International Journal of Mining Science and Technology 29 (2019) 745–755

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International Journal of Mining Science and Technology

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

Evaluation of flocculation characteristics of kaolinite dispersion system

using guar gum: A green flocculant
R.K. Dwari a,⇑, B.K. Mishra b
a
Mineral Processing Department, CSIR-Institute of Minerals and Materials Technology, Bhubaneswar 751013, India
b
Indian Institute of Technology, Goa 403401, India

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

Article history: This paper reports the systematic investigation on the flocculation, sedimentation and consolidation
Received 5 February 2018 characteristics of kaolinite using guar gum as a green flocculant. In-situ flocculation behavior of kaolinite
Received in revised form 17 January 2019 at various pH, guar gum dosages, and ionic strength were studied using a light scattering technique. The
Accepted 11 June 2019
effect of these parameters on the settling rate, solid consolidation, and supernatant liquid clarity was
Available online 18 June 2019
recorded. The morphology of kaolinite and flocculated kaolinite aggregates were analyzed using
FESEM. The morphology studies suggest that it is poorly crystalline with multiple steps on edge, broken
Keywords:
edge; laminar with high aspect ratio and have rough basal surface. The complex irregularity on the basal
Guar gum
Dewatering
surface and the presence of multiple steps in the edges, broken edges (hydroxyl groups) have facilitated
Kaolinite the guar gum adsorption. The isoelectric point of kaolinite is pH 3.96. The pH, ionic strength and floccu-
Light scattering lant dosage have a significant effect on the kaolinite settling rate. The guar gum has exhibited excellent
Morphology turbidity removal efficiency at pH 5. The turbidity removal is inefficient at pH 10. However, guar gum has
Flocculation shown high turbidity removal with 80% transmission at pH 10 in the presence of a KNO3 electrolyte.
Ó 2019 Published by Elsevier B.V. on behalf of China University of Mining & Technology. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
The removal of water from mineral tailings by flocculation is
one of the major mineral processing activities. Recently, synthetic
flocculants like polyacrylamide are in use for the sedimentation of
minerals from the process tailings and wastewater. However, their
environmental compatibility is a matter of great concern. Pre-
sently, the demand for green flocculants is increasing due to their
environmental compatibility.
Guar gum is also known as guaran. It is a natural non-ionic
polysaccharide composed of galactose and mannose. It is a chain
of (1 ? 4)-linked b-D-mannopyranose units with a-D-
galactopyranose units connected to the mannose backbone
through (1 ? 6) glycosidic linkages. The poly-mannose chain ran-
domly substituted with galactose units at mannose-to-galactose
ratio of 1.8–1.0 [1,2]. The molecular weight of guar gum is
1
105 to 20
105 [1,2].
Ma and Pawlik [3] studied the adsorption behavior of guar gum
on kaolinite and other oxide minerals at different pH, background
electrolyte, and ionic strength. One of the major conclusions of
their study is that the adsorption density of this polysaccharide
⇑ Corresponding author.
E-mail address: rkdwari@immt.res.in (R.K. Dwari).
does not depend on the pH. However, there is a significant increase
in adsorption density on kaolinite surface in the presence of chao-
tropic K+ ion. The hydrogen bonding is the primary mechanism of
guar gum adsorption onto the kaolinite surface. The polymer
adsorbed onto the mineral surface through hydrophobic interac-
tion, hydrogen bonding, chemical and electrostatic interaction
[4–8]. Wang et al. [9] concluded that the hydrogen bonding is
the principal force for the adsorption of guar gum onto the talc sur-
face. Mhlanga et al. [10] also reported the guar gum adsorption on
several pure minerals such as talc, pyroxene, plagioclase, chromite,
and chalcopyrite. The above studies show that guar gum has a nat-
ural affinity towards these mineral surfaces. The majority of these
works were carried out to understand its application as a depres-
sant in flotation and selective flocculation system. However, not
many reports are available regarding its possible use as a floccu-
lant. The effect of guar gum as flocculant on the flocculation
characteristics of kaolinite particle regarding floc growth, colloidal
stability and, solid consolidation are not well understood. More-
over, the flocculation characteristic method is poorly studied.
Guar gum has many applications in mining and mineral pro-
cessing industries. Many researchers have reported its use in froth
flotation and flocculation process [9,11]. In the froth flotation pro-
cess, guar gum is used as a depressant for talceous gangue minerals
for the flotation of base metals and platinum group metals bearing

