Colloids and Surfaces

A: Physicochemical and Engineering Aspects 186 (2001) 23 31

www.elsevier.nl/locate/colsurfa

Influence of ionic and nonionic dextrans on the formation

of calcium hydroxide and calcium carbonate particles
Vishwas V. Hardikar 1, Egon Matijevic *
Center for Ad6anced Materials Processing, Clarkson Uni6ersity, Box 5814, Potsdam, NY 13699 -5814, USA

Abstract
The effects of nonionic, cationic, and anionic dextrans on the precipitation of calcium hydroxide and calcium
carbonate particles in aqueous solutions were investigated by varying different experimental parameters. Nonionic
dextrans had no observable effect on the resulting dispersions. The addition of ionic dextrans in basic solutions
altered the morphology of calcium hydroxide. Precipitation of calcium carbonate particles, in the presence of urea,
was influenced significantly only by the anionic dextran, which affected both the morphology and the crystal structure
of the precipitated particles. In neutral or slightly acidic solutions, Ca2 + ions reacted with anionic dextrans to form
a coacervate, which was the result of neutralization of the sulfate groups of the polymer by this cation. The so formed
ion pairs could be eliminated by the addition of an excess of nonbinding Na+ ions, resulting in the dissolution of the
separated phase. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Calcium carbonate; Calcium hydroxide; Coacervates of Ca-dextran sulfate; Dextrans; Polyelectrolyte effects on precipitation

1. Introduction
It is a well-known fact that polymers, which
tend to adsorb at the solid liquid interface, may
greatly influence the formation of solid particles
in a solution. The extent of these effects, which
include the particle size, morphology, and stability, depends on the composition, structure, molecular weight, concentration, conformation, as well
as sign and the magnitude of the charge of the
extraneous solutes. A better understanding of the
* Corresponding author. Fax: + 1-315-2686656.
E-mail address: metcalf@agent.clarkson.edu (E. Matijevic).
1
Part of Ph.D. thesis.

nature of these findings could help our ability to

control the characteristics of the precipitated
solids for various applications and to explain
some phenomena of biological interest.
Calcium compounds are used in a variety of
industrially important processes and this has led
to a considerable interest in the formation of these
compounds, especially by precipitation in aqueous
solutions. For example, calcium hydroxide is an
important part of the Portland cement and the
effect of various additives on its crystals is of
relevance to the cement and concrete industry [1].
Recently, the use of calcium hydroxide as a bulk
low-cost filler has been suggested [2]. This approach differs from works in which organic

0927-7757/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 7 - 7 7 5 7 ( 0 1 ) 0 0 4 7 9 - 4

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V.V. Hardikar, E. Matije6ic / Colloids and Surfaces A: Physicochem. Eng. Aspects 186 (2001) 2331

molecules were grafted onto Ca(OH)2 particles in

order to alter their properties [3,4].
Calcium carbonates (calcite, aragonite, and vaterite) have been extensively studied due to their
industrial (as pigments, brighteners, fillers, adsorbents, etc.) and biomedical uses. For these reasons, various approaches for the preparation of
these solids have been described, which include
the growth of calcium carbonate crystals under
Langmuir [5 7] and self-assembled monolayers
[8,9], and their precipitation in the presence of
metal ions as dopants [10,11], polymers [12,13],
synthetic organic molecules [14 16], and macromolecules derived from mollusk shells or seaurchins skeletons (biomineralization) [1720].
Water soluble polysaccharides, especially dextrans, which are composed of repeated
monomeric glucose units mainly connected by
a-1,6 glycoside bonds with some a-1,3 bonds,
have been used as additives to investigate the
effects of polymers on the nucleation and growth
of solid particles in aqueous solutions [21,22],
stabilization of sols [23,24], adsorption on the
preformed particles [25 28] and subsequent influence on particle deposition [29]. Dextrans are
especially convenient for this purpose, because
they are available over a wide range of average
molecular weights of narrow distributions, and
with substituents which yield molecules of different signs of charge. This study describes the influence of various ionic and nonionic dextrans on
the size and morphology of calcium hydroxide
and calcium carbonate particles precipitated in
aqueous solutions. An evaluation of the effects of
these polymers has been facilitated by recently
described procedures, which yielded such inorganic particulates of different morphologies, but
rather uniform in size [30].

