Oxygen Plasma Treatment of Sisal Fibers

and Polypropylene: Effects on

Mechanical Properties of Composites
ELISETE COUTO', ING HWIE TAN'?,NICOLE DEMARQUEITE",
JOSE CLAUD10 CARASCH12*,and ALCIDES L m @

lEscola Polit&cnicad a Unwersidade de Sfio Paulo

Materials Engineering Department
Av. Prof. Melo Moraes 2463,W Paulo, Brazil
2Unwersidade Estadual P d i s t a - Campus d e Botucatu
Faculdade d e Ci ~31~ias Agronomicas
Depto. de Ci&cias Ambientais
Fazenda Experimental Lageado
Bobcatu, S. P. Brazil

Polypropylene powder and sisal fibers were oxygen plasma treated, and the me-
chanical properties of their composites were tested. Two main effects were investi-
gated: the incorporation of oxygen polar groups in the polypropylene surface and
the surface degradation and chain scission of both polypropylene and sisal fibers.
Prior to these treatments, three reactor configurationswere tested to invesbgate the
best condition for both effects to occur in PP films. Results showed that polypropy-
lene-cellulose adhesion forces are about an order of magnitude higher for PP f ilm
treatments at 13.56 MHZ than at 40 kHz owing to much hgher chain scission at
lower frequencies, although it probably also occurs at high frequency and high
power. Polypropylene powder treated with oxygen plasmas in optimum conditions
for polar group incorporation did not result in improvement in any composite me-
chanical property, probably owing to the polymer meltmg. Sisal fibers and PP pow-
der treated in conditions of surface degradation did not improve flexural or tensile
properties but resulted in higher impact resistance, comparable to the improve-
ment obtained with the addition of compatibilizer.

INTRODUCTION capability because of the low interfacial adhesion. A

T he growing need for environmentally friendlier
materials has stimulated research in composite
materials of thermoplastics reinforced with lignocellu-
losic fibers. Besides improvement in mechanical prop-
erties, the partial replacement of oil-based polymers
by renewable vegetable fibers reduces CO, emission
and creates ruraljobs, among many other advantages
(1). However, the lack of compatibility between most
commonly used nonpolar polymers and polar cellu-
lose-based fibers has limited the fiber reinforcement
To whom comspondence should be addnssed.
'Pnsent address:lnstituto Nadonal de Pesquisas Espaclals. Laboratoxio A
dado de Plasmas, Av. dos Astronautas 1758. CEP 12227-010, Sao J m do6
Campos. S.P., BI-azll.
*Pmsentad- Unfvusidade Estadd de Maringa. Departamento de Quimi-
ca.Marhga, PR,Brazil.
great deal of work has been done to improve the adhe-
sion of these materials through: chemical m&cation
of either one of the components, addition of compati-
bilizers (2).or plasma treatment. This last approach
has the advantage of being an environmentally friend-
lier process, owing to the reduced number of chemi-
cals involved and low treatment times.
When polymer surfaces are exposed to a glow dis-
charge plasma, different effects are often observed:
surface cleaning by removal of organic contamina-
tion, ablation or etching, which M e r s from cleaning
by the amount of material removed, and modification
of the chemical composition of the polymer surface
(3,4). Oxygen plasma treatment of nonpolar poly-
mers such as polypropylene and polyethylene is known
to increase the surface polarity of PP and PE Alms
and adhesion to cellulose-based materials (5,6).How-
ever, prolonged plasma exposure has been shown to

