ISSN 2635-1676, Nanobiotechnology Reports, 2024, Vol. 19, No. 6, pp. 947–958. © Pleiades Publishing, Ltd., 2024.

POLYMER, BIOORGANIC
AND HYBRID NANOMATERIALS

Polyurethane-Based Composite Materials Promising

for Dielectric Actuators
E. I. Zyrianovaa,b, S. V. Paka,b, V. A. Deminaa, A. E. Krupnina, S. N. Malakhova, P. V. Dmitryakova,
A. V. Bakirova,c, A. A. Puchkova, E. P. Banina, T. E. Grigorieva,b,
N. M. Kuznetsova,*, and S. N. Chvaluna,c
a
National Research Center “Kurchatov Institute,” Moscow, 123182 Russia
b
Moscow Institute of Physics and Technology (National Research University),
Dolgoprudny, Moscow Region, 141700 Russia
c
Enikolopov Institute of Synthetic Polymeric Materials, Russian Academy of Sciences,
Moscow, 117393 Russia
*e-mail: [email protected]
Received August 23, 2024; revised November 19, 2024; accepted November 19, 2024

Abstract—Novel composite materials based on two polyurethanes filled with silver microparticles in different
concentrations (1, 5 or 10 wt %) are produced. The properties of the initial and composite materials are stud-
ied by modern structural and physical–chemical methods. Significant differences in the electrical and
mechanical properties of native polymer matrices with identical chemical composition are revealed. The
quality of the filler distribution in the matrix is evaluated and the fractal structure of silver particle agglomer-
ates in the polyurethane matrix is established. The effect of a conductive filler (silver) on the electrical char-
acteristics (conductivity and permittivity) of the material is studied. Composite materials based on polyure-
thanes can be considered as promising for dielectric elastomer actuators in soft robotics, thanks to enhance-
ment of the dielectric permittivity while maintaining the mechanical properties.

DOI: 10.1134/S2635167624602262

INTRODUCTION A fundamentally different approach is to deform

the structures by processes taking place within the
Soft robotics is an actively developing direction of material [8]. Such functionality is implemented in
modern science. In this field, robotic devices are stimuli-sensitive materials, which are characterized by
designed from soft, f lexible materials. Such devices the development of mechanical deformations in
possess a greater number of degrees of freedom, are response to an external stimulus. Structures that
lightweight, biocompatible, and have increased respond to chemical [9, 10], temperature [11, 12],
safety compared to their rigid counterparts [1, 2]. electrical [13–15], and magnetic [16–18] stimuli are
Due to their advantages, soft robots are indispensable known.
in creating soft nondestructive grips [3], minimally Heart failure remains one of the most common
invasive surgery devices [4], and robotic implants [5, causes of death in the world. Almost a third of the dis-
6]. The easiest to implement and currently most ease is caused by dilated cardiomyopathy: a dysfunc-
common example are hydraulic and pneumatic tion of the myocardium, which is accompanied by
“muscles” [7]. However, such designs require addi- stretching of the heart chambers and a significant
tional air or f luid pressurization systems, which, decrease in blood ejection [19]. Today, the main
although not inside the soft devices themselves, must methods of treating acute heart failure in the terminal
nevertheless accompany them throughout their oper- stage are implantation of donor organs or the installa-
ation, which imposes a number of limitations on the tion of circulatory support systems [20, 21]. However,
application of such elements and precludes the pos- the disadvantages of such approaches are obvious: in
sibility of creating an autonomous soft robot. There- addition to the risks of open-heart surgery, the number
fore, the development of implantable or miniaturized of operations performed annually is insufficient, the
devices also requires a review of the actuator designs cost of implantable pumps is extremely high, and the
used, as their bulkiness limits the application of soft waiting time for a donor organ can reach several years
robots, for example, in medicine as well as in envi- [22]. Therefore, it is necessary to create affordable
ronmental research. alternative methods to maintain the contractile func-

947
948 ZYRIANOVA et al.

