Accepted Manuscript

Improvement on the Properties of Polylactic Acid (pla) using Bamboo charcoal

Particles

Mei-po Ho, Kin-tak Lau, Hao Wang, David Hui

PII: S1359-8368(15)00375-3
DOI: 10.1016/j.compositesb.2015.05.048
Reference: JCOMB 3647

To appear in: Composites Part B

Received Date: 5 December 2014

Revised Date: 25 May 2015
Accepted Date: 27 May 2015

Please cite this article as: Ho M-p, Lau K-t, Wang H, Hui D, Improvement on the Properties of
Polylactic Acid (pla) using Bamboo charcoal Particles, Composites Part B (2015), doi: 10.1016/
j.compositesb.2015.05.048.

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 ACCEPTED MANUSCRIPT

IMPROVEMENT ON THE PROPERTIES OF POLYLACTIC ACID (PLA) USING

BAMBOO CHARCOAL PARTICLES

Mei-po Ho1, Kin-tak Lau1,#, Hao Wang2 and David Hui3

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1
Department of Mechanical Engineering, The Hong Kong Polytechnic University
Kowloon, Hong Kong SAR China
2
University of Southern Queensland, Centre of Excellence in Engineered Fibre Composites,

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Queensland, Australia.
3
Department of Mechanical Engineering, University of New Orleans, New Orleans, LA 70148,
USA.

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#
Corresponding author: mmktlau@polyu.edu.hk

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Abstract

Bamboo charcoal (BC) derived from bamboo plants is one kind of well recognized muti-
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functional materials which has been used in various applications such as medical, cosmetic, food
processing and health-related products. In this paper, BC particle is used as reinforcement for
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polylactic acid (PLA) to enhance its mechanical, thermal and optical properties. The comparison
on tensile, flexural and impact properties of BC particle reinforced PLA composites (BC/PLA
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composites) with the content ranging from 2.5 to 10 wt. % is conducted. Experimental results
indicated that the maximum tensile strength, flexural strength and ductility index (DI) of
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BC/PLA composites increased by 43%, 99% and 52%, respectively as compared with those of
neat PLA. This phenomenon was attributed to the uniform distribution of high aspect ratio and
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surface area of BC particles. Further increasing the BC content to 7.5 wt.% would decrease the
glass transition temperature of BC/PLA composites. The mechanical properties of BC/PLA
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composites were reduced as compared with a neat PLA sample when they were exposed to
compost degradation. However, less reduction in these properties was found when they were
subject to UV irradiation. UV-VIS spectrometer analysis supported the results of UV irradiation.
Fracture surfaces of tensile test samples with and without compost degradation or UV irradiation
were analysed by using scanning electron microscopy (SEM). SEM images revealed that there
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was a good BC particle dispersion in the composites through extrusion and injection moulding
processes if the particle content was below 7.5 wt.%.

Keywords: A. Injection moulding, B. Particle-reinforcement, C. Mechanical properties, D. Optical

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properties, E. Thermal properties, F Compost degradation, G UV irradiation.

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1. Introduction

Excessive use of petroleum-based plastics, which induce huge amounts of non-decomposable

solid wastes causes a serious depletion of landfill capacities. The awareness of soared waste
problems on the environment has awakened a new interest in the area of materials science.

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Because of the increasing environmental consciousness in the society, it is a critical topic for
researchers to study different alternatives to replace non-renewable materials, especially for
petroleum-based plastics. Therefore, different types of fully biodegradable materials are being

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developed recently, as substitutions for non-biodegradable plastics, and even metallic
components [1-4]. Among various biodegradable polymers, polylactic acid (PLA) is particular

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interest for the development of industrial polymers. PLA belongs to the family of linear aliphatic
polyesters (without strong entanglement, branching between the chains). It is commonly derived

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from α-hydroxy acids, which are produced using monomer feedstock. Since PLA is compostable
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and derived from sustainable sources, it is viewed as a promising material to alleviate societal
solid waste disposal problems [5-7]. PLA is yielded by direct condensation polymerization of a
basic building block lactic acid, which is nowadays generally produced by bacterial fermentation
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of carbohydrates (mainly hexose) in corn (glucose), sugar cane (sucrose) or cheese whey
(lactose). However, industries normally utilize the more efficient conversion of lactide to PLA
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catalyzed by a Sn (II)-based catalyst through ring-opening polymerization (ROP) rather than

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poly-condensation [8-11]. The preparation method of the PLA influences its mechanical and
thermal properties i.e. PLA 3051D: Tg ~55-65°C, Tc ~ 150-165°C and tensile strength ~48MPa
[1]), which are quite similar to other polyesters (such as PET). The thermal properties are
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however a bit lower, due to the absence of the benzoic cycle (chain more free to move). Its
chemical properties and water resistance are weakened by the presence of the carbonyl group
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(C=O), which allows for hydrolysis degradation [12]. The degradation process of PLA through a
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simple hydrolysis of ester bonds is unnecessarily about the presence of enzymes or catalyses [8].
The degradation rate of PLA mainly depends on the temperature during hydrolysis, the size, the
shape and the isomer ratio of the PLA [13]. Landfill has been recognized as a cheapest and
economic way to bury wastes under the soil. However, some adverse effects such as the products
of harmful bi-products may be a concern to the environment. As PLA is commonly used as food
storage or packaging nowadays, many of its products would be disposed as wastes in the landfill,
and subsequently decomposed or degraded with time [14]. One of the disadvantages of landfill is
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that gases and chemicals are generated during the decomposition or degradation process of the
solid wastes. These gases and chemicals released from landfill into the air may be harmful for
animals and humans.

