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AZ9RBAYCAN KiMYA JURNALI № 4 2016
85
UDC 546(657+681+661)22
STUDY OF CHEMICAL INTERACTION IN SYSTEM (Ga2S3)0.3i5(Nd2S3)0.685 (e2)-(Ga2S3)o.33(EuS)o.67 (es) I.B.Bakhtiyarli, R.J.Gurbanova, R.I.Kerimov, E.N.Ismayilova, U.A.Hasanova,
F.M.Mammadova
M.Nagiyev Institute of Catalysis and Inorganic Chemistry, NAS of Azerbaijan
[email protected] Received 04.06.2016
The paper deals with the study of ternary system Nd2S3-Ga2S3-EuS. This research work was conducted in the direction of section (Ga2S3)0.315(Nd2S3)0.685 (e2)-(Ga2S3)o.33(EuS)o.67 (e5). The samples were studied using complex methods of physical-chemical analysis (differential thermal analysis (DTA), X-ray phase, microstructural analysis (MSA), measurement of microhardness and determination of density. According to obtained results phase diagram of section was plotted. It was determined that section (Ga2S3)0315(Nd2S3)0685 (e2)-(Ga2S3)o.33(EuS)o.67 (e5) is non-quasibinary section of ternary system Nd2S3-Ga2S3-EuS. Two primary crystallization curves are liquidus of section. Soliduses are three non-variant eutectic equilibria. Since this section passes through the field of four subordinate triangular in projection of liquidus, the phase diagram consists of four parts.
Keywords: system, phase equilibrium, synthesis, physico-chemical analysis.
Introduction
In a raw of promising semi-conducting substances lanthanide chalcogenides hold a unique place among the most required other substances which meet demands of modern technology. These demands are shown in optics, electronics, military industry, cosmic fields and so on. From this point studying complex ternary systems in the presence of lanthanide chalco-genides is expedient and is a topical problem.
The present paper the study of chemical interaction in ^283)0.315(^283)0.685 (e2>-Ga2S3)0.33(EuS)0.67 (e5) covers research of Nd2S3-Ga2S3-EuS triple system and continuation of our previous work. In earlier works several quasi-binary and non-quasibinary sections were studied [1-3].
In the paper research results of
e2[(Ga2S3)0.3i5(Nd2S3)0.685]-e5[(Ga2S3)0.33(EuS)0.67]
section which combines e2 and e5 double eutectics in Nd2S3-Ga2S3 and Ga2S3-EuS double systems which are the sides of Nd2S3-Ga2S3-EuS triple system were given.
In this research the main aim is to clarify phase equilibrium and chemical interaction between initial components in Nd2S3-Ga2S3-EuS triple system in the direction of e2-e5 section. The samples were synthesized from Nd2S3, Ga2S3, EuS - components. Nd2S3 and EuS are high pure plant products. Ga2S3 was synthesized from GL-00 Ga element and B-6 special pure sulfur.
Experimental part
Samples were synthesized in cooled quartz ampoules (l0-3 mm pressure) in the range of 1000-1500 K. Alloy was kept 8 hours by increasing the temperature of synthesis furnace gradually up to approximate melting temperature. Then temperature was decreased up to 900 K. Further cooling was up to room temperature in turned off furnace. Synthesized samples were kept at 900 K and 150 hours in fumes to homogenize them. Researches of all samples were conducted using complex methods of physico-chemical analysis. We may show differential-thermal analysis, X-ray phase analysis, microstructural analysis, measurement of microfirmness and density.
DTA was conducted in STA 429 CD NETZSCH synchronous thermal analysis device. X-ray phase analysis was conducted on DRON-2 diffractometer (CuK-radiation and Ni filter).
Microhardness was determined on PMT-3 microscope (20 g), MSA was observed on MiM microscope. Density was determined by picnometric method.
To determine (Ga2S3)0.315(Nd2S3)0.685 (e2)-(Ga2S3)0 33(EuS)067 (e5) section 17 samples were synthesized. These samples were studied by physico-chemical analysis methods.
Results of DTA shows that the processes in the system are complex and three and four effects are observed in thermograms (Table).
