DISSOLUTION OF SODA-LIME, SILICA, AND HIGH-LEVEL WASTE

GLASS BY STATIC AND SINGLE-PASS FLOW-THROUGH TESTS

A. Jiricka A. Helebrant
Department of Glass and Ceramics Department of Glass and Ceramics
Institute of Chemical Technology Institute of Chemical Technology
Technicka 5, 166 28 Prague Technicka 5, 166 28 Prague
Czech Republic Czech Republic


ABSTRACT
Static and single-pass flow-through tests (SPFT) were conducted on soda-lime (float and SK1)
glasses, silica glass, and a borosilicate (high-level waste high-chromium) glass at 85 and 50C
(static tests) and 90, 85, 60, and 30C (flow-through tests). Tests were performed at pH 10, 6, 5.5,
4 and 2; some static tests were unbuffered. Solution pH in unbuffered static tests on soda-lime
glass changed rapidly during the first 24 h, while in SPFT tests, the pH change was not significant.
Borosilicate glass dissolved minimally near pH 4 and more rapidly with increasing and decreasing
pH. Borosilicate glass dissolved much more incongruently in the initial dissolution stage than
soda-lime glasses, but less so with time. The activation energy of the final dissolution rate based
on the normalized Si release was 47.4t4 kJ/mol for SK1 glass, 55.4t11 kJ/mol for the float glass,
and 52.4t13 kJ/mol for the borosilicate glass.

INTRODUCTION
When glass is exposed to water, the process of glass dissolution begins by forming a thin
diffusion layer at the interface. This initial stage is controlled by two simultaneous processes
1,2
: 1)
interdiffusion of moveable ions (M
+
, H
3
O
+
), and 2) dissolution of the glass matrix. After the initial
rapid release of alkali ions, the rate that the diffusion layer forms equals the rate that the glass
matrix dissolves, and pseudo-congruent dissolution occurs.
3

This paper is a part of a high-level waste (HLW) high-chromium glass corrosion study. A
HLW high-chromium experimental glass is compared with an industrial float glass, soda-lime
glass (SK1), and silica glass. Static and single-pass flow-through tests (SPFT) were used to
determine the effects of temperature, pH, and glass surface area to solution volume ratio (S/V) on
the corrosion of these glasses.

EXPERIMENTAL
Float
1
glass and C16
2
high-chromium glass were obtained from the manufacturer. Soda-lime
glass (SK1) was melted in a platinum crucible at 1450C and subsequently annealed. Glass
compositions are given in Table I.

1
Glavunion, Teplice
2
Nuclear Research Institute - Rez
Glasses were crushed and sieved. The fraction between 0.3 and 0.5 mm, corresponding to the
specific surface 110 cm
2
/g, was used for testing.

Table I: Chemical Compositions of Tested Glasses (target, wt%)

S
i
O
2

N
a
2
O

C
a
O

A
l
2
O
3

B
2
O
3

K
2
O

L
i
2
O

S
O
3

C
r
2
O
3

F
e
2
O
3

M
g
O

T
i
O
2

Float 72.5 13.7 8.1 1.0 - 0.3 - 0.25 - 0.07 3.9 -
C16 53.15 8.0 - 4.5 14.4 3.84 3.15 - 2.85 4.5 0.36 5.25
SK1 75.15 15.5 9.35 - - - - - - - - -

Glass grains were cleaned ultrasonically several times to remove fine particles adhering on the
glass surface, dried at 140C, and stored in a desiccator. A flow-through apparatus consisting of a
corrosion solution supply, peristaltic pump, water bath, thermometer, ismaprene tubing, and
sampling bottles was used for SPFT tests. The flow rate was kept at 1 mL/min, allowing corrosion
solutions to be used without buffer. The temperature ranged from 30 to 90C. Most of the tests
were conducted in an 8-hour period.
An oven or water bath with a shaker was used for static tests at 85 and 50C. Solutions with
pH 2 and pH 10 were prepared by dropping nitric acid or sodium hydroxide into distilled water,
while pH was continuously measured by a pH-meter. A corrosion solution with pH 4 was prepared
by dissolving 10.2 g of potassium hydrogenphthalate in 1 L of distilled water. Distilled water with
pH adjusted by 0.01 M solutions of sodium hydroxide and nitric acid was used as a corrosion
solution for tests with pH 5.5 and 6. Polypropylene vessels tightened with a screw cap were used
for static tests.
To eliminate possible effects of sodium ions added to corrosion solution during the pH
adjustment, initial corrosion solutions were used to calibrate zero values for chemical analysis.
Concentrations of Na
+
and Ca
2+
ions released into the solution were obtained by flame photometry.
The concentration of SiO
2
released into the solution was obtained by spectrophotometry using the
yellow form of silicomolibdic acid.

