Colloids and Surfaces A: Physicochem. Eng.

Aspects 377 (2011) 251260

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

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

Wetting analysis and surface characterisation of coir bres used as reinforcement

for composites
L.Q.N. Tran a, , C.A. Fuentes a , C. Dupont-Gillain b , A.W. Van Vuure a , I. Verpoest a
a
b

Department of Metallurgy and Materials Engineering (MTM), Katholieke Universiteit Leuven, Kasteelpark Arenberg 44, B-3001 Leuven, Belgium
Institute of Condensed Matter and Nanosciences, Universit Catholique de Louvain, Louvain-la-Neuve, Belgium

a r t i c l e

i n f o

Article history:
Received 8 November 2010
Received in revised form
20 December 2010
Accepted 6 January 2011
Available online 18 January 2011
Keywords:
Natural bres
Coir
Wilhelmy
Wetting
Surface energy
XPS

a b s t r a c t
Vietnam grown coir bres have been studied for use in composite materials. In order to understand the
brematrix interfacial compatibility, it is necessary to investigate the wetting behaviour and surface
chemistry of the bres. The aim of this paper is to develop a wetting measurement procedure to determine stable and reproducible advancing static contact angles, and estimate the bre surface energy.
Dynamic contact angles are measured using the Wilhelmy technique. The experiments are carried out by
considering the effects on the contact angle results of irregular wetted perimeter along the bre and liquid
absorption, which commonly appear with natural bres. Dynamic wetting of coir bres is then modelled
using the Molecular-kinetic theory from which the advancing static contact angle can be approximated
by tting dynamic data. Besides, advancing static contact angle was determined experimentally using an
approach derived from the Wilhelmy technique, in which the relaxation of the liquid meniscus was monitored after stopping the bre movement. There is a good agreement between advancing static angles
from the experimental and modelling method. The bre surface energy comprising polar and dispersive components is estimated following the Owens/Wendt approach using the advancing static contact
angle of various test liquids. The bre surface chemistry examined by XPS shows a carbon rich surface
consisting of waxes and a low proportion of lignin and fatty substances. From the results of the wetting
measurements and surface characterisation, the coir bre surface seems to be hydrophobic.
2011 Elsevier B.V. All rights reserved.

1. Introduction
Natural bres such as ax, jute, sisal, coir, hemp and bamboo
have been used as reinforcement in polymer composites during
the last decades. They are available in large amounts, at low cost,
have low energy utilisation and are renewable and biodegradable.
In most cases the specic properties of the natural bre composites
were found to compare favourably with those of glass bre composite [1]. Among natural bres, coir bres have low density ranging
from 1.0 to 1.3 g/cm3 and high strain to failure up to approximately
40%. This has the potential to ameliorate the toughness when they
are used in composite [2].
In composite materials, the interfacial properties of bre and
matrix play an important role in the nal mechanical performance.
The interactions at the interface generally consist of physical
adhesion, chemical bonding and mechanical interlocking. A good
physical adhesion is controlled by good wetting between bres and
matrices, which is strongly dependent on the surface energies of the
materials. Studying bre wettability with different probe liquids

Corresponding author. Tel.: +32 16 321448; fax: +32 16 321990.

E-mail address: Ngoc.Tran@mtm.kuleuven.be (L.Q.N. Tran).
0927-7757/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2011.01.023

provides an understanding of bre hydrophilicity and bre surface polarity. Surface energies determine the interactions between
materials, and contact angles are the result of such interactions.
Hence, measurement of contact angles and surface energies leads
to a prediction of the compatibility of bre and matrix.
Wetting is the consequence of the change in nature of interfaces
driven by free energy minimisation [3]. The quantitative measure
of solidliquid interactions is the contact angle. The equilibrium
contact angle dened by Young [4] at the intersection of the three
phases, gasliquidsolid, was initially developed for a drop of liquid
on a smooth solid surface. In case of a single bre, contact angles
are reported to be measured either directly or indirectly, typically
by using the modied Wilhelmy technique [57]. The direct technique is carried out by introducing a drop of liquid on the bre. The
contact angle is usually calculated following the theoretical model
proposed by Carroll [8], Yamaki and Katayama [9]. Some difculties are observed experimentally, such as improper drop making
and high curvature variation at the interface. For the indirect way,
the Wilhelmy technique is usually recommended. The principle is
to use a microbalance to record the wetting force, which is the capillary force exerted by the liquid on the bre. The contact angle
is then deduced from the recorded force in relation to the liquid
surface tension and the bre perimeter.

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L.Q.N. Tran et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 377 (2011) 251260

2. Molecular-kinetic theory (MKT) of dynamic wetting

advancing
hysteresis
receding

-v

Fig. 1. Schematic presentation of the velocity-dependence of the contact angle 

(after Dussan [13]).

