Composites Science and Technology 60 (2000) 28572863

www.elsevier.com/locate/compscitech

Eects of corona discharge and UV treatment on the properties

of jute-bre epoxy composites
Jochen Gassan a,*, Voytek S. Gutowski b
a
Institut fur Werkstotechnik, University of Kassel, Germany
C.S.I.R.O. Polymer Surface Engineering Group, Melbourne-Highett, Graham Road, Victoria 3190, Australia

Received 4 April 2000; received in revised form 13 July 2000; accepted 1 August 2000

Abstract
In this paper, tossa jute bres were corona discharge and ultraviolet (UV) treated to improve the mechanical properties of natural-bre/epoxy composites. Corona-treated bres exhibited signicantly higher polar components of the free surface energy with
increasing treatment energy output. Owing to the diculties in eective treatment of three-dimensional objects with corona discharge, the increase of polarity of treated yarns is relatively small, in comparison to the results achieved with single bres. Furthermore a decrease in the yarn tenacity was observed with increasing corona energy level. The UV treatment of the single bres
and yarns led to signicantly higher gains in polarity in comparison with those observed in relation to corona-treated materials.
Increasing treatment time at a constant bulb-sample distance or alternatively decreasing the distance signicantly increased the
polarity and decreased yarn tenacity. To improve the overall mechanical properties of jute/epoxy composites, an appropriate balance needs to be achieved between increased polarity of bre surface and the decrease of bre strength subsequent to excessive
surface oxidation by corona discharge or UV radiation. At the optimum treatment conditions an increase in the composite exural
strength of about 30% was achieved. # 2000 Elsevier Science Ltd. All rights reserved.
Keywords: A. Polymer-matrix composites; B. Fibre/matrix bond; B. Interface; B. Mechanical properties; B. Surface treatment

1. Introduction
Composite materials made of cellulose-based bres such
as natural bres demonstrate remarkable environmental
and economical advantages. It is very well known, for
example that the mechanical or other physical properties of
composites depend on the properties of the individual
components and their interfacial compatibility. Cellulosebased bres are intrinsically polar owing to the presence
of hydroxyl and carboxylic groups in their structure.
Despite this inherent polarity, composite materials
made with unmodied natural bres frequently exhibit
unsatisfactory mechanical properties. To overcome this,
in many cases a surface treatment or compatibilizers need
to be used prior to composite fabrication [1,2]. An overview of chemical modications of the interface in natural
bre-reinforced plastics is given in earlier papers [2,3].
* Corresponding author at present address: Fraunhofer-Institut fur
Kurzzeitdynamik, Ernst-Mach-Institut (EMI), Eckerstrasse 4, 79104
Freiburg, Germany. Fax: +49-761-2714-316.
E-mail address: gassan@emi.fhg.de (J. Gassan).

This article deals with the eects of corona discharge

and ultraviolet (UV) treatment on natural bres, and the
inuence of these treatments on the physical properties
of the bres and their composites.
Belgacem et al. [1] showed that the use of a powder of
high-alpha cellulose, hardwood bres as reinforcing
material for polypropylene signicantly improves the
yield stress (approximately 25%) and elastic modulus
(approximately 50%) of compression moulded composites. The extent of improvement depends on the corona
treatment conditions, such as treatment time (up to 3
min) and corona current (up to 35 mA). No signicant
dierences in the yield stress between the composites
made of treated cellulose and untreated or treated
polypropylene was found. Dong et al. [4] found a
decrease in the apparent melt viscosity of cellulose lled
polyethylene composites if one (or both) of the constituents
was corona treated. Bataille et al. [5] used corona treatment
as a kind of pre-treatment to activate the cellulose to
improve the eciency of a grafting process.
It has been reported that corona treatment of the
surface of wet pulp sheets improved the ply-bond

0266-3538/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S0266-3538(00)00168-8

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J. Gassan, V.S. Gutowski / Composites Science and Technology 60 (2000) 28572863

