Journal of Advanced Manufacturing Technology (JAMT)

EFFECT OF ZIRCONIUM SILICATE CONTENT ON DIELECTRIC

AND MECHANICAL PROPERTIES OF POLYURETHANE
ELASTOMER

M.N.M. Zaharin1, K.Z. Ku Ahmad1*, R. N. Othman1, R. Yahaya2 and

Mou'ad A. Tarawneh3

1 Engineering Faculty, Universiti Pertahanan Nasional Malaysia, Malaysia.

2 Science and Technology Research Institute of Defense (STRIDE), Malaysia.

3 College of Science, Al-Hussein Bin Talal University, Ma'an, Jordan.

*Corresponding Author’s Email: [email protected]

Article History: Received 14 December 2022; Revised 22 July 2023;

Accepted 5 August 2023

©2023 M.N.M. Zaharin et al. Published by Penerbit Universiti Teknikal Malaysia Melaka. This is an
open article under the CC-BY-NC-ND license (https://creativecommons.org/licenses/by-nc-nd/4.0/).

ABSTRACT: Polyurethane (PU) is an interesting polymer that possesses

excellent high dielectric permittivity, low dielectric loss, and great flexibility,
which makes it promising to be applied as a dielectric elastomer generator
(DEG). However, enhancement in terms of dielectric permittivity is still
necessary to ensure PU practicability in the industry. On the other hand, while
holding the potential to considerably enhance polymer dielectric properties,
the investigation of zirconium silicate (ZrSiO4) as a nanofiller for DE
composites remains insufficient. In this paper, ZrSiO4 was incorporated with
PU matrix to study the impact of ZrSiO4 nanofillers on PU composite
dielectric, chemical, mechanical and morphology properties. ZrSiO4
nanofillers and PU matrix were synthesized through the melt-mixing method
at various weight percentages (10 wt.%, 20 wt.%, 30 wt.%, 40 wt.%, and 50
wt.%). Fourier Transform Infrared Spectroscopy (FTIR) was used to
investigate the chemical characteristic of the composite. The dielectric and
mechanical characterization of the composites was also studied. The results
from FTIR indicate that the ZrSiO4 nanofillers were successfully synthesized
within the PU matrix. Other than that, at 50 wt.% of ZrSiO4, the PU/ ZrSiO4
recorded dielectric permittivity up to 12.07 (33.5% higher than pristine PU)
while maintaining low dielectric loss and low conductivity. The ultimate
tensile stress and elongation at the break of the PU composites were affected
by the increment of ZrSiO4 contents but they still maintained excellent
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mechanical attributes. These PU/ZrSiO4 composites have the potential to be

used as dielectric elastomers in the DEG application.

KEYWORDS: Polyurethane, Dielectric elastomer, Zirconium Silicate, Electrical

properties, Polymer matrix composites

1.0 IN TROD UCTIO N

DE is a type of electroactive polymer (EAP) that exhibits deformation
with the presence of an electric field. It possesses superiorities such as
lightweight, large deformation, high energy density, rapid response,
and ease of processing [1]. It can convert electrical energy into
mechanical energy, and vice versa, making it suitable to be applied as
both an actuator and a generator. The capacitive of DE is changeable,
by manipulating the dielectric permittivity and mechanical properties
of the elastomer, as shown in Eq. 1. In that equation, 𝜺𝒐 represents
permittivity of free space, 𝜺𝒓 represents dielectric permittivity of the
material, A represents the elastomer surface area and z represents the
elastomer thickness.

A
C=ε o ε r (1)
Z

One of the applications of DE is a dielectric elastomer generator (DEG),

where the elastomer converts the oscillating mechanical power into
usable electrical energy, identical to piezoelectric energy harvesting
concept [2]. The working principle of DEG is illustrated in Figure 1 and
described in Table 1 [3]. Based on the working principle, it is
understandable that the performance of DEG relies on the dielectric
and mechanical properties of the elastomer. The DEG needs to possess
high dielectric permittivity, and also high elongation at break in order
to harvest high electrical energy. The net amount of harvested energy
can be calculated using Eq. 2, where U represents the harvested energy,
C represents the capacitance of the elastomer, V represents the induced
voltage, and 1 and 2 represent the relaxed and stretched states,
respectively.

