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Formulation study for softening of hard water using surfactant modified

bentonite adsorbent coating

Article  in  Applied Clay Science · March 2017

DOI: 10.1016/j.clay.2016.12.025

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 Applied Clay Science 137 (2017) 168–175

Contents lists available at ScienceDirect

Applied Clay Science

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

Research paper

Formulation study for softening of hard water using surfactant modified

bentonite adsorbent coating
Nur Nadia Ab Kadir a, Mohammad Shahadat b,⁎, Suzylawati Ismail a,⁎
a
School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Nibong Tebal, Penang, Malaysia
b
Department of Biochemical Engineering and Biotechnology, Indian Institute of Technology, IIT Delhi, 110016, India

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

Article history: As an adsorbent coating of surfactants, sodium dodecylbenzene sulfonate (SDBS) modified bentonite (SMB) has
Received 11 September 2016 been developed for the removal of Ca2+ and Mg2+ ions from hard water. The adsorbent was characterized using
Received in revised form 16 November 2016 SEM-EDX, Zeta-meter and FTIR analyses. It has the potential to replace expensive conventional softening treat-
Accepted 16 December 2016
ment techniques as well as reduce the usage of excess chemicals (chemical precipitation). Hard water can be eas-
Available online xxxx
ily treated using SMB by applying the adsorbent coating to the treatment area. Testing of adsorbent was carried
Keywords:
out in terms of effect of surfactant ratio, effect of different types of binder as well as binder ratio. The best formu-
Hard water softening lation of SMB was achieved by using polyvinyl acetate (PVAc) and bentonite in the ratio of 0.75:1.0 (w/w). Lang-
Characterization muir, Freundlich and Temkin isotherm models were tested to describe the optimum adsorption of Ca2+ and
Adsorption Mg2+ ions on SMB adsorbent coating. Thermodynamic and kinetic parameters were also examined for the ad-
Modified bentonite sorption of metal ions at different temperatures. SMB demonstrated the highest metal (Ca2+ and Mg2+) removal
Surfactant efficiency (29.27 mg g−1) in 90 min from 120 mg L−1 hardness. On the basis of good removal capacity for Ca2+
Metal ions treatment and Mg2+ ions, SMB can be effectively used for treatment of metal ions in industrial wastewater, as well as soft-
ening of hard water.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction as well as in bathing (Heidekamp and Lemley, 2005; Cameron, 2011).

Water is one of the most important sources of living beings and is
used in daily life (Archimede, 2016). Excess minerals content in water
can create lots of problems to human health (Nabi et al., 2011a,
2011b; Shahadat et al., 2015). Calcium and magnesium are two major
hardening cationic elements that cause the formation of hard water.
Water can be considered hard when the concentration of calcium and
magnesium is found to be above a permissible limit (120 mg L−1)
(Joseph Cotruvo, 2011). According to Malaysia Water Quality Standards,
the maximum acceptable value for hard water is 500 mg L−1 (Ministry
of Health, 2010). It contains minerals (Ca2+ and Mg2+) which can be
easily deposited on the surfaces of equipment such as kettles, coffee
makers, and heaters in the form of scale. The formation of scale causes
clogging of a piping system thus lowering the water flow (Reddiroot'r,
2016). While causing pipe clogging, however, it tends to protect their
surfaces by coating to prevent corrosion (Mcfarland et al., 2015). Be-
sides this, it also decreases the foamy nature of soap and detergent
soapy, leading to the use of additional soap to wash utensils and clothes,
⁎ Corresponding authors.
E-mail addresses: mdshahadat93@gmail.com (M. Shahadat), chsuzy@usm.my
(S. Ismail).
Moreover, hard water also affects the health and environment. Potential
health problems caused by hard water are kidney stones, dermatitis, re-
productive health issues and pancreatic cancer (Sengupta, 2014; Chiu et
al., 2010). Atopic dermatitis and chronic inflammatory diseases have
been found due to the intake of hard water. The United States, Canada,
and the Netherlands, as well as the state of Perlis in Malaysia, all face
the problem of hard water (Issa et al., 1998). The degree of water hard-
ness at Titi Tinggi (Perlis) was found to be 530 mg L−1. In order to over-
come the problem of water hardening, a number of commercial
available methods for hard water treatment methods such as chemical
precipitation, ion exchange (Bushra et al., 2012), adsorption (Moreira
et al., 2015), electrolysis (Agostinho et al., 2012), electrochemical
(Gabrielli et al., 2006) and nanofiltration (Izadpanah and Javidnia,
2012) have been applied. Ion exchange treatment is considered one of
the most commonly used methods. Salt of sodium chloride (NaCl),
Amberlite, titanate nanotube (TiONTs), and zeolite are potential ion
exchangers that have been used to exchange Ca2 + and Mg2 + ions
(Cetin, 2014; Madarasz et al., 2014; Skipton, 2008; Xue et al., 2014).
Although ion exchange is very effective in use, it is an expensive
treatment technique. Adsorption is one of the promising methods that
can be effectively used for softening hard water. A few studies have
shown that natural sand may be used as an adsorbent due to its