tion of the heart at the level of a healthy person. To Since elastomeric materials are almost incom-
solve such an ambitious task, various approaches to pressible (Poisson’s ratio ~0.5), a decrease in thick-
the development of support systems are proposed, ness leads to an increase in Maxwell pressure and
and, in this regard, soft robotics is becoming a prom- greater stretching of the material in the plane of the
ising direction. Thus, one of the significant steps is electrodes. In this case, the transverse deformation
the development of a soft robotic sleeve that repeats can be described by the equation
the direction of muscle fibers in the outer layers of
σM ε0εrU
2
the epicardium. The implant is actively compressed
and twisted due to pneumatic action and works as an δz = = 2
, (2)
Y Yd
auxiliary device for the ventricle of the heart. The
device was successfully tested on a pig heart during where δz is the transverse deformation of the mem-
the drug-induced modeling of a heart attack: the use brane and Y is Young’s modulus of the material.
of the device returns the ejection fraction and aortic
f low indices to normal values. The advantages of this Both a decrease in the film thickness and its
approach include the absence of contact with blood stretching in the plane of the electrodes can be used to
and, as a consequence, the need for anticoagulant create the working stroke of the future device [30, 31].
therapy, and the disadvantages include limitations Therefore, in order to improve the response of the
associated with the use of auxiliary hydraulic sys- material to an external stimulus, an urgent task is to
tems [5]. achieve the highest value of deformation δz. The trans-
verse deformation can be increased both by external
A simpler approach in concept, but not in imple- influences: an increase in the electric-field voltage
mentation is the use of passive devices that limit the and a decrease in the thickness of the DEA and by
volume of the heart muscle; products of this kind have influencing the properties of the material itself by
already been successfully used in clinical cases of acute increasing the permittivity or decreasing Young’s
heart failure both abroad [23] and in Russia [24, 25]. modulus. Since the first method greatly affects the
The use of a mesh polymer frame helped to reduce fault tolerance of the structure due to an increased risk
dilation of the heart chambers, thereby significantly of electrical breakdown, new materials with high per-
extending the lifespan and improving the quality of life mittivity and low elastic modulus are needed.
of patients. Myocardial damage in heart failure is often
accompanied by impaired cardiac conduction. To One of the ways to create materials with specified
restore this function, an epicardial mesh made of con- properties is to vary the chemical composition of the
ductive and elastic material resembling native cardiac polymer during synthesis, but this task is complex and
tissue was developed. The implantable framework was expensive [32]. Another classical approach is to obtain
mechanically integrated into a rat heart as a structural composite materials, which allows the properties of
element of the cardiac chambers and electrical signals the final product to be influenced by varying the com-
from the heart were recorded, which also made it pos- position and concentration of the filler, improving or
sible to stimulate ventricular contraction [6]. Further adding the necessary properties without worsening
improvement of the approach involves the creation of others. For example, introducing additives into the
a combined robotic device that performs the function elastomer matrix that increase the permittivity of the
of the outer layers of the epicardium and actively stim- material leads to an increase in deformation under the
ulates cardiac contraction. action of an electric field [33, 34].

In this regard, dielectric elastomer actuators (DEA) Polyurethane is one of the elastomer matrices that
are of great interest in the field of soft robotics due to are suitable for creating DEAs, due to its commercial
their ease of manufacture and wide variety of applica- availability and relatively high permittivity [35].
tions [26–28]. In the simplest case, DEAs are a flat Therefore, the goal of the presented study is to create
capacitor made of an elastomer membrane stretched new composite materials based on polyurethane with
in a rigid frame, with flexible electrodes applied to improved electrophysical properties.
both sides [29]. When voltage is applied to the actua-
tor, electrostatic voltage arises between the oppositely
charged electrodes, and Maxwell pressure (σM) arises, EXPERIMENTAL
reducing the thickness of the membrane: Two commercially available polyurethanes were
used as a polymer matrix in the work: TPU 95-A
2
(Raise3D, United States) and TPU Easy Flex (Rec,
σM = ε0εr E 2 = ε0εr U 2 , (1) Russia). The choice of the materials was due to the
d
biostability and biocompatibility of polyurethanes
where ε0 is the electric constant, εr is the permittivity [36], as well as the possibility of using additive tech-
of the membrane material, E is the electric-field nologies for the further processing of composite
strength, U is the applied voltage, and d is the thick- materials. The polyurethanes used differ in color:
ness of the dielectric membrane. TPU 95-A is a transparent polymer and TPU Rec is

