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org Research Article

Influence of Ferroelectric Filler Size and Clustering on the Electrical

Properties of (Ag−BaTiO3)−PVDF Sub-Percolative Hybrid
Composites
Leontin Padurariu, Nadejda Horchidan,* Cristina Elena Ciomaga, Lavinia Petronela Curecheriu,
Vlad Alexandru Lukacs, Radu Stefan Stirbu, George Stoian, Mihaela Botea, Mihaela Florea,
Valentin Adrian Maraloiu, Lucian Pintilie, Aurelian Rotaru, and Liliana Mitoseriu*
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sı Supporting Information

ABSTRACT: The paper presents a study concerning the role of ferroelectric filler
size and clustering in the dielectric properties of 20%BaTiO3−80%PVDF and of
20% (2%Ag−98%BaTiO3)−PVDF hybrid nanocomposites. By finite element
calculations, it was shown that using fillers with ε > 103 does not provide a
permittivity rise in the composites and the effective dielectric constant tends to
saturate to specific values determined by the filler size and agglomeration degree.
Irrespective of the ferroelectric filler sizes, the addition of metallic ultrafine
nanoparticles (Ag) results in permittivity intensification and the effect is even
stronger if the metallic nanoparticles are connected to a higher degree with the
ferroelectric particles’ surfaces. When using coarse ferroelectric fillers, the
probability of clustering is higher, thus favoring the permittivity increase by
field concentration in small regions close to the interfaces separating dissimilar
materials. The modeling results were validated by an experimental dielectric
analysis performed in a series of PVDF-based thick films with the same amount of BaTiO3 fillers or with Ag−BaTiO3 hybrid fillers.
Similar trends as predicted by simulations were found experimentally but with slightly higher permittivity values which were assigned
to the modifications of the polymer phase composition due to the presence of nanofillers and the local sample inhomogeneity (the
presence of clustering, in particular for coarse BaTiO3 grains), which create regions with enhanced local fields.
KEYWORDS: hybrid nanocomposites, finite element method, Ag−BaTiO3, PVDF, clustering

1. INTRODUCTION ments necessary for applications in electrostatic energy storage

Dielectrics are among the main materials used for realizing are rarely found in pure materials.2 Therefore, a route to fulfil
components for microelectronics or electric power systems both conditions is to find combinations of suitable materials in
devices, such as memories, computer central processing units, composites. In this sense, a wide range of composites based on
polymer matrices ensure flexibility, high insulation (large band
electrooptic and sensing elements, infrared detectors, tunable
gap), and high breakdown fields, filled with high permittivity
capacitors in wireless communications, and so forth. High
complex oxide inclusions; for example, ferroelectrics as BaTiO3
permittivity materials (so-called “high-k”) are characterized by
(BT) and its solid solutions, Pb(Zr, Ti)O3, and so forth have
a superior dielectric constant with respect to the reference
been proposed in the past years.3,4 Polymer−inorganic hybrids
relative permittivity value of ∼3.9 of the archetypical dielectric
produced from solution-based technologies have the advantage
material, SiO2. Such dielectrics are of high interest for
of using a low thermal budget and easy processing steps5 as
eliminating or at least strongly limiting the leakage between
well as the possibility to be implemented in printing
electrodes and ensuring the capacitive coupling of adjacent
technologies,6 providing flexible components and circuits
metals with semiconductors in electronic devices. Among
compliant with non-planar surfaces, easy integration, and low
them, either simple oxides such as HfO2, ZrO2, and Al2O3 or
various types of polymer-based composites are searched to
accomplish the simultaneous requirements for permittivity Received: August 30, 2022
above ∼20, low dielectric losses, and a band gap superior to ∼8 Accepted: January 9, 2023
eV, in order to suppress the leakage charge injection from Published: January 18, 2023
electrodes into the dielectric, which is detrimental to the device
functionality.1 Simultaneous high permittivity and large band
gap combined with effective high breakdown field require-

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ACS Applied Materials & Interfaces
weight. Among the proposed polymer matrices, ferroelectric
PVDF or its copolymers such as P(VDF-TrFE) compounds
are the most studied, due to their ferro-, piezo-, and
pyroelectric character found in specific molecular arrange-
ments, thus being interesting for flexible pressure and
temperature sensors and for their hysteretic polarization
switching properties (memory effect), magnetoelectric proper-
ties when filled with magnetic particles, and so forth.7,8 Higher
permittivity with respect to those of the pure polymers (εr of a
few units) is also required in flexible mechanical or thermal
energy-harvesting applications developed in capacitive config-
urations, in which the device should first store the collected
piezo-, pyro-, or triboelectric generated charges, which is
further used by an external circuit. For both types of
applications, in energy storage and energy conversion/
harvesting, BaTiO3−PVDF flexible composites are the most
frequently proposed materials.9 For such composites, the phase
composition, filler size, shape, or interfaces were engineered by
multistep synthesis methods, thermal treatments, or different
pressing strategies in order to obtain important permittivity
increase for electrostatic energy storage,9−11 superior sensing
properties,12,13 or mechanical−electrical energy-harvesting
capability.14,15
However, in spite of such a large number of publications, it
was noticed that the combination of high permittivity
ferroelectric particles with PVDF polymers did not provide
an outstanding dielectric constant, and storage properties
increase. As an alternative, the use of hybrid fillers (mostly
combining ferroelectric particles with other materials) was
proposed, as BaTiO3 with iron oxide,16,17 functional oxides
with high conductivity metallic NPs (Ag, Au, Pt, Cu),18−22 or
functionalized BaTiO3 fillers, for example, with phosphonic
acid TiO2, polydopamine, graphene, and so forth.13,23,24
To enhance the composites’ functional electrical properties,
a few parameters have been engineered. First of all, the use of
higher-permittivity ferroelectric fillers was expected to
automatically provide a strong permittivity increase. However,
ferroelectricity and the material constants of such nanofillers
(piezo, pyroelectric, and dielectric constants) are scale
dependent; that is, they show a decay when reducing the
physical size of the particles at the nanoscale.25,26 In BaTiO3
and other ferroelectric oxides, besides the intrinsic contribu-
tion, an important component of their permittivity is given by
the domain walls whose density and mobility are also size
dependent and reduce a lot when nanoparticles are ultrafine.