http://dx.doi.org/10.1016/j.clay.2016.12.025
0169-1317/© 2016 Elsevier B.V. All rights reserved.
 N.N.A. Kadir et al. / Applied Clay Science 137 (2017) 168–175
potential ability to soften hard water (Jayalakshmi et al., 2014;
Sivasankar and Ramachandramoorthy, 2011). Activated carbon from
agricultural waste, mainly coconut and cashew shell, is also used as a
low cost adsorbent for the treatment of metal ions (Rolence et al.,
2014). Development of the new inexpensive adsorbent has become a
primary motivation for researchers. In this regard, bentonite has been
discovered to be a potential adsorbent for softening of water because
of its ability to allow adsorption of cationic species such as Pb2 + and
Cu2 + (Melichová and Hromada, 2013) and acid dye (Alshammari,
2014). Native form of bentonite does not achieve high removal
efficiency; therefore, to improve its adsorption capacity, bentonite is
typically modified by the addition of other chemicals. Sodium dodecyl
benzene sulfonate (SDBS), a surfactant with a negative charge, has
potential to attract positive charge ionic component. It has been widely
used in detergent due to the presence of alkylbenzene sulfonate which
is a major constituent of synthetic detergent (Taffarel and Rubio, 2010).
Although the addition of SDBS improves hard water softening
properties, the presence of surfactant in water will cause the large-
scale formation of foam which is harmful to the aquatic environment
(Li et al., 2011). Thus, considerable amount of surfactant should be
used to reduce the pollution effect. The present article deals with the
fabrication of a new formulation of adsorbent coating using bentonite
clay modified with SDBS in softening hard water.
2. Experimental
2.1. Materials and methods
The materials for the development of adsorbents were bentonite,
kaolin, sodium dodecyl benzyl sulfonate (SDBS), and polyvinyl
(PVAl) purchased from Sigma Aldrich, Malaysia. Pumice stone and
polyvinyl acetate (PVAc) were bought from Watson Health Store
and Mydin Store Penang (Malaysia), respectively. Water based
paint was purchased from Sisson Company, Penang, Malaysia. For
preparation of synthetic water, CaCl2 .2H2O and MgSO4.7H2O salts
were supplied from R&M Chemicals, Malaysia. All experiments
were conducted according to the Standard Methods for the
Examination of Water and Wastewater (Federation, 1999). The
samples of synthetic hard water (120 mg L− 1) were prepared by
dissolving 2.6 g hydrated calcium chloride (CaCl2.2H2O) and 4.1 g
hydrated magnesium sulphate (MgSO 4 .7H2 O) in distilled water
(Fahmi et al., 2015).
2.2. Development of SMB adsorbent coating
To determine the optimal adsorption capacity of adsorbents,
bentonite, pumice stone, and kaolin were chosen for testing. All
three adsorbents were used to treat a synthetic hard water of
120 mg L− 1 using a fixed amount of each adsorbent (0.3 g) individu-
ally at the speed of 300 rpm at room temperature (25 ± 2 °C). The
amount of adsorbed metal ions on each adsorbent was determined
