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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
1038
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
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.
1040
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).
1041
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
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.
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