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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- Although many chemical treatments have been re-
posites using PP and many different lignocellulosic ported in the scientific literature, the available results
fibers and by using the most common processing are difficult to compare because of the intrinsic differ-
techniques (9, 10). However, poor thermal and environ- ences of natural systems coming from different geo-
mental stability with degradation of the mechanical graphical regions and different harvesting, production
properties due to their moisture sensitivity and poor and processing conditions. Thus, the aim of this work
fiber-matrix adhesion are the main problems of natural is not to review the extensive literature on fiber chemi-
fiber composites, hindering industrial-scale application cal treatments but to compare the effects of different
of these materials (11). treatments on two well-defined flax derived fibers. The
In order to improve the performance of the compos- proposed treatments and their effects on the fiber
ites based on natural reinforcements, fiber treatments properties were characterized by infrared spectroscopy,
are generally adopted to improve adhesion between the calorimetry, and thermogravimetry and by single fiber
fibers and the matrix. Previous studies have shown tensile tests. Then, in order to determine the surface
that independently of the matrix composition, natural energy values, contact angle measurements were used.
hydrophilic fibers do not present good chemical com- Furthermore, the effectiveness of the fiber treatments
patibility with hydrophobic polymer matrices, such as on the composite properties has been evaluated, as well
polypropylene (1216). So, the fiber surface must be as its effects on the matrix crystallinity, on the interfa-
treated to increase compatibilization with the matrix, cial shear strength, and on the mechanical properties
using different processes such as bleaching, grafting of (tensile, flexural) of the composites.
monomers, and acetylation. In addition to these treat-
ments, the use of a compatibilizer or a coupling agent EXPERIMENTAL
for effective stress transfer across the interface can be
Materials
adopted (1720). An effective chemical modification
method for natural fibers is graft copolymerization, Two different kinds of cellulose-based reinforcement
where the reaction is initiated by the free radicals or were used in this work. Natural flax fibers (NF), obtained
functional groups of the cellulose molecule, providing a by a retting process of flax plants from Finflax (Fin-
route to significantly modify the characteristics of the land), and flax pulp fibers (FP) obtained by flax cooking,
adhesion between the polymer and the fibers. Chemical in a process similar to Kraft pulping, from Celesa (Spain).
grafting involves attaching to the surface of a fiber/filler This pulp has 5 wt% shives content (wooden content of
a suitable polymer with a solubility parameter similar the pulp) and a permanganate index of 9.4. Maleic
to that of the polymer matrix, acting as an interfacial anhydride (MA) from Cepsa, maleic anhydride-poly-
agent and improving bonding between the fiber and the propylene copolymer (MAPP Epolene E-43) kindly sup-
matrix. The resulting copolymer has properties related plied by Eastman Chemical, and vinyltrimethoxy silane
to both the fibrous cellulose and the grafted polymer. (VTMO) kindly supplied by Degussa were used as cou-
For example, the treatment of cellulose fibers with hot pling agents. Epolene E -43 has a low molecular weight
polypropylene-maleic anhydride (MAPP) copolymers (Mn  3900, Mw  9100), 0.934 g/ml density and acid
provides covalent bonds across the interface (21). The number of 45. A commercially isotactic grade of poly-
reaction mechanism can be divided into two steps: the propylene (iPP), Eltex P HV200 from Solvay (Melt Flow
activation of the copolymer by heating (T  170C, be- Index: 2.9 dg/min at 190C and 5 Kg, and density 0.90
fore fiber treatment) and the esterification of cellulose. g/cm3), was used in this research.
As an effect of this treatment, the surface energy of
the fibers can be changed to a level much closer to the Fiber Treatments
surface energy of the matrix. Fibers were treated with two different amounts of
Acetylation, which is another chemical treatment for MA; in particular two different percentages respect of
natural fibers, has been extensively applied to wood fiber weight were used (5% and 10%). Fibers were es-
cellulose (22) to stabilize the cell wall, thereby improv- terified for 25 h with MA and dissolved in boiling ace-
ing dimensional stability and environmental resist- tone (T  50  5C) with a fiber/solvent ratio of 1:25
ance, since no adsorbed water can cause further swell- (wt/V). Thereafter, fibers were washed several times in
ing or shrinkage of the composite material. While the cold acetone and distilled water, and finally dried in an
acetylation treatment has long been used on textiles, oven at 105C for at least 24 h before testing (25).
research has only recently been carried out to assess Treatments with 5% and 10% wt MAPP were also
its usefulness in the case of natural fiberbased com- used. For these treatments, MAPP was dissolved in
posites (22). Organosilane is another important group boiling xylene (T  150  5C) with a fiber/solvent ratio
of coupling agents, mainly used for glass-fiber rein- of 1:25 (wt/V). Then, the fibers were soaked in the so-
forced polymers, that has recently shown its effectiveness lution for 56 minutes. As in the former case, the fibers
as a compatibilizer for natural fiber polymer compos- were washed and carefully dried (25, 26). For silaniza-
ites (23). The organo-functional group in the silane- tion, VTMO was dissolved in acidified water (pH  3.5)
coupling agent generally reacts with the polymer either for 10 minutes to get a better functionalization. Then,
through copolymerization or through the formation of the fibers were added and maintained for 1 h in the
an interpenetrating network (24). solution to obtain a 2.5 wt% (27).

