Phase behavior and structure of an ABC triblock copolymer dissolved in selective solvent

A mean-field lattice theory is applied to predict the self-assembly into ordered structures of an ABC triblock copolymer in selective solvent. More specifically, the composition-temperature phase diagram has been constructed for the system (C)₁₄(PO)₁₂(EO)₁₇/water, where C stands for methylene, PO for propylene oxide and EO for ethylene oxide. The model predicts thermotropic phase transitions between the ordered hexagonal, lamellar, reverse hexagonal, and reverse cubic phases, as well as the disordered phase. The thermotropic behavior is a result of the temperature dependence of water interaction with EO- and PO-segments. The lyotropic effect (caused by changing the solvent concentration) on the formation of different structures has been found weak. The structure in the ordered phases is described by analyzing the species volume fraction profiles and the end segment and junction distributions. A “triple-layer” structure has been found for each of the ordered phases, with each layer rich in C-, PO-, and EO-segments, respectively. The blocks forming the layers are not stretched. The dependence of the domain spacing on polymer volume fraction and temperature is also considered. Received 17 April 2002 Published online: 21 January 2003     

Phase equilibria in random multiblock copolymers

A mean-field theory for domain structures in random multiblock copolymer melts is developed. We focus on the finite molecular weight effects resulting in a competition between macroscopic phase separation and microdomain formation in the system. We identify an essential parameter N ε controlling the phase behavior of the system, where N is the number of blocks per chain and ε is the composition asymmetry parameter (= the difference between the mean copolymer composition and its critical value). The phase diagram involving N ε and the reduced temperature as variables is obtained. The regions of coexistence of two or more phases are identified. We show that a superstructure formation on cooling is always pre-empted by a macroscopic phase separation of the macroscopically homogeneous (disordered) system yielding two homogeneous phases: H ₀↦H ₁ + H ₂. The third (lamellar) phase separates on further cooling. Then hexagonal and body-centred-cubic phases take over if N ε 1. As the Flory interaction parameter χ increases further, the standard transitions BCC↦HEX↦LAM take place. Received 13 July 2001     

Switching of banana liquid crystal mesophases under field

Taking advantage of the great number of bent-core or “banana" compounds synthesized and studied in the laboratory, we describe their behaviour under the application of an external electric field. If the field were a static one, we would work within the frame of an equilibrium phase diagram in a (field E, temperature T) space where some phases would be simple dielectrics and others ferroelectric ones with a macroscopic polarization, either spontaneous or induced by the field. In this paper, we deal with the basic responses of “banana” liquid crystals under the application of a low frequency (1 to 100 Hz) AC field. Firstly square-wave voltages allow us to locate the phase boundary between dielectric (at lower field) and ferroelectric phases (higher field) at a given temperature and field threshold. Then we apply slowly varying AC voltages with shapes like triangle or “triple-plateau” to check out the stability of the induced ferroelectric phase versus field removal. Three behaviours are encountered, the unstable one (short lifetime of the high-field ferroelectric phase) where the macroscopic polarization is destroyed and then rebuilt in the opposite direction during each half period and usually called “antiferroelectric”; the stable one (long lifetime) with a polarization that rotates at constant modulus which is labeled as “ferroelectric” and a new one where the macroscopic polarization is proportional to the applied fied, we named this behaviour as “superparaelectric”. Let us stress that these observations apply to the ferroelectric phases of the (E, T) phase diagram not to the zero field (0,T) phases observed in the usual phase characterization experiments except for an eventual spontaneous ferroelectric phase. Received 18 April 2002 and Received in final form 17 January 2003 Published online: 16 April 2003 RID="a" ID="a"e-mail: marcerou@crpp.u-bordeaux.fr RID="b" ID="b"URL: http://www.crpp-bordeaux.cnrs.fr     

Statistical physics analysis of the computational complexity of solving random satisfiability problems using backtrack algorithms

