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The densities of xBi2O3䡠(100ⴚx)B2O3 binary melts (x ⴝ 0 –100 The objectives of this research were (i) to measure the density
mol%) have been measured systematically in the temperature of Bi2O3–B2O3 binary melts in the temperature range 973–1373 K,
range of 973 to 1373 K using the Archimedean double-bob (ii) to calculate some properties that can be derived from the
method. In addition, the molar volume and coefficient of density, such as the molar volume and the coefficient of volume
volume expansion have been determined from these density expansion, and (iii) to investigate the compositional and temper-
measurements. The density of melts in the Bi2O3–B2O3 binary ature dependency of these density-related properties.
system decreased with increasing temperature for all compo-
sitions, and increased with increasing Bi2O3 content. The
molar volume calculated at 1273 K showed a minimum at II. Experimental Procedure
around 20 –30 mol% Bi2O3. The deviation of molar volume (1) Preparation of Sample for Measurement
from ideality and the partial molar volumes of B2O3 and Bi2O3
single-component melts were calculated, and the relationships The batches of samples were prepared by mixing the appropri-
between these properties and Bi2O3 content were investigated. ate amounts of reagent-grade Bi2O3 and B2O3 needed to obtain the
The ⌬(MV) (deviation of molar volume from ideality) was required compositions. The batch of each composition was melted
negative in the Bi2O3–B2O3 binary melts and showed a mini- in a Pt crucible for 30 min in air at 1073–1473 K, and then poured
mum of ⴚ7.5 cm3 (ⴚ17.3%) at 40 mol% Bi2O3 and 1273 K. into a graphite mold. The samples obtained this way were then
The PMV (partial molar volume) of the B2O3 melt decreased pulverized with an alumina mortar and pestle until the particle size
with increasing Bi2O3 content, up to 70 mol% Bi2O3, and was was reduced to less than 5 mm. The total amount of each sample
constant above 70 mol% Bi2O3. The PMV of the Bi2O3 melt was 0.3– 0.4 kg.
was constant up to 30 mol% B2O3 (considered from the
viewpoint of Bi2O3), and then decreased sharply with further (2) Measurement Method and Procedure
addition of B2O3. The coefficient of volume expansion in- The densities of the glass melts were measured using the
creased sharply up to 20 mol% Bi2O3 and decreased with Archimedean double-bob method.8,9 The principle of the
further addition of Bi2O3 at 1273 K. From this result, it can be Archimedean double-bob method is to measure the buoyancy of
inferred that the temperature-induced structural changes tak- two platinum bobs with different volumes immersed in the glass
ing place in the melts are greatest at 20 mol% Bi2O3. melt. The buoyancy (W1) against the volume (V1) of the first
(large) bob immersed in the glass melt is determined by the
following equation:
I. Introduction
W 1 ⫽ V 1 ⫺ 2R␥ cos /g ⫹ A (1)
1677
1678 Journal of the American Ceramic Society—Hwang et al. Vol. 87, No. 9
had been taken. Differences between the analysis results and the
target batch compositions were within about 1.0 mol% Bi2O3.
melts and this negative deviation can also be seen in other systems, Bi2O3 single-component melts were considered. The determina-
such as alkali silicates and the Na2O–B2O3 system.10,11 The tion of PMV is based on the Gibbs–Duhem relation.13 This
⌬(MV) shows a minimum value of ⫺7.5 cm3 (⫺17.3%) at 40 equation expresses the interrelation between the PMVs of all
mol% Bi2O3 and 1273 K. This minimum of 7.5 cm3 may components in a binary mixture. In this work, the PMVs of B2O3
correspond to the fact that there is a change in the structure, for and Bi2O3 single-component melts were obtained by the method of
example a rearrangement of the network at around 40 mol% intercepts13 using the smooth curve plot of MV versus Bi2O3
Bi2O3. This is supported by the work of Stone et al.12 illustrated in content in Fig. 4. The method of intercepts is useful for the rapid
Fig. 6, where the coordination number of boron in the crystalline determination of tangents to the smooth curve. The results for
polymorphs was considered. The BO4 fraction is the ratio of PMV are shown in Fig. 7 as a function of Bi2O3 content at 1273
four-coordinated boron to total boron in the crystalline polymorph. K. The PMV of the B2O3 melt decreased with increasing Bi2O3
Comparing the ⌬(MV) and the BO4 fraction in the Bi2O3–B2O3 content up to 70 mol% Bi2O3, and was constant over 70 mol%
binary system, the ⌬(MV) goes through a minimum near 40 mol% Bi2O3. This trend observed for the PMV of the B2O3 melt is
Bi2O3 content and the BO4 fraction goes through maximum near similar to that for GeO2 in the Li2O–GeO2 system.14 The PMV of
the same content of Bi2O3. Consequently, the ⌬(MV) increases in the Bi2O3 melt was constant up to 30 mol% B2O3 (when
negative magnitude as the BO4 fraction increases. This can be considered from the viewpoint of Bi2O3), and beyond this, it
explained by the fact that the ⌬(MV) was calculated using the decreased sharply on further addition of B2O3. Comparison of the
value of pure B2O3 melt, of which the basic structural unit is BO3. PMVs of B2O3 and Bi2O3 single-component melts shows that
That is to say, this inverse proportional relationship between the there is an inversion of the PMV at around 20 –30 mol% Bi2O3
⌬(MV) and the BO4 fraction suggests that the conversion of BO3 where the MV of Bi2O3–B2O3 binary melts shows a minimum.
to BO4 units results in the decrease in the molar volume. The From the above results, it can be inferred that the initial decrease
above suggestion agrees with the report by Riebling2 that the in the MV (up to 20 –30 mol% Bi2O3) may be mainly due to the
coordination number shift from 3.2 to 3.4 (␣ to  form of B2O3) decrease in the PMV of the B2O3 melt, and the increase in the MV
is accompanied by a 4.7 cm3/mol MV decrease at room tempera- over 20 to 30 mol% Bi2O3 may be due to the increase in the PMV
ture. of the Bi2O3 melt. The PMV of the B2O3 melt decreases from 46.5
To obtain more information about the relationship between MV to 38.8 cm3 (⫺7.7 cm3) at 40 mol% Bi2O3, which is where the
and Bi2O3 content, the partial molar volumes (PMVs) of B2O3 and ⌬(MV) exhibited a minimum. Riebling10 reported that complete
Acknowledgments
The authors are grateful to Dr. Ken C. Mills of Imperial College, London, U.K.,
for valuable discussions and useful comments.
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