1 1
U= C2 V22 - C1V12 (2)
2 2
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Figure 1: Illustration of DEG working principle [3]

Table 1: Description of DEG working principle [3]

Phase Description
Phase 1 In its initial state (A), the DEG is at rest with minimal capacitance. When
(P1) subjected to external forces, it elongates and transitions to a stretched condition
(B), resulting in maximum capacitance. There is an absence of charge on the
DEG throughout this process.
Phase 2 The deposition of charge, Q onto the electrodes causes the DEG to enter a
(P2) charged state (C), characterized by the same capacitance as state (B). This stage
is referred to as "priming," and it entails expending an amount of electrical
energy to charge the device.
Phase 3 While maintaining a constant charge on the DEG, the interaction between
(P3) external forces and the elastic stress within the DEG counteracts the
electrostatic charge. This process leads the DEG to revert to a state (D)
characterized by the minimum capacitance, Cmin. Throughout this phase of
generation, the external forces are transformed into electrostatic energy, which
is then stored within the electric field of the DEG.
Phase 4 Ultimately, the DEG is stabilized in a setup with the lowest capacitance and
(P4) subsequently discharged, allowing for the extraction of the accumulated
electrostatic energy. The overall quantity of generated electrical energy is
determined by the disparity between the energy recouped during the
discharging stage (P4) and the energy invested during the priming phase (P1).

The industry's capacity to use dielectric elastomers is still up for debate.

Because of this, much research has been done over the years in the areas
of material synthesis and optimization to create a DE that can meet the
demands of the application. Researchers have often employed
polymers with functionalized nanofiller to develop dielectric
elastomers in order to accomplish specific objectives like high dielectric
permittivity, superior breakdown strength, high actuation strain, etc.
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to various applications [4–6].

Of late, researchers have investigated a few methods to enhance the

dielectric properties of DE. One of the methods is by incorporating
ceramics fillers into the polymer matrix. This type of filler usually
possesses high dielectric permittivity, which provides it with the ability
to enhance the dielectric permittivity of the elastomer [7]. PU possesses
high dielectric permittivity (~8) compare to other polymer such as
acrylic or silicone rubber. However, the dielectric constant of PU
elastomer is still necessary to ensure its practicality with industry
applications [8]. ZrSiO4 possesses high dielectric permittivity and it is
abundant, making it a very cost-effective filler to be used to enhance
polymer dielectric constant [9]. Despite its potential to significantly
enhance polymer dielectric properties, the study of ZrSiO4 as a
nanofiller for DE composites remains inadequate.

This study cooperates polyurethane (PU) matrix and zirconia silicate

(ZrSiO4) to study the impact of ZrSiO4 on PU composite’s properties.
The preparation of PU/ZrSiO4 elastomer is described in this paper. The
morphology, dielectric and mechanical properties of the PU/ZrSiO 4
composite were investigated and analyzed for DEG application.

2.0 MATERIALS AND METHODS

2.1 Materials

The polyurethane (PU) granules, Zirconia (IV) Silicate (ZrSiO4)

powder, and N-methyl-2-pyrrolidone (NMP) solvent were acquired
from Sigma-Aldrich and used without further purification.

2.2 Preparation of the PU/ZrSiO4 composites

The desired amount of ZrSiO4 nanoparticles (refer Table 2) was
dispersed in 100 mL of NMP under sonication for 30 minutes,
followed by adding 15g of PU and stirring the mixture mechanically
for three hours at 150 rpm and 140ᵒC. The mixture was poured into
the glass mold and dried in an 80ᵒC oven for 16 hours to eliminate all
solvents. All the casted films then were removed from the mold. The
films were then labelled as PU/ ZrSiO4-x, where x represents the
weight percentage of ZrSiO4 nanoparticles.
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Table 2: Amount of material used for each sample

Material PU/ZrSiO4- PU/ZrSiO4- PU/ZrSiO4-- PU/ZrSiO4- PU/ZrSiO4-
10wt.% 20wt.% 30wt.% 40wt.% 50wt.%
PU 15g 15g 15g 15g 15g

ZrSiO4 1.5g 3g 4.5g 6g 7.5g

2.2 Characterization of Dielectric and Mechanical Properties

The composition of the PU, ZrSiO4 and PU/ZrSiO4-50wt.% composite
was characterized using FTIR at spectra between 4000 and 400 cm−1.
The dielectric properties of the composites at different weight
percentage of ZrSiO4 were measured using an impedance analyzer
(4294A, Agilent Technologies) in a frequency range of 30 Hz to 120
MHz at room temperature. The mechanical properties of the
composite at different weight percentage of ZrSiO 4 were tested
through a tensile test using Instron Universal Testing Machine
according to ISO 37:2017 standard. The microstructural of PU/ZrSiO 4-
20wt.% and PU/ZrSiO4-50wt.% composites were characterized by
high resolution field emission scanning electron microscope solutions
(FESEM) (ZEISS GeminiSEM 500) and the elemental composition of
both composites were mapped using Energy Dispersive X-Ray
analysis (EDX).

