J. Am. Ceram. Soc.
, 87 [9] 1677–1682 (2004)
journal
Chawon Hwang,† Shigeru Fujino,*,‡,§ and Kenji Morinaga§
Department of Applied Science for Electronics and Materials and Department of Engineering Sciences for Electronics
and Materials, Kyushu University, 6-1, Kasuga, Fukuoka 816-8560, Japan
The densities of xBi2O3䡠(100ⴚx)B2O3 binary melts (x ⴝ 0 –100
mol%) have been measured systematically in the temperature
range of 973 to 1373 K using the Archimedean double-bob
method. In addition, the molar volume and coefficient of
volume expansion have been determined from these density
measurements. The density of melts in the Bi2O3–B2O3 binary
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
around 20 –30 mol% Bi2O3. The deviation of molar volume
from ideality and the partial molar volumes of B2O3 and Bi2O3
single-component melts were calculated, and the relationships
between these properties and Bi2O3 content were investigated.
The ⌬(MV) (deviation of molar volume from ideality) was
negative in the Bi2O3–B2O3 binary melts and showed a mini-
mum of ⴚ7.5 cm3 (ⴚ17.3%) at 40 mol% Bi2O3 and 1273 K.
The PMV (partial molar volume) of the B2O3 melt decreased
with increasing Bi2O3 content, up to 70 mol% Bi2O3, and was
constant above 70 mol% Bi2O3. The PMV of the Bi2O3 melt
was constant up to 30 mol% B2O3 (considered from the
viewpoint of Bi2O3), and then decreased sharply with further
addition of B2O3. The coefficient of volume expansion in-
creased sharply up to 20 mol% Bi2O3 and decreased with
further addition of Bi2O3 at 1273 K. From this result, it can be
inferred that the temperature-induced structural changes tak-
ing place in the melts are greatest at 20 mol% Bi2O3.
I. Introduction
T HE density of glass melt is a fundamental and important
property in industrial glass production, and is necessary for the
calculation of other properties, such as kinematic viscosity and
surface tension.1 In addition, important information concerning the
glass melt structure can be obtained from the molar volume and the
coefficient of volume expansion, which are calculated from the
density data. For these reasons, there are many reports on the
density of fundamental glass systems, such as alkali borates and
borogermanate.2,3 However, there is no report on the density of
Bi2O3–B2O3 binary melts.
Bi2O3-containing glasses have been studied for their possible
use in optical devices, because of both their high refractive index
and third-order nonlinear optical susceptibility.4,5 Furthermore,
because of the recent regulations concerning the utilization of
PbO,6 bismuth-containing systems have attracted attention as
possible candidates for Pb-free glass, because of their considerable
low thermal properties.7
C. Jantzen—contributing editor
Manuscript No. 10757. Received December 23, 2003; approved April 26, 2004.
*Member, American Ceramic Society.
†
Department of Applied Science for Electronics and Materials.
‡
Author to whom correspondence should be addressed. e-mail: fujino@asem.
kyushu-u.ac.jp.
§
Department of Engineering Sciences for Electronics and Materials.
1677
Density of Bi2O3–B2O3 Binary Melts
The objectives of this research were (i) to measure the density
of Bi2O3–B2O3 binary melts in the temperature range 973–1373 K,
(ii) to calculate some properties that can be derived from the
density, such as the molar volume and the coefficient of volume
expansion, and (iii) to investigate the compositional and temper-
ature dependency of these density-related properties.
II. Experimental Procedure
(1) Preparation of Sample for Measurement
The batches of samples were prepared by mixing the appropri-
ate amounts of reagent-grade Bi2O3 and B2O3 needed to obtain the
required compositions. The batch of each composition was melted
in a Pt crucible for 30 min in air at 1073–1473 K, and then poured
into a graphite mold. The samples obtained this way were then
pulverized with an alumina mortar and pestle until the particle size
was reduced to less than 5 mm. The total amount of each sample
was 0.3– 0.4 kg.
