Article

Influence of pH, Temperature and Sample Size on

Natural and Enforced Syneresis of Precipitated Silica
Sebastian Wilhelm and Matthias Kind *
Received: 22 October 2015; Accepted: 25 November 2015; Published: 1 December 2015
Academic Editor: Walter Remo Caseri

Karlsruhe Institute of Technology (KIT), Institute of Thermal Process Engineering, Kaiserstraße 12,
76131 Karlsruhe, Germany; Sebastian.Wilhelm@kit.edu
* Correspondence: Matthias.Kind@kit.edu; Tel.: +49-721-608-42390; Fax: +49-721-608-43490

Abstract: The production of silica is performed by mixing an inorganic, silicate-based precursor and
an acid. Monomeric silicic acid forms and polymerizes to amorphous silica particles. Both further
polymerization and agglomeration of the particles lead to a gel network. Since polymerization
continues after gelation, the gel network consolidates. This rather slow process is known as “natural
syneresis” and strongly influences the product properties (e.g., agglomerate size, porosity or internal
surface). “Enforced syneresis” is the superposition of natural syneresis with a mechanical, external
force. Enforced syneresis may be used either for analytical or preparative purposes. Hereby, two
open key aspects are of particular interest. On the one hand, the question arises whether natural
and enforced syneresis are analogous processes with respect to their dependence on the process
parameters: pH, temperature and sample size. On the other hand, a method is desirable that
allows for correlating natural and enforced syneresis behavior. We can show that the pH-,
temperature- and sample size-dependency of natural and enforced syneresis are indeed analogous.
It is possible to predict natural syneresis using a correlative model. We found that our model predicts
maximum volume shrinkages between 19% and 30% in comparison to measured values of 20% for
natural syneresis.

Keywords: silica; syneresis; consolidation; shrinkage; gelation; precipitation; polymerization;

membrane; extrapolation

1. Introduction
Precipitated silica (SiO2 ) is an amorphous solid and is applied in many fields of industrial
applications. It can be used not only for adsorption of impurities in liquids and gases, as a binder in
concrete or ceramics and an anti-caking agent in the food sector, but also as an inert filling material in
the pharmaceutical or polymer industry. Beside a gaseous reaction route, silica may be precipitated in
a stirred semi-batch process by mixing an acid (e.g., sulfuric acid) and a silicate (e.g., sodium silicate),
see Figure 1, in the liquid phase.
Monomeric silicic acid polymerizes to oligomeric silicic acid with water as a by-product.
These oligomers grow due to the further addition of monomeric silicic acid to primary particles
(~20–50 nm) that aggregate. Finally, a particulate gel is formed. The gel is characterized by a porous
solid skeleton of these primary silica particles and a liquid that is immobilized within the pores [1].
In the case of the stirred process, the gel is fragmented, resulting in gel fragments (~10–100 µm).
These fragments consolidate due to the continuing polymerization. As a direct consequence, the
gel fragments shrink and change their volume, porosity and internal surface with time. The liquid
contained in the pores is expulsed due to a pressure difference that is induced between the gel and its
environment. These processes are known as syneresis and are highly important for the final product
properties [1,2].

Polymers 2015, 7, 2504–2521; doi:10.3390/polym7121528 www.mdpi.com/journal/polymers

Polymers 2015, 7, 2504–2521
Polymers 2015, 7, page–page

Figure 1. Mechanisms of silica precipitation (after Schlomach [3]).

Figure 1. Mechanisms of silica precipitation (after Schlomach [3]).

Direct observation of syneresis of these gel fragments is difficult because the volume decrease,
respectively,observation
Direct the shrinkage of syneresis
and theofproperty
these gelchanges
fragments is difficult
cannot be clearly because the volume
assigned decrease,
to syneresis or
respectively,
mechanical crushing due to the stirrer. However, syneresis of precipitated silica is not limited or
the shrinkage and the property changes cannot be clearly assigned to syneresis to
mechanical
stirred gels, but crushing
can also duebeto the stirrer.
observed However,
in unstirred syneresis
samples. of precipitated
Macroscopic samplessilicamay be is appropriate
not limited
to stirred gels,
to determine thebut can also
syneresis be observed
behavior. in unstirred
Nevertheless, samples.to be
it is known Macroscopic
a slow process samples may be
[1]. Relative
appropriate to determine the syneresis behavior. Nevertheless,
volume changes in the order of only 7%–10% after ten days have been measured for cylindrical it is known to be a slow process [1].
Relative volume changes in the order of only 7%–10% after ten
samples with initial radii of 0.15 cm and 0.67 cm [1]. Analysis of the influences on syneresis of the days have been measured for
cylindrical
principal processsamples with initial
parameters, such radii of 0.15 cm pH
as temperature, andand 0.67ionic
cm strength,
[1]. Analysisis veryof the influences
time-consuming.
on
It has been shown, that syneresis can be accelerated by applying an external, compressivestrength,
syneresis of the principal process parameters, such as temperature, pH and ionic force to
is very time-consuming. It has been shown, that syneresis can
the gel sample [4,5], resulting in an additional pressure difference. This additional pressure differencebe accelerated by applying an
external, compressive force to the gel sample [4,5], resulting in an
superimposes the “naturally” present pressure difference. It is appropriate to define this process as additional pressure difference.
This additional
“enforced syneresis”pressure difference
in contrast to the superimposes the “naturally”
“natural syneresis”. As a result, present
the porepressure
liquid difference.
enclosed drains It is
appropriate
out of the sample to definemore this process
rapidly. Inas “enforced
addition syneresis”
to this analytical in contrast
purpose to in the “natural
terms syneresis”.
of a faster detectionAsof a
result, the pore liquid enclosed drains out of the sample more
the syneresis behavior, enforced syneresis may also be used for preparative objectives, e.g., rapidly. In addition to this analytical
purpose in terms
the production of a fasterphases
of stationary detection of the syneresis with
for chromatography behavior, enforced
well-defined syneresis may also be
porosity.
used Understanding
for preparative the objectives,
dependency e.g., the production
between the of stationary
process phases for
parameters andchromatography
the polymerization, with
well-defined porosity.
fragmentation and consolidation will give the opportunity to control the precipitation process of
silicaUnderstanding
in order to produce the dependency
a product with between
properties the specially
process parameters
designed forand the polymerization,
the application purpose.
fragmentation and consolidation will give the opportunity
However, this method shall not only be applied to silica, but is expanded to other materials to control the precipitation process
offeringof
silica in order to produce a product with properties specially
an analogous production route. In previous publications, we showed that the polymerization, designed for the application purpose.
However,
fragmentation this method shall not only
and consolidation be applied
of silica depend to not
silica, buton
only is pH,
expanded to otherand
temperature materials offering
ionic strength,
an analogous production route. In previous publications, we
but also on the energy dissipation in the case of the stirred process. It is known that pH affects showed that the polymerization,
fragmentation
the structure and andfirmness
consolidationof theofgels silica
[6].depend
Stronger notgels
onlyare onobtained
pH, temperature
for acidicand ionicthan
rather strength,
basic
but also on
reactant the energy
conditions. dissipation
Gelation in the casewith
is accelerated of the stirred process.
temperature and ionic It is strength.
known that An pH affects
increased
the structure
energy and firmness
dissipation results inofsmaller
the gels gel[6]. Stronger
fragments, in gels
analogyare to
obtained
a highlyfor acidicfluid
viscous rather [7].than basic
Enforced
reactant
syneresisconditions.
applied to a gel Gelation
with an is acidic
accelerated
reactant with temperature
condition shows an and ionic strength.
analogous temperature An increased
behavior
energy dissipation results in smaller gel fragments, in analogy
as natural syneresis [5]. Therefore, the consolidation mechanism itself is checked for its dependency to a highly viscous fluid [7].
Enforced
of the processsyneresis appliedthat
parameters to a also
gel with
affect anthe
acidic reactant condition
polymerization. This shows
work isanintended
analogous to temperature
expand this
behavior as natural syneresis [5]. Therefore,
knowledge to basic reactant conditions and different sample sizes. the consolidation mechanism itself is checked for its
dependency of the process parameters that also affect the polymerization.
In this publication, we concentrate on enforced syneresis as a rather fast means to a qualitative This work is intended to
expand this knowledge to basic reactant conditions and different sample
and quantitative description of the slow mechanisms of natural syneresis. The aim of this publication sizes.
In this On
is twofold. publication,
the one hand, we concentrate
it is necessary on enforced
to provesyneresis
the analogy as a inrather
pH-,fast means to aand
temperature- qualitative
sample
and quantitative description of the slow mechanisms of natural
size-dependency of both natural and enforced syneresis. On the other hand, a method is desirablesyneresis. The aim of this publication
is twofold.
that correlates On the the characteristics
one hand, it isof necessary
natural and to prove the analogy
enforced syneresis. in Different
pH-, temperature-
experimental and sample
set-ups
are required which allow for the measurement of both types of syneresis to pursue these aims.
Natural syneresis is measured with an adapted pycnometer device, whereas a specially designed
2505
2
Polymers 2015, 7, 2504–2521

size-dependency of both natural and enforced syneresis. On the other hand, a method is desirable
that correlates the characteristics of natural and enforced syneresis. Different experimental set-ups are
required which allow for the measurement of both types of syneresis to pursue these aims. Natural
syneresis is measured with an adapted pycnometer device, whereas a specially designed pressure
cell is proposed for the observation of enforced syneresis. These devices have already proven to be
suitable [5]. Nevertheless, some minor changes were necessary within the scope of this work.
In the first section, a brief review of the state-of-the-art in theory of precipitation of silica is given.
Following this part, an experimental set-up is proposed that permits the measurement of natural and
enforced syneresis. Subsequently, the results obtained for both types of syneresis are presented and
checked for their analogous behavior. Thereafter, the correlative model for the prediction of natural
syneresis is derived.

2. State-of-the-Art
This work succeeds some of our previous work [3–8]. We refer to the literature [1,2,9–11] for a
profound understanding of the polymerization and syneresis process of silica. Significant process
parameters for the precipitation of silica are the pH, temperature and sample size as well as the ionic
strength and the concentration of silicate in the mixed solution. The gelation process is accelerated
by addition of salts—synonymous with an increase of the ionic strength—due to charge screening.
Divalent ions screen the silica more effectively than monovalent ions [12]. An increase of the
concentration of silicate results in a maximum volume shrinkage up to 80% [13]. However, these
two process parameters are not considered within the scope of this publication. Nevertheless, the
influences of pH, temperature and sample size on the polymerization and syneresis are summarized
in the following.

