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What is This?
Abstract
The surface of recycled polyethylene (RPE)/chitosan composites was modified with polyethylene-graft-maleic anhydride
(MAPE). The mechanical properties, water absorption, morphology, and thermal properties were investigated.
The composites with MAPE improved tensile strength and Young’s modulus but reduced elongation at break and
water absorption. Scanning electron microscopy study of the tensile fracture surface of composites indicated that the
presence of MAPE increased the interfacial interaction between chitosan and RPE matrix. The incorporation of MAPE
improved the thermal stability and crystallinity of RPE/chitosan composites.
Keywords
recycled polyethylene, chitosan, compatibilizer, composites
have been made at blending plastic materials with RPE are given in Table 1. Chitosan used as fillers in
chitosan.4–20 RPE and chitosan composites, was obtained from
The most important issue associated with these Hunza Nutriceuticals Sdn. Bhd., in powder form. The
composites is the interfacial adhesion between the nat- average particle size of chitosan is 85.4 mm. Table 2 gives
ural reinforcing fillers and matrix polymers. In order to the properties of chitosan. Compatibilizer was used
obtain good properties by improving the compatibility in RPE/chitosan composites was MAPE, supplied by
between these two materials with their different Aldrich and the amount applied is 3 php based on the
properties, studies have been performed on surface weight of RPE. Table 3 gives the properties of MAPE.
modification or treatment using a compatibilizing
agent. PE-graft-maleic anhydride (MAPE), the newly
developed maleated PE couplers were expected and
Mixing process
shown to be superior in the PE composites based on The mixing of the composites was carried out using
physical property data.20–24 Z-blade mixer at a temperature of 180 C and at a
The thermal degradation of polymers has been at the speed of 50 rpm. RPE charges the chamber for 15 min
center of thermal analysis studies for many years. until it completely melts. After 15 min, filler was added
Thermal analysis is an important analytical method in and mixing was continued for another 10 min. The total
understanding the structure–property relationship and mixing was conducted for 25 min. Sample of compos-
mastering the technology for molecular design and ites was compression molded in an electrically heated
industrial production of different polymeric materials.25 hydraulic press. Hot-press procedures involved pre-
Fundamental information regarding the thermal stabil- heating at 180 C for 6 min followed by compressing
ity of the composite materials to be processed is for 4 min at the same temperature and subsequent
obtained from the thermogravimetric (TGA) and dif- cooling under pressure for 4 min. The formulation for
ferential scanning calorimetric (DSC) analyses. TGA
is one of the thermal analysis techniques used to quan-
tify weight change and thermal decomposition of the
sample. The chemical composition, heating rate, tem- Table 1. Properties of RPE
perature, and inorganic substances are the major fac- RPE
tors that affect the thermal behavior of biomass. On the
other hand, DSC provides the melting temperature Tm Melt index 5 g/10 min
at which a transition occurs. It also provides the Density 0.922 g/cm3
enthalpy H associated with the transition. Studies of Melt temperature 160–180 C
the dependence of H on temperature can also be used
to obtain the change in heat capacity that occurs with
melting.26 Thermal methods, such as TGA and DSC Table 2. Properties of chitosan
have emerged as powerful thermo-analytical techniques
to monitor characteristic physical and chemical changes Chitosan
in both natural and synthetic polymers. Further, some Physical properties
of these changes involve the loss of material in volatil- Appearance Off-white powder
ization which can be quantitatively measured by TGA. Powder fineness Finer than 120 mesh size
In fact DSC is ideally suited for rapid screening and Chemical properties
finger printing purpose of materials, in solid state, as a Degree of deacetylation >90.0%
function of temperature. A survey of recent literature Solubility of 1% chitosan >99.0%
shows that thermal methods have been rarely used for in 1% acetic acid
monitoring the chemical and physical changes during Viscosity 150–200 mPa s
various modifications of chitin and chitosan. Moisture content <10.0%
In this article, the research was focused on the effects
Ash content <1.0%
of chitosan loading and MAPE on the properties of
recycled polyethylene (RPE)/chitosan composites.
Table 3. Properties of MAPE
Experimental MAPE
RPE/chitosan composites with and without MAPE is were scanned from 50 C to 600 C using a nitrogen air
given in Table 4. flow of 50 mL/min and a heating rate of 20 C/min.
