Journal of Non-Crystalline Solids 293295 (2001) 752757

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Structural evolution of sodium silicate solutions

dried to amorphous solids
Hans Roggendorf *, Dorit B
oschel, J
org Trempler
Institut f
ur Werkstowissenschaft, Martin-Luther-Universitat Halle-Wittenberg, D-06099 Halle (Saale), Germany

Abstract
Sodium silicate solutions with a molar SiO2 :Na2 O ratio of 3.3 were dried at temperatures up to 100 C to solid,
amorphous and transparent materials with water contents between 45 and 12 wt%. A timetemperature-transition
diagram of the specic drying process was established. The dried materials were investigated by optical microscopy, X-
ray diraction, electron microscopy, and thermal analysis. Materials with higher water contents had structural units
with sizes of 50100 nm, whereas materials with lower water contents did not show a structure in this size range. At least
two thermal eects were detected and are discussed with respect to composition, glass transition and structure of the
materials. Hot stage microscopy was applied to correlate these eects to a liquidsolid transition. A model of the
structural evolution of the materials during drying is discussed. 2001 Elsevier Science B.V. All rights reserved.

1. Introduction applied static light scattering. Our measurements

Sodium silicate solutions are commonly pro-
duced by dissolving sodium silicate glasses in water
at hydrothermal conditions. Commercially avail-
able solutions have compositions characterised by
a molar SiO2 :Na2 O ratio of 1.83.8 (ratios of 2.0
and 3.3 are standard compositions) and a SiO2
content of 2530 wt%. Concentrated sodium sili-
cate solutions can structurally be described as
dispersions of colloidal amorphous silicates in an
aqueous solution. The sizes of the colloids re-
ported in the literature dier. Many publications
report sizes between 1 and 5 nm, e.g. Iler [1], who
extracted the colloids with tetrahydrofuran and
*
Corresponding author. Tel.: +49-34 61 37 39; fax: +49-34 61
38 39.
E-mail address: hans.roggendorf@iw.uni-halle.de (H. Rog-
gendorf).
of concentrated solutions (SiO2 content 25 wt%)
with dynamic light scattering yielded values be-
tween 30 and 100 nm [2]. Possibly, in the latter case
larger aggregates consisting of smaller colloids
were present.
For some applications the materials have to be
dried, e.g. for their use as re protecting layers in
glazings (e.g. PyrostopTM , Pilkington). In the ap-
plication case they are heated up and foam to a
porous thermal insulation layer. During drying the
viscosity of the solution raises within a narrow
concentration range by a few orders of magnitude
as a function of the water content [3].
Dent Glasser and Lee [4] investigated dried
sodium silicate solutions with a molar SiO2 :Na2 O
ratio of 3.42 and water contents between 10 and 37
wt% by thermal analysis. Two endothermic events
were detected: the rst at lower temperatures was
explained by the rearrangement of interstitial ions
and water molecules, whereas the second at higher

