Journal of Physics and Chemistry of Solids 67 (2006) 10371042

www.elsevier.com/locate/jpcs

Hydrocalumite-type materials: 1. Interest in hazardous waste immobilization

Rachid Segni a, Laetitia Vieille b, Fabrice Leroux a,*, Christine Taviot-Gueho a,*
a

Laboratoire des Materiaux Inorganiques, CNRS-UMR no. 6002, Universite Blaise Pascal, 63177 Aubie`re cedex, France
b
University of Bristol, School of Chemistry, Cantocks close, Bristol BS8 1TS, UK

Abstract
This study investigated the incorporation of Cr, V and Si oxoanions into hydrocalumite. Hydrocalumite together with ettringite form during the
hydration of Portland cement and the use of these materials in hazardous waste immobilization is of current concern. The anion uptake was
examined in terms of the structural characteristics by means of thermogravimetric analysis, infrared spectroscopy, X-ray diffraction (XRD) and
in situ high temperature X-ray diffraction (HTXRD). The syntheses were carried out by coprecipitation or exchange reaction. The short
, respectively, are explained by a grafting process onto
interlamellar distances observed for Ca2AlV2O7 and Ca2AlSiO4 phases, 7.90 and 10.93 A
the hydroxide layers. The good crystallinity of Ca2AlCrO4 allowed the refinement of the cell parameters in the P-3 space group with
and cZ20.164(2). A structural model is proposed with CrO4 species close to the seventh coordination position of Ca atoms. In
aZ5.7507(3) A
situ HTXRD measurements in the temperature range 25350 8C reveal different thermal behaviors depending on the oxoanion. At low
temperature, a dehydrationhydration process partly reversible was observed for Ca2AlV2O7 and Ca2AlCrO4 phases, between 100200 and
50120 8C, respectively. At higher temperature, strong interlayer contractions were observed due to a pillaring process: Dd/dZK13% for
Ca2AlV2O7 at 200 8C, Dd/dZK32% for Ca2AlCrO4 at 250 8C and Dd/dZK35% for Ca2AlSiO4 at 135 8C.
q 2006 Elsevier Ltd. All rights reserved.
Keywords: A. Multilayers; C. X-ray diffraction; D. Microstructure

1. Introduction
Interest in hazardous waste stabilization processes based on
the formation of ettringite and hydrocalumite has grown
steadily in the last few years [1]. Ettringite and hydrocalumite
are major hydration products of ordinary Portland cements.
Both of them are also commonly identified as secondary
precipitates during the hydration of fly ash and spent oil shale
or can be induced to precipitate in situ from the solid waste
materials [2]. It has been documented that extensive solidsolutions between different anions can form in both hydrocalumite and ettringite and that a conversion can occur between
these two phases [3].
This study focused on the anion uptake by hydrocalumite
which is larger than that by ettringite. Hydrocalumite is
an anionic clay mineral belonging to the layered double
hydroxide (LDH) family. Most of LDH resemble
* Corresponding authors.
E-mail addresses: Fabrice.leroux@univ-bpclermont.fr (F. Leroux), Christine.taviot-gueho@univ-bpclermont.fr (C. Taviot-Gueho).

0022-3697/$ - see front matter q 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jpcs.2006.01.081

