Structure and frustration in liquid crystalline polyacrylates II. Thin-film properties

We report on the thin-film behaviour of a polyacrylate with phenyl benzoate mesogenic side groups and a narrow polydispersity. Depending on the degree of polymerisation, these polymers show a nematic, a smectic-A _d, a re-entrant nematic and a C phase with a two-dimensional monoclinic lattice. X-ray reflectivity and atomic-force microscopy have been used to characterize the structure and surface morphology. The system exhibits two stable side-chain packing configurations with incommensurate spacings that can be both stabilized at a free surface. Thin films in the nematic phase show a structural dewetting induced by the growth of surface domains of the C phase. Additionally, surface-induced ripples with a nanoscale lateral period form at the air-film interface. We attribute these patterns to a coupling between the local liquid crystalline ordering of the mesogenic side groups and the surface curvature energy. Received 28 February 2001 and Received in final form 6 August 2001     

Spontaneous thermal expansion of nematic elastomers

We study the monodomain (single-crystal) nematic elastomer materials, all side-chain siloxane polymers with the same mesogenic groups and crosslinking density, but differing in the type of crosslinking. Increasing the proportion of long di-functional segments of main-chain nematic polymer, acting as network crosslinking, results in dramatic changes in the uniaxial equilibrium thermal expansion on cooling from the isotropic phase. At higher concentration of main chains their behaviour dominates the elastomer properties. At low concentration of main-chain material, we detect two distinct transitions at different temperatures, one attributed to the main-chain, the other to the side-chain component. The effective uniaxial anisotropy of nematic rubber, r(T) = / proportional to the effective nematic order parameter Q(T), is given by an average of the two components and thus reflects the two-transition nature of thermal expansion. The experimental data is compared with the theoretical model of ideal nematic elastomers; applications in high-amplitude thermal actuators are discussed in the end. Received 25 June 2001 and Received in final form 29 September 2001     

Orientation-dependent depletion interaction in rodlike colloid-polymer mixtures

Depletion interaction in a suspension of rodlike colloids with added non-adsorbing polymer coils is theoretically studied. We calculate an overlap volume of depletion zone between two rodlike colloids, based on the second virial approximation. We examine nematic-isotropic phase transition (NIT) and two-phase coexistence between an isotropic and a nematic phase at low polymer concentrations. We find that the depletion interaction is dependent on the orientational order parameter of rodlike colloids and leads to a decrease in the NIT concentration on the addition of polymer. The coexistence curves have a leaning-chimney shape and are shifted to lower rod concentrations on increasing the polymer concentration. Received 23 May 2001 and Received in final form 18 July 2001     

Tube model for the elasticity of entangled nematic rubbers

Dense rubbery networks are highly entangled polymer systems, with significant topological restrictions for the mobility of neighbouring chains and crosslinks preventing the reptation constraint release. In a mean-field approach, entanglements are treated within the famous reptation approach, since they effectively confine each individual chain in a tube-like geometry. We apply these classical ideas to calculate the effective rubber-elastic free energy of anisotropic networks, nematic liquid crystal elastomers, and present the first theory of entanglements for such a material. Received 25 June 2001     

Mobility in thin polymer films ranging from local segmental motion, Rouse modes to whole chain motion: A coupling model consideration

Large increases of mobility of local segmental relaxation observed in polymer films as the film thickness is decreased, as evidenced by decreases of the glass temperature, are not found for relaxation mechanisms that have longer length scales including the Rouse relaxation modes and the diffusion of entire polymer chains. We show that the coupling model predictions, when extended to consider polymer thin films, are consistent with a large increase of the mobility of the local segmental motions and the lack of such a change for the Rouse modes and the diffusion of entire polymer chains. There are two effects that can reduce the coupling parameter of the local segmental relaxation in thin films. One is the chain orientation that is induced parallel to the surface when the film thickness h becomes smaller than the end-to-end distance of the chains and the other is a finite-size effect when h is no longer large compared to the cooperative length scale. Extremely thin ( ≈ 1.5 nm) films obtained by intercalating a polymer into layered silicates have thickness significantly less than the cooperative length scale near the bulk polymer glass transition temperature. As a result, the coupling parameter of the local segmental relaxation in such thin films is reduced almost to zero. With this plausible assumption, we show the coupling model can explain quantitatively the large decrease of the local segmental relaxation time found experimentally. Received 1 August 2001 and Received in final form 1 December 2001     

