Applied Clay Science 169 (2019) 48–66

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Applied Clay Science

journal homepage: www.elsevier.com/locate/clay

Review article

Exfoliation of montmorillonite and related properties of clay/polymer T

nanocomposites
⁎
Ting Ting Zhua, Chun Hui Zhoua,b,c,d, , Freeman Bwalya Kabwea, Qi Qi Wua, Chun Sheng Lid,
Jun Rui Zhanga
a
Research Group for Advanced Materials & Sustainable Catalysis (AMSC), State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of
Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, China
b
Qing Yang Institute for Industrial Minerals (QYIM), Youhua Township, Qingyang County, 242804, Anhui, China
c
Centre for Future Materials, University of Southern Queensland, Toowoomba, Queensland 4350, Australia
d
Key Laboratory of Clay Minerals of Ministry of Land and Resources of the People's Republic of China, Engineering Research Center of Non-metallic Minerals of Zhejiang
Province, Zhejiang Institute of Geology and Mineral Resource, Hangzhou 310007, China

A R T I C LE I N FO A B S T R A C T

Keywords: Exfoliating montmorillonite (Mt) to nanolayers is a crucial step during producing clay/polymer nanocomposites
Montmorillonite (CPN). Only well-exfoliated and well-dispersed Mt. nanolayers in the polymer matrix can significantly improve
Exfoliation the properties of the nanocomposites. This review examines the latest scientific advances in the exfoliation
Intercalation methods of Mt., the insights into the exfoliation mechanisms, and the peculiar functionalities of the resultant
Nanolayers
CPN. The direct exfoliation of Mt. dispersed in water or organic solvents is often intensified by ultrasonication.
Polymers
Grinding of Mt. in the form of solid in a high-energy ball mill can directly exfoliate Mt. to some extent.
Nanocomposites
Exfoliating Mt. for producing CPN is mainly achieved through so-called in situ exfoliation, solution exfoliation
and melt exfoliation. The Mt./polymer nanocomposites exhibit typically improved barrier properties, mechan-
ical strength, thermal stability, and fire retardancy. The literature survey suggests that future work should place
emphases on developing green and effective exfoliation methods, and deepening understanding of exfoliation
mechanisms and the interfacial interactions between the inorganic Mt. nanolayers and organic monomers/
polymers. Future research is suggested to assembling exfoliated Mt. nanolayers with functional polymeric mo-
lecules or other nano-scale building blocks to produce functional hierarchical nanomaterials with practical
applications.

1. Introduction holding the layers together can be overcome by appropriate physical

Montmorillonite (Mt) is a phyllosilicate mineral (Alateyah et al.,
2013; Bergaya et al., 2013) and is characterized by nanolayered
structure. Its crystal structure (ca 1 nm in thickness) consists of stacked
layers and each layer is typically composed of two O-Si-O tetrahedral
sheets sandwiching one O-Al(Mg)-O octahedral sheet (ca 100 × 100
nm, in width and length). Neighboring layers are held together pri-
marily by van der Waals force and electrostatic force to form the pri-
mary particles of Mt. The particles then aggregate to form micrometer-
scale to millimeter-scale particles and (Diañez et al., 2015) (Fig. 1).
The layer structure of Mt. allows many strategies to modify Mt. and
to construct a variety of hybrids and composites (Zhou and Keeling,
2013). In particular, the van der Waals force and electrostatic force
and chemical methods. Namely, Mt aggregates can disassociate in
aqueous dispersion to Mt particles and then the Mt particles can be
exfoliated to form individual Mt. nanolayers. Since such Mt nanolayers
have a high aspect ratio and large surface area, it is highly expected that
the addition and dispersion of the Mt nanolayers into the polymer
matrix yields clay/polymer nanocomposites (CPN) with remarkably
enhanced mechanical (Devi et al., 2015; Shameli et al., 2015; Asgari
et al., 2017) and barrier properties (Yang et al., 2017; Ammar et al.,
2017;Bahreini et al., 2017), thermal stability (Nistor and Vasile, 2013;
Osman et al., 2015; Ejder-Korucu et al., 2016), and flame retardancy
(Chiou et al., 2014; Wu et al., 2014; Niroumand et al., 2016). As such,
exfoliating Mt. to nanolayers is crucial to successful production of CPN.
However, exfoliating Mt to nanolayers has so far remain a challenge.

⁎
Corresponding author at: Research Group for Advanced Materials & Sustainable Catalysis (AMSC), State Key Laboratory Breeding Base of Green Chemistry-
Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, China.
E-mail address: clay@zjut.edu.cn (C.H. Zhou).

https://doi.org/10.1016/j.clay.2018.12.006
Received 24 January 2018; Received in revised form 8 December 2018; Accepted 9 December 2018
0169-1317/ © 2018 Elsevier B.V. All rights reserved.
T.T. Zhu et al.
Many studies have clearly indicated that for producing Mt./polymer
nanocomposites, only well-exfoliated and well-dispersed Mt nanolayers
in the polymer matrix can significantly improve the aforementioned
properties of the Mt/polymer nanocomposites (Jia and Song, 2014). It
has been revealed that such factors as Mt sources, organic modifiers,
polymers, and exfoliation methods and conditions have an effect on the
exfoliation of Mt. In addition, previous studies have indicated that the
improvement of the properties of the Mt/ polymer nanocomposites is
closely related to the interactions between the polymer matrix and Mt
nanolayers. Accordingly, it depends heavily on the extent of exfoliation
of Mt. and the content and distribution of the Mt nanolayers in CPN.
The CPN with well-exfoliated Mt nanolayers in polymer matrix have
proved to possess significant enhanced properties in mechanical and
barrier properties, thermal stability and flame retardancy (Beyer,
2002).
This review aims to summarize the technological progress in ex-
foliating Mt to nanolayers for production of CPN and the related sci-
entific understanding of the exfoliation of Mt, followed by the survey
and discussion on the major functionalities of exfoliated Mt in CPN.
Firstly, exfoliating Mt in a liquid and even directly in solid form is
briefly discussed. Next, in situ exfoliation, solution exfoliation and melt
exfoliation are examined. Then, functions of exfoliated Mt nanolayers
in the CPN, which concern barrier, mechanical, thermal, and fire re-
tardancy properties, are overviewed. Finally, the existing problems and
future work are remarked.
2. Simple routes to exfoliation of montmorillonite
The inorganic cations in the interlayer space are usually hydrated
and are only loosely held by the negatively charged Mt layers. In
aqueous environments, water molecules are attracted into the inter-
layer space of Mt by the exchangeable cations, thereby expanding the
interlayer spacing. In a dilute aqueous dispersion, Mt aggregates can
spontaneously disassociate into particles and the particles can be partly
or even completely exfoliated to form Mt nanolayers. Because the Mt
nanolayers are charged, they have functions of a polyelectrolyte. Such
disassociation and exfoliation are mainly dependent upon the con-
centration of Mt suspension, and in particular upon the layer and the
cations in the interlayer space.
The interlayer cations direct the size of particles in an aqueous
system. Usually, the higher the charge of the cations, the larger are the
particles. When Na+-Mt powder is added into water, Na+ ions tend to
hydrated to form hydrated Na+ ions. As a result, a large number of
water molecules enter the interlayer space, causing the crystalline
structure of Mt to expand in the direction perpendicular to the layers.
Moreover, an electric double layer can be formed on the surface of
charged Mt layers. As such, Na+-Mt particles delaminate to be
49
Applied Clay Science 169 (2019) 48–66
Fig. 1. Schematic representation of the Mt structure.
(A) Side view: tetrahedrons units of Mt assembled
through weak van der Waals and electrostatic forces
to form the primary particles (B) Top view of Mt,
hexagonal structure of oxygen and hydroxyl ligands
of the octahedral layer.
Adapted and reprinted from Swearingen et al., 2003,
Copyright 2003, with permission from Elsevier.
nanolayers. For Ca2+-Mt, in contrast, the larger particles predominate
in an aqueous system. Moreover, the swelling stops when the distance
between the layers reaches about 1 nm. The calcium ions remain in the
interlayer space and on the hydroxyl plane between neighboring layers.
Electric double layers are merely formed on the outer surface of the Mt
particles. As a result, Ca2+-Mt appears to be difficult to delaminate in
water.
For achieving Mt nanolayers in a non-polar organic solvent, Mt is
needed to be organically modified to form organo-Mt (OMt) before-
hand. Such organic modification changes the hydrophilic surface of Mt
into hydrophobic one. This also enlarges the interlayer space because of
the introduction of organic cations into the interlayer space. The OMt
can spontaneously swell and delaminate more or less in an organic
medium. The OMt particles can be exfoliated into OMt nanolayers by
proper treatments (Nicolosi et al., 2013; Huang et al., 2016). The type
of organic species, the extent of organic modification, the polarity and
chemical nature of the solvent all influence the exfoliation level of OMt
For example, cetyltrimethylammonium (CTA+) - modified Mt exfoliates
poorly in alcohols with short carbon chains whereas it disperses and
exfoliates better in alcohols with longer carbon chains (Venugopal
et al., 2006). The amount of exfoliated nanolayers and the stability of
the resultant colloid increase with the increase of the carbon chain
length of the alcohol. Recently, Huang et al. (2016) directly exfoliated
Na+-Mt in isopropanol (IPA). Therein poly(oxyethylene-oxypropylene)-
amines (POA) were added into the IPA and used as an intercalating
agent. The POA contains hydrophilic poly(oxyethylene)-rich (POE-
amines) and hydrophobic poly(oxypropylene)-rich (POP-amines)
mono-amines or diamines. When POA-amine entered the interlayer
space of Mt, the hydrophilic POE backbones-amines got associated with
the Mt surface and the hydrophobic POP segments of POA-amines ag-
gregated to form micelle-like regime. The micelle-like regime expanded
the silicate platelets, causing exfoliation (Fig. 2A).
Exfoliation of Mt is usually conducted and achieved in a liquid
media with the aid of mechanical stirring and ultrasonication. In par-
ticular, ultrasonication is often used to enhance the exfoliation of Mt in
solution. Ultrasonication is a form of vibration that provides energy.
Such waves generate energetic cavitation and bubbles that rapidly
collapse into high-energy jets, breaking up the stacking of Mt layers and
thus producing exfoliated Mt nanolayers (Santos et al., 2011; Nicolosi
et al., 2013; Chaudhary and Liu, 2013) (Fig. 2B). The extent of dis-
persion and exfoliation of Mt in liquid are remarkably influenced by
such ultrasonic energy. However, the exfoliated nanolayers will usually
be restacked after ultrasonication (Martinez-Colunga et al., 2018).
To achieve exfoliation directly without using liquid media is desired
but it is a big challenge. Some recent studies have showed that grinding
of Mt powder in high-energy ball milling is conducive to exfoliating Mt
(Galimberti et al., 2014; Chatterjee et al., 2017). During high-energy
T.T. Zhu et al. Applied Clay Science 169 (2019) 48–66

