Nanostructured Polymer Stable Glasses via Matrix Assisted Pulsed Laser Evaporation

Abstract

Amorphous materials, or glasses, which lack a crystalline structure, are technologically ubiquitous with applications including structural components, pharmaceuticals, and electronic devices. Glasses are traditionally formed by rapid cooling from the melt state, where molecules become kinetically trapped into a non-equilibrium configuration. The temperature at which the material transforms from supercooled liquid to glass is the glass transition temperature. The glass transition temperature is the most important property of amorphous materials, as it determines the range of temperatures where they are fabricated, used and stored. Recent technological developments in which glasses are formed by alternative routes, such as physical vapor deposition and matrix assisted pulsed laser evaporation (MAPLE), enable tunability of Tg and related physical properties. High-Tg glasses formed by these techniques are termed “stable glasses” and exhibit a wide range of exceptional properties. This work focuses on the formation and characterization of stable polymer glasses fabricated via MAPLE.

Bulk films (>1 μm thick) of glassy polymers fabricated by MAPLE at slow growth rates (<1 nm/s) and controlled substrate temperature (Tsub = 0.85Tg,bulk) have greatly elevated Tg, low density, high enthalpy, increased kinetic stability and a spheroidal nanostructure. We focus on connecting the bulk and nanoscale properties of MAPLE-deposited polymer glasses. Building on molecular dynamics simulations from the literature on the MAPLE process, we experimentally study the origin of nanostructure in our MAPLE-deposited films. We measure the time-of-flight of MAPLE-deposited material, confirming that the velocity is sufficiently low for intact deposition of polymer nanoglobules. The size distribution of polymer nanoglobules fabricated in short MAPLE depositions provides insight into how nanostructured MAPLE films form.

Using our atomic force microscopy-based nanoscale dilatometry technique, we directly probe the nanoscale thermal behavior of individual polymer nanoglobules. We confirm that bulk and nanoscale glasses share many of the same physical behavior: enhanced stability above the glass transition temperature, and ~40% excess volume. We attribute these nanoscale properties to the rapid cooling and solvent stripping during the MAPLE process. As a further demonstration of the utility of MAPLE-deposited polymer nanoglobules we fabricate bi-functional patchy Janus nanoparticles for use in stabilization of emulsions.