Determination of thermal hazard from DSC measurements. Investigation of self-accelerating decomposition temperature (SADT) of AIBN
- 724 Downloads
The method of determination of the thermal hazard properties of reactive chemicals from DSC experiments is illustrated by the results of SADT simulations performed with azobisisobutyronitrile (AIBN). The kinetics of decomposition of AIBN in the solid state was investigated in a narrow temperature window of 72–94 °C, just below the sample melting. The kinetic parameters of the decomposition were evaluated by differential isoconversional method. The very good fit of the experimental results by the simulation curves, based on the determined kinetic parameters, indicated the correctness of the kinetic description of the process. Application of the kinetic parameters, together with the heat balance performed by numerical analysis, allowed scale-up of thermal behaviour from mg- to kg-scale and simulation of SADT. The study presents the evaluation of the influence of the overall heat transfer coefficient U on the SADT value. The results obtained clearly illustrate also the dependence of SADT on the sample mass. The tenfold increase of the mass from 5 to 50 kg results in the decrease of the SADT from 50 to 43 °C. Determination of the reaction kinetics, describing the rate of heat generation, and the heat balance in the system, based on Frank-Kamenetskii approach, was calculated using AKTS Thermokinetics and Thermal Safety software.
KeywordsThermal hazard simulation AIBN SADT Thermal decomposition DSC Kinetic parameters
- 1.UN Recommendations on the Transport of Dangerous Goods, Manual of tests and criteria, 5th revised edition. United Nations, New York and Geneva, 2009;28.3.7.Google Scholar
- 3.Erikson WW, Schmitt RG, Atwood AI, Curran PD. Coupled thermal-chemical-mechanical modeling of validation cookoff experiments. JANNAF 37th Combustion and 19th Propulsion Systems Hazards Subcommittees Joint Meeting, Monterey; 2000.Google Scholar
- 4.Roduit B, Folly P, Sarbach A, Berger B, Mathieu J, Ramin M, Vogelsanger B. Simulation of the cook-off, SADT and time to maximum rate for single-base propellant using DSC data. Proceedings of 39th International Annual Conference of ICT, Karlsruhe, Germany, 2008;24.Google Scholar
- 5.Kotoyori T. Critical temperatures for the thermal explosion of chemicals, vol. 7., Industrial safety seriesAmsterdam: Elsevier; 2005. p. 48–362.Google Scholar
- 10.Friedman HL. Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic. J Polym Sci Pol Lett. 1963;C6:183–95.Google Scholar
- 13.http://www.abaqus.com. Accessed 28 Jan 2014.
- 14.http://www.ansys.com. Accessed 28 Jan 2014.
- 16.Swiss Institute of Safety and Security, High pressure crucible M50 gold-plated, (patent N° 695 709), http://www.swissips.com/en/swissi-ps-ltd/high-pressure-crucibles-for-dsc.html. Accessed 18 Dec 2013.
- 17.Brown ME, Maciejewski M, Vyazovkin S, Nomen R, Sempere J, Burnham A, Opfermann J, Strey R, Strey R, Anderson HL, Kemmler A, Kueleers R, Janssens J, Dessseyn HO, Li C-R, Tang Tong B, Roduit B, Malek J, Mitsuhashi T. Computational aspects of kinetic analysis. Part A: The ICTAC kinetics project-data, methods and results. Thermochim Acta. 2000;355:125–43.CrossRefGoogle Scholar
- 21.Lebedeva ND, Gutner NM, Katin Yu A, Kozlova NM, Kiseleva NN, Makhina EF, Dobychin SL. Thermochemical study of bis-hydroxyethylpiperazine, N,N-dimethylpropylendiamine and 2,2-azodiisobutyrodinitrile. J Appl Chem USSR+. 1984;57:2118–22.Google Scholar
- 28.Frank-Kamenetskii DA, Diffusion and Heat Transfer in Chemical Kinetics. 2nd Ed., Translated from Russian by J. P. Appleton, Plenum Press, New York-London. 1969;375.Google Scholar
- 29.Health Council of the Netherlands: Dutch Expert Committee on Occupational Standards. Azobisisobutyronitrile. The Hague, publication no. 2002/01OSH. 2002;16–17.Google Scholar
- 30.Dellavedova M, Pasturenzi C, Gigante L, Lunghi A. Kinetic evaluations for the transportation of dangerous chemical compounds. Chem Ing Trans. 2012;26:585–90.Google Scholar