Thermodynamic model of gas permeability in polymer membranes

A new molecular thermodynamic model is developed of the gas permeability in polymer membranes on the basis of configurational entropy and Flory‐Huggins theory to predict permeability dependence on the concentration of penetrant. Three kinds of configurational entropy are taken into account by this model; that is, the disorientation entropy of polymer, the mixing entropy, and specific interaction entropy of polymer/gas. The validity of the mathematical model is examined against experimental gas permeability for polymer membranes. Agreement between experimental and predicted permeability is satisfactory. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 661–665, 2007     

Synthesis and eutectic behavior of liquid crystalline copolyesters

A series of liquid crystalline copolyesters, derived from 1,4‐hydroxy‐benzoic acid (HBA), 6‐hydroxy‐2‐naphthoic acid (HNA), terephthalic acid (TA), and hydroquinone (HQ), were prepared; crystallization, melting and solid‐state structure of the copolyesters were studied by using differential scanning calorimetry (DSC) and wide‐angle x‐ray diffraction (WAXD). It was found that the variation of melting point of the copolyesters with increasing HBA mol % exhibits eutectic melting behavior at a constant mole ratio of HNA, and the extrapolated eutectic temperature decreases linearly with increasing HNA mol %. WAXD analysis of the copolyesters indicates that the d‐spacing related to three‐dimensional order increases first and then decreases with increasing HBA mol %. The increase of the d‐spacing, consistent with looser packing of chains, leads to the reduction of melting point and most likely accounts for the eutectic behavior observed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2171–2177, 2009     

Microthermal analysis of the melting behavior in zone‐drawn isotactic polypropylene fibers

A microthermal analysis (μTA) method with an ultrahigh heating rate was applied to a zone‐drawn isotactic polypropylene fiber to evaluate the melting behaviors inherent to the microstructural changes occurring during the drawing process. The μTA melting point decreased with a reduction in the melting temperature because of the suppression of crystal reorganization and increased with an increase in the melting temperature because of the suppression of the relief of the orientation of the molecular chains, in comparison with the conventional melting point obtained by traditional differential scanning calorimetry. This study examined a convenient and powerful method for investigating the melting behavior for polymeric materials inherent to the original microstructure with less influence from thermal‐measurement heating. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3677–3681, 2004     

Diels–Alder modification of poly(ethylene terephthalate‐co‐anthracene‐2,6‐carboxylate) with N‐substituted maleimides

Dimethyl 2,6‐anthracene dicarboxylate is used as a comonomer in the synthesis of functional copolymers that are subject to modification with Diels–Alder reactions. The formation of poly(ethylene terephthalate‐co‐2,6‐anthracenate), containing less than 20 mol % of the anthracene‐2,6‐dicarboxylate structural units, provides materials that are tractable and soluble. The anthracene units of the copolymers undergo Diels–Alder reactions with N‐substituted maleimides. The grafting of N‐alkylmaleimides affords soluble, hydrophobic polymers, whereas grafting with maleimide‐terminated poly(ethylene glycol) affords hydrophilic polymers. Because this reaction proceeds below the melting point of the copolymers, the procedure can be applied to thin films, whereby the surface properties are modified. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3256–3263, 2002     

Structural relaxation of glass-forming polymers based on an equation for configurational entropy, 4. Structural relaxation in styrene-acrylonitrile copolymer

The structural relaxation process in styrene-acrylonitrile copolymer has been characterized by means of differential scanning calorimetry (DSC) experiments. The results in the form of heat capacity, c_p(T), curves are analyzed using a model for the evolution of the configurational entropy during the process recently proposed by the authors.^11,12 The model simulation allows one to determine the enthalpy (or entropy) structural relaxation times and the β parameter of the Kohlrausch-Williams-Watts equation characterizing the width of the distribution of relaxation times. This material parameters are compared with their analogues determined from the dielectric and dynamic-mechanical relaxation processes. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2201–2217, 1997     

Correlation between quasielastic Raman scattering and configurational entropy in an ionic liquid

Low-frequency (5-200 cm(-1)) Raman spectra are reported for the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, [bmim]PF(6), in glassy, supercooled liquid, and normal liquid phases (77-330 K). Raman spectra of [bmim]PF(6) agree with previous results obtained by optical Kerr effect spectroscopy and molecular dynamics simulation. Both the superposition model and the coupling model give reasonable fit to low-frequency Raman spectra of [bmim]PF(6). The configurational entropy of [bmim]PF(6) has been evaluated as a function of temperature using recently reported data of heat capacity. The calculated configurational entropy is inserted in the Adam-Gibbs theory for supercooled liquids, giving a good fit to non-Arrhenius behavior of viscosity and diffusive process, with the latter revealed by a recent neutron scattering investigation of [bmim]PF(6). There is a remarkable linear dependence between intensity of quasielastic Raman scattering and configurational entropy from 77 K up to the melting point of [bmim]PF(6). This correlation offers insight into the nature of dynamical processes probed by low-frequency Raman spectra of ionic liquids.     

