Fibers and Polymers

HYBRID POLYESTER COMPOSITES REINFORCED WITH CURAUÁ FIBRES AND

NANOCLAYS
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Manuscript Number:

Full Title: HYBRID POLYESTER COMPOSITES REINFORCED WITH CURAUÁ FIBRES AND
NANOCLAYS

Article Type: Regular articles

Corresponding Author: Tulio Panzera

Universidade Federal de Sao Joao del-Rei
BRAZIL

Corresponding Author Secondary

Information:

Corresponding Author's Institution: Universidade Federal de Sao Joao del-Rei

Corresponding Author's Secondary

Institution:

First Author: Gilberto García del Pino

First Author Secondary Information:

Order of Authors: Gilberto García del Pino

Antonio Claudio Kieling

Abderrezak Bezazi

Haithem Boumediri

Juliana Fontolan Rolin de Sousa

Francisco Valenzuela Díaz

Jose Luis Valin Rivera

Jamile Dehaini

Tulio Panzera

Order of Authors Secondary Information:

Funding Information:

Abstract: This work investigates a hybrid polyester composite consisted of Curauá natural fibres
and organophilic clay nanoparticles. A Taguchi method is used to identify the effects of
fibre fraction (10, 20 and 30 wt%), alkaline treatment concentration (NaOH, 2.5, 5 and
10 wt%), treatment time (2, 4 and 8 h) and nanoparticle content (2.5, 5 and 10 wt%) on
the mechanical behaviour of the hybrid composites under tension and three-point
bending. X-ray, FTIR and microstructural analysis are performed to assess the treated
and untreated fibre surfaces. The optimum combination of the process parameters for
the tensile and flexural properties is: fibre content at 30 wt%, NaOH concentration at 5
wt%, treatment time at 8h and nanoclay inclusions at 5wt%. A mean tensile and
flexural strength of 36.13 MPa and 32.55 MPa are obtained, which represents percent
increases of 39.22% and 25.43% compared to the polyester polymer in pristine
condition.

Suggested Reviewers: Harry Ku

University of Southern Queensland
ku@usq.edu.au
Dr Ku works on natural fibre composites. His paper was cited in the present work.

Abdul Khalil
Universiti Sains Malaysia
akhalilhps@gmail.com

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 Dr Khalil works on sustainable composites. His paper was cited in the present work.

Hassan Ebadi-Dehaghani
Islamic Azad University
ebadi@iaush.ac.ir
Dr Dehaghani works on nano clay composites. His paper was cited in the present
work.

