Journal of Physics and Chemistry of Solids 65 (2004) 385–393

www.elsevier.com/locate/jpcs

In situ polymerization of interleaved monomers: a comparative study

between hydrotalcite and hydrocalumite host structuresq
Laetitia Vieille, El Mostafa Moujahid, Christine Taviot-Guého, Joël Cellier,
Jean-Pierre Besse, Fabrice Leroux*
Laboratoire des Matériaux Inorganiques, UMR 6002, Université Blaise Pascal, Aubière Cedex 63177, France
Accepted 4 August 2003

Abstract
Vinyl benzene sulfonate (styrene sulfonate, VBS) and polystyrene sulfonate (PSS) were incorporated into Layered Double Hydroxides
(LDH) by templating reaction. The two host structures investigated are Zn2Al(OH)6Cl. n H2O of hydrotalcite-type and Ca2Al(OH)6Cl. n H2O
of hydrocalumite-type.
The electrostatic binding between sulfonate groups of VBS and the inner-surface of LDH host structure evaluated by 13C CP-MAS NMR
spectroscopy causes some shifts in the resonance lines. In situ polymerization of VBS molecules between LDH sheets is reached after soft
heat treatment. Its completion requires a good matching between the layer charge density and the projected surface area of the guest molecule
achieved by a ratio M2þ to M3þ of 2. For the pristine material, the change from Oh to Td aluminum site appears to be a collective process for
the hydrocalumite, whereas it is more progressive for the hydrotalcite-type material. For the corresponding organoceramics, the site
conversion before the breakdown of the lamellar structure is substantially reduced, and especially for PSS/LDH nanocomposite obtained by
in situ polymerization.
CaAl – VBS intercalate crystallizes in C2=c space group inducing a bilayer arrangement of VBS anions in the interlamellar space.
Furthermore, distances between anionic sites allow an in situ zig-zag polymerization of syndiotactic type along the a axis. For hydrotalcite,
p
the short Al3þ – Al3þ distance at a 3 prevents also the formation of PSS other than syndiotactic. The thermal stability of the nanocomposites
depends on the host structure but also on the synthesis pathway.
q 2003 Elsevier Ltd. All rights reserved.

1. Introduction Vinyl benzene sulfonate (styrene sulfonate, VBS) and

Since a decade, a lot of attention has been devoted to the
study of nanocomposites built from an assembly of lamellar
inorganic host structure and a polymer [1 – 4]. Owing to
their highly tunable properties, they may find applications in
a large number of fields such as those emphasizing the
mechanical enhancement, gas permeability or membrane
[5 – 8]. Such systems composed of cationic clay have been
largely studied, but in a lesser extent for anionic clay also
called Layered Double Hydroxide materials.
Here, we focused our attention on the polymerization
process between two host structures and the difference for
the obtained nanocomposites.
* Corresponding author. Fax: þ 33-4-73407108.
E-mail address: fleroux@chimtp.univ-bpclermont.fr (F. Leroux).
q
Keynote Lecture.
0022-3697/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jpcs.2003.08.029
polystyrene sulfonate (PSS) were incorporated into Layered
Double Hydroxides (LDH) by templating reaction. The two
host structures investigated are Zn2Al(OH)6Cl·n H2O of
hydrotalcite-type and Ca2Al(OH)6Cl·n H2O of hydrocalu-
mite-type.
The ordered cation repartition within the lamellae and the
peculiar environment of Ca2þ induce an order in the gap of
hydrocalumite, contrary to most of synthetic hydrotalcite
compounds [9]. In this respect, hydrocalumite can serve as a
model for less ordered LDH.
On the other hand, the incorporation of polymer into
hydrocalumite host is of current concern for cement
application [10]. Indeed, like calcium silicate (noted as
C – S –H), these calcium aluminium hydroxide salts called
Friedel salts occur in the hydration process of cement and
their role in the mechanical properties is of major
importance [11 – 12].
386 L. Vieille et al. / Journal of Physics and Chemistry of Solids 65 (2004) 385–393