RESULTS
Experimental data were plotted using i-th element concentration (c
i
), and other variables
defined in Table II: i-th element total mass release (Q
i
), normalized i-th element mass release
(NL
i
), and normalized i-th element dissolution rate (NR
i
).

Table II: Definition of Variables
(a)

Q
i
t
NL
i
t
NR
i
t

c
F
S
t Q
i
t
i
t t

+


c
f
V
S
NL
i
t
i
i
t t
+


NL NL
t
i
t
i
t t

(a) F is the flow rate, t the time, and t the time interval between two
subsequent samples, and f
i
the i-th element mass fraction in glass.

The following semiempirical equation was used for the SPFT normalized dissolution rate:

,
_

,
_

,
_

i
i
i
i i
t
W
t
NR

exp 1 exp
(1)

where
i
is the i-th component initial dissolution rate, W
i
is the i-th component final dissolution
rate, and
i
is i-th component time constant. Glass dissolution is congruent if W
i
has the same
value for each component.
An integration of Equation (1) yields


( ) t W
t
W NL
i
i
i i i i
+
1
]
1

,
_

exp 1
(2)

0.00
0.05
0.10
0.15
0.20
0.25
0 2 4 6 8 10 Time
N
L
i

[
g
/
m
2
]

tg(

)= W
i
tg(

)=
i

i

Figure 1: NL
SiO
2
, Float, pH 2, 1 mL/min, 85C
Equation (2) is equivalent to the
semiempirical equation used by Helebrant and
Tonerov
2
. The graphical representation of
i
,
W
i
, and
i
is displayed in Figure 1, including
the transition time (time needed for conversion
from the initial stage to the final stage of
dissolution), estimated as 3
i
. Experimental
data were fitted by Equation (2) to obtain the
coefficient values. An example of data fitting is
given in Figure 2. Figure 3 compares
experimental data plotted as NR
i
(t) and values
v
calculated from Equation (1). Time dependence NR
i
(t) indicates also congruent dissolution, which
occurs when the NR
i
(t) values for each element are equal. The coefficient values calculated from
SPFT tests are listed in Table III.

0.0
0.2
0.4
0.6
0.8
0 2 4 6 8
Time [h]
N
L
i

[
g
/
m
2
]
SiO
2
Ca
2+
Na
+

Figure 2: NL
i
(t), SK1 Glass, 85C, pH 6,
1 mL/min
0.0
0.1
0.2
0.3
0.4
0 2 4 6 8
Time [h]
N
R
i

[
g
/
m
2
/
h
]
SiO
2
Ca
2+
Na
+

Figure 3: NR
i
(t), SK1 Glass, 85C, pH 6,
1 mL/min

In static tests, component releases are affected by both glass dissolution and precipitation of
secondary corrosion products from the solution. Static test data cannot be fitted by Equation (2).
Instead, the initial dissolution rate in static tests was calculated as a slope between zero and the
NL
i
value of the first experimental data-point. The first data point was obtained at 24 h for all
glasses. The final dissolution rate was calculated as an NR
i
average for the last three data-points.
Coefficients calculated from the static tests and estimated transition times are given in Table IV.
Table III: Initial Dissolution Rates, Final Dissolution Rates, and Transition
Times for SPFT Tests
Float Glass SK1 C16 C16 SILICA
S/V 22 000 m
-1
22000 m
-1
22 000 m
-1
31000 m
-1
22 000 m
-1