Besides the consideration of measurement techniques, wetting measurements on plant bres present additional complexities,
which are typically not found for synthetic bres and which
may affect the measurement: liquid absorption/diffusion into the
surface layers/cell walls; diffusion of low-molecular-weight compounds from the surface layers into the liquid; physico-chemical
heterogeneity of the constituents (e.g., cellulose, hemicelluloses,
and lignin) of the surface layers; viscoelastic response of the surface
layers to the liquid [10].
In some specic studies, the measurement of the contact angle
is performed in dynamic conditions. There, the wetting of a liquid
on a solid surface is commonly known as the moving of the threephase line or wetting line across the surface of the solid. Associated
with this moving wetting line, dynamic contact angles and wetting
velocity are the main parameters used to quantify the dynamics
of wetting. It is experimentally reported that the dynamic contact
angle is usually found to depend on both the speed and the direction
of the wetting line displacement. The dynamic angles differ from
the corresponding static value and may refer to either an advancing
or receding interface. The measured angle will depend on the history of the system and varies according to whether the interface is
being advanced or receded. This phenomenon is known as contact
angle hysteresis (Fig. 1), and occurs in most real systems where
solid surfaces are often rough and chemically heterogeneous. In
this complex situation, the static contact angle is even unlikely to
be single-valued, but may show advancing and receding limits
[11,12].
The bre surface chemistry provides important information on
the chemical functionality that determines the interactions with
the chemical functionality of the matrix. The level of hydrophilicity and the surface energy of bres are also the result of chemical
groups on the surface. For surface chemical characterisation, Xray photoelectron spectroscopy (XPS) has shown to be a useful
tool to investigate the surface chemistry of several kinds of cellulose bres, which assists to determine a quantitative elemental
composition and certain functional groups present on the surface
[1417].
In this paper, dynamic contact angle measurements of coir
bres with different probe liquids are carried out based on the
Wilhelmy technique. Advancing static contact angle approximation is conducted by application of the Molecular-kinetic theory
and by using a modied Wilhelmy method. PET bres are also
examined as reference and to evaluate the employed methods.
Coir bre advancing static contact angles are used to estimate the
bre surface energy following the OwensWendt approach. XPS is
used to analyse the bre surface chemistry, linked with the wetting results, to obtain a deeper understanding of the coir bre
surface.

Several studies of dynamic wetting, centred on using the contact angle as a geometrical boundary condition for the moving
uid/uid1 interface at the solid surface, are described elsewhere
[11]. For the aim of this study, the Molecular-kinetic theory of
dynamic wetting is applied to study the relation between the
dynamic contact angle and the static contact angle.
According to the Molecular-kinetic theory [18], the macroscopic
behaviour of the wetting line depends on the overall statistics of the
individual molecular displacements that occur within the threephase zone. The wetting line is modelled by the displacements of
length  of the molecules from one adsorption site to another. The
molecules can move forward with a frequency K+ , or backward with
a frequency K . The net frequency is Knet = K+ K . Then the velocity
of the wetting line is given by v = Knet . At equilibrium, v = 0, Knet
is zero and K+ = K = K0 . Blake and Haynes assumed that the driving
force for the wetting line is the out-of-balance surface tension force
 LV (cos  0 cos ) where  LV is the surface tension of the liquid
in contact with vapour,  0 is the static contact angle and  is the
dynamic contact angle. Using Eyrings theory of absolute reaction
rates for transport in liquids gave the nal relationship between 
and v as:

 (cos 0 cos )
v = 2K0  sinh LV
2nkB T


(1)

where n is the number of adsorption sites per unit area, kB is Boltzmanns constant, T is the temperature.

3. Materials and methods

3.1. Materials
3.1.1. Fibres
Coir bre was supplied by the Can Tho University of Vietnam,
where it was extracted from the husk shell of coconut from the
coconut palm (Cocos nucifera L.). The extraction process was a
purely mechanical method without any retting process or chemical treatment. The extracted bres were soaked in hot distilled
water at 70 C for 2 h, then smoothly washed with alcohol to remove
greases which may attach on the bre surface during the bre
extraction process, rinsed with deionised water and dried under
vacuum at 90 C. The thus cleaned bres are considered as unmodied bres. In order to prevent the effect of a rough bre surface due
to unevenly distributed organic material (Fig. 2a), coir with a clean
surface (Fig. 2b) was selected with the help of a light microscope.
Polyethylene terephthalate (PET) monolaments (diameter
800 m) from Goodfellow were used as a reference synthetic bre
to evaluate the measurement methods and to compare with coir
bres. PET bres were washed with a detergent (RBS-35 from
Chemical Products) for 1 h with a magnetic stirrer to remove
organic residues on the surface, and rinsed in deionised water at
90 C for 1 h. The cleaned bres were then dried under vacuum at
90 C for 2 h and conserved under silicagel.

