Bergaya F. Handbook of Clay Science
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Review E 57, 4887–4890.
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montmorillonite and vermiculite. Clays and Clay Minerals 10, 123–149.
Pabst, W., Kunes, K., Havrda, J., Gregorova, E., 2000. A note on particle size analyses of
kaolins and clays. Journal of the European Ceramic Society 20, 1429–1437.
Pignon, F., Magnin, A., Piau, J.M., Cabane, B., Lindner, P., Diat, O., 1997. Yield stress
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Chapter 12.5: Small-Angle Scattering Techniques906
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References 907
Handbook of Clay Science
Edited by F. Bergaya, B.K.G. Theng and G. Lagaly
Developments in Clay Science, Vol. 1
r 2006 Elsevier Ltd. All rights reserved.
909
Chapter 12.6
FOURIER TRANSFORM INFRARED SPECTROSCOPY
S. PETIT
UMR 6532, HydrASA, F-86022 Poitiers Ce
´
dex, France
Infrared (IR) spectroscopy is a technique based on vibrations of atoms in a
molecule. The IR spectrum of a clay mineral is sensitive to its chemical composition,
isomorphous substitution and layer stacking order. This makes Fourier Transform
Infrared (FTIR) spectroscopy, the most informative single technique for assessing
the mineralogy and crystal-chemistry of a clay mineral sample. This chapter sum-
marizes the potential of FTIR for clay mineral studi es.
12.6.1. PRINCIPLE AND METHODS
The absorption of IR radiation by clay minerals depends critically on atomic
mass, and the length, strength and force constants of interatomic bonds in the
structures of these minerals. Absorption is also influenced by the overall symm etry of
the unit cell, and the local site symmetry of each atom within the unit cell. Since
theory alone gives only limited crystallo-chemi cal information, the interpretation of
IR spectra is generally done by empirically assigning the observed signals to vibra-
tional modes. Structural investigations of well-characterized families of natural and
synthetic clay minerals played an essential role in relating spectral features to mineral
structures. The monograph by Farmer (1974), provides one of the most useful texts
on the IR spectra of clay minerals. Since then, however, many spectr a were modeled
using increasingly complex calculations. The recent modeling study by Balan et al.
(2001) showed that the major features in the IR spectrum of kaolinite can be cor-
rectly reproduced.
The detector in FTIR spectrometers continuously monitors the full wavenumber
range of radiation emitted by the IR source. A computer is needed to transform this
information into an absorption spectrum. FTIR spectrometers may be either single
beam (where the background must be substracted to the sample) or double beam
(where the background is continuously substracted from the sample) producing a
transmittance spectrum. Most systems multiply the transmittance value by 100, to
give percent transmittance (T). However, the absorbance (A) scale, where
DOI: 10.1016/S1572-4352(05)01032-9
A ¼ln(T/100), is more and more used for quantitative analysis, following Beer’s
law that there is a linear relationship between absorbance and sample concentration.
So far, FTIR spectroscopy was mainly used in the middle infrared (MIR) region
(4000–300 cm
1
) where the fundamental vibrational modes appear. The pressed discs
technique is most used for routine studies in this region. Here the sample is dispersed,
(usually) in KBr, at a sample/KBr ratio of about 1% and pressed into a disc. Discs
may be heated at 120 1C ov ernight to remove absorbed water, whose IR bands can
overlap with those of the sample.
The near infrared (NIR) region (11,000–4000 cm
1
), showing the first overtone
(2n) and combination (n+d) vibrations of the OH groups, is useful for the study of
OH vibrations. The diffuse reflectance technique (DR IFT) is especially appropriate
in the NIR region. In contrast to the MIR region, this technique does not require
dilution of the sample. Thus, the IR analysis can be done very quickly and non-
destructively. It is worth noting that remote-sensing and field spectrometers work
exclusively in the NIR (and visible) region. Hunt and Salisbury (1970) and Hunt
et al. (1973) compiled the NIR spectra of some clay minerals.
Appropriate methods of sample preparation, such as sedimentation and precip-
itation are used for specific investigations. For example, microscopy allows IR
spectra to be obtaine d from samples as small as 12 mm in diameter.
