Colloids and Surfaces A: Physicochem. Eng.

Aspects 413 (2012) 712

Contents lists available at SciVerse ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Chitosan and mixtures with aqueous biocompatible temperature sensitive

polymer as occulants
Simona Schwarz a, , Sandra Montserrat Ponce-Vargas b , Angel Licea-Claverie b , Christine Steinbach a
a
Leibniz-Institut fr Polymerforschung Dresden e.V., Hohe Strasse 6, D-01069 Dresden, Germany
b
Instituto Tecnologico de Tijuana, Centro de Graduados e Investigacion, A.P. 1166, 22000 Tijuana, BC, Mexico

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

Article history: A novel strategy for faster and better occulation in solidliquid separation processes is reported: the
Received 3 November 2011 use of a natural polyelectrolyte (chitosan) in combination with a biocompatible thermosensitive polymer
Received in revised form 16 March 2012 [poly(N-vinylcaprolactam) (PNVCL)].
Accepted 19 March 2012
Clay dispersions were used as model and evaluated by means of analytical centrifuge, laser diffraction,
Available online 28 March 2012
streaming potential and turbidimetry studies.
Results show that at 45 C the density of the sediment is up to 15% higher, as compared to the use
Keywords:
of chitosan only. This results from the temperature sensitive behaviour of PNVCL that phase separate
Chitosan
Temperature sensitive polymers
expelling water at temperatures higher than its LCST (3234 C).
Flocculation By using this strategy the sediment is more compact, contains less water, and contains a very small
Clay amount of biodegradable chitosan and biocompatible PNVCL.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Solidliquid separation through coagulation and occulation
is an important stage of many technological processes. Typical
examples are waste water treatment, sludge dewatering, pulp and
paper production as well as the pharmaceutical, cosmetic and
metal working industry. The overwhelming majority of these pro-
cesses use polyelectrolytes to regulate the stability and occulation
properties of dispersed systems. This resulted in a great variety
of synthetic and natural occulants, which are now commercially
available to meet the specic demands of industrial elds, where
an efcient solidliquid separation is required [114].
In this work a novel strategy for a faster and better occulation
performance was investigated: the use of natural polyelectrolytes
like chitosan in combination with a biocompatible polymer show-
ing a lower critical solution temperature (LCST) in water. By this
strategy we envision to speed up the occulation process and to
decrease the water content of the sediment by taking advantage of
the change from hydrophilic to hydrophobic of a LCST polymer by
heating.
Normally the solubility of compounds in a good solvent is
increased by increasing the temperature, an example is sugar in
water. However for polymer solutions the solubility depends on
Corresponding author. Tel.: +49 351 4658333; fax: +49 351 4658231.
E-mail address: simsch@ipfdd.de (S. Schwarz).
specic interactions between the polymer chain with the solvent
but also on interactions within the polymer chain itself. Often, there
is a limit in concentration for the solution of a polymer in a given
solvent and if an increase in temperature worsens the solubility
leading to phase separation, we talk about the lower critical solution
temperature (LCST), of the system. Poly(N-isopropylacrylamide)
(PNIPAAm) is the most studied polymer showing a LCST behaviour
in water [1519]. By heating an aqueous solution of PNIPAAm it
can be observed that at temperatures around 32 C, the solution
becomes turbid, followed by the formation of ocks that nally
precipitate.
How do a temperature sensitive polymer inuences the aggre-
gation process of a dispersion in presence of another occulant?
Although since 1985 a Patent describes the use of temperature
sensitive occulation [20], currently there are only scarce litera-
ture reports in this specic area of research. For example Deng
et al. describes that a colloidal TiO2 suspension form ocks with
a particle diameter of 266 nm using a cationic modied NIPAAm
copolymer containing 2.2 mol% of diallyldimethylammonium chlo-
ride. A faster and broader occulation was reported to occur at
42 C as compared with 23 C. The authors explain that at 42 C
cationic colloidal particles with a diameter of 87 nm are formed
that works as occulants [21]. In other report, Sakohara et al. use
both cationic and anionic modied PNIPAAm copolymers for the
occulation of TiO2 [2224]. They introduce a new concept of oc-
culation/compactation, explaining that after occulation the ocks
are compacted by dewatering taking advantage from the change
from hydrophilic to hydrophobic of the PNIPAAm chains by heating.

