Water Soluble Polymer Flocculants Synthesis, PDF

REVIEW
Flocculation: The Big Picture www.mme-journal.de
Water Soluble Polymer Flocculants: Synthesis,

Characterization, and Performance Assessment
Vahid Vajihinejad, Sarang P. Gumfekar, Behnaz Bazoubandi, Zahra Rostami Najafabadi,
and João B. P. Soares*
unique requirements of some challenging

Water soluble polymer flocculants are important constituents of solid–liquid environments. A representative example
separation units for the treatment of a variety of process-affected effluents. comes from the effluents (tailings) of oil
The systematic development of a flocculant relies on a good understanding sands extraction process that contain high
solids organic-contaminated fine clays,
of flocculation process, polymer synthesis, polymer characterization, and,
where the use of conventional acrylamide-
not the least, flocculation performance assessment as desired for a particular based flocculants does not meet the dewa-
treatment process, all of which are essential to establish meaningful relation- tering criteria needed by this industry.[3]
ships between flocculant microstructure and flocculation efficiency. The aim Considering the bigger picture, efforts
of this article is to communicate the bigger picture of this research area to the to make new flocculants may not be
worthwhile if proper attention is not given
readers. The recent advances in the application of bio/natural, synthetic, and
to the detailed characterization of these
stimuli-responsive flocculants are reviewed. Then, the basic polymer reaction materials and assessment of their perfor-
engineering tools to control the microstructure of flocculants are provided mance. The performance of flocculants
and the techniques for the quantification of flocculant microstructure are is often assessed by macroscopic metrics
concisely discussed. This is followed by a review of the methods used for the such as hindered settling rate, superna-
characterization of particle-polymer force measurement, and flocculation/ tant turbidity, capillary suction time, fil-
tration resistance, and other macroscopic
dewatering assessment with attention to the characterization of aggregate
methods. These are adequate measures
structures. for screening flocculants, but are blind to
proper insight into flocculant microstruc-
ture/performance relationships that would
1. Introduction allow polymer scientists to optimize existing flocculants or to
make entirely new families of flocculants.
Flocculants are long chain water soluble polymers used to This review is divided into four sections. The first section
separate non-settling fine solids (=particles) from aqueous sus- gives an overview of flocculation by polymers and the involved
pensions. They are used in mineral processing, industrial and mechanisms. In the second section, we give a summary of
municipal wastewater treatment, oil sands tailings dewatering, recent advances in the development and application of floccu-
paper making, and biotechnology.[1–4] This work reviews dif- lants. For the sake of our discussion, we chose to classify floc-
ferent kinds of water soluble flocculants, focusing on advances culants in three major categories: i) synthetic flocculants, ii)
in synthesis, characterization, and performance assessment in natural/bio flocculants, with a separate category dedicated to iii)
solid–liquid separation in mineral processing, oil sands tail- stimuli-responsive flocculants. In the third section, we draw the
ings, and wastewater treatment. attention of readers to methods employed for the characteriza-
Increasing demands for high treatment efficiency combined tion of flocculants and the ways to control the microstructure
with the wide variation in the chemical and physical character- of flocculants through polymer reaction engineering. In the
istics of process effluents, requires the development of novel last section, we will discuss the performance characterization
and/or the optimization of existing flocculants to fulfill the of flocculants with attention to polymer–particle interaction
and the microscopic aggregates characterization techniques
reviewing some works that provide new insights to the develop-
V. Vajihinejad, Dr. S. P. Gumfekar, B. Bazoubandi, Z. Rostami N., ment of flocculants.
Prof. J. B. P. Soares
Department of Chemical and Materials Engineering
University of Alberta
Edmonton, AB T6G 2V4, Canada 2. An Overview of Flocculation
E-mail: jsoares@ualberta.ca
There is no universally accepted formal definition for floccula-
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/mame.201800526. tion, but it is generally accepted that flocculation is the aggrega-
tion of solids achieved with the help of high molecular weight
DOI: 10.1002/mame.201800526 polymers through the formation of bridges between particles.
Macromol. Mater. Eng. 2019, 304, 1800526 1800526 (1 of 43) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.mme-journal.de
This aggregation is different from that achieved by the manip-

ulation of solids surface charges through adjusting pH, addi- Vahid Vajihinejad is a Ph.D.
tion of salts, or very low molecular weight polymers, known as candidate at the University
coagulation.[5] Since this review is concerned with polymers, we of Alberta under the
will include aggregation induced by charge neutralization (use supervision of Professor
of low molecular weight charged polymers) within the discus- João Soares. His research
sion of polymer flocculants, although formally speaking these focuses on studying polymer
polymers cannot be correctly classified as flocculants. microstructure–flocculation
There is always a minimum amount of polymer needed performance relationships,
to adsorb onto the surface of particles before flocculation can flocculation modeling, and
start. Because of the low critical free adsorption energy of reaction engineering of
polymer chains on the particle surfaces, in the order of about water-soluble polymers.
0.3 kT per segment,[6] the rate of polymer adsorption equals He obtained his M.E.Sc. in
the rate of polymer loss from the solution, which explains the chemical engineering from
significant role of mixing in flocculation. Polymer adsorption the Western University, Canada and B.Sc. from the Sharif
can occur through hydrogen bonding (polyacrylamide on silica University of Technology, Iran.
silanol groups), electrostatic interaction (cationic polymers on
negatively charged sludge), hydrophobic interaction (poly(vinyl Sarang Gumfekar is a
alcohol) on silver iodide), and ion bridging (anionic polyacryla- postdoctoral fellow at the
mide on negatively charged clays with the help of divalent cal- University of Alberta, Canada.
cium ion).[7] His work focuses on the
Depending on the size of the polymer molecules in solu- design of new polymers and
tion and the surface properties of the particles, two major control of their microstruc-
modes of flocculation may happen: i) bridging and ii) charge tures. He obtained his Ph.D.
neutralization. If an adsorbed polymer chain is large enough in chemical engineering from
to extend its segments (loops and tails) into the solution at the University of Alberta,
least twice the thickness of the electrical double layer, then under the supervision of
chances are it will adsorb on more than one particle, giving Professor João Soares. He
access to bridging flocculation (Figure 1). On the other hand, also received a M.A.Sc.
short chain polyelectrolytes (charged polymers) often induce degree from the University of
flocculation by compression of the double layer thickness, Waterloo, Canada, and a B.Eng. degree from the University
allowing the particles to aggregate due to van der Waals attrac- of Pune, India, both in chemical engineering. Alongside
tion forces. They may also create patches of opposite charges polymer synthesis, he is interested in physicochemical pro-
on the surface of the particles, making them aggregate when cesses such as flocculation, nanofiltration, and advanced
in contact with the bare surfaces of other particles. Both mech- oxidation processes for water treatment.
anisms are classified as coagulation. Flocculation by bridging
or charge neutralization (coagulation), however, are not mutu-
ally exclusive. It is possible for flocculation to happen due to João Soares is a professor in
combined charge neutralization and bridging effects, as is the the Department of Chemical
case with high molecular weight polyelectrolytes. Another pos- and Materials Engineering
sible mechanism for particle aggregation is called depletion at the University of Alberta.
flocculation. When polymers are not adsorbed on the particle He is a Campus Alberta
surfaces, and the particle concentration in the suspension is Innovates Program Chair in
low, the concentration of nonadsorbing polymer chains in the interfacial polymer engi-
spaces between the particles is smaller than in the bulk phase. neering for oil sands pro-
In this case, liquid diffuses out of the spaces between the par- cessing, and a Tier I Canada
ticles toward the bulk phase (similar to the osmotic effect), Research Chair in advanced
causing the particles to aggregate due to van der Waals attrac- polymer reaction engineering.
tion forces.[8] This mechanism, however, will not be discussed His main research interests
in this paper. are polymerization reaction engineering, polyolefin
In addition to the rate of polymer adsorption and particle synthesis and characterization, and polymer flocculation
collisions, the rate at which the adsorbed polymer chains relax engineering.
on the particle surface (eventually forming a flattened confor-
mation) is crucial in determining the extent of flocculation,
defined by Gregory as equilibrium and nonequilibrium floc-
culation.[9] In the latter, the adsorbed polymer is still extended flocculation (Figure 1). The reconformation time could vary
when particles collide, while in equilibrium flocculation the from a fraction of a second,[10] to a few seconds[11] or even more,
rate of chain relaxation (reconformation) on the surface is faster depending on the polymer/particle charge characteristics, rate
than the particle collision frequency, thus hampering bridging of adsorption, and the amount of polymer adsorbed.
1/2
1
κ = 3.287  ∑ Ci zi2  nm −1 , T = 25 C (5)
2 
where Ci is ion concentration (mol L−1) and zi
is ion valence. Given the conditions in this
example, the electrical double layer thickness is
estimated to be 4.8 nm from Equation (5). For
nonionic linear polymers, the average radius of
gyration is estimated to be 0.06 M1/2 nm (M is
the polymer molecular weight).[7,14] Therefore,
the size of polymer molecules in solution for a
polymer with molecular weight of 2 × 106 is
approximately 85 nm, much greater than twice
the double layer thickness in this example, and
therefore able to induce bridging flocculation.
Figure 1. The concept of bridging flocculation of submicron particles by high molecular It is worth noting that the minimum polymer
weights polymers. The double layer thickness is estimated as reciprocal Debye length, 1/κ.
molecular weight needed to induce bridging
Small polymer chains do not give access to bridging. The polymer chains that have flat-
tened on the surface, before a contact is made with another particle, also lose their bridging flocculation in this example would be approxi-
capacity (as the case with some polyelectrolytes). Adapted with permission.[7] Copyright mately 30 000, a few orders of magnitude
2011, Elsevier. smaller than the molecular weight of conven-
tional flocculants. Assuming 50% of the dosed
polymer[15] is to be adsorbed before flocculation
If the number concentration of solid particles in suspension takes place, the characteristic times of adsorption and aggrega-
is ns (m−3), and the minimum fraction of the added polymer tion can be calculated using Equations (1)–(4).
needed to start the flocculation is f, then the characteristic As the estimates in Table 1 suggest, flocculation in stag-
adsorption time can be estimated by[12] nant flow (diffusion) should not be affected by the dynamics
of adsorption, that is, aggregation is the time-limiting step in
− ln(1 − f ) the process. In shear-induced flocculation, however, the rate of
τ ads =
kads ns (1) aggregation depends on the adsorption kinetics and the extent
of reconformation. In reality, not every collision leads to aggre-
where kads is the adsorption rate coefficient, which is a function gation. Aggregation, especially in dilute suspensions such as in
of mixing conditions, and the size of polymer molecules and wastewater treatment, mostly happens after the adsorption step
solid particles. is complete.[12] For concentrated slurries (e.g., >10 wt%) such as
The characteristic aggregation time, which is the average oil sands tailings, on the other hand, polymer adsorption may
time spent before a particle collides with another particle in be substantially influenced by mass transfer effects, which may
suspension, can be shown to be[12] thus influence the extent of flocculation.
The majority of the literature on flocculation modeling has
2 been developed ignoring the kinetics of polymer adsorption,
τ agg = (2)
kij ns with the exception of a few studies that considered the adsorp-
tion kinetics in the form of empirical parameters inside the
where kij is the collision rate constant between particles i and j. aggregation rate, which is far from adequate.[16] An interesting
Depending on the hydrodynamic conditions, [12] research topic in this area would be to couple the kinetics of
polymer adsorption and dynamics of polymer reconformation
2kT (di + d j )2 with the rate of aggregation of particles and subsequent shear-
kij = Perkinetic aggregation ( Brownian diffusion )
3µ di d j induced breakage of aggregates in order to fully model the floc-
(3) culation process. More discussion on this topic is beyond the
scope of this review. Interested readers are encouraged to read a
1 recent review on the population balance modeling for floccula-
kij = G(di + d j )3 Orthokinetic aggregation ( fluid shear ) (4) tion by Jeldres et al.[17]
6
Figure 2 is a typical response obtained by shear-induced pol-
where di and dj are the diameters of particles i and j, and G is ymer flocculation. There are several differences between aggre-
the shear rate (velocity gradient). In the case of particle-polymer gation induced by salts (coagulation) and flocculation by high
collision, kij = kads.
As an example, let us consider a 1 wt% suspension of mono- Table 1. Characteristic adsorption and aggregation time.
dispersed negatively charged silica particles (ρ = 2.65 g cm − 3)
of size 2 μm containing 0.001 mol L−1 NaCl and 0.001 mol L−1 Shear [s] Diffusion [s]
CaCl2 to be flocculated with a monodisperse polyacrylamide τ 45 63
(M = 2 × 106) at the shear rate of 200 s−1. The double layer
ads
τ 16 180
thickness, κ− 1, can be estimated as[13] agg
3. Recent Advances in the Development of Water

Soluble Flocculants
3.1. Synthetic Flocculants
Synthetic flocculants are made by polymerization of water sol-