12.6.2. MINERALOGICAL APPLICATIONS
The application of IR spectroscopy to the identification of clay minerals was
reviewed by Russell and Fraser (1994) who presented spectra of many types of clay
and associated minerals. They also included some repres entative soil clays, indicating
how IR spectra may be used to assess the constituent minerals in a given sample.
Other useful compilations of IR spectra are those by van der Marel and Beutel-
spacher (1976), Moenke (1962, 1966) and Ferraro (1982), but these are less focused
and detailed than the rewiew by Russell and Fraser (1994). IR spectroscopy is a
useful supplement to XRD for detecting mineral impurities, notably the presence of
kaolinite, calcite and quartz in bentonite (Madejova
´
and Komadel, 2005), and for
distinguishing between X-ray amorphous and poorly crystallized clay minerals. This
capability is very useful in following clay mineral crystallization during clay mineral
syntheses (Decarreau, 1980). IR spectroscopy is also a powerfull technique for dis-
criminating between different kaolinite polymorphs (Prost et al., 1989).
12.6.3. CRYSTALLO-CHEMICAL APPLICATIONS
The vibrations of layer silicates can be more or less separated into those of the
constituent units: the OH groups, the silicate anion, the octahedral cations and the
interlayer cations if any. Of these, the vibrations of the OH groups are very slightly
Chapter 12.6: Fourier Transform Infrared Spectroscopy910
dependent on the vibrations of the rest of the structure. However, they are markedly
influenced by the ions to which the OH groups are coordinated.
The vibrations of the OH groups are the most fully understood and studied
because they are very sensitive indicators of their environment. In published quan-
titative results, the absorption coefficients of the OH stretching (nOH) vibration
bands are assumed to be constant, whatever the local chemistry around OH groups
within dioctahedral (Slonimskaya et al., 1986; Madejova
´
et al., 1994; Besson and
Drits, 1997) and trioctahedr al clay minerals (Papin et al., 1997; Petit et al., 2004b).
The absorbance of each OH band is then proportional to the number of absorbi ng
centres of each type. When all the OH vibration bands occurring in the FTIR spectra
are correctly assigned, the FTIR spectra can be quantitatively used. Using an en-
vironmental IR microbalance cell, Xu et al. (2000) found that the molar absorptivity
of the OH bending vibrations (d OH) varies with the H
2
O content. A number of
reviews about the factors affecting the OH vibrations in clay minerals were published
(Vedder, 1964; Velde, 1983; Robert and Kodama, 1988; Petit et al., 1995; Besson and
Drits, 1997; Gates, 2005). The OH vibrations are affected by the octahedr al cations
to which the OH group is coordinated, and to a lesser degree, by the tetrahedral, and
interlayer environments.
A. The Octahedral Environment
In the simple case of talc where there are neither multivalent substitutions nor vacant
sites, the OH groups point perpendicularly toward the hole of the hexagonal cavity.
The nOH wavenumber of the Mg
3
OH group remains almost constant at 3677 cm
1
even when other divalent cations such as Ni
2+
,Co
2+
,Zn
2+
are present in the
octahedral sheet. Solid-solutions between end-members can be easily obtained by
hydrothermal syntheses (Petit, 2005). When Mg
2+
is replaced by another cation, the
difference in properties (electronegativity, atomic mass and cation size) between
Mg
2+
and the substituted ion changes the wavenumber of the nOH (Table 12.6.1).
Up to four OH vibration bands can be distinguished when Mg
2+
is partially re-
placed by another divalent cation. These bands correspond to the four possible
combinations of the two different cations within three octahedral sites that are
directly linked to an OH group (Fig. 12.6.1). The content of each octahedral cation
can be obtained as a sum of the absorbances of the bands of those OH groups to
which the cation is coordinated.
As low as o0.01 Fe
2+
or Al
3+
ions per half-unit cell can be detected in natural
talcs from the NIR region (2nOH bands), while the sensitivity is almost half that in
the MIR region (nOH bands) (Petit et al., 2004b). Using nOH bands, Madejova
´
et al.
