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2 0 1 8;7(4):520–527
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Original Article
Lucio Fabio Cassiano Nascimento ∗ , Sergio Neves Monteiro, Luis Henrique Leme Louro,
Fernanda Santos da Luz, Jheison Lopes dos Santos, Fábio de Oliveira Braga,
Rubens Lincoln Santana Blazutti Marçal
Military Institute of Engineering – IME, Department of Materials Science, Praça General Tibúrcio 80, Praia Vermelha, Urca, 22290-270
Rio de Janeiro, RJ, Brazil
a r t i c l e i n f o a b s t r a c t
Article history: The mallow fiber (Urena lobata, linn) is demonstrating a great potential as reinforcement
Received 10 November 2017 in polymer matrix composites. The difficulty in the use of the mallow, as in other natural
Accepted 13 March 2018 lignocellulosic fibers (NLFs), is its hydrophilic compatibility with polymeric matrices that
Available online 23 August 2018 are typically hydrophobic. In order to improve the adhesion between the fiber surface and
polymeric matrices, mallow fibers were subjected to mercerization treatment. In this work
Keywords: composites were produced with epoxy matrix reinforced with 30 vol% of mallow fibers, both
Mallow fibers untreated and mercerized. By means of XRD analysis it was verified the variation of crys-
Epoxy composite tallinity in fibers treated with different NaOH solutions as well as immersion times and
Mercerization agitation. After this XRD preliminary analysis, a treatment of 5% NaOH solution for 24 h
Charpy impact test without agitation was selected. The objective was to compare the Charpy impact energy of
composites specimens produced with untreated mallow fibers and treated for the higher
crystallinity obtained after the selected mercerization. For the analysis of impact energy
the Tukey test was applied from which it could be assured, with a confidence level of 95%,
that the epoxy specimens reinforced with 30 vol% of untreated mallow fibers, had the best
performance.
© 2018 Brazilian Metallurgical, Materials and Mining Association. Published by Elsevier
Editora Ltda. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
夽
Paper was part of technical contributions presented in the events part of the ABM Week 2017, October 2nd to 6th, 2017, São Paulo, SP,
Brazil.
∗
Corresponding author.
E-mail: lucio coppe@yahoo.com.br (L.F. Nascimento).
https://doi.org/10.1016/j.jmrt.2018.03.008
2238-7854/© 2018 Brazilian Metallurgical, Materials and Mining Association. Published by Elsevier Editora Ltda. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
j m a t e r r e s t e c h n o l . 2 0 1 8;7(4):520–527 521
0%
3. Results and discussion
30% no treat.
Fig. 4 shows the FTIR spectra for: (a) untreated and (b) mer-
cerized treated mallow fibers. These spectra reveal significant
changes in the wavenumber interval from 800 to 1800 cm−1 .
By comparing the values in Table 3 to the results of Fig. 4 one
notice that the strong absorption band around 1050 cm−1 for
Fig. 2 – Plates composite fiber percentage from 0 to 30 vol% the untreated fiber, Fig. 4(a), which might correspond to the
without treatment and 30 vol% with treatment C – O stretching in cellulose, hemicellulose and lignin, has
(mercerization – 5% NaOH). been considerably attenuated in the mercerized treated fiber,
Fig. 4(b). Similarly, the absorption band around 1400 cm−1 for
the untreated, Fig. 4(a), which could be associated with CH2
were performed in a Shimadzu diffractometer, model XRD- bending or wagging in lignin, is practically inexistent in the
6000, scan speed of 4◦ /min, power 30 mA × 40 kV and scanning treated fiber. One may then conclude that mercerization sig-
from 5◦ to 80◦ . nificantly affects the participation of lignin, which is a bonding
Fourier transform infrared (FTIR) analysis was conducted substance for the cellulose, in the mallow fiber.
in a model IR Prestige 21-FTIR Shimadzu equipment. Samples Fig. 5 shows DMA results for: (a) neat epoxy and (b) epoxy
of mallow fibers, both untreated and mercerized treated, were composites reinforced with 30 vol % of mallow fibers. By com-
first milled followed by sieved for 20 mesh and then mixed paring the two graphs, in general, it is observed an increase in
with KBr. The mixture was then pressed to produce a film suit- onset of softening temperature of the storage modulus E , as
able for the analysis. Table 3 shows the FTIR absorption bands well as displacement to higher of the perks in the loss mod-
for a natural fiber [32]. ulus “E”, and tangent delta. A possible interpretation for this
Dynamic mechanical analysis (DMA) test was carried out behavior is an interference of the mallow fibers in the mobility
from 20 to 200 ◦ C in a model DMA Q800 TA Instrument using of the epoxy chains, which postpones the occurrence of glass
single cantilever 3 points bending specimens according to transition temperature.