Fig. 2. Various routes to exfoliation of Mt: (A): Conceptual illustrations of organic intercalation and exfoliation of Mt by different procedures of pre-swelled or
unswelled in water and intercalation in water or IPA.
Adapted and reprinted by permission from Rights Link: Springer Nature: Journal of Polymer Research (Huang et al., 2016), Copyright 2016. (B) Scheme of exfoliation
Mt under shear field. Adapted and reprinted from Meng et al., 2007, Copyright 2007, with permission from Elsevier. (C): Schematic representation of the mechanisms
such as ultrasonic treatment and High energy ball milling for the exfoliation of Mt, it is to apply enough strong external force to disrupt attractive force between Mt
layers.

50
T.T. Zhu et al.
ball milling, impact force and friction force of the grinding ball can
destabilize the structure of Mt, promoting exfoliation of Mt (Ramadan
et al., 2010). With the ball milling, the ordered structure of Mt turns
disordered and some layers are finally peeled off Mt particles (Fig. 2C).
The exfoliation of OMt can also be conducted through high energy ball
milling (Ramadan et al., 2010; Chatterjee et al., 2017). In the process of
dry ball milling, the organic modifier of OMt appears to play a role in
stabilizing the structure of the Mt, thus making the exfoliation of OMt
more difficult. More recently, Chatterjee et al. (2017) demonstrated
that high-energy ball milling acted as an easy way to achieve the ex-
foliation of OMt. Under such a circumstance, ball milling at 400 rpm for
2 h was found optimal for the maximum exfoliation of OMt. Never-
theless, when milling time lasted longer, the final product was more
highly contaminated. To establish a milling method to exfoliate Mt,
new intensified methods need further developed.
3. Exfoliating Mt for producing clay/polymer nanocomposites
3.1. In situ exfoliation
In the in situ exfoliation of Mt, Mt is added in a liquid monomer or a
monomer solution so that Mt swells and the monomer enters the in-
terlayer space of Mts. After that, a polymerization reaction can occur in
situ in the interlayer space of Mt (Roghani-Mamaqani et al., 2011;
Gunning et al., 2014). The polymerization reaction can be initiated by
heat or radiation, in the presence of an initiator and a catalyst. The
initiator or catalyst can be in advance introduced into the interlayer
space of Mt through cationic exchange (Lepoittevin et al., 2002)
(Fig. 3). In situ polymerization can directly produce bulky and long-
chain polymers in the interlayer space of Mt In addition, exothermic
polymerization releases heat; the heat then could weaken the van der
Waals force and electrostatic force between layers of Mt As a result, Mt
layers can be better exfoliated and dispersed in the polymer matrix
(Pokharel et al., 2015; Atta et al., 2016; Behniafar et al., 2016).Thus far
Mt has been in situ exfoliated to form Mt/polymer nanocomposites
starting with such monomer as methyl methacrylate (MMA), bisphenol
A diglycidyl ether (DGEBA), phthalic anhydride (PA), propylene glycol
(PG), maleic acid (MA), an allyl condensed polynuclear aromatic
(ACOPNA), bismaleimide (BMI), 1,2,4-benzenetricarboxylic acid an-
hydride (TMA), 4,4-methylene diphenyl diisocyanate (MDI), acryloni-
trile, aniline, urea, paraformaldehyde (Pf), pyrrole, acrylamide (AAm),
bisacrylamide (BAAm), and β-butyrolactone (Table 1). The resultant
polymers are poly(methyl methacrylate) (PMMA), polyester, poly(4,4-
diaminodiphenyl ether phenyl dichlorophosphate) (PDEPD), polyamide
6 (PA6), poly(m-xylene adipamide) (MXD6), poly(vinylacetate-co-me-
thylmethacrylate), epoxyresin, poly(3-hydroxybutyrate-co-4-hydro-
xybutyrate), bisphenol-A epoxy resin, urea–formaldehyde polymer,
polypyrrole, poly(allyl condensed polynuclear aromatic-bismaleimide),
polyamide-imide, polyacrylonitrile (PAN), polyaniline(PANI), poly-
butadiene(PU), and hyperbranched poly(ester amide) (HBPEA).
In the aspect of Mt itself, critical factors affecting Mt exfoliation
include the type of Mt, the cation exchange capacity and the interlayer
cations. Moreover, the type of monomers and the conditions of in situ
Fig. 3. Illustration of in situ exfoliation Mt in polymer.
Adapted and reprinted from Zhang et al., 2015, Copyright 2015, with permission from Elsevier.
51
Applied Clay Science 169 (2019) 48–66
polymerization also significantly influence Mt exfoliation. Besides, in in
situ exfoliation, it is necessary for Mt to swell in a kind of monomer in
liquid form or in aqueous or organic solution in which a kind of
monomer is dissolved. In this way, the monomer can be introduced into
the interlayer space first. However, some monomers such as MMA,
DGEBA, PA, PG, MA are lipophilic. In such cases, judicious choice of
functional groups for pre-modifying Mt is also essential (Atta et al.,
2016; Behniafar et al., 2016; Wang et al., 2016). The chain length and
functional group of organic modifiers remarkably influences the ex-
foliation of Mt in a polymer. The organic modifier intercalates into the
interlayer space of Mt and expands it, allowing the easier exfoliation of
many more Mt platelets (Zhuang et al., 2017). Many studies have
clearly indicated that the exfoliation of Mt is more likely to take place
when organic modifiers with a longer carbon chain (e.g. dioctadecyl
dimethyl ammonium chloride; DODAC) are intercalated into the in-
terlayer space of Mt (Wang et al., 2016). By contrast, an organic
modifier with a short chain (e.g. methacrylatoethyltrimethyl ammo-
nium chloride; MTC) arranges incompactly in the interlayer space of Mt
and expands the interlayer space less effectively. An appropriate choice
of functional group of an organic modifier is also crucial to both in situ
polymerization and exfoliation. Some organic modifiers can serve as a
compatibilizer between the hydrophilic Mt and the hydrophobic
polymer (Briesenick and Bremser, 2015). Moreover, a judiciously-
chosen organic modifier with functional groups can even react with the
monomer or can initiate polymerization of monomers (Briesenick and
Bremser, 2015) (Fig. 4).
Apart from the chain length and the functional group of organic
modifiers, the inherent cation exchange capacity (CEC) of Mt affects the
exfoliation efficiency of Mt in polymer (Fu and Heinz, 2010; Beltrán
et al., 2014; Hojiyev et al., 2017). Mt with a high CEC is favorable for
more organic molecules to enter into the interlayer space of Mt and to
create large interlayer spacing. In addition, the OMt has higher surface
coverage of organic species and a high packing density of organic
modifiers. Also, such excess modifiers can restrict the diffusion of
monomers into the Mt interlayer space. Under such a circumstance, in
situ polymerization and exfoliation may deteriorate (Hojiyev et al.,
2017). Earlier, it was reported that the OMt with low surface coverage
of organic species yielded better exfoliation (Fornes et al., 2002). But
opposite phenomena have also been observed. For example, a study
showed that ocdadecyltriphenylphosphonium-modified Mt at 150%
CEC showed better exfoliation in PET matrix than the modified Mt at
80% CEC (Patro et al., 2009). Similarly, Beltrán et al. (2014) prepared a
high degree of exfoliation OMt in ethylene vinyl acetate copolymer
(EVA) when 80% of CEC exchanged with ethyl hexadecyl dimethyl
ammonium.
The frequently-used organic modifiers to be introduced into the
interlayer space of Mt are ammonium (Mallakpoura and Shahangia,
2012; Zahra et al., 2014; Huang et al., 2015) or phosphonium (Ezquerro
et al., 2015; Mousa et al., 2016). These organic modifiers can effectively
increase the interlayer space and the compatibility of Mt with polymers.
Behniafar and co-workers (Behniafar and Azadeh, 2015; Behniafar
et al., 2015, 2016) recently showed that Mt is initially intercalated by
bivalent ammonium salt of amine-telechelic poly (tetramethylene
 Table 1
Recent typical methods and results of in situ exfoliation of montmorillonite in polymer matrix.
Type of Mt Modification/intercalating Monomer Initiator Polymer Exfoliation conditions Exfoliated Mt Ref.
T.T. Zhu et al.

