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Assessment of Polyurethane Nanofiber with Nikel as

Terahertz Metamaterial and Strain Sensor
2022 12th International Conference on Electrical and Computer Engineering (ICECE) | 979-8-3503-9879-3/22/$31.00 ©2022 IEEE | DOI: 10.1109/ICECE57408.2022.10088932

Morshed Khandaker Sadegh Nikfarjam Hussain Ali Raj Dipannita Ghosh

School of Engineering
University of Central Oklahoma
Edmond, Oklahoma, USA
mkhandaker@uco.edu
School of Engineering
University of Central Oklahoma
Edmond, Oklahoma, USA
snikfarjam@uco.edu
School of Engineering
University of Central Oklahoma
Edmond, Oklahoma, USA
halizereej@uco.edu
Electrical and Computer
Engineering Department
U. of Texas Rio Grande Valley
Edinburg, Texas, USA
Dipannita.ghosh01@utrgv.edu

Nazmul Islam
Electrical and Computer
Engineering Department
U. of Texas Rio Grande Valley
Edinburg, Texas, USA
Nazmul.islam@utrgv.edu
Anis Rahman
Applied Research & Photonics,
Inc
Harrisburg, Pennsylvania, USA
a.rahman@arphotonics.net

Abstract— This study aims to develop mechanical tunable
metamaterials operating at wideband terahertz frequencies (up to
30 THz) for mapping strain in opaque composite materials. This
study has produced thermoplastic polyurethane (TPU) nanofiber
matrix with nickel nanoparticle (TPU-Ni) using electrospun
nanofiber technology. We have characterized the morphological,
electrochemical, and mechanical properties of produced TPU-Ni
composite. We also measured the response of the T-ray wave of
TPU-Ni as a function of strain by applying a stretching force to the
composite using a T-ray time-domain spectroscopy. Scanning
electron microscopy image with EDS analysis confirms the
embedding of Ni nanoparticles with the polymer matrix. Cyclic
voltammetry tests on TPU-Ni nanofiber measured a current peak
for the applied voltage. Pull-out tension tests found that the TPU-
Ni polymer matrix is flexible and has sufficient strength to be used
as a sensing material for highly sensitive strain gauge applications.
THz reflected intensity as a function of a strain of TPU-Ni for five
repeated reversal loading cycles shows fully recoverable strain in
repeated load cycles. This study concluded that the TPU-Ni
composite has the potential to be used for flexible terahertz
metamaterial-based sensor applications.
Keywords—Electrospun nanofiber, Metamaterial,
nanoparticle, Strain Sensor, Tera Hertz
I. INTRODUCTION
Composite materials are widely used in military, airplane,
and other industrial engineering sectors, which has created a
need for tools to monitor their structural health and warn of
incipient failure. Several techniques have been tried for mapping
strain fields in visually opaque structural composites, including
embedded sensors, laser surface mapping, acoustic transducers,
X-ray imaging, and terahertz imaging concepts. [1] Because
many of the above techniques fail to satisfy simultaneous
constraints of high sensitivity, reduced complexity, and cost-
effectiveness, significant interest remains in the industry for
innovative strategies that can image the spatial distribution of
strain resulting from the loading in composite materials.[2] The
traditional optical polarimetric techniques for measuring
photoelasticity are problematic due to composite material's
opacity. It is challenging to map the strain field as stress-induced
birefringence produces weak refractive index anisotropies at
terahertz frequencies.[3] Many of the above techniques can
identify damaged regions at the composite material interface.
Still, none can recover evidence of prior incidents that may
precipitate future composite failure if the local stress exceeds a
critical threshold [2]
A terahertz metamaterial is a class of composite
metamaterials produced to operate at terahertz (THz)
frequencies [4]. There is a need to develop terahertz
metamaterial laminates adhered onto or embedded within an
opaque composite host, whose polarimetric response is sensitive
to the local strain and may be mapped in reflection (preferable)
or transmission geometries. There are two types of
metamaterials that are currently being researched. The first type
includes those with permanently severable break junctions for
quantitatively recovering the amount of strain experienced
historically. The second type includes those that are reversibly
Nickel deformable for quantitatively recovering the amount of strain
experienced by the composite relative to time. Nanofiber-based
metamaterials belong to the second type.
The importance of strain gauges is very evident in the
engineering field and its various sub-disciplines. Among many
use, polyurethane can be utilized as a sealant or coating for
materials. For example, polyurethane adhesives can provide
strong bonding advantages, while polyurethane sealants provide
tighter seals. Furthermore, they carry a high recovery when
experiencing stress as well as resistance to many environmental
factors. In this study, the use of thermoplastic polyurethane
(TPU) nanofiber is investigated for its relevance and usage in
strain gauges.
This study will deliver a flexible electronics fabrication process
to produce a new mechanically tunable terahertz metamaterial

