Phase transitions study of the liquid crystal DIO with a ferroelectric nematic, a nematic, and an intermediate phase and of mixtures with the ferroelectric nematic compound RM734 by adiabatic scanning calorimetry.

High-resolution calorimetry has played a significant role in providing detailed information on phase transitions in liquid crystals. In particular, adiabatic scanning calorimetry (ASC), capable of providing simultaneous information on the temperature dependence of the specific enthalpy h(T) and on the specific heat capacity c_{p}(T), has proven to be an important tool to determine the order of transitions and render high-resolution information on pretransitional thermal behavior. Here we report on ASC results on the compound 2,3',4',5'-tetrafluoro[1,1'-biphenyl]-4-yl 2,6-difluoro-4-(5-propyl-1,3-dioxan-2-yl) benzoate (DIO) and on mixtures with 4-[(4-nitrophenoxy)carbonyl]phenyl 2,4-dimethoxybenzoate (RM734). Both compounds exhibit a low-temperature ferroelectric nematic phase (N_{F}) and a high-temperature paraelectric nematic phase (N). However, in DIO these two phases are separated by an intermediate phase (N_{x}). From the detailed data of h(T) and c_{p}(T), we found that the intermediate phase was present in all the mixtures over the complete composition range, albeit with strongly decreasing temperature width for that phase with decreasing mole fraction of DIO (x_{DIO}). The x_{DIO} dependence on the transition temperatures for both transitions could be well described by a quadratic function. Both these transitions were weakly first order. The true latent heat of the N_{x}-N transition of DIO was as low as L=0.0075±0.0005J/g and L=0.23±0.03J/g for the N_{F}-N_{x} transition, which is about twice the previously reported value of 0.115 J/g for the N_{F}-N transition in RM734. In the mixtures both transition latent heats decrease gradually with decreasing x_{DIO}. At all the N_{x}-N transitions pretransition fluctuation effects are absent and these transitions are purely but very weakly first order. As in RM734 the transition from the N_{F} to the higher-temperature phase exhibits substantial pretransitional behavior, in particular, in the high-temperature phase. Power-law analysis of c_{p}(T) resulted in an effective critical exponent α=0.88±0.1 for DIO and this value decreased in the mixtures with decreasing x_{DIO} toward α=0.50±0.05 reported for RM734. Ideal mixture analysis of the phase diagram was consistent with ideal mixture behavior provided the total transition enthalpy change was used in the analysis.

Anomalous dielectric and thermal properties of Ba-doped PbZrO3 ceramics.

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.

Evidence from adiabatic scanning calorimetry for the Halperin-Lubensky-Ma effect at the N-SmA phase transitions in mixtures of 7OCB+heptane with an injected SmA phase.

The high-resolution adiabatic scanning calorimetric technique has been used to investigate the nematic-smectic A transition (N-SmA in binary mixtures of the non-smectogenic liquid crystal heptyloxycyanobiphenyl (7OCB) and heptane, exhibiting a so-called injected smectic A phase. With the exception of a mixture with the lowest heptane mole fraction for which only an upper limit of 0.2 ± 0.2 J kg(-1) for a possible latent heat could be obtained, for all other mixtures finite latent heats were obtained. The mole fraction dependence of the latent heat could be well fitted with a crossover function consistent with a mean-field free energy expression with a non-zero cubic term arising from the Halperin-Lubensky-Ma (HLM) coupling between the SmA order parameter and the orientational director fluctuations. The mole fraction dependence of the heat capacity effective critical exponents is similar to that observed in mixtures of the two liquid crystals octyloxycyanobiphenyl (8OCB) and nonylcyanobiphenyl (9OCB). The thermal behavior observed along the N-SmA phase transition line yields further strong evidence for the HLM coupling effect.

Theoretical and experimental study of the nanoparticle-driven blue phase stabilisation.

We have studied theoretically and experimentally the effects of various types of nanoparticles (NPs) on the temperature stability range [Formula: see text] T (BP) of liquid-crystalline (LC) blue phases. Using a mesoscopic Landau-de Gennes type approach we obtain that the defect core replacement (DCR) mechanism yields in the diluted regime [Formula: see text] T (BP)(x) [Formula: see text] 1/(1 - xb) , where x stands for the concentration of NPs and b is a constant. Our calculations suggest that the DCR mechanism is efficient if a local NP environment resembles the core structure of disclinations, which represent the characteristic property of BP structures. These predictions are in line with high-resolution ac calorimetry and optical polarising microscopy experiments using the CE8 LC and CdSe or aerosil NPs. In mixtures with CdSe NPs of 3.5nm diameter and hydrophobic coating the BPIII stability range has been extended up to 20K. On the contrary, the effect of aerosil silica nanoparticles of 7.0nm diameter and hydrophilic coating is very weak.

Calorimetric study of the Paranematic-to-Nematic transition of polydomain side-chain liquid-crystalline elastomers with different mesogen composition.

The phase transition behaviour of various nematic side-chain liquid-crystalline elastomers with different mesogen composition has been explored by means of high-resolution ac calorimetry. Polydomain samples of the same crosslinking density and different type of mesogens have been investigated. The results show a strong dependence of the phase transition features upon the composition of the mesogen. The distance from the critical point, reflected in the sharpness of the heat capacity anomalies, increases when adding a shorter-length mesogen. The results provide new insight for the impact of mesogens on the thermodynamic behaviour and, thus, on the thermomechanical response of nematic liquid-crystalline elastomers.