790 POLYMER ENGINEERING AND SCIENCE, APRIL 2002. Vol. 42, No. 4
 Oxygen Plasma 'keatmenf
decrease adhesion, which can be caused by chain
scission resulting in low-molecular-weght, low-adher-
ing hgments (5, 71, or by differences in the chemical
groups incorporated during different plasma condi-
tions (6). Oxygen plasma treatment of cellulose has
also been shown to increase adhesion to polyethylene
(8, 91, the improvement being attributed by the au-
thors to the incorporation of hydroperoxides on the
fiber surface, resulting in covalent bonds at the inter-
face at high processing temperatures. The effect of
oxygen plasma treatment on the adhesion properties
between PP f ilm and wood was evaluated by means of
a peel test. The highest adhesion to wood resulted
fi-om the shortest treatment times used: the effects of
plasma on the adhesion properties were more pro-
nounced when both the PP film and the wood surface
were treated (10).
Several works on composites made with plasma-
treated components have led to different conclusions.
Treatment of cellulose fibers with Merent gas plasmas
and different polymer matrices showed that acid-base
interactions are important for several polymers but
were irrelevant to others like polypropylene (11).Di-
chlorosilane plasma treatment of sisal fibers and poly-
ethylene resulted in poor mechanical properties of their
composites, which was attributed to the degradation
of the fibers and the melting of the polymer, which
would incorporate the functiodized groups in the sur-
face into the bulk of the material (12). Oxygen corona
treatment of cellulose fibers and polypropylene has
somewhat surprisingly shown that the treatment of
the cellulose fibers was more efficient in improving the
composites' mechanical properties than the treatment
of the polypropylene matrix. This improvement corre-
lated well with an increase in the dispersive energy of
the treated fibers, which is directly proportional to the
work of adhesion, and was attributed to the low-molec-
ular-weight fragments formed (13, 14). Similar results
are observed for corona-modified cellulose/polyethylene
composites (15). Corona treatment of woodfiber and
polyethylene resulted in composites with decreased
melt viscosity, probably due to low- molecular-weight
moieties acting as lubricants at the interfaces (16).
There is therefore evidence that although oxygen
plasma treatment does improve cellulose-plastics ad-
hesion by the incorporation of polar groups in non-
polar polymers, the effects of low-molecular-weight
fragments formed by degradation and chain scission
caused by intense plasma exposure are still not clear.
I t can be deleterious in some cases and beneficial in
others.
The main objective of this work was to verify the ef-
fects of oxygen plasma treatment of polypropylene and
sisal fibers on the mechanical properties of their com-
posites. Two effects were investigated: 1) polar group
incorporation on polypropylene surfaces for adhesion
improvement, and 2) oxygen plasma-induced degra-
dation and chain scission in both polypropylene and
sisal fibers.
POLYMER ENGINEERING AND SCIENCE, APRIL 2002, Vol. 42, No. 4
In order to find the best conditions for these two ef-
fects to occur, three different plasma reactor configura-
tions were tested. Since chain scission is like@to be fa-
vored by high ionic bombardment, a low frequency (40
kHz)capacitive reactor was first tested and compared
to the case where the same reactor vessel is powered by
a high-frequency (13.56 M H z ) power source. Low-fi-e-
quency systems are characterized by high ion bom-
bardment, since during one-half cycle, electric fields
stay in the same direction during a time long enough
for the ions to respond and accelerate towards the elec-
trodes. At higher frequencies, ions are too massive to
respond to the rapidly changing electric fields in the
bulk of the plasma, and respond only to the average
potential Merence between plasma and substrate. A
third reactor configuration involves a second reactor
vessel powered by a 13.56 MHz source, but in this case
electrodes are outside the vacuum chamber. Ion bom-
bardment in this case is wen lower compared to the in-
ternal elecimde case, since there is no current conduc-
tion through the electrodes, current continuity being
achieved by displacement currents only.
Polypropylene films were oxygen plasma-treated in
these three reactor configurationswith varying power,
pressure and treatment times. The purpose for vary-
ing these three parameters was to try to find the best
condition for each reactor in which each of the two ex-
pected effects (polar group incorporation and chain
scission) would occur. The main effect of increasing
power is mainly to increase electron energies, which
affects the cross section and reaction rates responsi-
ble for the creation of the various reactive oxygen
species. Ion bombardment energies are also increased
with power, since voltages between electrodes in-
crease. These two effects will affect the number and
type of polar groups incorporated, as well as the de-