the naturally occurring hydrotalcite represented by the

xC mK
general formula MII1Kx MIII
x OH2
Ax=m $nH2 O
(abbreviated
II III
notation MR M KA with RZ(1Kx)/x) where MII and MIII
represent metallic cations and A the interlayer anion. The
layered structure of LDH is built by the periodical stacking
of positively charged (M2C, M3C)(OH)6 octahedral layers
related to brucite and negatively charged interlayers
consisting of anions and water molecules [4]. For hydrocalumite, Ca2C and M3C ions (Al3C, Fe3C, Ga3C and Sc3C)
are ordered within the hydroxide layers and the interlayer
water molecules are coordinated to Ca atoms, creating 7-fold
coordinated Ca sites [5]. These layered Ca-aluminate
hydrates are also know collectively as AFm phases in
cement science litterature [1].
The incorporation of Cr and V oxoanions into hydrocalumite was first examined. Experiments were performed at
conditions relevant to cement chemistry, either by directly
precipitating hydrocalumite from a solution containing
oxoanions or under exchange conditions by interlayer anionic
substitution of nitrate or chlorideanions. In addition, the
incorporation of silicate anions in hydrocalumite was reported.
These results should provide insights into the behavior of
chromium and vanadium in cement, as well as the ability of
hydrocalumite to bind silica.

1038

R. Segni et al. / Journal of Physics and Chemistry of Solids 67 (2006) 10371042

2. Experimental
2.1. Synthesis
The synthesis of LDHs is usually achieved using the
coprecipitation method [6]. We have used this method for the
preparation of Ca2AlCl and Ca2AlNO3 precursors as well as
Ca2AlCrO4cop. Practically, a mixed solution of 0.66 M
CaCl2$2H2O, and 0.33 M AlCl3$6H2O was added dropwise
to 250 mL of water (precursor compounds) or 250 mL of a
solution of K2CrO4 0.30M (Ca2AlCrO4cop). The pH was kept
constant at 11.5 by the simultaneous addition of 2 M NaOH.
The syntheses were carried out at room temperature under
vigorous stirring and nitrogen atmosphere. After the complete
addition of the metallic salts, the precipitates obtained were
aged in the mother solution for 24 h at 65 8C, then centrifuged,
washed twice with water and finally dried under vacuum at
room temperature.
The synthesis of the other phases intercalated with vanadate
and silicate species was carried out with the anion exchange
method. Ca2AlCrO4exch phase was also prepared using this
method. Practically, 0.10 g of Ca2AlCl or Ca2AlNO3
powders and 0.217 g of NaVO3 or 1.38 g of K2CrO4 or
3.80 g of Na2SiO3, were added to 50 mL of deionized water.
The mixture was stirred for 24 h under nitrogen atmosphere at
room temperature for Ca2AlV2O7exch and Ca2AlCrO4exch
and under refluxing conditions at 80 8C for Ca2AlSiO4exch.
The pH was fixed at a value of 11.5 with 2M NaOH,
compatible with both Ca2Al- host and anions stability.
Elemental analyses were performed at the Vernaison Analysis
Center of CNRS using inductive conduction plasma coupled to
atomic emission spectroscopy (ICP/AES).The chemical compositions are reported in Table 1.
2.2. Instrumentation
Powder X-ray diffraction patterns were recorded on XPert
Pro Philips diffractometer using Cu Ka radiation and a
diffracted beam graphite monochromator. For the structure
investigation, data were recorded in steps of 0.0128 with a
count time of 30 s at each point. The program FULLPROF was
used for the Rietveld refinement [7]. The intensities of the
reflections were calculated using the analytical pseudo-Voigt
peak-shape function; the background was defined by linear
interpolation between points in the pattern. A high-temperature
chamber (Anton Paar HTK-16) was installed, enabling in situ
high-temperature X-ray diffraction (HTXRD) measurements
under a controlled atmosphere. Measurements were carried out
Table 1
Chemical Analyses of Ca2Al-oxoanions phases.
Sample