uble monomers, which are produced from derivatives of hydro-
carbon cracking process. Synthetic flocculants are mostly made
by free radical solution or emulsion polymerization, making
polymers with average molecular weights in the range of mil-
lions, suitable for the formation of large aggregates at low dos-
ages. Average molecular weight, chemical composition, and
architecture (branched or linear) are the main characteristics
of a synthetic flocculant. Depending on the monomer(s) used,
synthetic flocculants may be classified based on their charges
Figure 2. Typical aggregate size evolution in flocculation versus as positively charged, negatively charged, neutral, or, in some
coagulation. cases, amphoteric.[33] They may alternatively be classified
according to their architecture as linear, branched, hyperbrac-
molecular weight polymers[5]: i) aggregates formed by polymer nhed, or grafted. We, however, will not adopt such classifica-
flocculation are stronger due to multiple points of adsorptions tions mainly because many synthetic flocculants fall into more
per particle, ii) in contrast with coagulation, aggregate breakage than one class. For instance, one flocculant may be ionic and
is often irreversible in polymer flocculation, iii) aggregates pro- branched, or it may be ionic and also contain hydrophobic
duced by polymer flocculation are substantially larger, and iv) comonomers that largely determine the extent of its perfor-
polymer flocculants can aggregate larger particles (up to 50 μm) mance in a particular effluent. Flocculants with less than 1%
than coagulation (<2 μm). charged functional groups are considered as nonionic floccu-
As represented by Figure 2, the aggregates formed by coagulants.[34] Nonionic flocculants normally have high molecular
lation eventually reach a maximum size and stay there, which weights, which helps them flocculate suspended particles
reflects the balance established between the rate of aggrega- through the bridging mechanism.[35] Polyacrylamide is the most
tion and breakage. In contrast, when polymer flocculants are important water soluble nonionic flocculant because its mon-
used (bridging flocculation), the aggregate size passes through omer, acrylamide, is highly water soluble, cost-effective, and
a maximum before gradually descending to a plateau. This very reactive. Although researchers have tried to replace poly-
behavior has been experimentally attributed to one of the two acrylamide with other flocculants due to the carcinogenic and
scenarios (or a combination of both) below. toxic nature of acrylamide, no other alternatives have yet been
synthesized with the same performance and cost advantages.[36]
• Restructuring: the particles in an aggregate become more
Cationic flocculants are normally used to flocculate nega-
compact because of multiple aggregations, breakage, and
tively charged particles, and are used in wastewater and sludge
elongation events. The aggregates gradually restructure,
treatment, paper production, oily water clarification, textile
eventually becoming smaller and more compact.[18] The re-
industry, paint manufacturing, dairy processing, and biotech-
structuring can be experimentally investigated by compar-
nology. Compared to nonionic monomers, cationic mono-
ing the fractal dimension of aggregates at different times.
mers are less accessible and stable. Ammonium, sulfonium,
A more compact aggregate will have a higher fractal dimen-
and phosphonium quaternaries[37] can be used as cationic
sion. Methods for the measurement of aggregate fractal di-
monomers to make cationic flocculants. Methacryloyloxyethyl
mensions will be discussed in Section 5.2. Selomulya et al.[18]
trimethylammonium chloride (DMC),[38] acryloyloxyethyl tri-
proposed a population balance model based on restructuring,
methylammonium chloride (DAC), diallyldimethylammo-
and that has been used by several researchers in modeling
nium chloride (DADMAC), [2-(acryloyloxy)ethyl]trimethyl-
the polymer flocculation of particulate systems.[19–23]
ammonium chloride (AETAC), acrylamide propyl trimethyl
• Irreversible breakage: aggregates break apart, losing any
ammonium chloride (APTAC) are the most common cationic
chance of further re-aggregation, likely due to polymer chain
monomers that have been used to synthesize cationic floccu-
rupture (carbon chain session)[24–27] or relaxation (reconfor-
lants.[34] Cationic monomers can be used either to synthesize
mation) of the adsorbed polymer chains.[28–30] Both phenom-
cationic homopolymers or to be copolymerized with nonionic
ena decrease the bridging capacity of the polymer chains,
monomers, especially acrylamide, to produce flocculants with a
thus reducing aggregate size. Empirical equations have been
desired charge density.[38]
proposed to address the irreversible breakage in modeling of
Recently, Ma et al. used acrylamide (AM) and methacryloxye-
flocculation through both inclusion in breakage[31] and aggre-
thyl trimethyl ammonium chloride (DMC) to synthesize a novel
gation rates.[32]
cationic polyacrylamide (CPAM) through low-pressure ultra-
violet (UV) initiation. Different grades of poly(AM-co-DMC)
After this brief overview on flocculation mechanisms, we with different DMC contents (10, 20, 30, and 40 wt%) were syn-
can now move on to examine recent advances pertaining to dif- thesized and the flocculation tests of 0.1 wt% kaolin suspen-
ferent categories of water soluble flocculants. sion showed that the polymer with 40% cationic monomer was
more successful to reduce turbidity at pH 4.0 because of the of bio/natural flocculants). However, these polymers are only
higher DMC content.[39] They used different monomer ratios effective in a small range of pH due to their limited solubility
in the feed prior to polymerization, but did not quantify the in water. Copolymerizing them (by grafting) with both cati-
comonomer composition in the copolymer. Consequently, the onic and anionic monomers to obtain an amphoteric polymer
40% cationic monomer fraction present in the feed may vary increases their solubility over a wider pH range, thus making
across the polymer population because of composition drift them more efficient flocculants.[45–47] Amphoteric polymers
caused by differences in reactivity ratios of the comonomers. often have a net nonzero charge which is due to the different
We will discuss control of copolymer chemical composition in incorporation rates of the anionic/cationic comonomers. The
detail in Section 4. performance of amphoteric polymers (especially of partially
Anionic flocculants normally have carboxylate or sulfonate hydrophobic monomers) could be deteriorated in effluents with
ions in their structures. They are used to flocculate positively high salt concentration by collapsing the chains due to charge
charged particles in many industrial units, such as munic- shielding. In such cases, zwitterionic polymers (of zero net
ipal wastewaters and sludge dewatering.[34] Acrylic acid (AA) charge) become useful alternatives.[48]
is a commonly used anionic monomer, and anionic deriva- In terms of molecular architecture, linear synthetic polymers
tives of polyacrylamide can also be obtained by post-polymer- may be replaced with branched polymers with many branches
ization hydrolysis with an alkali such as NaOH to create car- that extend into the solution, increasing the possibility of inter-
boxyl groups on the polymer chains. Moreover, acrylamide action between polymer segments and suspended particles.
and acrylic acid, or one of its alkali metals salts, can be used For instance, Xu et al. synthesized a hyperbranched cationic
together to synthesize anionic copolymers.[1] Methacrylic acid polyacrylamide by copolymerizing a cationic hyperbranched
(MAA) and 2-acrylamido-2-methyl-1-propanesulfonic acid oligomer, poly(N-acryloyl-1,2-diaminoethane hydrochloride)
(AMPS) can also be used as anionic monomers to synthesize (HADE), and acrylamide. The flocculation ability of the novel
anionic flocculants.[34] PAM-HADE was compared with that of poly(acrylamide-
At first sight, it may seem obvious that cationic poly- N-acryloyl-1,2-diaminoethane hydrochloride) (PAM-LADE) as
mers should be good options for the flocculation of nega- its linear alternative in 1 wt% kaolinite suspension. The authors
tively charged fine particles, but this is often not the case. For made the two polymers with nearly the same charge density,
example, in mineral systems, tailings of negatively charged clay the same intrinsic viscosity, and the same apparent molecular
particles in alkaline media are flocculated with high molec- weight so they could compare their molecular architectures.
ular weight anionic polyacrylamides. Anionic polyacrylamide However, one should be cautious regarding the interpretation
is chosen because the intramolecular electrostatic repulsion of their results, since the authors reported that both branched
between polymer segments forces the polymer chains to adopt and linear polymers had almost identical intrinsic viscosities
a more extended conformation, increasing the efficiency of and average molecular weights, which goes against the accepted
bridging flocculation. The electrostatic repulsion between pol- understanding of polymer conformation in solution. If one
ymer chains and negatively charged surface of clay allows for assumes that the viscosities of both samples were the same,
the polymer to adsorb only on neutral sites (primarily on the then the branched polymer must have had a higher average
edges of the clay particles), increasing the likelihood that the molecular weight than that of the linear sample, which to some
same polyacrylamide chain will extend into solution and adsorb extent could explain the enhanced flocculation performance of
on the surface of other particles, thus forming large and porous the branched polymer. They observed that PAM-HADE was a
aggregates. Techniques for the characterization of aggregates better flocculant, but the authors attributed the enhanced per-
will be discussed in Section 5.2. formance to two reasons: first, the cationic terminal groups in
In terms of charge characteristics, flocculants may also con- the hyperbranched polymer were better exposed in solution,
tain both positively and negatively charged groups (polyam- favoring adsorption on the kaolinite surfaces through more
pholytes). In a more precise classification, if the charges are points of contact; second, the hindrance repulsion in the hyper-
introduced by copolymerizing cationic and anionic monomers, branched polymer led to a more stretched conformation than
the polymer is called amphoteric, whereas if the polymer is in the linear counterpart, which may have been subject to more
made of a monomer that has both cationic and anionic groups severe chain entanglements[49] (Figure 3). Although this work
(overall zero charge), it is called zwitterionic or betaines.[40] reported some interesting observations, it also demonstrates
Comprehensive reviews on this special class of polymers how the lack of systematic characterization of polymer floccu-
can be found elsewhere.[40–43] The use of polyampholyte floc- lants could lead to a somewhat vague interpretation of the fun-
culants is desired when one needs to simultaneously remove damental reasons behind a flocculant’s performance.
more than one contaminant with opposite charges from an Some researchers have replaced acrylamide with other
effluent. For example, Zhu et al. used the amphoteric floccu- monomers. For example, Lu et al. synthesized a cationic copol-
lant poly(ethylene methyl propenoyl-tri-methyl ammonium ymer of methyl acrylate and [2-(acryloyloxy)ethyl]trimethylam-
chloride-co-acrylic acid) to simultaneously flocculate positively monium chloride (AETAC) with different charge densities via
charged chromium particles and negatively charged organic emulsion polymerization. Flocculation of clay suspensions and
particles from a tannery wastewater.[44] Another reason to use real wastewater showed that their flocculant with 55% charge
amphoteric flocculants is to widen the flocculation window density was comparable to acrylamide-based commercial
with respect to pH. For instance, environmentally friendly chi- flocculants.[36]
tosan or cellulose are popular flocculants for wastewater treat- A hydrophobic monomer can also be added to the polymer
ment (Section 3.2 gives a survey of recent advances in the use structure for the flocculation of organics in the oily wastewater.
poly(acrylamide-acryloyloxyethyl trimethyl ammonium chlo-

ride) (PAD) and commercially available cationic polyacrylamide
in flocculation of municipal waste sludges.[51]
Recently, Hripko et al. synthesized a series of partially hydro-
phobic copolymers of poly(AM-co-poly(ethylene oxide methyl
ether methacrylate)) with different comonomer compositions
and different lengths of the hydrophobic chain (ethylene oxide)
to flocculate clays in oil sands mature fine tailings. Their obser-
vations showed that increasing the length of the hydrophobic
chains could increase the rate of dewatering from aggregates by
a factor of five.[52]
In another novel attempt, Botha et al. synthesized a series
of anionic hyperbranched functional polyethylenes (HBf PE)
to flocculate oil sands mature fine tailings. Polyethylene, as a
purely hydrophobic polymer, was functionalized with carboxylic
acid groups (35 to 50 mol%). The authors showed that HBfPE
Figure 3. Structure of poly(PAM-co-HADE). Reproduced with permis- could be a promising flocculant in dewatering oil sands mature
sion.[49] Copyright 2017, Springer Nature. fine tailings because the hydrophobic cores of the polymer
chains could repel water in the sediments and interact with
Yang et al. synthesized a cationic terpolymer with DADMAC, bitumen and organics present on the clay surfaces.[53]
acrylamide, and butylacrylate (BA) monomers. They showed Another technique to increase the hydrophobicity of a floccu-
that the presence of BA, as a hydrophobic monomer, improved lant is to introduce hydrophobic functional moieties on one of
the flocculation ability of the polymer. However, the hydro- the monomers. Ma et al. synthesized copolymers of DADMAC
phobic monomer made the polymerization process difficult and acrylamide, where coconut diethanolamide (CDEA) was
because it did not easily dissolve in the reaction medium.[50] used as a hydrophobic functional moiety in the polymer struc-
Usually, when all monomers are soluble in water, free radical ture. CDEA can be easily used in polymerization medium as
solution polymerization can be easily performed to produce a water soluble hydrophobic molecule which has both hydro-
the polymer flocculant. However, when one of the monomers philic and hydrophobic groups. The polymerization was carried
is insoluble in water, micellar free radical polymerization may out in aqueous solution with a low-pressure UV initiation tech-
be an alternative, where a surfactant is added to form dispersed nique. CDEA is highly soluble in water thanks to its hydrophilic
micelles of the hydrophobic monomer in water. groups, and it can react with acrylamide, as shown in Figure 4.
Zheng et al. synthesized a hydrophobically modified cati- The hydrophobic CPAM produced in this study could success-
onic terpolymer, PADB, containing acrylamide, acryloyloxy- fully flocculate a dilute 0.05 wt% kaolin suspension via charge
ethyl trimethyl ammonium chloride (DAC), and butylacrylate neutralization and bridging mechanisms.[54]
(BA) monomers through micellar polymerization. When a Inorganic microparticles (0.1–100 µm) such as cationic col-
growing macroradical entered a monomer-swollen micelle, a loidal alumina, Al2O3, may also provide cationic charges to
short block of hydrophobic monomer, BA, was formed before help in the flocculation process. It has been shown that phys-
the macroradical left the micelle to continue polymeriza- ical blends of organic flocculants and inorganic microparti-
tion in the aqueous phase, where it continued to propagate cles could improve the flocculation of suspended particles, but
with acrylamide and DAC blocks until it encountered another because it is difficult to uniformly disperse the microparticles in
micelle. This procedure was supposed to continue many times the polyelectrolyte solution, they need to be added separately in
before the polymerization was stopped via a chain termina- two different steps which might increase the operational costs.
tion event. The authors observed that PADB outperformed Therefore, inorganic–organic hybrid or composite polymers
Figure 4. Synthesis of a hydrophobic CPAM. Reproduced with permission.[54] Copyright 2017, Elsevier.
Figure 5. Linear and cross-linkable cationic worms. Reproduced under the terms of the Creative Commons Attribution 3.0 Unported Licence.[59]
Copyright 2016, the Authors. Published by The Royal Society of Chemistry.
have been synthesized to bond inorganic microparticles and (HPMA) and statistical copolymerization of HPMA with gly-
organic electrolytes so they can be added simultaneously to the cidyl methacrylate (GlyMA), respectively. Figure 5 shows their
flocculation process. Recently, aluminum- and iron-based floc- structure in the core of each worm and macro-CTAs around the
culants have been widely used in water treatment applications, cores. GlyMA was used in the structure of the cross-linkable
and it has been shown that they can improve flocculation com- worms so that its epoxy functional groups could react with
pared to conventional flocculants.[55–58] 3-aminopropyl triethoxysilane (APTES) in a post-polymeri-
Leng et al. synthesized composite flocculant of magnesium zation cross-linking process that happened within the worm
salt and poly(DADMAC). Poly(DADMAC) was made by free cores. The cross-linked cationic worms showed promising per-
radical polymerization and physically blended with MgCl2 in formance in the flocculation of negatively charged silica parti-
an aqueous solution at five different ratios. The mixtures were cles at pH 9. They also performed better than linear cationic
then aged at room temperature for 24 h. Poly(DADMAC) also worms. Cross-linking of the worms efficiently improved their
improved the flocculation ability of the composite flocculant by flocculation ability because linear worms normally break up to
bridging the suspended particles. The hybrid composite floccu- form a mixture of nonionic and cationic pseudo-spherical block
lants with 30 and 70 wt% MgCl2 could flocculate 2 wt% kaolin copolymer nanoparticles, which are not as efficient flocculants
suspensions more efficiently than poly(DADMAC), and also as cross-linked worms.[59]
reduced the turbidity of the supernatant more efficiently. Nor- Some researchers also tried to use block cationic copolymers
mally, poly(DADMAC) flocculates suspended particles through as flocculants, because charge moieties concentrated in blocks
charge neutralization and bridging, but adding MgCl2 salt in the can promote stronger adsorption onto the surfaces of the sus-
composite flocculant enhanced its surface charge neutralization pended particles, as opposed to randomly distributed charges
ability.[58] The authors proposed that MgCl2 acted as a secondary along the backbone of a copolymer, which may eventually
destabilizer and neutralized some of the very fine suspended lead to the less efficient use of some charges on the backbone
particles. However, it is not entirely clear why MgCl2 is needed (Figure 6).[60]
to enhance the flocculation. It seems that charge neutralization Feng et al. synthesized a novel copolymer of acrylamide and
by polyDADMAC was not sufficient in their range of dosage. DADMAC through ultrasonic (US)-initiated template copoly-
Penfold et al. synthesized worm-like nanoparticles and merization with sodium polyacrylate as the template. Figure 7
used them to flocculate silica particles (1–8 µm). They syn- shows the process of template polymerization: first, the cati-
thesized both linear and cross-linked cationic block copol- onic monomers are adsorbed on the anionic template, and
ymer worms using a binary macromolecular chain transfer once the cationic microblock structure is formed, the template
agent (macro-CTA) via reversible addition–fragmentation is separated. The microblock structure of the cationic units
chain transfer (RAFT)-mediated polymerization-induced improved charge neutralization, and consequently sludge dewa-
self-assembly (PISA).[59] Poly(ethylene oxide) (PEO) and tering, of the flocculant compared to the randomly distributed
poly([2-(methacryloyloxy)ethyl]trimethylammonium chloride) copolymer.[61]
(PQDMA) were used as macro-CTAs. The linear and cross- Chen et al. synthesized copolymers of acrylamide (AM) and
linked worms were synthesized through RAFT aqueous dis- acryloyloxyethyltrimethylammonium chloride (DAC) through
persion homopolymerization of 2-hydroxypropyl methacrylate UV-initiated template polymerization with sodium polyacrylate
from the removal of the template (Figure 8). Surface porosity

increased surface area, and the likelihood of interacting with
the suspended particles. We, however, think that the surface
porosity of the polymer in the solid state may not play a role in
flocculation when it is completely dissolved in solution, but it
may speed up dissolving it because water can diffuse faster into
polymer particles of high porosity and surface area. Municipal
sludge dewatering showed that the porous structure of tem-
plate-poly(AM-co-MAPTAC) and the microblock structure of the
cationic MAPTAC units increased its flocculation ability com-
pared to randomly distributed copolymers.[62]
Zhang et al. also synthesized a template polymer (TPDA)
of dimethyldiallylammonium chloride (DMD) and acrylamide
(AM) with UV-initiated template polymerization. Sodium poly-
acrylate was used as the template and improved the reactivity
ratio of DMD, which increased the DMD segments in polymer
chains. TPDA was used to flocculate coal mine wastewater,
showing good performance and producing large, stable, and
compact aggregates.[63]
Table 2 summarizes the recently developed synthetic
polymer flocculants.
Figure 6. a) A randomly distributed cationic copolymer versus b) a cati-

onic block copolymer. Reproduced with permission.[60] Copyright 2016, 3.2. Bio/Natural Flocculants
American Chemical Society.
Natural polymers, or polymers derived from biomaterials, have
as the template. Compared to the randomly distributed copol- gained increasing attention for wastewater treatment. Chitosan,
ymer, the microblock structure showed better performance in starch, cellulose, alginate, and amylopectin are the main nat-
flocculating the activated sludge. Higher settling rates, with ural polymer choices due to their widespread availability, low
larger and denser flocs, were obtained in flocculation tests. This price, nontoxicity, and biodegradability.[64] This section reviews
better performance was attributed to the better adsorption and advances in the synthesis of functionalized natural polymers to
charge neutralization of the cationic microblocks.[60] treat various types of wastewater.
Li et al. synthesized copolymers of AM and methacrylamido
propyl trimethyl ammonium chloride (MAPTAC) with micro-
block structures through ultraviolet (UV)-initiated template 3.2.1. Chitosan
copolymerization with sodium polyacrylate as the template.
They showed that UV-initiated polymerization and template Chitosan is a natural copolymer of d-glucosamine and N-acetyl-
copolymerization techniques affected the characteristics of the d-glucosamine formed by alkaline deacetylation of chitin, the
template-poly(AM-co-MAPTAC) and poly(AM-co-MAPTAC). second most abundant natural polymer in the world after cel-
SEM images of poly(AM-co-MAPTAC) and template- lulose. The molecular weight and degree of deacetylation of chi-
poly(AM-co-MAPTAC) revealed that both polymers had porous tosan determine its water solubility, conformation, and chain
structure, likely because of UV light modification. Template- stiffness in solution.[65] Researchers have reported molecular
poly(AM-co-MAPTAC) had a more porous structure resulting weights and degrees of deacetylation as high as 1.3 × 106 and
Figure 7. Template polymerization. Reproduced with permission.[61] Copyright 2018, Elsevier.
Figure 8. SEM micrographs of poly(AM-co-MAPTAC) (left) and template-poly(AM-co-MAPTAC) (right). Reproduced with permission.[62] Copyright
2017, Elsevier.
Table 2. Summary of the recently developed synthetic polymer flocculants.
Polymer Charge type Properties Synthesis method Medium Reference

