Article

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Microstructure of Sodium Montmorillonite Gels with Long Aging

Time Scale
Yee-Kwong Leong,*,† Mingyong Du,† Pek-Ing Au,†,‡ Peta Clode,§ and Jishan Liu†
†
Department of Chemical Engineering and §Centre of Microscopy, Characterization and Analysis, The University of Western
Australia, Crawley 6009, Australia
‡
Department of Chemical Engineering, Curtin University, Miri, Sarawak, Malaysia, 98009

ABSTRACT: Purified sodium montmorillonite (SWy-2) gels

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of a few percent solids displayed pronounced time-dependent

rheological or aging behavior with a long time scale. The aging
behavior was characterized by an increasing yield stress with
rest time. This increase continued even after a week of rest.
An open sponge-like cellular microstructure of the aged gels
was captured by cryo-SEM with samples prepared at high
pressure. The size of the openings of the cellular structure is
small, generally less than 1 μm formed by thin flexible platelet
with curling edges. This structure was formed by strong
attractive and repulsive forces. The rapid yield stress increase in the early stage of aging is due to rapid bond formation
occurring between network platelets and free individual platelet, isolated aggregates, and platelet particles in network with free
edges. Over time, all platelets are bonded in the network. During aging, the platelets in the structure would have to adjust
continually in response to a net force acting on it by its neighbors. The high concentration of platelets responding to this force
imbalance is the cause of the long aging time scale. The operation of the attractive and repulsive forces, and the shape and
charge properties of the platelets are responsible for the cellular structure being built. At complete structural recovery, the
structure should attain the state of lowest free energy. The repulsive force regulates the development of the microstructure. The
aging data of the 3.3 wt % gel were fitted by different aging models.

■ INTRODUCTION
The investigation on the time-dependent rheological or aging
properties of bentonite (comprised of 70−90 wt % sodium
montmorillonite) gels commenced about 100 years ago.1−3
The thixotropic or aging behavior is thus well-known; however,
the microstructure responsible for this aging behavior is still a
subject of debate. This investigation will use the microstructure
captured to explain the aging behavior and, in particular, the
time scale of the aging process.
Sodium montmorillonite is an important clay with many
commercial applications;4 viscosity modifiers, personal care
products and others. As bentonite, it is an important ingredient
in drilling mud, impermeable slurry wall, facial treatment
products, iron making aid and etc. Sodium montmorillonite is
a smectite swelling clay displaying pronounced thixotropic or
aging behavior at very low solid concentration of a few weight
percent.1−3 Several types of microstructures have been
proposed to explain the time-dependent rheological proper-
ties.5−7 Capturing the microstructural image of this gel clearly
has been an issue until recently.8−10 The microstructure is
formed by the nature and strength of the surface forces
operating between the platelet particles. For ordered structure,
these forces also determine the architecture of the micro-
structure formed. The types of surface forces operating are van
der Waals force, electrostatic repulsive (electrostatic double
layer or EDL) and electrostatic attractive forces. According to
van Oss et al.11 nonelectrostatic polar (Lewis acid/base) forces
could also be present in smectite particle interactions.
Microstructure was suggested to form by electric double
layer (EDL) repulsive force6,12,13 immobilizing the montmor-
illonite particles by caging effect. The particle concentration
must be sufficient to occupy the whole gel volume for the EDL
caging effect to be effective. Swelling and EDL repulsion
should increase the particle number concentration of
montmorillonite platelets in water by delamination. Osmotic
pressure drives the water into the interlayer of the
montmorillonite platelets hydrating the sodium ions and
developing an electric double layer on each surface of the
interlayer platelet particles. The overlapping of these adjacent
double layers gives rise to the EDL force which increases the
interlayer separation distance to such an extent that the
platelets together with its thick double layer occupying the
whole volume of the suspension forming a repulsive gel with a
yield stress.
Other suggested structures are those formed by positive
edge and negative face attraction and van der Waals force.
Edge-face attraction formed card-house structure,5,14 zigzag
ribbon structure,7 and overlapping band or coin structure13,15
Received: February 1, 2018
Revised: June 1, 2018
Published: July 27, 2018

