Journal of Industrial and Engineering Chemistry 31 (2015) 374–384

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Journal of Industrial and Engineering Chemistry

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

Characterization of reactive amphiphilic montmorillonite nanogels

and its application for removal of toxic cationic dye and heavy metals
water pollutants
Ayman M. Atta a,b,*, Hamad A. Al-Lohedan a, Z.A. ALOthman c, Ahmed A. Abdel-Khalek e,
Ahmed M. Tawfeek d,e
a
Surfactants research chair, Chemistry Department, College of Science, King Saud University, Riyadh, Saudi Arabia
b
Petroleum Application Department, Egyptian Petroleum Research Institute, Cairo, Egypt
c
Chemistry Department, College of Science, King Saud University, Riyadh, Saudi Arabia
d
College of Science, King Saud University, Riyadh, Saudi Arabia
e
Chemistry Department, Faculty of Science, Beni Suef University, Beni Suef, Egypt

A R T I C L E I N F O A B S T R A C T

Article history: The present work aims to reduce the water surface tension using dispersed organophilic clay minerals to
Received 14 June 2015 increase the adsorption water pollutants (organic and inorganic) into the clay galleries. Therefore,
Received in revised form 7 July 2015 sodium montmorillonite (Na-MMT) was functionalized with amphphiles based on crosslinked nanogel
Accepted 19 July 2015
polymers of N-isopropylacrylamide (NIPAm), sodium 2-acrylamido-2-methylpropane sulfonate (Na-
Available online 26 July 2015
AMPS), acrylamide (AAm) and acrylamidopropyl)trimethylammonium chloride solution (APTAC) using
surfactant free technique. The chemical interactions between nanogels and Na-MMT and their chemical
Keywords:
structure were confirmed by FTIR analysis. The intercalation and exfoliation of Na-MMT were confirmed
Sodium montmorillonite
Water purification
by wide-angle X-ray diffraction. The morphology of Na-MMT nanogel composites was investigated by
Nanogel TEM analysis. The adsorption capacities of the prepared Na-MMT nanogels for methylene blue dye,
Methylene blue cationic dye cobalt and nickel cations from water were investigated. The data indicated that the Na-MMT nanogels
Heavy metal reduced the surface tension of water and efficiently remove dye and metal ions from water.
ß 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction such as fast removal, ion selectivity and reusability. Recently,

Water pollution, especially of heavy metals and dyes, is a
worldwide problem affecting economic and ecological system
around the world. The industrial toxic wastes are one of the main
sources of this pollutants [1–3]. There are several techniques were
used to control water pollution such as ion exchange [4],
adsorbents, reverse osmosis [3], precipitation, and coagulation
techniques [5]. Adsorbents attracted great attention due to
availability of various adsorbent types, eco-friendly, cost feasibili-
ty, and their high efficiency in removal of organic and inorganic
pollutants. The main adsorption mechanisms are based on
complexation and ion exchange mechanisms. There are several
important criteria controlling the selection and design adsorbents
* Corresponding author at: King Saud University, Surfactants Research, Chemis-
try Department, College of Science, Riyadh, Saudi Arabia. Tel.: +00966 561557975.
E-mail address: aatta@ksu.edu.sa (A.M. Atta).
adsorbents based on nanomaterials gained much attention due to
their high performance to adsorb pollutants from aqueous
environments such as carbon nanotubes, titania, silica and clay
polymer composites [2,3,6–8]. Ionic polymer clay nanocomposites
[9] showed high performance to remove organic and organic
pollutants [10,11]. The efficiency of nano-clay polymer composites
was affected by method of preparation, type of polymer
composites and application technique such as membrane, nano-
filters, etc.
Sodium montmorillonite (Na-MMT) has attracted great atten-
tion in recent years for its application in the field of water
purification [12,13]. The exfoliation of Na-MMT from multilayer
sheets to dispersed monolayer composites plays an important role
in the preparation of nanocomposites to apply in water treatments
[14–16]. The ion exchange, adsorption of organic compounds and
reactions with organic acid treatments are an effective methods
used to replace sodium cations between silicate layers to
intercalate the silicate layers and converting layers to organophilic

