Colloids and Surfaces A: Physicochemical and Engineering Aspects 611 (2021) 125824

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Effect and mechanism of cation species on the gel properties

of montmorillonite
Haowei Yan, Zepeng Zhang *
School of Materials Science and Technology, China University of Geosciences (Beijing), Beijing 100083, PR China

G R A P H I C A L A B S T R A C T

A R T I C L E I N F O A B S T R A C T

Keywords: Using montmorillonite (Mt) as the raw material, six kinds of metal cations with different valences (monovalent,
Montmorillonite divalent and trivalent) are used to modify montmorillonite through interlayer cation exchange and octahedral
Interlayer metal cation and tetrahedral central ion (Al3+ and Si4+) substitution to obtain the corresponding modified montmorillonite.
House of cards
XRD, ICP, NMR and other methods are used to study the effects of the metal cations on the structure, electrical
Gel properties
Isomorphic substitution
properties, morphology, dispersion and gel properties of montmorillonite. The XRD results show that the six
metal cations that have different valences can fully exchange with the interlayer cations, and the ICP results show
that the six cations undergo partial isomorphic substitution with central ions in the lattice, resulting in a change
in the negative charge for the faces of the montmorillonite sheets. The degree of influence of the cation valence
on the negative charge follows the order of trivalent > monovalent > divalent, and the contribution of metal
cations of the same valence to the negative charge is positively related to the atomic number. The change in
negative charge affects the zeta potential, and the influence law for the cations on the zeta potential is basically
the same as that for the negative charge. SEM and microscope results show that the degree of lamellar peeling is
negatively correlated with the valence of the cations, and the contribution of metal cations of the same valence to
the dispersion of montmorillonite is negatively correlated with the atomic number. The viscosity results follow
the order of Mt-Li > Mt-Na > Mt-Mg > Mt-Ca > Mt-Al > Mt-Fe. This result indicates that the zeta potential and
the degree of peeling affect the gel properties at the same time. Therefore, the electrical properties and interlayer
forces for the montmorillonite sheets are affected by the valence, electrostatic force and hydrated ion radius of
the metal cations, so that the gel properties of the montmorillonite are affected.

* Corresponding author.
E-mail addresses: yhwcugb2019@gmail.com (H. Yan), unite508@163.com (Z. Zhang).