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As the recent emphasis on materials and processes which are environmentally sustainable, there
has been increasing interest in the development of composites by using natural and degradable

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materials such as bamboo charcoal (BC). BC is plentiful, relatively cheap, renewable, relatively
non-toxic and sustainable [15]. BC can bind with a variety of molecules because it contains

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network of pores and high specific surface area as shown in Figure 1 [16, 17]. Besides, it is
easily processed into different shapes such as block, strip and particles [18, 19]. BC is made from
bamboo branches, shoots and roots by pyrolysis (carbonizing) process at temperature over 450oC,

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or being processed in a high-performance clay furnace oven heated to about 1000oC [20].
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Bamboo pyrolysis can be divided into four stages according to temperature and products
situation in a kiln or a pyrolyzing kettle [19]. These stages are drying, pre-carbonization,
carbonization and calcinations.
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The unique properties of BC include uniform composition, high porosity, anti-bacterial and anti-
fungal, breathability, thermal regulation, and odour control and absorption [18-19, 21]. In
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addition, BC possesses great absorption effect of microbes. There are innumerable pores and
gaps, lengthwise and crosswise in its structure. BC has an adsorption capacity as activated
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carbons have and can replace that of wood charcoal [22, 23]. The porosity (volume) of BC is
about 5 times as compared with those of wood charcoal, the mineral constituent is about 8 times
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and absorption efficiency is about 10 times more than those of wood charcoal. Furthermore, the
inner surface of wood charcoal is about 10 m2/g. It is lower than that of BC, which is about 250-
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399 m2/g [24]. This makes BC easily absorbing or trapping microbes.

Besides, BC possesses high absorption capability of ethylene gas [25-26], heavy metals (lead,
copper and cadmium) [27-28] and environmental hormone (Formaldehyde) [29]. These
absorption and removal actions would protect from food poisoning. Moreover, excellent
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moisture control capability of BC enables it to maintain food freshness at its optimal conditions.
BC is excellent for inhibiting the growth of bacteria and fungi, and also has the ability to absorb
far infrared energy from the environment and emit it to help the cell activation for promising
blood circulation for human. The far infrared rays emitted by BC are also expected to obstruct
decay bacteria and harmful insects [30]. BC possesses rich trace elements and natural minerals,

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such as calcium, potassium, sodium, iron, etc, which is thus widely used in the fields of food
cooking, baking, stocking and keeping food fresh [24]. BC can generate negative air ions

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spontaneously and permanently without generating excess amounts of radiation or ozone
molecules [31].

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Although BC has been commonly used as fuel to provide fire and heat, it can also be used as an

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odour (smell) adsorbent, catalyst support, humidity controller, and wastewater purification
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substance [31]. Apart from those aforementioned properties, BC could potentially improve the
properties of PLA while at the same time, its anti-bacterial properties are beneficial during the
PLA’s product life including disposal. The absorption capacity of BC can be used to dehumidify
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and deodorize air and also purify water. For the food storage applications, these properties are
not only excellent for retaining food quality as the smell can be de-odorized and moisture can be
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maintained to reduce the growth of fungi and bacteria, but also in the stage of waste disposal and
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land filling [32].

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Many researchers attempted to use particle to reinforce composites in order to enhance their
properties [33-39]. However, none of them focused on the properties of PLA composites
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reinforced by natural BC particle. The current study is aimed at investigating the mechanical,
optical and thermal properties of BC reinforced PLA composites with and without compost
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degradation and UV irradiation. Furthermore, morphology of fracture surface of the neat PLA
and BC/PLA composites with different BC contents are used to evaluate the degradation.
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2. Experimental Set-up

2.1 Materials

Semi-crystalline PLA pellets used in the current study were neat grade commercialized by
Cargill-Dow under the brand name “Ingeo biopolymer 3051D”. The 3051D PLA has an average

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molecular weight of 160 kDa. The melting point is 150-165 oC. The melt flow index and the
specific gravity of this polymer are 10 ~ 30 g/10 min and 1.24g/cm3, respectively. The glass

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transition temperature (Tg) of the pellet is between 55℃ and 65℃ and the melting temperature is
200oC [4, 40]. BC particle was supplied by Mt Meru Pte Ltd (Singapore). The average particle
size of bamboo charcoal was 10.00 µm and its specific surface area is 0.523 m2/g. The density is

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0.910–0.940 g/cm3.

