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THE PHASE DIAGRAM OF T H E SYSTEM BISMUTH

OXIDE -FERRIC OXIDE

(UDC 542.92)

E. I. S p e r a n s k a y a , V. M. Skorikov, E. Ya. Rode,


a n d V A. T e r e k h o v a
N. S. Kurnakov Institute for General and Inorganic Chemistry, Academy of Sciences, USSR
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5,
pp. 908-906, May, 1965
Original article submitted July 22, 1964

For the system BizOa-FezO a we have the following information. Royen [1] made a roentgenographic study of
samples which he prepared by fusing the starting components, and showed that in the system BizOa-F%O 3,in the
region of BizO s concentration 45-100%, there formed two incongruently melting compounds: Bi2Oa.Fe20 a at 935 ~ and
2BizOa-Fe203 at 825 ~ Also, at 765 ~ because of splitting of a high temperature phase, there forms a compound with
the composition 15BizOs'F%O a. The author determined the structure for alt these compounds. In studies [2-6]
roentgenographic results were given for conditions of synthesis of the compounds BizO a. FezO a, BiaOa-2FezOa and their
structures, and also the results of study of some physical properties of these compounds. A brief survey of the'. chief
work in this system showed that the authors studied only special compositions of the system, preferably using roent-
genographic methods. Evidently because of this, there were various contradictions in the conclusions of the same
author or of different authors. Therefore we cannot construct from the existing data a phase diagram based on crys-
t a l l i z a t i o n processes. In connection with our studies of the stabilizing influence of different ions on the BizO a type
of l a t t i c e , we undertook the investigation of the system BizO3-FezO a to obtain the full p h y s i c o c h e m i c a l c h a r a c t e r -
istics of this system.

EXPERIMENTAL

The m a i n method of study was thermal analysis. Differential thermal analysis was carried out as follows :
samples of the same weight (2 g) were placed in a platinum or platinum-rhodium crucible with cover; the crucibles
were put on a c e r a m i c block. For the thermocouple we used Pt-PtP.h, one of whose junctions was grounded. The
recording system was a Kurnakov pyrometer. Uniformity of heating the oven (enclosed heating) of 4 - 8 ~ was
carried out with a potential regulator. The starting preparations were C. P. BizO a and Fe20 a, a n a l y t i c a l l y pure.

The heating curves of several mixtures of different compositions showed that reaction of the components takes
place below the temperature of polymorphic conversion of BizO a (730~ This agrees with the data of [2-5]~ There-
fore, the samples for study were prepared thus: the mixture, carefully mixed, was heated in several ways. The h e a t -
ing temperature differed depending on the field of composition. The temperature of the heat effect was noted from
the heating curve. To judge of the reproducibility of the process we obtained heating curves both for powdered
samples and for melts. In the m e l t e d samples the temperature of the heat effect was 5-10 ~ lower because of better
heat conductance of the samples, but the number of effects and their character agreed. The resulting thermographic
data are shown in the graph (figure). For comparison of the temperatures and heat effects of the thermogram,we
constructed a T a m m a n triangle and thus determined the field of the crystallization phase formed in the system.

It follows from the diagram (figure) that three compounds are formed in the system : BizOa'2FezO s, melts in-
congruently at 960 ~ BizOa 9FezO a, melts ineongruently at 930 ~ and, at 885 ~ BiFeOa, which has reversible transformation.
In the field of composition rich in BizOa there forms a compound with the presumed composition 20BizOa 9Fe20 a, m e l t i n g
fneongruently at 795 ~ At 785 ~there crystallizes a e u t e c t i c mixture of the low temperature form BiFeO a and the compound
20 BizOa 9FezOa. On the liquids diagram there is drawn a dotted line, since there is a small heat of melting. Determination
of the liquidus line, establishing the composition and structure of compounds rich in BizOa, and some further details will be
presented in another paper.

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DISCUSSION OF R E S U L T S

We will give a brief comparison of our results with those


' %% in the literature. Our thermogram for BiFeO3 in the case of equi-
1000 o ~% "~tO00"
960 , I librium state of the samples has three endothermal effects, like
the thermogram of [4], but our temperatures are 70 ~ lower res-
pectively. These temperatures are 825 ~ (reversible transforma-
900 - l ~ JSgO tion of BiFeOs);930 ~ (incongruent melting of BiFeOs); and 960 ~
(incongruent melting of Bi2Fe4Og), concordantly repeated in
~---~-,
. s 2 .sr..x,,,....T
~ ~ ~ .,~a ~" J
AauQ
samples on either side of the ordinates. On the other hand, Royen
800 ~:2~c~uu [1] did not find the temperature 960 ~ for fully comprehensible
I reasons. In the region of 50-66% Bi20 s concentration,fused s a m -
'l,/oe pies on cooling should undergo two p e r i t e c t i c reactions with
700 ~ ;oo
I small temperature interval (30~ In case of inequalities of the
I
I process,the samples should contain Fe2Os, d e t e c t i b l e roentgeno-
2"1 I:I I:2~ graphically. Royen also showed a temperature of 825 ~ for an in-
soo 1 [ I congruently melting compound 2Bi2Os.FezO~,which we did not
obtain; the temperature of 765 ~ (according to our results 785 ~)
,,,,[,,,,[,, .... ,,fro was taken by Royen for the formation from the solid state of a
FezOslO 20 30 #0 50 GO 70 80 9J SizOs
BisO s , Mole, % compound 15Bi2Os'Fe2Os; according to our data, this is a eutectic
temperature.
Phase diagram of the system Bi2Os-Fe~O3
from thermographic data. This work shows that interactions in the system Bi203-
Fe203 are of great interest, and at the same time are complex.
They are e s p e c i a l l y interesting, we believe, from the viewpoint of structure and properties shown by the compound
rich in Bi20 s.

SUMMARY

1. The system Bi2Oa-Fe20 s was studied by the method of differential thermal analysis and we have given the
phase diagram of the system.

2. The curve of the liquidus system consists of six crystallization branches: Fe203, Bi2Fe40 m o~- and 8-BiFeOa,
a compound of the assumed composition 20Bi203. F%O a, and Bi203.

3. BiFeO s has a reversible transformation at 825~ this ferrite melts incongruently at 930 ~

4. Bi2Fe409 also melts incongruently at 960 ~

5. At 785 ~ there crystallizes a eutectic mixture of the low temperature form of BiFeO a and the compound of
supposed composition Bi40Fe2Oss.

LITERATURE CITED

I, P. Royan and K. Swars, Angew. Chemic, 69, 779 (1957).


2. V. S. Filip'ev, M. P. Smolyaninov, E. G. Fesenko, and I. N. BeIyaev, Kristallografiya, 5, 623, 968 (1960).
3. A. I. Zaslavskii and A. G. Tupov, Dokl. AN SSSR, 135, 816 (1960).
4. S. A. Fedulov, Yu. N. Venevtsev, G. S. Zhdanov, and E. P. Smazhevskaya, Kristallografiya, 6, 795 (1961).
5. A. G. Tupov, I. E. Myl'ntkova, I. N. Pargenova, and V. A. Bykov, Fizika Tverdogo Tela, 6, 1-240 (1964).
6. Yu. N. Venevtsev, G. S. Zhdanov, Yu. E. Roginskaya, and S. A. Fedulov, Izv. AN SSSR, Ser. fiz., 28, No. 4,
683 (1964).

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