POLYMER COMPOSITE, OCTOBER 2004, Vol. 25, No. 5 471


Jerico Biagiotti et al.

Fiber Characterization Composite Manufacturing


A Perkin-Elmer 16 PC FTIR spectrophotometer was Before their utilization, flax pulps (FP) were defibril-
used to obtain the IR spectra of the treated fibers. Pure lated in a blade mill. Afterwards, both short flax fibers
powdered potassium bromide (KBr) was used as a ref- and opened pulps were vacuum dried in an oven at
erence substance. Small quantities of the samples were 100C for 12 hours. Drying of vegetal fibers before pro-
dispersed in dry KBr and further ground to a fine mix- cessing is a fundamental step since the presence of
ture in a mortar before pressing, to form KBr pellets for water at the matrix-matrix interface prevents adhesion.
analysis. Additionally, water evaporation during compounding
The contact angle values were obtained using a can cause bubbles in the matrix. Both phenomena pro-
Krss K 12 tensiometer and using two different tech- duce a decrease in the mechanical properties of the
niques because of the morphology of each kind of fiber: composite. Blending of PP and 30 wt% flax fiber was
the Dynamic Contact Angle method based on the Wil- carried out in a twin-screw extruder (Haake Rheomex
helmy equation was adopted in the case of long natural CTW 100), at 40 rpm screw speed and barrel tempera-
flax fibers and of the polypropylene matrix, while the tures were set at 180C (zone 1), 182C (zone 2), 184C
Capillary Rise method based on the Washburn equa- (zone 3) and 185C at the die. The extrudate was pel-
tion was adopted in case of irregular flax pulps. The use letized and then maintained in an oven at 100C in a
of two different methods involved a small discordance vacuum to avoid moisture uptake. The molding of the
in the wettability values. The test liquids used were dis- dried pellets was carried out in an injection molding
tilled water, ethylene glycol and 1-bromonaphthalene. machine (Battenfeld Plus 250). Samples were molded
Surface energy values were calculated from the contact for flexural and tensile tests, according to ASTM D790M
angle values according to the Owens-Went equation: and ASTM D638M standards, respectively.