© XXXX American Chemical Society A DOI: 10.1021/acs.langmuir.8b00213

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have been proposed. Overlapping coin structure is formed by
the face of particle overlapping the face near the edge of
another particle. The time-scale of the structure forming
process should depend on the forces operating and type of
microstructure being built. Recently, evidence of other
microstructures was reported,9,10 where an open cellular
microstructure of SWy-2 sodium montmorillonite gel was
imaged by cryo-XRH-SEM, with the gel sample prepared at
high pressure.10 Microstructure derived from X-ray tomog-
raphy was found to lack clarity.9 Cryo-SEM image of gel
samples prepared at atmospheric pressure displayed a more
recognizable open ordered cellular structure, the honeycomb-
like structure.8−11 The formation of honeycomb micro-
structure by clay particles has long been suggested by
Terzaghi,16 which was not supported by experimental
evidence.17 The time scale for the formation of this open
cellular microstructure is unknown and remained not
investigated. This study is an attempt to address this issue.
In addition, the microstructure of SWy-2 gels prepared at high
and atmospheric pressure were compared and discussed.
Microstructure of low concentration bentonite suspensions,
up to 2.8 wt % solids, has been deduced from the phase state
determined as a function of clay concentration and ionic
strength by cross-polarizer optical birefringence technique.18,19
Phase states such as isotropic liquid, isotropic gel, nematic gel,
and flocculation have been identified. However, for some phase
states such as the ordered nematic state it is not possible to
deduce detailed features and architecture of the microstructure
from this optical technique. The location of the ordered
nematic state in terms of clay and salt concentration,
corresponded to the attractive gel state. The concentration at
sol/gel transition was found to increase with particle size of the
Na-montmorillonite.19 The flocculation state occurred at a
very high salt concentration, above ∼0.2 M NaCl independent
of clay concentration where the EDL thickness is only 0.7 nm.
The nematic state occurred at high clay concentration at all salt
concentration below 0.2 M NaCl. This state also applied to the
highest clay concentration of 2.8 wt %. In this study, the
microstructures of nominal 1 and 2 wt % SWy-2 suspensions
were presented, in addition to that obtained with the more
concentrated gels. The most dilute gel of 3.3 wt % solids used
in this study, should have a phase state corresponding to the
nematic or attractive gel state.
Aging behavior characterizes the kinetics of the structural
recovery process of a presheared gel. The recovery of the
structure upon resting is reflected by the progressive
strengthening of the mechanical properties such as the yield
stress and storage modulus or compliance.20,21 In aging study,
a well-defined initial state such as an equilibrium breakdown
state, is essential for the results to be reproducible and the
results of the different studies to be comparable. The
preshearing step and its protocol are thus important in
obtaining this well-defined initial state.21 With the preshearing
step being employed to breakdown the clay microstructure to
an equilibrium state, the objective of the aging study was to
evaluate the kinetics of structural recovery in a completely
undisturbed state. Ideally the sample should not be disturbed
in the recovery phase during measurement. A nondestructive
test would be ideal. However, this is not always possible. If the
recovery phase takes weeks and months, then it will not be
possible to follow this process over this time scale in a
rheometer without the sample drying out. The use of the vane
yield stress technique22 and a sample contained in a wide-open
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mouth (screw top) vessel overcome some of these short-
comings ensuring that many measurements with a small vane
can be conducted in the gel with its large exposed surface area.
The vane can measure the yield stress in locations not
disturbed by previous measurements.20,21 The insertion of the
vane was found to have only a negligible effect on the yield
stress result.22 In this investigation, the temporal yield stress
behavior of aging gels was characterized using this vane
technique. As a confirmation of the suitability of this vane
technique, the trend of the yield stress increase during aging of
transparent nanodiscotic synthetic hectorite gels was identical
to that obtained by a nondestructive yield stress technique, the
magnetic tweezer-fluorescent particle tracking technique23
developed at MIT.
■
EXPERIMENT AND METHODS
The SWy-2 sodium montmorillonite mined from Crook County
Wyoming, was sourced from the Clay Mineral Society. As-mined
SWy-2 contained 75% smectite, 8% quartz, 16% feldspar, and the
remaining 1% comprised of gypsum, mica, and Illite and others.24 A
sedimentation method was employed to purify the SWy-2 sodium
montmorillonite by exploiting the difference in the sedimentation rate
between the platy clay particles and the more spherical shaped
impurities. A very dilute concentration of the as-mined SWy-2
suspension was prepared: 40 g clay in 2 L of water. A small sample of
the suspension, ∼500 mL, was sonicated at a time with a sonic probe
to facilitate the separation of the impurities from clay platelets and the
delamination of the platelets. The samples were mixed together, and
the suspension was allowed to settle initially for several hours before
being decanted into an empty container. Settled impurities located at
the bottom of the first container were also collected and kept for
accounting purposes. The decanted suspension in the second
