See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/225386200

Physical-chemistry of sodium silicate gelation in an alkaline medium

Article  in  Journal of Sol-Gel Science and Technology · June 2011

DOI: 10.1007/s10971-011-2437-4

CITATIONS READS

7 1,075

3 authors, including:

Monique Tognonvi Sylvie Rossignol

Université Péléforo-Gbon-Coulibaly Center european ceramic
25 PUBLICATIONS   307 CITATIONS    227 PUBLICATIONS   2,991 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Materials & Structural Stability, View project

Wet air oxidation of acetic acid over platinum and ruthenium catalysts supported on cerium based materials View project

All content following this page was uploaded by Monique Tognonvi on 25 May 2015.

The user has requested enhancement of the downloaded file.

J Sol-Gel Sci Technol (2011) 58:625–635
DOI 10.1007/s10971-011-2437-4
ORGINAL PAPER
Physical-chemistry of sodium silicate gelation in an alkaline
medium
Monique Tohoué Tognonvi • Sylvie Rossignol •
Jean-Pierre Bonnet
Received: 18 November 2010 / Accepted: 1 March 2011 / Published online: 9 March 2011
 Springer Science+Business Media, LLC 2011
Abstract The behavior of sodium silicate solutions in an
alkaline medium has been studied in the 11.56–9 pH range
by adding different amount of hydrochloric acid into
a concentrated commercial solution ([Si] = 7 mol/L,
Si/Na = 1.71, pH = 11.56). The formed products and their
evolution during long ripening (up to 150 days) have been
characterized by cryo-SEM, elementary analysis (ICP-
AES), X-ray diffraction and surface area and relative
density measurements. In the studied narrow ranges of pH
(11.56–9) and silicon concentration (7–0.2 mol/L) four
different situations have been observed: (i) a stable and
clear solution, (ii) a reversible and transparent physical gel;
(iii) a soluble white gel characterized by a significant
contraction during ripening and (iv) an irreversible gel
which presents a slow syneresis leading to a consolidate
solid. The characterizations of the different solids, liquids
and gels have shown that the observed behaviors were the
results of the formation of nanometric soluble
NaSi1.87O4.24 particles and/or insoluble silica-like
(NaSi12.66O25.82) grains and of the contribution of a dis-
solution/precipitation mechanism.
Keywords Sodium silicate solution  Concentrated
solution  Acidification  Gelation in alkaline medium 
Syneresis  Dissolution/precipitation
M. T. Tognonvi  S. Rossignol (&)  J.-P. Bonnet
Centre Européen de la Céramique, Groupe d’Etude des
Matériaux Hétérogènes (GEMH E.A. 3278), ENSCI, 12 Rue
Atlantis, 87068 Limoges Cedex, France
e-mail: Sylvie.rossignol@unilim.fr
1 Introduction
Binders have been described by Englelleitner [1] as ‘‘an
additive to the material being agglomerated that provides
bonding strength in the final product. A binder can be a
liquid or solid that forms a bridge, film or matrix filler or
that causes a chemical reaction’’. The most commonly used
binder is the cement. It is a mineral powder, which behaves
as a hydraulic binder (consolidation also occurs in water).
The common Portland cement is a mixture of five main
phases: tricalcium silicate (3CaO,SiO2), dicalcium silicate
(2CaO,SiO2), tricalcium aluminate (3CaO,Al2O3), tetra-
calcium ferroaluminate (4CaO,Al2O3,Fe2O3) and calcium
sulphate. The presence of water in the system causes, via a
complex mechanism, the formation of hydrates, which
contribute to the consolidation of the product. It is gener-
ally considered that these silicon-rich hydrates form a gel
that behaves like a binder. The hardening of the cement
paste would correspond to the structuration of this gel that
contains solid particles with a composition of (CaO)x
(SiO2)(H2O)y where the values of x and y depend on the
calcium and silicate content in the aqueous phase [2]. The
attack of amorphous siliceous or silico-aluminate products
by lime saturated aqueous solutions leads also to the for-
mation of CSH gels. This so-called pozzolanic reaction is
at the origin of development of pozzolanic cements where
the Portland clinker is partially substituted by amorphous
silica and/or metakaolin.
During the last few years, a new family of mineral
binders, called geopolymers, has generated a great interest
[3, 4]. These materials are formed by reaction between
siliceous or silico-aluminate powders (metakaolin, fly
ash…) and concentrated alkaline solutions (KOH,
NaOH…). The consolidation of these materials would be
the result of the formation of either a zeolitic-type gel or a
123
626
siliceous or aluminosilicate hydrogel [5]. The formation of
a silicate-based gel seems to be responsible for the binder
behavior of both cement and geoplymer. In such systems
the gelation occurs in situ in a complex and evolving
system. Therefore, the formation mechanism of the binding
minor phase is difficult to analyze.
Alkaline solutions of sodium silicate (water glass) are
often introduced in the geopolymer starting mixture in
order to accelerate the consolidation process. In peculiar
conditions, water glass alone can even behave like a non-
hydraulic binder. In this case the binding gel is formed
directly from the liquid, without any significant reaction
with solid grains, and the progressive evolution from a
solution to a rigid network, via a gel, is characteristic of the
starting solution. In such conditions it is possible to study
the direct influence of the liquid composition on the gela-
tion and strengthening processes.
A combined analysis of 29Si NMR, SAXS and ICP-AES
experiments [6] performed on the concentrated sodium
silicate solution (pH = 11.56; [Si] = 7 mol/L; Si/Na
atomic ratio = 1.71) used in this study has shown that the
observed high siliceous species solubility results from the
formation of a Si7O18H4Na4 neutral complex. The dilution
of such a concentrated solution leads to a progressive
dissociation of these neutral complexes into (Si7O18H4-
Na4-n)n- charged entities and Na? ions (1 B n B 4) for
silicon concentration higher than 4 mol/L. The scattering
entities detected by SAXS being twice bigger in the most
diluted solutions than in the concentrated one, a polycon-
densation reaction between a limited number, between 2
and 8, of (Si7O18H4Na4-n)n- groups should occur. The
acidification of such concentrated or diluted solutions
could affect those neutral or charged species.
A study of the influence of pH and concentration on the
evolution of alkaline commercial solutions of sodium sili-
cate had been realized in order to identify the nature of the
involved gels and to determine the critical parameters for
gelation and consolidation.
2 Experimental part
2.1 The starting solutions
The sodium silicate solution used is a commercial product
from VWR Prolabo. Its molar chemical composition,
determined by emission spectrometry (ICP-AES), corre-
sponds to 3.41 SiO2 and 21 H2O for 1 Na2O). The solution
characteristics are: relative density = 1.32, pH = 11.56,
[Si] = 7.01 mol/L and Si/Na = 1.71.
Dilute hydrochloric acid solutions with concentration
ranging from 0.5 to 2 mol/L were also used in order to
modify both pH and [Si]. These solutions have been
123
J Sol-Gel Sci Technol (2011) 58:625–635
prepared from a 37 HCl wt% commercial solution (Norma
Prolabo) by adding deionized water.
2.2 Products preparation and aging conditions
The studied mixtures have been obtained by progressive
addition of HCl solution into the commercial sodium sili-
cate solution under magnetic stirring at room temperature.
The solutions with [Si] B 2.26 mol/L were firstly dilute
with deionized water before acidification. After acidificat-
ion, the [Si] and pH of the studied solutions were ranged
from 0.2 to 6 mol/L and from 9 to 11.56, respectively. The
pH value was measured all along the process using a
PHM240 METER LAB pH meter (radiometer) operating
with a ‘‘red rod’’-type glass electrode and a T201-type
temperature sensor.
The as-obtained homogeneous solutions (mixtures) were
then transferred into closed plastic vessels for aging at
room temperature.
Depending on pH, Si concentration and behavior during
ripening at room temperature, four different behaviors can
be distinguished:
– (A) a clear and stable solution;
– (B) a stable and transparent gel (Fig. 1a);
(a)
4 days 120 days
(b)
40 min 2 hours 9 days 30 days
(c)
16 min 30 min 5 days 30 days
Fig. 1 Photos showing the evolutions observed during ripening of the
three different gels obtained by acidification of the commercial
sodium silicate solution: a transparent gel (B-type gel) obtained for
[Si] = 5.2 mol/L and pH = 11.10, b white gel (C-type gel) obtained
for [Si] = 3 mol/L, pH = 10.67 and c white gel (D-type gel)
Obtained from [Si] = 2.26 mol/L, pH 10.56
J Sol-Gel Sci Technol (2011) 58:625–635 627

