Effects of electron-electron interactions on the electronic Raman scattering of graphite in high magnetic fields

We report the observation of strongly temperature (T)-dependent spectral lines in electronic Raman-scattering spectra of graphite in a high magnetic field up to 45 T applied along the c axis. The magnetic field quantizes the in-plane motion, while the out-of-plane motion remains free, effectively reducing the system dimension from 3 to 1. Optically created electron-hole pairs interact with, or shake up, the one-dimensional Fermi sea in the lowest Landau subbands. Based on the Tomonaga-Luttinger liquid theory, we show that interaction effects modify the spectral line shape from (ω-Δ)-1/2 to (ω-Δ)2α-1/2 at T = 0. At finite T, we predict a thermal broadening factor that increases linearly with T. Our model reproduces the observed T-dependent line shape, determining the electron-electron interaction parameter α to be ∼0.05 at 40 T. © 2014 American Physical Society.

Investigation of Interfacial Tensions for Carbon Dioxide Aqueous Solutions by Perturbed-Chain Statistical Associating Fluid Theory Combined with Density-Gradient Theory

The perturbed-chain statistical associating fluid theory and density-gradient theory are used to construct an equation of state (EOS) applicable for the phase behaviors of carbon dioxide aqueous solutions. With the molecular parameters and influence parameters respectively regressed from bulk properties and surface tensions of pure fluids as input, both the bulk and interfacial properties of carbon dioxide aqueous solutions are satisfactorily correlated by adjusting the binary interaction parameter (k(ij)). Our results show that the constructed EOS is able to describe the interfacial properties of carbon dioxide aqueous solutions in a wide temperature range, and illustrate the influences of temperature, pressure, and densities in each phase on the interfacial properties.

Defect evolution and hydrodynamic effects in lamellar ordering process of two-dimensional quenched block copolymers

The effects of hydrodynamic interactions on the lamellar ordering process for two-dimensional quenched block copolymers in the presence of extended defects and the topological defect evolutions in lamellar ordering process are numerically investigated by means of a model based on lattice Boltzmann method and self-consistent field theory. By observing the evolution of the average size of domains, it is found that the domain growth is faster with stronger hydrodynamic effects. The morphological patterns formed also appear different. To study the defect evolution, a defect density is defined and is used to explore the defect evolutions in lamellar ordering process. Our simulation results show that the hydrodynamics effects can reduce the density of defects. With our model, the relations between the Flory-Huggins interaction parameter chi, the length of the polymer chains N, and the defect evolutions are studied.

STUDY OF COARSENING OF MICRODOMAINS IN BLOCK COPOLYMERS BY LATTICE BOLTZMANN METHODS

In order to understand the coarsening of microdomains in symmetric diblock copolymers at the late stage, a model for block copolymers is proposed. By incorporating the self consistent field theory with the free energy approach Lattice Boltzmann model, hydrodynamic interactions can be considered. Compared with models based on Ginzburg-Landau free energy, this model does not employ phenomenological free energies to describe systems. The model is verified by comparing the simulation results obtained using this method with those of a dynamical version of the self consistent mean field theory. After that,the growth exponents of the characteristic domain size for symmetric block copolymers at late stage are studied. It is found that the viscosity of the system affects the growth exponents greatly, although the growth exponents are all less than 1/3 Furthermore, the relations between the growth exponent, the interaction parameter and the chain length are studied.

Formation of Two Kinds of Hexagonally Arranged Structures in ABC Triblock Copolymer Thin Films Induced by a Strongly Selective Solvent Vapor

An order-order transition (OOT) in the sequence of a hexagonally arranged core-shell cylinder to a double-hexagonally arranged dot in polystyrene-block-poly(butadiene)-block-poly(2-vinylpyridine) (SBV) triblock copolymer thin films is reported to be induced upon exposure to a solvent vapor that: is strongly selective for the two end blocks. These two kinds of hexagonally arranged structures could form when the film thickness is 44, 3.23, and 223 nm. When the film thickness is decreased to 13 nm, the ordered structure is absent. The sizes of the cylinder structures formed with the same annealing time in films of different thickness are compared to address the effects of film thickness on the phase structure. The mechanism is analyzed from the total surface area of the blocks and the effective interaction parameter in the solvent vapor.