by the titration of hard water using EDTA-titration at every interval
of 30 min for 4 h. Thus, on the basis of higher adsorption capacity
(among three adsorbents), bentonite was selected to fabricate
surfactant modified bentonite adsorbent.
Surfactant modified bentonite (SMB) was prepared by mixing a
fixed amount of bentonite (0.5 g) and SDBS (0.25 g) in distilled
water (5 mL). The mixture was stirred for 10 min to complete
dissolution of surfactant with bentonite. By adding 1.0 g binder
(PVAc) to the mixture, a slurry formed was coated on the fabric
material of 126 cm2 surface area and dried in an oven at 70 °C for
24 h. The schematic presentation for the preparation of SMB
adsorbent coating is shown in Fig. 1a. The proposed scheme for the
removal of Ca 2 + and Mg 2 + ions from synthetic hard water is
shown in Fig. 1b.
169
2.3. Instruments
The morphology of adsorbent was observed using a scanning elec-
tron microscope (SEM, Crest System (M) Sdn. Bhd, Quanta Feg 450)
and its composition was determined via energy dispersive X-ray (EDX,
Crest System (M) Sdn. Bhd, Quanta Feg 450). The surface charge of par-
ticles in the solution was determined using a zeta meter (Malvern idb
Zeta Sizer Nano Series). Fourier Transform Infrared Spectroscopy
(FTIR, NICOLET i10) was used to identify the existence of functional
group in the sample of adsorbent coating. The X-ray diffraction (XRD)
patterns of bentonite, SDBS and SMB were measured on a Bruker D/
Max-2200 X-ray powder diffractometer with Cu/Ka (k = 0.154 nm) ra-
diation (Bruker diffrac. suite eva version 1.4) AXS, Germany.
2.4. Effect of surfactant ratio
To improve the adsorption capacity of SMB, a fixed amount of ben-
tonite (0.3 g) was mixed with various amounts of the surfactant SDBS
(0.15 g, 0.3 g and 0.6 g). On the basis of higher adsorption efficiency,
the selected SMB adsorbent was used for further study.
2.5. Effect on type of binder
To examine the maximum supporting ability of a binder with ben-
tonite, polyvinyl alcohol, polyvinyl acetate, and also water based paint
were selected. The selection of binder was on the basis of their safety
use and without affecting the performance of adsorbent.
2.6. Effect on adsorbent to binder ratio
In order to determine the best adsorbent coating, an adsorbent to
binder ratio experiment was conducted. Adsorbent to binder ratios
with different dosages as studied are shown in Table 1.
2.7. Batch experiments
All experiments were conducted using a batch method in 250 mL
beakers. A solution of hard water (200 mL) was stirred for 4 h at
room temperature at 300 rpm with an initial concentration of
120 mg L − 1 . Concentrations of Ca 2 + and Mg2 + ions were deter-
mined at 15 min intervals for 4 h using EDTA-titration method
(Federation, 1999). The metal ions (Ca 2 + and Mg 2 +) removal
efficiency (RE) was determined using Eq. (1) and adsorption
capacity was calculated by Eq. (2). All experiments were repeated
in triplicate.
C O −C e
RE ¼  100 ð1Þ
Co
 