https://doi.org/10.1016/j.colsurfa.2020.125824
Received 8 August 2020; Received in revised form 23 October 2020; Accepted 25 October 2020
Available online 2 November 2020
0927-7757/© 2020 Elsevier B.V. All rights reserved.
H. Yan and Z. Zhang
1. Introduction
Montmorillonite (Mt) is a layered hydroaluminosilicate mineral
containing a small amount of alkali metal and alkaline earth metal el­
ements [1]. Its unit cell structure is a typical 2:1 layered clay mineral
structure, which consists of two layers of silicon tetrahedra and a layer of
aluminum octahedra. There is water and some exchange cations be­
tween the crystal structure layers [2]. The montmorillonite particles are
fine, approximately 0.2 μm–2 μm [3] in size and flaky montmorillonite
crystals are visible under an electron microscope. Because montmoril­
lonite has a typical cation exchange capacity, it has excellent water
absorption and water retention capacity, rheology, thixotropic proper­
ties and water swelling characteristics. When it absorbs water, it can
expand by more than several times its original volume [4]. Water
penetration between the montmorillonite sheets lead to the montmo­
rillonite layer to swell, peel and form nanosheets, and the edges and
faces of the dispersed montmorillonite sheets form a house-of-cards
three-dimensional structure by electrostatic action to form a gel sys­
tem [5]. There are a wide variety of isomorphous homomorphic sub­
stitutions in the montmorillonite lattice, forming a negative charge
between the layers, and the edges are broken to form a positive charge.
The silicon in the tetrahedra of the montmorillonite structure is often
replaced by aluminum; the aluminum in the octahedra is often replaced
by magnesium, iron, etc., and the amount of substitution can be varied
[6].
The use of montmorillonite is very extensive; it has been applied to
various fields and is known as universal soil. For example, fillers for
paper, rubber and cosmetics, rheological additives for inks, oil-based
and water-based paint, antifungal agents for animal feeds, carriers for
petroleum decolorants and petroleum cracking catalysts, geological
drilling, oil, shale gas drilling mud additives, metallurgical adhesives
and medicines, etc [7,8]. A montmorillonite gel is a viscous colloid that
can form a pseudoplastic fluid in an aqueous solution prepared by deep
processing of montmorillonite. The unique layered silicate structure
makes it highly hydrophilic and it can be highly dispersed, reforming a
spatial network structure in an aqueous solution. Free water becomes
bound water, improving the viscosity of the gel, and it has excellent
properties such as thixotropy, rheology, suspension and adsorption [9].
For research into the performance of montmorillonite gel, pre­
decessors have done much work. For example, Sun Hongjuan et al. [10]
studied the effect of interlayer metal cations (monovalent and divalent
cations) on the structure and hydration expansion properties of mont­
morillonite. It was found that the interlayer metal cations have a small
radius and high charge, and the expansion capacity of montmorillonite
increases with increasing ion hydration energy. Xu J et al. [11] and Li
Hongliang et al. [12] also performed similar studies. Jia Mengzi et al.
[13] explored the effect of sodium modification of montmorillonite and
gelling conditions on gel performance. When the amount of sodium
carbonate was 8%, 4% calcium oxide was used as a gelling agent, and 10
% sodium carboxymethylcellulose was used as a thickening agent, a
high viscosity inorganic gel was obtained. Louise Bailey et al. [14]
studied the effect of adding different sizes of anionic and cationic
modified spherical silica particles on the rheology of a montmorillonite
suspension. The results showed that the rheology can be significantly
changed in a suspension system by adding a small amount of silica
particles, and this phenomenon is universal. Ko Yeon Choo et al. [15]
studied the effect of montmorillonite solid content and suspension pH on
the rheological properties and long-term stability of montmorillonite
suspensions. The effect of pH on the montmorillonite suspension was
significant, and, as the amount of HCl added to the fresh suspension was
increased, significant initial stress values were observed at the initial
shear rate values. However, when the suspension was stored with a large
amount of added acid for 72 h, the pH was increased, and the viscosity
was lowered. CUI Jiarui et al. [16] also performed similar research. F.
Gridi-Bennadji et al. [17] studied the effect of the prior firing of mont­
morillonite with three different interlayer cations (Na+, Ca2+ and Mg2+)
2
Colloids and Surfaces A: Physicochemical and Engineering Aspects 611 (2021) 125824
on its gel properties. The results showed that for calcination until 200 ◦ C,
the relevant suspensions exhibited an increasing yield stress due to a
