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Inert Environment (inert + environment)

Distribution by Scientific Domains

Polymers and Materials Science	75%

Selected Abstracts

Modeling the Effect of Oxygen on Photopolymerization Kinetics

MACROMOLECULAR THEORY AND SIMULATIONS, Issue 2 2006
Allison K. O'Brien
Abstract Summary: A comprehensive one-dimensional photopolymerization model was utilized to investigate the effect of oxygen on the free-radical photopolymerization kinetics. The spatial profiling aspect of the model provided insight into the heterogeneity of the cure kinetics due to oxygen inhibition, specifically the variance in the concentration profile of monomer and oxygen. Double bond conversion was negligible for the top ten microns of the film due to continuous oxygen diffusion, and increased with increasing depth. Similarly, the oxygen concentration decreased with increasing depth due to the competition between oxygen diffusion time and the polymerization rate. The effect of initiation rate on the extent of oxygen inhibition was investigated for various oxygen concentrations. As the initiation rate increased, the polymerization rate increased, and eventually approached that of a sample in an inert environment. Similarly, as the oxygen concentration was decreased, the polymerization rate increased. The effect of varying the initiation rate on the cure profile in the oxygen-exposed film was also studied. It was found that the unpolymerized tacky layer decreased from 50 µm to 5 µm with a 3 order of magnitude increase in initiation rate. Using the pseudo steady state approximation, the relationship between polymerization rate and initiation rate was derived for films in an oxygen environment. A direct relationship between the polymerization and initiation rate was found for films in air. The polymerization model supported this derivation and found that as the oxygen concentration was decreased, the dependence on initiation rate, or alpha, decreased, reaching the accepted value of 0.5 for alpha in inert environments. Double bond conversion versus film depth and cure time. [source]

Gel point prediction of metal-filled castor oil-based polyurethanes system,

POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 10-12 2002
Anil Srivastava
Abstract Prediction of gel point conversion and network formation is of great importance in polycondensation during synthesis as well as processing. It enables one to estimate the safe conversions for reactor operation without gelation and the cycle time during processing, and plays an important role in controlling the molding parameters used for reinforced reaction injection molding (RRIM), reaction injection molding (RIM) and compression molding. Theories of gelation have been extensively published in the literature and supported by experimental data for various polycondensation systems. However, most such studies relate to unfilled systems. In this work, metal-filled polyurethanes have been synthesized in bulk by reacting toluene di-isocyanate with castor oil and its polyols possessing different hydroxyl values. Metallic aluminum powder (10,40% by weight) was dispersed thoroughly in castor oil and its polyols before reacting at different temperatures (30,60,°C) in a moisture-free, inert environment. The gel point conversions were measured experimentally and an empirical model from the experimental data has been developed to predict the gelation behavior. The proposed model could be of immense importance in the paints, adhesives and lacquers industries, which use castor oil in bulk. From these experiments it was concluded that: (i) fine metal powder gives a rise in viscosity; (ii) metal fillers not only restrict the molecular motion due to the increase in viscosity, but also lower the conversion; (iii) the vegetable oil and its polyols have a number of bulky groups, which also impart the delay tendency in gel time; (iv) there is a change in gelation dynamics at 50,°C , this is due to the change in reactivity of di-isocyanates; (v) the presence of metal filler does not initiate the intermolecular condensation; (vi) there is a gap between theoretical and experimental gel point owing to the unequal reactivity of the secondary alcohol position; (vii) there is an inverse relationship of gel time with the reaction temperature and hydroxyl value of polyols. An empirical model based on process parameters, i.e., hydroxyl value, temperature, shape factor and filler concentration, has been derived and found to be adequate for the metal-filled system. The correlation coefficient on the data is on the lower side in some cases because the following were not taken into account: (i) the first-order kinetics followed by the reaction in the second half while it is tending towards gelation; (ii) the error in observing the gel point viscosity; (iii) errors in assuming the spherical shape of aluminum metal powder; (iv) errors due to failure to maintain the constant speed in agitation. Copyright © 2003 John Wiley & Sons, Ltd. [source]

Kinetic study of the gasification of an Australian bituminous coal char in carbon dioxide

ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING, Issue 3 2010
Chetan R. Chodankar
Abstract Experimental work was carried out to study the kinetics of the carbon dioxide gasification of a coal char. The coal char was prepared from an Australian bituminous coal by pyrolyzing it at 900 °C in a tube furnace for 9 min in inert environment. The coal char was gasified in a thermo-gravimetric analyzer (TGA) with a mixture of carbon dioxide and nitrogen. The effects of gasification temperature (800,875 °C) and carbon dioxide concentration (10,80%) were studied. In the present study the reaction rate of the pyrolyzed coal was obtained and interpreted by Random pore model. Copyright © 2009 Curtin University of Technology and John Wiley & Sons, Ltd. [source]