3.1.2. Test liquids

Test liquids used in this study with surface tension [19], density,
and viscosity are described in Table 1.

In case of a surrounding vapour, usually air, this is also modeled as a uid.

L.Q.N. Tran et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 377 (2011) 251260

253

Fig. 2. SEM images of coir cross-section and coir surface: (a) organic residues on coir surface, (b) clean surface, (c) bre cross-section, and (d) longitudinally orientated cells.

3.2. Dynamic contact angle measurement

The dynamic contact angle measurement of the coir bres was
carried out according to the Wilhelmy method, using a Krss K100
tensiometer with 1 g weight resolution. The bre sample was
attached to a beam of an electrobalance and was held vertically at a
xed position during the measurement, while a beaker containing
the test liquid was raised and lowered via a driving platform. When
the test liquid touched the bre, a force was detected on the balance.
In contact with the liquid, the bre was scanned in both advancing
and receding directions, at a constant velocity, from which a forceposition plot was constructed with help of the software LabDesk.
Theoretically, the force on the balance is the sum of the wetting
force, the weight of the probe and the buoyancy force, as given by:
Ftotal = pLV cos  + mg + L gAd

(2)

where Ftotal is the total measured force on the electrobalance, p is

the bre wetted perimeter or,  LV is the liquid surface tension,  is
the contact angle at the three-phase contact line, m is the mass of
the bre, g is the acceleration of gravity, L is liquid density, A is the
bre cross sectional area and d is the immersion depth. The weight
of the bre probe can be measured beforehand and set to zero on the
balance, while the effect of buoyancy can be removed by extrapolating the force back to zero immersion depth. The remaining force
is the wetting force only:
Fwet = pLV cos 

(3)

The contact angle was then calculated from the received force
data at any depth. For both advancing and receding processes, the
obtained angles were called advancing contact angle and receding
contact angle respectively. Due to the effect of coir bre surface
roughness, the receding angles were apparently not stable. Therefore, only the advancing contact angles were studied.
The measurements were performed at a temperature of 20 C
and humidity of approximately 60%. Different measurement speeds
ranging from 2 m/s to 8000 m/s were used to study both
dynamic wetting and static contact angle approximation, the latter
is described in the following parts of this paper. The immersion
depth used for experiments was from 2 mm to 5 mm depending on the applied measurement speeds. As mentioned, water,

diiodomethane and benzyl alcohol were used as probe liquids in

both contact angle measurements and the surface energy calculation.
For a given measurement of the bre with a test liquid, the
calculation of contact angles was mainly affected by two parameters, namely the bre wetted perimeter and the measured force.
In contrast to synthetic bres, natural bres do not have a uniform geometry along the bre. Therefore, the bre perimeter may
change and this may lead to an incorrect result for the contact angle.
Besides, the liquid absorption into the bres may also create an
extra weight during the measurement. These above considerations
have been taken into account and the effects have been minimized
in the later experiments.
3.2.1. Determination of bre wetted perimeter
The method to determine the bre wetted perimeter was based
on tensiometric measurement. A low surface tension liquid, nHexane, was used for wetting measurements with the bre. At
relatively low speed, it is assumed that the bre is totally wetted
by the liquid. Then the contact angle is zero. Eq. (3) becomes:
Fmeasured = pLV

(4)

Following Eq. (4), the bre wetted perimeter, p, can be determined from the wetting force and liquid surface tension. Thus,
in principle, the bre wetted perimeter can be measured at any
position along the bre.
Another method was also carried out to make a comparison.
The microscope images of cross-sections of bre samples were then
examined by image analysis. For each bre, images of various crosssections were taken by a scanning electron microscope (SEM 30 XL
FEG). With help of the software Leica Qwin, the contour of each
cross-section was determined.
3.2.2. Estimation of the effect of liquid absorption
Using the electrobalance of the tensiometer, the bre sample was weighed before and after the wetting measurement. The
absorbed mass into the bre was determined to analyse the effect
on the nal contact angle results. The experiments were carried out
with the three test liquids.