Basically, a large majority of publications concerning this type
of composite mostly refer to the composition-dependent
properties. The role of size-dependent filler’s properties
(BaTiO3 or other ferroelectric oxides) on the effective
composite’s properties was scarcely reported.11,27−31 In these
publications, a dielectric constant increase to about 10−20 was
reported in the radiofrequency range, for compositions below
the percolation limits, that is, for volume filling factor below
25−30%. In surface-treated relaxor ferroelectrics with high
permittivity (PMN-PT filler) embedded into the PVDF matrix,
permittivity increased to a maximum value of ∼60,32 while
higher permittivity values above 100 were reported for over-
percolated BT−PVDF compositions33 or in some specific
multilayer or core−shell fillers designed to enhance interface-
related Maxwell−Wagner dielectric relaxations. Such high
permittivity values, usually reported at low frequencies, are
therefore not intrinsic, and they are usually accompanied by
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high dielectric losses, leakage, and a strong reduction of
breakdown fields.34
For providing further permittivity increase, the addition of
ferroelectric oxide fillers functionalized with metallic nano-
particles and in particular with high conductive materials (e.g.,
noble metals: Ag, Au, and Pt, but also as well as with Ni, Cu, or
carbonaceous species) was also explored in polymer-based
composites. The use of ultrafine noble metal NPs was
supposed to induce peculiar dielectric properties and reduced
conductivity and dielectric losses as a result of the Coulomb
blocking effect.20,35,36 Nevertheless, the use of Ag−BT fillers
provided a permittivity increase in a similar range of values as
with BT or with other ferroelectric fillers only, that is, ε of
about 20−35 for compositions below the percolation
limit,37−39 while higher values exceeding 100 are typical only
to percolated compositions: εr ∼ 160 for f = 56%40 or εr ∼ 250
for f > 50%.41 As pointed out in a recent review,42 permittivity
values of a few hundred (in the range of 200−400) were
reported for noble metal−BT composites in polymer matrices
but only at low frequencies (below 100 Hz), most probably
again produced by slow interface-related Maxwell−Wagner
dispersion mechanisms.
If the role of composition, type, filler permittivity, and their
size or shape43,44 in the dielectric and piezoelectric harvesting
capacity was explored and analyzed in more detail, the
microstructural modifications and in particular the role of
phase connectivity and clustering effects induced by changing
the filler size and filling factor were less discussed in the
literature. The microstructural modifications and their role in
the composite’s functional properties by embedding in PVDF
silver-decorated nano- and micro-BaTiO3 particles were only
recently recognized.22,45 With these above-mentioned consid-
erations, we analyzed in the present paper the modifications of
the dielectric and ferroelectric properties induced by the
presence of small amounts of ultrafine Ag NPs onto BaTiO3
(BT) grain fillers with a variable size in a PVDF matrix. In the
first part of the paper, simulations based on the finite element
method (FEM) were performed in order to investigate the
effect of high-permittivity filler clustering as a function of filler
permittivity. By preserving the same total filler amount, the BT
ferroelectric grains were further partially replaced with fine
metallic nanoparticles (Ag), which were placed in random
positions, either on the BT surfaces only or everywhere inside
the polymer matrix. The role of microstructures and of the
metallic addition in the composite’s permittivity was estimated.
Further, the evolution of the effective permittivity values of
such composites was determined for various types of hybrid
filler configurations with different sizes and clustering degrees.
As an experimental verification, a set of flexible hybrid
composites with the formula 20%(2%Ag−98%BT)−80%
PVDF and with variable BT grain size were produced and
analyzed. The role of BT size and clustering degree on the
dielectric and ferroelectric response was discussed.
2. FEM CALCULATIONS OF THE COMPOSITE’S
EFFECTIVE PERMITTIVITY AND DISCUSSIONS
2.1. Role of Oxide Filler’s Permittivity and of Particle
Clustering. Trying to reach a more substantial permittivity
increase in polymer-based composites, it was considered that
employing ferroelectric fillers (in particular relaxor oxides,
characterized by a very high permittivity of 104−105 in their
bulk form) would provide a significant increase in the
composite’s effective dielectric constant. However, values of
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Figure 1. Local field images computed for two types of polymer-based composites in a plane-parallel capacitor configuration, with a volume filling
factor of 24% in two cases: (a) perfectly isolated inclusions and (e) partially clustered inclusions. The local field images were represented for various
values of the inclusions’ permittivity: 102 (b,f), 103 (c,g), and 104 (d,h). The black curves are isopotential lines, while the intensity of the local
electric field is represented in a color scale.
the effective permittivity were in the same range as when using
BaTiO3 or other normal ferroelectrics with a permittivity of
about 102−103 or even non-ferroelectric simple oxide fillers
with permittivity of a few tens, in the same compositional
range.32,46−48
In order to explain this feature and to find out the most
favorable types of microstructures providing a larger
permittivity increase, 2D FEM simulations were performed
for 0−3 filler inclusions with variable filler permittivity. The
employed procedure was described in detail in refs 4950, and
consists of the discretization of the composite system in a large
number of elements and solving the Laplace equation with
boundary conditions in such small elements, to derive the local
potential and local field corresponding to each discrete
element. By evaluating the total electrostatic energy as the
sum of the corresponding energies of each element (i), the
composite’s effective permittivity was extracted by using the
relation
N For this reason, effective medium approximations (e.g.,
2 2
Wtot = iEi Vi /2 = eff Eext Vt /2
i=1
In all the simulations, a composite system contained in a
capacitor with a plane-parallel geometry was analyzed, under
an applied low voltage of 1 V. The composite consists of a
dielectric matrix with low permittivity�εmatrix = 10 (corre-
sponding to the PVDF polymer)�with inclusions having
variable increasing permittivity values in a broad range from 10
to 106, corresponding to the ferroelectric and relaxor oxide
fillers. The volume filler factor was maintained at the same
value (f = 24%) in all the simulations. Both the matrix and the
filler were considered as perfect lossless dielectrics, that is,
described by zero imaginary part of their complex permittivity.
In the first run, the role of filler particles clustering on the
effective permittivity of composites was analyzed. The
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simulated microstructures were built by considering the
following: (i) isolated particles (Figure 1a): the micro-
structures were randomly generated by avoiding the filler
particles to touch each other; and (ii) particles with a certain
degree of clustering: when building the microstructure, the
filler particles were randomly distributed and allowed to touch
each other (Figure 1e). The effect of filler addition on the local
electric field represented in a color scale and on the
isopotential curves corresponding to each type of micro-
structure is illustrated in Figure 1, for a progressive increase of
the filler’s relative permittivity, εparticles of 102 (Figure 1b,f), 103
(Figure 1c,g), and 104 (Figure 1d,h), respectively.
The simulations indicate that when εparticles = 100, the local
electric field inside the particles is low (light blue in Figure
1b,f) but not yet equal to zero. Inside the isolated particles, the
local field is rather homogeneous, but it becomes inhomoge-
neous when the filler particles are clustered. In this case, the
local field in the neck regions between particles is enhanced.
Maxwell−Garnett, Bruggeman, etc.)51,52 are very limited in
(1) describing systems similar to one shown in Figure 1e, and
numerical methods such as FEM are more appropriate. When
εparticles = 103, the local field inside the particles is strongly
reduced, while the field inside the matrix (especially in the
regions between the filler inclusions which behave as small
capacitors) is enhanced. When the filler grains are partially
connected (Figure 1g), there are some regions located at the
necks still subjected to a non-zero field, while in the case of
isolated particles (Figure 1c), the field is homogenously
reduced toward zero. The local field inside the filler grains is
almost completely canceled when εparticles = 103, while the field
enhancement on the matrix is maximized. It is very interesting
to note that the field distributions in Figure 1c,d are very
similar as well as the ones shown in Figure 1g,h. This result
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indicates that for both types of microstructures, further
permittivity increases above 103 would not bring any
substantial effective permittivity modifications.