Ca/Al

Al/AmK

n.H2O

Ca2AlV2O7exch
Ca2AlCrO4exch
Ca2AlCrO4cop
Ca2AlSiO4exch

2.08
2.31
1.97
1.95

0.24
0.54
0.66
0.27

2.94
3.53
2.97
2.26

under air atmosphere in the temperature range 25350 8C, after

10 min equilibration at each temperature, and the heat/cooling
rate was 5 8C/min. Repetitive treatments consisting of
calcinations at increased temperatures and subsequent coolings
to room temperature were performed, leading to two different
sets of data, those obtained in situ at high temperature and those
recorded ex situ after the sample was cooled down to room
temperature. Typical measurement conditions were in the 2q
range 2708, step size 0.088 (2q), and step counting time 4 s.
Thermogravimetric analyses (TGA) were performed on a
Setaram TGA 92 instrument with a linear heating of 5 8C/min
under air atmosphere. IR spectra were recorded from 200 mg
KBr pellets containing 2 mg of sample on a 16PC PerkinElmer FTIR spectrometer.
3. Results and discussion
3.1. Incorporation of V, Cr and Si oxoanions.
The aqueous chemistry of chromate, vanadate and silicate
anions has been thoroughly examined. The distribution of the
anions depends on the concentration and the pH. V2 O4K
7 are the
major species at pHO9 and acidification leads to the formation
6K
of V4 O4K
12 in the pH range 68 and of V10 O28 in the pH range
2K
46. At pHO6, CrO4 are the major anionic species while
Cr2 O2K
7 are stabilized at lower pH values. Eventually, the
2K
prepared silicate solution must contain both HSiOK
3 and SiO3
species.
One can see that the Ca/Al molar ratios are well maintained
after the intercalation of the oxoanions (Table 1). The Al/AmK
ratios are also those expected for free intercalated oxoanions
4K
2K
assuming that AmK are CrO2K
4 , V2 O7 and SiO3 . The water
contents are very similar, as well. It is worth noting that the
incorporation of all these oxyanions was attempted both using
the coprecipitation method and through anion exchange. Yet,
only the chromate phase was prepared successfully by the two
methods while the silicate and vanadate phases were obtained
only via exchange by nitrate anions and chloride anions
respectively. In addition, a moderate heating was required for
the formation of the silicate phase.
The powder X-ray diffraction patterns of the precursor
phases (Fig. 1a) are characteristic of well crystallized products
with a bidimensionnal structure of symmetry R-3 for Ca2AlCl
[5f] and P-3c1 for Ca2AlNO3 [5b]. As it is often the case, the
exchange process leads to a lowering of the crystallinity. For
Ca2AlV2O7exch and Ca2AlSiO4exch, the number of diffraction lines is very limited and it is only possible to give
approximated values of the intermetallic and interlayer
distances from, respectively, the (110) and the first observed
(001) diffraction lines. For Ca2AlCrO4, the X-ray diffraction
patterns are very similar to each other indicating that the same
intercalated phase was obtained by the two synthesis methods.
The good crystallinity of Ca2AlCrO4cop allowed the
indexation of the diffraction lines which was carried out in
the P-3 space group (Fig. 1b). This space group arises from a
peculiar ordering of chromate entities in the interlayer domain
as discussed below. The refined parameters of the hexagonal

R. Segni et al. / Journal of Physics and Chemistry of Solids 67 (2006) 10371042

1039

Fig. 1. (a) X-ray diffraction patterns of freshly prepared Ca2Al-oxoanion phases. (b) Cell parameters refinement for Ca2AlCrO4cop in P-3 space group:
experimental data (cross), calculated (line), Bragg reflections (ticks) and difference profile.

