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,

adsorbents based on nanomaterials gained much attention due to
Water pollution, especially of heavy metals and dyes, is a their high performance to adsorb pollutants from aqueous
worldwide problem affecting economic and ecological system environments such as carbon nanotubes, titania, silica and clay
around the world. The industrial toxic wastes are one of the main polymer composites [2,3,6–8]. Ionic polymer clay nanocomposites
sources of this pollutants [1–3]. There are several techniques were [9] showed high performance to remove organic and organic
used to control water pollution such as ion exchange [4], pollutants [10,11]. The efficiency of nano-clay polymer composites
adsorbents, reverse osmosis [3], precipitation, and coagulation was affected by method of preparation, type of polymer
techniques [5]. Adsorbents attracted great attention due to composites and application technique such as membrane, nano-
availability of various adsorbent types, eco-friendly, cost feasibili- filters, etc.
ty, and their high efficiency in removal of organic and inorganic Sodium montmorillonite (Na-MMT) has attracted great atten-
pollutants. The main adsorption mechanisms are based on tion in recent years for its application in the field of water
complexation and ion exchange mechanisms. There are several purification [12,13]. The exfoliation of Na-MMT from multilayer
important criteria controlling the selection and design adsorbents 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
* Corresponding author at: King Saud University, Surfactants Research, Chemis-
try Department, College of Science, Riyadh, Saudi Arabia. Tel.: +00966 561557975. used to replace sodium cations between silicate layers to
E-mail address: [email protected] (A.M. Atta). 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) 374–384 375

