Materials and Design 37 (2012) 379383

Contents lists available at SciVerse ScienceDirect

Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Mechanical properties of high density polyethylene reinforced with chemically

modied coir bers: Impact of chemical treatments
F.Z. Arrakhiz a,b, M. El Achaby a,b, A.C. Kakou c, S. Vaudreuil a, K. Benmoussa a, R. Bouhd a,
O. Fassi-Fehri d, A. Qaiss a,
a

Moroccan Foundation for Advanced Science, Innovation and Research (MASCIR), Institute of Nanomaterials and Nanotechnology, Morocco
Faculty of Science, Mohammed V University, Rabat, Morocco
Laval University, Department of Chemical Engineering, Ste-Foy, Quebec, Canada G1K 7P4
d
Hassan II Academy of Science and Technology, Rabat, Morocco
b
c

a r t i c l e

i n f o

Article history:
Received 19 December 2011
Accepted 14 January 2012
Available online 21 January 2012
Keywords:
A. Polymer matrix
E. Mechanical
F. Chemical-reaction

a b s t r a c t
In this work, high density polyethylene (HDPE) was compounded with chemically treated coir ber using
a heated two roll mill. Three chemical treatments denoted silane, sodium hydroxide (NaOH) and dodecane bromide (C12) were selected to improve the interface adhesion between bers and polyethylene
matrix. The mechanical properties of these composites were evaluated and compared against those of
neat polymer and untreated bers composites. A xed ber loading of 20 wt.% was used in all composites.
A chemical analysis using Fourier Transform Infrared spectroscopy (FTIR) was performed to see the
extent of chemical modication of the bers. Results have shown that tensile and torsional modulus
exhibited a signicant increase when compared to the neat HDPE. A notable increase in the Youngs modulus was observed when C12 and silane were used, corresponding to 120% and 70%, respectively. The
composites ductility was also evaluated by the plastic stored energy and showed a noted increase when
C12 and silane were used, an increase of 55% with C12 treatment and 23% when silane treatment was
used. Such results promise many applications for composite materials.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
Natural bers such as Coir, Alfa, and Hemp have been investigated as possible substitutes for synthetic bers such as carbon bers or glass bers in ber-reinforced polymer composites [1]. But
because these bers are covered with pectin and waxy materials,
the interactions between polymer and the bers surface are limited [2] and this can lead to debonding and voids formation [2].
This can be overcome by subjecting the natural bers to some
chemical or physical surface modications to increase their compatibility with the polymer matrix [3]. Several studies have been
focused on the development of specic methods to decrease the
hydrophilic aspect of bers against the hydrophobic character of
polymers [4].
The use of coupling agents as compatibilizer between bers and
matrix can be benecial in improving the water resistance of bers
and enhancing the wettability of bers by the polymer chains [5].
Graft copolymerization or treatment with either isocyanates or
organosilanes as coupling agent are possible approaches that
results in signicant increases in mechanical properties [6]. A

Corresponding author. Tel.: +212 662092719; fax: +212 530300671.

E-mail address: a.qaiss@mascir.com (A. Qaiss).
0261-3069/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2012.01.020

simpler chemical treatment using Alkali can also be used to modify

and purify the bers surface [6] and promote interfacial adhesion.
Physical treatments may also make the bers surface hydrophilic
or hydrophobic through changes in surface energy [7] with no
alteration of the bers chemical structure. Stretching [8], calendering [9] and thermal treatment [10] have been reported in many
studies as having inuence on the bonding of bers with the polymer matrix.
Amoung natural bers, coir ber is low cost and extensively
used in industrial application [11]. Coir is obtained from a coconut
trees which are found in tropical countries. In addition, coir present a versatile lignocellulosic ber with 43% cellulose content [4],
0.2% hemicelluloses content [11], and 4145% lignin content [11].
The Table 1 illustrates some physical and chemical properties of
coir ber to be compared with other plant ber, as Alfa and Jute.
The aim of this paper is to compare the impact of chemical
treatment on the mechanical properties of a coir ber-reinforced
high density polyethylene (HDPE) composite. The chemical treatments used in this work, namely NaOH, C12 and silane, have been
chosen because they exhibit a different interaction mechanism
with both bers and polymer matrix. The mechanical properties
of composites prepared with chemically-treated bers will be
compared to results obtained from untreated bers composite as
well as neat polymer.

