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12CHEMICAL SCIENCES
PHYSICO-CHEMICAL AND X-RAY STRUCTURAL INVESTIGATION OF ALLOYS OF THE As2S3-
TlInTe2 SYSTEM
Ahmedova C.
Ph.D., Associate Professor, Adiyaman University, Faculty of Arts and Sciences,
Department of Chemistry, Turkey https://doi.org/10.5281/zenodo.6912603
Abstract
Chemical interactions in the As^-TlInTe^ system were studied by the methods of physicochemical analysis (DTA, MSA, XPA), as well as the determination of microhardness and density, and a state diagram was constructed. It has been established that the As^-TlInTe^ system is a quasi-binary section of the As2S3-TlTe-InTe quasi-ternary system and belongs to the eutectic type. Solid solutions based on As2S3 are formed in the system at room temperature, reaching up to 1.5 mol. %, and on the basis of the TlInTe2 compound up to -7 mol. %. In the As2S3-TlInTe2 system, under normal cooling conditions, extensive areas of glass formation are obtained. The temperature dependences of the electrophysical properties of solid solution alloys (TlInTe2)1-x(As2S3)x (x=0.02; 0.03; 0.05) have been studied.
Keywords: quasi-binary, eutectic, incongruent, system, microhardness, syngony.
INTRODACTION
As a result of a review of the literature, it was established that ternary systems consisting of arsenic and thallium chalcogenides have been sufficiently studied [1-4], and a number of works have been studied in the field of quaternary systems [5-8]. Thallium chalcogen-ides, like arsenic chalcogenides, are prone to vitrification; under normal conditions, they are obtained in a glassy state.
Arsenic chalcogenides and alloys based on them have optical [9-13], photoelectric [14-18], and luminescent [19, 20] properties. In recent years, the attention of researchers has been attracted to chalcogenide glass fibers based on As2S3 and As2Se3, which are used to transmit light in the mid-IR range and have found application in various semiconductor industries [2125].
Currently, research is being carried out in the field of obtaining materials with functional properties that can meet the requirements of constantly developing microelectronics and computer technology, and the search for safer energy sources. The search for highly efficient optically sensitive and thermoelectric materials is an urgent task of research in this area. The preparation of materials with the participation of indium and thallium chalcogenides of complex phases based on them is also of theoretical and practical importance [26,27].
The purpose of this work is to study some of the physicochemical properties of the obtained phases with the construction of a state diagram of the As2S3-TlInTe2 system.
As2S3 melts with an open maximum at 310°C and crystallizes in a monoclinic system with lattice parameters: a=11.49; b=9.59; c=4.25 A, p=90°27' (sp. gr. P2/n) [28]. Density and microhardness of crystalline As2S3 are equal to 3.46 g/cm3 and 660 MPa, respectively, and glassy As2S3 density is 3.20 g/cm3, microhardness is 1300 MPa [28].
The TlInTe2 compound melts congruently at 772°C and crystallizes in the tetragonal system with lattice parameters: a = 8.482 A, c = 7.192 A, density p = 7.27 g/cm3, microhardness H^ = 1000 MPa [29].
EXPERIMENTAL PART
For the synthesis of alloys of the As^-TlInTe^ system, the primary components As?S3 and TlInTe? were first synthesized, and then the alloys of the system were synthesized directly by the ampoule method. Synthesis was first carried out in the temperature range of 500-900°C, then the temperature was lowered to 400°C and kept at this temperature for 200 h. Physical and chemical studies of alloys of the As^-TlInTe^ system were carried out both in the glassy and in the crystallized state by the methods of differential thermal (DTA), microstructural (MSA), X-ray phase (XRD) analysis, as well as measurements of microhardness and density.
The differential thermal analysis of the alloys of the system was carried out on a TERMOSCAN-2 device with a heating rate of 5 deg/min.