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1
2 HYBRID POLYESTER COMPOSITES REINFORCED WITH CURAUÁ FIBRES AND
3
4 NANOCLAYS
5
6 Gilberto García del Pino1, Antonio Claudio Kieling1, AbderrezakBezazi2, Haithem Boumediri2, Juliana Fontolan Rolin
7
8 de Sousa3, Francisco Valenzuela Díaz3, Jose Luis Valin Rivera4, Jamile Dehaini5, Tulio Hallak Panzera6
9
1
10 Departamento de Engenharia Mecânica, Universidade do Estado de Amazonas, Manaus-AM / Brazil.
11 2
Laboratoire de Mécanique Appliquéedes Nouveaux Matériaux (LMANM), B.P. 431, Université 08 Mai 1945 Guelma, Algeria.
12
3
13 Departamento de Engenharia de Materiais e Metalurgia, Universidade de São Paulo, São Paulo, Brazil.
14 4
15 Pontificia Universidad Católica de Valparaíso, Escuela de Ingeniería Mecánica, Chile. Avenida Los Carrera 01567, Quilpué,
16 Valparaíso, Chile.
17
5
18 Departamento de Meteorología, Universidade do Estado de Amazonas, Manaus-AM / Brazil.
19 6
Centre for Innovation and Technology in Composite Materials – CITeC, Department of Mechanical Engineering, Federal University
20
21 of São João Del Rei - UFSJ, Brazil. (*corresponding author: panzera@ufsj.edu.br)
22
23
24
25 Abstract. This work investigates a hybrid polyester composite consisted of Curauá natural
26
27
fibres and organophilic clay nanoparticles. A Taguchi method is used to identify the effects of
28
29
30 fibre fraction (10, 20 and 30 wt%), alkaline treatment concentration (NaOH, 2.5, 5 and 10 wt%),
31
32 treatment time (2, 4 and 8 h) and nanoparticle content (2.5, 5 and 10 wt%) on the mechanical
33
34 behaviour of the hybrid composites under tension and three-point bending. X-ray, FTIR and
35
36 microstructural analysis are performed to assess the treated and untreated fibre surfaces. The
37
38
39 optimum combination of the process parameters for the tensile and flexural properties is: fibre
40
41 content at 30 wt%, NaOH concentration at 5 wt%, treatment time at 8h and nanoclay inclusions
42
43 at 5wt%. A mean tensile and flexural strength of 36.13 MPa and 32.55 MPa are obtained, which
44
45 represents percent increases of 39.22% and 25.43% compared to the polyester polymer in
46
47
48 pristine condition.
49
50
51
52 Keywords: Hybrid composite, natural fibres, organophilic nanoclay, mechanical properties,
53
54 Taguchi.
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1
2 Introduction
3
4 In recent years, due to increasing environmental concerns, there has been a growing
5
6 renewal of interest in composite materials derived from lignocellulosic feedstock. A significant
7
8
9 amount of research has been conducted on different types of plant fibres, identifying some
10
11 promising substitutes for the traditional composite reinforcement, specifically E-glass. In
12
13 addition to biodegradability, availability and low cost, natural fibres can bring technical
14
15 advantages, such as high specific mechanical properties, damping and acoustics properties [1-
16
17
18
5].
19
20 The hybridisation process in composite materials has been used when a particular or
21
22 multifunctional performance is required. In this case, the system is composed of two different
23
24 dispersive phases, i.e. different fibres, particles or fibre-particle. In this work, nano clay particles
25
26
are combined with natural fibres in a polyester matrix phase. The advantages of using micro
27
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29 and/or nano particles in laminated composites are sometimes controversial in the literature.
30
31 Basically, the inclusion of rigid particles in laminates is focused on increasing their mechanical
32
33 properties and durability [6-8].
34
35 In theory, there are two effects attributed to the incorporation of rigid particles on
36
37
38 laminated composites: (i) the interlocking effect and (ii) the increase in matrix phase stiffness
39
40 [9]. The interlocking effect occurs when the particles lead to increased shear stress in the
41
42 interlaminar region attributed to additional friction against the fabric surfaces. The incorporation
43
44 of rigid particles in the matrix phase makes it stiffer, which contributes to the effective properties
45
46
47 of the composites [10]. The amount of particles within the laminates is extremely important to
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49 obtain such benefits, and is also related to particle size and geometry [7]. Not only nano
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51 particles, e.g. clays [11], carbon nano tube (CNT) [12], silica [13], but also micro particles, e.g.
52
53 alumina [14], silica [15], silicon carbide [16], Porland cement [17], have been added to
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55
composite materials. The fracture mechanism is also affected by the shape, size and
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58 distribution of the particle in the system. In general, the presence of particles delays the crack
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1
2 propagation which enhances the composite´s toughness [18]. In contrast, these ceramic
3
4 particles lead to increased matrix stiffness, which makes it more brittle with a consequent
5
6 premature failure [9].
7
8
9 Organophilic nano clays is a hydrophobic material which has been used as filler in
10
11 polymers to enhance their mechanical properties and thermal durability. This particular type of
12
13 particle can change the morphology of the polymer crystallising with fine grain structure [19-21].
14
15 The concentration and the processing conditions should be selected so that the bulk of the clay
16
17
18
tactoids are intercalated by the thermosetting polymer and the clay layers are separated from
19
20 each other, i.e., exfoliated or delaminated [22]. Araujo et al. [20] obtained mecanically improved
21
22 films of polypropylene nanocomposites (PP) containing 1% by mass of organically modified
23
24 bentonite. Oliveira et al. [21] used organophilic clay in Polyamide 6 revaling the increase of clay
25
26
content leads to the formation of partially exfoliated and/or intercalated structures, a fact that
27