Nomenclature
E0
E0untr
K
m
t
T
Tuntr
L
S
Ld
Sd
Lp
Sp
L

L
f
f;untr

storage modulus of composites

storage modulus of composites with
untreated bres
geometric factor
mass
time
tenacity at max. of yarns
tenacity at max. of untreated yarns
free surface energy of test liquid
free surface energy of bre
non-polar component of free surface
energy of test liquid
non-polar component of free surface
energy of bre
polar component of free surface energy of
test liquid
polar component of free surface energy of
bre
viscosity of test liquid
contact angle
density of test liquid
exural strength of composites
exural strength of composites with
untreated bres

strength of paperboards [6]. Sakata et al. [6] showed in

their results that the contact angle of a droplet of ureaformaldehyde resin on a wood surface decreases by
increasing the degree of corona treatment. In this case,
the improved wettability was reported to lead to higher
bond strength.
Corona treatment, however, is dicult to use on
three-dimensional objects [7]. This limitation applies not
only to 3-D shaped products, but also to brous materials,
particularly in the form of woven fabrics or strands. The
awareness of the existence of these limitations has highlighted the need for alternative, more 3-D `compliant'
surface modication techniques such as ozone and/or
ultraviolet radiation (e.g. UV) light. Investigations on
the UV triggered aging of wood surfaces showed a signicant increase in carbonyl groups [8]. Almost every
chemical constituent (cellulose, hemicellulose and lignin) of wood and natural bres is sensitive to UV
radiation with a consequential deterioration eect. Of
these chemical constituents, lignin (as the surface constituent of a natural bre [2]) appears to be oxidized and
degraded very rapidly by UV light. However, because of
the strong ultraviolet-absorbing characteristic of lignin
(due to the phenolic nature of its macromolecular
architecture), it may also perform the function of a
shielding agent to protect cellulosic components from
excessive photo-degradation [9,10].

Daneault et al. [19] used ozone as a sole treatment to

generate more hydroxyl groups on the surface of wood
bres with the aim of improved grafting eciency
through this activation.
2. Experimental
2.1. Materials and bre treatment
Commercially available tossa jute bres (J. Schilgen
GmbH and Co., Germany) with a twist of 277 t/m and
neness of 13.5 cN/tex were used throughout the study.
Their physical properties, composition and morphology
have been quantied in detail and reported elsewhere
[11]. An epoxy resin, Araldite F, with hardener HY 956
(mixing ratio 100:25 wt.%), both from Ciba-Geigy, was
used as matrix system for the composites. The composites
were cured at 60 C for 12 h. The volume bre content
for all composites was approximately 0.30.
The bres were treated in a corona treatment unit
HV200 from Tantec EST Systems. Treatment conditions used were as follows:
. power output range from 40 to 100 Watts;
. treatment speed varies from 10 to 88 cm/min
For the UV treatment, a Fusion UV Curing bulb with
UV emission spectrum according to Fig. 1 and a focal
point 53 mm away from the bulb was used. The energy
output at a wavelength of 254 nm, which is the most
important wavelength regarding ozone generation, is
approximately 80 W.
Fibres and yarns were dried at 60 C for 2 h before
any further treatment and processing of composites.
2.2. Surface energy determination
2.2.1. Single bres
Contact angle measurements for the single bres
(treated as single bres) were carried out using a CAHN
322 dynamic contact angle analyser. Single bres were
submerged into test liquids at a speed of 20.4 mm/s to a
depth of typically 3 mm. At this depth, the bres were held
shortly before being pulled out of the liquid. Distilled
water and diiodomethane were used as polar and nonpolar test liquids (Table 1).
The surface free energy components of the bres were
calculated using the geometric mean [Eq. (1)] based on
Owens and Wendt [12].
h

1=2 p p
1=2 i
L S
1
1 cos L 2 Ld Sd
with
i id ip for i L; S:

J. Gassan, V.S. Gutowski / Composites Science and Technology 60 (2000) 28572863

2859

(53131.5 mm) were tested with a frequency of 10 Hz

in three point bending mode.
3. Results and discussion
3.1. Free surface energy
Fig. 1. UV emission spectrum of the UV bulb used (Fusion UV Curing).

Table 1
Free surface energy, specic density and viscosity of the test liquids
used [12]
Test liquids

Viscosity
(mPas)

Density
(g/cm3)

Ld
(mJ/m2)

L
(mJ/m2)

n-hexane
Water
Diiodomethane

0.29
1.0
2.6

0.6595
0.9982
3.3254

18.4
21.8
48.5

18.4
72.8
50.8

2.2.2. Yarns
Contact angle measurements for the yarns (treated as
yarns) were carried out using the capillary rise method
(CAHN 322). The experimental procedure used has
been described in detail earlier [13]. By measuring the
time dependence of the liquid absorption in the bre
bundle, and subsequent liquid column rise, the contact
angles will be calculated by using the Washburn equation [Eq. (2)] [14].

