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     

Structure and frustration in liquid crystalline polyacrylates I. Bulk behaviour

The phase behaviour and structure are reported of a new type of frustrated side-chain liquid crystalline (LC) polymer, a polyacrylate with phenylbenzoate mesogenic side groups and a narrow polydispersity. At a high degree of polymerisation the LC polymers show a nematic, a smectic-A_d, a re-entrant nematic and a C phase, for shorter chains only a nematic and a C phase. This constitutes a new example of nematic re-entrance for which the driving field is the length of the polymer chain. The smectic-A_d layers consist of partially overlapped side groups while in the C phase the side chains are rearranged into chevron-like blocks of bilayers. We propose an explanation of the frustrated phase behaviour in terms of these two different competing length scales and their coupling to the backbone conformations. Received 28 February 2001 and Received in final form 6 August 2001     

Colloidal dipolar interactions in 2D smectic-C films

We use a two-dimensional (2D) elastic free energy to calculate the effective interaction between two circular disks immersed in smectic-C films. For strong homeotropic anchoring, the distortion of the director field caused by the disks generates topological defects that induce an effective interaction between the disks. We use finite elements, with adaptive meshing, to minimize the 2D elastic free energy. The method is shown to be accurate and efficient for inhomogeneities on the length scales set by the disks and the defects, that differ by up to 3 orders of magnitude. We compute the effective interaction between two disk-defect pairs in a simple (linear) configuration. For large disk separations, D, the elastic free energy scales as ∼D ^-2, confirming the dipolar character of the long-range effective interaction. For small D the energy exhibits a pronounced minimum. The lowest energy corresponds to a symmetrical configuration of the disk-defect pairs, with the inner defect at the mid-point between the disks. The disks are separated by a distance that is twice the distance of the outer defect from the nearest disk. The latter is identical to the equilibrium distance of a defect nucleated by an isolated disk. Received 26 October 2001 and Received in final form 14 December 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     

The chirality of exceptional points

Exceptional points are singularities of the spectrum and wave functions of a Hamiltonian which occur as functions of a complex interaction parameter. They are accessible in experiments with dissipative systems. We show that the wave function at an exceptional point is a specific superposition of two configurations. The phase relation between the configurations is equivalent to a chirality which should be detectable in an experiment. Received 9 April 2001 and Received in final form 19 July 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     

Effects of entanglement concentration on Tg and local segmental motions

The process of spin-coating to fabricate thin polymer films with high molecular weight can produce samples with entanglement concentrations that are far below the equilibrium value. It is not clear whether or not such low entanglement concentrations are responsible for the depression of the glass temperature in thin polymer films. In this work, we measure the calorimetric glass temperature and viscoelastic response of polystyrenes with molecular weights ranging from 3×10³ to 43.7×10⁶ g/mol, for both bulk material and for samples freeze-dried from dilute solution. We conclude that the reduction of the glass temperature observed in thin polymer films cannot be due to the reduced entanglement concentration in the samples. Received 15 August 2001 and Received in final form 2 March 2002     

Excluded-volume polymer-induced depletion interaction between parallel flat plates

The interaction between two parallel plates due to non-adsorbing polymer chains with excluded volume is calculated using the adsorption method. The adsorption is calculated from the profile of the polymer segment concentration between the plates, which is obtained from the product function of the concentration profile near a single wall, involving the correlation length. The renormalization group theory provides expressions for the osmotic pressure and consequently for the osmotic compressibility, chemical potential and correlation length of a polymer solution. Both the local polymer concentration profiles as well as the minimum of the interaction potential between the plates agree with recently published self-avoiding random walk computer simulations. Received 9 August 2001     

Confinement of columnar diblock copolymers: Simulations, theory and applications

The inherent nanoscale morphologies of self-organizing diblock copolymer melts are now being investigated for a variety of technological applications. To obtain global, well-oriented, regular patterns requires suitably confining and aligning the melt between two flat plates. Here we consider such confinement for an asymmetrical diblock melt, which forms columns of the minority phase in a matrix of the majority phase. We investigate this system with a combination of numerical simulations and strong segregation theory and make suggestions as to when perpendicular orientation should prevail over parallel orientation of the columns. Received 22 May 2001 and Received in final form 14 February 2002     

