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Magnetic iron oxide-silica nanocomposites. Synthesis and characterization

Corinne ChanCac, Elisabeth Tronc and Jean Pierre Jolivet

Chimie de la Matih-e Condensie, URA-CNRS 1466, Universiti Pierre et Marie Curie, T54, E 5, 4 Place Jussieu, 75252
Paris Cedex 05, France

Composite materials containing nanoparticles of maghaemite (y-Fe203)dispersed in a silica matrix have been made by
polymerizing a silica precursor (triethoxysilane or silicic acid) inside an aqueous sol of maghaemite particles. After gelation, the
examination of xerogels by electron microscopy does not reveal noticeable aggregation of particles. The structure and composition
of the silica matrices were deduced from ,'Si MAS NMR spectroscopy. Thermal analysis, FTIR and NIR spectroscopic studies
showed that the particles and silanol groups of the matrix remain solvated in the composite materials. No Si-0-Fe bonds are
formed in the xerogels and the dispersion of particles in the matrix seems to result from the mutual solvation of particle surfaces
Published on 01 January 1996 on http://pubs.rsc.org | doi:10.1039/JM9960601905

and remaining silanol groups, as indicated by strongly associated hydrogen-bonded water molecules.
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Nanophase materials are interesting for various technological
applications because of the specifically size-related properties
(mechanical, electronic, optical, magnetic, etc.) of crystalline
domains or particles.lY2Nanoparticles of ferrimagnetic oxides
are typically characterized by the superparamagnetic relaxation
phenomenon, which is strongly dependent on the particle size
and shape, on the magnetic interactions between particles and
on various surface effect^.^ The synthesis of calibrated and well
dispersed particles into a rigid matrix is consequently a pre-
requisite for the study of such p h e n ~ m e n a . ~
Composites formed by nanoparticles of maghaemite, y-
Fe203, a spinel iron oxide, dispersed in silica have been
tentatively synthesized by heating a mixture of iron nitrate
and silicon alkoxide between 700 and 900°C.5*6The size and
the dispersion of the maghaemite particles formed during the
thermal treatment seem to be determined by the porosity of
the silica matrix. It is, however, difficult to obtain only the
spinel phase in the form of calibrated and well dispersed
particles. Other attempts consisted of making multiple coatings
of silica on more or less oxidized magnetite particles peptized
in alkaline medium, but the aggregation of particles always
seems to O C C U ~ . ~ * ~
We showed previously that composites with well dispersed
y-Fe,03 particles can be obtained by in situ polymerization of
a silica precursor in a sol of well dispersed y-Fez03 particles,
and we focused on the behaviour of the composites at high
temperatures.' Here, we report the synthesis of composites
from a different silica precursor and we focus on the charac-
terization of the interactions between particles of varying mean
size and the silica matrices by IR spectroscopies and thermal
analysis.
Experimental
Syntheses
y-Fe,03 aqueous sols. y-Fe203 nanoparticles result from the
oxidation of nanoparticles of stoichiometric magnetite, Fe,O,.
They were prepared as described previously," by coprecipi-
tation of Fe( NO3), and FeC1, (Fe"/Fe"' =0.5) in alkaline
medium under vigorous stirring. The control of the precipi-
tation conditions [pH, nature of the base (NaOH or NH,),
ionic strength imposed by a salt, e.g. NaNO,] allowed us to
prepare calibrated particles with a mean size in the range
4-10 nm.'l,12 The black precipitate immediately formed was
first decanted by magnetic settling on a permanent magnet
and then isolated and treated with a concentrated HClO,
(3 mol 1-l) solution. The Fe" ions released in solution13 were
eliminated after centrifugation. The precipitate was treated
repeatedly with the perchloric acid solution until the Fe"/Fe"'
ratio in the solid was ca. 0.01. After the last separation by
centrifugation, the particles were dispersed in pure water,
giving a stable sol of y-Fe203 particles (iron concentration,
1 mol 1-l) at p H z 2 . Under such conditions, the aggregation
of the particles, which are electrostatically positively charged
(C104- counter ions), is at a minimum because of the high
surface charge density (ca. 0.9 C mV2) and the low ionic
strength.',
Dispersion in a silica matrix. Two precursors of silica glasses,
triethoxysilane and silicic acid, were used to prepare iron
oxide-silica nanocomposites. In acidic aqueous medium,
hydrolysis and condensation of the precursors yield a gel which
leads, after drying, to a transparent monolithic g l a ~ s . ' ~By, ~ ~
mixing the precursor with the aqueous maghaemite sol,
hydrolysis and condensation of the precursor take place in
situ, the gelation being catalysed by the acidity of the sol. Such
a procedure leads to homogeneous solid composites.
Triethoxysilane precursor. Acidic water contained in the
maghaemite solution was used for hydrolysis and condensation
of triethoxysilane according to the rea~tion.','~
HSi(OCH,CH,), + 3/2 H20-+HSiOl.,+ 3 CH,CH,OH
The alkoxysilane was added to the sol in a proportion corre-
sponding to a molar ratio H,O/Si>2. In every case, under
vigorous stirring, an emulsion formed initially, then a homo-
geneous solution and finally a gel after 30-45 mn at room
temperature. The gelation time seems to be independent of the
particle concentration. After drying at room temperature, a
brown monolith was obtained. Samples with an Fe/Si ratio
varying between 0.03 and 1.6 were thus prepared. Fe/Si=O.O3
corresponds to H,O/Si = 2 using a sol with an Fe concentration
of 1 moll-l. Fe/Si=1.6 corresponds to the amount of precur-
sor just needed to cover particles of diameter 10nm with a
monolayer of silica.
Silicic acid precursor. Na,Si03 (1 mol 1-l) was exchanged
on a Dowex 50 W X2 resin in H-form and a solution of silicic
acid (ca. 0.45 mol l-l, pH M 3) was collected. The pH was
adjusted to 2 by adding perchloric acid. For preparing com-
posites with Fe/Si 2 0.1, the silicic acid solution was introduced
directly into the sol of y-Fe20, particles. For low particle
concentrations (Fe/Si < O.l), the same procedure leads to a fast
flocculation of the particles. In order to prevent flocculation,