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sensing device. This study utilized electromagnetic device
design using electrospun nanofiber technology. In addition, this
study will evaluate the strain characteristics of the composite
that can operate at terahertz frequencies. The composite material
can be used for mapping strain fields within opaque composite
materials by using a terahertz-frequency metamaterial made of
electrospun membrane with nanoparticles (TPU-Ni). Here, Ni
nanoparticles will be used as a conductive material to improve
the electrical and THz optical characteristics of TPU.
II. METHODS
A. Materials
Thermoplastic polyurethane (TPU), dimethylformamide
(DMF), tetrahydrofuran (THF), and Nickel nanoparticles (<100
nm) will be purchased from Sigma Aldrich. Polypropylene (PP)
was used as a laminated film for protecting the cloth during
mechanical tests. PP was purchased from www.uline.com..
B. Sample preparation
DMF and THF were mixed at the volume ratio of 5:5. Then,
the same amount of TPU was added to the mixture to prepare a
solution at a concentration of 5% for electrospun fiber mat
production. A 0.1% wt of Ni nanopowder was added to the
solution. The mixture was stirred using a magnetic bar for 24
hours. Random TPU/Ni nanofibers were prepared using the
method presented in Khandaker et al. [5] (Fig. 1a). In short, TPU
fiber solution was ejected from the infusion pump glass syringe
via a charged needle. The fibers were deposited on a grounded
custom-made drum collector (Fig. 1b) that is mounted on a
linear stage. The needle was charged by a high voltage power
source (Gamma High Voltage Research, Inc., model # ES 30
series). The applied voltage of the electrospinning setup for the
nanofiber production will be 18 kV. The tip-to-collector distance
was 15 cm. The solution feeding rate was set at one mL/h. All
samples were prepared at room temperature. The nanofiber
meshes obtained from electrospinning were dried in the drum
collector, as seen in Fig. 1b, for 48 h to remove the residual
organic solvent. A razor blade was used to cut a 10 mm width
by 100 mm long piece from a bigger dimension cloth (Fig. 1c).
(c)
Fig. 1. (a) Schematic to produce nanofiber matrix using
electrospun technology. (b) A nanofiber machine to produce Ni-
embedded thermoplastic polyurethane (TPU) nanofiber matrix
on drum collector. (c) A cut TPU-Ni sample from the drum
collector.
C. Experiments
C.1 Morphology Characterization
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117
The surface structure and morphology of the present TPU-
Ni nanofiber composite mat were studied by field emission
scanning electron microscope (Zeiss Neon 40 EsB). The
samples were sputter-coated with approximately 5-6 nm of
AuPd. SEM images were taken at 5 kV using SE2 detector and
in-lens images were captured. The samples were coated with ~4
nm of iridium for Energy-dispersive X-ray spectroscopy (EDS)
analysis to make them conductive enough for high-resolution
imaging without significantly charging of the samples.
C.2. Mechanical properties
This study used a CellScale UniVert biomaterials testing
machine (Waterloo, On-tario, Canada) to evaluate the
mechanical properties of TPU-Ni nanofibers under tensile
loading. Three samples were prepared from a 15 cm × 20 cm
piece of TPU-Ni cloths extracted from the drum according to
ASTM D638 standard plastic specimen. Fig. 2 shows the
prepared sample under pre-tension loading conditions in the
mechanical setup. The dimension of the gauge length section
was 10 mm × 3 mm × 0.025 mm (length × width × thickness).
Each sample was mounted in two clip grippers, and tension tests
were conducted using a 100 N load cell with a 1 mm/min rate
for each test sample. The machine recorded the load and
displacement values from each experiment until the failure of
the samples. The tension modulus (slope of stress-strain curve)
and tensile strength(maximum value of the curve) were
calculated from the stress vs. strain curve.
Fig. 2. A TPU-Ni sample in the clip gripper during the
mechanical tests in CellScale UniVert biomaterials testing
machine.
C.3. Cyclic voltammetry
All the prepared samples were used directly as electrodes for
electrochemical (Cyclic voltammetry) analysis. For
electrochemical sensing, we have utilized an Autolab
Potentiostat. To conduct our experiment, we used a three-probe
setup with TPU-Ni as a working electrode, silver wire as a
counter electrode, and platinum wire as a reference electrode.
We have used 1 mM Fe 2+ /Fe 3+ solutions as a redox couple. For
the cyclic voltammetry method, the scan rate was 0.1 V/sec with
a voltage range of 0.35 V to -0.5 V. The upper current range was
10 mA and the lower current range was 5 mA. The experiment
 118

