Polymers & Composites
Polymers & Composites
Polymers & Composites
Ruey Shan Chen1,2 , Yao Hsing Chai3, Ezutah Udoncy Olugu3, Mohd Nazry Salleh4,2 and
Sahrim Ahmad1
Abstract
Enormous amounts of plastic wastes are generated worldwide and the approaches related to plastic recycling or reusing have
become the research focus in the field of composite materials. In this study, green composites were prepared via melt-
blending method using high-density polyethylene (HDPE) sourced from plastic bags as a matrix and sugarcane bagasse (SCB)
fiber as reinforcing filler. The effects of fiber loading (5, 10 and 15 wt%) and fiber modification on the mechanical and
dimensional stability (weight gain by water absorption) properties of the green composites were investigated. Results showed
that the inclusion of SCB fiber into recycled HDPE matrix increased the composite stiffness but decreased the mechanical
strength and resistance to water absorption. With the fiber modification through alkali treatment, the mechanical strength
was remarkably improved, and the modulus and water absorption of the composites were found to be reduced. From the
finding, it can be concluded that the prepared green composites free of coupling agent could add value to the plastic and
agricultural wastes, and serve a potential candidate to replace some conventional petroleum-based composites.
Keywords
Biocomposite, recycled thermoplastic, mechanical property, water absorption, diffusion coefficient
Introduction
The interest of using natural fiber as reinforcing agent in composite materials has increased considerably due to the aspects of
producing biodegradable and low-cost composites and also contributing in the reduction of waste accumulation.1 Thus,
research studies related to the development of eco-friendly composites being prepared from various recycled materials are
being actively approached, with the intention to substitute the sintetic filler, that is, glass fiber.2 Sugarcane bagasse (SCB) is the
byproduct of sugarcane stalk after extracting juice during milling.3 Bagasse accounts for 30% by mass of the stalk.4 Due to the
large availability and production of sugarcane in the world, that is approximately 1.7 × 103 million tons/year SCB, a
lignocellulosic fiber has been receiving researcher’s attention in the last decades.5 SCB possesses adequate tensile strength
(170–290 MPa) and Young’s modulus (15–19 GPa), which creates its potentiality to be utilized as reinforcement in natural
fiber composites.6 Recently, numerous studies have reported the use of SCB fibers as reinforcing filler for thermoplastic
matrices such as polyethylene (PE), polypropylene (PP), and polystyrene; plastics-based composites with superior mechanical
properties at different extent were developed.1 The development of green composites from postconsumer polymers as
matrices and natural reinforcement phases as well as the better understanding of their physical, chemical, and mechanical
interactions will escalate the aggregated values and expand the application in consumer goods.7
1
Department of Applied Physics, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, Bangi, Selangor, Malaysia
2
Advanced Polymer Group, Center of Excellence Geopolymer and Green Technology (CEGeoGTech), Universiti Malaysia Perlis, Arau, Malaysia
3
Department of Mechanical, Faculty of Engineering, UCSI University, Kuala Lumpur, Malaysia
4
Faculty of Chemical Engineering Technology, Universiti Malaysia Perlis, Kompleks Pusat Pengajian Taman Muhibah, Arau, Malaysia
Corresponding authors:
Ruey Shan Chen, Department of Applied Physics, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, Bangi, Selangor 43600, Malaysia.
Email: [email protected]
Ezutah Udoncy Olugu, Department of Mechanical, Faculty of Engineering, UCSI University, Kuala Lumpur 56000, Malaysia.
