Proceedings of the ASME 2018

Conference on Smart Materials, Adaptive Structures and Intelligent Systems

SMASIS2018
September 10-12, 2018, San Antonio, TX, USA

SMASIS2018-8093

ENERGY HARVESTING PERFORMANCE OF PRINTED BARIUM TITANATE

NANOCOMPOSITES
†
Mohammad H. Malakooti Florian Julé Henry A. Sodano*
Aerospace Engineering Department Aerospace Engineering Department Aerospace Engineering Department
University of Michigan University of Michigan University of Michigan
Ann Arbor, Michigan, USA Ann Arbor, Michigan, USA Ann Arbor, Michigan, USA

*Phone: +1(734)763-6728, Email:hsodano@umich.edu

ABSTRACT Many researchers have studied different combinations of

Development of nanostructured devices for sensing, energy
storage, actuating, and energy harvesting has attracted many
researchers. The most common type of functional
nanostructures is piezoelectric nanomaterials. Regardless of
numerous studies in this area, there is a need for rapid
fabrication of nanostructured devices, or simply functional
nanocomposites. Here we present a simple, scalable
fabrication technique for additive manufacturing of
nanocomposite energy harvesting devices composed of barium
titanate nanowires. Details on hydrothermal synthesis of
barium titanate (BaTiO3) nanowires and printable inks,
manufacturing process, and energy harvesting performance of
the printed devices are presented here. The experimental
results suggest that additive manufacturing of functional
nanocomposites allows controlling the microstructures and
enhancing device performance.
INTRODUCTION
Various types of monolithic piezoelectric materials with
high electromechanical coupling such as PbZrxTi1−xO3 (PZT)
and Pb(Mg1/3 Nb2/3 O3)1-x(PbTiO3)x (PMN-PT) have been
usually employed to convert ambient mechanical energy to
electrical power in microsystems called piezoelectric energy
harvesters [1-7]. Regardless of the high electromechanical
coupling in these materials, the brittle nature and extremely low
flexibility of these piezoceramics have considerably limited the
real life application of this class of smart materials.
Therefore, nanocomposites and multiscale fiber reinforced
composited consist of nanostructured piezoceramics have been
recently deployed to provide sufficient electromechanical
coupling in addition to either high flexibility or high structural
integrity [8-13]. It appears that nanocomposite devices are
one of the suitable replacements for monolithic piezoceramics
which lack sufficient mechanical flexibility.
†
Current affiliation: Mechanical Engineering Department, Carnegie
Mellon University, Pittsburgh, Pennsylvania, USA
active fillers (usually micro and/ nanostructure materials) and
polymer matrices in order to develop high performance
functional nanocomposites that can withstand mechanical
distributions for a long period of time. In recent studies, it has
been established that the functional performance of the
piezoelectric/ferroelectric nanocomposites for various types of
devices such as sensors, actuators, and energy harvesters is
directly dependent on their microstructure properties in addition
to the intrinsic electromechanical coupling coefficient of the
active phase embedded in the polymer matrix. Through
comprehensive research efforts, Sodano et al. have
demonstrated that the electromechanical response of the active
nanocomposites is governed by both the morphology and the
arrangement of nanofillers in polymer matrices [13-18].
Although, the influence of nanofiller orientation and role of
nanomaterials morphology is already stablished, there is a lack
of rapid fabrication technique for production of the functional
nanocomposites.
In this paper, we introduce a simple additive manufacturing
method for fabrication of energy harvesting nanocomposites
tailoring the arrangement of piezoelectric nanofillers in a
polymer matrix. The active energy harvesting units in the
nanocomposites are high aspect ratio barium titanate (BaTiO3)
nanowires. Although spherical nanoparticle can also be used
in this fabrication technique, the one dimensional nanomaterials
(e.g. nanowires, nanorods, etc.) usually demonstrate higher
electromechanical coupling [9]. The matrix of the
nanocomposite here is chosen to be polylactic acid (PLA) due
to its favorable physical properties suitable for extrusion,
direct-write and fused filament fabrication methods. The
materials characterization of BTO nanowires and printed
nanocomposites are studied with scanning electron microscopy
while the energy harvesting performance of these devices is
examined through electromechanical testing.

