Thermochimica Acta 496 (2009) 93–96

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Wetting and surface tension of bismate glass melt夽

Seung-Bo Shim, Dong-Sun Kim, Seongjin Hwang, Hyungsun Kim ∗
School of Materials Engineering, Inha University, 253 Younghyun-dong, Incheon 402-751, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Lead oxide glass frits are used widely in the electronics industry for low-temperature firing. On
Received 28 July 2008 the other hand, one of the low-sintering and low-melting lead-free glass systems available, the bis-
Received in revised form 22 June 2009 mate glass system, is considered to be an alternative to lead oxide glass. In order to extend the
Accepted 14 July 2009
applications of Bi2 O3 glasses, this study examined the thermophysical properties of low-melting
Available online 21 July 2009
Bi2 O3 –B2 O3 –ZnO–BaO–Al2 O3 –SiO2 glass frits with various ZnO/B2 O3 ratios. The fundamental thermal
properties, such as glass transition temperature and softening point, were examined by differential ther-
Keywords:
mal analysis and a glass softening point determination system. The wetting angles, viscosities and surface
Glass frit
Surface tension
tension of the various bismate glasses on an alumina substrate were measured using hot-stage microscopy
Thermophysical property and the sessile drop method. These thermophysical properties will be helpful in understanding the work
Work of adhesion of adhesion and the liquid spread kinetics of glass frits.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction 50Bi2 O3 –50SiO2 (mol.%) [7], and xBi2 O3 –(1 − x)GeO2 [8]. However,
bismate glasses have been found to be unsatisfactory compared to
Electronic applications, such as information displays, multilayer commercial lead oxide glasses due to their different thermal and
ceramic capacitors, low-temperature co-fired ceramics, and solar physical characteristics [1].
cells, all require various types of glasses that are fired as frits. Such This study examined the surface tension of Bi2 O3 –B2 O3 –
devices are produced as a thick film using methods, such as screen ZnO–BaO–Al2 O3 –SiO2 glasses containing minor oxide components
printing, green-sheet lamination and die coating with pastes fol- as well as the effect of temperature on the work of adhesion of the
lowed by firing. The firing of pastes is generally performed in a Bi2 O3 glasses. The viscosities, surface tension, and wetting angles of
furnace, which involves the sintering and fusing of pastes. Thick Bi2 O3 –B2 O3 –ZnO–BaO–Al2 O3 –SiO2 frits with various component
films after firing often require good optical, electrical, thermal, or ratios (ZnO/B2 O3 = 0.67, 0.86 and 1.3) were measured using hot-
mechanical properties [1]. Indeed, the thermophysical properties of stage microscopy and the sessile drop method [2,9].
a frit, such as glass transition temperature, softening point, wetting
angle, viscosity, and surface tension, affect the work of adhesion 2. Experimental procedure
and the spread kinetics of the glass [2,3].
Lead oxide glass frits are used widely in low-temperature Bismate glass systems were prepared by mixing powders at var-
sintering and melting processes in the electronics industry. How- ious ZnO/B2 O3 ratios (0.67, 0.86 and 1.3) with Bi2 O3 , B2 O3 , ZnO,
ever, lead oxide glass systems should be replaced with lead-free BaO, Al2 O3 , and SiO2 (Aldrich, USA) with >99% of purity (Table 1).
glasses due to the environmental pollution. One of the low- The mixed batches were melted in an alumina crucible at 1200 ◦ C
sintering and low-melting lead-free glass systems, the bismate for 1 h and then quenched on a ribbon roll. During the first crush,
glass system, has been considered as an alternative to lead oxide the cullet was crushed manually using an agate mortar and pestle.
glasses. This is because bismate glasses have similar thermal and It was then sieved using a 140 mesh (<106 ␮m) and pulverized in
optical properties to lead oxide glasses [1,4]. The surface ten- a planetary mono-mill (Fritsch, Pulverisette-7, Germany). The glass
sion of Bi2 O3 -containing glass melts have been studied to extend transition temperature (Tg ) of each glass composition was deter-
their applications. The following binary systems have mainly mined by thermogravimetry-differential thermal analysis (TG-DTA,
been investigated: xBi2 O3 –(100 − x)B2 O3 (x = 0–100 mol.%) [5,6], Rigaku, Japan) at a heating rate of 10 ◦ C/min to 1200 ◦ C. The Little-
ton softening point (Ts ) was measured using a glass softening point
determination system (Orton, SP-3A, USA).
夽 This paper was presented at 8th Symposium of the Korean Society of Thermo-
The fusion behavior of the bismate glass frits was analyzed using
physical Properties held at POSTECH, Korea from April 24–25, 2008.
an automatic hot-stage microscope (HSM, Ajeon Co. Korea) [10,11].
∗ Corresponding author. Tel.: +82 2 860 7545; fax: +82 2 864 3730. The measurements were taken in air at a heating rate of 10 ◦ C/min.
E-mail address: [email protected] (H. Kim). The samples for these HSM measurements were made using a

0040-6031/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.tca.2009.07.005
94 S.-B. Shim et al. / Thermochimica Acta 496 (2009) 93–96

Table 1 Table 2
Compositions of the Bi2 O3 –B2 O3 –ZnO glass frits (in mol.%)a . Glass transition point (Tg ), Littleton softening point (Ts )a and half ball point (Th )b .