mg ðC e −C O Þ  V
qt ¼ ð2Þ
g m
where Co is the initial concentration (mg L− 1), Ce is the final concen-
tration (mg L− 1), qt is the adsorption capacity at time (mg g− 1), V is
the volume of the solution (L), and m is the mass of the adsorbent
(g).
2.8. Adsorption isotherms
The adsorption behaviour of SMB for the removal of Ca 2 + and
Mg2 + was described in terms of isotherm models. Three adsorption
isotherms; Langmuir, Freundlich and Temkin isotherms can be
used to determine nature of the adsorption.
170 N.N.A. Kadir et al. / Applied Clay Science 137 (2017) 168–175

Fig. 1. (a, b). Preparation of SMB adsorbent coating (a), proposed scheme for the adsorption of Ca2+ and Mg2+ on SMB adsorbent coating (b).

2.8.1. Langmuir adsorption model In Langmuir isotherm, the dimensionless constant separation factor
According to this model the adsorption occurs at specific homoge- or equilibrium parameter, RL can be defined as:
neous sites on the adsorbent which demonstrates monolayer molecular
adsorption phenomenon (Langmuir, 1918). The Langmuir adsorption 1
RL ¼ ð2Þ
model was expressed by: 1 þ kL C O

where kL is Langmuir constant related to energy of adsorption and Co

Ce Ce 1 is the initial concentration of the solution (mg L−1).
¼ þ ð1Þ
qe qm kL qm
2.8.2. Freundlich adsorption model
This model can be applied for heterogeneous surfaces and multilayer
−1
where Ce is the equilibrium concentration (mg L ) and qe is the adsorption (Freundlich, 1907). The Freundlich equations are:
amount adsorbed per unit mass of adsorbent (mg g−1), qm is the max-
imum adsorption capacity (mg g− 1), kL is the Langmuir equilibrium qe ¼ k F ðC c Þ1=n ð3Þ
constant which is related to the heat of adsorption and b is the monolay-
er capacity.  
1
ln qe ¼ ln k F þ lnC e ð4Þ
n

Table 1
where kF is the measure of sorption capacity, 1/n is sorption intensity,
Adsorbent to binder ratio. and the rest of the terms have the usual significance, n is the degree of
non-linearity between solution concentration and adsorption. The de-
Adsorbent (g) SDSB (g) Binder (g) Adsorbent (g) SDBS (g) Binder (g)
gree of nonlinearity is as follows: if n = 1, the adsorption is linear; if
0.3 0.15 0.5 1.0 0.5 0.5 n N 1, the adsorption is a physical process; if n b 1, the adsorption is a
1.0 1.0
chemical process (Bushra et al., 2014).
1.5 1.5
2.0 2.0
0.5 0.25 0.5 1.5 0.75 0.5 2.8.3. Temkin isotherm
1.0 1.0 Temkin isotherm contains a factor which clearly describes adsor-
1.5 1.5 bent–adsorbate interactions. According to this model, by neglecting
2.0 2.0
the extremely low and high values of concentrations, the heat of
 N.N.A. Kadir et al. / Applied Clay Science 137 (2017) 168–175 171

adsorption (function of temperature) of all molecules in the layer could

be decreased linearly rather than logarithmic with coverage (Aharoni
and Ungarish, 1977; Temkin and Pyzhev, 1940). The equation of this
model is shown as:

qe ¼ B ln kT þ B lnC e ð5Þ

RT
B¼ ð6Þ
bT

where kT is the Temkin isotherm equilibrium binding constant

(L g−1), R is Universal gas constant (8.314 J mol−1 K−1), T is the tem-
perature (K), bT is the Temkin isotherm constant and B is related to
heat of sorption (J mol−1).

2.9. Thermodynamic study

To evaluate the feasibility of adsorption process, thermodynamics

parameters namely; standard Gibbs free energy change (ΔG0), standard
enthalpy change (ΔH0) and standard entropy change were calculated
using the following equations:

ΔGo ¼ ΔHo −TΔSo ð7Þ

ΔSo ΔH o
lnk ¼ − ð8Þ
R RT

By plotting a graph between lnKc and 1/T, a straight line with slope
ΔH0/RT and intercept ΔS0/R is obtained. The value of ΔH0 and ΔS0 was
calculated from the slope and intercept of the van't Hoff plots.