(MW 500 000) and dextran sulfate, (DexS-500,

MW 500 000 and DexS-1000, MW 1 000 000,
Polysciences Inc.), were used as received. All solutions were freshly prepared and filtered through
0.22 mm Millipore membranes before use. The
number of sulfate groups per glucose unit of
dextran sulfate molecule, reported earlier [22],
ranged from 1.8 to 2.

2.2. Preparation of calcium hydroxide particles

Particles of Ca(OH)2 were obtained in a typical
(standard) experiment by adding 20 cm3 of a 1
mol dm 3 NaOH solution at a flow rate of 5 cm3
min 1 into 100 cm3 of a 0.1 mol dm 3 CaCl2
solution, stirred at 400 rpm at room temperature.
To investigate the effect of some other parameters, the concentration of CaCl2 was varied from
0.01 to 0.1 mol dm 3, and Ca(NO3)2 or
Ca(CH3COO)2 were used instead of CaCl2. In
addition, some experiments were carried out at
50C under otherwise standard conditions. Dextrans were added to the CaCl2 solution in concentrations ranging from 0.01 to 1 wt.%. At the end
of the reaction, the solids were separated through
0.45 mm pore size MSI filters, rinsed with distilled
water, dried in a vacuum oven, and then stored in
a desiccator.

2.3. Preparation of calcium carbonate particles

The preparation of CaCO3 (aragonite) particles
was carried out using urea, by a method described
earlier, which also outlined the chemistry of their
formation [30]. In a standard experiment, 0.25
mol dm 3 of a CaCl2 solution was mixed with
0.75 mol dm 3 urea and aged in a forced convection oven at 90C for 4 h. Again, polymer concentrations (when used) varied between 0.01 and 1
wt.%.

2. Experimental

2.4. Characterization of particles

2.1. Materials
Nonionic dextrans of two different average
molecular weights, Dex-15 (MW 15 000) and Dex500 (MW 500 000, Fluka Chemicals) and the
cationic and anionic derivatives, Dex-DEAE-500

The size and morphology of particles were examined by scanning electron microscopy (SEM)
and their structure and lattice parameters were
evaluated by X-ray diffraction (XRD). Crystalline
phases of both calcium hydroxide and calcium

V.V. Hardikar, E. Matije6ic / Colloids and Surfaces A: Physicochem. Eng. Aspects 186 (2001) 2331

carbonate were identified according to the ICDD

Powder Diffraction File [31]. Infrared spectra
were recorded on pellets containing 2 mg of sample in 10 mg of KBr.
Viscosities of the polymer solutions were determined with an Ostwald Cannon Fenske size S100 viscometer, which was kept in a water bath at
2590.1C. Flow times were measured with a
stopwatch capable of registering 0.01 s and were
reproducible to 0.4 s.
In separate sets of experiments the interactions
of Ca2 + ions with dextran sulfate were studied in
the absence of base (NaOH) and the change in
turbidity was followed in systems containing varying concentrations of CaCl2, at a constant concentration (0.5 wt.%) of DexS-500 or in systems
containing varying concentrations of the polymer
at constant concentrations (0.1, 0.2, or 0.5 mol
dm 3) of CaCl2. The turbid samples were centrifuged and the deposit was analyzed by Fourier
transform infrared (FTIR), while the content of
Ca2 + in the supernatant solution was determined
by atomic absorption spectroscopy (AAS). The
disappearance of the separated phase in a system
containing CaCl2 and DexS-500, which gave maximum turbidity, was studied by the addition of
varying concentrations of NaNO3.

3. Results

3.1. Viscosities of polymer solutions

25

NaOH, as determined at the end of the precipitation process. The width of the particles was relatively uniform (4 mm), but their length varied
considerably. Similar results were obtained when
CaCl2 was replaced by Ca(NO3)2, yet the use of
Ca(CH3COO)2 resulted in irregular particles of
 1 mm in size. At a higher temperature (50C), a
larger number of smaller particles precipitated.
The lowest CaCl2 concentration at which a solid
phase appeared in 1 mol dm 3 NaOH was found
to be  0.1 mol dm 3.