Poly(AM-co-DMC) Cationic Linear Low-pressure ultraviolet 0.1 wt% Kaolin suspension [39]
(UV) initiation FRP
Poly(PAM-co-HADE) Cationic Hyperbranched Conventional FRP 1 wt% Kaolinite suspension [49]
Poly(MA-co-AETAC) Cationic AM free Emulsion polymerization Clay suspension and real [36]
wastewater
Poly(DAC-co-AM-co-BA) Cationic Hydrophobically modified Micellar free radical Oily wastewater [50]
terpolymer copolymerization
Poly(DAC-co-AM-co-BA) Cationic Hydrophobically modified UV initiation micellar FRP Municipal waste sludge [51]
terpolymer
Poly(DADMAC-co-AM) functionalized Cationic Hydrophobically modified Low-pressure UV 0.05 wt% Kaolin suspension [54]
by CDEA copolymer initiation FRP
MgCl2-polyDADMAC composite Cationic Improved charge neutraliza- FRP of poly(DADMAC) fol- 2 wt% Koalin suspension [58]
tion because of MgCl2 lowed by physical blending
Monomers: HPMA and GlyMA Cationic Worm-like cross-linked Macro-CTA approach via Macrometer-sized silica [59]
Macro-CTAs: PEO and poly(QDMA) nanoparticles RAFT-mediated PISA suspension
Poly(DADMAC-co-AM) Cationic Microblock structure Ultrasonic (US)-initiated Cyclic-activated sludge [61]
template polymerization
Poly(DAC-co-AM) Cationic Microblock structure UV-initiated template Activated sludge [60]
polymerization
Poly(MAPTAC-co-AM) Cationic Microblock structure and UV-initiated template Municipal sludge [62]
porous surface polymerization
Poly(DMD-co-AM) Cationic Microblock structure and UV-initiated template Coal mine wastewater [63]
increased in DMD reactivity polymerization
ratio
Hyperbranched functional Anionic Hydrophobically modified Chain walking polymerization Oil sands tailings [53]
polyethylene (HBfPE) copolymer
Poly(MA-co-AA) Anionic AM free Emulsion polymerization Clay suspension and real [36]
wastewater
Poly(AM-co-poly(ethylene oxide Neutral Hydrophobically modified Conventional FRP Clay suspension and real [36]
methyl ether methacrylate)) copolymer wastewater
Amphoteric grafted starch Amphoteric Grafted AA followed by Free radical grafting 0.1 wt% Kaolin and hema- [46]
modification with a cationic tite suspension
group
Poly(acrylamide-co-4-vinylpyridine) Zwitterionic Partially hydrophobic Conventional FRP 0.25 wt% Kaolin and hema- [48]
tite suspension
FRP, free radical polymerization.
had core-brush topologies, as shown in Figure 11. They were

used to remove two pharmaceuticals, diclofenac sodium and
tetracycline hydrochloride, from water. They reported that the
extended polycationic brushes collapsed after a monolayer of
pharmaceuticals was adsorbed onto the brushes because the
carboxyl groups of the brushes turned toward the inner Fe3O4
particles, exposing the hydrophobic alkyl chains of the polymer
to the aqueous phase.
Several monomers have been grafted onto chitosan back-
Figure 9. Chemical structure of chitosan (left) and chitin (right). Adapted bones using a variety of methods such as thermal, ultrasonic
with permission.[65] Copyright 2012, Elsevier. waves, gamma rays, or UV-radiation initiated polymerization.
Sun et al. grafted acrylamide and [2-(acryloyloxy)ethyl] trimeth-
75.4%, respectively.[66] Degrees of deacetylation above 50% ylammonium chloride onto chitosan by UV initiation to control
make chitosan soluble in aqueous acidic media; chitosan is, polymer microstructure and charge density of the flocculant,
however, difficult to solubilize in alkaline aqueous media.[67] since acrylamide can form high molecular weight polymers and
Figure 9 shows the structure of chitosan and chitin. In acidic the quaternary ammonium monomer imparts cationicity to the
medium, the free amino groups on chitosan protonate and flocculant.[73] They used the flocculant with CaCl2 to treat zinc
chitosan behaves as a cationic polyelectrolyte. The solubility phosphate–contaminated wastewater. The removal efficiency
and cationicity of chitosan in acidic media help it become an dramatically increased with the addition of CaCl2 because Ca2+
effective flocculant due to efficient charge neutralization and ions chelated the phosphate ions and precipitated them. The
bridging effects in wastewater that mostly contains negatively grafted flocculant was found to be effective compared to com-
charged particles.[68] mercial cationic polyacrylamide.
Researchers physically and chemically modified chitosan to Going beyond the traditional realms of using chitosan only
improve its performance in wastewater treatment. A decade as a flocculant, Ren et al. flocculated both organic and inor-
ago, Guibal et al. reviewed the use of chitosan for clay suspen- ganic contaminants using poly(N-n-propylacrylamide)-grafted
sions, organic suspensions, dyes, and humic acid solutions.[69] chitosan, and then regenerated the flocculant from the aggre-
Another review of the flocculation performance of chitosan- gates.[74] In addition to experimental observations, density func-
based flocculants in suspensions of organic contaminants was tional theory and molecular dynamics simulations showed that
written by Renault et al.[70] Since then, numerous bio/natural tetracycline (TC) (the organic contaminant) and Cu(II) (the
flocculants have been developed for different applications. Con- inorganic contaminant) attached to the flocculant at room tem-
zatti et al. prepared films of chitosan by plasticizing it with pol- perature via synergistic interactions. It was reported that Cu2+
yethylene glycol.[71] They further grafted the thermoresponsive interacted with both flocculant and TC via coordination bonds.
poly(N-isopropylacrylamide) on the chitosan films using novel Reducing the temperature to 5 °C released the contaminants
UV and plasma graft polymerization methods. Their method of due to increased hydrophobic associations among the poly-
grafting, and the molecular structure of the plasticized chitosan meric chains, and regenerated the flocculant. Figure 12 illus-
allowed it to be made into membranes that could be used to trates the flocculation, subsequent separation of contaminants,
treat wastewater. Figure 10 shows the UV and plasma grafting and flocculant regeneration.
routes used to functionalize chitosan films. Often, chitosan is functionalized with petroleum-based cati-
In another interesting attempt by Zhang and coworkers, onic or anionic monomers, which somehow defeats the pur-
magnetic Fe3O4 particles were coated with chitosan and grafted pose of making completely natural flocculants. It would be
with either 2-methylacryloyloxyethyl trimethyl ammonium more desirable, in this case, to use alternative environmentally
chloride, acrylic acid, or methylmethacrylate.[72] The composites friendly reagents for the chemical modification of chitosan,
Figure 10. UV and plasma grafting routes to functionalize chitosan films. Reproduced with permission.[71] Copyright 2018, Elsevier.
Figure 11. Synthesis of chitosan-based magnetic composite particles to remove pharmaceuticals from water. Reproduced with permission.[72] Copy-
right 2016, Elsevier.
in order to avoid secondary pollution. Amino acids, which are bio-contaminants (antibiotics), as well as commonly occurring
biodegradable and biocompatible modification reagents, can kaolin clays (30 mg L−1).[75] Positively charged l-tryptophan
provide such an alternative. Chitosan modified with l-tryp- indole groups and negatively charged l-tyrosine phenol groups
tophan and l-tyrosine amino acids could effectively flocculate were responsible for making chitosan cationic and anionic,
Figure 12. Illustration of the flocculation, subsequent separation of contaminants, and regeneration of the poly(N-n-propylacrylamide)-grafted chitosan
flocculant. Reproduced with permission.[74] Copyright 2017, American Chemical Society.
Figure 13. Modification of chitosan using A) l-tryptophan and B) l-tyrosine. Adapted with permission.[75] Copyright 2016, Elsevier.
respectively. Figure 13 shows modifications of chitosan using negatively charged C. vulgaris microalgae, forming aggregates
l-tryptophan and l-tyrosine. which became stronger upon air purging due to the gelation of
Although chitosan and its derivatives are widely used in CNC. They noted that air purging enhanced the enmeshment
wastewater treatment, their performance depends strongly on of adjacent microalgae-CNC aggregates, producing stronger
medium pH due to the structural changes that occur in chi- aggregates. The process of dispersion and gelation was revers-
tosan as a result of ionization. Since chitosan has pKa of approx- ible, by purging CO2 and air, respectively.
imately 6.5, it is positively charged when pH < pKa, becoming Although cellulose nanofibers have been used as floc-
water insoluble when pH > 6.5. Additionally, chitosan’s pH- culants after surface modification, their aerogels have also
dependence varies according to its degree of deacetylation. shown effective coagulation–flocculation ability. Typically,
These pH-dependent structural changes significantly affect the chemical or physical cross-linking (ionic interactions, entangle-
flocculation of wastewater. For instance, chitosan may not be a ments) routes are employed to induce effective entanglements
good candidate for the flocculation of negatively charged clay between individual nanocellulose fibers to fabricate high-per-
particles in alkaline media, and often requires additional modi- formance nanocellulose-based aerogels.[81] In a novel attempt
fications using cationic monomers that could pose some toxi- of preparing cellulose-based aerogel, Wang and coworkers
cological side effects to the recycled effluent. Stefan et al. have extracted carboxylated cellulose nanofibers from waste ginger
briefly reviewed the biological effects of chitosan and cationi- using one-step acid hydrolysis and formed robust bulk aero-
cally modified chitosan.[76,77] gels by hydrogen bonding.[82] The highest aspect ratio of 144
led to the formation of physically cross-linked/entangled ultra-
lightweight and robust aerogels via strong interfacial adhesion
3.2.2. Cellulose (hydrogen bonds) without any external chemical modifica-
tions. Moreover, these aerogels had low density, high porosity,
Cellulose is another potential candidate for wastewater treat- the ability to absorb 476 times their own mass of water, and
ment due to its wide availability, renewability, sustainability, better compression performance. The cellulose nanofiber aero-
and the possibility of surface modification. However, the use of gels had the strong coagulation−flocculation ability, uptake
untreated cellulose is limited because it is insoluble in water. of methylene blue dye, and Cu2+ absorption capacity due to
Most of the research on the use of cellulose as flocculant focus mechanisms of charge neutralization, network capture effect,
on preparing nanocellulose and modifying its surface. Nano- and chain bridging of the high aspect ratio carboxylated cel-
cellulose has a large surface area, which facilitates surface lulose nanofibers. Sedimentation of kaolin required the addi-
modification. tion of Ca2+ for coagulation, followed by the flocculation using
Vandamme et al. extracted cellulose nanocrystals (CNC) cellulose nanofibers. Figure 14 shows the extraction of cellu-
from cotton wool by acidic hydrolysis[78] and grafted cati- lose nanofibers from ginger, the formation of aerogel by acid
onic pyridinium groups onto them through esterification and hydrolysis, and coagulation–flocculation performance in kaolin
nucleophilic substitution reactions. These cationically modified and methylene blue suspensions.
CNCs were distinctly charged in a wide pH range from 4 to 11. The carboxyl content of cellulose nanocrystals significantly
Cationic CNCs (>95%) effectively flocculated Chlorella vulgaris depends on the extraction process and reaction conditions.
microalgae, whereas algal organic matter inhibited the floccula- Carboxyl groups further affect the flocculation efficiency of cel-
tion of microalgae when conventional polymers were used. It is lulose nanocrystals in wastewater. Thus, the desired extraction
not yet clearly understood why algal organic matter inhibits the process is expected to have precise control over charge den-
flocculation process with conventional polymers.[79] sity (carboxyl groups), hydrophilicity, and rigidity of cellulose
In a similar cationic modification attempt, Ge et al. added nanocrystals. Yu et al. addressed these issues by extracting cel-
CO2-switchable 1-(3-aminopropyl) imidazole groups to CNC to lulose nanocrystals containing carboxylic groups from micro-
reuse the CNC-based flocculant for harvesting microalgae.[80] crystalline cellulose.[83] Hydrolysis time, temperature, and acid
The modified CNC became acquired cationic surface charges to microcrystalline cellulose ratio had the significant effect on
upon CO2-treatment, allowing them to disperse in the medium. morphology, microstructure, thermal stability, and kaolin floc-
The dispersed, positively charged CNC interacted with culation efficiency of cellulose nanocrystals.
3.2.3. Alginate-Based Materials
Alginate is a linear anionic polysaccharide

consisting of two kinds of 1,4-linked hexu-
ronic acid residues, β-d-mannuronopyranosyl
(M) and α-l-guluronopyranosyl (G)
(Figure 16). Alginate has abundant free
hydroxyl and carboxyl groups distributed
along the polymer chain backbone.
Methods for the modification of hydroxyl
groups of alginate include oxidation, reduc-
tive-amination, sulfation, copolymerization,
and coupling of cyclodextrin units. Carboxyl
groups can be modified by esterification,
use of the Ugi reaction, and amidation. Yang
et al. succinctly summarized the work on
chemical modifications of alginate.[87] Raw
alginate is rarely used as a flocculant due to
its physicochemical properties, but its salts,
in conjunction with various other materials,
are widely used as flocculants.
Sodium alginate is a water soluble salt of
Figure 14. Extraction of cellulose nanofibers from ginger, formation of aerogel by acid hydrol-
ysis, and coagulation–flocculation performance in kaolin and methylene blue suspensions.
alginic acid among other water soluble salts
Reproduced with permission.[82] Copyright 2018, American Chemical Society. such as potassium alginate and ammonium
alginate. Sodium alginate is extracted from
brown green algae and seaweeds, which
Similarly, negatively charged dicarboxylic acid nanocellu- binds 200–300-fold weight of water to form gels. The ratio of
lose fibers could also effectively flocculate municipal waste- d-mannuronic acid and l-guluronic acid and their sequences
water.[84] Anionic derivatives were synthesized by periodate determine the alginate properties.
and chlorite oxidation of cellulose, as shown in Figure 15. The Sodium alginate grafted with another functional polymer has
lateral dimensions of the nanocellulose fibers varied from 3 been extensively used as a flocculant. Typically, a free radical ini-
to 5 nm, while their length was up to a few micrometers. The tiator creates active sites on sodium alginate backbones where
positively charged ferric species formed cationic patches on another functional monomer polymerizes (grafting redundant).
the surface of the solid contaminant particles, and the ani- This process, however, may affect the structural integrity of the
onic nanocellulose fibers were connected via these cationic alginate backbone. Microwave radiation can selectively excite
patches. only the polar bonds in the backbone, leading to their rupture/
An anionic cellulose flocculant was also synthesized by the cleavage and creating free radical sites.[88] Since the backbone
sulfonation of cotton using chlorosulfonic acid. [85] Although is mainly comprised of nonpolar CC bonds, it remains unaf-
raw cotton had long, individual, and rigid fibers, the surface fected by the microwave radiations. Microwave-based grafting
of anionic cellulose became smoother as the sulfonation time. can be classified into two types: microwave-initiated synthesis
Kaolin suspensions could be effectively flocculated by com- (using microwave radiation alone to initiate grafting) or micro-
bining positively charged alum and anionic cellulose. wave-assisted synthesis (combining microwave radiation and
Figure 15. Synthesis of negatively charged nanocellulose fibers and flocculation of municipal wastewater using ferric coagulant and nanocellulose
fibers. Reproduced with permission.[84] Copyright 2013, Elsevier.
presence of inorganic ions. They also noted that the presence