16
The thermogravimetric analyzer that has been used is 14
Perkin Elmer Instruments Technology by Seiko 12
Instruments (SII). Approximately, 5 mg of samples 10
8
6
4
Table 4. Formulations for RPE/chitosan composites
2
Materials (php) Without MAPE With MAPE 0
0 10 20 30 40
RPE 100 100
Filler loading (php)
Chitosan 0, 10, 20, 30, 40 0, 10, 20, 30, 40
MAPEa – 3
Figure 1. Effect of filler loading on tensile strength of RPE/
a
3 php from weight RPE. chitosan composites with and without MAPE.
loading due to increase in the ability of filler to support increased with increasing filler loading. Young’s mod-
stress transfer from matrix. At similar chitosan loading, ulus is an indication of the relative stiffness of compos-
the composites with MAPE shows higher tensile ites. The increase in the Young’s modulus also depends
strength compared to composites without MAPE. The on many factors such as the amount of filler used, the
higher tensile strength of composites with MAPE is due orientation of the fillers, the interaction and adhesion
to maleic anhydride group reaction with hydroxyl between the matrix, and the ratio of the filler to matrix.
group from chitosan. The application of compatibilizer At similar filler loading, the Young’s modulus of com-
in polymer composites was used to overcome the dis- posites with MAPE is higher compared to composites
persion problem and to enhance the mechanical without MAPE. The presence of compatibilizer
strength of composites by improving adhesion across becomes more effective on enhancing the modulus
the interface. Similar observation was also found by values. This is due to the higher chitosan stiffness of
some researchers.22–24 composites with MAPE and better interactions are
Figure 2 shows the effect of filler loading on elonga- obtained. The Young’s modulus of the MAPE-incorpo-
tion at break of RPE/chitosan composites with and rated composites was improved due to the better wet-
without MAPE. The elongation at break decreases stea- ting of MAPE to the PE matrix polymer.
dily with the increasing filler loading. The decrease in
elongation at break in filled polymer composites is due
to the fact that the deformation of the filler is generally Water absorption. Water absorption of composite is
much less than that of the polymer matrix; thus, the filler an important characteristic that determines end use
forces the matrix to deform more than the overall defor- applications of materials. Figure 4 shows the relation-
mation of the composite. At similar filler loading, the ship between percentages of water absorption of
elongation at break for RPE/chitosan with MAPE is
lower than the composites without MAPE. It is known 450
that fillers with higher stiffness than the matrix can 400
RPE/Chitosan without MAPE
Young’s modulus (MPa)
RPE/Chitosan: 100/30
Water absorption (%)
RPE/Chitosan: 100/40
500 1
400 0.8
300 0.6
200 0.4
100 0.2
0 0
0 10 20 30 40 0 5 10 15 20 25 30
Filler loading (php) Time (days)
Figure 2. Effect of filler loading on the elongation at break of Figure 4. Percentage of water absorption vs. time of RPE/
RPE/chitosan composites with and without MAPE. chitosan composites with different loadings.
RPE/chitosan composites without MAPE at different compatibilizer prevents water molecule entering the com-
filler loadings. The percentage of water absorption posites, thus, limiting water absorption. Figure 6 shows
increases with increasing filler loading until the equilib- the percentage of equilibrium water absorption of RPE/
rium achieved for 30 days. Chitosan contains numerous chitosan composites with and without MAPE of different
hydroxyl groups available for interaction with water mol- filler loadings. The equilibrium of composites with
ecules by hydrogen bonding. Chitosan-reinforced poly- MAPE is lower than the composites without MAPE.
mers can take up high amounts of water. Figure 5 shows This is attributed to the presence of compatibilizer that
the comparison of water absorption between RPE/chit- reduces water absorption of composites.
osan with and without MAPE at 0, 20, and 40 php of
filler loadings. It was observed that the composites with
MAPE showed lower water absorption when compared Morphological studies. SEM micrographs of tensile
to composites without MAPE. This indicates that com- fracture surface for RPE/chitosan composites with and
patibilizer improved the compatibility between filler and without MAPE for 20 and 40 php are shown in
matrix. Good wetting of filler by the matrix and adequate Figures 7–10. Figures 7 and 8 show the tensile fracture
filler–matrix bonding can decrease the amount of water
absorbed in the interphasial region of the composites.
