Determining Auto-Ignition Temperature of Metal Zirconium Dispersed Powder Using Differential Scanning Calorimetry


For citation.
Gezalian L.V., Rodin A.V., Dvoeglazov K.N., Inchikov A.P. Determining Auto-Ignition Temperature of Metal Zirconium Dispersed Powder Using Differential Scanning Calorimetry. Bezopasnost Truda v Promyshlennosti = Occupational Safety in Industry. — 2025. — № 5. — рр. 7-12. (In Russ.). DOI: 10.24000/0409-2961-2025-5-7-12


Annotation:

Significant volumes of substances and materials in a dispersed state, including metals and their compounds whose hazard indices have not been studied comprehensively, are handled in process media of nuclear fuel cycle facilities designed to process spent nuclear fuel. To establish the limiting conditions for safe workflows in terms of explosion and fire safety, a crucial index to be identified is the auto-ignition temperature. However, standard methods used for dispersed metals cannot be applied to radioactive media. The most appropriate methods to study products handled at such facilities are thermal methods of analysis, including differential scanning calorimetry. Using microquantities of substances for experimental studies, this method helps to obtain a mathematical model of chemical process development (kinetics). Therefore, knowledge of chemical transformation kinetics enables modelling a sample's behavior when heated. 
Parallel studies to determine the auto-ignition temperature of the same product have been conducted using two methods. Simultaneously, in the Federal State Budgetary Institution Fire Safety Research Institute of the EMERCOM of Russia, using the near-standard study method in accordance with GOST12.1.044—89, and the Federal Budgetary Institution “Scientific and Technical Center for Nuclear Radiation Safety” (NTC YaRB), using the developed differential scanning calorimetry method, the temperature of auto-ignition of finely dispersed zirconium powder has been identified; it is equal to 290 and 295 °С respectively. The check of reproducibility of the method of differential scanning calorimetry has shown that the difference between the values of auto-ignition temperature obtained by near-standard and experimental calculating methods does not exceed 5 %.
Using the method of differential scanning calorimetry helps to assess the index of explosion and fire hazard of materials not available for examination by standard methods. 
Notably, this method to identify auto-ignition temperature is applicable for dispersed materials and their compounds, whose oxidation during the induction period occurs in the kinetic region, but cannot be fully applied in cases when auto-ignition occurs in the diffusion region of oxidation reaction; however, it can be considered for a conservative estimate. 

References:
1. Technical Regulation on fire safety requirements: the Federal Law of July 22, 2008, № 123-FZ. Available at: https://docs.cntd.ru/document/902111644 (accessed: October 10, 2024). (In Russ.).
2. GOST 12.1.044—89 (ISO 4589—84). Explosion and fire hazard of substances and materials. Nomenclature of indices and methods of their identification. Available at: https://docs.cntd.ru/document/1200004802 (accessed: October 10, 2024). (In Russ.).
3. Chibisov A.L., Inchikov A.P. Combustion and extinguishment of metals. Pozharnaya bezopasnost = Fire Safety. 2012. № 2. pp. 32–35. (In Russ.).
4. Rao G.A.R., Jayanthi K., Mukerjee S.K., Vaidya V.N., Venugopal V. Oxidation behavior of U2N3. Thermochimica acta. 1990. Vol. 159. pp. 349–356. DOI: 10.1016/0040-6031(90)80120-N
5. Marchand M., Fiquet O., Brothier M. Oxidation kinetic analysis of a mixed uranium dicarbide and graphite compound. Journal of Nuclear Materials. 2013. Vol. 437. Iss. 1–3. pp. 310–316. DOI: 10.1016/j.jnucmat.2013.02.028
6. Mazaudier F., Tamani C., Galerie A., Marc Y. On the oxidation of (U, Pu)C fuel: Experimental and kinetic aspects, practical issues. Journal of Nuclear Materials. 2010. Vol. 406. Iss. 3. pp. 277–284. DOI: 10.1016/j.jnucmat.2010.07.041
7. Gromov A.A., Ilin A.P., Ditts A.A. Physics and chemistry of combustion of metal nanopowders in nitrogen-containing gaseous media. Tomsk: Izd-vo Tomskogo politekhnicheskogo universiteta, 2007. 332 p. (In Russ.).
8. Gezalyan L.V., Rodin A.V. Approaches to experimental studies for mathematical description of chemical processes occurring in process media of nuclear fuel cycle facilities for safety assessment. Modelirovanie tekhnologiy yadernogo toplivnogo tsikla: materialy 11-go nauch. seminara (Modelling nuclear fuel cycle technologies: proceedings of the 11th scientific seminar). Snezhinsk: RFYaTs-VNIITF, 2023. pp. 8–9. (In Russ.).
9. Benin A. I., Belokhvostov V. M., Kossoi A. A. Data recovery in the study of the kinetics of chemical reactions by the DSC method. Zhurnal fizicheskoi khimii = Russian Journal of Physical Chemistry. 1987. Vol. LXI. № 5. pp. 1205–1210. (In Russ.)
10. TSS-ARKS — CISP(R). The analog-free software for thermal hazard assessment. Available at: https://www.cisp.spb.ru/tss-arks (accessed: October 10, 2024).
11. Bakradze G. Initial oxidation of zirconium: oxide-film growth kinetics and mechanisms// Thesis for: Doctoral. Stuttgart: University of Stuttgart, 2011.
12. Bessmertnyy V.S., Stadnichuk V.I., Bondarenko N.I., Ilina I.A., Bondarenko D.O. Kinetics of oxidation of aluminum powder used in corundum-sillimanite ceramics. Vestnik BGTU im. V.G. Shukhova = Bulletin of BSTU Named after V.G. Shukhov. 2015. № 1. pp. 151–154. (In Russ.).
13. Zefirov N.S. Chemical encyclopaedia. In 5 volumes. Vol. 5. Мoscow, 1998. 783 p. (In Russ.).
DOI: 10.24000/0409-2961-2025-5-7-12
Year: 2025
Issue num: May
Keywords : кинетика differential scanning calorimetry auto-ignition nuclear fuel cycle finely dispersed powders metal powders
Authors:
  • Gezalian L.V.
    Researcher, gezalyan@secnrs.ru, Scientific and Engineering Centre for Nuclear and Radiation Safety, Moscow, Russian Federation
  • Rodin A.V.
    Cand. Sci. (Chem.), Senior Researcher, Institute of Physical Chemistry and Electrochemistry RAS (IPCE RAS), Moscow, Russian Federation
  • Dvoeglazov K.N.
    Cand. Sci. (Chem.), Assoc. Prof., Lead Researcher, JSC «Academician A.A. Bochvar High-Tech Research Institute of Inorganic Materials», Moscow, Russian Federation
  • Inchikov A.P.
    Cand. Sci. (Eng.), Deputy Head of the Department, EMERCOM of Russia, Balashikha, Russian Federation