http://dx.doi.org/10.1016/j.jiec.2015.07.012
1226-086X/ß 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
 A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 374–384
minerals [17]. Crosslinking of reactive monomers is another
preferred technique to disperse clay sheet in the polymer
composites [18,19]. In previous work, exfoliation of Na-MMT
sheets using crosslinking technique increased the performance of
Na-MMT to form anticorrosive thin film layer on the steel surfaces
[20,21]. The reactive anionic amphiphile nanogels attracted great
attention to exofilate Na-MMt sheets monomers due to their high
cation exchange capacities, surface area, surface reactivity,
adsorptive properties, and transparency in solution [13]. 2-
Acrylamido-2-methylpropane sulfonic acid (AMPS] and N-isopro-
pylacrylamide (NIPAm) have been reported as good clay modifiers
due to their ability to adsorp between Na-MMT sheets [22]. These
polymers were selected to modify Na-MMT because of they have
sulfonate group, an amido functional groups potentially able to
interact with the Na-MMT surface. NIPAm microgel crosslinked
with clay showed excellent surface activity because thermore-
sposive characteristics of microgels [23–25]. Generally, cross-
linked polyacrylamide (PAAm) clay nanocomposites, prepared in
the absence of chemical crosslinker, showed higher efficiency for
removal of toxic pollutants from water [26].
The present work reports the functionalization of Na-MMT
using crosslinking technique to produce reactive amphiphile
dispersed Na-MMT sheets having the affinity to reduce the surface
tension of water to increase clay adsorption of pollutants on their
surfaces. It was previously reported that, addition of organic
molecules to solid inorganic colloidal particles enhances the
material’s capability to absorb at the interface and forms an
interfacial adsorption layer [27]. To achieve this goal the present
work aims to use anionic, cationic and nonionic monomers to
prepare amphiphilic Na-MMT nanogels using radical crosslinking
technique. NIPAm was selected as amphiphilic nonionic monomer
to copolymerize with acrylamide (AAm), sodium 2-acrylamido-2-
methylpropane sulfonate (Na-AMPS) and acrylamidopropyltri-
methyl ammonium chloride (APTAC) to exfoliate clay with
nonionic, anionic and amphoteric nanogels, respectively. NIPAm
was selected to prepare nanogel due to their thermsensitivity at
temperature above polymerization temperature to form reactive
nanogels having ability to intercalate and exfoliate the Na-MMT.
Moreover, APTAC was selected due to their ability to exchange Na
cations of Na-MMT to form highly dispersed Na-MMT nanogels
[28]. The surface properties such as aggregation and adsorption at
interfaces of the modified Na-MMT nanogels were investigated
from surface tension measurements. The application of the
modified Na-MMT nanogels to absorb organic and inorganic
pollutants in the water treatment is another objective of the
present work.
Experimental
Materials
Sodium montmorillonite nanoclay (Na-MMT) with commercial
name nanometer PGV is obtained from Sigma-Aldrich Co. N-
isopropyl acrylamide (NIPAm), sodium 2-acrylamido-2-methyl-
propane sulfonate (Na-AMPS), acrylamide (AAm) and acrylami-
dopropyl trimethylammonium chloride solution (APTAC; 75 wt.%
in H2O) monomers are obtained from Aldrich Chemicals Co.
Poly(vinyl pyrrolidone (PVP) having molecular weight 40,000 g/
mol is used as dispersing agent for Na-MMT purchased from
Aldrich Chemical Co. N,N-Methylenebisacrylamide (MBA), ammo-
nium persulfate (APS) and N,N,N0 ,N0 -tetramethylethylenediamine
(TEMED) are used as crosslinker, radical initiator, and activator for
crosslinking polymerization at low temperature, respectively and
they purchased from Sigma-Aldrich Co. Deionized water and
ethanol are analytical grades used as solvent for crosslinking
polymerization.
375
Cobalt and nickel nitrate hexa hydrate produced from Sigma-
Aldrich CO. are used to prepare stock solution 100 ppm. Buffer
solution (H3PO4/NaH2PO4) was prepared by titration of 0.1 N of
NaH2PO4 against 0.1 M HCl (for pH range 2–3) or against 0.1 N
NaOH (for pH range 7–12) until the required pH is reached. The pH
value was monitored using pH meter.
Synthesis procedure
Na-MMT clay was not easy to disperse in water solution.
Therefor water/ethanol (60/40 vol%) mixture was used as solvent
to disperse Na-MMT. In this respect, Na-MMT (2 g) is dispersed in
water/ethanol (100 mL) and PVP (0.3 g) as stabilizer at room