– (C) an initial white gel leading during aging to a before its transferred on the cold stage of the SEM using a
progressive separation between a sediment and a protective transfer unit.
supernatant (Fig. 1b);
– (D) a white gel with a significant syneresis during 2.3.3 X-ray diffraction
ripening (Fig. 1c).
X-ray diffraction analysis was performed on powders
When a gel appeared (B-, C- or D-type gel), a gelation
obtained after a grinding of samples dried at 25 C for
time (tg) corresponding to the time which elapsed between
72 h. The diffraction diagram was obtained using an INEL
the solution preparation and the earliest moment at which
CPS (Curved Position Sensitive Detector) 120 device,
the gel broke away from the wall instead of flowing as a
working with CuKa1 radiation (k = 1.540598Å) at 40 kV
liquid when the beaker was tilted has been determined [7,
and 30 mA. The exposure and acquisition times for qual-
8].
itative analyses were both 20 min, the angular range was
After ripening, when a separation between a clear
10 \ 2h \ 90 and the pace was 0.029.
supernatant and a white viscous gel, sediment, or brittle
solid was observed (C and D cases), the two phases were
2.3.4 Specific surface area
analyzed after a careful separation.
The specific surface area of gels and sediments dehydrated
2.3 Characterization techniques
at 200 C for 2 h was determined by nitrogen adsorption–
desorption isotherms (Micromeritics Flow Sorb II 2,300)
2.3.1 Elementary chemical analysis
using the BET calculation method. The experiments were
carried out on solid mass of about 11 mg.
The Na and Si concentrations in solutions, gels or solids
were determined using a Thermo Jarrell Ash Corporation
IRIS spectrometer (ICP-AES). Before analysis, solids were
3 Results and discussion
washed and dried (110 C for 24 h) and then 20 mg were
dissolved in an HF solution using a microwave digestion
3.1 Acidification of the sodium silicate solution
technique.
The Cl concentration was determined by potentiometric
3.1.1 Qualitative description
titration of the reaction between Cl- and Ag? using a
MeterLab Ion450 Ion analyzer (Radiometer analytical).
The addition of hydrochloric acid and water in a com-
mercial sodium silicate solution ([Si] = 7 mol/L and
2.3.2 Cryogenic scanning electron microscopy pH = 11.56) leads before aging for pH [ 9 to the different
situations: All the obtained results are reported in Fig. 2.
Gels and sediments, previously submitted to a cryogenic It appears that each situation is associated with a specific
treatment, have been observed by scanning electron pH-[Si] domain:
microscopy (SEM). In order to minimize the volume
change of free or weakly bond water, the samples were 12
cooled under conditions appropriate to the formation of (c)
(d)
vitreous ice using a Leica EM PACT high-pressure freezer.
All SEM characterizations were done with a JEOL JSM- 11
7400F microscope equipped with a field-emission gun and (a)
pH value