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 MATERIALS AND METHODS not limited to nanocomposites and can be used for fabrication
of other piezoelectric materials. In a previous study, we
Nanowires Synthesis
utilized the custom-built 3D printer (shown in Figure 1a) for
BaTiO3 nanowires were synthesized using a two-step 3D printing of polyvinylidene fluoride (PVDF) polymer
hydrothermal reaction which was initially developed by Tang et actuator with possible applications in the development of
al. [14, 19, 20]. In the first reaction, relatively high aspect morphing trailing edge flap systems [23]. In this study we
ratio sodium titanate nanowires were synthesized in a closed used the printer for direct-write fabrication of nanocomposites.
reactor with a Teflon liner. 1.88 g of anatase titanium dioxide As shown in Figure 1b, six specimens of the energy harvesters
powder is mixed with 91 ml of a 10M sodium hydroxide DI in beam configuration are fabricated using. The print
water solution. Then, the prepared solution is sealed in a steel direction along the axis of the beam is clearly observable in
autoclave and heated in an oven at 200 °C for 24 hours. Next, these samples. Due to the presence of the shear forces in the
the product of this reaction which is sodium titanate nanowires nozzle of the syringe barrels, it is expected that the embedded
are soaked in a very dilute hydrochloric acid solution (about high aspect ratio BaTiO3 nanowires become aligned along the
0.2M concentraion) for 4 hours to form the final products of the print direction. Since the textured surface of the printed
first step, hydrogen titanate (H2Ti3O7) nanowires. Then, the specimen simply shows the print direction, scanning electron
H2Ti3O7 nanowires are washed multiple times with water using microscopy is used to identify the dominant alignment
centrifugation and vortex mixing. After drying this powder, orientation of the nanowires.
they are used in the second step of this synthesis. In the
second hydrothermal reaction, the H2Ti3O7 nanowires are
converted to BaTiO3 nanowires. First, the H2Ti3O7 NWs are
dispersed in barium hydroxide octahydrate solution
(Ba(OH)28H2O). After bath sonication of the solution, it is
transferred to another Teflon liner and sealed in stainless steel
reactor and kept at 210 °C for 120 min. After completing this
hydrothermal process, the precipitate was collected and washed
with diluted HCl aqueous solution. The BaTiO3 nanowires
with a powder-like appearance are obtained after additional
washing and drying steps upon completion of the second
hydrothermal reaction. It should be mentioned that based on
the reaction parameters, such as time, temperature, and solution
concentration, the morphology of the synthesized nanowires
can be controlled. However, the morphology (length and
diameter) of the nanowires does not typically change during the
conversion process.
Nanocomposites Printing
Once the BaTiO3 nanowire powder is prepared, it is
dispersed in a polymer solution to be dispensable using a 3D
printer system. Polylactic acid (PLA) thermoplastic is
selected at the matrix phase of the nanocomposite because of its
favorable physical properties suitable for extrusion, direct-write
and fused filament fabrication methods [21]. The prepared
Figure 1. (a) Custom-built 3D printer for both direct-write and
ink (with 30% weight fraction of nanowires) is printed on glass fused filament fabrication methods of functional materials, (b)
substrates using a custom-built 3D printer as shown in Figure an array of printed nanocomposite energy harvesters directly
1a. The stage and controller in this system is from Aerotech printed on a glass substrate.
and the high precision solution dispenser (Ultimus™ V) is
purchased from Nordson EFD. Both of the systems are
controlled using LabVIEW. In this study, 3D models of a EXPERIMENTAL RESULTS
rectangular energy harvesting device are created in SolidWorks, BaTiO3 Nanowires and Nanocomposites
and then using an open source slicing software, called Slic3r,
The two-step hydrothermal yields large amount of BaTiO3
the printing paths (G-code) is generated. The G-code is
nanowires sufficient for fabrication of 10-12 nanocomposite
directly used as an input to the custom-built LabVIEW program
energy harvesting devices. Figure 2a shows a scanning
to print the BaTiO3/PLA solution in dichloromethane. This
electron microscopy (SEM) image of the synthesized BaTiO3
method is commonly termed as direct-write fabrication method
nanowires. In order to demonstrate the morphology of
suitable for both 2D and 3D printing of nanocomposites [21,
nanowires, the nanowires were dispersed in ethanol then drop
22]. It should be mentioned that this fabrication technique is
casted on a silicon substrate. As seen in this SEM, the

