Morphology and dielectric properties of polymer dispersed liquid crystal with magnetic nanoparticles

It has been shown that introduction of magnetic nanoparticles (MN) of various shapes with the concentration 10⁻¹ wt.% into polymer dispersed liquid crystal (PDLC) causes two effects: the size of liquid crystal droplets decreases, and the amount of the latter with through holes increases. MN incre...

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Опубліковано в: :Semiconductor Physics Quantum Electronics & Optoelectronics
Дата:2010
Автори: Kopčanský, P., Timko, M., Mitrova, Z., Zavisova, V., Koneracká, M., Tomašovičov, N., Tomčo, L., Gornitska, O.P., Kovalchuk, O.V., Bykov, V.M., Kovalchuk, T.M., Studenyak, I.P.
Формат: Стаття
Мова:Англійська
Опубліковано: Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України 2010
Онлайн доступ:https://nasplib.isofts.kiev.ua/handle/123456789/118564
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Цитувати:Morphology and dielectric properties of polymer dispersed liquid crystal with magnetic nanoparticles / P. Kopcansky, M. Timko, Z. Mitrova, V. Zavisova, M. Koneracka, N. Tomasovicova, L. Tomco, O.P. Gornitska, O.V. Kovalchuk, V.M. Bykov, T.M. Kovalchuk, I.P. Studenyak // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2010. — Т. 13, № 4. — С. 343-347. — Бібліогр.: 11 назв. — англ.

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Digital Library of Periodicals of National Academy of Sciences of Ukraine
_version_ 1859470534159368192
author Kopčanský, P.
Timko, M.
Mitrova, Z.
Zavisova, V.
Koneracká, M.
Tomašovičov, N.
Tomčo, L.
Gornitska, O.P.
Kovalchuk, O.V.
Bykov, V.M.
Kovalchuk, T.M.
Studenyak, I.P.
author_facet Kopčanský, P.
Timko, M.
Mitrova, Z.
Zavisova, V.
Koneracká, M.
Tomašovičov, N.
Tomčo, L.
Gornitska, O.P.
Kovalchuk, O.V.
Bykov, V.M.
Kovalchuk, T.M.
Studenyak, I.P.
citation_txt Morphology and dielectric properties of polymer dispersed liquid crystal with magnetic nanoparticles / P. Kopcansky, M. Timko, Z. Mitrova, V. Zavisova, M. Koneracka, N. Tomasovicova, L. Tomco, O.P. Gornitska, O.V. Kovalchuk, V.M. Bykov, T.M. Kovalchuk, I.P. Studenyak // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2010. — Т. 13, № 4. — С. 343-347. — Бібліогр.: 11 назв. — англ.
collection DSpace DC
container_title Semiconductor Physics Quantum Electronics & Optoelectronics
description It has been shown that introduction of magnetic nanoparticles (MN) of various shapes with the concentration 10⁻¹ wt.% into polymer dispersed liquid crystal (PDLC) causes two effects: the size of liquid crystal droplets decreases, and the amount of the latter with through holes increases. MN increase the effective value of permittivity by more than one order within the frequency range 10⁻¹⁺ -10² HZ , as well as the electron and ion components of conductivity. MN reduce the exponent in the frequency dependence of the electron component of conductivity. The changes caused by the presence of the nanoparticles quantitatively depend on their shape.
