Advanced Powder Technology 24 (2013) 1119–1125

Contents lists available at SciVerse ScienceDirect

Advanced Powder Technology

journal homepage: www.elsevier.com/locate/apt

Original Research Paper

Development of a procedure for spherical alginate–boehmite particle

preparation
Aminul Islam a,b, Yun Hin Taufiq-Yap b, Pogaku Ravindra a, M. Moniruzzaman d, Eng-Seng Chan c,⇑
a
Materials and Minerals Research Unit, School of Engineering and IT, Universiti Malaysia Sabah, 88999 Kota Kinabalu, Malaysia
b
Catalysis Science and Technology Research Centre, Faculty of Science, University Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
c
School of Engineering, Monash University, Jalan Lagoon Selatan, 46150 Bandar Sunway, Selangor, Malaysia
d
Department of Materials and Metallurgical Engineering, Bangladesh University of Engineering and Technology (BUET), Dhaka 1000, Bangladesh

a r t i c l e i n f o a b s t r a c t

Article history: Herein we describe a versatile new strategy for producing spherical solid particles with 2 mm in size
Received 4 January 2013 using integrated gelling process. The method involves the formation of spherical droplets by using a peri-
Received in revised form 26 March 2013 static pump device and shaping the droplets in a liquid calcium chloride solution. The shape and size of
Accepted 28 March 2013
these calcium alginate macroparticles depend strongly on the calcium solution concentration. The shap-
Available online 16 April 2013
ing mechanism of the macroparticles and the impact of the experimental conditions on particle shape
and size are investigated. This method has the following features: (1) A new level of control over the
Keywords:
shapes of the particles is offered. (2) The procedure can be scaled up to produce large numbers of parti-
Integrated gelling
Spherical
cles. (3) The final porous structure of the developed particle can be designed for a specific application
Calcium chloride (adsorption, catalysis).
Calcium alginate Ó 2013 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Technology Japan. All rights reserved.

1. Introduction
Calcium alginate is a gelatinous, water-insoluble and biocompat-
ible compound of calcium and alginate with broad applications in
food, plant tissue culture, wound dressing and for immobilising en-
zymes [1,2]. Therefore, the preparation of different material forms
of calcium alginate, especially calcium alginate macroparticles has
been investigated intensively in recent years. A variety of fabrica-
tion methods have been used to prepare calcium alginate micropar-
ticles for different applications. For example, grinding dried
semi-product prepared by the reaction of sodium alginate and cal-
cium chloride to form microparticles has been reported by Wan
et al. [3] while Lim and Chen [4] used an electrostatic extrusion
method to prepare magnetic sorbent calcium alginate microparti-
cles. Calcium carbonate nanoparticles encapsulated by sodium algi-
nate droplets have been prepared using electrodispersion [5].
Schoubben et al. [6] used a spray-drying method to prepare sodium
alginate microparticles by an external gelation strategy.
Polymer colloids with sizes from 20 nm to approximately 1 mm
are usually prepared by a variation of emulsion polymerization
techniques [7]. Larger beads are accessible through miniemulsion
polymerization [8] membrane emulsification [9] and multistage
processes [10]. Currently, an approach for the preparation of a
macroscopic support was provided by Prouzet et al. [11]. According
⇑ Corresponding author. Tel.: +60 3 55145821; fax: +60 3 55146207.
E-mail addresses: aminul03211@yahoo.com (A. Islam), chan.eng.seng@monash.
edu (E.-S. Chan).
to the terminology proposed by Prouzet et al. [11], the method cor-
responds to a ‘integrated gelling’ process. The two basic compo-
nents involved in the integrated gelation process are sodium
alginate and boehmite, where the gelation of boehmite under
sol–gel process and the gelation of biopolymer (alginate) under
ion exchange process are taking place simultaneously. This process
has been applied to form ceramic supports, where sodium alginate
is dispersed drop wise from a needle into a magnetically stirred
gelling solution of aluminum chloride hexahydrate (AlCl36H2O)
to form rubbery, substantially hard supports.
One of the most important contributions in the field was made
by Bacov [12], who synthesized milimetric range of particles by
using integrated gelling process. In a similar approach, Prouzet
et al. [13] synthesized macroscopic support (2 mm) from boehmite
sol doped with sodium alginate, followed by calcination to give an
oxide phase. Whilst a substantial amount of work reported in the
literature, however, a technique sufficiently general to be applica-
ble to arrange of materials and allow the production of spherical
alginate–boehmite with control over shape and size has not been
demonstrated. It may be mentioned that the spherical shape of
the particle is significant as it minimizes the friction to transport
of reactants and products compared to irregular or non-spherical
shaped particle beds [14]. In addition, some limitations such as dif-
ficulties in controlling the system in terms of gelation of alginate–
boehmite droplet is still challenges.
Since the calcium cation has a much smaller size than the large
polymer molecule (sodium alginate), it can diffuse into the alginate
solution through crosslinking process according to the egg-box