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2.2 Sample Preparation

Although PLA pellets and BC particles are hydrophobic, they are sensitive to moisture [41- 45].
Therefore, BC particles and PLA pellets were mixed and dried in a chamber of a Mini hot air
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Moretto dryer at 70oC for 24 hours in order to minimise excessive moisture content prior to the
extrusion. Subsequently, different mixtures of BC particles and PLA pellets were blended by
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Axon Pacific Pty Ltd single screw extruder. The BC/PLA mixtures contained BC particles
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ranging from 2.5 – 10 wt% with the interval of 2.5 wt% each. The extruder was run at 80 rpm
and 190oC in the extrude zone and 180oC in blending zone. After cooling, the extruded mixtures
were chopped into pellets. These pellets were dried in the dryer at 70 °C for 2h prior to injection
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moulding. The injection moulding was carried out with four temperature zones. The nozzle
temperature was 183 °C and all other zones were kept at 180 °C. The mould was set to 50°C.
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The pressure was maintained at 1 bar.

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2.3 Characterizations

Samples were moulded for flexural, tensile and impact tests according to ASTM D 790M,
ASTM D 638 and ASTM D 4508 standards, respectively. All tests were carried out under an
ambient condition. Universal MTS system was utilized for the tensile test in the current study.
Grip separation was set to 100 mm in length and the crosshead speed was adjusted to 5 mm/min
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for the tensile test. Samples were further coated by gold for scanning electron microscope (SEM)
(JEOL Model JSM-6490) imaging to observe the fracture surface of neat PLA and BC/PLA
composites. Flexural moduli in bending and flexural strength of the samples were measured
through universal MTS system under an ambient condition. The default radii of the loading nose
and supports were 5.0 mm. The crosshead speed of the flexural strength tests was 0.946 mm/min.

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An instrumented drop weight impact tester (Instron Dynatup) was selected to perform falling
weight impact test under an ambient condition to study the impact properties including

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maximum load (Pmax), crack initiation energy (Em), propagation energy (Ep), total fracture energy
(Et) and ductility index (DI). Brinell hardness testing was conducted using 15 kgf load and

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1.5875 mm diameter indenter. The loading time was about 10 second according to ASTM E10
Standard Test Method.

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DSC and TGA measurement were made with a Thermogravimetric analyser/ Differential
Scanning Calorimeter (Netzch TGA/DSC). Sample of 5 to 10 mg were placed in ceramic pan
with cover and heated from 25oC to 800oC at the rate of 10oC/mm. Other than the glass
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transition temperature (Tg), crystallization temperature (Tc), melting temperature (Tm),

experimental melting enthalpy (△Hm) and degree of crystallinity (χ%) were measured. The
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thermal degradation properties taking into account were the T0 (oC) and Tf (oC) as the
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temperatures for starting and finishing PLA degradation.

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High resolution X-ray diffractometer (HRXRD) analysis was carried out by Rigaku SmartLab
system for phase identification of the samples. Scattered radiation was recorded in 2θ range from
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5 to 40o at 5o/min in reflection mode. For compost biodegradability test, the samples were carried
out in soil having initial pH value 6.32 at temperature 37oC. Water was added frequently to keep
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the humidity of the soil. The weight loss of composted sample can be evaluated using the
following equation:

୛౟ ି୛౜
Weight Loss (%) = ୛౟
X100%
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where Wi and Wf are sample weights before and after the composting test, respectively. The
samples with different BC contents were subsequently tested to measure their tensile properties.
SEM images captured on the fracture surfaces of the biodegraded samples after the tensile test
were highlighted.

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UV absorptance and transmission of the samples were studied through the UV-VIS double beam

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spectrometer (Halo DB-20, Dynamica) in a wavelength range 190- 1100nm at ambient
temperature. The accelerated UV techniques are extremely useful in assessing the durability of

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materials in the presence of UV irradiation. Samples were UV irradiated for 2000 hours using an
accelerated photoageing devices called UV Weatherometer (Biolab Pty Ltd). The irradiation
process was carried out at room temperature with humidity control. Tensile test with SEM

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imaging after UV irradiation were characterized.
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3. Results and discussion
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The mechanical properties of PLA composites with over 10 wt% BC particles were not evaluated
in this study because of the limitation in the manufacturing process. BC is a self-lubricity
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material [46], high content of the BC particles added into the PLA can reduce the viscosity in a
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great extent during the injection moulding. Although PLA reinforced by a small amount of BC
particles could produce a low-viscosity melt that easily flow into small gates, into thin wall
sections and even most complex mould cavities under low injection pressure, too much particles
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(> 10 wt%, based on the experimental finding[46]) would cause the difficulty in moulding
process as the viscosity is dramatically dropped. The viscosity of the BC/PLA mixture is too low
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and it would raise the leakage in the feed lines during the process.
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The tensile strength of neat PLA, 2.5 wt.%, 5 wt.%, 7.5 wt.% and 10 wt.% BC/PLA samples are
35.81, 39.39, 40.74, 51.14 and 36.99 MPa, respectively. Figure 2 shows that the tensile strength
of BC/PLA composites increases gradually with increasing the BC content until it reaches 7.5
wt.%. The maximum tensile strength among the samples obtained from 7.5 wt.% BC/PLA
composite is 43% higher than that of the neat PLA. Nevertheless, further increase in the BC
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content results in decreasing the tensile strength. The tensile strength of the BC/PLA composites
is strongly dependent on the stress transfer mechanism through interfacial bonding [47].

