Gas solubility of carbon dioxide in poly(lactic acid) at high pressures: Thermal treatment effect

The sorption of carbon dioxide in glassy Poly(lactic acid) (PLA) films was studied by quartz crystal microbalance (QCM) at high pressures. Two thermal treatments, melted and quenched, were performed in PLA with two different L:D contents, 80:20 and 98:2, films and compared with a third thermal protocol, annealed, and used in a previous work. The results obtained show that for pressures higher than 2 MPa, the carbon dioxide solubility is larger in PLA 80:20 than in PLA 98:2, indicating that the L:D plays a dominant role on this property. The thermal treatments only affect the gas solubility in PLA 98:2. Sorption isotherms at temperatures 303, 313, and 323 K, below the glass transition temperature of the polymer, and pressures up to 5 MPa were measured and analyzed with three different models, the dual‐mode sorption model, the Flory–Huggins equation, and a modified dual‐mode sorption model where the Henry's law term was substituted by the Flory–Huggins equation. This last model performs especially well for CO₂ in PLA 80:20, due to the convex upward curvature of the solubility isotherms for that system. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 616–625, 2007     

Viscometric properties of dilute polystyrene/dioctyl phthalate solutions

We report viscometric data collected in a Couette rheometry on dilute, single‐solvent polystyrene (PS)/dioctyl phthalate (DOP) solutions over a variety of polymer molecular weights (5.5 × 10⁵ ≤ M_w ≤ 3.0 × 10⁶ Da) and system temperatures (288 K ≤ T ≤ 318 K). In view of the essential viscometric features, the current data may be classified into three categories: The first concerns all the investigated solutions at low shear rates, where the solution properties are found to agree excellently with the Zimm model predictions. The second includes all sample solutions, except for high‐molecular‐weight PS samples (M_w ≥ 2.0 × 10⁶ Da), where excellent time–temperature superposition is observed for the steady‐state polymer viscosity at constant polymer molecular weights. No similar superposition applies at a constant temperature but varied polymer molecular weights, however. The third appears to be characteristic of dilute high‐molecular‐weight polymer solutions, for which the effects of temperature on the viscosity curve are further complicated at high shear rates. The implications concerning the relative importance of hydrodynamic interactions, segmental interactions, and chain extensibility with increasing polymer molecular weight, system temperature, and shear rate are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 787–794, 2006     

Rheology of a mixture of liquid-crystal polymers in solution

The rheological behavior of a mixture of two liquid-crystal polymers, hydroxypropyl cellulose and ethyl cellulose, in acetone solution is studied. The total polymer concentration in the solvent is held constant (40%) as the ratio of the two polymers is varied. The mixtures are anisotropic, isotropic, or biphasic (isotropic/anisotropic), depending on the concentration. Curves of viscosity vs shear rate for all the mixtures studied show three regions of viscosity, as described by Onogi and Asada for liquid-crystal polymers. The viscosity as a function of the weight ratio of the two polymers at constant shear rate exhibits deviations from additivity of viscosities of the two components at all concentrations. In mixtures of two polymers in the melt, deviations are also observed; the negative ones are attributed to phase separation and the positive ones to homogenous mixing (comparison with the phase diagram). All the mixtures studied (anisotropic, isotropic, or biphasic), show ranges of shear rates where the first normal-stress difference is negative, as is generally observed for anisotropic liquid-crystal polymers. It is concluded that the isotropic solutions become anisotropic under shear, as they are not far from the critical concentration. © 1994 John Wiley & Sons, Inc.     

Dialdehyde starch‐crosslinked chitosan films and their antimicrobial effects

For improved mechanical and water‐swelling properties of chitosan films, a series of transparent films were prepared with dialdehyde starch as a crosslinking agent. Fourier transform infrared and X‐ray analysis results demonstrated that the formation of Schiff's base disturbed the crystallization of chitosan. The mechanical properties and water‐swelling properties of the films were significantly improved. The best values of the tensile strength and breaking elongation were 113.1 MPa and 27.0%, respectively, when the dialdehyde starch content was 5%. All the crosslinked films still retained obvious antimicrobial effects toward S. aureus and E. coli, and they showed potential for biomedical applications. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 993–997, 2003     