Phase behaviors of partially ionized hydrogels in aqueous salt solutions: Applicability of the modified double‐lattice model

We investigated the effect of charge densities of the gel network and ionic strength of solution on swelling behaviors of ionized gels. We used the modified double‐lattice model, Flory–Erman's elastic model, and the ideal Donnan theory to describe swelling behaviors of the electrolyte bounded hydrogels. Energy parameters (?/k, δ?/k) were obtained from fitting liquid–liquid equilibria data of the linear poly‐N‐isopropylacrylamide/water system and two adjustable model parameters obtained from a nonelectrolyte hydrogel system. Calculated values agreed with experimental data for the given systems. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2333–2338, 2002     

Phase behaviors of hyperbranched solid polymer electrolyte/salt systems: The structure effect

We have derived a new molecular thermodynamic model based on the lattice cluster model and melting point depression theory to account for the structural effect on phase behaviors of hyperbranched solid polymer electrolyte/salt systems. The two structural parameters (the generation number and separator length) are introduced to characterize the architecture of the hyperbranched polymer. A thermooptical analysis technique is used to determine the melting points of hyperbranched polymer/ZnI₂ systems. Our results show that the eutectic point is presented at a higher weight fraction of the salt as the generation number increases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2254–2262, 2004     

Anomalous melting behavior of cyclohexane and cyclooctane in poly(dimethyl siloxane) precursors and model networks

Building on previous observations of anomalous melting behavior of solvents in polyisoprene, we have expanded our insight into the melting behavior of organic solvents in polymers and polymer networks through a calorimetric investigation of cylcohexane and cyclooctane in poly(dimethyl siloxane) (PDMS) precursors and model networks. The results are contrary to general expectations. Besides deviations between the predictions of the Flory-Huggins model and observed melting point depression of the small molecule organics, it is found that the melting point depression of cyclohexane in model networks is lower than that in the uncrosslinked precursors and unaffected by the molecular weight between crosslinks, which is not consistent with the general observation that higher crosslinking density leads to greater melting point depression. We interpret the observed phenomenon in terms of phase separation. In the case of cyclooctane, it exhibits a double melting peak in the model networks with high molecular weight between crosslinks. Furthermore, the heats of fusion of both cyclohexane and cyclooctane decrease with increasing polymer volume fraction which violates the underlying assumption that the heat of fusion of solvent in the polymer is the same as that in the bulk for both the Flory-Huggins model and the Gibbs-Thomson equation. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2779–2791, 2008     

Development of functional polymers with cyclic ether moieties. I. Synthesis and properties of polyesters with dioxane moiety in the main chain

A series of novel polyesters containing dioxane moieties in their main chains were synthesized by the bulk polycondensation of trans‐2,5‐bis‐(hydroxy‐ methyl)‐1,4‐dioxane with various aliphatic dicarboxylic acid chlorides. The obtained polyesters, analyzed by differential thermal analysis, possessed crystallinity, the melting point of which exhibited a weak odd–even effect on the methylene unit number and a small decreasing trend with an increase in the methylene unit number. These properties were compared with those of similar polyesters bearing cyclohexane moieties, and it was found that the rigidity of the dioxane moiety plays an important role in enhancing the effective packing of the corresponding polymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2536–2542, 2000     

Effect of crosslink on the characteristic length of glass transition of network polymers

The characteristic length of the glass transition temperature was evaluated for crosslinked bulk polystyrenes and poly(methyl methacrylate)s by differential scanning calorimetry. The characteristic length, which corresponds to a length scale of the cooperative rearrangement due to polymer segmental relaxation, was revealed to decrease with increase in the degree of crosslink. The relative values of configurational entropy for crosslinked polymers were evaluated based on a simple polymer network model on a cubic lattice. As a result, the configurational entropy of the smallest cooperatively rearranging region was revealed to decrease with increase in the degree of crosslink, which is responsible for the above behavior of the characteristic length. The effects of crosslink on the characteristic length and the glass transition temperature were found to be stronger for crosslinked poly(methyl methacrylate)s than for crosslinked polystyrenes, which reflects the difference in the structure of crosslink segment. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1958–1966, 2006     