first_indexed 2025-11-24T09:08:46Z
format Article
fulltext Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 343-347. PACS 61.30.Gd, 75.30.Hx, 77.84.Nh Morphology and dielectric properties of polymer dispersed liquid crystal with magnetic nanoparticles P. Kopčanský1, M. Timko1, Z. Mitrova1, V. Zavisova1, M. Koneracká1, N. Tomašovičová1, L. Tomčo1, O.P. Gornitska2, O.V. Kovalchuk2,3, V.M. Bykov3, T.M. Kovalchuk4, I.P. Studenyak5 1Institute of Experimental Physics, Slovak Academy of Sciences, 47, Watsonova str., 04001 Košice, Slovak Republic 2National Aviation University, Institute of Innovative Technologies 1, Cosmonaut Komarov str., 03058 Kyiv, Ukraine 3Institute of Physics, National Academy of Science of Ukraine, 46, prospect Nauky, 03028 Kyiv, Ukraine 4V. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine, 45, prospect Nauky, 03028 Kyiv, Ukraine 5Uzhgorod National University, 46, Pidhirna str., 88000 Uzhgorod, Ukraine Abstract. It has been shown that introduction of magnetic nanoparticles (MN) of various shapes with the concentration wt.% into polymer dispersed liquid crystal (PDLC) causes two effects: the size of liquid crystal droplets decreases, and the amount of the latter with through holes increases. MN increase the effective value of permittivity by more than one order within the frequency range , as well as the electron and ion components of conductivity. MN reduce the exponent in the frequency dependence of the electron component of conductivity. The changes caused by the presence of the nanoparticles quantitatively depend on their shape. 110− Hz1010 21 −− Keywords: magnetic nanoparticle, polymer matrix, liquid crystal, permittivity, electron and ion components of conductivity. Manuscript received 05.09.10; accepted for publication 02.12.10; published online 30.12.10. 1. Introduction The large scale study of dispersions of nematic liquid crystal in a polymer matrix (PDLC) began after publications [1, 2], where it was shown that these systems can be used to create electro-optical devices of a new type [3]. Wide spread of these systems in display technology is limited by two important factors: the rather high (as compared to homogeneous systems) value of voltage, for example, for transition from a state with a strong light scattering into the transparent one, as well as more longer times of transition from one state to another (especially when the voltage is turned off). Therefore, the PDLCs are currently considered as promising materials for specific applications such as creation of window blinds controlled by electric field, fog simulators, UV protective glasses, etc. In all these devices, the mechanism providing control of PDLC optical properties is of fundamental importance. It is known [4] that, when electric field acts on PDLC, the electric field inside droplets of liquid crystal can be significantly lower than the external electric field due to effects of polarization. This fact principally leads to controlling voltages that are significant in their magnitude (tens and even hundreds of volts). Polarization effects can be ignored if using the magnetic field for controlling the electro-optical properties of PDLC. Due to relatively low anisotropy of the diamagnetic susceptibility of liquid crystal, magneto- optical effects in PDLC are possible in the case of sufficiently strong magnetic fields that can be practically realized only in a few research laboratories over the world. The effect of magnetic field can be significantly enhanced by introducing the magnetic particles into PDLC. To have no influence on the light scattering, © 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine 343 Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 343-347. these particles should possess dimensions that are shorter than the light wavelengths, and their concentration must be relatively low. It is clear that for these purposes the magnetic nanoparticles (MN) are best matched, and great success in their manufacturing technology was presently achieved. © 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine a b c Fig. 1. Morphology of PDLC films: pure (a), with spherical MN (b) and with rod-like MN (c) obtained by using the scanning electron microscope JSM-35. The accelerating voltage was 35 keV. The arrow indicates the location where a hole was formed. These images are of the negative type. The analysis of publications has showed that the effect of MN on the properties of homogeneous liquid crystal was extensively investigated [5-8], but only few data for MN influence on the properties of PDLC were obtained. In our opinion, the properties of PDLC with the MN will be to a large extent determined by the fact how the MN act on the structure and dielectric properties of this matrix. The purpose of this work was to investigate this influence. 