Journal of Non-Crystalline Solids 19 (1975) 311-320

© North-Holland Publishing Company

ABSORPTION OF WATER IN WASTE GLASS AS A PRECURSOR FOR

FOAM FORMATION

S.K. GOYAL and Ivan B. CUTLER

Department of Materials Science and Engineering, University of Utah, Salt Lake City,
Utah 84112, USA

The objective of this research is to describe the formation of foam glass from waste
glass using water as a gasifying agent similar to natural perlite. Artificial perlite with up
to 10% water content may be made from waste soda-lime glass by subjecting the glass
to water vapor under moderate pressures (less than 250°C). The maximum rate of ab-
sorption requires a minimum amount of liquid water to be in contact with the glass. Ex-
cess liquid water dilutes the corrosion action of alkali formed. Rate of water absorption
as a function of water content and 1N NaOH solution content were examined on rods
of glass as well as glass powder. Water adsorption was obtained by heating glass composi-
tions in saturated steam in an autoclave. In general, the absorption of water was related
to particle size, liquid water content, hydroxide ion concentration and glass composition.

1. Introduction

Periite is a glassy volcanic rock containing 5 - 1 0 % chemically combined water.

Upon heating, perlite expands or 'pops' to a frothy mass of low density material.
Hydroxyl ions in these glasses in their natural state condense as water when heated
at atmospheric pressure and the temperature of the softening point of the glasses.
These h y d r o x y l ions act similar to alkali oxides in reducing the viscosity o f glass.
Natural glasses that contain water as hydroxyl ions actually soften at a lower tem-
perature than after the hydroxyl groups combine to form water molecules. In other
words, as the glass softens, it expels steam or molecular water and the viscosity
rapidly increases.
There are two features of the natural glasses that limit their utilization. First,
they occur in remote parts o f the United States and must be transported long dis-
tances to metropolitan areas. Also, it is not possible to control or regulate the
amount o f water in the form of hydroxyl groups that are contained in the perlite
or pumice glasses. Without this control over water content, it is not possible to con-
trol the expansion.
Because gases, such as water, contained in melted glass form bubbles that inter-
fere with the transparency and strength of glass, they have been given rather careful
study by scientists interested in glass manufacturing. These studies have always been

3ll
312 S~K. Goyal, I.B. Cutler / Formation of foam glass

directed toward processes for eliminating gases dissolved in glass. An extensive review
of the literature describing water in glass has been made by Scholze [1]. From this
review it can be concluded that: (1) water is soluble in glass; (2) its solubility decreases
as temperature increases; (3) water forms hydroxyl groups in glass; (4) water dissolves
to form two different types of hydroxyl groups - one associated with silicon-oxygen-
silicon framework and another type of hydroxyl group associated with the sodium
ions and other modifier ions. Water solubility in glass can greatly reduce glass viscosity
[2]. Combining these concepts one can visualize the incorporation of water into the
glass at temperatures below the glass point and then during reheating, drive the water
off as steam. As the water escapes and foams the glass, the glass viscosity rises imme-
diately as the glass returnsto its dehydrated initial state, thereby 'freezing' the foam.
To make the above concept viable for an industrial process, the kinetics and equi-
librium water content of glass as a function of water vapor pressure and temperature
must be investigated. It has long been known that water corrodes the surfaces of glas-
ses. Information about the nature of the surface attack and changes in the composi-
tion of the corrosive liquid are helpful in evaluating the autoclave process for water
adsorption.
As Charles [3] reports, when water comes in contact with soda-lime glass the fol-
lowing reaction takes place:
i I
- Si- O- [Na] + H 2 0 - ~ - Si-OH+ Na + + OH- . (1)
I I

This reaction is a typical hydrolysis reaction. A free hydroxyl ion is formed in

the process and the second important step in the glass corrosion takes place as
I I I
- Si- O - S i- + OH- - + - S~i- OH +- SiO-. (2)
I

Reaction (2) can occur only after the reaction (1) has already taken place. In reac-
tion (2) the very strong S i - O - S i bond is broken and gives rise to another active
group, which is capable of reacting with water as

-SiO-
I
+ H20 -+ - S Ii - O H + O H - . (3)

The overall reaction between water and glass may be written as

I I t
-Si-O-Si- + H20 4 2 [ - S i - O H ] . (4)

