Journal of Non-Crystalline Solids 351 (2005) 3503–3507

www.elsevier.com/locate/jnoncrysol

Thermal properties and glass formation in the

SiO2–B2O3–Bi2O3–ZnO quaternary system
Itay Dyamant a, David Itzhak b, Jacob Hormadaly a,*

a
Zandman Center for Thick-Film Microelectronics, Institutes for Applied Research, Institute of Chemistry and Chemical Technology,
Ben-Gurion University, Hashalom St. #1, P.O. Box 653, Beer-Sheva 84105, Israel
b
Department of Materials Engineering, Ben-Gurion University of the Negev, P.O. Box 653, Beer-Sheva 84105, Israel

Received 12 January 2005; received in revised form 21 August 2005

Abstract

Lead-free glasses in the SiO2–B2O3–Bi2O3–ZnO quaternary system were studied. The glass formation region, as determined by XRD
patterns of bulk samples, was limited to glasses having more than 40 mol% of the glass-forming oxides SiO2 and B2O3. Crystalline phases
of Zn2SiO4 (willemite) were detected in compositions of 30SiO2 Æ 10B2O3 Æ 20Bi2O3 Æ 40ZnO and 20SiO2 Æ 10B2O3 Æ 25Bi2O3 Æ 45ZnO.
Glass transition temperatures (Tg), dilatometric softening points (Td) and linear coefficients of expansion in the temperatures range of
25–300
C (a25–300) were measured for subsystems along the B2O3 join of 10, 20 and 30 mol%. For these subsystems, Tg ranged from
411 to 522
C, and Td ranged from 453 to 563
C, both decreasing with increasing Bi2O3 content. The measured a25–300 ranged from
53 to 95 · 10
7
C
1, with values increasing with increasing Bi2O3 content. The ZnO content had the opposite effect to the Bi2O3 content.
It appears that Bi3+ acts as a glass-modifier in this quaternary system.
 2005 Elsevier B.V. All rights reserved.

PACS: 61.43.Fs; 81.05.Kf; 81.70.Pg; 64.70.Pf

1. Introduction substance is toxic to man and animals and PbO-containing

Thick-film microelectronics applications usually require
low-softening glasses having excellent chemical durability
and the appropriate coefficient of expansion. These proper-
ties are essential for the preparation of long-lasting, stable,
and easily fabricated components for microelectronic
devices. Compositions with high PbO contents are used
in overglaze and binder applications to lower the glass
transition temperature (Tg) and to maintain good durabil-
ity [1–3]. This unique characteristic of PbO indicates that it
is not simply a conventional glass-modifying oxide [4]. At
present, the microelectronics industry is driving glass devel-
opment towards finding substitutes for thick-film glass
compositions having high concentrations of PbO, since this
*
Corresponding author. Tel.: +972 8 646 1929; fax: +972 8 647 2846.
E-mail address: hormadj@bgu.ac.il (J. Hormadaly).
electronic waste is damaging to the environment [5].
The similarity between the characteristics of Bi3+ and
those of Pb2+, e.g., both are iso-electronic and highly
polarizable [6], indicates that Bi2O3 could be a suitable sub-
stitute for PbO in the preparation of lead-free glass compo-
sitions. The role of Bi2O3 in the glass matrix changes from
that of a modifying oxide to that of a conditional former as
its concentration increases [7,8]. Therefore, glasses having
high Bi2O3 content do not devitrify upon cooling and have
relatively low Tg values [9,10].
Literature survey data from previous works underscores
the role of Bi2O3 in lead-free glass systems. Nitta et al. [11]
reported that ZnO causes a spread of the glass-forming re-
gion of Bi2O3–ZnO–10B2O3–M2O (M = Li, Na and K)
quaternary systems, in which Bi2O3 is a major component.
Stone et al. [12] reported that BO4 tetrahedra are present
throughout the glass formation range in the Bi2O3–B2O3