2.1. Polymerization and Syneresis

According to Figure 1, monomeric silicic acid (Si(OH)4 ) is formed due to mixing of sodium
silicate and sulfuric acid. The very low solubility of monomeric silicic acid (c˚Si(OH) « 192 mg/L,
4
corresponding to cr˚Si(OH) « 2 mmol/L for pH < 7 and ϑ = 25 ˝ C [2]) in combination with
4
concentrations of cSi(OH)4 « 105 mg/L at typical process conditions lead to a high supersaturation of
cSipOHq4
S “ ˚ « 500. This supersaturation is depleted by polymerization of silanol groups (Si–OH)
cSipOHq
4
to siloxane bonds (Si–O–Si), resulting in oligomers that grow further and agglomerate to larger
structures. Depending on the pH, polymerization is catalyzed either by H+ -ions or by OH´ -ions.
Eventually, a gel comprising a porous solid skeleton of nanoscale silica particles and of immobilized
pore liquid forms. In the case of mechanical energy input, gel fragments are obtained instead of a
continuous gel network. Both the gel fragments and the continuous gel network consolidate and
show syneresis behavior, but in different time scales and degrees. Smaller gel samples consolidate
faster and to a higher degree than larger samples [1]. This is due to an easier drainage of the pore
liquid and a higher flexibility of the gel network.
The polymerization reaction that causes particle formation and gelation is also responsible for
syneresis [1]. Figure 2 is a zoom of two primary particles and shows the process of syneresis
schematically. For reasons of simplicity, the pore liquid is represented by H2 O (blue) although it
is a mixture of water, sodium, sulfate ions and monomeric silicic acid.
Two silanol groups (red) at the surface of the two primary particles polymerize to a new siloxane
bond. This siloxane bond requires less space than the two silanol groups. Thus, the newly formed
siloxane bond acts like a spring and contracts the solid skeleton (depicted as ∆ in the right part of
Figure 2) as long as the skeleton remains flexible. A direct consequence is the development of a
pressure difference between the gel network and its environment, leading to expulsion of the pore
liquid. These two mechanisms, namely the formation of new siloxane bonds and the reduction of
the pressure difference through drainage of the pore liquid and subsequent contraction of the solid

2506
Polymers 2015, 7, 2504–2521

skeleton, lead
Polymers 2015, to natural syneresis. Contrarily, we define “enforced” syneresis as the superposition of
7, page–page
this “naturally” present pressure difference with an external one [4,5].
Polymers 2015, 7, page–page

Figure 2. Illustration of syneresis, pore liquid in blue and formation of a new siloxane bond in red.
Figure
Figure 2.
2. Illustration
Illustration of
of syneresis,
syneresis, pore liquid in
pore liquid in blue
blue and
and formation
formation of
of aa new
new siloxane
siloxane bond
bond in
in red.
red.
2.2. Influence of pH
2.2. Influence of pH
The influence
2.2. Influence of pH of pH is threefold. Firstly, it directly affects the solubility of the monomeric silicic
~
acid The
∗
cSi(OH)
The influence c~Si(OH)
∗
of pH is threefold.
. The solubility Firstly,
can it directly affects the solubility of the monomeric silicic
be calculated
influence of pH is threefold. Firstly, it directlyby:
affects the solubility of the monomeric silicic
acid ~
c
˚
∗
4
. The solubility ˚
~
c ∗
4
can be calculated by:
acid crSi(OH)
Si(OH) 4. The solubility c Si(OH) 4can be calculated by:
 c~ − c~ 
rSi(OH)
4 4 ∗ ∗
˜ ˚ ~Si(OH) Si(OH) 4 ,1 
log ~c∗Si(OH)44 ´−−crc~˚Si(OH)
crSi(OH) ¸= pH − pH 2
∗ 4 ∗ (1)
c ~Si(OH)
c ∗
4 ,41 ,1 pHpH
loglog˚ ~Si(OH) Si(OH) 4 ,1  = “ −´pHpH (1)
(1)
c ∗ ,2 ´−crc~˚Si(OH)
4 ,2
crSi(OH) ∗
,1
2 2

∗ ∗  44 , 2
Si(OH) Si(OH) 4 ,4
1 
where cSi(OH) ,1 = 2 mmol/L, cSi(OH) ,2 = 2.3 mmol/L and pH2 = 9 are found for a temperature of
where cr˚Si(OH)
∗ 4
= 2 mmol/L, cr∗˚Si(OH)
4
= 2.3 mmol/L and pH = 9 are found for a temperature
where cSi(OH) 4 ,1 = 2 mmol/L, c = 2.3 mmol/L and pH2 =2 9 are found for a temperature of
4 ,2
ϑ = 25 °C
˝ [13].
,1 The course
of ϑ = 25 C 4[13]. The course of the of the
Si(OH) 4 ,2 solubility
solubilityisisshown
shown inin Figure
Figure S1S1 that
that can
can bebe found
found in the
in the
Supplementary
ϑ = 25 °C [13].Material
Supplementary Material at the
The course
at theof
end
end the of solubility
of this publication.
this publication. For pH
is shown
For pH < 8,
8, the
in Figure
< solubility
the S1 that can
solubility is
is constant
be found
constant and
invery
and the
very
∗

low (crcSi(OH) == 22 mmol/L,
Supplementary
˚
Si(OH)44
Material at the end of this publication. For pH < 8, the solubility is
mmol/L, but it increases dramatically for pH > 8 by several orders of magnitude.constant and very
∗
This
This iscSi(OH)
low (is due
due to to
4
= 2equilibrium
an
an mmol/L, butbetween
equilibrium it increases
between dramatically
the monomeric
the monomeric for acid
silicic
silicic pH >and
acid 8 by
and itsseveral
its orders of
deprotonated
deprotonated magnitude.
anion
anion that
that can
can
be
be stabilized
stabilized by
by water
water molecules
molecules [1,14].
[1,14]. The
The equilibrium
equilibrium is
is shifted
shifted to
to the
the
This is due to an equilibrium between the monomeric silicic acid and its deprotonated anion that can anion
anion with
with increasing
increasing pH.
pH.
Thus,
Thus, pH
pH affects
be stabilized affects the
the supersaturation
by water supersaturation
molecules [1,14]. S.
S. The equilibrium is shifted to the anion with increasing pH.
Secondly,
Thus,Secondly,
pH affectspH pH influences
theinfluences the catalytic
the catalytic
supersaturation S. polymerization
polymerization reactionreaction andand the
the structure
structure of of the gel
the gel
network. For pH < +
network.
Secondly,For pH pH< pH
pH , the polymerization
iso, the polymerization
iso
influences is catalyzed
is catalyzed by
the catalytic polymerization by surface-bound
reaction and H
surface-bound -ions
H+-ions
the (acid-catalyzed),
(acid-catalyzed),
structure of the gel
whereas it is catalyzed by surface-bound OH ´ -ions (base-catalyzed) for pH > pH . The isoelectric
whereas
network. itFor is pH
catalyzed
< pHisoby, thesurface-bound
polymerization OH is -ions
− (base-catalyzed)
catalyzed by surface-boundfor pHH>-ions
+ pHiso . The isoelectric
iso(acid-catalyzed),
point
point
whereas is
is at
atit pH
pH « 1.7–2in
iso ≈ 1.7–2 by
iso
is catalyzed inthe
the case
case of
of sulfuric
surface-bound sulfuric
OH−acidacid [1,6,10].
-ions [1,6,10]. These two
These
(base-catalyzed) two different
different
for pH > pH regions
regions of catalysis
catalysis
iso. Theofisoelectric
have
pointto
have tois be
at considered
be considered
pH separately.
iso ≈ 1.7–2 separately.
in the caseIn the
Inof
the case
caseofofan
sulfuric anacid-catalyzed
acid acid-catalyzed
[1,6,10]. These polymerization,
polymerization, the
two different regions the silanol group
silanol groupis
of catalysis
protonated
is protonated
have and forms
and forms
to be considered a cationic monomeric
a cationic In
separately. monomeric silicic
the case ofsilicic acid, see Figure
acid, see Figure
an acid-catalyzed 3a [10].
3a [10].
polymerization, the silanol group
is protonated and forms a cationic monomeric silicic acid, see Figure 3a [10].

Figure
Figure3. Scheme
3. of pH-dependent
Scheme catalytic partial
of pH-dependent reactions,
catalytic acid-catalyzed
partial reactions, (a) and base-catalyzed
acid-catalyzed (b).
(a) and
Figure 3. Scheme(b).
base-catalyzed of pH-dependent catalytic partial reactions, acid-catalyzed (a) and base-catalyzed (b).
This cationic silicic acid polymerizes with neutral silanol groups of the least acidic silicon atoms
to anThis
intermediate state and
cationic silicic acid water. The H+with
polymerizes -ion neutral
of the intermediate
silanol groups state
of is
thelater removed
least by water
acidic silicon or
atoms
This cationic silicic acid polymerizes with neutral silanol groups of the least acidic silicon atoms
another neutral monomeric
to an intermediate silicic acid.
state and water. The HIn general,
+-ion of the the acidity
intermediate of a silicon
state is atom
later in
removedsilica
by increases
water or
to an intermediate state and water. The H+ -ion of the intermediate state is later removed by water
with theneutral
another greatermonomeric
number ofsilicicsiloxane
acid. bonds and the
In general, fewer number
acidity of silanol
of a silicon atomgroups [10].
in silica Thus,
increases
or another neutral monomeric silicic acid. In general, the acidity of a silicon atom in silica increases
the
withacid-catalyzed polymerization
the greater number yieldsbonds
of siloxane preferentially
and fewerlinearnumber
chains or of weakly
silanol branched structures.
groups [10]. Thus,
with the greater number of siloxane bonds and fewer number of silanol groups [10]. Thus, the
With proceeding polymerization, these rather linear structures bind to each other
the acid-catalyzed polymerization yields preferentially linear chains or weakly branched structures. into rather loosely
acid-catalyzed polymerization yields preferentially linear chains or weakly branched structures.
connected agglomerates
With proceeding [6,10]. these rather linear structures bind to each other into rather loosely
polymerization,
With proceeding polymerization, these rather linear structures bind to each other into rather loosely
The mechanism
connected of the
agglomerates base-catalyzed polymerization differs from the one described above. It is
[6,10].
connected agglomerates [6,10].
depicted in Figure 3b.ofAthe
The mechanism silanol group is deprotonated
base-catalyzed polymerization todiffers
its anionic
fromform.
the one The anion polymerizes
described above. It is
with neutral
depicted silanol3b.
in Figure groups of the
A silanol mostis acidic
group silicon atom,
deprotonated to its i.e.,
anionicthe silicon
form. The atom withpolymerizes
anion the largest
number of siloxane
with neutral silanolbonds.
groupsThese
of thearemost
rather middle
acidic thanatom,
silicon end groups
i.e., the(assilicon
in the atom
case of acid-catalyzed
with the largest
polymerization),
number of siloxane resulting
bonds. in highly
These arebranched 2507
clusters
rather middle than[6,10].
end groups (as in the case of acid-catalyzed
polymerization), resulting in highly branched clusters [6,10].

