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