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Polymeric flocculant based on cassava starch

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chloride: Flocculation behavior and mechanism

Article in Applied Surface Science May 2015

DOI: 10.1016/j.apsusc.2015.05.080

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 Applied Surface Science 351 (2015) 8994

Contents lists available at ScienceDirect

Applied Surface Science

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

Polymeric occulant based on cassava starch grafted

polydiallyldimethylammonium chloride: Flocculation behavior and
mechanism
M.A.A. Razali, A. Arifn
School of Materials and Mineral Resources Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia

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

Article history: In this work, occulation properties of cassava starch grafted polydiallyldimethylammonium chloride
Received 5 March 2015 (polyDADMAC) with different grafting percentages were investigated. Flocculation performance was
Received in revised form 11 April 2015 evaluated in simulated kaolin suspension. The grafting percentages used were 1.76 %, 14.84 %, and 21.98
Accepted 14 May 2015
%. The effectiveness of the occulation was measured based on the reduction of the turbidity and total
Available online 21 May 2015
suspended solids (TSSs), zeta potential measurements, particle size, and atomic force microscopy imaging.
Grafted polymers improved the removal rate of turbidity and TSS compared with gelatinized starch, and
Keywords:
the removal rate increased with increasing grafting percentage and dosage.
Flocculation
Grafted 2015 Elsevier B.V. All rights reserved.
Cassava starch
PolyDADMAC
Kaolin suspension

1. Introduction availability, renewability, and biocompatibility [12]. Grafting is

For several decades, synthetic polymeric occulants have been
largely used in wastewater treatment, particularly those contain-
ing suspended colloidal particles [1,2]. These occulants exhibit
high efciency in particle removal, but several occulants gen-
erate secondary pollution in the environment [3,4]. Synthetic
occulants and their derivatives pose a number of environmental
problems because some of the derivatives are non-biodegradable
and the intermediate products of their degradation are hazardous
to human health [5]. To address this issue, several researchers pre-
ferred natural polymers, such as exopolysaccharide [6], polyamino
acid [7], cationic tannin [8] starch, and chitosan [9,10]. Natural
polymers are biodegradable, cheap, and fairly shear stable, but
their shelf life depends on their biodegradability [11]. Thus, their
biodegradability reduces their shelf life. For these reasons, green
occulants with high efciency removal have attracted increasing
attention. Green occulants with high efciency removal can be
achieved by combining these two types of polymers by grafting
process.
Cassava starch has recently been receiving considerable inter-
est in grafting with various monomers because of its low cost,
Corresponding author. Tel.: +60 4 5946176; fax: +60 4 5941011.
E-mail address: srazlan@usm.my (A. Arifn).
the most frequently attempted method in imparting desirable
properties to cassava starch without sacricing its biodegrad-
able nature [13]. The structure of cassava starch is shown in
Fig. 1.
Aggregates are difcult to settle because of the charge repulsion
among particles that comes from the surface charges of colloidal
particles [14]. Most of the suspended particles in water and sludge
are usually negatively charged [15]. Therefore, grafting of cassava
starch with a cationic polymer, such as polydiallyldimethylam-
monium chloride (polyDADMAC) (Fig. 1), presumably improves
occulation capacity. PolyDADMAC molecules possess a charged
quaternary ammonium group in each chain unit [16] and a high
charge density polymer.
Flocculation performance of applied materials largely depends
on the control molecular structure. In 2014 according to Yang
et al., properly designed molecular architectures of occulants are
required to obtain the desired occulation performance [17]. In the
present research, the molecular structure of cassava starch graft-
ing PolyDADMAC differed from its single polymer hence it reected
their mechanism of occulation and occulation performance. Few
attempts have been carried out to reveal the occulation mecha-
nism of starch combined with cationic synthetic polymer [18,19].
However, no studies exist on the effect of grafting percentage on
occulation performance and mechanism. Thus, this work aimed
to study the capability of cassava starch grafted with polyDADMAC