reagents

OMt ammonium salt MMA AIBN PMMA Mechanical stirrer:55°C,40 min Partly exfoliated and the Kowalczyk et al.,
exfoliated nanolayers are 2014
aggregated
3 wt% Na-Mt APTES DGEBA - epoxy Sonication :30 min stirred None of the Mt exhibited Bruce et al.,
APDMES complete exfoliation 2014
PDMMS
1%, 3%, 5% Mt benzalkonium chloride PA,PG,MA - UP Stirred:24h Partly exfoliated Tsai et al., 2014
Reaction temperature:200°C ultra-centrifuged
and washed several times
Na+-Mt - DDE, - PDEPD Mechanical stirrer Well dispersed and a large Tai et al., 2014
PDCP Sonicated:0.5h number layers are close to
Refluxed: 24 h complete exfoliation
Mt quaternary bisphenol-A epoxy - epoxy resin Mechanically mixed: 30 minutes, 60°C Partially exfoliated and Bashar et al.,
alkylammonium resin blend in an oven at 120 °Cfor two hours intercalated 2014
4wt%Mt - - - PA6 Fully intermeshing corotating twin-screw A high level of Mt dispersion Fereydoon et al.,
extruder; vacuum oven at 130°C for 5 h and exfoliation 2015
4wt%Mt - - - MXD6 Fully intermeshing corotating twin-screw Well exfoliated Fereydoon et al.,
extruder 2015
Vacuum oven at 80°C for 24 h
Na-Mt CTAB MMA, VAc ADMVN PVAMMA Stirrer rotating by 450 rpm: 30min Random exfoliated Xu et al., 2014a
polymerization reactor was fixed at 50°C for 5 nanolayers and some stacks
h, filtrated and rinsed several times
Mt PANI nanofiber maleic anhydride, APS HBPEA Resinification reaction:150 °C for 30 min; Partly exfoliated; a uniform Pramanik et al.,
PA heating at 185 °C for 1.5 h;continuous distribution 2014

52
and isophthalic mechanical stirring under the blanket of
acid,diethanol amine nitrogen
l Mt methyl tallow bis-2- resin MEKP/ cobalt resin Mechanicallystirre:1200-1500rpm,60-120min Partially intercalated and Poncet-Malige
hydroxyethyl quaternary naphthenate Ultrasonic mixing: power:72-80w; partially exfoliated et al., 2015
ammonium salt 30-60min
Na+-Mt CTAB - - epoxy High-speed shear mixer at 3000 rpm:30 min Exfoliated OMt nanoplatelets; Eissa et al., 2015
resin Sonicated :1 h homogeneously distributed
Mt CTAB ACOPNA, BMI - ACOPNA-BMI Stirring and maintained: 130 °C;30 min Partly exfoliated and slightly Zhang et al.,
aggregated 2015
Cloisite 30B - TMA, MDI TBA PAI Three-necked glass reactor in nitrogen Partly exfoliated Briesenick and
Nanofil 9 atmosphere and heated to 60°C; stirred Bremser, 2015
Na+–Mt CTAB acrylonitrile APS PAN Shaking for 2h;refluxed and stirred at 70 °C for Successfully exfoliated Li et al., 2015
3h
+
Na –Mt CTAB aniline APS PANI Vigorous and steady stirring Exfoliated and intercalated Abd El-Ghaffar
et al., 2015
Mt - aniline - PANI Stirred: 6 h Partly exfoliated Tokarský et al.,
2015
Cloisite®Na+ – DGEBA - epoxy resin Sonication for 30 min; No exfoliated and aggregated Sene et al., 2016
Magnetic stirring at 200 rpm
®
Cloisite 30B Partly exfoliated and non-
homogeneous dispersed
Mt - urea, Pf - urea–formaldehyde Extruded at 35 °C in a counter-rotating double Partly exfoliated Yamamoto et al.,
polymer screw extruder running at 60 rpm; 2016
Na+–Mt DBSA pyrrole - Polypyrrole Magnetic stirring at room temperature; Most of Mt layers: exfoliated Ramôa et al.,
SDS Filtered, washed with distilled water and dried No exfoliation 2015
CTAB at 60 °C
(continued on next page)
Applied Clay Science 169 (2019) 48–66
T.T. Zhu et al. Applied Clay Science 169 (2019) 48–66

DBSA:dodecylbenzenesulfonic acid; HBPEA:hyperbranched poly(ester amide); MDI: 4,4-methylene diphenyl diisocyanate; MEKP:methyl ethyl ketone peroxide; MA: maleic acid; MMA: methyl methacrylate; MXD6: poly

dichlorophosphate); PMMA: poly(methyl methacrylate); PA6:polyamide 6; PVAMMA:poly (vinyl acetate-co-methylmethacrylate);Pf: paraformaldehyde; PAI: polyamide-imide; PANI: polyaniline; PU: polybutadiene; PHB:
AAm: acrylamide; AIBN:2,2′-Azobis(isobutyronitrile); APTES: aminopropyltriethoxysilane; APDMES: 3-aminopropyldimethylethoxysilane; APS: ammonium peroxydisulfate; ACOPNA: An allyl condensed polynuclear
aromatic; ADMVN:Azo-bis-isoheptonitrile; BMI: Bismaleimide; BAAm: bisacrylamide; CTAB:Cetyltrimethyl ammonium bromide; DGEBA:Bisphenol A diglycidyl ether; DDE: 4,40-Diaminodiphenyl ether;

(m-xylene adipamide); PAN: polyacrylonitrile; PDMMS: n-propyldimethylmethoxysilane; PA: phthalic anhydride; PG: propyleneglycol; PDCP:Phenyl dichlorophosphate; PDEPD: poly(4,40-diaminodiphenyl ether phenyl
oxide) (PTMO). The large bivalent cation can significantly enhance the

Malkappa et. al.,

Farahani et al.,
organophilicity of Mt and remarkably increase the interlayer space of

Msaadi et al.,

Farmahini-
Mt. When these PTMO-intercalated Mt nanolayers are present in a
2016 medium in which a polymer is being synthesized, the resulting mac-

2017

2015
Ref.

romolecules have a high capacity to incorporate into the interlayer

space of Mt As such, a full exfoliation of the OMt platelets in the

Highly dispersed and possibly

intercalated nanocomposites
polymer matrix is achieved (Fig. 5).
Although organic modifiers help to improve the exfoliation of Mt in
Clearly exfoliated and

completely destroyed
formation of primary

the polymer matrix, the use of organic modifier undoubtedly leads to

Layered structure is
nanoparticles and

exfoliated and/or
extra costs. Moreover, some organic modifiers could have a negative
Exfoliated Mt

agglomerates

effect on the mechanical and thermal properties of the resultant Mt/

polymer nanocomposites (Nie et al., 2014). Therefore, monomers have
been considered as organic modifiers. Moreover, polymerization of

polyhydroxybutyrate; SDS: sodium dodecyl sulfate; TMA: 1,2,4-benzenetricarboxylic acid anhydride; TBA: Tri-nbutyl amine; UP: Unsaturated Polyester; VAc: vinyl acrylate;
such monomers and crosslinking with other monomers or polymer can
be tactically used. (Atta et al., 2014, 2015) (Fig. 6). In particular, the
density = 5 mW/cm2, distance lamp-flask ∼13
cm, exposure time = 7200 s under permanent

cationic monomer can exchange the interlayer cations (such as Na+,

Ca2+) of Mt. For example, cationic (e.g. 3-acrylamidopropyl) tri-
washed three times with chloroform and
centrifuged subsequently at 10,000 rpm

methylammonium chloride; APTAC), anionic (e.g. acrylic acid; AA so-

Mechanical stirrer;at 85 °C for 5 h

dium 2-acrylamido-2-methylpropane sulfonate; Na-AMPS) and non-

Wave length = 365 nm, power

ionic (e.g. N-vinyl pyrrolidone; VP acrylamide; AAm Nisopropyl acry

Stirred overnight at 110 °C

lamide; NIPAm) monomers can be introduced into the interlayer space

of Mt via a cation exchange reaction. The cationic monomer is then
Exfoliation conditions

polymerized in situ and crosslinked with anionic and nonionic mono-

magnetic stirring

mers in the presence of a cross-linker (Atta et al., 2016). The reactions

bring about the in situ exfoliation of Mt (Pokharel et al., 2015).
For introducing of nonionic monomers into the interlayer space, the
nonionic ones normally should be transformed into cationic ones. In
this way, a monomer (e.g. N-[3-(dimethylamino) propyl] methacryla-
mide (DMAPMA) and anionic monomers (e.g. AA), have been suc-
Ion imprinted polymer

cessfully used to modify Mt (Nie et al., 2014). For example, a hydro-

philic monomer (e.g. DMAPMA) is nonionic and it cannot exchange
with cations in the interlayer space of Mt, but DMAPMA can transform
from nonionic one in neutral solution to cationic one in acid solution.
Polymer

As such, after the addition of an anionic monomer (e. g. AA; sodium 2-

PHB
PU

acrylamido-2-methylpropane sulfonate: Na-AMPS), the monomers be-

came positively charged and can thus be intercalated into the layer
space of Mt by a simple exchange reaction (Nie et al., 2014). Mean-
chlorotetrabutyldistannoxane

while,therein AA can also be introduced into the interlayer space of Mt.

