Miscibility studies of disc-like molecules

The total miscibility method is applied to study the recently discovered mesophases of disc-like molecules, benzene-hexa-n-alkanoates. These compounds do not form continuous solid solutions, but are totally miscible in the liquid and mesomorphic states. The virtual mesophase-isotropic transition temperature for the hexanoate compound derived from the miscibility diagram is in excellent accord with that obtained from the previously reported pressure-temperature phase diagram. With simplifying assumptions, it is possible to predict with acceptable reliability the isobaric binary phase diagrams of any two members of the series. The real and virtual mesophase-liquid transition temperatures are linear functions of the molecular weight. On the other hand, a plot of the crystal-liquid transition temperatures versus the molecular weight exhibits a minimum. Total miscibility in the mesomorphic state is not observed for two members of different discogenic series, but the existence of different mesophase types is not proved. Lyotropic mesomorphism for a disc-like mesophase is established.     

Polystyrene/decahydronaphthalene/propane phase equilibria and polymer conformation properties from intrinsic viscosities

The influence of dissolved propane (up to 31.2 wt %) on the phase equilibria of 5 wt % polystyrene (PS) dissolved in 66/34 wt % trans/cis‐decahydronaphthalene (DHN) was measured over the temperature range of 323–423 K. A suitable temperature, pressure, and propane composition operating space was defined to measure intrinsic viscosities of a single fluid phase. Intrinsic viscosities of PS in cosolvent mixtures of propane and trans/cis‐DHN were measured between 323 and 423 K and between 70 and 208 bar. The addition of propane to the isomeric mixture of DHN resulted in a decreased solvent quality for PS, causing a contraction of the PS coil. The most dramatic decrease in solvent quality with the addition of propane occurred at 323 K and 70 bar with approximately a 36% reduction in the viscometric radius with the addition of 45 mol % propane to DHN. At 423 K, the solvent quality was less sensitive to the addition of propane and only a 13% reduction in the viscometric radius was observed at 70 bar and 45 mol % propane in DHN. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Amorphous structure heat: Heats of solution versus temperature for polysulfone in o-dichlorobenzene

The data presented for polysulfone in o-dichlorobenzene support previous observations on other systems in which the heats of solution decrease linearly with increasing temperature of measurement. Consistent with similar measurements on polycarbonate and polyphenylene oxide, a dramatic slope change from 0.078 cal/g-C° below 120°C to 0.019 cal/g-C° above 120°C occur for the data on polysulfone. The source of these heats is due primarily to the enthalpy difference between the solid polymer and its corresponding liquid amorphous state at the measurement temperature since the heats of mixing are rationalized to be small.     

Self‐assembled complexes of poly(acrylic acid) and poly(styrene)‐block‐poly(4‐vinyl pyridine)

Polymer complexes were prepared from high molecular weight poly(acrylic acid) (PAA) and poly(styrene)‐block‐poly(4‐vinyl pyridine) (PS‐b‐P4VP) in dimethyl formamide (DMF). The hydrogen bonding interactions, phase behavior, and morphology of the complexes were investigated using Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), dynamic light scattering (DLS), atomic force microscopy (AFM), and transmission electron microscopy (TEM). In this A‐b‐B/C type block copolymer/homopolymer system, P4VP block of the block copolymer has strong intermolecular interaction with PAA which led to the formation of nanostructured micelles at various PAA concentrations. The pure PS‐b‐P4VP block copolymer showed a cylindrical rodlike morphology. Spherical micelles were observed in the complexes and the size of the micelles increased with increasing PAA concentration. The micelles are composed of hydrogen‐bonded PAA/P4VP core and non‐bonded PS corona. Finally, a model was proposed to explain the microphase morphology of complex based on the experimental results obtained. The selective swelling of the PS‐b‐P4VP block copolymer by PAA resulted in the formation of different micelles. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1192–1202, 2009     

Miscibility and isothermal crystallization behavior of polyamide 6/poly(vinyl alcohol) blend

An investigation of miscibility and isothermal crystallization behavior of Polyamide 6 (PA6)/Poly(vinyl alcohol) (PVA) blends was conducted. Fourier transform infrared spectra (FTIR) analysis indicated that the interactions between the carbonyl groups of PA6 and hydroxyl groups of PVA increase as the weight ratios of PA6 to PVA of PA6/PVA specimens increase. This interaction between PA6 and PVA leads to their miscibility in the amorphous region and even some extent effects on their crystal phase, respectively. Further isothermal crystallization behavior of PA6/PVA indicate that the miscibility of PVA in PA6 leading difficulty in crystallization of PA6. Several kinetics equations are employed to describe the effects of PVA on the crystallization properties of PA6 in PA6/PVA blends in detail. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1360–1368, 2008     

Preparation and characterization of cellulose and konjac glucomannan blend film from ionic liquid