http://dx.doi.org/10.1016/j.apsusc.2015.05.080
0169-4332/ 2015 Elsevier B.V. All rights reserved.
90 M.A.A. Razali, A. Arifn / Applied Surface Science 351 (2015) 8994
Fig. 1. Structure of cassava starch and PolyDADMAC.
as occulants and the effect of grafting percentage on occulation
performance and mechanisms.
2. Experimental
2.1. Materials
The cassava starch grafted polyDADMAC occulants used in this
study were prepared in the laboratory. Details of the preparation
are discussed in previous work [20]. The grafting percentage and
molecular weight of the grafted samples are shown in Table 1.
Negative colloid was simulated using hydrous aluminum sili-
cate or kaolin [Al4 Si4 O10 (OH)8 ] grade RC15. Deionized water was
used to prepare the grafted polymer solutions. Sodium hydrox-
ide (NaOH) and hydrochloric acid (HCl) with both concentration
was 1.0 mol/dm3 were used to adjust the pH. All the reagents were
employed without any further purication.
2.2. Preparation of negative colloid
Ten grams of kaolin was dispersed in 500 mL of deionized water
under stirring at 1500 rpm. Increasing the pH of the suspension
to about 11 was necessary to obtain full dispersion, which was
achieved by adding 1.0 mL of 1.0 mol/dm3 NaOH. After stirring for
3 h, the clay suspension was diluted to 1 L of distilled water and
allowed to stand overnight. The top 800 mL was decanted and used
as stock solution. The pH of the stock was 9.
2.3. Flocculation test
The occulation test for this study was carried out in a standard
occulation jar apparatus (Jar Test FC6S; Velp Scientica). The
equipment has six-bladed stirrer connected to a variable speed
motor through a gear system. Experiments were started by dilut-
ing 30 mL of stock solution into 470 mL of deionized water. The pH
of the solution was 7. The solution was stirred for about 1 h with
200 rpm before adding the grafted samples. The selected dosage
of the grafted samples was added to the solution and stirred for
2 min at 200 rpm, followed by slow mixing for 10 min at 35 rpm.
The ocs formed were allowed to settle for 15 min, and the turbid-
ity and total suspended solid (TSS) as well as the zeta potential of
the supernatants were determined.
Table 1
Grafting percentage and molecular weight for grafted polymer samples.
Sample Grafting percentage (%) Molecular weight (g/mol)
R11 1.76 2.2 104
R25 14.84 9.7 105
OPT 21.98 1.2 106
Table 2
Characteristics of kaolin suspension.
Parameter Value
pH 77.5
Turbidity (FAU) 500570
TSS (mg/L) 500560
Zeta potential (mV) 44 to 40
Particle size (d nm) 570590
2.4. Analytical procedure
A pH meter (CyberScan model; Eutech Instruments, Singapore)
was used to measure the pH of the prepared kaolin suspension.
About 10 mL of the supernatant samples was withdrawn for turbid-
ity and TSS measurements. The turbidity and TSS were measured
using a Hach spectrophotometer (DR/2000). The zeta potential was
determined using a Malvern zetasizer nano series machine, and the
supernatant samples were obtained 3 cm below the water surface
of the beaker for analysis.
2.5. Flocs characterization
2.5.1. Particle size analysis
Flocs were extracted from the bottom of the beaker and trans-
ferred into a Malvern 12 mm square polystyrene cuvette. The size
of the ocs was evaluated using the Malvern zetasizer Nano Series.
2.5.2. Morphology of particles and ocs formed
After occulation testing, aliquot ocs were withdrawn from the
beaker and transferred to a slide for morphology observation. The
morphology was evaluated using a polarizing microscope (Meiji
Techno MT9430) at 4 magnication.
3. Results and discussion
Kaolin suspension was selected for the observation of occula-
tion performance because of its negatively charged nature which is
suitable for the treatment of cationic grafted samples. The charac-
teristics of the simulated kaolin suspension are shown in Table 2.
3.1. Effect of dosages
Dosage is an important parameter that affects occulation per-
formance. The effect of grafted polymer and gelatinized native