Figure 3 shows that all BC/PLA composites have higher Young’s modulus than the neat PLA.

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The Young’s modulus of neat PLA, 2.5 wt%, 5 wt%, 7.5 wt% and 10 wt% BC/PLA samples are
2.9, 3.4, 3.5, 3.7 and 3.9 GPa, respectively. Due to the large surface area of BC, adding BC into

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PLA would improve the stress transfer properties between PLA to BC particles. Fu et al. [47] has
summarized that the Young’s modulus of composite can be improved by adding micro particles

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as rigid fillers. The resistance which created by BC particles reduced the deformability of the
PLA macromolecules. Therefore, incorporation of BC particles into PLA reduced the mobility of
PLA structures and resulted in enhancing the stiffness of BC/PLA composite. As a result,

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Young’s modulus increased with the content of BC particles in the composites increased [48].
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The tensile strain decreased with an increase of BC content which was due to the limited plastic
deformation. In Figure 4, neat PLA and the 2.5 wt.% BC/PLA samples show yielding behavior
in the stress-strain curve. However, the strain of the samples containing 5 wt%, 7.5 wt% and 10
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wt% BC particles localized beyond the maximum stress, led to the composite fracture
immediately as a quasi-brittle behavior under tensile deformation [5, 49-50]. Increasing the
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content of BC particle produced a sample that becomes progressively less plasticity and more
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resistant to deformation. It can be concluded that the elongations of BC/PLA composites

decreased as the BC particles reduced the ductility of the PLA.
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The tensile strength of a 10 wt% BC/PLA composite decreased obviously. This may be due to
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the reduction in the extensibility and the formation of clusters of the PLA matrix. The fracture of
the 10 wt. % BC/PLA composite with agglomeration of BC particles resulted in the increase of
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stress concentration zones and weakened the interfacial bonding strength of the sample [20, 51].
Thereafter, the generation, the growth and the propagation of flaws along the interfaces between
PLA and BC particles clusters, contributed to the final coalescence of the larger cracks [52]. The
agglomeration of the BC particles caused partially separation of micro-spaces between particle
and particle, and particle and polymer and thus, obstructed stress propagation when tensile stress
was loaded [53].
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The morphologies of the fracture surfaces of the BC/PLA composites and the neat PLA
explained the results of the samples obtained from the tensile test. The micrographs of neat PLA
(Figure 5a) shows a smooth surface, however, the micrograph of the other BC/PLA composites
(Figures 5b-e) show corrugated fracture surfaces with irregular cracks. The fracture of the
composite occurred as a result of the load transfer from PLA to the BC particles. 2.5 wt%, 5wt%

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and 7.5 wt% BC particles were well dispersed and firmly embedded in the PLA which was due
to the small particle size and good compatibility properties of BC particles with PLA. These

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reasons explain the enhancement of tensile strength and modulus of BC/PLA composites [54].
As mentioned earlier, 10 wt. % BC content in the PLA is expected to decrease the adhesion

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properties of BC to PLA and eventually reduce the mechanical properties of the composite. For
poorly bonded particles, the crack was attracted to the equators of the BC particles and moved

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around the particles. Weak interfacial adhesion between the cluster of BC particles and PLA
made crack pinning less effective because deboned particles were ineffective as pinning sites
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[55]. Figure 5e exhibits rough surface of 10 wt% BC/PLA composite with many tear lines and
branching. The tearing seemed to originate from the region around BC in the matrix. The
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fracture surface consisted of hemispherical holes and top surfaces of de-bonded particles. This
implies that BC acted as stress concentration and promoted the formation of cracks when the
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sample was loaded [54, 20].

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The influences of BC content on the flexural modulus and flexural strength of the samples are
shown in Table 1. The addition of BC particles significantly increased in both flexural strength
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and modulus of the BC/PLA composites compared with the neat PLA. From table 1, it can be
seen that BC particles resulted in reinforcing effect to the PLA as both flexural modulus and
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strength increased. PLA and BC are compatible as both of them are hydrophobic [15, 41].
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Greater interaction between the PLA and BC particles caused less de-bonding when a stress was
applied and consequently the flexural properties of the composites were increased [54, 56].
However, as the BC content increased up to 10 wt%, BC particles aggregated and the formation
of micro cracks would decreased the effective cross-sectional area of the composites and induced
its flexural properties weaker than the neat PLA.
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The results of the impact test are summarized in Table 2, All BC/PLA composites exhibit higher
Pmax, Em, Ep, Et and DI value than neat PLA, indicating that BC has a positive contribution to the
composites. Among all samples, the Pmax, Em, Ep and Et of 7.5% BC particle reinforced PLA
composite increased 24.3%, 29.6%, 96.8%, 49.5% and 52% compared with neat PLA. Ductility
index (DI) has proposed by Beaumont et al. which is the ratio of the propagation energy to the

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initiation energy for a sample under impact [57]. According to Table 2, BC/PLA composites with
different BC contents show higher DI value than the control neat PLA does. It was found that DI

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increased by 52% for the composite with BC content of 7.5 wt% compared with neat PLA. BC/
PLA composites are capable of absorbing higher amount of energy to stop crack propagation

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compared to the neat PLA. Besides, BC particle created stress concentrations in the PLA that
would be favoured sites for non-elastic deformations such as strain localization or cracks [53].