Table 1
Summary of surface tension, density, viscosity and purity of test liquids used in this paper;  p is the polar and  d is the dispersive component of the surface tension according
to the OwensWendt analysis.
Test liquid

 (mN/m)

 p (mN/m)

 d (mN/m)

 (g/cm3 )

 (mPas)

Purity

Supplier

n-Hexane
Diiodomethane
Benzyl alcohol
Ultrapure water

18.4
50.8
39.0
72.8

0
0
8.7
51.0

18.4
50.8
30.3
21.8

0.659
3.32
1.04
0.998

0.32
2.76
8.0
1

99.6%
>98%
>99.5%
18.2  cm resistivity

Acros
Merck
Acros
Millipore

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L.Q.N. Tran et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 377 (2011) 251260

3.4. Solid surface energy estimation

Contact angle measurements of a solid yield data that reect
the thermodynamics of the solidliquid interactions. These data
can be used to estimate the surface energy of the solid. Several
approaches for the surface energy calculation were proposed by
Zisman, Fowkes, Wu and Van Oss-Good. The method based on a
geometric-mean approach used in this paper was rst given by
Fowkes and later by Owens and Wendt [21]. In this method, the
surface energy of the solid,  SV , is divided into two components,
d , and polar,  p , using a geometric-mean approach
dispersive, SV
SV
to combine their contributions:
p

d
SV = SV
+ SV

(5)

The interfacial energy of two phases can be approximated by:

SL = SV + LV 2(

Fig. 3. Typical sorption measurement curves in water of coir bres having different
perimeters, showing that static equilibrium is reached after approximately 200 s.

3.3. Advancing static contact angle approximation

Since the signicance of the contact angle as a measure of wettability is based on equilibrium thermodynamic arguments, static
systems are most frequently studied [11]. It would be more reliable if static contact angles are introduced in the surface energy
calculation. In this paper, two methods were used to determine the
advancing static angle. The rst method is based on the relationship
between the advancing dynamic contact angles and the wetting
velocity following the MKT theory. By tting of the correlation plot
of the measured dynamic contact angle versus the velocity using
Eq. (1), the advancing static contact angle was obtained. The procedure followed by Vega et al. [20] was adapted to t the data using
the MKT.
Dynamic wetting of PET was previously studied and modelled
using the MKT theory by Blake [11]. Therefore, PET was used for
two purposes, one in which the wetting behaviour of the synthetic
bre and coir bre were compared and secondly PET was used as a
reference to evaluate MKT tting procedures.
As a second method to determine advancing static contact
angles, a variant of the Wilhelmy method was used for wetting
measurements with the different test liquids. During the advancing
phase, the vertical movement of the liquid beaker was stopped at
a certain immersion length of the bre during 360 s to allow relaxation of the liquid meniscus to approach a static condition. The last
data point of the wetting force at the end of the relaxation process
was used to calculate the static contact angle. In dynamic phase,
various measurement speeds ranging from 2 m/s to 500 m/s
were applied.
The relaxation time was selected based on measurements in
sorption test, in which coir bre was immersed in test liquids to
measure sorption mass as a function of time. The sorption mass
mainly was a sum of force created by wetting (transformed into
mass) and absorbed liquid into the bre. The results showed that
the recorded mass initially uctuated due to the movement of wetting line on the rough surface of the bres. Then, it typically reached
a stable value after approximately 200 s (Fig. 3); which indicates
that the static condition of wetting had been reached, and the
absorption process may completed.
The advancing static contact angle values obtained from the two
above approximations were applied in the OwensWendt method
to estimate coir bre surface energy and its polar and dispersive
components.

d d +
SV
LV

SV LV )

(6)

By combining with the Young equation,  SV =  SL +  LV cos , one

obtains:
LV (1 + cos )

d
LV




=

p
SV

LV

d
LV

 
+

d
SV

(7)

If one has obtained contact angle data on the bre for a series
of test liquids with known surface tension components, the two
d and  p are simultaneously solved by linear tting
unknowns SV
SV
using Eq. (7), referred to as the OwensWendt equation.
3.5. Fibre surface characterization using X-ray photoelectron
spectroscopy (XPS)
XPS analyses were performed on a Kratos Axis Ultra spectrometer (Kratos Analytical, UK) equipped with a monochromatized
aluminium X-ray source (powered at 10 mA and 15 kV).
One single bre was cantilevered xed on a at stainless steel
trough with a piece of double sided isolative tape. This way of
mounting insured that the bre surface only was analysed but not
its surrounding. The troughs, holding each bre sample, were then
inserted in the multispecimen holder. The pressure in the analysis
chamber was about 106 Pa. The angle between the normal to the
sample surface and the direction of photoelectrons collection was
about 0 . Analyses were performed in the hybrid lens mode with
the slot aperture and the iris drive position set at 0.5, the resulting analysed area was 700 m 300 m. The pass energy of the
hemispherical analyser was set at 160 eV for the survey scan and
40 eV for narrow scans. In the latter conditions, the full width at half
maximum (FWHM) of the Ag 3d5/2 peak of a standard silver sample was about 0.9 eV. Charge stabilisation was achieved by using the
Kratos Axis Ultra device. The electron source was operated with a
lament current between 1.9 and 2.1 A and a bias of 1.1 eV. The
charge balance plate was set between 3.3 and 3.9 V.
The following sequence of spectra was recorded: survey spectrum, C 1s, O 1s, N 1s, Ca 2p, Si 2p, and C 1s again to check for charge
stability as a function of time and the absence of degradation of the
sample during the analysis. The C(C, H) component of the C 1s peak
of carbon was xed to 284.8 eV to set the binding energy scale.
The data analysis was performed with the CasaXPS program
(Casa Software Ltd., UK). Mole fractions were calculated using
peak areas normalised on the basis of acquisition parameters
after a linear background subtraction and consideration of experimental sensitivity factors and transmission factors (depending on
kinetic energy, analyser pass energy and lens combination) provided by the manufacturer. C 1s spectra were decomposed with a
Gaussian/Lorentzian (70/30) product function, by constraining the
FWHMs of all components to be equal.