Blend films from cellulose and konjac glucomannan (KGM) in room temperature ionic liquid 1‐allyl‐3‐methylimidazolium chloride were satisfactorily prepared by coagulating with water. The composition of the blend films was gravimetrically analyzed, and the compatibility of the two natural polymers was characterized by Fourier transform infrared spectroscopy and wide‐angle X‐ray diffraction. The results indicate good compatibility and strong interactions between cellulose and KGM, resulting in almost no loss of the water‐soluble KGM from the blend films even after the water coagulating and washing. However, microstructure analyses portrayed phase separations in the blend films, namely, egg‐like new phase particles were embedded in a continuous matrix base (MB). Phase diagram analysis and differential scanning calorimetry of the phase inversion coagulation process suggest that relative low molecular mass part of both cellulose and KGM formed the continuous MB, whereas the egg‐like new phase particles were super patterns of relative high molecular mass of both polymers, which played an important role in strengthening the blend material. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1686–1694, 2009     

Molecular thermodynamics approach for polymer-polymer miscibility

We extended the previous lattice model for polymer solution systems to binary polymer blend systems. Based on Müller’s Monte-Carlo simulation data for symmetric system (r₁ = 32 and r₂ = 32), the energy of mixing is correlated as a function of temperature and composition using an empirical expression. In addition, we introduce new universal functions which reflect the characteristics of polymer-polymer miscibility behaviors. In associated blend systems, specific interactions between polymer segments are considered by using a secondary lattice. Using only one or two adjustable parameters, the proposed model satisfactory correlates the experimental data of real polymer blend systems with greater accuracy than those of other models.     

Miscible blends of nitro‐substituted polybenzimidazole and polyetherimide

A novel blend system was prepared by blending organosoluble nitro‐substituted polybenzimidazole (NO₂‐PBI) and polyetherimide (PEI) in a cosolvent at a moderate condition. It was shown that the NO₂‐PBI/PEI blends not only possess tractable processability owing to the enhanced solubility of NO₂‐PBI but also retain the desirable features of unmodified PBI/PEI blends. Apparent miscibility in the blends was observed and attributed to hydrogen‐bonding interactions between N? H groups in NO₂‐PBI and carbonyl groups in PEI. It was revealed that the NO₂‐PBI/PEI blends phase‐separate upon heating above the glass‐transition temperatures. The observed mixing of NO₂‐PBI and PEI in a molecular level, although sustainable only in the glassy region, was shown to lend synergy effects to the physical properties of the blends. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1778–1783, 2001     

Evaluation of the interaction parameter for poly(ε‐caprolactone)/poly(styrene‐co‐acrylonitrile) blends

In this article, the miscibility of poly(ε‐caprolactone) (PCL) with poly(styrene‐co‐acrylonitrile) (SAN) containing 25 wt % of acrylonitrile is studied from both a qualitative and a quantitative point of view. The evidences coming from thermal analysis (differential scanning calorimetry) demonstrate that PCL and SAN are miscible in the whole range of composition. The Flory interaction parameter χ_1,2 was calculated by the Patterson approximation and the melting point depression of the crystalline phase in the blends; in both cases, negative values of χ_1,2 were found, confirming that the system is miscible. The interaction parameter evaluated within the framework of the mean field theory demonstrates that the miscibility of PCL/SAN blends is due to the repulsive interaction between the styrene and acrylonitrile segments in SAN. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Comparison of glass transition and interpretation on miscibility in blends of amorphous poly(vinyl methyl ether) with highly crystallizable versus less‐crystallizable polyesters

Various phase behavior of blends of poly(vinyl ether)s with polyesters of two types (highly crystalline and less crystalline with different main‐chains) were examined using differential scanning calorimetry (DSC) and optical microscopy (OM). Effects of varying the main‐chain polarity of the constituent polyesters on the phase behavior of the blends were analyzed. Miscibility in PVME/polyester blends was found only in polyesters with backbone CH₂/CO ratio = 3.5 to 7.0). T_g‐composition relationships for blends of PVME with highly crystalline polyesters (PBA, PHS) were found to differ significantly from those for PVME blends with less‐crystalline polyesters (PTA, PEAz). Crystallinity of highly crystalline polyester constituents in blends caused significant asymmetry in the T_g‐composition relationships, and induced positive deviation of blends' T_g above linearity; on the other hand, blends of PVME with less crystalline polyesters exhibit typical Fox or Gordon‐Taylor types of relationships. The χ parameters for the miscible blends were found to range from ?0.17 to ?0.33, reflecting generally weak interactions. Phase behavior was analyzed and compared among blends of PVME with rapidly crystallizing vs. less‐crystallizing polyesters, respectively. Effects of polyesters' crystallinity and structures on phase behavior of PVME/polyester blends are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2899–2911, 2007