Coupled lubrication and Stokes flow finite elements

A method is developed for performing a local reduction of the governing physics for fluid problems with domains that contain a combination of narrow and non‐narrow regions, and the computational accuracy and performance of the method are measured. In the narrow regions of the domain, where the fluid is assumed to have no inertia and the domain height and curvature are assumed small, lubrication, or Reynolds, theory is used locally to reduce the two‐dimensional Navier–Stokes equations to the one‐dimensional Reynolds equation while retaining a high degree of accuracy in the overall solution. The Reynolds equation is coupled to the governing momentum and mass equations of the non‐narrow region with boundary conditions on the mass and momentum flux. The localized reduction technique, termed ‘stitching,’ is demonstrated on Stokes flow for various geometries of the hydrodynamic journal bearing—a non‐trivial test problem for which a known analytical solution is available. The computational advantage of the coupled Stokes–Reynolds method is illustrated on an industrially applicable fully‐flooded deformable‐roll coating example. The examples in this paper are limited to two‐dimensional Stokes flow, but extension to three‐dimensional and Navier–Stokes flow is possible. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis and characterization of liquid crystalline side‐chain block copolymers containing luminescent 4,4′‐bis(biphenyl)fluorene pendants

A series of new liquid crystalline homopolymers, copolymers, and block copolymers were polymerized from styrene‐macroinitiator ( SMi ) and methacrylates with pendent 4,4′‐bis(biphenyl)fluorene ( M1 ) and biphenyl‐4‐ylfluorene ( M2 ) groups through atom transfer radical polymerization (ATRP). The number‐average molecular weights (Mn) of polymers P1 ‐ P4 were 10,007, 14,852, 6,275, and 10,463 g mol^?1 with polydispersity indices values of 1.21, 1.15, 1.31, and 1.22, respectively. All polymers exhibit the nematic phase. The thermal, mesogenic, and photoluminescent properties of all polymers were investigated. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4564–4572, 2007     

Thickness dependence of free‐standing thin films

Below a critical thickness, of about 60 nm, the glass transition temperature of polystyrene (PS) films decreases with film thickness, as demonstrated using free‐standing films. A geometrical model is developed here describing this phenomenon in the case of ideal (Gaussian) chains. This model, which can be considered as an application of the free volume model, assumes that the decrease of the glass transition temperature from thick to ultrathin films is due to the modification of the interpenetration between neighboring chains. The theoretical curve deduced from the model is in excellent agreement with the PS experimental results, without using any adjustable parameters. From these results, it can be concluded that new chain motions, usually buried in bulk samples, are expressed by the presence of the surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 10–17, 2007     

Transient free‐surface flow of a viscoelastic fluid in a narrow channel

The interplay between inertia and elasticity is examined for transient free‐surface flow inside a narrow channel. The lubrication theory is extended for the flow of viscoelastic fluids of the Oldroyd‐B type (consisting of a Newtonian solvent and a polymeric solute). While the general formulation accounts for non‐linearities stemming from inertia effects in the momentum conservation equation, and the upper‐convected terms in the constitutive equation, only the front movement contributes to non‐linear coupling for a flow inside a straight channel. In this case, it is possible to implement a spectral representation in the depthwise direction for the velocity and stress. The evolution of the flow field is obtained locally, but the front movement is captured only in the mean sense. The influence of inertia, elasticity and viscosity ratio is examined for pressure‐induced flow. The front appears to progress monotonically with time. However, the velocity and stress exhibit typically a strong overshoot upon inception, accompanied by a plug‐flow behaviour in the channel core. The flow intensity eventually diminishes with time, tending asymptotically to Poiseuille conditions. For highly elastic liquids the front movement becomes oscillatory, experiencing strong deceleration periodically. A multiple‐scale solution is obtained for fluids with no inertia and small elasticity. Comparison with the exact (numerical) solution indicates a wide range of validity for the analytical result. Copyright © 2004 John Wiley & Sons, Ltd.     

Hydrogel‐like elastic membrane consisting of semi‐interpenetrating polymer networks based on a phosphorylcholine polymer and a segmented polyurethane

To obtain a hydrogel‐like elastic membrane, we prepared semi‐interpenetrating polymer networks (IPNs) by the radical polymerization of methacrylates such as 2‐methacryloyloxyethyl phosphorylcholine (MPC), 2‐hydroxyethylmethacrylate, and triethyleneglycol dimethacrylate diffused into segmented polyurethane (SPU) membranes swollen with a monomer mixture. The values of Young's modulus for the hydrated semi‐IPN membranes were less than that for an SPU membrane because of higher hydration, but they were much higher than that for a hydrated MPC polymer gel (non‐SPU). According to a thermal analysis, the MPC polymer influenced the segment association of SPU. The diffusion coefficient of 8‐anilino‐1‐naphthalenesulfonic acid sodium salt from the semi‐IPN membrane could be controlled with different MPC unit concentrations in the membrane, and it was about 7 × 10² times higher than that of the SPU membrane. Fibroblast cell adhesion on the semi‐IPN membrane was effectively reduced by the MPC units. We concluded that semi‐IPNs composed of the MPC polymer and SPU may be novel polymer materials possessing attractive mechanical, diffusive‐release, and nonbiofouling properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 68–75, 2003