Pseudo-gap and possible Spin-Peierls transition in the vanadium oxide VOSb 2 O 4

We report on the magnetic susceptibility and electron spin resonance measurements on polycrystalline samples of the vanadium oxide VOSb₂O₄, a quasi-one-dimensional S = 1/2 Heisenberg system. The susceptibility vanishes at zero temperature, but there is no cusp at the onset of the susceptibility drop, and the ESR linewidth exhibits an increase characteristic of a phase transition at a much lower temperature. We show that this behaviour is consistent with the formation of a pseudo-gap in a spin-Peierls system in the adiabatic limit. Received 7 February 2001 and Received in final form 24 April 2001     

Phase transitions in lyotropic nematic gels

In this paper, we discuss the equilibrium phases and collapse transitions of a lyotropic nematic gel immersed in an isotropic solvent. A nematic gel consists of a cross-linked polymer network with rod-like molecules embedded in it. Upon decreasing the quality of the solvent, we find that a lyotropic nematic gel undergoes a discontinuous volume change accompanied by an isotropic-nematic transition. We also present phase diagrams that these systems may exhibit. In particular, we show that coexistence of two isotropic phases, of two nematic phases, or of an isotropic and a nematic phase can occur. Received 15 February 2002 and Received in final form 14 June 2002     

Free energy of semiflexible polymers and structure of interfaces

The free energy of semiflexible polymers is calculated as a functional of the compositional scalar order parameter and the orientational order parameter of second-rank tensor S_ij on the basis of a microscopic model of wormlike chains with variable segment lengths. We use a density functional theory and a gradient expansion to evaluate the entropic part of the free energy, which is given in a power series of .The interaction term of the free energy is derived with a random phase approximation. For the rigid rod limit, the nematic-isotropic transition point is given by , N and w being the degree of polymerization and the anisotropic interaction parameter, respectively, and the degree of ordering at the transition point is 0.33448. We also find that the contour length of polymer chains becomes larger in a nematic phase than in an isotropic phase. Interface profiles are obtained numerically for some typical cases. In the neighborhood of isotropic-isotropic interfaces, polymer chains tend to align parallel to the interface on the polymer-rich side and perpendicular on the poor side. When an isotropic region and a nematic region coexist, orientational order parallel to the interface is preferred in the nematic region. Received: 28 May 1998 / Revised: 12 August 1998 / Accepted: 8 September 1998     

Polyelectrolyte chains in poor solvent. A variational description of necklace formation

We study the properties of polyelectrolyte chains under different solvent conditions, using a variational technique. The free energy and the conformational properties of a polyelectrolyte chain are studied by minimizing the free energy F_N, depending on N(N - 1)/2 trial probabilities that characterize the conformation of the chain. The Gaussian approximation is considered for a ring of length 2⁴ < N < 2⁸ and for an open chain of length 50 < N < 200 in poor- and theta-solvent conditions, including a Coulomb repulsion between the monomers. In theta-solvent conditions the blob size is measured and found in agreement with scaling theory, including charge depletion effects, expected for the case of an open chain. In poor-solvent conditions, a globule instability, driven by electrostatic repulsion, is observed. We notice also inhomogeneous behavior of the monomer-monomer correlation function, reminiscence of necklace formation in poor-solvent polyelectrolyte solutions. A global phase diagram in terms of solvent quality and inverse Bjerrum length is presented. Received 7 June 2001 and Received in final form 17 October 2001     

Isomorphous phase transition and orientational freezing in hexagonal mixed crystal C 70(1 - x) C60x. A pseudospin model

A four-state pseudospin model is constructed for the isomorphous phase transition hcp-2↦hcp-1 in pure C₇₀ and in C₇₀-rich mixed crystal C _{70(1 - x)} C_60x. With the specific anisotropic pseudospin interactions adapted to the C₇₀ crystal the model is equivalent to a two-state Ising model in a temperature-dependent field. Replica symmetric state of the model is shown to approach the critical point when the width of distribution of random fields and/or of random bonds increases. The temperature of the phase transition and the phase equilibrium temperature then are practically constant, whereas the experiment shows their strong decrease with x. The main effect of dilution resides in an x-dependence of the model parameters. Dilatometric data on the hexagonal C _{70(1 - x)} C_60x are used to fit these parameters. A metastable disordered phase subsisting below the phase transition is discovered in a range of the model parameters and is shown to be responsible for the macroscopic behaviour of the system. A good agreement with experimental data is obtained for the spontaneous strain and for the x-dependence of the hysteresis. Received 20 April 2001 and Received in final form 26 September 2001     

