Search

Recent advances in experimental studies of nanoparticle-driven stabilization of chiral liquid-crystalline phases are highlighted. The stabilization is achieved via the nanoparticles’ assembly in the defect lattices of the soft liquid-crystalline hosts. This is of significant importance for understanding the interactions of nanoparticles with topological defects and for envisioned technological applications. We demonstrate that blue phases are stabilized and twist-grain boundary phases are induced by dispersing surface-functionalized CdSSe quantum dots, spherical Au nanoparticles, as well as MoS2 nanoplatelets and reduced-graphene oxide nanosheets in chiral liquid crystals. Phase diagrams are shown based on calorimetric and optical measurements. Our findings related to the role of the nanoparticle core composition, size, shape, and surface coating on the stabilization effect are presented, followed by an overview of and comparison with other related studies in the literature. Moreover, the key points of the underlying mechanisms are summarized and prospects in the field are briefly discussed. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.

Over the past decades, there has been significant interest in new cooling technology based on the electrocaloric effect. The large electrocaloric effect observed in polymeric and inorganic ferroelectric materials made possible development of dielectric cooling devices of a new generation. We report a significant impact of annealing on the electrocaloric effect observed in 12/65/35 PLZT bulk ceramics. The electrocaloric data were obtained by direct measurements. Electrocaloric results confirm the existence of the significant electrocaloric response in this relaxor ferroelectric PLZT composition exceeding previously obtained electrocaloric values in perovskite relaxor ferroelectrics such as PMN-PT and x/65/35 PLZT ceramics., arXiv admin note: text overlap with arXiv:2006.05079

We report on the effect of reduced-graphene oxide nanosheets decorated by CoPt nanoparticles on the blue phase range of a chiral liquid crystal. By means of high-resolution ac calorimetry and polarizing optical microscopy, it is demonstrated that a small concentration of these nanosheets induces the stabilization of a single blue phase structure in comparison to three blue phases existing in the pure compound. The results are compared with other liquid crystal-dispersed graphene studies, and, moreover, a short theoretical discussion of the stabilization effect is included. © 2020 Author(s).

Liquid crystals hosting nanoparticles comprise a fascinating research field, ranging from fundamental aspects of phase transitions to applications in optics and photonics. Liquid-crystalline phases exhibit topological defects that can be used for assembly of nanoparticles in periodical arrays, and at the same time, the nanoparticles can increase the stability range of liquid-crystalline phases. This has been experimentally demonstrated over the past few years in the case of blue phases that are present in some strongly chiral liquid crystals. Experimental results in quantum dot-driven blue phase stabilization are presented here by means of high-resolution calorimetry and polarizing optical microscopy. It is demonstrated that quantum dots essentially stabilize the macroscopically amorphous blue phase III. There are discussed similarities and differences between the effects of spherical and anisotropic nanoparticles on blue phase stabilization; moreover, future prospects and trends in the field are addressed. © Copyright © 2020 Cordoyiannis, Lavrič, Trček, Tzitzios, Lelidis, Nounesis, Daniel and Kutnjak.

We report on high-resolution calorimetry and small-angle X-ray scattering measurements along the Smectic-A to chiral Smectic-C* phase transition of the liquid crystal 4-(2-methyl butyl) phenyl 4-n-octylbiphenyl-4-carboxylate with dispersed, CoPt nanoparticle-coated reduced-graphene oxide nanosheets. The temperature dependence of heat capacity and smectic layer spacing are obtained in the vicinity of Smectic-A to chiral Smectic-C* phase transition. Though no remarkable pretransitional effects are present, the critical fits show a crossover from mean-field near a tricritical point to classical mean-field compared to pure liquid crystal. The X-ray data yield a dilation of smectic layer thickness, indicating the assembly of graphene oxide nanosheets between the smectic layers. © 2019, © 2019 Informa UK Limited, trading as Taylor & Francis Group.

