S. Diez-Berart

Study of the critical behavior and scaling relationships at the N-to-I phase transition in hexyloxycyanobiphenyl.

An exhaustive analysis of the critical behavior of the nematic to isotropic (N-to-I) phase transition on the liquid crystal hexyloxycyanobiphenyl (6OCB) has been performed. To do so, the accurate evolution of various physical magnitudes (static dielectric permittivity data together with specific heat and volumetric determinations) around the N-to-I transition has been required. The specific heat data with the isobaric thermal expansion coefficient and the derivative of the static dielectric permittivity with temperature have been proven to be related to each other by a scaling relationship. However, some discrepancies have been observed for the dielectric data in relation to such a scaling relationship and the critical behavior of the N-to-I phase transition. All information has been used to get some insight on the strength of the first-order N-to-I phase transition of the 6OCB in relation to the other counterparts in the nOCB series of compounds.

Effect of Molecular Flexibility on the Nematic-to-Isotropic Phase Transition for Highly Biaxial Molecular Non-Symmetric Liquid Crystal Dimers

In this work, a study of the nematic (N)–isotropic (I) phase transition has been made in a series of odd non-symmetric liquid crystal dimers, the α-(4-cyanobiphenyl-4’-yloxy)-ω-(1-pyrenimine-benzylidene-4’-oxy) alkanes, by means of accurate calorimetric and dielectric measurements. These materials are potential candidates to present the elusive biaxial nematic (NB) phase, as they exhibit both molecular biaxiality and flexibility. According to the theory, the uniaxial nematic (NU)–isotropic (I) phase transition is first-order in nature, whereas the NB–I phase transition is second-order. Thus, a fine analysis of the critical behavior of the N–I phase transition would allow us to determine the presence or not of the biaxial nematic phase and understand how the molecular biaxiality and flexibility of these compounds influences the critical behavior of the N–I phase transition.

Tests of the tricritical point in the SmA-to-N phase transition of binary mixtures of butyloxybenzylidene octylaniline and hexyloxybenzylidene octylaniline

The present work arises from the significant difference between the experimental Landau tricritical point (LTCP) in the Sm A-to-N phase transition in binary mixtures of butyloxybenzylidene octylaniline (4O.8) and hexyloxybenzylidene octylaniline (6O.8) predicted by Stine and Garland, and that arising from the thermodynamic assessment using the Oonks Equal Gibbs Curve method. By use of specific heat measurements the 4O.8 + 6O.8, phase diagram has been determined anew. The results of the subsequent application of Oonks thermodynamic analysis are discussed and their compatibility with the behaviour universally exhibited by other liquid crystal binary mixtures for which a LTCP in the SmA-to-N phase transition has been experimentally determined are analysed.

Critical behaviour in liquid-crystalline phase transitions: a comparative study of 9OCB in bulk and Anopore membranes

As a humble contribution to this special commemorative issue to Professor Alfred Saupe, we present an experimental study on the critical behaviour of the nematic-to-isotropic (N–I) and smectic A-to-nematic (SmA–N) phase transitions of the liquid crystal 4-nonyloxy-4′-cyanobiphenyl (9OCB). Measurements of the specific heat and the dielectric permittivity were performed for bulk 9OCB as well as for 9OCB confined to Anopore membranes, and the influence of the slight-restrictive confinement was analysed. The possibility of driving the weakly first-order SmA–N phase transition to second-order in nature by means of the confinement was confirmed.

Influence of cylindrical submicrometer confinement on the static and dynamic properties in nonyloxycyanobiphenyl (9OCB).

Broadband dielectric spectroscopy (10(2)-1.9 x 10(9) Hz) and specific heat measurements have been performed on nonyloxycyanobiphenyl (9OCB) in the isotropic (I), nematic (N), and smectic A (SmA) phases confined to 200 nm diameter parallel cylindrical pores of Anopore membranes. Untreated and HTBA-treated membranes have been found to obtain axial and radial confinements, respectively. However, structural or configurational transitions in untreated membranes have been reported to exist in the SmA-mesophase of 9OCB. Both confinements clearly affect the N-I and SmA-N phase transitions. In the axial confinement, the analysis of the specific heat and static dielectric permittivity data leads to a second order SmA-N phase transition, which is known to be weakly first order for bulk 9OCB. Dynamic dielectric measurements have accounted for the different molecular motions in both confinements. On both mesophases, either N or SmA, the relaxation processes in axial configuration are faster than in the bulk. However, in radial confinement, they are either equal or slower than in the bulk. Additionally, there are no differences in the energy barrier hindering the molecular motions between the axial and radial confinements and even in relation to bulk. Likewise, dielectric results suggest that the extension inside the pores of the surface pinned molecular layer (proved to be temperature-dependent) persists at high enough temperature as a residual-thin layer adjacent to the pore wall.