2.10. Kinetic study

Kinetics parameters were measured on the basis of the effect of the

adsorbent dose (SMB), and the amount of adsorbate (dye) has been
studied under kinetic parameters. Pseudo firs-second order model is de-
scribed by:

ln ðqe −qt Þ ¼ ln qe −k1 t ð9Þ

where qe is the adsorption capacity at equilibrium (mg g−1) and qt is

the adsorption capacity of adsorbate on the surface at any time
(mg g−1), k1 is the pseudo first order rate constant (min−1), t is the con-
tact time (min). The pseudo-second-order model is expressed as:

dq Fig. 2. (a, b, c). Hard water removal efficiency using bentonite, kaolin, and pumice stone
¼ k2 ðqe −qt Þ2 ð10Þ
dt (a), the effect of surfactant ratio on hard water removal (b), the effect of binder (PVAc,
PVAl and water-based binder) (c).

where k2 is the pseudo second-order rate constant (g mg−1 min−1).

Integrating and applying boundary condition t = 0 to t = t and q = 0 to removal capacity. After 210 min, a sudden drop of adsorption was ob-
q = qt gives; served for kaolin and bentonite, which may be due to the presence of
  calcium and magnesium contents in the clay released into the solution
t 1 t and exchange of cations at the interlayer of clay (Mhamdi et al., 2013).
¼ þ ð11Þ
qt k2 qe2 qe Meanwhile, no adsorption was found using pumice stone owing to the
presence of high content of calcium in it (Canbolat et al., 2013), which
The values of k2 (g mg−1 min−1) and qe (mg g−1), can be calculated tends to be desorbed into the solution.
from the plot of t/qt verses t.
3.2. Effect of surfactant ratio
3. Results and discussions
To improve the adsorption performance of the adsorbents, as well to
3.1. Testing study for the removal of water hardness determine the suitable amount of surfactant to be used, different
amounts of SDBS were tested (0.15 g, 0.3 g and 0.6 g). Compared by
Hardness removal performances of three different adsorbents, using bentonite only (Fig. 2a), the adsorption performance was im-
namely kaolin, bentonite and pumice stone, are shown in Fig. 2a. proved and no desorption of Ca2+ and Mg2+ ions occurred by addition
Among the three adsorbents, bentonite showed superior hardness re- of SDBS at time duration 240 min (Fig. 2b). The surfactant introduced to
moval capacity in very short time (60 min); however, onward the clay penetrated into the interlayer part by altering the surface of clay
150 min both bentonite and kaolin demonstrated same hardness (Anirudhan and Ramachandran, 2015) and was strongly retained in the
172 N.N.A. Kadir et al. / Applied Clay Science 137 (2017) 168–175

Table 2
Hardness removal capacity (%) for adsorbent to binder ratio.

Adsorbent Binder Removal Adsorbent Binder Removal capacity

(g) (g) (%) (g) (g) (%)

0.45 0.5 33.33 1.50 0.5 33.33

1.0 33.33 1.0 50.00
1.5 33.33 1.5 50.00
2.0 33.33 2.0 50.00
0.75 0.5 66.67 2.25 0.5 33.33
1.0 66.67 1.0 33.33
1.5 33.33 1.5 33.33
2.0 66.67 2.0 33.33