of calcium and sodium salts strongly reduced the adsorption of
heavy metals, whereas the amine groups from PEI improved
the adsorption performance. This observation was attributed
to the competition of calcium ions with other heavy metals to
adsorb on the alginate composite. Similarly, Tian et al. modified
sodium alginate with thiosemicarbazide to introduce amino thi-
ourea groups on the flocculant.[93] Thiosemicarbazide-modified
sodium alginate showed more than 80% removal rate for lead,
cadmium, and copper metal ions. Electronic interactions and
chelation between the flocculant and heavy metal ions resulted
in effective adsorption. To elucidate the exact interactions
between alginate and heavy metal, Lim and coworkers studied
the adsorption of copper onto calcium alginate-encapsulated
magnetic sorbent.[94] They showed, using Fourier transform
infrared spectroscopy (FTIR) and X-ray photoelectron spectros-
Figure 16. Chemical structure of alginate. Reprinted with permission copy (XPS), that the CO in carboxyl groups of alginate directly
under Creative Commons Attribution License (CC BY).[86] Copyright 2014, attached to copper ions. Their comprehensive mathematical
the Authors. Published by Frontiers Research Foundation. model included ion exchange between calcium and copper,
coordination reactions between functional groups and copper,
chemical free radical initiation). Rani et al. demonstrated the as well as surface complex formation between iron oxide and
later approach to graft polymethylmethacrylate (PMMA) onto copper. The model could describe and predict the effects of
sodium alginate, combining microwave radiations and ceric various key operational parameters on the adsorption process,
ammonium nitrate to initiate the grafting reactions.[88] PMMA- such as initial pH, metal concentration, and dosage of sorbent.
g-sodium alginate (0.375 ppm) effectively flocculated coal fine
particles (1 wt%) from coal washery effluent treatment. Simi-
larly, N,N′-dimethylacrylamide was grafted onto sodium algi- 3.2.4. Microbial Bioflocculants
nate using microwave radiation and azobisizobutyronitrile
(AIBN) initiator.[89] It is important to note that the concentra- Microbial bioflocculants are natural organic macromolecules
tions of monomer, initiator, and sodium alginate, microwave that are derived from microorganisms and can flocculate parti-
power and polymerization temperature significantly affect the cles such as cells and colloidal solids. Such flocculants consist
grafting efficiency and the properties of the resulting grafted mainly of microbial polysaccharides, glycoproteins, proteins,
material. lipids, nucleic acids, and nucleoproteins. There is growing
Recently, Vijayalakshmi et al. prepared beads containing research interest in microbial bioflocculants to avoid environ-
nanochitosan, sodium alginate, and microcrystalline cellu- mental and health hazards caused by synthetic petroleum-
lose in 2:8:1 ratio to remove lead(II) from aqueous solution.[90] based polymers.
Although the three ingredients were used just as a mixture, Often, wastewater sludge contains bacteria that can produce
a small amount of calcium chloride transformed the mix- bioflocculants. Giri et al. isolated Bacillus subtilis F9 from local
ture into beads. The OH, NH2, and COO− functional groups activated sludge by optimizing the culture conditions such as
of the adsorbent beads contributed to bind with lead(II). The initial pH, temperature, carbon source, nitrogen source, and
authors also demonstrated that lead(II) could be desorbed inoculum size.[95] Interestingly, the bioflocculant was pH tol-
from the beads, allowing them to be reused. In a related work, erant in the range of 2–8 and temperature tolerant in the range
researchers synthesized beads of sodium alginate and caboxym- of 10–100 °C. A kaolin suspension (0.2 wt%) was effectively
ethyl cellulose by cross-linking them with calcium chloride and flocculated using the purified bioflocculant with a molecular
iron chloride.[91] The beads were used for lead(II) adsorption weight of 5.3 × 105.
from wastewater. Subudhi et al. isolated a new strain of Achromobacter xylosox-
Most studies on the removal of heavy metals using alginate- idans that had significant potential for bioflocculant produc-
based materials were carried out on model wastewater con- tion, along with biosorption of zinc, cadmium, lead, nickel,
taining defined amounts of contaminants. The behavior of alg- and copper.[96] The A. xylosoxidans strain was isolated from oil
inate-based materials in complex systems having varying ionic refinery waste and showed 73% bioflocculating activity in the
strength and containing several metals has not been extensively presence of multi-metals. Analytical studies revealed that the
studied. The incorporation of reactive groups that can tolerate biofloculant was mainly comprised of sugars (75%) and pro-
high ionic strength in the medium can improve the adsorption teins (11.5%).
capacity of alginate-based materials in such complex systems. Fermentation of mixed cultures can provide a variety of func-
Bertagnolli et al. immobilized polyethylenimine (PEI) deriva- tional groups to the extracted bioflocculant that can assist in
tives into an alginate matrix to take advantage of the adsorption effective flocculation. A mixed culture of Streptomyces and Cel-
properties of both PEI and alginate.[92] The adsorption proper- lulomonas was fermented to produce a bioflocculant with a yield
ties of the PEI-alginate composite were tested for the recovery of 4.45 g L−1.[97] The combination of the two cultures provided
of Cd(II), Cu(II), and Zn(II) ions from aqueous solutions in the aromatic, allylic, hydroxyl, carboxyl, ester, and amino moieties
to the bioflocculant, leading to high adsorption affinity. Scan- interactions between isopropyl groups, and by the breakage of
ning electron microscopy (SEM) images revealed that kaolin hydrogen bonds between polymer chains and water molecules.
sediments flocculated with this bioflocculant had compact This phenomenon favors the formation of intra-chain interac-
structures. tions over the interaction of polymer chains with water mole-
The combination of microbial bioflocculants and inorganic cules below the transition temperature. More information on
coagulants can reduce the dosage of harmful inorganic coagu- mechanistic of poly(NIPAM) phase transition at the molecular
lants, while keeping the flocculation performance the same. A level can be found elsewhere.[106–110]
microbial bioflocculant Klebsiella variicola B16 was used in com- Guillet et al. were the first to introduce stimuli-responsive
bination with polyaluminum ferric chloride (PAFC) to reduce flocculants,[111] and the idea was further brought forward by
the turbidity and remove suspended solids from drinking Sakohara et al.[112] and Franks.[113] Franks showed that floccu-
water.[98] lation/dewatering with stimuli-responsive polymers benefited
Most studies on the extraction of bioflocculant from microor- from the switch between attractive and repulsive forces that
ganism involve only one or two strain cultures. This approach drove water molecules out of the sediments (secondary consoli-
produces relatively small yields, which in turn raises the cost dation). He proved this hypothesis using temperature-respon-
of the bioflocculant and imposes economic constraints for its sive methylcellulose, where methylcellulose was added to a
wide use. Recently, Wu et al. reviewed the use of microbial stable suspension of positively charged zircon particles at room
aggregates to remove pollutants from wastewater.[99] Periphytic temperature. Methylcellulose is soluble in water below 50 °C
biofilms are microbial aggregates composed of bacteria, micro- (LCST), adsorbing to the zircon surfaces via hydrogen bonds.
algae, protozoa, and other microorganisms that grow in the A high dosage of 10 000 ppm (10 mg polymer per 1 g solids) of
sediment–water interface of paddy fields, shallow rivers, wet- methylcellulose ensured complete coverage of the particle sur-
lands, and other water ecosystems. Sun et al. extracted biofloc- faces, forming a stable suspension below LCST, as evidenced
culants from periphytic biofilms and demonstrated their use in by the absence of sedimentation. Upon heating the suspension
flocculation and turbidity reduction of water containing aniline above the LCST (75 °C), the particles aggregated and settled
blue dye and kaolin.[100] The authors obtained 491.8 mg biofloc- rapidly, leaving behind a clear supernatant. Franks showed that
culant per gram of periphytic biofilms, which is significantly by cooling the sediment once again below the LCST, the sedi-
higher than that achieved with single microbial extraction pro- ment volume shrank up to 11%. This was attributed to interpar-
cesses. The pH value strongly affected the degree of ionization, ticle forces in the sediment, switching from attractive (hydro-
surface charge, and dissociation of functional groups in their phobic attraction above LCST) to repulsive (steric repulsion
bioflocculant, with flocculation efficiency decreasing with the below LCST), causing the aggregate structures to rearrange and
increase in pH. It is interesting to note that, although proteins forcing water out of the sediments. In other words, the com-
in bioflocculant play an important role in the flocculation pro- pressive yield stress of the sediments was now low enough to
cess because of their abundant free amino groups, the floccu- allow the bed to collapse due to gravitational forces, forcing the
lation efficiency may be reduced with increasing temperatures water out of the aggregate network.[114] Figure 17 shows a sche-
due to protein degradation. matic of the proposed mechanism.
Table 3 summarizes recent bio/natural polymers used as Sakohara et al., however, used a slightly different approach:
flocculants. they achieved the rearrangement of particles in the sedi-
ments by applying mechanical force, giving water the chance
to escape the network when the hydrophobic particles came
3.3. Stimuli-Responsive Flocculants closer. One necessary condition to induce flocculation above
and then consolidation below LCST, is a sufficient coverage
Stimuli-responsive polymers are a class of macromolecules that of the particle surfaces to ensure a reversible switch between
undergo conformational changes and switch their solubility attraction and repulsion, which dictates the use of an excess
when the right stimulus is applied. The stimuli can be tempera- polymer as compared to conventional flocculation,[116] an eco-
ture, pH, electromagnetic field, ionic strength, redox species, or nomical drawback in large scale operations. A second draw-
even light intensity. Although the primary application of these back is the energy input to heat up the suspension above LCST.
materials is in drug delivery systems and biological sensors, The latter could be tackled by using an upper critical solution
these macromolecules have also been used as flocculants.[104] temperature (UCST) flocculant. These polymers are soluble in
temperatures above the UCST only. UCST flocculants can be
added to hot process effluent to utilize the thermal energy, as
3.3.1. Thermoresponsive Flocculants the case with the oil sands extraction process. UCST polymers
show less sharp transition temperature compared to LCST
Most stimuli-responsive flocculants are temperature sensi- polymers and their transition temperature strongly depends on
tive, with poly(N-isopropylacrylamide) poly(NIPAM) being the solution pH and ionic strength.[117,118] This perhaps explains
most widely used smart polymer. Poly(NIPAM) exhibits a lower the rare number of reports on UCST polymers being used as
critical solution temperature (LCST) of approximately 32 °C, flocculants. Recently, Bogacz et al. flocculated titania using
above which the polymer is no longer soluble in water: above poly(acrylic acid), showing a UCST of about 40 °C, adsorbing
this temperature, the polymer chains undergo a coil-to-globule to and aggregating particles above and below UCST, respec-
transition collapsing up to one-third of their original size.[105] tively.[117] A comprehensive review of the UCST polymers can
The phase transition is energetically driven by hydrophobic be found elsewhere.[118]
Table 3. Summary of chitosan, cellulose, and alginate-based flocculants used in the treatment of wastewater.
Base polymer Polymer modification Synthesis method Media Comment Reference

Chitosan 2-Methyl acryloyloxyethyl FRP Diclofenac sodium Magnetic composite with [72]
trimethyl ammonium Tetracycline hydrochloride core-brush topology
chloride Brushes collapse due to
Acrylic acid contaminant adsorption
Methylmethacrylate
Chitosan Raw chitosan dissolved in — Nejayote (high TOC) Works in acidic pH [101]
acetic acid Higher dosage (3 g L−1) required
Chitosan 3-Chloro-2-hydroxypropyl Only CTA molecule was Kaolin Amphoteric flocculant [65]
trimethyl ammonium chloride grafted, not polymerized Cationicity improved flocculant’s
(CTA) water-solubility and reduced the
required dosage
Chitosan Acrylamide UV polymerization Zinc phosphate Flocculation required Ca2+ aid [73]
2-(Acryloyloxy)ethyl] trimethyl-
ammonium chloride
Chitosan N-n-propylacrylamide Amidation reaction Tetracycline Reusable flocculant [74]
between chitosan and Cu(II)
poly(N-n-propylacrylamide)
with a carboxyl end group
Chitosan l-Tryptophan Activation by N-ethyl-N′-(3- Norfloxacin Flocculation due to synergistic coordination [75]
l-Tyrosine dimethylaminopropyl) carbodi- Sulfadiazine between contaminants and flocculant
imide Tylosin
hydrochloride Kaolin
Chitosan 3-Chloro-2-hydroxypropyl) tri- UV-initiated graft Microcystis aeruginosa >90% Contaminant removal rate at pH 7 [102]
methylammonium chloride copolymerization
Dimethyl diallyl ammonium
chloride
Cellulose Pyridinium salt Simultaneous esterification Chlorella vulgaris Flocculant performance was not affected by [78]
and nucleophilic substitution algal organic matter
reactions
Cellulose Conversion of aldehyde groups Periodate and chlorite Municipal wastewater Anionic flocculant worked with ferric sulfate [84]
of cellulose to carboxylic acid oxidation
Cellulose Conversion of cellulose to Sulfonation of cotton kaolin Works with alum [85]
cellulose sulfate
Cellulose 1-(3-Aminopropyl)-imidazole Chlorella vulgaris CO2-switchable flocculant [80]
Cellulose Cellulose fibers in dissolved Surface carboxylation Methylene blue CaCO3 in composite improved porosity [103]
cellulose matrix Methyl violet
Cellulose Carboxylation of CNC Hydrolysis of microcrystalline Methylene blue Higher content of carboxyl groups were [83]
cellulose Kaolin beneficial
Cellulose Cross-linked nanocellulose Acid hydrolysis and freeze drying Methylene Blue High compressive strength and shape [82]
aerogels Cu2+ recovery
Alginate Nanochitosan Formation of composite beads Lead (II) Beads contained OH, NH2, and COOH [90]
Microcrystalline cellulose using CaCl2 groups
Alginate Polymethyl methacrylate Microwave irradiation Coal fine particles Better flocculation than conventionally [88]
used alum
Alginate Carboxymethyl cellulose CaCl2 and FeCl3 assisted Lead (II) Flocculant removed 99% contaminant [91]
cross-linking
Alginate Polyethylenimine derivatives PEI powder dispersed in alginate Cadmium(II) Salts reduced the sorption efficiency [92]
matrix, beads formation using Copper(II)
CaCl2 Zink(II)
Alginate Magnetite encapsulation using Electrostatic extrusion process Copper Cu interacted with alginate and [94]
calcium alginate magnetite core
TOC, total organic carbon; CNC, cellulose nanocrystal.
The critical solution temperature of floc-

culants can also be tuned by altering the
microstructure and chemistry of the polymer
chains; for instance, adding hydrophilic or
charged comonomers generally increases
the LCST of the flocculant.[121] Hydrophobic
interactions among polymer chains get
stronger as the temperature is increased
above the LCST, as confirmed by atomic force
microscopy (AFM) and contact angle meas-
urements.[122] This has implications for floc-
culation: Ng et al. used focused beam reflec-
tance measurement (FBRM) to show that
the mean size of aggregates increased when
Figure 17. Secondary consolidation when using a temperature-responsive flocculant. Repro-
the temperature was raised above the LCST
duced with permission. [115] Copyright 2009, John Wiley & Sons. for poly(NIPAM).[116] Upon examining their
results (Figure 18), it is not entirely clear why
such dependency was not observed with ani-
For neutral LCST flocculants, such as poly(NIPAM) or onic poly(NIPAM-co-AA), the authors suggested that it could be
poly(N-vinylcaprolactam), no aggregation occurs if polymers due to a greater state of aggregation that had already occurred
are added to warm suspensions above LCST. This limitation, in temperatures below the LCST through charge neutralization.
along with the need for the selective flocculation of minerals For poly(NIPAM), for which aggregation occurs only above the
or wastewater pollutants, has led researchers to synthesize LCST, the dependency of aggregate size on temperature sug-
charged temperature-responsive copolymers. O’Shea et al. syn- gests that a higher number of polymer/water hydrogen bonds
thesized a series of random cationic poly(NIPAM-co-dimeth- are broken by increasing the temperature, strengthening the
ylaminoethyl acrylate quaternary chloride) poly(NIPAM-co- hydrophobic interactions between the polymer-coated particles.
DQA) and anionic poly(NIPAM-co-AA) to induce selective floc- This explanation is independently supported by Maeda et al.,
culation of silica and alumina, respectively.[114] They observed where the authors showed that even in the globule state (right
that the counter-charge flocculants adsorbed to the particles above LCST), poly(NIPAM) had still about 87% of its carbonyl
at temperatures above LCST, induced aggregation by charge groups hydrogen-bounded with water molecules, as measured
neutralization, but no secondary consolidation was observed by FTIR spectroscopy.[106] Furthermore, Lemanowicz et al.
when cooling the suspension below LCST. The authors showed that the rate of heating above the LCST did not impact
attributed this to the presence of charged comonomer units the maximum size of the aggregates during flocculation with
readily accessible throughout the backbone below and above
the LCST, creating attractive forces in the sediments that hin-
dered secondary consolidation. Zhang et al. also observed the
absence of secondary consolidation when thermoresponsive
random poly(AAm-co-DADMAC) was used to flocculate oil
sands tailings.[119]
In an attempt to achieve secondary consolidation with
charged copolymers, O’Shea et al. used RAFT polymerization
to synthesize a series of block cationic and anionic copolymers,
poly(NIPAM-b-DQA) and poly[NIPAM-b-(AAc-co-tBA)] (tBA =
tertiary butyl acrylate) and used them to flocculate silica and
alumina suspensions, respectively.[120] They observed aggrega-
tion above the LCST (similar to random copolymers), but this
time secondary consolidation was indeed obtained below the
LCST. Blocks of anionic or cationic comonomer adsorb onto the
suspended particles above the LCST, while the neutral NIPAM
blocks extend into solution below the LCST, inducing steric
repulsion in the sediments and eventually achieving secondary
consolidation. In other words, the block microstructure allowed
not only achieving secondary consolidation below the LCST,
but also led to the formation of micelles above the LCST (with
NIPAM being the core), promoting stronger adsorption onto
the particles and better aggregation above the LCST, as observed
by faster settling rates compared to those obtained with random
copolymers of the same charge density and molecular weight Figure 18. Effect of temperature on iron ore aggregate sizes as obtained
average. by FBRM. Adapted with permission.[116] Copyright 2017, Elsevier.
in charge state of these polymers. A com-

prehensive review of pH-responsive poly-
mers can be found elsewhere.[125] Yu et al.
used pH-responsive HM-alginate/chi-
tosan complexes to selectively flocculate
pollutants from synthetic wastewater.[126]
At acidic pH (below 4), the amphiphilic
HM-alginate was negatively charged and
dispersed in water as a colloidal phase,
attracting Sudan IV (a hydrophobic dye)
toward its hydrophobic core. Chitosan
becomes positively charged in acidic pH,
causing the hydrophobic dye-carrying
HM-alginate to aggregate with chitosan
molecules, separating the pollutant
from water. The authors observed that
the hydrophobic dye could be selectively
removed in the presence of methylene
blue dye as the hydrophilic compound.
Figure 19. Dye flocculation using a temperature-responsive grafted hydroxyethyl cellulose In another study, Wang et al. synthe-
(HBPEC). Reproduced with permission.[124] Copyright 2016, Elsevier. sized a dual pH/temperature-respon-
sive polymer for the removal of Avitera
Red SE dye from water. The polymer
cationic poly(NIPAM-co-DADMAC).[123] However, more work is (Figure 20) was prepared through a sequence of esterification
needed to investigate the effect of heating rate as the finding of and etherification reactions of 2-hydroxy-3-butoxypropyl starch
this study cannot be generalized to neutral thermoresponsive (HBS) in water and DMSO, respectively.[127] At pH below the
polymers for the same reason as just discussed for the study by critical solution pH (pH*) or temperature below LCST, the
Ng et al.[116]
Thermoresponsive polymers have
also been used to remove organic dyes
from wastewater. Tian et al. recently syn-
thesized an environmentally friendly
thermoresponsive polymer, 2-hydroxy-
3-butoxypropyl hydroxyethyl cellulose
(HBPEC), by grafting butyl glycidyl
ether (BGE) onto hydroxyethyl cellulose
(HEC).[124] The fraction of BGE, being the
hydrophobic monomer, greatly controlled
the LCST of HBPEC (LCST of 56 °C at
1% vs 20 °C at 2.5% molar substitution).
The flocculation proceeded as shown in
Figure 19. HBPEC added to a suspension
below the LCST formed micelles (with
HEC forming the outer surface) encap-
sulating the hydrophobic organic dye, as
confirmed by fluorescence spectroscopy.
Above the LCST, the HEC part of the
copolymer also became hydrophobic, coa-
lescing the dye-containing micelles into
large aggregates that settled more easily
out of the solution.
3.3.2. pH-Responsive Flocculants
Another class of stimuli-responsive floccu-

lants is pH-responsive polymers. Change
of pH drives solubility or conformational Figure 20. Cyclic flocculation regeneration of the thermoresponsive starch polymer. Reproduced
changes, generally affected by the change with permission.[127] Copyright 2016, The Royal Society of Chemistry.
positively charged starch (due to BDAT side chain) adopted that they could use CO2 as a trigger for the flocculant, instead
an open conformation due to hydrogen bonding between the of an acid or a base. They observed that the flocculation effi-
starch backbone and water, adsorbing the anionic dye. Upon ciency of modified CNC decreased from 90% at pH 4 to 20%
the increase of pH or temperature, the polymer switched to a at pH 8, an indication of the polymer becoming CO2 switch-
globule conformation, aggregating with other polymer chains able.[128] Other examples of CO2-responsive flocculants are
and flocculating the dye. The polymer showed large hysteresis listed in Table 4. A comprehensive review on CO2-responsive
(LCSTheating = 66 °C vs LCSTcooling = 20 °C) that was attributed polymers can be found elsewhere.[130]
to residual hydroxyl groups of TPRS in the aggregate.[127]
It is worth noting that the authors did not discuss any syner-
gistic advantages due to the simultaneous switch of the stimuli 3.3.3. Electromagnetic-Responsive Flocculant
(thermal/pH) for this polymer.
Another interesting application of pH-responsive polymers Another novel class of responsive flocculants is based on elec-
is to flocculate microalgae. Separation of microalgae from the tromagnetic-responsive macromolecules. In an interesting
growth medium is an important process for harvesting this work, Lü et al. attempted to treat oil-contaminated wastewater
valuable biomass for use in biofuel production. Biodegradable using chitosan-grafted magnetic nanoparticles (CS-grafted
polymers such as cellulose nanocrystals (CNC) are attractive MNPs).[131] Figure 21 shows the synthesis route for CS-grafted
options for this purpose.[128,129] Swinging the pH to trigger the MNPs. At acidic pH, the CS-grafted MNPs are positively
flocculant, however, leads to the accumulated salts eventually charged and adsorb to the negatively charged surface of emul-
damaging the microalgae growth medium. Ingeniously, Eyley sified oil droplets (about 2 µm) forming aggregates (about
et al. modified CNC with imidazole to obtain a pH-responsive 100 µm) which then further grew by coming together through
flocculant possessing a pKa close to that of H2CO3 in water, so applying a magnetic field. More information on the synthesis
Table 4. Summary of stimuli-responsive flocculants.
Flocculant type Polymer Properties Synthesis method Medium Reference