2. Materials and methods The samples of PDLCs have been prepared by the following method. Liquid crystal (6CHBT, i.e. 4-trans- 4'-n-hexyl-cyclohexyl-isothiocyanatobenzene) of amount 0.05 ml was added to 5 ml with 10% polyvinyl alcohol (PVA). This mixture was stirred at 10,000 rpm for 1 min. A creamy white emulsion was obtained. It was let to degas and a thin bead was placed on a slide. After the water evaporation, we got a thin film. This technique was also used for preparation of the PDLC films doped with various kinds of magnetic particles. The sample thickness was 50 μm. The structure of the films was investigated by using the scanning electron microscope JSM-35 with the accelerating voltage 35 keV. To eliminate the effect of charging the surface, before the measurements a graphite film was deposited onto the surface of the PDLC film. Dielectric measurements were performed using the oscilloscope method [9, 10] at the temperature close to 293 K. We applied to the sample the alternating voltage of a triangular shape with the amplitude value 0.25 V. The range of measuring signal frequency was within to 10110− 6 Hz. The PDLC film was placed between two glass plates covered with a transparent layer of ITO. To improve the electrical contact, a small amount of 6CHBT was deposited onto the surface of electrodes. 3. Results and discussion 1. The morphology of the samples Fig. 1 shows the morphology of the films PDLC (a), PDLC with spherical MN (b), and PDLC with rod-like MN (c). Our analysis of these data demonstrates that the MN act on the sizes of droplets of liquid crystal in the polymer matrix. In the case of PDLC films, the average LC droplet size was 5 to 8 μm (Fig. 1a). When introducing the MN, the average droplet size was decreased down to 3…5 μm for spherical MN and 4…6 μm for the rod-like MN. A decrease of the droplet sizes can be explained by an increase in the rigidity of 344 Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 343-347. the polymer film. In this case, MN act as rebar in concrete. Beside reduction of droplet sizes, presence of MN leads to an increase in the number of droplets with through holes (black dots in the center of the droplets). It follows from Fig. 1 that this effect is most pronounced in the films with rod-like MN. The difference in the amount of droplets with through holes for the MN of different shape is understandable, because the rod-like MN change geometrical parameters of the polymer matrix more significantly than the spherical ones. It should be noted that the concentration of spherical and rod-like MN was wt.%. I.e., even a small amount of MN may considerably change both morphology and other properties of PDLC (as will be shown below). 110− © 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine 10-1 100 101 102 103 104 105 106 101 102 103 104 3 2 1 ε ' f, Hz Fig. 2. Frequency dependence of the effective value of the permittivity for the PDLC films: pure (1), with spherical MN (2) and with rod-like MN (3). The film thickness is 50 μm. The amplitude value of the voltage of measured signal is 0.25 V. The temperature is 293 K. 2. Dielectric properties Fig. 2 shows the frequency dependence of dielectric films PDLC (1), PDLC with spherical MN (2) and PDLC with rod-like MN (3). The data obtained suggest that the greatest difference between the samples in the ε′ value is observed at the frequency f <102 Hz. Within this frequency range, the very ε′ value is sharply increased, too. As was shown in [11, 12], the sharp increase in the components of the permittivity (real and imaginary) is caused by redistribution of the electric field due to near- electrode processes. For non-uniform electric field, the ε′ value can be considered as the effective one. From the above analysis, we can conclude that the spherical and rod-like MN influence most significantly on the parameters of the near-electrode area. As seen from Fig. 2, the greatest difference in the ε′ magnitude (more than one order) is observed for f = 0.1 Hz. For this frequency range, the influence of the near-electrode area is the most essential. In [11, 12], it was shown that redistribution of the field in the near-electrode area is the most pronounced in liquids. Therefore, an analysis of Fig. 2 data demonstrates that the introduction of MN into PDLC leads to an increase in the amount of liquid crystal in the near-electrode area. Based on the analysis of morphology of these films, we concluded that significant increase in the number of holes in liquid crystal droplets in the presence of MN promotes this process. As follows from Fig. 1, for the case of rod-like MN the amount of liquid crystal droplets with holes is larger than that for PDLC with spherical MN. There is a complete correlation between the changes in the ε′ value and the amount of droplets with through holes. I.e., the main reason for the change of dielectric properties of PDLC, when introducing the MN, is a change in the parameters of the near-electrode area. A comparison of the ε′ value for three types of the samples measured at frequencies f > 102 Hz shows that for these frequencies also a change in the ε′ value is observed, but it is considerably smaller than the above changes. The largest change in the ε′ value for these frequencies is observed when f > 105 Hz and may be caused by the influence of MN on dipole polarization in LC droplets. This indicates that when phases are separated, as a result of polymerization, a part of MN goes into the polymer, but some of them remain in the LC droplets. Fig. 3 shows the frequency dependence of conductivity for films of PDLC (1), PDLC with spherical MN (2) and PDLC with rod-like MN (3). It follows that this frequency range can be separated into three sections. 