(2) Measurement Method and Procedure
The densities of the glass melts were measured using the
Archimedean double-bob method.8,9 The principle of the
Archimedean double-bob method is to measure the buoyancy of
two platinum bobs with different volumes immersed in the glass
melt. The buoyancy (W1) against the volume (V1) of the first
(large) bob immersed in the glass melt is determined by the
following equation:
W 1 ⫽ V 1 ␳ ⫺ 2␲R␥ cos ␪/g ⫹ A (1)
where W is the buoyancy of the bob immersed in the test liquid
(10⫺3 kg), V is the volume of the bob immersed in the test liquid
(10⫺6 m3), ␳ is the density of the test liquid (103 kg/m3), R is the
radius of the suspending wire (10⫺3 m), ␥ is the surface tension of
the test liquid (10⫺3 N/m), ␪ is the contact angle between the
suspending wire and the test liquid (degrees), g is the acceleration
of gravity (m/s2), and A is the constant that is related to the
adhesion and convection of air (10⫺3 kg).
The buoyancy (W2) against the volume (V2) of the second
(small) bob immersed in the glass melt is determined by the same
equation.
W 2 ⫽ V 2 ␳ ⫺ 2␲R␥ cos ␪/g ⫹ A (2)
From Eqs. (1) and (2), the density of glass melt can be
expressed by the following equation:
␳ ⫽ 共W 1 ⫺ W 2 兲/共V 1 ⫺ V 2 兲 (3)
Because the same suspension wire is used for each buoyancy
measurement, the effects of surface tension, adhesion, and con-
vection on the suspension wire are identical, and can be elimi-
nated. The volume of each bob at the measuring temperature was
calculated from the equation
V⬘ ⫽ V共1 ⫹ 3␣⌬T兲 (4)
where V⬘ is the volume of the bob at the measuring temperature, V
is the volume of the bob at room temperature, ␣ is the linear
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.

III. Results and Discussion

(1) Density of Bi2O3–B2O3 Binary Melts
The densities of xBi2O3䡠(100⫺x)B2O3 binary melts (x ⫽ 0 –100
mol %) were measured systematically. The density of each
composition is shown as a function of temperature in Fig. 2 and
Table I. The density of Bi2O3–B2O3 binary systems decreased
linearly with increasing temperature for all compositions, and this
is the general tendency in glass melts. In addition, the density to
temperature slope showed an increase with increasing Bi2O3
content. The densities of the present melts in the Bi2O3–B2O3
binary systems at 1273 K are shown in Fig. 3 as a function of
Bi2O3 content. The density increased with increasing Bi2O3
content, showing a positive deviation from the ideality that would
be expected from the densities of B2O3 and Bi2O3 single-
component melts. In the alkali borate and germanate systems, the
densities go through a maximum,3,8 but no maximum depending
on composition was observed for the density of Bi2O3–B2O3
binary melts.
Fig. 1. Experimental apparatus of density measurement.
(2) Molar Volume of Bi2O3–B2O3 Binary Melts
Since the density is strongly dependent on the molar weight, the
temperature expansion coefficient of Pt, and ⌬T is the temperature molar volume (MV), which is more sensitive to a change in
difference between the measuring temperature and room temper- structure than the density, was calculated using the following
ature. equation:
The volume of each bob at room temperature was determined
by measuring the buoyancy of each bob in distilled water, of which MV ⫽ ni䡠Mi/␳ (5)
the density is known, at room temperature. The overall error of this
method was estimated to be within ⫾1.0% of the density value (for where ni and Mi are the mole fraction and the molar weight of
the error and reproducibility of the measurement). component i, respectively. The MVs of Bi2O3–B2O3 binary system
The experimental apparatus for the determination of density is melts at 1273 K are shown in Fig. 4 as a function of Bi2O3 content.