Email: [email protected]
Chen et al. S1135
The global production of plastics accounts for 0.15 billion tons per year, while the accumulation of worldwide plastic
wastes in the environment is approximately 25 million tons per year.8 For that reason, postconsumer recycled plastic (PCR) is
established as a promising raw material source for polymeric matrices in the manufacture of composite materials, as a result of
the plentiful production of plastics and cost-competitive factor. The use of PCR could be a potential approach to solve plastic
waste pollution by minimizing or even eliminating the consumption of virgin plastic.9 High-density polyethylene (HDPE) is
one of the plastics that can be recycled because of the steady annual increase in HDPE production, which is commonly used for
oil container, colored milk bottles, shampoo bottles, mineral water bottle caps, and many more.8,10,11 Although HDPE is a safe
plastic material owing to its chemical resistance with packaged food or beverages, it is not recommended to be used repeatedly
due to the increasing release of antimony trioxide compounds with time.10 Good numbers of research articles are published
related to PE bagasse1,7,12,13 and PP bagasse3,5,14,15 composites. Agunsoye and Aigbodion have carried out the investigation
on the uncarbonized bagasse (UB) and carbonized bagasse (CB) particles (10–50 wt%) filled with recycled PE biocomposites,
and their results showed that the increase of tensile and bending strength achieved the maximum extent at 20 wt% UB and 30
wt% CB.12
It is established that poor adhesion between hydrophobic matrix and hydrophilic lignocellulosic fibers could be the main
challenge for the natural fiber-reinforced polymer composites, yielding composites with inferior mechanical properties.13 To
improve the interaction and adhesion between polymeric matrices and fibers, the use of either compatibilizing agent or surface
modification of natural fibers or both simultaneously has been carried out. El-Fattah et al. reported that the compatibility
between recycled HDPE and SCB fiber was effectively improved with the addition of 1.5–4.5 wt% maleic anhydride grafted
polyethylene (PE-g-MA) compatibilizing agent. This in turn led to an increase in tensile strength and modulus (due to better
fiber/polymer interfacial bonding), and lower water absorption capacity (which induced by the reduced hydrophilicity of the
lignocellulosic fiber).7 De Carvalho Neto et al.13 subjected the washed SCB fibers to mercerization using sodium hydroxide
and acetylation using acetic anhydride, and found that the acetylated SCB fiber improved the tensile and flexural modulus of
recycled HDPE composites as a consequence of better phase compatibility.13 Alkali treatment is stated as a common and the
most economical modification method applied to natural fibers,9 which helps to increase surface roughness and consequently
increase the matrix-fiber bonding via physical interlocking. The combination between chemical and gamma irradiation
modification was noted to enhance the fiber/matrix adhesion and the consequent improvement in mechanical properties, water
resistance, and thermal stability as irradiation treatment promoted the formation of crosslinked structure.1
Literature showed that numerous studies are more likely to employ coupling agents,7,16,17 and single and combined
chemical treatments,1,9,16,18–23 to improve the matrix-fiber interfacial adhesion, which in turn enhanced composite per-
formance. To our best knowledge, the comparison of solely washed and simple alkali-treated fiber on the composites is yet
limited. The main objective of this work was to prepare a fully green biocomposites which were made from the direct single-
used plastic material and waste of sugarcane. All the cleaning processes on the waste materials were self-carried out and none
of the coupling chemicals was used during the composite preparation. In this work, the effect of the presence of different
amounts of raw, washed, and alkali-treated SCB fibers on the mechanical and physical properties of the resultant green
composites was investigated. The water diffusion coefficient calculation was discussed.
Experimental
Materials
In this experiment, all raw materials were obtained from recycled sources. The high-density polyethylene (HDPE) used as the
polymer matrix was from clean unused semi-transparent plastic bags. The sugarcane bagasse was used as reinforcing filler.
The SCB wastes were collected from the local market. The HDPE plastic bags were self-processed to obtain the shredded
HDPE (Figure 1(a)), whereas the raw SCB was washed and dried before treatment or use (Figure 1(b)).
Figure 1 Preparation of HDPE/SCB green composites: (a) Processing step to obtain the shredded HDPE from plastic bag, (b) Modification
step to obtain the treated SCB fiber, and (c) Melt-blending and pressing steps to obtain composite panels for characterization. HDPE:
high-density polyethylene; SCB: sugarcane bagasse.