The calculations were further performed for coarser filler
particles, again in the situation of isolated particles or with a
degree of clustering, by keeping the same total amount of
inclusions. Figure 2 presents an overview of the simulation
Figure 2. Variation in the effective permittivity vs the inclusions’
permittivity obtained from 2D FEM calculations for fine or coarse
fillers, both isolated or partially aggregated. The results were derived
by averaging the effective permittivity values computed for several
generated microstructures.
results, in which the composite’s effective dielectric constant
versus the particle’s permittivity for fine/coarse isolated or
Figure 3. Local field representations (color scale) and isopotential curves (black lines) computed for a hybrid tri-component system of (6%Ag−
18%BT)−76%PVDF (vol) in a plane-parallel capacitor configuration and for various degrees of interconnectivity between the Ag NPs and the
outer surfaces of BT grains: (a) all the Ag particles randomly distributed everywhere; (b) 33% Ag NPs connected to the BT grain surfaces; (c) 67%
Ag NPs connected to the BT grain surfaces; (d) all the Ag NPs got placed on the BT grains and the corresponding local field images (e−h,
respectively).
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partially aggregated filler particles is shown. A fast dielectric
constant increase is observed for filler permittivity below 100;
then, a slower increase when εparticles ranges between (102, 103)
is likely, followed by saturation when εparticles > 103. The
saturation effect is caused by the fact that the electric field
located on the high-permittivity inclusions suffers a strong
depression for εparticles ≥ 103, and therefore, their contribution
to the total system’s energy tends to zero. This fact is also
indicated by the local field histogram (Figure S1a�Supporting
Information) showing that the number of regions subjected to
larger fields is higher for partially connected microstructures.
Due to the observed saturation effect, these simulations clearly
indicate the unfruitful approach to search for fillers with higher
permittivity above 103 (like the proposed ferroelectric
relaxors),48,53−55 to further increase the effective permittivity
in flexible composites. This limitation was not discussed in the
literature nor evidenced in other works related to similar
composites. A saturation εeff(εparticles) dependence was only
reported for BaTiO3 powders in liquid suspensions.56 The
present simulations show that this kind of dependence (Figure
2) is almost not modified by the filler size, but it is clearly
influenced by the filler particle agglomeration: a larger
saturation value for the effective permittivity is reached when
some degree of filler clustering exists. Therefore, the present
simulations provide a tool for improving the permittivity values
by employing partially aggregated filler particles instead of
using completely isolated ones. It is worth to mention that the
present data were systematically observed after simulating a
large number of microstructures for each value of inclusion
permittivity.
A first conclusion is that employing well-isolated permittivity
fillers with higher permittivity has practically no advantage to
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ACS Applied Materials & Interfaces
Figure 4. Overview showing the FEM predictions of the composite’s effective permittivity vs the proportion of Ag NPs connected to the BT grains,
computed for different types of microstructures containing isolated or partially clustered BT grains with small or finer size.
further increase the effective permittivity in sub-percolative
composites. This trend was observed in many experimental
studies, although it is not clearly pointed out.32,47,48 In addition
to this observation, exploring other microstructural parameters
like clustering or searching for peculiar microstructures seems a
valuable option to design local field concentration in specific
regions of the composite and to enhance its dielectric as well as
piezo- and pyroelectric responses.
As previously mentioned, the idea of embedding metallic
fillers emerged to ensure a more substantial effective
permittivity increase of composites.20,35,44,50 Toward this
aim, the role of decoration of high-permittivity filler grains
with small amounts of metallic fine NPs, while preserving the
under-percolative conditions (i.e., the total volume filler factor
was considered the same, of 24 vol %), was further examined
by using the same FEM procedure.
2.2. Influence of Metallic NP Addition and of Their
Connectivity with the Surface of High-Permittivity
Oxide Particles on the Composite’s Dielectric Proper-
ties. The presence of noble metallic NPs in the polymer matrix
and in particular whether they form a discrete shell on the
surface of BaTiO3 grains (i.e., a raspberry-like structure) was
reported to induce a higher permittivity with respect to the
case when BaTiO3 filler was embedded only in the polymer
matrix, either for small filler additions or for over-percolated
compositions.38,40,41,44,45 However, even some explanations for
the reached effective permittivity were proposed; the advantage
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of placing the metallic NPs on the surface of ferroelectric
grains was not explained in detail. Therefore, FEM calculations
are proposed for checking if using basic electrostatic equations
with boundary conditions would provide some new
information concerning the role of Ag NP connectivity with
the surface of high-permittivity oxide particles on the effective
permittivity of the hybrid composites. The aim of these
simulations was to find indications concerning the most
favorable filler microstructural characteristics to provide higher
permittivity with respect to one of the pure PVDF polymer
matrices, for a specific total filling factor below the percolation
limit, which was kept the same (24 vol %). Trying to simulate
some typical microstructures as ones reported in the
literature, 10,20−22,27,28,30,35,37−39 a few types of BaTiO 3
inclusions were considered: fine or coarse, isolated or partially
aggregated, and decorated with Ag NPs on top of their surfaces
with various degrees of interconnectivity between the Ag NPs
and the outer surfaces of the BT grains.
A tri-component system was simulated with the composition
(6%Ag−18%BT)−76%PVDF (εAg → ∞, εBT = 103, εmatrix =
10). Starting from the same initial position of the BT filler,
various microstructures were generated by distributing the Ag
NPs in different ways: (i) all the Ag NPs were randomly
distributed everywhere in the polymer matrix (Figure 3a); (ii)
increasing amounts of Ag NPs were progressively allowed to
attach to the external surfaces of BT grains in various
percentages (Figure 3b−d); and (iii) all the Ag NP were
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Figure 5. TEM micrographs of the dispersed Ag−BaTiO3 hybrid mixtures at two magnifications and the corresponding histograms showing the
particle size distributions for BT and Ag components: (a) Ag−BT1, (b) Ag−BT2, and (c) Ag−BT3 hybrid nanoparticles.
exclusively distributed only on the outer surfaces of the BT
grains, forming core−shell (“raspberry-like”) structures, as
shown in Figure 3d. The corresponding local fields and
isopotential lines are shown in Figure 3e−h, respectively.