https://doi.org/10.1016/j.ijmst.2019.06.001
2095-2686/Ó 2019 Published by Elsevier B.V. on behalf of China University of Mining & Technology.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
746 R.K. Dwari, B.K. Mishra / International Journal of Mining Science and Technology 29 (2019) 745–755
ores [9,11]. Guar gum adsorbs onto the talc surface to make it
hydrophilic. It also has application as a binder for water-
insoluble slimes in the potash flotation process [12]. Guar gum
and grafted derivatives of guar gum have been explored as floccu-
lants for dewatering applications [13–15]. Nasim et al. [13] have
reported a high settling rate of kaolinite using guar gum and poly-
vinyl alcohol grafted guar gum as flocculants. Apart from guar gum
other polysaccharides and their grafted derivative such as chitosan
[16,17], starch [18], xanthan gum [19] and tamarind kernel [20]
have also been explored as flocculants.
The Indian iron ore contains a significant amount of gangue
minerals such as silicates and aluminium silicates. These minerals
liberate at finer sizes. Therefore, the tailings generated in an iron
ore processing plant are fine in size. One of our earlier studies sug-
gests that d80 of the tailings is 12 mm. The tailings contain 5%-10%
solid (w/w) and the Al2O3, SiO2 content in the tailings are 18% and
14%, respectively [4]. The fine particle causes a serious problem in
the dewatering process. Thus, the consolidated solid in the thick-
ener contains high moisture, which in turn creates technical and
economic difficulties in handling, disposal, and water removal.
The basal faces of 1:1 tetra-octahedral aluminosilicate consists
of tetrahedral siloxane (-Si-O-Si-) species and octahedral, alumina
(Al2O3) sheet [21]. Van Olphen [21] showed that the basal faces
having a siloxane structure carry a permanent negative charge
due to the isomorphous substitution of Si4+ by Al3+ groups. Also,
aluminum (Al-OH) and silanol (Si-OH) groups occur at the edges.
Therefore, the edge faces are charged by protonation and deproto-
nation of hydroxyl groups depending on the pH [21,22]. These par-
ticles are highly charged at neutral and alkaline pH and shows
stable dispersion behavior. Therefore, authors choose kaolinite an
aluminium silicate to study its flocculation characteristics in the
presence of guar gum.
The design of a dewatering system requires a thorough analysis
of the solid-liquid system and slimes stability behavior. The stabil-
ity of particle can be changed by controlling the pH, ionic strength,
addition of flocculant and coagulant [4,23–28]. In flocculation, the
fine particles interact with the flocculating agent and aggregate to
form flocs. The flocs settle rapidly under the influence of gravity.
The characteristics of floc decide the rate of settling and moisture
contents of consolidated tailings [29]. The floc characteristics
depend on several factors such as particle surface chemistry, size
distribution, density, shape; viscosity and dielectric constant of
suspension; chemical nature, molecular weight, charge and charge
density of the flocculants [30,31].
The environmental policies have enforced legal rules for the dis-
posal of waste by the mineral industries. It is essential to redesign
the dewatering operation to meet the current challenges. The pre-
sent work has been undertaken to study the sedimentation behavior
of kaolinite using guar gum as a flocculant. The spectroscopic tech-
niques are used to understand the influence of different process
parameter on the flocculation and consolidation characteristics.
2. Experimental
2.1. Materials and procedure
The kaolinite sample was supplied by M/s. Ashapura Minechem
Ltd., Trivandrum, India for the sedimentation studies. The particle
size of the kaolinite sample was measured using Malvern particle
size analyzer (Mastersizer 2000). The surface area and density of
the kaolinite sample were determined by using smart BET surface
analyzer (SORB 92/93) and Helium-Mercury pycno meter (Smart
Pycno 30), respectively.
Guar gum was used as a flocculant for settling studies of kaolin-
ite dispersions. It was procured from M/s. Otto Chemicals Ltd,
India. The polysaccharide solution was prepared by dissolving
0.1 g of guar gum in 100 ml of distilled water. The guar gum pow-
der was poured into continuously stirred distilled water using a
magnetic stirrer. It was further stirred for 6 h to ensure complete
dissolution of the guar gum in water. The stirring rate was main-
tained at 1100 rpm during the preparation. The flocculant solution
was prepared every day to maintain its freshness. The ionic
strength of the solution was maintained using potassium nitrate,
and the pH was regulated by using analytical grade sodium
hydroxide and hydrochloric acid solutions.
2.2. Kaolinite suspension
The kaolinite dispersions of 5% solids (w/w) were prepared in
distilled water for the flocculation characteristic studies. The slurry
was agitated at 800 rpm for two hours to obtain the homogeneity.
The pH of slurry was maintained at pH 5 and pH 10. For each
experiment, 20 ml of the slurry was pipetted out from the homoge-
neous slurry and put into the glass cell for the light scattering anal-
ysis. The suspension was prepared with a known volume of KNO3
to study the effect of electrolyte on kaolinite flocculation and sed-
imentation at pH 10.
2.3. Zeta potential studies
The zeta potential (f) of kaolinite suspension was measured by
potentiometric titration using a Zeta probe (Colloidal Dynamics
Ltd., USA) instruments. The measurement was carried out on
kaolinite suspensions of 5% solids (w/w) dispersed in 103 mol
KNO3 electrolyte background solution. The electrolyte background
was used to avoid any effects of inconsistent surface conductance
on zeta potential [25]. The complete dispersion of the slurry sus-
pension was ensured using ultrasonic vibration. The zeta potential
of dispersed kaolinite suspension was measured at the slurry agi-
tation speed maintained at 250 rpm. The zeta potential measure-
ments were carried out in the pH range of 3–12. The detail zeta
potential measurement procedure has been discussed in our earlier
work [4].
2.4. Multiple light scattering measurements
The sedimentation/suspension stability of kaolinite dispersion
was studied by using optical analyzers (TUBISCAN LABexpert) based
on multiple light scattering technique. The stability of the disper-
sion was monitored by measuring the transmittance and backscat-
tering of the pulsed near-infrared light (k = 880 nm). Turbiscan
measurements were carried out for the entire vertical length of
the glass cell at regular time intervals. The transmittance detector
received the light that passed through the dispersion at an angle of
180° concerning the source while the backscattering detector
received backscattered light by the dispersion at an angle of 45°.
The technique is used to measure the transmittance and backscat-
tering of suspension. The method helped to monitor the particle in
the clarifying zone and the bed consolidation.
Approximately 20 ml of 5% (w/w) kaolinite dispersions was
taken in the glass cell of the turbiscan equipment. The height of
the cell filled with the suspension was 40 mm. The temperature
was maintained at 30 ± 2 °C during the analysis. A known volume
of freshly prepared starch solution was mixed into the kaolinite
dispersion, to study the effect of guar gum on the flocculation
behavior of kaolinite dispersion. Then the cell was closed with a
cap and was shaken by making it up and down for 20 times for bet-
ter mixing of both. The vertical glass cell height was scanned 100
times in 50 min at an interval of 30 s. After the scanning, the cell
was removed from TURBISCAN LABexpert and kept for 24 h and then
the height was measured. After the scanning the rate of settling,
 R.K. Dwari, B.K. Mishra / International Journal of Mining Science and Technology 29 (2019) 745–755 747