(1994) and Besson and Drits (1997) were able to estimate the populations of oc-
tahedral cati ons for dioctahedral smectites and fine-grained micaceous clay minerals,
respectively. Cuadros and Altaner (1998) also obtained good agreement between the
IR and chemical data of mixed-layer illit e-smectite in bentonites, using the d OH
bands (960–750 cm
1
). Gates et al. (2002) determined the Al
3+
and Fe
3+
site
12.6.3. Crystallo-Chemical Applications 911
occupancies in ferruginous smectites and nontronites from the octahedral Al
3+
content of the samples, using the OH combination bands in NIR. After ensuring that
the octahedral chemical composition agrees with chemical an alyses, the order–dis-
order cationic distribution can also be quantified. This was done by Wilkins and Ito
(1967) and Petit et al. (2004b) for talc; by Madejova
´
et al. (1994) for smectite; and by
Besson and Drits (1997) for celadonite-glauconite.
B. The Tetrahedral Environment
Synthetic talcs with subtitution of Ge
4+
for Si
4+
show a shift of the nR
3
OH bands of
almost 40 cm
1
toward lower wavenumbers (Table 12.6.1), indicating the strong
influence of the tetrahedral environment on the nOH bands.
In natural clay minerals, the major changes in tetrahedral environment are due to
multivalent substitutions of Al
3+
and Fe
3+
for Si
4+
. Even if the sensitivity is less
than for the octahedral environment, several features in the IR spectra are observed
Table 12.6.1. Wave numbers of the nR
3
OH bands for synthetic talcs
M
IV
R nR
3
OH (cm
1
)
Si Mg 3677
Si Ni 3627
Si Fe
2+
3624
y
Si Co 3631
Si Zn 3641
Si Cu 3656
y
Ge Mg 3635
Ge Ni 3584
Ge Co 3586
From Petit et al. (2004a)
y
For partially substituted samples from Wilkins and Ito (1967).
absorbance
2νMgFe
2
OH
7240 7200 7160 7120 7080 7020
wavenumber (cm
-1
)
2νMg
3
OH
2νMg
2
FeOH
2 Fe
3
OH
Fig. 12.6.1. First overtone R
3
OH vibration bands in the FTIR spectrum of a natural un-
usually iron-rich talc from the Sterling mine, Antwerp, USA.
Chapter 12.6: Fourier Transform Infrared Spectroscopy912
that are related to the degree of tetrahedral substitution such as the appearance of
the Si-O-Al
IV
band and the shift of nOH and dOH bands (Russell and Fraser, 1994).
C. Interlayer Cations
Vibrational modes of the interlayer cation are typically very low in frequency and
occur in the far IR region (50–150 cm
1
). This region is suitable for studying the
interlayer environment of clay minerals, using the interlayer cations as probes.
However, only cations with low hydration energies in anhydrous clay minerals can
be studied (Fripiat, 1981; Prost and Laperche, 1990; Laperche and Prost, 1991;
Schroeder, 1992; Diaz et al., 2002).
Especially for relatively high-charge clay minerals, the spectra in the nOH region
may change with the interlayer composition due to repulsion between the charge-
balancing cation and the protons of the OH groups. For example, in K
+
-saturated
synthetic saponites (Fig. 12.6.2), two bands are observed at 3712 and 3677 cm
1
.
Both are n Mg
3
OH bands, the latter being due to unperturbed Mg
3
OH groups as in
talc, and the former to Mg
3
OH groups perturbed by K
+
(Pelletier et al., 1999). The
position of the perturbed OH varies with the cation, revealing the strength of re-
pulsion (Diaz et al., 2002).
One interesting inorganic interlayer cation that can be studied in the MIR region
is ammonium. This cation shows two main absorption bands near 1400 and
3200 cm
1
due to the N2H vibrations. The band near 1400 cm
1
can be used to
measure the concentration of ammonium in clay minerals (Petit et al., 1998). The
only limitation is that the sample has to be free of carbonate because of band overlap.
The position and the shape of the band near 1400 cm
1
depend on the symmetry of
the NH
4
+
ion, and is indicative of where isomorphous substitution occurs (Chourabi
and Fripiat, 1981; Pironon et al., 2003). Using the pellet technique, this band can also
3712
3677
365037003750
wavenumber (cm
-1
)
absorbance
0.35
0.5
0.8
Fig. 12.6.2. FTIR spectra in the nOH region of K
+
-saturated saponites (synthesized by J.L.
Robert, Orle
´
ans, France). The bold numbers denote the layer charge per half unit cell.
