Accepted Manuscript

Title: Designing anionic lignin based dispersant for kaolin

suspensions

Authors: Mohan K.R. Konduri, Pedram Fatehi

PII: S0927-7757(17)31000-2
DOI: https://doi.org/10.1016/j.colsurfa.2017.11.011
Reference: COLSUA 22058

To appear in: Colloids and Surfaces A: Physicochem. Eng. Aspects

Received date: 16-9-2017

Revised date: 2-11-2017
Accepted date: 6-11-2017

Please cite this article as: Mohan K.R.Konduri, Pedram Fatehi, Designing anionic lignin
based dispersant for kaolin suspensions, Colloids and Surfaces A: Physicochemical and
Engineering Aspects https://doi.org/10.1016/j.colsurfa.2017.11.011

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Designing anionic lignin based dispersant for kaolin suspensions

Mohan K. R. Konduri, Pedram Fatehi*

Chemical Engineering Department,

Lakehead University,

955 Oliver Road,

Thunder Bay, ON P7B 5E1, Canada

*Corresponding author: email: pfatehi@lakeheadu.ca, tel: 807-343-8697; fax: 807-346-7943

1
Graphical abstract

ABSTRACT

To generate effective dispersants for kaolin suspensions, it is important to study how the properties

of dispersants affect their performance in suspensions. In this work, kraft lignin was modified via

oxidation with nitric acid under varied conditions to produce oxidized lignin (OL) with different

charge densities and molecular weights. The effects of anionic charge density and molecular

weight of the lignin based products on the dispersion and sedimentation of kaolin particles were

studied fundamentally. The adsorption of OLs on particles as well as the changes in the zeta

potential, relative turbidity, hydrodynamic diameter and sedimentation of particles under static

(non-stirring) and dynamic (stirring) conditions were systematically investigated. Dispersion

studies suggested that both charge density and molecular weight had great impacts on the stability

2
of kaolin particles. Sample OL8 with the charge density of -3.6 meq/g and molecular weight (Mw)

of 30,243 g/mol was the most effective dispersant for kaolin suspension. The hydrophilicity of

OLs were similar and thus did not affect the dispersion analysis.

Keywords: oxidized lignin, dispersion, charge density, colloid, polymer adsorption, molecular

weight

1. Introduction

Kaolin suspensions have been studied widely as raw materials for ceramic, paper and other

chemical industries [1,2] Also, kaolin suspensions (0.2-25 wt.%) have been used in health care

formulations and pharmaceutical applications [3-6]. In these suspensions, the fluidity of kaolin

particles without settling is crucial to produce final products with acceptable properties while

maintaining the production and energy costs low [7]. The stability of kaolin suspensions depends

on the size and interaction between the kaolin particles [8]. The fluidity of kaolin suspensions can

be enhanced by using dispersants [9]. When a charged dispersant is added to aqueous suspensions,

it adsorbs on particles and changes the overall surface charge density of particles inducing

electrostatic or steric repulsion among particles. To develop an efficient dispersant for the kaolin

suspension, its interaction with kaolin should be well understood [8].

Numerous synthetic polymers have been proposed as dispersants for kaolin suspensions [11,12].

However, their non-biodegradability and toxic nature are their main barriers for practical uses [13].

Alternatively, the use of natural or semi-natural polymers have been proposed to address this

challenge [7,14]. In one study, the use (0.2 wt.%) of an anionic lignin-based product produced via

chemical modification of hardwood kraft lignin improved their dispersion by 10% [15]. In another

work, carboxymethylated lignin produced via treatment of wheat straw alkali lignin with

chloroacetic acid was applied as a dispersant for graphite aqueous suspensions [16]. Calcium

3
lignosulfonate (1.0 wt.%) obtained from sulfite pulping process of pine wood improved the

stability of graphite suspension by 70 %, while a commercial dispersant, Reax-85A, improved it

only by 50% [17]. In this work, hardwood kraft lignin was oxidized with nitric acid under various

reaction conditions to produce anionic lignin products with varied molecular weights and charge

densities to be used as dispersants for kaolin suspensions.

Kaolin particles tend to aggregate due to interactions between positively charged edges and

negatively charged basal plane over a wide pH range [18]. The dispersion of colloidal suspensions

is a complex process, and is influenced by the adsorption of polymers and the characteristics of

adsorbed polymers [18-24]. The characteristics of polymers, such as charge density and molecular

weight, are known to affect their adsorption [7,25]. It was reported that the adsorption behaviour

of polymers depends on the amount of accessible charges associated with the polymers, which is

affected by their hydrodynamic sizes and molecular weights [25]. In a study on the stabilization of

TiO2 suspensions, an increase in the molecular weight of lignosulfonates from 1000 to 30,000

g/mol improved the dispersion stability of the suspension by 50 % [7]. In another study on the

stabilization of kaolin suspensions using carboxymethylated cellulose (CMC), an increase in the

molecular weight from 35,000 to 125,000 g/mol decreased the turbidity of kaolin suspension by

50 % [26]. Poly (acrylic acid-co-maleic acid) with a high carboxylate group exhibited superior

dispersion performance in lead zirconate titanate aqueous suspensions (60 wt.%) [9]. However,

the relationship between the chemical properties of oxidized kraft lignin and its performance as a

dispersant for colloidal suspensions has not been studied yet [27]. In this work, the correlation

between the molecular weight and charge density of oxidized lignin and its performance as a

dispersant for kaolin suspensions was studied under both dynamic and static conditions. The

4
primary novelty of this work is the investigation on the influence of charge density and molecular

weight of anionically charged lignin products on the stability of kaolin suspensions.