As shown in the pictures representing the local field
distributions (Figure 3e−h), the attachment of Ag NPs on
the BT surfaces plays a very important role in the local
electrical properties and in the final effective permittivity of the
composite. When all the Ag NPs are attached on the surfaces
of BT grains, there are large-scale regions that become
completely subjected to a high field, that is, red in the scale
color (e.g., the regions marked in Figure 3h, with respect to
Figure 3e). The fact that the core−shell structures with Ag
NPs on top of the BT surfaces favor the formation of more
regions inside the polymer subjected to high fields is also
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reflected in the histograms from Figure S1b (Supporting
Information), in which on the right side of the field
distribution extended toward higher fields for Elocal/Eapplied >
1.5, the number of elements is systematically larger when the
proportion of Ag NPs attached to the BT grains increases
toward 100%, with respect to the case of isolated Ag NPs
distributed everywhere.
The simulations were also repeated for larger BT grains,
either isolated or partially clustered, and the overview of the
obtained results is presented in Figure 4. This figure clearly
shows that for the same amount of Ag−BT hybrid filler, the
microstructural factors play a major role in the composite’s
effective permittivity values, as follows: (i) an important
increase is generated by the increasing proportion of the Ag
NPs connected with BT grain surfaces, and the maximum
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relative rise of about 19% is found for the case of core−shell
hybrid structures; (ii) there is a relative permittivity increase of
about 5% of the BT particles partially clustered with respect to
the case of fully isolated, irrespective of their size; and (iii)
there is a modest relative increase of maximum 1−2% when
the BT grain size is larger if the variation of permittivity with
the grain size is not considered. According to these overall
results, the most favorable microstructures providing a more
substantial permittivity increase correspond to the partially
clustered BT grains with core−shell structures, that is, with all
the Ag NPs attached to the BT surfaces, as a result of synergic
contributions of ferroelectric fillers, their clustering, and the
decoration of their surfaces with fine metallic nanoparticles
producing local field intensification in the polymer matrix
regions.
The field concentration in the polymer matrix mostly in
regions close to the interfaces with high permittivity fillers
would have a positive effect not only on the dielectric constant
enhancement but also on the properties induced by high fields,
such as ferroelectric polarization and switching, piezo- and
pyroelectric responses, or tunability in such composites. As a
side effect, the same regions of field concentrations (so-called
“hot spots”) are the first ones prone to breakdown, thus
reducing the ability of such composites to sustain the
application of high fields.
To illustrate the role of the discussed microstructural factors
in the electrical properties, a series of composites having the
same amount of filler (BT or hybrid Ag−BT) have been
designed, produced, and analyzed.
3. MATERIALS AND METHODS
Three types of BaTiO3 particles with different grain sizes�BT1, BT2,
and BT3, were dispersed into Ag3 (Sigma-Aldrich, purity 99.9999%)
solution in ethylene glycol (Acros Organics, purity 99.97%): BT1�
hydrothermally synthesized Sigma-Aldrich nanopowders, purity:
≥99%, with an average particle size of ∼60 nm; BT2 and BT3 were
produced by the solid-state reaction between wet-mixed BaCO3
(Sigma-Aldrich, purity: 99.98%) and TiO2 (Sigma-Aldrich, purity:
99.9%) by calcination at 1000 and 1100 °C, respectively. The BT
surfaces were decorated with fine 2 vol % Ag nanocrystals (“raspberry-
like”), by using a procedure similar to the one described in detail in
refs 4057, (Figure S2, Supporting Information). Further, the BT and
Ag−BT powders were embedded in a PVDF polymer (Sigma-Aldrich,
Mw = 175000) matrix by the solution casting method using 99.5%
N,N-dimethylformamide (DMF) (Merk) as a solvent. Flexible
composite thick films (thickness of 1−2 μm and compositions: 20%
BT−80%PVDF and 20%(2%Ag−98%BT)−80%PVDF (volume
ratios)), by using the three types of BT powders (BT1, BT2, and
BT3), were produced. The samples are denoted as follows: PVDF
(pure polymer), BT1,2,3−PVDF (the compositions with 20 vol %
BT1, BT2, or BT3 filler in PVDF), and (Ag−BT1,2,3)−PVDF for the
three types of 20%(2%Ag−98%BT)−80%PVDF (vol %) composites
produced by using the three types of BT powders, respectively.
The nanostructures of the hybrid Ag−BT fillers were examined by
using a transmission electron microscope, type JEM-2100 (Jeol Ltd.,
Tokyo, Japan) operating at 200 kV. The particle size distribution was
determined by using a ImageJ Image Processing and Analysis
Software and counting ∼640 Ag nanoparticles and ∼180 BT
nanoparticles. The microstructures of powders and of the polymer-
based composites were determined by using field effect scanning
electron microscopy FESEM (Gemini 500, Carl Zeiss, AG Germany,
Oberkochen, Germany). Cryo-fractured surfaces of the notched
hybrid composites obtained under liquid nitrogen temperature were
sputter-coated with a 15 nm gold layer for SEM characterization.
X-ray diffraction (XRD) with a Shimadzu LabX 6000 diffrac-
tometer (Ni-filtered CuKα radiation, λ = 1.54 Å) was employed for
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the phase structure analysis of nanopowders and flexible composites.
The ATR−FTIR spectroscopy analysis of composites was performed
with an FTIR spectrometer Nicolet Impact 4000, with Monolithic
Diamond as the internal reflection element (spectra were recorded in
the transmittance mode in the range of 4000−400 cm−1 with 4 cm−1
resolution and an incident angle of 45°).
The electrical characterization was performed in an MIM
configuration by using Au sputtered electrodes (20 mm × 20 mm)
applied onto the composite’s surfaces. The impedance spectroscopy
characterization was carried out with an Agilent E4980A Precision
LCR Meter (Agilent) in the frequency range of 100 Hz−1 MHz and
temperature range of 10−70 °C.
4. RESULTS AND DISCUSSION
4.1. Microstructural Characteristics. The microstruc-
tural details of the dispersed hybrid Ag−BT1, Ag−BT2, and
Ag−BT3 nanoparticles into the PVDF matrix are shown in
Figure S3, Supporting Information, and in the TEM images in
Figure 5, together with their corresponding determined size
distributions. The two individual components of the powder
composites can be clearly observed: (i) polyhedral grains with
well-defined interfaces corresponding to the BT phase, having
an increasing average particle size from ∼60 nm in BT1 to
∼200−300 nm in BT2 and reaching ∼400−500 nm in BT3
and (ii) ultrafine rounded Ag NPs, with average sizes of 4.5 nm
in Ag−BT1 and about ∼15 nm in the powder composites Ag−
BT2 (Figure 5b) and Ag−BT3 (Figure 5c). It is noticed that
hydrothermally synthesized fine BT1 particles are almost
equiaxed (many of them rounded) and show a well-defined
sharp distribution, with particles’ diameters ranging from 20 to
about 150 nm. Due to the largest specific surface acting as
primary nucleation centers for the formation of Ag crystallites,
the final size of Ag NPs is also the smallest in this composite,
from 1 to 17 nm (Figure 5a). The corresponding histograms,
realized by counting 638 Ag NPs and 180 BT NPs, both show
a log-normal aspect.