Multiferroic composites with the composition (1-x) BaTi0.8Sn0.2O3 - (x) La0.5Ca0.5MnO3 (x =0, 0.3, 0.5, 0.7, 0.9 and 1) were prepared by sol-gel techniques. Rietveld refinements of the composites with 0-3 and 3-0 type connectivities exhibit the formation of pure phases and confirm the fraction of the composite samples. It was found that the composites grain size decreases slightly with increasing the La0.5Ca0.5MnO3 content. Magnetic measurements of the composite ceramics exhibit a gradual increase in saturation and remanent magnetization with increasing La0.5Ca0.5MnO3 content. Dielectric data demonstrate that the composite materials show high values of the dielectric constant in comparison with the parent compound BaTi0.8Sn0.2O3 (BTSO). In addition, an attempt is made to measure the magnetoelectric coupling coefficient and to explain the negative permittivity and losses occurring in these materials at a certain frequency and temperature conditions.

We report on strong pretransitional effects across the isotropic liquid-plastic crystal melting temperature in linear and nonlinear dielectric response. Studies were carried out for cyclooctanol (C8H16O) in the unprecedented range of temperatures 120 K < T < 345 K. Such pretransitional effects have not yet been reported in any plastic crystals. Results include the discovery of the experimental manifestation of the Mossotti Catastrophe behavior, so far considered only as a hypothetical paradox. The model interpretations of experimental findings are proposed. We parallel the observed pretransitional behavior with the one observed in octyloxycyanobiphenyl (8OCB), typical liquid crystal (LC), displaying a reversed sequence of phase transitions in orientational and translational degrees of order on varying temperature. Furthermore, in its nematic phase, we demonstrate first-ever observed temperature-driven crossover between regions dominated by isotropic liquid and smectic A pretransitional fluctuations. We propose a pioneering minimal model describing plastic crystal phase behavior where we mimic derivation of classical Landau-de Gennes-Ginzburg modelling of Isotropic - Nematic - Smectic A LC phase behavior.

Dilute mixtures of nanoparticles (NPs) and nematic liquid crystals (LCs) are considered. We focus on cases where NPs enforce a relatively weak disorder to the LC host. We use a Lebwohl-Lasher semi-microscopic-type modeling where we assume that NPs effectively act as a spatially-dependent external field on nematic spins. The orientational distribution of locally favoured “easy” orientations is described by a probabilistic distribution function P. By means of a mean field-type approach, we derive a self-consistent equation for the average degree of nematic uniaxial order parameter S as a function of the concentration p of NPs, NP-LC coupling strength and P. Using a simple step-like probability distribution shape, we obtain the S(p) dependence displaying a crossover behaviour between two different regimes which is in line with recent experimental observations. We also discuss a possible origin of commonly observed non-monotonous variations of the nematic-isotropic phase temperature coexistence width on varying p. © 2019 by the authors. Licensee MDPI, Basel, Switzerland.

We report on the stabilisation of the liquid-crystalline, twist-grain boundary A (TGBA) phase in mixtures of a chiral liquid crystal and surface-functionalised spherical Au nanoparticles (NPs) of 10 nm diameter. The results, obtained by calorimetric, optical, small-angle X-ray and plasmon resonance measurements, demonstrate that a TGBA phase, which is metastable for the pure liquid crystal host, can be effectively stabilised for a 3 K range in the presence of NPs. Moreover, the role of NPs size on the TGBA stabilisation is briefly discussed. © 2017 Informa UK Limited, trading as Taylor & Francis Group.

We report on wide-angle X-ray scattering measurements along the smectic-A to chiral ferroelectric smectic-C* phase transition of the liquid crystal SCE9 and its mixture with maghemite magnetic nanoparticles of typical dimension 20 nm. The temperature profiles of the tilt angle are fitted by an extended mean-field model. Neither pre-transitional order effects nor variations in the SmA layer thickness are observed, indicating a rather negligible influence of these nanoparticles upon the molecular orientation at the smectic-A to smectic-C* phase transition of SCE9. These results are very different from what was observed for smaller CdSe nanoparticles (3.5 nm) where both a dilation of the smectic layers in the SmA phase and a crossover behaviour for the smectic-A to smectic-C* transition away from tricriticality have been observed for analogous concentrations. © 2015 Taylor & Francis.