Temperature Poly(NIPAM-b-DQA) (LCST = 34 °C, FDQA = 0.3, Mw = 17k) and RAFT Alumina suspension [120]
responsive Poly[NIPAM-b-(AAc-st-tBA)] (LCST = 33 °C, FDQA = 0.01, Mw = 300k) (10 wt%)
(LCST = 35 °C, FNIPAM = 0.86, Mw = 24k)
and (LCST = 33 °C, FDQA = 0.99, Mw = 50k)
Hyperbranched LCST = 36 °C, Mw = 120k, FNIPAM = 0.84, RAFT Kaolinite suspension [134]
poly(NIPAM-b-AEMA ) cross-linking density = 5% (5 wt%)
2-Hydroxy-3-butoxypropyl (LCST = 56 °C 1% graft density) Grafting Synthetic dye wastewater [124]
hydroxyethyl cellulose (LCST = 20 °C 2.5% graft density) (0.16 wt%)
(HBPEC)
Poly(pullulan-g-pNIPAAm) Mw = 260k, FNIPAAm = 0.56, Grafting Clay suspension (0.1 wt%) [135]
LCST = 34 °C
Poly(NIPAM) LCST = 32 °C, Mw = 1170k FRP Oil sands tailing (10 wt%) [119]
Poly(AEMA-st-NIPAm) LCST = 40 °C, Mw = 2200k,
FNIPAM = 0.86
Chitosan and poly(NVCL) — FRP Silica suspension (0.1 wt%) [136]
Poly(NIPAM-co-EXMA) LCST = 37 °C, Mw = 1000k — Chalcopyrite-quartz [29]
suspension (5 wt%)
pH responsive Imidazole grafted CNC pH* = 6.5 Grafting Microalgae (0.03 wt%) [128]
HM-alginate/chitosan complex Mw = 50k, pH* = 4.0 Self-assembly Synthetic wastewater [126]
(0.1 wt%)
CO2 responsive Amine-functionalized Mw = 120k, FMMA = 0.5 High temperature Clay suspension (7 wt%) [137]
poly(MMA), functionalization and acetonitrile in water
(50 wt%)
Electromagnetic Chitosan base — Grafting Oily wastewaters [131]
responsive (0.2 wt% diesel)
Electromagnetic Fe-poly(DADMAC) — Reaction of FeCl3 with Graphene oxide in water [138]
responsive poly-DADMAC suspension
Dual responsive Starch base LCST = 20–66 °C pH* = 2.5–3.0 Esterification and Synthetic dye wastewater [127]
(temperature and pH) etherification (0.5 wt%)
Dual responsive Poly(AEMA-st-NIPAM-st- Mw = 234k FAEMA = 0.1, FNIPAM = 0.15 FRP Kaolin suspension (5 wt%) [139]
(temperature and pH) MAAmBO) LCST = 43 °C (pH = 11), LCST = 33 °C
(pH = 7)
Figure 21. Synthesis of CS-grafted MNPs. Reproduced with permission.[131] Copyright 2017, Elsevier.
and characterization of magnetic flocculants and their applica- requires lengthy mathematical modeling, which is beyond the
tions can be found elsewhere.[132,133] scope of this work. Interested readers are encouraged to con-
Table 4 summarizes the recent stimuli-responsive polymers sult the appropriate references in the literature.[140–145] Herein,
used as flocculants. we will provide the readers with basic polymer reaction engi-
neering tools as applied to the free radical polymerization of
flocculants. Table 5 shows how the molecular weight of a pol-
4. Polymerization and Characterization of ymer produced with solution (or bulk) polymerization versus
emulsion polymerization is related to the conditions inside the
Flocculants
reactor and the rate of polymerization.
4.1. Polymerization In Table 5, Rp is the rate of polymerization (conversion of
monomers), Mn is the number average molecular weight of the
Despite continued advancements in novel polymer flocculants, polymer, [M] is monomer(s) concentration, [I] is initiator con-
little attention has been paid to controlling the microstructure centration, and N is the concentration of polymer particles in
of these materials by means of polymer reaction engineering emulsion polymerization.
techniques that are well established and widely used to produce Note that relations for the molecular weight in Table 5
other types of polymers. applies instantaneously, that is, it describes the Mn of polymer
Polymer microstructure is a generic term that encompasses made at a particular time during the polymerization. If the
polymer molecular weight averages and distributions, comon- concentrations of monomer and/or initiator are allowed to vary
omer composition averages and distributions, grafting frequen- during the polymerization (such as when the reactor is oper-
cies, long chain branching topologies, and ionic charge dis- ated in batch mode), the values of Mn will change as a function
tributions among any other molecular properties that may be of polymerization time, producing a polymer with less uniform
deemed to have an influence on polymer properties and appli- properties than a polymer that would be produced with these
cations. These molecular architecture properties determine conditions kept invariant. The effect of this property “drift”
how polymers perform in different applications. For example, on flocculant performance is not clearly understood, and even
polyolefin molecular weight average and distribution affect rarely mentioned in the publications in the literature.
polymer processing and mechanical strength, while polyolefin Moreover, one can also increase the molecular weight by
short chain branching influences their crystallinity and impact decreasing the initiator concentration. In solution or bulk
properties. Surprisingly, investigations on the influence of pol- polymerization, that means decreasing the rate of polym-
ymer microstructure on flocculation are quite limited, if not erization to achieve a high molecular weight flocculant, while
completely absent, in most publications in the area. In this sec-
tion, we aim at showing that this is a serious limitation, which Table 5. Rate of polymerization and average molecular weight of floc-
is likely preventing further advances in this field of knowledge. culants produced by solution (or bulk) polymerization versus emulsion
Being the most known economically viable and versatile polymerization.
polymerization technique for the production of water soluble
polymers, nearly all the commercially available polymer floc- Solution (or bulk) polymerization Emulsion polymerization
culants used in wastewater, mineral processing, or tailings Rp ∝ [M][I]0.5 N
Rp ∝ [M]
treatment applications are made by solution or emulsion free 2
radical polymerization. The control of the microstructure of
Mn ∝ [M][I] − 0.5 Mn ∝ [M][I] − 1N
homo- and copolymers made by free radical polymerization
emulsion polymerization does not have this limitation. Inter-

ested readers are encouraged to read the appropriate references
on the kinetics of emulsion polymerization.[146,147]
The majority of commercial flocculants are copolymers,
either anionic, such as poly(AM-co-AA), or cationic, such as
poly(AM-co-DADMAC). These comonomers often have con-
siderably different reactivity ratios, that is, the frequency of
reactions between the pairs (AA, AM), (AM, DADMAC), and
(DADMAC, DADMAC) may differ substantially. These dif-
ferent reactivity ratios result in a composition drift inside the
reactor, causing the concentration of the “fast” comonomer
(AM) to drop more rapidly than the concentration of the slow
comonomer (DADMAC). This trivial polymerization reaction
engineering fact is often dismissed during the production of
copolymer flocculants, when most assume, implicitly, that the
comonomer composition fed to the reactor at the beginning of
the copolymerization will be replicated in the comonomer com-
position in the copolymer. While it is true that, if the copoly- Figure 22. Simulation of chemical composition for the system of
poly(AM-co-DADMAC). Evolution of AM fraction in the monomers mix-
merization proceeds to full conversion, the overall comonomer ture (green line), in the polymer chains produced at a given instance
composition in the copolymer will be identical to the comon- of conversion (blue line), and the cumulative fraction of AM in the
omer composition fed to the reactor, the comonomer composi- whole polymer chains produced in the reactor until a given conversion ×
tion on the copolymer chains will vary depending on the time (red line). Reactivity ratios for this system rAM = 5.7, rDADMAC = 0.03 were
they were produced during polymerization. obtained from the work of Brand et al.[149]
If the reactivity ratios of monomers A and B are rA and rB,
respectively, then the classic Mayo–Lewis equation relates the
instantaneous fraction of monomer A in the copolymer, FA, to More information on the optimal design of water soluble floc-
the fractions of monomers in the reactor, fA and fB , as culants taking these phenomena into consideration can be
found elsewhere.[150] Through polymerization kinetics and a
rA f A2 + f A f B surface response methodology, Vajihinejad et al. studied the
FA = (6)
rA f + 2 f A f B + rB f B2
2
A
impact of copolymer microstructure on the flocculation of
oil sands tailings.[151] In another recent study, Gumfekar and
The FA obtained from Equation (6) is the instantaneous Soares showed how polymer reaction engineering tools can
copolymer composition; to get the cumulative copolymer com- help synthesize terpolymer flocculants with predefined and
position, FA, at any conversion, one needs to use Equations (7) well-controlled compositions.[152]
and (8)[148] Although the conditions during free radical polymeriza-
tion can be controlled to assure that the molecular weight and
f A,0 − f A (1 − x ) chemical composition distributions of polymer flocculants are
FA = (7)
x as narrow as possible, these statistical copolymers will always
display a distribution of molecular weight and chemical
df A f A − FA composition values, even if the conditions are perfectly con-
= (8)
dx 1− x trolled during the polymerization. Conventional free radical
polymerization processes cannot, therefore, precisely con-
where x and fA,0 are total molar conversion of monomers and trol the microstructure of polymers, which prevents it from
initial composition of the monomer A in the feed. making model polymer flocculants that would help establish
Figure 22 shows simulation results for the average chemical microstructure–flocculation performance relationships. Con-
composition for the AM/DADMAC system. It shows how the trolled radical polymerization is the most practical option
fraction of acrylamide in the reactor (fAM) drops more rapidly for the production of flocculants with well-defined structures
than that of DADMAC (fDADMAC = 1 − fAM). As a consequence, such as block or alternating polymers, polymers with narrow
after a total monomer conversion of about 0.70, only DADMAC molecular weight and comonomer composition distributions,
remains in the reactor. It is apparent from this figure how dif- and comb, star, or grafted polymers, that would allow us to
ferences in reactivity ratios can cause the comonomer composi- precisely correlate the microstructure details of flocculants to
tion to drift during batch polymerization, in such a way that their performance.
after a certain conversion (≈ 70%), all the acrylamides are used Controlled radical polymerization can be broadly classified into
up and only DADMAC polymerizes, leading to a product that is two classes: i) reversible deactivation, such as atom transfer rad-
actually a blend of homopolymers and copolymers if the polym- ical polymerization (ATRP), nitroxide-mediated polymerization
erization is carried out to full conversion. (NMP), or single electron transfer living radical polymerization
It is worthy to note that the reactivity ratios of water soluble (SET-LRP); and ii) degenerative transfer, such as RAFT polym-
monomers can significantly change with monomer concentra- erization. This is a fascinating topic, but the detailed description
tion, pH, and ionic strength of the polymerization medium. of these polymerization techniques is beyond the scope of this
work. Interested readers are encouraged to read the appropriate tools to optimize the structure of a polymer flocculant, the
references.[153–155] Simply put, the idea behind controlled radical absence of full polymer microstructure quantification such as
polymerization is to take control over the polymerization process molecular weight distribution (MWD) and chemical composi-
in a way that the free radicals are initiated at nearly the same tion distribution (CCD) does not provide the necessary insight
time (forming polymer radicals) and grow at approximately the into the relations between flocculant microstructure and their
same rate in the absence of termination/transfer reactions, to flocculation/dewatering performance.[161,162]
make a population of living chains with almost the same length This section briefly summarizes some of the techniques
and molecular weight dispersity approaching unity. The best way that can be used to quantify the microstructure of flocculants.
to achieve this goal is to keep the concentration of propagating Unfortunately, it is out of the scope of this paper to present a
radicals in the system low enough to decrease the likelihood of detailed discussion on the fundamentals of each technique, but
termination/transfer events taking place. This generally means appropriate references for interested readers are provided in
a slower polymerization rate is the price one pays to make poly- Table 6.
mers with more uniform microstructures.
There are not many studies on flocculation using poly-
mers produced from a CRP technique. As one example, Wang 5. Performance Assessment of Flocculants
et al. compared the performance (turbidity of the supernatant,
water released, and initial settling rate) of random copolymers 5.1. Flocculant–Particle Interaction Measurement Techniques
of NIPAM and 2-aminoethyl methacrylamide hydrochloride
(AEMA) poly(NIPAM-st-AEMA) and their hyperbranched block Interfacial forces between particles and polymers, which result
copolymers poly(NIPAM-b-AEMA) made by RAFT for the from the surface energies of particles and polymer chains, ulti-
flocculation of kaolinite suspensions.[134] Above and below its mately control the flocculation process. Often, the flocculation
LCST, the hyperbranched block copolymers performed better performance of a polymer reflects interactions of polymer mol-
than their random counterparts, with the differences being ecules and suspended. Additionally, these interactions strongly
more apparent above the LCST. These observations are indica- influence the rheological properties of the sediments, which are
tive of the impact of polymer architecture on polymer adsorp- important in several applications such as dewatering.
tion of kaolinite surfaces and flocculation performance. In this section, we briefly introduce and review the recent
Although chain extension or grafting may give access to the state of the art focused on the use of quartz crystal microbalance
production of higher molecular weight polymers for research with dissipation (QCMD), atomic force microscopy (AFM), and
purposes, generally one limitation of controlled radical polym- surface force apparatus (SFA), which are considered powerful
erization as a practical alternative to make polymer flocculants techniques to quantify flocculant–particle interactions.
is its inability to facilely and cost-effectively make polymers of
very high molecular weights (>107) suitable for flocculation
applications to replace the commercially available flocculants. 5.1.1. Quartz Crystal Microbalance with Dissipation (QCM-D)
The reason for this limitation in reversible deactivation sys-
tems such as ATRP is simply the longer reaction time required A QCM-D can be used to investigate the polymer adsorption on
to increase polymer chain length, which inevitably increases the surface of solid particles. QCM-D can provide both quali-
the probability of chain termination or transfer events, which tative and quantitative information. Moreover, the technique
decreases its ability to produce polymers with narrowly con- can detect conformational changes and adsorption geometry of
trolled microstructures.[156] Several groups have recently polymers at solid/liquid interfaces.
attempted to produce high molecular weight water soluble A typical QCM-D consists of a piezoelectric quartz crystal
polymers while maintaining the living character of the polym- sensor with gold electrodes on both surfaces. An alternating
erization. The typical molecular weight range achieved (max- electric field applied across the crystal determines the reso-
imum a few 100 000), however, is yet beyond what is easily nance frequency (f ) of the quartz crystal.[178] The crystal oscilla-
produced by conventional free radical polymerization.[157–160] tion frequency reduces due to an increase in mass (Δm) bound
to the quartz crystal surface, leading to a negative change in the
resonance frequency (−Δf ). Equation (9) shows how resonance
4.2. Flocculant Characterization frequency changes as a function of the mass adsorbed on the
quartz crystal (Δf)[179]
The detailed characterization of the microstructure of com-
modity polymers, such as polyolefins, is a well-studied subject, f
∆f = − × ∆m (9)
which has permitted enormous advances in this area over the tq ρ q
last decades. Unfortunately, the research community working
on the development of polymer flocculants often fail to prop- where tq and ρq are the thickness and density of the quartz
erly quantify the microstructure of their polymers, which plate, respectively. The model can be further refined using
would otherwise permit them to establish quantitative micro- film thickness, density, shear modulus, and viscosity to
structure-performance relationships for their flocculants. The accurately describe the viscoelastic behavior of the adsorbed
often-reported properties of flocculants are average molecular polymer.[180]
weights, intrinsic viscosities, and average chemical composi- Figure 25 shows typical responses of QCM-D to changes
tions. Although characterizing these properties provides some in mass as a result of adsorption or deposition.[181] Although
Table 6. Summary of techniques for the quantification of microstructure of flocculants.
Molecular weight
Viscometry and light scattering
Provide average MW but do not give information on the molecular weight distribution (MWD)
GPC (gel permeation chromatography)[163,164]
Characterizes MWD but fails to properly measure MWD when
• Ultra-high molecular weight flocculants (≈>107) are to be fractionated because GPC column has a pore size limit.
• The flocculants are cross-linked polymers or in the form of gels.
• Flocculants are partially soluble flocculants (e.g., polyacrylamide-grafted amylopectin). In that case, a portion of chains is lost in the GPC pre-injection filtration system.
• High molecular weight and bio-flocculants often experience chain scission in the GPC column, leading to invalid MWD results.
• There is an interaction between the polymer and the column packing materials. This limits the range of ionic flocculants that could be characterized by GPC.
FFF (field flow fractionation)
FFF is an open channel fractionation technique that does not have the limitations of GPC (Figure 23). It can readily characterize MWD of ultra-high molecular weight floc-
culants. A recent review on the advances of field flow fractionation techniques can be found elsewhere.[164]
Note: When measuring the MWD of different polymers to relate the MWD with flocculation or for comparison of different flocculant products, caution needs to be taken
for the appropriate time of polymer dissolution prior to injection. Owen et al. showed that aging strongly affects the flocculation performance of polyacrylamide floccu-
lants, in a way that their flocculant had maximum performance after 72 h of dissolution.[165]
Chemical (copolymer) composition
NMR (nuclear magnetic resonance) spectroscopy
1H- or 13C-NMR can readily quantify the average chemical (copolymer) composition of a flocculant,[166–168] but do not give information on the chemical composition distri-
bution (CCD).
Th-FFF (thermal field flow fractionation)
Could characterize CCD of a flocculant.[169] When coupled with detectors such as refractive index (RI), multiangle light scattering, and NMR, it can give the combined full
MWD and CCD.[170,171]
Branching quantification
Branching in flocculants can be quantified by NMR[172,173] spectroscopy, GPC, or FFF. Figure 24 shows how a branched polymer can be detected by a GPC or FFF. The
deviation from the straight line on a log–log plot of intrinsic viscosity versus molecular weights of fractionated samples gives access to the quantification of the degree of
branching in a flocculant. Soares and McKenna discussed a framework for the calculation of long-chain branching in polyolefins that could potentially be used for water
soluble flocculants.[163]
Grafting quantification
NMR can quantify the degree of grafting only if a unique peak can be assigned to the graft points.[174] Another challenge is the separation of physical blends of grafted
copolymers from ungrafted homopolymers, which often lead to peak overlap in the NMR.[175,176] The graft length and frequency can be theoretically estimated using the
stoichiometric calculation of concentration grafting monomers and free radicals. More information on this technique can be found elsewhere.[177]
adsorption of foreign materials on the crystal causes a frequency case). On the other hand, soft adsorbed layers on the quartz
drop, no significant change is observed in dissipation if the crystal significantly increase dissipation (upper case).
adsorbed film forms a rigid layer on the quartz crystal (lower Alagha et al. investigated the adsorption characteristics of
polyacrylamide (PAM)-based polymers on
anisotropic basal planes of kaolinite using
QCM-D.[182] They first deposited the kao-
linite nanoparticles on QCM-D sensor
and flowed 500 ppm of Al(OH)3-PAM
flocculant over the sensor at a flow rate
of 0.15 mL min−1. As shown in Figure 26,
a rapid decrease in the resonance fre-
quency was observed with an increase in
dissipation. Polymer quickly adsorbed on
kaolinite basal planes and subsequently
Figure 23. Field flow fractionation concept. Polymer solution laminarly passes through thin chan- reached steady state, giving a maximum
nels with high aspect ratio forming a parabolic velocity profile. A cross flow U, perpendicular to the mass uptake of 18 mg m−2.
inlet flow, forces the polymer molecules to go down toward the accumulation wall. This force with a Most of the research on polymer-
back diffusion force, induced by concentration gradient in the system, will eventually form a distri-
assisted flocculation investigates the effect
bution of polymers based on their size. Once the axial flow is restarted, the smaller polymer chains
will elute from the channel first, accompanied by the larger one. Instead of a cross flow, a thermal of polymer molecular weight and con-
gradient (∆T ≈ 30 - 100 °C) can also drive the perpendicular move of the molecules, which makes centration on flocculation performance.
the basis for thermal FFF (ThFFF). Adapted with permission.[163] Copyright 2012, John Wiley & Sons. The flocculation performance essentially
effluent wherein organic matter affect the interactions between

