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Combustion, Explosion, and Shock Waves, Vol. 46, No. 1, pp.

117120, 2010

URGENT COMMUNICATION

Optical Emission Spectrum


in Combustion with Formation
of Condensed Reaction Products

A. I. Kirdyashkin,1 V. G. Salamatov,1 Yu. M. Maksimov,1 UDC 536.46; 541.141.6; 535-31


E. A. Sosnin,2 V. F. Tarasenko,2 and R. M. Gabbasov1

Translated from Fizika Goreniya i Vzryva, Vol. 46, No. 1, pp. 132135, JanuaryFebruary, 2010.
Original article submitted June 6, 2009.

Broadband far ultraviolet (UV) emission (up to 200 nm) was recorded during com-
bustion of heterogeneous systems with the formation of condensed reaction products.
It was shown that UV emission occurred during combustion in various gases (He, Ar,
and N2 ) and had the highest intensity in helium at a pressure of 25 kPa. This emis-
sion is attributed to the chemiionization of gas, separation of charges in combustion
products, and subsequent microbreakdowns.
Key words: heterogeneous combustion, ultraviolet emission.

INTRODUCTION

Investigation of emission phenomena during com-


bustion is important for a deeper understanding of the
mechanism of high-temperature fast chemical reactions.
The characteristics of electromagnetic emission during
combustion of heterogeneous systems with condensed
reaction products have been studied insuciently. Pre-
liminary results in this direction are covered in [15].
In the present work, we studied optical ultraviolet
emission during self-propagating high-temperature syn- Fig. 1. Diagram of measurements: 1) vacuum cham-
ber; 2) starting mixture; 3) quartz cell; 4) molyb-
thesis (SHS) in the TiB and ZrB powder systems.
denum foil; 5) suspension cloud; 6) metal electrodes
(d = 0.2 mm); 7) ceramic insulator; 8) thermocouple;
9) oscillograph; 10) optical quartz glass; 11) high-
MATERIALS AND METHODS speed video camera; 12) spectrometer; 13) computer.

A diagram of the experiments is presented in Fig. 1.


Mixtures of bulk density in an amount of 1.01.5 g were face of a molybdenum foil. SHS was initiated in an
placed in a quartz cell of 20 mm diameter on the sur- atmosphere of He, Ar, and N2 at a pressure of 70 Pa
to 100 KPa by heating the foil by an electric current at
1
Department of Structural Macrokinetics, Tomsk Scientific a rate of 24 K/sec. Once the critical temperature of
Center, Siberian Division, Russian Academy of Sciences, 9001200 K was reached, the mixture was self-ignited
Tomsk 634021; maks@fisman.tomsk.ru.
2 and the reaction proceeded in a mode close to thermal
Institute of High-Current Electronics, Siberian Division,
Russian Academy of Sciences, Tomsk 634021; explosion. According to [6], the calculated adiabatic
badik@loi.hcei.tsc.ru. temperature of the products during SHS (ignoring pre-
0010-5082/10/4601-0117 
c 2010 Springer Science + Business Media, Inc. 117
118 Kirdyashkin, Salamatov, Maksimov, et al.