0022-3093/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 0 9 3 ( 0 1 ) 0 0 7 8 5 - 2
 H. Roggendorf et al. / Journal of Non-Crystalline Solids 293295 (2001) 752757
temperatures was attributed to the evaporation of
H2 O which is formed by the condensation of sil-
anol groups.
It is possible to melt crystalline sodium me-
tasilicate hydrates (e.g. Na2 O
SiO2
nH2 O, n: 5, 6,
9) and to solidify them in the vitreous state by
cooling to low temperatures [57]. Glass transition
temperatures below room temperature were mea-
sured either via vapour pressure [6] or by deter-
mining the peak shapes in 29 Si MAS NMR spectra
(MAS: magic angle spinning; NMR: nuclear
magnetic resonance) [7].
The aim of this paper is to discuss the results of
structural characterisations of commercial sodium
silicate solutions dried to amorphous solids.
2. Experimental
Technical-grade sodium silicate solutions
(Roth, Karlsruhe, Germany) were used as raw
materials. The composition of the starting mate-
rials was analysed chemically: 8.6 wt% Na2 O and
27.3 wt% SiO2 SiO2 :Na2 O mole ratio of 3.27). The
solutions (515 g) were dried in open polypropyl-
ene beakers with a volume of 120 ml. The beakers
were placed in closed drying ovens at temperatures
between 30 and 100 C above a desiccant. After
drying, the beakers were closed with a lid and
stored for further 24 h at the drying temperature in
order to minimise concentration gradients due to
the diusion of water. Drying times between 8 h
and 91 d were applied. The weight loss of the so-
dium silicate solutions was measured and was used
to calculate the residual water content. In one se-
ries of drying experiments designed to establish a
timetemperature-transition diagram the masses
of the samples were balanced at regular intervals.
The dried materials were examined by optical mi-
croscopy and X-ray diraction in order to identify
and eliminate crystallised or cracked samples. Be-
tween the analytical investigations, the samples
were stored in a desiccator.
The replica technique was applied for structural
characterisation. Fracture surfaces of dried so-
dium silicate solutions were etched (1 N HCl, 60 s)
and then coated with carbon and gold. The origi-
nal sample was dissolved and the replica of the
753
surface analysed with transmission electron mi-
croscopy (TEM; Jeol JEM 2010). Details of the
preparation method and rst results are published
in [8].
Thermal analysis was performed with a Simul-
taneous Thermal Analyser Netzsch STA 409 C.
The dried hydrous silicates were crushed to a
particle size of about 100 lm. The samples were
heated in a DSC furnace up to 350 C with a
heating rate of 10 K/min. A closed crucible
(Netzsch, autoclave crucible) with 27 ll volume
was used in order to suppress evaporation and
foaming reactions. The crucible consisted of
stainless steel coated with gold. The crucibles
(weight: 900 mg) were lled with 1220 mg of the
crushed samples. The application range of cruci-
bles is limited to 100 bar. At temperatures below
80 C the results obtained with the pressure-tight
crucible could not be evaluated, due to the high
thermal mass of the crucible. Details of the ther-
mal analysis are published in [9].
A hot stage microscope (Jenapol u, Carl Zeiss
Jena, combined with hot stage Mettler FP 84 HT)
was used to monitor the structural changes of the
samples during heating. Transparent samples
(fracture pieces, size ca. 1 mm) were heated at the
rate of 10 K/min up to 200 C. Photos were taken
in 5 K intervals. In two cases the combined DTA/
TG (dierential thermal analysis; thermogravime-
try) mode of the Netzsch STA 409 was used to
measure the water release of similar samples dur-
ing heating (up to 300 C; rate: 10 K/min) with
open crucibles.
3. Results
Concerning the results of the drying process the
following can be stated:
The solutions were usually dried to transparent
and brittle materials.
Solidication occurred gradually in less than 24
h at water contents of about 50 wt%.
At temperatures 6 60 C, crystallisation at wa-
ter contents between 24 and 30 wt% (decreasing
with temperature) was observed. The amount of
crystals was too low for X-ray identication.
Formation of carbonates cannot be excluded.
754 H. Roggendorf et al. / Journal of Non-Crystalline Solids 293295 (2001) 752757

Above 60 C cracks developed at water contents

of about 12 wt%, which are probably due to me-
chanical stresses induced by concentration gra-
dients.
Fig. 1 shows the timetemperature-transition dia-
gram for the applied conditions.
By transmission electron microscopy the fol-
lowing structural sequence was detected:
Samples dried at 4060 C for 6 48 h (H2 O con-
tent >30 wt%) have a particulate structure with
a size range between 30 and 100 nm (called 50
nm structure). A smaller substructure is indi- Fig. 1. Timetemperature-transition diagram for isothermal
drying of sodium silicate solution (molar ratio
cated (Fig. 2(a)). SiO2 :Na2 O 3:27; 27 wt% SiO2 ; eye-lines are drawn to loca-
Samples with more extensive drying (H2 O con- lise the `phases'; result valid for specic drying conditions ap-
tent <25 wt%) do not have a structure in the plied here (drying oven, sample above desiccant).
same size range. Instead, the distribution of