Establishment of bonds between hydroxyl group on
filler surface and maleic anhydride group from
RPE/Chitosan: 100/0
RPE/Chitosan: 100/20 (without MAPE)
RPE/Chitosan: 100/20 (with MAPE)
1.4 RPE/Chitosan: 100/40 (without MAPE)
RPE/Chitosan: 100/40 (with MAPE)
1.2
Water absorption (%)
0.8
0.6
0.4
1.4
Equilibrium water absorption (%)
0.8
0.6
0.4
0.2
0
0 10 20 30 40
Filler loading (php)
Figure 8. The SEM micrograph of tensile fracture surface of
Figure 6. Percentage of equilibrium water absorption for RPE/ RPE/chitosan at 40 php without MAPE at magnification 200.
chitosan composites with and without MAPE different filler Source: For more details about Figures 7–13 refer our website
loadings. www.unimap.edu.my or mail to irsalmah@unimap.edu.my.
Thermal properties
Figure 10. The SEM micrograph of tensile fracture surface of
Figure 11 shows the TGA curve of RPE/chitosan com-
RPE/chitosan at 40 php with MAPE at magnification 200.
posites for different filler loadings. The data of TGA are
Source: For more details about Figures 7–13 refer our website
given in Table 5. From the table, it is clear that the www.unimap.edu.my or mail to irsalmah@unimap.edu.my.
110
90
Weight loss (%)
70
50
30
RPE/Chitosan: 100/0
10 RPE/Chitosan: 100/20 (with MAPE)
RPE/Chitosan: 100/40 (without MAPE)
–10
0 100 200 300 400 500 600 700
Temperature (°C)
Figure 9. The SEM micrograph of tensile fracture surface of Figure 11. Thermogravimetry analysis curves of RPE/chitosan
RPE/chitosan at 20 php with MAPE at magnification 200. composites without MAPE at different filler loadings.
Source: For more details about Figures 7–13 refer our website Source: For more details about Figures 7–13 refer our website
www.unimap.edu.my or mail to irsalmah@unimap.edu.my. www.unimap.edu.my or mail to irsalmah@unimap.edu.my.
Table 5. Percentage weight loss of RPE/chitosan composites with and without MAPE at different temperatures
Temperature RPE/chitosan: RPE/chitosan: 100/20 RPE/chitosan: 100/40 RPE/chitosan: 100/20 RPE/chitosan: 100/40
( C) 100/0 (without MAPE) (without MAPE) (with MAPE) (with MAPE)
increase of chitosan content had decreased the total stability of composites because physico-chemical adsorp-
weight loss. This indicates that at higher chitosan loading tion of the volatile products on chitosan, which indicates
it has a better thermal stability of composites. However, that the dispersion of chitosan was improved by the addi-
at similar chitosan loading, the composites modified with tion of compatibilizer in polymer.29–32
MAPE have lower total weight loss compared with com- Figure 13 shows the DSC thermograms of RPE/chit-
posites without MAPE. This indicates that composites osan composites without MAPE at different filler load-
with MAPE have higher thermal stability than compos- ing. Table 6 gives the values of melting temperature
ites without MAPE. Figure 12 shows the TGA curve of (Tm), the heat of fusion of composites (Hf(com)), and
RPE/chitosan composites at 40 php with and without the crystallinity of the composites (Xcom). Table 6 gives
MAPE. The addition of MAPE has increased the thermal the enthalpy and crystallinity of RPE/chitosan without
MAPE which increases with increasing chitosan load-
ing. The increase in crystallization of composites with
110 increasing filler loading should be attributed to the
90 nucleation agent of the chitosan. At similar filler load-
Weight loss (%)
Conclusion
Figure 12. Thermogravimetry analysis curves of RPE/chitosan
composites at 40 php with and without MAPE. The properties of RPE/chitosan biopolymer composites
Source: For more details about Figures 7–13 refer our website were improved using the MAPE as a compatibilizer. The
www.unimap.edu.my or mail to irsalmah@unimap.edu.my. results show that the tensile strength, Young’s modulus,
and water absorption increase with increasing filler load-
ing. However, the elongation at break decreases with
9 increasing filler loading. The tensile strength and
8
Young’s modulus improved with the incorporation of
7
compatibilizing agents. The composites with MAPE
Heat flow (W/g)
6
5 show better resistance to water absorption compared
4 to composites without MAPE. The addition of MAPE
3 has positive effect on the properties and can overcome
RPE/Chitosan: 100/0
2
RPE/Chitosan: 100/20 (without MAPE)
the incompatibility problem between matrix and fillers
1 RPE/Chitosan: 100/40 (without MAPE) of the composites. SEM micrograph of RPE/chitosan
0 with MAPE shows better interfacial interaction. The
0 50 100 150 200 250 300
thermal stability and crystallinity of composites
Temperature (°C)
improved with the addition of MAPE.
Table 6. DSC analysis of RPE/chitosan composites with and without MAPE at different filler loadings