10-1 100 101 102 103 104 105 106 10-8 10-7 10-6 10-5 3 2 1 σ, Ohm-1m-1 f, Hz Fig. 3. Frequency dependence of the conductivity for the PDLC films: pure (1), with spherical MN (2) and with rod-like MN (3). Lines indicate the regions where the conductivity depends on the frequency in accord with a power law. 345 Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 343-347. For frequencies f < 102 Hz, the conductivity is almost independent of frequency. Such behavior is characteristic for ion conductivity in LC. Since most of the LC droplets in the presence of spherical and rod-like MN have through holes, it promotes charge transfer due to ion motion. This is the main reason for the change of the ion component of conductivity σi. In addition, the presence of MN in the LC droplets leads to increase in the ion conductivity of the very LC. Comparison of the σi value for the films of PDLC (1), PDLC with spherical MN (2) and PDLC with rod- like MN (3) (Fig. 3) shows that when introducing the MN into PDLC, the σi value is increased by more than one order. And in the case of rod-like MN, a change of σi is approximately 1.2 times higher than that in the case of spherical MN. This small difference in the magnitude of the ion component of conductivity does not give grounds to assert that the main reason for total increase is formation of through holes in the films. An increase in σi with introducing the MN is most likely caused by changes in the conductivity of the very LC, and the shape of nanoparticles has no special meaning in this case. The obtained experimental data do not allow to determine which of the mechanisms providing the change in the σi value is the main one. To solve this problem, additional experiments must be carried out. This is not an aim of this work and will be a subject of our further studies. As follows from Fig. 3, at frequencies f > ·103 Hz for all the samples, the conductivity depends on the frequency in accord with the power law σe = σDC + Aωs, (1) where σDC is the dc conductivity (f = 0), ω = 2πf – angular frequency, A – constant value for this process of changes in the conductivity, s – the exponent that characterizes mainly the transfer of charge carriers. The dependence (1) is characteristic for charge transfer in disordered solids, where the hopping process is inherent to charge carriers (mainly electrons) being in electric field and changing one stable state for another. It can be assumed that for PDLC films the conductivity that obeys relation (1) is caused by electron transfer in the polymer film. As noted above, the most important parameter characterizing the charge transfer process (1) is the s value. Fig. 3 shows that for the PDLC films s = 0.67 ± 0.03. For the PDLC with spherical MN s = 0.26 ± 0.03, and for PDLC with rod-like MN s = 0.23 ± 0.03. It enables one to conclude that the magnetic nanoparticles change the electrical properties not only of liquid crystal droplets, but the polymer (PVA), too. It is seen from Fig. 3 that the MN effect on the electron conductivity in the polymer is less than on the ion component in LC. But the influence of the MN shape on conductivity changes is more clearly expressed in this case. In contrast to σi, the σe value for PDLC with rod- like MN is more than 1.8 times greater than that for PDLC with spherical MN. If to compare the effect of MN on σi and σe values one can draw the following conclusions. At the presence of MN, the σi value increases 25 times, while the maximum change in σi (for f = 106 Hz) equals 15 for PDLC with rod-like MN. I.e., the presence of MN in PDLC has a greater effect on the magnitude of the ion component of conductivity than on the σe value. Since σi is caused by LC conductivity and σe – by conductivity of polymer, this comparison allows to suggest that, after separation of the phases, most of the MN is located in the LC droplets. Within the total frequency range, the conductivity can be represented as a sum of the ion conductivity in LC σi (its value does not depend on the frequency) and the electron conductivity in polymer σe: σ = σi + σDC + Aωs. (2) By using the equation (2), one can describe the frequency dependence in the transition parts, too. Conclusions 1. The presence of MN in PDLC films based on liquid crystal 6CHBT and polyvinyl alcohol leads to two effects: an increase in the amount of droplets with holes and decrease in droplet sizes. For PDLC films, the LC droplet size was 5 