0927-7757/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2012.03.048
8 S. Schwarz et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 413 (2012) 712
This effect was only found by use of PNIPAAm copolymers, not for
PNIPAAm alone. Furthermore this occulation/compactation was
optimized by use of a combination of cationic and anionic modi-
ed PNIPAAm. [24]. Temperature sensitive precipitation as concept
was also recently introduced for Silica- und Kaolin-Suspensions as
a model for mining-processes [25].
Instead of PNIPAAm as a temperature sensitive polymer we
studied poly(N-vinylcaprolactam) (PNVCL). On heating its aqueous
solutions, phase separation is observed in the range of 3238 C,
depending on molecular weight [26].
The use of PNVCL for occulation was reported by Somasun-
daran et al. [27]. The occulation capacity was proven in acidic
conditions and at 40 C.
We present our results showing how the stability of dispersions
is inuenced in the presence of chitosan and mixtures of chitosan
and PNVCL at different pH values of 2 and 4 and at different temper-
atures. The pH values were chosen do to chitosan being soluble in
the acidic range only. Various methods for particle characterization
such as particle charge determination, laser diffraction, and separa-
tion analysis in a centrifugal eld were used. By using this mixture
the sediment is more compact, contains less water, and contains
a very small amount of biodegradable Chitosan and biocompatible
PNVCL.
2. Materials and methods
2.1. Preparation of dispersions
Kaolin (USP-type, Sigma) was used in all experiments as sup-
plied. Dispersions of clay particles in Millipore-water (pH 5.6) were
prepared by dispersing 5.0 g of powder into 500 mL of water using a
high intensity ultrasonic processor (UP200s, Dr. Hielscher GmbH),
operating at 24 kHz and up to 200 W.
2.2. Polymers
Chitosan 2500 with deacetylation degree of 85% and
Mn = 2,500,000 g mol1 , was obtained by Heppe Biolog
GmbH and used as received. Poly(N-vinylcaprolactam) with
Mn = 67,200 g mol1 was synthesized according [28]. The structures
are shown in Table 1.
2.3. Flocculation
Flocculation was investigated as batch tests in a series of
beakers, each containing 10 mL of the clay dispersion. After addition
of different amount of the polyelectrolyte solution the mixtures
were stirred for 15 min and allowed to settle for 20 min. After that
2 mL of the supernatant was taken from the beaker surface. The
Nephelometer 2100AN IS of the HACH Company (Germany) was
used to determine the turbidity T of the supernatant. The method
is based on the determination of the scattered light intensity mea-
sured at a scattering angle of 90 . The device is equipped with an
IR-LED ( = 860 nm) as light source.
Table 1
Structures of the used polymers.
Chitosan (CH)
2.4. Flock size measurements
The particle size distribution of particles in aqueous dispersion
was determined by laser diffraction measurements (MasterSizer ,
Malvern). The samples were stirred at 2000 rpm during measure-
ments. Dispersions for ock size characterization were prepared
according to the above described procedure for occulation tests.
Flock sizes were measured at 2000 rpm rotation speeds equipped
with impeller mixer.
2.5. Determination of the charge density
The charge condition of the dispersions and the polymers has
been characterized by means of streaming potential-pH-proles.
The streaming potential of dispersions (0.1 g/l) was measured in
dependence on pH using the particle charge detector PCD-03 (BTG,
Germany) and 702 SM Titrino (Metrohm, Switzerland). First the
pH was adjusted to pH 9 by adding NaOH and than the potential
was measured in the pH range from 9 to 3 after HCl addition. All
measurements were repeated at least twice.
2.6. Characterization of dispersion stability
The stability of particle dispersions has been analysed using the
analytical centrifuge LUMiSizer (L.U.M. GmbH, Germany), which
permits a centrifugal separation analysis and thus allows the direct
calculation of stability parameters like sedimentation velocity and
predictions concerning shelf life. This microprocessor controlled
centrifuge is adapted for rapid classication of stability and sepa-
ration of even concentrated dispersions [29]. It records the kinetics
of transmission changes for 12 samples simultaneously, like a time
lapse motion picture, up to 25,000 times faster than tests at gravity
by naked eye.
3. Results and discussion
Most naturally occurring particles are clay minerals which have
a negative surface charge over a broad pH range. Clay minerals
from Kaolin-type have a wide range of its applications, such as in
papers, paints, ceramics, plastics, medicine, and construction mate-
rials. Related to the importance of its application, the interaction of
clay with polyelectrolytes was investigated in detail by different
scientists, in most cases with respect to occulation [3035].
In our experiments Kaolin USP-type (Sigma) with ne particles,
also known as China clay, was used. The shape of the Kaolin particles
was studied by Scanning Electron Microscopy (SEM). Clay miner-
als are characterised by forming two-dimensional sheets. In Fig. 1a
broad distribution of small and big Kaolin plates is shown.
Particles in aqueous dispersion become charged. The charge,
measurable by zeta potential, is an important parameter for the
stability of dispersion. The streaming potential of clay is shown in
dependence on pH in Fig. 2. The magnitude of the streaming poten-
tial gives an indication of the potential stability of the colloidal
system. If the particles have a large streaming potential they will
repel each other, and the dispersion is stable. If the particles have
Poly(N-vinylcaprolactam) (PNVCL)
 S. Schwarz et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 413 (2012) 712 9