shown in Fig. 1. The apparatus consists of three main parts: an At 1273 K, the MV showed a minimum at around 20 –30 mol%
electronic balance, an electric furnace, and a controller. The Bi2O3. The initial decrease in the MV may be related to the fact
electronic balance was modified to permit the Pt bobs to hang from that the added cations (Bi3⫹) can be accommodated in the
its arm, and it could weigh to within ⫾0.1 mg. The electrical interstitial space of the B2O3 network. Based on the assumption
furnace was equipped with SiC heating elements and alumina that the mixture of Bi2O3 and B2O3 single-component melts would
boards, and was designed to permit adjustable centering. A Pt–Rh form an ideal solution, the deviation of molar volume (⌬(MV))
13 wt% thermocouple was used to regulate the temperature of the from the ideality (additivity) at 1273 K was calculated using the
furnace within ⫾1 K while density measurements were being MV values of Bi2O3 and B2O3 single-component melts as shown
made. The temperature of the sample was measured using an in Fig. 5. The ⌬(MV) was negative for the Bi2O3–B2O3 binary
additional thermocouple, inserted through the hole of an alumina
tube, which was almost in contact with the Pt–Rh 20 wt% crucible
containing the sample (Fig. 1).
The straight-walled Pt–Rh 20 wt% crucible (diameter 40 mm
and height 40 mm) containing the sample was placed on an
alumina pedestal and the sample was remelted by increasing the
temperature up to the highest measuring temperature. The sample
was sustained at the highest temperature for 1 h before measure-
ment. After the remelting of the sample, the Pt bobs were
suspended from the balance by a Pt–Rh 13 wt% wire of 0.25 mm
diameter and the alumina pedestal was raised until the bottom of
the bob was in contact with the surface of the molten sample. After
contact was established, the furnace was slowly raised further,
until the bob reached a depth of 20 mm below the surface of the
molten sample. The height of the alumina pedestal was adjustable
to 1 mm by a laboratory jack and an axis micro-adjuster. The
buoyancy of each bob was measured at 10 time intervals without
taking the bob out of melt, and the mean value was taken as the
buoyancy value of each bob.
In general, the first determination of the density was made at the
highest temperature; this was carefully selected to be as low as
possible, to prevent any compositional change due to volatiliza-
tion. Subsequent measurements were made at 50 K intervals
during the cooling cycle until the molten samples were either too
viscous to yield reliable values or until crystallization occurred.
The temperature range of the measurements in this work was 973 Fig. 2. Density of each composition in xBi2O3–(100⫺x)B2O3 melts (x ⫽
to 1373 K. Changes in the composition of the samples were 0 –100 mol %). The symbol x is the content of Bi2O3 in each composition.
checked by X-ray fluorescence analysis after the measurements The straight line was fitted to data by means of least squares.
September 2004 Density of Bi2O3–B2O3 Binary Melts 1679

Table I. Properties Related to Density (␳) of Bi2O3–B2O3 Binary Melts

Bi2O3 Density, ␳ (⫻103 kg/m3), at temperature (K)
content MV† at
(mol%) 973 1023 1073 1123 1173 1223 1273 1323 1373 1273 K ␤‡

0 - - - 1.522 1.513 1.506 1.498 1.492 1.486 46.5 10.8

10 - - 2.466 2.454 2.437 2.426 2.411 2.400 2.393 45.3 11.8
20 - 3.719 3.668 3.633 3.582 3.548 3.515 3.476 3.438 42.4 22.5
30 - 4.730 4.664 4.599 4.555 4.505 4.459 4.418 4.379 42.3 20.8
40 - 5.523 5.462 5.405 5.370 5.316 5.275 5.231 5.181 43.2 16.4
50 6.271 6.206 6.163 6.109 6.063 6.011 5.966 5.919 5.866 44.9 16.0
60 6.823 6.771 6.719 6.662 6.609 6.565 6.516 6.471 6.426 47.2 15.0
70 7.305 7.249 7.181 7.134 7.088 7.045 7.000 6.962 6.935 49.6 12.8
80 - 7.745 7.698 7.647 7.595 7.550 7.499 7.461 7.419 51.6 13.1
90 - 8.102 8.050 8.002 7.957 7.905 7.863 7.826 7.782 54.2 11.8
100 - - - 8.303 8.261 8.216 8.164 8.112 8.062 57.1 11.3
†
The units of molar volume (MV) and coefficient of volume expansion (␤) are 10⫺6 m3 䡠 mol⫺1 and 10⫺5 K⫺1, respectively. ‡The range of temperature from which the volume
expansion coefficient was calculated is 1123 to 1373 K.