. In all cases, the

unit cell are aZ5.7507(3), cZ20.164(2) A
interlamellar distances indicate the presence of intercalated
anions. Indeed, these oxoanions have already been intercalated
in various hydrotalcite-like LDH and the following discussion
compares their incorporation into hydrocalumite with that in
hydrotalcite.
The short interlamellar distance observed for Ca2AlV2O7
exch is not compatible with free intercalated oxoanions at
hydrogen bond distances from hydroxyl planes. The d-spacing
is slightly higher than that reported by
value obtained 7.90 A
Depe`ge et al. for polyoxovanadates anions intercalated in
[8]. Like these authors, we
Cu2Cr-LDH at pH 10.0: 7.62 A
4K
assume a grafting of V2 O7 species onto the hydroxide layers.
Such a process has been reported for sulphate and chromate
anions in LDH and can occur either spontaneously during
ageing or storing, or under moderate thermal treatment
(100150 8C) [9]. In the infrared spectrum (Results not
shown) of this phase, the disappearance of the two typical
bands of the hydroxide layers (nCaO at 420 cmK1 and dOAIO at
530 cmK1) and the shift of the VO4 stretching band (nOVO at
950 cmK1 in NaVO3 salt) towards high energies (820 cmK1),
support the grafting phenomenon); a small band at 614 cmK1
(nVOV) can be attributed to corner-sharing VO4 tetrahedra.
As already said, the CrO4 phases obtained both by the
coprecipitation method and through anion exchange display the
. This value is higher
same interlamellar distance i.e. 10.02 A
than that reported in hydrotalcite system, ranging from 8.08 to
for freshly prepared Cu2Cr-LDH [9]. The capability of
8.42 A
chromate-containing LDH to intercalate variable amount of
water molecules has been demonstrated and strong variations
of the interlamellar distance have been observed relative to the
storage conditions. Considering previous structural data
reported by M. Francois et al. [5g], we attempted to perform
a structural refinement of the X-ray powder diffraction diagram
of Ca2AlCrO4cop material. Yet, due to a statistic and dynamic
disorder of the chromate species and the water molecules, the
minimization of the difference was obtained with rather high
conventional Rietveld factors (Rp Z15.7, Rwp Z21.1, RBragg

Z15.8, c2Z6.06). The structural informations are thus

approximate but a structural model can be proposed. The
structure projected along the [100] direction is shown Fig. 2.
This representation has been ordered for clarity. It can be
described as the stacking of two kinds of layers, one negatively
charged [Ca2Al(OH)6$CrO4$H20]K and the other positively
charged [Ca2Al(OH)6$ 2H20]C plus four interlayer free water
molecules. Such a stacking sequence is likely to be induced by
the size of chromate anions. The two adjacent [Ca2Al(OH)6]2C
. The
main layers are separated by a distance of 10.082 A
seventh coordination position of the Ca atoms is assumed
statistically either by a water molecule (OW1) or one of the
oxygen atoms of the chromate anions (OCr1). Because of the
great disorder, OW1 and OCr1 could not be localized

separately. The Ca1 OCr1/OW1 distance obtained 2.96(3) A

indicates that Ca atoms are nearly linked to chromate anions.
To check this assumption, we studied the reversibility of the

Fig. 2. Structural model for [Ca2Al(OH)6][0.5CrO4, 3.5H2O]. The structure is

represented in an ordered way with the seventh coordination position of the Ca
atoms occupied statistically either by a water molecule or a chromate oxygen
atom.

1040

R. Segni et al. / Journal of Physics and Chemistry of Solids 67 (2006) 10371042

exchange reaction by suspended Ca2AlCrO4cop sample in a

solution containing a large excess of chloride anions. After
24 hours of mixing, the formation of Ca2AlCl was observed
but a small amount of the Ca2AlCrO4 phase was still present
indicating strong interactions between CrO2K
4 and the hydroxide layers, yet the question of the existence of a grafting
remains since part of the solid has been exchanged.
Noteworthy here is the easiness of grafting at low temperature
in hydrocalumite system and the reversibility of this process as
already reported with intercalated oxygen-containing anions
such as nitrate and carbonate anions [5bd]. The interlamellar
is much shorter
distance observed for Ca2AlSiO4exch 10.93 A
for ZnRAl
than that reported in hydrotalcite phases: 12.45 A

