Composites Science and Technology 60 (2000) 2857±2863

www.elsevier.com/locate/compscitech

E€ects of corona discharge and UV treatment on the properties

of jute-®bre epoxy composites
Jochen Gassan a,*, Voytek S. Gutowski b
a
Institut fuÈr Werksto€technik, University of Kassel, Germany
b
C.S.I.R.O.Ð 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 nat-
ural-®bre/epoxy composites. Corona-treated ®bres exhibited signi®cantly higher polar components of the free surface energy with
increasing treatment energy output. Owing to the diculties in e€ective treatment of three-dimensional objects with corona dis-
charge, the increase of polarity of treated yarns is relatively small, in comparison to the results achieved with single ®bres. Fur-
thermore a decrease in the yarn tenacity was observed with increasing corona energy level. The UV treatment of the single ®bres
and yarns led to signi®cantly 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 signi®cantly increased the
polarity and decreased yarn tenacity. To improve the overall mechanical properties of jute/epoxy composites, an appropriate bal-
ance 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 This article deals with the e€ects of corona discharge

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. Cellulose-
based ®bres are intrinsically polar owing to the presence
of hydroxyl and carboxylic groups in their structure.
Despite this inherent polarity, composite materials
made with unmodi®ed 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 over-
view of chemical modi®cations of the interface in natural
®bre-reinforced plastics is given in earlier papers [2,3].
* Corresponding author at present address: Fraunhofer-Institut fuÈr
Kurzzeitdynamik, Ernst-Mach-Institut (EMI), Eckerstrasse 4, 79104
Freiburg, Germany. Fax: +49-761-2714-316.
E-mail address: gassan@emi.fhg.de (J. Gassan).
0266-3538/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S0266-3538(00)00168-8
and ultraviolet (UV) treatment on natural ®bres, and the
in¯uence 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 signi®cantly improves the
yield stress (approximately 25%) and elastic modulus
(approximately 50%) of compression moulded compo-
sites. 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 signi®cant
di€erences 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 eciency of a grafting process.
It has been reported that corona treatment of the
surface of wet pulp sheets improved the ply-bond
2858 J. Gassan, V.S. Gutowski / Composites Science and Technology 60 (2000) 2857±2863

