ISSN 1087-6596, Glass Physics and Chemistry, 2017, Vol. 43, No. 4, pp. 326–329. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © N.I. Krylov, L.N. Blinov, 2017, published in Fizika i Khimiya Stekla.
Halogen-Containing Chalcogenide Glasses: Synthesis and Properties
N. I. Krylov and L. N. Blinov*
Peter the Great St. Petersburg Polytechnic University, St. Petersburg, 195251 Russia
Received June 17, 2016
Abstract—Methods for the synthesis of chalcogenide glasses (CGs) containing active and volatile compo-
nents, in particular, bromine have been developed. The density, volume expansivity, microhardness, refrac-
tion index, and magnetic susceptibility of these glasses have been studied. Using the EPR method, the con-
centration of the intrinsic paramagnetic centers in bromide-modified CGs has been determined.
Keywords: halogen-containing chalcogenide glasses, bromide-modified chalcogenide glasses, physicochem-
ical properties, magnetic susceptibility, EPR spectroscopy
At present, considerable attention is being devoted
to develop and prepare new materials possessing
improved, novel, and practically valuable properties.
Among these materials, chalcogenide glasses (CGs),
whose composition and properties can be varied in a
broad range, are highly ranked. Analysis of the results
shows that vitreous materials, which are particularly
interesting in the fundamental and applied contexts,
can be prepared with the introduction of active and
volatile components to CGs [1–5].
However, the previously employed methods for the
synthesis of CGs containing active and volatile com-
ponents, in particular, halogens, did not allow prepar-
ing glasses of the given composition and properties
and were extremely labor-consuming, long-term, and
explosive. One example is that halogen-containing
CGs (HCGs) based on the arsenic–sulfur–iodine sys-
tem were synthesized by alloying the initial compo-
nents in the temperature range of 733 K ≤ T ≤ 873 K
under an inert gas atmosphere with the subsequent
slow cooling of the melt .
RESULTS AND DISCUSSION
To synthesize bromide-modified HCGs , the
initial components taken in certain ratios, which cor-
responded to the composition of the chosen glass,
were placed in an ampoule and heated at the rate of 3–
7 K/min. The melt was maintained for 2–3 h at the
maximum temperature of 873 K.
The melt was cooled in air at the rate of 3 K/min.
To decrease the reaction rates of arsenic and chalco-
gen with bromine, which are accompanied by exother-
mic effects, the latter was added to the cooling cham-
ber of a special design. The glasses prepared according
to this procedure contained traces of water, which
entered the glasses with the cooled bromine.
In order to decrease the amount of water in the
glasses, the silica vessel was preliminarily filled with
bromine and placed in the ampoule with arsenic sul-
fide . Then, the ampoule was filled with argon and
sealed. The sealed ampoule was maintained for 24 h at
room temperature, which provided a slow initial step
of the reaction of As
with bromine. Subsequent
synthesis of the glass was carried out under the condi-
tions described above. However, the glasses synthe-
sized according to this procedure still contained water,
which was adsorbed on the surface of the reaction
chamber and the components of the batch. In addition,
this technology did not allow preparing glasses of the
given composition due to the partial evaporation of bro-
mine during its introduction to the reaction chamber.
We developed the technology for the synthesis of
high-quality HCGs and the given composition with-
out traces of water [5, 7]. For this purpose, the silica
instrument was constructed, whose design is given in
The technology of the process involved the follow-
ing operations. The mass of the silica instrument was
measured on analytical balances; then, bromine was
poured into unit 1 and it was sealed. The mass of bro-
mine was determined according to the difference of
the filled and empty units. The amounts of other com-
ponents were calculated according to the weight of the
bromine and placed in unit 2. Then, unit 2 was
pumped up to the pressure of 10
Pa and sealed.
After that, lock 3 was opened and, in this case, bro-