Journal of Colloid and Interface Science 284 (2005) 204209

www.elsevier.com/locate/jcis

Improvement of red mud polymer-matrix nanocomposites by red mud

surface treatment
Soo-Jin Park , Byung-Ryul Jun
Advanced Materials Division, Korea Research Institute of Chemical Technology, P.O. Box 107, Yusong, Taejon 305-600, South Korea
Received 5 August 2003; accepted 29 September 2004
Available online 18 December 2004

Abstract
The effects of chemical treatments on red mud (RM) were investigated in terms of thermal stabilities of PMMA/RM and PVC/RM
nanocomposites. N2 /77 K adsorption behavior and contact angles were studied in the pore structures and surface energetics of RM, respectively. Thermal stabilities of the nanocomposites were investigated using a thermal mechanical analyzer (TMA) and thermogravimetric
analysis (TGA). As a result, the acidically treated RM (ARM) had higher adsorption properties, including specific surface area, than untreated
RM (VRM) or basically treated RM (BRM). A change in the structure of the ARM surface was due to hydrolysis or leaching a metal salt out
of RM. Also, the electron acceptor (S+ , acid) of ARM and the electron donor (S , base) of BRM were increased in the development of acid
and basic functional groups, respectively. PMMA/ARM nanocomposites had higher thermal stability and mechanical interfacial properties
than PMMA/VRM or BRM nanocomposites. These results were due to the improvements of the dispersion properties and acidbase interfacial interactions of basic PMMA and ARM. In this work, although the dispersion properties of the BRM decreased, the thermal stabilities
and mechanical interfacial properties of PVC/BRM nanocomposites increased, which could be attributed to improvement in the interfacial
interactions between acidic PVC and BRM.
2004 Published by Elsevier Inc.
Keywords: Red mud; Chemical surface treatment; Electron acceptordonor; Thermal stabilities; Surface energetics

1. Introduction
Filled polymer systems are very popular for the composite industry for both cost and performance objectives. The
use of inorganic fillers has been a common practice in the
plastics industry to improve the properties of thermoplastics. Effects of the filler on the thermal and other physical
properties of the composites depend strongly on its shape,
particle size, aggregate size, surface characteristics, and degree of dispersion. In general, the properties of the composites filled with micrometer-sized filler particles are inferior
to those filled with nanoparticles of the same filler [1,2]. In
addition, the physical properties, such as surface smoothness
and barrier properties, cannot be achieved by using conventional micrometer-sized particle. In the recent years, inten* Corresponding author. Fax: +82-42-861-4151.

E-mail address: psjin@krict.re.kr (S.-J. Park).

0021-9797/$ see front matter 2004 Published by Elsevier Inc.
doi:10.1016/j.jcis.2004.09.074

sive research efforts have been devoted to the development

of nanocomposites [36].
Red mud emerges as a by-product from the caustic leaching of bauxites to produce alumina, and approximately 35
40% of the processed bauxite goes into waste as red mud.
Red mud is the biggest problem in producing alumina. This
waste presents serious problems of storing and environmental pollution. The disposal of red mud is associated with
real estate near industry, cost of disposal, and pollution,
which are now crucial factors [7,8]. Serious disposal problems have led researchers to develop new methods for the
use of the red mud as a filler for polymer reinforcement,
an absorbent to remove H2 S from industrial emissions, and
a constituents in building materials. Park et al. [9] had reported that the mechanical properties of epoxy/treated red
mud nanocomposites were correlated with the improvement
of interfacial adhesion between the red mud surface and a
matrix.

S.-J. Park, B.-R. Jun / Journal of Colloid and Interface Science 284 (2005) 204209

It is well known that the interface plays a key role in determining the physical properties of composites. Therefore,
the composites do require strong adhesion at the interfaces
between constituent elements. Generally, surface treatments
of inorganic materials are used to improve the adhesive properties of inorganic material surfaces to a polymeric matrix
[10,11].
To enlarge physical interaction, various surface treatment
techniques are applied, such as oxidation in acid solutions
[12,13], dry oxidation in oxygen [14], anodic oxidation
[15,16], and plasma treatments [17]. It is due to the fact that
surface modification largely leads to a development of the
surface functional activity on the filler surface, resulting in
modification to achieve good interfacial adhesion between
the reinforcement and the matrix.
The aim of this work is to study the effect of chemical
surface treatments of red mud (RM) on thermal stabilities
and mechanical properties of the polymeric nanocomposites
based on different PMMA and PVC matrices with a view to
acid and base characteristics of solid surfaces.