Pressure effects on thermodynamics of phase behavior in polystyrene/methylcyclohexane solutions

The calculations presented in this paper are based on the Sanchez-Lacombe (SL) lattice fluid theory. The interaction energy parameter, g*(12)/k, required in this approach was obtained by fitting the cloud points of polystyrene (PS) /methyleyclohexane (MCH) polymer solutions under pressure. The SL lattice fluid theory was used to calculate the spinodals, the binodals, and the Flory-Huggins (FH) interaction parameter of the solutions. The calculated results show that the SL lattice fluid theory can describe the dependences of thermodynamics of PS/MCH solutions on temperature and pressure very well. However, the calculated enthalpy and the excess volume changes indicate that the Clausius-Clapeyron equation cannot be suitable to describe pressure effect on PS/MCH solutions. Further analysis on the thermodynamics of this system under pressure shows that the role of entropy is more important than the excess volume in the present case.

Crystallization behavior of poly(epsilon-caprolactone) in poly(epsilon-caprolactone) and poly(vinyl methyl ether) mixtures

The morphological development and crystallization behavior of poly(epsilon-caprolactone) (PCL) in miscible mixtures of PCL and poly(vinyl methyl ether) (PVME) were investigated by optical microscopy as a function of the mixture composition and crystallization temperature. The results indicated that the degree of crystallinity of PCL was independent of the mixture composition upon melt crystallization because the glass-transition temperatures of the mixtures were much lower than the crystallization temperature of PCL. The radii of the PCL spherulites increased linearly with time at crystallization temperatures ranging from 42 to 49 degrees C. The isothermal growth rates of PCL spherulites decreased with the amount of the amorphous PVME components in the mixtures. Accounting for the miscibility of PCL/PVME mixtures, the radial growth rates of PCL spherulites were well described by a kinetic equation involving the Flory-Huggins interaction parameter and the free energy for the nuclei formation in such a way that the theoretical calculations were in good agreement with the experimental data. From the analysis of the equilibrium melting point depression, the interaction energy density of the PVME/PCL system was calculated to be -3.95 J/cm(3).

Biodegradable poly(L-lactide)/poly(epsilon-caprolactone)-modified montmorillonite nanocomposites: Preparation and characterization

New nanocomposites were prepared by melt blending poly(L-lactide) (PLLA), poly(epsilon-caprolactone) (PCL), and organically modified montmorillonite (OMMT). The obtained nanocomposites showed enhanced tensile strength, modulus and elongation at break than that of PLLA/PCL blends. The dynamic mechanical analysis showed the increasing mechanical properties with temperature dependence of nanocomposites. Wide-angle X-ray diffraction analysis and transmission electron microscopy indicated that the material formed the nanostructure. Adding OMMT improved the thermal stability and crystalline abilities of nanocomposites. The morphology was investigated by environmental scanning electron microscopy, which showed that increasing content of OMMT reduces the domain size of phase-separated particles. The specific interaction between each polymer and OMMT was characterized by the Flory-Huggins interaction parameter, B, which was determined by the equilibrium melting point depression of nanocomposites. The final values of B showed that PLLA was more compatible with OMMT than PCL.