It was shown that the filling of the large voids present Table 1
initially within the cement was a key factor to reinforce the Chemical analysis of M2Al/Cl (M ¼ Ca, Zn) and the organic derivatives
(the basal spacing is displayed)
whole structure [11]. Those materials are defined as Macro
Defect Free cements. From a theoretical approach [13 – 15], Sample Chemical formulae d-Spacing (nm)
it was demonstrated that the cross-linking of polymer
chains, polyacrylate (PPA) and polyvinylalcohol (PVA), Ca2Al/Cl Ca0.67Al0.33(OH)2Cl0.33·n H2O 0.79
with either Ca or Al atoms could be done via the carboxylate Zn2Al/Cl Zn0.67Al0.33(OH)2Cl0.33·n H2O 0.78
Ca2Al/VBS Ca0.67Al0.33(OH)2(C8H7SO3)0.32·n H2O 1.77
and the termination –O – , respectively. In some cases, the
Zn2Al/VBS Zn0.67Al0.33(OH)2(C8H7SO3)0.32·n H2O 1.82
mechanical properties were achieved when the polymer was Ca2Al/PSS Ca0.67Al0.33(OH)2(C8H7SO3)0.32·n H2O 1.92
truly intercalated between the layers [16]. Zn2Al/PSS Zn0.67Al0.33(OH)2(C8H7SO3)0.33·n H2O 1.93
The incorporation of VBS and of PSS was characterized
by X-ray diffraction, and the interaction of the guest
molecule with the inner-surface of LDH type material was
analyzed by 13C solid state CP-MAS NMR spectroscopy. were placed in a sealed Teflonw tube, and kept at 120 8C for
in situ polymerization is mostly limited by two factors [4]: two days under autogenous pressure.
Elemental analysis (H, C, S, Ca and Al) was performed at
the distance between monomers in the interlamellar the Vernaison Analysis Center of CNRS using inductive
space, conduction plasma coupled to atomic emission spec-
the condition required for the polymerization (tem- troscopy (ICP/AES). The chemical compositions are
perature, pH or redox reaction) which must leave the reported in Table 1.
layered structure intact.
2.2. Instrumentation
The in situ polymerization of VBS is studied as a
function of the temperature and of the LDH layer charge Powder X-ray diffraction profiles (PXRD) were
density. Based on structural considerations, a simple obtained with a X’Pert Pro Philips diffractometer using
model is proposed to modelize the reaction of polym- Cu Ka radiation and equipped with a HTK16 Anton Paar
erization of VBS into the hydrocalumite gap. chamber and a PSD-50m Braun detector (aperture on 28,
155 channels). in situ temperature XRD measurements
were carried out under different conditions with a
2. Experimental sequential temperature increase/decrease of 108/min and
with a temperature holding time of 15 min between each
2.1. Syntheses of the organic derivatives measurement. Scans were performed over the 2u range
from 3 to 708 with a step of 0.03878 and a counting time
The preparation of the pristine host structures M2Al/Cl per step of 60 s.
(M2þ ¼ Ca2þ, Zn2þ) was described elsewhere [17]. Thermogravimetric (TG) analysis was performed on a
The incorporation of sodium styrene-4-sulfonate, noted as Setaram TGA 92 instrument with a linear heating rate of
VBS, CHCH2C6H4SO3Na (Fluka, .90%) and sodium poly 5 8C/min under air.
(styrene-4-sulfonate), noted as PSS (Mw ¼ 70 000; Acros) Scanning electron micrographs and EDX analysis were
was carried out using the ‘templating’ approach [18], i.e. recorded with a Cambridge Stereoscan 360 operating at
during the coprecipitation, an excess of five equivalents of 20 kV (Techinauv, A.S., Aubière, France).
organic anion over Al3þ content was used. Typically, 20 ml of
a solution containing a mixture of CaCl2 or ZnCl2 (0.66 M) and 2.3. Solid state NMR spectroscopy
AlCl3 (0.33 M) is added dropwise under nitrogen atmosphere
13
to 250 ml of an aqueous solution in which 5.155 g of organics C ðI ¼ 1=2Þ and 27Al ðI ¼ 5=2Þ solid state NMR
(VBS or PSS) has been previously dissolved. The conditions experiments were performed with a 300 Bruker spec-
for the coprecipitation were rigorously the same (T, pH and trometer at 75.47 and 78.20 MHz, respectively. For both
aging time) as for the preparation of the pristine sample M2Al/ nuclei, the experiments were carried out using magic angle
Cl, that is to say pH 11.5 and T ¼ 65 8C for M2þ ¼ Ca2þ, and spinning (MAS) condition at 10 kHz and a 4 mm diameter
pH 10.5 and T ¼ 25 8C for M2þ ¼ Zn2þ. The resulting size zirconia rotor. 13C spectra obtained by proton enhanced
powders were washed several times with decarbonated water, cross-polarization method (CP) are referenced to the
then dried under vacuum. carbonyl of the glycine calibrated at 176.03 ppm.
Hereafter, the pristine material and organic derivatives For 27Al nuclei, Al(H2O)3þ 6 was used as a reference.
will be written as M2Al/X (M ¼ Ca, Zn) where X represents Short radio frequency pulses associated to a recycling time
the interlayer anion. of 500 ms were used. Chemical shifts are not corrected from
In order to improve the crystallinity, a hydrothermal the second order quadrupolar effect which induces shift to
treatment was carried out for Zn2Al/PSS samples. They lower frequency [19].
 L. Vieille et al. / Journal of Physics and Chemistry of Solids 65 (2004) 385–393 387