2. Experimental
2.1. Materials
The red mud (RM) was provided by Korea Chemical Co.
and the composition of RM was analyzed using an elemental analyzer (E.A. Fisons EA-1108). It shown as Table 1. The
average size and density of the RM were about 80 nm and
2.4 g/cm3 , respectively. The PMMA (polymethylmethacrylate) was supplied by LG MMA (IH830) of Korea and the
PVC (poly(vinyl chloride)) was obtained from Aldrich Co.
(M n : 47,000, M w : 80,000). Dioctyl phthalate (DOP, Junsei
Chem. Co., Japan) was used as a plasticizer and butyltin stabilizer (TM-600P, Songwon Industrial Co., Korea) was used
as a heat stabilizer.
2.2. Pretreatment and sample preparation
The RM was chemically treated with 0.5 N HCl (ARM)
and 0.5 N NaOH (BRM) solution for modification of RM
surfaces at room temperature for 24 h. In addition, prior to
the following analysis, the RM was washed several times
with distilled water and dried in a convection oven.
Table 1
Chemical composition of the RM studied
Chemical composition

Composition ratio (%)

Fe2 O3
Al2 O3
SiO2
Na2 O
TiO2
CaO
Others

16.6
23.7
22.9
11.6
6.7
6.7
11.8

205

The preparation procedure for the nanocomposites was

as follows. PMMA, PVC, and treated red mud (5 phr) were
mixed mechanically in a barbender (Barbender Instruments
plastic corder) at 185 C for 1 h and cured on a hot press
(Carver Laboratory Press Model 2518) at 190 C for 20 min
using a vacuum bagging method [18]. The nanocomposites
made were cut into test specimens for mechanical testing.
2.3. Surface and adsorption properties
The pH of the RM was evaluated according to ASTM
Standard Procedure D 3838. Samples of 0.5 g of the RMs
were added to 20 ml of distilled water and suspensions were
stirred overnight to reach equilibrium. Then, the samples
were filtered and pH of the solution was measured.
The contents of acidic and basic surface groups were
quantitatively measured by Boehms titration method [19].
Samples of 1 g of RMs were placed in 100 ml of NaOH for
acid value measurement. The vials were sealed and shaken
for 24 h. Then, 20 ml of filtrate were pipetted and titrated
with 0.1 N HCl. Likewise, the base value was determined by
converse titration.
Nitrogen adsorption isotherms were measured using an
ASAP 2010 (Micromeritics) at 77 K. Prior to the analysis,
the samples were outgassed at 573 K for 6 h to obtain a residual pressure of less than 103 Torr. The amounts of nitrogen
adsorbed on RMs were used to calculate the specific surface
area (S BET ), BET constant (C BET ), total pore volume (V T ),
and pore size (R P ) by means of the BET equation [20,21].
2.4. Surface free energy, thermal stabilities, and
mechanical interfacial properties
Contact angles were measured using the sessile drop
method on a RameHart goniometer. About 5 l of wetting
liquids was used for each measurement at 20 C. A reading within 5 s of drop formation was taken for the critical
surface tension. Then the testing liquids used are deionized
water, diiodimethane, and ethylene glycol.
Thermal mechanical analyzer (TA Instruments, Model
943) was used for measuring the coefficients of thermal expansion (CTE). Size of specimens was 111 cm. Also, the
temperature range used was from 30 to 150 C and the heating rate was 20 C/min.
Thermogravimetric analysis (TGA) was performed using
a TGA 2950 (du Pont) at a heating rate of 10 C/min from
30 to 850 C under N2 atmosphere.
The mechanical interfacial properties of composites were
conducted to measure properties, which were sensitive to the
degree of adhesion of the filler-matrix interface. The critical
stress intensity factor (K IC ), which was one of the fracture
toughness parameters, can be characterized by, the singleedge notched (SEN) beam fracture toughness test (ASTM
E399) in three-point bending flexure. Notches were cut using a diamond wire saw, approximately half the depth of

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S.-J. Park, B.-R. Jun / Journal of Colloid and Interface Science 284 (2005) 204209

the specimen. A span-to-depth ratio of 4:1 and a cross-head

speed of 1 mm/min was used.