Stretch-Induced Melting and Recrystallization of Polyethylene-Plasticizer Film Studied by In Situ X-Ray Scattering: A Thermodynamic Point of View

With in situ synchrotron radiation X-ray scattering, the structural alteration of polyethylene-plasticizer film during uniaxial stretching is studied at temperature far below melting point of crystal. By analyzing the evolution rule of structural parameters quantitatively, stretch-induced melting and recrystallization process is validated to be the underlying mechanism of plastic deformation for the system. The physical essence of stretch-induced melting is proved to be phase transition driven by elastic energy which originates from lattice deformation. Conversely, the recrystallization process is proved to be controlled by temperature; furthermore, the growth of lamellae during recrystallization is in perfect accordance with kinetic theory by Lauritzen and Hoffman. This study provides a quantitative understanding to the long-existing melting–recrystallization model from a thermodynamics point of view. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1521–1528     

Structure of ionic aggregates of ionomers. II. Effect of humidity and temperature on ethylene and styrene ionomers

Small‐angle X‐ray scattering profiles of ethylene and styrene ionomers were studied to clarify the structure of ionic aggregates as a function of humidity or temperature. The intensity and position of ionic cluster peaks were observed for ionomers with a certain degree of neutralization. The intensity of the ionic cluster peak for the ethylene ionomer increased with increasing relative humidity, but it decreased for the styrene ionomer. With increasing humidity, the position of the ionic cluster peak shifted to smaller angles for both ionomers. The size of the ionic aggregates and the closest approach distance between the aggregates were analyzed, and the results varied with humidity for both ionomers. The size did not vary markedly with a change in temperature, whereas the closest approach distance and number of ionic aggregates changed slightly with the melting temperature of the ethylene ionomer and the glass‐transition temperature of the styrene ionomer. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 831–839, 2002     

Specific interactions and phase behavior of ternary poly(2‐vinylpyridine)/poly(N‐vinyl‐2‐pyrrolidone)/bisphenol A blends

Hydrogen‐bonding interactions between bisphenol A (BPA) and two proton‐accepting polymers, poly(2‐vinylpyridine) (P2VPy) and poly(N‐vinyl‐2‐pyrrolidone) (PVP), were examined by Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC). The Flory–Huggins interaction‐energy densities of BPA/P2VPy and BPA/PVP blends were determined by the melting point depression method. The interaction parameters for both BPA/P2VPy and BPA/PVP blend systems were negative, demonstrating the miscibility of BPA with P2VPy as well as PVP. The miscibility of ternary BPA/P2VPy/PVP blends was examined by DSC, optical observation, and solid‐state nuclear magnetic resonance spectroscopy. The experimental phase behavior of the ternary blend system agreed with the spinodal phase‐separation boundary calculated using the determined interaction‐energy densities. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1125–1134, 2002     

Crystallization and equilibrium melting behavior of PBT/PETG blends

The results of studies of equilibrium melting point and crystallization behavior of PBT/PETG blends are reported for the first time. A single composition‐dependent glass‐transition temperature is observed in the DSC studies. The isothermal crystallization studies of the blends indicate retardation in crystallization rate as evidenced by the increase in crystallization half time. The retardation in crystallization rate has been attributed to the miscibility in the molten state and the hindrance to the diffusion of crystallizable units. This assumption is further supported by the composition dependence of the crystallization half time. A composition‐dependent melting point depression has been observed which has been attributed to the possible thermodynamic and morphological effects. The interaction parameter calculated by analyzing equilibrium melting point depression shows composition‐dependent negative values confirming the miscibility of the systems. These results are in good agreement with our earlier results on mechanical and dynamic mechanical properties of PBT/PETG blends. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2439–2444, 1999     

Changes in the melting behavior with the radial distance in isotactic polypropylene spherulites

The melting of highly tactic i‐polypropylene occurs in two stages even for crystallization at 145 °C, a temperature at which reorganization during scanning is negligible. A comparison of two such polypropylenes, one nucleated and the other not nucleated, together with fractions from the latter, has been made with electron microscopy following permanganic etching, in addition to differential scanning calorimetry. This has allowed the two melting stages to be assigned to two components of the lamellar morphology, with progressive changes in both occurring with increasing radial distance within a spherulite. The highest melting temperature is for dominant radial lamellae far from a spherulite center. The lowest melting regions are the evenly crosshatched spherulite centers and a narrow peripheral band. Lower melting is attributed to the suppression of isothermal lamellar thickening paralleling recent direct demonstrations in polyethylene. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2342–2354, 2003