ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2008, Vol. 53, No. 8, pp. 1297–1299. © Pleiades Publishing, Ltd.

, 2008.
Original Russian Text © Yu.F. Kargin, S.N. Ivicheva, L.I. Shvorneva, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 8, pp. 1391–1393.

PHYSICOCHEMICAL ANALYSIS
OF INORGANIC SYSTEMS

Phase Relations in the MgO–Bi2O3–Bi2O3 System

Yu. F. Kargin, S. N. Ivicheva, and L. I. Shvorneva
Institute of Physicochemical Problems of Ceramic Materials, Russian Academy of Sciences,
Ozernaya ul. 48, Moscow, 119361 Russia
e-mail: yu.kargin@rambler.ru
Received September 03, 2007

Abstract—Phase relations in the MgO–Bi2O3–B2O3 system have been investigated by X-ray powder diffrac-
tion analysis and DTA. No ternary compounds have been found in the system. Quasi-binary sections have been
the 600°ë determined and isothermal section of the system has been constructed.
DOI: 10.1134/S003602360808024X

Synthesis and investigation of crystals of borates
such as lithium, cesium, and barium borates and com-
plex borates LnCa4O(BO3)3, K2Al2B2O7, etc., are driven
by prospects of their use as laser and nonlinear optical
materials [1, 2] and for detection of slow neutrons
(Li6LnB3O9 single crystals (Ln = Gd, Eu, Y) [3]). The
the 6s2 lone pair of the bismuth atom promotes realiza-
tion of noncentrosymmetrical crystalline phases in
mixed bismuth-containing oxides and manifestation of
ferroelectric, piezoelectric, and nonlinear optical prop-
erties by them (for example, BiB3O6 [4]).
The goal of this work is to find and synthesize new
ternary compounds in systems containing oxides of bis-
muth, boron, and alkali-earth metals. We previously
studied phase relations in the systems M2O–Bi2O3–B2O3
(M = Li, K, Na), MO–Bi2O3–B2O3 (M = Ba, Sr), and
Al2O3–Bi2O3–B2O3 [5–10]. Below, we present the
results of investigation of subsolidus phase equilibria in
the MgO–Bi2O3–B2O3 system.
We revealed no data on phase equilibria in the
MgO–Bi2O3–B2O3 system in the literature. Data on the
phase equilibria of the bordering systems MgO–Bi2O3,
SrO–B2O3, and Bi2O3–B2O3 are presented in [11–21]. In
steady-state equilibrium, five compounds are formed in
the Bi2O3–B2O3 system. These are 12Bi2O3 : B2O3 (melts
incongruently at 632°ë; or at 628°ë), 2Bi2O3 : 1B2O3,
3Bi2O3 : 5B2O3, 1Bi2O3 : 3B2O3, and 1Bi2O3 : 4B2O3 (melt
congruently at 675, 722, 708, and 715°ë, respectively)
[11]. The 1Bi2O3 : 4B2O3 compound undergoes poly-
morphic transformation at 696°ë. In the Bi2O3–B2O3
system, immiscible liquids exist above 709°ë in the
region 81–100 mol % B2O3. Cooling of overheated
melt leads to crystallization of metastable phases of
compositions 1Bi2O3 : 1B2O3 [13–15] and 5Bi2O3 :
3B2O3 [14].
The MgO–B2O3 system [16, 17] is characterized by
the presence of three compounds; 3MgO : 1B2O3 melts
congruently at 1410°ë; and 2MgO : 1B2O3 and 1MgO :
2B2O3 melt incongruently at 1146 and 995°ë, respec-
tively.
In the Bi2O3–MgO system, no intermediate com-
pounds are formed [18–20].
Phase equilibria in the MgO–Bi2O3–B2O3 system
were investigated by X-ray powder diffraction analysis
(Shimadzu diffractometer, CuKα radiation, λ = 1.54060 Å)
and DTA (STA-409 Netzch, heating rate of 5–12 K/min,
and sample weight of ~100 mg. As the starting compo-
nents, we used Bi2O3 of os.-ch. 13-3 grade, H3BO3 of
os.-ch. 12-3 grade, and MgO of reagent grade. Interac-
tion between the components was investigated using
solid-phase reactions at 600–750°ë (the subsolidus
region). Alloys were synthesized in a muffle furnace in
air with intermediate grindings. The compositions of
the samples and synthetic conditions are presented in a
table.
The experimental data on the phase composition of
synthesized samples (table) allow us to represent the
isothermal section in the studied region of the system at
600°ë by the following three-phase triangles (figure):
MgO + α-Bi2O3 + Mg3B2O6, α-Bi2O3 + Mg3B2O6 +
Bi24B2O39, Bi24B2O39 + Bi4B2O9 + Mg3B2O6, Bi4B2O9 +
Mg3B2O6 + Mg2B2O5, Bi4B2O9 + Mg2B2O5 + Bi3B5O12,
Bi3B5O12 + Mg2B2O5 + MgB4O7, Bi3B5O12 + BiB3O6 +
MgB4O7, BiB3O6 + MgB4O7 + Bi2B8O15, and B2O3 +
MgB4O7 + Bi2B8O15.
It follows from the figure and table that no new ter-
nary compounds are formed in the MgO–Bi2O3–B2O3
system.
X-ray powder diffraction data, the composition of
which corresponding to known double borates of rare-
earth elements and barium Ba3Ln(BO3)3 (Ln = Dy, Ho,