4
Polymers 2015, 7, 2504–2521

The mechanism of the base-catalyzed polymerization differs from the one described above. It is
depicted in Figure 3b. A silanol group is deprotonated to its anionic form. The anion polymerizes
with neutral silanol groups of the most acidic silicon atom, i.e., the silicon atom with the largest
number of siloxane bonds. These are rather middle than end groups (as in the case of acid-catalyzed
Polymers 2015, 7, page–page
polymerization), resulting in highly branched clusters [6,10].
Thirdly,
Thirdly, the the rate
rate of
of polymerization
polymerization is is influenced
influenced byby pH,
pH, see
see Figure
Figure4a.
4a. The
The gelation time ttgg and
gelation time and
the shrinkage of an acid-catalyzed and base-catalyzed gel is shown
the shrinkage of an acid-catalyzed and base-catalyzed gel is shown as a function of pH. as a function of pH. For pH
=ForpH
pHiso ,=the
pHgelation time tgtime
iso, the gelation attains its maximum.
tg attains This This
its maximum. is dueis to
duea to
minimum
a minimum concentration
concentration of theof
cationic and anionic monomer species that are necessary for the polymerization.
the cationic and anionic monomer species that are necessary for the polymerization. The gelation The gelation time
ttime
g drops sharply
tg drops with deviation
sharply from pH
with deviation fromiso because the concentrations
pHiso because of theseofcatalytic
the concentrations ionic species
these catalytic ionic
increase. In addition,
species increase. the rate
In addition, the of
rateshrinkage
of shrinkage is accelerated by by
is accelerated deviation
deviationfrom
frompHpH , ,as
isoiso asshown
shown in in
Figure 4b,c. The closer the pH is
Figure 4b,c. The closer the pH is to pHiso to pH , the slower syneresis
iso, the slower syneresis is. is.

Figure 4. Gelation time tg as a function of pH for increasing concentrations of monomeric silicic acid
Figure 4. Gelation time tg as a function of pH for increasing concentrations of monomeric silicic acid of
of 1.09 (1), 1.33 (2) and 1.78 mol/L (a); shrinkage for acid-catalyzed (b); and base-catalyzed (c)
1.09 (1), 1.33 (2) and 1.78 mol/L (a); shrinkage for acid-catalyzed (b); and base-catalyzed (c) cylindrical
cylindrical
gel samplesgel samples [11].
[11].

2.3. Influence of Temperature

2.3. Influence of Temperature
Temperature influences the polymerization of silica in various ways. Firstly, the solubility of
Temperature influences ∗
the polymerization of silica in various ways. Firstly, the solubility ∗
of
monomeric silicic
monomeric acidcr˚cSi(OH)4depends
silicic acid dependsononthethe temperature
temperature ϑ. ϑ. The
The mass-related
mass-related solubility
solubility c ˚ cSi(OH) can
4
Si(OH)4 Si(OH)4
∗:
c
be calculated by Equation (2), according to [2], and converted into the molar solubility c ˚
can be calculated by Equation (2), according to [2], and converted into the molar solubility r Si(OH) : 4Si(OH) 4

˜ ˚ ¸
 ccSi(OH)
∗
 731
731
log  Si(OH)4 4 “ 4.52 ´ (2)
log mg/L = 4.52 − ϑ ` 273.15 C (2)
 mg/L  ϑ + 273.15 °C
 
This relation plotted in Figure S2 is valid for pH < 7 because there is no dependence between
This relation
the solubility plotted
cr˚Si(OH) andinpH,
Figure
see S2 is valid
Figure forthe
S1 in pH Supplementary
< 7 because there is no dependence
Materials. For pH > between
7, the
∗
the solubility cSi(OH)
4
pH-dependency must4 beand pH,into
taken see account
Figure S1[2].inAs
thecan
Supplementary
be seen from Materials. Forthe
Equation (2), pHsolubility
> 7, the
cr˚ S. Equation (2), the solubility
Si(OH)4 rises withmust
pH-dependency temperature
be takenand,
intothus, affects
account theAs
[2]. supersaturation
can be seen from
∗ Secondly, the temperature affects the polymerization reaction rate [1]. This influence differs
cSi(OH)4 rises with temperature and, thus, affects the supersaturation S.
depending on the pH. In the case of an acid-catalyzed polymerization, a strong acceleration of
Secondly, the temperature affects the polymerization reaction rate [1]. This influence differs
gelation and syneresis can be detected with increasing temperature. The viscosity of the pore liquid
depending on the pH. In the case of an acid-catalyzed polymerization, a strong acceleration of
decreases, leading to its easier drainage out of the solid skeleton of silica. By contrast, the maximum
gelation and syneresis can be detected with increasing temperature. The viscosity of the pore liquid
shrinkage was found to be lower with increasing temperature [15]. Newly formed siloxane bonds
decreases, leading to its easier drainage out of the solid skeleton of silica. By contrast, the maximum
exert stress on the solid skeleton. It is assumed that the stress is lowered by shear deformation rather
shrinkage was found to be lower with increasing temperature [15]. Newly formed siloxane bonds
than by volume decrease with increasing temperature [1]. Thus, the maximum shrinkage is lower at
exert stress on the solid skeleton. It is assumed that the stress is lowered by shear deformation rather
higher temperatures. In contrast to the acid-catalyzed polymerization, an unrestricted acceleration of
than by volume decrease with increasing temperature [1]. Thus, the maximum shrinkage is lower at
gelation for base-catalyzed polymerization with increasing temperature cannot be stated. Gelation is
higher temperatures. In contrast to the acid-catalyzed polymerization, an unrestricted acceleration of
slowed down within a temperature range of 15 to 35 ˝ C, but it increases again for higher temperatures.
gelation for base-catalyzed polymerization with increasing temperature cannot be stated. Gelation is
slowed down within a temperature range of 15 to 35 °C, but it increases again for higher
temperatures. This peculiar behavior has been reported 2508 previously [1,6] and attributed to a possible
preequilibrium step involving an induction period during which small polymeric units react
preferentially with monomeric silicic acid instead of with other polymeric units.
Polymers 2015, 7, 2504–2521

This peculiar behavior has been reported previously [1,6] and attributed to a possible preequilibrium
step involving an induction period during which small polymeric units react preferentially with
Polymers 2015, 7,
monomeric page–page
silicic acid instead of with other polymeric units.

2.4. Influence of Sample Size

The shrinkage and its rate depend on the sample sample size.
size. As the gel network contracts, the pore
liquid within is squeezed out due to the pressure difference induced. induced. Small samples allow for an easy
drainage of of the
thepore
poreliquid,
liquid,whereas
whereasa steeper pressure
a steeper pressuredifference
differenceis necessary
is necessaryfor larger gels gels
for larger [1]. The
[1].
measured,
The measured, radialradial
shrinkage of gel of
shrinkage cylinders with different
gel cylinders initial radii
with different is given
initial radii in
is Figure
given in 5. As might
Figure 5.
be
As expected,
might be the smaller the
expected, gel smaller
sample (r 0 =sample
gel 0.15 cm)(r0shrinks
= 0.15 faster than thefaster
cm) shrinks largerthan
one the
(r0 =larger
0.67 cm).
one
The
(r0 = rate
0.67ofcm).
shrinkage slows
The rate down with
of shrinkage timedown
slows because
withthetime
gel network
becausestiffens
the geldue to thestiffens
network newly formed
due to
siloxane
the newly bonds.
formed siloxane bonds.

Figure
Figure 5.
5. Radial
Radial shrinkage
shrinkage of
of gel
gel cylinders
cylinders as
as aa function
function of
of different initial radii
different initial radii [1].
[1].

In summary, the influences of pH, temperature and sample size on the polymerization process
In summary, the influences of pH, temperature and sample size on the polymerization process of
of silica involving particle formation and subsequent consolidation, respectively, syneresis are
silica involving particle formation and subsequent consolidation, respectively, syneresis are reviewed.
reviewed. Different experimental set-ups (measurement of shrinkage and its rate) are suggested in
Different experimental set-ups (measurement of shrinkage and its rate) are suggested in order to
order to prove these influences and transfer them from “natural” to “enforced” syneresis. The aim of
prove these influences and transfer them from “natural” to “enforced” syneresis. The aim of our
our experiments which are explained in the next chapters is to check whether both types of syneresis
experiments which are explained in the next chapters is to check whether both types of syneresis
show an analogous dependency on pH, temperature and sample size.
show an analogous dependency on pH, temperature and sample size.
3. Experimental Set-Up
3. Experimental Set-Up

3.1. Gel
3.1. Gel Preparation
Preparation
The gels
The gels are
are prepared
prepared byby mixing
mixing sodium
sodium silicate
silicate and
and sulfuric
sulfuric acid
acid solutions
solutions in
in aa Y-mixing
Y-mixing
nozzle [16] with a volumetric ratio of 1:1. Both reactants are filled into syringes and
nozzle [16] with a volumetric ratio of 1:1. Both reactants are filled into syringes and pumped pumped through
the nozzle
through thevia an electrically
nozzle driven syringe
via an electrically drivenpump
syringe (Nexus
pump6000,
(NexusChemyx Inc., Stafford,
6000, Chemyx TX, USA)TX,
Inc., Stafford, to
assure constant mixing conditions. The sodium silicate solution is prepared by dilution
USA) to assure constant mixing conditions. The sodium silicate solution is prepared by dilution of of sodium
silicate silicate
sodium (consisting of 35.5%
(consisting Na2O·3.3SiO
of 35.5% 2 and 64.5%
Na2 O¨ 3.3SiO H2O by weight, Roth GmbH, Karlsruhe,
2 and 64.5% H2 O by weight, Roth GmbH, Karlsruhe,
Germany) with
Germany) with ultrapure
ultrapurewater
water(Milli-Q,
(Milli-Q,Millipore,
Millipore,Darmstadt,
Darmstadt,Germany)
Germany)andand has
has a mass
a mass fraction
fraction of
xSil x=Sil0.40.
of = 0.40. In order
In order to obtain
to obtain an acid-catalyzed
an acid-catalyzed (pH(pH
< pH< pH in, in
iso , iso this
this particular
particular case
case pHpH < 0)
< 0) and
and a
base-catalyzed gel (pH
a base-catalyzed gel (pH > pH > pH , in this particular case pH « 10), sulfuric acid solutions with
isoiso, in this particular case pH ≈ 10), sulfuric acid solutions with mass mass
fractions
fractions of of xx
H2 SO4 ==0.5
H 2SO 4
and
0.5 and0.032
0.032are used,
are which
used, whichwere
wereprepared
prepared from sulfuric
from acid
sulfuric (purity
acid of 96%
(purity by
of 96%
weight, Roth GmbH, Karlsruhe, Germany) upon dilution with ultrapure water. Both reactants and
by weight, Roth GmbH, Karlsruhe, Germany) upon dilution with ultrapure water. Both reactants and
the resulting mixture are thermostated at ϑ = 20 ˝ C to avoid a rise in temperature due to the released
the resulting mixture are thermostated at ϑ = 20 °C to avoid a rise in temperature due to the released
heat of mixing.
heat of mixing.