L.Q.N. Tran et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 377 (2011) 251260
Table 2
Fibre wetted perimeter (mm) from different methods.

0.018

Force (mN)

255

0.016

Fibre

Fibre no.

Coir

1
2
3
4
5

Methods
n-Hexane wetting

0.014
y = -0.0002x + 0.0157
R2 = 0.8676

0.012

PET

0.715
0.442
0.913
0.777
0.952

0.003
0.003
0.004
0.003
0.004

2.621 0.002

Image analysis
0.767
0.462
0.961
0.799
0.982

0.014
0.027
0.027
0.043
0.042

2.549 0.022

0.01
0

10

12

position (mm)
Fig. 4. A typical wetting forceposition curve in the experiment determining bre
wetted perimeter using n-Hexane.

Unmodied coir as used in the wetting measurements and modied coir were characterised. A surface modication procedure of
coir was carried out by soaking unmodied coir in n-Hexane for
24 h at ambient temperature, followed by washing with deionised
water, then drying under vacuum at 90 C for 2 h.
4. Results and discussion
4.1. Wetting measurements
4.1.1. Fibre wetted perimeter
Fig. 4. shows a typical plot of wetting force vs. immersion position during a wetting measurement of coir bre in n-Hexane. The
extrapolated value of the force at the position of zero immersion
depth was used for calculating the wetted perimeter (at zero buoyancy). In Fig. 5, an image of a coir bre cross-section was examined,
in which bre wetted perimeter is the sum of the bre contour and
the contour of the bre lacuna. It is reported that a lacuna occurs
in coir bres with different sizes depending on bre diameter and
position along the bre and that it would be bigger in thicker bres.
The lumen of single bre cells (elementary bres) has length and
width in ranges of 0.711.06 mm and 0.01070.0142 mm respectively [22,23]. Therefore, the effect of the lumens on the wetting

measurement is small, and can be eliminated. Thus, the wetted

perimeter is mainly determined by the contour of the bre and the
lacuna. In case of the PET bre, the wetted perimeter is identically
the bre perimeter.
The wetted perimeter of PET bres and ve samples coir bres is
shown in Table 2. For PET bres, there is a good agreement between
the results of two methods with less than 3% difference. For the coir
bres, a quite good agreement is also found. However, the results
of the image analysis are systematically higher than those of the
n-Hexane wetting, in the order of 37%. A possible explanation for
this slight discrepancy is that the wetting of n-Hexane may not
occur over the whole length of the bre lacuna, while image has
been selected where the contour of the bre lacuna is included in
the images analysis (although not necessarily the largest lacuna
cross-section may have been found). It is likely that the precise
value of the wetted perimeter is somewhere in between the values
measured with the two methods. When comparing the two methods, the wetting procedure is less time consuming than the image
analysis.
4.1.2. Advancing dynamic contact angles
Typical dynamic contact angle measurements of coir and PET
bres in water at a measurement speed of 25 m/s are shown in
Fig. 6, after buoyancy subtraction. The advancing angles of coir are
observably stable, while there is a big scatter of the receding contact angles. In case of PET, both advancing and receding angles are
steady. The difference of advancing and receding angles is known
as contact angle hysteresis and is explained by the nature of the
bre surface [11], mainly due to the effect of adsorbed liquid when

Fig. 5. Image analysis of bre cross-section using the software Leica Qwin to determine bre wetted length.

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L.Q.N. Tran et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 377 (2011) 251260

The dynamic contact angles of coir bres in water,

diiodomethane and benzyl alcohol at different measurement
speeds ranging from 2 m/s to 8000 m/s were determined using
the Wilhelmy method. The results indicate that the advancing
angles are speed-dependent in all the test liquids. The angles vary
from 80 to 105 in water, 55 to 64 in diiodomethane and from
29 to 36 in benzyl alcohol respectively (Fig. 7). This behaviour
of angle speed-dependence also occurs with PET having a contact
angle in water ranging from 82 to 110 in the same speed range
as above. Similar results with PET were also reported in the study
of Blake [11].