container was allowed to rest overnight to settle the finer impurities
and then decanted again. This was repeated a few times to remove as
much of the fine impurities as possible. After that, the 2 L suspension
was allowed to dry in the oven for several weeks at 60 °C. XRD of the
purified and as-received SWy-2 clay samples was characterized. The
result is shown in Figure 1a. Quartz and feldspar diffraction peaks
have virtually disappeared after purification. A large peak was
observed at the high diffraction angle ∼28° for the purified sample
and this was due to the diffraction of hkl 005 plane.25 It was not
possible to grind the dried purified SWy-2 into fine powder for the
XRD characterization. The purified layered agglomerates shown in
Figure 1b were found to be highly malleable.
Gels of purified SWy-2 at 3.3 (3.26), 4.5, and 6.5 wt % solids were
prepared by sonication with a sonic probe. Each gel sample weighed
only ∼50 g so that the size of the pH probe or spatula is sufficient to
mix the gel very well and uniformly. The total duration of the
sonication can be as long as 3 min. The sonication process was
stopped occasionally for inspection to ensure that all the particles are
wetted and well dispersed and partially wet lumps sticking to the
container wall were not present. If present they were dispersed by
directing the sonic probe to the area of the container. The freshly
prepared gels were rested several days to allow the surface transport
processes of hydration, charging and ions transport have time to reach
equilibrium.21
To start the aging or structural recovery experiment, the initial state
was set up by shearing or agitating the gel to an equilibrium state and
the yield stress was measured immediately. This yield stress, the first
point of the aging experiment, characterized the gel strength at the
equilibrium structural breakdown state. After that the yield stress was
measured at regular aging time interval in locations not disturbed by
previous measurements.21 In between yield stress measurements, the
sample was kept in a 100% humidity environment so that drying did
not occur. All gel samples were kept in a 100% humidity environment
even for storage after the investigation.
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Figure 1. (a) XRD diffraction results of as-received and purified SWy-
2 sodium montmorillonite. The quartz Q and feldspar F peaks were
virtually eliminated after the purification process. Illite I or mica peak
is still present and this material is platelet and difficult to remove. The
sharp peak of the purified particles at 2θ ∼ 28° is due to hkl 005
diffraction. (b) SEM image of purified dried SWy-2.
■
RESULTS AND DISCUSSION
Aging Behavior. The initial state of the gel chosen in the
aging experiment is the equilibrium breakdown state (EBS)
after the particles have achieved surface chemical equilibrium.
The surface transport processes such as charging, ions
transport hydration and others must have reached equilibrium.
Leaving the freshly prepared gels to stand for a few days would
be sufficient to reach surface chemical equilibrium. The
approach employed to determine of the surface chemical
equilibrium and the EBS is illustrated with the results in Figure
2, which showed the yield stress versus time since preparation
of a 6.5 wt % purified Swy-2 gel. The yield stress at each time
interval was measured immediately after the gel was broken
down with a spatula or a pH or conductivity probe. The vane
measures the static yield stress and not the dynamic yield stress
which can be obtained from by fitting Bingham model to the
shear stress−shear rate data. The Bingham yield stress is
related to the separation energy between two particles
interacting attractively.26 This gel displayed a pH of 8.5 and
a conductivity of 1.3 mS/cm (equivalent to 0.01 M KCl).
The freshly prepared gel displayed a gradual increase in the
yield stress with time at the beginning. This showed that the
clay platelets have not reached the surface chemical
equilibrium state. The surface transport processes such as
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Figure 2. EBS determination for 6.5 wt % purified Swy-2 Na
montmorillonite gel. The conductivity of the gel is 1.3 mS/cm
equivalent to 0.01 M KCl.
charging, hydration, and others have not reached equilibrium.
For synthetic hectorite gel this nonequilibrium state was
reflected by a temporal varying zeta potential and yield stress.21
A constant yield stress region was reached after 4000 min or
2.8 days. This means that at least 3 days of standing must be
allowed for the freshly prepared gel to attain the surface
chemical equilibrium state. After that the gel can be sheared or
agitated to the EBS for the commencement of the aging or
structural recovery experiment.
The well-defined initial state, the equilibrium breakdown
state, is also shown in Figure 2 in the region after 4000 min,
where the yield stress of the agitated gel remained constant.
The aging experiment can commence once this EBS is reached.
This EBS yield stress takes the value of 77 Pa and is the first
point of the aging result at zero aging time. During aging, no
agitation of the gel was allowed so that the structure recovery
of the presheared gel can be followed and the yield stress
measurement conducted at regular time intervals was
performed in locations not disturbed by previous measure-
ments.
The aging results characterizing the structural recovery
behavior are shown in Figure 3a for 6.5 wt % gel and Figure 3b
for 4.5 and 3.3 wt % gels. The recovery reflected by the
strengthening of the gel structure is characterized by an
increasing yield stress with aging time for all three gels. The
increase was sharp initially and then became more and more
gradual with time. The yield stress is very sensitive to gel solids
