A. Steiner and R. G. C.

Beerkens, Foam Glass from fly ash melts, Proceedings of the ICG annual meeting, July 1-6,
2001, Edinburgh, Scotland

FOAM GLASS FROM FLY ASH MELTS

*Arjen Steiner and Ruud G.C. Beerkens

Glass Technology Group, Eindhoven University of Technology, P.O. Box 513, Den Dolech 2, 5600MB Eindhoven,
The Netherlands

Introduction
Fly ashes from municipal solid waste (MSW)
incinerators contain considerable amounts of
environmentally harmful components [1]. Their
leaching characteristics make it critical to store them
on landfills without any prior treatment [2]. The
detoxification and reuse of these y ashes by a
thermal process is a proven and successful method,
which most of the time results in another waste
stream [3].
The foaming of glass to a building material is a
promising approach for the use of glasses prepared
from these waste materials. There are several
different foaming processes, but the mixing of glass
powder and foaming agent prior to the heat treatment
is one of the most effective methods [4]. Despite of
its high production costs, foam glass is one of the
best insulating materials, especially in wet
environments [5].
To foam glass, the wholes between the glass particles
must sinter together, forming closed bubbles. The
growth of the bubbles depend on the viscosity and the
surface tension of the glass and also on the gas
pressure inside the bubbles. This pressure is assumed
to behave according to the ideal gas law. If carbon is
the foaming agent, carbon monoxide will be the
foaming gas, working against the external forces. For
larger bubble growth rates it is necessary to increase
the molar amount of gas inside the bubble. Since the
amount of physically dissolved gases in glasses is
low [6], the redox potential of the glass, meaning the
chemical dissolved oxygen, which can be released by
a reduction reaction, plays an important role. Schulz
[7] refers to sulfur trioxide (SO
3
) as main oxygen
donor for the foaming agent. Glasses, melted from fly
ashes under oxidizing conditions contain up to
3 wt.% Fe
2
O
3
and up to 0.5 wt.% SO
3
. Kse [8]
assumes that only physically dissolved oxygen and
coalescence of the bubbles causes foaming.
The intention of this paper is a). to identify the main
chemical reactions and their starting temperatures,
which are primarily responsible for the gas forming
reactions inside a bubble b). to determine the
influence of the redox sensitive components on the
gas forming inside the bubble and c). to present a
model to calculate the bubble growth depending on
the redox potential of the glass

Experimental
The glasses for the foaming experiments were melted
from reagent grade chemicals. The composition is
given in table 1. The glasses were melted in platinum
crucibles (95 % Pt, 5 % Au) at 1450 C for 3 hours.
Afterwards the glasses were cooled, milled to powder
(< 63 m) and mixed with 5% active carbon
(d
50
< 30 m). Approximately 1 gram of the mixture
was transferred into a mullite reaction boat and
inserted into the alumina tube of a horizontal tube
furnace. The tube was flushed with helium gas. The
intention of these experiments was to avoid foaming
of the glass, but to allow the gases created at the
glass/carbon interface to leave the mixture rather than
being enclosed in the pores of the mixture when the
glass particles start sintering together. For the
qualitative determination of the evolving gases
during the experiment, a Balzers Thermostar type
GSD 300 T2 mass spectrometer was used.
Table 1: Glas Composition

Results

0 200 400 600 800 1000 1200
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Glass
Glass + Fe
2
O
3
Glass + Na
2
SO
4
Glass + Fe
2
O
3
and Na
2
SO
4

A
r
b
i
t
r
a
r
y

U
n
i
t
s
*
1
0
-
3
Temperature (C)

Figure 1: CO mass spectrometer peak intensities of
the four different glasses normalized by the He peak
intensity as a function of temperature.

