Formation of colloidal particles of hydrous iron oxide by

forced hydrolysis
Wagner R. Meyer
a
, Sandra H. Pulcinelli
a
, Celso V. Santilli
a,
*
, Aldo F. Craievich
b
a
Institute of Chemistry, UNESP, P.O. Box 355, 14801-970 Araraquara, SP, Brazil
b
National Synchrotron Light Laboratory, CNPq and Institute of Physics, USP, SP, Brazil
Abstract
The mechanism of formation and growth of hydrous iron oxide (FeOOH) during the initial stages of forced hy-
drolyses of ferric chloride aqueous solution was studied by small angle X-ray scattering (SAXS). The eect of the
hydrolysis temperature (60C, 70C and 80C) and of the addition of urea on the formation of colloidal particles under
isothermal conditions were investigated. Based on the experimental scattering functions in the Guinier range, we
suggest the presence of elongated colloidal particles. The particle diameter and length, and their variation with time,
were determined by tting the form factor of prolate ellipsoids to the experimental scattering functions. We have as-
sumed that our solutions are in a dilute state and that all colloidal particles are approximately of the same size. The
colloidal particles have geometrical shapes similar to those of the subcrystals that build up the superstructure of
b-FeOOH crystals, indicating that the formation of this hydrous iron oxide is governed by an aggregation process.
Otherwise, the addition of urea hinders the growth and yields smaller particles, with a reduction in size greater than
50%. 2000 Elsevier Science B.V. All rights reserved.
1. Introduction
The preparation of colloidal particles of iron
oxides (Fe
2
O
3
) or hydrous iron oxides (FeOOH)
has been the object of attention in many research
elds [1]. This system has received increasing in-
terest after the work of Matijevic and Scheiner
[2], which demonstrate that small changes in re-
action conditions produce particles with diering
morphologies. Under forced hydrolysis at elevat-
ed temperature, rods, spheres, cubes, double el-
lipsoid, star and cigar-shaped particles precipitate
[2,3]. The crystalline phase of rod, cigar and star-
shaped particles is akaganeite (b-FeOOH), while
double ellipsoidal particles are a mixture of he-
matite (a-Fe
2
O
3
) and goethite (a-FeOOH). The
particles with other shapes have a hematite
structure [2,3].
The chemical conditions for precipitation of
particles with dierent morphologies from ferric
salt solutions is well established [2]. However, the
mechanisms of formation of the particles are not
yet known. Sugimoto et al. [4] found that iron
hydroxide (Fe(OH)
3
) precipitates from concen-
trated (2 mol l
1
) ferric chloride solution and the
subsequent transformation to cubic hematite
particles proceeds in two-steps: Fe(OH)
3
-
brous b-FeOOHcubic-shaped a-Fe
2
O
3
. Each
step of the transformation occurs through a dis-
solutionrecrystallization process. Bailey et al. [3]
proposed that dissolutionrecrystallization is also
Journal of Non-Crystalline Solids 273 (2000) 4147
www.elsevier.com/locate/jnoncrysol
*
Corresponding author. Tel.: +55-16 2016 645; fax: +55-16
222 7932.
E-mail address: santilli@iq.unesp.br (C.V. Santilli).
0022-3093/00/$ - see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 0 9 3 ( 0 0 ) 0 0 1 4 2 - 3
involved in the formation of double ellipsoidal and
spherical hematite from akaganeite rods. How-
ever, these authors, in agreement with Kandori
et al. [5], have proposed that the growth of cubic-
shaped hematite is due to an aggregation mech-
anism. In this model, the initial akaganeite rods
aggregate into rafts of similar length, on which
the hematite nucleates heterogeneously. Other-
wise, de Blanco et al. [6] have suggested a simul-
taneous nucleation of a-Fe
2
O
3
and b-FeOOH,
with akaganeite nucleating at a much greater rate
than hematite.
These dierent mechanisms of a-Fe
2
O
3
forma-
tion producing dierently shaped particles were
proposed [36] based on results of measurements
of compositional changes of iron species and ob-
servations of the morphological evolution of a
solid phase. The morphological studies were per-
formed by means of ex situ transmission electron
microscopy on dried solutions after an aging time
of order of weeks.
Studies of morphological changes during the
initial stages of formation and growth of b-Fe-
OOH from hydrolysis of iron chloride aqueous
solution are not reported in literature to our
knowledge. Information concerning the kinetics
of the early stages may clarify the mechanisms,
which produce to the already observed a-Fe
2
O
3
particles with diering morphologies. Further-
more, b-FeOOH crystals have an unusual su-
