Phase behavior of medium-length hydrophobically associating PEO-PPO multiblock copolymers in aqueous media.

HYPOTHESIS: The micellization of block copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) is driven by the dehydration of PPO at elevated temperatures. At low concentrations, a viscous solution of isolated micelles is obtained, whereas at higher concentrations, crowding of micelles results in an elastic gel. Alternating PEO-PPO multiblock copolymers are expected to exhibit different phase behavior, with altered phase boundaries and thermodynamics, as compared to PEO-PPO-PEO triblock copolymers (Pluronics®) with equal hydrophobicity, thereby proving the pivotal role of copolymer architecture and molecular weight. EXPERIMENTS: Multiple characterization techniques were used to map the phase behavior as a function of temperature and concentration of PEO-PPO multiblock copolymers (ExpertGel®) in aqueous solution. These techniques include shear rheology, differential and adiabatic scanning calorimetry, isothermal titration calorimetry and light transmittance. The micellar size and topology were studied by dynamic light scattering. FINDINGS: Multiblocks have lower transition temperatures and higher thermodynamic driving forces for micellization as compared to triblocks due to the presence of more than one PPO block per chain. With increasing concentration, the multiblock copolymers in solution gradually evolve into a viscoelastic network formed by soluble bridges in between micellar nodes, whereas hairy triblock micelles jam into liquid crystalline phases resembling an elastic colloidal crystal.

Experimental Advances in Nanoparticle-Driven Stabilization of Liquid-Crystalline Blue Phases and Twist-Grain Boundary Phases.

Recent advances in experimental studies of nanoparticle-driven stabilization of chiral liquid-crystalline phases are highlighted. The stabilization is achieved via the nanoparticles' assembly in the defect lattices of the soft liquid-crystalline hosts. This is of significant importance for understanding the interactions of nanoparticles with topological defects and for envisioned technological applications. We demonstrate that blue phases are stabilized and twist-grain boundary phases are induced by dispersing surface-functionalized CdSSe quantum dots, spherical Au nanoparticles, as well as MoS2 nanoplatelets and reduced-graphene oxide nanosheets in chiral liquid crystals. Phase diagrams are shown based on calorimetric and optical measurements. Our findings related to the role of the nanoparticle core composition, size, shape, and surface coating on the stabilization effect are presented, followed by an overview of and comparison with other related studies in the literature. Moreover, the key points of the underlying mechanisms are summarized and prospects in the field are briefly discussed.

Test of Halperin-Lubensky-Ma crossover function at the N-Sm-A transition in liquid crystal binary mixtures via high-resolution birefringence measurements.

We report optical birefringence data for a series of mixtures of the liquid crystals octylcyanobiphenyl (8CB) and decylcyanobiphenyl (10CB). Nematic order parameter S data in the nematic and smectic A phases have been derived from phase angle changes obtained in temperature scans with a rotating analyzer method. These S values have been used to arrive at values for possible entropy discontinuities at the smectic A to nematic phase transition temperature T_{NA}. The 10CB mole fraction dependence of the obtained entropy discontinuities could be well fitted with a crossover function consistent with the mean-field free-energy expression with a nonzero cubic term arising from the coupling between the smectic-A order parameter and the orientational order parameter director fluctuations in the Halperin-Lubensky-Ma theory. The obtained results are in good agreement with existing results from adiabatic scanning calorimetry. By exploiting the fact that the temperature derivative of the order parameter S(T) near T_{NA} exhibits the same power law divergence as the specific heat capacity, we have extracted the effective critical exponent α values for the compositions under study. The critical exponent α has been observed to reach the tricritical value α_{TCP}=0.5 for the 10CB mole fraction of x=0.330.

The critical behavior of the refractive index near liquid-liquid critical points.

The nature of the critical behavior in the refractive index n is revisited in the framework of the complete scaling formulation. A comparison is made with the critical behavior of n as derived from the Lorentz-Lorenz equation. Analogue anomalies to those predicted for the dielectric constant ε, namely, a leading |t|(2ß) singularity in the coexistence-curve diameter in the two-phase region and a |t|(1-α) along the critical isopleth in the one phase region, are expected in both cases. However, significant differences as regards the amplitudes of both singularities are obtained from the two approaches. Analysis of some literature data along coexistence in the two-phase region and along the critical isopleth in the one-phase region provide evidence of an intrinsic effect, independent of the density, in the critical anomalies of n. This effect is governed by the shift of the critical temperature with an electric field, which is supposed to take smaller values at optical frequencies than at low frequencies in the Hz to MHz range.