2

m2 =
t K2L L cos =2L
The geometric factor `K' can be estimated using completely wetting liquids (cos 1) such as hexane. The
surface energy components of the yarns were calculated
using Eq. (1).
2.3. Mechanical properties
Tenacity at maximum was measured by using yarn
tensile test according to DIN 53 834 with an eective
specimen length of 50 mm (clamp distance) and a test
speed of 2 mm/min at room temperature (RT). The
values given are the means from at least ve individual
samples.
Flexural strength according to DIN EN 63 in 3-point
bending mode was determined with a test speed of
about 2 mm/min and a support prisms span of 51 mm at
RT. The geometry of the samples was 80151.5 mm
in each case. The strength values given are the means
from ve individual samples.
Dynamic mechanicalthermal properties of composites
were determined through DMTA procedure carried out
with the use of Rheometrics Solid Analyser RSA II, in a
temperature range between 50 and 120 C. The samples

3.1.1. Corona discharge treatment

The corona treatment of the jute bres leads to an
increase in the polar component of the free surface
energy (Fig. 2), mainly due to increasing the content of
carboxyl and hydroxyl groups. Sakata et al. [6] reported
on the oxidation of hydrophilic constituents of the surface
of dierent types of wood through corona treatments.
However, the chemical changes induced by corona
treatment were restricted to the substrate surface and
did not appear to aect the bulk properties of treated
wood [6].
In our experiments, the non-polar (dispersive) component of the free surface energy for the jute bres ( Sd )
was approximately 23 mJ/m2 and, as anticipated,
retained this constant value for both untreated and all
corona discharge treatment conditions. In contrast to these
results, Belgacem et al. [1] found for single (hardwood)
cellulose bres an increase in the dispersive component
of the free surface energy for increasing corona currents
and constant treatment times, i.e. increasing corona energy.
This unusual result, since d should remain constant,
can be attributed to a degradation of the material,
exposed to destructively excessive treatment energy.
For the untreated jute bres a contact angle of water
of 75 was determined, which is similar to the water
contact angle of lignin. In comparison, the water contact
angle on cellulose is only about 33 [15]. This may indicate that lignin may be the predominant constituent of
the surface layer of natural bres such as jute. This
observation conforms to physical models of the structure
of these types of bres (the total lignin content of the
jute bre used is about 10 wt.%) [11].
As known from other papers [16,17], the contact
angle of liquids on the surface of cellulose based bres/
materials is inuenced by the penetration (absorption)

Fig. 2. Inuence of the corona discharge energy on the polar component of the free surface energy of treated single bres and yarns.

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J. Gassan, V.S. Gutowski / Composites Science and Technology 60 (2000) 28572863

of the test liquid into the bre. Similarly to the results

reported earlier by Lee et al. [16] for lignin lms and
Toussaint et al. [17] for cellulose lms, the contact angle
of highly polar distilled water in contact with jute bres
decreases with total contact time [16,17]. In our experiments, this was observed through consecutive immersion
cycles (Fig. 3). For a predominantly non-polar diiodomethane the contact angles on the jute bres are initially
decreasing and become constant after the third cycle.
Similar behaviour was observed by Toussaint et al. [17]
after 25 minutes for the cellulose lms. Based on these
observations related to liquid absorption by porous
materials, Kawasaki (as published earlier in Ref. [16]),
has derived an expression relating the wettability of an
organic and absorbent solid to the diusion coecient
of the liquid into the solid.
Considering the above-mentioned dynamic character
of interfacial phenomena for a liquid in contact with a
porous/absorbent solid, the contact angles and the
components of the free surface energy, respectively, can
only be successfully used to compare the inuence of
dierent types of surface treatments (Fig. 2) under
strictly controlled test and processing conditions, e.g.
the same equilibrium moisture content of bres and
identical time of exposure to test liquid. These were
maintained constant through our experiments.
Data presented in Fig. 2 show that the average oxidation eects of corona discharge are lower for the
whole yarn than for single bres (bre bundles). This is
attributed to the diculties with eective use of corona
treatment on three dimensional objects [7], or those with
undertreatment of the `underneath' side not directly
exposed to the bombardment by ionised species present
in the discharge zone.
3.1.2. UV treatment
The results of the dynamic contact angle measurements for the UV treated bres reveal signicant
increase of the polar component of the free surface
energy (up to 88 mJ/m2) (Fig. 4) and that of bre
polarity (max. 0.96) with the treatment time increase (up