0921-8831/$ - see front matter Ó 2013 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.
http://dx.doi.org/10.1016/j.apt.2013.03.021
1120 A. Islam et al. / Advanced Powder Technology 24 (2013) 1119–1125
model [15]. Thus, the calcium chloride has been into the gelling
bath in this study to find a new direction to manufacture the
spherical alginate–boehmite macroparticles. The surface area and
porous properties of the alginate–boehmite particles were investi-
gated using nitrogen (N2) adsorption/desorption isotherm and the
structural properties were evaluated using scanning electron
microscope. The size and shape of the particles was also verified
by using image analyzing software.
2. Materials and methods
2.1. Materials
Boehmite (AlOOH) powder was provided by BASF chemical
company (G-250, medium density pseudoboehmite alumina, BASF
Catalysts LLC in USA). The properties of AlOOH are summarized in
Table 1. Sodium-alginate (Manugel GHB) with medium range
molecular weight of 97,000, 37% b-D-mannuronic acid residues
(M) and 63% a-L-guluronic acid residues (G) was supplied by ISP
Technologies Inc, UK. Calcium chloride was purchased from Merck,
Germany. Aluminum chloride (AlCl3) was supplied by Sigma–Al-
drich, Germany. The analytical grade hydrochloric acid and deion-
ized water was used in all experiments.
2.2. Preparation of particles
The particles were prepared by using integrative gelling process
described by Prouzet et al. [13]. In brief, 300 g of boehmite powder
was suspended into 1 L of deionized water. The suspensions were
then dispersed ultrasonically for 3 min at 70% amplitude. The
boehmite suspension was then mixed with suspension of 20 g L1
Na-alginate under magnetic stirring for 10 min, resulting suspen-
sion being left for 30 min. Subsequently, a mixture of alginate–
boehmite suspension was dropped by pump through a needle
(1.65 mm in diameter) into gently agitated a solution of 36.5 g L1
AlCl3 containing volume fraction of CaCl2 ranged from 0.5 to 3.0
g L1, which were acidified at pH 1 by addition HCl. The air pressure
of the pump regulated to ensure that the flow rate of the alginate–
boehmite mixed liquid was constant (0.5 mL min1) in all experi-
ments. The apparatus for particles formation is depicted in Fig. 1.
Drops of the mixture suspension were progressively gelled and form
particles that were left for aging in the gelling solution consisting of
AlCl3 and CaCl2 for 12 h. The particles separated by simple filtration
were subjected to drying in the air after being washed with water.
Finally, the particles were calcined at 800 °C to make the particle
porous, as reported by Islam et al. [16].
2.3. Particle shape measurements
Particle shape can be represented by a variety of quantitative
shape descriptors from image analysis. Lee et al. [17] developed
the concept of sphericity factor (SF) based on the perpendicular
Table 1
The parameters for the preparation of particle.
Parameter
Tip diameter
Boehmite concentration
Alginate concentration
Distance from the tip of the needle to the gelling batha
Aluminum chloride concentrationb
Aging time
Flow rate of alginate–boehmite mixed liquidc
a
Collecting distance was obtained from Chan et al. [18].
b
AlCl3 concentration was obtained from Eric Prouzet et al. [13].
c
Flow rate of alginate–boehmite mixed liquid obtained for Islam et al. [16].
dimensions of a particle. Sphericity factor (SF) was used to express
the divergence of a particle shape from spherical, where the value
zero indicates a perfect sphere and higher values indicate a greater
degree of shape distortion.
The shape analysis of the particles were carried out by analyz-
ing the digital images captured by a digital camera (Moticam-
350, version 2.0 ML, China) installed on a stereozoom microscop
(Stemi DV4, Carl Zeiss, Germany) using image analyzer (SigmaScan
Pro 5.0, SPSS Inc). This program determines the Dmax and Dper of the