Fig. 6. Typical dynamic contact angle measurements of coir and PET bres.

110

contact angle ( 0)

the liquid is receding. The effect seems to be stronger with coir

bre, which has higher surface roughness, and more chemical and
topographical heterogeneities than the PET bre. Observation of
coir bres by SEM, shows a circular cross-section and a relatively
smooth surface (Fig. 2a and b). This structure of the coir surface
apparently leads to stable advancing angles, but it does lead to
uctuating receding angles. This is an important reason why only
advancing contact angles have been analysed.

100
90
80
70
60

contact angle ( 0)

4.1.3. Effect of liquid absorption on the contact angles

Since the contact angle is calculated from the measured wetting force, any incorrect value of the force would lead to an error
for the contact angle result. Table 3 shows the amount of liquid
absorption in the bres and its effect on the calculated angles. The
results indicate that the effect is small with water and bigger with
diiodomethane and benzyl alcohol. The contact angles in water and
diiodomethane seem to be not altered by the absorption. However,
they change approximately 2 in case of benzyl alcohol. Among
these test liquids, the absorption of benzyl alcohol is quite high.
However, its inuence is not pronounced since the absorbed mass
is only approximately 2% of the total wetting mass. Another consideration is that the contact angles are calculated via a cosine function
in the Wilhelmy equation. Consequently, the nature of the cosine
function makes the angles close to 90 less sensitive to a change
in the force than those close to 0 or 180 . In this way, the bigger
variation in case of benzyl alcohol can also be explained by its low
contact angle with coir.

2000

4000

6000

8000

10000

2000

4000
6000
velocity (m/s)

8000

10000

120
100
80
60
40
20
0

water

diiodomethane

benzyl alcohol

MKT fitting

Fig. 7. Dynamic advancing contact angle at various measurement speeds of (a)

PET in water (b) coir in different liquids. Solid curve is non-linear regression of
experimental data following MKT.

4.1.4. Advancing static contact angle approximation using the

Molecular-kinetic theory
The dynamic advancing angles and MKT tting curves of PET
and coir in water are presented in Fig. 7. Using a characteristic
length  of 1.16 nm and an equilibrium displacement frequency K0
of 1.55 105 s1 for PET, the MKT tted well the experimental contact angle data with R2 = 0.95 (Fig. 7a). In a previous study of Blake,
which models the dynamic wetting of water on PET at low speeds,
values of  of 1.06 nm and K0 of 2.5 105 s1 were found, which are
quite similar. As noted in literature [11,20], some level of discrepancy can be explained by differences in bre surface roughness and
polymer crystallinity.
The same tting procedure is applied for the wetting of water on
coir with  of 1.21 nm and K0 of 0.12 105 s1 giving a good agreement between experimental data and the MKT theoretical curve
with R2 = 0.95. The tting parameters  and K0 are in the same order
of magnitude when comparing between coir and PET. The change
of K0 is more pronounced than for  but is not unusual. Vega et al.
worked with Nylon bre [20] and saw that K0 increased by a factor of 70 when Nylon was studied with ve different liquids. Here,
The MKT tting curve provides a static contact angle of 77.3 with
water, showing relatively hydrophobic properties of the coir bre
surface.

Table 3
The effect of absorbed liquid into coir bre on its dynamic contact angle with various test uids; mass range is presented due to different perimeter of test samples.
Liquids

Absorption (%)

Water
Diiodomethane
Benzyl alcohol

5.2 1.1
5.0 2.1
14.4 5.8

Absorbed mass
(mg) (range)
0.0130.023
0.0120.019
0.0210.073

Mass created by
wetting (mg)
(range)
0.1750.956
0.6981.986
1.3663.225

Contact angle ( )

Contact angle
variation ( )

Number of samples

82.9 4.4
54.4 2.4
24.3 3.6

0.2 0.1
0.3 0.1
1.9 0.9

5
5
5

L.Q.N. Tran et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 377 (2011) 251260

dynamic wetting after that the movement is stopped. A relaxation

process at maximum immersion depth is then followed in order
to approach a static condition after the relaxation of the liquid
meniscus. At the end of the process, an apparent static angle is
obtained.
Fig. 9 shows the relationship between the dynamic angles and
the static angles, as determined by the static angle approximation
procedure. It can be observed that the dynamic angles are speed
dependent, while the static angles are steady at different applied
measurement speeds. The obtained static angles are all distributed
around the same value in different measurements performed at a
range of speeds. In this study, the static angles are presented in two
ways: mean value of all static angles (W1) and the value obtained by
linear trend of the static angles corresponding to different immersion speeds in dynamic phase (W2). As summarized in Table 4, it is
likely that this angle is stable and can be conrmed as the advancing
static angles. Similar results of both W1 and W2 show that the static
angles are not inuenced by changing immersion speed in dynamic
phase. Moreover, there is a good agreement between the advancing
static contact angles of MKT tting and these of this method.
Based on the above approach, the results of advancing static
angles can be used to estimate the coir surface energy consisting of
polar and dispersive fractions.