1297
1298 KARGIN et al.

Phase composition of the samples of the MgO–Bi2O3–B2O3 system

Concentrations of components, mol % Synthetic conditions
Sample no. Phase composition
MgO Bi2O3 B2O3 T, °C τ, days
1 50.0 16.7 33.3 665 6 Bi4B2O9 + Mg2B2O5
2 25.0 25.0 50.0 700 9 Bi3B5O12 + Bi4B2O9 + Mg2B2O5
3 25.0 12.5 62.5 700 9 Bi3B5O12 + Mg2B2O5 + MgB4O7
4 21.0 14.0 65.0 650 7 Bi3B5O12 + MgB4O7
5 20.0 10.0 70.0 700 6 BiB3O6 + MgB4O7
6 20.0 8.03 72.0 700 6 Bi2B8O15 + MgB4O7
7 40.0 15.0 45.0 650 6 Bi3B5O12 + Mg2B2O5
8 65.0 9.0 26.0 650 9 BO4 + B18O46 + B2O4
9 65.0 13.0 22.0 750 9 α-Bi2O3 + Mg3B2O6
10 50.0 25.0 25.0 650 9 Bi24B2O39 + Bi4B2O9 + Mg3B2O6
11 50.0 5.0 45.0 700 7 Bi3B5O12 + Mg2B2O5 + MgB4O7
12 67.0 22.0 11.0 650 6 Bi4B2O9 + Mg2B2O5 + Mg3B2O6
13 70.0 20.0 10.0 650 6 Bi3B5O12 + Mg2B2O5 + MgB4O7
14 71.0 5.0 24.0 650 6 Bi24B2O39 + Mg3B2O6
15 73.0 7.0 20.0 600 6 Bi24B2O39 + Bi4B2O9 + Mg3B2O6

Tm, Yb, Lu; space group P63cm [21]), Ba3Ln2(BO3)4 [24–26]), BaBiBO4 [27], and borates of rare-earth ele-
(Ln = Nd, La, Pr; space group Pnma [22, 23]), and ments and magnesium LnMgB5O10 [28], indicate that
BaLnB9O16 (Ln = Y, La, Gd, Nd; space group P2/m) they are not single phases; i.e., no assumed magnesium

MgO
0 1.0

0.2 0.8

14
on
cti

9
fra

ol

0.4 8 12 0.6
ef
le

rac
mo

tio
n

10 1 11
0.6 0.4
7
13
2 3 0.2
0.8 15 4
5 6

1.0 0
Bi2O3 0 0.2 0.4 0.6 0.8 1.0 B2O2
mole fraction
Fig. 1. Triangles of coexisting phases in the MgO–Bi2O3–B2O3 system at 600°ë (point numbers correspond to sample numbers in
the table).

RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 53 No. 8 2008

 PHASE RELATIONS IN THE MgO–Bi2O3–Bi2O3 SYSTEM
bismuth borates are formed under the conditions of the
solid-phase synthesis.
ACKNOWLEDGMENTS
This work was supported by the Russian Foundation
for Basic Research, project no. 05-03-32506.
REFERENCES
1. A. A. Blistanov, Crystals in Quantum and Nonlinear
Optics (MISIS, Moscow, 2000) [in Russian].
2. T. Sasaki, Y. Mori, M. Yoshimura, et al., Mater. Sci. Eng.
R 30, 1 (2000).
3. B. V. Grinev, M. F. Dubovik, and A. V. Tolmachev, Opti-
cal Single Crystals of Complex Oxide Compounds (Inst.
for Single Crystals, Kharkov, 2002) [in Russian].
4. H. Hellwig, J. Libertz, and L. Bohaty, Solid State Comm.
109, 249 (1999).
5. Yu. F. Kargin and A. V. Egorysheva, Zh. Neorg. Khim.
47 (12), 2038 (2002) [Russ. J. Inorg. Chem. 12, 1874
(2002)].
6. A. V. Egorysheva, Yu. F. Kargin, and V. M. Skorikov, Zh.
Neorg. Khim. 50 (11), 1851 (2005) [Russ. J. Inorg.
Chem. 50 (11), 1733 (2005)].
7. Yu. F. Kargin and A. V. Egorysheva, Zh. Neorg. Khim.
50 (12), 2068 (2005) [Russ. J. Inorg. Chem. 50 (12),
1942 (2005)].
8. A. V. Egorysheva and Yu. F. Kargin, Zh. Neorg. Khim. 51
(7), 1185 (2006) [Russ. J. Inorg. Chem. 51 (7), 1106
(2006)].
9. Yu. F. Kargin, S. N. Ivicheva, M. G. Komova, and
V. A. Krut’ko, Zh. Neorg. Khim. 53 (3), 474 (2008)
[Russ. J. Inorg. Chem. 53 (3), 425 (2008)].
10. A. V. Egorysheva, A. S. Kanishcheva, Yu. F. Kargin, et al.,
Zh. Neorg. Khim. 52 (1), 63 (2007) [Russ. J. Inorg.
Chem. 52 (1), 58 (2007)].
11. E. M. Levin and C. L. McDaniel, J. Am. Ceram. Soc. 45
(8), 355 (1962).
12. Yu. F. Kargin and A. V. Egorysheva, Neorg. Mater. 34
(7), 859 (1998).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 53
1299
13. M. J. Pottier, Bull. Soc. Chim. Belg. 83 (7–8), 235
(1974).
14. Yu. F. Kargin, V. P. Zhereb, and A. V. Egorysheva, Zh.
Neorg. Khim. 47 (8), 1362 (2002) [Russ. J. Inorg. Chem.
47 (8), 1240 (2002)].
15. P. Becker and R. Frohlich, Z. Naturforsch. 59b, 256
(2004).
16. Phase Diagrams of Silicate Systems: A Handbook,
Vol. 1: Binary Systems, Ed. by N.A. Toropov, V.P. Barza-
kovskii, V.V Lapin., N.N Kurtseva (Nauka, Leningrad,
1969) [in Russian].
17. Phase Diagrams of Refractory Oxides: A Handbook,
Vol. 5, Part 1: Binary Systems (Nauka, Leningrad, 1985)
[in Russian].
18. A. V. Shevchuk, V. M. Skorikov, A. S. Kalutskov, and
Yu. F. Kargin, in Physicochemical Studies of Solution
Equilibria (Yaroslavl, 1984), Vol. 205, p. 55 [in Rus-
sian].
19. A. V. Shevchuk, Extended Abstract of Candidate’s Dis-
sertation in Chemistry (Inst. of General and Inorganic
Chem., Moscow, 1987).
20. Phase Diagrams of Refractory Oxide Systems: A Hand-
book, Vol. 6: Systems of Refractory High-Temperature
Superconductors (Nauka, St. Petersburg, 1997) [in Rus-
sian].
21. A. B. Ilyukhin and B. F. Dzhurinskii, Zh. Neorg. Khim.
38 (10), 1625 (1993).
22. J. F. Yan and H. Y.-P. Hong, Mater. Res. Bull. 22, 1347
(1987).
23. T. N. Hamaganova, V. K. Trunov, B. F. Dzhurinskii, and
V. A. Efremov, Kristallografiya 35, 856 (1990).
24. F. Tian, C. Fouassier, and P. Hagenmuller, Mater. Res.
Bull. 22 (3), 389 (1987).
25. Y. Ji, J. Liang, S. Xie, and X. Wu, J. Cryst. Growth 137,
521 (1994).
26. X. Z. Li, X. L. Chen, J. K. Jian, et al., J. Alloys Comp.
365, 277 (2004).
27. J. Barbier, N. Penin, A. Denoyer, and L. M. D. Cran-
swick, Solid State Sci. 7 (9), 1055 (2004).
28. B. Saubat, M. Vlasse, and C. Fouassier, J. Solid State
Chem. 34, 271 (1980).
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