gree of chain scission. Increasing treatment times will
increase the intensity with which incorporation and/or
chain scission will occur. In principle, longer treatment
times should increase oxygen incorporation, but could
also induce chain scission by oxygen degradation. The
effects of pressure are more uncertain, but one would
think that it will affect electron mean free paths, cross
sections and reaction rates.
Adhesion to cellulose was measured by peel tests of
laminates made with the treated samples and cello-
phane paper. XPS analysis of selected samples was
made in order to determine the oxygen polar groups
incorporated in the surface. Incorporation of polar oxy-
gen groups was also estimated by water contact angles.
The external electrode reactor was chosen for treat-
ing the sisal fibers and polypropylene powder since it
provided the best condition for adhesion improvement
of the PP films with cellophane, as will be shown below,
besides the fact thatt this reactor was spec&@built to
treat powders and fibers. Chain scission or surface
degradation was likely to occur in this same reactor at
higher power levels and long treatment limes. Sisal/PP
composites were olbtained in a twin-screw extruder,
791
 Elisete Couto et d
and then injected to form samples for tensile, fleMlral
and impact tests. For comparison, pure PP samples
and samples of sisal/PP composites with the addition
of maleated polypropylene (MA#'P, 1% in weight) were
obtained and tested for the same mechanical proper-
ties.
EXPERIMENTAL
Materials
The materials used in this work are listed in Table
1 . Polypropylene films were cut into 3 cm X 10 cm
samples and were cleaned with acetone and iso-
propanol prior to plasma treatment. Traces from the
organic fluids may be present during treatment, but
because of the small surface areas involved, they
should not influence the results significantly, since
base pressures are essentially the same (less than 20
mTorr, while treatments occur at 200 mTorr). Clean-
ing the samples by inert gas plasmas was avoided
since electron and ion impacts could not only remove
residues but also induce chain scission and creation
of free radicals. Cellophane paper was chosen as cel-
lulose substrate instead of filter paper because of its
smoother surface, which prevents mechanical adhe-
sion of the polymer by entanglement with the cellu-
lose fibers, so that adhesion is preferentially due to
physical-chemical interactions. Polypropylene pellets
were ground and screened to 325 mesh. Sisal fibers
were cut into lengths of less than 10 mm.
Table 1. Materials.
Material Supplier Characteristics
PP film Viopel PT25E homopolymer
Cellophane paper Nexon, UCB Films
Polypropylene pellets Solvay MFI 12 g / l O rnin
Sisal fibers < 10 mm in length
MAgPP Eastman G-3002pm
60,000
1
Rg. 1 . Schematics of the vacuum vessel of the reactor builtfor treatingrns and powder.
792
Plasma Reactors
One of the plasma reactors used has been described
elsewhere (17); it consists of a capacitively coupled re-
actor with two 20-cm-diameter electrodes, 3 cm apart,
with one of them grounded and used as a substrate
holder. It can be powered at 40 kHz or at 13.56 MEiz
using two different sources. A mechanical pump pro-
vides base pressures of about 20 mTorr. Prior to sam-
ple treatments, the reactor vessel was plasma cleaned
with argon at 200 mTorr, 200 W for 5 minutes.
The second reactor was specially built for beating
powders or other irregularly shaped substrates like
fibers and pellets. The vacuum vessel is a Pyrex cylin-
der with a 14-cm internal diameter, 80 cm long, with
stainless steel flanges at both ends, gas being injected
at one end and pumped away at the other end. Inter-
nally, a rotating substrate holder consisting of a Pyrex
cylinder (12 cm in diameter, 20 cm long connected to
a Pyrex rod is supported at both ends by the two &in-
ges, one end being connected to an external motor,
with controllable rotating speed (see Fig. 1). Fibers,
pellets or powder samples are therefore revolved,
while the holder rotates. For the PP film treatments,
samples were placed inside the substrate holder with-
out rotation. T w o silicone-greased dynamic O-rings
provided vacuum sealing during rotation. Two semi-
cylinder electrodes are placed externally, surrounding
the vessel, and are connected to a 13.56 M H z power
source. The same vacuum and gas injection system as
the first reactor provides base pressures of less than
20 mTorr.
Argon is preferentially used for cleaning the reactors
walls because of its inertness. However, when oxygen
plasmas are used for treatment, it can also be used as
cleaning gas. Any polar fragments eventually created
on the reactor walls during oxygen plasma cleaning
should be of the same nature as the ones created dur-
ing oxygen plasma treatment itself. This was the case
for the reactor with external electrodes. The lower ion
bombardment compared to the low frequency reactor
POLYMER ENGINEERING AND SCIENCE, APRIL 2002, Vol. 42, No. 4
 Oxygen Plasma neatrnent