11  cos 2 L  3 1 dL  dS 2 1>2  1 pL  pS 2 1>2 4 (1) Composite Characterization


where  is the contact angle of the sample with test liq- The following thermal history was adopted for DSC
p
uid; Ld, L , and L are the dispersive, polar and total characterization of natural fiber composites: samples of
p
surface energy of the test liquid, respectively; and Sd, S about 8 mg were heated from 30C to 200C at a scan
are the dispersive and polar components of the surface rate of 10C/min and held for 10 min at 200C to elim-
energy of the tested sample, respectively. inate any thermal history. The samples were then cooled
Degradation tests were performed using a thermo- to 50C at a cooling rate of 50C/min. After crystal-
gravimetric analyzer (TGA-Seiko Instrument SII Exstar lization, the samples were heated again to 200C to
6000). Dynamic scans were run from room temperature measure the heat and melting temperature.
to 600C at a heating rate of 10C/min for each kind of In order to analyze the transcrystalline growth of
fiber treatment. The average weight of the samples polypropylene spherulites, the injection molded speci-
tested was 10 mg. The residual weight measured during mens were observed by means of a Hund mod. Wetzlar
the TGA test was converted to the corresponding value H600 optical microscope, equipped with a Mettler FP-
of percentage of the residual weight fraction (wr %  100 82HT automatic hot-stage thermal control and a video
w(t)/wo ) where w(t) is the mass of the sample at each camera. Samples were melted and squeezed between
temperature and wo is the initial mass of the sample. two microscope cover glasses at 200C for 10 min, and
Derivative curves (DTG) were obtained in order to com- then rapidly cooled to the crystallization temperature of
pare the weight loss rate during the temperature scan. 130C.
In order to highlight the main phenomena associated Degradation tests on a thermogravimetric analyzer
to the intrinsic thermal instability of the natural fibers (TGA-Seiko Instrument SII Exstar 6000) were run from
(for example, water evaporation and cellulose decompo- room temperature to 600C and with a typical heating
sition), which may have consequences on the process- rate of 10C/min, under nitrogen flow.
ing, DSC scans were also performed. Samples of about The rheological properties were determined using a
8 mg were heated from 30C to 400C at a heating rate Rheometric Scientific Ares dynamic mechanical spec-
of 10C/min. trometer. Tests were conducted using parallel plate fix-
Single fiber tensile tests were carried out at room tures at a temperature of 190C in a range of angular
temperature, according to ASTM D 3379. The tensile frequency from 0.1 to 100 rad/sec. The strain ampli-
strength variation of the analyzed flax fibers was ob- tude was maintained at 1%.
tained by application of the Weibull distribution. Using Specimens for the pull-out test were prepared as fol-
two-parameter Weibull statistics, the cumulative den- lows. A small polymer particle was placed on a thin
sity function for the natural fiber is: cover glass placed on a hot stage. The temperature of
  the glass was 200C. After the polymer was melted, a
F 12  exp c a b d (2) fiber was placed on the droplet formed, carefully im-
0
mersing a length of fiber (embedded length) smaller
where F () is the probability of survival at stress, ,  than 500 m, in order to avoid fiber fracture during the
is a dimensionless shape parameter and 0 is a location tests. Then, the droplet with the fiber was covered with
parameter (28). a second glass plate. The specimen was kept in this

472 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


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
Fig. 6. DSC curves. Temperature range of water evaporation. 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: The effects of the studied fibers on the crystallization
ln 3ln 11>F 2 4   3ln 12 ln 10 2 4
behavior of PP were analyzed using non-isothermal
(4)
DSC experiments. Figure 9 shows the dynamic ther-
The slope of the above line yields a value for  and its mograms obtained on neat PP and on some of the
intercept provides the normalizing factor. Figure 7 PP/flax composites. The values of the exothermal crys-
shows the failure probability data obtained from Eq 4 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
Fig. 12. Variation of dynamic viscosity for PP and (a) natural
The effect of fiber treatment is very evident in the re- fiber composites, (b) natural pulp composites.
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- most effective one (see Fig. 12a), having the lower val-
ferent systems analyzed. From these curves, it can be ues of dynamic viscosity. A similar behavior was
observed that the rheological properties of the compos- observed in the case of the composites with cellulose
ites vary strongly as a function of the treatment. In the pulps (Fig. 12b). In fact, no substantial differences were
case of the natural flax composite (NFC), the untreated exhibited between the flow curves of both fibrous and
fiber systems exhibit the maximum flow hindrance, pulpous untreated systems. Also in this case, the treated
while the treated systems showed a high viscosity re- pulps reinforced composites presented a viscosity closer
duction approaching the behavior of the neat poly- to that of neat PP; this behavior was more evident in
propylene matrix. The MA treatment resulted to be the case of the treatment with MA.