S BET a (m2 /g) C BET b

VRM 30
475
ARM 58
908
BRM 30
554

3. Results and discussion

3.1. Surface and adsorption properties
pH and acid-base values of the treated RM with 0.5 N
HCl and 0.5 N NaOH solutions are given in Table 2. The major constituents of RM are a metal alkoxide, such as, Fe2 O3 ,
Al2 O3 , CaO, SiO2 , TiO2 , and Na2 O. Also, the surface of RM
has a high pH, due to the presence of sodium oxide [22].
The pH and base value of the surface-treated RM in
the 0.5 N HCl solution are decreased and the acid-value is
increased. It is due to a development of acidic functional
groups or active oxygen, whereas, the surface-treated RM
in the 0.5 N NaOH solution shows a slight increase in base
value, which can be a consequence of the presence of basic
functional groups.
Fig. 1 shows N2 gas adsorption isotherms of the RM studied. Adsorption isotherms of the RM studied show typically
Type II of a standard of IUPAC [23]. The acidic treatment
leads to a development of micropores or mesopores in RM
surfaces, resulting in increasing the adsorption volume of N2
gas at low relative pressure. However, it can be seen that the
adsorption behavior of the BRM is similar to that of VRM,
for which there is no significant change in adsorption behavior as a function of relative pressure, P /P0 . It is well
known that C BET provides information of adsorption, such
as, a shape of adsorption isotherm, net heat of adsorption
(E), and a comparison of relative amount of adsorption.
If C BET is high, a point of inflection is clear at low relative
Table 2
The pH and acidbase values of the RM studied

VRM
ARM
BRM

Table 3
N2 /77 K adsorption data of the RM studied

pH

Acid values (meq/g)

Base values (meq/g)

11.2
8.6
11.2

60
190
40

900
560
990

Fig. 1. Adsorption behavior of N2 gas at 77 K on the RM studied.

a
b
c
d
e

V T c (cm3 /g) R P d () E e (kJ/mol)

0.1047
140
3.96
0.1331
92
4.36
0.0991
132
4.04

Specific surface area from BET method by N2 /77 K adsorption.

BET constant.
Total pore volume.
Average pore diameter from empirical equation Rp = 4VT /SBET .
Net heat of adsorption.

pressure of adsorption isotherm. The net heat of adsorption

(E = E0 EL ) can be obtained from the C BET , as follows
[24,25],



E0 EL
,
CBET = exp
(1)
RT
where E 0 and E L refer to heat of adsorption and that of
liquefaction at the monolayer of the RM surface, respectively. Also, R is the gas constant and T is the temperature
in Kelvin.
Table 3 summarized the structural parameters of the RMs
determined from nitrogen adsorption isotherms according to
the BET equation, from which the ARM has higher S BET ,
C BET , E, and V T than those of VRM or BRM. Kasliwal
and Sci [26] reported that the RM surface was treated with
HCl to investigate a method for enrichment of titanium dioxide in RM. As a result, it is found that the metal oxides were
hydrolyzed and metal salts are leached out at RM surfaces,
which is confirmed by a decrease of pH in treating solution.
Similarly, it is then considered in the case of ARM that a
change of structure of the RM surface in this work is due
to hydrolysis or leaching a metal salt out RM, resulting in
increasing the micropores with a viewpoint of surface structures.
3.2. Surface free energy
The nature of hydrophilic or hydrophobic surface of clay
is concerned with a contact angle of the testing liquids, including water and diiodomethane at interfaces between solid
and wetting liquid. In addition, the surface of clay can be
represented by polar or nonpolar component.
To investigate an effect of the surface-treated RM, changes of the surface free energy of RM are determined by contact angle measurements. The total surface free energy (or
surface tension), nonpolar, and specific (or polar) components inducing surface electron acceptor (S+ )donor (S )
components for the wetting liquids are shown in Table 4.
Table 5 shows the surface free energies obtained under
water, diiodomethane, and ethylene glycol on VRM and
chemically modified RM (ARM and BRM). As a result, the
SL of the ARM is slightly increased, whereas the SL of
BRM is decreased. The surface free energy is a physical phenomenon caused by intermolecular interactions at interfaces.