to 8 μm. When introducing MN into PDLC, the droplet size was decreased down to 3…5 μm for spherical MN and 4…6 μm for rod-like MN. The decrease in sizes of droplets can be explained by rigidity of the polymer film in the presence of MN. Due to MN introduction, effect of an increase of holes in the droplets is more essential than the effect of reducing their size. 2. With MN introduction into PDLC, the most significant changes in the effective value of the permittivity were observed for frequencies f < 102 Hz. These changes may be caused by an increase in the amount of liquid crystal in the near-electrode area due to formation of holes in LC droplets. This assumption is confirmed by the influence of the droplet shape on the ε′ value and by correlation between the change in ε′ and amount of holes in the LC droplets with different shapes of MN. 3. The conductivity of PDLC within the frequency range has two components: the ion one σHz1010 61 −− i caused by transfer of ions in LC and electron one σe caused by transfer of electrons inside polymer. The ion component of conductivity does not depend on frequency, and it is the main component for frequencies f < 102 Hz. The determining contribution of the electron component is observed for frequencies f > ·103 Hz. This component of conductivity is characterized by the power dependence on the frequency. 4. The MN introduction into PDLC leads to an increase in the ion component of conductivity by a factor © 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine 346 Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 343-347. of more than 25. The shape of the nanoparticles does not practically influence on the change in the value of conductivity (in the case of rod-like MN, the change of σi is approximately 1.2 times higher than that for spherical MN). At the presence of MN, the maximum change in the electron component of conductivity is equal to 15. In this case, for the rod-like MN the change of σe value is 1.8 times larger than that for the spherical MN. The presence of MN in PDLC leads not only to a change in the conductivity value, but also to a decrease in the exponent for the dependence σe(f) from 0.67 ± 0.03 for the PDLC to 0.26 ± 0.03 for the PDLC with spherical MN and 0.23 ± 0.03 for the PDLC with rod-like MN. The smaller change of the σe value than the σi value when introducing MN into PDLC may be caused by the fact that, when phases are separated, the most of MN passes to LC in the process of structure formation. References 1. J. Fergason, Polymer encapsulated nematic liquid crystals for display and light control applications // SID Intern. Symp. Digest. Tech. Papers, 16, p. 68 (1985). 2. J.W. Doane, N.A. Vaz, B.-G. Wu, S. Zumer, Field controlled light scattering from nematic microdroplets // Appl. Phys. Lett. 48, No.4, p. 269- 271 (1986). 3. A.V. Kovalchuk, M.V. Kurik, O.D. Lavrentovich, Encapsulated nematic liquid crystals: a new class of display units // Zarubezhnaja radioelektronika, № 5, p. 44-58 (1989), in Russian. 4. H. Stark, Physics of colloidal dispersions in nematic liquid crystals // Phys. Repts. 351, No.6, p. 387-474 (2001). 5. P. Kopčanský, M. Koneracká, V. Zavisova et al., Study of magnetic Fredericksz transition in ferronematics liquid crystals doped with fine magnetic particles // J. Phys. IV (Paris), 7, p. C565- C566 (1997). 6. O. Buluy, E. Ouskova, Yu. Reznikov et al., Magnetically induced alignment of FNS // J. Magn. Magn. Mater. 252, p. 159-161 (2002). 7. P. Kopčanský, I. Potočova, M. Koneracká et al., The anchoring of nematic molecules on magnetic particles in some types of ferronematics // J. Magn. Magn. Mater. 289, p. 101-104 (2005). 8. P. Kopčanský, N. Tomašovičová, M. Koneracká et al., Structural changes in the 6CHBT liquid crystal doped with spherical, rodlike, and chainlike magnetic particles // Phys. Rev. E. 78, No.1, 011702 (2008). 9. A.J. Twarowski, A.C. Albrecht, Depletion layer in organic films: Low frequency measurements in polycrystalline tetracene // J. Chem. Phys. 20, No.5, p. 2255-2261(1979). A.V. Koval’chuk, Low- and infra-low dielectric spectroscopy liquid crystal – solid state interface. Sliding layers // Ukr. J. Phys. 41, No.10, p. 991- 998 (1996). 10. A.V. Koval’chuk, Generation of charge carrier and formation of antisymmetric double electric layers in glycerine // J. Chem. Phys. 108, No.19, p. 8190- 8194 (1998). 11. A.V. Koval’chuk, Relaxation processes and charge transport across liquid crystal – electrode interface // J. Phys.: Condensed Matter. 13, No.24, p. 10333- 10345 (2001). © 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine 347
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institution Digital Library of Periodicals of National Academy of Sciences of Ukraine
issn 1560-8034
language English
last_indexed 2025-11-24T09:08:46Z
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publisher Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
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spelling Kopčanský, P.