2. Experimental

2.1. Materials

Mixed hardwood lignin was supplied by FPInnovations from its pilot plant facilities located in

Thunder Bay, ON [28]. Sodium nitrate (99 %), potassium nitrate (99.99 %), kaolin, potassium

hydroxide (> 85 wt.%), sodium hydroxide and para hydroxybenzoic acid (PHBA) were obtained

from Sigma Aldrich Company and used as received. Nitric acid was obtained from Sigma Aldrich

company and diluted to 30 wt.% prior to use. Standard hydrochloric acid (HCl) solution (30-35

wt.%) was obtained from Fluka analytical and used as received. Sulphuric acid (95-98 %) was

obtained from Sigma Aldrich Company and diluted to 0.1 M prior to use. Cellulose acetate dialysis

membrane (molecular weight cut off of 1,000 g/mol) was obtained from Spectrum Labs. Inc, USA.

Polydiallyldimethylammonium chloride (PDADMAC) was obtained from Sigma Aldrich

Company and diluted to 0.005 M prior to use. Potassium polyvinyl sulfate (PVSK) was obtained

from Wako Pure Chemical Industries Ltd., Japan and diluted to 0.005 M prior to use.

2.2. Oxidation

The oxidation of kraft lignin was performed as described previously [29]. A 5 g sample of

hardwood lignin was treated with nitric acid at different temperatures for different time intervals

as shown in Table 1. After the reaction, the mixture was cooled to room temperature and its pH

was adjusted to 7 using 0.1 M NaOH. Unreacted nitric acid was separated using the dialysis

membrane, while changing water every 12 h for two days. The dialyzed samples were oven dried

at 105 °C and stored at 4 °C until further use.

2.3. Charge Density Analysis

5
The charge density of unmodified lignin (UL) and oxidized lignin samples (OL1 to OL 10) was

determined using a Particle Charge Detector (Mutek, PCD 04, Germany). The samples were

initially dried at 105 °C overnight to remove moisture. A 0.2 g sample of oxidized lignin samples

was dissolved in 20 mL of deionized water and incubated for 2 h at 30 °C in a water bath shaker

(Classic C76, New Brunswick Scientific, Edison, NJ, USA) at 150 rpm. After the incubation, the

samples were centrifuged at 1000 rpm for 10 min and supernatants were collected for the charge

density analysis.

To determine the surface charge density of particles, 0.2 g of kaolin was suspended in 50 mL of

PDADMAC (0.005M) solution and the suspension was incubated at 30 °C for 2 h at 150 rpm.

After the incubation, the samples were filtered using Whatman#1 filter papers and the filtrates

were titrated against PVSK (0.0055 M) solution with the titrator. Similarly, the titration analysis

was conducted for control sample (i.e., PDADMAC solution before mixing with kaolin) and the

difference was considered for quantifying the surface charge density of kaolin particles.

2.4. Surface Area Analysis of Kaolin Particles

The surface area of kaolin particles was determined by using Quantachrome surface area analyzer,

Nova 2200e, instrument. In this set of experiments, the samples were initially dried in an oven at

105 °C overnight and approximately 0.05 g of sample was pretreated for 4 h at 250 °C prior to

analysis. The specific surface area of the samples was then analyzed according to Branuer-

Emmett-Teller (BET) method via adsorption-desorption isotherms using nitrogen gas at -180 °C

with relative pressure range of 0.01 to 0.99 [30].

2.5. Carboxylate Group Analysis

The aqueous conductometric titration method was used to measure the amount of carboxylate

groups attached to unmodified or oxidized lignin samples using an automatic conductometric

6
titrator, Metrohm, 785 DMP Titrino, Switzerland. In this set of experiments, a 0.06 g sample was

added to 100 mL of deionized water containing 1 mL of 0.8 M potassium hydroxide in a 200 mL

beaker and stirred at 500 rpm for 10 min. To this mixture, 4 mL of 0.5 wt.% PHBA solution was

added as an internal standard and titrated against a standard 0.1 M hydrochloric acid solution. The

volume of HCl consumed to decrease the pH of the sample solution to specific end points are noted

as V2Ꞌ (pH 7) and V3Ꞌ (pH 3) and their corresponding end points for blank solutions (without sample)

are noted as V2 and V3, while V1Ꞌ and V1 correspond to volume of HCl consumed to decrease the

pH of sample to 10 for sample and control solutions. The carboxylate group content of the samples

was calculated according to Equation 1 [31].

{ (𝑉3Ꞌ − 𝑉2Ꞌ ) −(𝑉3 − 𝑉2 ) } × 𝐶𝐻𝐶𝑙

Carboxylate group content (mmol/g) = (1)
𝑊𝑠

where Ws is the weight of the sample (0.06 g), CHCl is the concentration of the HCl (0.1 M), V is

the volume of the titrant (mL) consumed to reach the end points of titration. Three replicates were

performed and the average values were reported.

2.6. Molecular Weight Analysis

To determine the molecular weight of the samples, they were first dried in an oven at 105 °C.

Approximately, 50 mg sample of UL or OL was dissolved in 5 mL of 0.1 mol/L NaNO3 solution

and filtered with a nylon 0.2 µm filter (13 mm diameter). The filtered solutions were used for the

molecular weight analysis. The molecular weight of unmodified lignin (UL) and oxidized lignin

(OL) samples were assessed using a gel permeation chromatograph instrument (Malvern GPCmax

VE2001 Module + Viscotek TDA305) equipped with refractive index and viscometer detectors.

PolyAnalytic columns, PAA206 and PAA203, were used at the column temperature of 35 °C.

Polyethylene oxide was used as standards. 0.1 mol/L NaNO3 solution was used as solvent and

eluent with the flow rate of 0.70 mL/min.

7
2.7. Elemental analysis

The elemental analysis of UL or OL samples was carried out using an elemental analyzer, CHNS

Elemental Vario EL, via combustion method. The samples were oven dried at 102 °C prior to

analysis. Approximately, 0.02 g was weighed and transferred into carousel chamber of elemental

analyzer. The combustion of the samples was carried out at 1200 °C and the gases were reduced

to analyze carbon, hydrogen, sulphur and nitrogen content of the samples.