Non-uniformities in polymer/liquid crystal mixtures

We theoretically model the nucleation of nematic droplets during phase ordering in mixtures of a flexible polymer and a low-molecular-weight liquid crystal. By appealing to classical nucleation theory (CNT), we calculate the energy barrier to nucleation and the size of a critical nucleus. We study the influence of a metastable intermediate phase on the nucleation of the nematic. Below a triple point in the phase diagram, there are two distinct mechanisms for the formation of a nematic nucleus: 1) direct nucleation from the isotropic phase and 2) nucleation via a precursor metastable isotropic phase. We calculate the crossover concentration as a function of temperature, delineating the regions of the phase diagram in which each mechanism prevails. In the latter case, the presence of a hidden metastable isotropic-isotropic binodal may either promote or delay the nucleation of a nematic phase. Received 9 August 2002 RID="a" ID="a"e-mail: matuyama@chem.mie-u.ac.jp     

Drift of a polymer chain in a porous medium --A Monte Carlo study

We investigate the drift of an end-labeled telehelic polymer chain in a frozen disordered medium under the action of a constant force applied to the one end of the macromolecule by means of an off-lattice bead spring Monte Carlo model. The length of the polymers N is varied in the range 8 < N < 128, and the obstacle concentration in the medium C is varied from zero up to the percolation threshold C≈ 0.75. For field intensities below a C-dependent critical field strength B _c, where jamming effects become dominant, we find that the conformational properties of the drifting chains can be interpreted as described by a scaling theory based on Pincus blobs. The variation of drag velocity with C in this interval of field intensities is qualitatively described by the law of Mackie-Meares. The threshold field intensity B _c itself is found to decrease linearly with C. Received 20 August 2001 and Received in final form 19 November 2001     

A FT-IR absorption analysis of vibrational properties of water encaged in NaA zeolites: evidence of a “structure maker” role of zeolitic surface

Linear polyisoprenes having dimethylamine end groups were prepared by high vacuum anionic polymerization techniques using 3-dimethylaminopropyllithium as the initiator. The amine group was reacted with 2-cholesteryl-2-oxo-1,3,2-dioxaphospholane to provide polymer chains having end zwitterionic groups chemically connected with cholesterol. The association behavior of these end-functionalized polymers was studied in cyclohexane by low angle laser light scattering, dynamic light scattering, and viscometry. The aggregation numbers, N _w were found to decrease by increasing the molecular weight of the precursor polymer, due to excluded volume repulsions. The ability of cholesterol to form liquid crystal mesophases facilitated the association process leading to higher N _w values. The hydrodynamic behavior of the aggregates was similar to that of star polymers. The dependence of the N _w values on the molecular weight of the base polymer, the polydispersity of the associates and the absence of critical micelle concentration, cmc are compatible with the linear head-packing model. Received 29 April 2002 and Received in final form 13 November 2002 Published online: 11 March 2003     

Frequency dependence of aging, rejuvenation and memory in a disordered ferroelectric

We characterize in details the aging properties of the ferroelectric phase of KTa_1-xNb_x O₃ (KTN), where both rejuvenation and (partial) memory are observed. In particular, we carefully examine the frequency dependence of several quantities that characterize aging, rejuvenation and memory. We find a marked subaging behaviour, with an a.c. dielectric susceptiblity scaling as ω, where t _w is the waiting time. We suggest an interpretation in terms of pinned domain walls, much along the lines proposed for aging in a disordered ferromagnet, where both domain wall reconformations and overall (cumulative) domain growth are needed to rationalize the experimental findings. Received 10 November 2000 and Received in final form 20 February 2001     

Tuning anisotropy by impurities: magnetocaloric experiments on CsNi 0.9 Fe 0.1 Cl 3

The magnetic phase diagram of the Fe²⁺ doped hexagonal ABX₃ compound CsNi_0.9Fe_0.1Cl₃ is investigated by heat capacity and magnetocaloric experiments. In spite of the high doping concentration, some phase boundaries appear surprisingly well-defined, while others are broadened significantly. The discussion of this behaviour clarifies the potentials and limitations of doping as a means to manipulate the effective anisotropy in quasi one-dimensional ABX₃ compounds. Received 20 April 2001     