temperature for 24 h.
The dispersed Na-MMT nanogels based on NIPAm were
prepared using surfactant free dispersion radical crosslinking
polymerization using temperature programmed technique. In this
respect, NIPAm monomer (0.5 g) is dispersed in Na-MMT solution
(water/ethanol 50 mL). The solution was initially pre-heated at
temperature 40 8C under nitrogen atmosphere for 30 min. APS
(0.015 g/mL) was added to start the polymerization. The reaction
temperature was increased to 50 8C at rate 5 8C per 15 min. The
NIPAm monomer (1.5 g), MBA (0.03 g) and 20 mL TEMED were
dispersed in the remained Na-MMT solution (water/ethanol
50 mL) and added dropwise to the reaction temperature during
1 h. After 15 min, APS (0.02 g) dissolved in 2 ml of deionized water
was injected into the reaction mixture. The reaction temperature
was decreased to 45 8C to complete the stirring for 24 h. The
dispersed Na-MMT/PNIPAm nanogel solution was centrifuged at
12,000 rpm for 30 min five times and washed with ethanol and
dried under vacuum at 30 8C.
The same procedure was repeated to prepare Na-MMT
nanogels with PNIPAm/APTAC, PNIPAm/Na-AMPS and PNI-
PAm/AAm as cationic, ionic and nonionic nanogels. The
remained NIPAm (1.5 g) was mixed with anionic (APTAC and
Na-AMPS) or nonionic (AAm) monomers in Na-MMT dispersed
aqueous solution (50 mL). The mol ratio between monomers
NIPAm/APTAC, NIPAm/Na-AMPS and NIPAm/AAm was 1:1. The
prepared Na-MMT nanogels were washed with water, ethanol
and acetone one time each, and the prepared particles were
centrifuged (24,680 rpm, at 20 8C) and then dried in an vacuum
oven at 35 8C. The purity of Na-MMT nanogels was confirmed
by measuring the surface tension of the supernatant was
above 72.1 mN/m that indicated that the uncrosslinked mono-
mers and polymers were completely removed from the Na-MMT
nanogels.
Characterization
The interaction between Na-MMT and nanogels and their
chemical structure were confirmed using Fourier transform
infrared (FTIR) spectrometer (Nicolet, NEXUS-670).
The intercalation and exfoliation of Na-MMT galleries by
nanogels was performed using wide-angle X-ray diffraction (WAX;
Rigaku D/MAX-3C OD-2988N X-ray diffractometer; CuKa radia-
tion; l = 0.15418 at 40 kV and 30 mA).
The morphology of Na-MMT nanogel was observed under
Transmission Electron Microscope (TEM, JEOL JEM-2100F) electron
microscope. High resolution HR-TEM images recorded at an
acceleration voltage of 200 kV.
The change in surface morphologies of Na-MMT nanogels after
adsorption of heavy metal ions were observed under scanning
electron microscope (SEM, model JSM-T 220A, JEOL) at an
accelerated voltage of 20 kV.
Energy dispersive X-ray spectroscopy (EDX, SEM 3200 Hitachi
electron microscope equipped with an EDX detector) was used for
376 A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 374–384
the determination of Na-MMT nanogel composition after adsorp-
tion of heavy metal ions.
Thermal stability and Na-MMT contents were determined using
thermogravimetric analysis (TGA-50 SHIMADZU) at a heating rate
of 10 8C/min.
Zeta potentials, particle size (nm) and particle size distribution
index (PDI) of the modified Na-MMT nanogel were measured in
aqueous solution in the presence of KCl (0.001 M) at different
aqueous pH solutions using Laser Zeta meter Malvern Instruments
Model Zetasizer 2000.
Double beam UV/vis spectrophotometer (model) was used to
determine the absorbance of methylene blue dye (at 662 nm).
Atomic absorption spectroscopy (AAS; Perkin-Elmer 2380) was
used to determine metal analysis in the direct aspiration into an
air-acetylene flame.
The surface activity, surface tension in aqueous solution and
interfacial tension between water and toluene are measured at
25 8C using drop shape analyzer model DSA-100.
Adsorption and desorption experiments
The adsorption kinetics of methylene blue onto Na-MMT
nanogels was measured at different initial concentrations 100 and
1000 ppm of MB. In this respect, 50 mL of aqueous methylene blue
solutions was introduced into a 100 mL conical flask under stirring
in the presence of 0.02 g of the Na-MMT nanogels at 25 8C. The
filtrate samples were analyzed at different time intervals after
filtration. The concentration of MB in the residual solution was
determined using UV–vis spectrophotometer at wavelength
662 nm. The amount of dye adsorption at equilibrium Q (mg/g)
and percent extraction (%E) was calculated from the following
equation:
 