J. Muter. Chem., 1996, 6(12), 1905-1911 1905

 View Article Online
it is necessary to control the pH during the mixing The silicic
acid solution was thus introduced drop by drop into the sol A 8 1
and the pH of the mixture was kept at 2 by adding perchloric
acid We prepared samples with Fe/Si varying between 003
and 0 7 In all cases, homogeneous gels were obtained after a
few days at 50 "C, the gelation time decreasing with increasing
particle concentration Drying at room temperature yielded
homogeneous brown monoliths
Aggregation phenomena observed for low Fe/Si ratios pre-
I I 1 I I I I
sumably result from the acidic catalysis of the condensation of
silicic acid l6 This reaction initially consumes protons from
solution as it is observed when hydrochloric acid is mixed
with silicic acid Thus, when a small quantity of sol ( p H = 2 )
bI
is introduced into a large excess of silicic acid ( p H 3 2 5,
Fe/Si <0 l), the reaction of silicic acid at the particle surface
rapidly lowers the surface charge density and leads to the
flocculation'' before the proton adsorption equilibna at
pH 3 2 5 take place As aggregates are embedded into silicic
acid polymers, the surface cannot be recharged On the other
Published on 01 January 1996 on http://pubs.rsc.org | doi:10.1039/JM9960601905

hand, if protons are supplied by perchloric acid addition, the C

flocculation is prevented If the concentration of particles is
higher (Fe/Si > 0 l),the amount of protons introduced is larger
This allows the protonation of silicic acid with a lesser relative
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decrease in surface charge density Consequently, the stability