0022-3093/$ - see front matter  2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnoncrysol.2005.08.031
3504 I. Dyamant et al. / Journal of Non-Crystalline Solids 351 (2005) 3503–3507

system. Sugimoto et al. [13] found changes of third-order Table 1

optical non-linear susceptibility with increasing Bi2O3 con- Thermal properties of glasses in the SiO2–10B2O3–Bi2O3–ZnO subsystem
centrations in glasses of the Bi2O3–B2O3–SiO2 system. Glass SiO2 Bi2O3 Tmax Tg Td a25–300 · 107
As a potential new lead-free glass system for thick-film [mol%] Fraction [
C] [
C] [
C] [
C
1]
microelectronics applications, the SiO2–B2O3–Bi2O3–ZnO 2 50 0.975 1200 442 466 76
quaternary system was investigated. The thermal properties 1 50 0.875 1200 446 486 70
3 50 0.800 1200 454 485 90
and the glass-forming ability of the system were studied, 4 50 0.750 1200 458 501 78
and the role of Bi2O3 in the glass matrix was investigated. 5 50 0.625 1200 457 500 70
6 50 0.500 1275 487 519 59
2. Experimental procedures 7 50 0.375 1350 489 527 57
8 50 0.250 1400 522 563 65
21 40 0.300 1175 505 537 67
Analytical grade SiO2, Bi2O3, ZnO and H3BO3 were 15 40 0.400 1125 495 532 66
used for the synthesis of the SiO2–B2O3–Bi2O3–ZnO 16 40 0.500 1100 466 501 84
glasses. Batch weights were calculated to produce 50 g glass 22 40 0.600 1075 441 475 91
samples. An electric box furnace was used for melting the 23 40 0.700 1025 438 464 86
batches at maximum temperatures in the range of 1000– 24 40 0.800 1025 430 458 85
25 40 0.900 1000 424 453 95
1450
C, depending on the glass composition. The heating 17 30 0.334 1075 444 493 69
profile depended on the type of crucible: For kyanite 18 20 0.357 1075 411 494 78
(SiO2 Æ Al2O3) crucibles, batches were heated at a rate of
20
C/min. For alumina (Al2O3) crucibles, batches were
melted in three stages to prevent the crucible from crack- Table 2
ing: at 3
C/min up to 600
C, at 10
C/min up to 800
C, Thermal properties of glasses in the SiO2–20B2O3–Bi2O3–ZnO subsystem
and at 20
C/min up to the maximum temperature (Tmax), Glass SiO2 Bi2O3 Tmax Tg Td a25–300 · 107
with a 6 min pause between stages 2 and 3. The samples [mol%] Fraction [
C] [
C] [
C] [
C
1]
were held at Tmax for at least 15 min to form homogeneous 26 40 0.875 1050 436 469 90
pourable melts. 27 40 0.750 1100 452 479 73
The melts were cast into pre-heated box-shaped stain- 28 40 0.625 1200 471 507 72
less-steel modular molds to form glass bars of 29 40 0.500 1250 n/aa n/aa n/aa
5 · 0.8 · 0.8 cm3. The bars were annealed for 0.5 h in 30 40 0.375 1375 517 559 56
31 50 0.833 1275 475 518 78
an electric box furnace. Annealing temperatures (Tan) were 32 50 0.667 1400 n/aa n/aa n/aa
estimated according to the formula: Tan = Tg + 10
C. 20 60 0.750 1450 480 n/ab 64
Dissolution of Al2O3 from the crucible was estimated by a
Dilatometry was not performed because of internal cracking of the
monitoring the weight of the crucible before melting and sample.
after batch melting and cleaning in hydrochloric acid. b
Measurement stopped after reaching 700
C without sample softening.
For most of the compositions, Al2O3 content was less than
2.5 wt%.
The glass bars were cut and polished to give parallel Table 3
faces. Linear coefficients of expansion in the temperature Thermal properties of glasses in the SiO2–30B2O3–Bi2O3–ZnO subsystem
range of 25–300
C (a25–300), the glass transition tempera- Glass SiO2 Bi2O3 Tmax Tg Td a25–300 · 107
tures (Tg) and the dilatometric softening points (Td) were [mol%] Fraction [
C] [
C] [
C] [
C
1]
measured with an Orton dilatometer, model 1000D, at a 33 40 0.833 1300 476 513 66
heating rate of 3
C/min. The measurement accuracy of 34 40 0.667 1300 n/aa n/aa n/aa
a25–300 was ±10%. 35 40 0.500 1375 496 535 53
19 45 0.600 1350 475 526 72
The glass-forming ability of the system was determined a
from X-ray diffraction (XRD) patterns of bulk samples Dilatometry was not performed because of internal cracking of the
sample.
taken from the bars. Scanning angles in the 10–65
2h
range gave the XRD patterns that were used to detect  
Bi2 O3 mol%
the vitreous and crystalline phases. Bi2 O3 fraction ¼ .
Bi2 O3 þ ZnO mol%
3. Results and discussion The decrease in Tg and Td with increasing Bi2O3 fraction
(Figs. 1 and 2, respectively) are a function of both the
3.1. Thermal properties increasing content of Bi2O3, and the decreasing content
of ZnO. In the SiO2–10B2O3–Bi2O3–ZnO subsystem, Tg
The thermal properties (Tg, Td, a25–300 and Tmax) of the ranged from 411 to 522
C (Fig. 1(a)), and Td, from 453
SiO2–B2O3–Bi2O3–ZnO glasses are given in Tables 1–3. to 563
C (Fig. 1(b)). In the SiO2–20B2O3–Bi2O3–ZnO sub-
These properties were also plotted as a function of the system, Tg ranged from 436 to 517
C (Fig. 2(a)), and Td,
Bi2O3 fraction (Figs. 1–4), defined as follows: from 469 to 559
C (Fig. 2(b)). The measured values of
 I. Dyamant et al. / Journal of Non-Crystalline Solids 351 (2005) 3503–3507 3505

