A Systematic Investigation on the Influence

of the Chemical Treatment of Natural Fibers

on the Properties of Their Polymer Matrix Composites
JERICO BIAGIOTTI, DEBORA PUGLIA, LUIGI TORRE,
and JOS M. KENNY*

Materials Engineering Center, University of Perugia

Loc. Pentima Bassa 21, 05100 Terni, Italy

and

AITOR ARBELAIZ, GUILLERMO CANTERO, CRISTINA MARIETA,

RODRIGO LLANO-PONTE, and IAKI MONDRAGON

Materials
Technologies Group, Escuela Ingeniera Tcnica Industrial

Dpto. Ingeniera Qumica y M. Ambiente, University of the Basque Country
Avda. Felipe IV, 1 B, 20011 Donostia San Sebastin, Spain

This paper reports a systematic study of the effects on composite properties of dif-
ferent chemical treatments on natural fibers. Both short flax fibers and flax cellulose
pulp in a polypropylene matrix have been investigated. The influence of treatments
on fiber properties was investigated by means of spectroscopic, thermal and me-
chanical tests. Moreover, the effects of fiber treatment on the crystallinity of the ma-
trix were analyzed using differential scanning calorimetry and optical microscopy.
The mechanical properties of the composites obtained were studied using tensile and
bending tests. It is shown that most of the main properties of the composites can
be improved by adequately treating the fibers. The results of this study provide a
database mainly devoted to material selection for the automotive industry. This
research has been performed as a part of the ECOFINA project in the framework of
the 5th European Research Program of the European Community. Polym. Compos.
25:470 479, 2004. 2004 Society of Plastics Engineers.

INTRODUCTION characteristics, depending on the type of composite

and the processing conditions used for their prepara-
T he increasing use of flax fibers as reinforcement in
polymer matrix composites takes advantage of
their intrinsic properties and of their established pro-
tion (17).
Natural fiberreinforced polypropylene composites
meet most of the requirements for mass production,
cess conditions. In particular, short fiberreinforced
being easily available and economical. In the automo-
polypropylene matrix composites are becoming very
tive industry, for example, natural fibers allow the pro-
popular as a result of the combination of the toughness
duction of composite parts with potentially complete
of the thermoplastic matrix, the stiffness and strength
recyclability, at least in terms of recovering energy by
of reinforcing fibers, and the advantages offered by
total combustion without production of toxic emissions.
simple and well-established processing technologies
The lower weight attainable because of their low den-
for mass production, such as injection molding. More-
sity allows the production of lighter and more efficient
over, most natural fibers can reduce material costs
vehicles, decreasing gas emission and reducing pollu-
yet provide materials with a large variety of physical
tion. Furthermore, the lower abrasiveness and ease of
handling of natural fibers as reinforcing agents, with
* To whom correspondence should be addressed. E-mail: kenny@unipg.it respect to traditional glass fiber reinforcements, can
2004 Society of Plastics Engineers
Published online in Wiley InterScience (www.interscience.wiley.com). offer less hazardous features during processing and
DOI: 10.1002/pc.20040 allow longer life of conventional processing equipment