a cooled stage. High-resolution images were obtained using (b)

low acceleration voltage (1–6 kV). 10

Each humid sample was introduced into the hollow

(/ = 200 lm) of a copper grid (/ = 1.2 mm) coated with 9
gold before very ultra-rapid freezing in liquid nitrogen
under a pressure of about 2,000 bars. The frozen sample
was then transferred into a cold chamber (Gatan, Alto 8
2,500) connected to the microscope, where it was firstly 0 2 4 6 8
fractured (freeze-fracture) and secondly warmed from [Si] (mol/l)
-150 up to -95 C in order to remove by sublimation the
Fig. 2 pH-[Si] domain corresponding at room temperature to
ice present on the sample surface. Then, the sample was (a) clear solutions, (b) transparent and reversible gels, (c) white and
cooled at -150 C for 5 min and coated with gold for 40 s soluble gels and (d) white and irreversible gels

123
628 J Sol-Gel Sci Technol (2011) 58:625–635

– clear solution (A) for 6 \ [Si] \ 7 mol/L and (a) 5

11.25 \ pH \ 11.56;
[Si] = 5.2 mol/l
– transparent and reversible gel (B) for 4.14 \ [Si]
\ 6 mol/L and about 10.90 \ pH \ 11.25; 4 [Si] = 3.6 mol/l
– white and soluble gel (C) for 3 \ [Si] \ 4.14 mol/L [Si] = 2.26 mol/l

log 10tg (min)

and about 10.56 \ pH \ 10.90; 3
– white and irreversible gel (D) for 0.2 \ [Si] \ 2.9 mol/L
and about 9 \ pH \ 10.75. 2

Results reported in Fig. 2 suggest that the nature of the

formed gel would be more dependent on the silicon con- 1
centration than on the pH.
0
3.1.2 Influence of chemical parameters on the gelation 10 10.25 10.5 10.75 11 11.25
time (tg) pH value
(b)
3.1.2.1 Influence of pH Figure 3a shows the influence of 5
pH on the gelation time for three different silicon concen- pH = 10.56
trations leading, to the formation, respectively, of B-type 4
pH = 11.10
gel ([Si] = 5.2 mol/L), C-type gel ([Si] = 3.6 mol/L) and
D-type gel ([Si] = 2.26 mol/L). In all three cases, the
gelation time increases with pH values. Only C- and D-type log 10tg (min) 3

gels can present a very short gelation time.

2
pH = 10.67
3.1.2.2 Influence of silicon concentration The influence
of silicon concentration on gelation time (tg) at constant pH 1
pH = 10.30
is plotted in Fig. 3b for pH = 11.10 (B-type gel), 10.67
(C-type or D-type gel), 10.56 (C-type or D-type gel) and 0
10.30 (D-type gel). The gelation time always decreases 0 2 4 6
when [Si] increases. [Si] (mol/l)
The very long ([100 h) and weakly [Si] dependent (c)
5 B-type gel
gelation times observed when the pH is maintained at
C-type gel
11.10, are characteristic of B-type gel behavior.
4 D-type gel
At constant pH, a strong tg increase observed for C- and
D-type gels when [Si] decreases (Fig. 3b) could be due to a
3
log10tg (min)

dilution effect. The transition between C- and D-type gels

observed at pH 10.67, when the solution is diluted from
[Si] = 3 mol/L down to [Si] = 2.9 mol/L, is not associ- 2
ated with a strong tg change, suggesting a common origin
for these two type of gels. 1

3.1.2.3 Chlorine concentration effect The studied solu- 0

tions are prepared by adding a concentrated or diluted
hydrochloric acid solution to the commercial sodium sili-
cate solution. The added chlorine atoms can act either
directly if Cl- ions are involved in the physico-chemical
process responsible for the gelation or indirectly by
changing the average charge present on the silicate species.
The charge equilibrium in solution leads to Eq. 1:
n   þ
n½Si  þ ½OH  þ ½Cl  ¼ ½Na  þ ½H  þ
ð1Þ
Where n- (average negative charge per solvated silicon
atom) is the ratio between the sum of charges associated to
0.1 0.2 0.3 0.4 0.5
[Cl] (mol/l)
Fig. 3 Gelation time of different acidified sodium silicate solutions
versus: a pH values for three different [Si]; b silicon concentration for
four different pH values and c chlorine concentration
the whole silicate groups and the number of solvated
silicon species. In our concentrated systems, concentra-
tions of OH- (\10-2 mol/L) and H? (\10-9 mol/L) are
negligible compared with [Sin-], [Na?] and [Cl-].
Therefore, charge equilibrium becomes:

123
J Sol-Gel Sci Technol (2011) 58:625–635 629

n½Sin  ¼ ½Naþ   ½Cl  ð2Þ
The gelation times observed for the different studied
solutions are reported in Fig. 3c versus chlorine concen-
tration. For 0.30 B [Cl-] B 0.40 mol/L, the three types of
gels can be obtained. Therefore, it is not possible to asso-
ciate a type of gel with a specific chlorine concentration
domain. These results suggest that Cl- ions are not directly
involved in the gelation process; it acts as a spectator ion.
3.2 Gel ripening
Figure 1 shows the apparent behavior of B-, C- and D-type
gels during aging. B-type gel seems to remain stable with
the time. C- and D-type gels show a significant contraction
during ripening associated with the formation of a super-
natant liquid.
3.2.1 B-type gels
been recovered carefully and filtrated to avoid the presence
of any solid residue in the liquid. Then the supernatant
volume, Vsur, has been measured using a burette. The
difference between the total volume (VT: liquid ? solid)
and the supernatant volume (Vsur) corresponds to the solid
phase apparent volume, consisting of a solid skeleton and
of the interstitial liquid. Some evolutions of the relative
apparent volume of solid phase derived from C-type gels
are shown in Fig. 4. All curves display a similar behavior:
a rapid contraction during the first 9 days, and an asymp-
totic value obtained after about 20 days.
The evolution observed in Fig. 4a is characteristic of the
influence of the starting silicon concentration at constant
pH value: the apparent volume fraction of the solid phase at
the end of the ripening process increases with the silicon
concentration in the solution before gelation and then with
the amount of available solvated silica in the starting
solution.

Transparent B-type gels appear at room temperature after a

relatively long maturation time (C4 days). After formation (a) 1
they do not show any detectable change during aging in [Si] = 4.14 mol/l
constant conditions (Fig. 1a). However, they are destroyed 0.75 [Si] = 3.8 mol/l
by a temperature increase ([50 C), by mechanical stirring [Si] = 3.6 mol/l
(VT-Vsur)/VT

or by water addition (reversible gels). These behaviors are

characteristic of physical gels constituted of entities 0.5
bounded by physical bond (Van der Waals, hydrogen,
Coulombian) [9]. These types of gels are obtained for sil-
0.25
icon concentrations ranging from 4 to 6 mol/L; i.e. in a
concentration domain where non-acidified dilute solution
were mainly composed of (Si7O18H4Na4-n)n- entities 0
(1 B n B 4) [6]. The H? ions added in solution are capable tg 25 50 75 100
to combine with these charged species (Si7O18H4Na4-n)n- Time (days)
leading to the formation of Si7O18H4?nNa4-n neutral
entities likely to aggregate. Therefore, B-type gels could be (b) 1
made up of aggregated Si7O18H4?nNa4-n particles. pH = 10.90
pH = 10.85
3.2.2 C-type gels 0.75
pH = 10.75
(VT-Vsur)/VT

pH = 10.67
The ripening of white C-type gels leads to the slow for-
mation of a white solid which present a progressive 0.5

anisotropic shrinkage. A supernatant liquid is detectable

30 min after gelation. Figure 1b shows a representative
0.25
example of an evolution observed during the ripening of a
C-type gel. After a long ripening, a weakly consolidated
solid can be separated from the supernatant. The obtained 0
solid can be easily dissolved in water. Therefore it appears tg 25 50 75 100
that the aging of C-type gels leads to the formation of Time (days)
soluble precipitate made up of weakly linked grains.
Fig. 4 Variation, versus ripening time, of the relative apparent
volume of the solid phase derived from different C-type-gels: a for 3
3.2.2.1 Solid phase of C-type gel In order to determine silicon concentrations at pH = 10.90 and b for four pH values and a
the apparent volume of the solid phase, the supernatant has [Si] = 3.6 mol/L

123
630
The evolution observed in Fig. 4b is characteristic of the
influence of pH on the ripening of C-type gels: at constant
initial silicon concentration, higher is the pH value lower is
the relative apparent volume of the final solid (VT-Vsur)/VT.
Such an evolution suggests that the formation of the solid
phase from C-type gels is strongly pH dependant.
3.2.2.2 Morphology and composition of C-type gel Gel
microstructure changes during ripening have been observed
using a scanning electron microscope equipped with a
cryogenic stage. The samples were previously frozen as
described in paragraph 2.3.2. Secondary electrons images
of representative situations observed immediately after
gelation of C-type gels and after a 30 days of ripening are
shown in Fig. 5a. Just after gelation (Fig. 5a1) the gel is
composed of particles homogeneously distributed. The
contraction that occurs during ripening is associated with
pore coalescence (Fig. 5a2). The absence of macroscopic
cohesion of the final solid could be explained by the ten-
dency of the resulting macropores to form macroporosity
lines leading to a microstructure comparable to a stack of
hard aggregates weakly bound each other.
The evolution during ripening of the liquid supernatant
composition has been studied. Each C-type derived gel
products has been let to ripen for a given times and then all
the supernatant formed since gelation has been taken off.
The concentrations of elements present in the supernatant
have been determined by ICP-AES spectrometry for silicon
Fig. 5 Secondary electron
images of fracture surfaces of
solid formed from a solution of
silicon concentration equal to:
a 4.14 mol/L and pH = 10.85
(C-type gel); b 1.76 mol/L and
pH = 10.75 (D-type gel): (1)
immediately after gelation, (2)
30 days after gelation
(accelerating voltage 3 kV,
frozen samples in a cryogenic
stage)
123
J Sol-Gel Sci Technol (2011) 58:625–635
and sodium elements and by potentiometry for chlorine
ions. The supernatant Si, Na and Cl concentrations deter-
mined for different ripening time are reported in Table 1
for two initial silicon concentrations [Si] (3.6 and
4.14 mol/L) and two pH (10.90 and 10.75). It appears that
silicon and sodium concentrations detected in the super-
natant after a 2 days of ripening are very inferior to those
present in the solution before gelation, indicating that the
white solid contains both silicon and sodium elements. A
significant increase of silicon and sodium concentrations in
the supernatant occurs between the 2nd and the 9th days of
ripening, a period also characterized by a strong contrac-
tion of the solid (Fig. 4), suggesting that this latter phe-
nomenon could be in relation with a dissolution of some
solid species. It can be noticed that the corresponding
increase of silicon and sodium concentrations in the
supernatant occurs without any change of the Si/Na atomic
ratio in the supernatant. After 9 days of ripening, the sili-
con and sodium concentrations in the supernatant appear to
be stabilized (Table 1). The contraction observed for aging
times longer than 9 days (Fig. 4) does not affect signifi-
cantly the silicon and sodium concentrations in the
supernatant.
Results reported in Table 1 show also that the final sil-
icon and sodium concentrations in the supernatant increase
with the pH of the starting solution. This result is in
agreement with the simultaneous decrease of the observed
relative solid volume (Fig. 4b).
J Sol-Gel Sci Technol (2011) 58:625–635 631