flocculant and clays. Using QCM-D, Klein et al. showed that
hydrolyzed polyacrylamide had a greater affinity for “clean”
surfaces (Al2O3) than for bitumen-contaminated surfaces.[183]
They also measured the initial settling rate of tailings as a
function of their bitumen content. Unexpectedly, an optimum
bitumen content of approximately 0.2 wt% helped solids settle
faster, but higher or lower bitumen contents reduced the set-
tling rate.
Water chemistry and solution properties are normally
extremely complex in wastewater suspensions, which signifi-
cantly influences surface properties of solid particles (surface
charges) and polymer behavior (chain conformation). Polymer
Figure 24. Detection of a branched structure; [η] is the intrinsic vis- adsorption and conformation effects were investigated for a
cosity of the polymer, M represents molecular weight of the fractionated system of chitosan-g-PAM and kaolinite clay.[184] Their QCM-D
(monodisperse) samples. The linear polymer follows the Mark–Houwink experiments under high salinity (NaCl and CaCl2) indicated
relationship where the intrinsic viscosity of the polymer is related to its
viscosity as [η] = K[M]a. K and a are Mark–Houwink constant for a given
that the adsorbed polymer layer had a more compact conforma-
polymer. tion than that under low salinity. They further reported that cat-
ionic groups of chitosan-g-PAM weakened the polymer adsorp-
reflects interactions between polymer chains and suspended tion on the alumina surface as compared to the silica surface.
particles. The effect of polyacrylamide molecular weight, In such case, hydrogen bonding was the main driving force to
104 and 106 , and concentration, 3–53 mg mL−1, on adsorption form aggregates, as reflected in settling experiments.
to gold and silver plates was investigated using QCM-D.[180] Reid and coworkers addressed a conflicting trend in the lit-
A lower amount of higher molecular weight polymers was erature that suggested that polyethylene glycol (PEG) adsorbed
required to form a thick layer than lower molecular weight onto CNC surfaces, using QCM-D.[185] They prepared a thick
polymers, as seen in Figure 27. This information can further CNC film on a QCM-D sensor and flowed PEG solution at
be used to determine interactions of polymer-adsorbed particles 100 µL min−1 until adsorption (rather deposition of PEG)
with other particles (bare-surface) to form aggregates. reached equilibrium. Further, the sensor was rinsed with water
Often, QCM-D is employed to study interactions between until the frequency reached equilibrium. Their observations
polymers and solid surfaces. Moreover, it may also be used suggested that PEG first slowly deposited (not adsorbed) onto
to quantify the adhesion between the two. However, these the CNC film, and that later was completely rinsed away by the
systems are often model systems that neglect the presence of water, indicating PEG did not absorb onto the CNC. Figure 28
organic matter that form complexes with the solids, and alter shows the change in frequency and dissipation during adsorp-
the interactions between polymer and solid particles. The tion and desorption of PEG onto cellulose. The results were
presence of bitumen in oil sands tailings is an example of an also compared with fumed silica.
Figure 25. Illustration of QCM-D experiments. Left: the resonance frequency of the crystal sensor decreases due to the increase in mass on the surface
of a QCM-D sensor. Lower: formation of a rigid layer disconnects the power source and slowly reduces the amplitude of crystal oscillation. Upper: for-
mation of a soft layer rapidly reduces the amplitude of oscillation due to the high energy loss in the viscoelastic film. Reproduced with permission.[181]
Copyright 2016, Elsevier.
Figure 26. Adsorption of Al(OH)3-PAM flocculant on kaolinite deposited on QCM-D silica sensor: A) mass uptake and B) plot of ΔD as a function of
Δf. Reprinted with permission.[182] Copyright 2013, American Chemical Society.
angstroms. It can quantify intermolecular forces in nano-

newton precision in both vapor and liquid media.
Figure 29 shows a schematic for SFA. Two round silica
disks, each polished on one side to gain a cylindrical curva-
ture, are placed into the SFA chamber in a cross-cylindrical
geometry (of the same radius R). This geometry approximately
resembles a sphere of radius R approaching a flat surface.[186] A
thin transparent layer of mica, coated with a silver layer on one
side, is then glued on a cylindrical silica disk with the silver-
coated side in contact with the silica. The chamber can be filled
by gas, vapor, or liquid medium, and then the disks approach
each other. A micrometer and a piezoelectric crystal trans-
ducer, attached to the upper disk, control the distance between
the two disks, while the lower disk is mounted on a supporting
spring.
The absolute surface separation (D) is measured by an optical
technique by multiple beam interference (MBI) using fringes
Figure 27. Effect of concentration and molecular weight of polyacryla- of equal chromatic order (FECO). Then the force between the
mide on the thickness of the adsorbed film. Reprinted with permis- two surfaces is calculated based on the separation distance of
sion.[180] Copyright 2004, American Chemical Society. the two disks, the deflection of the supporting spring, and the
spring constant.
5.1.2. Surface Force Apparatus (SFA) and Atomic Force Equation (10) shows the force between the spring-supported
Microscopy (AFM) surfaces depends on separation distance, where the k is force-
measuring spring and ΔDs is the spring displacement.[188]
SFA is widely used to investigate intermolecular and sur-
face forces when two surfaces are separated only for a few F(D) = k∆Ds (10)
Figure 28. Change in a) frequency and b) dissipation during adsorption and desorption of PEG onto cellulose. The results were also compared with
fumed silica. Reproduced with permission.[185] Copyright 2017, Springer Nature.
Figure 29. Schematic of a surface force apparatus. Reproduced with permission under University of Alberta Libraries.[187] Copyright 2012,
the Author.
Another similar method to SFA is AFM that has been used to

quantify different intermolecular and surface forces such as van
der Waals forces, electric double layer repulsion, and hydrophobic
interactions. It is similar to SFA, except that the forces are meas-
ured between a sharp tip and the surface of the sample. AFM can
also measure the surface topology while scanning the tip along
the surface. The surface topology is obtained by plotting the
deflection of the cantilever versus its position on the surface.[189]
A typical AFM (Figure 30) has a sharp tip that is mounted
onto the cantilever, which has a known spring constant. When
a surface is scanned by the sharp tip, the force between the
tip and the surface is measured by the deflection of the canti-
lever. The deflection of the cantilever is then detected through
a laser beam that is reflected from the cantilever to a photo-
diode detector. The force is then calculated by Hooke’s law
(Equation (11)), where x represents the deflection, k is the
spring constant of the cantilever, and F is the force.[189] More
detailed description of using SFA and AFM can be found
elsewhere.[188,190,191]
F = kx (11)
A number of studies on the interactions between parti-

cles and polymer flocculants with SFA and AFM are avail-
able.[192–199] For example, Wang et al.[192] studied the effect of
solution salinity in the interactions between a chitosan-graft-
polyacrylamide (chi-g-PAM) and mica-coated surface. They Figure 30. Schematic of an atomic force microscope. Reproduced with
showed that high salinity of the solution influences chi-g-PAM permission.[189] Copyright 2005, Elsevier.
Figure 31. Typical force–distance profiles between two mica surfaces in chi-g-PAM solutions. a) Milli-Q water with ≈39 nm range of repulsion, b) 1 m
NaCl with ≈32 nm range of repulsion, c) 1 m CaCl2 ≈21 nm range of repulsion, and d) summary of the adhesion measured in separation. Reproduced
with permission.[192] Copyright 2015, The American Chemical Society.
chain conformation and surface charge properties of kaolinite In another work, Lu et al. studied the effect of the flocculant
that weaken the bridging interaction of chi-g-PAM and kao- molecular weight on polymer–particle adhesion.[200] Surface
linite, resulting in poor flocculation performance. Figure 31 force measurements and AFM imaging for glycopolymers with
shows the force−distance profiles measured by SFA at different different molecular weights adsorbed on mica surfaces, as a
salt concentrations.[192] model for kaolin, show stronger polymer−particle adhesion and
Alagha et al.[193] used AFM imaging under tapping mode in bridging attraction by increasing the molecular weight of the
the air to investigate the adsorption of an organic–inorganic glycopolymer. This strengthened bridging attraction enhanced
hybrid polymer, Al(OH)3 polyacrylamide (Al-PAM), on silica the flocculation performance.[200]
and alumina. The randomly distributed bright dots, on the sil- SFA was used to probe interactions between polymer chains
icon surface in Figure 32A, are recognized as cores of Al(OH)3 of different molecular weights and kaolin. The authors used two
colloidal particles surrounded by the PAM molecules acting back-silvered mica sheets with the equal thickness of 1−5 µm,
like arms to connect these cores. In addition, AFM images of as kaolin model clay, glued on cylindrical silica disks with radius
samples with the silicon substrate and preadsorbed Al-PAM (R) of 2 cm. Two bare mica surfaces were at direct contact in
after immersion in suspensions of silica nanoparticles (SNPs, the air to measure the reference distance (D = 0). Then, the
15 nm; Figure 5C), show spherical particles of SNPs aggregated polymer solution was injected between the two mica surfaces.
on Al-PAM. The measured height of these particles by AFM is The polymer solution was 10 ppm poly(2-actobionamidoethyl
in the range of 50–100 nm, which is a clue of the formation of methacrylamide) (PLAEMA) in water. Figure 33 shows the typ-
aggregates on Al-PAM.[193] ical force–distance curves for their flocculants poly(LAEMA)177,
Figure 32. AFM images of A) Al-PAM on silicon wafer, B) bare silicon wafer, C) SNPs on silicon wafer with preadsorbed Al-PAM, and D) commercial
HPAM (Magnafloc1011) on silicon wafer. Reproduced with permission.[193] Copyright 2011, The American Chemical Society.
Figure 33. The typical force–distance profiles between the two mica surfaces in 10 ppm glycopolymers in water: a) poly(LAEMA)177, b) poly(LAEMA)397,
and c) poly(LAEMA)975. Reproduced with permission under ACS AuthorChoice License.[200] Copyright 2016, The American Chemical Society.
poly(LAEMA)397, and poly(LAEMA)975. The subscripts indicate characterize the performance of a flocculant in a given effluent:
the degree of polymerization of each flocculant. Their number i) macroscopic measurements, and ii) microscopic measure-
average molecular weights were reported to be 83 000, 186 000, ments. Macroscopic measurements, also referred to as indi-
and 456 000, respectively. As expected, repulsion was observed rect measurements with respect to state of aggregation,[201] are
when two mica surfaces approached, mainly due to the steric screening tests such as settling rate of aggregates, supernatant
interaction of the approaching polymer chains adsorbed on turbidity, or the net sediment dewatering. They provide a good
the mica surfaces. Adhesion forces (Fad) during the separa- ground for screening flocculant options, quantifying targeted
tion of the two surfaces increased by increasing the molecular performance parameters sought by a given treatment option,
weight of the polymer (Fad/R ≈ 3, 8, and 11 mN m−1), shown in and shedding light on possible reasons behind a successful or
red curves in Figure 33, which was attributed to the stronger unsuccessful flocculation. Such methods, however, are unable
hydrogen bonding resulting from more hydroxyl groups as to give a full picture of the flocculation mechanism in operation
polymer molecular weight increased. An enhanced flocculation during a process, nor link aggregate structure to dewatering
performance of the polymer on the kaolin particle suspension observations and flocculant properties. Microscopic measure-
was a consequence of this higher interaction forces.[200] ments, on the other hand, examine the structure of aggregates,
In this study, AFM in tapping mode was also used to monitor measuring their sizes, shapes, and density, and provide tools to
topographical changes due to the adsorption of glycopolymers relate polymer properties to the macroscopic behavior observed
with different molecular weights on mica surfaces. Typical with indirect measurements.
images are shown in Figure 34. Surface roughness and aggre-
gate size increase by increasing the molecular weight of the
polymer, showing that polymers with higher molecular weights 5.2.1. Dewatering Observations (Macroscopic Measurements)
adsorb more effectively on the mica surfaces.[200]
The effectiveness of flocculants in industrial applications is
often assessed based on a certain set of parameters that reflect
5.2. Flocculation Assessment how well the polymer can flocculate a given solids suspension.
For example, a polymer may produce a clear supernatant, but
Development of new, or optimization of existing, polymer floccu- it may take an unreasonably long time to reach this outcome.
lants relies upon the information obtained from the appropriate Such polymer, therefore, cannot be used for applications in
characterization of polymer performance in a range of operating which quick water recovery is required. In such a scenario, a set
conditions. There are often two types of measurements that of measures, applied to the combination of polymer and type of
Figure 34. Topographic AFM images of a) poly(LAEMA)177, b) poly(LAEMA)397, and c) poly(LAEMA)975 absorbed on mica surfaces. Reproduced with
permission under ACS AuthorChoice License.[200] Copyright 2016, The American Chemical Society.
Figure 35. Settling profile of flocculation obtained by monitoring A) mudline height. Reproduced with permission.[152] Copyright 2018, Elsevier. B) Sediment
volume. Reproduced under the terms of the Creative Commons license Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)
license.[202] Copyright 2017, the Authors. Published by Elsevier.
effluents, can provide a platform which is helpful for selecting Most recent studies on polymer-assisted flocculation have
a polymer for the desired requirement. This section provides an reported exponentially decreasing settling profiles, indicating a
overview of the measures that have been used to assess the per- high flocculant effectiveness. The slope of the initial linear part
formance of polymer flocculants for various types of effluents. of the settling profile is called the initial settling rate (ISR), which
Settling Rate: Settling rate is commonly employed to deter- determines the initial recovery of clean water from a suspen-
mine how quickly a contaminant is removed from an effluent. sion. Often, ISR is interchangeably used as settling rate. From
Indirectly, it reveals the kinetics of the process responsible the flocculation point of view, ISR is more relevant than the
for the flocculation such as adsorption and/or charge neu- average settling rate, calculated over the complete settling pro-
tralization. Typically, a solid–liquid or a color-separating inter- file. Recent studies have shown that ISR significantly depends
face (mudline) is monitored as a function of time after the on the molecular weight and chemical composition of copol-
addition of a flocculant to the suspension. This data is often ymer flocculants.[152,203] Figure 36 shows the effect of molecular
called a settling profile (Figure 35A). Feng et al. analogously weight and fraction of [2-(methacryloyloxy)ethyl]trimethylam-
monitored the time evolution of sediment volume instead of monium chloride in copolymer on the ISR of clay particles.
interface height to show the settling behavior of a quartz sus- The higher molecular weight favors the ISR due to the bridging
pension (Figure 35B).[202] Note that this unconventional way mechanism, and a comonomer, [2-(methacryloyloxy)ethyl]tri-
of reporting settling rates (Figure 35B) is only valid if all the methylammonium chloride, in flocculant increases the ISR by
flocculated samples under comparison have the same volume, increasing the interactions between polymer and solid particles.
and the height of the falling sediment is measured inside the In case of graft polymers, the grafting density also significantly
same cylinder. affects ISR of solid particles in wastewater.[204] Since grafts may
Figure 36. Effect of A) molecular weight and B) copolymer composition on the initial settling rate. Reproduced with permission.[152,203] Copyright 2018,
Elsevier.
have additional functionality, such as positive charges, their

