Structure of premixed flat burner-stabilized H 2 /O 2 /Ar flame doped with Ti(OC 3 H 7 ) 4 at 1 atm. A. G. Shmakov 1, O. P. Korobeinichev 1, D. A. Knyazkov.

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Structure of premixed flat burner-stabilized H 2 /O 2 /Ar flame doped with Ti(OC 3 H 7 ) 4 at 1 atm. A. G. Shmakov 1, O. P. Korobeinichev 1, D. A. Knyazkov 1, A. A. Paletsky 1, R. A. Maksutov 2, I. E. Gerasimov 2, S. A. Yakimov 1, T. A. Bolshova 1 1 Institute of chemical kinetics and combustion, Novosibirsk, Russia 2 Novosibirsk state university, Novosibirsk, Russia 7th INTERNATIONAL SEMINAR ON FLAME STRUCTURE and FIRST YOUNG RESEARCHERS’ SCHOOL ON FLAME STUDY Novosibirsk, Russia, July 11-19, 2011

Introduction Application of nanocrystaline mesoporous TiO 2 films : Dye sensitized solar cells, DSSC Sensors for gas analyzers

Traditional approaches for TiO 2 films fabrication: sol-gel method screen printing spray deposition doctor blading New approach for TiO 2 films fabrication by one step in premixed lean flame C 2 H 4 /O 2 /Ar  0.10% Ti(OC 3 H 7 ) 4 E.D. Tolmachoff, A.D. Abid, D.J. Phares, C.S. Campbell, H. Wang, Proceedings of the Combustion Institute 32 (2009) 1839–1845 S. Memarzadeh, E.D. Tolmachoff, D.J. Phares and H. Wang, Proc. Combust. Inst. 33 (2011) !

Chemistry and kinetics of reactions of Ti-containing compounds in flames: TiCl 4 – Pratsinis S.E. et al, Aerosol Sci. 2002, 33, 17. – Kraft M. et al, Combust. Flame 2009,156, Ti(OC 3 H 7 ) 4 – Okuyama K. et al, A.I.Ch.E Journal 36, 409. Ti(OC 3 H 7 ) 4(gas)  TiO 2 +4C 3 H 6 +2H 2 O k=3.96  10 5 exp( /T) the detailed mechanism and kinetics of TTIP thermal decomposition are practically unknown.

Research Objectives to study of the structure of premixed flame stabilized on a flat burner H 2 /O 2 /Ar (12.9%/14.4%/72.7%) + 0.1% Ti(OC 3 H 7 ) 4,  = 0.45 Numerical modeling of flame structure using one-step reaction for Ti(OC 3 H 7 ) 4 thermal decomposition.

Flame Burner with burner positioning mechanism EXPERIMENTAL APPROACH Measurement of Flame Structure Premixed laminar flame was stabilized on the flat burner. The profiles of concentration of flame species were measured using MBMS setup :

EXPERIMENTAL APPROACH Alumina ceramic probe (sonic probe) on an enlarged scale The probe was clogged by TiO 2 particles for s of experiment and demanded cleaning.

Perforated disk Ar Ti(OC 3 H 7 ) 4 Thermostat 90 0 С Thermostat 90 0 С Steel balls Combustible mixture Flame EXPERIMENTAL APPROACH Probe Combustible mixture (  = 0,45 ) H 2 /O 2 /Ar (13/14.5/72.5 %)+ 0,12% Ti(OC 3 H 7 ) 4

Speciesm/z H2H2 2 O2O2 32 H2OH2O 18 Ti(OC 3 H 7 ) TiO 2 80 TiO 64 HTiO 65 HTiO 2 81 Ti 2 O Ti 48 TiH 49 Identified flame species

Hydrogen combustion mechanism Konnov A.A. Combustion and Flame, V. 152, pp. 507–528, (2008) Gas-phase reaction for thermal decomposition of Ti(OC 3 H 7 ) 4 : Ti(OC 3 H 7 ) 4(gas)  TiO 2 +4C 3 H 6 +2H 2 O k=3.96  10 5 exp( /T) Okuyama K. et al, A.I.Ch.E. Journal, 36, 409–419 (1990) Thermochemistry for Ti(OC 3 H 7 ) 4 и TiO 2 PREMIX and CHEMKIN codes (Sandia National Laboratory, USA) MODELING

Spatial variations of H 2 O, O 2, H 2 mole fraction in H 2 /O 2 /N 2 flame doped with 0.1% Ti(OC 3 H 7 ) 4 stabilized on a flat burner. O2O2 H2OH2O Ar H2H2 Results and Discussion

Spatial variations of mass peak intensity m/z 269 and Ti(OC 3 H 7 ) 4 mole fraction in H 2 /O 2 /N 2 flame. Symbols – experiment, line - modeling

Spatial variations of mass peak intensity m/z=80 (TiO 2 ) and TiO 2 mole fraction in H 2 /O 2 /N 2 flame. Results and Discussion Symbols – experiment, line - modeling

Spatial variations of mass peak intensity m/z=48 (Ti) in H 2 /O 2 /N 2 flame. Results and Discussion Symbols – experiment, line - spline

Spatial variations of mass peak intensity m/z=49 (TiH) in H 2 /O 2 /N 2 flame. Results and Discussion Symbols – experiment, line - spline

Spatial variations of mass peak intensity m/z=64 (TiO) in H 2 /O 2 /N 2 flame. Results and Discussion Symbols – experiment, line - spline

Spatial variations of mass peak intensity m/z=65 (HTiO) in H 2 /O 2 /N 2 flame. Results and Discussion Symbols – experiment, line - spline

Spatial variations of mass peak intensity m/z=81 (HTiO 2 ) in H 2 /O 2 /N 2 flame. Results and Discussion Symbols – experiment, line - spline

Spatial variations of mass peak intensity m/z=96 (TiO 3 ) in H 2 /O 2 /N 2 flame. Results and Discussion Symbols – experiment, line - spline

Spatial variations of mass peak intensity m/z=144 (Ti 2 O 3 ) in H 2 /O 2 /N 2 flame. Results and Discussion Symbols – experiment, line - spline

Conclusion 1. We were the first to measure mass-peak intensity profiles of Ti(OC 3 H 7 ) 4 and products of its combustion: Ti, TiH, TiO, TiO 2, HTiO, HTiO 2, TiO 3, Ti 2 O 3 in premixed H 2 /O 2 /N 2 flame using the MBMS method. 2. A one-step reaction kinetic model for Ti(OC 3 H 7 ) 4 destruction used in the study, satisfactorily predicts the mass-peak intensity profile of TiO 2 which is the main combustion product of Ti(OC 3 H 7 ) 4 in the studied flame, but poorly predicts the concentration profile of Ti(OC 3 H 7 ) 4.

This research was supported by Russian Foundation for Basic Research under project # Thank you!

TiO 2 Ti(OC 3 H 7 ) 4 TiH Ti HTiO 2 HTiO TiO TiO 3 Ti 2 O 3 Spatial variations of mass peak intensity of Ti-containing species in H 2 /O 2 /N 2 flame. Results and Discussion lines – spline for experiment