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The comparison of Brinell hardness test results obtained from neat PLA and BC/PLA composites
with different BC contents is shown in Figure 6. The figure reveals that there was an increase in
Brinell Hardness Number (B.H.N.) value with the increase in BC content up to 7.5 wt.%.
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This is due to addition of hard filler content in the PLA which is at the surface and resists the
plastic deformation of PLA. The distribution of BC particles and decrease in inter-particle
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distance with increasing particle loading in the matrix increase the resistance to the indentation
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of the samples as the PLA and BC particles are pressed together and touch each other more
tightly. Thus the interface can transfer pressure more effectively [58- 59]. However, in the
hardness test of 10 wt.% BC/PLA composite, a pre-cracked particle can still support compressive
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traction across the crack surface, resulting in the composite not being affected by the already
fractured particles. The localized pressure causes the material directly under the indented surface
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to support most of the load, and the stress field is predominantly compressive. [60].
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The results of TGA and DSC are shown in Figure 7(a-b) respectively. Neat PLA decomposes
without formation of solid residue while 7.5 wt% BC/PLA composite produces around 7.5%
solid residue. BC particle blocks reactive chemical groups and suppress the weight loss of
BC/PLA composite. Table 3 is the summary of the results in the thermal analysis. The T0 & Tf of
7.5 wt.% BC/PLA composite is lower than that of neat PLA which means that 7.5 wt.% BC/PLA
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composite started and completed to decompose earlier than neat PLA. Moreover, It shows a
decrease in Tg and Tm of 7.5 wt.% BC/PLA composite. BC particles may act as a plasticizer in
the 7.5 wt.% BC/PLA composite. The decrease in Tg also means that 7.5 wt.% BC/PLA requires
less energy for its molecule movement. Similarly, the decrease in Tm would be obvious as
melting involves molecular movement. Besides, as the mobility of the molecules might increase,

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which means that the materials might need more energy to crystallize and hence Tc increases.
The degree of crystallinity (χ%) of PLA in the composites was calculated using the expression:

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∆‫ܪ‬௠ 100%
‫ݔ‬௖ ሺ%ሻ = ௢ ×
∆‫ܪ‬௠ ‫ݓ‬

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where Hm is the experimental melting enthalpy (J/g), H0 is the melting enthalpy of 100%
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crystalline PLA(93.7 J/g) and w is the weight fraction of PLA matrices in the composites[61].
The neat PLA shows 46.6% degree of crystallinity which is in accordance with the result of
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Parket et. al. [62-64]. It can be considered that the interface was fatally weakened by a loose
coupling between the micro BC filler and the polymer matrices. As a result, the glass transition
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temperature of 7.5 wt% BC/PLA composite decreases [65-67].

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The XRD results of the samples are shown in Figure 8. The peaks (2 θ = 9.5o & 16.7 o) are
assigned to the reflection of α–phase crystallite of PLA [68]. Although the shapes and positions
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of different samples were almost the same, the first peak (2 θ = 9.5o) of BC/PLA composites
exhibited a decrease in the peak intensity and the peaks were shifted compared with neat PLA.
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The intensity of the peak was decreasing and shifting to lower diffraction angles when BC
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content was increasing. The intensities at the peak 2 θ = 9.5o of PLA, 2.5 wt. % BC/PLA, 5 wt.
% BC/PLA and 7.5 wt. % BC/PLA were 1779 at 2 θ = 9.3o, 1767 at 2 θ = 9.3o, 1755 at 2 θ =
9.24o, 1756 at 2 θ = 9.18o and 1713 at 2 θ = 9.14o respectively. This was attributed to the
increase in the degree of “amorphousity” in the PLA polymer. The degree of crystallization of
polymer decreased with the increasing of the amount of BC particle [69].
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Analyzing the changes take place in the samples including the weight change, the changes in the
pH value of immersion medium, the mechanical properties and the fracture morphology during
compost degradation. In Figure 9, the pH value of the immersion medium shown during the
composting test is constant. An increase of the samples’ weight is a result of water absorption
(Figure 10). Based on the experimental results, the weight of the all samples increased with the

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increase of composting time which is because of the water absorption. Given the relatively thick
samples used here, water penetration rate of the neat PLA was relatively slow compared with

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BC/PLA composites. This result may be due to the capacity of water absorption of the porous
structure of BC particle. Although most of the BC particles were encapsulated, the water

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equilibrium effect induces the water diffusion from the soil to the composites so that BC/ PLA of
the composite absorbing water faster than neat PLA. Therefore, the BC/ PLA composite absorb