470 POLYMER COMPOSITES, OCTOBER 2004, Vol. 25, No. 5

 Investigation on the Influence of the Chemical Treatment of Natural Fibers
(8). At the moment, it is possible to obtain good com-
posites using PP and many different lignocellulosic
fibers and by using the most common processing
techniques (9, 10). However, poor thermal and environ-
mental stability with degradation of the mechanical
properties due to their moisture sensitivity and poor
fiber-matrix adhesion are the main problems of natural
fiber composites, hindering industrial-scale application
of these materials (11).
In order to improve the performance of the compos-
ites based on natural reinforcements, fiber treatments
are generally adopted to improve adhesion between the
fibers and the matrix. Previous studies have shown
that independently of the matrix composition, natural
hydrophilic fibers do not present good chemical com-
patibility with hydrophobic polymer matrices, such as
polypropylene (1216). So, the fiber surface must be
treated to increase compatibilization with the matrix,
using different processes such as bleaching, grafting of
monomers, and acetylation. In addition to these treat-
ments, the use of a compatibilizer or a coupling agent
for effective stress transfer across the interface can be
adopted (1720). An effective chemical modification
method for natural fibers is graft copolymerization,
where the reaction is initiated by the free radicals or
functional groups of the cellulose molecule, providing a
route to significantly modify the characteristics of the
adhesion between the polymer and the fibers. Chemical
grafting involves attaching to the surface of a fiber/filler
a suitable polymer with a solubility parameter similar
to that of the polymer matrix, acting as an interfacial
agent and improving bonding between the fiber and the
matrix. The resulting copolymer has properties related
to both the fibrous cellulose and the grafted polymer.
For example, the treatment of cellulose fibers with hot
polypropylene-maleic anhydride (MAPP) copolymers
provides covalent bonds across the interface (21). The
reaction mechanism can be divided into two steps: the
activation of the copolymer by heating (T  170C, be-
fore fiber treatment) and the esterification of cellulose.
As an effect of this treatment, the surface energy of
the fibers can be changed to a level much closer to the
surface energy of the matrix.
Acetylation, which is another chemical treatment for
natural fibers, has been extensively applied to wood
cellulose (22) to stabilize the cell wall, thereby improv-
ing dimensional stability and environmental resist-
ance, since no adsorbed water can cause further swell-
ing or shrinkage of the composite material. While the
acetylation treatment has long been used on textiles,
research has only recently been carried out to assess
its usefulness in the case of natural fiberbased com-
posites (22). Organosilane is another important group
of coupling agents, mainly used for glass-fiber rein-
forced polymers, that has recently shown its effectiveness
as a compatibilizer for natural fiber polymer compos-
ites (23). The organo-functional group in the silane-
coupling agent generally reacts with the polymer either
through copolymerization or through the formation of
an interpenetrating network (24).
POLYMER COMPOSITE, OCTOBER 2004, Vol. 25, No. 5
Although many chemical treatments have been re-
ported in the scientific literature, the available results
are difficult to compare because of the intrinsic differ-
ences of natural systems coming from different geo-
graphical regions and different harvesting, production
and processing conditions. Thus, the aim of this work
is not to review the extensive literature on fiber chemi-
cal treatments but to compare the effects of different
treatments on two well-defined flax derived fibers. The
proposed treatments and their effects on the fiber
properties were characterized by infrared spectroscopy,
calorimetry, and thermogravimetry and by single fiber
tensile tests. Then, in order to determine the surface
energy values, contact angle measurements were used.
Furthermore, the effectiveness of the fiber treatments
on the composite properties has been evaluated, as well
as its effects on the matrix crystallinity, on the interfa-
cial shear strength, and on the mechanical properties
(tensile, flexural) of the composites.
EXPERIMENTAL
Materials
Two different kinds of cellulose-based reinforcement
were used in this work. Natural flax fibers (NF), obtained
by a retting process of flax plants from Finflax (Fin-
land), and flax pulp fibers (FP) obtained by flax cooking,
in a process similar to Kraft pulping, from Celesa (Spain).
This pulp has 5 wt% shives content (wooden content of
the pulp) and a permanganate index of 9.4. Maleic
anhydride (MA) from Cepsa, maleic anhydride-poly-
propylene copolymer (MAPP Epolene E-43) kindly sup-
plied by Eastman Chemical, and vinyltrimethoxy silane
(VTMO) kindly supplied by Degussa were used as cou-
pling agents. Epolene E -43 has a low molecular weight
(Mn  3900, Mw  9100), 0.934 g/ml density and acid
number of 45. A commercially isotactic grade of poly-
propylene (iPP), Eltex P HV200 from Solvay (Melt Flow
Index: 2.9 dg/min at 190C and 5 Kg, and density 0.90
g/cm3), was used in this research.
Fiber Treatments
Fibers were treated with two different amounts of
MA; in particular two different percentages respect of
fiber weight were used (5% and 10%). Fibers were es-
terified for 25 h with MA and dissolved in boiling ace-
tone (T  50  5C) with a fiber/solvent ratio of 1:25
(wt/V). Thereafter, fibers were washed several times in
cold acetone and distilled water, and finally dried in an
oven at 105C for at least 24 h before testing (25).
Treatments with 5% and 10% wt MAPP were also
used. For these treatments, MAPP was dissolved in
boiling xylene (T  150  5C) with a fiber/solvent ratio
of 1:25 (wt/V). Then, the fibers were soaked in the so-
lution for 56 minutes. As in the former case, the fibers
were washed and carefully dried (25, 26). For silaniza-
tion, VTMO was dissolved in acidified water (pH  3.5)
for 10 minutes to get a better functionalization. Then,
the fibers were added and maintained for 1 h in the
solution to obtain a 2.5 wt% (27).
471
 Jerico Biagiotti et al.
Fiber Characterization
A Perkin-Elmer 16 PC FTIR spectrophotometer was
used to obtain the IR spectra of the treated fibers. Pure
powdered potassium bromide (KBr) was used as a ref-
erence substance. Small quantities of the samples were
dispersed in dry KBr and further ground to a fine mix-
ture in a mortar before pressing, to form KBr pellets for
analysis.
The contact angle values were obtained using a
Krss K 12 tensiometer and using two different tech-
niques because of the morphology of each kind of fiber:
the Dynamic Contact Angle method based on the Wil-
helmy equation was adopted in the case of long natural
flax fibers and of the polypropylene matrix, while the
Capillary Rise method based on the Washburn equa-
tion was adopted in case of irregular flax pulps. The use
of two different methods involved a small discordance
in the wettability values. The test liquids used were dis-
tilled water, ethylene glycol and 1-bromonaphthalene.
Surface energy values were calculated from the contact
angle values according to the Owens-Went equation:
11
cos 2 L
3 1 dL  dS 2 1>2
1 pL  pS 2 1>2 4
where  is the contact angle of the sample with test liq-
p
uid; Ld, L , and L are the dispersive, polar and total
p
surface energy of the test liquid, respectively; and Sd, S
are the dispersive and polar components of the surface
energy of the tested sample, respectively.
Degradation tests were performed using a thermo-
gravimetric analyzer (TGA-Seiko Instrument SII Exstar
6000). Dynamic scans were run from room temperature
to 600C at a heating rate of 10C/min for each kind of
fiber treatment. The average weight of the samples
tested was 10 mg. The residual weight measured during
the TGA test was converted to the corresponding value
of percentage of the residual weight fraction (wr %  100
w(t)/wo ) where w(t) is the mass of the sample at each
temperature and wo is the initial mass of the sample.
Derivative curves (DTG) were obtained in order to com-
pare the weight loss rate during the temperature scan.
In order to highlight the main phenomena associated
to the intrinsic thermal instability of the natural fibers
(for example, water evaporation and cellulose decompo-
sition), which may have consequences on the process-
ing, DSC scans were also performed. Samples of about
8 mg were heated from 30C to 400C at a heating rate
of 10C/min.
Single fiber tensile tests were carried out at room
temperature, according to ASTM D 3379. The tensile
strength variation of the analyzed flax fibers was ob-
tained by application of the Weibull distribution. Using
two-parameter Weibull statistics, the cumulative den-
sity function for the natural fiber is:
 