length and frequency affect the interactions between polymer
and suspended particles. The effect of polymer dosage on ISR
has also been widely studied to determine optimum dosages for
effective flocculation of wastewater.[119]
In comparing the settling rate of different flocculants in high
solids systems, the effect of wall adhesion of the measurement
cylinder must be taken into account. In high solids, a flocculant
(such as a high molecular weight polymer) that produces large
aggregates might have lower settling rate than a flocculant that
produces smaller aggregates (such as a low molecular weight
flocculant), which does not reflect a better performance of the
latter flocculant, but simply wall adhesion effects in a narrow
measurement cylinder. Such hindered settling also limits the
acquisition of accurate settling data, which could otherwise be Figure 37. Correlation between turbidity and total suspended solids and
used for sizing treatment unit and in sediment consolidation its experimental validation. Reproduced with permission.[209] Copyright
models. These effects are discussed in the recent publication 2012, Elsevier.
by Benn et al., where the authors used a detailed and controlled
(but complex) approach to study the sedimentation and consoli-
dation of aggregates of different physical properties obtained by increases with particle size. It also increases as small parti-
two distinct flocculants in an automated, large scale (2 m by cles aggregate. This phenomenon is semi-empirically used to
20 cm) settling measurement set up.[205] monitor relative coagulation rates and stability ratios.[211] In the
Turbidity of Supernatant: Supernatant is the liquor left on case of dilute suspensions and/or weak flocculation, the rela-
top of the sediments after the flocculation is completed. The tion between specific turbidity and wavelength can be used to
quality of the supernatant is quantified by its turbidity, which assess the state of aggregation.[212] Generally, the relationship
results from the presence of solid particles. A nephelometer, can be written as
often called turbidimeter, is used to measure the turbidity of
the supernatant in nephelometric turbidity unit (NTU). Several τ
= kλ − n (12)
studies measured supernatant turbidity to investigate the effect ∅
of polymer dosage,[36] the solids content in the suspension,[206]
and molecular weight of polymers.[207] where k and n are constants for a given particle size, ∅ is
Shaikh and coworkers studied the effect of polyacrylamide volume fraction of particles, and τ is the turbidity. The basis of
τ
structure on the flocculation of bentonite clay.[208] Using tur- Equation (12) is that the specific turbidity ( φ ) of a suspension
bidity as a powerful measure, they compared flocculations using depends on the light wavelength (λ). Gregory has comprehen-
cationic, anionic, and amphoteric polyacrylamides of varying sively reviewed the use of turbidity for monitoring the particle
molecular weights. Similarly, Zhang et al. measured the tur- aggregation process.[212]
bidity of the supernatant obtained after the flocculation of oil The use of turbidity measurements, and the interpretation
sands tailings.[119] Turbidity is known to be correlated with sus- of its results, largely depends on the desired properties of the
pended solids when the physical properties of particles remain released water (supernatant) for a given process. In the treat-
constant. Researchers have developed correlations to convert ment of oil sands tailings (water, clays, sands, bitumen), for
turbidity into suspended solids.[209] Turbidity changes linearly example, the released water is recycled to the bitumen extrac-
with total suspended solids (TSS) for homogeneous suspended tion process, where the accumulated fine clays (i.e., <44 µm)
particles with given size and refraction index. In practice, sensor are considered detrimental over time for the heating equip-
technology and the water matrix induce deviations from this ment, pumps, and the oil extraction process itself. Given the
linear behavior. Therefore, polynomial functions are used to influence of organics and residual bitumen on the readings of
determine the correlation functions. Figure 37 shows the experi- the turbidity measurements, and considering the changes in
mental and correlation data of TSS as a function of turbidity. concentration of these contaminants in a continuous tailings
Turbidity monitoring can also serve as a tool for assessing the stream, turbidity measurements may not be a reliable metric
performance of a continuous separation process. A UV–visible for effectiveness of a given flocculant. In such cases, an alter-
spectrophotometer can also be used to measure the turbidity of native technique (such as light scattering/laser diffraction) may
suspensions. Recently, Salam et al. evaluated the potential of a be used to characterize the amount of fines left in the released
UV–vis spectrophotometer method to measure polymer concen- water.
tration and determined the optimum polymer dose for achieving Capillary Suction Time: Capillary suction time (CST) is used to
the best thickening and dewatering performance from oil sands measure the filterability and the easiness of removing water from
tailings. Their method was sensitive enough to detect very low sediments. The CST method is a handy tool for testing dewat-
concentrations (0.37 mg L−1) of A3338 (SNF) polymer.[210] erability in numerous industrial, chemical, and environmental
Mostly, turbidity is used to assess the quality of the super- applications. The CST instrument consists of a cylindrical steel
natant but it can also be used to monitor aggregation kinetics. reservoir resting on filter paper fitted between two Perspex plates
The turbidity of particles smaller than the light wavelength with electrode sensors across the top plate. The instrument
records the CST value, which is a measure of the time required Similarly, Gumfekar and Soares attributed the reduced CST of
for the waterfront to move through a stretch of paper positioned their sediments to partially hydrophobic nature of their floc-
between the two electrodes. A higher CST value indicates the culants.[152,203] In a novel attempt of using the static magnetic
lower dewatering (high water retention) of the sludge. field during the sedimentation of activated sludge in a biore-
Researchers observed strong correlations between dis- actor, Zieliński et al. reported a significant reduction in CST of
persed mass concentration, CST, and rheological parameters the sediments due to filamentous bacteria present in the aggre-
for sludge suspensions containing varying solids contents.[213] gates under a static magnetic field.[217] The addition of filamen-
They also reported that the restriction of flow is caused by the tous bacteria induced floc formation due to its length, but an
development of interparticle networks that reduced dewater- excess amount of filamentous bacteria caused floc formation in
ability. Since most sludges form aggregates at an optimum secondary settling tanks.
dosage of flocculant or coagulant, their dewatering character- Some researchers also attempted to digest food waste and
istics depend on the equipment and the chemical, structural, activated sludge together to produce methane. The dewater-
and physical characteristics of the aggregates. Turchiuli and ability of the digestate of this mixed system still needs further
Fargues showed the relationship between floc structure and improvement. Wang et al. investigated the correlation between
the sludge dewaterability.[214] Further, Arimieari and Ademiluyi CST and protein and polysaccharide content of the mixture.[218]
modeled filtration resistance and CST wherein they used CaCl2 They noted that CST increased with an increase in activated
as a coagulant for treating sludges.[215] They empirically modi- sludge, and overall dewaterability improved under mesophilic
fied the equation established by Christensen et al.[216] to obtain anaerobic condition. The antibiotic mycelial residue (AMR)
the optimal coagulant dosage that yielded lower CST or specific obtained from fermentative processes for antibiotic produc-
resistance to filtration (SRF). Equation (13) shows the relation tion is categorized into hazardous waste due to the residue of
between CST and SRF. antibiotics. Cai et al. dewatered AMR using microwave irra-
diation and monitored its dewaterability using CST.[219] Their
CST = C1 × SRF × µ f × ω + C2 × µ f (13) study demonstrated that the microwave irradiation disinte-
grated the AMR matrix promoting the water release as shown
where C1 and C2 are coefficients related to CST, µf is the vis- in Figure 38.
cosity of the filtrate, and ω is the solid content in unit volume Often, coarse solids and/or heavy aggregates sediment on
of filtrate. the filter paper of the CST, thereby blocking the way for water to
A larger diameter cylinder was recommended to test heavy seep out of the sediments. The conventional CST test does not
sludge because the larger cylinder significantly reduces the var- account for such a phenomenon, which may lead to an over-
iability and the time taken to conduct the CST tests. Recently, estimation of filtration resistance (underestimation of dewater-
de Oliveira et al. used CST to quantify the dewaterability perfor- ability). To eliminate this shortcoming, some researchers exper-
mance of flocculants in oil sands tailings.[204] They showed that imentally and theoretically investigated a novel rectangular
increasing the graft density of a chitosan-g-3-chloro-2-hydroxy- CST apparatus in which, the sedimentation effects were negli-
propyltrimethylammonium chloride and its dosage reduced gible.[220] Scholz has critically assessed CST-based dewaterability
the CST of the sediments. The hydrophobic core of their testing research.[221] The review emphasized the importance of
graft polymer reduced the amount of water entrapped in the aggregate structure in explaining practical dewaterability prob-
aggregates and increased the dewaterability of the sediments. lems such as filter paper clogging.
Figure 38. The CST-based mechanism of dewatering of antibiotic mycelial residue using microwave irradiation. Reproduced with permission.[219]
Copyright 2017, Elsevier.
V
The term µrω represents the resistance from the filter
A
cake and μrLm represents the resistance from the filter paper.
For measurements at constant pressure, Equation (14) can be
integrated as
t µrω µrLm
= V+ (15)
V 2PA 2 PA
Equation (15) can be described as
t
= a + bV (16)
V
where
µrLm
a= (17)
PA
µrω
Figure 39. Schematic of a setup to measure the specific resistance of b= (18)
filtration. 2A 2
Plotting the t/V against V, the specific resistance to filtration

Specific Resistance to Filtration (SRF): Specific resistance to (Equation (19)) and the equivalent thickness of the filter paper
filtration is a widely accepted measure of dewatering properties (Equation (20)) can be calculated from the slope and intercept
of sludges and sediments. The concept of specific resistance to
filtration is based on Darcy’s law and is usually interpreted as 2PA 2
r= b (19)
being of purely hydrodynamical character. In the SRF measure- µω
ment, a sample is dewatered by a filter using positive pressure.
Figure 39 shows the schematic of a setup to measure the spe- aω
cific resistance of filtration. Lm =
2Ab (20)
The Equation (14) describes the volumetric flow rate during
the filtration.[222]
Figure 40A shows the water release profile as a function
dV AP of time and Figure 40B shows the plot of t/V against V, from
= (14)
dt µrωV which SRF can be calculated using Equation (19).
+ µrLm
A It is important to note that the SRF model assumes constant
mean porosity, mean cake size, and water pressure in pores. In
where V is volume of the filtrate (m3), A is the filter area (m2), reality, the porosity and pressure changes across the cake, and
P is the pressure applied (Pa), µ is the viscosity of filtrate the mean cake size rapidly varies when the solids concentra-
(Pa · s), ω is mass of solid cake formed per unit filtrate volume tions changes due to dewatering. Higher SRF values indicate
(kg m−3), r is specific resistance to filtration (kg m−1), and Lm is inferior dewatering properties while low SRF values indicate
the fictitious equivalent thickness of the filter paper (kg m−2). superior dewatering properties.
Figure 40. A) Water release profile as a function of time obtained from the filtration experiment and B) corresponding plot of t/V against V to calculate
SRF. The above data was obtained from the filtration of oil sands tailings treated with different flocculants. Reproduced with permission.[223] Copyright
2010, John Wiley & Sons.
increased functionality in flocculant to overcome the complex.

For example, oil sands wastewater contains bitumen adsorbed
onto the clay surface requiring additional flocculant dosage.[183]
Similarly, drinking water contains dissolved natural organic
matter (NOM) that adds turbidity to the water.[227] The absolute
values of surface charges on the solid surfaces and liquid media
collectively form a system of charges known as the electric
double layer (EDL).[228] Although researchers are interested to
measure the surface potential of the solid particles, practically,
a potential difference can only be measured within a single
phase. To overcome this issue, we can neglect all other interface
boundaries in the system and calculate the sum of the surface
potentials that lie very close to the solid particle surface. This
potential, measured close to the surface, is called zeta poten-
tial. A wastewater system is considered a stable suspension if
Figure 41. Increase in solid content from 15% to 30% over the 25 min the net interaction between the particles is repulsive. In the
filtration time. Reproduced with permission.[224] Copyright 2018, Elsevier.
context of consolidation and dewatering, the zeta potential of
the colloidal system can help design flocculants that effectively
Growing interest in renewable resources is capturing aggregate the solids and subsequently, dewater them. An effec-
researchers’ interest in biomass feedstock utilization. However, tive flocculant would compress the electrical double layer and
dewatering of biomass from various bioprocesses makes it less induce sedimentation. Thus, researchers use zeta potential as
economical and hinders its large-scale application. Koza et al. an effective tool to assess the destabilization efficiency of the
dewatered the fungal biomass from ethanol plant using various flocculant and propose the flocculation mechanism. However,
filtration processes and measured the solids content as a func- the majority of the state of the art measured the zeta poten-
tion of filtration time.[224] The centrifuge filter increased the tial of the supernatant showing the absence of charged con-
solids content from 15% to 30%, as shown in Figure 41. taminants due to the addition of flocculants. It is an indirect
Often researchers claim different types of polymer mor- method to show the contribution of charge neutralization in
phology depending on polymer composition and the method sedimentation. Direct measurement of particles’ or aggregates’
of polymerization. The polymer morphology, because of micro- zeta potential can provide evidence of suppression of particles’
structure, governs the flocculation properties of the polymer. electrical double layer.
Recently, Li et al. synthesized copolymer of acrylamide and As discussed in previous sections, several researchers syn-
methacrylamido propyl trimethyl ammonium chloride and thesized cationic, anionic, and amphoteric polymers to treat
claimed irregular, uneven, and porous surface area of the wastewater. Such ionic polymers mainly affect the electro-
polymer based on scanning electron micrographs.[225] Such kinetics, adsorption, and flocculation of the stable colloidal
morphology was claimed due to the cationic monomers and system in wastewater. The reduction in the negative zeta poten-
UV-initiated polymerization that induced surface modifica- tial was found to be considerably greater in the presence of cati-
tion. Their SRF measurements indicated that adsorption and onic polyacrylamide than anionic and amphoteric polyacryla-
bridging ability of the copolymer significantly increased due mide, due to an increased adsorbed layer thickness of cationic
to the porous surface area. They hypothesized that the porous polyacrylamide.[208] Amphoteric polymers exhibit both cationic
structure of the polymer helped entrap the particles and and anionic behaviors, and their strength and a relative number
increased the filtration ability of the polymer. SRF was found to of sites vary depending on surface charge density. Monitoring
be a powerful tool to assess the performance of polymers with the zeta potential during flocculation experiments indicated
a porous structure. that the adsorption ability of amphoteric polymers lies between
Filtration of organic slurries is important in many industries cationic and anionic polyacrylamide. Adsorption of polymer on
but challenging because the hydraulic resistance is high due solid surfaces and their rearrangement significantly depends
to gel materials in the slurries. Filtration resistance of mineral on surface charges of the polymer. Shaikh et al.[208] observed
slurries is well mathematically modeled but specific cake resist- that the aggregate sizes increased with increasing cationic sur-
ance of organic slurries is underestimated. Hinge and Chris- face charge density but decreased with increasing anionic sur-
tensen considered a model system of particles with solid poly- face charge density.
styrene core and poly(N-isopropylacrylamide) gel surface.[226] Effective flocculant reduces the stability of the suspensions,
Using a model for deformable particles, they modeled the spe- thereby reducing their zeta potential. Therefore, the technique
cific cake resistance as a function of the low amount of gel (thin is useful in determining the optimum flocculant dosage with
shell layer). At the high amount of gel (thick shell layer), the supernatant turbidity measurements. Malikova et al. dewatered
permeability of the gel governed the specific cake resistance. the floatation tailings using inorganic polymers such as polyalu-
Zeta Potential: The colloidal nature of wastewater and surface minium chloride at different temperatures and investigated the
charge of the solid particles make the solid–liquid separation temperature effect using a combination of zeta potential and
more difficult. Moreover, the presence of organic complexing turbidity measurements.[229] Figure 42 shows the optimization
agents reduces the effectiveness of flocculants or coagu- of flocculation temperature using a combination of zeta poten-
lants. Organic matter adsorbs onto solid particles that require tial and turbidity measurements. At 20 °C, the zeta potential
Figure 42. Optimization of flocculation temperature by combined use of zeta potential and supernatant turbidity. Reproduced under the terms of the
CC BY-NC-ND 4.0 license.[229] Copyright 2016, the Authors. Published by Elsevier.
and the turbidity were minimum, thus it was considered as an of the polyelectrolytes and to confirm the presence of ionic
optimum temperature. Although their optimization was mainly monomer in copolymers, the data should be interpreted with
based on zeta potential and turbidity, they had to consider the supplementary techniques such as turbidity measurement.
pH and mixing conditions to determine the reusability of the Zeta potential of polymers in liquid medium contributes to
recovered water. the hydrodynamic size of polymer, which in turn affects the
Researchers have also used the technique to confirm the bridging, and/or charge neutralization ability. Thus, a sche-
grafting of ionic monomer to the polymer backbone.[204] Since matic showing a particle and a polymer chain should be care-
the cationic grafts increase the positive zeta potential, the fully drawn considering the size of polymer chain at its zeta
technique was used to optimize the concentration of cationic potential. There are numerous reports showing the polymer
monomer required to obtain the highest charge density. Zeta chain bound to several clay particles of micrometer size; how-
potential of the supernatant was measured as a function of con- ever, realistically, the size of polymer chain is much smaller
centration of grafting agent. The concentration that brought (dependent on zeta potential) than that of clay particles.
the zeta potential near to zero was used as an
optimum concentration of grafting agent. Often,
anionic polyelectrolytes with cations are used for
effective flocculation of negatively charged par-
ticles. In such cases, the interaction of cations
with solid particles also play an important role
similar to that of the polymer. Lee et al. showed
that the adsorption of anionic polyacrylamide
on negatively charged kaolinite surface was
enhanced by the interaction of cations like Ca2+
and Mg2+ with kaolinite particles as well as poly-
meric flocculant chains.[230] Bridging of cations
with kaolinite surface and polyacrylamide chains
were investigated. CaCl2 and MgCl2, having
divalent cations, showed stronger adsorption
affinity and lowered the negative zeta potential
as compared to monovalent salts such as NaCl.
They reported a six-time increase in adsorption
capacity with divalent salts. Figure 43 shows the
schematic illustrating the conceptual model of
anionic polyacrylamide adsorption on kaolinite
and subsequent flocculation for two different
types of divalent cationic bridges. Figure 43. Schematic illustrating the conceptual model of anionic polyacrylamide adsorp-
Although zeta potential is widely used to tion on kaolinite and subsequent flocculation for two different types of divalent cationic
investigate the charge neutralization ability bridges. Reproduced with permission.[230] Copyright 2012, Elsevier.
5.2.2. Aggregates Characterization
Microscopic flocculation assessment includes the measure-

ment of aggregate structure peculiarities such as size, shape,
density, and strength that determine the final solids-water
separation efficiency as measured by the so-called indirect
metrics discussed in Section 5.2.1. For example, the implica-
tions of developing polymer flocculants that are able to form
dense aggregates are i) a denser aggregate hold less water, thus Figure 45. A simple illustration of light scattering method.
helping with dewatering efficiency of sediments; ii) with the
same size, the denser aggregates offer faster settling veloci-
ties reducing the size of the treatment unit; and iii) the denser The slope of log–log plot of I(q) versus q gives Df.
aggregates occupy less effective volume in suspension, allowing One important condition to use Equation (22) is to sat-
for the lower solids dilution before polymer flocculation.[231] isfy the RGD approximation assumptions being i) particles
The last feature is more useful in the context of high solids of low refractive index and ii) the size of primary particles in
effluents such as oil sands tailings. the system should be smaller than the wavelength of the inci-
Fractal Dimension: Aggregates formed by polymer floccula- dent light, otherwise fractal dimension cannot be extracted
tion are characterized as a permeable cluster of particles often from Equation (22) and the slope is then called only a scaling
having irregular (fractal) shape as one shown in Figure 44. exponent,[234] although using forward light scattering, Bushell
Fractal structure of aggregates has important implications showed that the RGD approximation could still be valid for the
for the kinetics of flocculation, as the aggregates with greater dense aggregates of monodispersed latex primary particles up
hydrodynamic size have greater chances of collision to other to 4.9 µm.[235]
aggregates or primary particles, eventually forming larger clus- Imaging: Direct imaging of aggregates obtained from optical
ters. If the mass of aggregate (mass of all the primary particles) or electron microscopy can be used to estimate 2D (projected)
is m, then the mass-fractal dimension, Df, relates the collision fractal dimension Di. Different calculation methods such as
(effective) size of the aggregate, d, to its mass as box counting and sand box can be used to measure 2D fractal
dimension.[236] As an example, plotting the projected area, A,
of individual aggregates versus their perimeter, P, can give the
m = dagg
Df
, 1.0 ≤ Df ≤ 3.0 (21)
perimeter fractal dimension, Di = Dpf, as
Different methods can be used to measure fractal dimen- 2