melts and this negative deviation can also be seen in other systems,
such as alkali silicates and the Na2O–B2O3 system.10,11 The
⌬(MV) shows a minimum value of ⫺7.5 cm3 (⫺17.3%) at 40
mol% Bi2O3 and 1273 K. This minimum of 7.5 cm3 may
correspond to the fact that there is a change in the structure, for
example a rearrangement of the network at around 40 mol%
Bi2O3. This is supported by the work of Stone et al.12 illustrated in
Fig. 6, where the coordination number of boron in the crystalline
polymorphs was considered. The BO4 fraction is the ratio of
four-coordinated boron to total boron in the crystalline polymorph.
Comparing the ⌬(MV) and the BO4 fraction in the Bi2O3–B2O3
binary system, the ⌬(MV) goes through a minimum near 40 mol%
Bi2O3 content and the BO4 fraction goes through maximum near
the same content of Bi2O3. Consequently, the ⌬(MV) increases in
negative magnitude as the BO4 fraction increases. This can be
explained by the fact that the ⌬(MV) was calculated using the
value of pure B2O3 melt, of which the basic structural unit is BO3.
That is to say, this inverse proportional relationship between the
⌬(MV) and the BO4 fraction suggests that the conversion of BO3
to BO4 units results in the decrease in the molar volume. The
above suggestion agrees with the report by Riebling2 that the
coordination number shift from 3.2 to 3.4 (␣ to ␤ form of B2O3)
is accompanied by a 4.7 cm3/mol MV decrease at room tempera-
ture.
To obtain more information about the relationship between MV
and Bi2O3 content, the partial molar volumes (PMVs) of B2O3 and
Bi2O3 single-component melts were considered. The determina-
tion of PMV is based on the Gibbs–Duhem relation.13 This
equation expresses the interrelation between the PMVs of all
components in a binary mixture. In this work, the PMVs of B2O3
and Bi2O3 single-component melts were obtained by the method of
intercepts13 using the smooth curve plot of MV versus Bi2O3
content in Fig. 4. The method of intercepts is useful for the rapid
determination of tangents to the smooth curve. The results for
PMV are shown in Fig. 7 as a function of Bi2O3 content at 1273
K. The PMV of the B2O3 melt decreased with increasing Bi2O3
content up to 70 mol% Bi2O3, and was constant over 70 mol%
Bi2O3. This trend observed for the PMV of the B2O3 melt is
similar to that for GeO2 in the Li2O–GeO2 system.14 The PMV of
the Bi2O3 melt was constant up to 30 mol% B2O3 (when
considered from the viewpoint of Bi2O3), and beyond this, it
decreased sharply on further addition of B2O3. Comparison of the
PMVs of B2O3 and Bi2O3 single-component melts shows that
there is an inversion of the PMV at around 20 –30 mol% Bi2O3
where the MV of Bi2O3–B2O3 binary melts shows a minimum.
From the above results, it can be inferred that the initial decrease
in the MV (up to 20 –30 mol% Bi2O3) may be mainly due to the
decrease in the PMV of the B2O3 melt, and the increase in the MV
over 20 to 30 mol% Bi2O3 may be due to the increase in the PMV
of the Bi2O3 melt. The PMV of the B2O3 melt decreases from 46.5
to 38.8 cm3 (⫺7.7 cm3) at 40 mol% Bi2O3, which is where the
⌬(MV) exhibited a minimum. Riebling10 reported that complete

Fig. 4. Molar volume of Bi2O3–B2O3 binary melts at 1273 K. The solid

Fig. 3. Density of Bi2O3–B2O3 binary melts at 1273 K. The dotted line line was fitted to data by least squares and the dotted line shows the ideal
shows the ideal density. molar volume.