clay, which prevented ion exchange migration (Díaz-Nava et al., 2012).
Hence, no desorption occurred. Thus, the lowest amount of SDBS
(0.15 g) was chosen to prevent use of surfactant equal to half the
mass of the adsorbent.
3.3. Effect of binder nature
Paint, PVAc, and PVAl were examined to select the best binder for
adsorbent coating formulation, as shown in Fig. 2c. Among all binders,
PVAc and water-based paint demonstrated same performance. Howev-
er, PVAl showed the lowest percentage removal of Ca2+ and Mg2+ ions.
It was also found that by using PVAl, the solution became very cloudy,
which might be due to the adsorbent coating peeling off into the solu-
tion. It was not so strong to stick on adsorbent surface. Although
water-based paint binder has good binding potential, it contains high
percentage of calcium which affects the stability of adsorption perfor-
mance. Thus, PVAc was selected for the fabrication of SMB adsorbent.
3.4. Effect of adsorbent to binder ratio
Adsorbent to binder ratio is an important factor to evaluate the best
formulation of adsorbent coating. The best formulation was obtained by
using bentonite modified SDBS with PVAc in 075:1.0 ratio (w/w) which
showed the highest hardness removal efficiency, 66.67% in 90 min con-
tact time (Table 2, Fig. 3b). This formulation provided good adsorption
performance, and no peeling adsorbent was found during the treatment
process. The strength of binder was also found to be strong enough to
bind perfectly with fabric material. However, adsorbent and binder ra-
tios of 0.75 g:1.5 g, and 0.75 g:2.0 g, provided lower removal hardness
percentage and the adsorbent coating easily peeled off. The adsorbent
Fig. 4. Adsorption capacity of SMB (0.75:1.0) using 120 ppm hard water at different times.
ratios 0.45 g:0.5 g, 0.45 g:1.0 g and 0.45 g:2.0 g (Fig. 3a) showed lower
adsorption performance owing to the low amount of adsorbent used.
Meanwhile, for 1.5 g adsorbent (Fig. 3c), the removal capacity was
found low due to adsorbent peeling off from the fabric. Therefore, the
solution turned cloudy due to the peeled off adsorbent coating. A
same phenomenon was also achieved for 2.25 g adsorbent (Fig. 3d).
The adsorption capacity of adsorbent dosage with selected amount of
adsorbent to binder ratio (0.75:1.0 by mass) was studied as shown in
Fig. 4. The adsorption capacity increased with increase in contact time
and equilibrium was achieved in 75 min (29.27 mg g−1). In order to in-
vestigate the adsorption potential of SMB adsorbent coating with other
adsorbent materials a comparative was carried out (Table 3). A number
of adsorbents such as from pumice stone, activated carbon based from
different plant parts (melon husk, phyllantusembilica wood) have
been used to treat hard water. Among these adsorb materials, SMB
demonstrate higher hard water removal capacity.
3.5. Characterization
3.5.1. SEM analysis
The SEM micrograph of SMB adsorbent coating before and after the
adsorption of hard water is shown in Fig. 5 (a, b) at a magnification of
10,000 ×. The surface of the modified bentonite after adsorption
shows more rough texture and aggregate formed in comparison to be-
fore adsorption which is due to the adsorption of cationic Ca2 + and
Mg2+ ions on the surface of SMB (Fatiha and Belkacem, 2016). The tex-
ture of SMB changed to some extent by the adsorption of metal ions
which shows corn flake like structure with fluffy appearance revealing

Fig. 3. (a, b, c, d). Adsorbent to binder ratio by mass (a) 0.45:(0.5–2.0), (b) 0.75:(0.5–2.0), (c) 1.5:(0.5–2.0) and (d) 2.25:(0.5–2.0).
 N.N.A. Kadir et al. / Applied Clay Science 137 (2017) 168–175 173