Dynamic light scattering and <Superscript>31</Superscript>P NMR spectroscopy study of the self-assembly of deoxyguanosine 5'-monophosphate

Self-assembling properties of deoxyguanosine 5'-monophosphate in isotropic solutions of concentrations from 0.5 wt% to 15 wt% were investigated by dynamic light scattering (DLS) and ³¹P NMR spectroscopy. A slow diffusive mode with a diffusion coefficient D _slow∼ 10^-12 m²/s was detected by DLS for the whole concentration range. This mode is assigned to the translational motion of large globular aggregates, similar to those observed in DNA and other polyelectrolyte solutions. The existence of such aggregates was confirmed by freeze fracture electron microscopy. Close to the isotropic-cholesteric phase transition, at 4 wt% c 10 wt%, also a faster diffusive mode is observed in the polarized DLS response and a very fast mode is detected by depolarized DLS. These modes are related to translational and rotational diffusion of the columnar stacks of guanosine molecules, which are favorably formed in the relatively narrow pretransitional region. The stacking was also revealed from the appearance of a secondary resonance line in the ³¹P NMR spectra. Using the hydrodynamic theory of Tirado and Garcia de la Torre, the length of the cylindrical stacks was found to be L = 364±78 ?, which is significantly larger than the values reported for other guanosine derivatives. Received 13 July 2001 and Received in final form 17 October 2001     

A multi-species lattice-gas automaton model to study passive and reactive tracer migration in 2D fractures

We developed a numerical model based on a multi-species lattice gas cellular automaton to study passive and reactive tracer migration in saturated geological media. The model was made of multiple lattice gases interacting via a two-species collision rule. For a binary mixture, the model displayed a negative deviation from Raoult's law and therefore behaved as a real solution. By biasing the initial two-species collision rule, our model was made to obey the tracer assumption which requires that the tracer species does not affect the velocity of the vehicle fluid. In a 2D fracture, we checked the Taylor-Aris relation. An irreversible adsorption between the tracer and the solid phase was numerically added to perform filtration of the colloids. A good agreement was found with the solution of the filtration equation. An attachment efficiency was defined and was found to bear a linear relationship to the filtration coefficient. We added a third species to study the potential role of colloids in the transport of contaminants. Contaminant migration was enhanced when contaminants were bound to colloids and was slightly reduced when colloids were allowed to adsorb on the solid phase. Received 14 January 1999 and Received in final form 8 June 1999     

Interactions and correlations of particulate inclusions in a columnar phase

We calculate the elastic-field-mediated interaction between macroscopic particles in a columnar hexagonal phase. The interaction is found to be long-ranged and non-central, with both attractive and repulsive parts. We show how the interaction modifies the particle correlations and the column fluctuations. We also calculate the interaction of particles with the topological defects of the columnar phase. The particle-defect interaction reduces the mobility of the defects. Received 14 March 2002 and Received in final form 13 August 2002 RID="a" ID="a"e-mail: rjoy@physics.iisc.ernet.in     

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     

CPA density of states and conductivity in a double-exchange system containing impurities

We study density of states and conductivity of the doped double-exchange system, treating interaction of charge carriers both with the localized spins and with the impurities in the coherent potential approximation. It is shown that under appropriate conditions there is a gap between the conduction band and the impurity band in paramagnetic phase, while the density of states is gapless in ferromagnetic phase. This can explain metal-insulator transition frequently observed in manganites and magnetic semiconductors. Activated conductivity in the insulator phase is numerically calculated. Received 13 June 2000 and Received in final form 5 January 2001     

Structure of gels and aggregates of disk-like colloids

The static structure factor (S(q)) of dispersions and gels of disk-like mineral colloids (Laponite) was investigated using time- and ensemble-averaged light scattering. The evolution of S(q) in time after increasing the ionic strength of well-dispersed Laponite suspensions shows that Laponite aggregates and forms fractal clusters. The structure of the aggregates does not depend on the ionic strength, but the rate of growth increases very strongly with the ionic strength. At concentrations below about 3 g/l (0.12% v/v) the aggregates sediment while at higher concentrations space-filling gels are formed. The gels are homogeneous on length scales larger than the correlation length which decreases strongly with decreasing ionic strength and increasing concentration. However, the local structure is the same, independent of the concentration and the ionic strength. Received 6 August 2000 and Received in final form 16 March 2001     