When the initiator is added, an in situ polymerization reaction occurs,
and according the Mt is in situ exfoliated. Moreover, the exothermic
heat of both the transformation and the polymerization help the ex-
foliation of Mt (Nie et al., 2014).
1-ethoxy-3-

Under weak alkaline conditions, dopamine (DA) can self-polymerize

Initiator

to polydopamine (PDA) and thus form a thin layer onto the surface of
Mt (Wei et al., 2010; Xuan et al., 2013). With active catechol and amine
-

groups, PDA can interact with many other polar polymers through
hydrogen bonding. Such reactivity can be employed for further mod-
ification (Lee et al., 2006; Ortega-Toro et al., 2014). Studies have found
β-butyrolactone
polymeric diol

AAm/ BAAm

that PDA coating on the Mt surface could prevent the regular stack of
Monomer

Mt lamellae and induce the exfoliated structure (Zhou and Xu,

2015;Zhou et al., 2016). During the process, DA was intercalated into
the interlayer space and onto the surface of Mt DA then in situ poly-
merized to form a PDA coating layer. Accordingly, the interlayer spa-
Modification/intercalating

cing of Mt increased. A PDA coating layer with catechol groups can

improve the compatibility between Mt and the polymer matrix. In other
words, PDA is not only able to enlarge the interlayer spacing of Mt to
diazonium salt

facilitate the in situ exfoliation, but also enhance the interactions be-
reagents

tween Mt and the polymer.

3.2. Solution exfoliation

-

-
Table 1 (continued)

3 wt% Closite-30B

When a polymer is soluble in a solvent such as chloroform, formic

Cloisite® 30B
Type of Mt

acid, ethyl alcohol and acetone, Mt can be exfoliated in the corre-

sponding polymer solution (Shameli et al., 2013; Sridhar et al., 2014).
Such polymers as polyurethane, poly(2,5-benzimidazole) (ABPBI), vi-
Mt

nylester, polyamide 6 (PA6), poly (vinyl alcohol), epoxy resin, poly

53
T.T. Zhu et al.
Fig. 4. Illustration of the role of quaternary ammonium cations on exfoliation of Mt by nylon-6.
Adapted and reprinted with permission from Fornes et al., 2004. Copyright 2004 American Chemical Society.
(lactic acid), poly(lactide-co-glycolide), sclerogluca, and polyamide-
imide, poly(3-hydroxybutyrate-co-4-hydroxybutyrate) have been suc-
cessfully used with Mt to produce CPN by solution exfoliation (Table 2).
Clearly, the solution exfoliation method is only applicable to exfoliate
Mt in a soluble polymer. However, this approach may have problems
associated with the use of large quantities of organic solvents.
In order to disperse Mt uniformly within a polymer solution, Mt
needs to be modified with hydrophobic surfactants. Such modification
can make the resultant OMt well dispersed in the polymer solution
(Panek et al., 2006; Junior et al., 2014). When OMt was added into a
polymer solution, both the solvent and the polymer molecule inter-
calates between the Mt layers to expand the interlayer space of OMt. In
particular, the long polymer chains tended to coil in order to decrease
the loss of conformational entropy, thus further expanding the inter-
layer spaces and ultimately exfoliating OMt (Devi et al., 2015). Besides,
the organic modification of Mt increases the polymer–Mt interfacial
interactions (Fig. 7).
Prolonging the swelling of OMt in the solution can promote the OMt
exfoliation. When OMt is exposed longer time in the solution, a larger
amount of solvent can enter the interlayer space of OMt In addition, the
process could be intensified by ultrasound treatment (Ejder-Korucu
et al., 2016). Recently, Devi et al. (2015) demonstrated a well-ex-
foliated OMt by prolonging the swelling of OMt in toluene by solution
exfoliation. The Mt was first modified by benzyl methyl hydrogenated
tallow. Such OMt was swollen in toluene for 10 h and 72 h under
magnetically stirring. The OMt swollen for 72 h exhibited a complete
exfoliation of the Mt Then the styrene butadiene rubber (SBR) polymer
was added, the SBR polymer chains can enter the OMt interlayer and
undergo conformational deformation and crosslinking reaction, thereby
producing the OMt/SBR nanocomposite with a highly exfoliated Mt
dispersed in it.
Acid-base reactions and hydrogen bonding between the polymer
and the OMt can promote exfoliation of Mt (Moreira et al., 2016). The
exothermic heat of acid-base reactions also helps the exfoliation of Mt.
He et al. (2015) fully exfoliated Mt in sulfonated poly (ether-ether-
54
Applied Clay Science 169 (2019) 48–66
ketone) (SPEEK) in DMAc solution. Due to the formation of hydrogen
bonding between the sulfonic acid groups of SPEEK and the carboxylic
acid groups of HOOC(CH2)17NH3 in OMt, the exfoliation and dispersion
of OMt were remarkably improved (and interface interaction between
OMt and SPEEK were enhanced.
Grafting of function groups onto the polymeric groups is an effective
way to increase the interfacial interaction between the nonpolar
polymer and the OMt to promote the exfoliation of Mt (Lei et al., 2014).
Alternatively, grafting of function groups onto the organic modifiers or
even Mt platelets can also enhance exfoliation of Mt in polymer. For
example, Abt et al. (2014) successfully promoted Mt exfoliation in poly
cyclic butylene terephthalate (pCBT) in tetrahydrofuran. Firstly, Mt was
modified by bis-2-hydroxyethyl, quaternary ammonium, which bears
two hydroxyl groups. The resultant OMt was further intercalated by
polymeric isocyanate (PMDI) into the interlayer space of Mt. A grafting
reaction occurred between PMDI and the hydroxyl groups of the qua-
ternary ammonium salt of the OMt. Consequently, the interlayer spa-
cing of Mt markedly increased and thus weakened the attraction be-
tween Mt layers. Hence, the OMt was well exfoliated and dispersed in
the resultant OMt/pCBT nanocomposites. Recently, Zhang et al. (2015)
obtained highly exfoliated Mt by via the ‘acetone-Mt slurry com-
pounding’ approach. Mt was organically modified by 2,4,6-tris-(di-
methylaminomethyl) phenol (DMP-30), which contains hydroxyl and
tertiary amine groups. Such OMt can absorb plenty of water (with water
absorption about 1700%), thereby preventing Mt platelets from re-
arranging and restacking. Nevertheless, the OMt is not compatible with
the epoxy. When the OMt was washed several times in acetone, the
acetone molecules replaced the water to form an acetone/OMt slurry.
The compatibility between OMt and epoxy was thereby improved.
When the acetone/OMt slurry was directly added into epoxy, the OMt
could ‘dissolve’ in epoxy polymer. Moreover, the chemical reaction
between epoxy and tertiary amine groups of organic modifiers provided
a strong driving force to promote the exfoliation of OMt in epoxy
(Zhang et al., 2015).
T.T. Zhu et al.
Fig. 5. The four-step reaction to QA-capped PTMO (a), intercalation of MMT platelets by QAPTMO (b), and exfoliation of the PTMO intercalated platelets by PTMO-
based SPU(c).
Adapted and Reprinted by permission from Rights Link: Springer Nature, Journal of Polymer Research (Behniafar et al., 2016), Copyright 2016.
3.3. Melt exfoliation
Compared to in situ polymerization exfoliation and solution ex-
foliation, melt exfoliation is the simplest technique (Fig. 8). In this
process, Mt is first mixed with thermoplastic polymers, followed by
heating the mixture and under shearing force. If the layer surfaces of Mt
have enough compatibility with the polymer, the polymer molecules or
chains can enter the interlayer space to form either a polymer inter-
calated-Mt or exfoliated Mt/polymer nanocomposites (Osman et al.,
2012, 2015; Rooj et al., 2012; Andriani et al., 2013). During the melting
treatment, intensifying the mechanical force will increase the mobility
and diffusion of the polymer and thus will improve the dispersion and
exfoliation of Mt in the polymer matrix (Ngo et al., 2009; Achaby et al.,
2013). So far polyethylene (PE), EVA, ethylene copolymers, polylactic
acid (PLA), poly (lactic acid)/poly (butylene succinate), polystyrene
(PS), and polycarbonate have been used to produce Mt/polymer na-
nocomposites by the melt exfoliation method (Table 3).
Although the screw or mixing blade can provide shearing forces to
55
Applied Clay Science 169 (2019) 48–66
break up large Mt particles, the treatment cannot fully exfoliate Mt
Moreover, dispersion of Mt in the polymer matrix is also usually poor
(Osman et al., 2012, 2015; Andriani et al., 2013). To create loosely
packed nanolayers of Mt prior to melting appears conducive to mitigate
such problems. For example, Osman et al. (2016) revealed that when
the loosely packed particles of Mt were added to ethyl vinyl acetate
(EVA) copolymers, exfoliation of Mt got improved under shearing
forces. A typical way to make loosely packed particles of Mt is to modify
Mt properly. Modified Mt with short interlayer distance is inefficient in
polymer intercalation because of diffusion limitations of polymer mo-
lecules into the interlayer space of Mt (Calderon et al., 2008). By con-
trast, when Mt was modified by large organic species, the interlayer
spacing of Mt can be significantly enlarged. Hence, more polymer
chains can enter the interlayer space of Mt, thereby promoting the
exfoliation and dispersion of Mt in the polymer matrix (Achaby et al.,
2013; Jian et al., 2015). For instance, Achaby et al. (2013) used the
benzimidazolium-N, N′-hexadecane-2-hydroxy-ethyl bromide (Bz) with
two geminal hexadecyl hydrophobic buttress to modified Na+-Mt. The
T.T. Zhu et al.
Fig. 6. The process of exfoliation Mt by crosslinking technique.
Adapted and reprinted from Atta et al., 2015, Copyright 2015, with permission from Elsevier.
resultant OMt can then be exfoliated and dispersed in high density
polyethylene (HDPE) and polyphenylene sulfide (PPS) via melt method.
A recent study reveals that glycerol can also improve the dispersion and
exfoliation of OMt during the mixing process in the polymer matrix
(Visentini et al., 2015).
In the process of melt exfoliation, the water-assisted extrusion
process is particularly efficient to exfoliate Mt in some polymer ma-
trices (Shahabadi and Garmabi, 2012; Stoeffler et al., 2013; Lee et al.,
2015). The water acts as a swelling agent to increase the interlayer
spacing of Mt. Typically, when the slurry of Mt and water, is added to
the melted polymer in the extruder barrel, the viscosity of polymer
decrease, and thus the mobility of polymer chains increases and the gel
formation reduces. Meanwhile, polyamide molecules can easily pene-
trate the interlayer space of Mt. For similar reasons, in the extrusion
process, injecting liquid water under high pressure into the extruder
barrel could be conducing to the melt exfoliation. Such a process can be
a continuous process by adding a low quantity of water with a large
amount of Mt (Lee et al., 2015) (Fig. 9).
Upon heating, the chemical blowing agent (BA) such as sodium
bicarbonate (SB) and azodicarboxamide (ADC) can yield gas molecules.
When BA degrade in the interlayer space of Mt at high temperatures,
the resultant gas molecules enhance the interlayer spacing of Mt and
drive the exfoliation of Mt (Istrate and Chen, 2012; Istrate and Chen,
2014). This can be applied to intensify the melt exfoliation process to
improve the exfoliation and dispersion of Mt in the polymer matrix a
(Fig. 10). As revealed by Istrate and Chen (2014), when dimethyl di-
hydrogenated tallow ammonium- Mt was pre-treated with two common
chemical BAs, namely sodium bicarbonate (SB) and azodicarboxamide
(ADC), the degree of exfoliation of OMt in PS and in PP/PPgMA were
remarkably improved.
In addition, the joint action of the compatibilizer and co-inter-
calated species can improve Mt exfoliation and dispersion. For example,
Moreira et al. (2016) successfully enhanced the Mt exfoliation in the
molten PP by adding maleic anhydride-grafted polypropylene (PP-g-
MA) as the compatibilizer and erucamide as the cointercalant by a
process of melt exfoliation. As PP chains are not easily inserted into the
interlayer space of Mt, and the exfoliation of Mt is difficult in PP
without compatibilizer. However, due to the low molecular mass of
compatibilizer, excessive use will distinctly weaken the mechanical
properties of Mt/nanocomposites (Zhu et al., 2011). Consequently, it is
imperative to choose the compatibilizer properly and the amount of it
need optimizing (Dintcheva et al., 2015).
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Applied Clay Science 169 (2019) 48–66
4. Functions of well-exfoliated Mt in Mt/polymer nanocomposites
With a very low level (< 5 wt%) of addition of Mt nanolayers into
the polymer matrix, CPN could show unique properties in barrier
properties (Yang et al., 2017; Ammar et al., 2017; Bahreini et al., 2017),
mechanical properties (Devi et al., 2015; Shameli et al., 2015; Asgari
et al., 2017), thermal stability (Nistor and Vasile, 2013; Osman et al.,
2015), and flame retardancy (Chiou et al., 2014; Wu et al., 2014;
Niroumand et al., 2016). To achieve CPN with substantial improvement
in those properties, Mt must be well exfoliated and dispersed in the
polymer matrix. The enhancements depend primarily on several fac-
tors: the size and aspect ratio of Mt nanolayers as the nanofiller, the
degree of dispersion, and the orientation of exfoliated Mt nanolayers
within the polymer, as well as interactions between exfoliated Mt na-
nolayers and the polymer matrix.
4.1. Barrier properties
Improvement of barrier properties are one of the most expected
functions from Mt nanolayers because the Mt nanolayers are considered
as large 2D platy inorganic particles which can hinder the penetration
of gases and water. As many studies prove that when the exfoliated Mt
nanolayers are well dispersed in the polymer matrix, the barrier prop-
erties of the resulting CPN can be enhanced (Mittal et al., 2015; Guo
et al., 2016; Sharma et al., 2018). The CPN with improved barrier
properties can be used for food packaging (Wang et al., 2007; Jin and
Zhong, 2013; Farmahini-Farahani et al., 2015). The CPN can also be
made as nanocomposite films (Ammar et al., 2017; Bahreini et al.,
2017; Yang et al., 2017;) and membranes (Zulhairun et al., 2014;
Villaça et al., 2017). Such nanocomposite films and membranes can be
used as functional coatings (Bahreini et al., 2017; Merachtsaki et al.,
2017) and sensors (Ammar et al., 2017).
Theoretically, the exfoliated Mt nanolayers can increase the tortu-
osity of the molecule diffusion path, thereby blocking the penetration of
water vapor and gas molecules (Sorrentino et al., 2006; Mohan and
Kanny, 2011; Hossain et al., 2014; Firdosh et al., 2015). The tortuosity
indicates the complexity of gas diffusion. The tortuosity factor is de-
fined as the ratio of d’/d (Ray and Okamoto, 2003; Ray et al., 2002).
d′ L
τ= =1+ ∅
d 2W (1)
d’ is the actual distance that a permeating molecule must travel to
pass through a film; d is the distance that a permeating molecule travel
 T.T. Zhu et al.