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

Nomenclature generate more hydroxyl groups on the surface of wood
®bres with the aim of improved grafting eciency
E0 storage modulus of composites through this activation.
E0untr storage modulus of composites with
untreated ®bres
K geometric factor 2. Experimental
m mass
t time 2.1. Materials and ®bre treatment
T tenacity at max. of yarns
Tuntr tenacity at max. of untreated yarns Commercially available tossa jute ®bres (J. Schilgen
L free surface energy of test liquid GmbH and Co., Germany) with a twist of 277 t/m and
S free surface energy of ®bre ®neness of 13.5 cN/tex were used throughout the study.
Ld non-polar component of free surface Their physical properties, composition and morphology
energy of test liquid have been quanti®ed in detail and reported elsewhere
Sd non-polar component of free surface [11]. An epoxy resin, Araldite F, with hardener HY 956
energy of ®bre (mixing ratio 100:25 wt.%), both from Ciba-Geigy, was
Lp polar component of free surface energy of used as matrix system for the composites. The composites
test liquid were cured at 60 C for 12 h. The volume ®bre content
Sp polar component of free surface energy of for all composites was approximately 0.30.
®bre The ®bres were treated in a corona treatment unit
L viscosity of test liquid HV200 from Tantec EST Systems. Treatment condi-
 contact angle tions used were as follows:
L density of test liquid
f ¯exural strength of composites . power output range from 40 to 100 Watts;
f;untr ¯exural strength of composites with . treatment speed varies from 10 to 88 cm/min
untreated ®bres
For the UV treatment, a Fusion UV Curing bulb with
UV emission spectrum according to Fig. 1 and a focal
strength of paperboards [6]. Sakata et al. [6] showed in point 53 mm away from the bulb was used. The energy
their results that the contact angle of a droplet of urea- output at a wavelength of 254 nm, which is the most
formaldehyde resin on a wood surface decreases by important wavelength regarding ozone generation, is
increasing the degree of corona treatment. In this case, approximately 80 W.
the improved wettability was reported to lead to higher Fibres and yarns were dried at 60 C for 2 h before
bond strength. any further treatment and processing of composites.
Corona treatment, however, is dicult to use on
three-dimensional objects [7]. This limitation applies not 2.2. Surface energy determination
only to 3-D shaped products, but also to ®brous materials,
particularly in the form of woven fabrics or strands. The 2.2.1. Single ®bres
awareness of the existence of these limitations has high- Contact angle measurements for the single ®bres
lighted the need for alternative, more 3-D `compliant' (treated as single ®bres) were carried out using a CAHN
surface modi®cation techniques such as ozone and/or 322 dynamic contact angle analyser. Single ®bres were
ultraviolet radiation (e.g. UV) light. Investigations on submerged into test liquids at a speed of 20.4 mm/s to a
the UV triggered aging of wood surfaces showed a sig- depth of typically 3 mm. At this depth, the ®bres were held
ni®cant increase in carbonyl groups [8]. Almost every shortly before being pulled out of the liquid. Distilled
chemical constituent (cellulose, hemicellulose and lig- water and diiodomethane were used as polar and non-
nin) of wood and natural ®bres is sensitive to UV polar test liquids (Table 1).
radiation with a consequential deterioration e€ect. Of The surface free energy components of the ®bres were
these chemical constituents, lignin (as the surface con- calculated using the geometric mean [Eq. (1)] based on
stituent of a natural ®bre [2]) appears to be oxidized and Owens and Wendt [12].
degraded very rapidly by UV light. However, because of hÿ
1=2 ÿ p p
1=2 i
…1 ‡ cos† L ˆ 2 Ld Sd ‡ L S …1†
the strong ultraviolet-absorbing characteristic of lignin
(due to the phenolic nature of its macromolecular
architecture), it may also perform the function of a with
shielding agent to protect cellulosic components from
excessive photo-degradation [9,10]. i ˆ id ‡ ip for i ˆ L; S:
 J. Gassan, V.S. Gutowski / Composites Science and Technology 60 (2000) 2857±2863 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). 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
Table 1 energy (Fig. 2), mainly due to increasing the content of
Free surface energy, speci®c density and viscosity of the test liquids carboxyl and hydroxyl groups. Sakata et al. [6] reported
used [12] on the oxidation of hydrophilic constituents of the surface
Test liquids Viscosity Density
Ld
L of di€erent types of wood through corona treatments.
(mPas) (g/cm3) (mJ/m2) (mJ/m2) However, the chemical changes induced by corona
n-hexane 0.29 0.6595 18.4 18.4
treatment were restricted to the substrate surface and
Water 1.0 0.9982 21.8 72.8 did not appear to a€ect the bulk properties of treated
Diiodomethane 2.6 3.3254 48.5 50.8 wood [6].
In our experiments, the non-polar (dispersive) com-
ponent of the free surface energy for the jute ®bres (
Sd )
2.2.2. Yarns was approximately 23 mJ/m2 and, as anticipated,
Contact angle measurements for the yarns (treated as retained this constant value for both untreated and all
yarns) were carried out using the capillary rise method corona discharge treatment conditions. In contrast to these
(CAHN 322). The experimental procedure used has results, Belgacem et al. [1] found for single (hardwood)
been described in detail earlier [13]. By measuring the cellulose ®bres an increase in the dispersive component
time dependence of the liquid absorption in the ®bre of the free surface energy for increasing corona currents
bundle, and subsequent liquid column rise, the contact and constant treatment times, i.e. increasing corona energy.
angles will be calculated by using the Washburn equa- This unusual result, since
d should remain constant,
tion [Eq. (2)] [14]. can be attributed to a degradation of the material,
ÿ
exposed to destructively excessive treatment energy.