550 550 100 100

500 500 90 90

α ×10 [˚C ]
-1
Tg [˚C]

80 80
450 450

7
70 70
400 400
60 60
350 350
0 0.2 0.4 0.6 0.8 1 50 50
0 0.2 0.4 0.6 0.8 1
Bi2O3 Fraction
(a) Bi2O3 Fraction

600 600 Fig. 3. a25–300 Values for glasses in the SiO2–10B2O3–Bi2O3–ZnO subsys-
tem. Lines are only as guide for eyes. (m) 50SiO2 Æ 10B2O3 Æ xBi2O3 Æ
(40
x)ZnO; (j) 40SiO2 Æ 10B2O3 Æ xBi2O3 Æ (50
x)ZnO; (n) 30SiO2 Æ
550 550
10B2O3 Æ 20Bi2O3 Æ 40ZnO; (h) 20SiO2 Æ 10B2O3 Æ 25Bi2O3 Æ 45ZnO.
Td [˚C]

500 500

450 450 100 100

90 90
400 400
0 0.2 0.4 0.6 0.8 1 α ×10 [˚C ]
-1

80 80
(b) Bi2O3 Fraction
7

Fig. 1. Glasses in the SiO2–10B2O3–Bi2O3–ZnO subsystem: (a) Tg values 70 70

and (b) Td values. (m) 50SiO2 Æ 10B2O3 Æ xBi2O3 Æ (40
x)ZnO; (j)
40SiO2 Æ 10B2O3 Æ xBi2O3 Æ (50
x)ZnO; (n) 30SiO2 Æ 10B2O3 Æ 20Bi2O3 Æ 60 60
40ZnO; (h) 20SiO2 Æ 10B2O3 Æ 25Bi2O3 Æ 45ZnO.
50 50
0 0.2 0.4 0.6 0.8 1
Bi2O3 Fraction
550 550
Fig. 4. a25–300 Values for glasses in the SiO2–20B2O3–Bi2O3–ZnO subsys-
tem. Line is only as guide for eyes. (m) 40SiO2 Æ 20B2O3 Æ xBi2O3 Æ
500 500 (40
x)ZnO; (j) 50SiO2 Æ 20B2O3 Æ 25Bi2O3 Æ 5ZnO; (h) 60SiO2 Æ 20B2O3 Æ
15Bi2O3 Æ 5ZnO.
Tg [˚C]

450 450

400 400 Tg and Td in the SiO2–30B2O3–Bi2O3–ZnO subsystem were

475–496
C and 513–535
C, respectively (Table 3).
350 350 The linear coefficients of expansion in the temperature
0 0.2 0.4 0.6 0.8 1 range of 25–300
C (a25–300) increased with increasing
(a) Bi2O3 Fraction Bi2O3 fraction (Figs. 3 and 4). It was found that a25–300 ran-
ged from 59 to 95 · 10
7
C
1 in the SiO2–10B2O3–Bi2O3–
600 600
ZnO subsystem (Fig. 3); from 56 to 90 · 10
7
C
1 in the
SiO2–20B2O3–Bi2O3–ZnO subsystem (Fig. 4); and from
550 550 53 to 72 · 10
7
C
1 in the SiO2–30B2O3–Bi2O3–ZnO sub-
system (Table 3).
Td [˚C]