Table 2
Recent typical methods and results of solution exfoliation of montmorillonite in polymer matrix.
Type of Mt Modification/intercalating reagent polymer solvent Exfoliation conditions Exfoliation Mt Ref.

Mt octadecylamine PU Ethyl alcohol and acetone High-shear mixing at 4000 rpm for 30 min; Well exfoliated in the Stratigaki et al.,
sonicated for 30 min with an ultrasonic nanocomposites at 0.32, 0.64, and (2014)
Sonotrode 400 W operating at 35 kHz 0.96 vol%
Mt hexadecyltrimethylammonium ABPBI DMAc High-speed stirring at 80°C for 2 h Partially exfoliated Eren et al. (2014)
Dired at 40 °C for 20 h
Cloisite Na/Cloisite _ Vinylester chloroform Ultrasonic bath at room temperature for Complete exfoliation is not achieved Sridhar et al. (2014)
Na resins 15min
Mt quaternary ammonium salt PA6 formic acid Magnetic stirrer: least 12h Good dispersion and exfoliation Wu et al. (2014)
Mt octadecylamine PVA water Stirred Well exfoliated Xu et al. (2014b)
Sonicated:30min
Mt bis-(2-hydroxyethyl)methyl-hydrogenated tallow epoxy - Mechanical stirring:24h A mixture of intercalated and Wang et al. (2014)
alkylammonium cation Sonication exfoliated structures
Dired: 80°C
Mt/90mequiv/100 g methyl-tallow-bis- epoxy 79 wt% of xylene; 10 wt% of Magnetic stirring:1000rmp,1h, Mainly exfoliated Tomić et al. (2014)
2-hydroxyethyl quaternary ammonium salt n-butanol and 11 wt% of sonication

57
MEK
Na-Mt - PANI anilinium sulfate/ sulfuric Stirred: 6 h Partly exfoliated Tokarský et al.
acid (2015)
Mt SWy-2 CTAB PLA chloroform Stirred under ultrasound:30min Partly exfoliated and non-uniformly Mansa et al. (2015)
dispersed
Mt dimethyl-benzylhydrogenated tallow quaternary PAI NMP Magnetic stirrer:1h Good degree of exfoliation and Briesenick and
ammonium nanolayer distribution at low Mt Bremser (2015)
loading
Cloisite30B - PHBV chloroform Magnetic stirrer Partially exfoliated and randomly Farmahini-Farahani
dispersed et al. (2015)
Cloisite® 30B - PLGA DCM Ultrasonication probe: 30min voltage of 115 Partial exfoliation Kaur et al. (2016)
V, power of 100 W and frequency of 60 Hz
Na+-Mt (1–5wt%) - PVA Chitosan Beaker and stirred Partly exfoliated and uniformly Reddy et al. (2016)
stirring: another 6h dispersed
MtSWy-2 - Sclera-glucan Water Stirred magnetically: up to 28 days A mixture of exfoliated and Mansa et al. (2015)
dried :60°C intercalated structures