2.8. Hydrodynamic Diameter Analysis

A static light scattering instrument (Brookhaven Instruments, BI-200SM, USA) equipped with a

laser light at a wavelength of 637 nm was used to determine the hydrodynamic diameter of UL

and OL samples [32]. All samples were oven dried at 105 °C overnight to remove moisture prior

to analysis. In this set of experiments, 0.1 g of samples was dissolved in 100 mL of deionized water

at pH 7 and incubated in water bath shaker at 30 °C for 2 h and 150 rpm. Subsequently, 3.2 mL of

potassium nitrate (0.4 M) solution was added to the samples and stabilized for 24 h. 20 mL of each

sample was prepared by filtering with 0.45 µm disposable syringe filters and measured at 90°

scattering angle for 2 min and 25 °C. Three replicates were performed for each experiment and

average values were reported.

2.9. Contact Angle Measurement

An optical tensiometer instrument, Theta lite (Biolin Scientific, Finland) equipped with camera

was used to determine the wettability of glass slides coated with OL samples. All samples (OL1-

OL10) including UL were oven dried, and a 0.2 g of each sample was dissolved in 20 mL of

deionized water (10 g/L) and incubated in water bath for 2 h at 30 °C. After incubation, 2 mL of

sample was loaded onto microscopic glass slides and allowed to dry using a spin coater, WS-650

(Laurell Technologies Corp) under vacuum with 60 Psi pressure, 250 rpm for 60 s. The contact

8
angle of water on the glass slides coated with OL or UL samples was determined using the sessile

drop method, by fitting the data to young laplace equation (Eq 2) [33].

𝛾𝑙𝑣 𝑐𝑜𝑠𝜃𝑌 = 𝛾𝑠𝑣 − 𝛾𝑠𝑙 (2)

where γlv, γsv and γsl represent the interfacial tensions of liquid vapour, solid vapour and solid liquid

in mN/m, respectively, and θY is the contact angle of water in degrees (°) with OL sample coated

on a glass slide. Approximately, 5 µL of water droplets were placed on the coated slides and the

contact angles of the droplets and the slides were determined using an optical tensiometer. Three

replicates were performed for each experiment and average values were reported.

2.10. Adsorption Analysis

The adsorption of UL or OL samples onto kaolin particles was studied as a function of OL dosage.

In this experiment, UL or OL with 2 to 256 mg/L concentrations were prepared in 250 mL glass

flasks containing 50 mL of a kaolin suspension (2 g/L) and incubated at 30 °C for 1 h and 150

rpm. After the incubation, the mixture was centrifuged at 2500 rpm (475.2 G) for 10 min to

separate kaolin particles from the suspensions. The concentration of UL or OL samples in the

supernatants was measured using a UV-Vis spectrophotometer, Genesys 10S, at a wavelength of

205 nm [34]. The interference of kaolin particles in UV test was also considered. A blank sample

of 50 mL kaolin suspension (2 g/L) without UL or OL was centrifuged under the conditions

described above and its supernatant was used for determining any interference from kaolin

particles with the UV analysis. The absorbance value for this black sample was deducted from that

of the actual samples in the UV concentration determination.

2.11. Zeta Potential analysis

The zeta potential analysis of kaolin suspensions was performed using a NanoBrook Zeta PALS

(Brookhaven Instruments Corp, USA). In this study, 2 g of kaolin suspension (100 g/L) was added

9
to 100 mL of deionized water and stirred at 150 rpm for 1 h at room temperature. After mixing, 1

mL of sample was used for zeta potential analysis. Similarly, the zeta potential of kaolin particles

in the presence of UL or OLs was measured at different polymer dosages (2 to 256 mg/L) under

the same conditions as described above. The experiments were carried out three times and the

mean values were reported in this study.

2.12. Particle Size analysis

In this study, 2 mL of kaolin suspension (100 g/L) was added to 100 mL of deionized water and

incubated in water bath shaker at 30 °C and 150 rpm. After the incubation, the samples were

analyzed by a MasterSizer 2000 particle size analyzer (Malvern Instruments) equipped with a light

scattering detector to measure the particle size distribution of the kaolin particles. Similarly, the

particle size analysis of kaolin suspensions was carried out as a function of UL or OL dosage from

2 to 256 mg/L under the conditions described above. All the measurements were carried out at

room temperature. Three measurements were carried out for each sample and average values were

reported.

2.13. Dispersion analysis

The dispersion affinity of OL samples in kaolin suspensions was studied using a photometric

dispersion analyzer (PDA 3000, Rank Brothers Ltd) that was connected to a dynamic drainage jar

(DDJ) fitted with a 70 mm mesh screen [35]. The degree of dispersion or flocculation of the kaolin

suspension was presented by relative turbidity, τr, which was quantified from the variation in the

direct current (DC) voltage signals of the PDA instrument [36]. In this set of experiments, 500 mL

of deionised water was transferred into the DDJ container and allowed to circulate from the DDJ

to the PDA through a 3 mm plastic tube until a steady state flow rate of 20 mL/min was achieved

using a peristaltic pump. Then, 10 mL of a 100 g/L kaolin suspension was added into DDJ (2 g/L

10
kaolin concentration) at a constant stirring rate of 300 rpm and allowed to circulate through PDA.

A decrease in the initial base DC voltage (V0) to a new DC voltage (Vi) was recorded. Different

amounts of UL or OL (10 g/L) were added to the suspension mixture to make from 2 to 256 mg/L

concentrations of UL or OL in the DDJ, and the increase or decrease in DC voltage was represented

as the DC voltage (Vf) of the final suspension. The pH of the kaolin suspensions was maintained

at 7 during the experiments. The relative turbidity of the kaolin suspension, 𝜏𝑟 , was measured

according to equation 3 [37].

𝑉0
𝜏𝑓 𝑙𝑛( )
𝑉𝑓
Relative turbidity, 𝜏𝑟 = = 𝑉0 (3)
𝜏𝑖 𝑙𝑛( )
𝑉𝑖

where τf is denoted as the final suspension turbidity, and τi is denoted as initial suspension turbidity.