Table 3 constituent of SMB which enhanced adsorption efficiency of Ca2+ and

Comparison between the adsorption capacity of SMB and other adsorbents. Mg2+ ions during treatment process. The EDX analysis also confirmed
Adsorption capacity the existence and increment of calcium and magnesium contents on
Adsorbent/exchanger (mg g−1) Reference the surface of SMB after adsorption (Table 4).
Melon husk (activated carbon) 1.8 (Ca2+), 1.0 Mustapha et al. (2016)
(Mg2+) 3.5.2. FTIR and XRD analyses
Pistaciavera shell 2.41 (Ca2+), 2.19 Pratomo et al. (2015) A comparative FTIR spectrum of SMB adsorbent coating before and
(Mg2+)
after adsorption is shown in Fig. 5e, f. The stretching frequency of Al-
Phyllantusembilica wood 4.71 (Ca2+), 1.45 Kannan and Mani
(activated carbon) (Mg2+) (2015) MOH (M can be Al, Fe, Mg) before and after adsorption was found in
Carbon nanotube sheet 5.47 (Ca2+), 7.15 Tofighy and the range 1000–650 cm−1 (Er-ramly and Ider, 2014). The adsorption
(Mg2+) Mohammadi (2011) peaks in the range of 1000–1260 cm−1 correspond to the stretching vi-
SMB adsorbent coating 14.63 (Ca2+), 14.63 Present study bration of Si\\O group (Paluszkiewicz et al., 2008; Holtzer et al., 2011;
(Mg2+)
Er-ramly and Ider, 2014). Meanwhile, after adsorption, a peak at
1375 cm− 1 is found owing to the carboxyl stretching adsorption
(Öztürk et al., 2007; Nabi et al., 2010). Both spectra show a small peak
fine platy morphology (Manohar et al., 2006). The SMB has a number of near 1730 cm−1 which could arise due to the presence of C _O group
heterogeneous cavities which enhanced adsorption efficiency of Ca2+ (Tinti et al., 2015). After adsorption, a medium intensity peak near
and Mg2+ ions on its surface (Basri et al., 2009). The elemental compo- 2920 cm−1 corresponds to C\\H bond (Silva et al., 2012). In addition,
sition of SMB adsorbent coating before and after adsorption was mea- a broad and intense band near 3400 cm−1 may be due to the Al\\OH
sured using energy dispersive analysis technique (Fig. 5c, d). It and Si\\OH stretching (Nafees et al., 2013). The adsorption peak at
confirms the existence of silicon, aluminium, and oxygen elements in 3631 cm− 1 arises as a result of free \\OH groups and/or physically
the adsorbent. The amount of silicon, oxygen and aluminium is found bound water (Nabi et al., 2011a, 2011b; Ma et al., 2012). The powder
almost same. Therefore, SiO2 and Al2O3 are considered as the main XRD patterns of native bentonite, SDBS and SMB composite coatings

Fig. 5. (a, b, c, d, e, f, g). SEM images of SMB before (a) and after (b), EDX analysis before (c) and after (d), FTIR spectra before (e) and after (f) adsorption of Ca2+ and Mg2+ ions, PXRD
patterns of bentonite, SDBS, and SMB adsorbent coating (g).
174 N.N.A. Kadir et al. / Applied Clay Science 137 (2017) 168–175