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29 has been associated with the increase in tensile strength and elastic modulus. Despite having
30
31 an ideally matched system, where unreacted polymeric precursors intercalate readily into
32
33 organoclay galleries, there is still a large possibility that these will not form a true
34
35 nanocomposite. A non-uniform dispersal of nanolayers limits stress transfer throughout the
36
37
38 composite, inhibiting ideal surface contact between the polymer and clay [22-23], hindering their
39
40 mechanical properties.
41
42 Cellulose is one of the main components of natural fibres, providing mechanical strength
43
44 and stiffness to the fibres. Cellulose is a polysaccharide composed of carbon, oxygen and
45
46
47 hydrogen. Cellulose has two polymorphs, type I and II, in which the second corresponds to the
48
49 arrangement of the cellulose chain with greater resistance, obtained through the process of
50
51 mercerisation or regeneration of native cellulose [24]. The chemical surface treatments of the
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53 fibre are widely used to optimise fibre/matrix bonding. Parameters such as type of treatment,
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55
solution concentration and immersion time of the fibres are relevant factors to reach the
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58 optimum mechanical behaviour of the composite [25-27].
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1
2 This work investigates a hybrid composite material composed of polyester matrix,
3
4 organophilic nanoclay and Curauá fibre. A Taguchi design (L9) is used to identify the effect of
5
6 the following factors (levels), fibre weight fraction (10, 20 and 30 wt%), NaOH concentration
7
8
9 (2.5, 5 and 10 wt%), fibre treatment time (2, 4 and 8 hrs) and nano particle inclusions (2.5, 5
10
11 and 10 wt%) on the mechanical properties of the hybrid composites. X-ray, FTIR and SEM
12
13 analysis are performed to better assess composite behaviour. Taguchi is a robust experimental
14
15 design that has the ability to analyse many parameters with fewer experiments than in
16
17
18
traditional experiments. In fact, this technique, widely used to improve the quality of
19
20 manufactured products, has recently been implemented in the manufacture of green
21
22 compounds [28-31].
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24
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26
Materials and methods
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29 The orthophthalic unsaturated polyester is supplied by Redelease Company (Brazil).
30
31 Curauá is a typical natural fibre from the Amazon rainforest. These fibres are collected and
32
33 processed by local producers in the state of Amazon. Figure 1 shows the bundles of Curauá
34
35 fibres used in the present work. Organophilic clays are obtained by the chemical modification of
36
37
38 smectite sodium clays with quaternary ammonium salts using bentonite from the city of Paraiva
39
40 (Brazil). First, the bentonite particles are sieved at 200 US-Tyler (74µm). The particles are
41
42 slowly added to 20 g in a beaker containing 480 g of deionized and distilled water under
43
44 mechanical stirring at 760 rpm for 20 min; with the subsequent incorporation of a 0.2 g/ml
45
46
47 Na2CO3 solution for additional 20 min. After standing for 24 hrs, the quaternary ammonium salt
48
49 in 50 wt% aqueous solution is added under mechanical stirring at 760 rpm, with subsequent
50
51 standing for 24 hrs. During this period the two parts are separated by flotation, the clay being
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53 washed and vacuum filtered (-230 mmHg). This organophilic clay is oven dried at 60°C for 6 hrs,
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55
and stored in a vacuum desiccator for further manual milling using a percelanum mortar. Finally,
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1
2 an analytical knife mill (Quimis 298A21) is used to disperse the particles with subsequent
3
4 sieving at 300 US-Tyler (48μm).
5
6 [Figure 1]
7
8
9 A Taguchi design is used to identify the effects of fibre weight fraction (10, 20 and 30 wt%),
10
11 alkaline treatment concentration (NaOH, 2.5, 5 and 10 wt%), treatment time (2, 4 and 8 hrs) and
12
13 nanoparticle content (2.5, 5 and 10 wt%) on the mechanical behaviour of the hybrid composites
14
15 under tension and three-point bending (Table 1). A fractional factorial design is conducted based
16
17
18
on Taguchi Method, which reduced the number of experimental conditions from 81 to 9. Taguchi
19
20 Method was manipulated using Minitab® v.18 software. Table 2 shows the design of Taguchi L9
21
22 (34) (orthogonal array), providing 9 experimental conditions. In this orthogonal array, factor
23
24 levels are weighted in the same way throughout the design [28].
25
26
[Table 1]
27
28
29 [Table 2]
30
31 The Curauá fibres are placed in 2.5, 5 and 10 by weight sodium hydroxide solutions at
32
33 different times (2, 4 and 8 hrs). The alkaline solution is prepared with distilled water at room
34
35 temperature (~23oC, 65%RH). After removal, the fibres are thoroughly rinsed in distilled water
36
37
38 until a pH 7 is obtained. Subsequently, the fibres are oven dried at 60°C for 24 hrs and at 100°C
39
40 for 20 min in order to prevent internal moisture. A microstructural analysis is performed to verify
41
42 the effects of alkaline treatment on the fibre surfaces. A Philips XL-30 Electronic Scanning
43
44 Microscope with secondary electron detector is used.
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46
47
48 The polyester polymer (Figure 2a) and the composite materials (Figure 2b) are
49
50 mecanically characterised. Tensile and three-point bending tests are carried out according to
51
52 ASTM D 638 [32] and D790 [33] protocols, respectively. A KRATOS® 5002 testing machine
53
54 equipped with 20 kN and 25 kN load cells for tensile and bendind tests, respectively, is used
55
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57 (Figure 2). Test speeds of 5 mm/min and 3 mm/min are used to perform the tensilte and bending
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 6