starch dosages on the turbidity removal and TSS removal of
supernatant are described in Fig. 2. The grafted samples showed
improvement in turbidity and TSS removal compared with the gela-
tinized starch. The gelatinized starch showed a removal rate of
5560 %, whereas the grafted samples achieved a removal rate of
6598 %.
Fig. 2 also shows that the removal increased with increasing
dosage. The removal rate rapidly increased from 5 ppm to 10 ppm
dosage. However, the removal rate decreased beyond 15 ppm with
increasing dosage except for R11, which is the lowest grafting
percentage sample. The upclimaxdown trend indicates that an
optimal dosage exists. According to Yang et al. [17], the trend
is important for industrial application because high dosages are
costly and dosage should be maintained at an optimum range. The
increase in removal rate with the increase in dosage is attributed to
charge neutralization or bridging of particle mechanism. Bridging
mechanism occurs in gelatinized starch, whereas both mecha-
nisms occur in grafted polymer. Adding polyDADMAC on the
backbone of the starch gives cationic charge; thus, the destabi-
lized particles are increased by charge neutralization. However, the
removal rate is not good at low dosage because of the low charge
 M.A.A. Razali, A. Arifn / Applied Surface Science 351 (2015) 8994
Fig. 2. Effect of dosage on (a) turbidity and (b) TSS removal.
neutralization and bridging activities. The low activities result from
insufcient polymer to form adequate bridging links between parti-
cles for gelatinized starch [21], whereas less charge neutralization
occurs for grafted samples [22]. Further addition of grafted poly-
mer dosage after optimal dosage increases polymer concentration,
thereby leading to restabilization of the particles and hindering the
formation of ocs. Excessive grafted polymer concentration results
in net positive ocs formed and increase repulsion. The increase
of repulsion may cause to breakage of ocs formed; thus, turbidity
removal decreases after optimal dosage [23].
3.2. Effect of grafting percentage
The grafting percentage of polyDADMAC into cassava starch
backbone exhibited a noticeable effect on turbidity and TSS removal
(Fig. 3(a)). The presence of polyDADMAC in the starch backbone
improved the removal rate of turbidity and TSS. Gelatinized starch
without present of polyDADMAC showed a removal rate of 60 % and
with present of grafting polyDADMAC (R11 sample; 1.97 %) showed
an increased removal rate from 70 % to 75 %. The grafted polymer
could reduce the turbidity and TSS even at a low grafting percentage
of 1.97 %, and a 99 % removal rate was obtained with grafting per-
centage of 21.98 % (OPT). Thus, increasing the grafting percentage
increased the removal rate of turbidity and TSS. These results can be
explained based on the increase of grafting percentage induced the
91
Fig. 3. Effect of grafting percentage on (a) turbidity and TSS removal and (b) zeta
potential supernatant at 15 ppm.
length of grafted polymer chain. The long grafted polymer creates
and enhances occulating via charge neutralization and bridging
mechanism.
Zeta potential is a key indicator of colloid stability. The high
magnitude of the zeta potential indicates that the degree of electro-
static repulsion between adjacent particles is very high. Meanwhile,
for lower magnitude or value nearest to zero, a rapid coagula-
tion and occulation occur. When the theory was implied into this
study, the simulated kaolin suspension initially resisted aggrega-
tion. The zeta potential value at this stage was 44 mV (Table 2).
When grafted polymers were introduced into the simulated kaolin
suspension, charge neutralization processes occurred, and these
enhancing particles come close to each other and results in agglom-
eration. High grafting percentage brings more cationic charge in
their chains; thus, more charge neutralization occurred as shown
in zeta potential (Fig. 3(b)). As an example, sample R25 reduced
the zeta potential to 15 mV, whereas sample R11 with low graft-