Table 4 the endothermic nature (Table S-2). Meanwhile on increasing tempera-

Elemental composition from EDX analysis for SMB adsorbent coating (before and after ture (5 °C to 70 °C), the standard Gibbs free energy decreased to lower
adsorption).
negative value which confirmed that adsorption process is not
Element Weight (%) before adsorption Weight (%) after adsorption favourable (Salehi et al., 2013) at higher temperature.
C 34.74 25.79
O 40.01 47.53 3.8. Kinetic study
Mg 0.69 1.0
Al 4.05 5.52
Si 11.66 16.18 The adsorption kinetic of Ca2+ and Mg2+ on SMB was measured by
S 3.18 0.96 applying the pseudo-first and pseudo-second-order kinetic models to
Ca 0.79 1.35 the experimental data obtained at different concentrations (120, 200,
Fe 1.18 1.68
400, 600 and 800 ppm), time intervals (30, 60, 90, 120, and 150 ppm)
Na 3.14 0.0
P 0.55 0.0 and temperatures (5, 30 and 70 °C). The values of the pseudo-first and
pseudo-second-order kinetics parameters calculated from their respec-
tive plots (Figs. S-4 and S-5 (a,b,c)) are shown in Tables (S-3, S-4 and S-
5), respectively. The adsorption of metal ions on dye on the SMB adsor-
(before and after adsorption) are shown in Fig. 5 (g), respectively. From bent coating follows both pseudo-first and second-order kinetics. How-
the PXRD results, modification of bentonite minerals by adsorbent in- ever, at all temperatures (5, 30 and 70 °C), the correlation coefficient
troduces some changes into the crystal structure of bentonite minerals shows relatively higher values for pseudo-second order model than
as evident by the disappearance of peak at 2theta = 28°. This peak ap- for pseudo-first order kinetic, established its best fits with pseudo sec-
pears again after the adsorption of Ca2 + and Mg2 + ions indicating ond order kinetic. Additionally, the values of Qe.calc are much close to
retaining its structure (Missana et al., 2004; Manohar et al., 2006). Qe.calc for pseudo-second order which signify pseudo-second order ki-
netics (Robati, 2013).
3.5.3. Measurement of zeta potential
To examine the alteration in the nature of charge on the surface of
SMB, a zeta potential experiment was performed for native bentonite, 4. Conclusion
SMB, and SMB adsorbent coatings (Table 5). Zeta potential experiment
revealed that all components surfaces showed negative charge. The na- The present work established the formulation of an SMB adsorbent
ture of charge was reduced by the addition of SDBS with bentonite SMB for the softening of hard water. Natural bentonite modified with surfac-
tant (SDBS) enhanced the adsorption removal capacity of Ca2 + and
(− 34.3 mV), which was further decreased by the mixing of binder
(PVAc) SMB adsorbent coating (−27.3 mV). The reduction of the nature Mg2+ ions. The amount of surfactant was set at half of the mass of the
adsorbent, as it provides same adsorption performance to prevent ex-
of this change may be due to the recovery of negative charge of benton-
ite with positive charge of surfactant, as well as binder, resulting in the cess use of surfactant. The PVAc binder demonstrated strong ability to
stick on the surface of SMB adsorbent without affecting its adsorption
development of a functional group on the surface of SMB which en-
hances its adsorption capacity. A rule of thumb states that a suspension performance. A bentonite modified surfactant to binder (PVAc) ratio
of 0.75:1 by (w/w) furnished the best formulation, with 66.67% removal
is found to be stable when the zeta potential is above ±30 mV and the
particles have sufficient enough mutual repulsion that result in stability. efficiency of Ca2+ and Mg2+ ions from synthetic hard water.
Meanwhile, values lower than ±30 mV result in an increasing tendency
of adsorbent surface (Dai, 1994). Acknowledgement

3.6. Adsorption isotherms
The plots of Freundlich and Langmuir and Temkin isotherms (Fig.
S1) and their slopes were used to calculate the adsorption constants
as shown in Table S-1. On the basis of obtained adsorption isotherms
data, the value of correlation coefficient for Langmuir isotherm
(R2 = 0.9914) is found to be much higher than Freundlich isotherm
(R2 = 0.936) and Temkin isotherm (R2 = 0.9626) (Table S-1). The
Langmuir isotherm assumes monolayer adsorption and it explains
that no further adsorption takes place once the active sites are fully
occupied (Desta, 2013). The adsorption capacity increases from 5
to 30 °C, and sudden drop at 70 °C because of low coating strength
thus influenced the adsorption process.
3.7. Thermodynamic study
The slope and intercept of the van't Hoff plots provided the value of
ΔH0 and ΔS0 which were 5.852 (kJ mol−1) and − 0.016 (kJ mol.K−1),
respectively (Figs. S-2 and S-3). The negative value of ΔH° indicated
Table 5
Surface charge.
Components Charge (mV)
Bentonite −46.3
SMB −34.3
SMB adsorbent coating −27.3
This work was supported by Research University Grant, RUI (1001/
PJKIMIA/814269) and Ministry of Higher Education for providing finan-
cial support during Masters.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.clay.2016.12.025.
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