ðC o  C e Þ  V
Q¼ (1)
ðmÞ
 
ðC o  C e Þ  100
%E ¼
ðC o Þ
where Co and Ce (mg/L) are the liquid phase concentrations of dye
at initial and equilibrium, respectively, V (L) the volume of the
solution and m (g) is the mass of adsorbent used.
The same equations are used to calculate the adsorption of Co2+
and Ni2+ cations using AAS.
Scheme 1. Interclation and exfoliation of Na-MMT using nanogels.
Desorption experiments were performed using 2 M HNO3 to
estimate the recovery of MB, Co2+ and Ni2+ cation from Na-MMT
nanogel. The acid treated samples were neutralized with 0.1 M
NaOH, washed with distilled water and subsequently used for
adsorption experiments. Reloading efficiency was calculated using
Eqs. (1) and (2).
Results and discussion
It is well established that the crosslinking polymerization of
reactive monomers is an effective technique for exfoliation of Na-
MMT clay mineral. In this respect, NIPAm, APTAC and AMPS-Na are
nonionic, cationic and anionic monomers, respectively used in the
presence of MBA as crosslinker and APS as initiator to form
crosslinked nanogel Na-MMT composites. The ability of nanogels
to intercalate or exfoliate the Na-MMT sheets based on the ability
of monomers to diffuse between the Na-MMT gallaries. The
technique of crosslinking of monomers and exfoliation of Na-MMT
is represented in Scheme 1. In this respect, PVP used as stabilizing
agent to disperse Na-MMT into ethanol/water solvent, as described
in the Experimental section, to increase Na-MMT wettability to
monomers. The NIPAm, APTAC or AMPS-Na start to partially
intercalated the Na-MMT layers. The polymerization of monomers
starts to completely intercalate the Na-MMT layers. The cross-
linking polymerization increases the distance between Na-MMT
sheets due to the formation of networks as illustrated in Scheme 1
to form partially or completely exfoliated Na-MMT layers.
NIPAm as amphiphilic monomer contains both hydrophilic and
hydrophobic groups is selected to prepare crosslinked copolymer
nanogels with AAm, Na-AMPS and APTAC without surfactants
because of the surfactants were not easily separated during
polymerization [29–31]. The crosslinking polymerization is carried
out using semi-batch temperature program technique as illustrat-
ed in the Experimental section. In this respect, NIPAm starts to
diffuse between Na-MMT layers at temperature above its lower
critical transition solution temperature (LCST; ranged from 33 to
(2) 38 8C). Above LCST, the NIPAm starts to form nanogels with AAm,
Na-AMPS and APTAC monomers in the presence of MBA and APS as
crosslinker and initiator, respectively without surfactants [32–35].
The crosslinking free radical polymerization of all monomers at
45 8C for 24 h led to a transparent dispersed Na-MMT polymer
colloids, with no evidence of any macroscopic precipitation.
Moreover, the crosslinking of monomers in absence of Na-MMT
 A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 374–384
produced polymer precipitates without colloidal formation. This
clearly demonstrates the crucial role played by the dispersed Na-
MMT in producing colloidally stable dispersions based on core-
shell technique as described in Scheme 1.
The interaction between Na-MMT layers and crosslinked
polymers will be the main factors to form intercalated or exfoliated
Na-MMT as discussed in the forthcoming section using different
analytical techniques.
Characterization of Na-MMT nanogels
FTIR is used to confirm the chemical structure of the Na-MMT
nanogels. Moreover, it can be used to elucidate the interactions
between Na-MMT and polymers [12]. FTIR spectra of Na-MMT
modified with PNIPAm/AAm, PNIPAm/APTAC, and PNIPAm/Na-
AMPS are illustrated in Fig. 1a–d. The disappearance of absorption
bands at 3000–3100 cm1, which assigned 5 5CH stretching
vibration, indicates the absence of monomers and complete
crosslinking copolymerization of monomers (Fig. 1a–c). Moreover,
the appearance of bands at 3350 cm1 (N–H stretching) 2980,
2930, and 2870 cm1 (C–H aliphatic stretching) 1655 cm1
(amide-I band assigned to C5 5O stretching) 1550 cm1 (amide-II
band attributed to N–H in-plane bending vibration) and 1008 cm1
(Si–O stretching of Na-MMT) in all spectra of Na-MMT nanogels
(Fig. 1a–c) indicates the incorporation nanogels with Na-
MMT. Spectrum of Na-MMT which shown in Fig. 1d, confirms
the appearance of bands at 1008, 650, and 445 cm1 that
attributed to alumina silicate bonds. The appearance of these
bands in Fig. 1a–c, confirms the presence of both inorganic Na-
MMT and the prepared nanogels. The overlaps between Na-MMT
band and polymers bands makes difficult to determine the
interaction between Na-MMT layers and polymers. Accordingly,
FTIR spectra (Fig. 1a–c) are used to confirm the formation of Na-
MMT organiphilic after removal uncrosslinked monomers and
polymers after washing several times with water.
Thermogravimetric analysis (TGA) is a commonly used to
determine the amount of polymeric materials in Na-MMT galleries
[13,19]. Hence, thermograms of Na-MMT and its nanogels were
represented in Fig. 2. All Na-MMT thermograms loss 5% of their
weights at temperature between 20 and 105 8C attributed to the
water loss that coordinated with Na+ from the interlayer
[36]. Moreover, it is determined that 2.6% (the weight loss %) of
Na-MMT loosed at the temperature range from 100 to 650 8C that
referred to the loss of hydrogen-bonded water molecules and of
some of the hydroxyl groups from the octahedral galleries of the
Fig. 1. FTIR spectra of Na-MMT with (a) PNIPAm, (b)PNIPAm-APTAC, (c) PNIPAm-
Na-AMPS and (d) Na-MMT.
377
Fig. 2. TGA of amphiphilic Na-MMT nanogels.
Na-MMT [36,37]. The differences between weight loss of Na-MMT
and their nanogels at 650 8C (remaining residues) are used to
determine the nanogel or Na-MMT contents in nanogel compo-
sites. The crosslinked polymer thermograms (not presented for
brevity) indicate that these polymers have not produced any
remaining residues at 600 8C. The amounts of PNIPAm/AAm,
PNIPAm/APTAC, and PNIPAm/Na-AMPS nanogels used to modify
Na-MMT determined from TGA analysis from the weight loss at
600 8C and listed in Table 1 to compare with the actual amount
used in the Experimental section. Careful inspection of TGA data
indicates that the amount of PNIPAm/APTAC is same to that used to
modify Na-MMT galleries. These data indicated that the cationic
nanogels have strong ability to exchange Na+ more than other
nanogels. The data of PNIPAm/AAm, and PNIPAm/Na-AMPS
indicate that the amount of nanogels determined from TGA were
lower than that used to modify the Na-MMT galleries. It is reported
that there is alternative mechanism used to modify clay with
anionic or nonionic polymers that correlated to the ability of
polymers to form strong hydrogen bonds with the hydroxyl groups
of Na-MMT galleries [38] or by formation of complexes with water
that solvate Na+ of Na-MMT [39]. Alternative mechanism based on
ion dipole force for molecules that possess a partial negative
charge is proposed for interaction of sulfonate groups of PNIPAm/
Na-AMPS with interlayer exchangeable cations of Na-MMT
[40]. The crosslinking polymerization percentages (wt%) can be
calculated from the differences between the actual weight of the
monomer used to modify Na-MMT and weight% determined from
TGA as listed in Table 1.
The morphology of the modified clay nanogels can be detected
by TEM. Moreover, the nanogels that do not contain any Na-MMT
can also detected by TEM micrographs as illustrated in Fig. 3a–
d. The intercalation and exfoliation of Na-MMT indicates that the
interaction between charged monomers such as APTAC, Na-AMPS
and Na-MMT layers increased more than nonionic monomers such
as AAm and NIPAm monomers. It is previously reported that [41],
there are three forces affect the exfoliation of clay layer. There are
two forces resist exfoliation such as electrostatic attractive force
and van der Waals force and one related to elastic force that causes
the exfoliation. Accordingly the non-charged monomers cannot
obtain enough elastic force for exfoliation of the Na-MMT layer.
TEM micrograph of PNIPAm (Fig. 3a) shows the formation of
PNIPAm nanogel with spherical morphologies. Moreover, Fig. 3b
indicates the formation of aggregates for PNIPAm/AAm nanogel
composites. The exfoliation of Na-MMT in the presence of PNIPAm/
APTAC and PNIPAm/AMPS-Na, confirmed in Fig. 3c and d,
respectively. The appearance of flocculated nanogel structure
378 A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 374–384

Table 1
TGA data of amphiphilic Na-MMT nanogels and percentages of crosslinking polymerization.