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Results of measurement of DTA, microhardness and density of section (Ga2S3)o.3i5(Nd2S3)o.685 (e2)-(Ga2S3)o.33(EuS)o.67 (e5)
Composition, mol Thermal effects, K Microhardness, mPa Density, g/sm3
0 CJ i-Л 00 ю о СО (N £ 1Л гя О П) m £ Ü и) г-ю о =3 & m гя о П) m (N Л о 3 8 m =3 к гч Ö а ад о"!4? £ ^ ад ö ~ m M (U ds £ JS 13 ад ^ й У ^ -и ад £ ~ а? 7 S, 3e S a <N ^ m 11 (E d )4 e, ^ % w> iS Д 0 О ST <N £ £ (ÜL ^ ад EuS
100 - 1425 - - - - - 4.72
95 5 1165, 1415,1450 2700 4240 not measured - - 4.72
90 10 1165,1385, 1470 2710 4245 2960 - - 4.73
80 20 1165, 1295, 1500 2710 4245 2960 - - 4.74
75 25 1165, 1200, 1515 2710 4240 2960 - - 4.74
70 30 1165, 1210, 1525 not measured 4240 2960 - - 4.75
60 40 1260, 1550 - 4250 2950 - - 4.77
50 50 1290, 1560 - 4250 2950 - - 4.78
40 60 1170, 1295,1585 - 4240 2960 - - 4.78
35 65 1170, 1245, 1590 - 4240 2960 2305 - 4.79
30 70 1170,1300,1600 - 4250 not measured 2310 - 4.79
25 75 1385, 1595 - 4250 - 2310 not measured 4.80
20 80 1320,1360,1535 - 4250 - 2310 not measured 4.80
15 85 1320,1450 - 4245 - 2305 - 4.80
10 90 1320,1360,1390 - 4245 - 2305 - 4.81
5 95 1320,1350,1395 - 4250 - 2305 - 4.81
- 100 1390 - - - - - 4.81
By microstructural analysis different phases were observed in all polished samples and in each sample three phases are clearly seen. During measurement of microhardness in alloys the following values were obtained. For light gray phase a(Nd6Ga10/3S14) microhardness is (27002710) mPa; for gray, brown phase 0(Nd2S3)i-x(EuNd2S3)x microhardness is (42404250) mPa; for dark phase a(EuNdGa3S7) microhardness is (2950-2960) mPa; for light phase y'(EuGa2S4) microhardness is (2305-2310) mPa.
X-ray phase analysis complicates these results. Results of density determination varies in the range of (4.72-4.81) and toluene was used as a filler.
Results were generalized and phase diagram of (Ga2S3)0.3i5(Nd2S3)0.685 (e2)-(Ga2S3)0 33(EuS)067 (e5) section was plotted (Figure).
As Figure shows (Ga2S3)o.3i5(Nd2S3)o.685 (e2) and (Ga2S3)o.33(EuS)o.67 (es) sections are non-quasibinary sections of triple system Nd2S3-Ga2S3-EuS and character of interaction is complex. Section passes through the field of 4 subordinate triangular in projection of liquidus surface of triple systems:
Nd2S3-Nd6Gaio/3Si4-EuNdGa3 S7; Nd2S3-EuNdGa3 S7-EuNd2S4 EuNd2S4-EuNdGa3S7-EuGa2S4 EuGa2S4-EuNd2S4-EuS and intersects two primary crystallization field [e(Nd2S3)i-x(EuNd2S4)J and EuS.
Liquidus of the section consists of two angles which characterizes initial crystallization of e(Nd2S3)1-x(EuNd2S3)x and EuS and they intersect in the point (58 mol.% EuS) where section intersects monovariant curve.
АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 4 2016
I.B.BAKHTIYARLI et al.
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^ cs <N m ^ ^t m ^
mol. %
Phase diagram of section (Ga2S3)0.315(Nd2S3)0.685 (e2)-(Ga2S3)0.33(EuS)0.67 te).
Since (Ga2S3)0.315(Nd2S3)0.685 (e2)-(Ga2S3)0 33(EuS)067 (e5) passes through field of 4 subordinate triple systems in projection of triple system, it is clearly seen that phase diagram consists of 4 parts. In the first part of section in subordinate triple triangular Nd6Ga10/3S14-EuNdGa3S7-Nd2S3 the crystallization ends in triple non-variant eutectic equilibrium [E6] at 1165 K.
Double crystallization processes occurs below (0+a') and (0+a).
Below solidus isotherm in solid phase mixture of a'+0+a phases were obtained.
In the second part interaction has simplier character, here solid phase consists of mixture of components 0(Nd2S3)1-x(EuNd2S4)x and EuNdGa3S7.
In the third part in the field where section intersects EuNdGa3S7-EuNd2S4-EuGa2S4 triangular primary crystallization ends at 1170 K temperature in E4 triple eutectics.
In this part below liquidus curve in average field (m+a+0 and m+0+y) double crystallization fields are observed and in solid phase y+0+a mixture was obtained.
The last part is the part where the section passes through [EuNd2S4-EuNdGa3S7-EuS] triangular. Here liquidus curve consists of primary crystallization of EuS and 0.
This crystallization ends by 4 phase triple eutectic equilibrium isotherm. Double crystallization occurs between 0+y and y+EuS phases.
Non-variant equilibria in section (Ga2S3)0.315(Nd2S3)0.685 (e2)-(Ga2S3)0.33(EuS)0.67 (e5) ends by the following reaction: E6 - m^a'(Nd6Ga!0/3S14) + 0(Nd2S3)1_x(EuNd2S4)x + a(EuNdGa3S7) .... (1165 K),
E4 - m-^y'(EuGa2S4) + 0(Nd2S3)1_x(EuNd2S4)x + a(EuNdGa3S7) .... (1170 K), E5 - m-o-0(Nd2S3)1_x(EuNd2S4)x + y'(EuGa2S4) + EuS .... (1320 K).