LDH, and 12.012.2 A for Mg3Al-LDH and 11.9 for Zn2Cr

LDH [10]. For these materials, a polymerization of SiO4 units
in the interlamellar domain as inverted tetrahedral layers has
been evidenced by 29Si NMR [10c]. A strong interlayer spacing
at 25 8C to 7.65 A
at 140 8C was also
contraction from 11.90 A
reported arising from a condensation of the silanol groups and
the metallic hydroxyls. In the case of Ca2AlSiO4exch, as the
exchange was carried out at 80 8C, we may assume a partial
grafting process. The infrared spectrum shows a band at
1150 cmK1 dSiOSi characteristic of corner-sharing SiO4

tetrahedra, yet the bands ascribed to the hydroxide layers are

still visible but strongly attenuated.
3.2. Thermal behavior
In the present study, we also aim at clarifying the thermal
behavior of Ca2Al-oxoanions phases in the temperature
interval 25350 8C. Of particular interest here is the use of
in situ high temperature powder X-ray diffraction (HTXRD)
technique as most of the thermal behavior investigations
published were carried out ex situ after cooling the sample at
room temperature. Recently, by means of HTXRD measurements, we have shown the reversibility of the hydration
dehydration process for the Friedels salt Ca2Al(OH)6Cl.2H2O
in the temperature range 80100 8C [11]. Besides, the
structural determination of the dehydrated phase at 116 8C
reveals a quasi-pillared layer structure with chloride anions

situated midway in the interlamellar space at only 2.904(3) A

from Ca atoms of adjacent hydroxide layers. Fig. 3 gives a
general view of the X-ray diffraction patterns of Ca2Aloxoanion phases between 25 and 350 8C recorded by means of
in situ HTXRD in air. Repetitive treatments consisting of
calcinations at increased temperatures and subsequent coolings

Fig. 3. High-temperature in situ (black line) powder X-ray diffraction patterns of (a) Ca2AlCrO4cop, (b) Ca2AlCrO4exch, (c) Ca2AlV2O7exch and (d)
Ca2AlSiO4exch at different temperatures compared with those recorded after cooling to room temperature (gray line).

R. Segni et al. / Journal of Physics and Chemistry of Solids 67 (2006) 10371042

to room temperature were performed. The thermal behavior

was also examined by thermogravimetric analysis and to
combine XRD and TGA results, the same thermal treatment
was applied. Changes in the diffraction patterns indicate three
steps in the thermal decomposition process over the temperature ranges 25%T%350, 350%T%650 and 650%T%950 8C
which are commonly ascribed to the following three main
processes: dehydration, dehydroxylation and anion decomposition or recombination. The evolution of the interlamellar
distances between 25 and 300 8C for both series of
measurements, i.e. in situ and ex situ measurements, is
depicted in Fig. 4. This evolution differs between compounds.
For Ca2AlV2O7exch, almost no change in the interlayer
distance is observed up to 100 8C confirming that the grafting
the of V2O7 units onto hydroxide layers has already occurred
during the preparation. Consistent with XRD results, the
material starts losing weight only at 100 8C on the TGA curve.
Above 100 8C, the interlamellar distance starts decreasing from
to c.a. 6.85 A
at 200 8C (Dd/dZK13%) however, the
7.90 A
sample was found to partly recover the original distance on
cooling. This reversible contraction is ascribed to the reversible
elimination of the interlayer water molecules. The air moisture
is sufficient to induce such reversibility. Above 200 8C, the
reversibility is lost and at 350 8C the sample is converted to an
amorphous phase.