perstructure [7,8] built up by an orthogonal
array of hollow rod subcrystals, with 3 and 6 nm
of internal and outside diameters, respectively.
An understanding of the mechanism of forma-
tion of these crystals may contribute to the
development of methods for preparation of hol-
low microbers, which can be used for separa-
tion processes by ionic changes or hyperltration
[9].
The aim of this investigation is to study the
initial stages of formation and growth of hy-
drous iron oxides by forced hydrolysis of ferric
chloride aqueous solution. The eects of the
hydrolysis temperature and of the addition of
urea on the kinetics of formation under iso-
thermal conditions were analyzed by means of
in situ small angle X-ray scattering (SAXS)
technique.
2. Experimental
2.1. Sample preparation
All reagent grade chemicals were used without
further purication and water was deionized
through a millipore apparatus (Elix 3). The stock
ferric chloride aqueous solution (0.l mol dm
3
) was
prepared at room temperature to minimize hy-
drolysis. The colloidal particles were prepared
from ferric chloride solutions and aged at constant
temperatures (6080C) during dierent periods of
time. Another ferric chloride solution containing
urea was also studied. In this case, 0.025 dm
3
of
ferric chloride solution was added to 3 g of urea
and aged at 60C, 70C and 80C. The isothermal
aging of the dierent solutions were performed
during in situ measurements of pH, optical trans-
mittance, and SAXS.
2.2. pH and optical transmittance measurements
After stirring, some drops of the initial solu-
tions were put into a cell between two Kapton
lms distant with a separation of 0.8 mm and the
cell placed in a hot stage (Metler FP82) coupled to
a central process (Metler FT90) to keep the tem-
perature constant and stable within 0X1C. A
control sample was submitted to similar forced
hydrolysis condition. The changes of pH and of
optical transmittance (k = 630 nm) of the sample
during isothermal treatment were monitored by
using a 3
1
2
digit pH meter and a photoeletric pho-
tocolorimeter (B-340 Micronal), respectively. The
glass electrode used for pH measurements was
calibrated with Electrofact buer solutions of pH
4.00 and 1.58 (Calisol from Micronal). The accu-
racy of pH measurements was about 0X03 pH
units.
2.3. SAXS measurements
SAXS experiments were carried out using the
D24 SAXS synchrotron beamline at LURE,
Orsay, France. The beam was horizontally focused
by a bent silicon crystal yielding a monochromatic
beam with a wavelength k = 0X149 nm. Two sets
of slits were used to dene a pinhole collimation.
42 W.R. Meyer et al. / Journal of Non-Crystalline Solids 273 (2000) 4147
The experimental scattering functions, I(q), were
determined as functions of the scattering vector, q,
(q = 4paksin(ea2), e being the scattering angle).
The scattering function was recorded using a linear
vertical position sensitive detector coupled to a
standard multichannel analyzer. Parasitic air and
slit scattering were subtracted from the total in-
tensity. An ionization chamber, placed down-
stream from the sample, was used to monitor the
intensity decay of the transmitted beam and to
determine the sample attenuation. The natural
decay in intensity of the incident beam was mea-
sured by recording the electronic current in the
synchrotron source. Due to the small size of the
incident beam cross-section at the detection plane,
no mathematical desmearing of the experimental
data was needed. SAXS data collection started just
after placing the sample into the temperature cell.
Each spectrum was collected during a time interval
of l50 s.
2.4. SAXS analysis
During the initial period of forced hydrolysis
the concentration of solid phase increases from
zero. Thus, the system can be considered during
the rst stages as a dilute solution of randomly
oriented particles. In the case of a dilute solution
of not too anisometric particles, the asymptote at
q ` 1aR
ge
of the scattering function is given by the
Guinier approximation [10]
I(q) = I(0) exp(R
2
ge
q
2
a3) (q ` 1aR
ge
)Y (l)
where R
ge
is the radius of gyration of the particle.
In the case of anisotropic and ellongated particles
(for example, cylinders with their length much
larger than the diameter), the asymptote of I(q) at
small q becomes
I(q)q = Aexp(R
gc
q
2
a2) (q ` 1aR
gc
)Y (2)
where R
gc
is the radius of gyration of the section of
the particle perpendicular to its long axis.
The shape of elongated particles can in some
cases be approximated by that of a prolate ellip-
soid. For this shape of particle, the scattering
function is given by Guinier and Fournet [10]
I(q) = I(0)