concentration. For example, the EBS yield stress is 77.6 Pa for
the 6.5 wt % gel and only 1.0 Pa for the 3.3 wt % gel. At long
aging time of 14 days, the yield stress of the 6.5 wt % gel
reached a high value of 578 Pa, representing a 7-fold increase.
The yield stress increase continued even after more than 10000
min or 1 week demonstration a long time scale for the
structural recovery process.
The time scale of the aging process appeared to be shorter
for the 3.3 wt % solids gel. The yield stress increase appeared
to stop after 8000 min of aging. However, it is not easy to
pinpoint the exact time needed to achieve this complete
structural recovery state. The yield stress increase continued by
a very small amount in the “plateaued” region. For example at
times of 8655, 10065, and 15945 min, the yield stress was 22.3,
23, and 26 Pa, respectively. These values should be very close
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Figure 3. Aging or structural recovery results for (a) 6.5 wt % (inset
showing locations of yield stress measurements) and (b) 4.5 and 3.3
wt % purified gels
to representing the yield stress at the state of complete
structural recovery. The yield stress of the 4.5 wt % gel is 20 Pa
at EBS and rose to 60 Pa after 9000 min of aging. The trend
showed a continued increase in the yield stress after 9000 min.
The long time scale of structural recovery lasting several
days, must reflect the type of microstructure formed and the
nature and strength of the interparticle forces controlling this
recovery process.
Gel Microstructures. Ice formation during cryo-freezing of
gel materials was reported to affect the microstructure
formed.27,28 In order to prevent ice crystal formation in the
samples during cryo-freezing, the sample was subjected to a
very high pressure. A Leica EM PACT2 equipment designed
for this purpose was used. A sample of SWy-2 slurries aged for
two months was placed on two flat carriers each with a
diameter of 1.5 mm and a depth of 0.2 mm and then pressed
together before being placed in a loader for pressurization and
rapid freezing in a liquid nitrogen bath. The sample was
pressurized up to 2000 bar. A freezing rate as high as 25000
°C/sec was achieved to prevent ice formation. The frozen
sample was transferred to a preparation system (Leica EM
MED020 preparation system fitted with a Leica EM VCT100
control system) and sublimated at −100 °C for 10 min before
coating with 8 nm Pt. The sublimation time was optimized
empirically to make sure the frozen water from the exposed
D DOI: 10.1021/acs.langmuir.8b00213
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surface was removed, while remaining the integrity of the
microstructure. Samples were imaged at 5 kV with a Zeiss 55
field emission SEM fitted with a Leica EM VCT100 cryo and
anticontamination system.
a. 0.93 and 1.84 wt % SWy2-gel Gels (Aged for 2 Months).
The cryo-SEM image of 0.93 wt % SWy-2 suspension prepared
at high pressure in Figure 4 showed that the particles are
Figure 4. Cryo-SEM image of 0.93 wt % SWy-2 suspension with
sample prepared at high pressure. The gel has a conductivity of 0.195
mS/cm (equivalent 0.001 M KCl) or a Debye length of 9.6 nm. The
red arrow indicate the region where the EDL repulsive force is within
the range of 10 nm.
flocculated forming aggregates with an open structure. The
suspension with a conductivity of 0.195 mS/cm equivalent to
∼0.001 M KCl should fall in the isotropic liquid phase state.18
Isolated platelet appeared not to be present in this state. The
platelet particles are very thin, nanometre in thickness, and
highly flexible. They displayed morphology similar to that of a
drying leave showing curling edges. This flexible platelet
interacting attractively in the edge-face or overlapping edge-
face configuration. The right angle edge-face interaction
configuration was rarely observed. Angular overlapping edge-
face configuration is more likely to occur. The edge of the
platelet located far away for this edge-face attractive junction
was observed to curl-up. The platelets in the aggregate are
separated by face−face repulsion opening up the aggregate.
Such repulsion would be strongest at the junctions where the
angular face−face separation is shortest. This suspension did
not exhibit a yield stress. There are insufficient platelet
particles to form a complete and strong 3D network structure
occupying the whole volume of the suspension.
At the equivalent ionic strength of ∼0.001 M KCl, the range
of the electric double layer (EDL) repulsive force is about 9.6
nm. This force is responsible for the separation of faces of the
interacting platelet. At this range the EDL force is very effective
near the overlapping edge-face (EF) interaction junctions
where the separation distance between the faces increased
from zero to tens of nanometres further along the platelets.
The red arrow in Figure 4 showed where the EDL repulsive
force is within range for face−face repulsion.
At higher concentration of 1.84 wt % SWy-2 gel the platelet
concentration is high enough to form a complete 3D network
structure. This gel contained an equivalent salt concentration
of 0.0025 M KCl. According to Gabriel et al.,18 this gel should
be located in the isotropic gel regime. The network structure
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shown in the cryo-SEM image in Figure 5a and 5b showed a
cellular microstructure of flexible platelet interacting attrac-
Figure 5. Cryo-SEM image of 1.84 wt % gel prepared at high pressure
(a) and (b) at lower magnification.
tively. Curling of the edges and curving/bending of the platelet
can also be seen. Some of the platelets appeared to be lying flat
with the edges curling upward which is highlighted in red dash
circle and labeled as C&C. The cellular microstructure did not