1041

HTXRD and TGA measurements on Ca 2 AlCrO 4

samples first show the effect of the crystallinity and the
structural order on the quality and the interpretation of such
experimental data. Indeed, while Ca2AlCrO4cop unequivocally exhibits a reversible interlayer contraction in the
temperature range 50120 8C due to the reversible elimination of the interlayer water, the process appears less
collective in Ca2AlCrO4exch sample of lower crystallinity
and reversibility is completely lost at 70 8C. Yet, in situ
measurements indicate a decrease of the interlayer distance
between 25120 8C of a comparable amplitude in both
(Dd/dZK20%). Above
cases, from 10.08 to c.a. 8.1 A
60 8C, both the dehydrated and hydrated phases are present
on cooling in the two samples. Comparatively, for Ca2AlCl
Friedels salt, the coexistence of the two phases was
observed only above 260 8C [11]. Although the rehydration
rate depends on the humidity level and other experimental
conditions, this result again indicates strong interactions
between the chromate anions and the hydroxide layers,
agreeing with the structural model. The short interlayer
probably is the lower limit under which a
distance of 8.1 A
pillaring process may occur, with adjacent hydroxide layers
bridged by chromate species. Indeed, above 120 8C
reversibility in Ca2AlCrO4cop is lost and the interlayer
at 120 8C down to
distance decreases rapidly from 8.1 A

Fig. 4. Variation of basal spacing d for (a) Ca2AlCrO4cop, (b) Ca2AlCrO4exch, (c) Ca2AlV2O7exch and (d) Ca2AlSiO4exch as a function of temperature
measured in situ (open circles) and after cooling to room temperature (filled circles). The corresponding TG curves are given in inset.

1042

R. Segni et al. / Journal of Physics and Chemistry of Solids 67 (2006) 10371042

at 250 8C (Dd/dZK16%).For Ca2AlSiO4exch,

c.a. 6.8 A
the behavior versus temperature is totally different. A strong
to c.a. 7.1 A
was
interlayer contraction from 10.93 A
observed at 135 8C (Dd/dZK35%), with no recovering of
the original distance upon cooling. Above 135 8C, the
reflections are strongly reduced in intensity and almost
disappeared at 165 8C. This irreversible contraction of the
interlamellar space must arise from a condensation process
of silanol groups onto the hydroxide layers as demonstrated
elsewhere [10]. Consistent with this interpretation, the
TGA curve indicates that dehydroxylation and anion
recombination are complete at 550 8C whereas for the
other phases the total decomposition requires heating at
higher temperature: 750 8C for Ca2AlV2O7exch and 700 8C
for Ca2AlCrO4.
Finally, raising the temperature up to 950 8C results in
the formation of mayenite Ca12Al14O33 and CaO in all
cases. Additional diffraction peaks are detected depending
on the intercalated oxoanions, however, owing to the
weakness of their intensity, the identification is sometimes
approximate: Ca 2 V6 O17 (PDF: 280250) for Ca 2Al
V2O7exch calcined derivative, CaCrO3 (PDF: 210137) or
Ca4Al6CrO16 (PDF: 440443) and Ca5Cr3O12 (PDF: 38
0292) or Ca6Al4Cr2O15 (PDF: 340381) for Ca2AlCrO4,
Ca9Al6O18 (PDF: 700839) and Ca2Al2SiO7 for Ca2Al
SiO4exch (PDF: 891489).

4. Conclusion
The anion uptake of Cr, V and Si oxoanions by
hydrocalumite was investigated. A partial grafting process
onto the hydroxide layers is assumed in all cases, for the freshly
prepared samples. In situ HTXRD experiments reveal different
thermal behaviors in the temperature range 25350 8C
depending on the oxoanion. At low temperature, a dehydration-hydration process partly reversible is observed for
Ca2AlV2O7 and Ca2AlCrO4 phases which does not occur in
Ca2AlSiO4. At high temperature, strong interlayer contractions are observed due to a pillaring process. Above
300350 8C, Ca2AlV2O7 and Ca2AlCrO4 are converted
into an amorphous phase while Ca2AlSiO4 turns amorphous
at 165 8C.

