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AZERBAIJAN CHEMICAL JOURNAL № 2 2019
UDC 546.72:546.815.2
QUASI-BINARY SECTIONS AND TRIANGULATION OF FeS-Ga2S3-PbS
QUASI-TERNARY SYSTEM
U.A.Hasanova, Sh.H.Mammadov, O.M.Aliyev, I.B.Bakhtiyarly
M.Nagiyev Institute of Catalysis and Inorganic Chemistry, NAS of Azerbaijan
[email protected] Received 15.11.2018
According to the results of differential thermal, X-ray phase and microstructural analyses the character of interaction in Fe-Ga2S3-PbS quasi-ternary system was studied and triangulated. It was determined that FeS-Ga2S3-PbS quasi-ternary system triangulates with eutectic type FeS-PbGa2S4, FeS-Pb2Ga2S5 and FeGa2S4-PbGa2S4 quasi-binary sections to pseudo-ternary systems. In this systems a new quasi-ternary phase has not been found.
Keywords: quasi-ternary system, antiferromagnets, quasi-binary sections, eutectics, triangulates.
https://doi.org/10.32737/0005-2531-2019-2-58-61
Production and study of perspective photosensitive luminescent and laser materials containing magnetic ions are of special importance. At present particularly, FeGa2S4 and Fe2Ga2S5 compounds obtained with the participation of iron monosulphide as Heisenberg's antiferromagnets attracts attention of scientists [1-4]. In these compounds the reason of antiferromag-netism is related to their crystal structure [1]. All iron ions in crystal structure are located in octahedral and have +2 oxidation degree. But in similar compounds iron ions exhibit variable oxidation degree. From this point study of FeS-Ga2S3-PbS quasi-ternary system is very relevant for searching a perspective material.
Side FeS-Ga2S3, FeS-PbS, PbS-Ga2S3 systems of FeS-Ga2S3-PbS quasi-ternary system as well as primary components found in binary systems (Fe-S, Pb-S, Ga-S) have been sufficiently studied in literature [5-18].
FeS-PbS system was studied by many authors [5, 6, 8-12] and its state diagram was plotted. State diagram of the system is quasi-binary, of an eutectic type, but in state diagrams the system differs for the composition and temperature of eutectics, as well as absence or presence of FeS phase transitions. Therefore, the system was reviewed and its state diagrams by us were constructed [18]. In our work we used troilite modification of FeS [18]. Coordinates of eutectic point: 45 mol % PbS and 7=1123 K. Limited solubility regions are formed on the
basis of components. a-FeS^P-FeS^SFeS phase transition is of eutectoid type, occurs at 410 and 560 K, correspondingly.
FeS-Ga2S3 system is a quasi-binary section of Fe-Ga-S ternary system and characterized by the formation of FeGa2S4 and Fe2Ga2S5 compounds. It should be noted that according to the authors [17] both compounds melt incongru-ently [16] and according to our researches FeGa2S4 melts congruently at 1418 K, Fe2Ga2S5 melts at 1043 K by decomposing. FeGa2S4 compound has a and P modifications: a-FeGa2S4 crystallizes in hexagonal syngony (a=3.654, c=12.056 A, Space group P3mi), P-FeGa2S4 crystallizes in rhombic syngony (a=12.89, b=7.51, c=6.09A) [17]. Fe2Ga2S5 compound forms 2H (hexagonal, a=3.67, c=30.0A, Space group P63/mmc) and 3R (rhombohedral, a=3.67, c=45.0A, Space group R3m) polytypes.
PbS-Ga2S3 system is quasi-binary and characterized by the formation of PbGa2S4 and Pb2Ga2S5 compounds melting congruently at 1163 and 1063 K correspondingly [14, 15]. PbGa2S4 and Pb2Ga2S5 are in an eutectic equilibrium between each other and primary components; Ga2S3-PbGa2S4 eutectics melts at 1133, PbGa2S4-Pb2Ga2S5 eutectics melts at 1043, Pb2Ga2S5-PbS eutectics melts at 1033 K.
Experimental part
Using pure elements (GL-000 gallium, "hp" 99.9999% pure sulphur, 99.9% pure iron obtained from decomposition of carbonyl and
99.99% pure lead) alloys were synthesized from FeS, Ga2S3 and PbS. Samples were melted for 8-10 hours in a vacuumed quartz ampoule. Depending on the composition of alloy maximum temperature of the synthesis was 1250-1400 K. During the process mechanical vibration was made for full mixing of an alloy. After keeping alloys at maximum temperatures for 30-45 minutes ampoule was cooled to 800-900 K with electrical furnace and was homogenized for a month in this mode. As a result of the interaction compact samples suitable for physical and chemical researches were obtained. FeS-Ga2S3-PbS quasi-ternary system was studied according to the complex results of physico-chemical analyses (DTA, X-ray phase, MSA). Thermal analysis was carried out on "Jupiter" STA440 F3 of "NET2SCH" (thermopair chromel-chromel alu-mel, heating rate 100/min sample Al2O3), X-ray phase analysis was carried out on D2 Pilsener X-ray diffractometer of Bruker (Cu^-radiation, Ni-filter), microstructural analysis was carried out on MIM-7 microscope, microhardness of alloys was measured on PMT-3.