gel-like behavior in relation to a card-house-like structure. Furthermore,
calcination above 300 ◦ C favored a decrease in the corresponding yield
stress. This behavior appeared to be related to the modification of the
surface properties of the clay platelets, more precisely, to the beginning
of clay dehydroxylation. J. M. Cases et al. [18–20] studied the mecha­
nism of adsorption and desorption of water vapor by montmorillonite
with different interlayer cations under different relative water vapor
pressure environments. The results showed that as the relative water
vapor pressure increases, the effective internal specific surface area of
montmorillonite increases. The heat of hydration of the exchangeable
cations and the surface pressure of the outer surface of the tactoids were
the driving forces for swelling within the montmorillonite crystals.
In the existing research on the gel properties of montmorillonite,
most studies focus on composite modification of montmorillonite or
improve the preparation process for the gel, and research on montmo­
rillonite interlayer cations mostly focuses on monovalent and divalent
cations. However, based on the above introduction, the current research
works still lack systematic research on the effects of different valence
metal cations on the lattice structure, layer structure, and layer charge of
montmorillonite, as well as the effects and interrelationships for the peel
ability, dispersion and gel properties.
In view of the above problems, this paper used cations of various
valences to modify montmorillonite through isomorphic substitution
and interlayer cation exchange to prepare six kinds of montmorillonite
with different interlayer cations and different central ions to study the
effects of metal cations on the substitution of ions in the center of the
crystal lattice, the interlayer structure, and the change in charge. The
effects of the valence state of the metal cations on the structure,
morphology, zeta potential, dispersion state and gel performance of
montmorillonite were investigated, and the influence and mechanism of
the valence state of metal cations on gel performance were discussed to
provide a basis for the research and application of improving the gel
performance of montmorillonite.
2. Experiment
2.1. Experimental reagents and raw materials
Montmorillonite (Mt) ore, originating from Fule Mining Develop­
ment Co., Ltd., Baotou, Inner Mongolia.; sodium carbonate, Beijing
Chemical Plant; lithium carbonate, Xilong Chemical Co., Ltd.; magne­
sium carbonate basic pentahydrate, Sinopharm Chemical Reagent Co.,
Ltd.; calcium chloride, Xilong Chemical Co., Ltd.; crystalline aluminum
chloride, Beijing Chemical plant; ferric chloride hexahydrate, Beijing
Yili Fine Chemicals Co., Ltd. The reagents were of analytical grade.
The XRD pattern for montmorillonite is shown in Fig. 1. The mont­
morillonite sample is calcium-based montmorillonite with a d001 value
of 15.0 Å. The content of montmorillonite is 98 %, and a content of
quartz and albite impurities is 1% each. The cation exchange capacity
(CEC) of montmorillonite is 96 mmol/100 g.
2.2. Preparation of different interlayer cation montmorillonite samples
A sample of montmorillonite ore after drying at 60 ◦ C for 24 h was
added to distilled water. One hundred grams of montmorillonite ore was
weighed for each sample, hydrated and dispersed in 2000 mL distilled
water for 8 h, stirred at 1000 rpm for 10 min followed by the removal of
precipitated impurities. The montmorillonite samples of different
interlayer metal cations were prepared by adding different metal cations
to replace Ca2+ by two times the montmorillonite CEC (in this case, the
amount of lithium carbonate is 7.09 g, sodium carbonate is 10.18 g,
magnesium carbonate basic pentahydrate is 9.34 g, calcium chloride is
10.66 g, crystalline aluminum chloride is 15.46 g, and ferric chloride
hexahydrate is 17.30 g.), stirred at 1000 rpm for 1 h, and then allowed to
H. Yan and Z. Zhang
Fig. 1. XRD pattern of the montmorillonite raw material sample and Mt, Ab,
Qtz standard card.
stand still for 24 h. Then, Mt-M was obtained, where M is Li+, Na+, Ca2+,
Mg2+, Al3+, and Fe3+.
2.3. Characterization
2.3.1. XRD
Each sample was characterized using a D8 Advance X-ray diffrac­
tometer manufactured by Bruker Scientific Instruments Hong Kong (Cu
target, step width of 0.02, voltage of 60 kV, X-ray wavelength of λ
=0.154 nm, scanning range of 3◦ - 70◦ ). All samples were dried in an
oven at 60 degrees Celsius for 24 h.
2.3.2. SEM
Each sample was characterized using a JSM-6700 F scanning elec­
tron microscope manufactured by JEOL. The voltage was 20 kV, and the
sample was sprayed with gold before the test.
2.3.3. ICP
Twenty-five milliliters of each sample in the viscosity test was taken
and centrifuged to obtain the supernatant. After each centrifugation, 25
mL of distilled water was added and centrifuged 4 times. Then, the su­