standard. A heating rate of 3 ◦ C/min and nitrogen atmosphere The results obtained from the Charpy impact test for epoxy
was applied for the test. matrix composite reinforced with continuous and aligned
A total of 7 specimens for Charpy impact test were obtained mallow fibers, in percentages 0, 10, 20 and 30 vol% without
by cutting each composite plates according to ASTM D6110 treatment as well as 30 vol% with treatment, CP4 in Table 2,
disclosed a good ability to absorb energy as compared to other
polymer composites reinforced with NLFs [23]. Fig. 6 shows the
results of Charpy absorbed energy (J/m) test for each group. It
Table 3 – FTIR absorption bands for a natural fiber [32].
should be noticed that, as in other works [33,34], occurs an
Frequency (cm−1 ) Assignment
increase in average energy values with the fiber volume frac-
3200–3600 OH stretching tion used in the composite. High impact energy values can be
2905 CH2 and CH3 stretching related to low interfacial bonding, obtained by pullout tests,
1740 Carbonyl (C O) Stretching of carboxylic acid or between the fibers and the matrix [35].
ester
A low interfacial bonding between the mallow fiber and the
1650 H O H bending of absorbed water
epoxy matrix allows for easier decohesion during the impact,
1616 Benzene ring stretching (lignin)
1500 Benzene ring stretching (lignin) which causes fracture by delamination. This mechanism of
1440 CH2 bending in lignin fracture is more effective in composites with greater amount
1411 CH2 and CH3 bending of reinforcement mallow fibers, above 10 vol%.
1357 CH2 bending In this case, it can increase the path to be followed by the
1320 CH2 wagging (lignin) crack, and therefore the absorbed energy required for fracture
1235 C O stretching of acetyl (lignin)
of the composite. Perhaps, because of this, there was a relative
1150 C O C antisymmetric bridge stretching in
cellulose and hemicellulose
reduction of impact energy in the specimens produced with
1110 O H association in cellulose and hemicellulose mercerized fibers as presented in Fig. 6. Due to the increased
1028 C O stretching in cellulose, hemicellulose and crystallinity of the fibers and consequently better adhesion
lignin to the epoxy matrix, cracks found difficult to propagate and
879 -Glucosidic linkage create fractured surfaces that would be associated with higher
600 Out of plant OH bending
impact energy.
j m a t e r r e s t e c h n o l . 2 0 1 8;7(4):520–527 523
Fig. 3 – Specimens with mallow fiber for Charpy test. (a) 0 vol%; (b) 10 vol%; (c) 20 vol%; (d) 30 vol% without treatment and (e)
30 vol% with treatment.
95
95
898
Transmitance (%)
Transmitance (%)
897
669
90
559
518
667
1649
15961504
429
90
1504
85
560
1645
1468
1334
2906
1401
1736
1026
1117
85 80
1399
2906
75
80
1051
3478
3424
4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500
Wavenumbers (cm-1) Wavenumbers (cm-1)
Fig. 4 – (a) FTIR to mallow fibers untreated; (b) FTIR to mallow fibers treated.
70.60°C(I)
Storage modulus (MPa)
200
0 0 0 0
0 50 100 150 200 0 50 100 150 200
Temperature (°C) Temperature (°C)
Fig. 5 – (a) DMA to neat epoxy; (b) DMA to epoxy composites reinforced with 30 vol% of mallow fibers.
Fig. 7 shows the diffractograms obtained for each mercer- fibers in epoxy matrix composites as well as the treatment of
ized sample, according to the various combinations of the mercerizing has different effects on the Charpy impact energy.
parameters: concentration, immersion time and agitation. In The Tukey test was applied for comparison, using a con-
this figure, 5% NaOH, 24 h immersion and without agitation, fidence level of 95%, to determine which volumetric fraction
CP4 was found in Fig. 7(a) to have a fiber crystallinity index of mallow fibers provided better results in terms of Charpy
(Ic ) of 84.49%. This is higher than the value obtained for the impact energy. The less significant difference (LSD) obtained
other mercerization combinations and for the untreated mal- was 77.34. The results for the differences between the mean
low fibers (82.24%) in Fig. 7(b). values of Charpy impact energy are shown in Table 5.