F 12
exp c a b d
0
where F () is the probability of survival at stress, , 
is a dimensionless shape parameter and 0 is a location
parameter (28).
472
Composite Manufacturing
Before their utilization, flax pulps (FP) were defibril-
lated in a blade mill. Afterwards, both short flax fibers
and opened pulps were vacuum dried in an oven at
100C for 12 hours. Drying of vegetal fibers before pro-
cessing is a fundamental step since the presence of
water at the matrix-matrix interface prevents adhesion.
Additionally, water evaporation during compounding
can cause bubbles in the matrix. Both phenomena pro-
duce a decrease in the mechanical properties of the
composite. Blending of PP and 30 wt% flax fiber was
carried out in a twin-screw extruder (Haake Rheomex
CTW 100), at 40 rpm screw speed and barrel tempera-
tures were set at 180C (zone 1), 182C (zone 2), 184C
(zone 3) and 185C at the die. The extrudate was pel-
letized and then maintained in an oven at 100C in a
vacuum to avoid moisture uptake. The molding of the
dried pellets was carried out in an injection molding
machine (Battenfeld Plus 250). Samples were molded
for flexural and tensile tests, according to ASTM D790M
and ASTM D638M standards, respectively.
(1) Composite Characterization
The following thermal history was adopted for DSC
characterization of natural fiber composites: samples of
about 8 mg were heated from 30C to 200C at a scan
rate of 10C/min and held for 10 min at 200C to elim-
inate any thermal history. The samples were then cooled
to 50C at a cooling rate of 50C/min. After crystal-
lization, the samples were heated again to 200C to
measure the heat and melting temperature.
In order to analyze the transcrystalline growth of
polypropylene spherulites, the injection molded speci-
mens were observed by means of a Hund mod. Wetzlar
H600 optical microscope, equipped with a Mettler FP-
82HT automatic hot-stage thermal control and a video
camera. Samples were melted and squeezed between
two microscope cover glasses at 200C for 10 min, and
then rapidly cooled to the crystallization temperature of
130C.
Degradation tests on a thermogravimetric analyzer
(TGA-Seiko Instrument SII Exstar 6000) were run from
room temperature to 600C and with a typical heating
rate of 10C/min, under nitrogen flow.
The rheological properties were determined using a
Rheometric Scientific Ares dynamic mechanical spec-
trometer. Tests were conducted using parallel plate fix-
tures at a temperature of 190C in a range of angular
frequency from 0.1 to 100 rad/sec. The strain ampli-
tude was maintained at 1%.
Specimens for the pull-out test were prepared as fol-
lows. A small polymer particle was placed on a thin
cover glass placed on a hot stage. The temperature of
the glass was 200C. After the polymer was melted, a
(2) fiber was placed on the droplet formed, carefully im-
mersing a length of fiber (embedded length) smaller
than 500 m, in order to avoid fiber fracture during the
tests. Then, the droplet with the fiber was covered with
a second glass plate. The specimen was kept in this
POLYMER COMPOSITES, OCTOBER 2004, Vol. 25, No. 5
 Investigation on the Influence of the Chemical Treatment of Natural Fibers