Fig. 8. Typical experimental results of static contact angle approximation during

stationary immersion of coir in water.

Fig. 7b also presents the MKT t of the wetting of diiodomethane

and benzyl alcohol on coir. In diiodomethane, a good tting is
obtained with  of 1.92 nm, K0 of 0.18 105 s1 and R2 = 0.92 providing a static contact angle of 48.2 . And a good t is obtained
with R2 = 0.91,  of 2.19 nm and K0 of 0.14 105 s1 in case of benzyl alcohol. The static angle of coir in benzyl alcohol following the
MKT t curve is 25.1 .

4.1.6. Surface energy of coir bre

Following Eq. (7), the advancing static contact angles of coir
bre in various test liquids
can be transformed into values of the

d and plotted as a function of the term
term lv (cos  + 1)/2 LV

100
90

100
90

contact angle ( 0)

contact angle ( 0)

110

d as shown in Fig. 10. From the slope and the intercept of

LV / LV
the linear relationship, respectively the polar and dispersive parts
of the coir bre surface tension are calculated, as can be seen in
Table 4. Since the advancing static contact angles of the test liquids

4.1.5. Advancing static contact angle from relaxation experiments

Fig. 8 shows a typical result of the static contact angle approximation at different speeds in dynamic contact angle measurements.
At a given speed, the dynamic contact angles are measured in

257

80
70
60
50
40
30

80
70
60
50
40

20
1

10

100

1000

10

100

1000

immersion speed (m/s)

70

60

contact angle ( 0)

60

contact angle ( 0)

immersion speed (m/s)

50

50
40
30
20

40
30
20
10

10
0

0
1

10

100

immersion speed (m/s)

1000

10

100

1000

immersion speed (m/s)

Fig. 9. Advancing contact angles () and static contact angles corresponding to different measurement speeds in dynamic phase () of (a) coir in water (b) PET in water (c)
coir in diiodomethane (d) coir in benzyl alcohol.

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L.Q.N. Tran et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 377 (2011) 251260

Table 4
Summary of advancing static contact angles in different test liquids, and estimated surface energy of coir bre according to 3 methods to determine the andvancing static
contact angles.
Advancing static contact angle ( )

Methods

MKT t
Wilhelmy static approximation

Mean value (W1)

Linear trend (W2)

Surface energy (mN/m)

Water

Diiodomethane

Benzyl alcohol

Total

Polar

Dispersive

77.3 0.3
75.6 5.9
74.9 1.2

48.2 0.3
50.9 2.1
50.6 0.7

25.1 0.6
26.1 3.1
26.5 0.5

38.8 3.8
38.4 4.0
38.7 4.4

5.7 1.5
6.9 1.8
7.2 2.0

33.1 3.5
31.5 3.6
31.5 4.0

of lignin lm is found to be 52.5 mN/m with dispersive component

of 4043.5 mN/m in the work of Lee and Lunar [28]. Our estimated
surface energy of coir is somewhat higher than that of waxes and
lower than that of lignin. It seems to reect well the properties of
the coir surface that exists not only of waxes with non-polar surface
energy but also of lignin and fats with polar components.
The result of the bre surface energy analysis provides meaningful information to characterise brematrix compatibility in
terms of matching surface energies. Based on this study, either bre
treatments or matrix modications can be selected to improve the
interface compatibility and adhesion of composites. For instance,
coir bres have potential in creating impact resistant composites
and for impact resistance optimising the interfacial adhesion is
crucial.
Fig. 10. Owens/Wendt plot to estimate the surface energy of coir bre using the
static contact angles obtained from different approaches (MKT, Wilhelmy with mean
value (W1) and linear trend (W2)).

on the coir bre can be obtained from three different ways (MKT
tting, W1 and W2), the surface energies were calculated using data
of three above described methods.
Considering the series of contact angles obtained from the different methods, the total surface energy of coir bre is around
38.5 mN/m with a high dispersive fraction of 3133 mN/m. The
surface energy is close to the range often quoted for hydrophobic
materials (from 28 to 34 mN/m) [24]. Several studies on coir bres
indicate that mainly waxes exist on the coir surface. Moreover, the
coir surface demonstrates the presence of longitudinally orientated
cells with more or less parallel orientations as seen in Fig. 2c. The
intercellular space is lled up by the binder lignin and fatty substances that hold cells rmly bonded in the bre [25,26]. Thus, the
surface energy of coir should be inuenced by a combination of
waxes, fatty substances and lignin. Bartell and Zuidema provide
values of the surface tension dispersive part of waxes of 26.5 mN/m
and for the polar part values of zero [27], while the surface energy