minerals [17]. Crosslinking of reactive monomers is another Cobalt and nickel nitrate hexa hydrate produced from Sigma-
preferred technique to disperse clay sheet in the polymer Aldrich CO. are used to prepare stock solution 100 ppm. Buffer
composites [18,19]. In previous work, exfoliation of Na-MMT solution (H3PO4/NaH2PO4) was prepared by titration of 0.1 N of
sheets using crosslinking technique increased the performance of NaH2PO4 against 0.1 M HCl (for pH range 2–3) or against 0.1 N
Na-MMT to form anticorrosive thin film layer on the steel surfaces NaOH (for pH range 7–12) until the required pH is reached. The pH
[20,21]. The reactive anionic amphiphile nanogels attracted great value was monitored using pH meter.
attention to exofilate Na-MMt sheets monomers due to their high
cation exchange capacities, surface area, surface reactivity, Synthesis procedure
adsorptive properties, and transparency in solution [13]. 2-
Acrylamido-2-methylpropane sulfonic acid (AMPS] and N-isopro- Na-MMT clay was not easy to disperse in water solution.
pylacrylamide (NIPAm) have been reported as good clay modifiers Therefor water/ethanol (60/40 vol%) mixture was used as solvent
due to their ability to adsorp between Na-MMT sheets [22]. These to disperse Na-MMT. In this respect, Na-MMT (2 g) is dispersed in
polymers were selected to modify Na-MMT because of they have water/ethanol (100 mL) and PVP (0.3 g) as stabilizer at room
sulfonate group, an amido functional groups potentially able to temperature for 24 h.
interact with the Na-MMT surface. NIPAm microgel crosslinked The dispersed Na-MMT nanogels based on NIPAm were
with clay showed excellent surface activity because thermore- prepared using surfactant free dispersion radical crosslinking
sposive characteristics of microgels [23–25]. Generally, cross- polymerization using temperature programmed technique. In this
linked polyacrylamide (PAAm) clay nanocomposites, prepared in respect, NIPAm monomer (0.5 g) is dispersed in Na-MMT solution
the absence of chemical crosslinker, showed higher efficiency for (water/ethanol 50 mL). The solution was initially pre-heated at
removal of toxic pollutants from water [26]. temperature 40 8C under nitrogen atmosphere for 30 min. APS
The present work reports the functionalization of Na-MMT (0.015 g/mL) was added to start the polymerization. The reaction
using crosslinking technique to produce reactive amphiphile temperature was increased to 50 8C at rate 5 8C per 15 min. The
dispersed Na-MMT sheets having the affinity to reduce the surface NIPAm monomer (1.5 g), MBA (0.03 g) and 20 mL TEMED were
tension of water to increase clay adsorption of pollutants on their dispersed in the remained Na-MMT solution (water/ethanol
surfaces. It was previously reported that, addition of organic 50 mL) and added dropwise to the reaction temperature during
molecules to solid inorganic colloidal particles enhances the 1 h. After 15 min, APS (0.02 g) dissolved in 2 ml of deionized water
material’s capability to absorb at the interface and forms an was injected into the reaction mixture. The reaction temperature
interfacial adsorption layer [27]. To achieve this goal the present was decreased to 45 8C to complete the stirring for 24 h. The
work aims to use anionic, cationic and nonionic monomers to dispersed Na-MMT/PNIPAm nanogel solution was centrifuged at
prepare amphiphilic Na-MMT nanogels using radical crosslinking 12,000 rpm for 30 min five times and washed with ethanol and
technique. NIPAm was selected as amphiphilic nonionic monomer dried under vacuum at 30 8C.
to copolymerize with acrylamide (AAm), sodium 2-acrylamido-2- The same procedure was repeated to prepare Na-MMT
methylpropane sulfonate (Na-AMPS) and acrylamidopropyltri- nanogels with PNIPAm/APTAC, PNIPAm/Na-AMPS and PNI-
methyl ammonium chloride (APTAC) to exfoliate clay with PAm/AAm as cationic, ionic and nonionic nanogels. The
nonionic, anionic and amphoteric nanogels, respectively. NIPAm remained NIPAm (1.5 g) was mixed with anionic (APTAC and
was selected to prepare nanogel due to their thermsensitivity at Na-AMPS) or nonionic (AAm) monomers in Na-MMT dispersed
temperature above polymerization temperature to form reactive aqueous solution (50 mL). The mol ratio between monomers
nanogels having ability to intercalate and exfoliate the Na-MMT. NIPAm/APTAC, NIPAm/Na-AMPS and NIPAm/AAm was 1:1. The
Moreover, APTAC was selected due to their ability to exchange Na prepared Na-MMT nanogels were washed with water, ethanol
cations of Na-MMT to form highly dispersed Na-MMT nanogels and acetone one time each, and the prepared particles were
[28]. The surface properties such as aggregation and adsorption at centrifuged (24,680 rpm, at 20 8C) and then dried in an vacuum
interfaces of the modified Na-MMT nanogels were investigated oven at 35 8C. The purity of Na-MMT nanogels was confirmed
from surface tension measurements. The application of the by measuring the surface tension of the supernatant was
modified Na-MMT nanogels to absorb organic and inorganic above 72.1 mN/m that indicated that the uncrosslinked mono-
pollutants in the water treatment is another objective of the mers and polymers were completely removed from the Na-MMT
present work. nanogels.

