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Colloidal and Rheological Properties of Natural Rubber Latex Concentrate

Article  in  Applied Rheology · March 2016

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 | DOI: 10.3933/APPLRHEOL-26-15659 | WWW.APPLIEDRHEOLOGY.ORG

Colloidal and Rheological Properties of Natural Rubber Latex

Concentrate

H. M. Lim1,2*, M. Misni2

1Malaysian Rubber Board, 47000 Sungai Buloh, Selangor, Malaysia

2Department of Chemistry, University of Science, 50603 Kuala Lumpur, Malaysia

* Corresponding author: evelyn@lgm.gov.my

Received: 10.12.2015, Final version: 3.2.2016

c Applied Rheology. Downloaded from terminal 58.26.127.142-Rheol-Society-Members-Only

Abstract:
Natural rubber latex concentrate (NRLC) is an important material used in manufacturing dipped products, yet thorough analysis
of their colloidal and rheological properties are still lacking in these areas. In this work, the colloidal and rheological behaviour
of the NRLC was studied. The NRLC particle size was in the range of 0.3 to 2 μm with narrow particle size distribution. The
response of NRLC to an applied deformation was assessed through rheological experiments which include dynamic oscillation
and steady state measurements. A change from liquid-like to solid-like behavior was observed as the volume fraction of the
NRLC was increased above 0.48. The plastic viscosity and yield stress of the NRLC increased with increasing volume fraction
according to the Bingham equation. The maximum packing volume fraction of the NRLC was found to be 0.75 with a diffused
double layer thickness of 14 nm at ϕ =0.61.

Key words:
Natural rubber latex, latex concentrate, rheology, SEM, Bingham, diffused double layer

1 INTRODUCTION motion, surface adsorption sedimentation and diffu-

Natural rubber latex (NRL) is harvested by tapping the
bark of Hevea brasiliensis, the natural rubber is con-
tained in the cells of tree which are formed by meta-
bolic processes that occurred in plants. The rubber tree
is originally found growing in the Amazon region of
South America, however in the latter part of the 19th
century it is grown extensively in plantation estate
especially in South East Asia. The liquid of milky appear-
ance that flows from the tree is a colloidal dispersion
Redistribution not permitted
sion properties.
The NRL exhibit non-Newtonian flow, its viscosity
varies with the shear rate and temperature. The mate-
rial may exhibit shear-thinning, shear thickening, dila-
tancy, pseudoplastic, thixotropy or hysteresis. In daily
manufacturing practice, the viscosity of NRL is obtained
using a flow cup or Brookfield viscometer which pro-
vides a means of determining the presence and extends
of structural viscosity and other rheological properties.
The rubber particles in the field latex are envisaged by

[1] of cis-1,4-polyisoprene particles in an aqueous medi-
um. The latex comprises of two phases namely the dis-
perse phase and dispersion medium. The disperse
phase consists of large number of small particles which
are polymeric in nature. The solid content of the latex
is found to be between 30 to 40 % and the remainder
being water. It consists of particles of rubber hydrocar-
bon and non rubbers [2] such as proteins, carbohy-
drates, phospholipids, amino acids, trace metals and
mineral salts. The colloidal properties of NRL dispersion
system are dependent on the composition at the inter-
face between the disperse particles and the dispersion
medium [3] and also the size of the disperse particles
similar to other dispersion system. They are subjected
to interfacial and kinetic phenomena such as Brownian
Blackley [4] to be surrounded by the double layer
whereby an inner layer of phospholipids resides be-
neath a protein layer on the outside of a rubber hydro-
carbon which is a body of very viscous liquid rubber.
However recent research proposed a new model of nat-
ural rubber particle consisting of a mixed layer of pro-
teins and phospholipids surrounding the latex particle
with polyisoprene rubber as the hydrophobic core [5].
In this study, we hypothesized the NRL particles having
a micellar structure (Figure 1). Whereby the NRL parti-
cles had a hydrophobic rubber core and mixed of lipids
and protein at the surface of the NRL particles. As pro-
teins could have dual characteristics similar to surfac-
tants, it mae NRL or partly embedded on the rubber
core. The colloidal properties namely particle size and