3. Results

3.1. Incorporation of VBS and PSS

The chemical analyses for the chloride LDH materials

and the organic derivatives are in well agreement with what
should theoretically be expected from the initial M to Al
ratio of 2 (Table 1); the amount of organic (given by C and S
contents) is equal to that of Al, and is directly related to the
anion exchange capacity. This led us to assume that the
coprecipitation in presence of organics was complete
leading to a single phase in each case as indicated by XRD.
The diffraction patterns for M2Al/Cl, M ¼ Zn and Ca,
are typical of the hydrotalcite and hydrocalumite structure,
respectively (Fig. 1(a)). For the former, the reflections were
indexed in a hexagonal lattice with a R-3m rhombohedral
symmetry, commonly used for the description of the
hydrotalcite-type structure. Miller indexation is given in
the diagram. Refined cell parameters are the following
a ¼ 3:07 Å and c ¼ 23:37 Å ð¼ 3d003 Þ: For the second, the
structure is described in the rhombohedral space group R-3;
with the refined cell parameters a ¼ 5:74 Å and
c ¼ 23:37 Å.
VBS incorporation between the layers of LDH related
samples is confirmed by a large increase in the basal spacing
(Table 1), the value of which representing the sum of the
layer thickness and gallery height. In both cases, the
interlayer space available is in agreement with VBS
molecules lying perpendicular to the sheets in a bilayer
arrangement [20]. The crystallinity of the two organic
derivatives are quite similar. Compared to the chloride
precursors, an increase in the harmonics ð00lÞ width for both
VBS derivatives was observed, which is likely to be
associated to a significant disorder along the stacking
direction, a phenomenon referred to turbostratic effects. For
Zn2Al host, the broadening of the diffraction line (110)
related to the cell parameter a also shows that a partial
disorder is occurring within the sheets. For the host Ca2Al,
this diffraction line is not modified, but a change from the
space group R-3 to C2=c was evidenced [21].
Conversely, the as-made PSS/LDH related nanocompo-
sites are poorly crystallized (Fig. 1). However, for Zn2Al, a
subsequent hydrothermal treatment improves greatly the
crystallinity of the sample. A basal spacing of d ¼ 19:3 Å
and the in-plane reflections (012) and (110) are observed,
showing that the stacking of the layers was improved as well
as the intralamellar organization after the hydrothermal
treatment. It is noteworthy that such a treatment is
unsuccessful for Ca2Al host which decomposes under
hydrothermal conditions.

3.2. Guest/host interaction

13
C CP-MAS spectra for the two VBS derivatives were Fig. 1. XRD patterns of M2Al/X (M ¼ Ca, Zn) samples, (a) X ¼ Cl, (b)
recorded and presented in the same figure (Fig. 2), for X ¼ VBS and (c) X ¼ PSS. Miller indexing is given for the samples
comparison, the spectrum of Na-VBS molecule is displayed M2Al/Cl (M ¼ Ca, Zn).
388 L. Vieille et al. / Journal of Physics and Chemistry of Solids 65 (2004) 385–393

Fig. 2. 13C CP-MAS spectra of (a) VBS molecule, (b) Ca2Al/VBS, and (c) Fig. 3. XRD patterns after a thermal treatment at 200 and 280 8C of
Zn2Al/VBS. See text for the assignments. M2Al/VBS samples, (a) M ¼ Ca, and (b) M ¼ Zn.