3.2. Measurement of Syneresis 2509

An adapted pycnometer device (for details see [5]) allows the measurement of natural syneresis
of cylindrical gel samples (dCyl =12 mm and VGel ≈ 3 mL), see Figure 6a. The measurement is based on
Polymers 2015, 7, 2504–2521

3.2. Measurement of Syneresis

An adapted pycnometer device (for details see [5]) allows the measurement of natural syneresis
Polymers 2015, 7, page–page
of cylindrical gel samples (dCyl =12 mm and V Gel « 3 mL), see Figure 6a. The measurement is
based on displacement
displacement and pycnometry.and pycnometry.
The volumeThe volume
of the of the Vgel
gel sample sample
gel can V gel can by
be calculated be subtraction
calculated by of
subtraction of the maximum filling volume V and the volume V poured
the maximum filling volume Vfill,max and the volume Vfill poured into the pycnometer flask. Both Vfill,max
fill,max fill into the pycnometer
flask.
and VfillBoth V fill,max andgravimetrically.
are determined V fill are determined gravimetrically.
The pycnometer The pycnometer
flask containing the gelflask
samplecontaining
can be
the gel sample
immersed can be immersed
in a thermostated waterinbath a thermostated water bath
for the investigation for the investigation
of syneresis of syneresis ϑ.
at different temperatures at
different temperatures ϑ. Three samples are averaged to obtain one
Three samples are averaged to obtain one measurement point. A different experimental set-up is measurement point. A different
experimental
necessary in orderset-up to is necessary
analyze in order
the natural to analyze
syneresis the natural
of smaller syneresis
gel samples. Weofdeveloped
smaller gel samples.
a cell, made
We developed
of PMMA, which a cell,
canmade
be usedof PMMA,
with a which can be(Stemi
microscope used with a microscope
2000-C, (Stemi 2000-C,
Zeiss, Oberkochen, Zeiss,
Germany).
Oberkochen, Germany).
Small gel droplets (dDropSmall
≈ 3 gelmm) droplets (dDrop « 3with
are prepared mm)aare prepared
syringe (VSyr with
= 1a syringe
mL) and (V Syr = 1 mL)
a cannula.
and a cannula. is The temperature ˝
The temperature constant at 20 °Cisduring
constantthe at 2020 C
first during
min, that isthe first 20 longer
negligibly min, thatthanisthe negligibly
gelation
longer than the gelation time of 12 min [6], and pictures of the droplets are
time of 12 min [6], and pictures of the droplets are taken with a macro lens. Thereafter, the gel dropletstaken with a macro lens.
Thereafter, the gel droplets are placed into the sample areas, see Figure
are placed into the sample areas, see Figure 6b. Each sample area is sealed with a cover glass on 6b. Each sample area is
sealed
the topwith a cover
of the glass
left part and onathe top ofcover
second the left
glasspart and a second
between the twocoverpartsglass between
of the the two
cell. Thus, parts
drying is
of the cell. Thus, drying is avoided and the temperature can be controlled
avoided and the temperature can be controlled by immersing the cell in a thermostated water bath. by immersing the cell in
aThe
thermostated
changes inwater bath. of
dimension Thethe changes in dimension
gel droplets of the gel optically
are determined droplets are withdetermined
the microscopeopticallyby
with thepictures
taking microscope of theby taking
top and pictures of the For
side view. top and side view.
the side view, For the side is
a reflector view,
useda reflector
with theis same
used
with the same
microscope. microscope.
Several measurement Several measurement
series were performed series were performedinand
and averaged orderaveraged in orderfor
to compensate to
compensate
measurement forinaccuracies.
measurement inaccuracies.

Figure
Figure6. 6.
Measurement equipment
Measurement for natural
equipment syneresis,
for natural cylindrical
syneresis, samples samples
cylindrical (a) [5] and(a)gel[5]
droplets (b).
and gel
droplets (b).
In the case of enforced syneresis, an external uniaxial force F is applied to the gel sample in
a specially designed measuring cell, see Figure 7. Compared to the cell previously used [5], some
In the case of enforced syneresis, an external uniaxial force F is applied to the gel sample
modifications were made. The cell is placed into a uniaxial testing machine (ProLine Z010,
in a specially designed measuring cell, see Figure 7. Compared to the cell previously used [5],
Zwick/Roell, Ulm, Germany) which applies the force F to the gel and records the resulting change in
some modifications were made. The cell is placed into a uniaxial testing machine (ProLine Z010,
gel height Δs. Considering the cross section, Δs can be converted into a corresponding volume
Zwick/Roell, Ulm, Germany) which applies the force F to the gel and records the resulting change
decrease. All components that are in contact with the gel or the pore liquid squeezed out (cell wall,
in gel height ∆s. Considering the cross section, ∆s can be converted into a corresponding volume
head, base and support plate, as well as the perforated filter plates) are made of POM
decrease. All components that are in contact with the gel or the pore liquid squeezed out (cell
(polyoxymethylene). In addition, threads, HPLC tubings and fittings are mounted to collect the pore
wall, head, base and support plate, as well as the perforated filter plates) are made of POM
liquid at minimum dead volume. The filter plates support the nanofiltration membranes that hold
(polyoxymethylene). In addition, threads, HPLC tubings and fittings are mounted to collect the pore
back the solid silica. Two different types of membranes are used (NF270, Dow Filmtec, Terneuzen,
liquid at minimum dead volume. The filter plates support the nanofiltration membranes that hold
The Netherlands and NP010, Microdyn-Nadir, Wiesbaden, Germany). They differ in molecular
back the solid silica. Two different types of membranes are used (NF270, Dow Filmtec, Terneuzen, The
weight cut-off and retention of ions. As with the pycnometer flasks, the cell is immersed in
Netherlands and NP010, Microdyn-Nadir, Wiesbaden, Germany). They differ in molecular weight
a thermostated water bath to assure a constant temperature ϑ during the experiment.
cut-off and retention of ions. As with the pycnometer flasks, the cell is immersed in a thermostated
water bath to assure a constant temperature ϑ during the experiment.

2510
Polymers 2015, 7, 2504–2521
Polymers 2015, 7, page–page

Figure
Figure 7.
7. Measurement
Measurement equipment
equipment for
for enforced
enforced syneresis, with small
syneresis, with small modifications
modifications compared
compared to
to [5].
[5].

3.3. Determination of Monomeric Silicic Acid in Pore Liquid

3.3. Determination of Monomeric Silicic Acid in Pore Liquid
An essential condition for comparing enforced and natural syneresis is that the mechanism of
An essential condition for comparing enforced and natural syneresis is that the mechanism
syneresis is not influenced by the external force. In particular, we assume the reduction of
of syneresis is not influenced by the external force. In particular, we assume the reduction of
the concentration of monomeric silicic acid and, thus, the depletion of the supersaturation S to be
the concentration of monomeric silicic acid and, thus, the depletion of the supersaturation S to
equal for both types of syneresis. To prove this assumption, the concentration of monomeric silicic
be equal for both types of syneresis. To prove this assumption, the concentration of monomeric
acid of the pore liquid squeezed out is determined with a colorimetric method described by
silicic acid of the pore liquid squeezed out is determined with a colorimetric method described by
Alexander [17]. According to this method, an aqueous reaction solution containing ammonium
Alexander [17]. According to this method, an aqueous reaction solution containing ammonium
molybdate tetrahydrate (Roth GmbH) and sulfuric acid (Roth GmbH) is prepared. When mixed with
molybdate tetrahydrate (Roth GmbH) and sulfuric acid (Roth GmbH) is prepared. When mixed
a sample of pore liquid containing monomeric silicic acid, a yellow silicomolybdate complex forms.
with a sample of pore liquid containing monomeric silicic acid, a yellow silicomolybdate complex
The extinction at a wavelength of λ = 400 nm [15] of this complex is measured with a UV/Vis
forms. The extinction at a wavelength of λ = 400 nm [15] of this complex is measured with a
spectrophotometer (Genesys 10S, ThermoScientific, Braunschweig, Germany). A standard solution
UV/Vis spectrophotometer (Genesys 10S, ThermoScientific, Braunschweig, Germany). A standard
(1000 mg/L Si Certipur®, Merck Millipore, Darmstadt, Germany, in 0.5 mol/L NaOH) is used
solution (1000 mg/L Si Certipurr , Merck Millipore, Darmstadt, Germany, in 0.5 mol/L NaOH) is
for calibration.
used for calibration.
4. Results
4. Resultsand
andDiscussion
Discussion

4.1. Natural Syneresis

The temporal courses
courses ofof the
therelative shrinkage∆V/V
relativeshrinkage ΔV/V00 of the cylindrical samples
samples (d(dCyl
Cyl =
= 12 mm
and VGel
Gel≈«3 mL)
3 mL)areare
determined
determined experimentally
experimentally forfor
three different
three temperatures
different temperatures and
andareare
depicted in
depicted
Figure
in 8 for
Figure anan
8 for acid-
acid-and
andbase-catalyzed
base-catalyzedgel.
gel.For
Forthe
theacid-catalyzed
acid-catalyzedgel,gel, aa maximum
maximum shrinkage of
∆V/V0|0max
ΔV/V |max= 0.20 is is
= 0.20 reached
reachedindependently
independentlyofofthe thetemperature.
temperature.The Thephenomenon
phenomenonof of aa slightly lower
value for the maximum shrinkage with increasing temperature stated by Ponomerova [15] cannot be
proved or disproved when the error bars are regarded. However, the temperature affects the kinetics
of syneresis reflected by the the different
different slopes
slopes for
for tt<<5050h.h.With
Withincreasing
increasing temperature,
temperature, syneresis is
syneresis
accelerated.
is accelerated.A simple
A simple model
model based
basedupon
upona akinetic
kineticrate
rateequation
equationisis proposed
proposed forfor aa quantitative
description of the courses, see Equation (3). A physically based model is still to be made.

ΔV ∆V
∆V ΔV    tt  
ˆ ˙ „ ˆ ˙
“=  ¨⋅ 11 ´
− exp
exp  −
VV0 max 
´  (3)
(3)
VV
0 0  0  max  ττ  
Equation
Equation (3)
(3)comprises
comprisestwo parameters
two parametersthatthat
represent the maximum
represent shrinkage
the maximum ∆V/V 0ΔV/V
shrinkage |max 0(the
|max
(the value for t→∞) and the characteristic time constant τ (taking into consideration the kineticsthe
value for tÑ8) and the characteristic time constant τ (taking into consideration the kinetics at at
beginning). These
the beginning). two two
These parameters are characteristic
parameters for thefor
are characteristic measurements and areand
the measurements usedareforused
further
for
comparison of the influence
further comparison of different
of the influence process process
of different conditions. Their values
conditions. Theirare listed
values areinlisted
Tablein1.Table 1.

2511
8
Polymers 2015, 7, 2504–2521
Polymers 2015, 7, page–page

Figure 8. Relative shrinkage ΔV/V0 of the cylindrical samples, natural syneresis for different
Figure 8. Relative shrinkage ∆V/V 0 of the cylindrical samples, natural syneresis for different
temperatures ϑ, acid-catalyzed [5] (a), and base-catalyzed (b).
temperatures ϑ, acid-catalyzed [5] (a), and base-catalyzed (b).

Table 1. Maximum shrinkage ΔV/V0|max and characteristic time constant τ for the cylindrical samples
Table 1. Maximum shrinkage ∆V/V 0 |max and characteristic time constant τ for the cylindrical
(dCyl = 12 mm and VGel ≈ 3 mL), natural syneresis, model parameters.
samples (dCyl = 12 mm and V Gel « 3 mL), natural syneresis, model parameters.

