Surface effects in thin films of antiferroelectric smectic liquid crystals in terms of the short-pitch long-pitch competition model

A theoretical model based on the competition between short-pitch and long-pitch types of helical order is developed for thin films of antiferroelectric smectic liquid crystals. In the case of the “bookshelf” structure of the film and non-polar surfaces, subsurface perturbations of the ordering are found out analytically. Corresponding contributions to the free energies of the different phases are analysed. The possibility of sufficient influence of the boundaries on phase sequences is predicted even in the case of weak surface anchoring. A consistent explanation of the controversial experimental information is given; further ways of experimental justification of the model assumptions are discussed. Received 23 May 2002 RID="a" ID="a"e-mail: mgorkoun@uos.de     

Nematic order-disorder state transition in a liquid crystal analogue formed by oriented and migrating amoeboid cells

In cell culture, liquid crystal analogues are formed by elongated, migrating, and interacting amoeboid cells. An apolar nematic liquid crystal analogue is formed by different cell types like human melanocytes (=pigment cells of the skin), human fibroblasts (=connective tissue cells), human osteoblasts (=bone cells), human adipocytes (=fat cells), etc. The nematic analogue is quite well described by i) a stochastic machine equation responsible for cell orientation and ii) a self-organized extracellular guiding signal, E₂, which is proportional to the orientational order parameter as well as to the cell density. The investigations were mainly made with melanocytes. The transition to an isotropic state analogue can be accomplished either by changing the strength of interaction (e.g. variation of the cell density) or by influencing the cellular machinery by an externally applied signal: i) An isotropic gaseous state analogue is observed at low cell density (melanocytes/mm^2) and a nematic liquid crystal state analogue at higher cell density. ii) The nematic state analogue disappears if the bipolar shaped melanocytes are forced to become a star-like shape (induced by colchicine or staurosporine). The analogy between nematic liquid crystal state analogue formed by elongated, migrating and interacting cells and the nematic liquid crystal phase formed by interacting elongated molecules is discussed. Received 2 August 1999 and Received in final form 5 January 2000     

Adsorption of a random heteropolymer with random self-interactions onto an interface

We consider the adsorption of a random heteropolymer onto an interface within the model of Garel et al. [#!gareletal89!#] by taking into account random self-interactions and ternary repulsive interactions between the monomers. Within the replica trick and by using a self-consistent preaveraging procedure we map the adsorption problem onto the problem of binding state of a quantum mechanical Hamiltonian. The analysis of the latter is treated within the variational method based on the 2nd Legendre transform. Our study reveals a complex behaviour of the localization of the heteropolymer. In particular, we predict a reentrant localization transition for moderate values of the asymmetry of the distribution function of the monomer sequences along the heteropolymer. Received 9 October 2001 and Received in final form 27 February 2002 Published online 6 June 2002     

Size dependence of dielectric properties and structural metastability in ferroelectrics

The size effect of the dielectric properties and the barrier height was investigated in the ferroelectric solid solution Ba_xSr_1-xTiO₃ system. The decrease of the grain size causes the suppression of the ferroelectricity, and the increase of the relaxation frequency. Barrier heights increase with increasing grain size. The result is analogous to magnetic phase transitions in nanocrystals and other solid-solid phase transitions in nanocrystals. It suggests a general rule that may be of use in the discovery of new metastable phases. An explanation of this phenomenon was given by an electric potential model that agrees well with the experimental results. For Ba_xSr_1-xTiO₃ system, the decrease of xcauses the decrease of the barrier height. Received 3 August 1998 and Received in final form 22 November 1998     

Structural study of the ferroelectric instability in SnPSe

The structural change occurring in between the paraelectric and the ferroelectric phases is investigated by means of X-ray diffraction. Details of the structure in both phases are obtained and the role of the lone pair is discussed in the light of structural data. In agreement with the 2/ m to m symmetry lowering, polar displacements are found within the m plane away from a particular crystallographic direction but antiparallel displacements occur also. These results are discussed in the frame of the phenomenological theory which predicts a particular temperature dependence of the dielectric polarization in this crystal. Received: 10 July 1998     