of the colloids is not affected significantly and no aggregation
occurs

Techniques
Transmission electron microscopy (TEM) experiments were
performed using a JEOL 100 CX I1 apparatus Observations
of the particles alone were achieved by evaporating a drop of
the very dilute aqueous sols onto a carbon-coated grid The
composites were examined in the form of thin sections,
80-100 nm thick
X-Ray diffraction (XRD) patterns were recorded using a
powder diffractometer (Philips PW 1830) operating in the
reflection mode with Cu-Ka radiation The average particle
size was deduced from the line broadening by applying the
Scherrer formula assuming Gaussian profiles for experimental
and instrumental broadenings
Quasi-elastic light scattering measurements were performed
on aqueous sols with an Amtec SM200 apparatus equipped
with a Brookhaven BI2030 correlator These were used to
control the lack of significant aggregation in the sols
Thermogravimetry and differential thermal analyses
(TG-DTA) were effected using a Netzsch STA 409 apparatus
IR spectroscopic studies were performed in the range
1800-400 cm-' using a FTIR Nicolet 550 spectrometer
Samples dehydrated at room temperature were pelleted with
dned KBr (1% by mass) Near-IR spectroscopic studies in the
wavelength range 2500-800 nm were performed in a closed
cell using a Vanan Cary 5E spectrometer with a 240 nm min-l
scanning rate
29S1 NMR spectra of silicic acid solutions were obtained
using a Bruker AM 250 spectrometer (49 6 MHz) The probe
signal was avoided by the use of a Hahn echo sequence with
a delay of 30ms The silica xerogels were studied using a
Bruker MSL 300 spectrometer (59 6 MHz) with standard
single-phase or cross-polanzation techniques under magic
angle spinning (MAS) conditions
Results and Discussion
Fig l a shows the XRD patterns of y-Fe20, particles of different
mean sizes The lattice parameter is 0 835 nm, independent of
the particle size The line broadening is essentially due to the
size effect The average sizes, deduced from the full width at
half maximum, are consistent with the mean sizes deduced
10 20 30 40 50 60 70 80
2Bldeg rees
Fig. 1 X-Ray diffraction patterns of samples dried at room tempera-
ture a, y-Fe,O, particles of different average diameter, D, composites
made from b, triethoxysilane (D = 10 nm) and c, silicic acid (D= 7 4 nm)
from TEM observations In the composites, the average particle
size remains unaltered (Fig lb,c)
Fig 2a and b show micrographs of composites made from
triethoxysilane and silicic acid, respectively In each case, the
particles appear to be well separated The condensation of
silicic acid is much slower than that of the hydrolysis products
of triethoxysilane In both cases, the polymerization of the
precursors inside the sol allows particles to be trapped without
significant aggregation, and allows the preparation of dispersed
materials in a silica matrix over a large range of iron oxide
concentration However, the two matrices are chemically very
distinct which leads to different effects on the particles during
thermal treatment of the composites (see above)
The dispersability of the particles in the silica matrices may
result from various types of interactions covalent, through
Si- 0- Fe bond formation, electrostatic, between negatively
charged S i r 0 terminal ligands and positively charged groups
on the particle surface, or by hydrogen-bond interactions
between hydration layers of silanol groups and the particle
surface In order to characterize the interactions between the
particles and the silica matrices, we studied separately the pure
silica xerogels and the particles in various states in the initial
aqueous sol, after drying at room temperature and in the
composites
Maghaemite particles
For particles with an average diameter of 5 nm, as deduced
from XRD and TEM, the average hydrodynamic diameter
measured by light scattering on a dilute sol at p H = 2 is
ca 8 nm The large difference in the two sizes shows that a
large amount of water is taken up by the particles in their
thermal motion in the sol, which results from the solvation of
the positively charged surface groups Of course, a rapid
exchange between water molecules in the solvation layer and
the bulk of the sol must occur

1906 J Muter Chem , 1996, 6( 12), 1905-1911

 View Article Online
Published on 01 January 1996 on http://pubs.rsc.org | doi:10.1039/JM9960601905

Fig. 3 DTA-TG curves: a, of 5 nm y-Fe203 particles; b, of composites

from silicic acid (molar ratio Fe/Si =0.7)
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0.
-2 '