The larger BaTiO3 grains BT2 and the coarser BT3 have a
faceted and irregular aspect and show a broader particle size
distribution, as typically reported in solid-state powders
calcined at high temperatures.58−60 Since they are more
agglomerated and coarse (having sizes between 55 and 700 nm
with an average value of 260 nm for BT2), the free surface for
the primary nucleation of Ag nanocrystals from the solution
was smaller, and therefore, the resulting Ag NPs are larger than
in the first case (diameters in the range 4−47 nm with an
average value of 18 nm for Ag−BT2). They are still transparent
for the electron beam, single crystalline, and very well
dispersed on top of the BT surfaces (Figure 5b). The
histogram realized by counting 390 Ag NPs has a log-normal
aspect, while the distribution obtained by counting 55 grains
shows a modified-Gauss feature.
BaTiO3 powders obtained by calcination at the highest
temperature of 1100 °C (BT3) are partially sintered and
agglomerated and show a broad size distribution, apparently
bi-modal, with grains from 70 nm to 2 μm (with an average
value around ∼415 nm, caused by counting 41 grains). In the
same synthesis conditions, Ag rounded NPs with sizes between
6 and 65 nm and an average value of 23 nm (obtained by
counting 318 silver NPs) have been formed in this case.
However, different from the Ag−BT1 and Ag−BT2 hybrid
composites, the Ag NPs are also agglomerated, forming some
clusters with variable sizes, as a result of multiple secondary
nucleations. The Ag clusters are located in some regions on the
BT3 surfaces and also out of them (Figure 5c). In all the types
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of hybrid nanocomposites, some isolated fine silver NPs have
been also formed out of the BT surfaces. Qualitative energy
dispersive X-ray analysis EDX mapping recorded in various
regions of agglomerated hybrid Ag−BT nanocomposite
particles (not shown here) have demonstrated the samples’
purity, that is, the presence of the expected chemical elements:
Ba, Ti, Ag, O (sample), and Cu/C (grid) only.57
The SEM analysis realized on the fresh cryo-fractured
surfaces of the flexible thick films with 20%(2%Ag−95%BT)−
80%PVDF composition is presented in Figure S4, Supporting
Information, and at a higher resolution in Figure 6. Globally,
Figure 6. SEM micrographs realized in cryo-fractured fresh surfaces of
flexible thick films with 20%(2%Ag−95%BT)−80%PVDF (vol)
composition and BT filler with variable grain size: (a) (Ag−BT1)−
PVDF, (b) (Ag−BT2)−PVDF, and (c) (Ag−BT3)−PVDF.
the inorganic filler is well dispersed into the polymer matrix,
but some clusters irregular in size and shape are observed for
all the types of fillers, with sizes in the range of 1−2 μm for
(Ag−BT1)−PVDF, 5−6 μm for (Ag−BT2)−PVDF, and
Figure 7. XRD diffractograms of (a) BaTiO3 starting powders and (b) 2%Ag−98%BaTiO3 hybrid powders and of the PVDF-based composites
with: (c) 20%BaTiO3 filler and (d) 20%(2%Ag−98%BaTiO3) hybrid filler, in which the BaTiO3 grains have different sizes.
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larger than 5 μm for (Ag−BT3)−PVDF. This type of
clustering is typical to solution-based processing of such
types of composites, and it was reported by many authors in
the literature.9,11,27,30 At a finer scale, it is observed that the
(Ag−BT1)−PVDF composite presents an average good
dispersion of the hybrid filler inside the PVDF polymer matrix
(Figure 6a); that is, the polymer chains isolated quite well the
inorganic nanoparticles and the silver ultrafine NPs remain
mostly attached to the BaTiO3 surfaces. However, some
regions of the composite are richer in Ag−BT inorganic filler,
which shows some degree of agglomeration (as indicated in
green in Figure 6a), while some areas are rich in polymer
(denoted with red in Figure 6a). Similar microstructures are
reported in refs 91127,. As noticed in Figure 6b,c, barium
titanate grains of BT2 and BT3 powders inside the composites
are faceted and partially sintered. They form in some regions
typical ceramic microstructures with clean grain boundaries
and perfectly connected triple points. Besides the sintered
ceramic grains, the composite (Ag−BT2)−PVDF also shows
some isolated BT2 grains (not visible anymore in the case of
BT3 filler), and all of them are well embedded into the
polymer matrix. The fine Ag NPs are well dispersed, and a
majority are placed onto the BT2 surfaces, but some of them
can be also found in the polymer volume, without forming
visible clusters (as indicated in blue in Figure 6b,c). (Ag−
BT3)−PVDF samples have a similar aspect, but silver NPs on
the BT3 surfaces are larger, as a result of their clustering
observed in the TEM images (Figure 6c). Silver NPs have no
preferential positions at grain boundaries, triple points, or
edges, and they are also located in the polymer-rich regions
(marked in blue in Figure 6c). The highest degree of clustering
both of BT and of Ag NPs is therefore characteristic for the
hybrid composite realized with BT3 particles due to the high
temperature used for BT calcination. Similar features can be
observed in the SEM micrographs realized on the starting Ag−
BT hybrid powders shown in Figure S3, Supporting
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Table 1. Relative Amount of Electroactive Phase FEA (β Phase) in the PVDF-Based Composites
sample PVDF BT1−PVDF BT2−PVDF BT3−PVDF
FEA (%) 38 37 38 38
Information, meaning that the solution processing does not
substantially modify the clustering degree of the hybrid Ag−
BT2 and Ag−BT3 nanocomposite powders. It is also worth to
note that a certain degree of porosity is also present for all the
compositions and also for the reference PVDF thick films,
which represents a typical drawback of solution-processed of
PVDF-based composites, irrespective of the type and nature of
the inorganic filler.9
4.2. Phase Analysis. The crystalline structure of the
starting BaTiO3 particles is pseudo-cubic for BT1 (JCPDS card
no. 01-075-0210) and for the 2%Ag−98%BT Ag−BT
composites (Figure 7a,b). The coarse BaTiO3 particles
produced by solid state synthesis have a tetragonal symmetry
(JCPDS card no. 01-075-0462), as indicated by the split of the
characteristic peak 2θ ∼ 45° (200)/(002), which is larger in
BT3 with respect to BT2 as result of a higher calcination
temperature. The presence of Ag nanoparticles (observed by
the presence of the main diffraction peaks at 2θ ∼ 38 and 44°)
preserves this tetragonal structure (Figure 7b). Figure S5,
Supporting Information, presents the XRD diffractograms of
the pristine PVDF thick film, in which we can observe the
presence of the predominant α phase (characteristic peaks at
2θ = 17.9, 18.4, 20.2, 27.9, 36.1, and 39.0°, attributed to
reflection planes of (110), (020), (021), (111), (200), and
(002), respectively) together with some characteristic peaks of
the β polar phase.61,62 Namely, the presence of a strong
intensity peak at 20.6° is a signature of the β-phase, while the
small peak at 2θ = 26.8° is usually assigned in the literature to
the γ-phase.61−64 Similar features are preserved in the XRD
diffractograms obtained for the composites with BT or Ag−BT
fillers with different grain sizes, embedded in the PVDF
polymer matrix (Figure 7d,e). When introducing as a filler the
coarse BT2 and BT3 particles and the corresponding hybrid
Ag−BT2 and Ag−BT3 fillers, the intensity of the characteristic
peaks of the polar phases is reduced below the detection limit
of the XRD equipment and the diffractograms are dominated
by the crystalline peaks characteristics of the perovskite BT and
cubic Ag. However, the most important peak corresponding to
the (200) diffraction planes of the β polar phase of PVDF at
∼20.6° is still visible in both types of nanocomposite thick
films with ultrafine fillers (BT1 and Ag−BT1), and this gives
the idea that the presence of ultrafine filler nanoparticles tends
to promote the formation of the ferroelectric β phase in the
crystalline part of the PVDF matrix.