© Appl. Rheol. 26 (2016) 15659 | DOI: 10.3933/ApplRheol-26-15659 | 1 |

 Figure 1: Hypothesized cross-section of NRL particle structure.
c Applied Rheology. Downloaded from terminal 58.26.127.142-Rheol-Society-Members-Only
Figure 3: Volume (●) and cumulative volume (○) distributions
as a function of latex particle diameter.
shape of the NRLC were characterized. While the rheo-
logical properties of the NRLC were thoroughly studied
and analyzed using the Bingham equation. Dynamic
oscillation and steady state measurements on the NRLC
were performed.
2 MATERIALS AND METHODS
2.1 VELOCITY PROFILES MEASURED BY UVP
Redistribution not permitted
Fresh NRL was collected from the rubber trees at the
RRIM Experimental Station Sungai Buloh, Selangor.
0.5 % of ammonia was added to the field latex at the
point of collection for preservation purpose. The field
latex was then diluted to 30 % dry rubber content (DRC)
and stirred overnight prior to centrifugation. The
ammoniated field latex was centrifuged using a Alfa
Laval centrifuge machine to yield 60 % of dry rubber
content. The field latex was fed into a constant head
device to ensure a constant central feed tube. The latex
passed through a distributor to the bottom of the bowl,
it was then broken up into thin layers by a number of
metal discs within the bowl which rotates at 12600 rpm.
The regulating screw was inserted to a certain length
to control the density differences between the cream
© Appl. Rheol. 26 (2016) 15659 | DOI: 10.3933/ApplRheol-26-15659
Figure 2: Mechanical stability time (●) and zeta potential val-
ue (○) at pH 8 of NRLC during 60 days of storage period.
and the skim latex. Finally, the NRL concentrate was
preserved to 0.7 % of ammonia before storage.
2.2 MECHANICAL STABILITY TIME
The NRLC (100 g) was diluted to 55 % total solids with
1.6 % aqueous ammonia solution. The diluted latex was
then warmed with gentle stirring to 36 °C. The diluted
and warmed latex was then sieved through a muslin
cloth, only 80 g of the latex was then weighed into the
flat-bottom cylindrical container. The test bottle was
placed in a stirring apparatus which consisted of a ver-
tical shaft high-speed stirrer, a Klaxon machine. The
latex was stirred at 14000 rpm until the first visible sign
of flocculation was reached [6], the mechanical stabil-
ity time (MST) is expressed in either seconds or min-
utes.
2.3 PARTICLE SIZE MEASUREMENTS
A Mastersizer 3000 particle size analyzer equipped
with a Hydro EV dispersing unit from Malvern, UK was
used to measure the particle size using laser light scat-
tering method. The equipment utilizes red (633 nm) and
blue (470 nm) laser lights to measure particle sizes be-
tween 0.01 to 3500 μm. The red light source is a He-Ne
type of 4 mW and the blue light source from LED of
10 mW. The angular range of the detector falls between
0.015 to 144 degrees.
2.4 ZETA POTENTIAL MEASUREMENTS
The zeta potential of the NRLC was measured using
Brookhaven Zeta Plus, US. The zeta potential analyzer
utilizes electrophoretic laser light scattering (solid state
laser of red light (660 nm), 35 mW) to determine the
electrophoretic mobility of charged colloidal disper-
sions. The latex was first diluted to 0.01 % and then
transferred into the plastic cuvette of 1 cm2, the palla-
dium electrodes mounted on acrylic support were then
inserted into the cuvette before being placed into the
| 2 |
 Figure 4: SEM micrograph of field latex.
c Applied Rheology. Downloaded from terminal 58.26.127.142-Rheol-Society-Members-Only
holder. A voltage of 100 V, yielding a field of 278 V/cm
was applied across the electrode (10 mm x 5 mm) with
a gap of 3.6 mm. Zeta potential meat 15 ° detection
angle.
2.5 SCANNING ELECTRON MICROSCOPE
The NRL and NRLC suspension was diluted with distilled
water in the ratio of 1:20. The suspension was dispersed