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 POLYURETHANE-BASED COMPOSITE MATERIALS PROMISING 949

black, which is probably due to the introduction of X-ray structural analysis (XRS) studies of the
an additive during production, for example, carbon mechanical and electrophysical characteristics of the
black. obtained composite materials and initial polymers
were performed on film samples 400 ± 20 μm thick,
Silver powder PS-1 (SPE Delta-Pastes, Russia) which were manufactured on a hydraulic press with
was chosen as a filler, since silver has biostability and heating plates. The pressing temperature was 190°C
biocompatibility along with conductive properties. and the pressure was ~0.7 atm. The films were
Size distribution: 90% of particles are less than 0.1 μm. quenched in cold water immediately after removal
The molecular weight distribution of the polymers from the press to prevent crystallization. Then, stan-
was studied by gel permeation chromatography (GPC) dard samples were obtained: disks 20 mm in diameter
on a COLUMN-THERMOSTAT JETSTREAM 2 for dielectric spectroscopy studies and blades with a
PLUS high-performance liquid chromatography sys- working area of 7.0 mm in length and 3.2 mm in width
tem (KNAUER, Germany) with a refractometric for mechanical characteristics studies.
detector. Measurements were performed using a PL Micrographs of cleavages of the composite materi-
gel MIXED-C 300 × 7.5 mm 5 μm column. The initial als of various compositions were obtained using a Phe-
materials were dissolved in tetrahydrofuran and the nom XL scanning electron microscope (SEM)
sample volume was 20 μL. (Thermo Fisher Scientific, the Netherlands) with a
The chemical structure of the polyurethanes (TPU backscattered electron detector at an accelerating volt-
95-A and TPU Rec) was studied by nuclear magnetic age of 5 kV in the low vacuum mode (pressure of
resonance (1H-NMR) at 30°C on a Varian VNRMS- 60 Pa) without the deposition of a conductive coating.
700 spectrometer at a sample concentration of To produce cleavages, the rod obtained at the exit of
40 mg/0.7 mL. Deuterated dimethyl sulfoxide the extruder was mechanically broken at the liquid-
(DMSO) was used as a solvent. The chemical shift (δ) nitrogen temperature.
of the residual signal of the nondeuterated solvent was Two-dimensional patterns of wide-angle X-ray
taken to be 2.5 ppm. Nine scans were obtained for both scattering (WAXS) and small-angle X-ray scattering
samples and the relaxation time was 20 s. Subsequent (SAXS) for films of various compositions were
processing and integration of the spectra was per- obtained at a wavelength of 0.1445 nm at the BioMUR
formed using the MestReNova program (Mestrelab station of the Kurchatov synchrotron radiation source.
Research, Spain). A DECTRIS Pilatus3 1M detector was used. The
sample-detector distance was 150 and 2500 mm for
The chemical composition of the polymers was WAXS and SAXS, respectively, and the beam size was
studied by IR spectroscopy on a Nicolet iS5 FTIR 500 × 400 μm. The exposure time was varied: 180 s
(Fourier transform infrared) spectrometer (Thermo (WAXS) and 10, 30, or 180 s (SAXS), depending on
Fisher Scientific, United States) using an iD5 ATR the scattering intensity of the sample. Calibration was
attenuated total internal reflection attachment. The performed using silver behenate (d001 = 58.38 Å). The 1
recorded spectral region was 4000–550 cm–1, the obtained 2D X-ray scattering images were integrated
spectral resolution was 4 cm–1, and the number of in the Fit2D program (ESRF, France).
scans was 32.
Mechanical tests under uniaxial tension were car-
The temperature range of stability of the initial ried out on an Instron 5965 tensile testing machine
polymers was studied using thermogravimetric analy- (Illinois Tool Works Inc., United States) at room tem-
sis (TGA) and differential scanning calorimetry perature with a strain rate of 42 mm/min. The mea-
(DSC). TGA curves were obtained on a combined sured parameters were normalized to the sample
Thermal Analysis System TGA/DSC3+ (thermal thickness using the built-in software. To obtain statis-
analyzer Mettler Toledo, Switzerland) in the tempera- tically reliable data, at least three samples of each type
ture range from 30 to 700°C in an air or nitrogen flow of material were studied. The obtained curves were
(99.999%). The flow rate was 50 mL/min. DSC data averaged and linearly approximated in the range of
were obtained on a DSC 8500 power-compensation 0‒0.5% relative elongation to calculate the elastic
differential scanning calorimeter (Perkin-Elmer, modulus of the materials. The yield strength was
United States) in the dynamic heating-cooling-heat- determined graphically by the intersection point of the
ing mode in the temperature range from 20 to 240°C. load-elongation curve with a straight line drawn paral-
The rate of temperature change was 20°C/min, with lel to the rectilinear initial section and cutting off the
an accuracy of ±0.1°C. elongation section equal to 1% from the abscissa axis,
The composite materials were manufactured by according to GOST (State Standard) 11262-80
three-stage extrusion in a MiniLab II twin-screw (ISO 527-2:2012).
extruder (Haake, Germany) with a filler concentra- The electrophysical characteristics of the materials
tion of 1, 5, and 10 wt %. The processing temperature were obtained using a Novocontrol Alpha-A dielectric
was selected from the temperature range of material spectrometer (Novocontrol Technologies GmbH &
stability and was 210°C. Co. KG, Germany) equipped with a ZGS Alpha