A further confirmation of the benefit of using ultrafine fillers
to promote the ferroelectric β phase is provided by the FTIR
analyses of the flexible composites (Figure S6, Supporting
Information). For all the samples, the main bands specific to
the majority α-PVDF phase are found around 490, 532, 614,
763, 795, 855, 973, 1148, 1212, 1382, and 1423 cm−1, together
with small contributions from the β and γ - PVDF polar
vibrations at 840, 1275, and 1402 cm−1.10,61,62,65,66 Among all
the composites, BT1−PVDF and mostly the (Ag−BT1)−
PVDF hybrid films realized with the finest nanoparticles as
fillers (Figure S6a, Supporting Information) show the most
intense feature at ∼840 cm−1, which is the main representative
vibration corresponding to the ferroelectric β/γ polar phases of
PVDF62 (Figure S6, Supporting Information).
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(Ag−BT1)−PVDF (Ag−BT2)−PVDF (Ag−BT3)−PVDF
46 45 37
The relative fraction of the electroactive β phase (FEA) in
the PVDF composite films was determined by applying eq 2, as
proposed by Cai et al.62
IEA
FEA = × 100
( )×I
K 840*
K 763 763 + IEA
(2)
where IEA is the absorbance of the band at about 840 cm−1 that
is assigned to the β and/or γ phase, I763 is the absorbance of a
characteristic band of the α phase, and K840* and K763 are the
absorption coefficients at the respective wavenumbers, whose
values are 7.7 × 104 and 6.1 × 104 cm2/mol, respectively. The
calculated values of electroactive phase FEA(β) are displayed in
Table 1 and express the electroactive polymorph content in
relation to the total amount of crystalline phase in the PVDF-
based composite samples.
The obtained results demonstrate that the formation of
polar polymorphs and in particular of β-PVDF in the
composite materials is promoted by the presence of ultrafine
silver nanoparticles, although α-PVDF conformation still
remains in the majority. The enhancement of β/γ polar phases
of PVDF when embedding fine particles such as with
ferroelectrics as BaTiO3 nanoparticles,67 sodium niobate
nanorods,68 simple oxide particles as GeO2 and SiO2,69 Ag
nanofillers,70,71 carbon nanotubes,72 graphene-based fillers,73
and so forth was reported. Various interactions have been
proposed for each type of filler-PVDF matrix,74 but a
clarification of the general mechanisms providing the enhance-
ment of the amount of polar polymorphs induced by
nanofillers in PVDF was demonstrated by a chemical mapping
of the interfacial coupling between the nanofiller and the
matrix.75 It was shown that the filler−polymer interfaces
become highly polar and inhomogeneous when reducing the
filler size. The augmentation of local conformational disorder
close to such interfaces causes the local stabilization of the all-
trans polar conformations in PVDF, and this feature is
enhanced as a scale-dependent effect. Likely, the present data
clearly demonstrate that among the various employed fillers,
the most effective in promoting the formation of ferroelectric
phases are Ag−BT1 and Ag−BT2 containing the smallest BT
particles decorated with the finest Ag NPs on top of their
surfaces, because in these specific composites the largest
specific interface hosts local inhomogeneities which would
stabilize the all-trans configurations. The use of larger BT3
nanoparticles is less favorable for the formation of polar PVDF
phases because of their clustering effect which leads to a
smaller BT−polymer specific surface as well as generates
during the silver crystallite formation more agglomerated and
coarser Ag NPs, thus reducing, even more, the amount of
disordered interfacial polymer−inorganic filler regions.
4.3. Dielectric Properties. Impedance spectroscopy
analysis revealed the temperature and frequency dependences
of the real and imaginary parts of permittivity
(f ) = (f ) i (f ) and of the dielectric modulus M̃ (f) =
1/ε( f) = M′( f) − iM″(f), tangent loss and ac-conductivity:
σac(f) = 2πfε″(ω) of the flexible thick film composites. A
selection of such properties versus temperature and frequency
is comparatively presented in Figure 8a−o for a selected set of
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Figure 8. Comparative frequency dependences of the dielectric properties for PVDF, BT2−PVDF, and (Ag−BT2)−PVDF flexible thick films when
temperature ranges between 25 and 150 °C, shown in color scale: (a−c) the real part of permittivity; (d−f) dielectric loss tan δ; (g−i) ac-
conductivity; (j−l) real part of dielectric modulus; (m−o) imaginary part of the dielectric modulus.

composites with BT2 and Ag−BT2 fillers, in comparison with
the properties of the pristine PVDF matrix. All the other
composites show similar trends, with small differences due to
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the various types of filler size and distributions inside the
composites, but basically, their main electrical properties are
derived from ones specific to the PVDF polymer.
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Figure 9. Temperature dependence of the real part of permittivity (a,c) and of the tangent loss (b,d) measured at a fixed frequency for the flexible
thick films with: 20%BT−80%PVDF (a,b) and of 20%(2%Ag−95%BT)−80%PVDF composites (c,d) having variable BT grain sizes fillers; (e)
Arrhenius analysis using the imaginary part of the dielectric modulus M″( f) maxima from Figure 8m−o; (f) comparison showing the permittivity
increase in composites with respect to PVDF at a few selected temperatures.

As in the case of other polymer-based composites, the
present ones based on the PVDF matrix contain local
heterogeneities and interfaces separating crystalline/amor-
phous regions or different polymorphs (α, β/γ phases, etc.),
fillers, pores, or impurities, where the electrical properties have
discontinuities and, in such positions, charged ionic or polar
species can be trapped and generate slow polarization
components. On the corresponding interfacial polarization
responses (mostly present at low frequencies, where the slow
species can follow the periodical field variations), conductivity
phenomena are also overlapped, and to better observe the
presence of interfacial and conductivity relaxation responses,
the dielectric modulus formalism was complementarily
used.76−78 Both conductivity and dipolar relaxation polar-
ization are thermally activated processes, and therefore, they
are enhanced at high temperatures and low frequencies. As a
consequence, at a fixed frequency, the real and imaginary parts
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of permittivity and of dielectric losses above unity in pure
PVDF and in all the composites strongly increase with
increasing temperature and reducing frequency (Figure 8a−c
and d−f), thus resulting in a “giant permittivity” above 103 at
100 Hz (Figure 8a−c), as a result of intrinsic contributions
from the inhomogeneities and interfaces. At any temperature,
permittivity and tangent loss increase when frequency
decreases. On this monotonous trend, some relaxation features
around 1−10 kHz and below 500 Hz (indicated with arrows in
Figure 8d−f) are overlapped. Such features are usually assigned
in the literature to different types of polymer chain relaxations
of PVDF.16,78,79
Due to the above-mentioned extrinsic relaxations, the
permittivity values to be compared as a function of
composition should be considered at high frequencies only,
so that the frequency of 10 kHz is considered for discussions.