Results and discussion
FeS-PbGa2S4 system is quasi-binary, there is an eutectic equilibrium between components (Figure 1). Liquidus of the system consists of primary crystallization curves of P'-solid solutions based on 5-FeS and PbGa2S4 and
mol %
Fig.1. Phase diagram of the system FeS-PbGa2S4.
cross at eutectic point relevant to 35 mol% of FeS at 875 K. a-FeS~ P-FeS~ 5-FeS phase transitions occur at 405 and 550 K correspondingly. The first phase transition is practically observed in all alloys, but P-FeS^-5-FeS phase transition occurs only in 0-20 mol% of PbGa2S4 concentration range.
On the basis of PbGa2S4 at room temperature solubility limit is restricted in the range of 85-100 mol% PbGa2S4. P'-solid solutions crystallize in rhombic syngony in the type of EuGa2S4 (a=20.44-20.32, 6=20.64-20.55, c=12.09-12.02Â, Z=32, Space group Fddd, ¿=4.94-5.15 g/sm3, H=2250-2500 MPa.
FeS-Pb2Ga2S5 system is a quasi-binary section of quasi-ternary system and is of eutectic type (Figure 2).
Coordinates of an eutectic point: 40 mol % FeS and T=850 K. On the basis of FeS solubility was not practically determined, but on the basis of Pb2Ga2S5 20 mol % of solid solution with rhombic structure is formed.
FeGa2S4-PbGa2S4 system is quasi-binary section of quasi-ternary system, its state diagram is of simple eutectic type. It should be noted that according to the results of X-ray analysis in primary researches the formation of FePbGa4S8 quaternary compound at 1:1 ratio of components was given in [19], but this did not prove its value in further studies.
mol %
Fig.2. Phase diagram of the system FeS-Pb2Ga2S5 .
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U.A.HASANOVA et al.
Ga2S3
Fig.3. The triangulation of the FeS-Ga2S3-PbS quasi-triple system: 1 - FeGa2S4-Ga2S3-PbGa2S4, 2 -FeS-FeGa2S4-PbGa2S4, 3 - FeS-PbGa2S4-Pb2Ga2S5,4 - FeS-Pb2Ga2S5-PbS..
It was determined that in the system eutectic equilibrium occurs. Coordinates of an eutectic point are 45 mol % FeGa2S4, 7=950 K. a-FeGa2S4^- P-FeGa2S4 phase transition is of eutectoid type and occurs at 920 K. On the basis of a-FeGa2S4 5 mol % of solid solution is formed, but on the basis of PbGa2S4 10 mol % of solid solution with rhombic structure is formed.
As it is seen all 3 sections are quasi-binary, triangulates FeS-Ga2S3-PbS quasi-ternary system to 4 subsystems (Figure 3).
Triangulation of quasi-ternary system can be used in future in projection of liquidus surface of FeS-Ga2S3-PbS quasi-ternary system and for determination of the composition of alloys to grow monocrystals of the compounds FeS, FeGa2S4 and Ga2S3 which melt at high temperatures.
References
1. Nakafsuji S., Tonomura H. Onuma K., Nambu Y., Sakai O., Maeno Y., Macaluso R.T., Chan J.Y. Spin disorder and order in quasi-2D triangular Heisenberg antiferromagnets: Comparative study of FeGa2S4, Fe2Ga2S5 and NiGa2S4. Phys. Rev. Letters. 2007. V. 99. No 1-4. P. 157-203.
2. Rushchanskii K, Z., Haeuseler H., Bercha D.M. Band structure calculations on the layered compounds FeGa2S4 and NiGa2S4. J. Phys. Chem. Solids. 2002. V. 63. No 11. P. 2019-2028.
3. Myoung, Bo Ra Lim, Jung Tae Kim, Chul Sung. Investigation of magnetic properties on spin-
ordering effects of FeGa2S4 and FeIn2S4. J. Magn. and Magn. Mater. 2017. V. 438. P. 121-125.
4. Dalmas de Reotier P., Yaouanc A., MacLaughlin D.E., Songrui Zhao. Evidence for an exotic magnetic transition in the triangular spin system FeGa2S4. J. Phys. Rev. B. 2012. V. 85. Issue. 14. P. 140407.1-140407.5.
5. Kubaschewcki O. Phase diagrams of binary iron alloys. Ed. ASM International 1993. P. 364-366.
6. Walder P., Pelton A.D. Thermodinamic modeling of the FeS-PbS system. J. Phase Equilib. and Diffus. 2005. V. 26. No 1. P. 23-38.