1680 Journal of the American Ceramic Society—Hwang et al.
Fig. 5. Deviation of molar volume from ideality at 1273 K.
conversion from BO3 to BO4 units may result in a volume decrease
of 20 –24 cm3 in pure crystalline B2O3. According to his report, the
decrease (⫺7.7 cm3) in the PMV of the B2O3 melt at 40 mol%
Bi2O3 suggests that about 35% of the total boron has a BO4
structural unit at 40 mol% Bi2O3 and 1273 K. This approximately
agrees with the BO4 fraction (⬇40%) present at around the same
content of Bi2O3 at room temperature in the crystalline state, as
shown in Fig. 6. Considering this fact and the suggestion that the
coordination changes from BO3 units to BO4 units at high
temperatures in alkali borates,15 it can be inferred that the volume
decrease in the PMV of the B2O3 melt up to 40 mol% Bi2O3 may
be mainly due to the coordination change from BO3 to BO4 units.
The decrease in the PMV of B2O3 at Bi2O3 contents over 40 mol%
may be due to depolymerization of the B2O3 network at Bi2O3
contents above this value. As regards the depolymerization of the
B2O3 network by the addition of Bi2O3, it is suggested that the
network of B2O3 would be completely decomposed to [BO33⫺] at
about 70 mol% Bi2O3, based on the following discussion. The
number of O2⫺ ions required for the complete decomposition of
the B2O3 network to [BO33⫺] is [3 ⫻ mole fraction of B2O3]. If
the Bi2O3 is completely ionized, 1 mol of Bi2O3 can create 3 mol
of O2⫺ ions. The ionic character of Bi–O bonding can be
determined by the electronegativity difference between Bi (1.9)
Fig. 6. BO4 fraction in crystalline polymorphs. The BO4 fraction in
crystalline polymorphs was referred from the report by Stone et al.12
Vol. 87, No. 9
Fig. 7. Partial molar volume of B2O3 and Bi2O3 at 1273 K.
and O (3.5) according to Pauling’s theory.15 This electronegativity
difference of 1.6 corresponds to an ionic character of 40%. Thus,
the number of O2⫺ ions created by the addition of Bi2O3 is [3 ⫻
0.4 ⫻ mole fraction of Bi2O3]. Therefore, the Bi2O3 content at
which complete decomposition of the B2O3 network to [BO33⫺]
occurs can be calculated by the following equation, if the mole
fraction of Bi2O3 is x:
3共1 ⫺ x兲 ⫽ 3 ⫻ 0.4x (6)
x ⫽ 0.71
Consequently, it is suggested that the B2O3 network would be
decomposed completely to [BO33⫺] at about 70 mol% Bi2O3, and
this suggestion can account for the constant PMV value obtained
for the B2O3 melt over 70 mol% Bi2O3.
(3) Coefficient of Volume Expansion of Bi2O3–B2O3 Binary
Melts
The coefficient of volume expansion (␤) can be calculated from
the densities at two temperatures by the following equation:
␤⫽ 冉 ␳1 ⫺ ␳2
␳2 冊冉 1
T2 ⫺ T1 冊 (7)
where ␳1 and ␳2 are the densities and T1 and T2 are the
corresponding temperatures. The ␤ values for the Bi2O3–B2O3
binary melts and glass7 are shown in Fig. 8 as a function of Bi2O3
content. The ␤ values of the melts increased sharply up to 20 mol%
Bi2O3, and then decreased with further addition of Bi2O3. On the
other hand, an approximate ␤ of solid-state glass (⬇3␣, ␣ is the
coefficient of linear expansion) increased linearly with increasing
Bi2O3 content. The magnitude of ␤ for the melts is 4 to 10 times
larger than for the solid-state glass. Since ␤ is calculated using the
densities at two different temperatures, ␤ corresponds to the extent
of change (slope) in the MV with increasing temperature. As
regards the change in MV of the melts with the change in
temperature, it has been reported that the displacement in structure
is the dominant term rather than the vibration and rotation terms,
by a factor of about 10.16 Considering that the maximum ␤ occurs
at 20 mol% Bi2O3, it can be inferred that the temperature-induced
structural change of the melts goes through a maximum at the
same content of Bi2O3. The extent of structural change with
increasing temperature can also be seen in the ⌬(MV) at each
temperature, as shown in Fig. 9. The absolute magnitude of ⌬(MV)
September 2004 Density of Bi2O3–B2O3 Binary Melts
Fig. 8. Coefficient of volume expansion in glass and melts.
decreases with increasing temperature and the extent of change in
⌬(MV) is the largest at 20 mol% Bi2O3.