-4

-6j
-8
h

8 -10
v
1
$-12C.,, , , , ,h
..,
-vu J o , . , . I . . , ,

8
'
-4
-8
-12
-16
-20
-24

0 100 200 300 400

in
Fig* TEM images Of Y-Fe203 matrix Obtained: a,
from triethoxysilane (10 nm y-Fe203 particles, molar ratio Fe/Si =
0.03); b, from silicic acid (7.4 nm y-Fe203 particles, molar ratio
Fe/Si = 0.07)
Fig. 3a shows typical DTA-TG curves of 5 nm y-Fe203
particles. They indicate a loss of water up to the transformation
into a-Fe203,at ca. 400-500°C depending on the sample. The
water hydration retained by the particles after drying depends
strongly on the mode of dessication. As shown in Fig. 4 the
thermal treatment of powders obtained by drying the sol at
pH = 2 for a few days at room temperature (RT) proceeds with
three successive mass losses, which represent in all ca. 12% by
mass for 10 nm particles (Fig. 4a) and 25% for 5 nm particles
(Fig. 4b); they take place from ca. RT to 180 "C, from 200 to
240°C and beyond 250"C, respectively. The first mass loss
corresponds to the elimination of hydration water which is
relatively weakly bonded (physisorbed) to the particles. For
both particle sizes, this hydration represents ca. three water
layers around each particle, taking into account the mean
volume of the water molecules (3 x l o p 2nm3) in the liquid
phase. The second mass loss corresponds to the removal of
the perchlorate counter ions which are always present because
the particles remain electrostatically charged after drying. The
T1"C
Fig. 4 Thermogravimetry curves: a, 10 nm y-Fe203 particles, pure
silica xerogel from triethoxysilane and composites [SiHo *O, 5(OH)0
(O), Fe/Si=O.17 (m),Fe/Si=1.6 (O), y-Fe203 (O)]; b, 5 nm y-Fe203
particles, pure silica xerogel from silicic acid and composites
[SOl 75(OH)o ( O ) ,Fe/Si = 0.03 (W), Fe/Si = 0.7 ( O ) ,y-Fe,03 (O)].
The y-Fe,03 particles were isolated from aqueous sols (pH = 2) and
dried at temperature.
presence of perchlorate was shown by its characteristic IR
absorption bands (see below), which are still present for
samples heated at 180 "C but are absent for samples heated at
240 "C. Such a temperature range for the removal of perchlorate
as perchloric acid corresponds well to the boiling point (200 "C)
of hydrated perchloric acid." The amount of perchlorate
remaining after drying of the sample is, however, smaller than
that expected from the surface electrostatic charge of the
particles determined in s01ution.l~This is an effect of the
drying process. The drying of particles, involving their progress-
ive concentration, induces a relaxation phenomenon of the
double layer between the oxide surfaces." The increase of the
electrostatic interactions between the particle surfaces leads to
a partial desorption of protons from charged surface groups
as perchloric acid, which evaporates during the drying. Above
250"C, the mass loss results from the removal of strongly
adsorbed water and from the dehydration of surface hydroxy
ligands. A sudden small mass loss is systematically observed
(Fig. 3a) when the y-Fe20, +a-Fe203 transformation occurs.
As the transformation begins by the sintering of aggregated

J . Muter. Chem., 1996,6(12), 1905-1911 1907

 View Article Online
particles,20 water trapped inside the aggregates is suddenly Table 1 Distribution of the different groups into a pure silica matrix
removed during the recrystallization of the aggregates formed by hydrolysis of tnethoxysilane (H,O/Si = 2, pH = 2)
When the drying conditions are harsher (at 50°C or at RT
6 YO
in the presence of P205),the total mass loss, of 5% for 10 nm
particles and 7 5% for 5 nm particles, represents only one OH
water layer around each particle Perchlorate is still present, I
-0-Sl-O- -76 6 13 5
but in a smaller amount, and the extent of hydration is I
comparable with that existing on particles flocculated at H
p H = 7 (near the point of zero charge) and then dried
FTIR spectra of the particles dried at RT (Fig 5a,b) show I
one band in the range 630-580 cm-' (denoted +) correspond- 0
-0-Sl-O- -85 1 66 2
ing to the stretching vibration v ~ of~tetrahedral
- ~ iron atoms I
Perchlorate groups present as counter ions exhibit two bands H
at 1110 and 630 cm-' (denoted *) 21
OH
I
Silica matrices - 0-SI-0 -
I -101 5 7
0
The matnx has a very different chemical composition I
depending on the precursor For tnethoxysilane-based silica,
Published on 01 January 1996 on http://pubs.rsc.org | doi:10.1039/JM9960601905

the relative amounts of various sites (Table 1) were deduced

from 29S1 MAS NMR spectra and refined by 29S1CP-MAS
NMR using MAS data The NMR studies of this pure silica -0-SI-0 - - 111 1 13 5
I
matrix show that, under the hydrolysis conditions employed,
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80% of the Si-H bonds of the precursor are preserved The 0

elimination of ethoxy groups is quasi-complete and the silicium
atoms are in different environments The high proportion of
trifunctional silicium atoms (HSiO, groups) suggests a rela-
Table 2 Distnbution of the different groups into a pure silica matrix
tively low degree of crosslinking of the matrix of mean composi- formed by condensation of silicic acid (pH z 2, Ca= 0 45 mol I I)
tion SiH, 5(OH),
The condensation of pure silicic acid was studied by 29S1 6 %
NMR spectroscopy in solution One hour after the exchange,
no monomer was observed The monomers condense rapidly OH
to form oligomers which aggregate to form a in which I
- 0-SI-OH
67% of the silicon atoms carry at least one Si-OH terminal I -91 5 71
0
bond After gelation and drying at room temperature, the I
relative proportions of the different groups in the xerogel
(Table2) deduced from the 29S1MAS NMR study, lead to a OH
mean composition of SiO, 75(OH)0 In view of the chemical I
-0-SI-0 -
compositions, the matnx appears more crosslinked and more -101 1 38 5
0
hydroxylated than that formed by triethoxysilane hydrolysis I
The xerogel formed from triethoxysilane is therefore more
flexible than the xerogel obtained from silicic acid I
The pure xerogel obtained from triethoxysilane is thermally 0
- O-SI-O- -1100 54 4
I
0
I