Experimental Characterization

Materials The interaction between Na-MMT and nanogels and their

chemical structure were confirmed using Fourier transform
Sodium montmorillonite nanoclay (Na-MMT) with commercial infrared (FTIR) spectrometer (Nicolet, NEXUS-670).
name nanometer PGV is obtained from Sigma-Aldrich Co. N- The intercalation and exfoliation of Na-MMT galleries by
isopropyl acrylamide (NIPAm), sodium 2-acrylamido-2-methyl- nanogels was performed using wide-angle X-ray diffraction (WAX;
propane sulfonate (Na-AMPS), acrylamide (AAm) and acrylami- Rigaku D/MAX-3C OD-2988N X-ray diffractometer; CuKa radia-
dopropyl trimethylammonium chloride solution (APTAC; 75 wt.% tion; l = 0.15418 at 40 kV and 30 mA).
in H2O) monomers are obtained from Aldrich Chemicals Co. The morphology of Na-MMT nanogel was observed under
Poly(vinyl pyrrolidone (PVP) having molecular weight 40,000 g/ Transmission Electron Microscope (TEM, JEOL JEM-2100F) electron
mol is used as dispersing agent for Na-MMT purchased from microscope. High resolution HR-TEM images recorded at an
Aldrich Chemical Co. N,N-Methylenebisacrylamide (MBA), ammo- acceleration voltage of 200 kV.
nium persulfate (APS) and N,N,N0 ,N0 -tetramethylethylenediamine The change in surface morphologies of Na-MMT nanogels after
(TEMED) are used as crosslinker, radical initiator, and activator for adsorption of heavy metal ions were observed under scanning
crosslinking polymerization at low temperature, respectively and electron microscope (SEM, model JSM-T 220A, JEOL) at an
they purchased from Sigma-Aldrich Co. Deionized water and accelerated voltage of 20 kV.
ethanol are analytical grades used as solvent for crosslinking Energy dispersive X-ray spectroscopy (EDX, SEM 3200 Hitachi
polymerization. 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- Desorption experiments were performed using 2 M HNO3 to
tion of heavy metal ions. estimate the recovery of MB, Co2+ and Ni2+ cation from Na-MMT
Thermal stability and Na-MMT contents were determined using nanogel. The acid treated samples were neutralized with 0.1 M
thermogravimetric analysis (TGA-50 SHIMADZU) at a heating rate NaOH, washed with distilled water and subsequently used for
of 10 8C/min. adsorption experiments. Reloading efficiency was calculated using
Zeta potentials, particle size (nm) and particle size distribution Eqs. (1) and (2).
index (PDI) of the modified Na-MMT nanogel were measured in
aqueous solution in the presence of KCl (0.001 M) at different Results and discussion
aqueous pH solutions using Laser Zeta meter Malvern Instruments
Model Zetasizer 2000. It is well established that the crosslinking polymerization of
Double beam UV/vis spectrophotometer (model) was used to reactive monomers is an effective technique for exfoliation of Na-
determine the absorbance of methylene blue dye (at 662 nm). MMT clay mineral. In this respect, NIPAm, APTAC and AMPS-Na are
Atomic absorption spectroscopy (AAS; Perkin-Elmer 2380) was nonionic, cationic and anionic monomers, respectively used in the
used to determine metal analysis in the direct aspiration into an presence of MBA as crosslinker and APS as initiator to form
air-acetylene flame. crosslinked nanogel Na-MMT composites. The ability of nanogels
The surface activity, surface tension in aqueous solution and to intercalate or exfoliate the Na-MMT sheets based on the ability
interfacial tension between water and toluene are measured at of monomers to diffuse between the Na-MMT gallaries. The
25 8C using drop shape analyzer model DSA-100. technique of crosslinking of monomers and exfoliation of Na-MMT
is represented in Scheme 1. In this respect, PVP used as stabilizing
Adsorption and desorption experiments agent to disperse Na-MMT into ethanol/water solvent, as described
in the Experimental section, to increase Na-MMT wettability to
The adsorption kinetics of methylene blue onto Na-MMT monomers. The NIPAm, APTAC or AMPS-Na start to partially
nanogels was measured at different initial concentrations 100 and intercalated the Na-MMT layers. The polymerization of monomers
1000 ppm of MB. In this respect, 50 mL of aqueous methylene blue starts to completely intercalate the Na-MMT layers. The cross-
solutions was introduced into a 100 mL conical flask under stirring linking polymerization increases the distance between Na-MMT
in the presence of 0.02 g of the Na-MMT nanogels at 25 8C. The sheets due to the formation of networks as illustrated in Scheme 1
filtrate samples were analyzed at different time intervals after to form partially or completely exfoliated Na-MMT layers.
filtration. The concentration of MB in the residual solution was NIPAm as amphiphilic monomer contains both hydrophilic and
determined using UV–vis spectrophotometer at wavelength hydrophobic groups is selected to prepare crosslinked copolymer
662 nm. The amount of dye adsorption at equilibrium Q (mg/g) nanogels with AAm, Na-AMPS and APTAC without surfactants
and percent extraction (%E) was calculated from the following because of the surfactants were not easily separated during
equation: polymerization [29–31]. The crosslinking polymerization is carried
  out using semi-batch temperature program technique as illustrat-
ðC o  C e Þ  V
Q¼ (1) ed in the Experimental section. In this respect, NIPAm starts to
ðmÞ
diffuse between Na-MMT layers at temperature above its lower
  critical transition solution temperature (LCST; ranged from 33 to
ðC o  C e Þ  100
%E ¼ (2) 38 8C). Above LCST, the NIPAm starts to form nanogels with AAm,
ðC o Þ
Na-AMPS and APTAC monomers in the presence of MBA and APS as
where Co and Ce (mg/L) are the liquid phase concentrations of dye crosslinker and initiator, respectively without surfactants [32–35].
at initial and equilibrium, respectively, V (L) the volume of the The crosslinking free radical polymerization of all monomers at
solution and m (g) is the mass of adsorbent used. 45 8C for 24 h led to a transparent dispersed Na-MMT polymer
The same equations are used to calculate the adsorption of Co2+ colloids, with no evidence of any macroscopic precipitation.
and Ni2+ cations using AAS. Moreover, the crosslinking of monomers in absence of Na-MMT