Maximum shrinkage ΔV/V0|max/- Time constant τ/h

Temperature Maximum Shrinkage ∆V/V 0 |max /- Time Constant τ/h
ϑ/˝ C
Temperatureϑ/°C Acid-catalyzed Base-catalyzed Acid-catalyzed Base-catalyzed
Acid-catalyzed
pH < pHiso Base-catalyzed
pH > pHiso Acid-catalyzed
pH < pHiso pHBase-catalyzed
> pHiso
pH < pHiso pH > pHiso pH < pHiso pH > pHiso
20 0.20 0.30 21.3 50.1
20 40 0.20
0.20 0.30
0.39 21.3
11.7 32.0 50.1
40 60 0.20
0.20 0.39
0.51 11.7
5.0 27.5 32.0
60 0.20 0.51 5.0 27.5

A different behavior is observed for the base-catalyzed gel, see Figure 8b. Both the maximum
A different
shrinkage and the behavior is observed
rate increase with for the base-catalyzed
temperature. In directgel, see Figure
comparison to8b.
the Both the maximum
acid-catalyzed gel,
shrinkage and the rate
the base-catalyzed increase with
gel exhibits largertemperature.
values for the In maximum
direct comparisonshrinkage. to theThey acid-catalyzed
reach from
gel,
ΔV/Vthe 0|maxbase-catalyzed
= 0.30 to 0.51.gelThis exhibits
can be larger values by
explained forthe
thedifferent
maximum shrinkage.
structure of the Theysolidreach from
skeleton.
∆V/V 0 |max = 0.30 gel
The acid-catalyzed to 0.51.
is builtThisup can be explained
of compact primary by particles
the different
that arestructure
connectedof the solid skeleton.
loosely, resulting
The acid-catalyzed
in a translucent gel is built
gel tending up offracture.
to brittle compactHowever,
primary particles that are connected
the base-catalyzed gel behaves loosely,
in an resulting
opposite
in
way. a translucent
It is composed gel tending
of loosely to connected
brittle fracture.
primary However,
particlesthe thatbase-catalyzed
form a softer gel behaves
network than in the
an
acid-catalyzed
opposite way. gel. It isAs a result of
composed of these
looselydifferent
connectedstructures,
primary theparticles
base-catalyzed
that form gelaexhibits a larger
softer network
maximum
than shrinkage [1].gel.
the acid-catalyzed TheAs shrinkages
a result of measured are fitted
these different with thethe
structures, same model, see Equation
base-catalyzed gel exhibits(3).
aThe base-catalyzed
larger maximum shrinkage gel consolidates[1]. The at ashrinkages
much slower velocity,
measured arereflected
fitted with by the
largersame values for see
model, the
characteristic
Equation (3). time
Theconstant τ (see Table
base-catalyzed 1). One explanation
gel consolidates at a muchmight slowerbevelocity,
the difference
reflected in bythelarger
solid
structure
values forofthe
thecharacteristic
gels. In the case time of the acid-catalyzed
constant τ (see Table gel,1).
theOne
poreexplanation
liquid can flow mightmorebe easily through
the difference
thethe
in gelsolid
network due to
structure ofthe
thecompact,
gels. In the butcase
loosely connected
of the primary
acid-catalyzed particles.
gel, the poreFor the base-catalyzed
liquid can flow more
gel, a denser
easily through network
the gelforms,
network resulting
due tointhe a slower drainage
compact, of the pore
but loosely liquid. primary
connected Scattering experiments
particles. For
of these
the differently gel,
base-catalyzed catalyzed
a denser gelsnetwork
emphasize forms,these differences
resulting in a in their drainage
slower solid structures
of the poreand optical
liquid.
appearances
Scattering [8]. Regarding
experiments of these thedifferently
maximum shrinkage,
catalyzed gels there are small
emphasize these deviations
differences in between the
their solid
measured and
structures andoptical
modeled data. The[8].
appearances measured
Regarding data
theseem
maximumto decrease
shrinkage, further
thereeven after deviations
are small t > 250 h,
especiallythe
between formeasured
higher temperatures.
and modeledThese data.deviations
The measured are accepted
data seem in order to facilitate
to decrease further a comparison
even after t
>to 250
the acid-catalyzed
h, especially for gel.higher temperatures. These deviations are accepted in order to facilitate a
The concentration
comparison of monomeric
to the acid-catalyzed gel. silicic acid in the pore liquid squeezed out is determined to
monitor a possible residual
The concentration of monomeric supersaturation
silicic acid inS.theTherefore,
pore liquidthe pore out
squeezed liquid is analyzed
is determined to
spectroscopically,
monitor as described
a possible residual by Alexander
supersaturation [17]. The the
S. Therefore, courses are shown
pore liquid in Figure
is analyzed 9. The initial
spectroscopically,
as described by
concentration cSi(OH) 4
(t = 0) [17].
Alexander The courses
of monomeric areacid
silicic shown in Figure and
is determined 9. The initial by
calculated concentration
the weight
crSi(OH)4 pt “ 0q of monomeric silicic acid is determined and calculated by the weight of sodium silicate
of sodium silicate solution used. A very strong reduction to concentrations in order of
solution used. A very strong reduction to concentrations in order of crSi(OH)4 = 0.2–0.4 mmol/L is
cSi(OH)4 = 0.2–0.4 mmol/L is obtained for the acid-catalyzed gel (Figure 9a). They are within the
obtained for the acid-catalyzed gel (Figure 9a). They are within the solubility limit of ď2 mmol/L
solubility limit of ≤2 mmol/L given by Iler [2]. There is no distinct change with time t and temperature.
The latter can be explained by the solubility of monomeric silicic acid that is nearly independent of
2512
9
Polymers 2015, 7, 2504–2521

Polymers 2015, 7, page–page

given by Iler [2]. There is no distinct change with time t and temperature. The latter can be
explained
temperature byinthe
thissolubility
range ofof pHmonomeric silicic
[3]. In the case of acid that is nearly gel
the base-catalyzed independent ofthis
(Figure 9b), temperature
reductionin
is
this range of pH [3]. In the case of the base-catalyzed gel (Figure 9b), this reduction is much less
much less distinct ( cSi(OH)4 = 100–200 mmol/L). This is due to the higher pH, resulting in the increase
distinct (crSi(OH)4 = 100–200 mmol/L). This is due to the higher pH, resulting in the increase of
∗
solubility cr˚ cSi(OH)
of solubility
Si(OH)4 . As
4
. As already
already stated
stated forfor theacid-catalyzed
the acid-catalyzedgel,
gel,there
thereisisno
nodistinct
distinct dependency
dependency on
temperature
temperature although
althoughthethesolubility
solubilityofofmonomeric
monomeric silicic acid
silicic increases
acid strongly
increases with
strongly temperature
with temperaturefor
the base-catalyzed polymerization. This might be due to the fact that the spectroscopic analysis
for the base-catalyzed polymerization. This might be due to the fact that the spectroscopic analysis could
not
couldbe not
performed at elevated
be performed temperature,
at elevated but at room
temperature, but attemperature (~20 ˝ C).
room temperature Thus,
(~20 °C). monomeric silicic
Thus, monomeric
acid can polymerize and lower the concentration in the pore liquid squeezed
silicic acid can polymerize and lower the concentration in the pore liquid squeezed out. out.

Figure 9.
Figure 9. Concentration
Concentration ofof monomeric
monomeric silicic
silicic acid
acid in
in the
the pore
pore liquid
liquid of cylindrical samples,
of cylindrical samples,
acid-catalyzed (a) and base-catalyzed (b), natural syneresis.
acid-catalyzed (a) and base-catalyzed (b), natural syneresis.

For reasons still not explained, the concentration measured is higher than the solubility
For reasons still not explained, the concentration measured is higher than the solubility
calculated with Equation (1). This fact is confirmed by the pore liquid that becomes turbid if stored
calculated with Equation (1). This fact is confirmed by the pore liquid that becomes turbid if stored
for several days at constant temperature. It seems as if new solid is formed when the pore liquid is
for several days at constant temperature. It seems as if new solid is formed when the pore liquid is
separated from the solid. However, an unambiguous increase of the concentration with temperature,
separated from the solid. However, an unambiguous increase of the concentration with temperature,
as presented previously in the state-of-the-art, cannot be stated. If any, there is only a small tendency
as presented previously in the state-of-the-art, cannot be stated. If any, there is only a small tendency
for both gels.
for both gels.
The sample size affects the syneresis behavior strongly. Therefore, small gel droplets (dDrop ≈ 3 mm)
The sample size affects the syneresis behavior strongly. Therefore, small gel droplets
instead of the cylindrical samples are prepared and examined for their syneresis behavior depending
(dDrop « 3 mm) instead of the cylindrical samples are prepared and examined for their syneresis
on pH and temperature. The courses of shrinkage of the gel droplets are depicted in Figure 10.
behavior depending on pH and temperature. The courses of shrinkage of the gel droplets are depicted
Compared to Figure 8, the different scaling of the x-axis should be noted. Smaller samples
in Figure 10.
consolidate much faster, clearly showing the dependency between the syneresis rate and sample size.
Compared to Figure 8, the different scaling of the x-axis should be noted. Smaller samples
Furthermore, the maximum shrinkage ΔV/V0|max increases for both types of catalysts and, in the case
consolidate much faster, clearly showing the dependency between the syneresis rate and sample size.
of the acid-catalyzed gel, even fans out with increasing temperature. This behavior cannot be
Furthermore, the maximum shrinkage ∆V/V 0 |max increases for both types of catalysts and, in the
observed for the cylindrical samples and, thus, must be attributed to the smaller sample size.
case of the acid-catalyzed gel, even fans out with increasing temperature. This behavior cannot be
There is no great difference between the courses for both types of catalyst during the first 30 min.
observed for the cylindrical samples and, thus, must be attributed to the smaller sample size. There is
This is due to the constant temperature of 20 °C during this period. Thereafter, the temperature is set
no great difference between the courses for both types of catalyst during the first 30 min. This is due
to the values given in Figure 10. Thus, each droplet must be heated firstly to this temperature.
to the constant temperature of 20 ˝ C during this period. Thereafter, the temperature is set to the
This might be the reason for the almost similar course in the case of 40 and 60 °C for t ≤ 2 h, especially
values given in Figure 10. Thus, each droplet must be heated firstly to this temperature. This might
for the base-catalyzed gel droplets. All model parameters for the gel droplets are summarized
be the reason for the almost similar course in the case of 40 and 60 ˝ C for t ď 2 h, especially for the
in Table 2.
base-catalyzed gel droplets. All model parameters for the gel droplets are summarized in Table 2.

2513

10
Polymers 2015, 7, 2504–2521
Polymers 2015, 7, page–page

Figure 10.
Figure 10. Relative
Relative shrinkage
shrinkage ∆V/V
ΔV/V0 ofofthe
thegel
geldroplets,
droplets,natural
natural syneresis
syneresis for
for different
different temperatures
temperatures
0
ϑ, acid-catalyzed (a) and base-catalyzed (b).
ϑ, acid-catalyzed (a) and base-catalyzed (b).

Table 2. Maximum shrinkage ΔV/V0|max and characteristic time constant τ for the gel droplets
Table 2. Maximum shrinkage ∆V/V 0 |max and characteristic time constant τ for the gel droplets
(d Drop ≈ 3 mm), natural syneresis, model parameters.
(dDrop « 3 mm), natural syneresis, model parameters.