Fig. 2. Electron micrograph of replicas of fracture surfaces of dried sodium silicate solutions; scale bar in the picture; (a) sample dried
24 h at 50 C, water content 32.5 wt%; (b) sample dried 26 d at 40 C, then 5 d at 60 C, water content 24.6 wt%.
 H. Roggendorf et al. / Journal of Non-Crystalline Solids 293295 (2001) 752757
the gold colloids suggests either a homogeneous
structure or a particulate structure with a size
range 6 5 nm (Fig. 2(b)).
Thermal analysis with pressure-tight crucibles
led to the detection of DSC steps similar to Dcp
steps occurring at glass transition. Two dierent
thermal events, a low temperature event h1 and a
high temperature event h2 , respectively, were
identied. The midpoints of the DSC steps were
evaluated. The h1 eect was observed in three
samples with 12 wt% H2 O content at temperatures
between 130 and 150 C. The h2 eect was detected
in all samples with water contents between 12 and
40 wt%, even in those samples which already
showed the h1 eect. Its midpoint temperature in-
creased from about 80 C (water content: 3540
wt%) to 270 C (water content: ca. 12 wt%). The
shape of the h1 and h2 eects is dierent: h1 covers
a smaller temperature range (DT ) but has a larger
step height (Dcp ). The temperatures of the mid-
points of the DSC steps are shown in Fig. 3 as a
function of the water content after drying. The
second eect found by Dent Glasser and Lee [4] is
included for comparison. It coincides with the h1
eect. However, Dent Glasser and Lee applied
open crucibles but did not correct their data with
respect to evaporation. The rst DTA eect de-
tected by Dent Glasser and Lee which is expected
at about 100 K lower than the second one was
not observed in the DSC runs with pressure-tight
crucibles.
Fig. 3. Midpoints of DSC steps (analysed with pressure-tight
crucibles) and foaming temperatures (hot stage microscopy) of
dried sodium silicates as a function of the water content after
drying; composition of the starting solution as in Fig. 1; heating
rate 10 K/min; higher temperature eect reported in [4] in-
cluded.
755
Fig. 4. DTA/TG analysis of a dried sodium silicate solution;
composition of the starting solution as in Fig. 1; water content
21.8 wt%.
In order to study the nature of these eects hot
stage microscopy was applied. The temperatures at
which the foaming of the materials was observed
are included in Fig. 3. Fig. 4 shows the result of
one of these DTA/TG runs for a sample contain-
ing 21.8 wt% water after drying. The following
observations can be reported:
Slight mass loss of 1.0 wt% during heating up to
138 C.
Signicant and unsteady increase of weight loss
rate (mass per time) at 138 C.
Foaming at 147 C (observed in hot stage).
Slight and unsteady increase of weight loss rate
at 157 C.
4. Discussion
Concerning the structural evolution, the fol-
lowing results can be reported:
The sodium silicate solutions are colloidal sols.
Drying between 30 and 100 C leads to a grad-
ual solidication. Dried sodium silicates with a
water content between 45 and 12 wt% are trans-
parent, non-crystalline, X-ray amorphous and
brittle if crystallisation and cracking are
avoided. According to [10] they can be recog-
nised as vitreous materials.
In the rst drying stage, structural units with
sizes between 30 and 100 nm can be detected.
At a later drying stage, a ner or even homoge-
neous structure is observed.
Two dierent reactions were observed during
heating of the materials, which show typical fea-
756 H. Roggendorf et al. / Journal of Non-Crystalline Solids 293295 (2001) 752757
tures of glass transition in thermal analysis: one
(h2 ) was observed in all samples with water con-
tents between 12 and 40 wt%, and the other (h1 )
only in samples with low water contents (<15
wt%). In the latter samples both eects, h1 as
well as h2 , were observed.
A macroscopic transition between a solid and a
deformable state was observed.
A correlation between foaming of the dried so-
dium silicates and the h1 or h2 eects, respec-
tively, was not found.
On the basis of these results a model of the
structural changes during drying is proposed:
1. The starting material of the drying process is a
colloidal dispersion consisting of aggregates
with sizes between 30 and 100 nm. They consist
of smaller primary particles with sizes of possi-
bly 15 nm, corresponding to the sizes reported
in the literature [1].
2. Drying of the sodium silicate solutions reduces
the volume of the interstitial solution until the
aggregates approximate each and form a rigid
structure at a water content of 50 wt% (experi-
mental result, room temperature). The interpre-
tation is that the aggregates form a random
close packing. Thus the solidication is ex-
plained as a solcolloid glass transition or a
solgel transition.