led us to choose a more aggressive cleaning method, Table 4. Peel Strength and Contact Angles for
using a reactive gas like oxygen. Plasma cleaning of Varying Treatment Conditions of PP Films
in the 13.56 HI! Reactor With External Electrodes.
the vacuum vessel is made with oxygen at 400 W, 200
mTorr, during 15 min. Peel Contact
Pressure Time Power Strength Angle
Oxygen Plasma Treaments of Polypropylene (mTorr) (5) (W) (N.25mm) (“1
Films and Adhesion Peed Tests
40 0.405 67
Power, pressure and treatment times were varied for 100 0.178 70
the three reactor configurations and are reported in 200 30 200 0.145 n
Tables 2.3 and 4. 300 0.043 66
Laminates of PP films and cellophane paper were 400 0 61
hot pressed at 130°C (below the PP melting point to 10 0.123 74
prevent mechanical entanglement), 19 MPa for 10 20 0.152 71
minutes. 200
40
60 0.194 72
We conducted 180”peel tests using an EMIC test- 80 0.205 73
120 0.295 66
ing machine, with a 5 kgf cell, with peeling velocity of 210 0.235 68
20 mm/min.
Contact angles of distilled water sessile drops were 400 0.305 -
measured using a Rame-Hart goniometer. 700 30 200 0.164 -
1000 0.066 -

