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P E T E R L. H A L L
Department of Chemistry, University of Birmingham, P.O. Box 363, Birmingham B15 2TT
ABSTRACT: Electron spin resonance (ESR) spectroscopy has contributed significantly to the
identification and characterization pf paramagnetic impurities associated with clays, Following a
brief discussion of the general principles of the technique, a review is given of the application of
ESR to the study of those paramagnetic species (chiefly iron and radiation-induced lattice defects)
located either within the aluminosilicate structure or present as an external impurity phase.
In recent years a number of relatively modern physical techniques have been increasingly
utilized in investigations of structural and physicochemical properties of clay minerals.
One of these, electron spin resonance (ESR) spectroscopy, has now become a significant
tool in clay mineral research and a large number of papers have been wholly or partially
devoted to the interpretation of ESR spectra arising from paramagnetic ions or radicals
associated with clays.
Though the ESR method is restricted to a certain range of paramagnetic species, it can
yield a wide range of detailed information relating to:
(a) the occurrence and location of paramagnetic substitutional impurities and lattice
defects (trapped hole or electron centres) in clays;
(b) the extent of structural disorder and nature of thermal phase transitions of clay
minerals;
(c) the nature of paramagnetic impurities associated with clay surfaces, including
organic radicals and transition metal oxides and hydroxides;
(d) the mobility of hydrated ions in the interlamellar space of expanding lattice clays
utilizing transition metal ions or organic radical cations as 'spin probes';
(e) the distribution of lattice charge sites in clays;
(f) the reactions of adsorbed molecules on the external and interlamellar surfaces
involving the formation and stabilization of free radicals.
It should not be forgotten, however, that natural materials are far from the spectro-
scopist's ideal of well-characterized, pure single crystals. Apart from work reported here
on micas and vermiculites, most studies have been made on powder samples containing
paramagnetic species either isomorphously substituted in the aluminosilicate lattice or
present as a surface-adsorbed or dispersed impurity phase. In these circumstances care is
required in the interpretation of experimental data. Moreover, it is desirable to compar e
0009-8558/80/12~)0-0321502.00 9 1980 The Mineralogical Society
322 P. L. Hall
the ESR data with that provided by other techniques (e.g. M6ssbauer or photoelectron
spectroscopy) and to utilize physical or chemical methods of sample refinement, e.g.
chemical pretreatment or magnetic separation.
A review of ESR studies on clays to the end of 1973 has been published (Che et al.,
1974).
Part I of the present review is confined to ESR phenomena associated with paramag-
netic species located within the aluminosilicate lattice, or on the external surfaces of
non-expanding clays. The application of ESR to studies of phenomena associated with
the interlamellar region of expanding-lattice clays, including the mobility, structure and
reactivity of hydrated transition metal ions, forms a distinct area which is covered in Part
II.
Energy ~ s=-89
I S:-+2
I :g/3H
I
I
~ s - +!
2
Doublet
[H Zero) H 9:ncreas:n-
I I
FIG. 1. The resonancecondition:case of a singleunpaired electronin an externalmagneticfield.
ESR of clays." Part I 323
g,,
gx
I
I
I gy
/ t / t igz
H ~"
the direct absorption curve, but as its first derivative. A typical resonance lineshape is
illustrated in Fig. 2a.
So far we have considered only a single unpaired electron whose interaction with its
environment may be neglected. In most cases, however, the unpaired electrons are
influenced by other interactions, such as the electric fields arising from neighbouring
atoms in the crystal, and magnetic interactions due to the proximity of nuclei having
non-zero spins. These effects influence the number and position of resonance lines
observed. The following discussion outlines a few general principles illustrative of the
features of the ESR spectra of some of the more common paramagnetic ions.