pernatant was adjusted to 100 mL, each sample was filtered through a
0.22 μm pore size polyether sulfone filter membrane, and the ICP test
sample was obtained. Each sample was characterized by an inductively
coupled plasma emission spectrometer ICAP 7600 from Thermo Fisher
Scientific.
2.3.4. Magic-angle spinning NMR
Samples were characterized using a Bruker AVANCE III HD 600 M
NMR Spectrometer manufactured by Bruker Technology Co., Ltd. Each
sample was sieved through 200 mesh. The angle between the axis of
rotation of the sample and the direction of the magnetic field is the
magic angle. Each sample was tested for the 27Al spectrum.
2.3.5. Zeta potential
Then, 0.01 g of each sample was weighed, 10 mL of distilled water
(5% solid content) added, and the sample ultrasonically shaken for 10
min to obtain a test sample. Each sample was tested using a Zetasizer
Nano ZS90 nanoparticle size and Zeta potentiometer manufactured by
Malvern Instruments, UK. The sample temperature was 25 ◦ C, and the
sample cell was a disposable folded capillary sample cell (DTS1070).
3
Colloids and Surfaces A: Physicochemical and Engineering Aspects 611 (2021) 125824
2.3.6. Viscosity
The montmorillonite colloid test samples of different interlayer
metal cations were prepared according to the GB/T 5005− 2010 Drilling
Fluid Material Specification [21].
Each sample was tested using an NDJ-8S digital rotational viscom­
eter manufactured by the Shanghai Jingtian Electronic Instrument Co.,
Ltd.
2.3.7. Microscope
Ten milliliters of each sample in the viscosity test were taken, and
then a drop was placed on each slide with a dropper. The coverslip was
covered to make a microscopic sample. Each sample was characterized
by using a polarizing microscope BX51-1 produced by Olympus Co.,
Ltd., Japan.
3. Results and discussion
3.1. Effect of substitution of different metal cations on the structure of
montmorillonite
The montmorillonite samples of different interlayer metal cations
were characterized by XRD, and the influence of the species of interlayer
metal cations on the structure was studied. The results are shown in
Table 1and Fig. 2.
It can be seen from Table 1 and Fig. 2 that the layer spacing of the
montmorillonite changes when the interlayer metal cation changes,
which shows that these six metal cations can fully exchange with the
cations between the montmorillonite layers. When the interlayer cal­
cium ions were replaced by Mg2+ of the same valence state, the layer
spacing did not change significantly, which remained at 15.0 Å; when
replaced by trivalent Al3+ and Fe3+, the layer spacing decreased slightly
to 14.4 Å and 14.1 Å, respectively; and when replaced by monovalent
Li+ and Na+, the layer spacing was greatly reduced to 12.5 Å and 12.6 Å,
respectively.
According to the literature [22], the hydrated ionic radii for the six
cations are in descending order rAl = 4.75 Å, rFe = 4.57 Å, rMg = 4.28 Å,
rCa = 4.12 Å, rLi = 3.82 Å, and rNa = 3.58 Å. According to the hydrated
ionic radius, the order of the montmorillonite layer spacing of different
interlayer cations should be montmorillonite of trivalent interlayer
cations > montmorillonite of divalent interlayer cations > montmoril­
lonite of monovalent interlayer cations, but the actual result is not the
same. The order is montmorillonite of divalent interlayer cations >
montmorillonite of trivalent interlayer cations > montmorillonite of
monovalent interlayer cations. This is because the electrostatic force
between the sheets compresses the layer spacing. As the valence of the
cation increases, the electrostatic force becomes larger [23,24]. The
hydrated ionic radii for cations of the same valence state are similar, but
the electrostatic forces for the same valence cations are different. When
the valence states for the interlayer cations are the same, the hydrated
ionic radii are similar in size, and ions with a large electrostatic force
result in a large compression between the montmorillonite layers,
thereby reducing the layer spacing. According to the theoretical calcu­
lations of Li Peiyu et al. [25], Li+ and Na+ have one layer of bound water
between the montmorillonite layers, and the other four ions have two
layers of bound water. Therefore, Mt-Li and Mt-Na have the smallest
layer spacing compared with the other four types of Mt. At the same
time, the layer spacing for the other four montmorillonites should be
equivalent, but due to the trivalent aluminum ions and iron ions having
a large electrostatic force, the Mt-Al and Mt-Fe sheets have a large de­
gree of compression, and the layer spacing is significantly smaller than
Table 1
d001 values for montmorillonite with different interlayer cations.
Sample Mt-Li Mt-Na Mt-Mg Mt-Ca Mt-Al Mt-Fe
d001 value/Å 12.5 12.6 15.0 15.1 14.4 14.1
H. Yan and Z. Zhang Colloids and Surfaces A: Physicochemical and Engineering Aspects 611 (2021) 125824