stable up to 350°C17 and exhibits only a slight mass loss

(<2%) at ca 100 "C (Fig 4a) corresponding to the elimination
of hydration water Above 350"C, the cleavage of the Si-H
bond occurs, up to the crystallization of the silica network
* into cristobalite near 1400"C Up to 350 "C the pure silica
xerogel obtained from silicic acid dned at RT (Fig 4b) shows
I I I I 1 * 1 1 similar behaviour 22 However, the water loss at ca 150°C
reaches 17% by mass showing greater hydration of the xerogel
in agreement with the NMR analysis Beyond 450"C, a con-
tinuous thermal condensation of the Si-OH groups, rep-
resented by a slight mass loss (2-3%), occurs up to the
transformation of the xerogel into glass
The IR absorption bands of the silica networks obtained
from tnethoxylsilane or from silicic acid in the range
1800-400 cm-' (Fig 5a,b) are listed in Table 3 on the basis of
the absorption spectra of conventional vitreous silica l5 23 24
Silanol group vibrations appear at 3680-3650 cm-' if the
I I I I I 1 9 1 J SiO-H group is isolated and at 3400 cm-' if it is hydrogen
1800 1400 lo00 600
bonded" However, in silica xerogel spectra, these bands are
vlcm
very broad and are not distinguishable from one another
Fig. 5 FTIR spectra of pure xerogels, y-Fe,O, particles and nanocom- because of superimposition of stretching vibrations of hydro-
posites a, from ethoxysilane, b, from silicic acid (symbols see Table 3) gen-bonded water molecules adsorbed on the surface 25 The