Incomplete ferroelectricity in SrTi 18O 3

Motivated by recent experiments demonstrating suppression of ferroelectricity with pressure in SrTi¹⁸O₃, the dynamics of the phase transition mechanism are reinvestigated within a nonlinear polarizability model. For temperatures far above the phase transition polar micro domains are formed which increase in size with decreasing temperature to freeze out at T_c without forming long range order. Experimentally, soft mode dynamics are simultaneously observed, evidencing that displacive and order/disorder features coexist. In the ferroelectric phase both components persist whereby an incomplete and inhomogeneous ferroelectric state is formed.     

Influence of the crystallite size on the phase transformation of yttria irradiated with swift heavy ions

The irradiation effects induced by swift heavy ions are now widely described in `bulk' materials. It is shown here that the behaviour of matter under irradiation depends on its crystalline state in the sense that a given material is all the more sensitive to swift heavy ion irradiations as the mean crystallite size L is small. The present paper relates the experimental results obtained in yttrium oxide from `in situ' X-ray diffraction measurements. Three kinds of sample have been irradiated: sintered samples (L = 1μm), non-ground powders (L = 45 nm) and ground powders (L = 28 nm). A cubic to monoclinic phase transformation appears if the electronic energy loss of the incident particle is higher than a threshold. The comparison between the different kinds of samples reveals that this phase transformation is all the easier as the mean crystallite size of the target is weak. Received 27 January 2000 and Received in final form 13 December 2000     

Frustration between syn- and anticlinicity in mixtures of chiral and non-chiral tilted smectic-C-type liquid crystals

We study the effects of mixing ferroelectric and antiferroelectric liquid-crystal compounds (FLCs and AFLCs) when the former are strictly synclinic and the latter strictly anticlinic, i.e. one mixture component exhibits only SmC* and the other only SmC a* as tilted phase. Three different paths between syn- and anticlinicity were detected: transition directly between SmC* and SmC a*, transition via the SmC_β* and SmC_γ* subphases, or by “escaping” the clinicity frustration by reducing the tilt to zero, i.e. the SmA* phase is extended downwards in temperature, separating SmC* from SmC a* in the phase diagram. The most common path is the one via the subphases, demonstrating that these phases appear as a result of frustration between syn- and anticlinic and, consequently, between syn- and antipolar order. For assessing the role of chirality, we also replaced the FLC with non-chiral synclinics. With one of the AFLCs, the route via supbhases was detected even in this case, suggesting that chirality --although necessary-- does not have quite the importance that has previously been attributed to the appearance of the subphases. The path chosen in the mixture study seemed to be determined mainly by the synclinic component, the subphase induction occurring only when the SmA*-SmC* transition was second order.     

Simple Landau model of the smectic- A-isotropic phase transition

A simple Landau-type free energy function is presented to describe the smectic-A-isotropic phase transition. Varying the coupling between orientational and positional order parameters, a smectic-A-isotropic or a nematic-isotropic phase transition occurs. Within this model the smectic-A-isotropic phase transition is found to be always more strongly first order than the nematic-isotropic phase transition. The theoretical results are found to be in good agreement with all published experimental results. Received 27 June 2000     

Copolymer at a selective interface and two-dimensional wetting: a grand canonical approach

We consider two different problems involving the localization of a single polymer chain: (i) a periodic AB copolymer at a selective fluid-fluid interface, with the upper (resp. lower) fluid attracting A (resp. B) monomers (ii) a homopolymer chain attracted to a hard wall (wetting). Self avoidance is neglected in both models, which enables us to study their localization transition in a grand canonical approach. We recover the results obtained in previous studies via transfer matrix methods. Moreover, we calculate in this way the loop length distribution functions in the localized phase. Some finite size effects are also determined and tested numerically. Received 13 April 2000     