S.-J. Park, B.-R. Jun / Journal of Colloid and Interface Science 284 (2005) 204209

207

Table 4
Surface free energy characteristics of the testing liquids, measured at 20 C
(mJ/m2 )
Wetting liquid

LL

LSP

L+

Water
Diiodomethane
Ethylene glycol

72.8
50.8
47.7

21.8
50.42
31.0

51.0
0.38
16.7

25.5
0
1.92

25.5
0
47.0

Table 5
Surface free energies of the untreated RM and chemically treated and measured at 20 C (mJ/m2 )

VRM
ARM
BRM

SL

SSP

S+

55.4
55.9
54.8

39.1
40.6
38.6

16.2
15.3
16.2

2.27
2.37
2.19

28.98
24.77
29.94

The SL of surface free energy is one of the main factors in

the solid capacity, together with the specific surface area of
the solid. An increase of SL of the ARM is effective in improving the stability of dispersion properties of the ARM,
relating to the increase of specific surface area [27].
Also, Table 5 shows the surface electron acceptor (S+ )
donor (S ) components VRM and chemically modified RM
(ARM and BRM). The results of modification show that S+
of ARM and S of BRM are systematically increased compared to that of VRM. The results indicate that the chemical
treatments induce an acidic and basic functional groups on
RM surfaces. Also, it is considered that a major portion of
the interfacial interaction lies in an intermolecular acidbase
interaction at interfaces between matrix and RM.

Fig. 2. Dimension vs temperature for the PMMA (or PVC)/RM nanocomposites studied.

Table 6
Coefficients of thermal expansions (CTEs) of PMMA (or PVC)/RM
nanocomposites studied (m/m C)
1

3.3. Thermal properties

The thermal properties of PMMA or PVC/RM nanocomposites are investigated in the coefficients of thermal expansion (CTE), initial decomposition temperature (IDT), and
decomposition activation energy (E t ).
All materials show temperature dependence in their coefficients of CTEs, especially above T g (glass transition temperature). Therefore, a single reported number for CTE cannot accurately reflect the expansion behavior, except below
T g , where CTE changes little. Nonetheless, it is customary
to select a representative value of CTE for comparison purposes [28]. The linear CTE of the material is the slope of the
relative dimension change vs temperature curve.
The dimension change vs temperature curves of the
PMMA/RM and PVC/RM nanocomposites are shown in
Fig. 2. All nanocomposites show similar behaviors in CTEs.
Below Tg (1 ) is low and relatively flat, whereas above
Tg (2 ) is high and steeply increasing. Below T g of the amorphous phase, we expect that the expansion behavior of the
glassy amorphous chains and the crystal chains can be very
similar. On the other hand, above T g , amorphous chains
have large-scale segmental motions.

PMMA/VRM
PMMA/ARM
PMMA/BRM

73.4
72.3
74.6

2
1025
529
986

PVC/VRM
PVC/ARM
PVC/BRM

71.4
80.2
73.3

425
443
358

1 , CTE below the T g . 2 , CTE above the T g .

Table 6 shows CTEs of both PMMA/RM and PVC/RM

nanocomposites studied. As a result, the CTEs of the
PMMA/RM nanocomposites are increased in order of
VRM > BRM > ARM. The results indicate that surface
modification can be attributed to the reducing of the CTEs on
the PMMA/RM nanocomposites. PMMA/ARM nanocomposites have lower CTE than that of nanocomposites made
from VRM or BRM. This is due to the improvements of
dispersion properties, resulting from the increase of SL or
specific surface area.
Generally, PMMA is considered a prototype basic polymer [29,30]. The electron lone pairs on the oxygen atoms of
the esterified carboxyl groups are effective Lewis base sites.
Decreasing of the CTE on PMMA/ARM nanocomposites
are due to the acidbase interfacial interactions between basic PMMA and acidically treated ARM, resulting in decreasing the internal stress and the crack growths. Meanwhile, the

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S.-J. Park, B.-R. Jun / Journal of Colloid and Interface Science 284 (2005) 204209

CTEs of the PVC/RM nanocomposites are increased in order

of ARM > VRM > BRM. Also, PVC/BRM has lower CTEs
than that of nanocomposites made from VRM or ARM. Although ARM has higher dispersion than that of the others
(VRM or BRM), the PVC/BRM nanocomposites show the
interior to CTE in these systems.
PVC has generally been considered by Berg [31] to be
monofunctionally acidic polymer. Therefore, it is found that
CTE of the PVC/BRM nanocomposites has been more influenced by the acidbase interfacial interactions than dispersion properties in improving the thermal stabilities of the
nanocomposites.
Thermal stabilities have also given by initial decomposition temperature (IDT) and energy of activation for decomposition (E t ). E t can be calculated from TGA curves by the
integral method of Horowitz and Metzger [32] according to
the equation


2
,
ln ln(1 )1 = Et /RTmax
(2)