state for about 2 min, which was sufficient for the drop-
let to flatten and for the fiber to immerse in the poly-
mer. The specimen was cooled at room temperature.
The prepared specimen was a polymer-flattened drop-
let with a diameter of about 15 mm and a thickness of
about 0.1 mm in which a natural fiber was embedded.
The real embedded fiber length, le , was measured by
means of an optical microscope Hund mod. Wetzlar
H600. The tensile measurements were carried out with
a Minimat 2000 Miniature Materials Tester (Rheomet-
ric Scientific) to a testing speed of 0.05 mm/min and
with a load cell of 20 N (sensitive in a range of 0.02 to
20 N). The samples were clamped in a machine in two
different ways. In the first method, the droplet was di-
rectly clamped to one side of the machine and the fiber
to the other side of the machine, having a free length Fig. 1. FTIR spectra of treated natural flax fibers.
of approximately 0.5 mm. In the second method, the
droplet was glued to a glass plate, which was clamped
to the machine and, like the first method, the fiber was
clamped to the other side of the machine, also having a
free length in the order of 0.5 mm. In both methods, the
curves and the values obtained were similar. The force
applied to the fiber was recorded as a function of the
displacement. The classic approach of Kelly-Tyson (29)
for the estimation of the apparent interfacial shear
strength, IFSS, is based on the hypothesis of circular
section of the fiber and calculated as:
Fmax
IFSS
(3)