Table 1 Evolution during the ripening of Si, Na and Cl concentra- Table 2 Evolution of the estimated solid volume (VS) and compo-
tions in the supernatant for different initial solutions: a) sition ((Si/Na)S) during the ripening of C-type gels obtained from 2
[Si] = 3.6 mol/L and [Na] = 2.11 mol/L; b) [Si] = 4.14 mol/L and solutions of silicon concentration equal to 3.4, 3.6 and 4.14 mol/L at
[Na] = 2.42 mol/L, at pH = 10.90 and 10.75 pH 10.75 (initial Si/Na atomic ratio = 1.71)
[Si] pH tg Ripening time 0 2 9 90 Initial [Si] (mol/L) Ripening time (days) 2 9 90
(mol/L) (min) (days)
3.4 VS (cm3) 2.98 2.09 2.08
3.6 10.90 342 [Si]sur (mol/L) 2.15 2.48 2.49 (Si/Na)S 1.73 1.87 1.87
[Na]sur (mol/L) 1.31 1.51 1.52 3.6 VS (cm3) 3.05 2.08 2.07
(Si/Na)sur 1.64 1.64 1.63 (Si/Na)S 1.79 1.88 1.87
[Cl]sur (mol/L) 0.31 0.32 0.32 0.32 4.14 VS (cm3) 2.82 2.18 2.14
10.75 120 [Si]sur (mol/L) 1.67 2.30 2.31 (Si/Na)S 1.81 1.88 1.87
[Na]sur (mol/L) 1.04 1.43 1.43
(Si/Na)sur 1.61 1.61 1.62
[Cl]sur (mol/L) 0.34 0.35 0.35 0.35 the solid skeleton always has a chemical composition
4.14 10.90 120 [Si]sur (mol/L) – 3.11 3.61 3.61 characterized by a Si/Na atomic ratio close to 1.87
[Na]sur (mol/L) – 1.86 2.16 2.16
(NaSi1.87O4.24). During the first part of contraction, sig-
(Si/Na)sur 1.67 1.67 1.67
nificant increase of silicon and sodium concentrations is
observed in the supernatant (Table 1). During the shrink-
[Cl]sur (mol/L) 0.38 0.39 0.39 0.39
age, the solid microstructure changes and the formation of
10.75 30 [Si]sur (mol/L) – 2.37 2.78 2.81
macropores is observed (Fig. 4a). All these evolutions can
[Na]sur (mol/L) – 1.45 1.71 1.72
result from a continuous process that would begin with the
(Si/Na)sur 1.634 1.626 1.634
formation of small NaSi1.87O4.24 solid particles, that grow
[Cl]sur (mol/L) 0.42 0.43 0.43 0.43
in number and size and interact to form a gel that occupies
all the available space [11, 12]. Then, the gel microstruc-
The measured chlorine concentrations in the supernatant ture evolves via dissolution and precipitation of these
after ripening and that introduced in the initial solution are particles leading, simultaneously, to a densification of the
always practically identical (Table 1). This result is in solid (strong contraction) and to the formation of macro-
accordance with the hypothesis that chlorine would not be pore by coalescence of nanopores.
directly implicated in the gelation process as enunciated in
part 3.1.2. 3.2.3 D-type gels
The white solid formed during ripening of C-type gels is
water-soluble; therefore, the separation of the solid skele- After gelation of D-type gels, a syneresis is always
ton from the interstitial liquid can affect the solid compo- observed (Fig. 1c). This almost isotropic contraction is
sition and/or quantity. However an estimation of the solid accompanied by a clear liquid discharge. The initial gel and
skeleton quantity and composition can be performed con- the consolidated material resulting from syneresis, are not
sidering the conservation of each species mole number and destroyed by a temperature increase or by a gradual dilu-
assuming that the chemical composition of interstitial tion, therefore, the D-type gels are irreversible. At the end
liquid and supernatant is the same [10]. The as-determined of the syneresis and after separation from the clear liquid,
volume of the solid skeleton is expressed according to the solid obtained is monolithic and strongly consolidated.
Eq. 3, 4 in the appendix. According to the Eq. 7 reported in The X-ray diffraction diagram of a solid obtained after
appendix it is possible to deduce the Si/Na atomic ratio in 5 months of ripening and 72 h of drying at room temper-
the solid from the solid skeleton volume. The results ature (silicon concentration = 2.26 mol/L and pH =
obtained for three systems ([Si] = 3, 3.6 and 4.14 mol/L) 10.56) reported in Fig. 6 highlights the amorphous char-
at pH 10.75 are reported in Table 2. Whatever the initial acter of the consolidated product.
composition, the (Si/Na)S atomic ratio tends to increase
slightly during ripening, it is remarkable to note that all the 3.2.3.1 Behavior of D-type gel during ripening The
Si/Na atomic ratios in the solid at the end of ripening are evolution during ripening of the solid relative apparent
close to 1.87 [10], in agreement with a solid final compo- volume ((Vsur-VT)/VT) for several D-type gels, is shown in
sition (Na2O)0.5(SiO2)1.87 or NaSi1.87O4.24. Fig. 7 for various silicon concentration and pH values. The
According to experimental results, the trend observed initial silicon concentration has a marked influence on the
during the ripening of C-type gel can be summarized as syneresis kinetics at constant pH (Fig. 7a): More concen-
follows. The gel rapidly evolves to form a white solid trated is the starting solution shorter is the gelation time and
which gradually contracts. Wathever the initial conditions, faster is the syneresis. When the initial silicon concentration