Glassy freezing dynamics was investigated in BaZr0.5Ti0.5O3 (BZT50) ceramic samples by means of dielectric spectroscopy in the frequency range 0.001 Hz-1 MHz at temperatures 10

We report on the appearance and stabilisation of twist-grain-boundary-A A* (TGB A*) phase in confined geometry samples of the liquid-crystalline compound CE8, by means of polarised optical microscopy. The chiral liquid crystal (LC) compound was chosen such as to undergo a cholesteric–smectic-A* transition with temperature (type-I smectic), and to be close to the triple point between the cholesteric, TGB A* , and smectic-A A* phases. We used several types of anchoring conditions and various effective anchoring strengths. The results reveal that (i) the TGB A* phase exists as a metastable phase with strong fluctuations in the bulk, and (ii) it can be stabilised by the sample boundaries for adequate anchoring conditions. This means that we probably observed a type-I to type-II smectic transition induced by the substrate. Some dependence of the stabilisation on the surface-anchoring conditions and on the cell thickness is reported. © 2016 Informa UK Limited, trading as Taylor & Francis Group.

The electrocaloric effect (ECE), i.e., the adiabatic temperature change ΔTEC, of the lead-free relaxor ferroelectric 0.85K0.5Na0.5NbO3-0.15SrTiO3 (KNN-STO) ceramics is investigated. The ECE data obtained by a direct method show the existence of a large ECE near the temperature of the dielectric permittivity maximum. Due to the high break-down electric field, a large ΔTEC exceeding 1.2 K at 300 K and 1.9 K at 340 K was observed at 159 kV/cm in a broad temperature range of 80 K. Such a high ECE response near the room temperature is comparable to that found in lead-based ceramic materials, thus making KNN-STO a strong candidate to replace lead-based materials in future electrocaloric applications. © 2015 AIP Publishing LLC.

The dielectric and thermal properties of an antiferroelectric (AFE) material characterised by an intermediate ferroelectric (FE) phase between the AFE and paraelectric phase in zero field are studied by means of a generalised Landau-Kittel model of AFEs. A temperature-dependent coupling of the two sublattices is introduced in accordance with the Rae-Dove (RD) model of re-entrant phase transitions. The sublattice polarisation components are calculated as functions of temperature and the applied electric field by minimising numerically the free energy. The calculated dielectric susceptibility shows anomalies at the boundaries of the intermediate FE phase, characteristic for first-order phase transitions. It is shown that this behaviour is in qualitative agreement with the measured dielectric constant in Ba-doped PbZrO3 ceramics. The model also predicts a negative adiabatic electrocaloric temperature change δT in a broad temperature range in the AFE phase, in qualitative agreement with experiments. The dipolar heat capacity is also predicted to be negative in the intermediate phase in zero field, in analogy with the results of the RD model. � 2015 IOP Publishing Ltd.

We study the impact of anisotropic nanoparticles (NPs) on the nematic liquid crystal (LC) order. Within a mesoscopic Flory–Huggins-type approach we have estimated regimes where LC–NP mixtures are essentially homogenous. Using a lattice Lebwohl–Lasher type approach we have also studied the impact of anisotropic NPs on LC ordering. We analysed the cases where the orientations of NPs are either frozen-in or could be varied, to which we refer as random field mixtures and annealed mixtures, respectively. In the latter case we have demonstrated the existence of qualitatively different regimes. In particular, we determined the concentration regime, where LC configurations resembling a transparent nematic phase could be observed. Such domain patterns are stabilised by NPs hindering the annihilation of topological defects in LC order. © 2015 Taylor & Francis.