dle
where d is the fiber diameter, le is the embedded length
and Fmax is the maximum value of the load displace-
ment curve. In the case of vegetable fibers the non-cir- Fig. 2. FTIR spectra of treated flax pulps (FP).
cular shape of their cross sections was often observed
(30, 31). Then, some authors suggest the use of the
fiber real perimeter instead of the mean diameter for 36). MA treatment leads to a more intense peak at about
the calculation of the IFSS (23, 32). However, in order 1735 cm1, due to the esterification reaction. Also the
to obtain simple results that could indicate the effec- shape of the 3700 3000 cm1 broadband changes after
tiveness of the proposed treatments in a comparative MA treatment, thus indicating a variation in the ratio
way, an equivalent diameter can be assumed (33, 34). of intermolecular to intermolecular OH bonds. MAPP
In our case, the measurement of the fiber diameters treatment also produces a new ester group, which ap-
was performed by optical microscopy. pears at 1740 cm1, while VTMO treatment produces a
Finally, tensile tests and three-point bending tests on narrow peak around 1650 cm1.
composite samples were carried out using a universal
mechanical testing machine, Instron model 4206, ac- Thermal Degradation of Fibers
cording to ASTM D790M and ASTM D638M standards, Figures 3ab compare the effect of treatments on the
respectively. polar component and on the total surface energy of
natural treated flax fibers and flax pulps. The surface
RESULTS AND DISCUSSION energy values for PP are also shown. The treatments
produced an increase in the contact angle of NF with
Spectroscopic Analysis of Fibers
water, therefore decreasing its polarity. However, in the
Figures 1 and 2 compare the IR spectra of the natural case of FP, the contact angle does not depend on the
flax fibers (NF) and the flax pulps (FP) before and after treatments because the initial contact angle of the un-
the treatments. The zone between 1800 1600 cm1, re- treated pulp is very high. While the contact angle with
lated to the formation of new ester groups between hy- bromonaphthalene decreases, the contact angle with
droxyl groups from cellulose and applied agents, is the ethylene glycol varies in an irregular way. The Wilhelmy
most interesting area of the spectra (35). The presence technique used for NF shows lower values than the
of an intense peak in the NF spectra at about 1735 cm1 Washburn technique used for FP. MAPP seems to be
associated to carbonyl (CO) stretching of acetyl groups the better treatment for both flax fiber and pulp be-
of hemicellulose in the natural flax is remarkable (24, cause it reaches a polar component similar to that for

POLYMER COMPOSITE, OCTOBER 2004, Vol. 25, No. 5 473

 Jerico Biagiotti et al.

(a) (b)
Fig. 3. Effect of fiber treatments (a) on the polar component and (b) on the total surface energy of natural flax fibers and pulps.

PP, which is strongly non-polar. The VTMO treatment The specific effects of the fiber treatment on the en-
also produces a high reduction of the polar component dothermic water evaporation peak can be observed in
(Table 1). Fig. 6. MA and MAPP treatments restrict the evolution
In thermogravimetric tests on natural fibers, a com- of retained water; while VTMO treated fibers have a
mon behavior observed for all samples is the dehydra- worse response.
tion process in which 5%8% of water is removed at low
temperatures. According to the existing literature (37),
it has been established that there is no fiber degra-
dation up to 160C. Above this temperature, thermal
stability decreases and the decomposition of the fibers
takes place. Figure 4 shows the derivative curves of the
cellulose thermal degradation process obtained by
thermal dynamic scans for fibers with different treat-
ments. In particular, the peak of maximum weight loss
was investigated for all the treatments. The fiber treat-
ments analyzed slightly improve the thermal stability of
the fibers, showing a higher temperature of decomposi-
tion and a lower weight loss rate with respect to un-
treated flax fibers. This effect is more evident with MAPP
treated fibers at higher weight percentages (10%). Fig-
ure 5 shows the endothermic DTA peak of flax fibers in
the temperature range of 320C 370C. Trends similar
to those shown by DTG curves are observed. Fig. 4. DTG curves for treated flax fibers.

Table 1. Contact Angle Values for Analyzed Natural Fibers.

Contact Angle ()

Water Ethylene Glycol 1-Bromonaphthalene

Flax fibers
Untreated 52.5 57.4 46.0
5% MA 59.6 40.0 35.8
10% MA 61.2 37.4 33.7
5% MAPP 85.4 76.2 32.6
10% MAPP 88.0 79.6 40.0
2.5% VTMO 81.3 52.9 32.8

Flax pulps
Untreated 90.0 78.5 49.6
5% MA 84.3 63.2 48.7
10% MA 85.9 60.1 47.2
5% MAPP 88.8 80.7 46.4
10% MAPP 89.5 82.8 44.3
2.5% VTMO 86.5 72.5 43.8 Fig. 5. DTA curvesendothermic peak of cellulose decompo-
sition.