show any order as the platelets particles could be lying in any
position; flat and at various angles, are interacting attractively
via overlapping edge-face configuration with other platelet
particles lying in all sort of positions. The high flexibility and
edge curling of the platelets facilitate edge-face interactions in
all positions. The cellular structure showed some cell openings
did not have clear complete boundary. The size of the
maximum dimension of the openings with clear boundary
ranged from 250 to 1065 nm with an average of 604 nm based
on 7 measurements. Some of the larger openings have within it
smaller cells of size less than 100 nm, examples as highlighted
in green dash circle. There is no regular pattern in this cellular
structure.
The morphology of this network structure appeared to be
similar to that formed by curve dried leafs with curl edges
coming together forming an interlocking structure. The
interlocking force is friction. However, with SWy-2 gel, the
overlapping edge-face attractive is holding the network
structure together. The range of EDL repulsive force in this
gel with a conductivity of 0.33 mS/cm or 0.0025 M KCl is
∼6.0 nm. Again EDL repulsive can only operate at the
E DOI: 10.1021/acs.langmuir.8b00213
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overlapping edge-face junctions. This cellular structure is
formed by strong attractive and repulsive force. Attractive force
occurred at the junctions where the platelet particles are
interacting in the overlapping EF configuration. Strong EDL
repulsive force occurred near the junctions where the face−
face separation is in range of the EDL force. The angle
between the faces at overlapping edge-face junction opened up
in response. As many of the cells are very small with diameters
of less than a hundred nanometre or a few hundred
nanometres, very close contact repulsion between neighboring
platelets that are not junction partners, are possible. The
curving or bending of the sheets are in response to this EDL
repulsive force.
b. 3.6 wt % SWy-2 Gel (Aged for 2 Months). At 3.6 wt %,
the gel displayed the sponge-like cellular microstructure with
well-defined openings as shown in Figure 6a. This gel with an
equivalent salt concentration of 0.005 M KCl should fall in the
nematic gel regime18 by extrapolation as phase state data were
not available at clay concentration beyond 3 wt %. This means
that the well-developed sponge-like microstructure is nematic
in nature, that is, it has certain degree of directional order.
However, the openings of cells came in all shapes and sizes.
The size of the openings were measured using images with a
higher magnification shown in Figure 6b and 6c. The boundary
wall of the openings formed by the thin flexible platelets is
more complete. The size of the openings is also more uniform
in size. From 10 measurements it ranged from 250 to 707 nm
with an average of 543 nm. All the platelets forming the
network are bend with curling edges. With a conductivity of
0.7 mS/cm or 0.005 M KCl, the EDL repulsive force range is
slightly shorter, ∼4.3 nm. With a smaller opening, the platelets
are closer together providing a greater opportunity for both
EDL repulsion between faces and attraction in the overlapping
EF configuration to occur.
c. 6.5 wt % SWy-2 Gel (Aged for 2 Years). The cryo-SEM
images of the 6.5 wt % gel prepared at high pressure are shown
in Figure 7a and at higher magnification in Figure 7b. This gel
has been aged for 2 years and was used in the aging
experiment. Again, several flexible curve platelets with curling
edges are clearly seen in this image. The cellular microstructure
is formed by a higher density of platelet interactions. All the
flexible platelet particles are interconnected, that is, they come
together to form a strong 3D network, as reflected by its high
yield stress. The size of the openings are thus smaller. Over 12
measurements, the average maximum length of the opening is
409 nm calculated for sizes ranging from 240 to 709 nm.
At a conductivity of 1.36 mS/cm or 0.01 M KCl, with a
Debye length of 3 nm, the range of the EDL repulsive force is
even shorter. This, however, compensated by the higher
platelet concentration bring the platelet closer together. The
curving of the sheets and the curling-up of the edges could be
in response to the interplay of the attractive and repulsive
forces. The curling up of the edges and the orientation of the
platelets enhanced overlapping attractive EF interactions with
other platelets in all types of position and orientation. Face−
face EDL repulsion is diminished to a certain extent as the
platelet curving and curling hindered face−face alignment.
d. Microstructures of Samples Prepared at High and
Atmospheric Pressure. For the 6.5 wt % gel, the micro-
structure of the samples prepared at high and atmospheric
pressure appeared to be similar, see the comparison in Figure
8a and b. This suggests that the microstructure of concentrated
gel is less affected by pressure. Nakazawa et al.29 found that the
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Figure 6. Cryo-SEM of 3.6 wt % gel with the sample prepared at high
pressure: (a) low, (b) higher, and (c) high magnifications.
effect of the freezing rate, which affects ice crystal formation on
the cellular sponge-like microstructure was diminished if
concentrated bentonite gel was used. The particle interaction
configurations and the shape of some of the openings were
quite similar for the samples prepared at high and ambient
pressure. A significant difference is the scale of the structure.
The one frozen at ambient pressure is much larger, 3× larger.
The diameter of a similar opening highlighted in red dash
circle in both figures showed that the sample prepared at
ambient pressure is roughly 3× larger. There are fewer