1
2 tests, respectively. Five specimens for each experimental condition are fabricated and tested. In
3
4 addition, fiffteen Curauá fibres are tested under tensile loads at 0.5 mm/min (Figure 2c). An
5
6 average diameter of 85µm is obtained via SEM, being used to calculate tensile stress.
7
8
9 [Figure 2]
10
11 Composite specimens are fabricated by cold pressing at 3 MPa using a metal mould
12
13 (Figure 3a) designed and fabricated based on the dimensions provided in ASTM D638 [32].
14
15 Curauá fibres are aligned within the mould. The nano clay is hand mixed by 10 min with the
16
17
18
polyester, then the hardener fraction is added with subsequent mixing for 5 min. This blend is
19
20 spread over the fibres within the mould. A metal dog-bone shaped lid (Figure 3b) is used to
21
22 compact the samples after a gel time of 15 min.
23
24 [Figure 3]
25
26
To determine the optimal configuration of the parameters to maximize the tensile and
27
28
29 flexural properties, the experimental data is transformed into a signal-to-noise ratio (S / N) for
30
31 the analysis. As the objective of Taguchi's analysis is to maximize tensile strength and flexural
32
33 strength, the S/N ratio chosen is the larger the better (LBT), which is calculated as a logarithmic
34
35 transformation of the loss function, as shown in Equation 1:
36
37
38 1 n
1 
39   10 log   2
(1)
 i1 Y i 
n
10
40
41
42
43 Where
44
45  = signal noise ratio (dB)
46
47 n = number of observations,
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49
50
Y = response values obtained in the tests (output).
51
52
53
54 A Rigaku brand X-ray diffractometer is used to analyse the Curauá fibres, the polyester
55
56 polymer, the nano clay and the composites with CuKα radiation source. X ray analysis is
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 7