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950 ZYRIANOVA et al.

RESULTS AND DISCUSSION

1
2 Characterization of Polyurethanes
Since the polyurethanes used in the study are com-
mercial products, the chemical composition and
molecular weight distribution of the polymers were
characterized. The typical IR spectra of both polyure-
thanes are shown in Fig. 1. The spectra reveal the pres-
ence of hydrocarbon (768, 1413, 2958 cm–1), amine
(1527, 3330 cm–1), and ether (1174, 1219 cm–1) groups,
as well as a typical “fingerprint,” i.e., an absorption
band that is characteristic of the urethane group as a
3200 2800 1600 1200 800 whole (doublet 1697, 1726 cm–1) [39, 40]. It is evident
1
that the polymer matrices used have the same chemi-
Wavenumber, cm cal composition; however, taking into account the dif-
ferences in the intensity of some peaks, the percentage
Fig. 1. IR spectra of the studied polyurethanes: TPU Rec of functional groups may differ.
(1) and TPU 95-A (2).
The 1H-NMR absorption spectra of both polyure-
thanes have identical chemical shifts, which indicates
the similarity of their chemical structures (Fig. 2). The
Active Sample Cell dielectric cell, with a Quatro presented spectra reveal absorption peaks that are
Cryosystem temperature control system, in symmet- characteristic of the hydrogen atoms of water
rical sandwich cells: brass electrode/sample/brass (3.31 ppm), the amine group (9.48 ppm), the benzene
electrode, 20 mm in diameter. The measurements ring (doublets at 7.07 and 7.35 ppm), the aliphatic part
were carried out in a nitrogen atmosphere at an of the molecule (range 1.5–1.7 ppm), and the methy-
effective voltage of 1 V, in the frequency range of lene groups at the ether (4.0–4.1 ppm) and ester
1 Hz–1 MHz. (2.28 ppm) bonds [39–41].

x y
Hard segment Soft segment

DMSO

DMSO

2
10 9 8 7 6 5 4 3 2 1
Chemical shift

Fig. 2. 1H-NMR spectra of the polyurethanes TPU 95-A (1) and TPU Rec (2). (d, f, g) characteristic absorption bands of hydro-
gen atoms of methylene groups associated with the ether, ester, and methylene groups in polyols, respectively.

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 POLYURETHANE-BASED COMPOSITE MATERIALS PROMISING 951

100 (а) 100 (b)

Residual weight, %

Residual weight, %
80 80

60 60

40 40
2 2
20 1 20
1
0 0
200 300 400 500 600 700 200 300 400 500 600 700
Temperature, ˚C Temperature, ˚C

Fig. 3. Weight loss of TPU 95-A (a) and TPU Rec (b) samples upon heating in nitrogen (1) and air (2).