thoroughly by hand and subsequent with magnetic
stirrer. A few drops of latex suspension were then
placed in a microcentrifuge tube, 2 % of aqueous osmi-
um tetroxide was added and left for 30 minutes. The
latex suspension with osmium tetroxide was then cen-
trifuged for 10 min at 5000 rpm. After centrifugation
the upper layer of supernatant was removed. Distilled
water was then added and thoroughly dispersed. The
centrifugation of solution, removal of supernatant and
addition of distilled water steps was repeated until the
solution appears to be colorless. A drop of specimen was
then placed onto the sample grid before being air dried
overnight in the desiccator. The sample was then coat-
ed with ultra-thin layer of platinum film of less than 1
nm thick using the JOEL JFC_1600 Auto Fine Coater
under high vacuum. Finally the sample grid was placed
into the field emission scanning electron microscope
Redistribution not permitted
(JOEL FESEM JSM-6701F, Japan) to obtain the micro-
graph.
2.6 RHEOLOGY
Oscillatory and steady state measurements were car-
ried out on the NRLC dispersions using a Bohlin CVO-R
Rheometer, England. A coaxial cylinder with a moving
bob (radius = 14 mm) and a fixed cup (radius = 15.4 mm)
was used. The Bohlin Rheometer performs rheological
measurements by turning the bob back and forth in a
sinusoidal manner. Time sweep test, dynamic oscilla-
tion and steady state measurement were performed.
All measurements were made at 25 ± 0.1 °C.
© Appl. Rheol. 26 (2016) 15659 | DOI: 10.3933/ApplRheol-26-15659
Figure 5: SEM micrograph of NRL concentrate.
3 RESULTS AND DISCUSSION
3.1 PROPERTIES OF NRL CONCENTRATE
After the NRL was concentrated through centrifugation,
the MST and zeta potential of the latex were measured
at intervals during the storage period as shown in Figure
2. Upon achieving the MST of 1200 seconds, the latex
was used as a starting material for other experiments
as the MST plateaus. Large coagulum was observed in
the shaft of the Klaxon machine when the MST test was
carried out on the third day after the field latex has been
centrifuged. The graph clearly showed a rapid rate of
increase in stability over the first twenty days followed
by a slower rate of increase. The maturation of a latex
concentrate is known to have a strong influence on its
mechanical stability [7], while metal ions reduce its sta-
bility [8]. The mechanical stability increased during the
storage of a fresh latex concentrate is a consequence of
hydrolysis of the phospholipids, which produces fatty
acid, phosphate anions and organic bases. The fatty
acids which have been identified in NRL include oleic,
linolenic, palmitic, steric and arachidie [9]. The adsorp-
tion of these fatty acids at the particle interface would
produce an increase in mechanical stability, due to par-
tial deprotonation of fatty acid at pH 8, consequently
caused a higher surface charge and therefore a higher
repulsive energy between approaching particles as
reflected by the increasing zeta potential magnitude
during the storage period.
3.2 PARTICLE SIZE OF NRL CONCENTRATE
The volume distribution of concentrated NRL obtained
by diffraction method is shown in Figure 3. The volume
average diameter of the NRLC expressed as D[4,3] was
equal to 0.98 μm with a span of 0.99 indicating a wide
particle distribution. The surface area average diame-
ter, D[3,2] was equal to 0.86 μm. The value of d(0.5) rep-
resenting the 50 % percentiles of the size distribution
was found to be 0.93 μm which was closer to the D[4,3].
| 3 |
 Figure 6: Time sweep curve of NRLC at 25°C: □ elastic modulus
G’, ○ viscous modulus G”. tions as a function of strain at 25°C: □ = 0.61, ○ = 0.58, = 0.52,
Figure 7a: Elastic modulus of NRLC at different volume frac-
c Applied Rheology. Downloaded from terminal 58.26.127.142-Rheol-Society-Members-Only