aluminum element, the substitution of the aluminum element cannot be

Fig. 2. XRD pattern of montmorillonite with different interlayer cations.
that of Mt-Mg and Mt-Ca. Therefore, the order of the layer spacing for
the six montmorillonites with different interlayer metal cations is
montmorillonite of divalent interlayer cations > montmorillonite of
trivalent interlayer cations > montmorillonite of monovalent interlayer
cations.
3.2. The result of the amount of silicon and aluminum in the
montmorillonite structure substituted by different metal cations
The aluminum and silicon content in six supernatant samples pre­
pared in 2.3.3 were determined by ICP. The content of aluminum and
silicon in the six suspensions was compared with the montmorillonite
ore (Mt-Raw) suspension to investigate the degree of substitution of
various metal cations with different valence states for Al3+ and Si4+ in
the montmorillonite structure.
ΔE =
CAl− M − CAl− Raw
× (nAl − nM ) × NA × 1L +
CSi− M − CSi−
MAl MSi
− nM ) × NA × 1L
discussed. Because the size of montmorillonite particles generally ranges
from 0.2 μm to 2 μm, after filtering through a polyethersulfone filter
membrane with a pore size of 0.22 μm, it can be considered that most of
the montmorillonite particles are removed by filtration. Therefore, it can
be considered that the influence of silicon and aluminum in the mont­
morillonite sheets on ICP is negligible.
According to the principle of isomorphic substitution, the more
similar the ionic radius is, the more likely it is to undergo isomorphic
substitution. Since the low valence cations replace the montmorillonite
tetrahedral and octahedral high valence silicon and aluminum ions, the
face of the montmorillonite sheet has a larger negative charge. Ac­
cording to the ICP results for the substitution of silicon and aluminum
and the difference in valence between silicon and aluminum ions and
substituted ions (See ΔE in Table 2), the negative charge contributed by
the isomorphous homomorphic substitution of different metal cations
follows the order of Fe = 3.15*1020 > Na = 2.82*1020 > Ca = 2.53*1020
> Al = 2.48*1020 > Li = 2.31*1020 > Mg = 1.15*1020. From these re­
sults, the contribution of metal cations of the same valence to the
negative charge is positively related to the atomic number; according to
the relative number of electron layers of cations of the same valence
state, the cations are divided into two groups: Na, Ca, Fe and Li, Mg, Al,
both of which have a resulting charge difference that follows the order of
trivalent cation > monovalent cation > divalent cation.
3.3 Effect of the substitution of different metal cations on the
chemical environment of silicon and aluminum in the montmorillonite
structure
The ore and three kinds of montmorillonite with interlayer metal
cations of different valences were selected for the solid-state 27Al magic-
angle spinning NMR test.
According to the literature [26], the chemical shift at the 3 ppm
position shown in the graph in Fig. 3 is due to the chemical shift of the
hexacoordinate aluminum, and the chemical shift at approximately 70
ppm is due to the chemical shift of the tetracoordinate aluminum, which
should be due to a small amount of aluminum replacing silicon in the
silicon tetrahedra. It can be seen from Fig. 3 that the chemical shift at the
3 ppm position of the Mt-Fe is most shifted to the high field compared
with the Mt-Raw, which is 0.87 ppm, while the chemical shifts for Mt-Li
and Mt-Mg at the same position are shifted by -0.15 ppm and 0.09 ppm,
Raw
× (nSi respectively. This may be because the radii for the iron ions and
aluminum ions are similar, and they have the same valence, so the

ΔE represents the amount of negative charge increase, CAl represents

the concentration of Al, CSi represents the concentration of Si, MAl
represents the relative atomic mass of Al, Msi represents the relative
atomic mass of Si, M represents the type of montmorillonite, n repre­
sents the charge number of the ion, and NA represents the Avogadro
constant.
It can be seen from Table 2that the content of silicon in the super­
natant of montmorillonite obviously increases, and that the content of
aluminum is increased to different degrees except for the montmoril­
lonite of the divalent interlayer cation, which indicates that the six
cations have partially replaced silicon and aluminum in the montmo­
rillonite crystal structure, and that the degree of substitution is different.
The content of aluminum in the supernatant of the montmorillonite of
the divalent interlayer cation is similar to that of Mt-Raw. Since the
supernatant of the aluminum-based montmorillonite contains the added

Table 2
Aluminum and silicon content in seven supernatants of montmorillonite.
Mt Mt- Mt- Mt- Mt- Mt- Mt-Al Mt-
Concentration Raw Li Na Mg Ca Fe

Al/ppm 0.69 2.16 2.87 0.38 0.38 387.96 14.20

Si/ppm 1.89 4.46 4.75 4.70 7.93 13.44 16.56
Fig. 3. Solid-state 27Al magic-angle spinning NMR spectra for montmorillonite
ΔE/(*1020) 0 2.31 2.82 1.15 2.53 2.48 3.15
ore and montmorillonite with three different valence interlayer metal cations.