Fig. 1. (a) SEM picture and (b) particle size distribution in water at pH 5.6 of China clay. (b) The particle size distribution for aqueous clay dispersions. The particle size
distribution of China clay is very broad at pH 5.6, thus very small particles of 200 nm up to big particles of about 10 m are detected. The average size for both kinds of
particles is 0.35 m and 2 m.

low streaming potential, then there is no force to prevent the parti- 2000
cles from coming together. The dispersion is unstable and particles
1800 pH 2
aggregate.
pH 4
It is well known that Kaolin has positively charged edge faces 1600
pH 6
and negatively charged basal faces. In dependence on the pH the pH 7
1400
Silanol groups are effective in the aqueous dispersion. The net
charge is negative if the pH is higher the 3.5, see Fig. 2.
Turbidity (NTU)

1200
If the charge is high, the particles will remain separate, dispersed
1000
and in dispersion. In Fig. 2 it is shown that dispersions of clay are
negatively charged in the range of pH from 3.5 to 10. Near the iso- 800
electric point of pH = 3.5 the clay dispersion is very unstable. In the
basic pH range the clay dispersions have a higher stability than at 600

lower pH-values. 400

The occulation efciency of the used polymers is determined
by a variety of parameters; among these the pH range within which 200
the occulant is effective. Chitosan is soluble in water with addi-
0
tion of acetic acid. The solution of CH demonstrates, as shown in 0 1 2 3 4 5 6 7 8 9 10 11 12 13
Fig. 2, an isoelectric point at pH 7.6. That means chitosan has a Cp/Cs (mg/g)
positive charge up to pH 7.6. With decreasing pH the charge of CH
increases. But at pH values higher than 7.6 chitosan is unsoluble. Fig. 3. Flocculation of clay dispersion with CH at different pH values.
The thermosensitive polymer PNVCL behaves like a weak polyelec-
trolyte positively charged until pH 4.5 and in the pH range from 4.5 Clay dispersions were occulated with chitosan at different pH
to 10 is negatively charged. values. Turbidity measurements of the supernatant resulting a oc-
culation time of 20 min versus the amount of polyelectrolyte used
are shown in Fig. 3. The occulation window is the range of poly-
mer dosage (Cp/Cs: ratio of polymer to substrate in mg/g) where
800
the turbidity is low. If the polymer amount is to high, restabilization
clay occurs because of repulsion. Finally, the optimum occulant con-
600
CH centration of chitosan depends strongly on the pH. The occulation
PNVCL window is much broader if the pH is low. With increasing pH the
400 amount of chitosan for optimum occulation increases to, ranging
streaming potential [mV]

from about 1.8 up to 3 mg/g for pH 6 and 7.

200

4. Stability of dispersion
0
2 3 4 5 6 7 8 9 10
The dispersion stability has been analyzed in dependence on
-200 pH
pH value and in dependence on the addition of chitosan and on
the addition of mixtures chitosan/PNVCL. Fig. 4 shows different
-400
transmission proles of clay dispersions at tree different pH values,
obtained with LUMiSizer . The rst line in each of the gures is the
-600
rst transmission prole, followed by the second (10 s later) and so
on. China clay dispersions in water at pH of 6 are relatively stable
Fig. 2. Streaming potential pH proles of clay dispersion, CH and PNVCL. (short term). Most particles suspended in aqueous solution have a
10 S. Schwarz et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 413 (2012) 712

Fig. 4. Transmission proles of clay at different pH values.

