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Materials Letters 63 (2009) 6163

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Effect of pre-treatment of Luffa bres on the structural properties


L. Ghali a,, S. Msahli a, M. Zidi b, F. Sakli a
a
b

Textile Research Unit of ISET Ksar Hellal 5070, Monastir, Tunisia


Laboratory of Mechanical Engineering, National School of Engineering of Monastir 5000, Tunisia

a r t i c l e

i n f o

Article history:
Received 26 March 2008
Accepted 1 September 2008
Available online 9 September 2008
Keywords:
Luffa bres
Electron microscopy
X-ray techniques
Crystallinity
Chemical treatment

a b s t r a c t
Recently, the use of lignocellulosic bres to reinforcing composite has received an increased attention.
However, lack of good interfacial adhesion makes important the treatment of raw materials. Chemical
treatment prepared the raw material to be useful by elimination of gummy and waxy substances. In this
study, the Luffa bres were treated by tow methods: alkali treatment and mixed treatment (sodium
hydroxide and hydrogen peroxide). The effect of these treatments on the structure of bres was showed
using SEM and XRD (X-Ray Diffraction) analysis. The SEM results revealed that both treatments resulted in a
removal of lignin, pectin and hemicellulose substances, and change the characteristics of the surface
topography. The XRD analysis shows the increase of crystallinity index by many treatment conditions. We
nd that the alkali treatment (120 C; 3 h; 4% NaOH) shows a good cleaning and the higher crystallinity index
of treated bres. It is also interesting to note that mixed treatment can change the Luffa bres from mat
structure to brils structure.
2008 Elsevier B.V. All rights reserved.

1. Introduction

2. Materials and methods

The sponge gourd, fruit of Luffa cylindrica, has a ligneous netting


system in which the brous cords are disposed in a multidirectional
array forming a natural mat. This brous vascular system is composed
of brils glued together with natural resinous materials of plant tissue.
Gianpietro et al. [1] has reported that the bres of L. cylindrica were
composed of 60% cellulose, 30% hemicellulose and 10% lignin.
Recently, the L. cylindrica have been used as support of immobilization for the discolouration of certain solutions [210] and dyeing
water [59]. Indeed, Akhtar et al. [24] showed that the Luffa sponge
gave good results during its use as support to produce a new system of
sorption to remove the cadmium, the Chromium III and nickel II ions
from the contaminated aqueous mediums.
Some other studies characterized the Luffa bres [11] for other
technical applications such as reinforcing composite materials [12,13].
Tanobe et al. [11] prepared a data characterizing bres extracted from
Brazilian sponge gourd. It has been found that the physical properties of
Luffa bres must be enhanced by chemical or physical modications to
make them more useful in composite. In this work, we investigate the
inuence of changing chemical treatment parameters on the structure
of pre-treated Luffa bres. The conservation of the mat structure of Luffa
bres and a high crystallinity index after chemical treatment has a good
interest in their technical use. The Luffa bre samples are characterized
by using Scanning Electron Microscopy (SEM) and X-Ray Diffraction
(XRD) to explore the structure change.

2.1. Treatment of Luffa bres

Corresponding author. Tel.: +216 97 66 33 93.


E-mail address: ghali_las@yahoo.fr (L. Ghali).
0167-577X/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2008.09.008

The Luffa sponge, collected from Tunisia, used in this study was
washed three times in hot water, then with 0.2% lauryl sulphate solution
under continuous stirring at 60 C for 30 min to ensure good cleaning [14].
Cell-bres of L. cylindrica were extracted from brous stands by
tow methods. In the rst method, a solution containing both sodium
hydroxide and anthraquinone is used to remove waxy and gummy

Table 1
Crystallinity index of untreated and treated Luffa bres
Treatment method

Treatment conditions (TCTemps% of NaOH% H2O2)

Icr (%)

Untreated
Alkali treatment

Untreated
8038
10038
12034
120112
1001210
1001410
1001610
100185
1001810
1001815
1002810
1003810
10011010
120185
1201810
1201815

50.00
66.32
70.56
70.84
68.18
65.18
65.24
65.72
67.66
67.40
68.88
67.61
67.82
67.09
69.03
66.07
70.10

Mixed treatment

62

L. Ghali et al. / Materials Letters 63 (2009) 6163

Fig. 1. SEM micrographs of a) untreated Luffa bres; b) Alkali treated Luffa bres.