2.14. Stability analysis

The stability of the kaolin suspension in the presence OLs was investigated using a Turbiscan Lab

Expert, Formulaction, France. This analysis was conducted in the past to study the stability of

emulsion and concentrated colloidal dispersions. In this set of experiments, kaolin suspensions (2

g/L) in the presence of OLs at varying concentrations (2-256 mg/L) were prepared and changes in

the suspension stability was analyzed for 1 h (single scans were collected every 2 sec) by the

instrument at 30 ºC. Based on obtained data, the destabilization index was determined using

Turbisoft 2.1 software by comparing the transmittance signals generated by the sample with those

generated by the standard silicon oil, which is used as a calibration chemical for the instrument

[38]. These transmittance signals were recorded as a percentage of transmittance signals in regard

to that of the silicon oil.

Equations 4 [39] presents the procedure used for determining the destabilization index of the

sample

11
 Ʃℎ |𝑠𝑐𝑎𝑛 (ℎ)− 𝑠𝑐𝑎𝑛
𝑖 𝑖−1 (ℎ)|
DSI = Ʃi (4)
𝐻

where scani (h) and scani-1 (h) are the transmission signals for two consecutive time intervals at a

given height (h) and H is the total height of sample.

The size of clay particles in the suspended state (i.e., not settled) and their volume fractions can be

obtained based on the backscattering data collected in this test. Based on the Mie theory [40], the

backscattering data measured by the instrument can be expressed as a function of photo transport

mean free path, I* in equation 5:

1
BS = √𝐼∗ (5)

In addition, the photo transport mean free path, I*, could be obtained via following equation 6

[40]:

2𝑑
I* (d, 𝜃) = 3𝜃 (1−𝑔)𝑄 (6)
𝑠

Where d is the particle diameter (µm), θ is the particle volume fraction (%), g and Qs are the

scattering efficiency factors, which depend on the particle diameter (d), wavelength of light (λ),

refractive index of dispersed kaolin particles (np) and the refractive index of continuous phase (nf).

In this work, the refractive indices of kaolin particles and water were considered to be 1.54 and

1.33, respectively, and the size of particles was determined following this equation using

backscattering data [39].

12
3. Results & Discussion

3.1. Preparation of Oxidized Lignin and Kaolin

Kaolin was found to have a surface area and particle size of 25.65 m2/g and 7.2 µm, respectively.

The surface charge density of kaolin particles was -6.3 μmol/g, which is probably due to the

presence of oxide anions on its surface [41]. The oxidation of lignin with nitric acid and possible

side reactions were shown in Figure 1. The oxidation reaction of lignin with nitric acid produces

low molecular weight lignin compounds containing carboxylate groups and other products, such

as 4-hydroxy-3-methyl benzaldehyde (Figure 1a) [29]. Furthermore, nitro lignin could be produced

as a by-product due to possible side reactions as shown in Figure 1b [42,43].

a OH O O
C H C O

HNO3
R R
CH3O R CH3O CH3O
OH OH R = H (or) OH (or) OCH3
OH

b OH OH
OH

HNO3 HNO3
H 2O HNO2
CH3O NO CH3O NO2
CH3O OH
OH OH
OH

Figure 1. Reaction of lignin with nitric acid a) oxidation scheme and b) nitration scheme

13
The properties of oxidized lignin samples produced via nitric acid treatment of kraft lignin under

different conditions are listed in Table 1. The reaction was carried out at high temperatures and

acidic conditions due to limited reactivity of hardwood kraft lignin [44].

Table 1. Reaction conditions and properties of produced anionic lignin polymers and kaolin

particles

Sample Conditions Charge M w, Mn, Carboxyl hy, nm Contact Nitroge

density, g/mol g/mol ate group angle, ° n, wt.%
meq/g content,
mmol/g
Time Tempe HNO3 HNO3/
,h rature, concen lignin,
°C tration wt./wt.
, wt.%
UL - - - - 0.2 28,274 19,105 0.16 3.72 28.3 0
OL1 1 100 20 4 1.22 26,700 18,623 1.05 3.65 5.2 4.4
OL2 1 100 20 6 1.80 25,862 18,825 1.63 3.61 4.8 4.6
OL3 1 100 20 8 2.45 26,278 18,457 2.28 3.66 4.7 4.6
OL4 1 100 20 10 3.06 25,121 18,233 2.86 3.62 4.6 4.8
OL5 1 100 20 12 3.63 26,432 19,341 3.46 3.67 4.6 4.8
OL6 1 100 30 8 3.58 11,654 3,280 3.45 2.21 4.5 4.6
OL7 1 100 20 8 3.64 21,889 11,121 3.46 3.57 4.8 4.6
OL8 1 100 25 8 3.68 30,243 22,861 3.47 3.81 4.6 4.6
OL9 1 100 35 10 3.57 42,558 35,154 3.43 4.06 4.7 4.8
OL10 1 100 35 12 3.62 83,543 52,578 3.47 7.33 4.8 4.9

The OLs were all soluble in water at 10 g/L concentration, but UL had a limited solubility of 0.2

g/L at this concentration. The OL1 to OL5 had a similar molecular weight of 26,000 g/mol, but

altered charge densities. The OL6 to OL10 had a similar charge density of 3.6 meq/g, but varied

molecular weights. The carboxylate group content of the OL samples followed the same trend as

their charge densities. As expected, this phenomenon describes that the main source of anionic

charge density of OLs was carboxylate group. Previously, an increase in the carboxylate group
14
was well associated with the increase in the charge density of softwood kraft lignin treated with

nitric acid [29]. The hydrodynamic diameter (hy) of OL1-OL5 was approximately 3.6 nm, while

that of OL6-OL10 was in the range of 2.2-7.3 nm. A comparison between the contact angles of

water droplet on the glass slides coated with OLs samples reveals that 1) the contact angle of water

droplet was significantly small (4 °) for OL samples compared with that for UL (28 °) confirming

the hydrophilicity of the OL samples, 2) the contact angles of all OL samples were similar

confirming similar hydrophilicity of OL samples. UL was found to have a negligible nitrogen

content, while all OLs contained 4.4 and 4.9 wt.%, nitrogen (Table 1), which suggests that lignin

was nitrated with possible incorporation of nitro group into the aromatic ring via nitric acid

treatment, as shown in Figure 1b [45]. Previously, Grushnikov and Shorygina also reported nitro

lignin formation during treatment of a model lignin compound, guaiacylethylcarbinol, with nitric

acid [42].