T[C] pH 2 pH 6 pH 10 pH 6 pH 2 pH 4 pH 5.5 pH 5.5 pH 2 pH 6 pH 10
Initial Dissolution Rate -
i
[g/m
2
/h]
90 0.040 0.010 0.045 0.039
85 0.132 0.108 0.086 0.153 0.012 0.008 0.039
60 0.023 0.044 0.003
Si
30 0.007 0.001
90 0.287 0.065 0.200 0.130
85 0.140 0.148 0.161 0.701
60 0.041 0.081 0.002
Na
30 0.026 0.001
85 0.096 0.062 0.073 0.177
60 0.053 0.088 Ca
30 0.014


Final Dissolution Rate - W
i
[g/m
2
/h]
90 0.039 0.002 0.018 0.007
85 0.016 0.008 0.041 0.011 0.006 0.003 0.021
60 0.003 0.006 0.001
Si
30 0.001 0.0005
90 0.074 0.012 0.031 0.017
85 0.019 0.015 0.054 0.032
60 0.005 0.008 0.001
Na
30 0.002 0.0001
85 0.028 0.026 0.046 0.030
60 0.004 0.008 Ca
30 0.002


Transition Time 3
i
[h]
90 3.600 1.932 2.496 1.605
85 1.935 2.499 1.926 1.927 1.527
60 2.376 3.060 1.608
Si
30 2.382 1.611
90 2.727 1.986 2.082 4.959
85 4.761 1.875
60 2.844 4.980 4.224
Na
30 2.382 2.190
85 4.029 2.499 3.177 3.75
60 2.265 4.010 Ca
30 2.961



DISCUSSION
Table III and IV can be used to compare the initial dissolution rate, final dissolution rate, and
transition time for various conditions. Table V provides a general comparison of
i
and W
i

coefficients calculated from SPFT tests. In the initial dissolution stage, the SK1 glass is the fastest
dissolving glass, followed by the float/C16 glass. In the final dissolution stage, the C16 glass
shows the highest dissolution rates, indicating possible low durability in long-term corrosion tests.
Table IV: Initial Dissolution Rates, Final Dissolution Rates,
and Transition Times for Static Tests
S/V [1/m]
300 300 300 300 300 300 300
T [C]
85 C 85 C 85 C 50 C 50 C 50 C 85 C
Duration
45 days 45 days 45 days 45 days 45 days 45 days 18 days
Si Na Ca Si Na Ca Si
Initial Dissolution Rate - [g/m
2
/h] - SK1 Silica
pH 2 0.0100 0.0290 0.0180 0.0023 0.0090 0.0061 0.0010
pH10 0.0230 0.0380 0.0170 0.0017 0.0027 0.0023 0.0020
Final Dissolution Rate - [g/m
2
/h] - SK1 Silica
pH 2 0.0002 0.0015 0.0005 0.0001 0.0002 0.0001 0.0001
pH10 0.0012 0.0046 0.0006 0.0002 0.0003 0.0003 0.0009
Transition Time [h] - SK1 Silica
pH 2 360 360 456 168 360 360 144
pH10 312 408 312 168 360 168 144

Table V: General Comparison of SPFT Dissolution Rates
Initial Dissolution Rate (
i
) Final Dissolution Rate (W
i
)
Si SK1>float>C16>Silica C16>SK1>float
Na SK1>C16>float C16>SK1>float
Ca SK1>float SK1>float