Table 2. Peel Strength and Contact Angles for Varying

Power and Pressure (Treatment Time is 10 Seconds)
of PP Films in the 40 kHz Reactor. X-ray Photoelectron Spectroscopy (Kratos Analytical
model XSAM HS with a 1253,6 eV, 180 W Mg Ka radi-
Pressure Power Peel Strength Contact Angle ation) were made on PP samples treated at various
(mTorr) (w) (N.25 mm) (“1 conditions for elemental analysis.
2 0.034
5 0.062 73 oxygen Plasma Ikeatment of
10 0.052 68 PP Porrdu md Sisal F i b
200 50 0.052 44
..
100 0.049 33
For each composite, 500 g of sisal fiber were used
200 0.027 30 with 1500 g of PP powder. The reactor chosen for
treating the PP powder and sisal fibers was the exter-
4 0.01 73 nal electrode, 13.616M H z reactor, which was specially
0 0.014 72 built with a rotatig sample holder, and, as will be
500 50 0.012 73
100 0.016 69 shown in the next section, provided the best condi-
200 0.008 57 tions for oxygen polar group incorporation. Based on
the results obtained for the PP f ilm treatments, two
plasma conditions were chosen. In order to incorporate
oxygen polar groups on the PP surface, 200 mTorr,
Table 3. Peel Strength and Contact Angles for 40 W gave the best condition for adhesion with cellu-
Varying Treatment Conditions of PP Films
in the 13.56 Hz Reactor With Internal Electrodes.
lose. Considering that the optimum treatment time for
PP fXms was around 2 minutes, and that the powder
Peel Contact had to be revolved in order to expose all of its sur-
Pressure Time Power Strength Angle face, PP powder was exposed to the plasma for 10
(mTorr) ($1 (W) (N.25mm) (“1 minutes. For degradation and chain scission condi-
5 0.114 75.1 tions, 200 mTorr, 400 W, 30 s resulted in no adhesion
10 0.183 76.1 of the PP f ilm to cellophane, so that this was the con-
20 0.208 73.3 dition chosen with treatment time of 15 minutes. PP
200 10 50 0.158 76.3
100 0.120 76.2
powder was treated in the rotating sample holder in
200 0.085 79.5 batch treatments of about 70 g. Care was taken to
maintain the same plasma conditions and treatment
5 0.119 78.5 time.
200 40 30 0.196 73 Sisal fibers wene also treated for degradation and
80 0.402 71.8
chain scission at the same conditions as the PP fiber
200 0.110 75.7 (200mTorr, 400 MI, 15 minutes). Because of the large
300 0.060 77 amount of fibers necessary (about 500 g) and its low
400 10 30 0.107 76.1 mass density, treating it inside the substrate holder
500 0.072 77.2 would have been too slow (only 15 g would be treated
600 0.189 77.3
at each time). Therefore, 125 g of fiber was spread