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moisture more quickly for water penetration into interfacial bonding and trapped into the porous
of the BC and thus the weight increase faster. For the 7.5 wt.% BC/PLA composite composted
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for 24 weeks, it was found that the weight increases by 2%. However, the weight of neat PLA
increases by 0.6%. Thus, PLA degrades slowly in soils because of the slow rate of hydrolysis
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[70].
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The first step of compost degradation process of degradable polymer is water absorption when a
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sample is contacted with moisten soil. The high molecular weight polymer chains are then
hydrolyzed to form lower molecular weight chains (oligomers) [8]. The hydrolysis rate depends
on pH value, temperature and humidity [8], [24] and [31]. During this step, some
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microorganisms in the compost are able to catalyze the degradation. Finally, the lower molecular
chains convert to CO2, water and humus [71]. However, PLA is less susceptible to microbial
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attack in the natural environment than other microbial and aliphatic polyesters [72]. Therefore,
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increases of the hydrolysis of PLA is a principle factor to accelerate the compost degradation of
PLA [72]. As the water absorption of BC/PLA composites are higher than neat PLA, there is
slower degradation rate of neat PLA compared with BC/PLA composite [73-74].

The proceeding degradation of the materials after composting can also be verified by the changes
in the mechanical properties shown in Figure 11-13. The presence of the BC modified the
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mechanical properties of such composite. The speed of the process can be controlled by means of
combining the polymer with BC particle with high water absorption. With this porous BC
particles added which should provide easy entry for water, decline in Young’s modulus, tensile
strength and strain are more significant (Figure 11-13) [75]. All samples became brittle after soil
burial because of the plasticizing effect of PLA through water absorption. It can be observed a

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dropping strength tendency both neat PLA and BC/PLA composite during the composting.
However, for the composite, we observed a significant loss of strength already after 7weeks of

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compost degradation. The initial BC/PLA composites possess the strength comparable to neat
PLA. For the composites containing 2.5 wt.%, 5wt.% and 7.5wt.% concentration of BC particle,

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the strength decreases by 41%, 44% and 37% already after 7 weeks of composting, and after 14
weeks, the strength drops already by approximately to 54%, 50% and 45%. The further decrease

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in strength in 70%, 77% and 47% in 21 weeks in case that the biodegradation were obtained [76].
The higher rates of the BC/PLA composites can also be attributed to their lower crystallinity
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compare with neat PLA since amorphous regions are more susceptible to degradation. It agrees
with the results of DSC/TG study mentioned in this study as the crystallinity of PLA is lower
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than 7.5 wt.% BC/PLA composite.

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Figure 14 shows the fracture surface micrographs of neat PLA and BC/PLA composites with
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different percentages during compost degradation. An increment in surface roughness after

compost degradation was observed in all samples. As the polymers with a non-homogenous
surface decompose faster than those whose surface is characterized in a lower roughness [76],
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with the increment in the weight content of BC particle, the surface roughness is increasing while
in PLA, there is less degradation and smoother appearance. The microvoids because of the
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debonding of the BC particle with PLA and degradation are significance in 7.5 wt. %. This
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indicates that the extent of biodegradation increased more as BC particle concentration is

increased.

The optical absorption, particularly, studying the shape and shift of the absorption edge, is a
useful technique for understanding the basic mechanism of optically-induced transitions in
crystalline and non-crystalline materials, as well as providing information about the band
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structure. The basic principle behind the technique depends on the absorption of photons with
energies greater than the band gap energy by carrier undergoing transitions from occupied states
in the valence band to unoccupied states in the conduction band [77-78]. Absorbance units are
converted to absorption coefficients [79]
ூ

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= ݁ ିఈ௭ (1)
ூబ

௟೚
‫݃݋݈ = ܣ‬ (2)

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௟

Combining (1) & (2) to eliminate l୭ /l, absorption coefficient α is obtained as,

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ଶ.ଷ଴ଷ஺
ߙ= (3)
௭

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Where ‫ܫ‬଴ is the intensity of incident, ‫ ܫ‬is the intensity of transmitted, z is the thickness and A is
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the absorbance. The UV-Vis spectra of neat PLA and BC/PLA samples are shown in Figures 15-
17. It is shown that the adding of BC particles to PLA leads to an increase of the peak intensity.
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Critical analysis of UV-Vis spectra of BC/PLA composites shows that the highest shift in
absorption wavelength is in the range 270-380 nm. For UV wavelengths, there is strong
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absorption up to 320 nm, resulting in 0% transmittance. This significant change in the spectra
may indicate the occurrence of the photodegradation of PLA matrices.
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PLA is a semi-crystalline polymer which undergoes significant changes in the primary structure
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by chain scission under UV irradiation. Chain scission releases chain segments in the amorphous
phase from entanglements which increase the crystallinity and molecular weight distribution of
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PLA [73]. In general, there are two main methods for stabilising PLA, namely protection and
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inhibition from UV irradiation. Different stabiliser acts through different mechanisms to retard
the UV irradiation of the material. Some stabilizers absorb UV light and thereby protect the
polymer from degradation, whereas other stabilisers inhibit the chemical reactions taking place
in photodegradation mechanisms by trapping the radicals responsible for photodegradation
reactions [80]. A dark pigment is usually added to the resin to standardize the color and to
decrease its sensitivity to UV light. In this study, BC particle act as stabilizer to hinder the UV
aging ability of PLA by UV light absorption.
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Neat PLA and BC/PLA composites were subjected the accelerated UV ageing. The UV
irradiation leads to the alteration of the chemical structure which influences the colour change of
the surface, mechanical response and fractography of the samples directly. Injected PLA contain
chromophoric groups, such as carbon-carbon double bonds (C=C) and carbonyl groups (C=O),
which are capable of absorbing UV energy and are involved in the photoreactions that result in

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the degradation of the polymer [81]. The colour changes mainly occur as a consequence of
chemical changes within the polymer structure, lead to erosion and fading of the surface of

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polymer. Figure 18 shows that neat PLA becomes rosin yellowing as the conjugated double bond
arise from oxygen addition, isomerization and other reactions [82]. Many tiny cracks and crack

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propagation could be seen in the surface of neat PLA.