500 500 The data presented in Figs. 1–4 and Tables 1–3 show
that increases in the Bi2O3 content served to reduce the
450 450 Tg and Td values and to increase the a25–300 values, charac-
teristics that are attributed to glass-modifying oxides [14].
400 400 Hence, Bi2O3 may be considered as a modifying oxide in
0 0.2 0.4 0.6 0.8 1 the studied glass system. The ZnO content had the opposite
(b) Bi2O3 Fraction effect on the measured thermal properties of the glasses.
Although classified as a modifying oxide, ZnO tends to
Fig. 2. Glasses in the SiO2–20B2O3–Bi2O3–ZnO subsystem: (a) Tg values
and (b) Td values. (m) 40SiO2 Æ 20B2O3 Æ xBi2O3 Æ (40
x)ZnO; (j) form bonds that are more covalent than those of alkali oxi-
50SiO2 Æ 20B2O3 Æ xBi2O3 Æ (50
x)ZnO; (h) 60SiO2 Æ 20B2O3 Æ 15Bi2O3 Æ des due to its high electronegativity value (1.66, Allerd–
5ZnO. Rochow). Therefore, increased ZnO content leads to a
3506 I. Dyamant et al. / Journal of Non-Crystalline Solids 351 (2005) 3503–3507

decrease in the thermal coefficient of expansion of a glass

system [15].
The increase in the measured values of Tg and Td and the
decrease in a25–300 values with increasing contents of the
glass-forming oxides, SiO2 and B2O3 may 2
be attributed to
the high field strength of Si4+ ð1:57 V=Å Þ and to the 3- to
4-coordination change of B3+ [16].
The value of the maximum temperature for obtaining
pourable melts (Tmax) followed the trend of the results of
the dilatometric measurements. Tmax ranged from 1000 to
1450
C, and its value increased with decreasing Bi2O3 frac-
tion. It should, however, be remembered that Tmax is an
experimental parameter, which was defined during the
melting procedures.

3.2. Glass formation

Figs. 5–7 show cross-sections of the SiO2–B2O3–Bi2O3– Fig. 6. Glass formation region in the SiO2–20B2O3–Bi2O3–ZnO subsys-
ZnO phase diagram, along the join of the B2O3 content tem. (d) Opaque; (s) transparent.
(mol%). The glasses were characterized by their appearance
after casting and annealing and by their XRD patterns. The
glass formation regions of the studied glass system lie in the
composition range of 40–60 mol% SiO2, 10–30 mol% B2O3,
10–45 mol% Bi2O3 and 1–35 mol% ZnO.
Fig. 5 shows glass compositions in the SiO2–10B2O3–
Bi2O3–ZnO subsystem, in which crystalline Zn2SiO4 (wil-
lemite) phases were detected in glasses having a content
of glass-forming oxides not exceeding 40 mol% (glasses
17 and 18, Table 1). These glasses also have a high ZnO
content, which is reflected in the crystalline phases detected
by XRD. As can be seen from Figs. 6 and 7 (respectively),
only vitreous phases were detected in the SiO2–20B2O3–
Bi2O3–ZnO and in the SiO2–30B2O3–Bi2O3–ZnO subsys-
tems. The vitreous phases were evident as a broadened
intensity peak in the vicinity of a Bragg angle of 26
(2h).

Fig. 7. Glass formation region in the SiO2–30B2O3–Bi2O3–ZnO subsys-

tem. (d) Opaque.

4. Summary

The thermal properties and glass-forming ability of the

Fig. 5. Glass formation region in the SiO2–10B2O3–Bi2O3–ZnO subsys-
tem. (d) Opaque; (s) transparent; (h) partially crystallized.
lead-free SiO2–B2O3–Bi2O3–ZnO quaternary system were
investigated. In addition, the glass formation regions and
the role of Bi2O3 in the glass structure were determined.
Tg, Td and Tmax were found to decrease and a25–300 was
found to increase with increasing Bi2O3 fraction. The effect
of decreasing concentration of glass-forming oxides (SiO2
and B2O3) was found to be the same as that of increasing
the Bi2O3 fraction. Bi2O3 was found to act as a modifying
oxide in the studied glass system.
The glass-forming ability was determined for glasses of
the SiO2–10B2O3–Bi2O3–ZnO subsystem that have a con-
 I. Dyamant et al. / Journal of Non-Crystalline Solids 351 (2005) 3503–3507
centration of glass-forming oxides exceeding 40 mol%. The
glass formation regions of the studied glass system were ob-
tained within the composition range of 40–60 mol% SiO2,
10–30 mol% B2O3, 10–45 mol% Bi2O3 and 1–35 mol%
ZnO.
Acknowledgements
The authors wish to thank the technical staff of the
Zandman Center for Thick-Film Microelectronics. This
work was partially supported by a scholarship from
PBC–NRCN (Planning and Budgeting Committee, the
Council for Higher Education in Israel, and Nuclear
Research Center – Negev).
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