ABPBI: poly(2,5-benzimidazole);CTAB: cetyltrimethylammonium bromide; DMAc: Dimethylacetamide;DCM: dichloromethane;NMP: N-methyl pyrolidone; PU: polyurethane; PA6: polyamide 6; PVA: polyvinyl alcohol;
PANI: polyaniline; PLA: poly (lactic acid); PAI: polyamide-imide; PHBV: poly(3-hydroxybutyrate-co-4-hydroxybutyrate); PLGA: poly(lactide-co-glycolide); VE: Vinylester resins.
Applied Clay Science 169 (2019) 48–66
T.T. Zhu et al.
Fig. 7. Illustration of solution exfoliation Mt in polymer. The basic idea of solvent exfoliation was to intercalate Mt’s interlayer with polyamide-imide molecules to
cause exfoliation due to enlargement of interlayer space beyond limits of interlayer attractive forces.
Adapted and reprinted from Briesenick and Bremser, 2015, Copyright 2015, with permission from Elsevier.
to pass through a film in the absence of barriers; L is the width of the
rectangular platelets; W is the thickness of rectangular platelets; ∅ is
the volume fraction of the nanoparticles. For example, when τ in-
creases, the gas molecules are forced to find alternative longer path-
ways to diffuse through a Mt/polymer nanocomposite film (Fig. 11). As
the diffusion path becomes longer, the required time to travel through a
nanocomposites film is prolonged. The overall rate of diffusion is re-
duced.
The improvement of the gas barrier properties by the exfoliated Mt
nanolayers in Mt/polymer nanocomposites is mainly related to the as-
pect ratio of Mt nanolayers, the volume fraction and orientation of Mt
in the polymer matrix (Choudalakis and Gotsis, 2012; Stratigaki et al.,
2014). In other words, the extent of the improvement of the barrier
properties of the Mt/nanocomposite are greatly dependent on the
content of Mt, the extent of exfoliation of Mt and the dispersion of
exfoliated Mt in the polymer matrix. Tomić et al. (2014) investigated
the influence of the content of Cloisite 30B (1–10 wt%) on the corrosion
resistance of clay/epoxy nanocomposite coatings. The best exfoliation
and the most homogeneous macromolecular network were found for
the CPN with 1 wt% of Cloisite 30B, which exhibited the highest im-
provement of anticorrosive properties. Risse et al. (2014) showed that
dispersed and exfoliated OMt in poly (lactic acid) (PLA)/poly (butylene
succinate) (PBS) had a direct impact on the permeability of O2 and
water vapor in the CPN. The value of permeability of OMt/PLA/PBS
nanocomposites with 7 wt% of OMt was reduced by 40% for O2 and by
50% for the water vapor. The presence of Mt aggregates appeared to be
harmful to the impermeability. Horst et al. (2014) observed that oxygen
permeability for high-density polyethylene (HDPE) nanocomposite
films decreased when a much larger concentration of Mt (15 wt%) was
used. The deterioration was ascribed to the negative change when the
polymer got solidified from the melted state. Namely, the volume
contraction during solidification may produce small holes and/or im-
perfections in the bonding between the polymer matrix and the clay
minerals, hence facilitating the diffusion of the small gas molecules in
the nanocomposite films (Horst et al., 2014).
The nanocomposites with properly exfoliated Mt nanolayers in a
polymer matrix can be made into packaging materials, for example
CPN-coated paper and plastic bags which have good barriers against gas
and water penetration (Charlon et al., 2016; Li et al., 2016; Bandara
Fig. 8. The illustration of melt exfoliation Mt in polymer.
58
Applied Clay Science 169 (2019) 48–66
et al., 2017). Farmahini-Farahani et al. (2015) intercalated β-butyr-
olactone in the Cloisite 30B to produce Mt/ poly(3-hydroxybutyric acid-
co-3-hydroxyvaleric acid) (PHBV) nanocomposites. The ring-opening
polymerization of β-butyrolactone in the interlayer space of Cloisite
30B is an effective way to enhance the exfoliation of Mt. This nano-
composite-coated paper had a water vapor transmission rate (WVTR)
value as low as 26.4 g/m2/day. Thus, it could be a very promising
green-based packaging material. Recently, Bandara et al. (2017) suc-
cessfully produced a type of surface-modified Mt to reinforce canola
protein adhesive with improved water resistance and adhesion
strength. The improvement in adhesive strength at a low Mt addition
was attributed to adequate exfoliation of Mt in protein matrix and in-
creased exposure of functional groups for enhancing interaction with
wood surface. Owing to enhanced barrier properties, Mt/polymer na-
nocomposites can act as an anticorrosive coating (Tomić et al., 2014;
Stratigaki et al., 2014; Choudalakis and Gotsis, 2014; Merachtsaki et al.,
2017). In general, the introduction of exfoliated Mt nanolayers into
organic coatings increases the length of diffusion pathways of oxygen
and water to pass the coatings and decreases the permeability of the
coating. Therefore, the metal surface coated by such CPN can better
resist the corrosion (Atta et al., 2017a, 2017b; Merachtsaki et al., 2017).
In particular, such Mt/polymer coated steel become more anti-corrosive
in marine environments.
4.2. Mechanical properties
When the exfoliated Mt nanolayers are homogenously dispersed in
polymer matrix, the mechanical properties of the resultant CPN can be
remarkably improved (Behniafar et al., 2016; Wang et al., 2016; Zabihi
et al., 2017). The level of enhancement of mechanical properties of CPN
is heavily dependent upon the extent of exfoliation of the Mt layers into
individual nanolayers and their dispersion in polymer matrix
(Nikolaidis et al., 2011; Nikolaidis et al., 2012; Wang et al., 2016). The
improvement of mechanical properties is also related to interactions
between Mt nanolayers and polymer molecules. Thus, the compatibility
of exfoliated Mt nanolayers with the organic polymer should be en-
hanced and thereby appropriate surface-modification of Mt nanolayers
are commonly necessary. For example, in a recent study, with a 2.5 wt%
loading of highly exfoliated quaternized chitosan-modified Mt
 T.T. Zhu et al.

Table 3
Recent typical methods and results of melt exfoliation of montmorillonite in polymer matrix.
Type of Mt Modification/intercalating reagent polymer Melt temperature/ Other Exfoliation condition Exfoliation Mt Ref.
°C

Mt/104 eq/100 g 1-dodecylamine PE 180 Twin-screw extruder: 200 rpm Disorderly dispersed and partly exfoliated Liu (2014)
injection molding machine
Na+-Mt/120 meq/100 g ethyl hexadecyl dimethyl ammonium EVA 110 Mixing chamber: mixing rate of 15 rpm,10min Better dispersion of the OMt particles and a Beltrán et al. (2014)
higher degree of exfoliation
Mt alkylammonium cation surfactants EVA 100 A screw speed of 50 r/min The 001 refection of OMt disappeared and Duan et al., (2014)
possibly exfoliated completely
Mt quaternary ammonium chlorides Ethylene 120 Rotor speed: 30 rpm, 3 min High level of exfoliation and/or disordered Filippi and Polacco
copolymers intercalation (2014)
Mt/85 meq/100 g single-tail and double-tail alkyl EVA 170~180 Extensive exfoliation Massinga et al.
ammonium cationic surfactants (2014)
Mt methyl dihydroxylethyl hydrogenated PLA 200 Traditional twin–screw extruder Coexistence of intercalated and/or exfoliated Jia et al. (2014)
tallow ammonium structure
Mt methyl dehydrogenated tallow PLA 170~180 A screw speed of 40 rpm and acceleration rate of 50 Not exfoliated or significantly intercalated Mohapatra et al.
ammonium rpm/min Better exfoliation and dispersion (2014)
Methyl dehydrogenated tallow Microinjection moulding machine:180°C,7–7.5 bar
ammonium injection pressure and a cycle time of 10 s
Mt methyl tallow bis(2-hydroxyethyl) PLA/PBS 60 Extrusion conditions:screw speed was set-up at 250 Partly exfoliated and evenly dispersed Risse et al. (2014)

59
quaternary ammonium chloride rpm, the feed rate at 6 kg h-1
Mt dimethyl dihydrogenated tallow PE 160 Cam blades rotating:40 r/min A high degree of exfoliation Horst et al. (2014)
ammonium halide mixer chamber
Viscogel S4 montmorillonite bis(Hydrogenated Tallow Alkyl) PS 150~190 Twin-screw extruder, with screw diameter of 20 mm Mixed intercalated/exfoliated Jorge et al., (2014)
clay Dimethyl Ammonium and L/D ratio of 36 rotation speeds:either 450 or
600
rpm
Na+-Mt/ 92 meq/100 g methyl tallow-bis-2-hydroxyethyl PVC 135 High shear mechanical mixing:7500 rpm for 10 min Good exfoliation Silva et al. (2014)
quaternary ammonium salt dry blends:60 rpm for 5 min in a Plastograph
Mt dimethyl benzylhydrogenated tallow PC 245~260 Co-rotating twin-screw extruder (Thermo Electron Partly exfoliated Meri et al. (2015)
ammonium Corporation) with barrel length 400 mm and L/D
ratio 25
2 wt% Mt dimethyl dihydrogenated tallow PS 135–190 A co-rotating twin-screw extruder Exfoliated and good dispersed in polymer Niroumand et al.
ammonium cation Extruder pressure:12.5 bars (2016)
Na+-Mt RDP PLA 180 Chamber under 20 rpm oscillatory shear mode: Mostly exfoliated Guo et al. (2016)
frequency sweep from 0.01 Hz to 100 Hz
Mt SA PBTA 160 Closed brabendermixer, Model: total compounding Intercalated and exfoliated; uniformly Moustafa et al.
time of 10 min at 50 rpm dispersed; a high degree of OMt exfoliation (2017)
rather than intercalation state

EVA: Ethylene vinyl acetate copolymer; PE: Polyethylene; PLA: Polylactic acid; PBS: Poly(butylene succinate); PS: Polystyrene; PC: Polycarbonate; PVC: Polyvinyl chloride; PBTA: poly(butylene adipate-co-terephthalate);
RDP: resorcinol di(phenyl phosphate); SA: stearic acid
Applied Clay Science 169 (2019) 48–66
T.T. Zhu et al. Applied Clay Science 169 (2019) 48–66

Fig. 9. Water-assisted extrusion with attached Mt slurry injection system.