For reasons discussed elsewhere (Abragam & Bleaney, 1970), with iron-group transi-
tion ions one can frequently neglect the influence of the higher orbital energy levels as a
first-order approximation, and consider only the spin energy levels associated with the
orbital groundstate (L = 0). There are 2 S + 1 such spin levels, where S is the spin
quantum number of the ion. In a free ion, as for the simple case discussed above where
S = 89 these levels will be of the same energy until split by an applied magnetic field. For
an ion in a crystal lattice, however, there are mechanisms which may split the 2 S + 1 spin
levels even in the absence of an external magnetic field. These splittings, termed zero-field
splittings (ZFS), are attributable to the anisotropy of the crystal field, i.e. the local electric
field in the vicinity of the paramagnetic ions due to the charges on neighbouring atoms.
324 P. L. H a l l
The overall effect of the electric and magnetic interactions is to produce a series of spin
energy levels whose separations depend on both the magnitude and direction of the
applied magnetic field. If the crystal field is highly symmetrical (octahedral or cubic
symmetry) the ZFS will be zero or very small, and no significant deviations from g-values
of 2.0 would be expected. For lower symmetries (axial or orthorhombic) significant
g-shifts may occur, resonances being in general anisotropic. In a single crystal this results
in a single ESR line associated with each possible transition, whose g-value, and hence
magnetic field position, will be dependent on the orientation of the magnetic field with
respect to the symmetry axes of the crystal field. In a polycrystalline material the spectra
will be averaged over all possible crystallite orientations.
Resonances in powders and amorphous materials are most easily resolved when the
resonance field value varies only slowly with angle, i.e. near a maximum or minimum. In
fact, stationary values of g (or H) occur when the magnetic field lies along one of the
principal symmetry axes of the crystal field (Dowsing & Gibson, 1969; Aasa, 1970). In a
single crystal, location of these maximum and minimum g-values as the sample is rotated
determines the orientation of the crystal field symmetry axes with respect to the crystallo-
graphic axes. In a powder, this is not generally possible, but broader resonances are
usually observed whose features are related to the principal g-values. These are conven-
tionally designated gt~ and g~ in the axial case and gx, gy and gz in the rhombic case. The
appearance of powder spectra arising from paramagnetic species of axial and rhombic
symmetry are illustrated in Figs 2b and 2c respectively (Searl et al., 1961; Kneubuhl,
1960).
For clay minerals it is frequently possible to obtain some orientational information,
even when single crystals are unavailable, by exploiting the natural tendency of clay
platelets to adopt preferential orientation. Thus ESR measurements on sedimented films
or compressed powders with the magnetic field orientated at different angles to the sample
may be expected to show some anisotropy. Recently, Swartz et al. (1979) have shown that
ESR lineshape simulations can provide a quantitative determination of the degree of
orientation in clays and other lamellar structures.
More complex ESR spectra arise in cases where the paramagnetic ion (or its nearest
neighbour) possesses a non-zero nuclear spin. Here, interactions between the electronic
and nuclear spins produce a further small splitting of the energy levels of the unpaired
electrons. This splitting, termed hyperfine splitting (HFS), separates individual ESR
transitions into multiplets. For example, the interaction of an unpaired electron with a
nucleus of spin I results in an ESR line having 21+ 1 equally spaced components. The
magnitude of the HFS is a direct measure of the strength of the electron-nucleus
interaction, and can be related to the degree of ionic (or covalent) character of metal-
ligand bonds (Boucher et al., 1969).
A brief survey will now be given of the typical features of the ESR spectra of a few
paramagnetic species which commonly occur in association with clay minerals.