backscattering, transmission, floc growth, were calculated using backscattering percentage in the thickening zone increases as more
TURBISCAN LABexpert software. particles settled to the bottom.
The diffuse reflectance in terms of back scattering is considered
to obey Eq. (1) [32]: 2.6. Particle and floc morphology
(
BS ¼ p1ffiffiIffi
ð1Þ The surface morphology of kaolinite particles and their flocs
I ðd; /Þ ¼ 3/ð1g
2d
ÞQ s formed at pH 5 and 800 g guar gum/tonne of solid dosage was
studied using the scanning electron microscope (FESEM), Supra
where, BS is the diffuse reflectance at 45° detector, %; I* is the pho-
55, Carl Zeiss, Germany. The kaolinite particles were dispersed in
ton transport mean free path; d is the particle diameter, lm; / is
an aqueous solution and a drop of this dispersion was carefully
particle volume fraction, %; g and Qs are optical parameters accord-
placed on aluminium foil. The suspension drop was dried at room
ing to Lorenz and Mie theory [33]. Hence, backscattering measure-
temperature and put on an FESEM stub to determine its morphol-
ment made by the Turbiscan directly depends on the particle mean
ogy. In case of flocs, they were carefully collected from the consol-
diameter (d) and volume fractions (/). Therefore, Turbiscan LAbExpert
idated sediment and placed on aluminium foil. After drying, the
enables the computation of I*, which represents the dispersion state
floc was placed on a FESEM stub for studying floc morphology
of the product. The computation of the particle mean diameter (d) is
and external surface structure. The consolidated sediment was also
possible by knowing the volume fraction (/) and the refractive
sheared using a magnetic stirrer rotating at 150 rpm. The flocs
indices of disperse and the continuous phase. The Lambert-beer
were collected at a different interval of time and subjected to mor-
law gives an analytical expression of the transmitted flux T (%) mea-
phology investigation as mentioned above.
sured by the turbiscan as a function of the photon mean free path (I)
and expressed as Eq. (2) [33].
2r i
3. Results and discussion
T ðI; ri Þ ¼ T o e i ð2Þ
3.1. Material characterization
where To is the transmittance of continuous phase and ri is the mea-
surement cell internal diameter. The particle size distribution of kaolinite sample is shown in
Fig. 2. The figure shows that the average particle size (d50) of the
2.5. Flocculation studies kaolinite is 3.69 mm whereas d90 is 24 mm (Fig. 2). The BET surface
area and density of kaolinite sample is 17.75 m2/g and 2520 kg/m,
The flocculation studies were carried out using the multiple
light scattering techniques with 5% (w/w) kaolinite dispersions.
The experiments were conducted at pH 5 and pH 10 using different
dosages of flocculant in the range of 0–1000 g guar gum/tonne of
solid, i.e., 0, 50, 100, 200, 400, 600, 800, 1000 g/tonne of solid.
The Turbiscan light scattering data (both transmission and
backscattering) obtained for kaolinite dispersions in distilled water
at pH 5 without starch dosage is shown in Fig. 1. The source infra-
red light cannot transmit through a stable dispersion and get scat-
tered by fine suspended particles. The backscattered detector
detects the scattered light. A high percentage of backscattering
suggests stable dispersions. However, as the particles get aggre-
gate, the sedimentation occurs. The particulates present in the sus-
pension decreases which allows the source light to pass through
the medium and detected by the transmittance detector. Fig. 1 sug-
gests that the transmission percentage in the clarified zone and Fig. 2. Particle size distribution of kaolinite.