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-
Fig. 11. Degradation process DTG peaks of natural flax in PP cal properties, MAPP and VTMO treatments produce a
matrix composites analyzed. 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 REFERENCES


for Studied Composite Systems.
1. B. D. Park and J. J. Balatinecz, J. Thermoplastic Comp.
0 (MPa)  Mat., 9 (1996).
2. D. Hull, An Introduction to Composite Materials, Cam-
Flax fibers bridge University Press, Cambridge, UK (1981).
Untreated 8.85 2.85 3. M. A. Lpez-Manchado, J. Biagiotti, L. Torre, and J. M.
5% MAPP 9.85 3.65 Kenny, Polym. Eng. Sci., 40 (2000).
10% MAPP 9.42 3.18 4. J. J. Balatinecz and B. D. Park, J. Thermoplastic Comp.
5% MA 7.23 3.04 Mat., 10 (1997).
10% MA 6.77 2.67 5. F. H. M. M. Costa and J. R. M. DAlmeida, Polym.-Plast.
2.5% VTMO 9.76 1.95 Technol. Eng., 38 (1999).
6. A. Arbelaiz, G. Cantero, F. Mugika, R. Llano-Ponte, and I.
Mondragon, MATCOMP 99, III Congreso Nacional de Ma-
teriales Compuestos, Malaga, Espaa (December 1999).
reported that the addition of MAPP could lead to a 7. P. Gaan and I. Mondragon, Polym. Compos., 23 (2002).
sharp increase in strength due to a better stress trans- 8. Annual Book of ASTM Standards, D 4762-88, Reapproved
1995.
fer from the matrix to the fiber. A pull-out test on flax 9. P. V. Joseph, K. Joseph, and S. Thomas, Comp. Sc. Tech.
pulp could not be carried out because of its small geo- 59, 11 (1999).
metrical dimensions, which hinder a correct execution 10. F. M. B. Coutinho and T. H. S. Costa, Polymer Testing,
of the test. 18, 8 (1999).
For all mechanical properties, no substantial differ- 11. J. C. M. de Bruijn, European Conference on Composite
Materials, 8, Naples, Italy (1998).
ences were observed between fiber and pulp reinforced 12. J. Biagiotti, M. A. Lpez-Manchado, M. Arroyo, and J. M.
composites. Kenny, Polym. Eng. Sci., 43, 1031 (2003).
13. A. K. Bledzki and J. Gassan, Prog. Polym. Sci., 24 (1999).
CONCLUSIONS 14. A. R. Sanadi, R. A. Young, C. Clemons, and R. M. Rowell,
J. Reinf. Plast. Comp., 13 (1994).
The effect of different fiber treatments on the final
15. R. T. Woodhams, G. Thomas, and D. K. Rodgers, Polym.
properties of PP/flax composites was studied and re- Eng. Sci., 24 (1984).
ported in this work. Contact angle measurements have 16. E. P. Plueddemann, Silane Coupling Agents, 2nd Ed.,
shown that wettability with a PP matrix of both flax Plenum Press, New York (1991).
fibers and pulp can be improved by chemical treat- 17. D. N. Saheb and J. P. Jog, Adv. Polym. Technol., 18 (1999).
18. J. Gassan and A. K. Bledzki, Composites Part A, 28 (1997).
ments, owing to the reduction of the polar components 19. F. M. B. Coutinho, T. H. S. Costa, and D. L. Carvalho,
of their surface energies. MAPP treatment produces the J. Appl. Polym. Sci., 65 (1997).
best surface energy values. Moreover, TGA and DSC re- 20. X. Yuan, Y. Zhang, and X. Zhang, J. Appl. Polym. Sci., 71
sults confirm that this treatment improves the thermal (1999).
21. M. N. Ichazo, C. Albano, J. Gonzlez, R. Perera, and M.
stability of flax fibers, as indicated by the maximum
V. Candal, Comp. Struct., 54 (2001).
peak and the temperature range of cellulose decom- 22. L. Y. Mwaikambo and M. P. Ansell, Angew. Makromole.
position. These properties confirm the suitability of Chem., 272 (1999).
this treatment for the production of composites with a 23. A. Valadez-Gonzalez, J. M. Cervantes-Uc, R. Olayo, and