ing percentage reduced the zeta potential to 25 mV. Concurrently,
the increase of grafting percentage has the probability of increasing
the chain as proved by the molecular weight properties in Table 1.
The highest grafting percentage (OPT) had a molecular weight of
1.2 106 g/mol, whereas the lowest grafting percentage (R11) had a
molecular weight of 2.2 104 g/mol. Long chains have the tendency
to create bridging between particles, thereby helping improving the
removal rate.
92 M.A.A. Razali, A. Arifn / Applied Surface Science 351 (2015) 8994
Fig. 4. Effect of pH on (a) turbidity and TSS removal and (b) zeta potential at 15 ppm.
3.3. Effect of pH
OPT samples were selected for further study on their behav-
ior in treating kaolin suspension with varying pH because of their
good occulation performance. The effect of pH on turbidity and
TSS removal and the zeta potential is indicated in Fig. 4. Dosage
used in this section was 15 ppm. The pH had a signicant impact on
the performance of the grafted polymer. Good occulation perfor-
mance was observed at pH below 7. The highest turbidity and TSS
removal was achieved at pH 1 at approximately 99 % and started to
decrease with the increase of pH value. Turbidity and TSS removal
decreased about 2 % when entering the neutral region. The removal
was much worst when entering the alkali region with a decrease of
about 30 %. Similar behavior is also reported by Yeap et al. [24]. They
reported that the color removal of disperse terasil yellow dye by
polyaluminum chloride is efcient in the acid region as compared
in the alkali region.
An acid is a substance that donates hydrogen ions (H+ ) when dis-
solved into a solution. The concentration of hydrogen ion increases
with the introduction of acid into kaolin suspension and is much
greater at low pH especially at pH 1. The hydrogen ions help reduce
the repulsion force between particles, thus making the job of
grafted polymer much easier in destabilizing particles. Meanwhile,
an alkali is a substance that soaks up hydrogen ions, creating a
solution with more hydroxide ion (OH ) as compared to hydrogen
ion. Hydroxide ion concentration increases with the increase in
pH values. The increase in resulting repulsion between negative
particles becomes stronger. The grafted polymer has difculty
in destabilizing the particles and presumably, the dosage at
this stage is inefcient as other pH value in neutral and acid
region.
The zeta potential measurement in Fig. 4(b) showed that
the acidic and neutral regions had low values compared with
the alkali region. The removal was good as the zeta poten-
tial was approaching zero. The zeta potential measurement
is known to indicate the repulsion forces between similarly
charged particles. The increase of zeta potential values either
positive or negative indicate that the repulsion between parti-
cles become stronger. The repulsion becomes weak as the zeta
potential values approach zero. No repulsion between charged
particles was observed when the zeta potential became zero.
The same reason applies to the turbidity and TSS removal; they
are good in acidic and neutral regions as their values approach
zero.
The zeta potential value for the acid region was positive,
whereas negative for the alkali region. In the acid region (pH 15),
the zeta potential value ranged from 1.34 mV to 3.8 mV and in
the alkali region (pH 911), the value ranged from 21.8 mV to
25.3 mV. The transition between positive and negative values is
said to occur in the range of pH 67 as pH 7 (neutral region) showed
a negative value of 2.77 mV. This trend supports the previous
statement of increasing the pH values increases the hydroxide ion
and vice versa.
3.4. Characteristics of ocs
Flocs characteristic comprising particle size and morphology of
the particles will be discussed in detail in this section and the results
will support previous purpose mechanism.
Fig. 5 shows the particle size and images of kaolinite parti-
