J. Salud

Anisotropy of Intermolecular Interactions from the Study of the Thermal-Expansion Tensor

The anisotropy of the intermolecular interactions in the low-temperature ordered phases of three chemically and structurally related compounds [neopentylglycol, (CH3)2C(CH2OH)2, pivalic acid, (CH3)3C(COOH), and neopentylalcohol, (CH3)3C(CH2OH)], all of which display an orientationally disordered high-temperature phase, has been shown by means of the isobaric thermal-expansion tensor. The variation of the directions of the principal components of the thermal-expansion tensor as a function of temperature, as well as the variation of its principal coefficients, is evidence of the large differences in the intermolecular interactions for each compound; or, more precisely, between the strong intermolecular hydrogen bonds and the weak van der Waals interactions. In addition, the differences in the hydrogen-bonding schemes expected a priori from the molecular structures of the studied compounds have been enhanced. Finally, the volume expansivity as well as the packing coefficient have been analysed in the orientationally disordered high-temperature phase of each of the three compounds.Part of this work was presented at the EPDIC 1997 meeting (5th European Powder Diffraction Conference).

Binary mixtures of nCB and nOCB liquid crystals. Two experimental evidences for a smectic A–nematic tricritical point

Modulated differential scanning calorimetry (MDSC) has been used to obtain specific heat measurements on octyloxycyanobiphenyl (8OCB), octylcyanobiphenyl (8CB) and nonyloxycyanobiphenyl (9OCB) liquid crystals and on several binary mixtures of 8OCB + 9OCB and 8CB + 9OCB. The order of the mesophase transitions, smectic A(SmA) to nematic(N) and N to isotropic (I) on pure components and on binary mixtures has been studied and, in addition, both binary mesophase diagrams have been built. For each set of mixtures, there exists a tricritical point (TCP) composition at the SmA–N transition. The TCP compositions have been found to be X9OCB = 0.63 for the system 8OCB + 9OCB and X9OCB = 0.42 for the system 8CB + 9OCB. In addition, the specific heat critical exponents (α) through second order SmA to N transition have been obtained between 8OCB(or 8CB) and the TCP composition for the two sets of binary mixtures. When these α-values were plotted against the normalised nematic range, a common and uniform crossover trend was found. Indeed, this fact suggests a uniform behaviour in terms of the McMillan ratio for the nCB and nOCB series of liquid crystals. Moreover, for these compounds there exists a common value of (TAN/TNI)TCP of 0.99 and also a value of (TAN/TNI)3D-XY of about 0.96.

Two-component systems of isomorphous orientationally disordered crystals. Part 1: Packing of the mixed crystals

Five experimental two-component phase diagrams between orientationally disordered crystals (ODICs) have been established from the low-temperature phase to the liquid state using thermal analysis and X-ray powder diffraction techniques. The high-temperature orientationally disordered phases for the pure components, which belong to the series (CH 3 ) 4–n1 C(CH 2 OH) n1 (n 1 =1,2,3) and (NO 2 )(CH 3 ) 3–n2 C(CH 2 OH) n2 (n 2 =0,1) are all face centered cubic. Continuous disordered mixed crystals in the whole range of concentration have been found, which indicates the existence of an isomorphism relationship. The intermolecular interactions in the ODIC state of these systems and other related two-component systems are discussed using the evolution of the packing coefficient as a function of the composition.

Miscibility study in stable and metastable orientational disordered phases in a two-component system (CH3)CCl3+CCl4

The orientationally disordered stable and metastable mixed crystals of the two-component system methylchloroform ((CH3)CCl3)+carbon tetrachloride (CCl4) have been characterised from a crystallographic and thermodynamic point of view. The monotropic behaviour of the metastable phase in the pure components is maintained for the whole range of composition. The lattice symmetry of the stable orientationally disordered phase of methylchloroform has been found to be isostructural with that of the carbon tetrachloride compound. Continuous series of both stable and metastable mixed crystals give rise to a double isomorphism relationship, one for the stable state and another for the metastable stable of the pure components.

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.

On the nature of the smectic mesophase in 8CB + 10CB binary mixtures. Evidences for a smectic A to nematic tricritical point

The two-component system octylcyanobiphenyl(8CB) + decylcyanobiphenil(10CB) has been studied by means of Modulated Differential Scanning Calorimetry, optical microscopy and X-ray diffraction. Although the general trends of the phase diagram are similar to that proposed by Marynissen et al., additional evidences for the existence of TCP have been reported, the composition being about 0.2, which is slightly lower than that proposed in the aforementioned work. Additionally, the smectic mesophase of the 8CB + 10CB mixtures has been characterised through X-ray diffraction and optical measurements as smectic A for the whole composition range. Such a result is against the recent work of Oweimreen and Hwang.

First experimental demonstration of crossed isodimorphism: (CH3)3CCl + CCl4 melting phase diagram

The melting phase diagram of the two-component system 2-methyl-2-chloro-propane ((CH3)3CCl) and carbon tetrachloride (CCl4) has been determined by combining X-ray powder diffraction and thermal analysis. The isomorphism relation between the orientationally disordered (OD) stable face-centered cubic (FCC) phase of (CH3)3CCl and the metastable FCC phase of CCl4 has been demonstrated throughout the continuous evolution of the lattice parameters and the existence of the two-phase equilibrium [FCC + L] for the whole range of composition, despite the monotropy of the FCC phase for the CCl4 component. This equilibrium interferes with a rhombohedral plus liquid ([R + L]) equilibrium giving rise to a peritectic invariant. A thermodynamic analysis, in terms of the crossed isodimorphism, has also been performed in order to obtain the excess properties of the FCC and R OD phases.

Dielectric relaxation in bulk and cylindrically confined octylcyanobiphenyl (8CB)

The dielectric relaxation spectrum over the frequency range 102 to 1.8×109 Hz of 4‐octyl‐4′‐cyanobiphenyl, 8CB, in bulk and confined to 200 nm diameter cylindrical pores is reported. We used matrices with parallel cylindrical pores, obtaining different alignments of the molecular director depending on the treatment. Results show that there are two relaxations in the isotropic phase and in the mesophases for parallel alignment and three for perpendicular alignment. The molecular origin of theses modes and the effect of the confinement on their dynamics are discussed. To compare properly the results for bulk and confined 8CB, a re‐scaling of the experimental data is proposed.

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.

Stable and metastable orientationally disordered mixed crystals of the two-component system (CH3)2CCl2+CCl4

Orientationally disordered stable and metastable mixed crystals of the two-component system 2,2-dichloropropane ((CH3)2CCl2)+carbon tetrachloride (CCl4) have been characterised from crystallographic and thermodynamic points of view. The monotropic behaviour of the metastable phases in the pure components is retained by the mixed crystals. Continuous series of mixed crystals in the stable rhombohedral phase gives rise to an isomorphism relationship. The lattice symmetries of the metastable mixed crystals are found to be simple cubic and face centred cubic, the latter corresponding to a large concentration domain. A strong correlation between thermodynamic functions and optical properties is proposed.