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Physical-chemistry of sodium silicate gelation in an alkaline medium

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DOI: 10.1007/s10971-011-2437-4

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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 1 Introduction


alkaline medium has been studied in the 11.56–9 pH range
by adding different amount of hydrochloric acid into Binders have been described by Englelleitner [1] as ‘‘an
a concentrated commercial solution ([Si] = 7 mol/L, additive to the material being agglomerated that provides
Si/Na = 1.71, pH = 11.56). The formed products and their bonding strength in the final product. A binder can be a
evolution during long ripening (up to 150 days) have been liquid or solid that forms a bridge, film or matrix filler or
characterized by cryo-SEM, elementary analysis (ICP- that causes a chemical reaction’’. The most commonly used
AES), X-ray diffraction and surface area and relative binder is the cement. It is a mineral powder, which behaves
density measurements. In the studied narrow ranges of pH as a hydraulic binder (consolidation also occurs in water).
(11.56–9) and silicon concentration (7–0.2 mol/L) four The common Portland cement is a mixture of five main
different situations have been observed: (i) a stable and phases: tricalcium silicate (3CaO,SiO2), dicalcium silicate
clear solution, (ii) a reversible and transparent physical gel; (2CaO,SiO2), tricalcium aluminate (3CaO,Al2O3), tetra-
(iii) a soluble white gel characterized by a significant calcium ferroaluminate (4CaO,Al2O3,Fe2O3) and calcium
contraction during ripening and (iv) an irreversible gel sulphate. The presence of water in the system causes, via a
which presents a slow syneresis leading to a consolidate complex mechanism, the formation of hydrates, which
solid. The characterizations of the different solids, liquids contribute to the consolidation of the product. It is gener-
and gels have shown that the observed behaviors were the ally considered that these silicon-rich hydrates form a gel
results of the formation of nanometric soluble that behaves like a binder. The hardening of the cement
NaSi1.87O4.24 particles and/or insoluble silica-like paste would correspond to the structuration of this gel that
(NaSi12.66O25.82) grains and of the contribution of a dis- contains solid particles with a composition of (CaO)x
solution/precipitation mechanism. (SiO2)(H2O)y where the values of x and y depend on the
calcium and silicate content in the aqueous phase [2]. The
Keywords Sodium silicate solution  Concentrated attack of amorphous siliceous or silico-aluminate products
solution  Acidification  Gelation in alkaline medium  by lime saturated aqueous solutions leads also to the for-
Syneresis  Dissolution/precipitation 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
M. T. Tognonvi  S. Rossignol (&)  J.-P. Bonnet siliceous or silico-aluminate powders (metakaolin, fly
Centre Européen de la Céramique, Groupe d’Etude des
ash…) and concentrated alkaline solutions (KOH,
Matériaux Hétérogènes (GEMH E.A. 3278), ENSCI, 12 Rue
Atlantis, 87068 Limoges Cedex, France NaOH…). The consolidation of these materials would be
e-mail: Sylvie.rossignol@unilim.fr the result of the formation of either a zeolitic-type gel or a

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

siliceous or aluminosilicate hydrogel [5]. The formation of prepared from a 37 HCl wt% commercial solution (Norma
a silicate-based gel seems to be responsible for the binder Prolabo) by adding deionized water.
behavior of both cement and geoplymer. In such systems
the gelation occurs in situ in a complex and evolving 2.2 Products preparation and aging conditions
system. Therefore, the formation mechanism of the binding
minor phase is difficult to analyze. The studied mixtures have been obtained by progressive
Alkaline solutions of sodium silicate (water glass) are addition of HCl solution into the commercial sodium sili-
often introduced in the geopolymer starting mixture in cate solution under magnetic stirring at room temperature.
order to accelerate the consolidation process. In peculiar The solutions with [Si] B 2.26 mol/L were firstly dilute
conditions, water glass alone can even behave like a non- with deionized water before acidification. After acidificat-
hydraulic binder. In this case the binding gel is formed ion, the [Si] and pH of the studied solutions were ranged
directly from the liquid, without any significant reaction from 0.2 to 6 mol/L and from 9 to 11.56, respectively. The
with solid grains, and the progressive evolution from a pH value was measured all along the process using a
solution to a rigid network, via a gel, is characteristic of the PHM240 METER LAB pH meter (radiometer) operating
starting solution. In such conditions it is possible to study with a ‘‘red rod’’-type glass electrode and a T201-type
the direct influence of the liquid composition on the gela- temperature sensor.
tion and strengthening processes. The as-obtained homogeneous solutions (mixtures) were
A combined analysis of 29Si NMR, SAXS and ICP-AES then transferred into closed plastic vessels for aging at
experiments [6] performed on the concentrated sodium room temperature.
silicate solution (pH = 11.56; [Si] = 7 mol/L; Si/Na Depending on pH, Si concentration and behavior during
atomic ratio = 1.71) used in this study has shown that the ripening at room temperature, four different behaviors can
observed high siliceous species solubility results from the be distinguished:
formation of a Si7O18H4Na4 neutral complex. The dilution
– (A) a clear and stable solution;
of such a concentrated solution leads to a progressive
– (B) a stable and transparent gel (Fig. 1a);
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 (a)
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 4 days 120 days
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
(b)
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.