7. Zhilang X.U., Lin Suwen, Xu Fengxin. Sono-chemical Synthesis of PbS nanorods. J. Alloys and Comp. 2008. V. 457. No 1-2. P. 9-11.
8. Sharma R., Lin J., Chang Y.A. Thermodynamic analysis of the FeS system and calculation of the phase diagram. Metal. Trans. 1987. 18 B. No 1. P. 237-244.
9. Skala R., Cisarova I., Drobek M. Inversion twinning in troilite. Am. Mineral. 2006. V. 91. P. 917-920.
10. Eric H. Timucin M. Activities in Cu2S-FeS-PbS melts at 12000C. Metallurgical Trans. B. 1981. V. 12 B. P. 493-500.
11. Hannu Johto, Pekka Taskinen. Stabilities of phase in the Cu2S-FeS-PbS system. J. Minerals, Metals and Mater. Soc. 2012. P. 205-212.
12. Johto H., Tasinen P. Experimental research and thermodynamic model of the FeS-PbS system. Proc. EMC 2011. Düsseldorf. June 26-29. 2011. (Düsseldorf, Germany, DG. BM.2011), P. 1127-1136.
13. Samsonov G.V., Drozdova S.V. Sulfidy. M.: Metallurgiia, 1972. 304 s.
14. Par A.Chilouet, Mazurier A., Guittard M. Systeme Ga2S3- PbS. Diagramme de Phase, etude crystallographique. Mater. Res. Bull. 1979. V.14. P. 1119-1124.
15. Badikov D., Doroshenko M., Fintisova A., Shevyr-diaeva G. Novyi nizkofononnyi kristall tiogallata svintca v kachestve matritcy dlia lazerov srednego IK-diapazona. Fotonika. 2008. № 4. S. 14-17.
16. Allazov M.R. Issledovanie sistemy FeS-GaS-S. BDU-nin xabarlari. Tabiat elmlari seriyasi. 2009. № 3. S. 42-46.
17. Pardo M-P., Dogguy-Smiri L., Flahant J. Nguyen Huy Dung. Systeme Ga2S3 -FeS, diaqramme de fhase, etude crystallographiqe. Mater. Res. Bull. 1981. V. 16. P. 1375-1384.
18. Gasanova U.A. Sintez i issledovanie tverdykh rastvorov (FeS)1-x(PbS)x. Tr. XVIII Mezhdun. nauchno-prakt. konf. "Perspektivy razvitiia nauki i obrazovaniia". Moskva, 2017. S. 170-172.
19. Hasanova Ü.A., Mammadov §.H., Oliyev Ö.M. FeS-FePbGa4S8-FeGa2S4 alt sisteminin tadqiqi. Akad. H.B. Abdullayevin 100 illiyina hasr olun-mu§ beynalxalq konfrans va maktab. Baki. 2018. S. 105-106.
FeS -Ga2S3-PbS KVAZГОCLU SiSTEMiNiN KVAZiвiNAR KЭSiKLЭRl УЭ TRlANQULYASiYASI
U.A.Hэsэnova, §.H.Mэmmэdov, б.M.Эliyev, ЬВ.ВэхйуагИ
Differensial-termiki, rentgenfaza, mikroqurulu§ analizlэrin nэticэlэrinэ эsasэn FeS-Ga2S3-PbS kyazшglu sistemindэ qar§lllqll tэsirin xarakteri ага§йшИт1§ уэ trianquliyasiya edilmi§dir. МИЭУУЭП ейПт^йи- ki, FeS-Ga2S3-PbS kyazшglu sistemi evtektik tipli FeS-PbGa2S4, FeS-Pb2Ga2S5 vэ FeGa2S4-PbGa2S4 kvazibinar kэsiklэri ilэ dбrd рБеуйоидШ sistemэ trianqulyasiya edir. Sistemdэ ует dбrdlu faza a§kar edilmэmi§dir
Адаг sдzlэr: kvaziuglu sistem, antiferromaqmtlэr, ^а21Ьтаг кэ^чкЬг, ву(вШка, Мапди1уа&1уа.
КВАЗИБИНАРНЫЕ СЕЧЕНИЯ И ТРИАНГУЛЯЦИЯ КВАЗИТРОЙНОЙ СИСТЕМЫ FeS ^а283-РЬ8
У.А.Гасанова, Ш.Г. Мамедов, О.М.Алиев, И.Б.Бахтиярлы
По результатам дифференциально-термического, рентгенофазового и микроструктурного анализов изучен характер взаимодействия в квазитройной системе FeS-Ga2S3-PbS и осуществлена триангуляция. Установлено, что квазитройная система FeS-Ga2S3-PbS триангулируется по квазибинарным сечениям FeS-PbGa2S4, FeS-Pb2Ga2S5 и FeGa2S4-PbGa2S4 на четыре псевдотройные системы. В системе не наблюдается образование новой четверной фазы.
Ключевые слова: квазитройная система, антиферромагнетики, квазибинарные сечения, эвтектика, триангуляция.