POLYMER ENGINEERING AND SCIENCE, APRIL 2002, Vol. 42, No. 4 793

around the base of the reactor at each time, without
substrate holder, treated on one side, turned on the
other side, and treated again.
Preparation of the Composites
Sisal/PP composites were extruded with 25% in
weight of fiber. The composites were prepared in a
twin-screw extruder (B&P Process Equipment and
System, model-H.P. 20191, with five zones of tempera-
tures ranging from 170°Cto 200°C along the barrel of
the extruder. The screw speed ranged from 170 to 180
rpm. This 19-mm diameter, laboratory-size extruder
is capable of processing up to 10 kg of material per
hour.
Composites were cut into 7-mm-long pellets and
oven dried at 50°C for 2 hours and then at 105°C for
2 hours prior to injection molding.
Five different composites were manufactured. Their
compositions are given in Table 5.
Mechanical Analysis
For mechanical property analysis. samples for ten-
sile and impact tests were obtained by injection mold-
ing (in a Mannesmann Demag, model Ergo Tech pro
350-1151, with four zones of temperatures ranging
from 170°C to 190°C along the barrel of the injection
unit, at a n injection speed of 200 rpm. Mold tempera-
ture was kept at 40°C.Besides the five different com-
posites described above, samples of PP were also ob-
tained for the sake of comparison. Ten samples were
manufactured for each composite and each mechani-
cal test.
prior to mechanical testing, the samples were condi-
tioned at (40? 51% relative humidity, (23 ? 21°C for
40 hours. Notched Izod Impact tests were made using
a Zwick + Co.Kg - Einsingen Uber Ulm, type 5102 ac-
cording to ASTM -D256, tensile and flexural tests
were made in an Emic testing machine according to
ASTM - D790/98 and ASTM - D638, type 1, respec-
tively.
RESULTS AND DISCUSSION
Peel Tests, Contact Angles aud XPS
Analpsis of Oxygen Treated PP Films
Tables 2, 3 and 4 show the results of peel tests
made on hot pressed laminates of cellophane paper
and PP films and contact angles of the PP films
treated on the three Werent reactor configurations.
Table 5. Types of Composites.
Composite Label Sisal Polyprolyplene MagPP
SisallPP Untreated Untreated
SisaVPP/MagPP Untreated Untreated
SisaKrPP func Untreated Treated for best adhesion
SisaUTPP degr. Untreated Treated for degradation
TsisaWP Treated Untreated
794
Elisete Couto et aL
Table 2 shows the results of PP samples treated in
the 40 kHz reactor. It can be seen that while contact
angles decrease with increasing power, indicating more
incorporation of oxygen polar groups, peel strengths
decrease with power. Very low power (5 W) with very
short treatment time (10seconds) gave the best peel
strength, showing that this low-frequency reactor with
high ion bombardment is probably inducing too much
chain scission, resulting in low-molecular-weght, low-
adhering fi-agments. This effect was also observed by
Carlsson et d (5),in another low-frequencyreactor (127
KHz). Increase in pressure decreased peel strengths
and increased contact angles, probably because at
hlgher pressures, electron mean free.paths are smaller,
resulting in lower electron energies, which in turn can
result in less reactive oxygen species, as also shown
by XPS analysis described below.
Table 3 gives the peel strengths and contact angles
for treatments of PP films made with the same previ-
ous reactor but with a 13.56 M H z power source. Peel
strengths are much higher compared to the low-fi-e-
quency case, and have a n optimum condition some-
where around 30 W with more than a minute of treat-
ment time. This corroborates the hypothesis that
higher ion bombardment in low-frequency systems
causes chain scission. At this higher frequency, poly-
mer degradation seems to occur at hgher powers, as
shown by the lower peel strengths. Dependence on
pressure seems to be more complex, and we could not
find a reasonable explanation for the variations meas-
ured. Optimum treatment times are over a minute for
lower powers. Contact angle measurements showed
very little variation, in all treatment conditions. As will
be shown by the XPS analysis, the amount of oxygen
incorporated at higher frequencies does not seem to
vary with treatment conditions, so that longer or more
intense plasma exposure probably results in polymer
degradation.
Results of PP films treated in the 13.56 M H z reactor
with external electrodes are showed in Table 4. Peel
strengths are of the same order as in the case of the
internal electrodes, with optimum conditions for ad-
hesion at about 30 W to 60 W, 200 mTorr and 2 min-
utes of treatment time. There is a strong dependence
of peel strength upon power, with 400 W resulting in
no adhesion at all with cellophane paper. There is a
moderate dependence of peel strength upon treatment
time, a maximum for this case being around 2 min-
utes. Contact angles are similar to the internal elec-
trode case, and do not vary with treatment conditions,
being around 70".
Figure 2 shows a typical XPS survey spectrum of
oxygen plasma-treated PP film,and Flg. 3 shows the
high-resolution Cls spectrum of the same film. Table 6
~
0 shows the XPS analysis results for PP films treated at
1% some plasma conditions at low and hgh frequencies.
0 The C l s spectra were fitted in four peaks, relative to
0
0
atoms with zero, one, two, and three carbon-oxygen
bonds. It can be seen that at low frequency, oxygen
POLYMER ENGINEERING AND SCIENCE, APRIL 2002, Vol. 42, No. 4
 Oxygen Plasma Tkeatrnent
8
0
4
41
3.1
r(
* 30
d
J
Y
0,
"1
1100
, . . ,
1000
,. . , .
90,
, . , , . . . .,
800
Binding Energy (ev)
FQ. 2. XPS survey specbum of polypropylene_filmtreated with oxygen plasma at 40 kkk,200 rnTorr, 5W,
incorporation is higher at a higher power, while at high
ii-equency, oxygen content is much lower, and longer
treatment times do not increase oxygen content. These
results are consistent with contact angle measure-
ments, which seem to depend mainly on the amount of
oxygen incorporated in the surface. The relative con-
centrations of the four different carbon-oxygen bonds
are roughly the same for all treatment conditions
tested. These results corroborate the hypothesis that
chain scission is the most probable cause of low peel
strengths a t lower frequencies and high power, al-
though incorporation of different oxygen groups (with
the same number of oxygen-carbon bonds) at different
conditions could not be ruled out (for example and
ether type less polar group being incorporated at one
condition, while hydroxyl is incorporated at another
condition).
Mechanical Roperties of SisallPP Composites
Table 7 gives the results of the mechanical tests
performed on the five different composites and on
pure PP samples.
It can be seen that sisal/PP composites have much
higher flexural moduli of elasticity than pure PP sam-
ples, as expected, but no effect of plasma treatment
POLYMER ENGINEERING AND SCIENCE, APRIL 2002, Vol. 42, No. 4
700
, . .., . .. . , ... .,. ..
600 500 400
.T'l!i
3010
-.
200 100
0
tn
cu
+
. . -4
10s.
or addition of MA&1PPis observed. Addition of MAgPP
results in a slightly higher elastic modulus. Flexural
yield strengths of sisal/PP composites are also higher
than pure PP samples, and only the addition of MAgPP
results in strength improvement, plasma treatments
being also ineffective in this case.
For tensile tests, sisal/PP composites have better
modulus of elasticily compared with pure PP samples,
but tensile strengths are about the same. In both
tests, plasma treatments have no effect on mechanical
properties. However, addition of MAgPP results in
about 25% improvement in yield strength.
Sisal/PP composites have much larger impact re-
sistance than pure PP samples. This impact resis-
tance is improved by both the addition of the compat-
ibilizer or by plasma treatment. The plasma treatment
that is most effective is the treatment of the sisal
fibers, which presented similar effects as the addition
of MAgPP. Treatment of PP for degradation also re-
sulted in impact resistance improvement, while PP
plasma treatment for the functionalhation of oxygen
polar groups was even detrimental to this mechanical
property.
The results shown above indicate that although
some improvement in impact resistance was observed
795
 Elisete Corrto et al.