40 min 2 hours 9 days 30 days


2 Experimental part (c)

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- 16 min 30 min 5 days 30 days
sponds to 3.41 SiO2 and 21 H2O for 1 Na2O). The solution
characteristics are: relative density = 1.32, pH = 11.56, Fig. 1 Photos showing the evolutions observed during ripening of the
[Si] = 7.01 mol/L and Si/Na = 1.71. three different gels obtained by acidification of the commercial
sodium silicate solution: a transparent gel (B-type gel) obtained for
Dilute hydrochloric acid solutions with concentration
[Si] = 5.2 mol/L and pH = 11.10, b white gel (C-type gel) obtained
ranging from 0.5 to 2 mol/L were also used in order to for [Si] = 3 mol/L, pH = 10.67 and c white gel (D-type gel)
modify both pH and [Si]. These solutions have been Obtained from [Si] = 2.26 mol/L, pH 10.56

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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

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

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

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

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

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

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)

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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

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

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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


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

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

M
MSiO2  ½VT  ð½Si   ½SiSur Þ þ Vs  ½SiSur  þ Na2 2 O  ½VT  ð½Na   ½NaSur Þ þ Vs  ½NaSur 
Vs ¼ ð4Þ
2:2

entities bounded by physical bond. The constitutives where MS is the mass of the solid skeleton. 2.2 corresponds
aggregates would be the Si7O18H4?nNa4-n entities. to an estimate solid density (g/cm3). [Na] and [Si] are
iii. In the pH range from 10.56 to 10.90, when the initial respectively the sodium and silicon initial concentrations in
silicon concentration is between 2.9 and 4.14 mol/L, a the solution before gelation. MSiO2 = 60 g is the mass of
soluble white gel (C-type) appears after a short time. M
SiO2 per mol of silicon and Na2 2 O = 31 g the mass of
It turns, in few hours, into a white solid with a Na2O = 31 g per mol of sodium. Eq. 3 becomes:
chemical composition, NaSi1.87O4.24, independent of
starting conditions. The solid shrinkage observed Vs
during ripening is associated with a silicon and VT ½27;27ð½Si0  ½SiSur Þþ14;09ð½Na0  ½NaSur Þ103
sodium enrichment of the supernatant, a solid grain ¼ :
1 ð27;27½SSur þ14;09½NaSur Þ103
growth and a pore coalescence. This solid can be ð5Þ
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 2) Si/Na atomic ratio (Si/Na)S
of the formed gel (D-type) is not destroyed by adding
water, raising the temperature or mechanical stirring. In the solid skeleton, we have
These ‘‘irreversible’’ gels present a syneresis phe- nSiS ¼ nSi0  ðnSisur + nSiL Þ
nomenon. Longer is the gelation time (high pH and ¼ VT ½Si0   ðVT  VS Þ  ½Sisur  ð6Þ
low initial silicon concentration) slower is the syner-
esis kinetics. This phenomenon is associated with a and
strong consolidation of the product. The characteriza- nNas ¼ nNa0  ðnNasur + nNaL Þ
tion of the consolidated product shows the presence of ¼ VT ½Na0   ðVT  VS Þ  ½Nasur  ð7Þ
two solid phases. The first one soluble in pure water,
could be the compound (NaSi1.87O4.24) formed during The combination of relations 6 and 7 leads to Eq. 8
ripening of C-type gels. The second corresponds to  
Si VT ½Si   ðVT  VS Þ½Sisur 
nanometrics of an insoluble product whose composi- ¼ ð8Þ
Na S VT ½Na   ðVT  VS Þ½Nasur 
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 References
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