particle and computed using Microsoft Excel. SF was calculated
according to the following equation:
SF ¼ ðDmax  Dper Þ=ðDmax þ Dper Þ ð1Þ
where Dmax is the maximum diameter passing through a particles
centroid (mm) and Dper is the diameter perpendicular to Dmax pass-
ing through the particle centroid (mm).
2.4. Particle size measurements
Particles can have many shapes, including spheres, ellipsoids,
irregular bodies, etc. For a spherical particle, it is straightforward
to use diameter to describe its size. It is also possible and useful
to define the size of a non-spherical particle in terms of an equiv-
alent diameter as defined in terms of either a circle or a sphere. In
this study, the size of particle was estimated by using image ana-
lyzing software.
The progression of droplet injection at different stages were
photographed by using a digital camera (Canon, Japan) with a syn-
chronized stroboscope light (Monarch, Nova-Strobe) having a fre-
quency controller (100–14,000 flashes per minute). The resultant
photographs of the particle were then transferred to image ana-
lyzer software (SigmaScan Pro 5.0, SPSS Inc). Diameter of the par-
ticles at different stages was measured directly from the image
analyzer software, from which at least 100 measurements for each
stage were analyzed to obtain an average value as well as the stan-
dard deviation.
2.5. Surface area and pore structure
The surface area, pore volume and pore size of the air-dried and
calcined particles were measured from the nitrogen adsorption–
desorption isotherms at liquid nitrogen temperature (196 °C).
All of the samples were degassed at 150 °C under vacuum condi-
tions until no pressure gradient could be detected. The analysis
was conducted using Thermo Finnigan Sorptomatic 1900 series
nitrogen adsorption/desorption analysis software. The total surface
Value
1.65 mm
300 g L1
20 g L1
10 cm
36.5 g L1
12 h
0.5 mL min1
Fig. 1. Particles production experimental apparatus for integrated process.
 A. Islam et al. / Advanced Powder Technology 24 (2013) 1119–1125
(a)
Fig. 2. Droplet formation while falling from the tip of the needle.
area of the catalysts was obtained by the Brunauer, Emmett and
Teller (BET) method from the linear part of the nitrogen adsorption
isotherms. Total ‘pore volume was calculated according to the
Gurvitch method for P/Po = 0.95. The pore size distribution was ob-
tained according to the Barrett, Joyner and Halenda (BJH) method
from the desorption branch of the isotherm.
2.6. Surface morphology
A scanning electron microscope (SEM, Model: JSM-5G1DLV,
JEOL, Tokyo, Japan) was used to observe the surface morphologies
of the particles. The cross-sectioned particles were mounted on
metal stubs using double sided adhesive tape, dried under vacuum
and spatter coated with platinum using a fine coater (JEOL, Japan,
Model: JFC-1600) prior to SEM observation. The platinum samples
were mounted in the samples stub inside the scanning electron
microscope and the images were viewed and captured under dif-
ferent magnifications.
2.7. Mechanical strength
The mechanical strength of the calcined and air-dried particle
was determined by texture analyzer (TA.XT. Plus). The particles is
placed at the lower plate and the upper plate is lowered gradually
until it breaks the particle and the maximum force applied to break
the single particle was taken as mechanical strength. Triplicate
observations were made for each sample.
3. Results and discussion
3.1. Formation of alginate–boehmite spherical millimetric particle
The formation of Na-alginate droplets from the breakup of the
dispersed phase under the impact of the continuous phase stream
has been reported by Hirama et al. [19]. A similar method has been
used by Lee et al. [17] who attempt to relate the alginate droplet
shape and size to the flow rate, dispersed solution viscosity and
channel geometry. Further, it has been shown by other workers
[20] that the shape and size of the prepared alginate particles were