474 POLYMER COMPOSITES, OCTOBER 2004, Vol. 25, No. 5

 Investigation on the Influence of the Chemical Treatment of Natural Fibers

while the slope and intercept of the fitting solid line

Fig. 6. DSC curves. Temperature range of water evaporation.
indicate the Weibull shape factor () and the location
parameters (0 and E0), respectively. As can be seen, a
good agreement is obtained, indicating the right appli-
cation of the proposed model. The same procedure was
applied to all systems and the obtained parameters are
reported in Table 2. The statistical distributions of the
experimental results obtained from the single fiber ten-
sile tests of the fibers studied are illustrated in Fig. 8.
Regarding the two characteristic parameters, it can be
seen how fiber mechanical properties are affected by
the treatments. All treated fibers show lower tensile
strength than untreated ones, with an average reduction
of this parameter ranging from 5% to 40%, indicating a
clear damage of the fiber after treatment. On the other
hand, the dispersion degree, represented by , does not
undergo significant changes after treatment.

Mechanical Properties of Fibers Effects of Fibers on Matrix Crystallization

Taking the natural logarithm of Eq 2 twice we obtain:
ln 3ln 11>F 2 4
 3ln 12 ln 10 2 4
(4)
The slope of the above line yields a value for  and its
intercept provides the normalizing factor. Figure 7
shows the failure probability data obtained from Eq 4
The effects of the studied fibers on the crystallization
behavior of PP were analyzed using non-isothermal
DSC experiments. Figure 9 shows the dynamic ther-
mograms obtained on neat PP and on some of the
PP/flax composites. The values of the exothermal crys-
tallization temperature peaks (Tc ), the crystallization

Table 2. Weibull Parameters of Tensile Properties

for Analyzed Natural Fibers.

Elastic Modulus Tensile Strength

E0 (GPa)
0 (MPa)

Flax fibers
Untreated 33.2 2.6 1054 2.6
10% MAPP 32.9 1.9 959 2.1
10% MA 35.8 3.2 992 2.4
2.5% VTMO 33.4 2.9 635 1.9

Flax pulps
Untreated 20.9 3.6 727 2.8
10% MAPP 20.7 2.8 689 2.4
Fig. 7. Logarithmic plot of stress vs failure probability for 10% MA 18.3 3.3 332 2.2
untreated flax fibers. Solid line is a best fit straight line to the 2.5% VTMO 20.5 3.3 589 2.7
experimental data points shown.

Fig. 8. Weibull distribution of tensile strength for (a) flax fibers and (b) flax pulps.

POLYMER COMPOSITE, OCTOBER 2004, Vol. 25, No. 5 475

 Jerico Biagiotti et al.

Fig. 9. Non-isothermal crystallization curves of PP and natural

flax composites.

enthalpies and the apparent melting temperatures of (a)

the crystallized samples (Tm ), were calculated and re-
ported in Table 3. From this data, it is possible to ob-
serve that the onset of melt crystallization takes place
at higher temperatures in presence of the fibers, indi-
cating a faster crystallization process, which is basi-
cally due to the heterogeneous nucleation of the fibers.
A reduction of this effect with the fiber treatments can
be used as an indication of a good treatment. In fact,
better compatibility with the thermoplastic polyolefin
can reduce the heterogeneous nucleation process and
the consequent transcrystalline growth (38). Moreover,
it has been shown that also the physical modifications
associated with the chemical treatment can play a key
role in the development of transcrystallinity (39) as the
smoothing of the fiber surfaces due to fiber washing
hinders the nucleation of spherulites. The crystalliza-
tion behavior was also confirmed by optical micros-
copy. Figures 10ab show, in fact, the absence of any
transcrystalline region on the treated samples while (b)
abundant transcrystallization is observed in the case of Fig. 10. Micrographs of crystalline growth after 260 sec at
130C for PP with (a) untreated natural flax and (b) 2.5% VTMO
treated natural flax.
Table 3. Melting Temperatures and Enthalpies,
Crystallinity Peaks, and Degradation Temperatures
of PP and Natural Flax Composites.
DSC Tests TGA Tests untreated fibers, while the spherulitic size in both cases
remains unchanged. On the other hand, regarding the
Tc Hc Tm Td fiber Td PP effect of the fibers on the melting temperature, no sub-
(C) (J/g) (C) (C) (C)
stantial differences were detected between treated and
PP 101.1 69.6 166.3 462.8 untreated fiber composites.