160°C. The hot pressing cycle was fixed with pre-heating of 3 min, venting of 1 min, and full pressing of 3 min, whereas the
cooling cycle was fixed at 4 min.
Characterization
The tensile, impact, and flexural properties of compression molded specimens were determined in accordance with ASTM
D638-03 (Type I), ASTM D 256 (sample dimension: 63.5 mm × 12.7 mm × 3 mm), and ASTM D790-03 (sample dimension:
127 mm × 12.7 mm × 3 mm), respectively. Both tensile and flexural mechanical tests were conducted in a Testometric M350-
10CT with a crosshead speed of 5 mm/min. The impact test was performed using a Ray-Ran Impact tester operating with a
0.452 kg load, a velocity of 3.46 m/s, and a calibration energy of 2.765 J.
Water absorption test was performed on the oven-dried specimen (dimension: 76.2 mm × 25.4 mm × 3.2 mm) following the
procedure of ASTM D 570-98 method. The weight of oven-dried specimen (Wo) was measured using a digital weighing
balance with the precision of 0.01 g. The specimen was soaked in tap water at room temperature and removed periodically for
weight measurement up to 28 days. The percentages of water absorption were calculated using the equation of water ab-
sorption (%) = (Wt–Wo)/Wo x 100, where Wo denotes the initial weight and Wt denotes the specimen weight after water
immersion at time t.
Figure 1 Continued.
Figure 2. (a) Tensile strength of recycled HDPE/SCB fiber green composites and (b) TS changes of investigated composites compared with
pure recycled HDPE. HDPE: high-density polyethylene; SCB: sugarcane bagasse.
S1138 Polymers and Polymer Composites 29(9S)
Figure 3. (a) Young’s modulus of recycled HDPE/SCB fiber green composites and (b) YM changes of investigated composites compared
with pure recycled HDPE. HDPE: high-density polyethylene; SCB: sugarcane bagasse.
Figure 4. (a) Strain at break (SB) of recycled HDPE/SCB fiber green composites and (b) SB changes of investigated composites compared
with pure recycled HDPE. HDPE: high-density polyethylene; SCB: sugarcane bagasse.
less than 20 wt% chemically modified (with NaOH and acetic anhydride) SCB fiber, which can be correlated to the dewetting
effect13 between polymer matrix and reinforcing filler. In Figure 2(a), the NaOH-treated fiber composites exhibited greater
tensile strength than untreated (raw) fiber composites because the swollen fiber due to mercerization could give higher tensile
strength when they are stretched, as stated by Ameer et al.26 It is believed that the alkali treatment was shown to increase the
surface roughness of natural fiber which consequently promote the mechanical interlocking or bonding with polymer
matrix.9,15 However, the chemical interaction or bonding was lacking in the composites since the HDPE is hydrophobic and
natural fiber (SCB in this study) is hydrophilic.12 Although the tensile strength results showed an improvement for the
modified fiber composites, however, the values were still lower than that of neat HDPE sample.
Young’s modulus in Figure 3 shows a different trend compared to that of the tensile strength. By adding SCB fibers, the
Young’s modulus increased with the increasing fiber content. Young’s modulus is stated as the indication for rigidity and
stiffness of a material where the higher values of Young’s modulus represent the increasing rigidity and stiffness.1 It was
established that the natural fibers (SCB fiber in this study) are high stiffness filler, while polymers are comparatively less stiff;
therefore, the higher content of fibers is expected to contribute to higher stiffness property of composites.