1
2 perfomed considering a step size of 0.04° and time per step of 4 seconds within the range of 2θ
3
4 between 0 the 90°. The crystallinity indexes are also calculated using the Segal empirical
5
6 method that provides an approximate value [19].In order to evaluate the interactions between
7
8
9 resin, clay and fibre, the Fourier Transform Infrared (FTIR) spectroscopy is used. By observing
10
11 the occurrence of absorption or scattering of the radiation, it is possible to identify types of
12
13 binding and, consequently, functional groups and even intermolecular interactions present in the
14
15 sample [23]. The spectrograms of the individual and combined materials are analysed. Changes
16
17
18
in the width, intensity, or position of peaks and bands indicate interactions between phases.
19
20
21
22 Results & Discussion
23
24 X-ray diffraction analysis
25
26
Figure 4 shows the diffractograms of Curauá untreated fibres and treated fibres with 5
27
28
29 wt% and 10 wt% of NaOH. Studies with lignocellulosic materials including Curauá fibres point to
30
31 a reflection in the crystallographic plane (002) with greater intensity, which corresponds to the
32
33 planes of the glycosidic rings with a denser structure of type I cellulose revealed by angle 2θ =
34
35 22º. Two other peaks of lower intensity in 16º and 35º, corresponding to the respective planes
36
37
38 (101) and (040), are also indentified. Curauá fibres treated with 10 wt% NaOH present lower
39
40 peak values in relation to the fibres in pristine condition, which implies some damage to the
41
42 phase of cellulose type II, with possible decrease of the mechanical strength of the fibres.
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44 Excess alkalinity and/or exposure time can damage the fibre as it removes a portion of the
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46
47 crystalline structure, thereby reducing its mechanical performance [10, 24, 26]. The crystallinity
48
49 index obtained for each fibre is presented in Table 3. In general, it is noted an increment of
50
51 crystallinity index by NaOH concentration increase. The crystallinity index also increases by
52
53 exposure time, except for 5 wt% and 10 wt% concentrations, which reveal a slight reduction
54
55
from 4 to 8 hrs.
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57
58 [Figure 4]
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1
2 Figure 5 shows the X-ray analyses for polyester (Fig. 5a), nano clay (Fig. 5b), Curauá
3
4 fibres (Fig. 5c) and S4 composite (Fig. 5d) consisted of 5 wt% nano clay and 20 wt% Curauá
5
6 fibres. Nano clay shows seven different peaks at 2θ = 4°; 2θ = 12.7°; 2θ = 20°; 2θ = 35.7°; 2θ =
7
8
9 55°; 2θ = 62° and 2θ = 73.5°, while Curauá fibres show peaks at 2θ = 16°; 2θ = 22.7° e 2θ =
10
11 34.7°. The curves obtained for the polyester (Figure 5a) and the composite (Figure 5d) have
12
13 similar behaviour, including two peaks at 2θ = 22° and 2θ = 43° of similar intensities. Although
14
15 the composites contain organophilic clay and Curauá fibres, it is not possible to distinguish the
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17
18
peaks related to these materials individually, as shown in Figures 5b and 5c; this phenomenon
19
20 is interpreted as exfoliation of clay and fibre [37].
21
22
23 [Figure 5]
24
25
26 [Table 3]
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28
29
30 Fourier-transform infrared spectroscopy analysis
31
32 The infrared absorption spectra obtained for polyester (Fig. 6a), nano clay (Fig. 6b),
33
34 Curauá fibre (Fig. 6c) and composite (Fig. 6d), consisted of Curauá and nano inclusions, are
35
36 shown in Figure 6. The clay shows a peak at 3690 cm-1 which is typically associated with
37
38
39 stretching the Si-O bond. This peak is a characteristic of smectite clays. This peak can not be
40
41 observed in the spectrum of the composite material (Figure 6d), indicating a possible
42
43 intercalation of the clay with the polymer. The complete dispersal, or exfoliation, of the clay
44
45 nanolayers yields composites with the highest degree of property enhancement [23]. The
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47
polyester resin exhibits a peak at nearly 1036 cm-1 (Figure 6a), which undergoes an increase in
48
49
50 the composite spectrum. This change is typically observed when nanoclay is combined with a
51
52 polymer matrix, being attributed to the interactions between the Si-O clay layer and the polymer
53
54 [23]. Curauá fibre (Figure 6c) shows a peak at 3350 cm-1 which is typically associated with the
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56
hydroxyl groups present in cellulose, hemicellulose and lignin [34]. Note that in the composite
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1
2 spectrum, there is widening and displacement of this peak, which indicates a possible
3
4 interaction between the fibres and the polymer matrix [34].
5
6 [Figure 6]
7
8
9 Microstructural analysis