The computational complexity of solving random 3-Satisfiability (3-SAT) problems is investigated using statistical physics concepts and techniques related to phase transitions, growth processes and (real-space) renormalization flows. 3-SAT is a representative example of hard computational tasks; it consists in knowing whether a set of αN randomly drawn logical constraints involving N Boolean variables can be satisfied altogether or not. Widely used solving procedures, as the Davis-Putnam-Loveland-Logemann (DPLL) algorithm, perform a systematic search for a solution, through a sequence of trials and errors represented by a search tree. The size of the search tree accounts for the computational complexity, i.e. the amount of computational efforts, required to achieve resolution. In the present study, we identify, using theory and numerical experiments, easy (size of the search tree scaling polynomially with N) and hard (exponential scaling) regimes as a function of the ratio α of constraints per variable. The typical complexity is explicitly calculated in the different regimes, in very good agreement with numerical simulations. Our theoretical approach is based on the analysis of the growth of the branches in the search tree under the operation of DPLL. On each branch, the initial 3-SAT problem is dynamically turned into a more generic 2+p-SAT problem, where p and 1 - p are the fractions of constraints involving three and two variables respectively. The growth of each branch is monitored by the dynamical evolution of α and p and is represented by a trajectory in the static phase diagram of the random 2+p-SAT problem. Depending on whether or not the trajectories cross the boundary between satisfiable and unsatisfiable phases, single branches or full trees are generated by DPLL, resulting in easy or hard resolutions. Our picture for the origin of complexity can be applied to other computational problems solved by branch and bound algorithms. Received 10 March 2001     

Monte-Carlo simulation of transient gel formation and break-up during reversible aggregation

Monte-Carlo simulations of reversible aggregation on a cubic lattice were done by introducing a finite probability (P) of nearest neighbours to form a bond. Depending on the volume fraction of occupied sites (φ) and P we observed different phenomena by monitoring as a function of time the space filling and the distribution of the aggregates and the gel fraction. At smaller values of P the system develops into an equilibrium distribution of aggregates of which the average size increases with increasing φ until above a critical value the system percolates. At larger values of P the system phase separates into two phases with different densities. Above a critical value of φ the system percolates during a finite time. The life time of the gel and the maximum gel fraction were studied as a function of P. Received 1st March 2001 and Received in final form 24 April 2001     

Zpif's law in the liquid gas phase transition of nuclei

Zpif's law in the field of linguistics is tested in the nuclear disassembly within the framework of isospin dependent lattice gas model. It is found that the average cluster charge (or mass) of rank n in the charge (or mass) list shows exactly inversely to its rank, i.e., there exists Zpif's law, at the phase transition temperature. This novel criterion shall be helpful to search the nuclear liquid gas phase transition experimentally and theoretically. In addition, the finite size scaling of the effective phase transition temperature at which the Zpif's law appears is studied for several systems with different mass and the critical exponents of ν and β are tentatively extracted. Received: 2 June 1999 / Revised version: 8 October 1999     

Integrable correlated electron model with next-nearest-neighbour interactions

The exactly solvable model of supersymmetric t - J chains (STJC) of correlated electrons with next-nearest-neighbour (NNN) interactions is proposed and studied. The model with interactions between nearest neighbours and NNN interactions in one chain can also be considered as a two-chain model with zigzag-like coupling between the chains. The NNN interaction (coupling between chains) causes the onset of additional Dirac seas for low-lying charge and/or spin excitations. These Dirac seas change the low-energy (conformal) behavior of the model. The filling of those seas depends on the values of the NNN coupling (interactions between chains), external magnetic field and applied voltage. We identify the new ground state phases which appear due to the NNN as incommensurate ones. The NNN coupling in the incommensurate phases induces spontaneous magnetization and/or spontaneous filling of the Dirac sea for charge excitations (“spontaneous charge ordering”). The onset of this order implies a first order quantum phase transition driven by the field with hysteresis phenomena. Received 13 September 2000     

Exchange coupling in ultrathin epitaxial yttrium iron garnet films

Magnetic exchange coupling has been observed for ultrathin films of yttrium iron garnet (Y₃Fe₅O₁₂ or YIG). Single-crystalline YIG films were prepared on yttrium aluminium garnet (Y₃Al₅O₁₂ or YAG) substrates by pulsed laser deposition. (111) and (110) oriented substrates were used. Film thicknesses were varied from 180 ? to 4600 ?. Epitaxial growth of YIG on YAG was obtained in spite of the lattice mismatch of 3%. Magnetic hysteresis loops recorded for ultrathin YIG films have a “bee-waist” shape and show a coupling between two different magnetic phases. The first phase is magnetically soft YIG. A composition study by secondary ion mass spectroscopy shows the second phase to be Y₃Fe_5-xAl_xO₁₂ due to the interdiffusion of Fe and Al at the film/substrate interface. This compound is known to be magnetically harder and to have weaker magnetization than YIG. The coupling of the two phases leads to a hysteresis loop displacement at low temperatures. This displacement varies differently with film thickness for two substrate orientations. Assuming an interfacial coupling, the maximal interaction energy is estimated to be about 0.17 erg/cm² at 5 K for (111) oriented sample. Received 3 June 2002 / Received in final form 7 October 2002 Published online 27 January 2003 RID="a" ID="a"Presently at LPM, Université H. Poincaré, BP 239, 54506 Vandœuvre-lès-Nancy e-mail: popova@lpm.u-nancy.fr     