On the other hand, fiber modification was found to positively affect the Young’s modulus of composites. The raw SCB
fiber-reinforced composites exhibited the lowest Young’s modulus, regardless of fiber loading. The improved modulus via
fiber surface modification was similarly reported in the previous study on recycled PE filled with washed and combined
mercerized-acetylated SCB fiber.13 Nevertheless, the rate of improvement in Young’s modulus affected by treatment types
was varied with different fiber loading. In the case of lower SCB content of 5–10 wt%, the increment of composite modulus
was optimum for soaked SCB fiber and closely followed by alkali-treated fiber, as observed in Figure 3(b). The higher tensile
modulus for soaked SCB than NaOH-treated fiber at this content implies that soaking method is more efficient than alkali
treatment. The soaking method of 3 days used in this study was anticipated to result in greater effect in fiber swelling as
Chen et al. S1139
compared to NaOH treatment of 40 min, and consequently promoted better physical attachment with very little amount
polymer matrix. However, when the fiber loading was higher, this effect seems insufficient to adherent with polymer as the
distribution and compatibility of filler with polymer matrix could be the important factors to affect the composite stiffness. As
stated by Serra-Parareda et al.,27 the cellulose content of the fibers will contribute to the stiffness if they are properly dispersed
inside the composite. In this regard, surface treatment through chemical reaction such as mercerization would show better
effect, as shown at higher SCB fiber content of 15 wt% where the greatest improvement of Young’s modulus was achieved for
NaOH-treated fiber with an increment of 70.6%. This result is close to that of soaked fiber composites with 69.7% increment,
as agreed by the previous study of PE/SCB composites with a combined surface treatment of mercerization and acetylation in
comparison to washed SCB fiber.13 This increment could be ascribed the improved adhesion between cellulosic fiber and
polymeric matrix due to the removal of grassy and gummy layer from the fiber surface via mercerization, as well as the
reduced hydrophilicity via acetylation.1
Figure 4 shows that 5–15 wt% fiber incorporation led to decrease in the strain at break of 72–90% compared to that of the
matrix. The large decrement in strain at break was similarly reported in the previous research on recycled polyolefin matrix
reinforced with bagasse fibers.5,7 This implies that the bagasse fibers had imparted the brittleness and rigidity to the recycled
HDPE matrix.7 The loss of drawability for composites could be further explained by the increased number of defect points
which were induced by the SCB fiber to initiate and propagate stress cracking in the HDPE matrix.5 Nevertheless, by looking
at the fiber modification, the NaOH-treated fiber improved the strain at break of composites the most (recorded for 14.7–
19.0%) followed by soaked fiber (recorded for 9.7–17.7%) as compared to the raw fiber at 6.8–9.1%. This may be ascribed to
the mercerization process which enhanced the fiber-matrix adhesion as a result of the elimination of impurities from the SCB
surface.1
Impact properties
The impact strength of recycled HDPE composites reinforced with SCB fiber is displayed in Figure 5(a). The impact strength
results showed a similar trend with strain at break (Figure 4(a)). In Figure 5(b), a reduction of 61–78% was observed for raw
SCB fiber composites, whereas 49–71% and 24–64% decrement in impact strength were shown for soaked and NaOH-treated
SCB fiber composites, respectively. As the SCB fiber content increased, the ability of polymer matrix to absorb energy
reduced and resulted in the consequent reduction of composite toughness.12 Besides, the rigid interface between the fiber and
the matrix could decrease deformability of the composite in the meantime to induce the micro-cracks occurrence with ease and
its subsequent propagation in the composites at the impact point.7,12 Similar to strain at break, the impact strength trend
showed the sequence of NaOH-treated SCB fiber > soaked SCB fiber > raw fiber composites, regardless of fiber contents. This
might be explained by the improved fiber–polymer interaction (mechanical interlocking) via the removal of impurities during
the washing and alkali treatment. Thus, this interaction can act to impede the propagation of cracks created during the impact
tests.