Maximum
Maximum shrinkage
Shrinkage ΔV/V|0|max/-
∆V/V /- Time constant
Time τ/h τ/h
Constant
Temperature 0 max
Temperature ϑ/˝ C Acid-catalyzed Base-catalyzed Acid-catalyzed Base-catalyzed
ϑ/°C Acid-catalyzed Base-catalyzed Acid-catalyzed Base-catalyzed
pH < pHiso pH > pHiso pH < pHiso pH > pHiso
pH < pHiso pH > pHiso pH < pHiso pH > pHiso
20 0.37 0.30 0.40 0.67
20 40 0.37
0.41 0.30
0.39 0.40
0.64 0.57 0.67
40 60 0.41
0.48 0.39
0.51 0.64
0.77 0.95 0.57
60 0.48 0.51 0.77 0.95

An analysis of the pore liquid as performed for the cylindrical gel samples is not possible due to
An analysis
the very of the pore
small amounts liquid
of pore as performed
liquid squeezed out for the cylindrical
of the gel droplets.gel samples is not possible due to
the very small amounts of pore liquid squeezed out of the gel droplets.
4.2. Enforced Syneresis
4.2. Enforced Syneresis
An additional process parameter, that is the pressure difference Δp induced by the external force
An additional
F, is introduced process parameter,
for enforced syneresis. that is the pressure
Generally, a membrane difference ∆p induced
is necessary by the
to retard the external force
solid formed.
F, is introduced for enforced syneresis. Generally, a membrane is necessary
Two different membranes are investigated with regard to their suitability for enforced syneresis. to retard the solid formed.
Two different
A simple and easymembranes
to perform are experiment
investigatedcomprising
with regard to their nutsch
a pressure suitability
and forthe enforced syneresis.
specific membrane
A simple and easy to perform experiment comprising a pressure nutsch and
is set up. The pressure nutsch is filled with Si standard solution (Certipur , Merck Millipore) already
® the specific membrane
is set up. r , Merck Millipore) already
used for The pressure nutsch
the calibration is filledmeasurements.
of UV/Vis with Si standard Thesolution
nutsch(Certipur
is operated with pressurized air at
used
Δpair =for theand
4 bar calibration of UV/Visinmeasurements.
the concentration the permeate is The nutsch is
determined operated
with the same with pressurized
method describedair in
at
∆p = 4 bar and the concentration in the permeate is determined with
theairprevious section. Figure 11 shows the courses of permeate concentration for the two different the same method described
in the previous section. Figure 11 shows the courses of permeate concentration Std for the two different
membranes. The Si standard solution has a molar concentration of cStd Si(OH) 4 = 35.7 mmol/L and is
membranes. The Si standard solution has a molar concentration of crSi(OH) = 35.7 mmol/L and is
P
concentrations crcPSi(OH)
4
depicted as
depicted as aa horizontal
horizontal line.line. The
The permeate
permeate concentrations Si(OH) 4 (a(apermeate
permeatevolume volumeofofVVPP == 11 mL mL
4
is chosen) for the membrane Dow Filmtec NF270 (Figure 11a) is always lower than the standard
solution that
that isisfilled
filledinto
intothe pressure
the pressure nutsch.
nutsch.Thus,
Thus,thatthat
membrane
membrane retards the monomeric
retards the monomeric silicicsilicic
acid
and,
acid when applied
and, when to enforced
applied syneresis,
to enforced an influence
syneresis, on the syneresis
an influence process cannot
on the syneresis process be cannot
excluded. be
Using
excluded.the membrane
Using the Microdyn-Nadir
membrane Microdyn-NadirNP010, the permeate
NP010, concentrations
the permeate reach the concentration
concentrations reach the of
the standard solution
concentration almost immediately.
of the standard solution almostThis immediately.
means that much Thisless monomeric
means that much silicic
lessacid is stored
monomeric
inside or held
silicic acid back by
is stored the or
inside membrane.
held backFor thismembrane.
by the reason, theFor latter
thismembrane
reason, theislatter
used membrane
to retard the is solid
used
in
to the case
retard ofsolid
the enforced
in the syneresis. In the previous
case of enforced syneresis. publication [5], experiments
In the previous publication of[5],
the experiments
acid-catalyzed of
gel
the were performed with
acid-catalyzed the membrane
gel were performed Dowwith
Filmtec
the NF270.
membraneAll these Dow experiments
Filmtec NF270. are repeated with
All these
the membraneare
experiments Microdyn-Nadir
repeated withNP010. There is no
the membrane significant difference
Microdyn-Nadir NP010.inThere the results
is nobetween the
significant
two membranes. However, this is not valid for the base-catalyzed
difference in the results between the two membranes. However, this is not valid for the gel.
base-catalyzed gel.

2514
11
Polymers 2015, 7, 2504–2521
Polymers 2015, 7, page–page

Polymers 2015, 7, page–page

Figure 11.
Figure 11.Concentration
Concentrationof monomeric silicicsilicic
of monomeric acid in the in
acid permeate for membrane
the permeate Dow Filmtec
for membrane DowNF270 (a)
Filmtec
and Microdyn-Nadir NP010 (b) upon filtration of Si standard solution (Certipur®, Merck Millipore).
NF270 (a) and Microdyn-Nadir NP010 (b) upon filtration of Si standard solution (Certipur , Merck r
Figure 11. Concentration of monomeric silicic acid in the permeate for membrane Dow Filmtec NF270 (a)
Millipore).
and Microdyn-Nadir
The NP010
courses of enforced (b) upon for
syneresis filtration
ϑ = 20of°C Si standard solutiongel
with an initial sample®, height
(Certipur Merck Millipore).
s0 = 16 mm are
shown in Figure 12. Both measured (solid lines) ˝and modeled data (dashed lines), see Equation (3),
The
The courses
are given. courses of
As mightof enforced
enforced syneresis
be expected,syneresis for
forϑϑ=are
all curves =20 C with
withtoan
20shifted
°C an initial gel
gelsample
initialmaximum
larger sample heightss00 ==and
height
shrinkages
16
16 mm
mm are
are
shorter
shown in
shownwith Figure
in Figure 12. Both
12. Both measured
measured (solid
(solid Δp,lines)
lines) and modeled
and modeledof data
data (dashed lines), see Equation (3),
times increasing pressure difference independently the(dashed
catalyst.lines),
Whensee Equation the
comparing (3),
are
are given.
given. As might
As might be
be expected,
expected, all
all curves
curves are
are shifted
shifted to
to larger
larger maximum
maximum shrinkages
shrinkages and
and shorter
shorter
acid- with the base-catalyzed gel, the latter exhibits a less distinctive spread although the same range
times
times with
with increasing
increasing pressure
pressure difference
difference ∆p,
Δp, independently
independently of
ofthe
the catalyst.
catalyst. When
When comparing
comparing the
the
of pressure differences Δp is covered. A reason might be the softer solid structure, leading to a lower
acid-
acid- with
with the
the base-catalyzed
base-catalyzed gel,
gel, the
the latter
latter exhibits
exhibits aa less
less distinctive
distinctive spread
spread although
although the
the same
same range
range
resistance against the pressure difference. This is supported by a larger maximum shrinkage for equal
of
of pressure
pressure differences
differences ∆p isis covered. A reason might be the
the=softer solid structure, leading
leading to to aa lower
pressure differences Δp Δp
(e.g., covered.
ΔV/V0|maxA=reason 0.8 andmight
0.63 atbeΔp softer
1.54 andsolid structure,
1.50 bar, respectively). lower
resistance against the pressure difference. This is supported by a larger maximum
resistance against the pressure difference. This is supported by a larger maximum shrinkage for equal shrinkage for equal
pressure differences∆p
pressuredifferences (e.g.,∆V/V
Δp(e.g., ΔV/V00||max max = 0.8
= 0.8 and
and 0.63
0.63 Δp∆p
at at = 1.54
= 1.54 andand 1.50
1.50 bar,
bar, respectively).
respectively).

Figure 12. Relative shrinkage ΔV/V0 of enforced syneresis for s0 = 16 mm and ϑ = 20 °C,
acid-catalyzed (a) and base-catalyzed (b).
Figure 12. Relative shrinkage ΔV/V0 of enforced syneresis for s0 = 16 mm and ϑ = 20 ˝°C,
Figure 12. Relative shrinkage ∆V/V 0 of enforced syneresis for s0 = 16 mm and ϑ = 20 C,
acid-catalyzed
All (a)the
values for(a) and base-catalyzed (b).
acid-catalyzed andmaximum shrinkage
base-catalyzed (b). ΔV/V0|max and the characteristic time constant τ are
summarized in Table 3. As can be seen, the maximum shrinkage almost halved from maximum to
minimum All values for the
pressure maximum
difference forshrinkage ΔV/V0|maxgel,
the acid-catalyst andwhereas
the characteristic time constant
the base-catalyst τ are
gel shows
All values for the3.maximum shrinkage ∆V/V 0 |maxshrinkage
and the characteristic time constant τ are
a reduction of merely one fifth. Exactly the inverse applies for the characteristic time constant to
summarized in Table As can be seen, the maximum almost halved from maximum τ.
summarized
minimum in Table difference
pressure 3. As can for be seen,
the the maximumgel,
acid-catalyst shrinkage
whereas almost
the halved from gel
base-catalyst maximum
shows
A 13-fold increase stands against a 6–7-fold increase.
to minimumofpressure
a reduction difference for the the
acid-catalyst gel, whereas the base-catalyst gelconstant
shows τ. a
Until now,merely one fifth. Exactly
the concentration of monomeric inverse applies
silicic acid inforthe
the characteristic
permeate is given timemerely for Si
reduction of
A 13-fold solution merely
increase stands one fifth.
against Exactly the
a 6–7-fold inverse
increase. applies for the characteristic time constant τ.
standard filled in. Adopting the same procedure, the concentration in the permeate is
A 13-fold
Until increase
now, thestands against a of
concentration 6–7-fold increase.
monomeric silicic to
acid in the them
permeate
measured for the acid- and base-catalyzed gel in order compare withisthe given merely for of
concentrations Si
Until solution
standard now, thefilledconcentration
in. Adoptingof monomeric
the same silicic acid inthe
procedure, theconcentration
permeate is given in the merely
permeatefor Siis
natural syneresis. This is done exemplarily for Δp = 3.80–3.92 bar and ϑ = 20 °C. The courses are given
standard
measured solution
forInthe filled in. Adopting the same procedure, the concentration in the permeate is
in Figure 13. theacid-
case ofand thebase-catalyzed
acid-catalyzedgel gel,inthere
orderis to compare
a strong them with
reduction in thethe concentrations
concentration fromof
measured
natural for the acid-
syneresis. This and
is donebase-catalyzed
exemplarily gel Δp
for in order
= to compare
3.80–3.92 bar andthem
ϑ = with
20 °C. the concentrations
The courses are givenof
natural t = 0) = This
cSi(OH)4 (syneresis. 1000 mmol/L to cSi(OH) ∆p≈there
=1.0–1.5 mmol/L. ϑA= 20decrease
˝ C. The in concentration
in Figure 13. In the caseisofdone exemplarily
the acid-catalyzed for4gel, 3.80–3.92 bar and
is a strong reduction courses
in the concentration are given
from
(from 1000 to 25 mmol/L) and a subsequent increase to approximately
in Figure 13. In the case of the acid-catalyzed gel, there is a strong reduction in the concentration 55 mmol/L is observed for
cSi(OH)4 (t = 0) = 1000 mmol/L to cSi(OH)4 ≈ 1.0–1.5 mmol/L. A decrease in concentration
the base-catalyzed gel. Neither are determined for natural syneresis (see Figure 9). We assume
(from
an 1000 tosolid
additional 25 mmol/L)
formation and a subsequent
directly increase todue
on the membrane approximately 55 mmol/L
to the rising turbidity of is
theobserved
pore liquidfor
2515
the base-catalyzed gel. Neither are determined for natural syneresis (see Figure 9). We assume
an additional solid formation directly on the membrane 12 due to the rising turbidity of the pore liquid