Figure 9 shows the role of BT and of hybrid Ag−BT in various
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ACS Applied Materials & Interfaces
types of fillers on the permittivity of nanocomposites. With
respect to the pure PVDF thick films (room temperature real
part of permittivity of about ∼10), a permittivity increase is
induced by the presence of BT fillers (Figure 9a): the
permittivity is higher as the BT filler is coarser, and the
maximum value is doubled for BT2 and BT3 at room
temperature. The addition of only 2 vol % Ag results in a
further permittivity increase, which becomes about 4 times
larger than in PVDF for the samples denoted as (Ag−BT3)−
PVDF (Figure 9b). At higher temperatures, the permittivity
increase is even more prominent (Figure 9c). However, this is
not an intrinsic increase, and it is likely to be caused by
thermally activated relaxation contributions. When compara-
tively observing the temperature dependence of permittivity
and losses induced by the presence of fillers (Figure 9a−c and
b−d), it is clear that the apparent permittivity increase above
100 °C is larger when increasing the BT size either in BT−
PVDF composites or in the hybrid (Ag−BT)−PVDF
compounds, but all of them are accompanied by the same
trend of increasing losses at higher temperatures, which
confirms the extrinsic character of this permittivity increase.
The fact that permittivity and losses in samples with larger BT
grains are higher in all the temperature range is related to the
contributions of ferroelectric domain walls, whose density is
higher when the BT particle size increases from nanometric to
micron-sized range by partial sintering.25 On the other hand,
the stronger increase of permittivity and losses at higher
temperatures above 100 °C are related to the increasing
contributions from more interfaces in the BT−PVDF thick
films with respect to the pristine PVDF and of the (Ag−BT)−
PVDF thick films with respect to the BT−PVDF ones. Based
on these observations, it is worth to mention that at high
frequency where the extrinsic contributions are minimized, the
room temperature permittivity cannot exceed a few tens, for a
total filler composition below the percolation limit, of 20 vol %.
In all the investigated composites, the room temperature
permittivity increase is not accompanied by the deterioration
of their dielectric character; that is, the dielectric loss remains
at about 9% for (Ag−BT3)−PVDF and below 2% for all the
others at room temperature (Figure 8). Similar values have
been reported in the literature for other BaTiO3−PVDF
composites.9,16,78
Other modifications induced by the presence of fillers in the
PVDF-based composites are observed on the ac-conductivity
versus frequency data (Figure 8g−i). For example, for the BT2
filler (Figure 8g−i), the dc-conductivity in BT2−PVDF is
about 10−8 S/m, 1 order higher than in PVDF (∼10−9 S/m),
while the presence of 2 vol % Ag in (Ag−BT2)−PVDF hybrid
composite causes an increase of conductivity with 1 order of
magnitude more (∼10−7 S/m). Similar observations concern-
ing the increasing conductivity in composites with respect to
the pure polymer matrices and values for losses and
conductivity were reported in refs 1145, where they were
assigned to the increase of internal friction between the filler
particles and the polymer matrix chains. The conductivity of
the present composites is smaller than that reported in ref 18,
where σdc ∼ 10−5, 10−7 S/m, but slightly higher than ones
found in PVDF-based composites with improved micro-
structures by using Ag@BaTiO3 core−shell nanofillers.38 As
expected, for all the types of composites, the temperature
causes a conductivity increase, in particular at low frequencies,
thus indicating a thermally activated conduction mechanism.
The thermally activated relaxations observed in the frequency
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and temperature dependences of the dielectric loss and of the
imaginary part of dielectric modulus M″( f) (Figure 8m−o)
have been analyzed by Arrhenius calculations, which provided
for all the composite values of the activation energies in the
range of 0.66−0.84 eV (Figure 9e), which are very similar to
ones reported for core−shell Ag@BT fillers in PVDF in ref 38.
By comparing the dielectric properties in the composites
with fine versus coarse BaTiO3 fillers (Figure 9f), it is clearly
noticed that permittivity increases when BT is coarser in both
types of BT−PVDF and (Ag−BT)−PVDF series of
composites. A similar trend was reported in a recent paper,11
in which BT fillers with variable GS in the range of 60−500 nm
were used in different types of polymer matrices such as PVDF
and PMMA. The trend remains similar when the temperature
increases to 90 °C, but it slightly changes at higher
temperatures (140 °C), when thermally activated extrinsic
contributions overlap on the increasing trend induced by the
presence of BT and Ag−BT fillers into the PVDF matrix
(Figure 9f). For some reasons not yet understood, the best
composites from the dielectric point of view, in terms of low
extrinsic contributions to the dielectric relaxation and lower
losses, are (Ag−BT1)−PVDF with the finest filler nano-
particles, followed by (Ag−BT2)−PVDF with a larger BT size
and certain agglomeration level.
It is worth to mention that for the present composites, the
coarsening of ferroelectric particles obtained in BT2 and BT3
powders by using high calcination temperatures is accom-
panied by partial sintering, giving rise to clustering effects
inside the composite. Larger ferroelectric grains allow the
formation of a polydomain structure and trans-granular
domains, that is, the formation of a larger number of domain
walls than in ultrafine particles, giving rise to domain wall
contributions to the dielectric constant of ferroelectric fillers. It
is therefore expected that permittivity in larger BT grains is
higher than in finer particles as a size/scale effect. However, a
rough estimation by considering the results of FEM
calculations from Section 2.1 (Figure 2) indicates that even
if the filler permittivity would increase from 100 to 1000 as a
scale effect, the permittivity increase of the composite cannot
exceed ∼15%, while the experimental data show a relative
increase of 22% in BT2−PVDF and of 38% in BT3−PVDF
with respect to the values corresponding to BT1−PVDF.
Similarly, when using the 2%Ag−BT hybrid filler, relative
permittivity increases of 24% in (Ag−BT2)−PVDF and of 32%
in (Ag−BT3)−PVDF with respect to the values of (Ag−
BT1)−PVDF composite are reached. Thus, the main factors
causing permittivity enhancement are related to micro-
structural modifications (as clustering which create regions
with enhanced field), rather than by the BaTiO3 filler size (and
its permittivity). Another factor promoting a permittivity
increase in the hybrid composites containing Ag with respect
to ones containing only BT is related to modifications of the
polymer matrix induced by the presence of an ultrafine filler,
that is, the increased amounts of polar phases β, γ of PVDF on
the expense of nonpolar one α by the addition of ultrafine
particles of Ag.