Fig. 2. SEM micrographs of a) gross morphology of untreated Luffa bres; b) brillary structure of treated bres.

substances (Table 1). In the second method, cleaned Luffa bres are
treated by solution containing both sodium hydroxide and hydrogen
peroxide mixed treatment (Table 1). In these two methods the sodium
hydroxide was used as a reagent for the delignication of Luffa bres,
the anthraquinone to catalyse the reaction of delignication and the
hydrogen peroxide as bleaching reagent. The duration of treatment,
the soda concentration, percentage of hydrogen peroxide and the
temperature are variable parameters. The obtained bres are washed
several times with distilled water and dried at 80 C during 2 h.

diffraction of the amorphous material, which is taken at a 2 angle


between 18 and 19 when the intensity is minimal.
3. Results and discussions
Fig. 1 shows the morphology of treated and untreated Luffa bres obtained using
SEM analysis. We note that the alkali treatment removes the waxy and gummy
substances observed in the untreated Luffa bres. The topography of the surface of

2.2. Scanning microscopy analysis


A Phillips Scanning Electron Microscopy (SEM) is used to examine
the morphology and the bre surface topography before and after
chemical treatments.
2.3. X-Ray Diffraction analysis
The crystallinity index of the tested bres was calculated from XRay Diffraction patterns recorded on an X'Pert pro MPD X-ray
diffractometer. Diffractograms were obtained by varying angle (2)
from 4 to 65. The crystallinity index (Icr %) of the bre was calculated
using the following formula [15]:
Icrk

I002 Iam
 100
I002

where I002 is the maximum intensity of diffraction of the (002) lattice


peak at a 2 angle between 22 and 23 and Iam is the intensity of

Fig. 3. X-Ray Diffraction patterns of untreated and treated Luffa bres.

L. Ghali et al. / Materials Letters 63 (2009) 6163


alkali treated bre shows the formation of the scratches due to the removal of the lignin
and hemicelluloses. This characteristic may improve the adhesion between bre and
matrix when it is used in reinforcing composite material. As shown in Fig. 2, the Luffa
bres change their morphology with changing treatment parameters. Fig. 2a shows the
morphology of untreated Luffa sample. The bres, formed by brils glued together by
gummy substances, are disposed in a multidirectional array forming a natural mat. The
treatment of this mat by solution containing 4% of NaOH and 10% H2O2 at 120 C during
3 h transforms the technical bres to brils (Fig. 2b).
The XRD examination of treated and untreated Luffa bres shows that only the
crystal polymorph I of cellulose is present [15]. Fig. 3 shows the X-Ray Diffraction
patterns of untreated Luffa bres, alkali treated (120 C1 h12% NaOH) and Luffa bres
treated with mixed treatment. This gure shows many peaks at 2 = 15.1, 16.4, 22.4
and 34.4. The peaks at 2 = 15.1 and 16.4 correspond to respectively crystallographic
planes (110) and (110). Tserki et al. [15] reported that these two peaks will be confused
in the case of the samples showing a high rate of amorphous products such as
hemicelluloses, lignin and amorphous cellulose. We can see in Fig. 3 that, for alkali
treated bres and treated bres with mixed treatments (with exception of the
treatment with 2% NaOH), the peaks at 2 = 15.1 and 16.4 are not confused indicating a
low rate of amorphous products such as hemicelluloses, lignin and amorphous
cellulose. The peaks at 2 = 22.4 and 34.4 indicate respectively the (002) and (023)
crystallographic planes. The peak intensity at 2 = 22.4 increases with the increase of
temperature in the alkali treatment. This can be explained by the enhancement of the
crystallinity index dened above.
Table 1 presents the data of crystallinity index for several treatments. In the case of
alkali treatment, this index increases from 50% for untreated Luffa bres to about 70%
for treated at 120 C, 3 h and 4% NaOH.
As shown in Table 1 the treatment of Luffa bres with mixed treatment improves
their crystalline structure. We note that an increasing rate of sodium hydroxide in the
mixed treatment (100 C, 1 h and 10% H2O2) from 2% to 10% enhances the crystallinity
index to reach a maximum value (67.4%) for 8% of NaOH. Then, this rate decreases to
67.09% for 10% of NaOH. We can conclude that the chemical reagents react rst of all
with the chain ends on the surface of the crystallites and eliminate the amorphous
products such as hemicellulose and lignin. When the concentration of sodium
hydroxide increases, the reagents can diffuse into the crystalline region, resulting in
the rupture of some benzenic cycles of cellulose chains by oxidation and transform
them into aliphatic chains. In this case, some amorphous zone of cellulose can be
formed. Table 1 shows also that the variation of temperature; duration and rate of
hydrogen peroxide generally enhance the structure of Luffa bres.

4. Conclusion
The aim of this work is to investigate the inuences of the chemical
treatment parameters on the structure of Luffa bres. The treatment
should enhance the crystalline structure of bres with the elimination of
amorphous materials. SEM micrographs and XRD patterns show the
change of the bre structure after alkali and mixed treatment. The
crystallinity index of many treated and untreated samples was found

63

and showed that their value depended on the parameter's choice. The
analysis showed that many treatments conditions enhanced the
crystalline structure of technical bres of Luffa. It was shown also that
other treatment conditions of mixed method can damage the crystalline
structure of technical Luffa bres. In this case, a ne structure of Luffa
bre can be obtained.
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