(Fig. 2(a)). The resonance peaks are assigned according to
the literature [22], C1: 113.9 ppm, C2: 137.4 ppm, C3:
141.5 ppm, C4: 125 ppm, and C 5: 143.8 ppm for
C1H2yC2H – C3(C44H4)C5 – SO3(Na). When incorporated
between the clay related sheets, some resonance peaks are
substantially shifted (Fig. 2(a) and (b)). It is associated to
high-field shifts for C2, C3, and C5 carbon atoms. These
shieldings may be explained from an electrostatic inter-
action between SO3 function with the clay inner-surface,
thus weakening the electrophilic character toward C5. Such
an effect propagates through the benzene backbone down to
C1 carbon atoms, which is shifted to down-field values.
It is interesting to note that both structures present a
similar interaction with VBS, leading to similar shifts,
indicating that the forces of attraction are equivalent
probably related to the small difference in the layer charge
between the two host structures, 0.247 and 0.286 nm2/e- for
M2Al, M ¼ Zn and Ca, respectively. The interlayer structure
and the chemical nature of the intralamellar cations seems to
have no effect on the amplitude of interaction.
Similar contractions were observed elsewhere after
thermal treatment and were associated to in situ polymeriz-
ation: for a,b-aspartate (from 11.0 to 9.0 Å) [23] or for
acrylate (from 13.6 to 12.6 Å) [24,25] into hydrotalcite type
compounds and for 1-aminocaproic acid conversion to
nylon into a-ZrP matrix (from 16.3 to 12.2 Å) [26]. To
ascertain whether the polymerization has occurred, 13C
solid state NMR technique was employed, since the
polymerization should change the signal of the carbon
atoms C1 and C2 by the removal of the vinyl bond.
13
C CP-MAS spectra of M2Al/VBS (M ¼ Ca, Zn) were
recorded after thermal treatment at different temperatures
(Fig. 4). In details, C1 contribution associated to the vinyl

3.3. In situ polymerization process

XRD patterns of the VBS exchanged phases after thermal

treatment at 200 and 280 8C is displayed (Fig. 3). In both
cases, the lamellar structure is greatly contracted down to
14.5 and 13.9 Å for d003 of M2Al/VBS, M ¼ Zn and Ca,
respectively. ð00lÞ diffraction lines becomes much broader,
whereas (110) line is unchanged, which implies a slight
disorder in the stacking sequence, leaving unmodified the
intralamellar organization at this temperature. Above
280 8C, the two host structures behave differently: for
Zn2Al, (110) line disappears although the lamellar organ-
ization is maintained, while for Ca2Al, the intralamellar
organization is still present indicating a stronger cohesion in Fig. 4. 13C CP-MAS spectra of M2Al/VBS samples (a) M ¼ Ca, and (b)
the latter host structure. M ¼ Zn. The temperature of treatment is indicated.
 L. Vieille et al. / Journal of Physics and Chemistry of Solids 65 (2004) 385–393 389

bond disappears progressively with the increase in tem-

perature and large humps located at < 40 – 50 ppm,
characteristic of CH and CH2 responses, are observed. For
Zn2Al/VBS, the polymerization happens at lower tempera-
ture than for the other system, the inception of the process
occurs at 120 8C, whereas it is initiated at 180 8C for Ca2Al/
VBS, and the conversion is spread over a large temperature
range. In this latter case, few monomers VBS are still
observed at 200 8C, and thermal treatment at higher
temperature is needed to observe the complete disappear-
ance of vinyl bond signal. The resonance peaks of the
materials resemble that of PSS (Fig. 4(c)). This shows
clearly that VBS molecules were polymerized in the
interlayer space of the two host structures. FTIR analysis
should also give evidence for the polymerization, since this
reaction is accompanied with the formation of CH, CH2
bonds.