From the results obtained, the analysis of variance (Table 4) Based on these results, with 5% significance level, the
rejects the hypothesis that the means are equal to 5% signifi- reinforced composite with 30 vol% mallow fibers without
cance level for the statistical “F”, on this account: F calculated treatment showed better performance since it exhibited a
>F critical (tabled). Therefore, the volume fraction of mallow higher average energy value of Charpy impact (905.49 J/m).
524 j m a t e r r e s t e c h n o l . 2 0 1 8;7(4):520–527
Table 4 – Analysis of variance of the average impact energies obtained for the epoxy matrix composites reinforced with
percentages from 0% to 30 vol% of mallow fibers.
Variation causes DF Sun of squares Mean square F calc. F crít (tab.)
Total 34 3543620.88
Table 5 – Results for the differences between the mean values of Charpy impact energy in the volume fractions of mallow
fiber 0 to 30% after application of the Tukey test.
Volumetric fraction of mallow fibers 0% 10% 20% 30% without treatment 30% with treatment
1000
One possible explanation would be that the percentage of
10 vol% in mallow fibers were not sufficient to produce an
800
effective reinforcement in the epoxy matrix, which is asso-
ciated with low results in Charpy impact energy. In all test
600 specimens there was a similar complete rupture, making valid
the results. In Fig. 8 it is shown the specimens ruptured after
905.49 the Charpy test.
400
By visual analysis it can be seen a brittle fracture tendency
566.71
in specimens with 0% and 10 vol% untreated and 30 vol%
200
treated, which was confirmed by the impact energy values pre-
142.66 161.44 sented in Fig. 4. This figure shows a higher increase of more
96.07
0 than 6 times in going from 10% to 20 vol% mallow fibers. The
0% 10% 20% 30% 30%
Untreated Treated (CP4) SEM images in Figs. 9–11 show the way fracture mechanisms
Volumetric fraction mallow fibers (%vol) are involved in the impact process.
In Fig. 9(a) and (b) it is perceived clearly the brittle fracture
Fig. 6 – Results of Charpy impact test for the epoxy matrix
mechanism by the presence of “river marks”, both in the spec-
composites reinforced with mallow fibers.
imen with 100% epoxy as well as the composite with 10 vol%
of fiber. These show that there was no effective reinforcement
with low percentage of fibers.
This is significantly distinct from the others because the dif-
For untreated composites with 20 vol% of mallow fibers it
ferences are higher than LSD (77.34). Another important point
was observed a greater amount of energy absorption owing to
to emphasize is the comparatively lower for the impact energy
l (Counts)
600
a lc = 82.24%
400
200
0
10 20 30 40 50 60 70
Theta-2Theta (deg)
l (Counts)
1500
b lc = 84.49% (CP4)
1000
500
0
10 20 30 40 50 60 70
Theta-2Theta (deg)
Fig. 7 – (a) Diffractogram for untreated mallow fibers; (b) diffractogram for mallow fibers mercerizing (CP4).
j m a t e r r e s t e c h n o l . 2 0 1 8;7(4):520–527 525
Fig. 9 – (a) Epoxy composite with 0 vol% mallow fibers; (b) composite with 10 vol% mallow fibers.
Fig. 10 – (a) Composite with 20 vol% mallow fibers; (b) mallow fiber detail in composite with 20 vol% of fibers.
526 j m a t e r r e s t e c h n o l . 2 0 1 8;7(4):520–527
Fig. 11 – (a) Epoxy composite reinforced with 30 vol% untreated mallow fibers; (b) epoxy composite reinforced with 30 vol%
mallow fibers mercerized (5% NaOH, 24 h and without agitation – CP4).
Table 6 – Comparison between tensile strength, young modulus and Charpy impact energy to composites reinforced
with mallow fibers.
Percentage of mallow fibers Tensile strength (MPa) Young modulus (GPa) Charpy impact energy (J/m)
4. Conclusions Acknowledgements
The Charpy impact energy increase with the volume fraction The authors thank the support to this investigation by the
of mallow fibers incorporated into the epoxy matrix. Among Brazilian agencies: CNPq, CAPES and FAPERJ; and UENF for
the specimens evaluated by the Tukey test with 95% con- supplying the mallow fibers.
fidence level, the composite with 30 vol% of mallow fibers
without treatment was the one that exhibited the best results
in terms of Charpy impact energy. This particular case indi-
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