Scheme 1. Interclation and exfoliation of Na-MMT using nanogels.

 A.M. Atta et al. / Journal of Industrial and Engineering Chemistry 31 (2015) 374–384 377

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
Fig. 2. TGA of amphiphilic Na-MMT nanogels.
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 Na-MMT [36,37]. The differences between weight loss of Na-MMT
(amide-I band assigned to C5 5O stretching) 1550 cm1 (amide-II and their nanogels at 650 8C (remaining residues) are used to
band attributed to N–H in-plane bending vibration) and 1008 cm1 determine the nanogel or Na-MMT contents in nanogel compo-
(Si–O stretching of Na-MMT) in all spectra of Na-MMT nanogels sites. The crosslinked polymer thermograms (not presented for
(Fig. 1a–c) indicates the incorporation nanogels with Na- brevity) indicate that these polymers have not produced any
MMT. Spectrum of Na-MMT which shown in Fig. 1d, confirms remaining residues at 600 8C. The amounts of PNIPAm/AAm,
the appearance of bands at 1008, 650, and 445 cm1 that PNIPAm/APTAC, and PNIPAm/Na-AMPS nanogels used to modify
attributed to alumina silicate bonds. The appearance of these Na-MMT determined from TGA analysis from the weight loss at
bands in Fig. 1a–c, confirms the presence of both inorganic Na- 600 8C and listed in Table 1 to compare with the actual amount
MMT and the prepared nanogels. The overlaps between Na-MMT used in the Experimental section. Careful inspection of TGA data
band and polymers bands makes difficult to determine the indicates that the amount of PNIPAm/APTAC is same to that used to
interaction between Na-MMT layers and polymers. Accordingly, modify Na-MMT galleries. These data indicated that the cationic
FTIR spectra (Fig. 1a–c) are used to confirm the formation of Na- nanogels have strong ability to exchange Na+ more than other
MMT organiphilic after removal uncrosslinked monomers and nanogels. The data of PNIPAm/AAm, and PNIPAm/Na-AMPS
polymers after washing several times with water. indicate that the amount of nanogels determined from TGA were
Thermogravimetric analysis (TGA) is a commonly used to lower than that used to modify the Na-MMT galleries. It is reported
determine the amount of polymeric materials in Na-MMT galleries that there is alternative mechanism used to modify clay with
[13,19]. Hence, thermograms of Na-MMT and its nanogels were anionic or nonionic polymers that correlated to the ability of
represented in Fig. 2. All Na-MMT thermograms loss 5% of their polymers to form strong hydrogen bonds with the hydroxyl groups
weights at temperature between 20 and 105 8C attributed to the of Na-MMT galleries [38] or by formation of complexes with water
water loss that coordinated with Na+ from the interlayer that solvate Na+ of Na-MMT [39]. Alternative mechanism based on
[36]. Moreover, it is determined that 2.6% (the weight loss %) of ion dipole force for molecules that possess a partial negative
Na-MMT loosed at the temperature range from 100 to 650 8C that charge is proposed for interaction of sulfonate groups of PNIPAm/
referred to the loss of hydrogen-bonded water molecules and of Na-AMPS with interlayer exchangeable cations of Na-MMT
some of the hydroxyl groups from the octahedral galleries of the [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/
Fig. 1. FTIR spectra of Na-MMT with (a) PNIPAm, (b)PNIPAm-APTAC, (c) PNIPAm- APTAC and PNIPAm/AMPS-Na, confirmed in Fig. 3c and d,
Na-AMPS and (d) Na-MMT. 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- at 2-theta about 4.408 with the basal space of 1.52 nm which is
MMT (ranged from 30 to 45 wt.%; Table 1) which increases the obtained from the peak position (d 0 0 1—reflection) using Bragg
viscosity of polymerization reaction mixture [16]. equation: 2d 0 0 1sin u = l. In contrast, no peak was observed for
It is necessary to determine the effect of nanogel on the modified Na-MMT with NIPAm/APTAC and NIPAm/AAm con-
crystal structure and spacing of Na-MMT sheets that can be firming the exfoliation of Na-MMT. While, reflection of modified
confirmed using WAXD and TEM analyses. TEM is time-intensive Na-MMT with NIPAm/AMPS-Na show slightly low peak at
analysis, and gives qualitative information on the morphology of 2 theta equals 2.98 indicating that the clays in the nanogel
particles. While, low-angle peaks in WAXD determine the composite are intercalated and are not completely exfoliated.
quantitative changes in layer spacing. The analysis is based on This can be attributed to the van-der Waals force interaction
monitoring the intensity, position, shape, and the basal reflec- between Na-MMT galleries.
tions from the distributed silicate layers that can confirm the
intercalation or exfoliation of silicate layers. It is reported that, Surface properties of amphiphilic clay nanogel
the spacing between layers is controlling the intercalation or
exfoliation of Na-MMT layers as they exceeded 6–7 nm [42]. The The behavior of the prepared Na-MMT nanogels in the water is
XRD patterns of Na-MMT with and without nanogels are very important to determine their ability to form dispersion or
represented in Fig. 4a–c. Unmodified Na-MMT shows a peak 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) 374–384 379