Samples Bi2 O3 B2 O3 ZnO Samples Tg (◦ C) Ts (◦ C) Th (◦ C)

ZnO/B2 O3 = 0.67 11 40 27 ZnO/B2 O3 = 0.67 502 558 700
ZnO/B2 O3 = 0.86 11 36 31 ZnO/B2 O3 = 0.86 494 547 684
ZnO/B2 O3 = 1.3 11 29 38 ZnO/B2 O3 = 1.3 484 537 675
a a
The summation of 10BaO, 4Al2 O3 , and 8SiO2 is 22 mol.% of the total composition. Littleton softening point (Ts ) is defined as the temperature at which the viscosity
of the glass is in the vicinity of log  = 7.6 (dPa s) [13].
b
Half ball point (Th ) is the temperature at which the sample forms a half shape
during the HSM analysis [14].

phase without crystallization up to a melting temperature for each

composition. The Tg , Ts , and Th values decreased with increasing
ZnO/B2 O3 ratio (0.67 → 0.86 → 1.3), (Table 2). The Tg , Ts , and Th
values are obviously related to the viscosity of the bismate glass
systems:  = 1013.3 dPa s at Tg ;  = 107.6 dPa s at Ts ;  = 104.6 dPa s at
Th .
The sintering and fusion reactions were divided into three stages
in terms of the change in pellet shape, which are the HSM samples
(Fig. 2). In the 1st stage (RT (537–558 ◦ C)), the pellet changed from
a square to a trapezoid shape and then to a square shape. The glass
particles that existed on the top of the pellet and heat energy first
reacted at the corner with the largest surface area. Therefore, it
Fig. 1. Sessile drop of solid–liquid–vapor system in equilibrium on a substrate [12].
appears that the corner of the pellet contracts rapidly to reduce the
surface energy. This process is related to the rearrangement and
hand press to compress the frits (<26 ␮m), which were contained contraction of the glass particles. The fusion of the glass actually
within a small cylindrical metal mold (about 3 mm × 3 mm). An alu- began after stage 1. The 2nd stage proceeded in the temperature
mina plate (5 mm × 5 mm × 0.7 mm) was used as the substrate. A range of (537–558 ◦ C) to (675–700 ◦ C). The pellet was eventually
computerized image analysis system automatically recorded and formed into a swollen sphere in the lateral direction and maintained
analyzed the sample geometry during heating. The wetting process its longitudinal height in the 2nd stage. The corners of the pellet
between the bismate glasses and alumina was measured using HSM first reacted, resulting in a rounded shape. This is known as the
to help understand the sintering and fusion behavior of the frits at softening point. The glass particles on the surface first melted due to
elevated temperatures. the fastest thermal conductivity from the outside. The internal solid
The surface tension for each composition of bismate frits melted phase changed gradually into a liquid phase with the continuous
on an alumina substrate was determined using the sessile drop supply of heat energy. Thus, the shape of the pellet changed into
method (Fig. 1). A drop with a wetting angle >90◦ was regarded as a an ellipsoid with an angle >90◦ . In the 3rd stage, the wetting angle
spheroidal-type drop. The surface tension of each sample was deter- of the molten glass was <90◦ . The molten glass spread over the
mined easily using the tables produced by Bashforth and Adams [9]. substrate due to viscous flow resulting from the high temperature
However, only the surface tension of droplets with wetting angles conditions.
>90◦ could be determined due to the limitations of the sessile drop The wetting starting temperature, the starting and ending
method [2]. temperatures of the 3rd stage, and the hemisphere temperature
decreased significantly with increasing ZnO/B2 O3 ratio. The wet-
3. Results and discussion ting angles of the frits in the temperature range, 570–700 ◦ C, were
recorded using the HSM measurements (Fig. 3). In the case of each
The bismate glass frits did not show any exothermic peaks composition, the end point of the 1st stage is related to the soften-
up to 900 ◦ C in the DTA curve, which indicates an amorphous ing point. Therefore, the lower temperature of the ending point of

Fig. 2. Schematic diagrams for the sintering and fusion reaction of Bi2 O3 –B2 O3 –ZnO frits on a substrate: (a) 1st stage, (b) 2nd stage, and (c) 3rd stage.
 S.-B. Shim et al. / Thermochimica Acta 496 (2009) 93–96 95