The ratio between the final and the initial dissolution rates equals approximately 10 for
float/SK1 glass, approximately 5 for C16 glass, and almost 2 for silica glass. The ratio between the
initial dissolution rate of sodium and silica is highest for C16 glass, where it equals approximately
6, than for float glass, where it equals approximately 1.8, and SK1 glass, where it equals
approximately 1.6.
This shows that the highest difference between the initial/final dissolution stage occurs for
soda-lime glass and is smaller for borosilicate glass. The dissolution is more incongruent for
borosilicate glass than for the soda-lime glass; however, the ratio between the initial dissolution
rate of sodium and silica decreases strongly with time for the borosilicate glass (C16), but shows
only a small difference for the soda-lime glass (float/SK1). In static tests, the initial and final
dissolution rates are highest for Na and lowest for Si. The dissolution remained incongruent during
the whole experimental run, just like in SPFT tests.
Unlike dissolution rates, the transition time does not show any obvious dependence on
experimental conditions and does not seem to be affected by the element released. The average
transition time is approximately 3 h for all glasses except silica, where it equals 2 h (3.36 h for
SK1, 2.88 h for float, 2.67 h for C16, and 1.88 h for silica glass). In static tests, the transition time
for SK1 glass ranges from 168 to 456 h and equals 144 h for silica glass. No correlation between
transition time and experimental conditions was found.
The dissolution rate of glasses and minerals is significantly affected by the pH. The
dissolution rate is minimal in a neutral pH range
4,5,6
. As Figure 4 shows,
Si
and W
Si
for silica
glass show an increase in initial and final dissolution rate at pH>6 and slightly decrease at pH<6.
C16 glass shows a sharp minimum in both initial and final dissolution rates near pH 4.
Surprisingly, the initial dissolution rate for float glass does not show a significant change with pH,
and the final dissolution rate shows similar dependence on pH as the silica glass. Float/SK1
glasses show incongruent dissolution in both the initial and final dissolution stages. Ca release is
always higher than Si release and the NR(Na)/NR(Si) ratio does not change with temperature and
pH.

0.001
0.01
0.1
1
0 2 4 6 8 10 12
pH

i
,

W
i

[
g
/
m
2
/
h
]
Float- (Si)
Float- (Na)
C16- (Si)
C16- (Na)
Silica- (Si)
Float-W(Si)
Float-W(Na)
C16-W(Si)
C16-W(Na)
Silica-W(Si)

Figure 4:
i
, W
i
=f(pH) for Float, C16, and Silica Glass

Some static and dynamic tests were conducted without buffered solutions in nearly neutral pH
to simulate corrosion behavior in conditions that are likely to occur in a real environment. Figure 5
shows nearly constant pH in unbuffered SPFT tests. Figure 6 shows the results from static
unbuffered tests on SK1 model glass. These tests showed a rapid increase of pH during the first 24
hours causing an increasing dissolution rate that was equal to the dissolution rate at
pH 10.

0.00
0.10
0.20
0.30
0.40
0.50
0 2 4 6 8
Time [h]
N
L
(
S
i
O
2
)

[
g
/
m
2
]
0.0
2.0
4.0
6.0
8.0
10.0
12.0
p
H
pH 2
pH 6
pH 10

Figure 5: NL
SiO
2
(t), Float Glass, 85 C, pH 2,
6, 10, 1 mL/min
0.0
0.5
1.0
1.5
2.0
2.5
0 100 200 300 400 500
Time [h]
N
L
(
S
i
O
2
)

[
g
/
m
2
]
0
2
4
6
8
10
12
p
H
pH 10
pH 2
pH 6
Unbuffered

Figure 6: NL
SiO
2
(t), SK1, 85 C, pH 2, 6, 10,
Static Test

The Arrhenius equation,

NR NR
E
RT
i i
ia

_
,

0
exp (3)

where E
a
is activation energy [kJ/mol], R is the gas constant [J/mol/K], and T is temperature
[K] was used to determine the activation energy of the dissolution rate. Activation energies for
glass dissolution were determined by several authors, and show a dependence on glass
composition and experimental conditions. G. Leturq
7
found a characteristic activation energy of
60 t 5 kJ/mol for several aluminosilicate glasses (approx. 50% SiO
2
, 14% Al
2
O
3
, 18% CaO), and
he suggests that the resulting activation energy is given by the breakdown of Si-O and/or Al-O
bonds and depends on the nature of glass modifiers. Perrera and Doremus
8
calculated E
a
of the
dissolution rate for several industrial glasses and concluded that the surface structure of glasses is
the most important parameter determining the rate of dissolution. They found that soda-lime
glasses dissolve faster because the open structure of the hydrated layers allows the water
molecules easier access to the silicate network. Table VI provides a short overview of these
results.