3.2.1. Effect of dextrans

The addition of Dex-15 and Dex-500 in concentrations ranging from 0.01 to 0.5 wt.% had no
effect on the size or morphology of particles
precipitated under standard conditions.
The presence of varying concentrations of the
anionic dextrans affected both the size and the
morphology of Ca(OH)2 particles. Thus, with increasing concentration of DexS-500 from 0.01 to
1 wt.%, the shape changed from highly irregular
to more or less spherical and the average particle
size decreased from 10 to 23 mm. In contrast, the
addition of DexS-1000 at 1 wt.% resulted in reasonably uniform discs of 3 mm in diameter, as
illustrated by the SEM in Fig. 2(b).
The cationic polymer had a significant effect on
the morphology of the particles. There was a
gradual variation from hexagonal to ellipsoidal to
polyhedron shaped particles as the Dex-DEAE-

Viscosities of the polymer solutions used in this

work are given as a function of their concentrations in Fig. 1. Ionizing groups cause a substantial
increase in viscosity as compared with the nonionic forms of the same polymer at the same
concentrations.

3.2. Calcium hydroxide particles

Using the standard conditions, hexagonal prismatic crystals of calcium hydroxide were generated as illustrated in Fig. 2(a). The XRD pattern
of these particles was shown to be characteristic
of portlandite. The pH of the CaCl2 solution was
5.8, which changed to pH 12 on addition of

Fig. 1. Viscosity of solutions of nonionic Dextran-15, 500, of

Dextran-DEAE-500 and of DexS-500 as a function of polymer
concentration (wt.%).

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V.V. Hardikar, E. Matije6ic / Colloids and Surfaces A: Physicochem. Eng. Aspects 186 (2001) 2331

including the flower-like structure of vaterite,

described elsewhere [30]. Changing the concentration of DexS-500 from 0.1 to 1 wt.%, resulted in
polydispersed spherulites of CaCO3, similar to
those shown in Fig. 3(b).

3.4. Interactions of dextran sulfate with Ca 2 +

ions
Earlier studies [3234] indicated that dextran
sulfate did not form precipitates with Ca2 + ions
even at 2 mol dm 3 concentration of the latter in
aqueous solutions, but no information was offered regarding the pH of the investigated systems. Since no new phase was observed, the
solutions must have been either neutral or acidic.
Contrary to these reports, it was established in the

Fig. 2. SEM of (a) calcium hydroxide particles prepared by

adding 20 cm3 of a 1 mol dm 3 NaOH solution at a flow rate
of 5 cm3 min 1 into 100 cm3 solution of 0.1 mol dm 3 CaCl2,
and (b) calcium hydroxide particles formed under the same
(standard) conditions in the presence of 1 wt.% DexS-1000.

500 concentration varied from 0.01 to 0.1 to

0.5 1 wt.% (Fig. 3).

3.3. Calcium carbonate particles

Fig. 4(a) shows uniform needle-like aragonite
particles precipitated as described before [30]. The
particles have a mean length of 45 mm and an
aspect ratio of 8.
Nonionic dextrans had no effect on the formation of these crystals at concentrations ranging
from 0.01 to 1 wt.%. Varying the content of
Dex-DEAE-500 from 0.1 to 1 wt.% resulted in a
mixture of all three polymorphs (calcite, vaterite,
and aragonite) of calcium carbonate (Fig. 4(b)),

Fig. 3. SEM of calcium hydroxide particles formed under

otherwise standard condition in the presence of (a) 0.1 wt.%
Dex-DEAE-500, and (b) 1 wt.% Dex-DEAE-500.

V.V. Hardikar, E. Matije6ic / Colloids and Surfaces A: Physicochem. Eng. Aspects 186 (2001) 2331

27

Fig. 5. Turbidity, ~, of solutions containing 0.5 wt.% DexS500, as a function of varying CaCl2 concentrations.

Fig. 4. SEM of (a) calcium carbonate particles obtained by

aging a solution containing 0.25 mol dm 3 CaCl2 and 0.75
mol dm 3 urea at 90C for 4 h (standard condition), and (b)
a mixture of calcite, vaterite and aragonite polymorphs obtained in the same system in the presence of 1 wt.% DexDEAE-500.

present work that dextran sulfate reacted with

CaCl2 in aqueous solutions in concentrations as
low as 0.01 mol dm 3 at pH  6, resulting in
opaque dispersions. Specifically, a turbidity maximum appeared when the concentration of Ca2 +
was varied at constant wt.% of DexS-500 (Fig. 5),
or when wt.% of DexS-500 was changed at constant Ca2 + concentration (Fig. 6). These turbidity
results were found reproducible. The separated
phase, as observed by optical microscopy, consisted of droplets of various sizes illustrated in
Fig. 7, which are characteristic of coacervates
[35,36].