Fig. 1. Transmission and backscattering data of kaolinite dispersion at pH 5.

748 R.K. Dwari, B.K. Mishra / International Journal of Mining Science and Technology 29 (2019) 745–755

respectively. The surface morphology of kaolinite particles is

shown in Fig. 3. The SEM images in Fig. 3a demonstrates that the
kaolinite has a complex surface structure on the extensive basal
surface. The dimension of the particles is in the range from
100 nm to 2000 nm. The high magnification of particle shows that
the particles are poorly crystallized with individual crystallite,
micro-islands, microcrystallite on the extensive basal surface
(Fig. 3b). The multiple steps in the edge and broken edges on the
kaolinite particle are also evident (Fig. 3c). Investigation on many
areas of the particle shows that it has lamellate plates with high
aspect ratio, edge to face platelet orientation and rugged basal face
(Fig. 3d).
Fig. 4. Zeta potential of 5% (w/w) kaolinite dispersion in 0.001 mol KNO3
background electrolyte.
3.2. Zeta potential studies

The zeta potential of kaolinite dispersions at 0.001 mol KNO3
background electrolyte solution is shown in Fig. 4. The figure
shows that the isoelectric point of kaolinite is pH 3.96. This value
is close to the value observed by other workers [34–36]. Fig. 4
shows that the zeta potential of kaolinite at pH 5 and 10 are
20 mV and 79 mV, respectively. The result suggests that the col-
loidal kaolinite particulates are highly negatively charged at alka-
line pH indicating strong electrostatic repulsion existing between
them.
3.3. Effect of starch dosages on the rate of settling
The effect of starch dosages on the particulate migration veloc-
ity or rate of settling at pH 5 and 10 are calculated from the light
scattering data and is shown in Fig. 5. Fig. 5a shows the rate of set-
tling of kaolinite at pH 5 at different dosages of guar gum. The fig-
ure demonstrates that there is a time lag on the settling of particles
in the absence of starch and they start to settle at 186 s. The time
lag period is attributed to the time taken by the particulates to
form aggregate. Further, there is an exponential increase in the rate
of settling. At 248 s, the particulates reached the maximum settling
rate of 0.36 mm/min and further maintained a steady state of set-
tling. The time lag decreases with the addition of guar gum to the
kaolinite suspension. The time lag observed for 50, and 100 g guar
gum/tonne of solid dosages is 62 s while it is 31 s for starch
dosages between 200 and 800 g guar gum/tonne of solid. The fig-
ure shows that the particle settling rate increases with the increase
in starch dosage, and maximum settling rate is observed at
800 g guar gum/tonne of solid dosage. The maximum settling rates
observed at 50, 100, 200, 400, 600 and 800 g guar gum/tonne of
solid dosages are 0.77, 1.09, 2.25, 2.82, 4.44 and 4.78 mm/min,
respectively. It is fascinating to observe that the maximum settling
rate is obtained at 93 s, and a curve peak is observed at this point. A
steady-state settling rate is observed after reaching the maximum