a 12,5 b
china clay 12,5
+ 0.25 mg/g CH china clay

+ 0.50 mg/g CH + 0.25 mg/g CH

10,0 + 1.00 mg/g CH + 0.50 mg/g CH
10,0 + 1.25 mg/g CH
+ 1.25 mg/g CH
+ 1.87 mg/g CH
Volume (%)

7,5 Volume (%) 7,5

5,0 5,0

2,5 2,5

0,0 0,0
0,1 1 10 100 0,1 1 10 100
particle size (m) particle size (m)

Fig. 5. Particle size distributions of the untreated clay and of occulated clay using various CH concentrations and different pH values. (a) pH = 2; (b) pH = 4.

negative surface charge. Because particles have charges, they repel shows the average coil size of PNVCL in dependence on the temper-
each other and therefore they will not stick together. For exam- ature at pH 4. However, rather large aggregates with average sizes
ple, the transmission for the pure clay dispersion at pH 6 is 50% of around 34 m were observed when the measurement was car-
at position 118 after the measuring time. The stability changes in ried out at temperatures higher than 34 C. This strong increase in
dependence on the pH. With decreasing pH the stability decreases. the average size has not been expected and can only be explained
At the same position (118) the transmission is 55% at pH 9 and 88% by a strong aggregation tendency of the small particles to large
at pH 3. A high transmission of 100% means air or clear supernatant. particles above the transition temperature.
That means clay dispersions have a stability in the following range:
pH 9 > pH 6 > pH 3. At pH 6 and 9 the net charge is negative and at
pH 3 the dispersion is positive charged. 4000 PNVCL 67,200 g/mol
The particle size distribution of untreated clay show small differ-
ences in dependence on pH 2 and 4. At pH 2 few very big aggregates 3500
of about 30 m are obtained, see Fig. 5a). Increasing the amount
of the polymer used for the occulation of clay leads to increased 3000
oc size. At low concentrations (0.25 mg/g) of chitosan a substan-
Z-Average (d.nm)

tial number of particles demonstrating a size distribution prole 2500

similar to that of clay is present with a little shift to bigger par-

2000
ticle sizes. At higher polymer dosages the low sized population is
rather limited and the large ocks become the dominant feature
1500
of the size distribution prole. The largest ock size (20 m) was
obtained in the occulation optimum with clear supernatant at a 1000
polymer dosage 1.25 mg/g for pH 2. The occulation of clay at pH
4 gives bigger aggregates of about 40 m at a polymer dosage of 500
1.87 mg/g. The largest ock size is encountered at the concentration
where the lowest turbidity values were encountered. The ock size 0
measurements were conducted while mixing, reducing probably 26 28 30 32 34 36 38 40 42 44
the number of large ocks, which are more prone to rupture.
Temperature (C)
The temperature dependent change of the PNVCL due to the
phase transition has been veried by dynamic light scattering. Fig. 6 Fig. 6. LCST of PNVCL Mn = 67,200 g mol1 at pH 4.
 S. Schwarz et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 413 (2012) 712 11

a 12,5
china clay
b 12,5
china clay
+ 1.0 mg/g CH + 0.2 mg/g PNVCL + 1.0 mg/g CH + 0.2 mg/g PNVCL
+ 1.0 mg/g CH + 0.4 mg/g PNVCL + 1.0 mg/g CH + 0.4 mg/g PNVCL
+ 1.0 mg/g CH + 0.8 mg/g PNVCL + 1.0 mg/g CH + 0.8 mg/g PNVCL
10,0 + 1.0 mg/g CH + 1.2 mg/g PNVCL 10,0
+ 1.0 mg/g CH + 1.2 mg/g PNVCL
+ 1.0 mg/g CH + 1.6 mg/g PNVCL + 1.0 mg/g CH + 1.6 mg/g PNVCL
+ 1.0 mg/g CH + 2.0 mg/g PNVCL + 1.0 mg/g CH + 2.0 mg/g PNVCL
Volume (%)

Volume (%)
7,5 7,5

5,0 5,0

2,5 2,5

0,0 0,0
0,1 1 10 100 0,1 1 10 100
particle size (m) particle size (m)

Fig. 7. Particle size distributions of the untreated clay and of occulated clay using various mixtures of chitosan and PNVCL and different pH values.

a b
80
80
70

Integral Transmission [%]