affected by both flow rate and the concentration of calcium chlo-
ride. Similar principles applied in the present study for assessing
alginate–boehmite particle formation. In all cases of particle prep-
aration; the mode of alginate–boehmite droplet formation was
fixed at a alginate–boehmite solution flow rate of 0.5 mL min1.
The other parameters maintained during the particle preparation
process were shown in Table 1. Fig. 2 is the photograph of droplet
formation through the nozzle. As can be seen from Fig. 2, the shape
of the droplet remained spherical while falling from the tip of the
needle. However, the shape of particles was changed markedly
after falling into gelling bath (Fig. 3). Hence, an experiment was
1121
(b)
carried out to evaluate the effect of CaCl2 concentration in gelling
bath on shape of alginate–boehmite particles.
As can be seen from Fig. 3, the shape of the particle was changed
from disk (Fig. 3a and b) to near spherical shape (Fig. 3f and g). The
formation of disk-shaped particle might be due to the inadequate
amount of calcium (Ca2+) ions in the gelling bath which is not en-
ough to accommodate in the largest sphere of particle. A somewhat
related conclusion has been reached by Maestrelli et al. [21] who
studied on the shape of calcium pectinate microparticles. It was re-
ported that the low concentration of Ca2+ reduce the gelation rate
and the penetration speed of Ca+2 into particle interface. Therefore,
the low penetration speed may not allow to facilitate the diffusion
of calcium ions into the gel network, resulted in the formation of
disk-shaped particles.
As the concentration of CaCl2 was increased to 2.5 g L1, parti-
cles with round shape were observed, as shown in Fig. 3f. The for-
mation of spherical calcium alginate particle has been reported by
Dang et al. [22], who concluded that the high concentration of cal-
cium chloride in gelling bath favors the fast gelation process in the
particle, resulted in the formation of spherical particle. Other
workers [23] have discussed a similar phenomenon for the case
of spherical calcium alginate particle formation and have reported
that higher concentration of calcium means a higher concentration
gradient and a faster gelation reaction speed. Therefore, the devia-
tion of shape from spherical might be reduced. Moreover, the gel-
ling process involving in the particle formation might affect the
shape of particle. Mørch et al. [24] reported that the interior
cross-linking between the alginate chains was accompanied by
divalent cations (Ca+2). Since the calcium cation has a much smal-
ler size than the large polymer molecule, it can diffuse into the
alginate solution, and according to the egg-box model [15], this
leads to the crosslinking process. Calcium alginate particles were
formed through the gelation of alginate by the ion exchange
reaction:
2Na-alginate þ CaCl2 ! Ca-alginate þ 2NaCl ð2Þ
1
Thus, the addition (2.5 g L ) of salt (CaCl2) to the gelling bath
can lead to sufficient internal ionic cross-links within a three
dimension lattice resulting in the instantaneous formation of
spherical-shaped particles. The shape of the particle thus, depends
strongly on the calcium ion exchange reaction. However, it is to be
underlined that there was no significant change observed in shape
of particle when the amount of CaCl2 was increased from 2.5 to
3.0 g L1 (Fig. 3g). Hence, it can be inferred from this observation
that the amount of Ca ions appear to be a very critical factor for
controlling the shape of alginate–boehmite particles.
A quantification of the deviation from a perfect sphere, particles
sphericity factor is plotted in Fig. 4 as a function of calcium chlo-
ride (CaCl2) concentrations (g L1). It might be noted that the sphe-
ricity factor provides brief classification about the degree of
1122 A. Islam et al. / Advanced Powder Technology 24 (2013) 1119–1125

