Elevation of the glass transition temperature in flexible‐chain semicrystalline polymers

In the idealized two‐phase model of a semicrystalline polymer, the amorphous intercrystalline layers are considered to have the same properties as the fully‐amorphous polymer. In reality, these thin intercrystalline layers can be substantially influenced by the presence of the crystals, as individual polymer molecules traverse both crystalline and amorphous phases. In polymers with rigid backbone units, such as poly(etheretherketone), PEEK, previous work has shown this coupling to be particularly severe; the glass transition temperature (T_g) can be elevated by tens of degrees celsius, with the magnitude of the elevation correlating directly with the thinness of the amorphous layer. However, this connection has not been explored for flexible‐chain polymers, such as those formed from vinyl‐type monomers. Here, we examine T_g in both isotactic polystyrene (iPS) and syndiotactic polystyrene (sPS), crystallized under conditions that produce a range of amorphous layer thicknesses. T_g is indeed shown to be elevated relative to fully‐amorphous iPS and sPS, by an amount that correlates with the thinness of the amorphous layer; the magnitude of the effect is severalfold less than that in PEEK, consistent with the minimum lengths of polymer chain required to make a fold in the different cases. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1198–1204, 2007     

The effect of crystallinity on chain mobility and free volume in the amorphous regions of a miscible polycarbonate/polyester blend

Homopolymers and blends of polycarbonate/ThermX have been investigated by differential scanning calorimetry, dynamic mechanical analysis, density measurements, and positron annihilation lifetime spectroscopy. The study focuses on the chain mobility and free volume in the amorphous miscible regions of the blends and how this mobility and free volume are affected by increasing crystallinity. It is proposed that judicious annealing, which results in increasing crystallinity (while avoiding ageing or transesterification), induces a constraint on the amorphous region leading to an increase in T_g and coalescence of free volume sites. © 1994 John Wiley & Sons, Inc.     

On accurate boundary conditions for a shape sensitivity equation method

This paper studies the application of the continuous sensitivity equation method (CSEM) for the Navier–Stokes equations in the particular case of shape parameters. Boundary conditions for shape parameters involve flow derivatives at the boundary. Thus, accurate flow gradients are critical to the success of the CSEM. A new approach is presented to extract accurate flow derivatives at the boundary. High order Taylor series expansions are used on layered patches in conjunction with a constrained least‐squares procedure to evaluate accurate first and second derivatives of the flow variables at the boundary, required for Dirichlet and Neumann sensitivity boundary conditions. The flow and sensitivity fields are solved using an adaptive finite‐element method. The proposed methodology is first verified on a problem with a closed form solution obtained by the Method of Manufactured Solutions. The ability of the proposed method to provide accurate sensitivity fields for realistic problems is then demonstrated. The flow and sensitivity fields for a NACA 0012 airfoil are used for fast evaluation of the nearby flow over an airfoil of different thickness (NACA 0015). Copyright © 2005 John Wiley & Sons, Ltd.