Iron
Fe 2+ (3d 6) is a non-Kramers ion (see Abragam & Bleaney, 1970) and is generally
unobservable by ESR. Fe 3+ (3d 5) has been extensively studied in a wide range of
materials. In environments approximating to cubic symmetry, resonances at or near
g = 2.0 are expected, having a maximum of five fine-structure components due to the
E S R of clays: Part I 325
selection rule AS = + 1. In axial symmetry where the ZFS terms are relatively weak,
resonances close to g = 2.0 of the form of Fig. 2b have been observed in oxide powders
(Lunsford, 1965). In cases of axial or rhombic symmetry with relatively large ZFS terms,
powder spectra are frequently described by means of the spin Hamiltonian
= g f l H . S + D [ S z 2 - 1 S ( S + 1)] +E[Sx 2 - Sy2]
where the first term describes the Zeeman splitting and the second and third terms
represent the axial and rhombic components of the ZFS. The latter split the six-fold
ground state into three Kramers doublets. The g-values are dependent on both the ratio
2 = E/D and the ratio D/hv, where hv is the energy of the microwave quantum. The
parameter 2 is directly related to the symmetry of the environment of the ion, 2 = 0
representing axial symmetry and 2 = ] the 'completely' orthorhombic case in which the
three Kramers doublets are equally split by the crystal field. When D > hv, it can be
predicted that for ). = 0 one expects resonances at gl = 2.0 and gi = 6.0 for the lowest
doublet. For 2 = 89 an isotropic resonance atg = 4-3 is predicted for the central doublet,
and extremely anisotropic resonances are predicted for the upper and lower doublets
(Aasa & Vanngard, 1965; Wickman et al., 1965; Dowsing & Gibson, 1969). All symme-
tries can be described by 2 values lying between 0 and 89depending on the definition of the
axes (Blumberg, 1967; Hall et al., 1974a).
Manganese
Like Fe 3+, the Mn 2+ ion has the unpaired electron configuration 3d 5, so that in general
there are six spin levels (5: = + 25, + 23, + 89 between which a maximum of five allowed
transitions are possible according to the selection rule AS -- + 1. In addition, however,
the spin of the 55Mn nucleus (I = ~-) results in a splitting of each fine-structure line into
2 I + 1, i.e. six, hyperfine components. The ZFS is usually smaller than in the case of Fe3+;
frequently in a powder or solution spectrum the five AS transitions are unresolved due to
their small anisotropy and only six lines are therefore usually observed near g = 2.0. The
value of the hyperfine splitting constant may vary between approximately 55 and
95 x 10 -4 cm-1 depending on the nature of the ligands surrounding the Mn 2+ ion.
Copper
The Cu + ion has the configuration 3d l~ and is therefore diamagnetic. The Cu 2+ ion
(3d 9) has been most commonly observed in axially symmetric crystal fields (tetragonal or
trigonal) in which the ground state is a spin doublet. Typical g values are glt ~ 2.3-2.4 and
gi ~2.0-2.2. Furthermore, both 63Cu and 65Cu nuclei have spin I = 3, which leads to the
observation in some cases of a weak four-line hyperfine structure.
Vanadium
The divalent and tetravalent oxidation states are Kramers ions. V 2+ has configuration
3d 3, while V 4+, and the vanadyl oxycation, VO 2+, have the configuration 3d 1. Here only
the tetravalent case will be considered, for which g-values close to 2-0 are invariably
observed, frequently with axial symmetry. The 51V nucleus has spin I = 5, which gives rise
to 8 hyperfine components associated with each principal g-value. The HFS is usually
326 P. L. Hall
markedly anisotropic, the splitting constants being approximately AII ~ 150 x 10 _4 c m -
and At ~50 x 10 -4 cm-1, but can be averaged to produce an isotropic spectrum in cases
where the ion is rapidly tumbling in a solution-like environment (see Part II).
Kaolinite
Most kaolinites exhibit a characteristic ESR spectrum consisting o f two main groups of
resonances: (i) a group of lines at low magnetic field values, centered at g = 4-2, and (ii)
overlapping groups of lines at higher field values, centered at g = 2.0. Heating the clays in
air at 500~ causes the collapse of the low-field resonances to a single line while the
features at g = 2-0 disappear, as illustrated in Fig. 3 (Angel & Hall, 1973). Although the
first observation of ESR in kaolinite dates back to the work of Boesman & Schoemaker
(1961) and later reports by Friedlander et al. (1963) and Wauchope & Haque (1971), the
detailed identification of the species responsible for the observed spectral features has
only been achieved recently as a result of systematic and detailed investigations of a wide
range of natural and doped synthetic clays (Angel & Hall, 1973; Jones, 1974; Jones et al.,
Resonance B. Resonance A.
400~c b
FIG. 3. ESR spectra of a Cornwall kaolinite heated for 24 h at various temperatures (Angel & Hall, 1973).