Fig. 3. Inuence of test liquid penetration into the bre on the contact
angle of test liquids on untreated jute bres (the contact with the test
liquid during one cycle was approximately 2.5 min).

to 15 min in our experiments). This increased polarity

can be attributed to an increase of concentration of
carboxyl groups on the bre surface, as shown in earlier
investigations of the UV-aging of wood surfaces [8].
Signicantly, elevated temperatures (particularly during
long exposure times combined with high energy of the
UV radiation during the treatment) provide synergetic
eects to a rapid increase of surface density of these
polar groups [8]. Other scientic reports on UV oxidation of dierent types of thermoplastic materials such as
PE, PEEK, and PP demonstrated (by the means of
contact angle of water) that prolonged treatment times
up to 4, 5, 1560 min, respectively, are commonly
essential to reach maximum polarity on these surfaces
[7,18], by the means of exposure to UV radiation other
than excimer laser.
As for all UV related surface treatments carried out in
ambient atmosphere (i.e. in absence of vacuum), apart
from the treatment time, the distance between the substrate and the UV bulb has a signicant inuence on the
degree of eective oxidation of the bre surface (see Fig.
5). UV radiation emitted by high energy lamp results in
the formation of the atomic oxygen. In absence of
vacuum, as in our experiments, the atomic oxygen can
recombine or react with other gas molecules before it
reaches the polymer surface [7]. Due to this phenomenon,

Fig. 4. Inuence of the UV treatment time on the polar component of

the free surface energy and the polarity of jute bres.

Fig. 5. Inuence of the UV bulb-substrate distance on the polar component of the free surface energy and the polarity of jute bres treated
with UV radiation source.

J. Gassan, V.S. Gutowski / Composites Science and Technology 60 (2000) 28572863

the increase of surface density of oxygenated species such

as carboxylic and hydroxyl groups, as demonstrated by
higher value of polar component of the free surface
energy becomes smaller with the increasing distance
between substrate and UV source. Regardless of the
above it has been observed (see Fig. 5) that increasing
the bulb-substrate distance up to 160 mm, the surface
polarity values for the treated bres are distinctly higher
than those for the untreated ones (Fig. 5).
3.2. Mechanical properties
3.2.1. Corona discharge treatment
The corona treatment of the jute bres with increasing
energy output leads to a remarkable decrease in the
tenacity of the bre (Fig. 6). Lower treatment speeds
[which result in higher specic energy output (mJ/mm2)
at xed generator power] increased this tendency for
reducing the bre tenacity (T). It is well documented in
the literature (see, for example, the work of Sakata et al.
[6]) that chemical changes through the corona treatment
only happen on the wood surface. On the other hand,
the surface ablation and subsequent weakening of the
supercial region of the material is known to occur as a
results of excessive treatment of polymeric materials by
corona or plasma [20,21]. It has been observed in our
work, that although the above observations are conrmed by the decrease in bre tenacity, the elasticity
modulus was approximately constant over the whole
range of energy output. These observations and results
on the inuence of corona treatment on surface polarity,
bre tenacity and composite strength are consistent with
the underlaying surface chemistry and the materials'
mechanical performance. The increased treatment level
on individual bres does increase the bre polarity. The
ablation-related bre's surface roughness acts as a
supercial micro-crack initiator. This, in turn, do not
adversely aect the elasticity modulus of the bres (in
the linear part of the stress-strain characteristic). The
adhesion at the matrix-bre interface may be increased

2861

due to the rise of the number of OH and COOH groups,

as demonstrated by the increase in the surface polarity. The
overall strength and fracture performance of the composite
material is, however, lowered when bres are over-treated
due to the decrease of the strength and fracture energy
of the individually treated (over-treated) bres.
In addition to the above, other factors require consideration. As a result of warming up of the bres by the
high energy source, a degradation of, for instance, degree
of polymerisation or the crystallinity can be possible. For
example, even short exposure times at 190 C reduce the
degree of polymerisation and, as result, the strength of
the jute bres decreases distinctly [11].
As already discussed above, the results of the contact
angle measurements proved an increase in bre polarity
for increasing treatment energies. The associated better
wettability of the bre by the matrix material was thought
to lead to improved composite properties. However, the
loss in mechanical bre strength as discussed, prevents
these higher composite strength properties (Fig. 6) to be
attained.
In contrast to the composite strength, the storage
modulus, E0 , at 60 C (see Fig. 7) increases with higher
corona energy and follows the trend of increase of the
polar component of free surface energy (Fig. 2), due to
the unchanged bre stiness. It can be seen from Figs. 2
and 7 that the improved wettability at a corona energy
level of 155 mJ/mm2 leads to an increase of the storage
modulus, E0 , at 60 C of at least 15%.