The critical behavior of the dielectric constant in the polar + polar binary liquid mixture nitromethane + 3-pentanol: an unusual sign of its critical amplitude in the one-phase region.

Dielectric constant measurements have been carried out in the one- and two-phase regions near the critical point of the polar + polar binary liquid mixture nitromethane + 3-pentanol. In the two-phase region, evidence for the |t|(2ß) singularity in the coexistence-curve diameter has been detected, thus confirming the novel predictions of complete scaling theory for liquid-liquid criticality. In the one-phase region, an "unusual" negative sign for the amplitude of the |t|(1-α) singularity has been encountered for the first time in an upper critical solution temperature type of binary liquid mixture at atmospheric pressure. Mass density measurements have also been carried out to provide additional information related to such experimental finding, which entails an increase of the critical temperature T(c) under an electric field.

Large heat capacity anomaly near the consolute point of the binary mixture nitromethane and 3-pentanol.

The large critical anomaly in the isobaric heat capacity C(p,x)(T) of the binary mixture nitromethane + 3-pentanol is measured using high-resolution adiabatic scanning calorimetry. The unique features of this technique provided an alternative approach to the study of the critical behavior of C(p,x)(T), providing further C(p,x)(T) related quantities from which valuable information could be extracted. Our data are in full agreement with the predictions of the Modern Theory of Critical Phenomena; specifically, 3D-Ising model values for the critical exponent α and the universal amplitude ratio values of the leading critical amplitudes, as well as for the first correction-to-scaling ones, provide the optimum fits to represent the experimental data. Evidence for the need of higher-order terms, i.e., first correction-to-scaling term, is given. The large value of the coefficient E for the linear temperature dependence of the background obtained is ascribed to a possible contribution of the regular linear background term, of a higher-order asymmetry term, and of the second correction-to-scaling term. Internal consistency of C(p,x)(T) and its related quantities is successfully checked.

Critical behavior of static properties for nitrobenzene-alkane mixtures.

We present experimental data of the isobaric heat capacity per unit volume C(p,x)V(-1) for mixtures containing nitrobenzene and an alkane (C(N)H(2N+2), with N ranging from 6 to 15) upon approaching their liquid-liquid critical points along a path of constant composition. Values for the critical amplitude A(+) have been determined. They have been combined with the previously reported ones for the leading term of the coexistence-curve width to obtain, with the aid of well-known universal relations, the critical amplitudes of the correlation length and of the osmotic susceptibility. The trends of all these critical parameters, which exhibit anomalous behavior in the low N region, are discussed in terms of particular microscopic phenomena characterizing NB-C(N)H(2N+2) mixtures. The work is completed with an analysis of the analog of the Yang-Yang anomaly in liquid-liquid criticality: the behavior of the partial molar heat capacities of the two liquid components is found to illustrate previously uncovered asymmetry effects.

Dielectric constant of fluids and fluid mixtures at criticality.

The behavior of the dielectric constant epsilon of pure fluids and binary mixtures near liquid-gas and liquid-liquid critical points is studied within the concept of complete scaling of asymmetric fluid-fluid criticality. While mixing of the electric field into the scaling fields plays a role, pressure mixing is crucial as the asymptotic behavior of the coexistence-curve diameter in the epsilon-T plane is concerned. Specifically, it is found that the diameters, characterized by a |T-Tc|1-alpha singularity in the previous scaling formulation [J. V. Sengers, D. Bedeaux, P. Mazur, and S. C. Greer, Physica A 104, 573 (1980)], gain a more dominant |T-Tc|2beta term, whose existence is shown to be supported by literature experimental data. The widely known |T-Tc|1-alpha singularity of epsilon along the critical isopleth in the one-phase region is found to provide information on the effect of electric fields on the liquid-liquid critical temperature: from experimental data it is inferred that Tc usually decreases as the magnitude of the electric field is enhanced. Furthermore, the behavior of mixtures along an isothermal path of approach to criticality is also analyzed: theory explains why the observed anomalies are remarkably higher than those associated to the usual isobaric path.