Glass/
Oxide
SiO
2
CaO Na
2
O Al
2
O
3
Fe
2
O
3
SO
3
FG 1 70 15 10 5 0 0
FG 2 70 15 10 5 3 0
FG 3 70 15 10 5 0 0.3
FG 4 70 15 10 5 3 0.3


Both components, Fe
2
O
3
and Na
2
SO
4
decrease the
gas forming temperature considerably compared to
the glass without any additives (FG 1). Looking at
the iron containing glasses, the reduction of ferric to
ferrous iron is presumably the gas forming reaction.
The reduction of ferrous iron to elementary iron (Fe)
is also possible. Since the measurement is only
qualitatively, no verification can be given at this
stage. The reduction of sodium sulfate, according to
Na
2
SO
4
+ C Na
2
O + SO
2
+ CO would also create
sulfur dioxide gas, which was not detected. In fact no
sulfur containing species could be detected during
any of the experiments. This leads to the assumption
that Na
2
SO
4
was reduced according to reaction:
Na
2
SO
4
+4C Na
2
S +4CO and that Na
2
S was
dissolved in the glass.
Regarding glass FG 4, containing iron and sulfate,
the gas forming reactions can be compared to the
glass containing only iron. Since no quantitative
measurement was done, differences in peak height or
peak surface cannot be taken as differences in
concentration. However, the location of the second
peak maximum lies between the one of FG 2 and
FG 3. This temperature shift is approximately 75 C
and shows the influence of the sulfate in the glass

Conclusion
Ferric iron and sodium sulfate both influence the
foaming capability of glasses. The onset temperatures
of the gas forming reactions and thus the influence of
these two mentioned components could be shown.
The combination of ferric iron and sodium sulfate
allow a better control of the temperature dependence
of the gas release of the foam glass. The absence of
sulfur containing species in the off gases indicates
that sodium sulfate is reduced to sulfide.
It has further to be investigated in what extent the
redox potential, influences the flux of oxygen to the
bubble

Bubble Model
Important for the foam glass quality is the
distribution of the closed bubbles, their size and
stability. The initial bubble radius can be adjusted by
the grain size of the initial glass powder. The final
size of the bubble depends on the growth rate of the
bubbles and the coalescence of the bubbles at higher
temperatures and lower viscosities. Neglecting
coalescence, the bubble growth can be described
using the model of Scriven [9], which was applied to
foam glasses by Kse [8].
Assuming that the O
2
reacts instantaneous to CO
(CO
2
at lower temperatures), there is a driving force
for the reduction of the redox sensitive components
and of course for the oxygen diffusion into the
bubble. This means that the amount of oxygen from
the reduction reactions must be included into the
calculations. The oxygen concentration at the bubble-
glass interface can be described as [10]:

F
H
G
I
K
J
L
N
M
O
Q
P

+
C
t R R
D R
C
R
C
R
P
R r
1
2
2

where C is the concentration, t the time, R the radius,
r
0
the radius at t=0, D the diffusion coefficient,
R
the
velocity in radial direction and P
r
the molar rate of
production. The expression P
r
is important
considering redox reaction for O
2
formation.

Outlook

More quantitative data will be presented to
support the influence of the redox condition
on the foaming capability of the glass.

Calculations will be presented using the
above stated model

References
[1] Gutmann R. & Vonmont H. Z. Umweltchem.
kotox. 1994, 6(5), 257
[2] Cernuschi S., Giugliano M.,& de Paoli I., Waste
Management &Research, 1990, 8, 419
[3] Schmidt K.G. & Leclaire T., Abschlubericht zum
Forschungsvorhaben 103 10 902 (Teil A) des
Bundesministeriums fr Umwelt, Naturschutz und
Reaktorsicherheit, 1996.
[4] Hbscher M., Silikattechnik, 1954, 5(6):243 247.
[5] Strebel B. & Welter M., Schweizer Ing. und
Architekt, 1991, 47,1128
[6] Scholze H., Glas Natur, Struktur und
Eigenschaften, 1988, Springer-Verlag, Berlin
Heidelberg New York
[7] Schulz E.O., Silikattechnik, 1954, 5(8), 343
[8] Kse S., Ph.D. Thesis, ETH Zrich, Switzerland,
1981.
[9] Scriven L. E., Chem. Eng. Sci., 1959, 10, 1
[10] Bird R. B., Steward, W. E. & Lightfoot E. N.
Transport Phenomena. John Wiley & Sons, Inc.,
1963.