3. The packing density of a random close packing
is about 58 vol.% [11]. Assuming that the pri-
mary colloids have a similar packing density
within the aggregates, the total volume of the
solid phase at the point of solidication can
be calculated as 34 vol.% (0:582 0:34). The
rest of the volume contains the solution phase.
4. The density of these materials at the point of
solidication is about 1:56 g=cm3 . 100 cm3 of
the just solidied hydrous sodium silicate
( 156 g; water content: 50 wt% 78 g) consist
of 34 cm3 solid phase and 76 cm3 solution
phase. Estimating the density of the solution
3 3
as 1:05 g=cm yields 2:24 g=cm as density of
the colloids.
5. The density is a function of the water content.
An approximation based on own density mea-
surements allows one to calculate the density
of dried sodium silicate solution with a molar
SiO2 :Na2 O ratio of 3.3 with an accuracy of
5%: density q 0:017c 2:41 (c: concentra-
tion of H2 O in wt%; 30 < c 6 100).
6. Further loss of solvent requires a reorganisa-
tion of the aggregate structure towards a more
dense random close packing of the primary col-
loids.
7. Further drying requires the vanishing of the
voids between the primary colloids.
On the basis of the presented model the relative
volume distribution of the primary colloids, the
voids between the colloids, and the voids between
the aggregates was calculated as a function of the
water content (Fig. 5).
The starting point of the calculation is a mate-
rial having a H2 O content of 50 wt%. According to
point 3 of the model, the colloids occupy 34% of
the volume of this material ( 217:9 cm3 for 1 kg),
the aggregates ( colloids + voids between col-
loids) 34/0.58 58 vol.%, whereas the rest ( 42
vol.%) represents the volume fraction of the voids
between the aggregates. Further drying reduces the
water content.
Example: 1 kg of the dried material containing
50 wt% H2 O ( 0:5 kg H2 O) is dried to 0.98 kg
containing 0:48 kg H2 O ( 48:98 wt% H2 O).
Point 5 of the model allows to calculate the density
3
of the new material ( 1:577 g=cm ), a value,
which in turn gives the volume of the residual
material (621:4 cm3 for 980 g of a dried material
with 48.98 wt% H2 O). One further assumption was
used: The absolute volume of the solid colloidal
Fig. 5. Calculated volume distribution of the solid phase, the
voids between aggregates and colloids and the free solution in
materials prepared by drying sodium silicate solutions as a
function of the water content; composition of the starting so-
lution as in Fig. 1.
 H. Roggendorf et al. / Journal of Non-Crystalline Solids 293295 (2001) 752757
phase is unchanged during drying. The absolute
volume of the colloids of 217:9 cm3 is the basis for
calculating the absolute volumes of the aggregates
and the absolute volume of the voids between the
aggregates. These data were then converted to
relative volumes by using the volume calculated
from the density values as 100%. When the volume
of the aggregates plus the calculated volume of the
voids between them is greater than the volume
calculated by the density, the relative volume is set
to 100%.
Some conclusions can be drawn: A rough esti-
mation of the density of the solid colloids yields
2:24 g=cm3 , which is close to the density of a silica
glass. At water contents between 50 and 30 wt%
both structures, the 50 nm structure and the 2 nm
structure, are expected to exist. At about 30 wt%
the 50 nm structure vanishes. Between 30 and 10
wt% H2 O content the voids between the colloids
should vanish progressively. Below 10 wt% H2 O
content a homogeneous structure is expected. One
experimental remark: at about 10 wt% water
content some kind of barrier seems to exist. It was
not possible to dry the sodium silicate solutions to
water contents below 12 wt% under the conditions
described in this paper without aecting the dense
amorphous structure.
5. Summary
Transparent, solid and amorphous materials
were obtained by drying sodium silicate solutions.
The combined application of simultaneous ther-
mal analysis, electron microscopy and hot stage
microscopy helps to identify thermal reactions
occurring upon heating these materials. At least
one of these reactions is a solgel or a solcolloid
757
glass transition. Based on these structural ndings
a model of the structural evolution of the solutions
during drying was developed. In this process the
structure of the solutions is converted from a sol to
a particulate structure. Further drying leads to the
formation of a ner structure.
Acknowledgements
The kind support of the electron microscopy
team of Professor Dr G.H. Michler and the ex-
perimental assistance of Mrs S. Brinke and Mrs H.
Schwalbe are gratefully acknowledged.
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