Flax fibers Thermal Degradation of Natural Fiber Composites

Untreated 109.5 73.4 166.1 356.1 463.3
5% MAPP 109.5 72.4 164.3 359.5 464.9 The thermogravimetric curves obtained by TGA anal-
10% MAPP 105.3 64.3 167.6 358.6 465.7 ysis of all composites and PP show that separate ther-
5% MA 109.5 72.4 164.1 356.4 464.4
10% MA 105.3 65.3 168.3 358.7 464.4 mal degradation processes occur for natural flax fibers
2.5% VTMO 103.7 70.3 164.4 355.9 463.2 and PP. The temperatures for the maximum rate of deg-
radation are reported in Table 4 for the different mate-
Flax pulps
Untreated 107.4 75.1 168.0 465.0 356.6
rials studied. Figure 11 shows the temperature range at
5% MAPP 109.6 73.9 167.5 463.2 359.0 which the degradation process of the natural flax fibers
10% MAPP 106.3 75.1 168.3 464.6 359.7 occurs (40 42). It was observed that in case of fiber
5% MA 111.3 74.6 166.5 461.1 354.8 treatment, the onset of the decomposition is shifted at
10% MA 110.5 73.5 166.0 462.3 354.5 higher temperature. This behavior indicates that the
2.5% VTMO 107.9 72.2 166.8 465.3 359.8
treatment improves the thermal stability of the fibers,

476 POLYMER COMPOSITES, OCTOBER 2004, Vol. 25, No. 5

 Investigation on the Influence of the Chemical Treatment of Natural Fibers

Table 4. Mechanical Properties for Natural Flax Composites.

Tensile Properties Flexural Properties

Young Tensile Bending Max.

Modulus Strength Modulus Strength
(MPa) (MPa) (MPa) (MPa)

PP 901  27 32.4  0.4 1294  13 37.3  0.5

Flax fibers
Untreated 1558  37 26.9  0.6 3446  55 47.1  0.6
5% MAPP 1830  120 33.9  2.0 3208  70 45.2  0.3
10% MAPP 1605  180 35.4  1.1 2989  63 47.6  0.6
5% MA 1733  102 30.2  1.2 3629  39 43.4  0.3
10% MA 1632  107 30.0  1.4 3827  99 42.9  0.1
2.5% VTMO 1828  58 30.4  0.4 3392  58 41.2  0.9
(a)
Flax pulps
Untreated 1558  37 30.4  0.9 2651  150 41.7  1.6
5% MAPP 1830  120 38.1  1.4 2812  36 49.9  0.7
10% MAPP 1605  180 38.9  1.9 2747  57 50.9  0.5
5% MA 1733  102 27.9  3.9 2933  19 38.7  0.3
10% MA 1632  107 28.1  1.0 2637  61 36.4  0.4
2.5% VTMO 1828  58 33.0  1.7 2730  62 40.3  0.6

20% Glass 2347  98 52.4  1.4 2879  91 69.0  1.6

eliminating unstable impurities from the fibers and

yielding a cleaner and smoother surface (43). Better re-
sults in terms of thermal stability of the composites
produced were observed when MAPP-treated fibers were
used.

