Chitosans having three different degrees of acetylation (DA) were studied in acid solution using the uranyl staining technique and electron microscopy. Strings of approximately spherical aggregates were seen. The aggregates were interpreted as micelle-like agglomerates formed by almost fully acetylated polysaccharide, interconnected by blocks of almost fully deacetylated polysaccharide stretched by electrostatic repulsion. These agglomerates include NH3 + groups which produce electrostatic swelling of the agglomerates, giving a radius proportional to the degree of deacetylation. The length of the strings are also proportional to the deacetylation degree. These strings are extended because of the electrostatic repulsion between charged ammonium groups.

Two model linear polyethylenes of different molecular weights and very narrow molecular weight distributions were subject to γ-ray irradiation under vacuum. Irradiations were conducted at two temperatures: 25 and 135°C. Number average and weight average molecular weight of irradiated samples was measured by LALLS and membrane osmometry, and the distribution of molecular weights was studied by GPC. The presence of a low but measurable amount of scission was verified. A mathematical model of the irradiation process was developed, which gave very good predictions of the measured values.

High energy radiation has been successfully employed to modify the chemical structure of commercial polymers. It induces at least two types of reaction in polyethylene: crosslinking and chain scission. In addition the efficiency of the radio-induced reactions can be affected by the presence of antioxidants. The purpose of this work is to study the effect of the irradiation on a model polyethylene containing a phenolic type antioxidant. Samples containing 0.1% and 1% by weight of Irganox 1010 (Ciba-Geigy) were irradiated under vacuum at room temperature with different doses of gamma rays from a 60Co source. Changes in structure and the average molecular weight were followed by gel permeation chromatography and low angle laser light scattering. The critical doses for gelation were determined as a function of the antioxidant concentration. Theoretical calculations to predict the evolution of molecular structure with extent of radiation were performed using a probability model. The agreement between the calculated and the measured molecular weights is very good.

Well characterized model copolymers are used to study the effects of ionizing radiation. Linear copolymers of ethylene and butene-1 with uniform chemical microstructure and very narrow molecular weight distributions are irradiated at room temperature with γ-rays from a 60Co source. Changes in the molecular hydrodynamic volume can be readily detected by GPC. Changes in molecular weight averages Mn and Mw are measured by membrane osmometry and light scattering.