1908 J Muter C h e m , 1996, 6 ( 12), 1905-1911


Table 3 Assignments of the absorption bands (in cm-') in pure
SiH, 801 5(OH)0 and SiO, 75(OH)0 xerogels
SiHO 8(OH)0 Z o l
v,, (Sl-0-S1) v 1154 (LO)
1065 (TO)
V, (Si-0-S1) A 824
v (Si-OH) 0 936
6 (Si-H) 0 880
6 (Si-0-Sl) 0 452
" Longitudinal mode. 'Transverse mode.
contributions of various silanol species and water molecules
to the envelope of vibrations near 3400cm-' may be deter-
mined using near-IR spectro~copy.'~
Near-IR studies have been performed in the wavelength
range 2500-800nm where the main groups of absorption
bands of Si-OH and H 2 0 have been a ~ s i g n e d .In ~ ~prin-
,~~
Published on 01 January 1996 on http://pubs.rsc.org | doi:10.1039/JM9960601905
ciple, it is possible to separate free or hydrogen-bonded silanol
groups2, and isolated or associated H 2 0 molecules. The spec-
trum of the pure xerogel obtained from silicic acid (Fig. 6)
essentially shows the vibrations of the silanol groups and water
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molecules.29Three main domains can be distinguished. In the
2400-2250 nm region only the stretching vibrations of Si- OH
groups and a contribution from the bulk of the matrix arise.
In the 2050-1850nm region, there are the combinations of
stretching and deformation vibrations of water, and in the
range 1600-1300 nm are the overtones of the stretching fre-
quencies of silanol groups and water molecules. For each
vibration, the band is asymmetrical. At low energy, the main
band corresponds to isolated groups, free silanol or isolated
water hydrogen-bonded to a silanol group. At higher energy,
the shoulder corresponds to hydrogen-bonded groups, silanol
groups or hydrogen-bonded water molecules.30
Composites
Fig. 3b shows typical TG-DTA curves for a silicic acid-based
composite. The exothermic peak characteristic of the y+a-
Fe203 transformation (Fig. 3a) is no longer observed. XRD
patterns of composites after heating at various temperatures
up to 1400°C are shown in Fig. 7. It is clear that the y-Fe203
particles are stabilized in the composite up to at least 1000"C.
At 1200"C, is the major iron oxide phase and
a-Fe203 appears only beyond 1200 "C. The matrix containing
the particles acts as an antisintering agent, and stabilizes the
spinel structure. In composites with low particle concentration,
structural transformation of the iron oxide occurs only when
the matrix crystallizes into cristobalite. Similar features were
observed with the triethoxysilane-based composites in an oxid-
izing atmosphere.'
Below ca. 400"C, all composite materials exhibit the com-
bined thermal behaviour of the maghaemite particles and the
pure matrix (Fig. 4a,b). This suggests that the formation of
Isolaud H 2 0
,- -
+Bonded SiOH Isolated H70
0.3 .
Q,
c
0
([I
4! 0.2 .
8
n I
([I
0.1 1 l...I.V.l...l...l...I
I I I I
1200 1400 1600 1800
Alnm
Fig. 6 Reflectance NIR spectrum of SiO, 75(OH)* xerogel dned at
100°C for 2 h
View Article Online
I I, Cnstobi
E-Fe,03 + a-Fe203
5 Si(OH)O 5Ol 75 1
1205"
1082'
797
959
-
459
10 20 30 40 50 70 80
2Bldeg rees
Fig. 7 X-Ray diffraction patterns of a silicic acid-based composite
(Fe/Si =0.07) after heating at different temperatures: a, 25 "C; b,
750°C; c, 1000°C; d, 1200°C; e, 1400°C
nanocomposites involves neither the dehydration of the par-
ticles nor that of the matrix.
The FTIR spectra of RT-dried nanocomposites obtained
with the highest and intermediate particle concentrations
[Fe/Si= 1.6 and 0.17 for SiH, ,O, 5(OH), matrix and Fe/
Si=0.7 and 0.07 for SiOl 75(OH)o matrix] are shown Fig. 5.
The absorption bands due to the matrix and those due to the
iron oxide are not shifted. No additional band characteristic
of Si-0-Fe bonds appears, especially around 900 or
680 cm-', as is observed for Fe-substituted silicalite in ZSM5
zeolites33 or ferrisilicates with the sodalite structure.34 The
spectra of the composites can thus be described as superim-
posed spectra of the iron oxide and of the silica matrix. In
Fig. 8 are shown FTIR spectra of composites after heating at
high temperature and characterization using the XRD patterns
given in Fig. 7. The continued polycondensation of the silica
matrix manifests itself (Fig. 8) by the decreasing intensity of
the 970cm-' band assigned to Si-OH vibrations and the
evolution of Si-0-Si vibration bands at 1100, 790 and
500 cm-I is in agreement with the structural transformation
of the silica network. After heating at 1200 and 1400"C, well
resolved bands appear at 580-620 cm-', due to Fe-0-Fe
bonds in E- and a-Fe,03.35,36In these spectra, there is no band
which can reasonably be attributed to Si-0-Fe bonds.
In order to prove the existence of weak interactions between
the surface of the particles and the matrix, it is important to
examine the spectral range 3800-3000 crn-', characteristic of
the stretching vibration of SiO- H and water molecules.
Near-IR investigations on silicic acid-based composites were
carried out on materials dried for 4 days at various tempera-
tures up to 450°C and corresponding to different degrees of
dehydration. The spectra (Fig. 9) of all samples, pure
Si(OH), 501 75 xerogel and composites, show bands located
between 2100 and 1250 nm characteristic of both isolated and
1
1600 1400 1200 loo0 800 600 400
2000 2200 2400 v1crn-l
Fig. 8 FTIR spectra of a silicic acid-based composite (Fe/Si = 0.07)
heated at different temperatures: a, 25°C; b, 750°C; c, 1000°C; d,
1200°C; e, 1400°C.
J . Muter. Chern., 1996, 6(12), 1905-1911 1909