Flexural properties
Figures 6 and 7 display the effect of fiber content and fiber type (modification) on the flexural properties of recycled HDPE-
reinforced SCB fiber composites. As observed in Figure 6(a), the highest flexural strength obtained was 20.8 MPa which was
recycled HDPE with 5 wt% of the NaOH-treated SCB fiber, whereas pure recycled HDPE had 18.5 MPa. Further addition of
Figure 5. (a) Impact strength (IS) of recycled HDPE/SCB fiber green composites and (b) IS changes of investigated composites compared
with pure recycled HDPE. HDPE: high-density polyethylene; SCB: sugarcane bagasse.
S1140 Polymers and Polymer Composites 29(9S)
Figure 6. (a) Flexural strength (FS) of recycled HDPE/SCB fiber green composites and (b) FS changes of investigated composites compared
with pure recycled HDPE. HDPE: high-density polyethylene; SCB: sugarcane bagasse.
Figure 7. (a) Flexural modulus (FM) of recycled HDPE/SCB fiber green composites and (b) FM changes of investigated composites
compared with pure recycled HDPE. HDPE: high-density polyethylene; SCB: sugarcane bagasse.
this fiber caused the decrease in flexural strength, which were 16.7 MPa and 12.8 MPa for 10 wt% and 15 wt% NaOH-treated
fiber composites, respectively. The same reduction trends were shown for raw and soaked SCB fiber composites with different
decreasing rates. The decreasing trend of flexural strength with filler content has been reported in literature3 which investigated
on PP incorporated with 10–40 wt% SCB fiber. The fiber modification with soaking and alkali treatment gave the similar
(positive) effects as tensile strength, except for higher filler content of 15 wt% which showed the adverse effect. This is
because the performance in bending stress was claimed to be different from the normal stress applied.3 Flexural failure
involves both extension and compression stresses which could be correlated to the homogeneity of the overall composites as
well as the properties of the constituents and the interfacial interaction.9 This could also explain the flexural modulus trend
shown in Figure 7(a) where the addition of 5–10 wt% SCB fiber exhibited lower flexural modulus than that of pure recycled
HDPE. The 15 wt% filler recovered the flexural modulus of pure polymer matrix, which correlated to the intrinsic high
stiffness characteristic of natural fiber, as described in the result of Young’s modulus. Additionally, the soaked SCB fiber
composite was the stiffest followed by composites with NaOH-treated fiber and raw fiber.
Water absorption
Figure 8 illustrates the water absorption of recycled HDPE green composites reinforced with different types of SCB at 5, 10,
and 15 wt%. The trend clearly shows that the presence of SCB fiber had greatly affected the water absorption of the
composites. The weight gain caused by water uptake in composites showed a significant increment with increasing SCB fiber
Chen et al. S1141
content from 5 to 15 wt%. This is anticipated for natural fiber composites as the polymer matrix absorbs very small quantity of
moisture or water while the reinforcement phase absorbs majority of the water.28 At the end of water immersion period (840 h),
the maximum water absorption was achieved at 5.00%, 5.86%, and 10.30% for 5 wt%, 10 wt%, and 15 wt% SCB fiber
composites, respectively. This remarkable increase in water absorption can be explained by three possible reasons. First, the
inter- and intra-molecular hydrogen bondings are formed between the accessible hydroxyl groups of hydrophilic fibers and the
water molecules. Second, water molecules diffuse into the matrix-fiber interface. Finally, there are large number of porous
tubular fiber structures that expedite the water penetration via capillary action.7,29
In Figure 8, the effect of fiber modification on water absorption of recycled HDPE green composites as compared to 5 wt%
raw SCB fiber composite is presented. Generally, the water absorption of soaked and alkali-treated SCB fiber green
composites, except for 15 wt% soaked SCB fiber composite, exhibited lower amount of weight gain than that of 5 wt% raw
fiber. This could be explained by a possible reason that the washed and treated SCB fiber would promote better fiber-matrix
interface adherence and reduced voids in the composites, thereby slowing down the water penetration.18 It has been reported