Influence of the nematic order on the rheology and conformation of stretched comb-like liquid crystalline polymers

We have studied the rheology and the conformation of stretched comb-like liquid-crystalline polymers. Both the influence of the comb-like structure and the specific effect of the nematic interaction on the dynamics are investigated. For this purpose, two isomers of a comb-like polymetacrylate polymer, of well-defined molecular weights, were synthesized: one displays a nematic phase over a wide range of temperature, the other one has only an isotropic phase. Even with high degrees of polymerization N, between 40 and 1000, the polymer chains studied were not entangled. The stress-strain curves during the stretching and relaxation processes show differences between the isotropic and nematic comb-like polymers. They suggest that, in the nematic phase, the chain dynamics is more cooperative than for a usual linear polymer. Small-angle neutron scattering has been used in order to determine the evolution of the chain conformation after stretching, as a function of the duration of relaxation t _r. The conformation can be described with two parameters only: , the global deformation of the polymer chain, and p, the number of statistical units of locally relaxed sub-chains. For the comb-like polymer, the chain deformation is pseudo-affine: is always smaller than (the deformation ratio of the whole sample). In the isotropic phase, has a constant value, while pincreases as tr. This latter behavior is not that expected for non-entangled chains, in which p varies as t _r ^1/2 (Rouse model). In the nematic phase, decreases as a stretched exponential function of t _r, while p remains constant. The dynamics of the comb-like polymers is discussed in terms of living clusters from which junctions are produced by interactions between side chains. The nematic interaction increases the lifetime of these junctions and, strikingly, the relaxation is the same at all scales of the whole polymer chain. Received 5 May 1999 and Received in final form 18 October 1999     

On the connection between off-equilibrium response and statics in non disordered coarsening systems

The connection between the out of equilibrium linear response function and static properties established by Franz, Mezard, Parisi and Peliti for slowly relaxing systems is analyzed in the context of phase ordering processes. Separating the response in the bulk of domains from interface response, we find that in order for the connection to hold the interface contribution must be asymptotically negligible. How fast this happens depends on the competition between interface curvature and the perturbing external field in driving domain growth. This competition depends on space dimensionality and there exists a critical value d _c = 3 below which the interface response becomes increasingly important eventually invalidating the connection between statics and dynamics as the limit d = 1 is reached. This mechanism is analyzed numerically for the Ising model with d ranging from 1 to 4 and analytically for a continuous spin model with arbitrary dimensionality. Received 10 July 2001     

Infrared spectra and lattice vibrations of the spin-chain compound LiCuVO 4

The infrared spectra of the one-dimensional antiferromagnet LiCuVO₄ are measured in the frequency range from 10 cm^-1 to 10 000 cm^-1 and at temperatures from 2 K to 300 K, for the electric field vector E of the radiation polarized either along the a- or along the b-crystallographic directions. For each polarization six infrared active phonon modes are observed in accordance with factor group analysis of the crystal structure of LiCuVO₄. The theoretical group analysis of the possible spinel low-symmetry phases is performed within the framework of Landau's theory of phase transitions. The parameters of several phonon lines show noticeable anomalies around 150 K where the magnetic correlations appear in the copper chains, which may indicate a finite interaction between the phonon and the magnon subsystems in LiCuVO₄. Received 19 February 2001 and Received in final form 26 June 2001     

Hopping conductivity and activated transport in InxGa1-xAs quantum wells

We present measurements of the diagonal R_xx and off-diagonal R_xy magnetoresistance under quantum Hall conditions on several high electron mobility transistors (HEMT) based on In_xGa_1-xAs quantum wells. From the magnetoresistance tensor we obtain the longitudinal conductivity σ _xx . We study the transport mechanisms near the σ _xx minima at temperatures ranging between 2 K and 35 K; activated transport is the dominant mechanism for temperatures above 7 K while variable range hopping conductivity is significant for lower temperatures. We show that electron-electron correlations should be taken into account to explain the conductivity vs temperature behaviour below 5 K. Finally, we study the behaviour of the localization length as a function of Landau level filling and obtain a critical exponent γ = 3.45±0.15. Received 6 June 2001 and Received in final form 16 October 2001