70
Integral Transmission [%]

60
60
50
50
40
40

china clay
30 china clay
30 + 1.0 mg/g CH2500
+ 1.0 mg/g CH2500
+ 1.0 mg/g CH2500 + 0.2 mg/g PNVCL
20
+ 1.0 mg/g CH2500 + 0.2 mg/g PNVCL 20
+ 1.0 mg/g CH2500 + 0.4 mg/g PNVCL + 1.0 mg/g CH2500 + 0.4 mg/g PNVCL
+ 1.0 mg/g CH2500 + 0.8 mg/g PNVCL + 1.0 mg/g CH2500 + 0.8 mg/g PNVCL
10 + 1.0 mg/g CH2500 + 1.2 mg/g PNVCL 10 + 1.0 mg/g CH2500 + 1.2 mg/g PNVCL
+ 1.0 mg/g CH2500 + 1.6 mg/g PNVCL + 1.0 mg/g CH2500 + 1.6 mg/g PNVCL
+ 1.0 mg/g CH2500 + 2.0 mg/g PNVCL + 1.0 mg/g CH2500 + 2.0 mg/g PNVCL
0 0
0 250 500 750 1000 1250 1500 1750 2000 2250 2500 2750 0 250 500 750 1000 1250 1500 1750 2000 2250 2500 2750
Time [s] Time [s]

Fig. 8. Flocculation of China clay with chitosan and PNVCL.

Fig. 7 shows the particle size distributions of the untreated But at pH values in the range of 4 or higher no additional occulation
clay and of occulated clay using various mixtures of chitosan and was observed.
PNVCL at pH values of 2 and 4. At pH 4 no inuence of the ock Fig. 8 shows the variation of integral transmission during sample
sizes on the amount of PNVCL was observed. Independent of pH centrifugation of clay dispersions at pH 4 in presence of mixtures of
and amount of PNVCL the ock size is 20 m. CH and PNVCL as occulants. The lines correspond to the stability of
At pH 2 PNVCL has a positive charge and is a occulant too. The the clay dispersion. The slope of the curves indicates the sedimen-
oc sizes are shifted a little bit to higher values. The addition of tation velocity. At pH 4 CH and PNVCL are both occulants because
PNVCL to a clay dispersion (without CH) show a little occulation. of the low positive charge of PNVCL. That means addition of PNVCL

Fig. 9. Schematically solid liquid separation process with thermosensitive polymers.

12 S. Schwarz et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 413 (2012) 712
at temperatures of 25 C leads to a rapid sedimentation. In all cases
the slope is higher in presence of PNVCL (170224%/h) than CH
168%/h) alone. As can be seen, increasing temperature decreases
the stability of dispersions. Generally the slope was higher at 45 C
than 25 C. The calculated velocity was about 2 times higher. But
at 45 C the sedimentation velocity using chitosan is the highest
with 348%/h. In presence of PNVCL the velocity is lower in all cases.
But nevertheless the sediment is more compact in all cases where
PNVCL was added.
Fig. 9 schematically solid liquid separation process with ther-
mosensitive polymers.
At temperatures higher than the LCST of PNVCL it is signicant
that the ocks formed showed a positive inuence on the occu-
lation behavior of inorganic particles in dispersion. The velocity
was very fast and the aggregates of ocks from inorganic particles
and thermosensitive polymers were very dense. The position of the
bottom in the measuring cell was at 124.7 mm. The height of the
sediment was 1.29 mm but in the case of use of mixtures of CH and
PNVCL at 45 C there was more compact sediment of 1.1 mm. At
temperatures higher than the LCST temperature the thermosensi-
tive polymers form coils and this leads to more compact sediment.
A lot of applications like paper production or dewatering of sludge
takes place in the temperature range from 20 to 60 C. Thus it is
a big advantage to have a minimum of water in the sediment. In
presence of PNVCL the sediment showed up 15% lower water con-
tent. Similar results were obtained with Silica OX 50 in presence of
mixtures of chitosan and PNVCL at a constant pH of 5.6 [36].
5. Summary
Suspended clay particles were characterised with different
methods in presence of chitosan, and mixtures of chitosan and
PNVCL at pH 2 and 4. At pH values lower than 4.5 PNVCL has a
positive charge; that means we have studied occulation with two
polycations. At temperatures lower than the LCST of PNVCL the
velocity of sedimentation increases when PNVCL is added together
with chitosan. At temperatures higher than LCST, the thermosensi-
tive polymer leads to a more compact sediment than chitosan alone
as occulant. Low content of water in the sediment is an important
factor in applications in solid liquid separation process.
Acknowledgement
The research project has been supported with budgetary funds
of the DAAD.
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