3.2. Adsorption of OLs

Figures 2a and 2b present the adsorption of OLs on kaolin as a function of OL dosage. Although

kaolin particles exhibit an overall negative charge density, the basal surface of kaolin carries

positive charges [17]. Thus, the adsorption of OLs on the kaolin surface occurs via electrostatic

interaction between the cationic sites present on the surface of kaolin particles and carboxylate

groups of OLs [21]. Upon adsorbing OLs, the surface charge density of kaolin particles was

enhanced, which improved the repulsion of particles [9]. In a similar work, Wisniewska and his

co-authors reported that the aluminium oxide suspension was electrostatically stabilized by

polyacrylamide-based dispersants due to the adsorption of anionic polyacrylamide on the

aluminium oxide surface [46]. As shown in Figure 2a, the higher concentration of OLs led to their

higher adsorption on kaolin surface. However, the higher the charge density (i.e., the more negative

15
charges) of OL, the more the OL adsorbed on kaolin particles [47]. This increase in the adsorption

of OLs on kaolin particles can be attributed to the improvement in the hydrophilicity of OL samples

(Table 1). On the other hand, the molecular weight of OLs showed an insignificant influence on

the adsorption of OLs on kaolin particles (Figure 2b). OL6 with the charge density of 3.6 meq/g

and molecular weight of 11,654 g/mol exhibited the maximum adsorption of 0.81 mg/g.

Based on the amount of UL or OLs adsorbed on kaolin particles (Figure 2a and 2b) and the charge

density of UL and OLs (Table 1), the surface charge density of kaolin can be theoretically

calculated. Figures 2c and 2d depict the impact of adsorbed UL or OLs on the theoretical surface

charge density of kaolin particles. In these figures, the surface charge density of unmodified kaolin

was experimentally determined as described in the Methodology section, but it was not possible

to experimentally measure the surface charge density of kaolin particles after OLs adsorption. As

expected, the negative surface charge density of kaolin particles was increased with the increase

in adsorption of OLs. This increase induced kaolin particles with a more negative surface charge

density, while increasing the molecular weight of OLs had a marginal impact on the surface charge

density of kaolin particles.

16
 OL1 OL2 OL3 OL4 OL5 UL

0.9
a
0.8
Amount adsorbed, mg/g

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 50 100 150 200 250 300
Concentration of polymer at equilibrium, mg/L

OL6 OL7 OL8 OL9 OL10

0.9
b
0.8
Amount adsorbed, mg/g

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 50 100 150 200 250 300
Concentration of polymer at equilibrium, mg/L

17
 OL1 OL2 OL3 OL4 OL5 UL

-5
Surface charge of clay particles, μeq/g

c
-6

-7

-8

-9

-10
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Amount of adsorbed lignin, mg/g

OL6 OL7 OL8 OL9 OL10

-5
Surface charge of clay particles, μeq/g

d
-6

-7

-8

-9

-10
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Amount of adsorbed lignin, mg/g

Figure 2. Adsorption isotherms of OLs on kaolin particles when a) OLs with the molecular weight

of 26,000 g/mol but with different charge densities, b) OLs with a charge density of 3.6 meq/g but

18
with different molecular weights were used. Theoretical surface charge density of kaolin particles

as a function of adsorbed amounts of c) OLs with a molecular weight of 26,000 g/mol but with

different charge densities, d) OLs with a charge density of 3.6 meq/g but with different molecular

weights were used (other conditions were 30 °C, pH 7 and 2 g/L kaolin dosage).

3.3. Zeta Potential

Figures 3a and 3b present the effect of adsorbed amount of UL/OLs on the zeta potential of kaolin

particles. The zeta potential of kaolin suspension was reduced as the adsorption of OL was

increased in the suspensions. The effect of UL was found to be insignificant on the zeta potential

of the suspensions. OL6 with the charge density of 3.6 meq/g and molecular weight of 11,654

g/mol caused the maximum decrease in the zeta potential of kaolin particles from -22 to -56 mV.

This behavior is due to its maximum adsorption on the kaolin surface. An increase in the charge

density of OLs resulted in a significant decrease in zeta potential. OLs have more carboxylate

group when their charge density was higher (Table 1) causing them to introduce more negative

charges on kaolin surface. In the past, Boisvert and co-authors reported that the reduction in the

zeta potential of titanium dioxide particles was attributed to the increased adsorption of sodium

polyacrylate on titanium dioxide particles [48]. In another study on the stabilization of raw

porcelain suspensions using acrylic copolymers, the zeta potential of the suspension was reduced

to -60 mV with an increase in dispersant dosage from 1 to 250 mg/L [4]. As expected, OLs with

different molecular weights did not alter the zeta potential of the suspensions (Figure 3b) as their

adsorption amounts and charge densities were similar (Figure 2b).

19
 -20 OL1 OL2 OL3 OL4 OL5 UL

-25
a
-30
Zeta potential, mV

-35

-40

-45

-50

-55

-60
0 0.2 0.4 0.6 0.8 1
Amount adsorbed, mg/g

-20 OL6 OL7 OL8 OL9 OL10

-25

-30
b
Zeta potential, mV

-35

-40

-45

-50

-55

-60
0 0.2 0.4 0.6 0.8 1
Amount adsorbed, mg/g

Figure 3. Zeta potential of kaolin suspension as a function of adsorbed amount of a) OLs with

varied charge densities but with a 26,000 g/mol molecular weight, b) OLs with varied molecular

weights but with 3.6 meq/g charge density (other conditions were 30 °C, pH 7 and 2 g/L kaolin

dosage).