10
11 Figure 7 shows the micrographies of the untreated fibres (a) and treated under 5wt% (b)
12
13 and 10wt% (c) NaOH solution for 4 hrs. Separation of cellulose fibrils and increased surface
14
15 roughness are observed as the NaOH concentration is increased. The microfibrillar angle can
16
17
18
also be modified by the removal of lignin and hemicellulose, which directly affects the increase
19
20 in fibre stiffness [10, 24, 26]. In addition, the modification of the fibre surface can improve its
21
22 physical adhesion with the matrix phase, since it can facilitate the penetration into the internal
23
24 parts of the fibre, increasing, consequently, the mechanical properties of the composite material
25
26
[35].
27
28
29
30 [Figure 7]
31
32 Mechanical charaterisation
33
34 Table 4 shows the mechanical properties of polyester polymer and Curauá fibre. The
35
36
properties of Curauá fibres are shown based on the range limits due to the wide variation
37
38
39 achieved. Table 5 shows the results of Taguchi's experimental design, showing the mean values
40
41 of tensile and flexural strength and their respective S/N ratios for each condition. The mean
42
43 tensile (flexural) strength of the composites is 36.13 MPa (32.55 MPa) with mean S/N ratio of
44
45 31.01 dB (30.02 dB). The highest tensile and flexural strength is obtained by C8 composites
46
47
48 consisted of 30 wt% of fibre fraction treated at 5 wt% NaOH for 2 hrs and 10 wt% of
49
50 nanoparticle inclusions. In contrast, the lowest mechanical strength is achieved by C1
51
52 composite made with less amount of treated fibres (10 wt%) using 2.5 wt% NaOH concentration
53
54 for 2 hrs and the lower nano sized clay content (2.5 wt%).
55
56
57 [Table 4]
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1
2 [Table 5]
3
4 Table 6 shows the ANOVA for mean tensile and flexural strength. P-value less or equal to
5
6 0.05 indicates the factor significantly affects the response. The underlined P-values shown in
7
8
9 Table 6 reveal that the fibre fraction factor affects tensile and flexural strength. F – value
10
11 indicates the contribution of each factor on the response. Fibre weight fraction is the main factor
12
13 affecting the responses, obtaining 31.96 and 21.43 for tensile and flexural strength, respectively.
14
15 The other factors do not statiscally affect the mechanical properties, with P-values higher than
16
17
18
0.05. This finding is not in agreement with Fartini et al. [36], which investigated unsaturated
19
20 polyester polymer with 0-5 wt% nanoclay content under compression. The strength and elastic
21
22 modulus of the nanomodified polymer were significantly affected by the type of mixing methods
23
24 and the ratio of nanoparticles content. Compressive strength and stiffness were increased by
25
26
the incorporation of nanoclay content. It is noteworthy that the effect of nano clays within natural
27
28
29 fibre composites can be minimised, due to the large variation of the natural fibres and reduced
30
31 amount of polymer in the system. Shahroze et al. [37] also reported some reductions in the
32
33 mechanical properties of natural fibre polyester composites by the incorporation of organo-
34
35 nanoclay. This behaviour can be attributed especially to the non-efficiency of the mixing process,
36
37
38 leading to the agglomerate of nano particles within the composite material.
39
40 R-Sq values shown in Table 6 indicate the data are well fitted in the regression models.
41
42 Eqs (2) and (3) show the regression models for tensile and flexural strength, respectively. Figure
43
44 8 shows a comparative graph between the experimental and predicted data.
45
46
47 [Table 6]
48
49
50
51 Tensile strength (MPa) = 21.16 +0.715 Fibre fraction (wt%) + 0.282 NaOH (wt%)
52
53 + 0.039 Treatment time (h) - 0.197 Clay content (wt%) (2)
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1
2 Flexural strength (MPa) = 16.61 + 0.781 Fibre fraction (wt%) + 0.358 NaOH (wt%)
3
4 + 0.017 Treatment time (h) - 0.317 Clay content (wt%) (3)
5
6
7
8
9 In order to evaluate the effect of each factor on tensile and flexural properties, the analysis
10
11 of the means (ANOM) was performed using Minitab® v.18 software. This analysis involves
12
13 calculating the mean of the response criteria for each factor level. The highest average
14
15 response is selected to determine the optimal level for each factor. Figure 9 summarises the
16
17
18
ANOM analysis for the mean tensile (a) and flexural (b) strength. The increase of fibre weight
19
20 fraction from 10 to 30 wt% provides a percentage increase of 50% in tensile strength (Figure 9a)
21
22 and 64% in flexural strength (Figure 9b). The alkaline concentration also contributes to enhance
23
24 the mechanical properties up to 5 wt% NaOH, revealing a reduction at 10 wt% NaOH level. The
25
26
treatment time does not present significant changes in mechanical strength. Although the
27
28
29 nanoclay factor did not statistically affect the mechanical properties of the composites, as