1a2
0
u
2
qR cos
2
w
h
&
LaR ( )
2
sen
2
w
i
1a2
'
cosw dwY (3)
where u
2
(x) = [3( sin x xcosx)ax
3
[
2
and R and L
are the minor and major semi-axes, respectively.
3. Results
pH and transmittance were determined as
functions of aging time at 60C and 80C. The
results are plotted in Fig. 1(a) and (b), respectively,
for solutions prepared with (squares) and without
(circles) urea. Three stages of the aging process can
be identied:
(a) An initial stage (t ` 20 min) in which pH
and transmittance decrease. The decreasing rate
in this period and the minimum reached de-
crease, for the sample prepared at the lower
temperature (60C) and by adding urea.
(b) An intermediate stage (t b 20 min) has a
slower decrease of pH and transmittance. The
time corresponding to the end of this period is
less for sample temperature of 80C and by add-
ing urea.
(c) An advanced stage with a decrease in trans-
mittance without changes in pH or with an in-
crease in pH for samples containing urea. At
the end of this period, the transmittance tends
to zero and the beginning of the sedimentation
of precipitates occurs.
Logarithmic plots of the experimental SAXS
functions, I(q) versus q
2
(open symbols), corre-
sponding to samples prepared at 70C with and
without addition of urea, are shown in Fig. 2(a)
and (b), respectively.
In the upper part of Fig. 2(a) and (b), some of
the scattering functions are also plotted as log I(q)
versus q
2
(full symbols). These data do not have
the linear dependence at small q expected from the
classical Guinier approximation (Eq. (1)). On the
contrary, the set of experimental scattering func-
tions plotted in log I(q)q versus q
2
scale have the
linear dependence predicted by Eq. (2), which
corresponds to the model of scattering by elon-
gated particles.
W.R. Meyer et al. / Journal of Non-Crystalline Solids 273 (2000) 4147 43
The linear dependence predicted by Eq. (2) is
observed only within the q range 0X1 nm
2
` q
2
` 0X5 nm
2
(Fig. 2) for samples prepared at
70C with and without addition of urea. A similar
dependence was observed during forced hydrolysis
of ferric chloride aqueous solutions aged at 60C
and 80C. The negative deviations of linearity
observed at small q (q
2
` 0X1 nm
2
) indicate that
the scattering is produced by elongated but not
`innitely' long particles.
To theoretically determine the whole scatter-
ing function, we have assumed that all elongated
particles have nearly the same size and that their
shape can be approximated by that of a prolate
ellipsoid of revolution. The theoretical scattering
function of ellipsoidal particles (Eq. (3)) was
tted to all experimental scattering functions.
The results of the ttings, plotted in Fig. 2(a)
and (b) as continuous lines, indicate agreement
between the theory and experiments to within
6%.
The minor and major semi-axes of the ellip-
soidal particles are plotted in Fig. 3 as functions
of aging time for dierent synthesis conditions.
The results indicate a particle growth during an
initial stage (t ` 20 min) and a constant size in a
Fig. 1. Time evolution of pH (a) and transmittance (b) during
forced hydrolysis of solution with (circles) and without
(squares) addition of urea. The lines are drawn as guides to the
eye; the data error is of the order of the data symbol size.
Fig. 2. Guinier plots for the approximation of globular (full
symbol) and elongated (open symbol) shaped particles corre-
sponding to the forced hydrolysis of ferric chloride aqueous
solution at 70C, with (a) and without (b) addition of urea. The
continuous lines are ttings of Eq. (3) to the experimental
scattering functions. The curves were vertically displaced for
clarity. The error bar indicated holds for q
2
>0.1; for smaller q,
the data error is of order of data symbol size.
44 W.R. Meyer et al. / Journal of Non-Crystalline Solids 273 (2000) 4147
later stage for all synthesis conditions. In the
later stage, the elongated particles prepared in
absence of urea at 60C and 70C have a minor
radius of 4X8 0X2 and 4X2 0X2 nm and a major
semi-axis of 26 230 2 nm, respectively.
Solutions containing urea under forced hydroly-
sis at 70C are composed of particles with a
minor radius R = 2X2 0X1 nm and a major
semi-axis L = 11 1 nm. These results demon-
strate that the addition of urea limits particle
growth.
4. Discussion
The results of this study indicate that the initial
stages of the forced hydrolysis of ferric chloride
aqueous solutions protonate, increase light ab-
sorption at 675 nm, and elongated small particles
grow. In this reactional system, protons may be
released by coordinated water molecules (olation)
or from coordinated hydroxo-groups (oxolation)
[11] as a consequence of condensation reactions
involving intermediate hydrolysis products
[Fe(H
2
O)
6n
(OH)
n
]
(3n)
[11].
Reviewing data of literature, Flynn [1] proposed
that olation and oxolation reactions involved in
the growth of iron(III) hydrolytic polymer can be
represented as
Fe(OH)
2
(H
2
O)