liminary heating) is 3190 K for TiB and 3310 K for suspension cloud. The value of topt characterizes the in-
ZrB. Optical measurements were performed at wave- tegrated duration of the process, including the reaction
lengths = 2001100 nm. The chemical transforma- and cooling of the products.
tions in the reaction systems follow the schemes The emission spectrum is a rapidly changing su-
perposition of continuous and selective spectra. The
Ti + 2B TiB2 + 1 eV/atom;
continuous visible and infrared spectrum is typical of
Zr + 2B ZrB2 + 1.1 eV/atom. thermal emission. It is similar to the emission from
a photometric lamp at the corresponding temperature
For the studies, we prepared stoichiometric powder mix-
of the tungsten ribbon. It was found that, in a reac-
tures of Ti and Zr (PTM and PTsRK Russian trade
tion time close to ti , an intense ultraviolet spectrum
marks) and amorphous black boron (98% purity).
(Fig. 2) of nonthermal nature is generated. The short-
The reaction of the mixtures was observed using
wave emission boundary UV (200 nm) corresponded to
high-speed video recording (Motion Pro X-3 video cam-
the spectrometer sensitivity range. The brightness of
era). The current through the reaction products was
the UV emission of the SHS is comparable to that of the
recorded by electrodes powered by a constant-voltage
exilamp emission and far exceeds the level of the similar
supply source. In the absence of the external power
short-wave emission of gas ames (hydrogen, hydrocar-
supply, the electrodes recorded the spontaneous elec-
bon). We note that in ames, UV emission has previ-
tric polarization of the products. The emission from
ously been recorded only around 235400 nm [7]. The
the reaction products was analyzed through an opti-
observed selective lines of the spectrum reect the u-
cal quartz window by means of HR4000 spectrometers
orescence of partly ionized Ti and Zr vapors. Emission
(Ocean Optics B.V.; = 200300 nm), EPP2000C-25
from atoms with a degree of ionization of 23 indicates
(StellarNet Inc.; = 250350 nm), and Spectrum
a high energy of their excitation (in excess of 20 eV).
(ITM; = 3001100 nm). Spectra were measured in
The intensities of the short-wave spectra depend
a dynamic mode with a time resolution up to 5 msec.
greatly on the composition and pressure of the gas en-
The spectrometers were calibrated by the continuous
vironment in which SHS proceeds. The emission power
spectrum of a SI 10-300u tungsten lamp (visible range)
(in standard units) was determined from the formula
and, in the near ultraviolet, by the spectrum of a
 nm
400
XeCl-BD-P exilamp ( = 307309 nm) and XeBr-CD-P
( = 275285 nm) (Institute of High-Current Electron- P = I d, where I is the emission intensity. The
ics of the Siberian Division of the Russian Academy 200 nm
of Sciences). most intense emission is observed in a He environment
at a pressure of 25 kPa (Figs. 2 and 3). The time inter-
vals of the continuous emission spectrum (4060 msec)
and selective lines (2530 msec) dier markedly, indi-
RESULTS AND DISCUSSION
cating dierent mechanisms of their excitation.
The studies showed that gas emission (gasication It can be suggested that the generation of the con-
of volatile impurities, evaporation of components) dur- tinuous spectrum is related to recombination phenom-
ing the SHS led to the formation of a radiating sus- ena of the gas plasma, and selective lines are due to
pension cloud up to 10 cm in diameter. The cloud the direct excitation of atoms (ions) by an electron
consisted of 10200 m droplets of condensed products ow. It is known [3, 9] that SHS is accompanied by
and ionized gas. The droplets were formed by capillary a chemically stimulated plasma ow from the free sur-
coalescence of molten particles of the starting compo- face of condensed phases. The plasma is character-
nents with the subsequent development of a chemical ized by a high concentration of charged particles (up
reaction inside the droplets in the stage of formation to 1021 1023 m3 ) and the presence of electrons with
of the cloud. The characteristic times of the process an energy of up to 150 eV. The eect of the composi-
were as follows: time of heating of the droplets to the tion and pressure of the gas environment on the emis-
maximum temperature tc 110 msec (high-speed mi- sion characteristics during SHS is apparently similar to
crovideo recording data), duration of the ionized state the role of buer gases during excitation of gases by
of the cloud ti 4060 msec (signal of the current an electron beam (for example, in a laser plasma [10]).
between the electrodes), and maximum time of opti- It involves the accumulation of electron energy by gas
cal emission topt 100150 msec. The quantities tc molecules, followed by its subsequent transfer to ionized
and ti reect the duration of chemical reactions and pairs of metals in the suspension cloud, a decrease in
the dierence between them is due to nonsynchronous the decay of excited electronic states, and other kinetic
development of the reaction in various droplets of the eects in the plasma.