Timko, M.
Mitrova, Z.
Zavisova, V.
Koneracká, M.
Tomašovičov, N.
Tomčo, L.
Gornitska, O.P.
Kovalchuk, O.V.
Bykov, V.M.
Kovalchuk, T.M.
Studenyak, I.P.
2017-05-30T16:18:37Z
2017-05-30T16:18:37Z
2010
Morphology and dielectric properties of polymer dispersed liquid crystal with magnetic nanoparticles / P. Kopcansky, M. Timko, Z. Mitrova, V. Zavisova, M. Koneracka, N. Tomasovicova, L. Tomco, O.P. Gornitska, O.V. Kovalchuk, V.M. Bykov, T.M. Kovalchuk, I.P. Studenyak // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2010. — Т. 13, № 4. — С. 343-347. — Бібліогр.: 11 назв. — англ.
1560-8034
PACS 61.30.Gd, 75.30.Hx, 77.84.Nh
https://nasplib.isofts.kiev.ua/handle/123456789/118564
It has been shown that introduction of magnetic nanoparticles (MN) of various shapes with the concentration 10⁻¹ wt.% into polymer dispersed liquid crystal (PDLC) causes two effects: the size of liquid crystal droplets decreases, and the amount of the latter with through holes increases. MN increase the effective value of permittivity by more than one order within the frequency range 10⁻¹⁺ -10² HZ , as well as the electron and ion components of conductivity. MN reduce the exponent in the frequency dependence of the electron component of conductivity. The changes caused by the presence of the nanoparticles quantitatively depend on their shape.
en
Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
Semiconductor Physics Quantum Electronics & Optoelectronics
Morphology and dielectric properties of polymer dispersed liquid crystal with magnetic nanoparticles
Article
published earlier
spellingShingle Morphology and dielectric properties of polymer dispersed liquid crystal with magnetic nanoparticles
Kopčanský, P.
Timko, M.
Mitrova, Z.
Zavisova, V.
Koneracká, M.
Tomašovičov, N.
Tomčo, L.
Gornitska, O.P.
Kovalchuk, O.V.
Bykov, V.M.
Kovalchuk, T.M.
Studenyak, I.P.
title Morphology and dielectric properties of polymer dispersed liquid crystal with magnetic nanoparticles
title_full Morphology and dielectric properties of polymer dispersed liquid crystal with magnetic nanoparticles
title_fullStr Morphology and dielectric properties of polymer dispersed liquid crystal with magnetic nanoparticles
title_full_unstemmed Morphology and dielectric properties of polymer dispersed liquid crystal with magnetic nanoparticles
title_short Morphology and dielectric properties of polymer dispersed liquid crystal with magnetic nanoparticles
title_sort morphology and dielectric properties of polymer dispersed liquid crystal with magnetic nanoparticles
url https://nasplib.isofts.kiev.ua/handle/123456789/118564
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