380

F.Z. Arrakhiz et al. / Materials and Design 37 (2012) 379383

Table 1
Chemical and physical properties of some plant bers from literature.
Chemical properties

Coir
Alfa
Jute

Physical properties

Cellulose content (%)

Hemicellulose content (%)

Density (g/m3)

Tensile strength (MPa)

Young modulus (GPa)

43 [4]
45 [4]
5971 [11]

0.2 [11]

1213 [11]

1.29 [12]
1.2 [4]
1.39 [12]

186345 [12]
134220 [4]
39310,000 [12]

47 [11]
1317.8 [4]
1030 [11]

2. Materials and methods

2.1. Materials
The thermoplastic polymer high density polyethylene (HDPE)
used in this work was supplied by Hostalen, with a density of
0.959 g/cm3 and melting temperature of 180220 C. The coir bers
originated from Ivory Coast and were supplied as bundles of roughly
20 cm length bers. Before use, the bers were grinded into small 2
3 mm length pieces, using a Fritsch pulverisette 19 Germany. The
list of chemicals used to treat modify coir include sodium hydroxide
NaOH (SigmaAldrich France), acetic acid CH3COOH (Riedel-de
Haen), dodecane bromide (SigmaAldrich France) and 3-(trimethoxysilyl)propylamine (C9H23NO3Si) (SigmaAldrich France).
2.2. Treatment of coir bers
2.2.1. Preparation of CoirAlkali
Crushed coir bers are rst washed with water and then kept
for 48 h in a 1.6 mol/L sodium hydroxide aqueous solution [13].
After removal of the bers from the NaOH solution, they were treated with acetic acid (100 mL) to neutralize the remaining hydroxide [14] after which they were air-dried for 24 h.
2.2.2. Preparation of CoirEther
Dodecane bromide (3 mL) was added to a solution of coir bers
(5 g) and NaOH (20 mL) in isopropanol. The solution was vigorously stirred at room temperature for 12 h. The coir bers were
recovered by ltration, washed thoroughly with isopropanol and
ethyl ether and then dried for 12 h at 50 C. The obtained etheried
bers are denoted Coir-C12 (Fig. 1).
2.2.3. Preparation of coir-silane
A solution of 0.5 wt.% silane coupling agent 3-(trimethoxysilyl)propylamine was prepared in acetone. The pH of the solution
was adjusted to 3.5 with acetic acid, after which the solution was
stirred continuously for an additional 5 min. Fibers were immersed
in the resulting solution for 45 min, after which they were dried at

65 C for 12 h to initiate the chemical reaction between bers and

silane coupling agent (Fig. 2). The bers were then thoroughly
washed with water to remove chemical residues until a pH value
of 7 was measured. The last step involves drying the bers at
80 C for 48 h [15].
2.2.4. Compounding and casting of test specimens
Composites of high density polyethylene (HDPE) with 20 wt.%
of chemically treated coir bers were blended using a heated
two roll mill (Thermo Haake Rheomix, Germany). Compounding
of each 30 g composite batch was performed at 200 C with the roll
mill operating at 60 RPM for 3 min. Under these conditions, a
homogeneous dispersion and distribution of the bers can be
achieved in the HDPE matrix. The neat HDPE matrix is rst lled
in the heated mixing cavity while the mills are under constant
rotational speed. After 30 s, the bers were carefully added onto
the melted HDPE and mixed for 3 min. At that point, the measured
torque was found constant. The rolls are then stopped and the
composite removed from the heated rolls before being cut into
small pieces for hot press molding.
Hot press molding was performed using a semi-automatic press
(CARVER INC, USA) with both platens heated at 190 C. The sample
being molded was held 30 s at that temperature under compression before being cooled to room temperature. The mold used
was shaped according to ISO 527-1(1993) [16] for mechanical
testing.
2.3. Chemical analysis
Fourier Transform Infrared (FTIR) spectroscopy of raw and treated coir was performed on an ABB Bomem FTLA 2000-102
spectrometer equipped with a single reection ATR accessory (SPECAC GOLDEN GATE).
2.4. Mechanical testing
The mechanical properties of the composites, namely their tensile and torsion properties were characterized to evaluate the

Fig. 1. Schematic illustration of the reaction involved in producing the CoirEther (C12 Coir).

F.Z. Arrakhiz et al. / Materials and Design 37 (2012) 379383

381

Fig. 2. Schematic illustration of the reaction involved in producing the CoirSilane.

improvement achieved by the various chemical treatments performed on the coir bers. For each type of composites and tests,
ve specimens were used and the results averaged. Tensile tests
were performed at room temperature according to ISO 527-01,
1993 [16] (Fig. 3a), using an INSTRON 8821S Universal Testing Machine operating at a cross-head speed of 3 mm/min.
Torsion tests were performed on an ARES-LS rheometer operating in rectangular torsion mode, using 5.5 mm width, 56.5 mm
length, and 2 mm thick samples (Fig. 3b). The torsion modulus G
is obtained at room temperature in oscillatory tests performed under various frequencies ranging from 0.1 Hz to 40 Hz. For each
composite, ve specimens were tested and the average value
reported.