Nanoparticle-induced widening of the temperature range of liquid-crystalline blue phases.

Liquid-crystalline blue phases exhibit exceptional properties for applications in the display and sensor industry. However, in single component systems, they are stable only for very narrow temperature range between the isotropic and the chiral nematic phase, a feature that severely hinders their applicability. Systematic high-resolution calorimetric studies reveal that blue phase III is effectively stabilized in a wide temperature range by mixing surface-functionalized nanoparticles with chiral liquid crystals. This effect is present for two liquid crystals, yielding a robust method to stabilize blue phases, especially blue phase III. Theoretical arguments show that the aggregation of nanoparticles at disclination lines is responsible for the observed effects.

Temperature, concentration, and frequency dependence of the dielectric constant near the critical point of the binary liquid mixture nitrobenzene-tetradecane.

Detailed results are reported for the dielectric constant epsilon as a function of temperature, concentration, and frequency near the upper critical point of the binary liquid mixture nitrobenzene-tetradecane. The data have been analyzed in the context of the recently developed concept of complete scaling. It is shown that the amplitude of the low frequency critical Maxwell-Wagner relaxation (with a relaxation frequency around 10 kHz) along the critical isopleth is consistent with the predictions of a droplet model for the critical fluctuations. The temperature dependence of epsilon in the homogeneous phase can be well described with a combination of a (1-alpha) power law term (with alpha the heat capacity critical exponent) and a linear term in reduced temperature with the Ising value for alpha. For the proper description of the temperature dependence of the difference Deltaepsilon between the two coexisting phases below the critical temperature, it turned out that good fits with the Ising value for the order parameter exponent beta required the addition of a corrections-to-scaling contribution or a linear term in reduced temperature. Good fits to the dielectric diameter epsilon(d) require a (1-alpha) power law term, a 2beta power law term (in the past considered as spurious), and a linear term in reduced temperature, consistent with complete scaling.

Order of phase transitions and tricriticality in mixtures of octyloxycyanobiphenyl and nonyloxycyanobiphenyl liquid crystals: a high-resolution study by adiabatic scanning calorimetry.

A detailed study has been performed for mixtures of octyloxycyanobiphenyl (8OCB) and nonyloxycyanobiphenyl (9OCB) liquid crystals and nine of their mixtures by means of high-resolution adiabatic scanning calorimetry. The isotropic to nematic transitions are weakly first order with latent heat values in the range usually encountered for this transition in other liquid crystals. With the exception of pure 8OCB, for which only an upper limit of 1.8 J kg(-1) for the latent heat could be established, finite latent heats have been obtained for the nematic to smectic-A transition of all the mixtures and of pure 9OCB. The concentration dependence of their latent heats could be well fitted with a crossover function consistent with a mean-field free-energy expression that has a nonzero cubic term induced by the Halperin-Lubensky-Ma (HLM) coupling between the smectic-A order parameter and the orientational director fluctuations. Clearly first-order transitions with measurable latent heats are found for mole fractions of 9OCB in the mixtures where the effective critical exponent for the specific-heat capacity has substantially lower values than the tricritical one (0.5). This is qualitatively different from what has been observed so far in other liquid-crystal systems and yields strong experimental evidence from a calorimetric experiment for the HLM coupling between the smectic-A order parameter and the director orientation fluctuations.

Effects of magnetic nanoparticles with different surface coating on the phase transitions of octylcyanobiphenyl liquid crystal.

The impact of magnetic nanoparticles with different surface coating upon the isotropic-to-nematic and nematic-to-smectic- A phase transitions of the liquid crystal octylcyanobiphenyl is explored by means of high-resolution adiabatic scanning calorimetry. A shrinkage of the nematic range is observed, which is strongly dependent on the surface coating of the nanoparticles. The isotropic-to-nematic transition remains weakly first order while the nematic-to-smectic- A is continuous with the effective critical exponent alpha values (0.35 and 0.39, depending on the coating) between the pure octylcyanobiphenyl value of 0.31+/-0.03 and the theoretical tricritical value of 0.5.