The present letter explores the electrocaloric effect (ECE) in the lead free oxide Ba0.8Ca0.2Ti0.95Ge0.05O3 ceramics (BCTG). The electrocaloric responsivity (dT/dE) was determined by two different methods using the Maxwell relationship (dT/dE)~(dP/dT)_E. In a first well-known indirect method, P-E hysteresis loops were measured in a wide temperature range from which the pyroelectric coefficient p_E=(dP/dT)_E and thus (dT/dE) were determined by derivation of P(T,E) data. In the second novel method the pyroelectric coefficient p_E and consequently the electrocaloric responsivity was determined by direct measurements of the pyroelectric currents under different applied electric fields. Within the experimental error good agreement was obtained between two methods with an electrocaloric responsivity equal to 0.18 +/- 0.05 10-6 K.m.V-1 was obtained at about 410 K, Comment: 5 pages, 4 figures

We report on the widening of blue phase range induced by surface-functionalised laponite nanoplatelets dispersed in a chiral liquid crystal. The results are obtained by means of high-resolution ac calorimetry and optical microscopy and they are reproducible upon heating and cooling, identifying thermodynamically stable blue phases. It is shown that nanoplatelets target mostly the cubic structure of blue phase I and increase its temperature stability range by a factor of two. The present results are in agreement with recent findings that anisotropic nanoparticles tend to effectively stabilise blue phase I. © 2015 Copyright © Taylor & Francis Group, LLC.

By means of high-resolution ac calorimetry and polarizing optical microscopy, it is demonstrated that surface-functionalized spherical CdSSe nanoparticles induce a twist-grain boundary phase when dispersed in a chiral liquid crystal. These nanoparticles can effectively stabilize the one-dimensional lattice of screw dislocations, thus establishing the twist-grain boundary order between the cholesteric and the smectic-A phases. A Landau-de Gennes-Ginzburg model is used to analyze the impact of nanoparticles on widening the temperature range of molecular organizations possessing a lattice of screw dislocations. We show that in addition to the defect-core-replacement mechanism, the saddle-splay elasticity may also play a significant role. © 2014 American Physical Society.

The existence of an indirect magnetoelectricity in a soft composite material prepared as a mixture of magnetite ferromagnetic nanoparticles (NPs) and the ferroelectric liquid crystal (FLC) Felix 015/100 was verified by using a SQUID-based magnetometer. It was observed that the orientation of nanoparticles is directly coupled to the liquid crystal director field. Such a coupling allows the possibility of indirect coupling between the magnetic and ferroelectric order. This gifts the mixtures of FLC and magnetic nanoparticles (MNPs) with a great potential for soft indirect magnetoelectrics. © 2013 Copyright Taylor and Francis Group, LLC.

The layered FeTe2O5Cl compound was studied by specific-heat, muon spin relaxation, nuclear magnetic resonance, dielectric, as well as neutron and synchrotron x-ray diffraction measurements, and the results were compared to isostructural FeTe2O5Br. We find that the low-temperature ordered state, similarly as in FeTe2O5Br, is multiferroic - the elliptical amplitude-modulated magnetic cycloid and the electric polarization simultaneously develop below 11 K. However, compared to FeTe2O5Br, the magnetic elliptical envelop rotates by 75(4) deg and the orientation of the electric polarization is much more sensitive to the applied electric field. We propose that the observed differences between the two isostructural compounds arise from geometric frustration, which enhances the effects of otherwise subtle Fe3+ (S = 5/2) magnetic anisotropies. Finally, x-ray diffraction results imply that, on the microscopic scale, the magnetoelectric coupling is driven by shifts of the O1 atoms, as a response to the polarization of the Te4+ lone-pair electrons involved in the Fe-O-Te-O-Fe exchange bridges., Comment: 10 pages, 10 figures. (http://link.aps.org/doi/10.1103/PhysRevB.88.224421)