Broad-band dielectric spectroscopy of Ba 2NaNb 5O 15 single crystal

Barium sodium niobate (BNN) single crystals are studied by IR spectroscopy, time-domain THz transmission spectroscopy, HF coaxial wave-guide technique and LF dielectric spectroscopy to cover the frequency range 10²-10¹⁴ Hz in a wide temperature interval. The dielectric response parallel and perpendicular to the polar c-axis is discussed. The ferroelectric transition at T _c = 830 K is driven by a relaxational soft mode coupled with another central-mode type relaxation which both gradually disappear on cooling in the ferroelectric phase. Below T _i the parameters of the expected IR active amplitudon were estimated. The low-temperature permittivity increase on cooling for the field direction has been explained by an incipient proper ferroelectric-ferroelastic transition driven by an IR and Raman active B₂-symmetry soft mode. Received 24 August 2002 Published online 19 December 2002 RID="a" ID="a"e-mail: buixader@fzu.cz     

Nucleation-and-growth problem in model lipid membranes undergoing subgel phase transitions is a problem of time scale

In this Rapid Note, we show that the problem of growth of molecular superlattice in a fully hydrated dipalmitoylphosphatidylcholine (DPPC) membrane during the gel-to-subgel phase transformation process is a problem of time scale. There are, in fact, two time scales. The first is an “integrated” or, in some sense, stagnant time scale, that reflects the well-known isotropic growth effect in the d-dimensional space, but assigns the problem to be still in a category of Debye relaxation kinetics. The fraction of old (parent) phase does not suit the Paley-Wiener criterion for relaxation functions, and the time behavior is exclusively due to the geometrical characteristics of the kinetic process. The second (multi-instantaneous) time scale, in turn, is recognised to be a “broken” (fractional time derivative) or memory-feeling (dynamic) scale, which carries some very essential physics of the phenomenon under study, and classifies the problem to be of non-Debye (viz., stretched exponential) nature. It may, in principle, contain all the important effects, like small scale coexistence, presence of collisions between domains, with possible annihilation and creation of domain boundaries, and/or a headgroup packing, hydration against lipid mobility behavior, and finally, a multitude of quasi-crystalline states. It turns out, that within the range of validity of the dynamic scale approximation proposed, the criterion for relaxation functions is very well fulfilled. Received 30 November 1998     

The mechanisms of recrystallization after melting in syndiotactic polypropylene and isotactic polystyrene

Several semicrystalline polymers show a recrystallization after melting during a heating scan. We have studied the mechanisms of such recrystallization processes for two different polymers, namely syndiotactic polypropylene (sPP) and isotactic polystyrene (iPS). This was done by monitoring the structure evolution during the recrystallization process and its changes during a subsequent heating scan via time- and temperature-dependent SAXS measurements, respectively. The results of this study showed that the sPP samples exhibited a recrystallization mechanism similar to the multi-stage route found upon initial crystallization of semicrystalline polymers from an entangled melt. Meanwhile, a different recrystallization mechanism was shown by the iPS samples. In this case, the recrystallization process proceeded as a direct growth into the melt in a one-step process. This is the first time we have observed such a mechanism which resembles the picture presented by the classical models for crystallization from an entangled polymer melt. The reason for such different mechanisms may be related to the initial melt state prior to crystallization. It seems as though, when crystallization sets in an entangled polymer melt, it follows the multi-stage route, whereas if the melt is locally disentangled, it proceeds by a direct growth mechanism. Received 23 July 2001 and Received in final form 4 October 2001     

Landau theory of ferroelectric transition in long cylindrical nanoparticles

Using a phenomenological Landau theory, the size dependence on ferroelectric transition for free-standing long cylindrical nanoparticles is discussed. We derive the size dependence of the transition temperature, polarization profile as well as the static susceptibility. The transition temperature vanishes below a critical size where the static susceptibility shows divergence obeying Curie-Weiss law. In order to make this result compared with experiments, the average polarization and the susceptibility is computed with a Gaussian particle size distribution. The average polarization in such a case shows smearing with respect to the particle size whereas the divergence in the susceptibilty gets rounded. This might correspond to a size dependent soft mode which can be observed in Raman measurement.     

