ABSTRACT
The CO2 transport process was studied in a series of amine-modified epoxy resins having different cross-linking densities but the same chemical environment for the penetrant molecules. Positron Annihilation Lifetime Spectroscopy (PALS) was used to monitor the free volume structure of the samples and experimentally evaluate their fractional free volume fh(T) and its temperature evolution. The analysis of the free volume hole size distribution showed that all the holes have a size large enough to accommodate the penetrant molecules at temperatures T above the glass transition temperature Tg. The measured gas diffusion constants at T > Tg have been reproduced in the framework of the free volume theory of diffusion using a novel procedure based on the use of fh(T) as an input experimental parameter.
ABSTRACT
Chitosan-NiO nanocomposite (CNC) is shown to be a potential dielectric material with promising properties. CNCs containing NiO nanoparticles (0.2, 0.6, 1, 2, 5 wt %) are prepared through chemical methods. The inclusion of NiO nanoparticles in the chitosan matrix is confirmed by scanning electron microscopy (SEM) and X-ray diffraction. The morphology of the NiO nanoparticles and the nanocomposites is investigated by transmission electron microscopy and SEM, respectively. Positron annihilation lifetime spectroscopy (PALS) and the coincidence Doppler broadening (CDB) technique are used to quantify the free volume and molecular packing in the nanocomposites. The triplet-state positronium lifetime and the corresponding intensity show the changes in nanohole size, density, and size distribution as a function of NiO loading. Small-angle X-ray scattering indicates that the NiO aggregates are identical in all the CNCs. The momentum density distribution obtained from CDB measurements excludes the possibility of a contribution of vacant spaces (pores) available in NiO aggregates to the free volume of nanocomposites upon determination by using PALS. The results show systematic variation in free-volume properties and nano-level molecular packing as a function of NiO loading, which is presumed to play a vital role in determining the various properties of the nanocomposites.
Subject(s)
Chitosan/chemistry , Nanocomposites/chemistry , Nanocomposites/ultrastructure , Nickel/chemistry , Electrons , Scattering, Small Angle , Spectrum Analysis , X-Ray DiffractionABSTRACT
Epoxy/clay nanocomposites are synthesized using clay modified with the organic modifier N,N-dimethyl benzyl hydrogenated tallow quaternary ammonium salt (Cloisite 10A). The purpose is to investigate the influence of the clay concentration on the nanostructure, mainly on the free-volume properties and the interfacial interactions, of the epoxy/clay nanocomposite. Nanocomposites having 1, 3, 5 and 7.5 wt. % clay concentrations are prepared using the solvent-casting method. The dispersion of clay silicate layers and the morphologies of the fractured surfaces in the nanocomposites are studied using X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The observed XRD patterns reveal an exfoliated clay structure in the nanocomposite with the lowest clay concentration (≤1 wt. %). The ortho-positronium lifetime (τ(3)), a measure of the free-volume size, as well as the fractional free volume (f(v)) are seen to decrease in the nanocomposites as compared to pristine epoxy. The intensity of free positron annihilation (I(2)), an index of the epoxy-clay interaction, decreases with the addition of clay (1 wt. %) but increases linearly at higher clay concentrations. Positron age-momentum correlation measurements are also carried out to elucidate the positron/positronium states in pristine epoxy and in the nanocomposites. The results suggest that in the case of the nanocomposite with the studied lowest clay concentration (1 wt. %), free positrons are primarily localized in the epoxy-clay interfaces, whereas at higher clay concentrations, annihilation takes place from the intercalated clay layers.
