Overview: Clay Preparation, Properties,

Chapter
1
Modification
Khouloud Jlassi1, Igor Krupa1 and Mohamed M. Chehimi2
1
Qatar University, Doha, Qatar; 2Paris Est University, CNRS, Thiais, France

1. OVERVIEW ON CLAYS
1.1 Introduction
The word “clay” has two connotations, one related to grain size and
the other to mineralogy, and this depends on the relevant discipline because
there is no single definition of the term. According to geologists and
pedologists, “clay” is any fine-grained mineral, the limit being set at 2 or
4 microns as appropriate. In mineralogical terms, clay minerals are generally
the small hydrated phyllosilicates.
Clay minerals and clays are explored in many areas. For geologists, clays
provide information on environmental conditions (source, formation
conditions, diagenesis, etc.). Petroleum engineers deduct the thermal
conditions from deposits (degree of maturation). Civil engineers focus on
clay properties as industrial equipment (refractories, building materials).
Agronomists and physical chemists analyze, for example, the hydration
and adsorption properties of clays to design fertilizers, catalysts, or modified
clays for decontamination or nanocomposites based on clays for various
applications.
The great deal of attention in the research field of clay by many laboratories
in the world is because of their abundance in nature and low cost, but
mostly because of their unique crystal structures, which give clay materials
special properties, including high surface area, surface electric charges, and
cation exchange capacity (CEC). CEC is responsible for hydration,
swelling, plasticity, and thixotropy that certain clays exhibit in water.

1.2 Crystal Structure and Classification of Clays

Most clay minerals are made by a stack of sheets. These layers are made by
a stack of tetrahedral and octahedral layers that shape the frame of all clay

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2 CHAPTER 1 Overview: Clay Preparation, Properties, Modification

mineral assemblage. Tetrahedrons are linked to each other by a corner, thus

forming a hexagon, while octahedrons are by one side.
Chemically, four oxygen atoms form tetrahedrons, the tetrahedral cavity
being occupied by a cation, usually Si4þ or Al3þ. Ideally, octahedral layers
are constituted by six OH groups, but OH groups of layers included in the
structure are replaced by the apical oxygen atoms of tetrahedrons. However,
octahedrons are known to bear a negative valence of 6, which is compen-
sated by the cationic filling of the three octahedral cavities. Two main groups
can be identified for each clay family: dioctahedral clays, for which
two-thirds of octahedral cavities are filled with trivalent cations (Al3þþ,
Fe3þ, etc.), and trioctahedral clays where all the octahedral cavities are filled
by divalent cations (Fe2þ, Mg2þ, etc.).
The arrangement of these tetrahedral and octahedral layers makes it possible
to discern three main types of clay (Table 1.1):
n 1:1 or TO type (1 octahedral sheet and 1 tetrahedral sheet; Fig. 1.1A),
with equidistance (interlayer distance) of 0.7 nm. The 1:1-type clays
vary according to the position of available vacancies in sheets. All
elements are disturbed so that the elementary sheet is electrically
quasineutral. Interlayer space thus includes almost no cations.
Successive sheets are stacked such that the oxygen level of a sheet is
in front of the hydroxyl groups of the close sheet. As a result of such
a layout, the network is stabilized by interlayer hydrogen bonds.
Particles (stack of sheets) are tough platelets whose lateral extension is
a few hundred nanometers and thickness a few tens of nanometers.
n 2:1 or TOT type (1 octahedral sheet between 2 tetrahedral sheets;
Fig. 1.1B), for which the interlayer distance is 1 nm when sheets are
closed.
Generally, for 2:1 clays, isomorphic substitutions are observed, e.g.,
possible substitutions of Si4þ in tetrahedrons by Al3þ or those of
Al3þ in octahedrons by Fe2þ. Such substitutions lead to permanent
negative surface charge at the sheet level. This negative charge is
compensated by the presence, in the interlayer space, of cations
called “compensator cations” or “interlayer cations” or in some
cases “exchangeable cations.”
For certain clays of this type, with a sheet filler deficit of between 0.2
and 0.9, the compensator cations with their hydration water enter the
interlayer space and thus induce a particle swelling. In this case the
basal distance is a function of the valency of the cation, and thus of
the number of water molecules related to those cations. The basal
distance increases according to the number of water molecules
 1. Overview on Clays 3