From the melt via mesomorphic and granular crystalline layers to lamellar crystallites: A major route followed in polymer crystallization?

Based on broad and detailed evidence from a large variety of experiments on several polymer systems carried out by other authors and ourselves, a novel concept for understanding the crystallization of polymers from the melt is developed. The experiments generally indicate that the formation and growth of the lamellar crystallites is a multi-step process passing over intermediate states. We suggest a specific route which is compatible with the observations. It is proposed that the initial step is always the creation of a mesomorphic layer which spontaneously thickens, up to a critical value, where it solidifies through a cooperative structural transition. The transition produces a granular crystalline layer, which transforms in the last step into homogeneous lamellar crystallites. The model leads to predictions about the temperature dependencies of the crystal thickness and the growth rate which are at variance with conventional views but in agreement with findings in recent experiments. Received 17 February 2000 and Received in final form 30 March 2000     

Some relevant parameters affecting the glass transition of supported ultra-thin polymer films

We have measured, the thickness dependence of the glass transition temperature T(g)( h), using ellipsometry at variable temperature, for poly(methyl-methacrylate) (PMMA) of various tacticity in confined geometry. We report that several factors significantly affect T(g)( h): i) polymer microstructure (stereoregularity of PMMA) related to local dynamics; ii) interfacial interactions; iii) conformation of the polymer chains. These results raise many fundamental questions on the origin of the thickness-dependent glass transition. Why and how do the interactions with the substrate significantly affect T(g)( h)? Does T(g)( h) depend on the modifications of conformational parameters of the chains (their entropy)? What is the correlation between local dynamics and T(g)( h) in thin films? The aim of this paper is to summarise these open questions, which should stimulate further investigations in the thin polymer film scientific community.     

Nature of the Peierls- to Mott-insulator transition in 1D

In order to clarify the physics of the crossover from a Peierls band insulator to a correlated Mott-Hubbard insulator, we analyze ground-state and spectral properties of the one-dimensional half-filled Holstein-Hubbard model using quasi-exact numerical techniques. In the adiabatic limit the transition is connected to the band to Mott insulator transition of the ionic Hubbard model. Depending on the strengths of the electron-phonon coupling and the Hubbard interaction the transition is either first order or evolves continuously across a narrow intermediate phase with finite spin, charge, and optical excitation gaps. Received 7 July 2002 / Received in final form 21 October 2002 Published online 27 January 2003 RID="a" ID="a"e-mail: holger.fehske@physik.uni-greifswald.de     

Thermophysical properties of fluorinated acrylate homopolymers: Mixing and phase separation

The thermophysical properties of fluorinated acrylate homopolymers are investigated by differential scanning calorimetry (DSC) and optical microscopy and discussed in terms of relative lengths of the fluorinated chain and the hydrocarbon spacer between the acrylate moiety and the fluorinated chain. These compounds exhibit an intrinsic microphase-separation (Isotropic+Isotropic morphology) occurring between the fluorinated chains and the acrylate polymer backbone. It is shown that the enthalpy of mixing is a function of the length of the lateral fluorocarbon chains. The thermophysical behaviour of these materials may be regarded as demixed systems exhibiting an Upper Critical Solution Temperature. The photopolymerization process of one of the monomer is studied by isothermal photocalorimetry. High acrylate double-bond conversion and fast curing rates were obtained thus demonstrating the promising use of these materials for coating and film processing applications using UV-curing techniques. Received 30 January 2002