Table VI: Activation Energies Found in the Literature, E
a
[kJ/mol]
Reference Material Solution T range [C] E
a
[kJ/mol]
G. Leturq et al.
7
Aluminosilicate glass deionized water 200-90 60 t 5
Perera, Doremus
8
Corning 015 soda-lime buffered pH 7 140-43 84
Pyrex borosilicate buffered pH 7 130-50 54
PPG float glass buffered pH 7 153-50 68
Bird et al.
9
Quartz deionized water 155-121 51-55
Rimstidt, Barnes
10
Silica deionized water 300-25 60.9-64.9
Perera, Doremus
11
Pittsburgh Plate Glass pH 4 193-114 79
Pittsburgh Plate Glass pH 7 90-50 66
Pittsburgh Plate Glass pH 9 197-50 60

Activation energies, calculated from the final dissolution rate of silicon (W
Si
), are given in
Table VII. SK1 glass shows the lowest E
a
, followed by C16 and float glass. Activation energies,
calculated for three temperatures, are lower than values found in the literature, mainly because of
values measured at 30C.

Table VII: Calculated Activation Energies E
a
[kJ/mol]
Material Solution T range [C] E
a
[kJ/mol] E
a
*
[kJ/mol]
SK1 glass pH 6 85-50 - 49.7
SK1 glass, static test pH 2 85-50 - 43.1
SK1 glass, static test pH 10 85-50 - 49.3
C16 glass (31000m
-1
) distilled water 90-30 39.6 65.2
float glass pH 2 85-30 44.5 66.4
*
E
a
calculated from two highest temperatures

Both the initial and final dissolution rates for Float and C16 glass depend much more on
temperature between 90/85 and 60C than between 60 and 30C. Because of this observation, E
a

was also calculated from data points measured at the two highest temperatures. Resulting values
are also given in Table VII. These values are higher and more consistent with experimental results
found in the literature, which leads to the conclusion that more experimental points, at higher
temperatures, are needed to correctly determine dissolution activation energy.

CONCLUSIONS
SPFT and static tests were used to measure the dissolution rates of soda-lime (SK1 and float)
glasses, silica glass, and a borosilicate (high-level waste high-chromium) glass.
Dissolution remained incongruent for all glasses during the entire 8-h SPFT test period and
1080-h static test. The degree of incongruence was highest for borosilicate glass (C16), but
decreased faster with time than by the soda-lime glasses.
The initial and final dissolution rates for borosilicate glass showed a sharp minimum near
pH 4 and increased with both increasing and decreasing pH. Surprisingly, pH had little effect on
the dissolution rate of soda-lime glasses.
The activation energy of the final dissolution rate based on the normalized Si release was
47.4t4 kJ/mol for SK1 glass, 55.4t11 kJ/mol for the float glass, and 52.4t13 kJ/mol for the
borosilicate glass.

REFERENCES
1
M. A. Rana and R. W. Douglass, The reaction between glass and water. Part I: Experimental
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A. Helebrant and B. Tonerov, A mathematical model used to compare glass durability tests
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3
R. H. Doremus, Chemical durability of glass; pp. 41-69 in Treatise on Material Science and
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4
A. Helebrant and A. Jiricka: Modeling of glass corrosion under dynamic conditions, pp. 80-87
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J. J. Mazer, J. V. Walther, Dissolution kinetics of silica glass as a function of pH between 40 and
85C,Journal of Non-Crystalline Solids, 170, 32-45, (1994).
6
R. K. Iler, The occurrence, dissolution, and deposition of Silica, pp. 42-43 in The chemistry of
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G. Leturq, G. Berger, T. Advocat, C. Fillet, O. Halgand, and E. Vernaz, Chemical durability of
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506, 199-206, (1998).
8
G. Perera and R. H. Doremus, Dissolution of silicate glasses in water at pH 7, J. Am. Ceram.
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9
G. Bird, J. Boon, and T. Stone, Silica transport during steam injection into oil sands, Chem.
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10
J. D. Rimstidt and H. L. Barnes, The kinetics of silica-water reactions, Geochim Cosmochim
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ACKNOWLEDGMENT
This study was supported by the Grant Agency of the Czech Republic under the project
numbers GA CR 106/960/0560 and GA CR 106/99/1419, which is a part of the research program:
Chemistry and Technology of Materials, No. CEZ: J19/98:223100002.