30
31 presented by ANOVA (Table 6), the mean analysis classifies its contribution as a third in rank
32
33 (Table 7). The inclusion of 5 wt% of nanoclay leads to an increase in strength of approximately 4
34
35 - 5%. In contrast, a large concentration of nanoclays (10 wt%) provides a reduction in strength,
36
37
38 being attributed to the formation of clusters, which hinder the load distribution within the
39
40 composite structure.
41
42 [Figure 9]
43
44 Table 7 shows the results of ANOM analysis for mean tensile and flexural strength. The
45
46
47 optimal points for adjusting the factor level are those with the highest mean. This analysis
48
49 shows the best response with the least effect due to noise. Delta is the difference between the
50
51 highest and lowest average response values. The optimum combination of the process
52
53 parameters for the tensile and flexural properties is A3 (fibre content, 30 wt%), B2 (NaOH, 5
54
55
wt%), C3 (time, 8h), D2 (nanoclay, 5 wt%).
56
57
58 [Table 7]
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1
2 In general, a mean tensile and flexural strength of 36.13 MPa and 32.55 MPa are
3
4 obtained, which represents percent increases of 39.22% and 25.43% compared to the polyester
5
6 polymer in pristine condition.
7
8
9
10
11 Conclusion
12
13 A hybrid polyester composite consisted of Curauá fibres and nano clay is evaluated via
14
15 Taguchi analysis. The findings reveal the fibre content is the main factor affecting the
16
17
18
mechanical properties of the composites, followed by the NaOH concentration, nanoclay
19
20 inclusions and immersion time. The optimum combination of the process parameters for the
21
22 tensile and flexural properties is fibre content at 30 wt%, NaOH concentration at 5 wt%,
23
24 treatment time at 8h and nanoclay inclusions at 5 wt%. A mean tensile and flexural strength of
25
26
36.13 MPa and 32.55 MPa are obtained, which represents percent increases of 39.22% and
27
28
29 25.43% compared to the polyester polymer in pristine condition. Higher amount of nanoclays
30
31 (10 wt%) provided reduced mechanical properties being attributed to non-effficiency of the
32
33 mixing process and particle agglomeration.
34
35
36
37
38 Acknowledgments
39
40 The authors thank the collaboration of the State University of Amazonas (UEA) and the
41
42 State University of São Paulo (USP).
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47
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18 Figure 1. Curauá fibres.
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40 Figure 2. Tensile test of polyester (a), three-point bending of composites (b) and tensile test of
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42 Curauá fibre (c).
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2 Figure 3. Metal dog-bone shaped mould (a) and lid (b).
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20 Figure 4. X-ray analysis for treated and non-treated Curauá fibres.
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42 Figure 5. X-ray analysis for polyester (a) nano clay (b), Curauá fibres (c) and composite (d).
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21 Figure 6. Infrared spectra obtained for polyester (a), nano clay (b), Curauá fibre (c) and hybrid
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Figure 7. Micrographs of the fibres: a) without treatment, b) with treatment of 5wt% NaOH and
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42 immersion time of 4 hrs, c) with treatment of 10wt% NaOH and immersion time of 4 hrs.
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21 Figure 8. Comparison between experimental and predicted data for
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23 tensile and flexural tests.
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29 Figure 9. Main effect plots for mean tensile (a) and flexural (b) strength.
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2 Table 1. Factors and levels of the experiments according to Taguchi's design (34).
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4 Factor Level 1 Level 2 Level 3
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A: Fibre weight fraction (wt%) 10 20 30
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9 B: Treatment concentration – NaOH (wt%) 2.5 5 10
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11 C: Treatment time (h) 2 4 8
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13 D: Nanoparticle content (wt%) 2.5 5 10
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18 Table 2. Representation of the Taguchi matrix (L9).
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21 Setup Factor / Levels
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23 A B C D
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26 S1 10 2.5 2 2.5
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28 S2 10 5.0 4 5.0
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30 S3 10 10.0 8 10.0