To understand if the zeta potential of kaolin particles was affected by the charges of particles or

by diffused OL layer surrounding the particles in the suspension, the zeta potential of kaolin

20
suspension was plotted against the theoretical surface charge of kaolin particles in Figure 4. The

zeta potential of kaolin particles was -24 mV when its surface charge density was -6 μeq/g (kaolin

particles with no OLs adsorption). With decreasing the surface charge density of kaolin particles,

the zeta potential of kaolin particles was decreased as a result of more OL adsorption. on the

positive sites of kaolin surface. OL with a more negative charge density decreased the zeta

potential of particles to a greater extent, as it adsorbed more (Figure 2). However, OL with different

molecular weights impacted the zeta potential and theoretical charge density of particles similarly.

The results depict that the charge density and molecular weight of OLs minimally affected the

surface charge-zeta potential correlation, but the OL adsorption had a greater influence on the

surface charge density and zeta potential of kaolin particles. Furthermore, points “s” on Figure 4a

and 4b represents the conditions for saturation levels of adsorption. Based on the results, the zeta

potential of kaolin particles depends on surface charge introduced by the adsorbed amount of OLs,

and not by the unadsorbed OLs that were present in the suspension. This indicates that both zeta

potential and surface charge density of kaolin particles were interrelated and only dependent on he

adsorbed amount of OLs.

21
 OL1 OL2 OL3 OL4 OL5
-20 a
-25

-30
Zeta potential, mV

-35

-40

-45 s
-50

-55 s
s
-60
-6 -7 -8 -9 -10
Theoretical surface charge density of kaolin, μeq/g

OL6 OL7 OL8 OL9 OL10

-20
-25 b
-30
Zeta potential, mV

-35
-40
-45
-50
s
-55 s
-60 s
-5 -6 -7 -8 -9 -10
Theoretical surface charge density of kaolin, μeq/g

Figure 4. Zeta potential of kaolin suspensions as a function of theoretical surface charge density

of kaolin particles in the presence of a) OLs with varied charge densities but molecular weight of

26000 g/mol, and b) OLs with varied molecular weights but a charge density of 3.6 meq/g (other

conditions were 30 °C, pH 7 and 2 g/L kaolin dosage).

22
3.4. Dispersion under Dynamic Conditions

Figure 5 presents the relative turbidity of kaolin suspensions as a function of OL adsorbed amount.

The relative turbidity of the kaolin suspension was improved as the charge density of OL increased

(Figure 5a). Kaolin suspensions containing OL5 exhibited the maximum relative turbidity of 1.3.

This is because OL5 with a high charge density induced more electrostatic repulsion between the

kaolin particles by adsorbing more on the kaolin particles. Figure 5a also depicts that low charged

OLs (e.g., OL2) needed a higher dosage to improve the relative turbidity. Jiang and co-authors

also stated that sodium poly(acrylic acid-co-maleic anhydride-co-itaconic acid) with a higher

charge density (-6.6 meq/g) produced a more stable ceramic dispersion [49].

In Figure 5b, the increase in adsorption of OL6, OL7, and OL8 amplified the relative turbidity of

kaolin suspensions to 1.28, 1.3 and 1.31, respectively. This is possibly due to an increase in steric

repulsion between the particles as they adsorbed on kaolin particles. In one study, the dispersibility

of TiO2 suspensions was increased with an increase in the molecular weight of sodium

lignosulfonate (4 g/L) to 30,000 g/mol [7]. Interestingly, OLs with a higher molecular weight (e.g.,

OL9 and OL10) increased the relative turbidity at low adsorption amounts, but the improvement

was hampered at higher adsorption amounts. As these OLs had relatively higher hydrodynamic

sizes (Table 1), they could interact with more than one kaolin particles via bridging. The higher

adsorption of these OLs improved the possibilities for this bridging effect. Therefore, the less

improvement in relative turbidity at higher adsorption amounts of these OLs is most likely due to

the bridging and thus flocculation affinity of these OLs on kaolin particles. A similar phenomenon

was observed on the dispersion of coal water slurries (CWS) using sodium polystyrene sulphonate

(SPS), where the maximum stability was obtained for SPS at a concentration of 64 mg/L [50].

23
These results suggest that charge density, molecular weight and concentration of OLs significantly

affected the relative turbidity and thus the dispersibility of OLs in kaolin suspensions.

OL1 OL2 OL3 OL4 OL5 UL

1.35 a
1.3
1.25
Relative turbidity

1.2
1.15
1.1
1.05
1
0.95
0.9
0 0.2 0.4 0.6 0.8 1
Amount adsorbed, mg/g

OL6 OL7 OL8 OL9 OL10

1.4
b
1.3
Relative turbidity

1.2

1.1

0.9
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Amount adsorbed, mg/g

Figure 5. Relative turbidity of kaolin suspension as a function of OL adsorbed amount when a)

OLs with varied charge densities and 26,000 g/mol molecular weight and b) OLs with varied

24
molecular weights and 3.6 meq/g charge density were used (other conditions were 30 °C, pH 7

and 2 g/L kaolin dosage).

Figure 6 present the relative turbidity of the kaolin suspension as a function of theoretical surface

charge density of particles. As seen in Figure 6a, the decrease in surface charge density of kaolin

particles led to an increase in the relative turbidity. At the same surface charge density, the OL

with the higher charge density improved the relative turbidity of the suspension more greatly. As

the theoretical surface charge density of kaolin particles increased, more repulsion was introduced

between particles, which increased the relative turbidity of the suspension.

In Figure 6, OLs with a similar charge density but varied molecular weights modified the surface

charge density of the particles in a similar fashion, which resulted in a similar relative turbidity

behavior. This is a confirmation that the change in the surface charge density of particles was

indeed a crucial factor in the relative turbidity change. However, for OLs with a high molecular

weights (and thus a large hy), the increase in the relative turbidity of the particles was hampered

when the dosage of OL was higher than 0.7 mg/g. This indicates that the larger OLs may also

develop bridging that hampered their affinity in dispersing kaolin particles.