3.0 RESULTS AND DISCUSSION

Figure 2 displays the FTIR spectra of PU, ZrSiO4, and PU/ZrSiO4-

50wt.%. The absorbance observed around ~3335 cm–1 aligns with the
NH bond stretching, indicative of the urethane and urea groups.
Additional distinctive bands are observed: around ~2900 cm–1
corresponding to the alkane -CH stretching vibration, at 1174 cm–1
reflecting the coupled C-N and C-O stretching vibrations, and at 1062
cm–1 attributed to the symmetric stretching vibration of the ester C-O-
C [10]. The spectral peaks at approximately ~431 and ~860 cm-1,
evident in the ZrSiO4 nanoparticles spectrum, can be associated with
the asymmetric bending vibration and stretching vibration of Si−O−Si
bonds, respectively. Furthermore, the peak at around ~650 cm-1 is
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attributable to the Zr–O stretching vibrations [11], [12]. The presence

of these bands in PU/ ZrSiO4 composite indicates that the ZrSiO4
nanofillers are well dispersed in the PU matrix. All characteristic
peaks are summarized in Table 3. There is no new band or peak
presence in any composite samples, indicating there was no chemical
reaction between PU and ZrSiO4.

Figure 2: FTIR spectra of PU, ZrSiO4 nanofillers and PU/ZrSiO4-50 wt.%

composite

Table 3: FTIR characteristic band of PU, ZrSiO4 and PU/ZrSiO4-50 wt.%

composite
Frequency (cm-1) Assignment

3050-3750 NH stretching vibration

2800-3000 CH stretching vibration: anti-symmetric and symmetric stretching

vibration mode
1600-1800 Amide I: C=O stretching vibration

1500-1540 Amide II: C-N stretching

1200-1289 Amide III: in-plane N-H formation

1070-1074 C-N stretch

860 Stretching vibration of Si−O−Si

650 Zr–O stretching vibrations

431 Bending vibration of Si−O−Si

Figure 3 presents the dielectric constant of PU/ ZrSiO4 composites at

various weight percentages. The dielectric behavior of all composites
suggests a frequency dependence of dielectric constant values, as the
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dielectric constant of all composites decreases with the increment of

frequency. All composites displayed significant improvement in
dielectric constant compared to conventional PU. The dielectric
constant of the composite increase with the increment of ZrSiO4
content, which similar trend was reported in other literature [13].
This increase in permittivity can be attributed to both the high
permittivity of ZrSiO4 nanoparticles and the interfacial polarization
between the nanoparticles and the PU matrix. As the ZrSiO4 content
increases, the inherent high permittivity of the filler increasingly
impacts the overall permittivity of the composites. Additionally, the
dielectric constant of the filled elastomer is strongly influenced by
interfacial polarization at the interface between PU and the ZrSiO4
nanoparticles, resulting in higher permittivity at low frequencies as
ZrSiO4 loading concentration increases.

Figure 3: Dielectric permittivity of PU/ZrSiO4 composite at different weight

percentages and frequencies

Figure 4 presents the dielectric losses for the PU/ ZrSiO4 elastomer at
different ZrSiO4 content. Notably, all composites exhibit lower dielectric
loss values than the pure PU matrix, even at high ZrSiO4 loadings. The
composite with 50 wt.% of ZrSiO4 demonstrated a particularly
impressive dielectric loss of just 0.03 at 1 kHz, which is even lower than
the dielectric loss of the pure PU matrix (0.05). This reduction in
dielectric loss may be attributed to the insulative characteristics of
ceramic materials found in ZrSiO4, which limit current leakage and
therefore influence the dielectric loss of the composite. Figure 5 displays
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the conductivity of the PU/ ZrSiO4 composite at various weight

percentages. The conductivity of the composites is lower than that of
the pure PU elastomer. Increasing the content of ZrSiO4 did not
significantly impact the conductivity of the elastomer, as the
conductivity remained low even at high ZrSiO4 content. This suggests
that no conducting network was formed, indicating an insulation
structure for this PU/ ZrSiO4 composite film. The insulative
characteristics of the ceramic materials found in ZrSiO4 are
responsible for limiting current leakage and reducing the
conductivity of the composite [14].