The system containing 0.1 mol dm 3 of Ca2 +

and 0.5 wt.% of DexS-500 was centrifuged and
the FTIR spectrum of the separated phase
matched exactly that of pure DexS (Fig. 8), indicating the absence of covalent bonds between
DexS and calcium. The concentration of the
Ca2 + ions in the supernatant solution, determined by the AAS, was found to be  0.09 mol
dm 3, showing that only  0.01 mol dm 3 of
Ca2 + was bound to DexS. It was assumed that
the coacervate was formed by ion pairing of Ca2 +
with sulfate groups of DexS. Consequently, it was
reasoned that it should be possible, in principle,
to dissolve the coacervate by replacing Ca2 + with
Na+, which is only weakly associated with dextran sulfate. Indeed, when NaNO3 was added in

Fig. 6. Turbidity, ~, of solutions containing 0.1 mol dm 3

CaCl2, as a function of varying concentrations of DexS-500.

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V.V. Hardikar, E. Matije6ic / Colloids and Surfaces A: Physicochem. Eng. Aspects 186 (2001) 2331

Fig. 7. Optical micrograph of the separated phase obtained in

the system containing 0.1 mol dm 3 CaCl2 and 0.5 wt.%
DexS-500.

sufficiently high concentration, dissolution of the

coacervate took place as evidenced by the decrease in the turbidity (Fig. 9).

4. Discussion
When discussing the effects of polymers on the
precipitation of inorganic solids one must evaluate the possible interactions of ionic constituents
with polyelectrolytes and the influence of macromolecules on the morphology, size, and the stabil-

Fig. 9. The change in the turbidity, ~, of solutions containing

0.1 mol dm 3 CaCl2 and 0.5 wt.% DexS-500, in the presence
of increasing concentrations of NaNO3.

ity of the resulting solids. To explain the

observations in the studied systems, it is necessary
to consider the nature of the surface groups on
the Ca(OH)2 and CaCO3 particles and their arrangement, which is affected by the crystal structure of both.
Studies on the precipitation of Ca(OH)2 prismatic crystals have revealed that the initial growth
took place parallel to the (0001) plane (i.e. perpendicular to the c-axis) resulting in platelet like
crystals [37]. Further growth occurred layerwise
along the c-axis, which explained the constancy of
the particle width, but their irregular length. Electron diffraction studies [3,4] have indicated that
the hexagonal face of the prismatic crystal is the
(0001) plane, rich in OH groups aligned with the
c-axis.
In aragonite, the (001) face consists of
unicharged layer of the Ca2 + plane with two
layers of carbonates between each Ca2 + plane
and exhibits a net dipole along the 001 direction
[11], which means that one may expect certain
effects due to the addition of ionic dextrans.

4.1. Effect of nonionic dextrans

Fig. 8. FTIR spectrums of (a) DexS-500 and (b) the separated

phase shown in Fig. 7.

The adsorption of nonionic dextran on the

surface of the growing particles has been explained previously to take place through attachment of polarized atoms, such as of oxygen in the

V.V. Hardikar, E. Matije6ic / Colloids and Surfaces A: Physicochem. Eng. Aspects 186 (2001) 2331

ether linkage, and hydroxyl groups [21]. It has

also been pointed out that the polymers affect the
formation of particles in solution, either by interacting with solutes, or with the precipitated solids.
Since there was no effect of Dex-500 on the size
or the morphology of the Ca(OH)2 or CaCO3
(aragonite) particles over the concentration range
(0.011 wt.%) used in this work, one may conclude that there was no interaction between the
polymer and the reactants.

4.2. Effect of cationic dextrans

The presence of 0.1 1 wt.% Dex-DEAE-500
during the formation of CaCO3 particles resulted
in a mixture of needle-like aragonite, rhombohedral calcite, and spherulitic vaterite particles. No
single polymorph could be obtained by modifying
the experimental conditions within the range of
parameters varied in this study.
The morphology of Ca(OH)2 particles however,
was greatly affected by the concentrations of DexDEAE-500 ]0.1 wt.%. Thus, ellipsoidal particles
(Fig. 3(a)) with the average length of 10 mm were
generated at 0.1 wt.% polymer, while polyhedron
particles (Fig. 3(b)) of 7 8 mm at 0.5 and 1 wt.%.
These changes must have been caused by the
adsorption of the Dex-DEAE-500 on the (0001)
face, which is rich in OH groups and by the
change of the viscosity of the electrolyte environment (Fig. 1). The attenuated total reflectance
(ATR) spectrum of Ca(OH)2 particles with adsorbed Dex-DEAE-500 (not shown) did not reveal any covalent bonding between the cationic
polymer and the surface of the crystal, suggesting
that the observed effects are due to physical adsorption of the polymer.