Temperature-driven mixing-demixing behavior of binary mixtures of the ionic liquid choline bis(trifluoromethylsulfonyl)imide and water.

The ionic liquid (2-hydroxyethylammonium)trimethylammonium) bis(trifluoromethylsulfonyl)imide (choline bistriflimide) was obtained as a supercooled liquid at room temperature (melting point=30 degrees C). Crystals of choline bistriflimide suitable for structure determination were grown from the melt in situ on the X-ray diffractometer. The choline cation adopts a folded conformation, whereas the bistriflimide anion exhibits a transoid conformation. The choline cation and the bistriflimide anion are held together by hydrogen bonds between the hydroxyl proton and a sulfonyl oxygen atom. This hydrogen bonding is of importance for the temperature-dependent solubility properties of the ionic liquid. Choline bistriflimide is not miscible with water at room temperature, but forms one phase with water at temperatures above 72 degrees C (equals upper critical solution temperature). 1H NMR studies show that the hydrogen bonds between the choline cation and the bistriflimide anion are substantially weakened above this temperature. The thermophysical properties of water-choline bistriflimide binary mixtures were furthermore studied by a photopyroelectric technique and by adiabatic scanning calorimetry (ASC). By photothermal analysis, besides highly accurate values for the thermal conductivity and effusivity of choline bistriflimide at 30 degrees C, the detailed temperature dependence of both the thermal conductivity and effusivity of the upper and lower part of a critical water-choline bistriflimide mixture in the neighborhood of the mixing-demixing phase transition could be determined with high resolution and accuracy. Together with high resolution ASC data for the heat capacity, experimental values were obtained for the critical exponents alpha and beta, and for the critical amplitude ratio G+/G-. These three values were found to be consistent with theoretical expectations for a three dimensional Ising-type of critical behavior of binary liquid mixtures.

High-resolution calorimetric study of a liquid crystalline organo-siloxane tetrapode with a biaxial nematic phase.

High-resolution adiabatic scanning calorimetry and differential scanning calorimetry have been employed to study the thermal behavior of an organo-siloxane tetrapode reported to exhibit a biaxial nematic phase. No signature of the uniaxial to biaxial nematic phase transition could be retraced in sequential heating and cooling runs under different scanning rates, within the experimental resolution. The results obtained reveal that an extremely small heat should be involved in the uniaxial to biaxial nematic phase transition. The isotropic to uniaxial nematic transition at 318+/-0.01 K is very stable, and it is weakly first order with a rather small latent heat of 0.20+/-0.02 J/g .

Accelerated dielectric relaxation in the isotropic phase of associating liquid crystals dispersed with aerosils.

The dielectric response of liquid crystals in their nematic phase shows an acceleration of the relaxation associated with the rotation around the short molecular axis when dispersed with aerosils. However, in the isotropic phase, this acceleration is only seen for certain liquid crystalline molecules. In this paper, an associating liquid crystal (5CB) and a shorter monotropic liquid crystalline member of the same homologous series (4CB), a liquid crystal that does not show association (5NCS) and a nonassociating liquid crystal (5O5) have been studied by dielectric spectroscopy in the isotropic phase. Both 4CB and 5CB show a constant acceleration in the isotropic phase, observed over a broad temperature range. 5NCS and 5O5 do not show an acceleration in their isotropic phase. It seems that the disturbance of the dipole-dipole association process for the associating molecules is an important factor in the explanation of the acceleration of the relaxation in the isotropic phase.

Temperature dependence of the electrical conductivity of imidazolium ionic liquids.

The electrical conductivities of 1-alkyl-3-methylimidazolium tetrafluoroborate ionic liquids and of 1-hexyl-3-methylimidazolium ionic liquids with different anions were determined in the temperature range between 123 and 393 K on the basis of dielectric measurements in the frequency range from 1 to 10(7) Hz. Most of the ionic liquids form a glass and the conductivity values obey the Vogel-Fulcher-Tammann equation. The glass transition temperatures are increasing with increasing length of the alkyl chain. The fragility is weakly dependent on the alkyl chain length but is highly sensitive to the structure of the anion.