0
0
z
f 0

Y
P
i

Rg. 3. High resolution C1s XPS spectrum of the polypropylenej?hshown in Rg. 2.

for plasma-treated sisal fibers, comparable to addition CONCLUSIONS

of compatibilizer, tensile and flexural strengths of
sisal/PP composites are not improved by oxygen plas-
ma treatments. In particular, functionalization of polar
oxygen groups on the surface of the PP powder failed
to cause any beneficial effect, most probably because
of the melting of the polymer. Surface degmdation of
the sisal fibers (and to a lesser extent of the PP pow-
der) did have a modest effect on impact tests, but this
could be due to the fact that the fibers were not re-
volved and thus not sufficiently exposed to the plas-
ma. The installation of an agitator could help solve
this problem.
Polypropylene powder and sisal fibers were oxy-
gen plasma-treated in selected plasma conditions, in
order to functionalize oxygen polar groups in the
polypropylene, and to induce chain scission and low-
molecular-weight fragments in both polypropylene
and sisal fibers. These treatments were tested for their
effectiveness in improving mechanical properties of
sisal/PP composites.
Oxygen plasma treatment of polypropylene is an ef-
ficient method for functionalizing surface polar groups
and improving adhesion to cellulose-based materials

Table 6. Relative Concentrations (in %) of the Four C l s and Two 01s Peaks, and the Atomic Ratio OIC
Measured by XPS, for PP Films Treated At Different Plasma Conditions.

C1 c2 c3
CO 286.2 287.5 289.1
Treatment Condition 284.8 eV 20.3 eV k0.4 eV 20.2 eV C 0 OIC
40 kHz, 0.2 Tom, 70W 77 13 6 3 81.55 18.45 0.23
40 kHz, 0.2 Torr, 5W 79 12 6 3 86.02 13.98 0.16
40 kHz, 0.5 Torr, 5W 80 11 5 4 89.32 10.68 0.12
13 MHz, 0.2 Torr, 20W, 10s 83 12 3 2 91.17 8.82 0.097
13 MHz, 0.2 Torr, 20W, 80s 78 15 5 2 91.26 8.74 0.096
C,: C-C, C-H
C,: C-OH, C - 0 6
c,: 0-c-o, c=o
C,: COOH, COOR

796 POLYMER ENGINEERING AND SCIENCE, APRIL 2002, Vol. 42, No. 4
 Oxygen Plasma neatment

Table 7. Flexural and Tensile Modulus of Elasticity (MOE) and Yield Strength and Notched lzod
Impact Results of Composites, With Corresponding Standard Deviations.

Flexural Tensile Impact

MOE Strength MOE Strengh Resistance
Composite (MPa) (GPa) (MPa) J/M
PP 1.21 t 0.06 38.5 2 0.9 0.76 +- 0.05 29.5 2 0.2 17.6 t 3.7
PP/Sisal 2.44 ? 0.1 49.2 +- 1. 1.09 2 0.06 302 1.1 106 t 17
PP/SisaVMagPP 2.7 ? 0.13 61 21.2 1.23 +- 0.12 39 -t 1.4 127 t 24
PPrrSisal 2.42t 0.05 48.2 2 1.1 1.02 +- 0.06 31 -t 0.5 130 t 24
TPP/Sisal (func.) 2.51 % 0.12 48.2 2 0.9 1.05 -t 0.07 30.4 +- 1.0 93 t 22
TPP/Sisal (deg.) 2.56 t 0.09 50.7 2 0.75 1.1 +- 0.04 32.5 2 1.2 118 t 27