12.6.3. Crystallo-Chemical Applications 913
indicate the exchangeability of NH
4
+
by other cations (Petit et al., 1999). This allows
the amount and the origin of the layer charge (compensated by NH
4
+
) to be quan-
tified. Similarly the proportion of different clay minerals in mixtures such as NH
4
+
-
illite/smectite (Lindgreen, 1994), gel/illite crystallization ratio in syntheses experi-
ments (S
ˇ
ucha et al., 1998) can be assessed by this method. Using the ammonium
signal, Mortland and Raman (1968) studied the surface acidity of smectites, while
Joussein et al. (2001) used this signal to measure the molar absorption coefficient
ratio between kaolinite and smectite. They found a value of about 5, which accords
with the value deduced by Madejova
´
et al. (2002) from spectral decompositions.
12.6.4. ADSORPTION PHENOMENA
A. Clay– Water Interactions
Water molecules that are strongly hydrogen-bonded exhibit different vibrational
properties from those that are weakly bonded to the oxygen atoms of the silicate
anions. This offers a good opportunity for IR studies. The interactions of water with
smectites were extensively investigated (e.g. Prost, 1976 ; Farmer, 1978; Poinsignon et
al., 1978; Sposito and Prost, 1982; Johnston et al., 1992; Xu et al., 2000).
Two distinct environments of sorbed water can be shown: (i) water molecules
directly coordinated to exchangeable cations; and (ii) those occupying the pores. When
the water content is low, the water molecules strongly coordinated to the exchangeable
cations are polarized, the more so when the cation has a high hydration energy.
One point to emphasize for quantitative studies is that the absorption coefficient
for the n
2
band of water (near 1630 cm
1
) varies with the water content of the clay
mineral (Johnston et al., 1992). In the overtone range (NIR region), the extinction
coefficient of OH involved in strong hydrogen bonding is much smaller than that in
the fundamental range (MIR region). This facilitates the study of water molecules that
interact with clay minerals (Prost, 1975; Cariati et al., 1981, 1983; Bishop et al., 1994).
B. Clay– Organic Interactions
IR spectroscopy is extensively used to study the clay–organic intercation. An abun-
dant literature exists on the use of IR to study pesticides adsorption by clay minerals
(Cox et al., 1994; Pusino et al., 2003) and organo-clays (Hermosı
´
n and Cornejo,
1993; Cox et al., 2001). Dichroism measurement s are often used to study the ori-
entation of the functional groups of the organic species ( Serratosa, 1966; Vimond-
Laboudigue and Prost, 1995; Sheng et al., 2002).
The surface acidity of pillared clay minerals is commonly measured by pyridine
adsorption followed by IR spectroscopy. Besides being able to identify the type of
acid sites present, this method can provide a semi-quantitative evaluation of acid
strength (Carvalho et al., 2003).
Chapter 12.6: Fourier Transform Infrared Spectroscopy914
IR spectroscopy was often used to show the intercalation and solvation of organic
molecules into kaolinite. Upon intercalation, the hydrogen bonds between the inner
surface hydroxyls and the siloxane of the next adjacent layer is replaced by those
between the kaolinite and the intercalated molecules.
IR spectroscopy was used to calculate the contribution of hydrogen bonding to
the intercalation process. A recent review of IR (and Raman) studies dealing with the
intercalation of organic compounds (formamide, hydrazine, dimethyl sulphoxide
(DMSO), potassium and cesium acetates) is that by Frost and Martens (2005). Yariv
et al. (2000) used IR spectroscopy to study the intercalation of potassium halides by
DMSO-kaolinite. Only in the case of KCl does a new band appear at 3652 cm
1
due
to the inner OH groups. They suggested that the Cl
ions penetrate into the di-
trigonal holes forming hydrogen bonds with the inner OH groups. On the other
hand, Br
and I
ions are too large to enter the ditrigonal cavities.
12.6.5. CONCLUSIONS
FTIR spectroscopy is a rapid, economical, easy and non-destructive technique
deserving of being used more widely in clay mineral investigations. The development
in FTIR spectrometers greatly enhanced the field of applications. Modern instru-
ments high sensitivity, speedy data collection, enhanced spectr al precision and re-
producibility. Efficient computers enable routine transmission methods to be
improved. They also allow the use of different reflectance techniques that are diffi-
cult to implement with classical dispersive instruments.
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Chapter 12.6: Fourier Transform Infrared Spectroscopy916