328 P. L. Hall
1974; Meads & Malden, 1975; Angel et al., 1974, 1976, 1977). Discussion of the results of
these studies falls into two parts.
Low-fieMresonances. The ESR spectra of most kaolins exhibit three peaks in the region
of g = 4, together with a peak at lower magnetic field corresponding to a g-value of
approximately 9.0. Considerable variations in the overall lineshape occur between differ-
ent samples, which can only be partially explained by contributions from Fe 3+ resonances
due to relatively iron-rich mineralogical impurity phases such as micas (Angel & Hall,
1973).
Based both on experimental studies and theoretical considerations, the X-band spectra
are assigned to two distinct Fe 3+ substitutional sites, whose resonances partially overlap:
(i) Centre I, giving an isotropic line at g = 4-2 (requiring 2 = ~ and D >~0-8 cm-1);
(ii) Centre II, giving three lines corresponding to g-values gz = 4-9 gx = 3.7 and
gy = 3-5, the latter two frequently being unresolved in powder spectra. Those resonances
are consistent with partially orthorhombic symmetry having 2 = 0.22 + 0.01.
From X-band measurements Jones et al. (1974) found, in addition, two higher field
resonances whose g-values could only be explained on the assumption that Centre II itself
is a composite feature arising from two Fe 3+ sites differing slightly in symmetry (IIa and
IIb). Both centres appeared to be consistent with spin Hamiltonian parameters in the
range E/D = 0-22 0-01 and D =0.45 _ 0.02 c m - i. From a combination of X-band and
Q-band measurements, Meads & Malden (1975) also observed three distinct Fe 3 sites in
kaolinite, although their data indicated slightly different best-fit parameters correspond-
ing to Centres IIa and lib (2 =0-234, D = 0 . 4 8 cm-1; and 2 - 0-207, D =0-32 c m - I).
The results are, however, essentially in good agreement. Taking the ESR data in
conjunction with M6ssbauer studies (Malden & Meads, 1967) and phosphorescence
studies (Jones et al., 1974) it appears that all three sites can be attributed to octahedrally
coordinated Fe 3+ ions.
A correlation between the lineshape of the composite Fe 3+ spectrum and the crystal-
linity index as defined by Hinckley (1963) was observed (Jones et al., 1974; Meads &
Malden, 1975). The relative population of Centre I in comparison with Centre II increases
as the crystallinity index of the kaolinite decreases. Centre I is thus attributable to Fe 3+
ions in sites adjacent to layer stacking disorders such as random nb/3 displacements or
120 ~ rotations (Noble, 1971). Centres IIa and IIb, in contrast, are associated with Fe 3+
ions in regions of high crystallinity and regular stacking. The difference between Centres
IIa and IIb may be attributed to the two distinct orientations of surface OH groups
suggested by the calculations ofGiese & Datta (1973). The low-field resonances of natural
clays can be identically reproduced in Fe 3+ doped synthetic kaolinite, as illustrated in Fig.
4 (Jones et al., 1974; Angel et al., 1976). Intercalation of kaolinite with urea, dimethylsul-
phoxide or potassium acetate causes the three-line Fe 3+ resonance to collapse to a single
line at g = 4-2. Thus, disruption of the regular interlayer bonding accompanying inter-
calation of such molecules reduces the symmetry of the local environment of the ferric
ions from that of Centre IIa or IIb to that of Centre I.
Further studies of the relationship between the ferric ion ESR spectra and the iron
content and crystallinity of kaolinites have been made by Mestdagh et al. (1980). Their
results indicate an inverse relationship between the intensity of the single isotropic
g = 4.3 resonance and the Hinckley crystallinity index. The clear association of this
resonance with crystalline imperfection and stacking disorder is in good agreement with
ESR of clays: Part I 329
[g--4-O g=2-O
J Natural kaolinite
Mg dopedkaolinite
O ~
(no signals)
Fe3+doped kaolinite
Mg dopedkaolinite
X- irradiated
Mcj dopedkaolinite
- X-irradiated
and annealed
~ F'eS+andMg doped
F . ~ kaolinite
X-irradiated and
annealed
FIG. 4. ESR spectra of natural and doped synthetic kaolinites (Angel et al., 1976).