PVC/RM nanocomposites begin to degrade at about 340 and

240 C, respectively.
From the plots of ln[ln(1 )1 ] vs , which are shown
in Fig. 4, the activation energy for decomposition can be calculated from the slope of the straight line Eq. (2).
PMMA/ARM has higher IDT and E t than those of
PMMA/VRM or PMMA/BRM, and PVC/BRM also has
higher thermal properties than those of PVC/VRM or ARM,
as listed in Table 7. As mentioned above, the improvement of
thermal stabilities on PMMA/ARM nanocomposites are due
to the improvement of the dispersion properties on ARM
and the acidbase interfacial interactions between PMMA
and acidically treated ARM, whereas, although dispersion
properties of the BRM is decreased, thermal stabilities of
PVC/BRM nanocomposites are increased, resulting from

where is the decomposed fraction, E t is the activation energy for decomposition, Tmax is the temperature at maximum
rate of weight loss, = T Tmax , and R is the gas constant.
The TGA analysis of the (a) PMMA/RM and (b) PVC/
RM nanocomposites studied are shown in Fig. 3, respectively. As results, the final residual weight of PMMA/RM
and PVC/RM nanocomposites studied can be very similar, and TGA thermograms reveal that PMMA/RM and

Fig. 4. Plot of the ln(ln(1 )1 ) vs for determining the decomposition

activation energy.

Table 7
Initial decomposition temperature (IDT) and decomposition activation energies (Et ) of the PMMA/RM and PVC/RM nanocomposites studied

Fig. 3. TGA curves of PMMA (or PVC)/RM nanocomposites studied.

IDT ( C)

E t (kJ/mol)

PMMA/VRM
PMMA/ARM
PMMA/BRM

341
352
342

196
205
191

PVC/VRM
PVC/ARM
PVC/BRM

241
235
246

205
167
241

S.-J. Park, B.-R. Jun / Journal of Colloid and Interface Science 284 (2005) 204209

Table 8
The K IC of the PMMA and PVC/RM nanocomposites studied
PMMA
PVC

None

VRM

ARM

BRM

2.9
2.5

3.4
2.8

3.7
2.7

3.4
3.3

the improvement of the acidbase interfacial interactions

between acidic PVC and basically treated RM. From this
it is then recognized that the acidbase interfacial interactions are more important than dispersion properties in
improvement the thermal stabilities of the PVC/RM nanocomposites.
3.4. Mechanical interfacial properties
The degree of adhesion at interfaces between the RM and
the matrix can be measured in terms of the critical stress
intensity factor (K IC ). For the single-edge notched (SEN)
beam fracture toughness test, the value of K IC is calculated
as
PL
KIC = 3/2 Y,
(3)
bd
where P is rupture force, L the span between the supports,
Y the geometry factor described in ASTM E399, and b and
d are the specimen width and thickness, respectively.
Table 8 shows results of the K IC tests of PMMA (a)
and PVC (b)/RM nanocomposites studied. It is found that
PMMA/ARM has a higher K IC value (MPa m1/2 ) than that
of PMMA/VRM or PMMA/BRM. And it is also found that
the K IC value of PVC/ARM is higher than other PVC/RM
nanocomposites.
These results are similar tendency with those of the thermal stabilities of PMMA and PVC/RM nanocomposites.
Thus, it indicates that the acidbase interfacial interaction of
the filler and matrix is also strongly affected on the resulting
mechanical interfacial properties of the composites.

4. Conclusions
In this work, the RM, which was a by-product discharged from an Al2 O3 production factory with bauxite,
was chemically treated with 0.5 N HCl (ARM) and 0.5 N
NaOH (BRM) solution to prepare PMMA/RM and PVC/RM
nanocomposites, respectively, and the effects of chemical
treatments on RM were investigated in thermal stabilities
of nanocomposites. The treatments influenced the pH and
acidbase values of the RM studied, resulting from developments of acidic or basic functional groups on RM surfaces.
Moreover, the surface treatments played an important role in
a change of structure of RM surfaces, such as S BET , C BET ,
V T , and E due to hydrolysis or leaching out of a metal salt
at RM surfaces.
The SL of the ARM was slightly increased, which could
be attributed to the improvement of the dispersion prop-

209

erties. Also, both the S+ of ARM and the S of BRM

were increased. These results indicated that ARM and BRM
were largely influenced by the chemical functional groups
as a result of the treatments. The thermal stabilities and
the mechanical interfacial properties of PMMA/ARM or
PVC/BRM nanocomposites could be higher than those of
the nanocomposites made which RM. It was then found
that the chemical nature of the RM surfaces had a major
role in improving the degree of adhesion at the interfaces
between fillers and polymeric matrix in a composite system.

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