(a) Without adding CaCl 2 (b) 0.05 g/L CaCl2

(c)1.0 g/L CaCl2 (d) 1.5 g/L CaCl2

(e) 2.0 g/L CaCl2 (f) 2.5 g/L CaCl2

(g) 3.0 g/L CaCl2

Fig. 3. Effect of CaCl2 concentration on the shape of alginate–boehmite particle.

deviation of the irregular particle from the true sphere shape. As
can be seen from Fig. 3, when the concentration of the calcium
chloride in gelling bath is low, the particles had an elongated
shape, characterized by a narrower terminal part. With increasing
concentration of the CaCl2 solution, the impacting droplets eventu-
ally become egg-shaped, as seen in Fig. 4. Results indicated that
concentration of the CaCl2 up to 2.5 g L1 caused decrease in the
sphericity factor. It has been shown by Chan [25] that a particle
with SF less than 0.05 can be considered as spherical. Increasing
the CaCl2 concentration higher than 2.5 g L1, however, caused
no significant change (SF < 0.03) in the sphericity factor of parti-
cles. The most likely reasons for this are difference in Ca+2
concentration in gelling bath for the formation of spherical parti-
cles. Hence, it can be inferred from the results of this study that
the CaCl2 concentration of 2.5 gL1 could be sufficient for spherical
alginate–boehmite particle formation.
To obtain information on the size of particles, the size predic-
tion model was therefore, used to measure the size of particles. It
may be mentioned that the particles with a sphericity factor of
0.03 named as spherical particles will be used for the future discus-
sion. The relationship between the size of the microdroplets pre-
pared, in terms of flow rates and solution concentrations, have
been reported by Herrero et al. [26], Senuma et al. [27], Nie et al.
[28] and Senuma and Hilborn [29] among others. The absolute size
 A. Islam et al. / Advanced Powder Technology 24 (2013) 1119–1125 1123

Sphericity factor

CaC
Cl2 conceentrrattion
n (gg/L))

Fig. 4. Effect of CaCl2 concentration on sphericity factor of the alginate–boehmite particles.

of droplets produced varies due to differences in materials proper-

ties as well as the size of the orifice. For this particular case, the size
of the droplets seems consistent with that of the orifice, 1.65 mm Droppletts w
D whille ffalliing intto (a)
(present study), 0.40 mm [16] and 1.65 mm [15]. The particle size geelliing batth ((3.775m
mm in
of the various steps of preparations was obtained in the range be- diiam
meteer)
tween 3.75 and 2.12 mm in diameter, as shown in Fig. 5. The drop-
let falling from the tip of the needle had the size of approximately
3.75 mm in diameter, as shown in Fig. 5a. sizze redduceed
As can be seen from Fig. 5b that the size of the particles after by 15%
gelation was a little smaller than the size of the droplet filling from
the tip of the needle. Generally, the dimensions of alginate particle
were 5–10% smaller than the corresponding droplets owing to Partiiclees aafterr geellinng ffor
P (b)
shrinkage during gelation process [21]. The gelation process initi- 122 hhourrs (33.48 m mm in
ates to diffuse calcium cations into the alginate–boehmite droplets diiam
meteer)
and penetrate towards the core of the particle and decrease the
particle size. The decreased particle size could also be explained
by gelling mechanism associated with particles formation process. siize reeduccedd
The mechanism of the gelation of alginate–boehmite has been de- bby 440%
%
scribed by Prouzet et al. [13]. The alginate–boehmite gelling pro-
cess consists of two steps- gelation of a biopolymer, sodium
alginate, followed by gelation of mineral species such as boehmite
(c)
[13]. When a drop of alginate solution comes in contact with cal- Partiiclees aafterr air drryinng
P
cium ions, gelation occurs instantaneously. As Ca2+ ions penetrate foor 112 hhouurs ((2.445 m
mm m in
into the interior of droplets, water is squeezed out of the droplets diiam
meteer)
resulting in contraction of particles [11]. After completing the pro-
cess, condensation of inorganic part of the droplets further oc- siize rreduucedd
curred once the droplets were in contact with the acidic pH (pH bby 48%
less than 1) [30]. This process was also associated with water re-
lease and thus, reduced the volume of the particle. However, when
(d)
the particles were dried in the air (Fig. 5c), it was found that the Partiiclees aafterr caalcinattionn
P
particles contracted significantly (up to 40%). During air drying, att 8000 oC ffor 3 ( 2.112 m mm m
the particle is transformed into hard agglomerates by formation inn diiam
meteer)
of solid bridges. Finally, the calcination of particles could lead the
cohesion of mineral (boehmite) framework and thus, the reduction
of particles size reached a maximum size reduction of 48% (Fig. 5d),
as the additional water is removed via a condensation process.
Thus, it can inferred the size analysis.
Fig. 5. Particles size for different preparation steps.
3.2. Surface area and porous properties of alginate–boehmite spherical
millimetric particle according to the IUPAC classification, exhibiting characteristic hys-
teresis loops. The major uptake observed at high relative pressures
The nitrogen adsorption–desorption isotherms, recorded for (P/Po) range 0.62–0.80 for particles dried with air (Fig. 6a) and at
both of the air-dried and the calcined particles are displayed in 0.41–0.85 for the calcined particles (Fig. 6b). According to the
Fig. 6. These isotherms possess features reminiscent of IV type theoretical considerations, the linear portion of the curve repre-
1124 A. Islam et al. / Advanced Powder Technology 24 (2013) 1119–1125