4
H. Yan and Z. Zhang
isomorphic substitution of iron ions by aluminum ions is more likely to
occur, and the aluminum in the octahedra is more likely to be replaced
by iron. Because iron ions have higher electronegativity and field
shielding effects, the chemical shift of hexacoordinate aluminum shifts
to a high field. The chemical shift displacement of the hexacoordinate
aluminum of Mt-Al and Mt-Mg is not obvious. Compared to the Mt-Raw,
the chemical shift of the hexacoordinate aluminum of Mt-Li is shifted by
0.15 ppm to the high field, while the chemical shift of the hex­
acoordinate aluminum of Mt-Mg is shifted to the low field by 0.09 ppm.
This is consistent with the amount of three cation-substituted aluminum
in the ICP results. At the same time, it can be seen that as the valence
state of the substituted cation increases, the intensity of the chemical
shift of tetracoordinate aluminum increases, and the diffraction in­
tensity of the (001) peak for the sample decreases, which shows that the
regularity of montmorillonite in the (001) direction deteriorates, which
is consistent with the literature results [27].
Therefore, in the cations of the three valence states, as the valence
state of the cation increases, the degree of substitution of the aluminum
in the octahedra by the isomorphous homomorphic substitution is
greater, and the greater the intensity of the chemical shift of the tetra­
coordinate aluminum.
3.3. Effect of substitution of different metal cations on the zeta potential
of montmorillonite
A zeta potential test was carried out for all the samples prepared in
1.2. The effect of interlayer cation species on the surface electrical
properties of montmorillonite samples is shown in Table 3.
As seen from Table 3, the interlayer metal cations have a significant
influence on the zeta potential of montmorillonite. Among the six cat­
ions, the absolute values of the zeta potentials for Mt-Na, Mt-Li, Mt-Al
and Mt-Fe are significantly higher than that for Mt-Raw; the absolute
value of the zeta potential for Mt-Mg and Mt-Ca is equivalent to that for
Mt-Raw, and both values are small.
The results are consistent with the ICP results, i.e., the absolute value
of the zeta potential of the iron-based montmorillonite is larger than that
of the monovalent interlayer cation and larger than that of the divalent
interlayer cation. Since the amount of Si4+ in the tetrahedra substituted
by Al3+ in Mt-Al is less than that of Fe3+, the absolute value of the zeta
potential of Mt-Al is much smaller than that of Mt-Fe. That is, the species
of metal cation has a significant influence on the surface potential of
montmorillonite, and, depending on the cation, the effect is different. In
general, the influence degree of the valence state of cations on the zeta
potential of montmorillonite follows the order of trivalent cation >
monovalent cation > divalent cation. The matched zeta potential value
is favorable for forming a gel system. The larger the absolute value of the
zeta potential, the better the dispersion of montmorillonite particles.
3.4. Effect of substitution of different metal cations on the morphology of
montmorillonite
SEM analysis of montmorillonite with different interlayer metal
cations was carried out to study the effects of different interlayer metal
cations on the morphology of montmorillonite. The results are shown in
Fig. 4.
As shown in Fig. 4, the degree of peeling of the montmorillonite
particles in different montmorillonite samples is different. The accu­
mulation of the Mt-Raw sheets is relatively tight. The montmorillonite
Table 3
Zeta potential value of montmorillonite with different interlayer cations.
Mt Mt- Mt-Li Mt- Mt- Mt- Mt-Al Mt-Fe
Raw Na Mg Ca
Zeta potential − 8.3 − 25.9 − 26.6 − 6.6 − 6.5 − 12.2 − 27.3
value/(mV)
5
Colloids and Surfaces A: Physicochemical and Engineering Aspects 611 (2021) 125824
sheets in the figures for Mt-Li and Mt-Na (see Fig. 4) are loosely packed,
and more montmorillonite sheets are peeled off. The montmorillonite
sheets in the other four pictures of Mt-Mg, Mt-Ca, Mt-Al and Mt-Fe are
more closely packed.
From the analysis and discussion of the XRD results, it can be seen
that the higher the interlayer cation valence of montmorillonite, the
stronger the interaction force with the montmorillonite sheet. Therefore,
the degree of peeling of montmorillonite sheets is negatively correlated
with the valence of the interlayer cations, which is consistent with the
SEM results.
3.5. Effect of substitution of different metal cations on the dispersibility of
montmorillonite suspension
All samples prepared in this paper were microscopically observed to
study the size and dispersion state of montmorillonite particles in water.
The result is shown in Fig. 5.
Fig. 5 shows that the interlayer metal cations also significantly affect
the dispersion properties of montmorillonite in water. The montmoril­
lonite in the Mt-Li and Mt-Na suspensions has a small particle size and
good dispersion; the particle size of montmorillonite in the Mt-Mg and
Mt-Ca suspensions is slightly larger than that of Mt-Li and Mt-Na, and
there is obvious agglomeration between the particles, and the dispersion
is poor. The montmorillonite in the suspensions of Mt-Al and Mt-Fe has
the largest particle size, which indicates that they have a low degree of
peeling, but the degree of aggregation between particles is lower than
that for Mt-Mg and Mt-Ca. Obviously, the dispersibility of montmoril­
lonite particles in water is the result of the comprehensive influence of
the degree of sheet peeling and the electrical properties of the particle
surface (zeta potential). The contribution of metal cations to the dis­
persibility of montmorillonite is negatively correlated with its valence;
the contribution of metal cations of the same valence to the dispersibility
of montmorillonite is negatively correlated with the atomic number.
This result is consistent with the zeta potential and SEM results. The
monovalent cation-substituted montmorillonite has the smallest elec­
trostatic force between the sheets, and the sheets are easily peeled off,
resulting in montmorillonite nanosheets in the suspension. In addition,
it has a larger absolute value for the zeta potential, so it has good dis­
persibility. The electrostatic force of the divalent cation between the
sheets is higher than that of the monovalent interlayer cation, which is
difficult to peel off, so the degree of peeling is lower than that of the
monovalent cation-substituted montmorillonite. In the meantime, the
zeta potential of the divalent cation-substituted montmorillonite has the
smallest absolute value, so the dispersion of montmorillonite particles in
the suspension is the worst. The trivalent cation-substituted montmo­
rillonite has the largest electrostatic force between the sheets, which
makes it more difficult to peel off. The particles in the suspension are the
largest, but because of the high absolute value of the zeta potential, the
dispersibility is better than that for the montmorillonite of the divalent
interlayer cation.
3.6. Effect of substitution of different metal cations on the viscosity of
montmorillonite
The viscosity of all the samples prepared in 1.2 was determined, and
the influence of the gel performance of the samples was studied. The
results are shown in Table 4.
As given in Table 4, the species of metal cation has a significant effect
on the viscosity of the montmorillonite suspension. The viscosity of the
montmorillonite follows the order of Mt-Li > Mt-Na > Mt-Mg > Mt-Ca >
Mt-Al > Mt-Fe. The results show that the viscosity of montmorillonite is
negatively correlated with the valence of the cations and their hydrated
ion radius, and the viscosity of the montmorillonite substituted with
cations of the same valence is negatively correlated with the atomic
number of cations and their hydrated ion radius, while an absolute value
of the zeta potential that is too large or too small will not help to improve
H. Yan and Z. Zhang Colloids and Surfaces A: Physicochemical and Engineering Aspects 611 (2021) 125824