Composite spin-triplet superconductivity in an symmetric lattice model

The two-channel Anderson lattice model which has SU (2) ⊗ SU (2) symmetry is of relevance to understanding of the magnetic, quadrupolar and superconducting phases in U_1-xTh_xBe₁₃ or Pr based skutterudite compounds such as PrFe₄P₁₂ or PrOs₄Sb₁₂. Possible unconventional superconducting phases of the model are explored. They are characterized by a composite order parameter comprising of a local magnetic or quadrupolar moment and a triplet conduction electron Cooper-pair. This binding of local degrees of freedom removes the entropy of the non Fermi-liquid normal state. We find superconducting transitions in the intermediate valence regime which are suppressed in the stable moment regime. The gap function is non analytic and odd in frequency: a pseudo-gap develops in the conduction electron density of states which vanishes as |ω| close to ω = 0. In the strong intermediate valent regime, the gap function acquires an additional -dependence. Received 28 February 2002 / Received in final form 18 April 2002 Published online 9 July 2002     

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     

The association of octadecyl-end-capped poly-(sodium 2-acrylamido-2-methylpropanesulfonates) in water and salt solutions: A study by fluorescence spectroscopy and isothermal titration calorimetry

Steady-state fluorescence spectroscopy and isothermal titration calorimetry (ITC) have been used to study the aggregation in aqueous solutions of poly-(2-acrylamido)-2-methylpropanesulfonic acids, sodium salt mono-endcapped with either N,N-di-n-octadecyl or N-4-[(1-pyrenyl)butyl]-N-n-octadecyl which were prepared by free radical polymerization of 2-(acrylamido)-2-methylpropane sulfonic acid (AMPS) initiated with the azo compounds, 4,4'-azobis{cyano-N,N-di-n-octadecyl}pentanamide and 4,4'-azobis{cyano-N,N-[4-(1-pyrenyl)butyl]-n-octadecyl}pentanamide, respectively. Both techniques indicate the occurrence of multimolecular aggregates in solutions of the polymers in water and in 0.2 M NaCl. The concentration range for aggregation is about 1-14 mmol AMPS l^-1 (0.5-2.7 g l^-1) in 0.2 M NaCl and the enthalpy of micellization, estimated from ITC data, is ∼100 J [mol AMPS]^-1. The accessibility of the chromophores to neutral molecules and to cationic species was assessed by quenching of fluorescence with nitromethane and thallium nitrate, respectively. The association of the mono-endcapped polymers is compared to that of PAMPS derivatives carrying hydrophobic groups randomly attached along the chain. Received 7 August 2000 and Received in final form 26 October 2000     

Structures and energetics of carbon bridged C 60 clusters

The structures and energetics of carbon bridged C₆₀ clusters (C ₆₀ ) _n C_m have been studied by simulated annealing technique within the tight-binding molecular-dynamics. The “sp² addition” ball-and-chain dimers exhibit odd-even alternations over the number of chain atoms, with the dimers containing even chain atoms more stable against dissociation than their immediate neighbors containing odd chain atoms. In addition to the usual “sp² addition” dimers, a pentagon-linked C₁₂₁ isomer and a hexagon-linked C₁₂₂ isomer are also found to be stable. Based on our tight-binding calculations, trimers and larger clusters can be simply regarded as being made up of independent or weakly interacting dimers, if the C-C₆₀ joints on a single cage are not too close to each other. Large C₆₀ clusters connected by chains each containing only one or two carbon atoms have similar stability to that of constituent dimers, indicating the possibility to form stable C₆₀-carbon polymers. Received 17 January 2001 and Received in final form 26 February 2001     

Association behaviour of glucitol amine gemini surfactants

The association behaviour of a number of glucitol amine gemini surfactants has been investigated by means of molecular dynamics and self-consistent-field calculations. We have shown that the titratable head group of the surfactant is responsible for a micelle-to-membrane transition when changing the pH. Furthermore, the association structure of this group of surfactants is shown to be very sensitive to ionic strength. The combination of a charged head group, a spacer, and the hydrophilic glucitol side chains is responsible for the possible structural transitions in the associates as a function of ionic strength and pH. Received: 12 January 2002 and Received in final form 10 March 2002     