(a) 0.5 (a)

300 0.015

0.4

0.010

dV/dr / cm3nm-1g-1
200

VPore / cm3g-1
0.3
Vads / cm3g-1

0.2

0.005
100

0.1

0.0 0.000
0
0.0 0.2 0.4 0.6 0.8 1.0 0 10 20 30 40 50
p/p0 r / nm

1.0
500 (b) 0.020
(b)
0.8
400
0.015

dV/dr / cm3nm-1g-1
VPore / cm3g-1

0.6
Vads / cm3g-1

300

0.010

0.4
200

0.005
0.2
100

0.0 0.000
0
0 10 20 30 40 50
0.0 0.2 0.4 0.6 0.8 1.0
r / nm
p/p0
Fig. 7. Pore size distribution of the (a) air-dried and (b) calcined particles.
Fig. 6. Nitrogen adsorption–desorption isotherms for (a) air-dried and (b) calcined
(800 °C) particles.
area of 244 m2 g1 after calcination at 800 °C (Table 2). This in-
crease in the surface area may be attributed to the effect of the cal-
Table 2 cination, where the pores may originate from the void spaces
The porous and mechanical properties of the particles.
within the alumina particles due to the removal of water from
Parameters Air-dried Calcined the crystal planes of the aluminum oxide [31]. The surface area re-
particles particles sults of the particles reported here are comparable with previously
BET Surface area (m2 g1) 119 244 published surface area data of alginate–boehmite particles [13].
Average pore diameter (nm) 8.40 11.60 The pore-size distribution curves for both the air-dried and cal-
Pore volume (cm3 g1) 0.44 0.83
cined samples, calculated by Barret–Joyner–Halenda (BJH) method
Mechanical strength (N/ 5 ± 1.0 3 ± 0.5
particle) ± S.D. using nitrogen desorption branch are presented in Fig. 7. This is
clearly seen in the corresponding pore size distribution plots
(Fig. 7), that the pore-size distributions are unimodal since one
sents multilayer adsorption of nitrogen on the internal surface of peak is observed in the mesopore region (2–50 nm). The peaks
the sample, and the concave upward portion of the curve repre- are centered at 9.2 and 12.2 nm in diameter for the air-dried
sents filling up of mesopores (2–50 nm) and macropores (Fig. 7a) and calcined particles (Fig. 7b) respectively. As shown in
(>50 nm). Table 2 summarizes the total BET surface area, average Table 2, the calcination of the particle leads to an increase in pore
pore diameters and pore volumes obtained from air-dried and cal- volume of the particles. It is reasonable to assume that any alter-
cined particles. The surface area of the air-dried particles ation in mean pore volume after calcinations is attributed to re-
119 m2 g1 where the particles are able to hold a higher surface moval of alginate from the particles.
 A. Islam et al. / Advanced Powder Technology 24 (2013) 1119–1125
Fig. 8. Scanning electron micrograph of the particles showing the cross-sectioned
surface morphology: (a) air dried particles and (b) calcined particles.
From the data reported in Table 2, it is evident that the value of
mechanical strength of the air-dried particles was higher than
those for the calcined particles. The higher mechanical strength