References
[1] (a) H.F.W. Taylor, Cement Chemistry, Academic Press, London, 1990;
(b) C.D. Palmer, Environ. Sci. Technol., 34 (2000) 4185;
(c) M. Drabik, R.C.T. Slade, Inter. Sci., 12 (2004) 375;
(d) L. Raki, J.J. Beaudoin, L. Mitchell, Cem. Conc. Res., 34 (2004) 1717;
(e) F.P. Glasser, J. Hazard. Mater., 52 (1997) 151;
(f) C. Palmer, Environ. Sci. Technol., 34 (2000) 4185;
(g) R. Perkins, C.D. Palmer, Cem. Concr. Res., 31 (2001) 983;
(h) M. Zhang, E.J. Reardon, Environ. Sci. Technol., 37 (2003) 2947;
(i) I. Baur, C.A Johnson, Cem. Conc. Res., 33 (2003) 1741;
(j) J.R. Fitch, C.R. Cheeseman, J. Hazard. Mater., A101 (2003) 239.
[2] Z. Zhou, R. Dayal, Waste Manag. 10 (1990) 53.
[3] H.F.W. Taylor, Mineral. Mag. 39 (1973) 377.
[4] A. de Roy, C. Forano, J.P. Besse, Layered double hydroxide: synthesis
and post-synthesis modifications, in: V. Rives (Ed.), Layered Double
Hydroxides: Present and future, Nova Science Publishers, New York,
2001.
[5] (a) E. Passaglia, M. Sacerdoti, N. Jb. Miner. Mh. (1988) 454;
(b) G. Renaudin, M. Francois, Acta. Cryst. C55 (1999) 835;
(c) G. Renaudin, M. Francois, O. Evrard, Cem. Concr. Res. 29 (1999) 63;
(d) G. Renaudin, J.P. Rapin, B. Humbert, M. Francois, Cem. Concr. Res.
30 (2000) 307;
(e) J.P. Rapin, G. Renaudin, E. Elkaim, M. Francois, Cem. Concr. Res.
32 (2002) 513;
(f) I. Rousselot, C. Taviot-Gueho, F. Leroux, P. Leone, P. Palvadeau,
J.P. Besse, J. Solid State Chem. 167 (2002) 137; J.P. Rapin,
University thesis, 2001, no. 543, Nancy.
[6] S. Miyata, Clays Clay Miner. 23 (1975) 369.
[7] J. Rodriguez-Carvajal, FULLPROF, a Program for Rietveld Refinement
and Pattern Matching Analysis, 1990.
[8] (a) C. Depe`ge, L. Bigey, C. Forano, A. de Roy, J.P. Besse, J. Solid State
Chem. 126 (1996) 314;
(b) M. Menetrier, K.S. Han, L. Guerlou-Demourgues, C. Delmas, Inorg.
Chem. 36 (1997) 2441;
(c) C. Barriga, W. Jones, P. Mallet, V. Rives, M.A. Ulibarri, Inorg.
Chem. 37 (1998) 1812.
[9] (a) C. Depe`ge, C. Forano, A. de Roy, J.P. Besse, Mol. Cryst. Liq. Cryst.
244 (1994) 161;
(b) F. Malherbe, L. Bigey, C. Forano, A. de Roy, J.P. Besse, J. Chem.
Soc., Dalton Trans. (1999) 3831;
(c) M. Khaldi, A. de Roy, M. Chaouch, J.P. Besse, J. Solid State Chem.
130 (1997) 66.
[10] (a) A. Schuzt, P. Biloen, J. Solid. State Chem. 68 (1987) 360;
(b) S.K. Yun, V.R.L. Constantino, T. Pinnavia, Clays Clay Miner. 43
(1995) 503;
(c) C. Depe`ge, F.Z. El Metoui, C. Forano, A. De Roy, J. Dupuis,
J.P. Besse, Chem. Mater. 8 (1996) 952;
(d) M. Del Marco, S. Gutierrez, C. Martin, V. Rives, J. Rocha, J. Solid
State Chem. 151 (2000) 272.
[11] L. Vieille, I. Rousselot, F. Leroux, J.P. Besse, C. Taviot-Gueho, Chem.
Mater. 15 (2003) 4361.