Rheological Properties (b)

of Natural Fiber Composites
The effect of fiber treatment is very evident in the re-
sults of the rheological characterization. The variation
of dynamic viscosity (d ) as a function of the angular
frequency is represented in Figs. 12a and b for the dif-
ferent systems analyzed. From these curves, it can be
observed that the rheological properties of the compos-
ites vary strongly as a function of the treatment. In the
case of the natural flax composite (NFC), the untreated
fiber systems exhibit the maximum flow hindrance,
while the treated systems showed a high viscosity re-
duction approaching the behavior of the neat poly-
propylene matrix. The MA treatment resulted to be the
Fig. 12. Variation of dynamic viscosity for PP and (a) natural
fiber composites, (b) natural pulp composites.
most effective one (see Fig. 12a), having the lower val-
ues of dynamic viscosity. A similar behavior was
observed in the case of the composites with cellulose
pulps (Fig. 12b). In fact, no substantial differences were
exhibited between the flow curves of both fibrous and
pulpous untreated systems. Also in this case, the treated
pulps reinforced composites presented a viscosity closer
to that of neat PP; this behavior was more evident in
case of the treatment with MA.

Fig. 11. Degradation process DTG peaks of natural flax in PP
matrix composites analyzed.
Mechanical Properties
of Natural Fiber Composites
The influence of fiber treatment on flexural and tensile
properties for natural flax/PP as well as for flax pulp/PP
composites with a 30 wt% fiber content is shown in
Table 4. Except for the MA-treated flax pulp (FP) com-
posites, flexural and tensile strengths were improved
in all cases. Moreover, MAPP-treated fiber composites
showed the highest strength values. On the other hand,
the flexural and tensile modulus slightly changed with
the treatments.
The effects of the treatments on the IFSS, measured
by means of pull-out tests, are reported in Table 5. Ac-
cording to the surface energy values and the mechani-
cal properties, MAPP and VTMO treatments produce a
slight improvement of adhesion. Other studies (4446)

POLYMER COMPOSITE, OCTOBER 2004, Vol. 25, No. 5 477

 Jerico Biagiotti et al.
Table 5. Weibull Parameters of Interfacial Shear Strength
for Studied Composite Systems.
0 (MPa)
Mat., 9 (1996).
Flax fibers
Untreated 8.85 2.85
5% MAPP 9.85 3.65
10% MAPP 9.42 3.18
5% MA 7.23 3.04
10% MA 6.77 2.67
2.5% VTMO 9.76 1.95
reported that the addition of MAPP could lead to a
sharp increase in strength due to a better stress trans-
fer from the matrix to the fiber. A pull-out test on flax
pulp could not be carried out because of its small geo-
metrical dimensions, which hinder a correct execution
of the test.
For all mechanical properties, no substantial differ-
ences were observed between fiber and pulp reinforced
composites.
CONCLUSIONS
The effect of different fiber treatments on the final
properties of PP/flax composites was studied and re-
ported in this work. Contact angle measurements have
shown that wettability with a PP matrix of both flax
fibers and pulp can be improved by chemical treat-
ments, owing to the reduction of the polar components
of their surface energies. MAPP treatment produces the
best surface energy values. Moreover, TGA and DSC re-
sults confirm that this treatment improves the thermal
stability of flax fibers, as indicated by the maximum
peak and the temperature range of cellulose decom-
position. These properties confirm the suitability of
this treatment for the production of composites with a
thermoplastic matrix. Thermal analysis studies have
indicated a compatibilizing effect on the proposed treat-
ments, which was also confirmed by microscopic anal-
ysis, and, in some cases, an improvement of the me-
chanical properties of the composites was obtained.
Furthermore, rheological studies have pointed out the
difference of the viscoelastic behavior of neat PP and
treated and untreated fiber composites. From these
studies, it was also observed that the viscosity of a
treated fiber reinforced system is lower than that for an
untreated one, enhancing therefore the processability.
These studies have confirmed the potential that these
systems can have in view of their utilization as com-
posites for massive application. However, as no sub-
stantial differences were observed between fiber and
pulp reinforced composites, processing and cost con-
siderations indicate the greater convenience of the use
of flax fibers compared to pulp.
ACKNOWLEDGMENTS
This research has been performed as a part of
the ECOFINA project in the framework of the 5th
European Research Program of the European Commu-
nity (www.ecofina.org).
478
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