12
Polymers 2015, 7, 2504–2521

from crSi(OH)4 pt “ 0q = 1000 mmol/L to crSi(OH)4 « 1.0–1.5 mmol/L. A decrease in concentration

(from 1000 to 25 mmol/L) and a subsequent increase to approximately 55 mmol/L is observed for
Polymers 2015, 7, page–page
the base-catalyzed gel. Neither are determined for natural syneresis (see Figure 9). We assume an
additional solid formation directly on the membrane due to the rising turbidity of the pore liquid
for natural syneresis described already in Section 4.1. To prove this assumption, the pore liquid of
for natural syneresis described already in Section 4.1. To prove this assumption, the pore liquid of
natural syneresis (base-catalyzed gel) is filled into the pressure nutsch. Therefore, the influence of
natural syneresis (base-catalyzed gel) is filled into the pressure nutsch. Therefore, the influence of the
the solid is eliminated and only the behavior of pore liquid and membrane is investigated.
solid is eliminated and only the behavior of pore liquid and membrane is investigated. The analysis
The analysis of the pore liquid with respect to monomeric silicic acid yields a very similar diagram
of the pore liquid with respect to monomeric silicic acid yields a very similar diagram to Figure 13b.
to Figure 13b.
Table shrinkage ∆V/V
Table 3.3. Maximum shrinkage ΔV/V00||max andcharacteristic
maxand characteristictime
time constant
constant τ, enforced syneresis,
τ, enforced
ss0 == 16
16 mm
mm and
and ϑϑ == 20 ˝ C.
20 °C.

Pressure
Maximum
Maximum shrinkage∆V/V
Shrinkage ΔV/V0 |
0|max /-
max/- Time
TimeConstant
constant τ/h
τ/h
Pressure difference
Difference ∆p/bar
Δp/bar
Acid-catalyzed
Acid-catalyzed Base-catalyzed
Base-catalyzed Acid-catalyzed
Acid-catalyzed Base-catalyzed
Base-catalyzed
pH<<pH
pH pHiso
iso pH>>pH
pH pHiso
iso pH<< pH
pH pHiso
iso pHpH >> pHiso
iso

0.23–0.29
0.23–0.29 0.38
0.38 0.69
0.69 13.1
13.1 6.5
6.5
0.63–0.77
0.63–0.77 0.52
0.52 0.76
0.76 5.9
5.9 3.2
3.2
1.50–1.54
1.50–1.54 0.63
0.63 0.81
0.81 3.8
3.8 2.1
2.1
2.24–2.24
2.24–2.24 0.67
0.67 0.83
0.83 2.3
2.3 1.7
1.7
3.80–3.92
3.80–3.92 0.72
0.72 0.85
0.85 1.7
1.7 1.1
1.1
6.15–6.46
6.15–6.46 0.77
0.77 0.87
0.87 1.1
1.1 1.0
1.0
7.41–7.76
7.41–7.76 0.80
0.80 0.88
0.88 1.0
1.0 0.9
0.9

Figure 13. Concentration of monomeric silicic acid in the pore liquid, acid-catalyzed (a) and base-
Figure 13. Concentration of monomeric silicic acid in the pore liquid, acid-catalyzed (a) and
catalyzed (b), enforced
base-catalyzed syneresis
(b), enforced for Δp
syneresis for= ∆p
3.80–3.92 bar. bar.
= 3.80–3.92

A decrease and a subsequent increase of permeate concentration is observed. In addition, the

A decrease and a subsequent increase of permeate concentration is observed. In addition, the
time which elapsed between two samples to collect a permeate volume of VPP = 1 mL increased from
time which elapsed between two samples to collect a permeate volume of V = 1 mL increased from
a few minutes directly at the beginning to several hours for the last sample although the driving
a few minutes directly at the beginning to several hours for the last sample although the driving
pressure was constant (Δp = 4 bar) and there was still enough retentate volume present in the cell
pressure was constant (∆p = 4 bar) and there was still enough retentate volume present in the cell
(VRR ≈ ¾ VR R(t = 0)). This is an indication of a buildup of an additional flow resistance. Indeed, there is
(V « ¾ V (t = 0)). This is an indication of a buildup of an additional flow resistance. Indeed, there
a thin layer on the membrane after the termination of the experiment. However, this layer is found
is a thin layer on the membrane after the termination of the experiment. However, this layer is
only for pore liquid of the base-catalyzed gel. We conclude that the layer is built up during enforced
found only for pore liquid of the base-catalyzed gel. We conclude that the layer is built up during
syneresis, but has no significant influence on the maximum shrinkage due to its negligibly small
enforced syneresis, but has no significant influence on the maximum shrinkage due to its negligibly
thickness. By contrast, there is an influence on the kinetics of syneresis that has not been able to be
small thickness. By contrast, there is an influence on the kinetics of syneresis that has not been able
eliminated up to now. The courses and model parameters of enforced syneresis for ϑ = 40 and 60 °C
to be eliminated up to now. The courses and model parameters of enforced syneresis for ϑ = 40
are given in the Figures S3 and S4 and in the Tables S1 and S2 in the Supplementary Materials.
and 60 ˝ C are given in the Figures S3 and S4 and in the Tables S1 and S2 in the Supplementary
Due to the increased temperature, the rate of syneresis is accelerated (smaller values for the
Materials. Due to the increased temperature, the rate of syneresis is accelerated (smaller values for
characteristic time constant τ) for both types of catalyst. However, the maximum shrinkage ΔV/V0|max
the characteristic time constant τ) for both types of catalyst. However, the maximum shrinkage
is almost unaffected for the acid-catalyzed gel, whereas larger values are obtained in the case of
the base-catalyzed gel. Thus, this is a first indication of an analogous behavior between natural and
enforced syneresis. 2516
The distances that are flowed through by the pore liquid have to be equal for a quantitative
comparison between natural and enforced syneresis. Assuming a radial flow within the cylindrical
Polymers 2015, 7, 2504–2521

∆V/V 0 |max is almost unaffected for the acid-catalyzed gel, whereas larger values are obtained in
the case of the base-catalyzed gel. Thus, this is a first indication of an analogous behavior between
natural and enforced syneresis.
Polymers 2015, 7, page–page
The distances that are flowed through by the pore liquid have to be equal for a quantitative
comparison between natural and enforced syneresis. Assuming a radial flow within the cylindrical
gel samples, this distance corresponds to the radius, that is r = ddcyl = 6 mm. For the enforced
c yl cyl
gel samples, this distance corresponds to the radius, that is rcyl “ 2 = 6 mm. For the enforced
2
syneresis presented above, this distance matches half of the initial gel sample height, ss00 = 8 mm.
syneresis presented above, this distance matches half of the initial gel sample height, 2 = 8 mm.
2
These differences, albeit small, affect at least the kinetics
kinetics and,
and, potentially,
potentially, the maximum shrinkage.
Therefore, the initial sample height is reduced
reduced to to ss00 = 12 mm. The
The temporal
temporal courses
courses of
of shrinkage are
shown in Figure 14.

Figure 14. Relative

Relative shrinkage
shrinkage ΔV/V
∆V/V 0 of enforced syneresis for s0 = 12 mm and ϑ = 20 ˝ °C,
Figure 14. 0 of enforced syneresis for s0 = 12 mm and ϑ = 20 C,
acid-catalyzed
acid-catalyzed (a)
(a) and
and base-catalyzed (b).
base-catalyzed (b).

As might be expected from the results of natural syneresis, the kinetics of syneresis is
As might be expected from the results of natural syneresis, the kinetics of syneresis is accelerated,
accelerated, compared with Figure 12. This is expressed by smaller values for the characteristic time
compared with Figure 12. This is expressed by smaller values for the characteristic time constant
constant τ, e.g., from τ = 2.3 to 1.5 h for the acid-catalyzed gel with Δp = 2.24 and 2.19 bar, respectively.
τ, e.g., from τ = 2.3 to 1.5 h for the acid-catalyzed gel with ∆p = 2.24 and 2.19 bar, respectively.
Thus, enforced syneresis behaves analogously to natural syneresis with respect to initial sample size.
Thus, enforced syneresis behaves analogously to natural syneresis with respect to initial sample size.
However, the maximum shrinkage ΔV/V0|max is virtually unaffected by the reduction of the initial gel
However, the maximum shrinkage ∆V/V 0 |max is virtually unaffected by the reduction of the initial
sample height, contrary to the results of the cylindrical gel samples and droplets. All values can be
gel sample height, contrary to the results of the cylindrical gel samples and droplets. All values can
found in Table S3 in the Supplementary Materials. A possible explanation is the very different order
be found in Table S3 in the Supplementary Materials. A possible explanation is the very different
of size reduction between the cylindrical gel samples and droplets for natural syneresis, i.e.,
order of size reduction between the cylindrical gel samples and droplets for natural syneresis, i.e.,
the reduction of gel sample height by 4 mm for enforced syneresis. The courses of shrinkage for
the reduction of gel sample height by 4 mm for enforced syneresis. The courses of shrinkage for
elevated temperature of 40 and 60 °C and their model parameters can be found in Figures S5 and S6
elevated temperature of 40 and 60 ˝ C and their model parameters can be found in Figures S5 and S6
and Tables S4 and S5 in the Supplementary Materials. The maximum shrinkage ΔV/V0|max is nearly
and Tables S4 and S5 in the Supplementary Materials. The maximum shrinkage ∆V/V 0 |max is nearly
independent of the temperature for the acid-catalyzed gel, whereas it increases with temperature in
independent of the temperature for the acid-catalyzed gel, whereas it increases with temperature in
the case of the base-catalyzed gel. In direct comparison to the larger initial gel sample height,
the case of the base-catalyzed gel. In direct comparison to the larger initial gel sample height, see
see Figure 12, the maximum shrinkage is equal with a small tendency to larger values. However,
Figure 12, the maximum shrinkage is equal with a small tendency to larger values. However, the rate
the rate of syneresis is accelerated due to the reduced initial gel sample height, represented by smaller
of syneresis is accelerated due to the reduced initial gel sample height, represented by smaller values
values for the characteristic time constant τ. In summary, enforced syneresis behaves analogously to
for the characteristic time constant τ. In summary, enforced syneresis behaves analogously to natural
natural syneresis with respect to changes in the initial sample dimensions.
syneresis with respect to changes in the initial sample dimensions.
4.3.
4.3. Correlative
Correlative Model
Model
The
The model
model correlates the maximum
correlates the maximum shrinkage
shrinkage ∆V/V
ΔV/V0|| max and the characteristic time constant τ
0 max and the characteristic time constant
to
τ to the applied pressure difference ∆p. They are representedby
the applied pressure difference Δp. They are represented bythe
thefilled
filled symbols
symbols in
in Figure
Figure 15.
15.
Their dependence on the pressure difference Δp may be fitted separately for each temperature
Their dependence on the pressure difference ∆p may be fitted separately for each temperature with with
the
the following
following equations:
equations:
∆V ˇˇ
ˆ ˙ˇ
B
 ΔV ˇ “ A` B (4)
V0 max = A + C ` ∆p (4)
V
 0  max C + Δ p