These results indicate that the performance of OL9 and OL10 was dosage dependent. At the

adsorbed amount of 0.7 mg/g, the amount of these OL polymers on kaolin particles was sufficiently

high to bridge kaolin particles due to their large hydrodynamic size (Table 1). The last points on

each curve show the relative turbidity of kaolin suspensions when the maximum adsorption

amount (i.e., saturation adsorption) was achieved (Figure 2). For these points (point s on Figure 5a

and 5b), the total adsorption amount was similar, but the amounts of unadsorbed OLs remained in

the suspensions were different. These results confirm that, the amount of adsorbed OLs (and not

25
the amount of unadsorbed OLs in suspensions) played a major role in the relative turbidity of

kaolin suspension.

1.45 OL1 OL2 OL3 OL4 OL5 UL

a
1.35
s
Relative turbidity

1.25 s

s
1.15
s
1.05 s

0.95
-6 -6.5 -7 -7.5 -8 -8.5 -9 -9.5
Theoretical surface charge density of clay, µeq/g

OL6 OL7 OL8 OL9 OL10

1.35
b s s
1.3
s
Relative turbidity

1.25
1.2 s
1.15 s
1.1
1.05
1
0.95
-6 -6.5 -7 -7.5 -8 -8.5 -9 -9.5
Theoretical surface charge density of clay, µeq/g

Figure 6. Relative turbidity of kaolin suspension as a function of adsorbed amount of lignin when

a) OLs with varied charge densities and a molecular weight of 26,000 g/mol and b) OLs with

26
varied molecular weights and a charge density of 3.6 meq/g were used (other conditions were 30

°C, pH 7 and 2 g/L kaolin dosage).

To further determine the mechanism of OLs in dispersing kaolin suspensions, the relative turbidity

of kaolin suspension was studied as a function of zeta potential in Figure 7. For OLs with different

charge densities (Figure 6a), the relative turbidity of the kaolin suspensions was found to increase

continuously with the reduction in zeta potential of kaolin suspension, which indicates that these

OLs dispersed kaolin particles via charge repulsion mechanism. A similar trend was observed for

OL6, OL7 and OL8 with different molecular weights (Figure 7b). In case of OL9 and OL10, the

increase in the zeta potential change did not improve the relative turbidity. This means that the

increase in the repulsion between particles was not sufficiently high to overcome the bridging

effect of OL9 and OL10. Therefore, within the range studied, both charge density and molecular

weight play significant roles in dispersion of kaolin suspensions. The charge density seemed to

always play a significant role, but molecular weight play a role at a high adsorption level.

1.35 OL1 OL2 OL3 OL4 OL5

1.3 a
1.25
1.2
Relative turbidity

1.15
1.1
1.05
1
0.95
0.9
-20 -25 -30 -35 -40 -45 -50 -55 -60
Zeta potential, mV

27
 OL6 OL7 OL8 OL9 OL10
1.4
b
1.3
Relative turbidity

1.2

1.1

0.9
-20 -30 -40 -50 -60
Zeta potential, mV

Figure 7. Relative turbidity of kaolin suspension as a function of zeta potential when a) OLs with

varied charge densities and a molecular weight of 26,000 g/mol, and b) OLs with varied molecular

weights and a charge density of 3.6 meq/g were used (other conditions were 30 °C, pH 7 and 2 g/L

kaolin dosage).

3.5. Dispersion under Static Conditions

Figure 8 shows the destabilization index of clay suspension in the presence of OLs. The increase

in the charge density of OL improved the stability of clay particles, which was evident from the

drop in the destabilization index (Figure 8a). OL5 with a high charge density exhibited the

maximum reduction in the destabilization index at the 16 mg/L dosage. As can be seen, OLs with

a low charge density need a higher dosage to increase the stability of the clay particles. UL has no

effect on the stability of clay particles, because of its low charge density. Previously, anionic

polyacrylamide (APAM), with a high charge density (-4.2 meq/g) stabilized kaolin particles better

than APAM with a low charge density (-1.8 meq/g), which was attributed to the maximum

adsorption of high charge APAM on the clay surface [27].

28
Figure 8b presents the influence of molecular weight of OLs on the destabilization index. All OLs

(OL6-OL10) exhibited an increase in the stability of clay particles with dosage. Increasing

molecular weights stabilized the clay particles more effectively for OL6, OL7 and OL8. In case of

high molecular weight OLs (OL9 and OL10), the destabilization index is lower than OL8 at 8

mg/L polymer concentration. However, a higher concentration resulted in a lower stability

(increase in destabilization index to 2.5 and 3.3 for OL9 and OL10, respectively). A similar trend

was also observed under dynamic conditions with decreased relative turbidity of clay suspensions

at higher dosages of OL9 and OL10. Lentz and co-authors demonstrated that the efficiency of clay

particles stabilization decreased with increasing the molecular weight of anionic polyacrylamide

(10 mg/L) [51]. These results suggest that both molecular weight and charge density of OLs has a

strong influence on the stabilization of clay particles under static conditions.

OL1 OL2 OL3 OL4 OL5 UL

16
14 a
Destabilization index

12
10
8
6
4
2
0
0 0.2 0.4 0.6 0.8 1
Amount adsorbed, mg/g

29
 OL6 OL7 OL8 OL9 OL10

16
14 b
Destabilization index

12
10
8
6
4
2
0
0 0.2 0.4 0.6 0.8 1
Amount adsorbed, mg/g

Figure 8. Destabilization index of kaolin suspension as a function of polymer adsorbed amount

when a) OLs with varied charge densities and a similar molecular weight and b) OLs with varied

molecular weights and a similar charge density were used (other conditions were 30 °C, pH 7 and

2 g/L kaolin dosage).

