expansion coefficient and good
0.05
mechanical properties, thus offering some advantages
0
over traditional materials, such as thermoplastics. As
–0.05
the economics and availability improve, these nano-
–0.1
materials are expected to find a variety of commercial
–0.15
applications in functional devices.
–0.2
–0.25
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