and ◊ = 0.50.

As the NRLC is polydispersed these three values do not

exactly provide the same numbers. The z-average diam-
eter and polydispersity of the latex was determined
using photon correlation spectroscopy (PCS). The NRLC
particle size was in the range of 0.3 to 2 μm. The low
polydispersity indicated that the NRLC contains narrow
particle size distribution.

3.3 MICROGRAPHS OF NRL PARTICLES

The NRL particles are predominantly small spheres with

a few larger pear-shaped or elongated particles. The
particle size of the NRL (Figure 4) was observed to have
wider distribution of particle sizes as compared to the
NRLC which contained of a more narrowed range of par-
ticle sizes (Figure 5). During the centrifugation process,
the larger latex particles move more rapidly as com-
Figure 7b: Elastic modulus of NRLC as a function of volume
pared to the smaller particles, as such the NRLC tend to
fractions at γ = 0.031 at 25°C.
contain predominantly larger and uniform particles as
compared to the NRL. The process also increases the
proportion of the rubber in the latex and removes unde- sions such as NRL may undergo micro structural re-
sirable impurities. arrangement with time which influences its rheological
properties. The time sweep oscillatory experiments
3.4 RHEOLOGICAL PROPERTIES OF NRL CONCENTRATE were performed to determine the modulus value after
the NRLC has been loaded and pre-sheared. The true
Redistribution not permitted

The NRL system is a complex and multi component sys-
tem [10], having a solid-liquid system at its interfacial
region [11]. Interparticle interactions between NRL par-
ticles are electrostatic interaction, as the NRL particles
have a surface charge due to the ionization of the car-
boxylate groups on its surface. An unequal distribution
of counter-ions and co-ions compensated the surface
charge to form the electrical double layer. Thus, the rhe-
ology of the NRLC dispersion is influenced by the elec-
trostatic stabilization arising from its double layer
repulsion. The response of NRLC to an applied deforma-
tion was assessed through rheological experiments
which include elastic and viscous modulus, steady
shear viscosity and yield stress as these are acknowl-
edged as material properties of dispersions. Disper-
rheological properties of the NRLC can only be observed
if it remains stable before data collection. The rebuild
in elastic modulus G’ and viscous modulus G’’ of the
NRLC as a function of time is shown in Figure 6. Initially
G” was larger than G’, the crossover of G” and G’ coin-
cides at approximately 500 s. The NRLC became more
elastic as time lapses where G’ increased at a faster rate
compare to G’’. The NRLC system had a time dependent
rheological properties as such the required equilibra-
tion time to conduct the subsequent rheology experi-
ments was fixed at 1800 seconds as the G’ was larger
than G’’ steadily and recovery of structures has
occurred after it had been disturbed [12].
Dynamic oscillatory technique was used to study
the response of NRLC to sinusoidal strain at 1 Hz frequen-

© Appl. Rheol. 26 (2016) 15659 | DOI: 10.3933/ApplRheol-26-15659 | 4 |

 tions as a function of frequency at 25°C: □ = 0.61, ○ = 0.58, =
Figure 8: Elastic modulus of NRLC at different volume frac-
0.52, and ◊ = 0.50 .
c Applied Rheology. Downloaded from terminal 58.26.127.142-Rheol-Society-Members-Only
Redistribution not permitted
Figure 9: Elastic modulus (●) and viscous modulus (○) of NRLC
at different volume fractions as a function of strain at 25°C.
cy. The linear viscoelasticity region (LVR) was deter-
mined by conducting a strain sweep test. The strain level
to which the NRLC was subjected to, was gradually
increased until significant non-linearity appeared in the
response. The nonlinear oscillatory behavior shows that
destruction of structure has occurred [13]. The modulus
decreased with increasing strain as expected. The LVR
was found to be from 0.01 to 0.07 strain, where the G’
was independent of strain as shown in Figure 7a. The
critical strain γcr was found to be in the range of 0.05 to
0.07 for volume fraction of 0.61 to 0.50. The volume frac-
tion is calculated based on the DRC of the NRLC. The elas-
© Appl. Rheol. 26 (2016) 15659 | DOI: 10.3933/ApplRheol-26-15659
Figure 10: Viscous modulus (○) and elastic modulus (●) of
NRLC at various volume fractions at 4 % strain and 1 Hz at
25°C.
tic modulus of the NRLC at different volume fraction ϕ
as a function of strain γ is shown in Figure 7a. Each incre-
ment of volume fraction corresponded to the replace-
ment of the medium by more NRLC particles. The elastic
behavior of the NRLC measured by G’ increased as the
volume fraction increases. The particle-particle distance
becomes relatively small compared to the particle
radius when the volume fraction increases as the parti-
cle number concentration increases. Such particles
demonstrate elastic response and behave like a “solid”.
From here, it can be observed the elastic modulus of the
dispersion particles were strongly dependent upon the
volume fraction and the surface interaction between
particles. Generally, the modulus becomes larger when
the concentration of the disperse phase increases [14],
this was observed in the study as shown in Figure 7b.
When the volume fraction was increased from about
0.50 to 0.61, there was a reduction in G’ value indicating
a change from liquid-like to solid-like behaviour.
The elastic modulus of NRLC as a function of fre-
quency ω at different volume fractions is shown in Fig-
ure 8. The frequency sweep was performed at 4 % strain
which falls within the LVR. This oscillatory experiment
probes the interactions between the disperse phase
entities and the continuous medium within the LVR,
where materials response is independent of the magni-
tude of deformation and the materials structure is
maintained. The change from liquid-like to solid-like be-
havior was observed as the volume fraction is increased
above 0.50, this was in agreement with the strain sweep
observation. The increase in elastic modulus as volume
fraction increases is also observed in hard sphere sus-
pensions [15]. The elastic modulus at the higher volume
fraction was found to be independent of the frequency,
however G’ of the low volume fractions increased with
increasing frequency. This may be due to the particle
being unable to reconfigure at higher frequencies [16].
The relative magnitude of the elastic modulus and vis-
cous modulus for the NRLC dispersion at different vol-
ume fractions at 1 Hz frequency is shown in Figure 9. In
| 5 |