4.3. Effect of anionic dextrans

The effects of the anionic dextrans in calcium
salt solutions were greatly influenced by the pH.
In slightly acidic solutions (pH 6), a phase
separation consisting of coacervates took place,
while in basic solutions solids precipitated. As
indicated above, the coacervate formation must
be due ion pairing between the Ca2 + and the
sulfate groups of the polymer. It is therefore, of

29

interest to evaluate the stoichiometry of this

interaction.
As reported earlier, the number of sulfate
groups per glucose unit of dextran sulfate
molecule ranged between 1.8 and 2 [22]. The
maximum turbidity was obtained in a system
containing 0.1 mol dm 3 Ca2 + and 0.5 wt.%
DexS-500. It was established that under these
conditions  10% of calcium ions was bound by
the polyelectrolyte, which amounts to 0.01 mol
dm 3 of Ca2 + associated with sulfate groups. In
the same system, the number of sulfate groups
amounts to 0.025 mol dm 3 assuming 1.8
groups per glucose unit. Thus, it appears that the
maximum in turbidity corresponds to complete
neutralization of the sulfate groups on dextran by
Ca2 + . The decrease in turbidity beyond the maximum in the systems in which the concentration
was varied (Fig. 6) can be understood to be due to
the formation of larger number of much smaller
droplets, stabilized by the anionic polyelectrolyte.
The analogous turbidity charge an excess concentration of Ca2 + (Fig. 5), may be caused by the
effect of increasing ionic strength on the solubility
of the droplets.
The FTIR spectrum of the centrifuged complex
was identical to that of pure dextran sulfate,
ruling out the possibility of a covalent bond between the Ca2 + ion and the sulfate group. This
would indicate a mechanism of ion binding (site
or ion atmosphere binding) as suggested earlier
[22,39].
The ion pairing mechanism was further corroborated by dissolution of coacervates when Na+
ions were introduced in the system. It is known
that binding of sodium ions does not result in
phase separation. Therefore, when NaNO3 was
added to this system, the Na+ ions exchanged the
calcium ions bound to the polyelectrolyte and the
coacervate dissolved. Since the calcium ion is
bound more strongly to dextran sulfate, an excess
of sodium ions was required for the exchange to
take place. The interaction of Na+ with dextran
sulfate has been reported before [3234].
When pH was raised in the same system by the
addition of NaOH, colloidal Ca(OH)2 precipitated under otherwise the same conditions. Indeed, if the base was added first to DexS-500

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V.V. Hardikar, E. Matije6ic / Colloids and Surfaces A: Physicochem. Eng. Aspects 186 (2001) 2331

solutions, the solid phase appeared as soon as

CaCl2 solution was admixed. Alternately, if
NaOH was added to the system containing the
coacervates, the latter dissolved followed by the
formation of Ca(OH)2. The size of the resulting
particles was of the order of 2 3 mm, which is
much smaller than the diameter observed with the
same system in the absence of the polymer. It is
known that polyelectrolytes may affect the nucleation process leading to the change in the size of
the precipitated solids. In this particular system,
the higher viscosity due to the presence of DexS500 may have also caused the decrease in the
particle size. Within a homologous series, the
adsorption of polymers is expected to be enhanced with increasing molecular weight, which
was also found to apply to polysaccharides [38].
Consequently, DexS-1000 retarded the particle
growth more efficiently than DexS-500 and resulted in smaller discs.
The ATR spectrum of Ca(OH)2 particles with
adsorbed DexS-500 shown in Fig. 10, is a superposition of individual spectra, an indication that
the polymer was not covalently bound to the free
surface atoms or groups.
Finally the presence of DexS-500 during the
precipitation of CaCO3 (aragonite) resulted in a
mixture of polydispersed spherulites of calcite and
vaterite.

Fig. 10. ATR spectrum of (a) calcium hydroxide (b) DexS-500

and (c) particles shown in Fig. 2(b).

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