These concepts are consistent with the data of Charles [3], who found that a
rather large amount of water could be diffused into glass at relatively low tempera-
tures and pressures. He followed an interface between the diffused and undiffused
volume of the glass. This boundary between the diffused and undiffused region ap-
pears to proceed linearly rather than parabolically as would be expected for a dif-
fusion process. Rana and Douglas [4] explain, when typical soda-lime-silica glasses
 S, K. Goyal, L B. Cutler / Formation of foam glass 313

react with water the initial rate of reaction varies with the square root of time, sug-
gesting a diffusion-controlled process. Moreover, the activation energy of the reac-
tion is about the same as that for sodium ion diffusion in the glass. However, it has
been emphasized that this is merely convenient [5] and not to be intended as an as-
sessment of the actual mechanism involved.
Roberts and coworkers [6] have shown through IR absorption measurement that
the equilibrium concentration of hydroxyl groups formed in the glass varies as the
square root of the pressure of water vapor in the environment, suggesting that each
molecule of water vapor reacts with an oxygen of the glass network to produce a
pair of hydroxyl groups, according to reaction (4). Das and Douglas [7] describe
that equilibria are never established between water and complex silicate materials
such as glass under normal conditions of temperature and pressure.
This paper summarizes the results obtained with the purpose of incorporating
the maximum water into a soda-lime glass structure. Although no detailed obser-
vations have been made of the foaming of glass containing water vapor, prelimin-
ary experiments have confirmed that water in glass gives rise to a foamed product
when heated at 900°C for only a few seconds.

2. Experimental

To find out whether the amount of water in contact with a glass surface has some
effect on the glass-water reaction, seven closed-end tubes of soda-lime glass [5]
and borosilicate glass [2] of od = 8 - 2 0 mm and id = 5.8-12.2 mm, containing
soda-lime glass rods (od = 4 mm each) were prepared for insertion in an autoclave.
The tubes were filled with distilled water up to 15 cm height and the remaining 18
cm of the tubes and rods were to be in contact with steam. These were covered in
order to prevent condensed water from entering into the tubes. This package of
tubes and rods was placed in a 2.5 ~ autoclave which had 400 cm 3 of distilled water
to generate steam and to keep the bottom part of tubes in water. This arrangement
is shown schematically in fig. 1.
The autoclave was heated to produce saturated steam at 250°C and was main-
tained for 6 h. The od and id of the reacted rods and tubes were measured at the
bottom part, which was in contact with water, and the top part, which was in con-
tact with steam. The observations and the results obtained are tabulated in table 1.
Further, it was observed that the reacted glass on the surface of rods and tubes
peeled off like flakes, leaving a transparent interior, implying that the boundarY be-
tween reacted and unreacted glass remains sharp.
The amount of water adsorbed in the flakes was found to be 9.8% on a dry basis
when heated slowly up to 900°C and maintained for ~1 h. The reacted glass flakes
having 9.8% combined water expanded or popped to a frothy mass of low density
material upon heating at 900°C for 15 s. The foamed product looked like commer-
cial perlite.
314 S.K. Goyal, LB. Cutler/Formationoffoam glass

PRESSURE GAUGE

AUTOCLAVE

GLASS RODS

T.C. WELL

TUBEE

WATEF

WATER (400cc

Fig. 1, Schematic representation of the autoclave corrosion of glass rods and tubes.

Table 1
Autoclave reaction of glass with water.

Sample Original size Water Glass thickness reacted (mm)

number a) (gm/cm 2 of
tube rod glass surface) on od of tube on od of rod

od(mm) id(mm) od(mm) top bottom top bottom

1 8.0 5.8 4.1 0.0425 0.40 0.00 0.45 0.35

2 9.0 6.6 4.0 0,065 "0.40 0.00 0.45 0.10
3 9.9 7.5 4.0 0,0875 0.50 0.00 0.40 0.10
4 11.0 8.6 4.15 0,111 0.40 0.00 0.40 0.10
5 11.8 9.4 4.15 0.131 0.45 0.00 0.45 0.10
6 15.0 12.8 4.20 0,216 0.00 0.00 0.45 0.00
7 20.0 17.2 4.0 0,33 0.00 0.00 0.45 0.00

a) Samples 6 and 7 were pyrex glass. All other glasses were soda-lime-silica.
 S.K. Goyal, I.B. Cutler/Formation of foam glass 315

Soda-lime glass powders of - 3 5 + 60 and - 1 0 0 + 200 sieve sizes with 10, 20,
40, 80 and 160% added water (on a dry basis) were reacted at different tempera-
tures in saturated steam. For this purpose, glass powder and water were enclosed
in small steel bombs and put together in a large autoclave having water in it, to
avoid any pressure difference between the large autoclave and steel bombs. This ar-
rangement provided good thermal conductivity. The large autoclave containing in-
dividual steel bombs was introduced in a preheated furnace and the desired constant
temperature was attained in ½ h. After heating for the desired time, the furnace was
switched off and the autoclave was allowed to cool in the furnace, which took ½ h
to cool to 100°C.
After cooling to room temperature, the steel bombs were opened and the glass
powders were dried for a long time ( ~ 10 h) at 115°C. The reacted water absorbed
was found in the same way as in the case of the previous experiment. The percentage
of water absorbed was calculated on a dry basis.