Results
Thus, according to results of complex methods of physico-chemical analysis phase diagram of (Ga2S3)0.315(Nd2S3)0.685 (e2)-(Ga2S3)033(EuS)067 (e5) was plotted. It was determined that the section is a non-quasibinary section of triple Nd2S3-Ga2S3-EuS system.
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STUDY OF CHEMICAL INTERACTION IN SYSTEM
References
1. Бахтиярлы И.Б., Керимов Р.И., Курбанова Р.Д., Ахмедова Н.Р. Система EuNdGa3S7-EuGa4S7 // Журн. неорг. химии. 2014. Т. 59. № 5. С. 694-697.
2. Керимов Р.И. Фазовые равновесия в тройных системах Ln2S3-Ga2S3-EuS (Ln-La, Nd) и физико-химические свойства новых фаз. Дисс. ...докт. философ. по химии. 2011. 165 с.
(Ga2S3)o.3is(Nd2S3)o.68s (e2)-(Ga2S3)o.33(EuS)o.67 (es) SiSTEMlNDO QAR§ILIQLI KlMYOVl TOSlRlN TODQlQi
LB.Baxtiyarli, R.C.Qurbanova, RLKarimov, E.N.ismayilova, U.A.Has3nova, Ф.М.Мэmmэdova
Nd2S3-Ga2S3-EuS uglu sisteminin fiziki-kimyavi tadqiqi naticalari verilmi§dir. Bu tadqiqat (Ga2S3)0)315(Nd2S3)0>685 (e2)-(Ga2S3)0,33(EuS)0,67 (e5) kasiyi istiqamatinda apanlm§dir. Hazirlanmi§ numunalar fiziki-kimyavi analizin kompleks metodlari (differensial termiki analis (DTA), rentgenfaza analizi (RFA), mikroqurulu§ analis (MQA), mikrobarkliyin olgulmasi va sixligin tayini) ila tadqiq edilmi§dir. Alinan naticalara asaslanaraq kasiyin faza diaqrami qurulmu§dur. Muayyan edilmi§dir ki, (Ga2S3)0.315(Nd2S3)0.685 (e2) -(Ga2S3)0,33(EuS)0,67 (e5) kasiyi Nd2S3-Ga2S3-EuS uglu sistemin qeyri-kvazibinar kasiyidir. Kasiyin likvidusunun iki ilkin kristalla§ma ayrisi ta§kil edir. Soliduslar isa ug nonvariant uglu evtektik tarazliq muayyan edilmi§dir. Bu kasik uglu sistemin likvidus sathinin proyeksiyasinda dord tabelikda olan ugbucagin sahasindan kegdiyindan qurulan faza diaqrami dord hissadan ibaratdir.
Agar sozlar: sistem, faza tarazligi, sintez, fiziki-kimyavi analiz.
ИССЛЕДОВАНИЕ ХИМИЧЕСКОГО ВЗАИМОДЕЙСТВИЯ В СИСТЕМЕ
(Ga2S3)o.3i5(Nd2S3)o.685 (e2)-(Ga2S3)o.33(EuS)o.67 (es)
И.Б.Бахтиярлы, Р.Дж.Курбанова, Р.И.Керимов, Э.Н.Исмаилова, У.А.Гасанова, Ф.М.Мамедова
Приведены результаты физико-химического исследования тройной системы Nd2S3-Ga2S3-EuS. Приготовленные образцы были изучены комплексными методами физико-химического анализа: дифференциально-термическим (ДТА), рентгенофазовыми (РФА), микроструктурным (МСА), измерением микротвердости и определением плотности. По совокупности полученных данных построена фазовая диаграмма разреза (Ga2S3)0.315(Nd2S3)0685(e2)-(Ga2S3)0.33(EuS)0 67 (е5). Было установлено, что разрез является не квазибинарным сечением тройной системы Nd2S3-Ga2S3-EuS и проходит через поля четырех подчиненных треугольников, поэтому фазовая диаграмма его состоит из четырех частей.
Ключевые слова: система, фазовое равновесие, синтез, физико-химический анализ.
3. Бахтиярлы И.Б., Курбанова Р.Д., Керимов Р.И., Мамедова Ф.М., Абдуллаева А.С., Исмайлова Э.Н. Фазовая диаграмма разреза (Ga2S3)o.75(EuS)o.25-(EuGa2S4)o.86(EuNd2S4)o.14 // XIX Междунар. конф. "Физика прочности и пластичности материалов". 8-11 июня 2015. Самара. Россия. Сб. тезисов. С. 224.
АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 4 2016