3. Results and discussion

Fig. 4. FTIR spectra of coir bers (untreated, Alkali treated, etheried, and silane
treated) (4000600 cm 1).

3.1. Chemical analysis

FTIR spectroscopic analysis was used to characterize and compare the chemically modied coir bers against untreated coir ber. Fig. 4 shows the IR spectra in the 4000600 cm 1 range for
untreated (raw Coir), Alkali-treated (ALK Coir), etheried (C12
Coir), and silane treated (Silane Coir) coir bers.
Fiber treatment using NaOH results in the disappearing of the
C@O (carbonyl) peak at 1725 cm 1 from the removal of reducible
hemicelluloses found on the bers surface [4]. The change in the
1235 cm 1 peak associated to the CAO stretching of the acetyl

groups of lignin indicates that lignin is partially removed from

the coir ber surface after the Alkali treatment [17].
The spectrum of C12 Coir is easily distinguished from that of
untreated coir by the increase of both the 1420 cm 1 band attributed to the CH2 symmetric bending and the 873 cm 1 band assigned to the symmetric in-phase ring stretching mode [4]. Both
of these bands are associated with the grafting of the dodecane
chain. It is also noted the disappearance of the carbonyl stretching
shoulder at 1725 cm 1 which was already attributed to noncellulosic impurities in the native bers [4].
In the case of silane treated coir ber (Silane Coir), two new
absorption bands at 704 and 756 cm 1 can be observed. The rst
one corresponds to a SiAOASi symmetric stretching bond while
the second is a SiAC symmetric stretching [18]. A slight increase
in the broad peak found in the 9561149 cm 1 region should also
be noted. The growth of this band could be attributed to the presence of asymmetric stretching of SiAOASi and/or SiAOAC bonds
[18]. The formation of such siloxane bond is indicative of a polysiloxane coating on the ber, while the alkoxysilane bond tends to
conrm the occurrence of a condensation reaction between the silane coupling agent and the coir bers.
3.2. Tensile properties

Fig. 3. Test specimen pictures. (a) Tensile specimen, and (b) torsion specimen.

A good dispersion and interfacial adhesion between the matrix

and bers are both critical factors for the resulting composites to
achieve improved mechanical properties [5]. Chemical treatment
of the bers surface to improve interfacial adhesion in the composite was used in this study. These results were compared with
a composite prepared with untreated coir bers and with neat
HPDE.
As shown in Fig. 5, the addition of raw coir bers improved the
composites Youngs modulus by 77% compared to neat HDPE. The
chemically treated bers further improve the Youngs modulus but
the extra gains are smaller than those obtained through the addition of raw bers. The use of Alkali treated bers led to an increase
of 94% compared to neat HDPE, but this is only a 10% increase from

382

F.Z. Arrakhiz et al. / Materials and Design 37 (2012) 379383

the untreated ber composite. This is also seen with C12-treated

coir bers composites where a 120% improvement against neat
HDPE is measured, but this represents only a 24% gain against untreated ber composite. Only with silane treated bers that a slight
decrease (4%) is observed against untreated bers, but the composites Youngs modulus is still 70% higher than the one of neat HDPE.
The increase in Youngs modulus of Alkali treated coir composites originate from the removal of non-cellulosic components
found at the surface of individual bers. Removal of this non-cellulosic material reduce the bers density and rigidity in the interbrillar region and makes the brils more capable of rearranging
themselves during stretching results in a better load sharing. The
Alkali treatment reported by many studies [19] affects the spiral
angle by decreasing it to be closer to the bers axis, yielding an increase in molecular orientation. This better ordered structure can
explain the increase in elastic modulus of composite made with Alkali treated coir bers [6].
The highest increase in Youngs modulus observed in HDPE
composite with C12 treated coir bers can be attributed to two
things. First is the NaOH treatment performed on the bers before
the ether chain grafting. The second is the length of the grafted aliphatic chain which, with 12 carbon atoms, improved the wetting of
treated bers with the HDPE matrix by creating a steric effect
(Fig. 1).
The last treatment used was a silane modication of the bers.
From Fig. 5 it is clear that bers modied by this treatment do not
have the same interaction mechanism compared to the other
chemical treatments. Composites with silane-modied bers have
roughly the same Youngs modulus as those obtained with untreated bers but a greatly improved tensile strength. And because
the tensile strength of composites with raw coir is only slightly
higher than the tensile strength of neat HDPE, the use of silanereinforced bers offers the greatest gains.
Interfacial bonds formed by silane and bers surface are illustrated in Fig. 2. From this scheme it is clear that the silane macromolecule formed [5] can act both as reinforcement for the bers
and as anchor in a way similar of the C12 chains.
Grafting of aliphatic chains on the bers surface will increase
its hydrophobicity and this will be further exacerbated with silanes. It can be anticipated that (CH2)3 groups will appear after
grafting all along each ber in addition to alkyl chains [20].
In the case of NH2 groups, they will rather bond with free OH
groups through hydrogen bonding thus resulting in the withdrawal
of the grafted chains from the polymer. Furthermore, as C12 chains