of air-dried particles could be a result of the contribution at molec-
ular level of binding of alginate gel combined with boehmite par-
ticles. However, calcining the particles caused alginate matrix to
be removed from the particle network. Thus, the alginate matrixes
do not contribute anymore to the binding of the calcined particles
which would reduce the mechanical strength. There is evidence of
increase in the volume of pores through the observation of N2
desorption isotherms in the calcined particles (see Table 2). In gen-
eral, lower defect (less porous) structure of a particle provides the
benefit of higher mechanical strength. Thus, an increased pore vol-
ume may have led to a higher number of defects and this is likely
to reduce the mechanical strength.
As evidenced in Fig. 8, the images of the calcinated particles at
different magnifications exhibited a porous channeling morphol-
ogy with interconnectivity of pores (Fig. 8b) in comparison to
the air-dried particles which were characterized with a smooth
surface (Fig. 8a). Porous particles with an open and interconnected
pore space are established in a wide range of applications, such as
catalyst supports [32]. Although the level of porosity and the pore
size distribution are important characteristics of the porous struc-
ture, parameters such as the fraction of open porosity in conjunc-
tion with the degree of connectivity between the pores (cells) and
1125
the size of the pore openings (cell windows) have a strong effect on
pore space accessibility [32]. The size of pore openings, also called
cell windows or throats, often act as constrictions between con-
nected pores to limit the flow of gas or fluid. A high degree of con-
nected porosity and a hierarchical pore size distribution is typically
required for catalysis applications to achieve high permeability,
accessibility to the active surface area and a low pressure drop
[33]. More efficient catalytic processes require improvement in
catalytic activity and selectivity. Both aspects will rely on the tai-
lor-design of catalytic materials with desired structure and active
site dispersion. Porous materials offer such possibilities with con-
trolled large and accessible surface area [33]. This is one of the sig-
nificant contributions to be underscored in this study.
4. Conclusion
This work provides a route to produce spherical particles having
a size of the order of a millimeter. The shape and size of the pre-
pared alginate–boehmite particles depends strongly on the con-
centration of calcium chloride solution. The spherical particles
(sphericity factor = 0.03 ± 0.01) was obtained at the volume frac-
tions of 2.5 g L1 CaCl2, followed by calcination at 800 °C, afforded
a porous network of the particles. In many applications involving
adsorption, catalysis, the shape and porosity can be a deciding fac-
tor. Precise sphericity control thus will provide a new dimension