was conducted at 20˚C room temperature and normal B. Energy-dispersive X-ray spectroscopy (EDS) analysis
atmospheric pressure. EDS spectra and an EDS map are shown in color (Fig 5a)
C.4. THz response under strain and strain mapping and black-white (Fig. 5b) images. EDAX was performed to
analyze qualitatively (element presence and weight percentage)
This study used Applied Research & Photonics, Inc (ARP) the TPU-Ni composite at various locations in the SEM image.
developed terahertz techniques to access T-ray reflection as a Fig 6 reported the analysis value in an arbitrary location. Ni peak
function of strain. The technique and the system for the indicates the presence of Ni on the surface of TPU nanofiber.
assessments based on ARP terahertz scanning reflectometry and
terahertz time-domain spectroscopy are given in detail
elsewhere, see A. Rahman et al. [6]. We have manufactured a
pull-out tension test stage for ARP terahertz scanning
reflectometry (Fig 3a). A 1D motion collector of the system was
connected with the tensile stage center rod and pulled with a
speed of 0.5 mm/sec. The reflected intensity of the specimen
was measured at every 0.1-second interval and plotted against (a) (b)
the calculated strain value. The measured reflectance matrix Fig. 5. SEM images used for EDAX analysis.
termed as the Beer-Lambert reflection (BLR) matrix, is utilized
for generating the surface image or the volume image via ARP's
algorithm for camera-less reconstructive 3D imaging with
respect to the applied strain [7]. ARP's nanoscanner has a
hardware resolution of <24 nm and a synthetic resolution of <1
Å [8-9].

Fig. 6. EDS spectrum of a TPU-Ni sample.

(a) (b) Table 1. Elemental results of the EDAX analysis
Fig 3. (a) A PP laminated TPU-Ni sample on a mechanical Element Atomic % Atomic % Error Weight % Weight % Error
stage, (b) attachment of the mechanical stage on the ARP C 50.2 0.3 20.3 0.1
terahertz scanning reflectometry platform,
N 5.8 0.6 2.7 0.3
III. RESULTS AND DISCUSSION O 8.0 0.3 4.3 0.1