Fig. 4. SEM images of Mt-Raw, Mt-Li, Mt-Na, Mt-Mg, Mt-Ca, Mt-Al and Mt-Fe.

the viscosity. formation of the gel structure of the montmorillonite nanosheet. The
Because the montmorillonite substituted by the interlayer metal viscosity test results are consistent with the above analysis results.
cation with a small electrostatic force is easily peeled off, it provides
conditions for the formation of the gel structure. At the same time, the
metal cations affect the zeta potential value through isomorphic sub­
stitution, while the matched zeta potential value facilitates the

6
H. Yan and Z. Zhang Colloids and Surfaces A: Physicochemical and Engineering Aspects 611 (2021) 125824

Fig. 5. Microscopic images of montmorillonite with different interlayer metal cations.

better the gel properties of the montmorillonite. From the structural

Table 4
aspect of montmorillonite, there are various factors that affect the de­
Viscosity of montmorillonite with different interlayer cations.
gree of peeling and dispersion of montmorillonite sheets in water.
Mt Mt- Mt-Li Mt- Mt- Mt- Mt- Mt- As shown in Figs. 6 and 7, when different metal cations replace
Raw Na Mg Ca Al Fe
interlayer cations of montmorillonite, aluminum in octahedra and sili­
Viscosity/ 61.7 222.4 79.2 1.18 1.16 1.12 1.10 con in tetrahedra, then the structure, layer spacing, zeta potential and
(mPa⋅s)
morphology of montmorillonite is changed.
The monovalent metal cation-substituted montmorillonite has the
3.7. Effect and mechanism of interlayer cation species on the gel smallest hydrated ionic radius of the interlayer cation and the smallest
properties of montmorillonite layer spacing, but the montmorillonite particles are easily peeled off in
water because the electrostatic force of the monovalent metal cation is
From the process of montmorillonite gel formation, it can be the smallest; in the structure of the monovalent metal cation-substituted
concluded that there are two main factors affecting the gel performance montmorillonite, the occurrence of isomorphous substitution in the
of montmorillonite: the degree of peeling and the degree of dispersion of aluminum octahedra is slightly more frequent than that of the divalent
the montmorillonite sheets in water. The more easily the montmoril­ metal cation, and the occurrence of isomorphous substitutions in silicon
lonite sheet is peeled off in water, and with proper dispersibility, the tetrahedra is least frequent, so montmorillonite particles have a large