are relatively long, only a few will bond to the same ber. This will
limit the increase in the bers hydrophobicity [21], enabling C12modied coir bers to have the highest tensile strength.
This reinforcement through silane and polysiloxane chains
results in a 16% increase in tensile strength while a 6% gain is obtained with the use of C12 side chains. The simple Alkali treatment
results however in a 6% decrease in tensile strength.In order to evaluate the ductility of each composite, the stored energy was evaluated by integration under stressstrain curves. Fig. 6 illustrates
the energy stored by the various coir composites. As seen in this gure, there are big differences between the stored energy by neat
HDPE and by the different composites. This can exceed more than
200% in the case of pure matrix plastic value when compared to untreated coir composite. The ductility of the various composites was
evaluated through the plastic energy. It can clearly be seen that C12
coir composite and Silane Coir composite store respectively 55% and
23% more energy compared to raw coir composite, while the Alkali
coir composite shows a slight decrease (5%).
The fragile behavior of bers reinforced polymer limits the plasticity behavior compared to a pure polymer matrix. The increase in
plastic energy observed for both silane and C12 coir composites
can be attributed to the use of a coupling agent which took the
same orientation as the stretching [22] and thus stored more energy in the composite material.
As noted earlier other research was investigated in the eld of
natural ber reinforced thermoplastic matrix and showed a variability of results, which are depending even in the polymer matrix
or in the chemical and/or physical properties of bers [23].

Fig. 5. Youngs moduli and tensile strength of HDPE composites made with the
various chemically treated bers.

Fig. 6. Stored energy for neat HDPE and its composites as determined by the stress
strain diagrams.

3.3. Torsion properties

The evolution of the torsion modulus in the frequency range between 0.1 Hz and 40 Hz is illustrated in Fig. 7 for all composites
and neat HDPE. It can clearly be seen a steady evolution in modulus
from the low to the highest frequency. Both curves for Alkali and
C12 treated composites are similar enough to be almost superposed. These two composites exhibit a torsion modulus higher
than the one measured for neat polymer and raw-ber composite.
This can be explained by the NaOH treatment used that gives brils
more exibility under a twisting force [6]. For the composite made
from silane-modied bers, the presence of surface polysiloxane
reinforced the bers by making them more rigid, thus slowing
down their rotation with any applied twisting movement. When
compared to an untreated-coir ber composite, composites pre-

F.Z. Arrakhiz et al. / Materials and Design 37 (2012) 379383

383

References

Fig. 7. Evolution of the torsion modulus under a dynamic sweep frequency for the
various composites.

pared with chemically treated bers exhibit higher and lower torsion moduli depending on the chemical treatment performed. In
the case of a simple NaOH treatment or the more complex C12
grafting, the torsion modulus increased by roughly 2%. In contrast,
the silane treatment resulted in a 10% decrease in torsion modulus
and raw composite decreased by 2% compared to HDPE matrix at
the quasi static state of 0.1 Hz.

4. Conclusion
In this work, HDPE composites with a 20 wt.% coir ber content
were prepared by compounding. Because an emphasis was put on
evaluating the effects of chemical treatment on mechanical properties, three chemical treatments were performed on coir bers to enhance their wettability with the polymeric matrix. These chemicals
treatment include a simple NaOH surface etch to remove undesired waxes and lignin to the more complex 12-carbon chain graft
or even polysiloxane ber coating. Results have shown that composites obtained with treated bers possess better mechanical
properties than those of composites made with untreated bers,
the calculated Youngs modulus in the composites was higher for
the Alkaline treated bers than the raw bers, also the C12 composite shows a signicant tensile modulus when compared to raw bers reinforced polymer. Moreover, torsional test shows that the
NaOH treatment gives more exibility to the bers when the used
silane treatment makes them more rigid. A study of the plastic energy absorbed by all the composites has shown a clear limitation
of the added bers. But the use of coupling agents such as silane
or C12 chains did increased noticeably the stored energy when compared to composites made from raw coir or Alkali treated bers.