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 diameter of the BaTiO3 nanowires varies between tens of
nanometers to a few microns while their length changes from a
few microns to ~1 micron. Similar wide variation is
observable for the length of the nanowires. As mentioned
earlier, the average length and diameter of nanowires are highly
dependent on the reaction parameters and can be controlled by
varying the time and temperature in the first and second
reaction. Figure 2b illustrates the top view of a printed
BaTiO3 nanocomposite energy harvester. The embedded
BaTiO3 nanowires in the composite can be identified.
However, the low contrast between nanowires and matrix phase
make it difficult to see the individual nanowires. Moreover,
the nanowires are not deposited on the surface of the printed
composite and they are partially exposed which makes it more
challenging to demonstrate the nanowires alignment and study
the microstructural properties of the printed nanocomposites.
In a follow up study, we will utilize image techniques to
quantify the alignment of the nanowires in PLA matrix. The
printing speed, ink viscosity, and needle size affect the level of
nanowire or nanorod alignment in printed nanocomposites.
However, all the printed nanocomposites in this study
composed of BaTiO3 nanowires and PLA matrix showed some
level of orientation along the print direction. In the next step,
we sputtered gold and electrically poled these devices in order
to study their energy harvesting performance.
Energy Harvesting Performance
There are several common characterization techniques
suitable for studying the energy harvesting performance of
devices composed of nanomaterials. One of the most
common methods for characterization of these devices (usually
termed as nanogenerators) is subjecting the nanocomposites
under impact excitations. This type of device characterization
results in high output voltage due to the application of large Figure 2. Scanning electron micrographs: (a) morphology of
mechanical strain on nanomaterials, the measurement is not BaTiO3 nanowires dispersed on a silicon substrate, (b) BaTiO3 -
very reliable due to the unknown mechanical input energy. PLA nanocomposite with aligned nanowires (inset: zoomed in
Although, simple tapping on a piezoelectric energy harvester image with an arrow showing the nanowires).
will produce an electric signal indicating the electromechanical
coupling in these devices, a better approach is needed for study Figure 3 shows the open circuit voltage and short circuit
these miniaturized devices [24]. An alternative is mounting current signals from directly printed BaTiO3 nanocomposites.
an energy harvester in a cantilever configuration on a vibrating The configuration of the specimen under electromechanical
host structure (e.g. shaker). In this way, the input mechanical testing is shown in Figure 3a-inset. The applied tensile
energy can be monitored and correlated to the electrical output. loading is along the dominant orientation of the nanowires
However, this method is mostly suitable for rigid structure which is the longitudinal axis of the nanocomposite. Under
rather than flexible or thin nanocomposites due to their only 0.25% axial strain the nanocomposite shows a high value
nonlinear deformations at high input dynamic accelerations [6, for the open circuit voltage with a peak to peak value of
9, 11, 25]. In this study, we utilized a novel approach for approximately 800 mV with a root-mean-square (RMS) value
characterization of flexible piezoelectric devices. The energy of 290 mV (Figure 3a). The short circuit current response of
harvesting devices were strained using a dynamic mechanical the nanocomposite was also measured under the same
analyzer (DMA). The nanocomposites were subjected to a mechanical loading condition. As shown in Figure 3b, a
controlled applied strain in a DMA (TA instruments Q800) sinusoidal current signal with a peak-to-peak value of ~95 nA
while two electrodes were connected to the conductive surfaces and a root-mean-square value of ~32 nA was captured by
of the nanocomposite. The generated voltage and current electrometer. The harmonic electrical response of the
were measured using an electrometer (Keysight B2985A). nanocomposites is because of the applied 5 hertz sinusoidal
Therefore, the device performance was captured under strain through DMA where the maximum strain was kept
precisely controlled axial tensile loading. constant at 0.25%.

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Figure 3. Electromechanical response of the printed BaTiO3
nanocomposites under 0.25% strain: (a) open circuit voltage
(b) short circuit current. (Inset shows the nanowires
orientation with respect to the applied tensile strain).
This energy harvesting performance of barium titanate
nanocomposites along with their rapid fabrication address
current challenges in transition of nanostructured devices from
development stage into industrial use. Furthermore, the
arrangement of nanostructure within the nanocomposite
governs the electromechanical coefficient as well as
performance of active composites [15, 16], thus it is expected
that the tailored nanocomposites prepared using direct-write
method possess higher energy harvesting efficiency when
compared with cast nanocomposite with randomly distributed
functional nanowires or nanorods. We are currently
investigating this aspect of the 3D printed barium titanate
nanocomposite energy harvesters.
CONCLUSION
In this research it was demonstrated that additive
manufacturing is a feasible, cost-effective, and rapid fabrication
method for development of tailored functional materials and
structures. All the synthesis and fabrication steps consisting
of barium titanate nanowires synthesis, nanocomposite ink
preparation, fabrication through 3D printing, and finalized
device preparation were discussed. Scanning electron
micrographs were used to characterize the diameter and length
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of the synthesized BaTiO3 nanowires as well as the level of
alignment and dispersion of these nanostructures in the printed
nanocomposites. Through electromechanical testing of the
nanocomposites, it was revealed that these piezoelectric
nanocomposites with alignment nanofillers are able to generate
an open circuit voltage with a peak-to-peak value of ~800 mV
and a short circuit current with a peak-to-peak value of ~32 nA
when subjected to a harmonic tensile strain with a maximum
strain of only 0.25%. The well alignment of the nanowires
along the axial direction of the cantilever beam is considered as
the possible reason for the high energy harvesting performance.
Since the proposed manufacturing technique significantly
increases the fabrication speed of nanocomposites, it is
expected that this method enables large scale fabrication of
active nanocomposites with controlled micro-/nanostructured
properties.
ACKNOWLEDGMENTS
This research was supported by the Air Force Office of
Scientific Research under Contract No. FA9550-16-1-0087.
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