3. Results and discussion

The results in table 1 clearly confirm the data of Charles [3] that the glass reacts
faster in steam than in water at the same temperature and pressure. Charles explained
this as due to a pH increase at the glass/vapor interface in contrast to a dilution of
pH at the liquid/glass interface. Higher concentrations of hydroxyl ions at the vapor/

I I I I i I I I

A1/) 5 175*C
6 hrs
o
r, 0 - 3 5 * 6 0 MESH
Q - 1 0 0 + 2 0 0 MESH

W
m
0 3
II1

w 2

0
0 20 40 60 80 I00 120 140 160 180
% W A T E R A D D E D (dry bosis)
Fig. 2. E f f e c t o f w a t e r c o n t e n t on the w a t e r a b s o r b e d in the c o r r o d e d glass.
316 S.K. Goyal, LB. Cutler / Formation of foam glass

i i ; i

5 200"C
6 hrs
O - 3 5 + 6 0 MESH
g • - 1 0 0 + 2 0 0 MESH
~4
1:3
b.I
r~ 3
0
¢o
rn

.
I

L I I I I I I L
20 40 60 80 100 120 140 160 180
%WATER A D D E D (dry basis)

Fig. 3. E f f e c t o f w a t e r c o n t e n t o n t h e w a t e r a b s o r b e d in t h e c o r r o d e d glass.

I i i [ [ l I I

5 225°C
2hrs
f~ - 3 5 + 6 0 MESH
• - 1 0 0 + 2 0 0 MESH
4

LIJ
m
n,"
o 3

2
F-

At

I I I I I I I I
20 40 60 80 100 120 140 160 180
% W A T E R A D D E D (dry bosis)

Fig. 4. E f f e c t o f w a t e l ~ o n t e n t o n t h e w a t e r a b s o r b e d in t h e c o r r o d e d glass.
 S.K. Goyal, LB. Cutler / Formation of foam glass 317

12 I I I I I I I I I

°t

n," 4 1 - / /," / I/ & I0

tu / // /// D 20
I- / // / //
I,',' /// o
v
,o
80
//J 0 160

0
0 2 4
,
6
I
8 I0
L L
12
I
14 16
I i
18 20
TIME (hours)

Fig. 5. Effect of time and water content on the water absorption of 35 + 60 mesh glass at
225°C in saturated steam.

glass interface break the silica network bonding according to reaction (2).
This is further illustrated in figs. 2 - 5 , showing results with glass powders where
water content, temperature and time of reaction were variables. It should be noted
that rapid corrosion required small water contents, high surface areas, and of course
proceeded more rapidly at higher temperatures and pressures. Here the amount of
water in contact with glass powder determines the hydroxyl ion concentrations and
consequently the rate of breaking of the silica chains and water absorbed.
Further, to confirm the increased rate of reaction [7] due to hydroxyl ion con-
centration, glass powder ( - 1 0 0 + 200) was added with 160% water in three differ-
ent steel bombs. One was left as is; a few drops of H2SO 4 were added to the second;
and a few drops of NaOH solution were added to the third. All these were autoclaved
at 225°C for 6 h. The water absorbed was found to increase with hydroxide ion con-
centration, as shown in table 2.
This result indicated the importance of a high pH in the corrosion process and
the need for further study of the effect of alkali. Further experiments were made in
the same type of steel bombs with different amounts of a 1N solution of NaOH. The
results are shown in figs. 6 and 7. It is evident that glass reacts rapidly with water
when the hydroxyl concentration is high.
Glasses are more rapidly attacked in alkaline solutions than in neutral or acid so-
lutions because the alkali supplies hydroxyl ions for reaction (2) with the silica net-
work and gives rise to more silanol groups. From figs. 6 and 7, it seems that there is a
critical amount of NaOH solution necessary for the highest rate of reaction, above
 318 S.K. Goyal, LB. Cutler / Formation of foam glass

Table 2
Effect o f h y d r o x y l ion c o n c e n t r a t i o n o n absorbed water.

