The process of micro-and nanolayer coextrusion of polymeric systems with good layer uniformity is described. Coextrusion through a series of layer multiplying die elements has enabled the production of films containing tens to thousands of layers with individual layer thicknesses from the micro-to the nanoscale. Improvements in layer uniformity are discussed through optimization of layer multiplier die design, selection of viscosity matched polymer systems, and incorporation of surface layer capabilities. Design of 'uneven' split layer multiplication dies has enabled the coextrusion of layered films with a wide variety of layer thickness distributions having up to a 10Â difference in the individual film layer thicknesses. Coextrusion of layered polymer films with individual layer thicknesses down to the nanoscale has resulted in the production of novel systems with improved properties. Nanolayered polymer films were utilized to develop an all-plastic polymer laser, to fabricate gradient refractive index lenses, and to investigate gas barrier enhancement of crystalline polymer nanolayers confined to induce a high aspect ratio, in-plane, single-crystal-like lamellar structure.

Abstract

Layer multiplying coextrusion was used to create films with hundreds or thousands of alternating layers of two polymers. The constituent polymers were chosen to create a temperature window in which a crystallizable polymer could melt and recrystallize within the glassy confinement of an amorphous polymer. This enabled the study of polymer crystallization behavior under nanoscale confinement. In this article, we examined the crystallization of poly(ε-caprolactone) (PCL) confined by polystyrene and poly-(methyl methacrylate). We used AFM, WAXS, and SAXS to demonstrate that confined PCL nanolayers crystallized as large in-plane lamellae of high aspect ratio. This phenomenon, previously observed only for poly(ethylene oxide) (PEO), may be more general to crystalline polymers. We found that the in-plane PCL lamellae were at least as effective as PEO lamellae in reducing the oxygen permeability by more than 2 orders of magnitude. The substrates examined did not affect the crystallization habit of PCL but surprisingly had a large effect on the crystallization kinetics. The results supported the hypothesis that heterogeneous nuclei could diffuse to the interface from the confining polymer during melt processing, thereby substantially increasing the crystallization rate. In the absence of these additional nuclei, the crystallization kinetics was quantitatively described by a model that considered truncation of the growing spherulite. The retardation in crystallization rate over a very large range in layer thicknesses was described by the change in layer thickness only without any change in the linear growth rate. To our knowledge, this is the first time that the model has been quantitatively verified by experiment.

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Forced assembly polymer coextrusion utilizes layer multiplication to produce films with tens or thousands of micrometer to nanometer thick layers. The development of novel uneven split layer multiplying dies has produced gradient multilayer films with at least a 10 times difference between the thickest and thinnest layers. Coextrusion through a series of equal and uneven split multiplier dies allows for flexibility in the unique design of layer thickness distributions by: (1) altering the multiplier offset and (2) changing the sequence of a series of uneven split multiplying dies with different splitting ratios. This new technology has created highly reflective, multilayered photonic films with gradient layer thickness distributions exhibiting, as examples, a 600 nm wide reflection band and dual optical reflection bands within a single film. Also, gradient multilayers exhibit unique mechanical behavior. A layer thickness dependent craze to shear banding deformation mechanism was observed. In addition, gradient controlled buckling was observed across a single film due to foaming-induced layer delamination.

With the fast development of high-temperature metal oxide semiconductor field effect transistors for power electronics in electric vehicles, current state-of-the-art biaxially oriented polypropylene (BOPP) film capacitors need further improvement because they have a temperature rating of only 85 °C without derating the voltage to maintain a long lifetime. If a high-temperature polymer can replace BOPP without sacrificing the overall dielectric performance and cost, it is possible to remove the current water-cooling system for capacitors and significantly reduce the cost of the power electronic unit. In this work, we demonstrated new polycarbonate (PC)/nylon multilayer films (MLFs), which has a potential for even higher temperature rating because of the higher melting temperature for nylons (e.g., nylon-6). Structural and dielectric studies showed that these PC/nylon MLFs had a similar dielectric performance, such as dielectric constant, dielectric loss, and breakdown strength, as the PC/poly­(vinylidene fluoride) PVDF MLFs, which were developed in the past. These PC/nylon MLFs could perform well up to 120 °C, which was limited by the glass transition temperature of PC at 145 °C. More intriguingly, packaged PC/nylon-12 MLF capacitors exhibited a self-healing capability, which had been difficult for packaged high-temperature film capacitors. Because self-healing is such a fundamental requirement for polymer film capacitors, our PC/nylon MLFs offer a potential for next-generation high-temperature and high-energy density film capacitors.

A new type of solid-state variable focal length lens is described. It is based on shape changes in an elastomeric membrane driven by compression of a reservoir of a polymer gel. A novel fabrication process based on individual lens components allows for customization of lens power based on the desired application. The lens shape as a function of applied compressive strain is measured using direct surface profile measurements. The focal length of a solid state lens was reversibly changed by a factor of 1.9. Calculated back focal lengths of the lens were consistent with experimental measurements.

Current development of advanced power electronics for electric vehicles demands high temperature, high energy density, and low loss polymer dielectrics. Multilayer films (MLFs), which are comprised of alternating high temperature/low loss linear dielectric polymer such as polysulfone (PSF) and high energy density polymer such as poly(vinylidene fluoride) (PVDF), are promising for this application, because high temperature tolerance, high energy density, and low loss can be achieved simultaneously. This study explored the reduction of impurity ion conduction loss in PSF/ PVDF MLFs (e.g., the dissipation factor is as low as 0.003 at 1 Hz and 100 °C) without sacrificing high dielectric constant and high energy density. Various electric poling processes were explored at a temperature slightly below the glass transition temperature (T g ∼ 185 °C) of PSF. Compared with pure alternating current (AC) and pure direct current (DC) poling methods, unipolar (DC + AC) poling was found to be the most effective in polarizing impurity ions from the PVDF layers into the PSF layers. Because of the low segmental mobility below T g , impurity ions were largely "locked" in PSF. The immobilization of impurity ions was thermally stable up to 120 °C. Because DC-link capacitors work with unipolar charge and discharge processes, these PSF/PVDF MLFs with low dielectric losses are promising for the application of advanced power electronics for the automobile industry.