Adapted and reprinted from Lee et al., 2015, Copyright 2015, with permission from Elsevier.

nanolayers, the tensile strength of Mt/epoxy nanocomposites got more
significant enhancements than the Mt/epoxy nanocomposites in which
trimethyl stearyl ammonium- modified OMt was used (Zabihi et al.,
2017) (Fig. 12). The interfacial interactions between the quaternized
chitosan-modified Mt and epoxy were dominated by covalent bonds
and hydrogen bonding(Park and Jana, 2003; Zabihi et al., 2017). Such
strong interfacial interactions promote the effective transfer of inter-
facial stress, leading to significantly improved mechanical properties. In
addition, the exfoliated Mt nanolayers can hinder the motion of the
polymer chains, thereby resulting in the enhancement of tensile
strength and Young's modulus of the CPN (Osman et al., 2015; Sharma
et al., 2017). The incorporation of exfoliated Mt nanolayers into the
polymer can remarkably increase the flexural modulus and flexural
strength of the CPN (Kowalczyk et al., 2014). The increase is usually
attributed to the high stiffness and the aspect ratio of exfoliated na-
nolayers (Parija et al., 2010; Zhang et al., 2015; Zabihi et al., 2017). On
the country, aggregated particles, unexfoliated Mt, can act as stress
concentrators and cause the loss of fracture strain. (Jin et al., 2010;
Wang et al., 2016).
It should be noted that the amount of the Mt nanoalayers used in the
CPN should well optimized (Gunning et al., 2014; Osman et al., 2015;
Zhang et al., 2017)) If excess Mt is used, the distribution of Mt particles
in the polymer matrix tends to be non-uniform, leading to the ag-
glomeration of Mt in the CPN (Sharma et al., 2017). The agglomerated
Mt particles leads to a reduction in tensile strength. In particular, the
agglomerated Mt are weak sites and act as points for the development
and propagation of cracks. Recently, Zhang et al. (2017) revealed that
for Mt/PP nanocomposites prepared by melt intercalation, When the
OMt loading was 3 wt%, the tensile strength of the Mt/PP nano-
composites increased by up to 49.6 MPa while the PP alone was
42.3 MPa. But when the Mt content in the CPN was above 3 wt%, the
tensile strength decreased instead. A recent study from Echeverría et al.
(2016) showed a series of active nanocomposite films prepared by
casting from aqueous dispersions containing soy protein isolates (SPI),

Fig. 10. (a) Exfoliation Mt process in polymer with the aid of blowing agent. Adapted and reprinted from Istrate et al., 2014, Copyright 2014, with permission from
John Wiley and Sons. (b) Propose mechanism for the exfoliation of BA-treated OCs during an extrusion process.
Reprinted from Istrate et al., 2014, Copyright 2014, with permission from John Wiley and Sons.

60
T.T. Zhu et al. Applied Clay Science 169 (2019) 48–66

Fig. 11. The effect of parallel arrayed platelets on the oxygen diffusion inside polymer matrix. (b) The effect of random arrayed platelets on the oxygen diffusion
inside polymer matrix.
Adapted and reprinted from Lee et al., 2015, Copyright 2015, with permission from Elsevier.

Fig. 12. Schematic representation of self-assembled quaternized chitosan nanoparticles (QCn) within Mt and its TEM images, the mechanicals properties of highly
exfoliated Mt/epoxy nanocomposites.
Adapted and reprinted from Zabihi et al., 2017, Copyright 2017, with permission from Elsevier.

glycerol, different concentrations of Mt and clove essential oil. Clove
essential oil can help the exfoliation of Mt into the soy protein matrix.
The tensile strength and the Young's modulus of nanocomposite films
containing 10 g Mt/100 g SPI was increased by 105% and 200%. But a
decrease of 340% in elongation at break was also observed. The notable
improvement of tensile strength and Young's modulus were attributed
to the beneficial interactions between the exfoliated Mt nanolayers and
the soy protein isolates in the films (Osman et al., 2005). However,
these interactions can constrain the movement of the soy proteins and
then reduces the film's elongation.
In addition to Mt content, some other factors related to the treat-
ment of Mt also influence the mechanical properties of nanocomposites
(Beltrán et al., 2014; Pandey et al., 2014; Shameli et al., 2015; Zhou
et al., 2016; Sharma et al., 2017). For instance, when the OMt are added
to the EVA copolymer matrix, Young's moduli increase with the in-
crease of the surfactant content of OMt (Beltrán et al., 2014). As the
content of surfactant increases, better dispersion and a higher degree of
exfoliation are achieved. The tensile strength, Young's modulus, and