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During UV irradiation, the degradation of PLA layers and the loss of BC particles from the
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surface deteriorated the mechanical properties severely. The more serious effects of UV aging
include microcracking and embrittlement of polymer [80].The tensile strength, strain and
Young’s modulus of the samples with different BC particle contents before and after 2000 hrs
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UV irradiation are shown in Figure 19 & 21, respectively. The PLA after the UV exposure was
noticeably brittle with the formation of cracks that provoke failure. However, composites have
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better overall resistance UV irradiation.

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Closer examination of samples using SEM reveals substantial deterioration to the surface of the
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samples shown in Figure 22. The surface cracks and voids because of the degradation of PLA
can be seen in Figure 22(a). The chalking phenomenon creates an uneven surface on the polymer,
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which scatters the light and leads to a faded appearance to the material. Severely cracking and
lost fragments by UV irradiation results in a chalky appearance to the neat PLA surface. High
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fracture surface roughness of BC/PLA composites shown in figures 22 (b)-(d) proved the
embrittlement by the UV irradiation. However, as BC particles absorb UV light and hinder PLA
from UV irradiation. There is no micro void exist in BC/PLA composites.
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4. Conclusion

The excellent absorption capacity of bamboo charcoal (BC) can be used for retaining food and
inhibiting the growth of bacteria and fungi. In this paper, BC was used to reinforce polylactic
acid (PLA) for food storage applications. This study is aimed at investigating the mechanical,

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optical and thermal properties of BC reinforced PLA with and without compost degradation and
UV irradiation. According to experimental results, the mechanical properties of BC/PLA
composites increases gradually with increasing BC content until it reaches 7.5 wt%. However,

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as the BC content up to 10 wt%, aggregation of BC particles reduced the mechanical properties
of the composites. Moreover, neat PLA has a lower compost degradation rate but higher UV

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irradiation rate as compared with BC/PLA composites. SEM images revealed the aggregation
effect of a 10 wt.% BC/PLA composite and the compost and UV irradiation of the samples.

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However, It has been found that a good dispersion of BC in PLA up to 7.5 wt.% through
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extrusion and injection moulding.
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Acknowledgement

This project was supported by The Hong Kong Polytechnic University Grant (G-YK84).
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Figure. 1. The porous structure of bamboo charcoal [15].
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Figure. 2 The tensile strength of pure PLA sample and BC/PLA composite with different BC contents.
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4.5

3.5

3
Young's modulus (GPa)

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Weight of charcoal (%)
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Figure 3. Young’s modulus of pure PLA and BC/PLA composite with different BC contents.
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Figure 4. Tensile stress-strain curves of pure PLA sample and BC/PLA composite with different BC
contents.

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(c) (d)

De-bonded
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(e)
Figure 5. SEM images of (a) pure PLA, (b) 2.5% BC/PLA, (c) 5% BC/PLA, (d) 7.5% BC/PLA and (e)
10% BC/PLA composites.

28

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26

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Brinell hardness (HBW)

25

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23

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21
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20
0% 2% 4% 6% 8% 10%
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wt. % of BC

Figure 6. Brinell hardness of the samples with different BC particle content.

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7.5 wt. % BC/PLA composite

Pure PLA
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(a)

120

100 TG of 7.5% BC sample

TG of pure PLA sample

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Mass/%

60

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40

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25 225 425 625
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Temperature / degree

(b)
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Figure 7. (a) DSC curves and (b) Temperature dependence weight loss of pure PLA and 7.5 wt. %
BC/PLA composite.
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10 wt.%BC/PLA
7.50 wt.%BC/PLA
5% wt.BC/PLA
2.5 wt.%BC/PLA
Intensity

Pure PLA

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5 10 15 20 25 30 35 40
2θ (deg)
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Figure 8. Diffraction pattern of PLA and BC/PLA composites.