Temperature and pressure dependence of phase separation of trans-decahydronaphthalene/polystyrene solution

The cloud-point temperatures (T-c1's) of ti-ans-decahydronaphthalene (TD)/polystyrene (PS, M-w = 270 kg/mol) solutions were determined by fight scattering measurements over a range of temperatures (1-16 degreesC), pressures (100-900 bar), and compositions (4.2-21.6 vol% polymer). The system phase separates upon cooling and the T-c1 was found to increase with the rising pressure for the constant composition. In the absence of special effects this finding indicates positive excess volumes. The special attention was paid to the demixing temperatures as a function of the pressure for the different polymer solutions and the plots in the T-volume fraction plane and P-volume fraction plane. The cloud-point curves of polymer solutions under changing pressures were observed for different compositions, demonstrates that the TD/PS system exhibits UCST (phase separation upon cooling) behavior. With this data the phase diagrams under pressure were calculated applying the Sanchez-Lacombe (SL) lattice fluid theory. Furthermore, the cause of phase separation, i.e., the influence of Flory-Huggins (FH) interaction parameter under pressure was investigated.

Effects of casting solvents on the formation of inverted phase in block copolymer thin films

Previously, an inverted phase (the minority blocks comprising the continuum phase) was found in solution-cast block copolymer thin films. In this study, the effect of casting solvents on the formation of inverted phase has been studied. Two block copolymers, poly(styrene-b-butadiene) (SB) (M-w = 73 930 Da) and poly(styrene-b-butadiene-b-styrene) (SBS) (M-w = 140 000 Da), with comparable block lengths and equal polystyrene (PS) weight fraction (similar to30 wt %) were used. The copolymer thin films were cast from different solvents, toluene, benzene, cyclohexane, and binary mixtures of benzene and cyclohexane. Toluene and benzene are good solvents for both PS and PB, but have a preferential affinity for PS, while cyclohexane is a good solvent for PB but a Theta solvent for PS (T-Theta = 34.5 degreesC). The differential solvent affinity for PS and PB was estimated in terms of a difference between the polymer-solvent interaction parameter, chi, for each block. Under an extremely slow solvent evaporation rate, the time-dependent phase behavior during such a solution-to-film process was examined by freeze-drying the samples at different stages, corresponding to different copolymer concentrations, rho.

Study on the origin of inverted phase in drying solution-cast block copolymer films

In a previous study, we reported observation of the novel inverted phase (the minority blocks comprising the continuum phase) in kinetically controlled phase separating solution-cast poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymer films [Zhang et al. Macromolecules 2000, 33, 9561-7]. In this study, we adopt the same approach to investigate the formation of inverted phase in a series of solution-cast poly(styrene-b-butadiene) (SB) asymmetric diblock copolymers having nearly equal polystyrene (PS) weight fraction (about 30 wt %) but different molecular weights. The microstructure of the solution-cast block copolymer films resulting from different solvent evaporation rates, R, was inspected, from which the kinetically frozen-in phase structures at qualitatively different block copolymer concentrations and correspondingly different effective interaction parameter, chieff, can be deduced. Our result shows that there is a threshold molecular weight or range of molecular weight below which the unusual inverted phase is accessible by controlling the solvent evaporation rate. In comparing the present result with that of our previous study on the SBS triblock copolymer, we find that the formation of the inverted phase has little bearing on the chain architecture. We performed numerical calculations for the free energy of block copolymer cylinders and found that the normal phase is always preferred irrespective of the interaction parameter and molecular weight, which suggests the formation of the inverted phase to have a kinetic origin.

Crystallization and melting behaviors of PPC-BS/PVA blends

The isothermal crystallization and melting behaviors of poly(propylene carbonate) end-capped with benzenesulfonyl/poly (vinyl alcohol) (PPC-BS/PVA) blends over rich PVA composition range were first investigated by differential scanning calorimetry (DSC). PPS-BS/PVA interaction parameter, chi(12), calculated from equilibrium melting temperature depression was -0.44, revealing miscibility of PPC-BS with PVA in the melt and favorable interactions. The temperature dependence of crystallization rate constant at initial crystallization stage was analyzed using the modified Lauritzen-Hoffman expression. The chain width, a(0), the thickness of a monomolecular layer, b(0), the fold and lateral surface-free energies, sigma(e) and sigma, and the work of chain folding, q, for neat PVA were first reckoned to be 4.50 Angstrom, 4.78 Angstrom, 76.0 erg.cm(-2), and 4.70 kcal.mol(-1), respectively. The values of sigma(e) and q for PVA in PPC-BS/PVA blends exhibited a maximum in the neighborhood of 10/90 PPC-BS/PV, respectively.