5. CONCLUSIONS
The permittivity increase of PVDF-based composites with
ferroelectric BT and hybrid Ag−BT fillers, in which BT has an
average particle size from ∼60 nm (BT1), ∼200−300 nm
(BT2) up to ∼500−600 nm (BT3), and 2 vol % silver
nanoparticles in the range of 4−15 nm deposited predom-
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ACS Applied Materials & Interfaces
inantly on their surfaces, was analyzed. Numerical calculations
demonstrated the substantial role of microstructural factors as
the size and clustering degree of the ferroelectric and metallic-
ferroelectric hybrid particles in the dielectric properties of
composites, for a total filler amount of 20%, below the
percolation limit. Contrary to the generally accepted opinion
considering the increase of the filler’s permittivity as being a
tool to enhance permittivity in polymer-based composites, it
was shown here by finite element modeling calculations that
the composite’s permittivity values tend to saturate for filler
permittivity ε > 103. The calculations indicated that the perfect
dispersion of high permittivity fillers into the low permittivity
matrix is not always favorable to provide permittivity rise,
although it is required for technological applications. When
using coarse ferroelectric particles, agglomerated particles,
and/or high filler amounts, the probability of clustering is
higher, thus favoring the permittivity increase by field
concentration in small regions close to the interfaces separating
dissimilar materials. Irrespective of the ferroelectric filler sizes,
the addition of metallic ultrafine particles results in a
permittivity intensification and the effect is even stronger if
the metallic nanoparticles are connected with the ferroelectric
particles’ surfaces. The calculations also show that the effective
permittivity of such composites is strongly dependent on the
local microstructures and mostly by the interfaces separating
dissimilar materials in the case of the hybrid fillers like Ag−BT.
The present results are general and not related to a specific
material filler or polymer matrix. The beneficial role of high
permittivity oxide filler and mostly of the metallic nanoparticle-
decorated oxide filler additions with specific microstructures
(clustered arrangements) to increase permittivity with respect
to the pristine polymer values is predominant even over the
possible presence of a small porosity level below 10%, as
shown in the calculations presented in Figure S7, Supporting
Information.
Experimentally determined permittivity values for compo-
sites containing BT fillers or Ag−BT hybrid fillers, in which the
ferroelectric particles have variable grain size and present
clustering for coarse BT, confirmed the trends resulting from
the finite element calculations, but the level of permittivity rise
is higher than predicted. This can be explained as a result of
modifications of the PVDF matrix acquiring a higher amount
of polar phases β, γ when including fine nanoparticles (Ag
nanoparticles and fine BT1 powders). In addition, in a series of
composites with variable filler additions, clustering may appear
in an uncontrolled way, causing a strong variation of the local
fields from one region to another. In conclusion, exploring
microstructural parameters like the filler’s particle size, their
agglomeration, and the degree of connectivity between
ferroelectric surfaces and metallic particles or searching for
specific favorable microstructures remains an option to design
local field concentration in specific regions of the composite
for enhancing the dielectric response.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.2c15641.
Additional experimental details, materials, and methods;
histograms indicating the local field distribution;
schematic illustration for the preparation; SEM micro-
graphs; SEM micrographs of the PVDF-based compo-
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sites; XRD patterns of pristine PVDF thick films; FTIR
spectra; and role of porosity analyzed by FEM (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Nadejda Horchidan − Dielectrics, Ferroelectrics &
Multiferroics Group, Faculty of Physics, Al. I. Cuza University
of Iasi, 700506 Iasi, Romania; orcid.org/0000-0002-
4013-018X; Email: nadejda.horchidan@uaic.ro
Liliana Mitoseriu − Dielectrics, Ferroelectrics & Multiferroics
Group, Faculty of Physics, Al. I. Cuza University of Iasi,
700506 Iasi, Romania; Email: lmtsr@uaic.ro
Authors
Leontin Padurariu − Dielectrics, Ferroelectrics & Multiferroics
Group, Faculty of Physics, Al. I. Cuza University of Iasi,
700506 Iasi, Romania
Cristina Elena Ciomaga − Department of Exact & Natural
Sciences, Institute of Interdisciplinary Research, Al. I. Cuza
University of Iasi, 700506 Iasi, Romania; orcid.org/
0000-0002-1287-7702
Lavinia Petronela Curecheriu − Dielectrics, Ferroelectrics &
Multiferroics Group, Faculty of Physics, Al. I. Cuza University
of Iasi, 700506 Iasi, Romania
Vlad Alexandru Lukacs − Dielectrics, Ferroelectrics &
Multiferroics Group, Faculty of Physics, Al. I. Cuza University
of Iasi, 700506 Iasi, Romania
Radu Stefan Stirbu − Dielectrics, Ferroelectrics & Multiferroics
Group, Faculty of Physics, Al. I. Cuza University of Iasi,
700506 Iasi, Romania
George Stoian − National Institute of R&D for Technical
Physics, 700050 Iasi, Romania
Mihaela Botea − National Institute of Materials Physics,
077125 Magurele, Romania
Mihaela Florea − National Institute of Materials Physics,
077125 Magurele, Romania; orcid.org/0000-0002-6612-
6090
Valentin Adrian Maraloiu − National Institute of Materials
Physics, 077125 Magurele, Romania; orcid.org/0000-
0002-4400-5060
Lucian Pintilie − National Institute of Materials Physics,
077125 Magurele, Romania; orcid.org/0000-0002-4934-
2912
Aurelian Rotaru − Faculty of Electrical Engineering and
Computer Science & MANSiD Research Center, Stefan Cel
Mare University, 720229 Suceava, Romania; orcid.org/
0000-0002-8782-7988
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.2c15641
Author Contributions
The manuscript was written through the contributions of all
authors: L.P.�methodology, resources, formal analysis,
software, validation, and writing. N.H.�investigation, vali-
dation, and writing. C.E.C., L.P.C., V.A.L., G.S., M.B., M.F.,
and V.A.M.�investigation and formal analysis. L.P.�
resources and investigation. A.R.�resources, investigation,
and funding acquisition. L.M.�conceptualization, funding
acquisition, writing�review & editing, and supervision. All
authors have given approval to the final version of the
manuscript.
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ACS Applied Materials & Interfaces
Funding
This study was supported by the Executive Unit for the
Financing of Higher Education, Research, Development, and
Innovation.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This study was supported by the Executive Unit for the
Financing of Higher Education, Research, Development, and
Innovation within the Romanian Research Grants: PN-III-P4-
ID-PCCF-2016-0175�HighKDevice (experimental) and PN-
III-P1-1.1-TE-2019-1929�ElectroChargEng (simulations).
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