Figure 11: tan δ of NRLC at various volume fractions at 4%
strain and 1 Hz at 25°C.
c Applied Rheology. Downloaded from terminal 58.26.127.142-Rheol-Society-Members-Only
this figure, the strong impact of concentration on the G’
and G’’ is observed. At higher volume fraction the solid-
like behavior was observed as G’ exceeded G’’ indicating
a predominantly elastic response, and at the lower vol-
ume fraction G’’ exceeded G’ and the behavior was liq-
uid-like. Polystyrene solution at several concentrations
has also exhibits similar behavior as the NRLC [17]. At
ϕ > 0.44, G’ was larger than G’’. At ϕ < 0.44, G’’ was larger
than G’, where the NRLC showed more viscous response
than elastic response. The cross over point where
G’ = G’’ occurred at approximately 0.43, which is shown
in Figure 10. Figure 11 also shows tan δ > 1 occurred at
ϕ = 0.43. As the volume fraction increases to 0.44 the
probability of particle-particle attraction became larger
thus increasing the electrostatic interaction. Compres-
sion of the electrical double layer may have occurred as
the NRLC particle-particle distance reduces. This led to
the increase in the plateau elastic modulus value with
the dispersion at higher volume fraction behaving like
an elastic solid [18]. By subjecting the NRLC dispersion
to shear deformation, the NRLC was found to behave as
a viscoelastic fluid.
The steady state viscosity of NRLC as a function of
shear rate at different volume fractions is shown in Fig-
ure 12. The ratio of the measured shear stress to the
Redistribution not permitted
applied shear rate is the apparent viscosity at a specific
shear rate [19]. The viscosity of the NRLC increased with
increasing volume fraction was as expected. Overlap-
ping of double layers cause the increase in viscosity
such effect is known as secondary electroviscous effect
[20]. Increased resistance to flow at higher volume frac-
tion is also due to closer packing of particles resulting
in greater interparticle interactions [21]. As the shear
rate increases, the NRLC exhibited shear thinning
behavior. At such high shear rates, the hydrodynamic
interactions determined by the double layer repulsion
will predominate over the Brownian diffusion thus the
NRLC system showed a low viscosity [22]. The NRL poly-
mer molecules may have also oriented and aligned with
the flow direction as the shear rate is increased [23].
© Appl. Rheol. 26 (2016) 15659 | DOI: 10.3933/ApplRheol-26-15659
ume fractions at 25°C: □ 0.61, ○ 0.60, 0.59, ◊ 0.57, and + 0.55.
Figure 12: Viscosity versus shear rate of NRLC of various vol-
Alignment with the flow became more complete as the
shear rate is increased, thus the viscosity decreased fur-
ther [24]. Yield behavior was observed at low shear rate
for latex at high volume fraction [25]. At high shear rate
region, all volume fractions exhibited Newtonian flow,
where viscosity was independent of shear rate. The
steady state viscosity investigates the hydrodynamic
effects of the NRLC system as it deformed. The relative
viscosity of NRLC over a function of volume fraction is
shown in Figure 13. The viscosity data is commonly ana-
lyzed using the Krieger-Dougherty equation [26]. The
experimental data was found to deviate from the
Krieger Dougherty curve as the NRLC is a soft sphere
system. The viscosity changed exponentially with vol-
ume fraction. When the effective volume fraction
becomes sufficiently large, relative viscosity increased
to infinity [27].
As the volume fraction increases, interaction be-
tween particles at the surface increases, which contri-
buted to the increase in viscosity. Increase in viscosity