individual platelets in the atmospheric pressure prepared
sample. These platelets are consumed in the formation of
multilayered and larger platelets. The resultant platelets are
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Figure 7. Cryo-SEM image of 6.5 wt % SWy-2 gel prepared at high
pressure: (a) low and (b) higher magnification.
also more rigid and orientated in the vertical direction forming
the honeycomb-like microstructure. At lower solids of 3.3 wt
%, the contrast of the gel microstructure is even greater, see
Figure 8c. The size of the openings are several microns in
diameter compared to 500 nm for the high pressure sample.
The larger and thicker platelet particle is highlighted in the
figure. Ice crystals formed in the freezing process caused the
platelets to come together to form large multilayer platelets.
The thicker and larger platelets driven to form by the ice
crystals must have the platelets adhered in the overlapping EF
configuration. Only in this configuration will the platelet
particle be able to grow in size, as shown in Figure 9a. The
increase in the thickness can also occur in these interaction
configuration. The rigid multilayer platelets formed by ice
crystals can be as large as several hundred microns, as shown in
Figure 9b.
e. Microstructure Development and Aging. The face or
basal plane of smectite platelet is negatively charged while the
edge possesses pH-dependent charges. The negative face
charge is permanent due to isomorphic substitution with a
lower valency metal ions such as Al with Mg in the octahedral
alumina sheet and Si with Al in the tetrahedral silica sheet. For
this SWy-2 Na montmorillonite, the substitution occurred
mainly in the octahedral alumina sheet with a net negative
charge of −0.53. The total tetrahedral charge of the silica sheet
is only −0.02. The interlayer charge is therefore equal to
−0.55. This face charges are responsible for the EDL repulsion
between faces in the gel opening up the microstructure. The
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Figure 8. Microstructure of (a) 6.5 wt % gel prepared at high
pressure, (b) 6.5 wt % prepared at atmospheric pressure, and (c) 3.3
wt % of gel prepared at atmospheric pressure.
range of the EDL repulsive force in the 1.8−6.5 wt % gels is 3−
6 nm based on the electrical conductivity data measured.
The platelets came together to form the open sponge-like
cellular structure presented earlier. Both the repulsive and
attractive forces formed this microstructure. The repulsive
force however regulates the formation of this structure and the
two platelets should approach to form the overlapping EF
attraction. The formation of overlapping EF bond is more
favorable if the faces of two platelets approach at an angle.
Without the repulsive force, the microstructure formed will not
be that open and may even not be cellular and sponge-like. In
contrast, the microstructure formed by attractive forces alone
even with platelets should be very short, with time scale, on the
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Figure 9. (a) Schematic showing the particle interaction configuration
in the formation of large and thicker multilayer platelet by ice crystals.
Top view. (b) Some of the platelets formed are several hundred
microns in length for 3.3 wt % gel.
order of minutes. Platelets bonding would occur immediately
upon contact leading to production of a relatively compact
microstructure.
Thin flexible curve platelets with curl edges are clearly seen
in the microstructure of the clay gels at 1.84−6.5 wt %. The
size of these platelets is usually less than 1 μm in length. Its
thickness is of the order of tenth of nanometers. These
platelets formed EF bonds in the microstructure. The pH-
dependent edge charge contribution to the total charge of
sodium montmorillonite platelets was reported to be quite
small, 5−10%, estimated based on the contribution of the edge
area to the total surface area.30 It is quite remarkable that such
charge distribution could produce a strong EF attraction.
The curving of the platelets and the curling of its edges
facilitated EF interaction by enabling platelets in more
positions to participate in such inteaction. The curve sheets
make face−face alignment more difficult. The platelets in the
network structure are restricted in movement due to
overlapping edge-face attraction at several positions on the
edges. There are two possible causes for the curving or bending
of the sheets. Multiple overlapping EF attractive contacts with
other sheets in a restricted network environment is one such
cause. Strong repulsive interaction with neighboring platelets is
another. The platelets can be very close as reflected by the
small size of the cells, much smaller than 1 μm for the
maximum dimension of the cell. A mixture or combination of
both mechanisms is most likely to occur in the network.
The sharp increase in the yield stress of a presheared gel in
the initial period of aging is an indication of the rapid
reformation of platelet−platelet bonds in the network. The
rapid bond formation could be via (i) individual platelets
navigating through the complex force field to attach on to
platelets in the network, (ii) isolated aggregates with an open
structure, as seen Figure 4, formed bonds with the network,
and (iii) platelets in the network with free ends formed bonds
with other platelets in the network. All platelets do not have
straight edges. This allowed overlapping EF interactions to
occur at several locations with other platelets, thereby
increasing the probability of such interactions. At longer
aging time, all the platelets should be bonded in the network.
Each of these platelets experiences both attractive and
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Langmuir Article