3.4. Behavior in temperature

3.4.1. Thermogravimetric analysis

The thermal behavior of the chloride samples has been
previously reported [17,27]. The loss of intracrystalline
water and the dehydroxylation process are partly concomi-
tant appearing as a smooth slope for Zn2Al/Cl whereas it
corresponds to well defined thermal events for Ca2Al/Cl
(Fig. 5(a)) consistent with the well-ordered structure of
Ca2Al/Cl. For both cases, the weight loss between 500 and
650 8C is attributed to the departure of chloride anions.
On the other hand, the thermal decomposition processes
are well separated for Zn2Al/VBS (Fig. 5(b)), while Ca2Al/
VBS exhibits an undisrupted TGA curve with superimposed
thermal events. Finally, the thermal behavior for both M2Al/
PSS nanocomposites is quite similar (Fig. 5(c)).
At high temperature (1000 8C) under ambient atmos-
phere, Zn2Al/X decomposes into ZnO and ZnAl2O4,
whereas the decomposition for Ca2Al/X depends on the
nature of the interlayer anions. For X ¼ Cl, the formation of
CaO and mayenite Ca12Al14O33 was evidenced by XRD;
with X ¼ VBS and PSS, CaO and yeelimite Ca3Al6O12SO4
are formed. Under nitrogen atmosphere, the formation of
ZnS and CaS was evidenced, respectively [21,28].

3.4.2. 27Al MAS NMR

Largely employed for Al containing materials, 27Al
NMR is extremely sensitive in identifying the coordination
state of aluminum atoms [29 –32] 27Al spectra for the
chloride form M2Al/Cl (M ¼ Ca, Zn) were recorded at
different temperatures (Fig. 6). The strong second quad-
rupolar effect for 27Al nuclei ðI ¼ 5=2Þ arises from the non
symmetrical distribution of electrons around the nuclei, it is
also enhanced through the chemical bonds, i.e. the ligands,
making any comparison difficult to establish between
different samples. Nevertheless, two main contributions
are observed, one in the vicinity of 10 –15 ppm ascribed to
the presence of Al atoms in an octahedral environment;
Fig. 5. TG curves for M2Al/X, (a) X ¼ Cl, (b) X ¼ VBS, and (c) X ¼ PSS.
The black line for Ca2Al host and grey line for Zn2Al.
the second in the range of 60 –80 ppm is associated to the
presence of Al in tetrahedral site. A narrow resonance peak
is observed for Ca2Al/Cl until T ¼ 275 8C, that corresponds
to the isotropic contribution, whereas for Zn2Al/Cl, the
resonance peaks are much broader, enlarged by the second
quadripolar effect more important in this latter case. In
temperature, a slight distribution in Al site may also
contribute to the broadness of the signal. The conversion
of Al atoms from Oh to Td site is involved in a narrow
390 L. Vieille et al. / Journal of Physics and Chemistry of Solids 65 (2004) 385–393

Fig. 6. 27Al MAS spectra of M2Al/Cl samples after thermal treatment at (a)
25 8C, (b) 150 8C, (c) 200 8C, (d) 250 8C, (e) 275 8C, and (f) 300 8C. The
black line for M ¼ Ca and grey line for M ¼ Zn. The chemical shifts are
not corrected from the second effect of the quadrupolar interaction.

temperature range (275 – 300 8C) for hydrocalumite,

whereas it is a progressive process for Zn2Al/Cl starting at
150 8C.
For the VBS intercalates, the evolution of the 27Al
spectra is quite similar (Fig. 7). In both materials, it is likely
that the polymerization process has suppressed the collec-
tive conversion of Al site initially present for the host
structure Ca2Al. At 200 8C, both contributions Oh and Td
are observed. For Ca2Al/VBS, an additional contribution at
middle chemical shift d < 50 ppm is observed, which may
be ascribed to Al in pentahedral site (coordination of 4 þ 1).