is simply due to the hydrodynamic interaction of the
NRLC particle with the continuous medium [28]. Inter-
particle forces that give rise to structure formation may
also cause increase in viscosity [29]. The relative viscos-
ity showed a rapid increase at 0.5 volume fraction. The
results suggested that the NRLC system showed elastic
behavior at volume fraction above 0.5, at lower volume
fraction values it showed viscous behavior. These ob-
servations also corresponded to the dynamic oscillatory
results. As the concentration of the NRLC dispersion in-
creases, it exhibited a change from fluid-like to more
elastic-like behavior. In the dispersion systems, the in-
crease in concentration brings the particles closer
together. As the particles come closer together, the re-
pulsive interparticle forces become stronger and the
particles are physically restricted by other particles in
their motion in response to the applied deformation.
The restriction requires the particle to move in conjunc-
tion with other surrounding particles. Both effects keep
the particle in their equilibrium positions thus promot-
| 6 |
 25°C: ● experimental data, ○ Krieger-Daugherty fit.
Figure 13: Relative viscosity-volume fraction curve for NRLC at
c Applied Rheology. Downloaded from terminal 58.26.127.142-Rheol-Society-Members-Only
Figure 15: Plastic viscosity of NRLC as a function of volume
fraction at 25°C.
ing elastic behavior [30]. The rheology of highly concen-
trated NRLC dispersions was significantly different
from the less concentrated dispersion and may resem-
ble an elastic solid [31].
The ascending curve data of shear stress versus
Redistribution not permitted
shear rate of the NRLC were fitted to the Bingham mod-
el [32]. The Bingham model equation (Equation 1) de-
scribes the shear stress behavior of many shear thin-
ning materials at low shear rates [33]. It is acceptable
to use an equation to describe data over a limited shear
rate range that contains a yield stress term such as the
Bingham equation [34]. Rheological parameters were
obtained by fitting to the linear equation to determine
the slope (plastic viscosity) and intercept (yield stress).
(1)
Yield stress σy is a measurement of the attractive forces
in the NRLC system. The yield stress of the NRLC in-
© Appl. Rheol. 26 (2016) 15659 | DOI: 10.3933/ApplRheol-26-15659
Figure 14: Yield stress of NRLC as a function of volume frac-
tion at 25°C.
Figure 16: Volume fraction as a function of 1/(ηrel) ½ curve for
NRLC at 25°C: slope = - 1.0173, y-intercept = 0.7491, R2 = 0.997.
creased with increasing volume fraction (Figure 14),
which indicated the higher volume fraction NRLC
required a higher shear stress to flow to overcome the
forces that hold the NRLC particles in place. When the
bonds are broken, the material behaves as fluid [35]. The
appearance of yield stress indicates dominion of inter-
action between particles over hydrodynamic interac-
tions in disperse system [36]. The concept of yield stress
may be a very good approximation for practical purpos-
es. As a large number of latex products are mainly made
by dipping process, yield stress enables thin films to be
formed and without excessive dripping during the
process. It is the attractive forces that contribute to the
overall gel strength of the latex. Plastic viscosity ηp is a
parameter of the Bingham model. It represents the vis-
cosity of latex when extrapolated to infinite shear rate.
Plastic viscosity is the resistance to flow due to mechan-
ical friction. The friction occurs between the solids in
the NRLC, between the solids and the liquid that sur-
rounds them, and the shearing of the liquid itself. At
| 7 |