123
632 J Sol-Gel Sci Technol (2011) 58:625–635

(a)
1
[Si] = 0.5 mol/l

[Si] = 1 mol/l
0.75

(VT-Vsur)/VT
0.5 [Si] = 1.76 mol/l
[Si] = 2.26 mol/l

0.25
[Si] = 2.81 mol/l

0
tg 40 80 120 160 200
Time (days)

Fig. 6 X-ray diffraction diagram of the solid obtained after 5 months (b) 1
of ripening of a D-type gel and 72 h of drying at room temperature pH = 10.75
(initial silicon concentration = 2.26 mol/L and pH = 10.56) pH = 10.56
0.75 pH = 10.30
is equal to 1.76 mol/L, the syneresis kinetics is only weakly pH = 10.10

pH-dependent (Fig. 7b). When the pH decreases, the solid
apparent relative volume at the end of the ripening process
increases. This observation is in agreement with the
simultaneous increase of the silicon concentration observed
in the supernatant (Table 3). Those results suggest that the
solubility of the solid increases with pH values.
The chemical composition of the liquid phase is reported in
Table 3 for different systems and ripening times. The silicon
and sodium concentrations are always lower in the superna-
tant than in the initial solution. The concentration decrease
affects more silicon than sodium especially for the less con-
centrated solutions. For each given system, it also appears that
the composition of the supernatant does not significantly
change during ripening. This result leads to conclude that the
gel shrinkage takes place without changing the composition of
the supernatant. A decrease of the pH values of solutions of
same initial silicon and sodium concentrations (Table 3) leads
to a decrease of supernatant silicon and sodium concentra-
tions, suggesting an increase of the amount of silicon and
sodium in the solid. It can be also noticed that the Si/Na atomic
ratio in the supernatant decreases with pH: e.g. (Si/Na)sur =
1.29 at pH = 10.75 and 1.08 at pH = 10;56 when the initial
silicon concentration = 1.76 mol/L. This result shows that
the pH value decrease leads to a silicon enrichment of the solid
composition.
3.2.3.2 Morphology and composition of D-type gel The
skeleton volume and the Si/Na atomic ratio, (Si/Na)S, of
the solid formed in these systems had been estimated using
the hypothesis previously considered for the calculation of
the same parameters for C-type gel derived solids. As these
solids are amorphous and silica rich, the relative density of
amorphous silica equal to 2.2 g/cm3 [8, 13] was retained
for calculation. The as-calculated values of solid skeleton
(VT-Vsur)/VT
0.5
0.25
0
tg 40 80 120 160 200
Time (days)
Fig. 7 Variation of the solid phase relative apparent volume versus
time during ripening of various D-type gels: a different starting
silicon concentrations at pH = 10.56 and b different pH values for an
initial silicon concentration = 1.76 mol/L
volume (VS) and (Si/Na)S atomic ratio are reported in
Table 4 for different ripening times for three systems
corresponding to initial solutions of pH = 10.56 and sili-
con concentrations = 1.76, 2.26 or 2.81 mol/L respec-
tively. At constant pH, VS increases with the silicon
concentration in the initial solution, i.e. with the amount of
silicon and sodium present in the system. The Si/Na atomic
ratio in the solid is also very sensitive to dilution; when the
initial solution concentration decreases, (Si/Na)S increases.
The microstructure of a D-type gel obtained from a
solution with a starting silicon concentration equal to
1.76 mol/L and a pH = 10.75 was observed by cryogenic
scanning electron microscopy immediately after gelation
and after a 30 days (Fig. 5b). The evolutions of the
microstructure of D-type gels during ripening (Fig. 5a, b)
are rather similar to C-type gels. In both case a pore
enlargement (probably by coalescence) occurs during rip-
ening. However, this pore growth is less pronounced for
D-type gels and the porosity does not seem to move
towards the anisotropic organization responsible for the