Na-MMT nanogels modifier Remaining Actual amounts relate to Na-MMT (wt%) Crosslinking copolymerization (%)

Temperature range(8C) Weight loss (%)

PNIPAm/AAm 50–300 8 51 96.1

300–650 43
Residue at 650 8C 49
PNIPAm/Na-AMPS 50–300 8 31 90.32
300–650 64
Residue at 650 8C 28
PNIPAm/APTAC 50–250 8 32 96.8
250–650 61
Residue at 650 8C 31
PNIPAm 50–275 8 42 95.2
350–650 52
Residue at 650 8C 40

observed for these nanogels can be referred to high contents of Na-
MMT (ranged from 30 to 45 wt.%; Table 1) which increases the
viscosity of polymerization reaction mixture [16].
It is necessary to determine the effect of nanogel on the
crystal structure and spacing of Na-MMT sheets that can be
confirmed using WAXD and TEM analyses. TEM is time-intensive
analysis, and gives qualitative information on the morphology of
particles. While, low-angle peaks in WAXD determine the
quantitative changes in layer spacing. The analysis is based on
monitoring the intensity, position, shape, and the basal reflec-
tions from the distributed silicate layers that can confirm the
intercalation or exfoliation of silicate layers. It is reported that,
the spacing between layers is controlling the intercalation or
exfoliation of Na-MMT layers as they exceeded 6–7 nm [42]. The
XRD patterns of Na-MMT with and without nanogels are
represented in Fig. 4a–c. Unmodified Na-MMT shows a peak
at 2-theta about 4.408 with the basal space of 1.52 nm which is
obtained from the peak position (d 0 0 1—reflection) using Bragg
equation: 2d 0 0 1sin u = l. In contrast, no peak was observed for
modified Na-MMT with NIPAm/APTAC and NIPAm/AAm con-
firming the exfoliation of Na-MMT. While, reflection of modified
Na-MMT with NIPAm/AMPS-Na show slightly low peak at
2 theta equals 2.98 indicating that the clays in the nanogel
composite are intercalated and are not completely exfoliated.
This can be attributed to the van-der Waals force interaction
between Na-MMT galleries.
Surface properties of amphiphilic clay nanogel
The behavior of the prepared Na-MMT nanogels in the water is
very important to determine their ability to form dispersion or
aggregates in the solution and ability to adsorb at the interfaces.

Fig. 3. TEM micrographs of Na-MMT with (a) PNIPAm, (b) PNIPAm/AAm, (c) PNIPAm/APTAC and PNIPAm/Na AMPS.
 A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 374–384
Fig. 4. WAXD of (a) Na-MMT, (b) Na-MMT/PNIPAm/AAm, (c) Na-MMT/PNIPAm-
NaAMPS and (d) Na-MMT/PNIPAm-APTAC.
The TEM micrographs and WAXD diffractograms indicated that the
nanogels intercalate, exfoliate and adsorbed on the Na-MMT
galleries to change the performance of clay galleries. In previous
work it was reported that the nanogel particles and modified solid
particles have a tendency to reduce the water surface tension and
adsorbed at interfaces especially that contains PNIPAm amphiphiles
[43–45]. Therefore, the relation between the surface tension of
water (g; mN/m) and different concentrations (ln c; mol/L) of Na-
MMT nanogels is used to determine their surface activity as
presented in Fig. 5. The equilibrium surface tension data (Fig. 5) are
the average of 5 times repeated measurements. The curves indicate
that the prepared Na-MMT nanogels have great tendency to reduce
the surface tension of water (gcac; mN/m) to the critical aggregation
concentration (cac; mol/L) at which the Na-MMT nanogels start to
form aggregates or completely adsorbed at air/water interfaces. The
cac, gcac and slope of straight lines (g/ln c) are determined from
adsorption isotherms (Fig. 5) and listed in Table 2. The aggregation
process is an alternative mechanism for adsorption of dispersed
particles at interface for amphiphilic or surface active soluble
materials. The nanogels are crosslinked networks can be interacted
with water to disperse Na-MMT in the aqueous solutions and they
are aggregated with increment of the Na-MMT nanogel concentra-
tions through hydrophobic interactions among the hydrophobic
polymeric backbone or isopropyl group of NIPAm. The aggregates
can be assembled to form monolayer, baitlayers or multilayer
aggregates. The purity of the prepared Na-MMT nanogels was
confirmed from the presence of one phase as indicated in Fig. 5. The
data indicate that the Na-MMT nanogels reduced the water surface
tension in the order PNIPAm > PNIPAm/AMPS-Na > PNIPAm/
APTAC > PNIPAm/AAm nanogels (Table 2). Moreover, it is also
observed that the cac of Na-MMT nanogels can be arranged in the
Table 2
Surface activity parameters of amphiphilic Na-MMT nanogels in water at 25 8C.
Na-MMT Nanogels Cmc (mol/L) 103 gcmc (mN/m) Dg = go  gpcmc (mN/m)
modifier
PNIPAm/Na-AMPS 2.7 32.2 42.0
PNIPAm/APTAC 7.4 45.0 27.2
PNIPAm 5.6 30.2 42.0
379
Fig. 5. Adsorption isotherms of Na-MMT modified with nanogels dispersed in
aqueous solutions at 25 8C.
following order PNIPAm/APTAC > PNIPAm > PNIPAm/AMPS-Na.
Therefore, the dispersability of Na-MMTnanogels in water without
aggregates increased for ionic more than nonionic nanogels. This
behavior can be referred to ionic repulsive forces between cations
and anions reduced their aggregation tendency.
The adsorption is an alternative mechanism for interaction of
Na-MMT nanogels with water. The quantity of Na-MMT nanogels
adsorbed at air/water interface is expressed as surface excess
concentration ’max and can be calculated from the relation:
’max = 1/RT  (@g/@ ln c)T, where (@g/@ln c)T is the slope of the
plot of g versus ln c at constant temperature (T) and R is the gas
constant (in J mol1 K1) [46]. Moreover, the area per molecule of
Na-MMT nanogels at the interface is calculated using the equation:
Amin = 1016/N ’max, where N is Avogadro’s number. The values of
both ’max and Amin are calculated and listed in Table 2. It is
observed that Na-MMT coated with PNIPAm/AAm nanogel does
not show any adsorption at interfaces as indicated from Fig. 5. The
data listed in Table 2, indicate that Na-MMT coated with PNIPAm
and PNIPAm/Na-A MPS have high affinity to adsorb at air water
interface more than that coated with PNIPAm/APTAC due to high
’max and low Amin values of Na-MMT coated with PNIPAm and
PNIPAm/Na-A MPS than PNIPAm/APTAC at interface. This means
that Na-MMT coated with PNIPAm and PNIPAm/Na-A MPS form
strong layers at interface. Moreover, the amphiphilic Na-MMT
nanogels can be obtained due to exfoliation of layers and
adsorption of PNIPAm, PNIPAm/Na-AMPS and PNIPAm/APTAC
on the surface of the Na-MMT. Accordingly, the amphiphilic layer
at the solid particles form stronger layers at interfaces than that
obtained by conventional surfactants [27].
The mechanism of nanogel adsorption at Na-MMT interfaces
cannot be easily predicted due to their surface charges and its
heterogeneous structure. The droplet photo of dispersed Na-MMT
nanogels and toluene was represented in Fig. 6. It can be observed
that the hydrophilic Na-MMT easily desorbs to the toluene phase
at the toluene/water interface (Fig. 6a). It is expected that the
(@g/@ ln c) Gmax 1010 (mol/cm2) Amin (nm2/molecule)
8.774 0.370 0.450
5.185 0.218 0.765
10.23 0.645 0.258
380 A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 374–384