Thermoplastic polyurethanes are block copoly- that the residues of the polyurethanes noncombustible
mers consisting of hard and soft segments, the ratios in nitrogen differ by approximately 2% (6.7 and 4.6%
between which determine the mechanical and thermal for TPU 95A and TPU Rec, respectively), which con-
properties of the material. Taking into account the firms the differences in the quantitative ratios of the
availability and mass commercial production of the functional groups indicated by the IR spectrometry
studied polyurethanes as well as a fairly high melting data.
point, it can be assumed that the studied materials are
varieties of ESTANE. The ratio of hard to soft seg- Figure 4 shows the DSC results for the studied
ments of the molecule (the x : y ratio in the chemical polyurethanes. The heating curves in the temperature
formula shown in Fig. 2) can be quantitatively deter- range from 140 to 190°C show extended peaks of low
mined by the ratio of the doubled intensity of the intensity corresponding to the melting of the crystal-
group of peaks e to the peak f. Thus, TPU 95-A con- linity regions of the polyurethanes. Thus, at tempera-
sists of 44% of the hard block, which is a polyurethane tures above 190°C, the material is in a viscous-flow
based on methylene diphenyl diisocyanate and state. The crystallization and melting peaks of the
butanediol, and 56% of polyester, which determines polyurethanes differ; thus, the enthalpy changes
the soft segment [42]. For TPU Rec, the block ratio during the phase transition for the melting and crystal-
was 63 and 37%, respectively. lization processes are 13 ± 1 and 15 ± 1 J/g for TPU
According to the GPC data, significant differences Rec and 21 ± 1 and 18 ± 1 J/g for TPU 95-A, respec-
were found in the average molecular weight of the tively. The differences in the values indicate different
polyurethanes: 50 and 128 kDa for TPU 95-A and
TPU Rec, respectively. The polydispersity index for
both materials was 2.0. 2 1
Change in heat capacity, J/g K

2
Study of the Temperature Range 1
of Polyurethane Stability
The temperature range of polyurethane stability in 0
a viscous-flow state was determined to select the pro-
cessing temperature. The TGA results show that up to –1
a temperature of ~250°C, the mass of both polyure-
thanes is constant (Fig. 3). As the temperature 3
increases, mass loss begins, which is associated with –2
the evaporation of low-molecular impurities and the
onset of polymer destruction. For both polyurethanes, 4
–3
there are differences in the behavior of the curves in a
nitrogen and air atmosphere in the range from 430 to 50 100 150 200
650°C, which are associated with the thermal oxida- Temperature, ˚C
tion process that is characteristic of polyurethanes
[43]. Complete destruction in air at a temperature Fig. 4. DSC curves of the studied polyurethanes: TPU 95-
above 650°C for the materials under study indicates A (1 is cooling, 3 is heating) and TPU Rec (2 is cooling,
the absence of mineral impurities. It should be noted 4 is heating).

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952 ZYRIANOVA et al.

(а) 30 Pm (b) 30 Pm

(d)
140
Number of particles, units 120
100 10-wt-% Ag
5-wt-% Ag
80
1-wt-% Ag
60
40
20
0
0.1 0.4 0.7 1.0 1.3 1.6 1.9 2.2 2.5 2.8
Particle size, Pm
(c) 30 Pm

Fig. 5. SEM images of cleavages of TPU 95-A–Ag composite materials with filler concentrations of 1 (a), 5 (b), and 10 wt % (c),
histogram of filler-particle size distribution (d).

degrees of crystallinity of the materials, which is con- agglomerates by size, the sizes of about 500 particles
sistent with differences in the quantitative ratios of were determined for each of the compositions
functional groups. (Fig. 5d). The values of the minimum, maximum, and
Thus, to ensure a stable viscous-flow state, it is average sizes of filler agglomerates inside the compos-
necessary to maintain the temperature of the polyure- ite materials are presented in Table 1. The average sizes
thane in the range from 190 to 250°C. The tempera- of filler-particle agglomerates for materials of all com-
ture of the extruder for processing the materials was positions are almost the same. At the same time, the
selected experimentally and was 210°C for the poly- composite material with a filler concentration of
urethane to flow through the extruder without the risk 10 wt % is characterized by a finer particle distribution
of destruction. compared to the other materials: a greater number of
individual small-sized particles with a diameter of up
to 0.4 μm as well as a greater number of agglomerates
Study of the Filler Distribution in the Matrix up to 1 μm are observed.
Figures 5a–5c show SEM images of cleavages of
the composite materials with different filler concen- Study of the Structure of the Composite Materials
trations using the TPU 95-A matrix as an example.
The filler is uniformly dispersed inside the matrix. For To study the structure of the obtained composite
a more detailed analysis of the distribution of particle materials, WAXS studies were conducted. The scatter-