Table 1.1 Classification of Clay Minerals [3]

MINERALS 1/1 DIOCTAHEDRALS TRIOCTAHEDRALS

1T þ 1O ¼ 4,5 Å KAOLINITE SERPENTINE

Sheet electric charge Kaolinite, dickite, nacrite Amesite, berthierine,
1T þ 1O þ Interlayer space z 7 Å chrysotile, antigorite,
lizardite, cronstedtite,
greenalite

MINERALS 2/1 DIOCTAHEDRALS TRIOCTAHEDRALS

1T þ 1O þ 1T ¼ 7 Å PYROPHYLLITE TALC
Sheet electric charge
1T þ 1O þ 1T þ Interlayer space z 9 Å
Sheet electric charge: from 0.2 to 0.6 SMECTITES SMECTITES
1T þ 1O þ 1T þ Interlayer space z 18 Å Al: montmorillonite, Mg: saponite, stevensite,
Interlayer space: cations  hydrated beidellite hectorite
(Ca, Na) Fe: nontronite
(Ch: 10 Å; 2H2O: 14 Å; EG: 17 Å)
Sheet electric charge: from 0.6 to 0.9 VERMICULITES VERMICULITES
1T þ 1O þ 1T þ Interlayer space z 15 Å
Interlayer space: cations  hydrated
(Ca, Na)
(Ch: 10 Å; 2H2O: 14 Å; EG: 14 Å)
Sheet electric charge [ 0.9 ILLITE, GLAUCONITE
1T þ 1O þ 1T þ Interlayer space z 10 Å
Interlayer space: nonhydrated cations (K)
Sheet electric charge [ 1 SOFT MICA MICAS
1T þ 1O þ 1T þ Interlayer space z 10 Å Al: muscovite, MgeFe: biotite, lepidolite,
Interlayer space: nonhydrated cations phengite, paragonite phlogopite
(K, Na) Fe: celadonite
Sheet electric charge: 2 HARD MICA
1T þ 1O þ 1T þ Interlayer space z 10 Å Al: margarite, clintonite
Interlayer space: nonhydrated cations (Ca)

MINERALS 2/1/1 DIOCTAHEDRALS TRI-TRIOCTAHEDRALS

Variable sheet electric charge CHLORITES CHLORITES

1T þ 1O þ 1T þ 1O Interlayer Donbassite Diabantite, penninite,
space z 14 Å CHLORITES chamosite, brunsvigite
Interlayer space: octahedral sheets

Ch, chloroforme; EG, ethylene glycol.

(w1.26 nm for a water monolayer, w1.4e1.5 nm for a bilayer, and

w1.9 nm for a trilayer). When sheet filler deficit is greater than or
equal to 0.9, compensation can be provided by the presence in
the interlayer space of nonhydrated cations (Kþ). Basal distance
is close to 1 nm. The main 2/1 clay groups are smectites,
vermiculites, and illites.
4 CHAPTER 1 Overview: Clay Preparation, Properties, Modification

Si Couche octaédrique
Al
O Espace interfoliaire
OH

Couche tétraédrique
(A) Type 1:1 d

Couche octaédrique

Si
Al Couche tétraédrique
O
H
Espace interfoliaire

(B) Type 2:1

Couche tétraédrique
d

Couche octaédrique

Couche tétraédrique

n FIGURE 1.1 Crystal structures of clay minerals: (A) type 1:1 and (B) type 2:1. d stands for the basal
distance [1].

n 2:1:1 or TOTO type for which the feature equidistance is about 14 Å.