Distinctive dielectric properties of nematic liquid crystal dimers

ABSTRACT We provide an overview of the effect of the molecular structure on the dielectric properties of dimers exhibiting nematic and twist-bend nematic phases with special focus on how the conformational distribution changes are reflected by the dielectric behaviour. Nematic dimers show distinctive dielectric properties which differ from those of archetypical nematic liquid crystals, as for example, unusual temperature dependence of the static permittivity or dielectric spectra characterised by two low-frequency relaxation processes with correlated strengths. The interpretation of such characteristic behaviour requires that account is taken of the effect of molecular flexibility on the energetically favoured molecular shapes. The anisotropic nematic interactions greatly influence the conformational distribution. Dielectric behaviour can be used to track those conformational changes due to dependence of the averaged molecular dipole moment on the averaged molecular shape. Results for a number of dimers are compared and analysed on the basis of the influence of details of the molecular structure, using a recently developed theory for the dielectric properties of dimers. GRAPHICAL ABSTRACT

Overall analysis of first‐order phase transitions in some alkyloxycyanobiphenyl liquid crystals

Measurements of pressure, molar volume and specific heat as functions of temperature in the isotropic (I) phase as well as in the smectic A (SmA) and nematic (N) mesophases of some alkyloxycyanobiphenyl compounds (nOCB, n = 6–10) were carried out using differential thermal analysis under pressure, densitometry, X‐ray powder diffraction and modulated differential scanning calorimetry. Thermodynamic properties, such as latent heats and volume jumps at the different phase transitions, were determined. The coherence of this whole set of data was tested using pressure–temperature data through the slopes associated to their phase transitions, extrapolated at normal pressure in the light of the Clausius–Clapeyron equation.

Influence of the chain length on the nematic-to-isotropic phase transition for the odd members of a highly non-symmetric pyrene-based series of liquid crystal dimers

ABSTRACT This paper describes a detailed study of the nematic (N)-isotropic (I) phase transition in the homologous series of liquid crystal dimers, the α-(4-cyanobiphenyl-4ʹ-oxy)-ω-(1-pyreniminebenzylidene-4ʹ-oxy)alkanes (CBOnO.Py) by means of calorimetric and dielectric measurements as a function of temperature. It is concluded that for this transition, the latent heat or the entropy change decreases as the chain length of the odd dimers decreases, and this decrease is consistent with the observed tricritical behaviour. Graphical Abstract

Two glass transitions associated to different dynamic disorders in the nematic glassy state of a non-symmetric liquid crystal dimer dopped with gamma-alumina nanoparticles

In the present work, the nematic glassy state of the non-symmetric LC dimer α-(4-cyanobiphenyl-4′-yloxy)-ω-(1-pyrenimine-benzylidene-4′-oxy) undecane is studied by means of calorimetric and dielectric measurements. The most striking result of the work is the presence of two different glass transition temperatures: one due to the freezing of the flip-flop motions of the bulkier unit of the dimer and the other, at a lower temperature, related to the freezing of the flip-flop and precessional motions of the cyanobiphenyl unit. This result shows the fact that glass transition is the consequence of the freezing of one or more coupled dynamic disorders and not of the disordered phase itself. In order to avoid crystallization when the bulk sample is cooled down, the LC dimer has been confined via the dispersion of γ-alumina nanoparticles, in several concentrations.

Dispersion of gamma-alumina nano-sized spherical particles in a calamitic liquid Crystal. Study and optimization of the confinement effects

We report an experimental study on confined systems formed by butyloxybenzylidene octylaniline liquid crystal (4O.8) + γ-alumina nanoparticles. The effects of the confinement in the thermal and dielectric properties of the liquid crystal under different densities of nanoparticles is analyzed by means of high resolution Modulated Differential Scanning Calorimetry (MDSC) and broadband dielectric spectroscopy. First, a drastic depression of the N-I and SmA-N transition temperatures is observed with confinement, the more concentration of nanoparticles the deeper this depression is, driving the nematic range closer to the room temperature. An interesting experimental law is found for both transition temperatures. Second, the change in shape of the heat capacity peaks is quantified by means of the full width half maximum (FWHM). Third, the confinement does not noticeably affect the molecular dynamics. Finally, the combination of nanoparticles and the external applied electric field tends to favor the alignment of the molecules in metallic cells. All these results indicate that the confinement of liquid crystals by means of γ-alumina nanoparticles could be optimum for liquid crystal-based electrooptic devices.