3.6. Impact on the Size of Kaolin Particles under Dynamic and Static Conditions

The addition of dispersants to colloidal solutions causes a decrease in the size of particles by

minimizing the aggregation of particles [52]. Analysis of kaolin particle size in the suspensions is

crucial at determining the dispersability of colloidal suspensions. Figure 9 shows the impact of

charge density and molecular weight of OLs on the size of kaolin particles under dynamic and

static conditions. It is seen that the size of kaolin particles was reduced with an increase in adsorbed

amount of OL. The increase in the charge density of OLs caused a significant reduction in the size

of kaolin particles (Figure 9a). The size of particles dropped the most via adding OL with the

highest charge density of 3.6 meq/g (OL5). This trend may provide evidence for improvement in

the dispersion of kaolin particles. Furthermore, the reduction in the size of kaolin particles

30
followed a similar trend under both dynamic and static conditions indicating that OLs are effective

as dispersants under both static and dynamic conditions. However, UL with negligible charges

exhibited insignificant reduction in the particle size. In one study, the dispersion of red kaolin

based ceramic suspensions decreased with increasing the starch dosage from 0.1 to 0.8 wt.% as

evident by particle size changes from 2.8 to 1.5 μm at pH 7 [53]. Studies by Li and co-authors also

confirmed that the charge of the polycarboxylate copolymer is significant in contributing to the

dispersion of kaolin particles [54].

Figure 8b presents the influence of OLs molecular weight on the size of kaolin particles under both

dynamic and static conditions with an increase in adsorbed amount of OLs. Interestingly, an

adsorbed amount of 0.7 mg/g OL was sufficient to reduce the size of particles under both dynamic

and static conditions, and a higher adsorption amount (specially for OL9 and OL10) had a negative

impact on the size of particles. This increase provides evidence for the aggregation of particles by

the configuration of large size polymers at solid/liquid interface [55]. OL8 with charge density of

3.6 meq/g and molecular weight of 30,000 g/mol reduced the size of the kaolin particles the most.

These results also support the trend observed in the relative turbidity (Figure 5) and destabilization

index analysis (Figure 8). In a study on the stabilization of kaolin suspensions using polyacrylic

acid (PAA), PAA with the molecular weight of 1800 g/mol was effective in dispersing particles

[56].

31
 OL1 OL2 OL3 OL4 OL5 UL
8
7
Particle size under dynamic

6
conditions, µm

5
4
3
2
1
0
9 8 7 6 5 4 3 2 1 0
Particle size under static conditions, µm

OL6 OL7 OL8 OL9 OL10

8
Particle size under dynamic

7
6
conditions, µm

5
4
3
2
1
0
9 8 7 6 5 4 3 2 1 0
Particle size under static conditions, µm

Figure 9.a) Correlation between the sizes of particles under dynamic and static conditions when

OLs having a similar molecular weight of 26,000 g/mol but with different charge densities and b)

OLs having a similar charge density of 3.6 meq/g but with different molecular weights were used

(other conditions were 30 °C, pH 7 and 2 g/L kaolin dosage).

3.7. Kinetic of Dispersion

To further understand the effect of charge density and molecular weight of OLs on the dispersion

of kaolin particles, the kaolin particle size was studied in the presence of OLs under static

32
conditions in Figure 10. The kaolin suspension exhibited insignificant decrease in kaolin particle

size as time elapsed to 60 min in the presence of UL. All the three OLs (OL1, OL5 and OL 10)

reduced the particle size with time extension up to 60 min. OL1 reduced the particle size from 8

μm to 5.4 µm, while OL5 and OL10 reduced the particle size to 0.3 and 2.4 µm, respectively, with

time extension up to 60 min. Upon adsorbing on kaolin particles, OLs tended to introduce negative

charges on particles (as discussed in section 3.3), causing them to repel each other and thereby

separating aggregated particles and reducing the size of kaolin aggregates [52]. The minimal

decrease in kaolin particle size by OL1 with time is due to its low charge density. On the other

hand, OL5 with a high charge density enhanced the dispersion of kaolin particles by introducing

more negative charges on kaolin as time progressed. The time extension may help expose more

charges of OLs via reconfiguring on the particle surface. In case of OL 10, even though the size of

kaolin particles reduced with time, the overall reduction in size is less than that made by OL5. This

is because OL10 possesses a larger hydrodynamic size (Table 1). Increased adsorption with time

results in the entanglement of long polymer chains in the suspension, and the possible bridging

may counteract the electrostatic repulsion between the particles [57].

33
 OL1 OL5 OL10 UL

9
8
7
Partcile size, μm

6
5
4
3
2
1
0
0 10 20 30 40 50 60 70
Time, min

Figure 10. Effect of molecular weight and charge density of OLs on kaolin particle size as a

function of time.

4. Conclusions

This work provided evidence for property-performance relationship of oxidized lignin as a

dispersant for kaolin suspension. A kraft lignin-based dispersant with excellent properties was

introduced for the first time in this work. The adsorption of OLs on kaolin particles was influenced

by their charge density. OL6 having the charge density of 3.6 meq/g and molecular weight of

11,000 g/mol showed the maximum adsorption of 0.81 mg/g on kaolin surface at 32 mg/g OL

concentration. The adsorbed OL affected the zeta potential and relative turbidity of kaolin

suspensions. The zeta potential of kaolin particles is directly affected by the charge density of OLs,

while molecular weight has an insignificant effect. Both charge density and molecular weight of

OLs affected the relative turbidity and size of kaolin particles under dynamic conditions. Sample

OL8 with the charge density of -3.6 meq/g and molecular weight of 30,243 g/mol was the most

effective dispersant for kaolin suspensions. Dispersion studies under static conditions also proved

that the stability of kaolin particles was affected by both charge density and molecular weight of

34
OLs. Kinetic studies suggested that OLs improved the dispersion of kaolin particles quickly and

charge density and molecular weight had strong impacts on the stabilization of particles. To design

kraft lignin-based dispersant for different systems, the property-performance relationship of

oxidized lignin in different suspension and solution systems should be studied in future.

ACKNOWLEDGEMENTS

The authors would like to thank NSERC-Canada, Canada Foundation for Innovation, Onrtario

Research Fund, Canada Research Chairs and Northern Ontario Heritage Fund Corporation

programs for funding this research.

ORCID

Pedram Fatehi: 0000-0002-3874-5089

Notes

The authors declare no competing financial interests.

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