2.5 I 1 0.8
0.6
0.4
0.2
n matrices becomes very different at high temperatures in an
$j 0.8 0.8
-0
a A
0.6 0.6
0.4 0.4
0.2 0.2
n , . . . . . . I L
Published on 01 January 1996 on http://pubs.rsc.org | doi:10.1039/JM9960601905
7200 1400 1600 lsoo 2000
Xlnm
Fig. 9 NIR spectra of silicic acid-based samples thermally treated for
4 days at different temperatures: A, 25°C; B, 100°C; C, 250°C; D,
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450 "C. a, Pure xerogel; composites with 7.4 nm y-Fe,O, particles and
molar ratios b, Fe/Si=O.O3 and c, Fe/Si=O.O7; d, 4.5 nm y-Fe203
particles and Fe/Si =0.07.
associated water molecules. After dehydration above 100 "C,
the band at 1900nm becomes more defined. The hydrogen-
bonded water molecules are eliminated progressively as shown
by the relative decrease of the shoulder near 1950nm and
some isolated water molecules attached to Si-OH groups are
still present. Simultaneously, free silanol groups appear as
shown by the sharp peak at 1360 nm. After thermal treatment
at 25O-45O0C, the spectra are practically the same for all
samples. This is in good agreement with the quasi-complete
dehydration of the samples as shown by the T G curves
(Fig. 4b).
The near-IR spectra (Fig. 9) do not allow us to differentiate
clearly the hydration of the matrix from that of the particles.
However, for the pure silica matrix, free silanols are the main
groups remaining after prolonged drying at 100°C and no
evolution is observed after heating to 250°C (Fig. 9a). In the
composites, (Fig. 9b,c,d), the band near 1450 nm, characteristic
of associated water molecules, is still present after treatment
at 250 "C and such hydration water probably forms multilayers
between the particles and the matrix, as shown schematically
in Fig. 10. This also suggests that the surface of the iron oxide
particles is more strongly solvated than the matrix and the
remaining water is in fact essentially a solvation layer of the
particles. This could indicate that the dispersal of the particles
into the silica matrix results from solvation of silanol groups
Multilayers ,,-HI k ..._ 6 Synthesis, Properties, Applications, ed, G. C. Hadjipanayis and
Fig. 10 Schematic representation of the interactions between the
surface of the y-Fe20, particles and the silica matrix
1910 J. Muter. Chem., 1996, 6( 12), 1905-1911
View Article Online
of the matrix by the associated water layers around the colloids,
without other chemical surface interactions.
Very similar results are obtained for the composites made
from ethoxysilane in the same thermal treatment range. An
advantage given by the ethoxysilane precursor is the rapidity
of the gelation. This matrix is much less hydrated than the
matrix formed from silicic acid. It is also less crosslinked which
is likely to favour particle dispersal. The behaviour of these
inert atmosphere when the cleavage of the Si-H bond leads
to the reduction of the iron oxide particles to U - F ~ . ~
Preliminary Miissbauer spectroscopy investigations of the
same y-Fe203 particles dispersed, at the same concentration,
in silica matrices or in polyvinylic alcohol4 indicate no signifi-
cant changes either in the low-temperature spectra or in their
temperature dependence, Since the superparamagnetic relax-
ation rate is, in principle, very sensitive to surface effect^,^'
these observations support the results of the IR spectroscopic
studies, namely the presence of only weak interactions between
the particle surface and the matrix, and the absence of
Fe-0-Si bonds in our materials. This is in contrast with the
conclusions of Jung3* for silane-coated spinel iron oxide
particles.
Conclusion
In this study, we showed that the polymerization of silica
precursors in an aqueous dispersion of iron oxide nanoparticles
allows the formation of nanocomposites free from aggregation
of particles. This evidently requires control of the particles
dispersion in the starting aqueous sol. Note that the inter-
actions between the surface of particles and the matrix are
very weak and probably involve only the solvation layers.
References
1 H. Gleiter, Nanostruct. Muter., 1995,6, 3.
2 Nanophase Materials. Synthesis, Properties, Applications, ed.
G. C . Hadjipanayis and R. W. Siegel, NATO ASI Ser. E, Applied
Sciences, Kluwer Academic Publishers, Dordrecht, 1993, vol. 260.
3 J. L. Dormann, D. Fiorani and E. Tronc, Adu. Chem. Phys., 1996,
98, in press.
4 E. Tronc, P. Prene, J. P, Jolivet, F. D'Orazio, F. Lucari, D. Fiorani,
M. Godinho, R. Cherkaoui, M. Nogubs and J. L. Dormann,
Hype$. Interact., 1995, 95, 129; J. L. Dormann, F. DOrazio,
F. Lucari, E. Tronc, P. Prene, J, P. Jolivet, D. Fiorani,
R. Cherkaoui and M. Nogues., Phys. Rev. B, 1996,53,14291.
5 M. N. Asuha, J. Muter. Sci. Lett., 1993, 12, 1705.
6 D. Niznansky, J. L. Rehspringer and M. Drillon, IEEE Trans.
Mag., 1994, 30,821.
7 A. P. Philipse, M. P. B. van Bruggen and C. Pathmamanoharan,
Langmuir, 1994,10,92.
8 T. Gacoin, F. Chaput and J, P. Boilot, J. Sol-Gel Sci. Technol.,
1994,2,679.
9 C. Chaneac, E. Tronc and J. P. Jolivet, Nanostruct. Muter., 1995,
6,715.
10 J. P. Jolivet, J. M. Fruchart and R. Massart, Nouv. J. Chim., 1983,
7,325.
11 J. P. Jolivet, E. Tronc and L. Vayssieres, in Nanophase Materials.
R. W. Siegel, NATO ASI Ser. E, Applied Sciences, Kluwer
Academic Publishers, Dordrecht, 1993, vol. 260, p. 45.
12 L. Vayssibres, E. Tronc and J. P. Jolivet, J. Colloid Interface Sci.,
submitted.
13 J. P. Jolivet and E. Tronc, J. Colloid Interface Sci., 1988, 125, 688.
14 C. Chantac, L. Vayssitres, E. Tronc and J. P. Jolivet, J. Colloid
Interface Sci., submitted.
15 C . J. Brinker and G. W. Scherer, Sol-Gel Science, Academic Press,
New York, 1990.
16 R. K. Iler, The Chemistry of Silica, Wiley, New York. 1979.
17 V. Belot, R,J. P. Corriu, D. Leclercq, P. H. Mutin and A. Vioux,
J. Muter. Sci. Lett., 1990, 9, 1052.
18 J. P. Jolivet, De la solution ci I'oxyde, Inter Editions, Paris, 1994.
19 Handbook of Chemistry and Physics, 64th edn., CRC Press Inc.,
Boca Raton, FL, 1983.