Figure 4: Dielectric loss of PU/ ZrSiO4 composite at different weight

percentages and frequencies

Figure 5: Conductivity of PU/ZrSiO4 composite at different weight

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percentages and frequencies

The mechanical properties of the elastomer have a vital influence on

mechano-electrical energy conversion. Figure 6(a) shows the ultimate
tensile stress of PU and PU/ZrSiO4 composites. By increasing the ZrSiO4
filler content to 20 wt.%, the tensile strength also increased due to
particle enhancement. At 20 wt.% of ZrSiO4, the tensile stress of the
composite reaches 6.74 MPa, which is a 122% increment. The
enhancement in tensile strength is credited to the favorable interaction
between the PU matrix and ZrSiO4 fillers, which facilitates efficient
stress transfer. The achievement of notable tensile strength relies
significantly on the effective and consistent distribution of stress [15].
However, when the ZrSiO4 content increases from 30 wt.% and above,
the tensile strength decreases. This is due to the agglomeration of ZrSiO4
filler within the PU matrix. It creates voids and acts as a flaw that limits
tensile strength, as experienced in other literature [16]. On the other
hand, the elongation of breaks of all elastomers was also investigated.
Figure 6(b) shows the elongation at breaks of PU and PU/ZrSiO4
composites. The findings demonstrate a decrease in elongation at break
as the ZrSiO4 content increases, signifying a transition in the PU matrix
from a ductile material to a composite material with increased
brittleness. However, even at 50 wt.% of ZrSiO4 content, the composite
still possesses high elongation at 587%.

(a) (b)
Figure 6 Mechanical characteristics of PU/ZrSiO4 composites (a) ultimate
tensile stress, (b) elongation at the break

The dispersion state of the ZrSiO4 nanofillers within the PU matrix was
further confirmed with FESEM images, as shown in Figure 8 (a-b).
Figure 8(a) confirmed that the ZrSiO4 nanofillers in PU/ZrSiO4-20 wt.%
nanocomposite exhibit a more well-dispersed state where less
agglomeration of nanofillers was observed, compared to PU/ZrSiO4-50
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wt.% nanocomposite in figure 8(b). The agglomeration of nanofillers

provides a stress concentration effect and reduces the tensile strength of
nanocomposite [17]. Other than that, the agglomeration nucleates voids
and accelerates the propagation of internal cracks, causing the reduction
of ductility, as reported in other literature [18]. These explained the
differences in tensile strength and elongation capability between
PU/ZrSiO4-20 wt.% and PU/ZrSiO4-50 wt.% nanocomposite. Further
investigation using EDX analysis in Figure 9 (a-f) shows the dispersion
of ZrSiO4 nanofillers within the PU matrix. It is proven that the ZrSiO 4
nanofillers in PU/ZrSiO4-20 wt.% nanocomposite dispersed better
compare to PU/ZrSiO4-20 wt.% nanocomposite, where agglomeration of
nanofillers were presented.

(a) (b)
Figure 7 FESEM images of composite: (a) PU/ZrSiO4-20 wt.%; (b) PU/ZrSiO4-
50 wt.% (red arrows indicate the location of ZrSiO4 agglomerate).
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(a) (b) (c)

(d) (e) (f)

Figure 8 Nanocomposite EDX Mapping:
(a) FESEM: PU/ZrSiO4-20 wt.% (b) Zr Mapping: PU/ZrSiO4-20 wt.%
(c) Si Mapping: PU/ZrSiO4-20 wt.% (d) FESEM: PU/ZrSiO4-50 wt.%
(e) Zr Mapping: PU/ZrSiO4-50 wt.% (f) Si Mapping: PU/ZrSiO4-50 wt.%

4.0 CO N C L U S ION
This study has successfully incorporated ZrSiO4 with PU matrix, as
demonstrated by the FTIR characterization. The presence of ZrSiO4
helps in increasing the interfacial polarization with the PU matrix,
which directly increases the dielectric permittivity of PU/ZrSiO4
composites up to ~12 at 1 kHz (50% of enhancement compare to pure
PU). Interestingly, the dielectric loss and the conductivity remain low
(< 0.1), even at high ZrSiO4 content. The mechanical characterization
shows that the elongation of the composite deteriorates with the
presence of ZrSiO4 contents, but it still possesses high flexibility. The
PU/ZrSiO4 nanocomposite has promising potential for applications in
the energy harvesting industry using elastomer, which requires high
energy storage capability, low losses, and excellent flexibility.

ACKNOWLEDGMENTS
The authors would like to thank the Ministry of Higher Education
Malaysia and the National Defense University Malaysia for providing
financial support under FRGS/1/2020/TK0/UPNM/02/10.
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AUTHOR CONTRIBUTIONS

M.N.M. Zaharin: Conceptualization, Methodology, Data Curation

Writing-Original Draft Preparation; K.Z. Ku Ahmad:
Conceptualization, Methodology, Validation, Supervision, Writing-
Reviewing and Editing; R. N. Othman: Data Curation, Writing-
Original Draft Preparation, Writing-Reviewing and Editing; R. Yahaya:
Validation, Supervision; Mou'ad A. Tarawneh: Validation, Supervision

CONFLICTS OF INTEREST

The manuscript has not been published elsewhere and is not under
consideration by other journals. All authors have approved the review,
agree with its submission and declare no conflict of interest on the
manuscript.

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