Fig. 3. High resolution FESEM images of kaolinite colloidal fraction (a) kaolinite particulates; (b) poorly crystallised with individual crystallite, microislands, micro crystallite
on the extensive basal surface; (c) multiple steps in the edge, broken edges; (d) laminated plates with high aspect ratio, edge to face platelet orientation, rugged basal surface.
 R.K. Dwari, B.K. Mishra / International Journal of Mining Science and Technology 29 (2019) 745–755
Fig. 5. Effect of guar gum dosages on the rate of settling of kaolinite dispersions at (a) pH 5 and (b) pH 10 in distilled water.
settling velocity at lower starch dosages, i.e., 50–100 g guar gum/
tonne of solid.
Fig. 5b shows the rate of settling of kaolinite particle at different
dosages of starch at pH 10. The result shows that the rate of set-
tling increases with the increase in starch dosages. The maximum
settling rate is obtained at 31 s for each dosage, and at this point, a
peak curve is also observed. The maximum settling rate occurred at
0, 50, 100, 600, 800, 1000 g guar gum/tonne of solid dosages are
0.35, 1.01, 1.4, 2.26, 3.74 and 3.69 mm/min, respectively. The set-
tling rate of kaolinite particles decreases continuously after attain-
ing the maximum settling velocity. The stability of kaolinite
suspension at different dosages of starch at pH 5 and pH 10 after
24 h are shown in Fig. 6a and b, respectively. Although a settling
rate is obtained at pH 10, unlike pH 5, no phase separation is
observed at lower dosages. However, a phase separation occurs
at the higher starch dosage (1000 g guar gum/tonne of solid). The
consolidated sediment height increases with the increase in the
starch dosage.
Figs. 5a and 6a reveals that particle aggregation occurs without
the addition of flocculating reagent at pH 5, which resulted in pre-
cise solid and liquid phase separation. The rate of solid-liquid
phase separation expedites with the increase in starch dosages.
Several researchers reported that the isoelectric points of Al-OH
and Si-OH edge sites are between pH 5.0 to 7.0 [35,37,38]. The
edge-face kaolinite structures exist because of the electrostatic
attraction of positively charged edges and negatively charged basal
faces before flocculation at pH below the isoelectric point of edge
hydroxyls. The pH of kaolinite slurry is 6.38. It is in between the
isoelectric point of hydroxyl edge sites. The edge face attraction
and edge face structure are expected at this pH. The FESEM analy-
sis of floc structure confirmed the presence of the edge-face struc-
Fig. 6. View of kaolinite dispersions stability at 24 h (a) pH 5 and (b) pH 10 after addition of guar gum dosages.
749
ture. At pH above the isoelectric point of edge hydroxyls, both the
edge and basal surface potential are negative which make the sys-
tem deflocculated [39]. Du et al. [29] reported that self-aggregation
might also occur due to hydrogen bonding between SiAOH and
AlAOH edge sites at alkaline pH. The step sites of the poorly crys-
tallized kaolinite may produce some hydrogen bonded edge face
and face-face structures. Therefore, at pH 10 the kaolinite particles
were highly negatively charged and due to electrostatic repulsion
very fine colloidal particle remained in the suspension. However,
with the addition of starch dosages the –OH sites available on
the poorly crystallized edge and basal faces facilitate the adsorp-
tion of organic polymer flocculants by hydrogen bonding [29].
Ma and Pawlik [3] carried out guar gum adsorption studies on
various types of mineral surfaces such as alumina, rutile, hematite,
quartz, and kaolinite as a function of pH, ionic strength and back-
ground electrolyte. They showed that adsorption density of guar
gum on these minerals surface is very much pH independent and
reported that hydrogen bonding is the primary mechanism of guar
gum adsorption onto the mineral surface. In the present investiga-
tion, it is observed that the settling rate of kaolinite particles
increased with the increase in starch dosages at pH 5 and pH 10.
The results confirmed the guar gum adsorption onto the kaolinite
surface at both acidic and alkaline pH and induced higher floccula-
tion at former pH than the later. The observations commensurated
well with the earlier study done by Ma and Pawlik [3]. A significant
amount of highly charged kaolinite particles are not settled at alka-
line pH 10 and remain suspended in the solution. After one hour of
settling studies, the supernatant solution was decanted and dried.
The amount of kaolinite present in the supernatant at different
starch dosages is shown in Fig. 7. The figure shows that the kaolin-
ite particle in the clarifying zone decreases with the increase in
750 R.K. Dwari, B.K. Mishra / International Journal of Mining Science and Technology 29 (2019) 745–755

starch dosage. About 22% of kaolinite particles remain unsettled

without any starch. However, at 1000 g guar gum/tonne of solid
dosage, only 7% of kaolinite stay in the suspension. The rest of
the particles are flocculated and get settled at the bottom.

3.4. Effect of starch dosages on transmission and backscattering

The multiple light scattering measurements were carried out on

Fig. 7. Effect of guar gum dosages on the kaolinite concentration in the supernatant
after 1 h of addition of the starch at pH 10.
a 5% (w/w) kaolinite suspension using different dosages of guar
gum at pH 5 and 10. The scanning process monitors the downward
particle movement in the suspension. The particle moves vertically
downward by gravity and consolidated at the bottom and formed a
clarifying and thickening zone at the top and bottom, respectively.
The effect of guar gum on the percentage transmission and
backscattering as a function of time is shown in Figs. 8 and 9 at
pH 5 and 10, respectively. The backscattering (%) is analyzed at dif-
ferent starch dosages in the entire length of the cell, clarifying zone
and the thickening zone at pH 5 (Fig. 8a, c and d) and pH 10
(Fig. 9b, c, and d), respectively. The transmission (%) is analyzed