m2 =
t ˆ K2L
L cos =…2L † …2† For the untreated jute ®bres a contact angle of water
of 75 was determined, which is similar to the water
The geometric factor `K' can be estimated using com- contact angle of lignin. In comparison, the water contact
pletely wetting liquids (cos ˆ 1) such as hexane. The angle on cellulose is only about 33 [15]. This may indi-
surface energy components of the yarns were calculated cate that lignin may be the predominant constituent of
using Eq. (1). the surface layer of natural ®bres such as jute. This
observation conforms to physical models of the structure
2.3. Mechanical properties of these types of ®bres (the total lignin content of the
jute ®bre used is about 10 wt.%) [11].
Tenacity at maximum was measured by using yarn As known from other papers [16,17], the contact
tensile test according to DIN 53 834 with an e€ective angle of liquids on the surface of cellulose based ®bres/
specimen length of 50 mm (clamp distance) and a test materials is in¯uenced by the penetration (absorption)
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 mechanical±thermal properties of composites
were determined through DMTA procedure carried out
with the use of Rheometrics Solid Analyser RSA II, in a Fig. 2. In¯uence of the corona discharge energy on the polar compo-
temperature range between 50 and 120 C. The samples nent of the free surface energy of treated single ®bres and yarns.
2860 J. Gassan, V.S. Gutowski / Composites Science and Technology 60 (2000) 2857±2863
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 experi-
ments, this was observed through consecutive immersion
cycles (Fig. 3). For a predominantly non-polar diiodo-
methane 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 2±5 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 di€usion coecient
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 in¯uence of
di€erent 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 oxi-
dation e€ects of corona discharge are lower for the
whole yarn than for single ®bres (®bre bundles). This is
attributed to the diculties with e€ective 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 measure-
ments for the UV treated ®bres reveal signi®cant
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. In¯uence 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].
Signi®cantly, elevated temperatures (particularly during
long exposure times combined with high energy of the
UV radiation during the treatment) provide synergetic
e€ects to a rapid increase of surface density of these
polar groups [8]. Other scienti®c reports on UV oxida-
tion of di€erent 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, 15±60 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 sub-
strate and the UV bulb has a signi®cant in¯uence on the
degree of e€ective 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. In¯uence of the UV treatment time on the polar component of
the free surface energy and the polarity of jute ®bres.
Fig. 5. In¯uence of the UV bulb-substrate distance on the polar com-
ponent 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) 2857±2863
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 speci®c 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
super®cial 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 con-
®rmed 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 in¯uence 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
super®cial micro-crack initiator. This, in turn, do not
adversely a€ect 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
Fig. 6. In¯uence 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.
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 con-
sideration. 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 sti€ness. 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. In¯uence of corona discharge energy on the storage modulus,
E0 , at 60 C (treatment speed=79 cm/min).
Fig. 8. In¯uence of UV treatment time on the ¯exural strength of the
composites.
2862 J. Gassan, V.S. Gutowski / Composites Science and Technology 60 (2000) 2857±2863
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 substrate±UV 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
Sp
conditions, such as short distances or long treatment
Sp ˆ
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 e€ects on ®bre, but are asso-
Sp ˆ 26 mJ/m2), due to the diculties of
ciated with a smaller increase in the ®bre's surface
polarity.
Fig. 9. In¯uence of UV bulb±substrate distance and UV treatment
time on the ¯exural strength of the composites.
Fig. 10. In¯uence of UV bulb±substrate distance and treatment time
on the tenacity (at max) of UV treated jute ®bres.
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 e€ectively (67 mJ/m2) with an approxi-
mately 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
signi®cant increase in the polar component of the free
surface energy with increasing corona energy. For output
energies of approximately 130 mJ/mm2 a maximum
value of 46 mJ/m2 was reached, in comparison to
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
treating three dimensional objects with corona. Unfor-
tunately, 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 sti€ness (modulus of
elasticity) is una€ected 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 signi®cant
e€ect on the polarity as well as to the tenacity of the
yarn. To improve the mechanical properties of jute-
epoxy 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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