cles before and after treatment of gelatinized starch and grafted
polymers. In general, the size of kaolinite particle increases with
the increase in grafting percentage. The size of kaolinite parti-
cles before the treatment was 0.578 m, and the particles seemed
to be homogenized and very ne. The size of ocs increased to
0.970 m with the added gelatinized starch. The increase was
about 68 %, and the particles became more rough; thus, the
gelatinized starch can destabilize negatively charged kaolin par-
ticle by bridging mechanism as gelatinized starch is non-ionic
polymer. Individual gelatinized starch chain adsorbs into several
particles simultaneously by hydrogen bonding forming molecular
bridges [25]. Hydrogen bond is a weak bonding, but the adsorp-
tion is strong because of the number of bonds that can be formed
[26].
Introducing polyDADMAC into the backbone of cassava starch
enhanced ocs size. Flocs size increased with the increase of graft-
ing percentage. The highest achieved grafting percentage (OPT)
sample size of ocs was 107.200 m, which is 100 times bigger
than the lowest grafting percentage sample (R7). As mentioned
earlier, destabilization increases with the increase in grafting per-
centage, thus the ocs become rougher and bigger. In Fig. 5(e),
ocs treated with OPT samples showed occurrence of bridging
compared with other grafted polymer samples. The OPT sam-
ples had higher molecular weight (Table 1) and the increasing
molecular weight helped the chain to adsorb many particles simul-
taneously. A similar result was also observed by Wang et al.
in their study on the removal of kaolin suspension by using
starch-graft-poly (2-methacryloyloxyethyl) trimethyl ammonium
chloride) [27].
 M.A.A. Razali, A. Arifn / Applied Surface Science 351 (2015) 8994
Fig. 5. Particle size and images of (a) kaolin particles and ocs formed after treated with (b) gelatinized starch, (c) R7, (d) R11, and (e) OPT samples.
4. Conclusion
The occulation performance of cassava starch grafted Poly-
DADMAC and its different grafting percentage properties into
occulation behavior were studied. Grafting polyDADMAC into
the backbone of cassava starch enhanced the capability in treat-
ing kaolin suspension and was better compared with gelatinized
starch. The occulation performance improved with the increase
of grafting percentage. Charge neutralization and bridging mech-
anism were the main factors that contribute to turbidity and TSS
removal and ocs size increase.
Acknowledgments
M.A.A. Razali gratefully acknowledges the personal nancial
support under the MyPHD Scheme provided by the Ministry
of Higher Education (Malaysia) and USM PGRS (1001/PBAHAN
93
8046028). A. Arifn would also like to thank the USM Research
University (RU) (Grant No. 1001/PBAHAN/814131) for the support.
References
[1] Q. Lin, S. Qian, C. Li, H. Pan, Z. Wu, G. Liu, Synthesis, occulation and adsorption
performance of amphoteric starch, Carbohydr. Polym. 90 (2012) 275283.
[2] V.S. Pandey, S.K. Verma, M. Yadav, K. Behari, Guar gum-g-N,N -
dimethylacrylamide: Synthesis, characterization and applications, Carbohydr.
Polym. 99 (2014) 284290.
[3] C. Xie, Y. Feng, W. Cao, Y. Xia, Z. Lu, Novel biodegradable occulating agents
prepared by phosphate modication of Konjac, Carbohydr Polym. 67 (2007)
566571.
[4] W. Xing, H.-H. Ngo, W. Guo, Z. Wu, T.T. Nguyen, P. Cullum, A. Listowski, N.
Yang, Enhancement of the performance of anaerobic uidized bed bioreac-
tors (AFBBRs) by a new starch based occulant, Sep. Purif. Technol. 72 (2010)
140146.
[5] Y. Ho, I. Norli, A.F.M. Alkarkhi, N. Morad, Characterization of biopolymeric oc-
culant (pectin) and organic synthetic occulant (PAM): A comparative study
on treatment and optimization in kaolin suspension, Bioresour. Technol. 101
(2010) 11661174.
94 M.A.A. Razali, A. Arifn / Applied Surface Science 351 (2015) 8994
[6] K. Szewczuk-Karpisz, M. Wisniewska, M. Pac, A. Choma, I. Komaniecka, Sinorhi-
zobium meliloti 1021 exopolysaccharide as a occulant improving chromium