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S4 20 2.5 4 10.0
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35 S5 20 5.0 8 2.5
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37 S6 20 10.0 2 5.0
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39 S7 30 2.5 8 5.0
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42 S8 30 5.0 2 10.0
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44 S9 30 10.0 4 2.5
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48 Table 3. Crystallinity index (%) for Curauá fibres (a), polyester polymer (b) and nano clay (c).
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52 NaOH Treatment time (hrs)
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54 Concentration 2 4 8
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56 0 32 32 32
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2 2.5 35 36 38
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11 Table 4. Mechanical properties of the polyester polymer in pristine.
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14 Mechanical Tensile Tensile Elongation Flexural
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17 properties strength modulus (%) strength
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19 (MPa) (GPa) (MPa)
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21 Polyester 25.95±0.43 2.94±0.09 2.09±0.03 19.00±0.23
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23 Curauá 749-1390 43-79 1.80-2.00 -
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26 Table 5. Mechanical properties of the composite materials with the respective signal/noise ratio
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28 (S/N).
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30 Setup A B C D Tensile Ratio S/N Flexural Ratio S/N
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32 strength (dB) strength (dB)
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35 (MPa) (MPa)
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37 S1 10 2.5 2 2.5 26.45±0.21 28.45 21.22±0.99 26.53
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39 S2 10 5.0 4 5 31.23±0.56 29.89 29.33±0.68 29.35
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S3 10 10.0 8 10 28.22±0.67 29.01 23.23±0.12 27.32
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44 S4 20 2.5 4 10 32.45±0.13 30.22 27.43±0.44 28.76
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46 S5 20 5.0 8 2.5 39.76±0.76 31.99 36.45±0.56 31.23
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48 S6 20 10.0 2 5 38.3±0.94 31.66 34.67±0.78 30.80
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51 S7 30 2.5 8 5 41.43±0.53 32.35 38.22±0.23 31.65
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53 S8 30 5.0 2 10 44.57±0.77 32.98 41.77±0.48 32.42
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55 S9 30 10.0 4 2.5 42.78±0.43 32.62 40.63±0.88 32.18
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2 Table 6. Analysis of Variance (ANOVA) for tensile and flexural strength.
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4 Tensile strength Flexural strength
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6 Factors P-
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8 F-Value F-Value P-Value
9 Value
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11 A- Fibre fraction 31.96 0.005 21.43 0.010
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13 B- NaOH
14 0.73 0.442 0.66 0.463
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concentration
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18 C- Treatment time 0.01 0.929 0.00 0.976
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20 D- Clay inclusion 0.36 0.583 0.51 0.513
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22 R-sq 89.21% 84.96%
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25 R-sq(adj) 78.41% 69.93%
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27 Table 7. ANOM analysis for Means (Larger is better)
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29 Level Fibre (wt%) NaOH (wt%) Time (hr) Nano clay (wt%)
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31 Tensile strength
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34 1 28.63 33.44 36.44 36.33
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36 2 36.84 38.52 35.49 36.99
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38 3 42.93 36.43 36.47 35.08
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Delta 14.29 5.08 0.98 1.91
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43 Rank 1 2 4 3
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45 Flexural strength
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47 1 24.59 28.96 32.55 32.77
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50 2 32.85 35.85 32.46 34.07
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52 3 40.21 32.84 32.63 30.81
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54 Delta 15.61 6.89 0.17 3.26
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