(23)
sions, the most widely used of them are light scattering, A = P Dpf
imaging, and settling.
Light Scattering: A detailed description of light scattering by One disadvantage of imaging is that the value of the 2D
fractal aggregates can be found elsewhere.[232] But simply put, fractal dimension (Di) can be regarded as the mass fractal
if one assumes an aggregate of radius ragg formed by mono- dimension (Df =Di ) only if Df < 2 . A few solutions have been
dispersed primary particles of radius rp, then Rayleigh–Gans– suggested to use 2D fractal dimension to estimate mass fractal
Debye (RGD) approximation correlates the scattered light inten- dimensions of dense aggregates (Df > 2). One way as suggested
sity I(q) to the magnitude of the scattering vector q (Figure 45) by Liao et al. is to construct a calibration curve relating imaging
in the region where rp ≪ q− 1 ≪ ragg as[233] 2D fractal dimensions to known mass fractal dimensions of dif-
ferent samples,[237] which seems to be tedious. Using simula-
tions, Lee and Kramer created populations of about 2000 aggre-
I(q) ∝ q − Df (22) gates with different radii of gyration and estimated masses,
2D, and 1D fractal dimensions, eventually plotting calibration
curves that seem to give a good correlation between mass and
2D fractal dimensions.[238] Confocal scanning laser microscopy
(CSLM), on the other hand, is a special 3D imaging technique
for the measurement of mass fractal dimension. Assuming the
aggregate structure is isotropic and provided that thickness of
aggregate slice under the microscope is infinitely thin, Thill
et al. showed that the 2D fractal dimension obtained by the
CSLM is equal to (Df − 1).[239]
Settling: Due to nonspherical geometry, aggregates experi-
ence more drag force than spherical particles in the classic
Stokes law of settling velocity, at the same time less drag
force is expected because aggregates are permeable objects.
If gravity, drag, and buoyancy are the only forces acting on
Figure 44. A fractal aggregate of hydrodynamic (effective) diameter d that an aggregate falling down a fluid of Stokes regime (Re ≪ 1),
contains 40 primary particles. Bushell et al. showed that fractal dimension can be estimated
by the plotting of terminal velocities versus aggregates relative Aggregate Size: Aggregate size can be obtained by different
sizes as[236] methods such as laser diffraction spectroscopy, dynamic image
analysis, optical imaging, and sensing zone techniques.[233,242]
We, however, focus our discussion here to focused beam reflec-
 k  dp ( ρ p − ρ l ) g  dagg 
2 Df − 1
Ut =   (24) tance measurement (FBRM) as a relatively new and effective

 K correct  18 µ  d 
p aggregate sizing technique, that allows for on-line and in situ
characterization of aggregate size without the need for sam-
where Ut is terminal velocity of aggregate; dp and dagg are pling and dilution even in very high concentration slurries (i.e.,
the average size of primary particles and size of aggregate, 20%).[243,244]
respectively; μ, ρp, ρl, g are viscosity and density of suspending Figure 46 represents a schematic of FBRM. The optic ele-
fluid, density of primary particles, and gravitational con- ments, generating a focused laser beam (near infrared), rotates
stant, respectively; k and Kcorrect are structure prefactor and a at a fixed speed of about 2–8 ms−1 scanning across aggregates
correction factor for geometry and permeability of aggregates, in suspension close to the sapphire window. The time taken for
respectively. the beam to travel across one edge to another on the aggregate
Estimation of Df from Equation (24) is valid only if the set- or particle multiplied by the scan speed then gives a distance
tling of individual aggregates are unhindered, implying the called chord length.
condition of high dilution, for example, adding a few drops of One aggregate is likely to be scanned more than once
aggregates to a settling cylinder and recording the size and set- on multiple edges giving different chord lengths, but even-
tling velocity of many individual aggregates by a high resolu- tually the software plots all the measured chord lengths
tion camera.[237] versus their counts forming a chord length distribution plot
In an attempt to model settling velocity of aggregates in a that provides valuable information about the distribution of
thickener, Heath et al. used the hindered settling function of aggregates and particles in the system as a function of the
Richardson and Zaki[240] to model hindered settling velocity of extent of flocculation. We should stress that FBRM meas-
aggregates of fractal properties as[241] ures chord length and counts but not the number and size
of aggregates. The change in mean chord length and distri-
Df − 3
 dagg  bution over time provides useful information in assessing
dagg 2 g ( ρ p − ρ l ) 
 dp 
4.65
  dagg 
3 − Df
 the extent of flocculation by polymers. However, when using
(25)
Uh =  1 − ∅p    FBRM data to model settling velocities of aggregates[241] or to
18 µ   dp   model the flocculation,[31] one needs to calibrate their FBRM.
For example, Vajihinejad and Soares calibrated FBRM chord
where Uh is initial hindered settling velocity of aggregates length data with sphere-equivalent sizes obtained from
(initial mudline settling velocity), dagg is the average size of laser diffraction spectroscopy using sieved clay before they
aggregates obtained by FBRM, ∅p is solids (primary particles) could use FBRM data to model polymer flocculation of oil
volume fraction. sands tailings.[32] FBRM also assigns several weightings
Df can be estimated by minimizing the difference between on the chord lengths, with the square-weighted counts in
experimental hindered settling rates measured by initial macro mode being more favorable for assessing the extent
velocity of aggregates mudline in a cylinder and the hindered of flocculation with respect to the large aggregate formation.
settling velocity obtained by Equation (25) as Unweighted counts in prime mode are more sensitive to
fines and surface features.[32,243]
 U h,exp − U h,model 
2 Aggregate Density: The density of aggregates often decreases
min
Df
= ∑  U  (26) by size, mainly due to the occurrence of a greater proportion
h,exp
of aggregate–aggregate collision rather than particle–particle or
Figure 46. A view of FBRM device and its measurement principle. Reproduced with permission.[245] Copyright 2009, Mettler Toledo.
particle–aggregate collisions. It can be shown that the aggre- a recent work, Costine et al.[231] characterized the structure of
gate density, ρagg, relates to its size as aggregates formed by polymer flocculation of oil sands tail-
ings using two different classes of flocculants and found out
ρagg − ρ l  dagg  that sediments with hyperbranched functionalized polyethylene
Df − 3
= (HBf PE) produced denser aggregates than with anionic poly-
ρp − ρ l  dp  (27)
acrylamide, giving access to faster dewatering as indicated by
CST measurements.
The aggregate density can be readily calculated by Equa- Combination of aggregate size with density or fractal dimen-
tion (27) provided that the aggregate size and fractal dimension data can provide valuable insight to the effect of polymer
sion are known, but that is not always the case. Farrow and type on flocculation process. Grabsch et al.[250] studied floccula-
Warren developed a simple method to estimate aggregate den- tion of calcite in a turbulent pipe flow under tight mixing con-
sity based on the assumption that aggregates are impermeable ditions in a wide range of solids concentrations and dosages
and ellipsoidal in shape. Their method may not give the true using Magnafloc and Rheomax DR 1050 (BASF), two anionic
density of aggregates, but it serves to be a good quantitative polyacrylamide-based flocculants with different characteristics.
measure to relate the apparent aggregate density of polymer Following the mean aggregate size over the time of mixing
flocculated slurries to the process conditions and polymer prop- using an FBRM probe (inserted in angle inside the slurry)
erties. The full description of their method can be found else- allowed the authors to observe Magnafloc tendency to form
where,[231,246,247] but simply put: aggregates are diluted down to larger aggregates in low to medium range solids concentration
0.1–0.5 wt% freely falling down a cylindrical graduated vessel (2–4%) than Rheomax DR 1050. Rheomax DR 1050 was a supe-
(no interaction with other aggregates), where their settling rior flocculant for high solids slurry (6–8%) suggesting that
velocity and size are captured by a high resolution camera. The Rheomax DR 1050 consistently formed more compact aggre-
vertical and horizontal diameters of the smallest ellipse encom- gates than Magnafloc, which was further proved by the estima-
passing the aggregate, a and b, respectively, are measured from tion of fractal dimensions. Unfortunately, the authors failed to
the recorder photos, and then the following equation is used report the details of their flocculants microstructure, that oth-
to find the diameter of a sphere with the equivalent Stokes set- erwise would provide insight into the further development of
tling velocity, dst, as more optimized polymer structure.
 2 3
a 
4
dst = 0.8248 + 0.168   + 1.033 × 10 −2   − 1.264 × 10 −3   + 3.728 × 10 −5    b, 0.1 ≤ ≤ 20 (28)
a a a a
  b   b   b   b   b
The apparent density of aggregate, ρa , is then estimated by Another example is the work by Costine et al., where the
authors used the settling velocities and density measurements
18 U t µ (Figure 47) to study kaolin flocculation response to variations
ρa = + ρl (29)
dst2 g in average molecular weight of a series of anionic polyacryla-
mides of the same average anionicity under tight shear control
where Ut is the free terminal seedling velocity of aggregate in a continuous coquette flocculator.[249] The authors found out
obtained by the camera. that flocculation response to variations in molecular weight is
This method has gained much attention recently in the a strong function of the applied mixing intensity. When the
characterization of aggregates and sediment structures formed applied mixing was mild, they observed that low molecular
in the polymer flocculation of mineral and oil sands tailings, weight flocculant consistently formed denser aggregates and
from which quantitative evaluation of polymer microstructure more dose-effective settling profiles, giving access to faster set-
on aggregate structure has also been possible.[231,246,248,249] In tling velocity in low (starving) dosages. The latter was attributed
Figure 47. Aggregate density and hindered settling profiles of kaolin suspension flocculated with high and low molecular weight anionic polyacrylamide
under mild mixing. Reproduced with permission.[249] Copyright 2018, Elsevier.
Table 7. Summary of techniques for aggregate characterization. formed larger and faster settling aggregates, due to the stronger
bridges formed by long chain polymer, able to sustain higher
Aggregate fractal dimension shear rates. The implication of their result is that the choice of
Light scattering right flocculant for a dewatering process depends on the applied
• Suitable for low refractive index systems with primary particles smaller than the mixing conditions and the targeted settling velocity limit.
wavelength of the incident light.[212,236] Quantification of Aggregates Water Content: Sharma et al.
• Requires dilution and may not be used for high solids systems without the risk of used high resolution X-ray microtomography (HRXMT) and
aggregate breakage and restructuring. cryo-SEM to, respectively, quantify for the water content in
Imaging the aggregates and aggregate microstructure formed by the
• Suitable for aggregates with low fractal dimensions (Df < 2). Confocal scanning
polymer treatment of kaolinite suspensions.[251] Using different
laser microscopy is an alternative to estimate higher fractal dimensions.[239]
water-kaolinite mixtures, they constructed a calibration curve
• Requires dilution and may not be used for high solids systems without the risk of
aggregate breakage and restructuring.
between HRXMT CT number and water content, from which
Settling they could quantify the water contents in the aggregate struc-
• Equation (24) estimates mass fractal dimensions through ex situ settling tures. Cryo-SEM micrographs (Figure 48) revealed the structure
measurements, provided that the settling is unhindered, implying high dilution of flocculated clay particles. The fiber-like polymer chains were
conditions. characterized by the cryo-SEM to have lengths up to 5 μm, sug-
• Equation (25) estimates mass fractal dimensions through ex situ/in situ settling gesting the polymer chain(s) are stretched between two points
measurements, and does not require dilution. A good option for continuous of adsorption contact giving rise to bridging effect; this length
measurement of fractal dimensions in industrial settings.[241] is way longer than polymer chain hydrodynamic size in solu-
• In practical applications, fractal dimension measurements are used for floc-
tion, about 0.2−0.3 μm for average molecular weight of 107.[7]
culation modeling (population balance models) and estimation of the rate of
In addition, the measured thickness of polymer chains up to
aggregates settling and sediment consolidation.
80 nm suggests stacking of the several polymer chains forming
Aggregate size
the strings shown in Figure 48. Table 7 summarize the micro-
Imaging scopic methods used for the characterization of aggregates.
• Tedious process requiring multiples sizing (image analysis) on several samples.
• Requires dilution and ex situ measurements for more accurate sizing.
• Can be used for in-line sensors as an alternative to human eye assessment in
industrial applications, when rough estimation of the flocculation state (e.g., 6. Conclusion
optimal polymer addition) is desired.
Light scattering The great demand for saving water resources for future gen-
• Requires dilution, not a reliable option for high solids flocculation. erations and protecting the environment from pollutants has
• Good choice for the sizing of the primary particles prior to flocculation. driven researchers to synthesize efficient polymer flocculants
FBRM that could increase the performance of dewatering units
• Gives real time in situ measurements of aggregate chord length; suitable choice with minimum cost. Our review indicates that there has
for low and high solids systems. been a large body of literature in the recent years focusing
• Can be used in line in industrial applications to assess the state of flocculation. on introducing new polymer materials as water soluble floc-
May need to be periodically cleaned to avoid probe deposition with dirt and
culants for a variety of applications including wastewater
organics.
treatment, mineral processing, and oil sands tailings treat-
• Obtaining actual aggregate size requires calibration with other techniques such
as imaging or light scattering.[32,241]
ment. We reviewed the recent examples in the development
• Not a good choice for the sizing of the primary particles prior to flocculation of synthetic, bio/natural, and stimuli-responsive flocculants.
because the sizing resolution is above 1 µm.
• A powerful choice for flocculation modeling studies. When coupled with com-
putational fluid dynamics (CFD), it gives an online map of solids concentration
within large scale treatment units such as thickeners or pipe flows.[252]
Aggregate density
• The current methods, such as Equation (29), all require dilution prior to meas-
urement, increasing the risk of aggregate restructuring.
• The implication of using flocculants that give high density aggregates in indus-
trial applications are requiring lower dilution prior to flocculation in high solids
and easier dewatering primarily because inter-aggregate liquor is easy to be
removed than intra-aggregate liquor.[231,250]
• A good measure of impact of flocculant properties on the structure of
aggregates.[231]
to the presence of larger number of short chains in low molec-

ular weight polymer than a fewer number of long chains in high
molecular weight polymer that eventually was not being able to
form enough bridges in low dosages. In more intense mixing,
however, the difference between aggregate density was almost Figure 48. Cryo-SEM image of polymer flocculated kaolinite. Reproduced
diminished and high molecular weight flocculants consistently with permission.[251] Copyright 2017, Elsevier.
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Flocculation: The Big Picture www.mme-journal.de

Water Soluble Polymer Flocculants: Synthesis,

unique requirements of some challenging

This aggregation is different from that achieved by the manip-

3. Recent Advances in the Development of Water

Synthetic flocculants are made by polymerization of water sol-

poly(acrylamide-acryloyloxyethyl trimethyl ammonium chlo-

from the removal of the template (Figure 8). Surface porosity

Figure 6. a) A randomly distributed cationic copolymer versus b) a cati-

Table 2. Summary of the recently developed synthetic polymer flocculants.

Polymer Charge type Properties Synthesis method Medium Reference

FRP, free radical polymerization.

had core-brush topologies, as shown in Figure 11. They were

3.2.3. Alginate-Based Materials

Alginate is a linear anionic polysaccharide

presence of inorganic ions. They also noted that the presence

Base polymer Polymer modification Synthesis method Media Comment Reference

TOC, total organic carbon; CNC, cellulose nanocrystal.

The critical solution temperature of floc-

in charge state of these polymers. A com-

3.3.2. pH-Responsive Flocculants

Another class of stimuli-responsive floccu-

Table 4. Summary of stimuli-responsive flocculants.

Flocculant type Polymer Properties Synthesis method Medium Reference

emulsion polymerization does not have this limitation. Inter-

Table 6. Summary of techniques for the quantification of microstructure of flocculants.

effluent wherein organic matter affect the interactions between

angstroms. It can quantify intermolecular forces in nano-

Another similar method to SFA is AFM that has been used to

A number of studies on the interactions between parti-

have additional functionality, such as positive charges, their

Plotting the t/V against V, the specific resistance to filtration

increased functionality in flocculant to overcome the complex.

5.2.2. Aggregates Characterization

Microscopic flocculation assessment includes the measure-

Different methods can be used to measure fractal dimen- 2

Ut =   (24) tance measurement (FBRM) as a relatively new and effective

to the presence of larger number of short chains in low molec-

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Ut =   (24) tance measurement (FBRM) as a relatively new and effective