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 POLYURETHANE-BASED COMPOSITE MATERIALS PROMISING 953

Table 1. Silver-particle size distribution in the TPU 95-A matrix at different concentrations
Filler concentration, wt % Average particle size, μm Maximum particle size, μm Minimum particle size, μm

1 0.59 ± 0.02 2.75 ± 0.01 0.07 ± 0.01

5 0.53 ± 0.02 2.56 ± 0.01 0.13 ± 0.01
10 0.52 ± 0.02 2.68 ± 0.01 0.09 ± 0.01

ing curves show an amorphous halo characteristic of composite materials, long linear sections are observed
polymers: the samples are predominantly in a glassy on the scattering curves in double logarithmic coordi-
state (Fig. 6). Narrow intense reflections at 27 and nates, which indicates a fractal type of scattering
31 nm–1 correspond to diffraction scattering from the objects. The size of the scattering object can be esti-
filler for planes with the Miller indices (111) and (200), mated using the formula [45]:
respectively [44]. The intensity of the filler reflections
increases with increasing concentration of particles in R = 2π , (4)
the composite material. The average crystallite sizes qt
were determined using the Scherrer equation: where qt is the value of the scattering vector.
Since the scattering range on the left is limited by
d = Kλ , (3) ~0.03 nm–1, the size of the scattering object can be
β cos θ estimated from below by 210 nm. The obtained value
where d is the average size of the coherent-scattering correlates in order of magnitude with the data on the
regions, K is the dimensionless particle shape factor, average size of filler agglomerates determined using
λ is the X-ray wavelength, β is the half-height of the SEM (~0.5 μm).
reflection in radians, and θ is the diffraction angle. The slope coefficient of the linear section in loga-
The particle shape was assumed to be spherical, rithmic coordinates can be used to estimate the surface
with the coefficient K in this case being equal to 0.9. dimension of fractal objects [45]:
Since the purpose of this study was to estimate the
average crystallite sizes, the increase in error due to , I (q ) ∝ B
(5)
2 dm − d s
this assumption is not critical. Anisotropy of the linear q
dimensions is observed for silver crystallites: from 23 ± where B is the proportionality coefficient, ds is the sur-
1 nm in the (111) direction to 32 ± 1 nm in the (200) face dimension of the fractal, dm is the mass dimension
direction. of the fractal, and dm = 3 for particles with uniform
To study the structural organization of filler density.
agglomerates in the composite materials, two-dimen- The surface dimension of the fractal can take values
sional SAXS patterns were obtained (Fig. 7). For all from 2 to 3, where the value 2 corresponds to an object

(а) (b)
Intensity, arb. units

Intensity, arb. units

1
1
2 2
3 3
4 4
5 5

6 6
10 15 20 25 30 10 15 20 25 30 35
q, nm 1 q, nm 1

Fig. 6. WAXS curves of TPU 95-A (a) and TPU Rec (b) composite materials compared to the initial polymer matrices and filler:
1 is the silver powder, 2 is 10-wt-% Ag, 3 is 5-wt-% Ag, 4 is 1-wt-% Ag, 5 is the polymer matrix, 6 is background scattering (air).
The curves are shifted along the intensity axis for clarity.

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954 ZYRIANOVA et al.