for the application of alginate–boehmite particles.
References
[1] T. Suksamran, P. Opanasopit, T. Rojanarata, T. Ngawhirunpat, U. Ruktanonchai,
P. Supaphol, J. Microencapsulation 26 (2009) 563–570.
[2] B.G. Chung, K.H. Lee, A. Khademhosseini, S.H. Lee, Lab Chip 12 (2012) 45–59.
[3] J. Wan, J.B. Gordon, K. Muihead, M.W. Hickey, M.J. Coventry, Lett. Appl.
Microbiol. 24 (1997) 153–158.
[4] S.F. Lim, J.P. Chen, Appl. Surf. Sci. 253 (2007) 5772–5775.
[5] Y. Zhao, M.T. Carvajal, Y.Y. Won, M.T. Harris, Langmuir 23 (2007) 12489–
12496.
[6] A. Schoubben, P. Blasi, S. Giovagnoli, C. Rossi, M. Ricci, Chem. Eng. J. 160 (2010)
363–369.
[7] A. Elaissari (Ed.), Colloidal Polymers, Marcel Dekker, New York, 2003.
[8] M. Antonietti, K. Landfester, Prog. Polym. Sci. 27 (2002) 689–757.
[9] S. Omi, G.-H. Ma, M. Nagai, Macromol. Symp. 151 (2000) 319–330.
[10] J.S. Song, F. Tronc, M.A. Winnik, J. Am. Chem. Soc. 126 (2004) 6562–6563.
[11] E. Prouzet, M. Tokumoto, A. Krivaya, Patent No. WO2004009229, 2004.
[12] R. Backov, Soft Mater. 2 (2006) 452–464.
[13] E. Prouzet, Z. Khani, M. Bertrand, M. Tokumoto, V. Guyot-Ferreol, J.F.
Tranchant, Microporous Mesoporous Mater. 96 (2006) 369–375.
[14] M. Campanati, G. Fornasari, A. Vaccari, Catal. Today. 77 (2003) 299–314.
[15] L. Li, Y. Fang, R. Vreeker, I. Appelqvist, Biomacromolecules 8 (2007) 464–468.
[16] A. Islam, Y.H. Taufiq-Yap, E.-S. Chan, P. Ravindra, J. Porous Mater. (2011) 1–11.
[17] B.B. Lee, P. Ravindra, E.S. Chan, Colloids Surf. A 332 (2009) 112–120.
[18] E.S. Chan, B.B. Lee, P. Ravindra, D. Poncelet, J. Colloid Interface Sci. 338 (2009)
63–72.
[19] H. Hirama, T. Kambe, K. Aketagawa, T. Ota, H. Moriguchi, T. Torii, Langmuir
(2012) 1–22.
[20] T.D. Dang, S.W. Joo, Colloids Surf. B 102 (2013) 766–771.
[21] F. Maestrelli, M. Cirri, G. Corti, N. Mennini, P. Mura, Eur. J. Pharm. Biopharm. 69
(2008) 508–518.
[22] T.D. Dang, Y.H. Kim, H.G. Kim, G.M. Kim, J. Ind. Eng. Chem. 18 (2012) 1308–
1313.
[23] X.D. Liu, D.C. Bao, W.M. Xue, Y. Xiong, W.T. Yu, X.J. Yu, X.J. Ma, Q. Yuan, J. Appl.
Polym. Sci. 87 (2003) 848–852.
[24] Y.A. Mørch, I. Donati, B.L. Strand, G. Skjak-Break, Biomacromolecules 7 (2006)
1471–1480.
[25] E-.S. Chan, Carbohydr. Polym. 84 (2011) 1267–1275.
[26] E.P. Herrero, E.M. Martin Del Valle, M.A. Galan, Chem. Eng. J. 117 (2006) 137–
142.
[27] Y. Senuma, C. Lowe, Y. Zweifel, J.G. Hilborn, I. Marison, Biotechnol. Bioeng. 67
(2000) 616–622.
[28] Z.H. Nie, M.S. Seo, S.Q. Xu, P.C. Lewis, M. Mok, E. Kumacheva, G.M. Whitesides,
P. Garstecki, H.A. Stone, Microfluid. Nanofluid. 5 (2008) 585–594.
[29] Y. Senuma, J.G. Hilborn, Mater. Res. Innovations 3 (1999) 42–49.
[30] B.E. Yoldas, Mater. Sci. 10 (1975) 1856–1860.
[31] M.F.L. Johnson, J. Mooi, J. Catal. 10 (1968) 342–354.
[32] T. Linssen, K. Cassiers, P. Cool, E.F. Vansant, Adv. Colloid Interface Sci. 103
(2003) 121–147.
[33] J. Cejka, S. Mintova, Catal. Rev. 49 (2007) 457–509.