20 E. Tronc, J. P. Jolivet and J. Livage, Hyperfine Interact., 1990,
54, 737.
21 G. Socrates, Infrared Characteristic Group Frequencies, 2nd edn.,
Wiley, Chichester, 1994.
22 A. Bertoluzza, C. Fagnano, M. A. Morelli, V. Gottardi and
M. Guglielmi, J. Non-Cryst. Solids, 1982,48, 117.
23 J. Y. Ying and J. B. Benziger, J. Am. Ceram. Soc., 1993,76,2571.
24 M. Prassas, J. Phalippou, L. L. Hench and J. Zarzycki, J. Non-
Cryst. Solids, 1982,48, 79.
25 M. L. Hair, J. Non-Cryst. Solids, 1975,19,299.
26 J. H. Anderson, Jr. and K. A. Wickersheim, Surf. Sci., 1964,2,252.
27 C. Morterra and M. Low, Ann. N . Y. Acad. Sci., 1973,220, 133.
28 F. Orgaz and H. Rawson, J. Non-Cryst. Solids, 1986,82, 57.
29 C . C. Perry and X. Li, J. Chem. Soc., Faraday Trans., 1991, 87,
761; 3857.
30 D. L. Wood and E. M. Rabinovich, J. Non-Cryst. Solids, 1986,
82, 171.
Published on 01 January 1996 on http://pubs.rsc.org | doi:10.1039/JM9960601905
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31 S. Schrader and G. Buttner, Z . Anorg. Allg. Chem., 1963,320,220.
32 L. Walter-Levy and E. Quemeneur, C. R . Acad. Sci., 1963,6,3410.
33 D. Scarano, A. Zecchina, S. Bordiga, F. Geobaldo, G. Spoto,
G. Petrini, G . Leofanti, M. Padovan and G.Tozzola, J. Chem. Soc.,
Faraday Trans. 1993,89,4123.
34 R. Szostak, V. Nair and T. L. Thomas, J. Chem. Soc., Faraday
Trans. 1,1987,83,487.
35 I. Dezsi and J. M. D. Coey, Phys. Status Solidi A , 1973,15, 681.
36 F. Vratny, M. Dilling, F. Gugliotta and C. N. R. Rao, J . Sci. Znd. B,
1961,20, 559.
37 E. Tronc and J. P. Jolivet, Hyperfine Interact., 1986,28, 525.
38 C. W. Jung and P. Jacobs, Magn. Reson. Imaging, 1995, 13, 661;
C. W. Jung, Magn. Reson. Imaging, 1995,13,675.
Paper 6/04363A; Received 24th June, 1996
J. Muter. Chern., 1996, 6(12), 1905-1911 1911