From the data presented, it is evident that the

mechanical properties change little upon adding a
filler for both polyurethane matrices. We note that the
corresponding stress-strain curves of the composite
Intensity, arb. units

materials lie within the confidence interval of the

stress-strain curves of the original polymer matrices.
The values of the elastic modulus for pure polymer
1 matrices indicate differences in the structure of the
2 3 original substances: TPU 95-A polyurethane is almost
5 4
2.5 times stiffer than TPU Rec.
6
7
8 Study of the Dielectric Properties
9
10 As an example, we will consider the frequency
dependences of conductivity and permittivity for the
101 100 polymer matrices and composite materials with a
q, nm1 maximum filler concentration of 10 wt % (Fig. 9). The
dependences of the electrophysical characteristics of
Fig. 7. SAXS curves for the studied composite materials the remaining composite materials obtained take
based on TPU Rec (2–5) and TPU 95-A (6–9) compared intermediate values depending on the filler concentra-
to the initial polymer matrices and filler: 1 is the silver tion. We note that the frequency dependences of the
powder, 2, 6 are 10-wt-% Ag, 3, 7 are 5-wt-% Ag, 4, 8 are
1-wt-% Ag, 5, 9 are the polymer matrix, 10 is background conductivity of the original polymer matrices behave
scattering (air). The curves are shifted along the intensity differently: for TPU 95-A, a steady increase in values
axis for clarity. is observed over the entire measured range, while TPU
Rec has a conductivity plateau in the low-frequency
region, which, due to the smallness of the value, is
with a smooth surface, and the value 3 corresponds to most likely associated with the tunneling effect and is
a highly branched structure. For pure silver and com- probably due to the presence of carbon black in the
posite materials of all compositions, the slope coeffi- polymer. When adding silver, the conductivity of the
cient of the linear section modulo was ~3.7. Then the TPU 95-A-based material remains almost unchanged,
surface dimension of the fractal is ds = 6 – k = 2.3. The while for the TPU Rec-based material the conductiv-
obtained value indicates the formation of sufficiently ity value in the low-frequency region (for plateau)
soft, weakly branched aggregates of silver crystallites. decreases by almost 2 times. The observed effect may
be associated with the disruption of conductive paths
in the matrix during the production of the composite
Study of the Mechanical Properties material. It is obvious that in both cases the concentra-
Averaged stress-strain curves for composite materi- tion of the introduced filler is below the percolation
als and pure polymer matrices and the calculated cor- threshold.
responding mechanical properties of the studied The nature of the change in the conductivity of the
materials are shown in Fig. 8 and Table 2, respectively. materials under study also correlates with the behavior

(а) 80 (b)
70
70
60
60
50
Stress, mPa

Stress, mPa

50
40 40
30 30
20 20
10 10
0 0
0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200
Deformation, % Deformation, %

Fig. 8. Strain–extension curves of native polymers and composite materials based on TPU 95-A (a) and TPU Rec (b).

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 POLYURETHANE-BASED COMPOSITE MATERIALS PROMISING 955

Table 2. Mechanical properties of composite materials and initial polyurethanes

Filler
Yield strength Yield strength Fracture Fracture Young’s
Matrix concentration,
(stress), MPa (strain), % stress, MPa stress, % modulus, MPa
wt %

TPU 95-A 0 4.95 5.20 67 ± 1 1010 ± 40 118 ± 3

1 4.87 5.24 61 ± 6 950 ± 110 115 ± 2
5 4.82 5.12 61 ± 2 950 ± 50 117 ± 2
10 4.78 5.09 60 ± 2 980 ± 60 117 ± 9

TPU Rec 0 2.93 6.64 73 ± 1 1150 ± 20 52 ± 2

1 2.76 6.42 74 ± 5 1120 ± 50 51 ± 2
5 2.84 6.46 69 ± 4 1080 ± 50 52 ±1
10 3.02 6.59 74 ± 2 1120 ± 30 54 ± 3

of the permittivity graphs. For TPU 95-A, the ulation by an electric field in accordance with the
expected increase in permittivity from 5 to 7 arb. units change in the permittivity values (Fig. 9b). In this case,
is observed in the entire range of the frequencies under the deformation value is expected to increase to ~40%
study, which is consistent with the data in [34, 46]. for the composite material containing 10-wt-% filler
The permittivity values upon adding silver to TPU Rec relative to the initial matrix. For the materials based on
decrease from 15 to 10 arb. units in the low-frequency
region, since the conductivity value makes the greatest TPU Rec, an inverse dependence is observed, which is
contribution to this value, and change slightly with also caused by a corresponding decrease in the permit-
increasing frequency. tivity values. In this case, the values of the expected
Maxwell pressure are 1.5–3 times higher compared to
Next, on the basis of the data obtained, we will esti- the materials based on TPU 95-A due to the lower val-
mate the expected change in the DEA response based ues of Young’s modulus. It should be noted that,
on the obtained materials using Eq. (2). The results of despite the expected increase to 40% in the DEA
estimating the deformation values for all the materials
under study with a conditional film thickness of 10 μm response from TPU 95-A filled with 10-wt-% silver,
and an electric-field strength of 1 kV/mm are given in the high Young’s modulus of the initial polymer
Table 3. It is evident that the materials based on TPU matrix can complicate the implementation of real
95-A show an increase in the Maxwell pressure and, as deformation of the membranes by an electric field.
a consequence, the expected deformation upon stim- However, measuring the deformation response of