Competition of disorder and interchain hopping in a two-chain Hubbard model

We study the interplay of Anderson localization and interaction in a two chain Hubbard ladder allowing for arbitrary ratio of disorder strength to interchain coupling. We obtain three different types of spin gapped localized phases depending on the strength of disorder: a pinned 4k _F Charge Density Wave (CDW) for weak disorder, a pinned 2k _F CDW^π for intermediate disorder and two independently pinned single chain 2k _F CDW for strong disorder. Confinement of electrons can be obtained as a result of strong disorder or strong attraction. We give the full phase diagram as a function of disorder, interaction strength and interchain hopping. We also study the influence of interchain hopping on localization length and show that localization is enhanced by a small interchain hopping but suppressed by a large interchain hopping. Received 6 April 2001     

A molecular theory of smectic C liquid crystals made of rod-like molecules

Organic compounds exhibiting the smectic C phase are made of rod-like molecules that have dipolar groups with lateral components. We argue that the off-axis character of the lateral dipolar groups can account for tilt in layered smectics (SmC, SmC*, SmI etc.). We develop a mean-field theory of the smectic C phase based on a single-particle potential of the form U _C ∝ sin(2θ)cosφ, consistent with the biaxial nature of the phase, where θ and φ are the polar and azimuthal angles, respectively. The hard-rod interactions that favour the smectic A phase with zero tilt angle are also included. The theoretical phase diagrams compare favourably with experimental trends. Our theory also leads to the following results: i) a first-order smectic C to smectic A transition above some value of the McMillan parameter α, leading to a tricritical point on the smectic C to smectic A transition line and ii) a first-order smectic C to smectic C transition over a very small range of values of the model parameters. We have also extended the theory to include the next higher-order term in the tilting potential and to include the effect of different tilt angles for the molecular core and the chain in the SmC phase. Received 3 August 2002 RID="a" ID="a"Present address: Department of Physics, Vijaya College, R. V. Road, Bangalore - 560 004, India. RID="b" ID="b"e-mail: nvmadhu@rri.res.in     

Effects of properties of the surfactant on its aggregate behavior

The effects of the solvent-surfactant interaction, chain length and stiffness of surfactants on the formation of aggregates and the aggregation degree of surfactants in the two-dimension solution have been investigated using discontinuous molecular-dynamics simulations. When the tail-water repulsion increases or the head-water attraction decreases, the aggregation degree increases. Increasing the chain length and raising the stiffness of surfactants lead to the increment of the aggregation degree. Received 25 July 2001 and Received in final form 7 May 2002     

Elastic properties of polymer-doped dilute lamellar phases: A small-angle neutron scattering study

We investigate experimentally, using small-angle neutron scattering the elastic properties of polymer-doped dilute lamellar phases. In our system the polymer is water-soluble but nevertheless partially adsorbs onto the negatively charged surfactant bilayers. The effective polymer-mediated interaction between bilayers is less repulsive than the weakly screened electrostatic interaction that prevails at zero polymer content. It even becomes attractive in some regions of the phase diagram. Small-angle neutron scattering allows us to measure directly the Caillé exponent η characterizing the bilayer fluctuations in lamellar (smectic A) phases, and thus indirectly estimate the compression modulus as a measure of the strength of the bilayer-bilayer interactions. The compression modulus appears to be vanishing at a point located on the lamellar-lamellar phase separation boundary, a candidate critical point. Received: 7 August 2000     

Phase behavior of organic-inorganic crystal

We have investigated the structure and phase behavior of nonmolecularly layered silver stearate by means of temperature-dependent diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. Upon heating the sample, remarkable spectral changes took place. The first phase transition took place that might be associated with a premelting event characterized by the formation of gauche conformers at 390-420 K. A second phase transition took place in which silver nanoparticles with a size of ∼4 nm were formed by thermal decomposition of silver stearate at 520-550 K. These silver nanoparticles, derivatized by stearate, were readily spread as a monolayer at air/water interface, and could be packed in 3-D assemblies by the Langmuir-Blodgett method. Received 29 November 2000     

Deconfinement transition: a three dimensional model

We present a three–dimensional model for quark matter with a density dependent quark–quark (confining) potential, which allows to describe a sort of deconfinement transition as the system evolves from a low density assembly of bound structures to a high density free Fermi gas of quarks. We consider different confining potentials, some of which successfully utilized in hadron spectroscopy. We find that a proper treatment of the many–body correlations induced by the medium is essential to disentangle the different nature of the two (hadronic and deconfined) phases of the system. For this purpose the ground state energy per particle and the pair correlation function are investigated. Received: 10 June 1998 / Revised version: 24 September 1998