Central European Journal of Energetic Materials Volume 10, Number 2, 2013

The Applicability of Chromatographic Methods in the Investigation
of Ageing Processes in Double Base Rocket Propellants


Brodarski Institute, Ave.V. Holjevca 20, HR-10020 Zagreb, Croatia 2Nanyang Technological University, Energetics Research Institute, Singapore 3Ministry of Defense, Zagreb, Croatia 

Abstract: The ageing of double base (DB) rocket propellants is the result of chemical decomposition reactions and physical processes, causing degradation of a number of relevant propellant properties (such as reduction in stabilizer and nitroglycerine (NG) content, reduction of the mean molecular mass of nitrocellulose (NC) etc.), which is reflected in a decrease in the reliable service life time of DB propellants. This is the reason why the study of processes of ageing and their consequences (effects) is so important. In this paper we have studied the kinetics of DB rocket propellant decomposition during their artificial ageing, i.e. at elevated temperatures. The kinetic parameters were obtained by measurements of the stabilizer/Ethyl Centralite (EC) content and the mean molecular mass reduction of NC, during artificial ageing at temperatures of 80, 85 and 90 °C. Consumption of the EC was observed using High Performance Liquid Chromatography (HPLC), whilst the reduction in the mean molecular mass of NC was monitored using Gel Permeation Chromatography (GPC). It has been shown that artificial ageing of DB propellant causes significant EC consumption and a reduction in the mean molecular mass of NC, from the very beginning of ageing. EC is entirely consumed after 120 days at 80 °C, and is followed by the intensive reactions of NC decomposition. Significant changes in the mean molecular mass of NC starts after 60 days of ageing at 90 °C (or ~250 days at 80 °C). The results obtained from the kinetic data have shown that the activation energy of DB propellant decomposition, determined on the basis of changes in the mean molecular mass of NC is 145.09 kJ·mol-1, whilst the activation energy 246 S. Matečić Mušanić, M. Sućeska, R. Čuljak of decomposition obtained on the basis of EC consumption is 142.98 kJ·mol-1, which is consistent with available literature values [1, 2]. 

Keywords: activation energy, artificial ageing, DB rocket propellants, decomposition, Ethyl Centralite (EC), Gel Permeation Chromatography (GPC), High Performance Liquid Chromatography (HPLC), kinetics of degradation, mean molecular mass of NC

Institute of Industrial Organic Chemistry

Warsaw, Poland