repulsive forces in the network. The net force experienced by structural recovery or equilibrium state yield stress (Pa), 1/
any platelet in the network is not zero initially, that is, there is a Kr is the time constant, τy∞, τy0, and the model time constant
net force acting on it by neighboring platelets. If this net need to be determined from experimental yield stress−time
repulsive force becomes too large, the platelet will break free at data.32−34
the weak EF bonds from some of its neighbors at the joints or The two-parameter model of Chow31 is given by
bend or move in response. Any movement, however slight, of a t
platelet in the network will cause force imbalance to be τy(t ) = β ln
experienced by all neighboring platelets. All these platelets will tm (2)
have to move and adjust or bend in response. This action where β is a constant and tm is the microstructural
percolates down the network with large number of platelets development time constant. If these models described the
responding. This force imbalance is experienced continually by aging behavior accurately then having a single time constant is
the platelets in the network during the period of structural more advantageous than those models needing a relaxation
recovery or rejuvenation. The continual adjustment or time spectrum to describe the behavior. There is no need to
movement of the platelets could be large initially but will invoke a multiple relaxation mode.
become smaller as the structure reformation approaches the The results of the model fit to the aging data are shown in
fully recovered equilibrium state. This particle adjustment Figure 10, a log−log plot of yield stress versus aging time. The
process involving high concentration of platelets takes time
and is responsible for the long time scale of the aging process
lasting many days. At the end of the aging process, each
platelet in the network should be in stress free equilibrium
state. The maximum yield stress at the state of complete
structural recovery is a reflection of the network attaining
maximum strength. This maximum strength state usually
denotes the attainment of the state of minimum free energy.
A similar microstructure obtained by extra high resolution
cryo-SEM of sodium montmorillonite SWy-2 gel prepared at
high pressure was reported by Mouzon et al.10 The sequence
of cryo-XHR-SEM images captured at various time of
sublimation of the high pressure frozen samples also showed
a similar open cellular structure.
According to the phase state diagram,18 the phase of the 1.84
wt % Swy-2 gels should be isotropic gel and that at 3.6 wt %
should be isotropic gel at the salt concentration of ∼0.005 M
KCl. However, their microstructures captured in this study was
found to be similar. The 6.5 wt % gel with salt concentration of Figure 10. Model fit to the aging data of the 3.3 wt % gel.
0.01 M KCl is very similar to the 3.6 wt % gel. This
microstructure more resembled that in the attractive gel state.
Bentonite in suspension is well-known to intercalate a range Leong model provided a better fit of the data. The parameters
of compounds including water-soluble “hydrophobic” mole- used in the Leong model fit have the following values; τy0 = 1
cules such as surfactants. These molecules can reside within Pa, τy∞ = 29 Pa, and Kr = 0.00022 min−1 or 1/Kr = 3.15 days.
the interior of the micron size cells without the need to interact For the two-parameter model, the values of the model
with the particle surfaces. Upon drying, the cellular sponge-like parameter used are β = 3.5 Pa and tm = 44 min. This model
structure collapsed forming layered platelets, as shown in predicts a zero yield stress at t = tm and negative yield stress at t
Figure 1b, trapping the molecules in the interlayer. < tm. At t just greater than tm, the aging yield stress is much
Aging Modeling. The aging data of the 3.3 wt % gel smaller than the experimental value.
showed that its structure recovery process is close to
completion. In some aging models, the yield stress at this
complete structural recovery state is required. Two aging
■ CONCLUSIONS
The time scale of the aging process takes a long time, lasting
models were used to fit the aging data for this purified 3.3 wt % several days and increases with clay concentration. An open
gel; the three-parameter Leong model and the two-parameter cellular sponge-like structure of the aged gels prepared at high
model developed by Chow31 for the physical aging of glassy pressure was captured by cryo-SEM. The length scale of the
polymer and adopted by Rich et al.23 for describing the yield opening of the cells is generally less than 1 μm. The platelet
stress of aging synthetic hectorite gel. The Leong model is particles within the cells are very close together. The thin
given by platelets forming the structure are flexible and bent with