61
T.T. Zhu et al.
percentage of elongation at break Mt/PP nanocomposites can even be
improved by extensive thermal treatment of Mt without any chemical
modification, because the thermal treatment can induce the dehy-
droxylation of Mt and thus can promote exfoliation of Mt (Pandey et al.,
2014).
Besides, the methods and the conditions for preparing the Mt/
polymer nanocomposites substantially affected the mechanical prop-
erties of the Mt/polymer nanocomposites (Zhou et al., 2011). For in-
stance, Shameli et al., 2015 prepared OMt/PLA nanocomposite films by
solution-casting and melt blending. As the exfoliation and dispersion of
Mt nanolayers by melt blending was better than that by solution-
casting, the mechanical properties of the former CPN films were su-
perior to the latter one (Shameli et al., 2015). Recently, Sharma et al.
(2017) discovered that ultrasound-assisted in-situ emulsion poly-
merization can cause more uniform and homogeneous distribution of
the exfoliated nanolayers in the polymer matrix through the generation
of intense microturbulence in the reaction mixture, thereby enhancing
the mechanical properties of the OMt/ poly (methyl methacrylate-co-
butyl acrylate) (poly(MMA-CO-BA)) nanocomposites.
4.3. Thermal properties and fire retardancy
With addition of a very small amount of (0.25–5 wt%) of Mt into the
polymer, the nanocomposites can show superior thermal stability
(Cheng et al., 2012; Hristodor et al., 2013; Nistor and Vasile, 2013;
Osman et al., 2015). The Mt nanolayers in the polymer matrix can act as
superior insulator, heat barrier, and mass barrier to the volatile pro-
ducts generated during thermal decomposition of the polymer (Mahesh
et al., 2013; Niroumand et al., 2016; Sharma et al., 2017). The barrier
of Mt nanolayers can also prevent oxygen penetration into the under-
lying polymer (Eren et al., 2014). In addition, the Mt nanolayers can
assist in the formation of char during thermal decomposition of the
polymer (Becker et al., 2003; Ray and Bousmina, 2005; Taghizadeh
et al., 2013; Behniafar et al., 2016). Hence, the presence of exfoliated
Mt nanolayers in the CPN can enhance the thermal stability of CPN.
Usually, improved dispersion of exfoliated OMt nanolayer within the
polymer matrix can enhance the interactions between exfoliated OMt
and the polymer matrix. However, it is worth noting that, when the Mt
content is increased, thermal stability can be increased or decreased.
Hassan et al. (2015) found that the amount of Mt in the CPN had a
remarkable influence on the thermal stability of polyamide 12 (PA12)
in the CPN. The thermal degradation rate of the nanocomposite gra-
dually decreased as the Mt content increased. The degradation tem-
perature for the Mt/PA nanocomposites with 5% Mt in it was higher
than that of the PA12 alone. Osman et al. (2015) reported that pre-
dispersed OMt in toluene helped exfoliate Mt effectively and then better
improved the thermal stability of the resultant Mt/EVA co-polymer
nanocomposites. By contrast, the incorporation of 5 wt% OMt which
was pre-dispersed by water resulted in the reduction of the thermal
stability of the EVA co-polymer nanocomposites. This was ascribed to a
weakening effect to the interphase bonding between the PE and PVA
components in the EVA. The content of Mt in the CPN needs judiciously
chosen. For example, Eissa et al. (2015) showed that the decomposition
temperature of the epoxy in the CPN containing 2 wt% of OMt shifted to
a higher temperature than that in the CPN with 5 wt% OMt in it.
When well-exfoliated Mt nanolayers are added in polymer matrix, a
large number of nanolayers with higher aspect ratios contact with
polymer molecules. Accordingly, such exfoliated Mt nanolayers impose
serious constraints on polymer molecules. In particular, the exfoliated
Mt nanolayers can hinder or retard the movement of polymer chain or
the segments of the chains, as usually indicated by the reduction in the
thermal expansion coefficients of the Mt/nanocomposites (Lin et al.,
2010; Wang et al., 2015). The extent of such reduction depends on the
level of exfoliated and dispersed of Mt nanolayers in polymer matrix.
For example, when 1 wt% OMt was added into thermoplastic elastomer
(TPE), compared with pure TPE, the thermal expansion coefficient of
62
Applied Clay Science 169 (2019) 48–66
the Mt/TPE nanocomposites decreased by 87% (Wang et al., 2015).
The strong interactions, including covalent bonds and hydrogen
bonding between Mt layers and polymer, constrain the motion of the
polymer network to some extent and cause Tg to shift to a higher
temperature (Shiravand et al., 2014; Kumar and Kannan, 2014;
Mohapatra et al., 2014). The well-exfoliated OMt nanoparticles offers
greater interfacial regions and stronger interactions in the nano-
composites, allowing more effective hindering of chain mobility of
polymers. Istrate and Chen (2014) showed that the Mt/PP-PPgMA na-
nocomposites has the onset thermal degradation at 65.7 °C and thermal
degradation at 46.6 °C, higher than those of PP-PPgMA at 24.4 °C and at
32.3 °C, respectively. It has been found that the combination of a
phosphorous component, for example hexachlorocyclophosphazene
(HCP), and the exfoliated Mt nanolayers leads to better thermal stabi-
lity of the Mt/epoxy nanocomposites (Chiou et al., 2014). Such en-
hancement was ascribed to positive synergistic behavior of phospha-
zene and exfoliated Mt nanolayers in the epoxy matrix. The synergistic
behavior was mainly attributed to the fact that the phosphorus com-
ponent decomposed at low temperatures and in turn produced highly
stable oxides in char formation. Nevertheless, it is noteworthy that al-
though OMt nanolayers are generally better dispersed and exfoliated in
the polymer matrix than the Mt (Lecouvet et al., 2011), the poor
thermal stability of OMt, namely the organic modifier molecules or
ions, (Cervantes-Uc et al., 2007) often induces polymer chain de-
gradation upon heating (Bordes et al., 2009).
The Mt nanolayers can also be used as flame retardants for the Mt/
polymer nanocomposites (Mahesh et al., 2013; Chiou et al., 2014; Tai
et al., 2014; Wu et al., 2014; Niroumand et al., 2016). Such nano-
composites with good flame retardancy are highly demanded in air-
crafts, vehicles, electronic devices, construction and housewares (Zhao
and Tan, 2013; Kaynak and Ibibikcan, 2014; Liu, 2014; Niroumand
et al., 2016). The exfoliated Mt nanolayers act as a heat ‘barrier’ and
can form a protective layer of exfoliated Mt nanolayers on the surface of
the polymer during upon heating (Suparanon et al., 2017). The Mt
barriers inhibit mass and heat transfer and prevent oxygen penetration
into the underlying polymer (Mahesh et al., 2013; Niroumand et al.,
2016). Furthermore, exfoliated Mt nanolayers in the polymer matrix
form the tortuous pathways, hence slowing the diffusion of volatiles
upon heat and fire.
When the Mt was added in polymer matrix to produce CPN, the fire
retardancy of CPN can be improved more or less (Kiliaris and
Papaspyrides, 2010; Lao et al., 2011; Tsai et al., 2014). However, the
fire retardancy of many Mt/polymer nanocomposites reported in the
literature still fails to meet the requirements of fire-safety regulations
and standards (Lu and Wilkie, 2010; Lao et al., 2011; Wu et al., 2014).
Namely, Mt nanolayers alone can be used as a simple flame-retardant,
but they only have low effectiveness in flame retardancy. Hence,
combination of additional flame retardants (FR) with Mt (especially
exfoliated Mt nanolayer) remains necessary (Wu et al., 2011; Wu et al.,
2014; Tai et al., 2014; Niroumand et al., 2016). Such flame retardants
include halogenated FR (e.g. hexabromocyclododecane; HBCD;)
(Niroumand et al., 2016), non-halogenated FR (e.g. poly(4,40-diami-
nodiphenyl ether phenyl dichlorophosphate); PDEPD) (Tai et al., 2014;
Niroumand et al., 2016), phosphorus-containing FR (e.g. triphenyl
phosphate; TPP;) (Kandare et al., 2006; Lu and Wilkie, 2010;
Niroumand et al., 2016), nitrogen-containing FR (e.g. melamine cya-
nurate; MCA;) (Tai et al., 2011; Tai et al., 2012; Zhao et al., 2017) and
inorganic FR (e.g. aluminum hydroxide; magnesium hydroxide; boron
compounds) (Liu, 2014; Ibibikcan and Kaynak, 2014). Upon exposure
to the flame, the FR and the Mt nanolayers in the CPN act synergisti-
cally as a protective barrier and are more conducive to forming a stable
char as a thermal shield on the surface of the polymer (Lao et al., 2011;
Niroumand et al., 2016; Yan et al., 2018)). Besides, to improve the
efficiency of flame retardancy, a good method is to disperse exfoliated
Mt in organic flame retardants in advance (Tai et al., 2011; Tai et al.,
2014). Then the flame retardancy of the resultant Mt/polymers can be
T.T. Zhu et al.
better improved.
An opposite paradoxical example is that in OMt/PS nanocompo-
sites, despite good dispersion and exfoliation of OMt nanolayers in the
PS, the flame retardancy properties have even been found to be dete-
riorated in the presence of exfoliated OMt nanolayers (Kiliaris and
Papaspyrides, 2010; Niroumand et al., 2016). A possible main reason is
that the organic surfactants might have a negative influence on flame
retardancy. In addition, many organic flame retardants are not en-
vironmentally friendly or toxic. For instance, when halogenated flame
retardants is added to polymer to resist flame, they produce hazardous
organic compounds or residuals and fumes when the CPN is burnt.
These chemicals are not easily further decomposed and cause toxic
bioaccumulation (Kiliaris and Papaspyrides, 2010; Liu, 2014). There-
fore, a combination of Mt layers with green organic flame retardants are
highly desirable. Nitrogen-containing fire-retardant melamine cyanu-
rate (MCA) had higher thermal stability and low toxicity. Recently, it
has been revealed that Mt-MCA showed excellent dispersion of ex-
foliated Mt nanolayers in the PA6 and the resultant Mt–MCA/PA6 na-
nocomposites showed improved fire retardancy (Zhao et al., 2017).
In addition to the combined use of Mt with organic flame retardants,
recently there are also studies that suggest the use of Mt along with
other inorganic compounds as flame retardants (Waaijers et al., 2013;
Wang et al., 2013; Kaynak and Ibibikcan, 2014; Liu, 2014;). Typically,
thermal decomposition of metal hydroxide produces oxides that can
both retard flame and suppress smoke. Such metal hydroxides can be
magnesium hydroxide (Liu, 2014), aluminum hydroxide, and alu-
minum hydroxide–zinc borate system (Kaynak and Ibibikcan, 2014).
More recently, the OMt and graphene nanosheets as synergistic flame-
retardants have been explored for EVA copolymer nanocomposites
(Wang et al., 2018). Both Mt and graphene are two dimensional, in-
organic, and halogen-free. When the OMt and graphene were well ex-
foliated and dispersed in EVA copolymer matrix, the nanocomposites
exhibited a peak heat release rate value of 529.58 kW m−2 and an
oxygen index value of 24.8%. The excellent flame retardancy was
mainly attributed to the formation of a complete and compact protec-
tive char layer as a result of synergistic facilitation from Mt nanolayers
and graphene nanosheets.
5. Concluding remarks and outlook
Currently, the main routes to exfoliation of Mt for the production of
montmorillonite/polymer nanocomposites are in situ exfoliation, solu-
tion exfoliation and melt exfoliation. For in situ exfoliation, Mt is first
dispersed in a monomer solution, followed by in situ polymerization.
Comparatively speaking, this process can lead to well exfoliated and
dispersed Mt nanolayers in the polymer matrix. However, such in situ
exfoliation of Mt is only feasible when the monomer is soluble and also
needs an in situ polymerization process. To achieve solution exfoliation,
Mt, organic modifiers, additives, solvent and polymer are added into a
single reactor. Solution exfoliation suffers from the difficulty in practice
if the solvent is expensive or toxic. By contrast, melt exfoliation is much
simple and commercially attractive. However, complete exfoliation of
Mt platelets is very difficult to achieve. Of the three techniques above,
melt exfoliation has thus far been shown to be the least satisfactory.
The exfoliation of Mt in a polymer matrix in a cost-effective and
environmental friendly way needs to be explored further. Recent stu-
dies indicate that Ar plasma etching could destroy the van der Waals
forces of layered materials. Such treatment is clean, time-saving, and
non-toxic. It is possible to use such intensification process to exfoliate
Mt In addition, even if Mt alone in the form of solid powder can be well
pre-exfoliated, the reaggregation of exfoliated Mt nanolayers during
storage must be tactically avoided.
Complete exfoliation and homogeneous dispersion of Mt in polymer
matrix remains challenging. The combination of ionic liquid (IL)-
modified Mt and microwave treatment would rapidly facilitate Mt ex-
foliation in a polymer matrix. Furthermore, the underlying mechanism
63
Applied Clay Science 169 (2019) 48–66
of exfoliation in different polymer system and under different circum-
stances remains unclear. To get the deep understanding of the ex-
foliation mechanisms and the interfacial interactions between the ex-
foliated inorganic Mt nanolayers and organic polymer is of paramount
importance. To this end, fine analysis and characterization at a mole-
cular and atomic level, along with molecular simulation or modelling,
are needed.
Undoubtedly, many studies have proved that Mt nanolayers are
conducive to improving the properties of the Mt/polymer nano-
composites in gas barrier, mechanical strength, thermal stability and
fire retardancy. However, for Mt/polymer nanocomposites, the ambi-
tion to take advantage of the Mt nanolayers with substantial improve-
ment of functionalities has not yet been achieved. Besides, the new
assembly of exfoliated Mt nanolayers with functional polymeric mole-
cules and nanomaterials are still open for creating more advanced
functional materials.
Acknowledgments
The authors wish to acknowledge the financial support from the
National Natural Scientific Foundation of China (41672033;
21373185), Zhejiang “151 Talents Project”, the State Key Laboratory
Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang
University of Technology (GCTKF2014006)) and the financial support
by the open fund from Key Laboratory of Clay Minerals of Ministry of
Land and Resources of the People's Republic of China, Engineering
Research Center of Non-metallic Minerals of Zhejiang Province,
Zhejiang Institute of Geology and Mineral Resource, China
(ZD2018K04), China. TTZ drafted the manuscript under the supervision
of CHZ. CHZ conceived the work and made revision many times. KFB
contributed to proofreading.
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