3.4.3. In situ X-ray diffraction

The interlayer distances recorded under in situ conditions
are reported (Fig. 8). By comparison to the chloride phases
M2Al/Cl, the nanocomposites sustain a lamellar structure at
higher temperature. The presence of polymer thus reinforces
the inorganic framework.
For Zn2Al/Cl, the variation occurring in the temperature
range 25– 150 8C is progressive and small (Dd=d of 5%),
Fig. 7. 27Al MAS spectra of the sample M2Al/VBS after thermal
whereas it is rapid and of greater amplitude (11%) for
treatment at (a) 25 8C, (b) 150 8C, (c) 200 8C, and (d) 250 8C.
Ca2Al/Cl. Afterwards, for the latter, the interlayer distance is The black line for M ¼ Ca and grey line for M ¼ Zn. The chemical
not further modified, whereas a slight increase is observed for shifts are not corrected from the second effect of the quadrupolar
the former. As previously stated [33 –35], the materials keep interaction.
 L. Vieille et al. / Journal of Physics and Chemistry of Solids 65 (2004) 385–393 391

a lamellar organization even if a large Al site conversion has

occurred. It is also remarkable that the variation of the
interlayer distance is not directly related to the Al conversion
rate. Ca2Al/Cl after a thermal treatment at 300 8C shows a
large conversion of Al site from octahedral to tetrahedral
environment, whereas the d-spacing remains the same. The
present work allows us to surmise that the increase of the
basal spacing cannot be directly related to the migration of
AlO4 entities in the interlayer gap, as previously thought. For
M2Al/VBS, the conversion is similar between the two
organoceramics though the variations of the interlayer
distance are different (Fig. 8(b)). The variation is important
in the case of VBS exchanged phase (Dd=d of 20%),
attributed to the dehydration process followed by the linkage
of the VBS molecules. For M2Al/PSS, the interlayer distance
increases above 200 8C and recovers its initial value; one may
interpret this phenomenon by some rearrangement of the
polymer located in the interlayer gap.
Owing to the size of VBS, a d-spacing smaller than 15 Å
is indicative of a highly confined arrangement of VBS in
both structure. Considering the distance between anionic
sites in the ordered hydrocalumite [9,17], the in situ
polymerization can only proceed via a syndiotactic way.
For the less ordered hydrotalcite type sample, few studies of
the local order by XAS have shown the absence of
contribution between trivalent centers [36 – 38]. Hence, the
p
shorter distance Al3þ-Al3þ is of a 3 [39], thus a
syndiotactic polymer can only be considered.
Interestingly, the organoceramics heated in nitrogen
atmosphere transform into inorganic solids of different
composition from the products obtained under ambient
atmosphere. CaS and ZnS are formed after thermal
treatment under nitrogen atmosphere for Ca2Al/VBS and
Zn2Al/VBS, respectively.

3.5. SEM micrographs

The morphological changes accompanying the exchange

of Cl by VBS and PSS and the in situ polymerization of
VBS are shown in Fig. 9(a) –(h). The typical thin platelet
morphology of LDH is only maintained for Ca2Al/VBS. In
the other cases, the microtexture of the material has been
greatly altered. Such changes in morphology have been
observed for poly(vinyl alcohol)/hydrocalumite nanocom-
posite [40]. The Ca2Al/PSS sample appears much more
compact with almost no open structure. For Zn2Al/VBS and
PSS, a crumpled flaky aspect is observed.

4. Conclusion

The interlayer distances are indicative of close contact

between host and guest parts. Interaction of same amplitude
was evidenced by NMR. The confinement into LDH
Fig. 8. Variation of the basal spacing as a function of the temperature for interlamellar space is necessary to complete the polymeriz-
M2Al/X samples (a) X ¼ Cl, (b) X ¼ VBS, and (c) X ¼ PSS. ation, since the reaction is not complete for free VBS
392 L. Vieille et al. / Journal of Physics and Chemistry of Solids 65 (2004) 385–393

Fig. 9. SEM pictures of M2Al/X samples (a) M ¼ Ca, X ¼ Cl, (b) M ¼ Ca, X ¼ VBS, (c) M ¼ Ca, X ¼ VBS after treatment at 250 8C, (d) M ¼ Ca, X ¼ PSS,
(e) M ¼ Zn, X ¼ Cl, (f) M ¼ Zn, X ¼ VBS, (g) M ¼ Zn, X ¼ VBS after treatment at 250 8C, and (h) M ¼ Zn, X ¼ PSS. The bars represent 2 mm.

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