The interlayer space may be empty or filled by anhydrous or hydrated
cations. The 2:1:1 clays are composed of mica-type sheets (2:1) with
negative charge (mainly caused by tetrahedral substitution of Si4þ per
Al3þ), but the deficit this time is compensated for in the interlayer
space with a layer of positively charged octahedrons. Octahedral
cations, either in 2:1 sheet or in the octahedron in the interlayer
position, are mainly Fe2þ and Mg2þ. The positive charge in the
interlayer octahedron is mainly induced by the presence of Al3þ or
Fe3þ ions in substitution for divalent cations. These many substitutions
are theoretically divided into four types: tri-tri, tri-di, di-tri, and
dioctaedric (the first for the 2:1 sheet, the second for an interlayer
sheet). Di-tri and trioctahedral are most frequently encountered and
form the chlorite group (Fig. 1.2).
 1. Overview on Clays 5

n FIGURE 1.2 Representation of a chlorite structure [2].

For different types of clay sheets are held together through cohesive forces
(van der Waals force) and possibly, in the case of 1:1 clays (TO),
by hydrogen bonds between hydroxyl groups of the octahedral layer and
oxygen atoms of the tetrahedral layer of the close sheet. The sheet
thicknesseinterlayer space is called the “basal distance” and it is an essen-
tial feature of clays, particularly the modified ones.
The classification of clay minerals remains difficult because microcrystal-
line species that form them are subject to variations in composition
because of the many possibilities of substitutions. Therefore the nomen-
clature and classification of clay minerals have evolved over time. The
classification adopted by the Nomenclature Committee of the Interna-
tional Association for the Study of Clays (AIPEA) relies on major
structural data:
n The combination of sheets (T/O or 1/1; T/O/T or 2/1; T/O/T/O or
2/1/1);
n The type of cation in the octahedron;
n The cationic filler interlayer;
n The type of compounds in the interlayer space (cations, water
molecules, etc.).
And three main groups are identified:
n The phyllitic clays;
n The fibrous clays;
n The interlayered clays.
6 CHAPTER 1 Overview: Clay Preparation, Properties, Modification

1.2.1 The Phyllitic Clays

The phyllitic clays are by far the most widespread and most studied. Their
classification into large groups is based, first, on how structural layers are
associated and, second, on the extent of occupancy of the octahedral layer
sites (di- or trioctahedral character).
The most famous group of 1:1 clays is the kaolinite group marked by a
basal distance of about 7 Å, a dioctahedral character, and a surface charge
of almost zero. The ideal structural formula is Al4Si4O10 (OH).
The best known and most studied group of 2:1 clays is the smectites marked
by a very variable structure because of the many tetrahedral and octahedral
substitutions. Therefore there are many varieties of dioctahedral and
trioctahedral smectites (Table 1.2).
One of the smectites’ characteristic properties is that their interlayer cations
are hydrated and easily exchangeable (Fig. 1.3). The physicochemical
characteristic properties of this group will be detailed in Section 1.3 because
it is the most used clay for clayepolymer nanocomposite synthesis.
The most usual and best known 2:1:1 clay group is the chlorite group.

Table 1.2 Different Types of Smectites [4]

 1. Overview on Clays 7

n FIGURE 1.3 Structure of a hydrated smectite [5]. The smectite clay unit cell is framed by the assembly of an Al octahedral sheet inserted between two Si
tetrahedral sheets. The arrangement is known as TOT, where water molecules and cations invade the space between the TOT layers as described in (A). Two
outer tetrahedral layers comprised of silica and oxygen atoms are stacked with an inner octahedral layer (B) containing Al and Mg atoms, which are bonded to
oxygen or the hydroxyl group.

1.2.2 The Fibrous Clays

The fibrous clays are aluminosilicates whose crystalline structure is 2/1
type having a lateral extension limited to a few numbers of tetrahedrons
and octahedrons according to the b-axis, thus turning sheets into
rectangular sectioned strips. The width of these strips is characteristic
of each group. The two main fibrous clay groups are sepiolites and palygor-
skites (Fig 1.4).

n FIGURE 1.4 Schematic representation of the structural and textural characteristics of fibrous clays:
(A) sepiolite structure and (B) palygorskite structure. Reproduced with permission of Elsevier from
E. Ruiz-Hitzky, M. Darder, F.M. Fernandes, B. Wicklein, A.C.S. Alcântara, P. Aranda, Fibrous clays based
bionanocomposites, Progress in Polymer Science 38 (2013) 1392e1414.
8 CHAPTER 1 Overview: Clay Preparation, Properties, Modification