Fig. 7. Inuence of corona discharge energy on the storage modulus,

E0 , at 60 C (treatment speed=79 cm/min).

Fig. 6. Inuence of the corona discharge energy on the exural

strength of the composites and the tenacity (at max) of the bres:
symbols without parentheses are for bres treated at the speed of 79
cm/min; symbols with parentheses are for those treated at 61 cm/min.

Fig. 8. Inuence of UV treatment time on the exural strength of the

composites.

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J. Gassan, V.S. Gutowski / Composites Science and Technology 60 (2000) 28572863

3.2.2. UV treatment
As shown in Figs. 4 and 5, the UV treatment leads to
higher polarities of the bre surface. Consequently, the
wettability of bres and the composite strength were
improved. The trend observed in Fig. 8 shows, that in
the case of appropriately treated jute bres an increase
of 30% in composite strength is possible, after a 10 min
treatment at a distance of 150 mm away from the UV
lamp. This respectively relates to 97 mm distance for the
focal point to UV source. For a shorter distance of 120
mm, the same trend can be observed.
Increasing the substrateUV bulb distance for constant
treatment time (see Fig. 9 providing data for two treatment
times: 5 and 10 min) at rst leads to improvements in
composite exural strength. However, once the optimum
distance is exceeded (e.g. 150 mm for 10 min treatment
time) the increase in the polarity (Fig. 5) is too small to
enhance the composite properties. Excessive treatment
conditions, such as short distances or long treatment
times, result in the degradation of bre tenacity as shown
in Fig. 10. Mild treatment conditions, in comparison, as
shown for 5 min treatment time, result in comparatively
small, or no degradation eects on bre, but are associated with a smaller increase in the bre's surface
polarity.

Fig. 9. Inuence of UV bulbsubstrate distance and UV treatment

time on the exural strength of the composites.

For instance, a 5 min treatment at a distance of 135

mm increases the polar component of free surface
energy up to 49 mJ/m2 but reduces the bre tenacity by
18%. A 10 min treatment at 150 mm improves the
polarity more eectively (67 mJ/m2) with an approximately similar decrease in bre tenacity (15%).
Based on these results, a balance between an increase in
polarity of the bre surface and decrease of the bre
strength is necessary to successfully improve the composite
strength.
4. Conclusions
Corona discharge treated individual jute bres exhibit
signicant increase in the polar component of the free
surface energy with increasing corona energy. For output
energies of approximately 130 mJ/mm2 a maximum Sp
value of 46 mJ/m2 was reached, in comparison to Sp
10 mJ/m2 for untreated bres. In comparison with the
results relevant to individually treated bres, the increase
of polarity of treated yarns is only small (maximum of
approximately Sp 26 mJ/m2), due to the diculties of
treating three dimensional objects with corona. Unfortunately, the oxidation of the bre surface always leds
to a decrease in the yarn tenacity (decrease in bre tensile
strength), which prevents higher composite strength
values to be easily achieved. Fibre stiness (modulus of
elasticity) is unaected by these corona energy levels
and an improved (by approximately 15%) of storage
modulus, E0 , at 60 C was achieved for optimised treatment
conditions.
The UV treatment of the jute yarn led to higher
polarity (up to 200% increase) with increased treatment
time and constant bulb-substrate distance. Furthermore,
the treatment distance was showed to have a signicant
eect on the polarity as well as to the tenacity of the
yarn. To improve the mechanical properties of juteepoxy composites by the use of UV-oxidation of bres a
balance between increased polarity of bre surface and
decrease of bre strength is necessary. Under optimum
treatment conditions an increase of the composite exural
strength of about 30% was achieved.
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Fig. 10. Inuence of UV bulbsubstrate distance and treatment time

on the tenacity (at max) of UV treated jute bres.

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