Flow properties of the optically isotropic tetrahedratic phase

We discuss the coupling between flow and other hydrodynamic variables that can occur in the optically isotropic tetrahedratic phase (T_d) characterized by a third rank tensor order parameter T_ijk. We point out that an applied electric field or an applied temperature gradient will lead to flow. Reciprocally we predict that, for example, a shear flow applied to a tetrahedratic phase leads to an induced electric field and a temperature gradient. Similarities to recent experimental observations in the vicinity of the isotropic-B7 phase transitions in materials formed by banana-shaped molecules are discussed. Received 31 July 2001     

Coexistence of superconductivity and spin density wave orderings in the organic superconductor (TMTSF) 2 PF 6

The phase diagram of the organic superconductor (TMTSF)₂PF₆has been revisited using transport measurements with an improved control of the applied pressure. We have found a 0.8 kbar wide pressure domain below the critical point (9.43 kbar, 1.2 K) for the stabilisation of the superconducting ground state featuring a coexistence regime between spin density wave (SDW) and superconductivity (SC). The inhomogeneous character of the said pressure domain is supported by the analysis of the resistivity between T _SDW and T _SC and the superconducting critical current. The onset temperature T _SC is practically constant ( 1.20±0.01 K) in this region where only the SC/SDW domain proportion below T _SC is increasing under pressure. An homogeneous superconducting state is recovered above the critical pressure with T _SC falling at increasing pressure. We propose a model comparing the free energy of a phase exhibiting a segregation between SDW and SC domains and the free energy of homogeneous phases which explains fairly well our experimental findings. Received 3 September 2001 and Received in final form 9 November 2001     

Oppositely charged polyelectrolytes grafted onto planar surface: Mean-field lattice theory

Equilibrium structures of planar polyelectrolyte brushes formed by grafted chains carrying charges of opposite sign are examined by employing mean-field lattice theory. Two brushes of different architecture are considered: one formed by grafted diblock copolymers with oppositely charged blocks and the other being a mixed brush composed of oppositely charged homopolymers. The systems display nontrivial intrinsically inhomogeneous brush structures originating from the chain connectivity and the electrostatic interaction among the segments. In addition, a coexistence of stretched and coiled chains inside the brush is observed. The influence of the charges of the blocks, the relative length of the oppositely charged blocks, and the ionic strength of the solution on the brush inhomogeneity and structural differences between the two types of brushes are discussed. Received 14 March 2001 and Received in final form 18 June 2001     

Catching the PEG-induced attractive interaction between proteins

We present the experimental and theoretical background of a method to characterize the protein-protein attractive potential induced by one of the mostly used crystallizing agents in the protein-field, the poly(ethylene glycol) (PEG). This attractive interaction is commonly called, in colloid physics, the depletion interaction. Small-Angle X-ray Scattering experiments and numerical treatments based on liquid-state theories were performed on urate oxidase-PEG mixtures with two different PEGs (3350 Da and 8000 Da). A “two-component” approach was used in which the polymer-polymer, the protein-polymer and the protein-protein pair potentials were determined. The resulting effective protein-protein potential was characterized. This potential is the sum of the free-polymer protein-protein potential and of the PEG-induced depletion potential. The depletion potential was found to be hardly dependent upon the protein concentration but strongly function of the polymer size and concentration. Our results were also compared with two models, which give an analytic expression for the depletion potential. Received 29 April 2002 RID="a" ID="a"Present address: CRMC2-CNRS, Campus de Luminy, case 913, F-13288 Marseille Cedex 09, France; e-mail: vivares@crmc2.univ-mrs.fr RID="b" ID="b"e-mail: bonnete@crmc2.univ-mrs.fr RID="c" ID="c"Laboratory associated to Universities Aix-Marseille II and III.