(III) oxide removal from aqueous solutions, Water Air Soil Pollut. 225 (2014)
113.
[7] I. Ostolska, M. Wisniewska, Investigation of the colloidal Cr2 O3 removal possi-
bilities from aqueous solution using the ionic polyamino acid block copolymers,
J. Hazard. Mater. 290 (2015) 6977.
[8] R. Gutirrez, F. Passos, I. Ferrer, E. Uggetti, J. Garca, Harvesting microalgae
from wastewater treatment systems with natural occulants: Effect on biomass
settling and biogas production, Algal Res. 9 (2015) 204211.
[9] C.Y. Teh, T.Y. Wu, J.C. Juan, Potential use of rice starch in
coagulationocculation process of agro-industrial wastewater: Treatment
performance and ocs characterization, Ecol. Eng. 71 (2014) 509519.
[10] Z. Yang, H. Li, H. Yan, H. Wu, H. Yang, Q. Wu, H. Li, A. Li, R. Cheng, Evaluation
of a novel chitosan-based occulant with high occulation performance, low
toxicity and good oc properties, J. Hazard. Mater. 276 (2014) 480488.
[11] T. Tripathy, R. Singh, High performance occulating agent based on par-
tially hydrolysed sodium alginate-g-polyacrylamide, Eur. Polym. J. 36 (2000)
14711476.
[12] S.B. Nair, A.N. Jyothi, Cassava starch-graft-polymethacrylamide copolymers as
occulants and textile sizing agents, J. Appl. Polym. Sci. (2014), http://dx.doi.
org/10.1002/APP.39810
[13] V.D. Athawale, V. Lele, Thermal studies on granular maize starch and its graft
copolymers with vinyl monomers, Starch-Strke 52 (2000) 205213.
[14] E. Guibal, M. Van Vooren, B.A. Dempsey, J. Roussy, A review of the use of chitosan
for the removal of particulate and dissolved contaminants, Sep. Purif. Technol.
41 (2006) 24872514.
[15] S. Pal, G. Sen, S. Ghosh, R.P. Singh, High performance polymeric occulants
based on modied polysaccharides: Microwave assisted synthesis, Carbohydr.
Polym. 87 (2012) 336342.
[16] A. Arifn, M. Razali, Z. Ahmad, PolyDADMAC and polyacrylamide as a hybrid
occulation system in the treatment of pulp and paper mills waste water, Chem.
Eng. J. 179 (2011) 107111.
View publication stats
[17] Z. Yang, H. Wu, B. Yuan, M. Huang, H. Yang, A. Li, J. Bai, R. Cheng, Synthesis of
amphoteric starch-based grafting occulants for occulation of both positively
and negatively charged colloidal contaminants from water, Chem. Eng. J. 244
(2014) 209217.
[18] J. Cao, S. Zhang, B. Han, Q. Feng, L.f. Guo, Characterization of cationic
polyacrylamide-grafted starch occulant synthesized by one-step reaction, J.
Appl. Polym. Sci. 123 (2012) 12611266.
[19] M. Gao, Z.Q. Xu, Preparation of cationic polyacrylamide-grafted starch occu-
lant and its application in the treatment of coal slurry wastewater, Adv. Mater.
Res. 466 (2012) 485489.
[20] M.A.A. Razali, H. Ismail, A. Arifn, Graft copolymerization of polyDADMAC to
cassava starch: evaluation of process variables via central composite design,
Ind. Crop Prod. (2014), http://dx.doi.org/10.1016/j.indcrop.2014.10.010
[21] L. Ghimici, M. Constantin, G. Fundueanu, Novel biodegradable occulanting
agents based on pullulan, J. Hazard. Mater. 181 (2010) 351358.
[22] Y. Lu, Y. Shang, X. Huang, A. Chen, Z. Yang, Y. Jiang, J. Cai, W. Gu, X. Qian,
H. Yang, Preparation of strong cationic chitosan-graft-polyacrylamide oc-
culants and their occulating properties, Ind. Eng. Chem. Res. 50 (2011)
71417149.
[23] H. Xiao, Z. Liu, N. Wiseman, Synergetic effect of cationic polymer microparticles
and anionic polymer on ne clay occulation, J. Colloid Interface Sci. 216 (1999)
409417.
[24] K.L. Yeap, T.T. Teng, B.T. Poh, N. Morad, K.E. Lee, Preparation and characteriza-
tion of coagulation/occulation behavior of a novel inorganicorganic hybrid
polymer for reactive and disperse dyes removal, Chem. Eng. J. 243 (2014)
305314.
[25] B. Dobias, Coagulation and Flocculation: Theory and Applications, CRC Press,
1993.
[26] P.A. Williams, Handbook of Industrial Water Soluble Polymers, Wiley Online
Library, 2007.
[27] J.-P. Wang, S.-J. Yuan, Y. Wang, H.-Q. Yu, Synthesis, characterization and appli-
cation of a novel starch-based occulant with high occulation and dewatering
properties, Water Res. 47 (2013) 26432648.