We study the characteristics of nematic structures in a randomly perturbed nematic liquid crystal (LC) phase. We focus on the impact of the samples history on the universal behavior. The obtained results are of interest for every randomly perturbed system exhibiting a continuous symmetry-breaking phase transition. A semimicroscopic lattice simulation is used where the LC molecules are treated as cylindrically symmetric, rod-like objects interacting via a Lebwohl-Lasher (LL) interaction. Pure LC systems exhibit a first order phase transition into the orientationally ordered nematic phase at T=Tc on lowering the temperature T. The orientational ordering of LC molecules is perturbed by the quenched, randomly distributed rod-like impurities of concentration p. Their orientation is randomly distributed, and they are coupled with the LC molecules via an LL-type interaction. Only concentrations below the percolation threshold are considered. The key macroscopic characteristics of perturbed LC structures in the symmetry-broken nematic phase are analyzed for two qualitatively different histories at T≪Tc. We demonstrate that, for a weak enough interaction among the LC molecules and impurities, qualitatively different history-dependent states could be obtained. These states could exhibit either short-range, quasi-long-range, or even long-range order. © 2013 A. Ranjkesh et al.

It is demonstrated that interactions between nanoparticles and topological defects induce a twist-grain boundary phase in a chiral liquid crystal. The occurrence of this phase, the analogue of the Shubnikov phase in type-II superconductors, is driven by direct interactions between surface-functionalized CdSe quantum dots and screw dislocations. It is shown that, within an adaptive-defect-core-targeting mechanism, nanoparticles of appropriate size and functionalization adapt to qualitatively different cores of topological defects such as disclination lines and screw dislocations. This mechanism enables the effective reduction of the energetically costly, singular defect core volume, while the surrounding phase ordering remains relatively weakly affected. The findings suggest new pathways towards the controlled assembly of superstructures in diverse, symmetry-broken, condensed-matter systems, ranging from nanoparticle-decorated liquid crystals to superconductors. © The Royal Society of Chemistry 2013.

Direct measurements of the electrocaloric effect (ECE) in bulk lead-free relaxor K0.5Na0.5NbO3-SrTiO3 (KNN-STO) ceramics sintered in air have been performed by using electrocaloric thermometry, i.e., a high-resolution calorimetry with a small modification to the experimental setup and software. The obtained results confirm the existence of a large ECE in this material in the vicinity of the ferroelectric phase transition, where the electrocaloric temperature change ΔTEC around 0.5 K was achieved under a field of 80 kV/cm. At room temperature ΔTEC is comparable with that observed in lead-based ceramic materials, so far the most studied electrocaloric materials, which, however, are less environmentally friendly due to the toxicity of lead. Copyright © Taylor & Francis Group, LLC.

The stabilization of liquid-crystalline blue phases is recently attracting considerable interest because of the envisioned applications in fast optical displays and tunable photonic crystals. We report on the effect of surface-functionalized graphene nanosheets on the blue phase range of a chiral liquid crystal. Calorimetric and optical measurements, reproducible on heating and cooling, demonstrate that the resulting soft nanocomposite exhibits an increased blue phase temperature stability range for a minute concentration of dispersed graphene. The impact is stronger on the ordered, cubic structured blue phase I. These findings suggest that anisotropic nanoparticles may be of great usefulness for stabilizing blue phases. © 2013 AIP Publishing LLC.

Spherical CdSe nanoparticles, surface-treated with oleylamine and tri-octylphosphine, dispersed in ferroelectric liquid crystals, can efficiently target disclination lines, substantially altering the macroscopic properties of the host compound. Here we present an ac calorimetry and x-ray diffraction study demonstrating that for a large range of nanoparticle concentrations the smectic-A layer thickness increases monotonically. This provides evidence for enhanced accumulation of nanoparticles at the smectic layers. Our results for the Smectic-A (SmA) to chiral smectic-C (SmC*) phase transition of the liquid crystal S-(+)4-(2′-methylbutyl)phenyl-4 ′-n-octylbiphenyl-4-carboxylate (CE8) reveal that the character of the transition is profoundly changed as a function of the nanoparticle concentration. Large transition temperature shifts are recorded. Moreover, the heat-capacity peaks exhibit a crossover trend to a step-like anomaly. This behavior may be linked to the weakening of the SmA and SmC* order parameter coupling responsible for the observed near-tricritical, mean-field character of the transition in bulk CE8. At lower temperatures, the presence of nanoparticles disrupts the phase sequence involving the tilted hexatic phases most likely by obstructing the establishment of long-range bond-orientational order. © 2013 American Physical Society.