Fig. 6. DSA photo of dispersed (a) Na-MMT coated with PNIPAm/APTAC and (b) Na-MMT coated with PNIPAm nanogels at water/toluene interface.

anionic nanogels such as PNIPAm/Na-AMPS and PNIPAm/APTAC
(Fig. 6a) are desorbed at the interface. It can be concluded that the
Na-MMT nanogels based on PNIPAm/Na-AMPS and PNIPAm/
APTAC showed good wetting properties at the interfaces. On the
other hand, nonionic PNIPAm nanogel (Fig. 6b) is able to form
stable interfacial layer via formation of flocculated nanoclay. It can
be suggested that there is a strong interfacial structure formed at
the droplet surfaces.
Adsorption and desorption of MB dye
MB as water pollutant has hazardous effects on the environment
[47,48]. Clay acts as cost-effective adsorbent to remove toxic
materials although it has low adsorption capacity than synthetic
adsorbents. Moreover, the clay filtration cake problem prevents the
industrial application of clay without modifications. The present
work aims to modify Na-MMT with anionic and nonionic nanogels to
accelerate the dye adsorption on the surface of Na-MMT clay. It is
well known that MB is cationic dye containing highly electronegative
heteroatoms, such as sulfur and nitrogen, can form hydrogen bonds
with water to affect the diffusion of MB into Na-MMT clay galleries.
The dispersion of Na-MMT nanogels into the MB aqueous solution
affects the hydrogen bonding between MB and water. Moreover, the
amphiphilic characteristics and high surface activity of Na-MMT
nanogels can reduce the surface tension of water to facilitate the
diffusion of MB into Na-MMT clay galleries. The interactions between
MB cations and clay are carried out using three different modes [49]
such as: (i) formation of electrostatic interaction or neutral
complexes between negative sites of clay and positive cations of
organic dye or inorganic cations, (ii) formation of non-coulombic
interaction or formation of positive charges single complex between
two positive charges of organic dyes and one negative charge of Na-
MMT clay galleries. These types of interaction are produced from
hydrophobic interaction between hydrophobic moiety of MB that
can produces charge reversal at high loads. The third type of
interaction between clay and MB produced from the formation
of monovalent charged complex due to interaction of neutral site of
Na-MMT clay galleries with one dye cation. This type of interaction is
responsible for adsorption of large amounts of dye on clay galleries.
Accordingly, it is expected that the formation of electrostatic
interactions between negative sites of Na-MMT clay galleries and
MB cation is preferred as illustrated in Scheme 2. It indicates that the

Scheme 2. Interaction between MB and amphiphilic Na-MMT nanogels in aqueous solutions.

 A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 374–384 381

presence of both highly negative charges on Na-MMT surfaces and Table 3

The DLS and Zeta Potential measurements of the Na-MMT nanogels.
nanogels chains are responsible for fast diffusion of large amount of
MB dye into the Na-MMT layers. It is expected that the nanogels are Na-MMT nanogels DLS Zeta potential (mV)
responsible for hydrogen bond formation with water that facilitates Particle PDI
the electrostatic interactions between MB cations and negative size (nm)
charge edges of Na-MMT layers (Scheme 2). Na-MMT 35  16 1.23 22.44  1.67
The adsorption behavior of MB onto modified Na-MMT Na-MMT/PNIPAm 45  10 0.856 50  1.57
nanogels is investigated at 100 and 1000 ppm aqueous solution Na-MMT/PNIPAm-AAm 55  17 0.735 28.01  1.17
(as described in the Experimental section). The adsorption Na-MMT/PNIPAm-APTAC 50  1.3 0.0457 40.06  0.76
Na-MMT/PNIPAm-Na-AMPS 60  8 0.134 60  1.36
isotherms of MB as adsorpate onto Na-MMT nanogels as adsorbent
are described by the Langmuir isotherm Eq. (3), [50] or Freundlich The all measurements were carried out in 103 M KCl.
Eq. (4) [51] to describe the homogeneity and heterogeneity of the
adsorption behaviors:
      with the experimental data Qmax and %E and listed in Table 3. The
Ce 1 Ce
¼ þ (3) Langmuir model achieve good regression coefficients R2 than that
Qe Q 0 Kl Q0
of the Freundlich model that suggests that the Langmuir isotherm
   fits better with the adsorption of MB on Na-MMT nanogels.