that alkali treatment aids in cleaning the surface of the bagasse fibers by eliminating hemicellulose and lignin, which
consequently reduces fiber diameter (due to fibrillation) which turn in increases of the interface regions, resulting in the
decrement in moisture content.14,30 As the number of hydrophilic hydroxyl groups reduced by NaOH, the hydrophilic nature
of modified fiber had changed into a more hydrophobic nature.19,20 Furthermore, the removal of surface impurites is stated to
increase the surface roughness which results in better mechanical interlocking (promoting adhesion) between the fiber and
matrix.9 The decreased water absorption has been similarly reported in epoxy/bagasse fiber composites by chemical treatment
with 1% NaOH and 1% acrylic acid.21 However, it should be mentioned that there are some cases where the water absorption
of sugarcane bagasse fiber polymer composites increases after washing6 or alkali treatment.4,31 This is due to the strong
influence of treatment parameters such as concentration of alkali solution and treatment period on the water absorption
characteristic of the resultant composites.6 Moreover, the improvement in water absorption resistance was more obvious when
the fiber content was higher (in this study was at 15 wt%). This is due to the increased amount of the fiber-matrix interface at
higher fiber content, thus causing a greater extent of improvement in interfacial interaction.
According to Fick’s second law of diffusion, the diffusion coefficient (D) can be calculated by equation (1) to understand
the rate of water diffusion process into polymer composites32,33
2
θh
D ¼ π (1)
4Mm
where θ is the slope of the linear part of Mt against t1/2 curve (which is the initial absorption) and h is the height (thickness) of
the composite sheet. With the determination of D, the parameters of thermodynamic solubility (S) and permeability (P) can be
ascertained using the following equations25:
Wm
S ¼ (2)
Wc
P ¼ D:S (3)
where Wm and Ww are the total mass of composites after water absorption in the equilibrium state and initial mass of the
composite panel, respectively. The calculated D, S, and P values of 5 and 15 wt% SCB fibers with different fiber modification
Figure 8. Water absorption of recycled HDPE/SCB fiber green composites with different fiber types and contents. HDPE: high-density
polyethylene; SCB: sugarcane bagasse.
S1142 Polymers and Polymer Composites 29(9S)
Table 1. Water absorption constants for raw and treated SCB fiber-recycled HDPE green composites.
are listed in Table 1. It showed that the fiber modification, either soaking or NaOH treatment, lowered the water diffusion
parameters of recycled HDPE composites.
Conclusions
Three types of HDPE composites reinforced with 5–15 wt% SCB fibers of different fiber conditions were successfully
fabricated by extrusion followed by compression molding. The SCB fibers were washed (by soaking) and treated with NaOH
before incorporating with polymer matrix. The as-prepared green composites were characterized by tensile, impact, flexural,
and water absorption tests. In the presence of stiff SCB fiber, the Young’s and flexural modulus of green composites increased
with the fiber content. As the SCB fiber loading increased from 5 to 15 wt%, the mechanical strengths including tensile,
impact, and flexural mode of fracture decreased accordingly. The hydrophilic SCB fiber had contributed to the increase in
water absorption capacity. By modifying SCB fiber via washing and alkali treatment, the mechanical and water absorption
resistance of the resultant composites were significantly enhanced.
Acknowledgments
The authors gratefully thank UCSI University for financial support and Universiti Kebangsaan Malaysia (research grant from the Ministry of
Higher Education Malaysia, through a Fundamental Research Grant Scheme with code FRGS/1/2019/TK05/UKM/02/3) for the equipment
services.
Funding
The author(s) disclosed receipt of the following financial support for the research, authorship, and/or publication of this article: This study
was supported by the Ministry of Higher Education Malaysia, through a Fundamental Research Grant Scheme (FRGS) with code FRGS/1/
2019/TK05/UKM/02/3.
ORCID iD
Ruey Shan Chen https://orcid.org/0000-0002-2713-942X
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