7
H. Yan and Z. Zhang
Fig. 6. Schematic diagram of interlayer cation substitution and isomorphous homomorphic substitution for different valence cations in montmorillonite.
absolute value of zeta potential in water, which has good dispersibility.
With a high degree of peeling and good dispersibility, the montmoril­
lonite substituted by the monovalent metal cation has good gel
performance.
The montmorillonite substituted by divalent metal cations has a
large hydrated ionic radius for the interlayer cation and the largest layer
spacing. Due to the large electrostatic force of the divalent metal
interlayer cation, the montmorillonite sheet can only be partially peeled
off; in the structure of the divalent metal cation substituted montmo­
rillonite, the least isomorphous substitutions occur in the aluminum
octahedra, and the occurrence of the isomorphic substitution in the
silicon tetrahedra is slightly more frequent, so the zeta potential of the
divalent metal cation substituted montmorillonite has the smallest ab­
solute value, which has the worst dispersibility. The divalent metal
cation-substituted montmorillonite that only showed partial peeling
with the worst dispersibility has poor gel performance.
The trivalent metal cation-substituted montmorillonite has a me­
dium layer spacing and the largest hydrated ionic radius for the inter­
layer cation. Montmorillonite particles in water are hardly peeled off,
and in the structure of the trivalent metal cation-substituted montmo­
rillonite, the isomorphic substitutions in the aluminum octahedra and
silicon tetrahedra occur most frequently. The trivalent cation-
substituted montmorillonite has a large zeta potential, so the dis­
persibility is better than that of the divalent cation-substituted mont­
morillonite. Therefore, the montmorillonite substituted by the trivalent
metal cation has the worst degree of peeling and has a certain dis­
persibility, and the gel performance is the worst.
Therefore, from the above results and analysis, it is known that metal
cations affect the gel performance of montmorillonite in different forms.
The electrostatic force of cations affects the degree of peeling, and the
negative charge produced by isomorphic substitution affects the zeta
potential, which, thus, affects the dispersibility. Cations with less
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Colloids and Surfaces A: Physicochemical and Engineering Aspects 611 (2021) 125824
electrostatic force and more frequent isomorphous homomorphic sub­
stitution in the aluminum octahedra and silicon tetrahedra of mont­
morillonite can ensure better gel performance.
4. Conclusion
Using montmorillonite ore as the raw material, montmorillonite
substituted by six different metal cations and their suspensions were
prepared. It was found that metal cations can affect the structure,
morphology, zeta potential, dispersion state and gel performance of
montmorillonite. The structure of montmorillonite is affected by cations
through changes in interlayer cations and isomorphic substitution in the
montmorillonite structure. The influence of the cation valence on the
peeling degree of montmorillonite follows the order of monovalent >
divalent > trivalent; the lower the electrostatic force of the cations be­
tween layers, the easier the montmorillonite is to peel off. The degree of
influence of the cation valence on the negative charge follows the order
of trivalent > monovalent > divalent, and the contribution of metal
cations of the same valence to the negative charge is positively related to
the atomic number. The larger the negative charge produced by
isomorphic substitution, the better the dispersion of montmorillonite.
The degree of peeling and dispersibility of montmorillonite affects the
gel properties of montmorillonite.
Therefore, among the cations for the three valence states, the
monovalent cation has the smallest electrostatic force as the interlayer
cation, and the negative charge produced is larger, so it has the best gel
performance; the electrostatic force for divalent cations is relatively
large, and the negative charge produced by these cations is the smallest,
so the gel performance is poor; although the negative charge produced
by trivalent cations is also large, its electrostatic force is also the largest,
so the gel performance is the worst.
H. Yan and Z. Zhang
Fig. 7. Schematic diagram of the hydration process of montmorillonite with different valence interlayer cations.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was financially supported by Shale Gas-Bearing Key
Parameter Test and Intelligent Evaluation System (No. 41927801) and
National Key Research & Development Program of China (No.
2017YFB0310901).
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