123
J Sol-Gel Sci Technol (2011) 58:625–635 633

Table 3 Evolution during ripening of Si, Na and Cl concentrations in Table 5 Chemical composition and specific surface area of the solids
the supernatant for different systems at pH = 10.75 or 10.56 and of obtained after syneresis (150 days) and water washing (70 times) of
initial concentrations: a) [Si] = 1.76 mol/L and [Na] = 1.03 mol/L; D-type gels derived from three initial solutions of same pH (10.56)
b) [Si] = 2.26 mol/L and [Na] = 1.32 mol/L and different silicon concentrations
[Si] (mol/ pH tg Ripening time 0 2 9 150 [Si]initial (mol/L) 1.76 2.26 2.81
L) (min) (days)
Atomic ratio Si/Na of washed solid 13.56 12.46 11.91
1.76 10.75 1560 [Si]sur (mol/L) – 1.03 1.04 1.07
Molar composition (%) SiO2 96.40 96.15 95.97
[Na]sur (mol/L) – 0.80 0.80 0.83
Na2O 3.60 3.85 4.03
(Si/Na)sur – 1.29 1.29 1.29
SBET (m2/g) 291 282 276
[Cl]sur (mol/L) 0.22 0.22 0.22 0.22
10.56 240 [Si]sur (mol/L) – 0.88 0.89 0.90
detected by ICP analysis in the first leaches. After 70
[Na]sur (mol/L) – 0.82 0.82 0.83
washing, silicon and sodium are not yet detected, sug-
(Si/Na)sur – 1.07 1.08 1.08
gesting that the remaining solid is insoluble in water at
[Cl]sur (mol/L) 0.26 0.26 0.26 0.26
room temperature [10].
2.26 10.75 740 [Si]sur (mol/L) – 1.33 1.35 1.36
These observations suggest that the consolidated solid
[Na]sur (mol/L) – 0.98 1 0.99
formed during ripening of D-type gels is constituted at least
(Si/Na)sur – 1.36 1.35 1.37
of two phases, one is dissolved in water during the washing
[Cl]sur (mol/L) 0.28 0.28 0.28 0.28 step and the other is insoluble. The continuous evolution of tg
10.56 16 [Si]sur (mol/L) – 0.95 0.96 0.95 observed at the transition between C- and D-type gel
[Na]sur (mol/L) – 0.88 0.87 0.87 domains (Fig. 3b, c) and the presence of Si and Na in the
(Si/Na)sur – 1.08 1.10 1.09 leaches lead to consider the assumption that the soluble
[Cl]sur (mol/L) 0.34 0.34 0.34 0.34 phase present in the D-type gel derived solid and the C-type
derived solid (with a Si/Na atomic ratio = 1.87) are the
Table 4 Evolution of solid skeleton volume (VS) and composition
same. The insoluble phases obtained after syneresis and
(Si/Na)S during the ripening of D-type gels obtained from three dif- water washing of the solids formed from three solutions of
ferent solutions of pH 10.56 and initial silicon concentration equal to pH = 10.56 and of initial silicon concentration equal to 1.76,
1.76, 2.26 or 2.81 mol/L 2.26 or 2.81 mol/L have been analyzed. The results reported
Initial [Si] (mol/L) Ripening time (days) 2 9 150 in Table 5 show that the composition of washed solids is very
sodium poor: average molar composition is (0.038 ± 0.003)
1.76 Vs (cm3) 1.28 1.27 1.24
Na2O to (0.962 ± 0.003) SiO2; e.i. NaSi12.66O25.82. The
(Si/Na)S 3.90 3.87 4.04
determination by the BET method of the surface area
2.26 VS (cm3) 1.96 1.96 1.97 (Table 5) of these washed solids, with a composition very
(Si/Na)S 2.83 2.75 2.77 close to silica, leads to results very close to the values
2.81 VS (cm3) 2.57 2.56 2.54 (*280 m2/g) observed for silica xerogels [15, 16].
(Si/Na)S 2.46 2.47 2.48

fragmentation of the C-type gel derived solid. According to

results reported in Table 4, it appears that the volume of
solid skeleton (VS) obtained from a given D-type gel
doesn’t change during syneresis. Therefore, the contraction
observed during ripening (Fig. 7) must correspond to a
gradual decrease of the volume of the interstitial liquid
(VL). The whole of these behaviors (grain growth, pore
growth, consolidation, densification and shrinkage) sug-
gests a microstructural evolution controlled by a dissolu-
tion/precipitation mechanism similar to that which controls
the second step of liquid phase sintering [14].
In order to check the irreversibility of the solids
obtained at the end of the syneresis phenomenon, different
D-type gel derived samples ripened for 150 days have been
washed 70 times with distilled water at room temperature.
A significant amount of silicon and sodium has been
4 Conclusion
The acidification of sodium silicate solution with silicon
and sodium concentrations, respectively, equal to 7 and
4.1 mol/L, leads to several situations in relatively narrow
ranges of pH and concentrations.
i. For the highest pH (11.25 B pH B 11.56) and silicon
concentrations (6 \ [Si] B 7 mol/L), the solution
remains clear and stable with time.
ii. For slightly lower silicon concentrations (4.14 \ [Si]
B 6 mol/L) and pH (10.90 B pH B 11.25), a trans-
parent gel (B-type) is formed. This gel doesn’t show any
change during ripening but it can be destroyed by water
dilution, heating or mechanical stirring. These behav-
iors are characteristic of physical gels constituted of