ij ij τy0 yz yzz
jj
curling edges enhancing its probability of overlapping edge-

jj j τy∞ z zzzz
j z
2/3

jj
3/2

k { zz
face interaction and limiting its ability for face−face repulsive

τy(t ) = τy ∞jj1 −
K rt zzzz
1 −
jj
interaction. This structure is formed by attractive and repulsive

jj zz
jj
forces operating simultaneously. The repulsive interaction
z
k {
1 + opened up the structure, while the overlapping edge-face
(1) attraction formed the network.
The bending of the platelets could be in response to the
where τy(t) is time-dependent yield stress, τy0 is the agitated forces acting on it in the network structure. Attractive and
state equilibrium yield stress (Pa), τy∞ is the complete repulsive forces occurred at the network junctions and close-by
H DOI: 10.1021/acs.langmuir.8b00213
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Langmuir
neighboring platelets can also exert a repulsive force. In the
early stage of structural recovery, rapid bond formation occurs
with (i) individual platelet having navigated through the
repulsive force field of the recovering network, (ii) isolated
aggregates, and (iii) platelet particles in network with free ends
or edges. The platelets forming the bond will all have to
approach at a favorable angle for EF bond formation in the
network. Initially, the platelets in the network are not stress-
free as they will experience both repulsive and attractive forces.
The platelets forming the network junctions in particular will
encounter more strongly these opposing forces. These platelets
will response to this force imbalance by movement or bending
or bond breaking. This, in turn, causes force imbalance to be
experienced by the neighboring particles. The high concen-
tration of particles in the structure continually responding to
this force imbalance is a reason for the long time scale of the
aging process. The repulsive force regulates the development
of the open cellular sponge-like microstructure.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: leong@mech.uwa.edu.au.
ORCID
Yee-Kwong Leong: 0000-0001-7864-5931
Mingyong Du: 0000-0001-7006-2125
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors thank Lyn Kirilak and Jeremy Shaw for technical
support and acknowledge the use of the facilities of the
Australian Microscopy and Microanalysis Research Facility at
the Centre for Microscopy, Characterization and Analysis, and
the University of Western Australia, a facility funded by the
University, State and Commonwealth Governments. We wish
to thank the reviewer for making this a better paper.
■
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J DOI: 10.1021/acs.langmuir.8b00213
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