[1] Mominul Haque Md, Mahbub H, Saiful Islam Md, Ershad Ali Md. Physicomechanical properties of chemically treated palm and coir ber reinforced PP.
Bioresour Technol 2009;100:49036.
[2] Moyeenuddin AS, Kim LP, Fernyhough A. Effect of various chemical treatments
on the ber structure and tensile properties of industrial hemp ber.
Composites Part A 2011;42:88895.
[3] Cordeiro N, Gouveia C, Jacob John M. Investigation of surface properties of
physico-chemically modied natural bers using inverse gas chromatography.
Indust Crop Prod 2011;33:10815.
[4] Arrakhiz FZ, Elachaby M, Bouhd R, Vaudreuil S, Essassi M, Qaiss A. Mechanical
and thermal properties of polypropylene reinforced with Alfa ber under
different chemical treatment. J Mater Des 2012;35:31822.
[5] Yanjun X, Callum AS, HillZefang X, Holger M, Carsten M. Silane coupling agents
used for natural ber/polymer composites: a review. Composites Part A
2010;41:80619.
[6] Bledzki AK, Gassan J. Composites reinforced with cellulose based bers. Prog
Polym Sci 1999;24:2217.
[7] Li Rongzhi, Ye Lin, Ma Yiu-Wing. Application of plasma technologies in brereinforced polymer composites: a review of recent developments. Composites
Part A 1997;28:738.
[8] Botaro VR, Gandini A, Belgacem N. Heterogeneous chemical modication of
cellulose for composite materials. J Thermoplast Compos 2005;18:10717.
[9] Maldas D, Kokta BV. Improving adhesion of wood ber with polystyrene by
chemical treatment of ber with coupling agent and the inuence on the
mechanical properties of the composites. J Adhes Sci Technol 1989;3:52939.
[10] Rider AN, Arnott DR. Boiling water and silane pre-treatment of aluminium
alloys for durable adhesive bonding. Int J Adhes Adhes 2000;20:20920.
[11] Tran HN, Shinji O, Nguyen HT, Satoshi K. Effect of alkali treatment on
interfacial and mechanical properties of coir ber reinforced poly(butylene
succinate) biodegradable composites. Compos Part B-Eng 2011;42:164856.
[12] Defoirdt N, Biswas S, De Vriese L, Ngoc Tran LQ, Van Acker J, Ahsan Q, et al.
Assessment of the tensile properties of coir, bamboo and jute bre. Composites
Part A 2010;41:58895.
[13] Le Trodec M, Rachini A, Peyratout C, Rossignol S, Max E, Kaftan O, et al.
Inuence of chemical treatments on adhesion properties of hemp bre. J
Colloid Interf Sci 2011;356:30310.
[14] Le Trodec M, Sedan D, Peyratout C, Bonnet JP, Smith A, Guinebretiere R, et al.
Inuence of various chemical treatments on the composition and structure of
hemp bers. Composites Part A 2008;39:51422.
[15] Pickering KL, Abdalla A, Ji C, McDonald AG, Franich RA. The effect of silane
coupling agents on radiata pine bre for use in thermoplastic matrix
composites. Composites Part A 2003;34:91526.
[16] ISO 5271:1993.Plastics determination of tensile properties-Part 1: General
principles.
[17] Paiva MC, Ammar I, Campos AR, Cheikh RB, Cunha AM. Alfa bres: mechanical,
morphological and interfacial characterization. Compos Sci Technol
2007;67:11328.
[18] Valadez-Gonzalez A, Cervantes-Uc JM, Olayo R, Herrera-Franco PJ. Chemical
modication of henequen bers with an organosilane coupling agent. Compos
Part B-Eng 1999;30:32131.
[19] Jochen G, Bledzki AK. The inuence of ber-surface treatment on the
mechanical properties of Jutepolypropylene composites. Composites Part A
1997;28:10015.
[20] Bledzki AK, Reihmane S, Gassan J. Properties and modication methods for
vegetable bers for natural ber composites. J Appl Polym Sci 1996;59:2936.
[21] Nabi Saheb D, Jog JP. Natural ber polymer composites: a review. Adv Polym
Technol 1999;18:35163.
[22] Jeffrey GA. An introduction to hydrogen bonding. New York: Oxford University
Press; 1997.
[23] Ku H, Wang H, Pattarachaiyakoop N, Trada M. A review on the tensile
properties of natural ber reinforced polymer composites. Compos Part B: Eng
2011;42:85673.