thermoplastic matrix. Thermal analysis studies have P. J. Herrera-Franco, Composites Part B, 30, 309 (1999).
24. J. Gassan and A. K. Bledzki, in ECCM-8-European Conf.
indicated a compatibilizing effect on the proposed treat- Comp. Mat., Naples, Italy (June 1998).
ments, which was also confirmed by microscopic anal- 25. M. Kazayawoko, J. J. Balatinecz, and R. T. Woodhams,
ysis, and, in some cases, an improvement of the me- J. Appl. Polym. Sci., 66 (1997).
chanical properties of the composites was obtained. 26. R. G. Raj, B. V. Kokta, and J. D. Nizio, J. Appl. Polym. Sci.,
45 (1992).
Furthermore, rheological studies have pointed out the
27. R. Karnani, M. Krishnan, and R. Narayan, Polym. Eng.
difference of the viscoelastic behavior of neat PP and Sci., 37 (1997).
treated and untreated fiber composites. From these 28. P. K. Mallick, Fiber Reinforced Composites, Marcel Dekker,
studies, it was also observed that the viscosity of a Inc., New York.
treated fiber reinforced system is lower than that for an 29. A. Kelly and W. R. Tyson, J. Mech. Phys. Solids, 12, 329
(1965).
untreated one, enhancing therefore the processability. 30. A. Stamboulis, C. A. Baillie, and T. Peijs, Composites: Part
These studies have confirmed the potential that these A, 32, 1105 (2001).
systems can have in view of their utilization as com- 31. P. J. Herrera-Franco, A. Valadez-Gonzalez, and M. Cer-
posites for massive application. However, as no sub- vantes-Uc, Comp. Eng. Part B, 28, 331 (1997).
32. J. O. Karlsson, J. F. Blachot, A. Peguy, and A. Gaten-
stantial differences were observed between fiber and
holm, Polym. Compos., 17, 300 (1996).
pulp reinforced composites, processing and cost con- 33. A. Stamboulis, C. A. Baillie, and E. Schulz, Die Ange-
siderations indicate the greater convenience of the use wandte Makromolekulare Chemie, 272, 117 (1999).
of flax fibers compared to pulp. 34. R. Joffe, J. Anderson, and L. Wallstrm, Composites: Part
A, 34, 603 (2003).
35. B. V. Kokta, R. G. Raj, and C. Daneault, Polym. Plast.
ACKNOWLEDGMENTS Technol. Eng., 28 (1989).
This research has been performed as a part of 36. H. Zhu, Y. Ma, Y. Fan, and J. Shen, Thin Solid Films, 397
(2001).
the ECOFINA project in the framework of the 5th 37. B. Wielage, Th. Lampke, G. Marx, K. Nestler, and D.
European Research Program of the European Commu- Starke, Thermochim. Acta, 337 (1999).
nity (www.ecofina.org). 38. C. Saujanya and S. Radhakrishnan, Polymer, 42 (2001).

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


Investigation on the Influence of the Chemical Treatment of Natural Fibers

39. G. Cantero, A. Arbelaiz, F. Mugika, A. Valea, and I. Mon- 43. A. K. Rana, R. K. Basak, B. C. Mitra, M. Lawther, and
dragon, J. Reinf. Plast. Comp., 22, 37 (2003). A. N. Banerjee, J. Appl. Polym. Sci., 64 (1997).
40. B. Wielage, Th. Lampke, G. Marx, K. Nestler, and D. 44. J. M. Felix and P. Gatenholm, J. Appl. Polym. Sci., 42
Starke, Thermochimica Acta, 337, 1 2 (1999). (1991).
41. A. M. A. Nada and M. L. Hassan, Polym. Degrad. and 45. K. Oksman and C. Clemons, J. Appl. Polym. Sci., 67
Stab., 67, 111115 (2000). (1998).
42. C. Albano, J. Gonzlez, M. Ichazo, and D. Kaiser, Polym. 46. M. A. Lpez-Manchado, M. Arroyo, J. Biagiotti, and J. M.
Degr. Stab., 66, 2 (1999). Kenny, J. Appl. Polym. Sci. (in press).

POLYMER COMPOSITE, OCTOBER 2004, Vol. 25, No. 5 479