the observation of the single-line resonance in metakaolin (Angel & Hall, 1973) and in
iron-containing silicate glasses (Castner et al., 1960; Loveridge & Parke, 1971). Similar
resonances occur also in a wide range of amorphous materials, including natural organic
residues such as humic acids containing traces of iron (Hall et al., 1974b). There is an
apparent difficulty in reconciling the very common occurrence o f this resonance in
structurally disordered or amorphous materials with the theoretical explanation of its
origin. The latter requires a rather specific crystal field symmetry described by the spin
Hamiltonian parameter 2 = k. This lends support to the ideas of Peterson et al. (1974)
whose calculations indicate that a resonance of this type in glassy systems might well arise
from a broad statistical distribution of site symmetries in which there are little or no
correlations between the principal g-values.
High-field resonances (g ~2.0). Numerous features have been observed in the ESR
spectra of kaolins in the region of g --- 2.0. These are attributable to both lattice defect
centres (labelled below as A, B ! and B2) and also transition metal impurities other than
substitutional Fe 3+. In the latter category may be included resonances due to iron oxide or
330 P. L. Hall
hydroxides, manganese (Mn2+), vanadium (V 4+ or VO 2+) and organic free radicals. The
experimental results may be summarized as follows:
4.48
9T Ob
/
Oa Centre V
T~ / f ~ "q' . 2 - 0 0
I I I I ~ 1 I J l I p I I I J ~
IOOQ 2000 3000 H (oe)
FIG. 5. ESR spectra o f ( l ) Wyoming and (2) Camp Berteau montmorillonites (Olivier et al., 1975).
Olivier et al. (1975) also examined the ESR spectra of chlorite and a variety of smectites.
Detailed spectra were observed in all cases, dominated by broad features at g = 4-3
together with numerous additional lines. ESR spectra of two montmorillonites (Wyom-
ing and Camp Berteau) are illustrated in Fig. 5, these indicating the presence of Fe 3+ ions
in two distinct octahedral sites and two tetrahedral sites. It is not clear, however, whether
the difference between the symmetries of the two octahedral sites arises from the two
alternative (cis and trans) configurations o f the hydroxyl groups in the FeO4(OH)2
octahedra, or from the nature of the cations in the neighbouring octahedral sites.
McBride et al. (1975a, 1975b) observed that the g = 4 resonances in smectites were
influenced by both the nature of the exchange cations and the degree of hydration of the
minerals. A weaker signal on the high-field shoulder of the main g = 4.3 line was
observed, which could be reversibly removed and restored by dehydration and resolva-
tion respectively for sodium- and calcium-exchanged montmorillonites. The weaker
resonance was attributed to Fe 3+ ions occupying octahedral sites adjacent to Mg 2+ ions,
while the more intense resonance was attributed to ferric ions in octahedra adjacent to
A13+. For Li-montmorillonite, the weaker signal did not reappear on resolvation. This
effect was attributed to the migration of the small Li + ions into vacant octahedral sites
during the thermal dehydration, where they provided local charge compensation. The
ESR spectra are illustrated in Fig. 6.
Other relevant recent ESR studies have been reported by Elsass & Olivier (1978) and
G o o d m a n (1978). The former workers studied a range of natural clays and classified the
Na
I
2 J/'
FIG. 6. ESR spectra of sodium, lithium and calcium montmorillonites, l. Hydrated under ambient
conditions. 2. After heating at 205~ for 24 h. 3. Resolvated in ethanol (McBride et al., 1975b).
ESR of clays: Part I 333
sites of iron substitution and the nature of the defect centres present. Goodman (1978)
investigated the mode of occurrence of iron in some iron-deficient montmorillonites by a
combination of ESR and M6ssbauer studies. He concluded that a part of the iron content
of these clays was in the form of iron-rich clusters probably associated with external
particle surfaces, giving very broad ESR lines. In addition, sharper lines were observed
indicative of the presence of isolated substitutional Fe 3+ ions.
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