107 (а) 14 (b)

Permittivity, arb. units

108
Conductivity, S/cm

12
109
1
10
1010
1011 8 2
1
1012 6 3
2 3
1013 4
4 4
101 100 101 102 103 104 105 106 101 100 101 102 103 104 105 106
Frequency, Hz Frequency, Hz

Fig. 9. Dependence of the conductivity (a) and permittivity of materials (b) on the frequency of the electric field: 1 is TPU Rec,
2 is TPU Rec + 10-wt-% Ag, 3 is TPU 95-A, 4 is TPU 95-A + 10-wt-% Ag.

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956 ZYRIANOVA et al.

Table 3. Expected change in DEA deformation based on the obtained materials with a membrane thickness of 10 μm and
an electric-field strength of 1 kV/mm
Filler concentration, Maxwell pressure Strain value (δz),
Matrix Strain change, %
wt % (σM, MPa) arb. units

TPU 95-A 0 0.43 0.0036 ± 0.0001

1 0.50 0.0043 ± 0.0001 20.4
5 0.56 0.0048 ± 0.0001 32.5
10 0.59 0.0050 ± 0.0004 39.9

TPU Rec 0 1.31 0.0252 ± 0.0010

1 1.28 0.0252 ± 0.0010 0.25
5 0.96 0.0185 ± 0.0004 –26.4
10 0.91 0.0169 ± 0.0009 –32.9

materials under external influence is the subject of a permittivity while maintaining the mechanical char-
separate study and is beyond the scope of the pre- acteristics of the matrix have been obtained, which
sented work. allows us to expect increased deformation of the mate-
rial under the action of Maxwell pressure in an electric
field. The prospects of the approach to obtaining com-
CONCLUSIONS posite materials with silver particles in the creation of
Composite materials based on two different poly- DEAs are shown.
urethanes filled with silver microparticles at a concen-
tration of 1, 5, and 10 wt % were obtained. The three- ACKNOWLEDGMENTS
stage extrusion technique used in the work allows for
uniform distribution of the filler in the polymer We thank A. Yu. Vdovichenko for conducting the dielec-
matrix. tric spectroscopy studies, S. V. Krasheninnikov for con-
ducting the mechanical tests, and A. V. Koroteev for the
The WAXS method was used to determine the idea of creating stimuli-sensitive materials for stimulating
average sizes of individual silver crystallites: 23 ± 1 and cardiac activity.
32 ± 1 nm in the directions (111) and (200), respec-
tively. The SAXS method showed that the agglomer-
ates of silver crystallites have a fractal, weakly FUNDING
branched structure, and the average size of such
agglomerates was ~0.5 μm according to SEM data. The study was carried out with financial support of the
State Assignment of the National Research Center “Kurch-
As a result of a set of complementary studies, it was atov Institute” using equipment of the resource centers
revealed that differences in the molecular weight and “Polymer”, “Optika”, and “Nanozond” of the National
quantitative ratio of functional groups significantly Research Center “Kurchatov Institute,” as well as the
affect the initial properties of materials as well as their Kurchatov Complex for Synchrotron-Neutron Research.
change upon the addition of filler, despite the coinci-
dence of the chemical composition of polyurethanes.
Thus, a significant difference in the elastic modulus of CONFLICT OF INTEREST
the initial materials was revealed: 118 ± 3 MPa for The authors declare that they have no conflicts of interest.
TPU 95-A versus 52 ± 2 MPa for TPU Rec. It was
found that the addition of up to 10 wt % of filler does
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SPELL: 1. behenate

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