Pressure effects on the thermodynamics of trans-decahydronaphthalene/polystyrene polymer solutions: Application of the Sanchez-Lacombe lattice fluid theory

The cloud-point temperatures (T-cl's) of trans-decahydronaphthalene(TD)/polystyrene (PS, (M) over bar (w) = 270 000) solutions were determined by light scattering measurements over a range of temperatures (1-16degreesC), pressures (100-900 bar), and compositions (4.2-21.6 vol.-% polymer). The system phase separates upon cooling and T-cl was found to increase with rising pressure for constant composition. In the absence of special effects, this finding indicates positive excess volume for the mixing. Special attention was paid to the demixing temperatures as a function of pressure for different polymer solutions and the plots in the T-phi plane (where phi signifies volume fractions). The cloud-point curves of polymer solutions under different pressures were observed for different compositions, which demonstrated that pressure has a greater effect on the TD/PS solutions when far from the critical point as opposed to near the critical point. The Sanchez-Lacombe lattice fluid theory (SLLFT) was used to calculate the spinodals, the binodals, the Flory-Huggins (FH) interaction parameter, the enthalpy of mixing, and the volume changes of mixing. The calculated results show that modified PS scaling parameters can describe the thermodynamics of the TD/PS system well. Moreover the SLLFT describes the experimental results well.

Thermodynamics of phase behavior in PEO/P(EO-b-DMS) homopolymer and block co-oligomer mixtures under pressure

The cloud-point temperatures (T-cl's) of poly(ethylene oxide) (PEO) and poly(ethylene oxide)-block-polydimethylsiloxane (P(EO-b-DMS)) homopolymer and block-oligomer mixtures were determined by turbidity measurements over a range of temperatures (105 to 130degrees), pressures (1 to 800 bar), and compositions (10-40 wt.-% PEO). The system phase separates upon cooling and T-cl was found to decrease with an increase in pressure for a constant composition. In the absence of special effects, this finding indicates negative excess volumes. Special attention was paid to the demixing temperatures as a function of the pressure for the different polymer mixtures and the plots in the T-phi plane (where phi signifies volume fractions). The cloud-point curves of the polymer mixture under pressures were observed for different compositions. The Sanchez-Lacombe (SL) lattice fluid theory was used to calculate the spinodals, the binodals, the Flory-Huggins (FH) interaction parameter, the enthalphy of mixing, and the volume changes of mixing. The calculated results show that modified P(EO-b-DMS) scaling parameters with the new combining rules can describe the thermodynamics of the PEO/P(EO-b-DMS) system well with the SL theory.

Theoretical estimation of thermodynamic properties of the system PS/PPO on the basis of modified combining rule of Sanchez-Lacombe lattice fluid model

The three scaling parameters described in Sanchez-Lacombe lattice fluid theory (SLLFT), T*, P* and rho* of pure polystyrene (PS), pure poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and their mixtures are obtained by fitting corresponding experimental pressure volume-temperature data with equation-of-state of SLLFT. A modified combining rule in SLLFT used to match the volume per mer, v* of the PS/PPO mixtures was advanced and the enthalpy of mixing and Flory-Huggins (FH) interaction parameter were calculated using the new rule. It is found that the difference between the new rule and the old one presented by Sanchez and Lacombe is quite small in the calculation of the enthalpy of mixing and FH interaction parameter and the effect of volume-combining rule on the calculation of thermodynamic properties is much smaller than that of energy-combining rule. But the relative value of interaction parameter changes much due to the new volume-based combining rule. This effect can affect the position of phase diagram very much, which is reported elsewhere [Macromolecules 34 (2001) 6291]