Fig. 8. Effect of guar gum dosages on the (a) backscattering (%) in entire length of cell; (b) Transmission (%) in clarification zone; (c) backscattering (%) in clarification zone; (d)
backscattering (%) in thickening zone at pH 5.
 R.K. Dwari, B.K. Mishra / International Journal of Mining Science and Technology 29 (2019) 745–755
for the clarification zone of the cell at pH 5 (Fig. 8b) and pH 10
(Fig. 9a) at different starch dosages. Fig. 8a shows that the
backscattering (%) decreases with time in the entire length of the
cell. The backscattering (%) also decreases with the increase in guar
gum dosage. Similar observations are also found in the clarifying
zone (Fig. 8c). The backscattering (%) decreases with time, and
the fastest decrease is observed at higher starch dosages. The
backscattering is decreased from an initial value of 50% to 15% at
higher starch dosages. On the other hand, the backscattering (%)
is increased with time in the thickening zone (Fig. 8d). The particle
consolidation and compaction took place with time in the thicken-
ing zone making it more opaque for the source light to penetrate
through the bed. Therefore, the backscattering (%) increases with
time at each flocculant dosage. Also, it is observed that the
backscattering curves shifted towards left with the increase in
starch dosages. The particle flocculates and settle fast at higher
guar gum dosage and attended a steady state compaction. The
steady-state backscattering (%) are attained in 3000, 2883, 2635,
1395, 450, and 450 s, at 0, 50, 100, 200, 400, 600 and
800 g guar gum/tonne of solid dosage, respectively. The corre-
sponding steady backscattering (%) at these dosages are 57.21,
61.86, 64.88, 63.89, 62.2, 61.55 and 61.55, respectively. The highest
backscattering of 65% is observed at 100 g guar gum/tonne of solid
flocculent dosage. However, with further increase in the starch
Fig. 9. Effect of guar gum dosages on the (a) transmission (%) in the entire length of the cell; (b) backscattering (%) in the entire length of the cell; (c) backscattering (%) in
clarification zone; (d) backscattering (%) thickening zone at pH 10.
751
dosages the backscattering (%) decreases. The floc size increases
with the increase in starch dosage. The consolidated bed with large
flocs increases the bed height as well as porosity. Therefore, bed
opaqueness to source light decreases and backscattering (%)
decreases at a higher dosage. Fig. 8b shows that the transmission
(%) in the clarification zone increases with time and with the
increase in starch dosages. About 85% transmission is observed at
800 g guar gum/tonne of solid dosage with no particle in suspen-
sion at this zone.
The transmission (%) in the entire length of the cell, backscatter-
ing (%) in the entire length of the cell, clarifying zone and thicken-
ing zone are shown in Fig. 9a–d, respectively at pH 10 and different
guar gum dosages. No transmission is observed with time at vari-
ous starch dosages at pH 10 (Fig. 9a). The zeta potential of kaolinite
is 79 mV at pH 10. That means the electrostatic repulsion
between the particles is high. Therefore, their stability in water is
high. Even at the high starch dosage (1000 g guar gum/tonne of
solid), there are 7% of the particle remained in the suspension
which obstructs the transmission of source light through the med-
ium. However, the backscattering (%) decreases in the entire cell
length with time (Fig. 9b). The backscattering (%) decreases at a
faster rate with the increase in starch dosages. The backscattering
is reduced from 49% to 38% at 1000 g guar gum/tonne of solid
starch dosage. The backscattering (%) in the clarification zone
752 R.K. Dwari, B.K. Mishra / International Journal of Mining Science and Technology 29 (2019) 745–755

shows that it decreases with the increase in time and starch dosage
(Fig. 9c). It is reduced from 49% to 24% at 1000 g guar gum/tonne of
solid dosage. However, the backscattering in the thickening zone
shows that it increases with time (Fig. 9d). The higher backscatter-
ing (%) in this zone without the addition of starch is related to the
size of the aggregated settled mass as explained earlier.
3.5. Effect of starch dosages on floc growth, surface area per volume
The effect of starch dosages on the rate of floc growth and sur-
face area per volume of floc were calculated using Turbiscan lab
expert software and are shown in Figs. 10 and 11 at pH 5 and pH
10, respectively. Fig. 10a shows the floc growth at different dosages
(0–800 g guar gum/tonne of solid) at pH 5. The figure shows that
the initial kaolinite particle size is 5–6 mm. The results indicate that
at 500 s, the particles start to aggregate, and the size increases up
to 348 mm at 0 g guar gum/tonne of solid dosage. With further
increase in time, there is an exponential increase in kaolinite par-
ticle growth. The time lag exists at the start of aggregation. After
the addition of starch (50 g guar gum/tonne of solid), the time lag
in the floc formation is reduced to 186 s. The floc formation is
instantaneous at higher dosages of starch. The highest rate of floc
formation is observed at 800 g guar gum/tonne of solid dosage.
At this dosage, the rate of sedimentation is also highest. Fig. 10b
shows that the particle surface area per volume decreases with
time. Also at a particular time, it decreases with the increase in
guar gum dosage. Fig. 11a shows the rate of floc formation at dif-
ferent dosages (0–1000 g guar gum/tonne of solid) at pH 10. The
result shows that the floc growth is slow at a lower concentration
of starch and increases with the increase in starch dosage. The par-
ticle size is increased from 5 mm to 9.5 mm at a very high dosage of
starch (1000 g/t). The surface area per volume of the kaolinite par-
ticle decreases with the increase in starch dosage (Fig. 11b) which
is corresponding to the observation made in Fig. 11a.
According to the DLVO (Dejaguin-Landau-Verwey-Overbeek)
theory [40,41], the stability of colloidal dispersions is due to the
existence of the potential energy barrier between the particles.
The barrier arises as a result of the interactions of the electric dou-
ble layer and Van der Waals force of attraction. The van der Waals
forces are very strong at a short separation distance. The rate of
aggregation of these particulates depends on the resultant net
forces. The aggregation will reduce at higher net resultant force.
Rao et al. [42] showed that for the kaolinite particles, the resultant
net force increases from 10 KBT to 109 KBT in aqueous solution
with an increase in pH from 2.5 to 11.5. Verwey and Overbeek
[41] and Lu et al. [43] reported that there would not be any

Fig. 10. Effect of guar gum dosages on (a) rate of change of floc growth and (b) rate of change of the surface area per volume of kaolinite dispersions at pH 5.

