We present a study of homogeneous and heterogeneous nucleation in polymer crystallisation. In bulk samples the crystallization is typically dominated by nucleation from defects (heterogeneous nucleation), and consequently studies must rely on sample preparation to minimize this effect. We present a study of nucleation within discrete droplets of poly(ethylene oxide) that are formed by the dewetting of a thin film on an unfavourable substrate. The samples provide an ensemble of impurity-free droplets, with length scales that can easily be measured. We show that the data for heterogeneous and homogeneous nucleation is qualitatively different, and that the data mirrors the fundamental differences in the underlying mechanisms for the two nucleation processes. The experiments presented here provide a simple method that can be used to study heterogeneous and homogeneous nucleation in great detail.

The birth of a crystal is initiated by a nucleus from which the crystal grows--a dust grain in a snowflake is a familiar example. These nuclei can be heterogeneous defects, like the dust grain, or homogeneous nuclei which are intrinsic to the material. Here we study homogeneous nucleation in nanoscale polymer droplets on a substrate which itself can be crystalline or amorphous. We observe a large difference in the nucleating ability of the substrate. Furthermore, the scaling dependence of nucleation on the size of the droplets proves that the birth of the crystalline state can be directed to originate predominantly within the bulk, at the substrate surface, or at the droplets' edge, depending on how we tune the substrate.

We have studied crystallization in poly(ethylene oxide) droplets with volumes ranging over several orders of magnitude. In all samples, homogeneous nucleation is observed, scaling with the volume of the droplet, down to systems with as few as approximately 10 polymer chains. Surprisingly, nucleation is unaffected by the high degree of confinement, despite a large surface-to-volume ratio and the restriction of chains to length scales much smaller than the radius of gyration. Nucleation was also found to be independent of chain length for two molecular weights studied, differing by an order of magnitude. The results suggest that, for these highly supercooled systems, the formation of a nucleus is influenced by its immediate surroundings and does not depend on the entire length of the constituent chains.

The division of semi-crystalline polymeric material into small domains is an effective tool for studying crystal nucleation. The scaling behavior of the nucleation rate as a function of domain size can reveal important information about the mechanism responsible for the birth of a crystal nucleus. We have investigated the process of crystal nucleation in a system of dewetted polyethylene droplets. Through the use of a correlation sample analysis, we are able to differentiate between heterogeneous and homogeneous nucleation mechanisms in a droplet sample. An analysis of the dependence of the nucleation rate on droplet size reveals that the nucleation probability scales with the surface area of the droplet.

ABSTRACT:We present results on the use of ellipsometry as a novel probe for the crystallization kinetics in thin films of a diblock copolymer. Ellipsometry makes use of the change in polarization induced upon the reflection of light from a film-covered substrate to enable the calculation of the refractive index and thickness of the film. The information obtained with these measurements can be compared with information from differential scanning calorimetry, with the additional advantages that small sample volumes and slow cooling rates can be employed and that expansion coefficients can be determined. By studying the temperature dependence of these quantities, we are able to measure the crystallization kinetics within very small volumes ($10 À10 L) of a poly(butadiene-b-ethylene oxide) diblock copolymer. Through a comparison of two different poly (ethylene oxide) block lengths, we demonstrate a reduction in both the crystallization and melting temperatures as the domain volume is reduced.

Evidence for the existence of an equilibrium epitaxial complexion at the Au-MgAl2O4 interface has been observed. The growth of crystalline MgAl2O4 nanostructures, from a previously stable substrate in the presence of an Au overlayer and heat, is associated with this complexion. Prior to the nanostructures' self-assembly, Au nanoparticles crystalize, then reorient to align with the MgAl2O4 substrate. The presented results contradict earlier conclusions based solely on SEM studies of the final assembled nanostructures. Those results suggested that the MgAl2O4 grown pedestal and associated Au nanoparticle atop were both gold.

Since short polymer chains have a higher mobility than long molecules, conventional expectations are that the growth rate, G, of polymer crystals should decrease as the concentration of large chains increases in a binary blend.Here we present results on G as the blend concentration, ϕ, is varied from short chains of poly(ethylene oxide) (PEO), which are well above the entanglement molecular weight, to long PEO chains. Contrary to the simple mobility argument, G(ϕ) is nonmonotonicclear evidence that another mechanism can dominate. We propose a tentative model based on the simple idea that chain ends retard the crystal growth. Thus, increasing the chain end concentration with the addition of short chain molecules can reduce the crystal growth rate.

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