123
634
M
MSiO2  ½VT  ð½Si   ½SiSur Þ þ Vs  ½SiSur  þ Na2 2 O  ½VT  ð½Na   ½NaSur Þ þ Vs  ½NaSur 
Vs ¼
2:2
entities bounded by physical bond. The constitutives
aggregates would be the Si7O18H4?nNa4-n entities.
iii. In the pH range from 10.56 to 10.90, when the initial
silicon concentration is between 2.9 and 4.14 mol/L, a
soluble white gel (C-type) appears after a short time.
It turns, in few hours, into a white solid with a
chemical composition, NaSi1.87O4.24, independent of
starting conditions. The solid shrinkage observed
during ripening is associated with a silicon and
sodium enrichment of the supernatant, a solid grain
growth and a pore coalescence. This solid can be
easily dissolved by water addition.
iv. When the pH and the initial silicon concentration are
in the range 9–10.75 and 0.2–2.9 mol/L, at least a part
of the formed gel (D-type) is not destroyed by adding
water, raising the temperature or mechanical stirring.
These ‘‘irreversible’’ gels present a syneresis phe-
nomenon. Longer is the gelation time (high pH and
low initial silicon concentration) slower is the syner-
esis kinetics. This phenomenon is associated with a
strong consolidation of the product. The characteriza-
tion of the consolidated product shows the presence of
two solid phases. The first one soluble in pure water,
could be the compound (NaSi1.87O4.24) formed during
ripening of C-type gels. The second corresponds to
nanometrics of an insoluble product whose composi-
tion has been estimated as close to NaSi12.66O25.82.
For a constant pH value (e.g. pH = 10.56), both C- and
D-type gels can be obtained while for a constant [Si], only
one kind of gel exists. Concerning the reaction kinetics, for
a given type of gel (B, C or D), the reaction kinetic depends
on both pH value and [Si], for it increases when the pH
value decreases and [Si] increases.
The microstructual changes of reversible (C-type) and
‘‘irreversible’’ (D-type) gels during ripening are rather
similar. The whole of the observations suggests an evolu-
tion controlled by a dissolution/precipitation process,
leading to grain growth, pore enlargement, consolidation
and densification.
Appendix
1) Volume of the solid skeleton VS
MS
VS ¼ ð3Þ
q 88–108
123
J Sol-Gel Sci Technol (2011) 58:625–635
ð4Þ
where MS is the mass of the solid skeleton. 2.2 corresponds
to an estimate solid density (g/cm3). [Na] and [Si] are
respectively the sodium and silicon initial concentrations in
the solution before gelation. MSiO2 = 60 g is the mass of
M
SiO2 per mol of silicon and Na2 2 O = 31 g the mass of
Na2O = 31 g per mol of sodium. Eq. 3 becomes:
Vs
VT ½27;27ð½Si0  ½SiSur Þþ14;09ð½Na0  ½NaSur Þ103
¼ :
1 ð27;27½SSur þ14;09½NaSur Þ103
ð5Þ
2) Si/Na atomic ratio (Si/Na)S
In the solid skeleton, we have
nSiS ¼ nSi0  ðnSisur + nSiL Þ
¼ VT ½Si0   ðVT  VS Þ  ½Sisur  ð6Þ
and
nNas ¼ nNa0  ðnNasur + nNaL Þ
¼ VT ½Na0   ðVT  VS Þ  ½Nasur  ð7Þ
The combination of relations 6 and 7 leads to Eq. 8
 
Si VT ½Si   ðVT  VS Þ½Sisur 
¼ ð8Þ
Na S VT ½Na   ðVT  VS Þ½Nasur 
References
1. WH Engelleitner (1990) Glossary of agglomeration terms, pow-
der and bulk engineering. AME Pittsburg, New York
2. Viallis-Terrisse H (2000) Interaction des silicates de calcium
hydratés, principaux constituants du ciment, avec les chlorures
d’alcalins. Analogie avec les argiles. PhD thesis, Université de
Bourgogne, France
3. Davidovits J (1991) J Therm Anal 37:1633–1656
4. Phair JW, Van Deventer JSJ (2002) Ind Eng Chem Res
41:4242–4251
5. Phair JW, Van Deventer JSJ, Smith JD (2000) Ind Eng Chem Res
39:2925–2934
6. Tognonvi MT, Massiot D, Lecomte A, Rossignol S, Bonnet J-P
(2010) J Colloid Interface Sci 352:309–315
7. Merrill RC, Spencer RW (1950) J Phys Chem 54:806–812
8. Iler RK (1979) The chemistry of silica. John Wiley and Sons,
New York
9. Fernández-Barbero A, Suárez IJ, Sierra-Martı́n B, Fernández-
Nieves A, de Las Nieves FJ, Marquez M, Rubio-Retama J,
López-Cabarcos E (2009) Adv Colloid Interface Sci 147–148:
J Sol-Gel Sci Technol (2011) 58:625–635 635

10. Tognonvi MT (2009) Physico-chimie de la gélification du silicate
de sodium en milieu basique. PhD thesis, Université de Limoges,
France
11. Brinker CJ, Scherer GW (1985) J Non Cryst Solids 70:301–322
12. Tanaka T (1981) Sci Am 244:124–138
13. Sosman RB (1965) The phase of silica. Rutgers University Press,
New Brunswick
14. Randell MG (1985) Liquid phase sintering. Plenum Press, New
York
15. Wijnen BPWJG, Beelen TPM, Rummens KPJ, Saeijs HCPL, Van
Santen RA (1991) J Appl Cryst 24:759–764
16. Christy AA (2008) Colloids Surf A Physicochem Eng Asp
322:248–252

123

View publication stats