The electrocaloric effect (ECE) is the entropy and temperature change of a dielectric when subject to a change of electric field. This chapter will discuss briefly thermodynamic considerations for materials that exhibit large ECE and review previous results of the ECE in polar crystals, ceramics, and thin films. ECE results from direct measurement and deduced from Maxwell's relations will be presented along with the phenomenological modeling for ferroelectric polymers, which have been recently discovered to exhibit a large ECE. Finally the ECE of polar materials are modeled to forecast their potential in future devices.

Magnetic and ferroelectric properties of layered geometrically frustrated cluster compound FeTe$_2$O$_5$Br were investigated with single-crystal neutron diffraction and dielectric measurements. Incommensurate amplitude modulated magnetic order with the wave vector $\bf{q}$=($\half$, 0.463, 0) develops below $T_N=10.6(2) {\rm K}$. Simultaneously, a ferroelectric order with the spontaneous polarization perpendicular to ${\bf q}$ and to Fe$^{3+}$ magnetic moments emerges. The observed ferroelectricity and extraordinary linear scaling of the ferroelectric and magnetic order parameter are provoked by the striction of the intercluster Fe-O-Te-O-Fe bridges leading to the shift of Te$^{4+}$ ions and polarization of their lone-pair electrons.

We show that the phase diagram of the (001) Pb Mg1 3 Nb2 3 O3 -x PbTiO3 (PMN- x PT) (x=0.00, 0.06, 0.13, and 0.24) and (111) PMN-0.24PT lead-magnesium niobate mixed with lead titanate possesses a quasivertical line in the E electric field - T temperature plot, which hardly depends on the field. The existence of this line has been confirmed by independent studies of single crystals grown in different laboratories, by measuring the dielectric permittivity, compliances, and optical transmission, also in different laboratories. A thermal hysteresis inherent to first order phase transitions complicates the phase diagram. The piezoelectric coefficients of the (001) PMN- x PT (x = 0.06 and 0.13) have two peaks versus temperature, at finite fields. The first peak is due to the quasivertical phase boundary. The second is in the vicinity of a turning point of the Tm (E) temperature of the dielectric permittivity diffuse maximum. We show that the second peak prevails at reasonable fields, and the piezoelectric coefficients have comparatively large values at this peak, even at small x. © 2007 The American Physical Society.

The low-temperature magnetic phase diagram of the multiferroic system FeTe$_2$O$_5$Br down to 300 mK and up to 9 T is presented. Short-range magnetic correlations within the crystal layers start to develop already at $\sim$50 K, i.e., far above $T_{N1} \sim$ 11.0 K, where the system undergoes a magnetic phase transition into the high-temperature incommensurate (HT-ICM) phase. Only 0.5 K lower, at $T_{N2}$, the system undergoes a second phase transition into the low-temperature incommensurate amplitude-modulated (LT-ICM) phase accompanied by a spontaneous electric polarization. When the magnetic field is applied, the transition temperatures shift depending on the field orientation. In the case of $B||b$ and $B >$ 4.5 T, the HT-ICM phase disappears along with the electric polarization in the LT-ICM phase. The field dependence of the magnetic transition temperatures is explained in the context of the magnetic susceptibility behavior. Similarities and differences between the novel amplitude-modulated and well-established helicoidal magnetoelectrics are discussed.

The magnetic and ferroelectric properties of the layered geometrically frustrated cluster compound FeTe2O5Br were investigated with single-crystal neutron diffraction and dielectric measurements. An incommensurate transverse amplitude modulated magnetic order with the wave vector q = (1/2, 0.463, 0) develops below T-N = 10.6(2) K. Simultaneously, a ferroelectric order due to exchange striction involving polarizable Te4+ lone-pair electrons develops perpendicular to q and to Fe3+ magnetic moments. The observed magnetoelectric coupling is proposed to originate from the temperature dependent phase difference between neighboring amplitude modulation waves.