X-ray phase analysis was performed on a D2 PHASER X-ray instrument using CuKa radiation with a Ni filter. The MSA alloys of the system were examined using a MIM-8 metallographic microscope. When studying the microstructure of the alloys, an etchant of the composition 10 ml NaOH + 10 ml H2O2 = 1:1 was used, the etching time was 15-20 s. The microhardness of the alloys of the system was measured on a PMT-3 microhardness tester at a load of 0.10 N. The density of the alloys of the system was determined by the pycno-metric method; toluene was used as the working fluid. The electrical conductivity was measured by the usual compensation method. The samples used had the shape of a parallelepiped. The experimental error was 2.7-3.0 % [30].
RESULTS AND ITS DISCUSSION
Alloys of the As2S3-TlInTe2 system are compact; with an increase in the content of TlInT2, their color changes from red to dark gray. Alloys of the As2S3-TlInTe2 system are resistant to water and air. They dissolve well in mineral acids (HNO3, H2SO4) in alkalis (NaOH, KOH).
As a result of the study of differential thermal analysis, it was found that on the thermograms of the alloys of the system As2S3-TlInTe2 in the concentration range of 0-30 mol % TlInTe2, there are softening temperatures Tg 170-190oC, typical for glassy samples.
a)
c)
Fig.1. Microstructures of alloys of the As2S3-TlInTe2 system. a)-10 mol % TlInTe2, 6J-40 mol % TlInTe2, e) 95 mol % TlInTe2.
Microstructural analysis of these alloys 0-20 mol. % TlInTe2 showed that one cloudy phase is visible on the microstructure of the sample. Within 20-30 mol % TlInTe2, crystalline inclusions gradually appear in the microstructure. On fig. 1 a, b, c show the microstructures of alloys of the As2S3-TlInTe2 system from different regions. On fig. la shows the microstructure of a
glass alloy with a content of 10 mol % TlInTe2, b)-mi-crostructures of two-phase, c) - microstructures of a solid solution alloy based on the TlInTe2 compound. To confirm the results of DTA, MSA, alloys of the As2S3-TlInTe2 system, we carried out X-ray phase analysis containing 10, 20 30 mol % TlInTe2 (Fig. 2).
Fig. 2. Diffractograms of alloys of the As2S3-TlInTe2 system. 1-10 mol %, 2-20 mol %, 3-30 mol %, TlInTe2.
As can be seen from fig. 2, on diffraction patterns of alloys containing 10, 20 mol % TlInTe2 has no diffraction maximum. These alloys are glassy. On the diffraction pattern of the alloy 30 mol % TlInTe2, a diffraction maximum appears that this alloy is glass-ceramic. And so, X-ray phase analysis fully confirms the results of differential thermal and microstructural analyses.
According to the results of physicochemical analysis, the T-x phase diagram of the As2S3-TlInTe2 system was constructed (Fig. 2). It has been established
that the state diagram of the system is quasi-binary, of the eutectic type. In terms of interaction patterns, the As2S3-TlInTe2 systems are identical to the As2S3-TlInSe2 systems [31]. In the system at room temperature, solid solutions based on As2S3 reach 1.5 mol %, and based on TlInTe2 up to -7 mol %. Under normal conditions, glass formation based on As2S3 extends up to 20 mol % TlInTe2, and the glass-ceramic region reaches from 20 mol % TlInTe2 up to 30 mol % TlInTe2.
The liquidus of the As2S3-TlInTe2 system consists of monovariant curves of a-solid solutions based on As2S3 and P-solid solutions based on TlInTe2. In the concentration range of 0-15 mol % TlInTe2, the a-phase is released from the liquid. In the system, the a-phase and P-phase form a eutectic with a composition of 15 mol % TlInTe2 and a temperature of 260°C. Below the solidus line, two-phase alloys (a + P) crystallize. As can
be seen from Table 1, in the As2S3-TlInTe2 system, softening temperatures (Tg), density and microhardness of alloys of the As2S3-TlInTe2 system increase depending on the composition. Alloys in the range of 0-20 % TlInTe2- glass, and alloys with a composition of 20-30 mol %. TlInTe2 belongs to the glass-ceramic region. After prolonged annealing at 200°С for 400 h, the softening temperature Tg disappears (170-190°С), and the solidus and liquidus temperatures remain (Table 2).