1
log ðQ e Þ ¼ log K f þ  log ðC e Þ (4) Moreover, the Qmax values for the adsorption of MB onto the
n
nanogels calculated from the Langmuir model are all the same as
where Qe and Q0 are the equilibrium and maximum amount of dye the experimental data. These data confirm that all of the Na-MMT
(mg/g) adsorbed on Na-MMT nanogel composites. Ce is the nanogel adsorption sites have equal adsorbing affinities. This result
concentration of dye solution at equilibrium (mg/L). The Kl and can be confirmed by calculation of the dimensionless constant
Kf are Langmuir and Freundlich constants that determined from called equilibrium parameter, RL [52] that can be obtained from
relation of Ce/Qe against Ce and ln Qe as the function of ln Ce, Langmuir isotherm as
respectively at 25 8C as presented in Fig. 7. These values used to  
1
investigate the adsorption capacity. While n is an empirical RL ¼ (5)
ð1 þ K l C 0 Þ
constant which gives valuable information about the isotherm
shape. Moreover, 1/n values investigate the adsorption intensity. where, C0 is the highest initial MB concentration (mg/L). The RL
The linear plot of Langmuir and Freundlich isotherms for values are calculated and found in the range of 0.0195–0.02434
removal of 1000 ppm of MB on Na-MMT nanogels are presented which confirms the favorability of the adsorption process of MB to
in Fig. 7. The Langmuir and Freundlich model parameters correlate form monolayer Langmuir adsorption isotherm onto nanocompo-
sites [53].
The effect of the pH of dispersed Na-MMT nanogel solutions on
the removal of MB at constant temperature (25 8C) and ionic
strength (0.1 M) is represented in Fig. 8. The data indicate the
removal of MB dye increased with increasing pH solution up to pH
8. However, the MB uptake capacities were not changed from pH
8 to 12. This result is referred screening of negative charges of Na-
MMT at low pH and also to collapse of amino, sulfate and carboxyl
groups of nanogels which are affected by the pH of solutions. It is
well known that the electrostatic attraction (Scheme 2), ionic
characteristics and chemical interactions of MB dye and Na-MMT
nanogels affect the dye adsorption on Na-MMT nanogel adsor-
bents. Moreover, it is expected that there are high electrostatic
attractions between positive charges of MB dye and negative
charges of Na-MMT nanogel composites at neutral and alkaline pH

Fig. 7. Adsorption isotherm of (a) Langmuir and (b) Freundlich models for removal Fig. 8. Relation between adsorption capacity for removal 1000 ppm of MB and pH of
of 1000 ppm of MB dye using amphiphilic Na-MMT nanogels at 25 8C. aqueous solutions at constant temperature 25 8C and ionic strength (0.1 M).
382 A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 374–384

Fig. 9. Relation between zeta potential (mV) and pH of aqueous solution in the Fig. 10. Relation between adsorption capacities and contact time for removal
presence of 0.001 M KCl. 1000 ppm of MB from water using Na-MMT nanogels at 25 8C and pH 9.

aqueous solutions (Scheme 2). While the positive charges Na-MMT nanogels. Also, the presence of lone pair of electrons on
increased with decreasing pH to acidic region which prevents or amino group of amide plays an important role on fast adsorption of
reduces the adsorption of cationic dyes due to electrostatic MB. It can be concluded that the hydrogels containing higher
repulsions between clay galleries and MB molecules [54]. More- amounts of Na-MMT are better adsorbents for the MB dye
over, the excess H+ ions of acidic region adsorb on the Na-MMT solutions. Moreover, the ability of amphiphilic Na-MMT nanogels
nanogel surfaces and contest with the MB dye cations. to reduce the water surface tension increases their adsorption
The effect of pH of aqueous dispersed solutions of Na-MMT on capacities to remove cationic dye in short time.
their zeta potentials is used to investigate the variation of charges It is important to study the desorption and reuse the adsorbents
with pH of solutions. The relation between zeta potential (z) of to as sure that the adsorption process is more economical. The
dispersed Na-MMT nanogel aqueous solutions (mV) in the results show that the initial dye concentrations of 100 ppm for Na-
presence of 0.001 M of KCl and their pH is plotted in Fig. 9. The MMT with PNIPAm, PNIPAm/Na-AMPS, PNIPAm/APTAC and
z (mV), particle size and PDI were determined at pH 7 and listed in PNIPAm/AAm are 93.2%, 88.4%, 80.3% and 41.5%, respectively.
Table 3. As observed, (z) is negative value for the whole pH interval The low desorption of MB dye indicates there is a strong
for all modified Na-MMT nanogels. It is also observed that the (z) interaction between MB dye and nanogels.
value of Na-MMT/PNIPAm nanogel has more negative value than
that unmodified with nanogels. It is proposed that the exfoliation Adsorption and desorption of heavy metal
and intercalation of Na-MMT through formation of hydrogen
bonds between amide groups and hydroxylated silicates in The removal of heavy metal ions from water and interaction
montmorillonite enhances the zeta potential of silica and alumina between metal ions and adsorbents are different than that used in
edges [55,56]. The results of (z) were in agreement with the data of MB removal. The ability of adsorbents to chelate or chemically
MB adsorption at different pH using Na-MMT nanogel composites interact with adsorbents is an important factor to remove metal
which indicate that the more negative (z) values achieved both ions from water [57]. Hence, adsorbents containing amide and
high MB removal and dispersion in aqueous solutions.
The relation between adsorption of different MB concentrations
and contact time is very important to determine the rate of dye
adsorption. The effect of contact time on the adsorption capacity of
Na-MMT nanogels for MB was illustrated in Fig. 10. The plateau
curves (Fig. 10) indicate the rapid adsorption capacities (60–80%)
were achieved in first 20 min due to the mass transfer of dye to the
Na-MMT nanogel surfaces. This stage followed by slow rate of
adsorption that referred to interaction of MB dye with nanogel
network. The last stage reflects the adsorption equilibrium of Na-
MMT nanogels. The three stages completed in 60 min at which the
nanogel composites reach the equilibrium without losses more
than 72 h. This data indicate that there is no soluble materials in
the nanogel composites and all monomers are crosslinked with
MBA. It was also noticed that Na-MMT nanogels having ionizable –
SO32 groups, can be considered as the adsorption sites for
adsorption of MB, these groups enhance repulsive forces of –SO32
with the neighboring chains. This electrostatic repulsion is
responsible for the net-work swelling and fast uptake of MB.
Moreover, the surface of nanogel is negative due to the presence of
sulfonate group of sodium sulfonate, and negatively charged sites Fig. 11. Relation between adsorption capacities and contact time for removal
on the surface of nanogel particles increase with the exfoliation of 1000 ppm of Ni2+ from water using Na-MMT nanogels at 25 8C and pH 9.
 A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 374–384 383