1.2.3 The Interlayered Clays

Interlayering occurs as a result of the random or ordered stacking, as per the
c-axis, of two species or more of clay minerals. The possible combinations
between different minerals are extremely numerous, but only a few of them
represent the majority of natural interlayered clays. Three categories are
identified:
Alternating interlayered: In this case the clay particle contains
A-type sheets and B-type sheets stacked alternatively (ABABAB), etc.
Therefore a structure stage appears perpendicular to sheets equal to the
individual sum of the two types of sheets.
Segregated interlayered: Stacking is AAABBB type. The X-ray
diffractogram characteristic of such a binary interlayer is the sum of A
and B phase diffractograms.
Irregular interlayered: In this case the law of succession obeys the
law of chance. There is no periodicity along the c-axis.

1.3 Physicochemical Properties of Smectites

1.3.1 Specific Surface Areas
One of clays’ characteristics, particularly smectites, is their large surface
relative to their mass (specific surface area). As per all finely divided
minerals, this characteristic gives smectites the property of adsorbing water
or organic molecules such as glycerol or ethylene glycol. Two specific
surface areas for smectites are identified: the external surface between
particles and the internal surface corresponding to the interlayer space.
The total specific surface area is defined as the sum of both.
Table 1.3 reports the usual values of specific surface area of smectites and
other clays.

Table 1.3 Specific Surface Areas of Some Clays [5]

Internal Surface External Surface Total Surface
Clay (m2/g) (m2/g) (m2/g)

Kaolinite 0 10e30 10e30

Illite 20e55 80e120 100e175
Smectites 600e700 80 700e800
Vermiculite 700 40e70 760
Chlorite e 100e175 100e175
 1. Overview on Clays 9

1.3.2 Cation Exchange Capacity

CEC measures the ability of clay to exchange its interlayer cations. It
is defined as the amount of matter of elementary fillers carried by the
interlayer cations that can be exchanged to balance the electrical charge
of 100 g of calcined clay. It is expressed in milliequivalents per 100 g
of calcined clay so that results do not vary with the degree of hydration
(moisture) of the clay.
The CEC is the principal key in clay organic modification. Table 1.4
includes the usual values of the CEC of smectite and other clays.

1.3.3 Swelling of Smectites

This property is generally attributed to smectitic clays, which have the
characteristic of swelling in the presence of water and are called “swelling
clays.” Their ability to absorb a large amount of water is caused by two
factors: the large specific surface area that has a large number of hydrophilic
compensating cations on the one hand, and sheet flexibility that creates
pores within sheets, particles, and aggregates, on the other hand. Water
related to sheets by cation hydration and free water contained in the pores
can be identified at different scales.
When a dry smectitic clay powder comes into contact with water, three
swelling steps occur.
On initial contact with water, water molecules enter the interlayer space and
hydrate cations through a cationedipole bond. Water molecules are also
adsorbed on sheet surfaces and form successively a first, a second, and
then a third pseudolayer of adsorbed water, and therefore contribute to
the interlayer distances, respectively, distinct values of 1.2e1.5 and
1.9 nm without intermediate values.
By further increasing the amount of water, an osmotic swelling occurs,
causing a separation of particles that increases the interlayer distance

Table 1.4 Cation Exchange Capacity (CEC) of Some Clays [5]

Clay CEC (meq/100 g of Calcined Clay)

Kaolinite 5e15
Illite 10e40
Smectites 80e150
Vermiculite 100e150
Chlorite 10e40
10 CHAPTER 1 Overview: Clay Preparation, Properties, Modification

from 19 to 40 Å. The coexistence area of the two interlayer distances 19 and

40 Å is called the “osmotic transition” area.
The second step relates to clay paste formation, characterized by a constant
increase of interlayer distance as the amount of water increases.
When clay paste passes from the “rigid gel” to the “soft gel,” this change is
called the third step of swelling. When “soft gel” passes to a suspension
to the ground state it is no longer part of the swelling, but it is the
so-called solegel transition, which is so important in clay studies and
applications [7e9] such as dynamic light scattering alteration, fluidity
loss, and fluorescence enhancement [10].