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.

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

PNIPAm/Na-AMPS 2.7 32.2 42.0 8.774 0.370 0.450

PNIPAm/APTAC 7.4 45.0 27.2 5.185 0.218 0.765
PNIPAm 5.6 30.2 42.0 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 The dispersion of Na-MMT nanogels into the MB aqueous solution
(Fig. 6a) are desorbed at the interface. It can be concluded that the affects the hydrogen bonding between MB and water. Moreover, the
Na-MMT nanogels based on PNIPAm/Na-AMPS and PNIPAm/ amphiphilic characteristics and high surface activity of Na-MMT
APTAC showed good wetting properties at the interfaces. On the nanogels can reduce the surface tension of water to facilitate the
other hand, nonionic PNIPAm nanogel (Fig. 6b) is able to form diffusion of MB into Na-MMT clay galleries. The interactions between
stable interfacial layer via formation of flocculated nanoclay. It can MB cations and clay are carried out using three different modes [49]
be suggested that there is a strong interfacial structure formed at such as: (i) formation of electrostatic interaction or neutral
the droplet surfaces. complexes between negative sites of clay and positive cations of
organic dye or inorganic cations, (ii) formation of non-coulombic
Adsorption and desorption of MB dye interaction or formation of positive charges single complex between
two positive charges of organic dyes and one negative charge of Na-
MB as water pollutant has hazardous effects on the environment MMT clay galleries. These types of interaction are produced from
[47,48]. Clay acts as cost-effective adsorbent to remove toxic hydrophobic interaction between hydrophobic moiety of MB that
materials although it has low adsorption capacity than synthetic can produces charge reversal at high loads. The third type of
adsorbents. Moreover, the clay filtration cake problem prevents the interaction between clay and MB produced from the formation
industrial application of clay without modifications. The present of monovalent charged complex due to interaction of neutral site of
work aims to modify Na-MMT with anionic and nonionic nanogels to Na-MMT clay galleries with one dye cation. This type of interaction is
accelerate the dye adsorption on the surface of Na-MMT clay. It is responsible for adsorption of large amounts of dye on clay galleries.
well known that MB is cationic dye containing highly electronegative Accordingly, it is expected that the formation of electrostatic
heteroatoms, such as sulfur and nitrogen, can form hydrogen bonds interactions between negative sites of Na-MMT clay galleries and
with water to affect the diffusion of MB into Na-MMT clay galleries. 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

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