Fig. 11. Effect of guar gum dosages on (a) rate of change of floc growth and (b) rate of change of surface area per volume of kaolinite dispersions at pH 10.
 R.K. Dwari, B.K. Mishra / International Journal of Mining Science and Technology 29 (2019) 745–755
aggregation if the energy barrier is more than 15 KBT. Therefore,
the particles will aggregate at isoelectric point (kaolinite isoelectric
point: pH 3.96) with a smallest potential energy barrier. The elec-
tric double layer repulsion increases above the isoelectric point
and potential energy barrier increase significantly at higher pH
that prevents the particle from aggregation. As mentioned above,
in an aqueous solution there was a time lag of 500 s before the par-
ticle aggregation starts at pH 5, and the energy barrier slowed
down the rate of floc growth. The energy barrier is very high at
alkaline pH with high electric double layer repulsion. Therefore,
no floc growth is observed at pH 10 with highly stable kaolinite
dispersion in aqueous solution. The results are good agreement
with the observation made by Rao et al. [42], and kaolinite disper-
sion stability in aqueous solution corroborated well to the DLVO
theory. However, the effect of guar gum on the DLVO forces
between kaolinite particles needs to establish further.
3.6. Kaolinite floc morphology
Fig. 12 show the SEM micrographs of kaolinite flocs formed at
pH 5 and 800 g guar gum/tonne of solid dosage. The SEM images
of flocs obtained from the consolidated sediment bed are shown
in Fig. 12a and b. The figure shows that the kaolinite particles
has formed the aggregate structures during flocculation using guar
gum by edge-edge, edge face, and face-face interaction. The edge
face interaction leads to form a cavity in the floc aggregates. The
sizes of the cavity were varying from 100 nm to 2 mm. The floc
aggregates are characterized by the presence of extensive particle
Fig. 12. High resolution SEM images of kaolinite floc at pH 5 and 800 g guar gum/tonne of solid dosage (a and b) porous flocculated kaolinite, face face and edge face flakes
structure; (c and d) stretching of flocs by shearing action at 15 min, adsorbed starch onto kaolinite clearly visible, fibrous network of starch chain connecting edge edge, edge
and basal face.
753
network and cellular structure known as card house structure. A
large conglomeration of particles is also observed in the floc aggre-
gates. The SEM image provides direct insight into the real aggre-
gate structure in an aqueous medium without disturbing the
aggregate structure. In an attempt to microscopically investigate
the flocculation bridging mechanism, the sediment floc aggregates
are sheared. They are sheared by using a magnetic stirrer and
aggregates are collected at a different interval of time. Fig. 12c
and d shows the SEM images of floc aggregate collected at
15 min. The figure shows the stretch of particles in the floc aggre-
gate by shearing action with a fibrous network of starch chains. It
is visible that fibrous network of starch chains are bridging the
edge-edge and edge-basal surface of kaolinite particle. The kaolin-
ite particle characteristics suggest that the particles are poorly
crystallined with complex nanometer scale irregularity with bro-
ken steps, edges, the presence of microcrystallite and micro-
islands on the extensive basal surface. These edges are the sites
for the polysaccharide adsorption and bridging formation. The
bridge formations are observed between the edge-edge, edge face
of kaolinite particle with polysaccharide chains. The high amount
of starch adsorption on the edges and the basal surface is visible
due to complex irregularity. The bridge is formed between these
surface sites as proposed by Du et al. [29] and Nabzar et al. [44].
The polysaccharides adsorbed to the surface sites (hydroxyl
group on the surface), oriented to the bulk of the solution
and adhered to the other particle thereby facilitate the bridge
formation. These polysaccharides are also adsorbed at multiple
sites on the basal surface preventing bridge formation.
754 R.K. Dwari, B.K. Mishra / International Journal of Mining Science and Technology 29 (2019) 745–755
However, edge face and edge-edge bridge formation are more
prominent.
3.7. Effect of electrolyte on the kaolinite sedimentation at pH 10
The effect of KNO3 electrolyte concentration on the rate of set-
tling of kaolinite particle at pH 10 and 800 g guar gum/tonne of
solid dosage is presented in Fig. 13. The result shows that with
the increase in electrolyte concentration the rate of settling
increases. Also, the initial 31 s time lag reduced to zero at
0.1 mol KNO3 dosage. The effect of electrolyte concentration on
the rate of transmission, backscattering and floc growth at pH 10
and 800 g/t of guar gum dosage is shown in Fig. 14a–c, respec-
tively. Fig. 14a displays the rate of transmission for the entire
length of the cell at different dosages of the electrolyte. The result
indicates that the transmission percentage increases with the
increase in electrolyte concentration. At 0.01 mol KNO3, the trans-
mission of source infrared reaches 80%, signifies that all the parti-
cles are flocculated and settled at this electrolyte concentration.
The percentages backscattering also decreased with the increase
in the electrolyte concentration (Fig. 14b). The rate of floc growth
also increased with the increase in electrolyte concentration
(Fig. 14c). The floc size increased from 5 mm to 850 mm at a period