Fig. 5. Surface tensions of the Bi2 O3 –B2 O3 –ZnO glass frits on an alumina substrate
Fig. 3. Wetting angles of Bi2 O3 –B2 O3 –ZnO glass frits on an alumina substrate [15].
[15].

the 1st stage and the start point of the 3rd stage was induced by the 220 mN/m at more than 40 and 50 mol.% ZnO in the temperature
higher ZnO/B2 O3 ratio in the samples. range of 1050–1300 ◦ C [16]. However, the effect of the two compo-
The viscosity curves of the bismate glasses were determined nents (ZnO, B2 O3 ) from those studies cannot explain the change in
as a function of temperature to quantify the wetting behavior surface tension in our glass system.
of the glasses. The viscosity curves were calculated using the Previous studies reported that the surface tension of bismuth
Vogel–Fulcher–Tamman (VFT) equation: log  = A + B/(T − T0 ) [13]. silicate glass (50Bi2 O3 –50SiO2 , mol.%), and lead borosilicate glass
Fig. 4 shows the three constants in the VFT equation, A, B and T0 , (63PbO–25B2 O3 –12SiO2 , wt%) was 136–144 mN/m (in the range
for the glass frits. The viscosity of the melted glasses was estimated 1030–1060 ◦ C) [7] and 168–225 mN/m (in the range of 635–733 ◦ C)
from the HSM measurements based on the three known reference [17], respectively. The latter viscosity range is close to the present
points (Tg , Ts and Th ). The 2D images of the HSM and the viscosity results. As shown in Fig. 6, the temperature coefficient of the
values at elevated temperatures showed the expected variations in surface tension (d/dT) of the Bi2 O3 –B2 O3 –ZnO melt is positive
wetting behavior with composition ratios. The melting viscosity of (0.0011 × 10−3 N/m)/K, while the d/dT values of many glasses
the bismate glasses decreased with increasing ZnO/B2 O3 ratio. are negative [5]. According to Hwang et al. [5], the temperature
The surface tension of the bismate glass frits decreased slightly coefficient of the surface tension of a Bi2 O3 –B2 O3 binary mixture
with increasing ZnO/B2 O3 ratio (Fig. 5). In the Bi2 O3 –B2 O3 binary changed from positive to negative in the range of 30–80 mol.%
melts, pure Bi2 O3 and B2 O3 have surface tensions of 216.1 and Bi2 O3 : d/dT = 0.0367 × 10−3 N/m/K for 10Bi2 O3 –90B2 O3 and
84.8 mN/m, respectively, at 900 ◦ C [5]. Increasing the B2 O3 con- d/dT = −0.0193 × 10−3 N/m/K for 60Bi2 O3 –40B2 O3 . A similar tem-
tent decreases the surface tension of the binary melts significantly perature dependence of the surface tension was reported for
because B2 O3 has a parallel arrangement of triangular planes of xBi2 O3 –(1 − x)GeO2 [8]; d/dT changed from positive to negative
three-oxygen-coordinated BO3 at the melt surface. This leads to at x ≈ 0.38. The change in d/dT was explained by changes in the
a weak binding force perpendicular to the surface [5,13]. On the structural units, changes in the arrangement of the structural units,
other hand, regarding the effect of ZnO on the surface tension of the and changes in the surface concentrations of the constituents [5].
BaO–ZnO–P2 O5 melts, the surface tension decreased with increas- Future studies will examine the effect of temperature on the surface
ing ZnO content up to 30 mol.% ZnO. It showed a constant value of tension of glass systems.

Fig. 6. Temperature dependence of the surface tension for Bi2 O3 glasses

Fig. 4. Predicted viscosities of the Bi2 O3 –B2 O3 –ZnO frits from using the VFT equa- (38Bi2 O3 –62SiO2 [17], 10Bi2 O3 –90B2 O3 , 60Bi2 O3 –40B2 O3 [5], 40Bi2 O3 –60GeO2 ,
tion. 67Bi2 O3 –33GeO2 [8], 10Bi2 O3 –40B2 O3 –27ZnO).
96 S.-B. Shim et al. / Thermochimica Acta 496 (2009) 93–96

elevated temperatures. The surface tension of the bismate glass

frits decreased slightly with increasing ZnO/B2 O3 ratio. The
temperature coefficient of the surface tension (d/dT) of the
Bi2 O3 –B2 O3 –ZnO–BaO–Al2 O3 –SiO2 melt was positive. The work
of interfacial adhesion between the bismate glass systems and
alumina substrate decreased with increasing the ZnO/B2 O3 ratio.
Overall, knowledge of the fundamental thermophysical properties
of glass frits is important for predicting their work of adhesion and
surface tension.

Acknowledgements

This work is financially supported by the Ministry of Educa-

tion and Human Resources Development (MOE), the Ministry of
Commerce, Industry and Energy (MOCIE) and the Ministry of Labor
(MOLAB) through the fostering project of the Lab of Excellency.

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