Effect of nonmesogenic impurities on the liquid crystalline phase transitions of octylcyanobiphenyl.

The effect of the nonmesogenic solutes cyclohexane (CH), biphenyl (BP), and water (W) on the nematic-isotropic (N-I) and the nematic-smectic- A (N-SmA) phase transitions in the liquid crystal octylcyanobiphenyl (8CB) has been studied by means of adiabatic scanning calorimetry. For BP and CH a linear decrease of both transition temperatures was observed with increasing solute mole fraction. For water the transition temperature stayed nearly constant (after a slight decrease for mole fractions of water up to 0.1) over the entire investigated region. For all concentrations of biphenyl and water studied the N-SmA transition remains second order. For 8CB+CH, however, crossover from second order to first order is observed at a tricritical point of the mole fraction x of CH around 0.046. For water it was found that for mole fractions of water above 0.1 phase separation between an 8CB rich and a water rich phase occurred. The changes in the transition temperatures and differences between the three systems, and in particular the crossover from second order to first order in the 8CB+CH system, is explained in terms of a mean-field free energy density expression including coupling terms of the solutes mole fraction with the nematic and smectic- A order parameters.

Effect of nonmesogenic impurities on the order of the nematic to smectic-A phase transition in liquid crystals.

By means of adiabatic scanning calorimetry, we have studied the effect of the nonmesogenic solutes cyclohexane (CH) and biphenyl (BP) on the nematic-smectic-A phase transition in the liquid crystal octylcyanobiphenyl (8CB). For all concentrations of BP studied, the transition remains second-order. For 8CB+CH, however, crossover from second-order to first-order is observed at a tricritical point of the mole fraction x of CH around 0.0460. The difference between the two systems and the crossover is explained in terms of a mean-field free energy density expression including coupling terms of x with the nematic and smectic-A order parameters.

Task-specific ionic liquid for solubilizing metal oxides.

Protonated betaine bis(trifluoromethylsulfonyl)imide is an ionic liquid with the ability to dissolve large quantities of metal oxides. This metal-solubilizing power is selective. Soluble are oxides of the trivalent rare earths, uranium(VI) oxide, zinc(II) oxide, cadmium(II) oxide, mercury(II) oxide, nickel(II) oxide, copper(II) oxide, palladium(II) oxide, lead(II) oxide, manganese(II) oxide, and silver(I) oxide. Insoluble or very poorly soluble are iron(III), manganese(IV), and cobalt oxides, as well as aluminum oxide and silicon dioxide. The metals can be stripped from the ionic liquid by treatment of the ionic liquid with an acidic aqueous solution. After transfer of the metal ions to the aqueous phase, the ionic liquid can be recycled for reuse. Betainium bis(trifluoromethylsulfonyl)imide forms one phase with water at high temperatures, whereas phase separation occurs below 55.5 degrees C (temperature switch behavior). The mixtures of the ionic liquid with water also show a pH-dependent phase behavior: two phases occur at low pH, whereas one phase is present under neutral or alkaline conditions. The structures, the energetics, and the charge distribution of the betaine cation and the bis(trifluoromethylsulfonyl)imide anion, as well as the cation-anion pairs, were studied by density functional theory calculations.

Experimental investigation of leaky lamb modes by an optically induced grating.

By removing the symmetry of a free plate configuration, fluid loading significantly modifies the nature of acoustic waves travelling along a plate, and it even gives existence to new acoustic modes. We present theoretical predictions for the existence, dispersive behavior, and spatial distribution of leaky Lamb waves in a fluid-loaded film. Although Lamb modes are often investigated by studying the radiated fluid waves resulting from their leakage, here their properties are assessed by detecting the wave displacements directly using laser beam deflection. By using crossed laser beam excitation, the detection and analysis of the different modes is done at a fixed wavelength, allowing one to verify the existence, the velocity, and the damping of each predicted mode in a simple and unambiguous way. Our theoretical predictions for the nature of the modes in a water-loaded Plexiglas film, including parts of looping modes, are experimentally confirmed.