In addition, the decrease in the absolute magnitude of ⌬(MV)
with increasing temperature indicates that the structure of the melt
undergoes a change as the temperature increases. In the previous
discussion on the ⌬(MV) at 1273 K (Fig. 5), it was suggested that
the increase in the absolute magnitude of ⌬(MV) may be mainly
due to the conversion of BO3 to BO4 by the change in composition.
Considering this suggestion, the decrease in the absolute magni-
tude of ⌬(MV) with increasing temperature suggests that the
conversion of BO3 units to BO4 units in the Bi2O3–B2O3 binary
melts is temperature dependent.
IV. Conclusions
(1) Density of Bi2O3–B2O3 Binary Melts
(1) The density of the Bi2O3–B2O3 binary system decreased
with increasing temperature for all compositions.
Fig. 9. Deviation of molar volume from ideality at various temperatures.
1681
(2) The density increased with increasing Bi2O3 content and
showed a positive deviation from the ideality that would be
expected from the densities of B2O3 and Bi2O3 single-component
melts.
(2) Molar Volume (MV) of Bi2O3–B2O3 Binary Melts
(1) The MV showed a minimum at around 20 –30 mol%
Bi2O3 at 1273 K.
(2) The ⌬(MV) (deviation of molar volume from ideality) was
negative for melts along the Bi2O3–B2O3 binary and showed a
minimum of ⫺7.5 cm3 (⫺17.3%) at 40 mol% Bi2O3 and 1273 K.
The inverse proportional relationship between the ⌬(MV) and the
BO4 fraction suggests that the conversion of BO3 units to BO4
units results in the decrease in the MV.
(3) The PMV (partial molar volume) of the B2O3 melt
decreased with increasing Bi2O3 content up to 70 mol% Bi2O3 and
was constant over 70 mol% Bi2O3. By comparing the PMVs of
B2O3 and Bi2O3 single-component melts, it can be inferred that the
initial decrease in the MV of Bi2O3–B2O3 binary melts up to 20 to
30 mol% Bi2O3 may be due to the decrease in the PMV of the
B2O3 melt and the increase in the MV over 20 to 30 mol% Bi2O3
may be due to the increase in the PMV of the Bi2O3 melt.
Considering this fact and the suggestion that the coordination in
alkali borates changes from BO3 units to BO4 units at high
temperatures, it can be inferred that the decrease in the PMV of
B2O3 liquid up to 40 mol% Bi2O3 may be mainly due to the
coordination change from BO3 to BO4 units and that the decrease
in the PMV of the B2O3 melt over 40 mol% Bi2O3 may be due to
depolymerization of the B2O3 network above 40 mol% Bi2O3.
Considering the depolymerization of the B2O3 network on the
addition of Bi2O3, it is suggested that the B2O3 network would be
decomposed completely to [BO33⫺] at about 70 mol% Bi2O3, and
this suggestion can account for the constant value of the PMV of
the B2O3 melt over 70 mol% Bi2O3.
(3) Coefficient of Volume Expansion (␤) of Bi2O3–B2O3
Binary Melts
␤ increased sharply up to 20 mol% Bi2O3 and decreased on
further addition of Bi2O3 at 1273 K. Considering that the maxi-
mum in ␤ occurs at 20 mol% Bi2O3, it can be inferred that the
temperature-induced structural change of melts goes through a
maximum at this Bi2O3 content. In addition, the decrease in the
absolute magnitude of ⌬(MV) with increasing temperature indi-
cates that the conversion of BO3 units to BO4 units in the
Bi2O3–B2O3 binary melts is temperature dependent.
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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