Figure 17: Diffused double layer thickness as a function of vol-
ume fractions of NRLC at 25°C.
c Applied Rheology. Downloaded from terminal 58.26.127.142-Rheol-Society-Members-Only
high volume fraction, the friction between the NRLC
particles increased and caused the plastic viscosity to
increase as shown in Figure 15. The plastic viscosity was
also observed to increase accompanied by an increased
in apparent viscosity η.
The Krieger-Dougherty equation (Equation 2) re-
lates viscosity to the particle concentration, where [η]
is the intrinsic viscosity having a value of 2.5 for spher-
ical particles and ϕp is the maximum packing volume
fraction. ϕp can be obtained using the empirical proce-
dure (Equation 3), where ϕp was obtained from a plot of
ϕ versus 1/(ηrel)½ and extrapolation to 1/(ηrel)½ = 0 [37].
The plot of volume fraction versus 1/(ηrel)½ is shown in
Figure 16. The ϕp for NRLC was found to be 0.75, which
corresponds to hexagonal packing [38] due to particle
polydispersity. The experiment data fitted well with the
equation.
(2)
(3)
Redistribution not permitted
As the effective volume fraction, ϕeff of the NRLC system
will correlate to the double layer thickness, it was deter-
mined using Equation 4.
(4)
From the ϕeff value, the diffused double layer thickness,
δ can be calculated using Equation 5. A plot of diffused
double layer thickness a function of volume fraction is
shown in Figure 17. As the volume fraction of the NRLC
increased, the adsorbed diffused double layer thickness
decreased which indicated elastic interaction at higher
© Appl. Rheol. 26 (2016) 15659 | DOI: 10.3933/ApplRheol-26-15659
0.61 volume fraction at 25°C: ● 0 minutes, ○ 20 minutes
Figure 18: Shear stress as a function of shear rate of NRLC at
(arrow denotes ramp up and ramp down).
volume fraction [39]. The diffused double layer thick-
ness depends on the volume fraction. By using rheolog-
ical measurement, the diffused double layer thickness
of the NRLC at ϕ = 0.61 was found to be 14 nm. This value
was very near to the diffused double layer thickness elu-
cidated using atomic force microscope in conjunction
with confocal fluorescence microscope [5].
(5)
A plot of shear stress versus shear rate of NRLC is shown
in Figure 18. The NRLC at ϕ = 0.61 was subjected to an
increasing and linearly shear rate in a loop test from
time zero to a maximum value and then decreased to
zero under the same condition. The NRLC exhibited
shear thinning behavior as its viscosity decreased with
increasing shear rate followed by a gradual recovery of
structure when the stress was removed. The ramp up
and ramp down curves did not coincide in the graph.
This hysteresis loop was caused by the decrease in the
NRLC viscosity with increasing time of shearing. This
showed that the NRLC was thixotropic. Decrease of vis-
cosity with time of shearing is called thixotropic [40]. It
is due to reversible breakdown of structure under shear
and is encountered frequently in dispersion [41, 42]. The
NRLC also exhibited “elastic overshoot” behavior from
the peak that was observed in the lower shear rate when
the NRLC was sheared 20 minutes after rest. A sudden
application of shear rate can cause an initial overshoot
in stress, a progressive decrease towards equilibrium
value followed after that. This is one of the behaviors of
concentrated dispersions [43].
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4 SUMMARY
The NRLC particles were predominantly small spheres
with a few larger pear-shaped or elongated particles,
having an average particle size of 0.98 μm. A change
from liquid-like to solid-like behavior was observed
when the volume fraction was increased from about
0.48 to 0.61 as there was a reduction in the elastic mod-
ulus value. The viscosity of the NRLC increased with
increasing volume fraction was as expected. The yield
stress and plastic viscosity of the NRLC increased with
increasing volume fraction. The ϕp for NRLC was found
to be 0.75, which corresponds to hexagonal packing.
c Applied Rheology. Downloaded from terminal 58.26.127.142-Rheol-Society-Members-Only
The NRLC also exhibited “elastic overshoot” behavior.
ACKNOWLEDGEMENTS
We would like to acknowledge and sincere gratitude to
both, the Malaysian Rubber Board (MRB) and University
of Malaya (UM) for the financial supports provided for the
research project. Special thanks to Dr Manroshan Singh
for useful discussion in the rheology experiments. The
authors are also grateful to Syahril Zainul for the technical
assistance rendered at MRB. The project is under the UM
Postgraduate Research Grant No. PG123-2012B.
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