2517 E
τ= D+ (5)
F + Δp
Polymers 2015, 7, 2504–2521

E
τ“ D` (5)
F ` ∆p
Polymers 2015, 7, page–page

Figure
Figure 15.
15. Maximum
Maximumshrinkage
shrinkageΔV/V
∆V/V0|max and characteristic time constant τ for acid-catalyzed (a) and
0 |max and characteristic time constant τ for acid-catalyzed (a)
base-catalyzed (b) gel as a function of
and base-catalyzed (b) gel as a functionpressure difference
of pressure Δp. ∆p.
difference

These equations are chosen with respect to the course of the values and to the possibility of
These equations are chosen with respect to the course of the values and to the possibility of
a mathematical extrapolation towards Δp = 0 bar. All values for the coefficients A–F can be found in
a mathematical extrapolation towards ∆p = 0 bar. All values for the coefficients A–F can be found
Tables S6 and S7 in the Supplementary Materials. The courses of these equations are split in two
in Tables S6 and S7 in the Supplementary Materials. The courses of these equations are split in
regions. The first region comprises the pressure differences that are covered experimentally and is
two regions. The first region comprises the pressure differences that are covered experimentally
depicted as solid lines in Figure 15. Equations (4) and (5) reflect the progression of enforced syneresis
and is depicted as solid lines in Figure 15. Equations (4) and (5) reflect the progression of enforced
sufficiently. This region is used to compare the temperature-dependent behavior of enforced with
syneresis sufficiently. This region is used to compare the temperature-dependent behavior of enforced
natural syneresis. The second region of the courses deals with the extrapolation towards Δp = 0 bar,
with natural syneresis. The second region of the courses deals with the extrapolation towards
shown as dotted lines in Figure 15. The values obtained for Δp = 0 bar are shown by the blank symbols.
∆p = 0 bar, shown as dotted lines in Figure 15. The values obtained for ∆p = 0 bar are shown by
A slightly smaller value for the maximum shrinkage ΔV/V0|max can be detected with increasing
the blank symbols.
temperature for the acid-catalyzed gel (Figure 15a). This is not in accordance with the temperature
A slightly smaller value for the maximum shrinkage ∆V/V |max can be detected with increasing
behavior for natural syneresis (see Figure 8). The extrapolation 0towards Δp = 0 bar yields maximum
temperature for the acid-catalyzed gel (Figure 15a). This is not in accordance with the temperature
shrinkages for natural syneresis of ΔV/V0|max = 0.19 to 0.30 that are in the range of the values measured
behavior for natural syneresis (see Figure 8). The extrapolation towards ∆p = 0 bar yields maximum
for natural syneresis. In the case of the base-catalyzed gel (Figure 15b), larger values for the maximum
shrinkages for natural syneresis of ∆V/V 0 |max = 0.19 to 0.30 that are in the range of the values
shrinkage are obtained with increasing temperature as already measured for natural syneresis
measured for natural syneresis. In the case of the base-catalyzed gel (Figure 15b), larger values for
(Figure 8). The extrapolated values for Δp = 0 bar are ΔV/V0|max = 0.52 to 0.75 depending on the
the maximum shrinkage are obtained with increasing temperature as already measured for natural
temperature and, thus, almost twice as large as those measured for natural syneresis. Here,
syneresis (Figure 8). The extrapolated values for ∆p = 0 bar are ∆V/V 0 |max = 0.52 to 0.75 depending
the correlative model overestimates natural syneresis. Nevertheless, larger shrinkages for the
on the temperature and, thus, almost twice as large as those measured for natural syneresis.
base-catalyzed gel are predicted in comparison to the acid-catalyzed gel that is accordance with
Here, the correlative model overestimates natural syneresis. Nevertheless, larger shrinkages for
the measurements. Independent of the catalyst, the syneresis velocity increases with temperature,
the base-catalyzed gel are predicted in comparison to the acid-catalyzed gel that is accordance with
reflected by smaller values for the characteristic time constant (Figure 15). This behavior is analogous
to natural syneresis. However, the acceleration is less distinctive and less unambiguous for the
base-catalyzed gel. The values predicted through 2518extrapolation towards Δp = 0 bar vary between
17.4 h ≤ τ (Δp = 0 bar) ≤ 21.2 h for the acid-catalyzed gel. They match partially or are at least in the
range of the values determined for natural syneresis, see Table 1. In the case of the base-catalyzed
Polymers 2015, 7, 2504–2521

the measurements. Independent of the catalyst, the syneresis velocity increases with temperature,
reflected by smaller values for the characteristic time constant (Figure 15). This behavior is analogous
to natural syneresis. However, the acceleration is less distinctive and less unambiguous for the
base-catalyzed gel. The values predicted through extrapolation towards ∆p = 0 bar vary between
17.4 h ď τ (∆p = 0 bar) ď 21.2 h for the acid-catalyzed gel. They match partially or are at least in the
range of the values determined for natural syneresis, see Table 1. In the case of the base-catalyzed gel,
the characteristic time constant takes values of 13.2 h ď τ (∆p = 0 bar) ď 50.6 h. Again, these values are
related to those of natural syneresis, but the correct assignment to temperature is not given. Here, the
largest value for τ is assigned to ϑ = 40 ˝ C and not to the lowest temperature of ϑ = 20 ˝ C. This is due
to the sensitivity of the extrapolation especially for small pressure differences. Thus, special attention
must be paid to the correlative model to predict natural syneresis.

5. Summary and Conclusions

“Natural syneresis” of silica can be measured with a pycnometer device adapted to determine
the influence of the process parameters. In particular, an acid- and base-catalyzed polymerization
reaction is investigated at different temperatures and sample sizes. It is found that the maximum
shrinkage for rather large gels (cylindrical gel samples) is independent of the temperature range
investigated (20, 40 and 60 ˝ C) and has a value of ∆V/V 0 |max « 0.20 for the acid-catalyzed gel,
whereas a dependency on temperature is detected in the case of the base-catalyzed gel. The maximum
shrinkage is ∆V/V 0 |max « 0.30, 0.39 and 0.51 for the three temperatures. These differences between
the two catalysts can be explained with the different chemical mechanisms of solid formation and
the resulting differences in gel structure. The rate of syneresis, represented by the characteristic time
constant τ, rises with increasing temperature. This is synonymous to a reduced characteristic time
constant, i.e., for the acid-catalyzed gel τ(20 ˝ C) = 21.3 h, τ(40 ˝ C) = 11.7 h and τ(60 ˝ C) = 5.0 h,
respectively, τ(20 ˝ C) = 50.1 h, τ(40 ˝ C) = 32.0 h and τ(60 ˝ C) = 27.5 h in the case of the base-catalyzed
gel. Reducing of the characteristic length that must be flowed through by the pore liquid leads to
smaller characteristic time constants and larger maximum shrinkages.
The duration of experiments for the larger samples (dCyl = 12 mm and V Gel « 3 mL) is
approximately ten days. This duration can be reduced significantly by applying an additional,
external force to the gel sample (“enforced syneresis”). In comparison to the natural syneresis of
the acid-catalyzed gel, larger values for the maximum shrinkage are reached (e.g., ∆V/V 0 |max = 0.79
for ∆p = 7.20 bar and ϑ = 20 ˝ C), whereas the kinetics of syneresis is strongly accelerated (characteristic
time constant of τ = 0.8 h). With increasing temperature, a slight reduction in the maximum shrinkage
can be detected. This reduction is in contrast to the natural syneresis behavior. Thus, enforced
and natural syneresis differ in temperature behavior with respect to the maximum shrinkage.
The characteristic time constant τ decreases monotonously with temperature, as already stated for
natural syneresis, to τ(40 ˝ C) = 0.34 h and τ(60 ˝ C) = 0.23 h. There is no difference in temperature
dependence between enforced and natural syneresis for the base-catalyzed gel. The values for the
maximum shrinkage become larger (e.g., from ∆V/V 0 |max = 0.86 to 0.90 for ϑ = 20 to 60 ˝ C) and the
characteristic time constant reduces (from τ(20 ˝ C) = 0.5 h to τ(60 ˝ C) = 0.3 h). As already shown
for natural syneresis, a reduction in the initial sample dimensions results in a faster syneresis, but to
almost unchanged maximum shrinkage. This might be due to a reduction factor of merely one fourth.
This factor was chosen to allow for a comparison between enforced and natural syneresis with equal
characteristic lengths.
An empirical, correlative model based on enforced syneresis is used for the prediction of
natural syneresis due to extrapolation of the two model parameters ∆V/V 0 |max and τ towards
∆p = 0 bar. The extrapolation of these parameters for the acid-catalyzed gel yields values in the range
of ∆V/V 0 |max = 0.19 to 0.30 and τ = 17.4 to 21.2 h for the three temperatures (20, 40 and 60 ˝ C)
and, thus, match partially or are in the range of measured values. In the case of the base-catalyzed
gel, the predicted values are ∆V/V 0 |max = 0.52 to 0.75 and τ = 13.2 to 50.6 h. Here, the maximum

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Polymers 2015, 7, 2504–2521

shrinkages are overestimated by a factor of two, but the characteristic time constants are related to
the values measured, even though the temperature assignment is incorrect. The largest value for τ is
not obtained for the highest temperature, but for ϑ = 40 ˝ C. This is because of the sensitivity of the
extrapolation, especially for the small pressure differences applied. As a result, special attention must
be paid to the extrapolation.
The process parameters which influence the formation of particles and their subsequent
consolidation, i.e., the syneresis, can be identified in a much shorter time with the concept of
enforced syneresis. Beside this analytical aspect, one can think of a preparative application of
enforced syneresis. Furthermore, influencing and stopping the polymerization (i.e., with an additive
inactivating the hydroxyl groups) will give the possibility of producing stable silica at any desired
intermediate state. The phenomenology of syneresis is described in this work by means of an
empirical model. The development of a physically based model is part of the actual research and
will be presented in the future.

Supplementary Materials: Supplementary materials can be found at www.mdpi.com/2073-4360/7/12/1528/s1.

Acknowledgments: This research project is supported financially by Deutsche Forschungsgemeinschaft DFG
within the priority program “SPP 1273 Kolloidverfahrenstechnik” (KI 709/22-3, colloid process engineering).
We would like to thank the assisting students who performed parts of the measurement and analyses, as well as
our colleagues for their advice.
We acknowledge support by Deutsche Forschungsgemeinschaft and Open Access Publishing Fund of
Karlsruhe Institute of Technology.
Author Contributions: Sebastian Wilhelm and Matthias Kind conceived and designed the experiments
and wrote the publication. Sebastian Wilhelm performed the experiments and analyzed the data, assisted
by students.
Conflicts of Interest: The authors declare no conflict of interests. The founding sponsors had no role in the
design of the study, in the collection, analyses, or interpretation of data, in writing of the manuscript, and in the
decision to publish the results.

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