2. ORGANOMODIFICATION OF SMECTITE
All clay types employed for clayepolymer nanocomposite preparation are
premodified materials. Modification starts with a purification step, which
is a long and time-consuming process, leading most of the time to sodium
clays. This purification step is beyond the scope of this chapter, which
concentrates rather on the modification of purified clays. There are simple
and more elaborated chemical and physical processes of modification;
herein we concentrate on organomodification using onium salts and organo-
silanes. For Brönstedt acidic or basic pretreatment over the entire pH range,
modification affects the clay as follows.
Hydroxylation is conducted at basic medium, as described by Wenbo Wang
et al. [11]. With moderate alkali activation at pH < 5, adsorptive removal
capability for methylene blue was found to be improved. Indeed, this alkali
activation can moderately break the SieOeM and SieOeSi bonds and
remove the metal cations (i.e., Al3þ, Mg2þ) and Si in the crystal backbone
of phyllosilicate by which new adsorption sites were created and the surface
negative charges were increased. In contrast, some acid treatment leads to an
effective modification method to increase the surface area of clay. Note,
however, that moderate acidic modification can be an inexpensive and
effective method to increase the surface area of clay from 103 to 272 m2/g
as described by Irani et al. [12]. However, extensive dissolution of the inner
AleOH surface is initiated, which is catalyzed by acid or basic species,
which might alter the structure of clay, therefore leading to a decrease in
the Si/Al atomic ratio. In addition, the rod-like morphology is severely
altered or even disappears, while BrunauereEmmetteTeller specific surface
area increases [13].
In the following, and where appropriate, we will indicate whether or
not pretreatment at controlled pH was conducted for the case studies of
 2. Organomodification of Smectite 11

organomodification of smectites because such modification affects this kind

of layered silicate significantly compared to other clay series.
Smectites being highly hydrophilic are incompatible with the majority
of polymer matrices, usually organophilic. Therefore the purpose of a
smectitic clay organic modification is to make the clay organophilic for
the manufacture of clayepolymer nanocomposites. Of the methods of
organophilic modification, cation exchange is the most commonly
implemented [12e14], and has been since the 1987 seminal work of
researchers at Toyota Central Research and Development Labs [15]. These
researchers intercalated montmorillonite (MMT) with ammonium salts with
terminal carboxylic acid groups prior to mixing with nylon-6 to provide
intercalated clayepolymer nanocomposites. However, other interesting
and original methods were developed, such as organosilane [16], iodonium
[17], and diazonium salt grafting [18]. The main routes of clays modifica-
tions are summarized in Table 1.5.

Table 1.5 Summary of Main Organomodification Routes of Clays

Method/ d Spacing Mass
Organic Compounds Clays Conditions (nm) Loading Structure References

3-Aminopropyl MMT Silylation 1.49 0.33 g: Intercalated [19]

triethoxy silane 50 C 1.63 1 g MMT
24 h 2 0.53 g:
2.1 1 g MMT
1.00 g:
1 g MMT
1.5 g:1 g
MMT
Sodium dodecyl MMT 3.87 nm 3 CEC Intercalated [20]
sulfate acidic medium
ultrasound assisted
Diazonium Bentonite Cation 1.37 0.6 CEC Intercalated [21]
4-diphenylamine exchange 1.62 1.3 CEC Intercalated
diazonium salt and covalent d(001) peak 2 CEC Exfoliated
grafting disappear
60 C
3h
Ionic liquids: Smectite Cation 4.2 nm 2 CEC Intercalated [22]
exchange
Octadecyl triphenyl 80 C 3.7 2 CEC
phosphonium salt
N-octadecyl-N0- 6h
octadecylimidazolium salt
Phosphonium salt MMT Ion exchanged d(001) peak 1 g salt: Exfoliated [23]
RT, 24 h, HCl disappear 1 g MMT

CEC, cation exchange capacity; MMT, montmorillonite; RT, room temperature.