4.2. Surface chemical analysis of coir bre

Relative atomic percentages of the elements detected by XPS,
together with the oxygen to carbon atomic ratio of unmodied and
modied coir bres are provided in Table 5. It is observed that a high
proportion of carbon in unmodied coir may represent a hydrocarbon rich waxy layer on the surface. In the same fashion, the low
oxygencarbon ratio also indicates a high proportion of aliphatic
and aromatic carbons [29]. After the modication of the coir surface with n-Hexane, the carbon percentage decreases while the O/C
ratio increases. The O/C value of 0.38 is close to that reported for
thio lignin (O/C of 0.38) and dioxane lignin (range of 0.310.36), but
still far different from cellulose having an O/C ratio of 0.83 [30,31].
Therefore, the surface of modied coir likely has a greater proportion of lignin. It is probable that waxes and fatty substances on the
coir surface are washed away by n-Hexane, to expose the lignin
which binds the elementary bres [32].
In Fig. 11, typical results of C 1s spectra for unmodied and modied coir are compared. The C 1s peak is decomposed into four
sub-peaks C1C4 representing: carbon solely linked to carbon or
hydrogen CC or CH (C1), carbon singly bound to oxygen or nitro-

Fig. 11. Typical C 1s spectra, decomposed into four components C1C4 for (a) unmodied coir (b) n-Hexane modied coir.

L.Q.N. Tran et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 377 (2011) 251260

259

Table 5
Relative atomic percentages, O/C ratio, and decomposition of C 1s peaks obtained by XPS on unmodied and modied coir bres.
Fibres

C (%)

O (%)

N (%)

Si (%)

O/C

Binding energy (eV)

284.8 0.1

286.3 0.1

287.5 0.3

288.8 0.1

C1 (%)

C2 (%)

C3 (%)

C4 (%)

(CC/CH)

(CO)

(C O/OCO)

(OC O)

Unmodied coir

74.9 3.3

21.8 4.5

1.7 0.4

0.9 0.7

0.29 0.07

66.2 10.4

23.1 5.9

6.2 3.0

4.5 2.4

n-Hexane modied coir

69.7 1.4

26.6 1.5

3.1 0.5

0.4 0.1

0.38 0.03

53.0 1.0

30.2 0.8

9.2 0.6

7.6 0.9

gen CO or CN (C2), carbon doubly bound to oxygen OCO or

C O (C3) and carbon involved in ester or carboxylic acid functions
O CO (C4), as also shown in Table 5. For both unmodied and
modied coir bres, C1 is higher than C2C4. The high value of
C1 indicates the presence of unoxidised carbon atoms at the surface, which can be attributed to hydrocarbon in extractives and
lignin [33]. In the unmodied coir, the high proportion of C1 carbon (66.2%) suggests a combination of hydrocarbon rich waxes
and lignin. This is supported by the low proportion of C2C4. The
modied bre shows lower C1 and higher C2C4 than in case of
the unmodied one. This again points at a larger amount of lignin
present at the surface after removing the waxes by the n-Hexane
as discussed above.
5. Conclusions
The wetting behaviour of coir bre was characterised by
dynamic wetting measurement in various test liquids using the
Wilhelmy technique. The dynamic advancing contact angles corresponding to different measurement speeds were well tted by
the Molecular-kinetic theory, which allows modelling the dynamic
wetting of coir and determining its advancing static contact angle.
Another experimental approach for static contact angle measurement was carried out based on the Wilhelmy technique, in which
the relaxation of the liquid meniscus after stopping the bre movement was monitored. The obtained advancing static contact angles
were stable and reproducible. Moreover, there was a good agreement between the two methods for advancing static contact angle
approximation. The values of the advancing static angles were further used to estimate bre surface energy.
The estimated surface energy of coir bre, comprising of high
dispersive and low polar contributions pointed to a surface with
rather hydrophobic properties. Surface chemical analysis of the
bre by XPS indicated a high proportion of hydrocarbon rich material, which could be attributed to waxes, fatty substances and lignin,
in agreement with the results from the wetting measurements.
The study of wetting and surface chemistry offers a deeper
understanding of the coir bre surface, which will assist in the
selection of bre treatments or matrix modications for future
improvements of the interface in coir bre composites.
Acknowledgments
The authors wish to thank Sylvie Derclaye for help in performing wetting measurements, Yasmine Adriaensen and Michel Genet
for running XPS experiments. We also gratefully acknowledge K.U.
Leuven for providing I.R.O Scholarships and Belgian Science Policy
Department (BelSPO) for supporting our research in IAP network
6/27 and the collaboration with Vietnam.
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