of 125 s.
The zeta potential measurement of kaolinite particles in
0.001 mol KNO3 electrolyte solution shows that the particle poten-
tial at pH 10 is 79 mV. Therefore, the electrostatic repulsion
between them is high and their stability in water becomes high.
The measurements of guar gum adsorption onto kaolinite surface
at both pH 5 and pH 10 has confirmed that adsorption is pH inde-
pendent. Although guar gum adsorbed onto the kaolinite surface,
Fig. 13. Effect of ionic strength on the rate of settling of kaolinite particles at 800 g/t
guar gum dosages.
Fig. 14. Effect of ionic strength on the rate of change in (a) transmission (%) (b) backscattering (%) (c) change in floc growth at 800 g guar gum/tonne of solid dosage.
strong electrostatic repulsion prevented the particles from
flocculation.
It is clear that the rate of settling of kaolinite particles increases
in the presence of electrolyte KNO3. The high affinity of guar gum
adsorption onto kaolinite surface in the presence of an electrolyte
is realized from the fact that the floc growth and rate of transmis-
sion increases significantly at higher electrolyte concentration. The
mechanism prevailing the polymer adsorption onto the mineral
surfaces includes hydrophobic interaction, hydration forces, hydro-
gen bonding, chemical and electrostatic interaction [5–8,45]. Wang
et al. [9] also suggested that adsorption of guar gum on talc is inde-
pendent of pH in the presence of 0.1 mol KCl and concluded that
electrostatic interaction is not dominant force for its interaction
with talc. Similarly, in the present study the electrostatic interac-
tion is not the dominant force for the adsorption of guar gum on
the kaolinite surface. The extensive studies carried out by Ma
and Pawlik [3] also confirmed the strong affinity of guar gum onto
kaolinite surface in the presence of K+ counter ion and independent
of pH. The maximum guar gum adsorptions of 1 mg/m2 were
reported at K+ counterion concentration in the range of 0.1 mol/L
to 1 mol/L [3]. Hiemenz and Rajagopalan [46] showed that mono-
valent counter ion (Na+ and K+) compressed the electric double
layer and consequently reduce the electrophoretic mobility of the
kaolinite particle. The reduced mobility may allow the particles
to flocculate, and same is observed in the present case where the
rate of settling, floc growth and transmission in the clarification
zone increases significantly at high ionic strength.
Apart from DLVO theory another significant factor that required
to be considered for the adsorption of guar gum on kaolinite and
their aggregation with or without electrolyte is a non-DLVO force
of interaction. Peschel et al. [47] suggested that a short-range
repulsive force known as the hydration force is inherently present
on quartz/silica surfaces. The hydration force between the quartz
surface decreases in the presence of K+ counter ions [48,49]. The
quartz surface becomes weakly hydrophobic at the higher ionic
strength with K+ counter ion. Similar analogy may also draw for
the kaolinite particles that it may become weakly hydrophobic at
higher ionic strength at higher K+ ion. The interfacial water layers
present on the kaolinite surface get disrupted by poorly hydrated
structure breaking ion (K+). The short range hydration force elimi-
nated between the kaolinite surfaces in the presence of chaotropic
electrolyte KNO3. The lack of hydration force at higher ionic
strength allowed the kaolinite particles to form the floc with higher
growth rate. It resulted in a higher rate of settling of the particles.
4. Conclusions
The present work on the influence of guar gum on the sedimen-
tation behavior of kaolinite is significant since it creates a major
 R.K. Dwari, B.K. Mishra / International Journal of Mining Science and Technology 29 (2019) 745–755
problem in the tailings dewatering. The scanning electron micro-
scope images of the kaolinite particle show that the particles are
poorly crystalline and have micro islands and microcrystallite in
the basal surface. The particles have broken edges and multiple
steps on the edges. These step sites on the edge and rough basal
surface are the sites for guar gum adsorption and promote face-
face and edge-face bridging during flocculation. The zeta potential
study shows that the isoelectric point of kaolinite particle is pH
3.96. The sedimentation studies were carried out at different pH,
ionic strength and flocculant dosage. The pH and ionic strength
have a significant effect on the flocculation characteristics of
kaolinite using guar gum as a flocculant. Guar gum has shown
excellent turbidity removal efficiency with 83% transmission at
pH 5 using 200 g guar gum/tonne of solid dosage. However, it has
performed poorly at pH 10. Conversely, its turbidity removal effi-
ciency has improved significantly in the presence of potassium
nitrate with 80% transmission in the clarifying zone. The opaque-
ness of consolidated tailing decreases with the increase of guar
gum dosage at pH 5 as floc size increases with the increase of
dosage. The analysis of the settling rate, supernatant clarity and
sediment consolidation suggests that 200 g guar gum/tonne of
solid is the optimized dosage for dewatering of the kaolinite dis-
persions at pH 5.
Acknowledgment
The authors gratefully acknowledge the financial support from
the Ministry of Steel, Government of India, India (GAP 214).
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