Tab.1.
Composition of alloys of the As2S3-TlInTe2 system, DTA, results of measurements of density and
Composition, mol % Thermal effects, K Density, g/cm3 Microhardness, MPa
As2S3 TlInTe2 a P
=0,15 H
100 0,0 170,310 3,20 1300 -
95 5,0 175,260,310 3,40 1350 -
90 10 180,260,305 3,61 1420 -
85 15 180,260 3,82 1420 -
80 20 185,260,340 4,03 1420 -
70 30 190, 260,445 4,42 - 1040
Tab.2.
Composition of alloys of the As2S3-TlInTe2 system, DTA, results of measurements of density and __microhardness before annealing_
Composition, mol % Thermal effects, K Density, g/cm3 Microhardness, MPa
As2S3 TlInTe2 a P
P=0,10 H
100 0,0 310 3,46 740 -
95 5,0 260,310 3,55 770 -
90 10 260,305 384 810 -
85 15 260 4,03 840 -
80 20 260,340 4,22 Эвтек. Эвтек.
70 30 260,445 4,,30 - -
60 40 260,525 4,97 - 1030
50 50 260,590 5,38 - 1040
40 60 260,640 5,74 - 1050
30 70 260,670 6,13 - 1050
20 80 260,715 6,51 - 1050
10 90 260,750 6,90 - 1050
5,0 95 500,760 7,30 - 1050
0,0 100 772 7,27 - 1000
The microhardness of alloys of the As2S3-TlInTe2 system has been studied both in glass and in crystalline form. Values of microhardness of alloys from the area of 0-30 mol % TlInTe2 glasses are within (1300-1420) MPa (Table 1). After crystallization of the same areas, the microhardness changes within (740-840) MPa (Table 2). The value of microhardness (1000-1050) MPa corresponds to the microhardness of p-solid solutions
based on TlInTe2. It has been established that the microhardness of glassy alloys is higher than that of crystalline alloys. These results are in good agreement with the literature data.
The temperature dependence of the electrical conductivity of the (TlInTe2)1-x(As2Ss)x (x=0.02; 0.03; 0.05) solid solution was studied in the temperature range 290-500 K (Fig. 4). The samples used had the shape of a parallelepiped.
Fig.4. Temperature dependence of the electrical conductivity of solid solutions (TlInTe2)i-x(As2S3)x (x=0.02; 0.03; 0.05). 1-2 mol %, 2-3 mol %, 3-5 mol % As2S3.
As can be seen from fig. 4, the curves of the temperature dependence of the electrical conductivity show that alloys of solid solutions based on TlInTe2 in the temperature range of 290-500 K have a semiconductor character of conductivity.
With increasing temperature, the electrical conductivity of the alloys increases. With the introduction of TlInTe2 into the composition, high resistances of compositions of 2, 3, and 5 mol % As2S3, the electrical conductivity of the composition gradually decreases.
Conclusion
The nature of the chemical interaction and glass formation in the As2S3-TlInTe2 system was studied by a complex method of physicochemical analysis: differential thermal, X-ray phase, microstructural, as well as the determination of density and microhardness, a state diagram was constructed. built. It is established that the state diagram of the system is quasi-binary of the eu-tectic type. In the system at room temperature, solid solutions based on As2S3 reach up to 1.5 mol %, and those based on TlInTe2 up to -7 mol %. The a-phase and p-phase form a eutectic between themselves, the composition of which corresponds to 15 mol % TlInTe2 and melts at 260°C. Under normal conditions, glass formation based on As2S3 continues up to 20 mol %TlInTe2. For solid solutions (TlInTe2)1-x(As2S3)x (x=0.02; 0.03; 0.05) the temperature dependence of electrical conductivity was studied.
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