4a2
h i
n
Fe(H
2
O))
6

3
Fe(OH)
2
(H
2
O)

4a2
h i
n1
2H

2H
2
O (4)
and
2 FeOH)
2
(H
2
O)
(42p)a2
(OH)
(1p)
2pa2
h i
n(single chain)
Fe(H
2
O)(OH)
2a2
O
3a3
h i
2n(double chain)
2n(1 p)H

2nH
2
OX (5)
As a consequence of these polycondensation re-
actions, the initial yellow-colored solution, char-
acteristic of monomer species, changes to deep
red-brown, which absorbs in the visible region [1].
These features are in general agreement with our
experimental results of the optical transmittance
obtained during rst 20 min of forced hydrolysis.
The presence of elongated particles was detect-
ed in scattering spectra after aging times, t = 150 s,
which time indicates a faster reaction between the
initial monomers. This rate is consistent with the
olation reaction rate (10
3
M
1
s
1
) of iron(III)
species [11]. On the contrary, the oxolation is a
slower process and does not proceed as fast as
olation [11]. Thus, the slow particle growth ob-
served experimentally by SAXS (t ` 20 min)
would correspond to oxolation reactions.
The elongated (ellipsoid-like) shape and the size
of the particles determined by SAXS are consistent
Fig. 3. Time evolution of the major L and minor, R, radius of
the elongated particles prepared under dierent conditions of
forced hydrolysis of solution with (circle symbol) and without
(square symbol) addition of urea. The lines are drawn as guides
to the eye; the data error is of order of data symbol size.
W.R. Meyer et al. / Journal of Non-Crystalline Solids 273 (2000) 4147 45
with transmission electron microscopy results re-
ported by Dousma [12] and more recently by
Bayley [3], for b-FeOOH obtained at room tem-
perature by base addition to an acidied ferric
chloride solution. They observed that short and
long radius of isolated particles decrease from
R = 3X0 0X2 nm, L = 15 2 nm to R = 2X0 0X1
nm, L = 10 1 nm, respectively, by increasing
base addition. Furthermore, the ratio LaR = 5 is
similar to the ratio obtained in the present study
for samples containing urea. In the absence of
urea, the LaR ratio corresponding to reaction time
equal to 150 s increases from 5X8 0X3 to 80 as
temperature increases from 60C to 80C. Fur-
thermore, the LaR ratio of particles prepared at
80C decreases from 80 to 23 during the initial
time period (t ~ 20 min), while under the other
synthesis conditions, LaR remains practically time
invariant. Such features indicate that, initially, the
particles are large ribbon-like polymers, formed
preferentially by end-on addition of soluble species
(Eq. (4)). The tendency to lateral addition (Eq. (5))
to the growing polymer increases with addition of
urea and by decreasing temperature.
This dierence in the growth process is fre-
quently attributed to limited hydrolysis due to the
presence of complexing anions [1,2,11]. The pres-
ence of chloride complexing ligands along poly-
meric chains inhibits lateral addition, so forming
ribbon-like species. Since chloride is a weak com-
plexing anion [11], a rapid exchange of chloride
and hydroxyl ions in polymer complexes should
occur by increasing the amount of OH

in solution
due to urea decomposition. Thus, oxolation and
lateral growth take place which reduces the LaR
ratio of the particles.
The cross-section diameters, 2R, of the colloidal
cyllindrical particles, determined by SAXS (2 62R6
10 nm), approximately correspond to the size re-
ported in the literature [6,7] for the subcrystals
that build up the b-FeOOH crystals. Based on our
results of transmittance measurements (Fig. 1), we
suggest that the observed shaped b-FeOOH crys-
tals are formed by an aggregation process starting
from suspensions of isolated and colloidal pri-
mary particles such as those that we have mea-
sured by SAXS. This aggregation leads to the
observed decrease in light transmittance (Fig. 1)
at advanced stages of synthesis and to further
sedimentation. This advanced stage would corre-
spond to the formation of the superstructures
consisting of cigar-shaped particles of micrometer
size observed [6,7] in sediments of similar colloidal
suspensions.
5. Conclusion
The formation of b-FeOOH colloidal particles
by forced hydrolysis consists of several stages.
During the early stage, the end-on addition of
soluble species to the growing polymer leads to the
formation of ribbon-like particles. The lateral ad-
dition to polymer chains occurs slowly resulting in
the formation of elongated particles. The size and
the ratio between the major and minor semi-axis of
these particles are determined by the conditions of
forced hydrolysis. The presence of urea during
synthesis limits particle growth.
The elongated particles formed in the early
stage have the size and the shape characteristic of
the subcrystals that build up the superstructure of
b-FeOOH, which indicates the formation of the
b-FeOOH crystals occurs in an advanced stage
and is determined by an aggregation process.
Acknowledgements
This work has been supported by CAPES/
COFECUB, FAPESP and PRONEX (Brazil).
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W.R. Meyer et al. / Journal of Non-Crystalline Solids 273 (2000) 4147 47