provided that care is taken in preventing degradation REFERENCES

and chain scission. This is best achieved with plasma
reactors with higher frequencies and low ion bombard-
ment. Oxygen functionalities with one carbon-oxygen
bond (hydroxylsand/or ether type groups) are the main
groups incorporated, and seems to be independent of
frequency, power or time. At low frequencies, higher
power increases oxygen content, causing a decrease
in water contact angles, but decreases adhesion to
cellulose, indicating that chain scission has occurred,
producing low-molecular-weight, low-adhering frag-
ments. At higher frequencies, hgher power also de-
creases adhesion to cellulose without altering the con-
tact angles, so that polymer degradation is probably
occurring without increasing oxygen incorporation.
Functionakation of PP powder surfaces, however,
does not improve mechanical properties of composites
when the treated powder is used as a matrix, probably
because of the melting of the polymer, which “buries”
the incorporated surface’s groups. Degradation and
chain scission on the fiber or PP surfaces do not im-
prove tensile and flexural properties but increase the
composite impact resistance. In the case of fibers, this
improvement is comparable to addition of compatibi-
lizer, and could be improved by a better revolving sys-
tem for a more uniform fiber surface exposure to the
plasma.
ACKNOWLEDGMENTS
This work was supported by FAPESP (process num-
bers 94/03351-4-2. 95/09287-0, 96/06947-2.97/
06071 and 01/05382-11, and CNPq (process no.
104670/99-1). We would also like to thank Dr. Elias
Hage for the use of the twin-screw extruder, Erica
Weruth Ambrozin for contact angle measurements,
the Plastics and Rubber Laboratory of the Technologi-
cal Research Institute for mechanical and peel-
strength analysis, and our materials suppliers, Vitopel,
Nexon, Solvay, and Eastman.
1. Proceedings of the Third International Symposium on
Natural Polymers and Composites and Workshop o n
Progress inProduction and Processing o j ’ C e ~ s iFibers
c
and Natural Pofyrners, SHo Pedro, S P., Brazil (May
2000).
2.LignOceUulosic-Plastic Composites, edited by A. LeHo, F.
X. Carvalho, and E. Frollini, 1997,invited papers from
the First InternaiionaJ Symposium on Lignocellulosic-
Plastic Composites, S5o Paulo, S.P., B r a d (March 1996).
3. E. M. Liston, L. IUartinu, and M. R Wertheimer, J. Ad-
hesion Sci TechoL, 7 , 1091 (1993).
4.R M. France and R D. Short, Iangmuir, 14: (17).4827
(1998).
5. C. M. G. Carlssoii and K. S. Johansson, Surf:And Inter-
face Analysis, 2a1.441(1993).
6.X. Tu, R. A. Young, a n d F. Denes, Cellulose, 1, 87
(1994).
7.C. Oehr, M. Muller, B. Elkin, D. Hegemann, and U.
Vohrer, Surf& CCmL Tech., 119,25(1999).
8. J. M. Felix, C. M. G. Carlsson, and P. Gatenholm, J. Ad-
hesion Sci Techno&,8 (2).163 (1994).
9.C. M. G. Carlsscln and G. Strom, Surf:Intmfme AnaL,
17. 511 (1991).
10. R Mahlberg, H. E. M. Niemi, F. S. Denes, and R. M.
Rowell, Langmuir, l5(8),2985 (1999).
11. J. Felix, P. Gatenholm, and H. P. Scllreiber, J. AppL
PoZym Sci, 51, 2!85(1994).
12.A R Martim. S. Manolache, L. H. Mattoso, R M. Row-
ell, and F. Denes, in Proc. Third I n t Symp. on Nafural
Polymers and Composites, 431 (2000).
13. M. N. Belgacem, P. Bataille, and S. Sapieha. J. AppL
Pozyn. Sci, 53,379(1994).
14.M. N. Belgacem, G. Czeremuszkin, S. Sapieha, and A
Gandini, cellulose, 2(3),145 (1995).
15.S. Dong, S. Sapieha, and H. P. Schreiber, Polym Erg.
Sci,55, 343 (19!33).
16. S. Dong, S. Sapieha, and H. P. Schreiber, Polgrn. Eng.
Sci, 52 (22).1734 (1992).
17. H.Tan,N. Demarquette, M.L. da Silva, F. T.Degasperi,
and R Dallacqua, Prm. 14th I n L Confeence on Plasma
Ckmistrg, Vol. FJ, 1907 (1999).

POLYMER ENGINEERING AND SCIENCE, APRIL 2002, Vol. 42, No. 4 797