A. Scanning electron microscope analysis Ni 35.7 0.1 70.5 0.1

Fig. 4a illustrates FE-SEM images of TPU-Ni samples. The Ir 0.3 0.0 2.2 0.1
image shows sphere shaped Ni nanoparticles incorporated TPU
nanofiber. The higher magnification images (especially the C. Mechanical properties
35,000x as shown in Fig 4b) showed a smooth and porous The mechanical test results shows a long extension of the
structure. The nanofibers were randomly distributed into a wide sample before catastrophic failure. The calculated average
range of 240-600 nm in a diameter. The morphology of the TPU- tensile strength was 11.17 MPa and elastic modulus was 6.70
Ni composite showed the deposition of particles into the MPa. This result means that the TPU-Ni composition is flexible
nanofibers. Pristine TPU is an insulating polymer. This image and it has the necessary strength for sensor production.
confirms that Ni nanoparticles can be incorporated in TPU 12

nanofiber matrix by direct embeddeing in the nanofiber and

entrapping in the nanofiber matrix. Therefore, our developed 10

process can improve the electrical conductivity of the insulating

material. 8.0
Stress (MPa)

6.0

4.0

2.0

0.0
0.0 0.50 1.0 1.5 2.0 2.5
Strain (mm/mm)

Fig. 4. SEM image of TPU-Ni cloth (a) 1000 x and (b) 35000 x
Fig 7. Stress-strain curve of a TPU-Ni sample..
magnification.

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D. Cyclic voltammetry (CV) analysis
Fig. 8 illustrates current-volt (I-V) graph of cyclic
voltammetry. Pristine TPU nanofiber matrix (not shown in this
study) did not give a current peak difference. TPU-Ni composite
shows a current peak difference. However, the difference was
low. This study used 0.1 wt% of Ni for producing the composite.
The SEM image shows the presence of Ni. Further addition of
Ni to the polymer is required to increase the electric conductivity
of the polymer.
Fig. 8. Cyclic voltammogram of TPU-Ni
E. THz reflection intensity
The reflected intensity of the specimen was measured at
every 0.1-second interval and plotted against the calculated
strain value (Fig 9a). As seen from Fig. 9a (X-axis), the reflected
intensity exhibits decreasing trend as the strain increases. The
fluctuations in the intensity indicate the rise of porosity with the
increase of strain. The fluctuation is higher after 2% of strain.
More photons are escaped via transmission through the porosity,
thus, decreasing the reflected intensity with strain increase. A
clear relation between reflected intensity and % of strain is
visible from this plot. Fig 9b shows the surface of the TPU-Ni
from scanning over an arbitrary area using ARP continuous-
wave T-ray scanning reflectometer (CWTSR) measurement
system. ARP's camera-less imaging algorithm generated the
image of the area. The strain map thus generated is shown in Fig.
9b. The strain map clearly shows the uneven strain produced on
the TPU-Ni.
6
1.2x10
6 [5]
1.0x10
Reflected Intensity (counts)
5
8.0x10
5 Bioelectronics, 2016. 82: p. 64-70.
6.0x10
5
4.0x10
5
2.0x10
0.0
0.0 1.0 2.0 3.0 4.0 5.0
Strain (%)
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119
(b)
Fig. 9. (a) THz reflected intensity as a function of a strain of our designed
laminated metamaterial sensor for five repeated reversal loading cycles.
(b) Strain map of a sensor of metamaterial at 0.5% strain.
IV. CONCLUSION
In this research, the electrical conductivity of non-
conducting thermoplastic polyurethane (TPU) nanofibers was
improved through the embedding of Ni nanoparticles (0.1 wt%)
with the TPU. TPU nanofibers coupled with Ni nanoparticles
were fabricated using electrospun nanofiber technology. Ni
nanoparticle amount is a key parameter for increasing the
electrical conductivity of TPU-Ni since a higher amount of Ni
can be embedded into TPU fiber and entrapped in the nanofiber
matrix. Terahertz scanning spectroscopy analysis revealed that
TPU-Ni has reversibly deformable metamaterial characteristics
and is sensitive to a wide range of strains – down to a fraction of
a percent. Therefore, TPU-Ni can be successfully applied to
biosensors and bioelectronics fields.
ACKNOWLEDGMENT
We thank Preston Larson at Samuel Roberts Noble
Microscopy Laboratory for imaging. Funding for this project
was acquired through the University of Central Oklahoma, the
CURE STEM Program, and the faculty merit Credit award.
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