added reagent H2SO 4 none NaOH

% water absorbed 2.37 7.70 13.55

which the rate of reaction becomes constant. Addition of more NaOH solution does
not increase water absorption. This may be due to the saturation point reached in
the glass structure to accommodate the maximum number of hydroxyl groups.
Glasses react at a very slow rate with acids. Attack of glasses by acids differs
from that by water in that any alkali dissolved is neutralized by the acid; also the
alkali and basic oxide components may be preferentially dissolved, leaving a silica
surface layer which reduces the rate of attack with time. Presence of a protective
surface fdm was found by Brueche and Poppa [8] having a thickness o f ( ~ 0.1/am).
Reaction (1) leads to a weakened network through which large ions can rapidly
diffuse. The results of Eisenman [9] are consistent with this requirement, since he
found that in the hydrated layer Na ÷ diffused only about 5 - 1 0 times faster than
K +, whereas in the dry glass the Na + is about 1000 times more mobile than K +.
This can be explained on the ion-exchange mechanism. As the ion exchange pro-
ceeds the surface layer becomes more open and the water molecule can diffuse in
it more rapidly, thus increasing the rate of reaction of water with the silica lattice.

I I I I J I I I

IO
.gl

a~

t-~
lad
en
• 175°C
er- 4 hrs
O
O'J
6 -100+200 MESH
II1 0 WATER
• NoOH SOLUTION
t~
Ld 4

2 ~ ' - ' 0 0
o I I I ~ I I I I
0 20 40 60 80 I00 120 140 160 180
% WATER OR NOOH SOLUTION ADDED (dry basis)

Fig. 6. Effect o f w a t e r or a 1 N N a O H solution content on the water absorbed in t h e c o r r o d e d

glass.
 S.K. Goyal, LB. Cutler / Formation of foam glass 319

12

I0-
1/)

J~

;8
bJ 225"C
IZl 4 hrs
- 3 5 + 6 0 MESH
O3 t~ WATER
n't
• NaOH SOLUTION

Lu 4

0 I I I I I I I i
0 20 40 60 80 I00 120 140 160 180
% W A T E R OR NaOH S O L U T I O N A D D E D (dry basis)

Fig. 7. E f f e c t o f w a t e r or a 1 N N a O H s o l u t i o n c o n t e n t on the w a t e r a b s o r b e d in the c o r r o d e d

glass.

Also, the silicon-oxygen bonds in the surface layer may be more reactive after ion
exchange because of the strain resulting from the replacement of a larger ion (Na ÷)
with a smaller ion (H+).
Lack of reaction between borosilicate glass and water (table 1) may be due to
the special phase-separated structure of these glasses [10]. These glasses have a silica
matrix with a very fine ( 2 0 - 3 0 ) ~ diameter) second phase of sodium borosilicate.
The matrix of low soda content appears to be resistant to water corrosion by sup-
pression of reaction (1).
The sharp boundary obtained between reacted and unreacted glass suggest the
corrosion reaction can occur at an interface. As the hydroxyl ion concentration
builds up the reaction proceeds more and more rapidly. Therefore, the water-glass
reaction is an accelerating process which at least initially can be related to Na + ion
diffusion in the bulk glass.

4. Conclusion

Steam reacts with glass at a faster rate than water due to a more rapid increase in
pH at the steam/glass interface. Hydroxyl ion concentration determines the initial
rate of reaction. Soda-lime glass was found to react with steam faster than a boro-
silicate glass. There exists a sharp boundary between reacted and unreacted glass.
320 S.K. Goyal, LB. Cutler / Formation of foam glass

The rate limiting build-up of pH can be avoided by supplying a small amount of

caustic solution for the initial reaction with steam. Acidic solutions reduce the rate
of reaction.

Acknowledgement

The authors gratefully acknowledge the financial support of the Environmental

Protection Agency through Grant R800937.

References

[1] H. Scholze, Glass Ind. I 47 (1966) 546-551; II 47 (1966) 622-628; 1II 47 (1966) 670-675.
[2] I.B. Cutler, J. Am. Ceram. Soc. 52 (1969) 11-13.
[3] R.J. Charles, J. Appl. Phys. 29 (1958) 1549--1553.
[4] M.A. Rana and R.W. Douglas, Phys. Chem. Glasses 2 (1961) 179-196.
[5] M.A. Rana and R.W. Douglas, Phys. Chem. Glasses 2 (1961) 196-205.
[6] G.J. Roberts, J.P. Roberts and T. Drury, Advances in glasses (Plenum Press, New York,
1962) pp. 249-255.
[7] C.R. Das and R.W. Douglas, Phys. Chem. Glasses 8 (1967) 178-184.
[8] E. Brueche and H. Poppa, Glastech. Ber. 30 (1957) 163.
[9] G. Eisenman, Glass electrodes for hydrogen and other cations (Dekker, New York, 1967)
p. 133.
[10] R.H. Doremus, Glass science (Wiley, New York, 1973) p. 245.