Table 4
Adsorption isotherm parameters for removal of 1000 ppm of MB dye using amphiphilic Na-MMT nanogels at 25 8C.

Adsorbents Langmuir isotherm parameters Freundlich isotherm Exp. Adsorption capacity

parameters

Qmax (mg/g) Kl (L/mg) R2 1/n Kf R2

Qmax (mg/g) %E

1000 ppm 100 ppm 1000 ppm 100 ppm

Na-MMT 344.3 0.0271 0.9817 0.6863 0.049 0.906 310 33 82 80

Na-MMT/PNIPAm 625.1 0.0245 0.9933 0.2369 0.190 0.8402 600 65 99 99
Na-MMT/PNIPAm-AAm 500.1 0.041 0.9704 0.5643 0.201 0.8935 490 38 89 82
Na-MMT/PNIPAm-APTAC 526.1 0.040 0.9954 0.5973 0.203 0.8822 484 52 97 95
Na-MMT/PNIPAm-Na-AMPS 769.2 0.034 0.9635 0.5827 0.196 0.9077 689 58 99 97

Fig. 12. SEM and EDX data of Na-MMT nanogels (a) PNIPAm/Na-AMPS after removal of Co 2+, (b)PNIPAm/AAm and (c) PNIPAm after removal of Ni2+ cations from aqueous
solution at pH 8 at constant temperature 25 8C and ionic strength (0.1 M).
384 A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 374–384
sulfonic acid groups exhibit better attraction to adsorb metal ions
from water [58]. Moreover, the exfoliated clay galleries possess
high affinity to exchange metal ions and hence, they are valuable
material for water treatment [59]. In the present work, different
Na-MMT nanogel composites having different ionizable and
hydrogen bonding capacity are used to remove heavy metal ions
such as Co2+ and Ni2+ salts from water at pH 8 that selected from
previous section at temperature at 25 8C and constant ionic
strength (0.1 M) solutions. The values of Qmax (mg/g), % E and
equilibrium time (minute) are determined and listed in
Table 4. The relation between metal uptake and contact time is
presented in Fig. 11. From these plateau curve values (Fig. 11) the
data confirm that the rapid interaction of metal ions with the
adsorbent is very favorable for the feasible processes. The Na-MMT
modified with PNIPAm/Na-AMPS nanogel achieved high results
during 60 min and that can be attributed to the presence of
ionizable sulfonate groups that can chemically interacts with Co2+
and Ni2+ [60].
The SEM and EDX micrographs of the hydrogel loaded with Co2+
and Ni2+ cations are selected and presented in Fig. 11. The SEM
micrographs of the Na-MMT nanogels after absorbing cations
show a different morphology in which the pores are not observed.
SEM micrographs clearly illustrated the dependence of morpholo-
gy on the types and contents of nanogels. It was observed that
PNIPAm/Na-AMPS display a more open and porous channel
structure than other nanogels. Moreover, SEM and EDX analyses
(Fig. 12) proved that the metal ions are adsorbed and the lower
metal uptake was due to agglomeration of nanogel particles on the
bead surface that reduces the metal diffusion in the beads.
The desorption and reusability of adsorbents are very important
for economical consideration. The data show that the adsorption
capacities of Na-MMT/PNIPAm-NaAMPS nanogel increased sharp-
ly after treatment with NaOH due to the greater electrostatic
attraction between the positive charge of metal ions and the
negative charge of sulfonate group. Also, the adsorption capacity in
the second cycle is approximately similar to that of first cycle, this
indicates that treatment of nanocomposite with HNO3 and NaOH
provide a good way of regeneration of metal ions loaded adsorbent.
The data show that even after four cycles of adsorption-desorption
over 95% regeneration efficiency was retained by these gels.
Conclusions
The Na-MMT layers were exfoliated using temperature modified
program for crosslinking polymerization technique to prepare Na-
MMT nanogels using anionic and nonionic monomers such as Na-
AMPS, APTAC, AAm and NIPAAm. The Na-MMT nanogel composites
achieved reduction of water surface tension of water from 72.1 to
30.1 mN/m. All dispersed Na-MMT nanogel composites possess
good surface activity except that prepared with PNIPAm/AAm
nanogel. The ability of Na-MMT nanogels to reduce the water surface
tension reflects to increase the ability of Na-MMT nanogel to remove
MB, Co and Ni cations from water within 60 min. The prepared Na-
MMT nanogels desorbed and reused four times to remove the heavy
metal from water with the same efficiency.
Acknowledgment
The project was financially supported by King Saud University,
Vice Deanship of Research Chairs.
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