10
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pH value

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5
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4
0 5 10 15 20
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Number of weeks
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Figure 9. pH value of samples including pure PLA, 2.5 wt.% BC/PLA composite, 5 wt.% BC/PLA
composite, 7.5 wt.% BC/PLA composite as a function of compost degradation time.
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0.3

0.25 Pure PLA 2.5% BC 5% BC 7.5% BC 10% BC

Change of weight (g)

0.2

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0.15

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0.1

0.05

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0
0 5 10 15 20 25
Week

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Figure 10. weight change of samples including pure PLA, 2.5 wt.% BC/PLA composite, 5 wt.% BC/PLA
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composite, 7.5 wt.% BC/PLA composite as a function of compost degradation time.
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Tensile Strength (MPa) 50

40

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30

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20
Pure PLA
10 2.50 wt.% BC/PLA composite

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5 wt.% BC/PLA composite
7.5 wt.% BC/PLA composite
0
0 5 10 15 20

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Figure 11. Tensile strength as a function of time for the samples after compost degradation.
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0.6 Pure PLA

2.5 wt.% BC/PLA composite
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0.5 5 wt.% BC/PLA composite

7.5 wt.% BC/PLA composite
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0.4
Strain (mm/mm)

0.3
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0.2
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0.1
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0
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weeks

Figure 12. Tensile strain as a function of time for the samples after compost degradation.
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3.05 14.1

14
3

Young's Modulus (GPa) of original samples

Young's Modulus (GPa ) of tje samples after

13.9

13.8
2.95

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13.7
composted)

2.9 13.6

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13.5
2.85 7weeks 13.4
14 weeks

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13.3
2.8 21weeks
13.2
original
2.75 13.1

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wt% of BC
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Figure 13. Young’s modulus as a function of time for the samples after compost degradation.
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Figure 14. SEM surfaces under tensile test of pure PLA, 2.5 wt.% BC/PLA composite, 5 wt.% BC/PLA
composite, 7.5 wt.% BC/PLA composite exposed to compost degradation for 6 weeks, 14 weeks
and 21 weeks.
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Figure 15. UV/Vis spectra of pure PLA and BC/PLA composites.
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Figure 16. The absorption coefficient for pure PLA and BC/PLA composites.
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Figure 17. UV transmittance of pure PLA and BC/PLA composites.
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(a) (b) (c) (d)

Figure 18. photographs of samples after tensile test including (from left to right), pure PLA
without UV weathering, pure PLA with UV weathering, 7.5 wt.% BC/PLA composites without UV
weathering and 7.5 wt.% BC/PLA composites with UV weathering.
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100

90

80
Tensile Strength (MPa)

70

60

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50

40

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30 original

20 UV irradiated

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10

0
0% 2% 4% 6%

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Figure 19. Effect of UV irradiation on the Tensile strength of pure PLA and BC/PLA composites with
different BC contents.
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0.6
original
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0.5
UV irradiated
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0.4
Strain (mm/mm)

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0.3

0.2
C

0.1
AC

0
0% 2% 4% 6%
wt% of BC

Figure 20. Effect of UV irradiation on the strain of pure PLA and BC/PLA composites with different
BC contents.
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14.5 2

14.3 1.9

Young's Modulus (GPa) of UV irradiated sample

14.1 1.8
Young's Modulus (GPa) of original sample

13.9 1.7

PT
13.7 1.6

13.5 1.5

RI
13.3 1.4

13.1 1.3

SC
original
12.9 1.2
UV irradiated
12.7 1.1

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12.5 1
0% 2% 4% 6%
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wt% of BC

Figure 21. Effect of UV irradiation on the Young’s modulus of pure PLA and BC/PLA composites
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with different BC contents.

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PT
RI
SC
(a) (b)

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AN
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D
TE

(c) (d)
EP

Figure 22. SEM surfaces of (a) pure PLA, (b) 2.5 wt.% BC/PLA composite, (c) 5 wt.% BC/PLA
composite, (d) (2) 7.5 wt.% BC/PLA composite.
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Table 1. Experimental results extracted from the flexural test.

Flexural Flexural
Standard Standard
Modulus Strength
Deviation Deviation
(MPa) (MPa)

PT
Pure PLA 700 4.24 19.60 3.40

2.5% bamboo
723.81 9.52 22.73 1.63
charcoal/PLA composite

RI
5% bamboo charcoal/PLA
733.33 7.14 27.48 3.57
composite

SC
7.5% bamboo
756.41 11.10 38.98 1.97
charcoal/PLA composite

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10% bamboo
789.08 8.27 23.32 0.67
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charcoal/PLA composite
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Table 2. Impact data for control pure PLA and BC/PLA composites with different BC contents.

Sample Pmax(kN) Em (J) Ep (J) Et (J) DI

Pure PLA 0.21 1.27 0.53 1.80 0.42

PT
2.5 wt% BC/PLA 0.21 1.300 0.43 1.73 0.33

5 wt% BC/PLA 0.23 1.39 0.76 2.15 0.55

RI
7.5 wt% BC/PLA 0.26 1.64 1.05 2.69 0.64

SC
10 wt% BC/PLA 0.19 1.38 0.73 2.11 0.53

Pmax is the maximum load, Em is the crack initiation energy, Ep is the propagation energy, Et is

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the total fracture energy and DI is the ductility index.
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Table 3. Thermal properties of pure PLA and 7.5 wt.% BC/PLA composite.

TG-DSC Tg (oC) Tc (oC) Tm (oC) △Hm (Jg-1) Χ/% To (oC) Tf (oC)

Pure PLA 67.29 129.09 159.84 46.40 49.50 348.70 380.10

PT
7.5%
BC/PLA 63.90 135.11 156.68 13.00 13.90 332.40 371.40

RI
compoiste

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D
TE
C EP
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