World Engineering Congress 2010, 2nd – 5th August 2010, Kuching, Sarawak, Malaysia

Conference on Advanced Processes and Materials

CAPM2
COMPOSITE FILMS FROM KENAF DERIVED CELLULOSE (KDC) FIBERS AND
POLYLACTIC ACID (PLA)
Rahman, S.H.A.1, Talib, R.A.*,1, Abdan, K.2, Chin, N.L.1, Yusof, Y.A.1 and Yunos K.F.M.1
1
Department of Process and Food Engineering, Faculty of Engineering, Universiti Putra Malaysia (UPM), 43400
Serdang, Selangor D.E., Malaysia.
2
Institute of Tropical Forestry and Forest Products (INTROP), Universiti Putra Malaysia (UPM), 43400 Serdang,
Selangor D.E., Malaysia.
*Email: rosnita@eng.upm.edu.my

ABSTRACT

Composite films were prepared from kenaf derived cellulose fibers (KDC) and polylactic acid (PLA) resin by melt
blending using an internal mixer. Cellulose was derived from kenaf via standard ASTM D1104 method. The
composites were incorporated with 0 to 60 % (dry weight basis) of KDC fiber loading into PLA, then were hot
pressed to produce films with thickness of 0.30 to 0.35 mm. Oxygen permeability test and Differential Scanning
Calorimetry (DSC) measurement in the KDC-PLA composites were conducted. Increasing the loading of KDC (up
to 60 %) in KDC-PLA films exhibited reduction of 77 % and 85 % in oxygen transmission rates (OTR) and
permeation coefficient (P) respectively, as compared to neat PLA. Whereas, addition of KDC into composites has
reduced the crystallinity of composites. Even though incorporation of KDC fibers has negative influence on the
crystallinity of composites, the overall blocking effect of the fibers counteract this negative effect and produced
better oxygen barrier as compared to the commercial PLA for packaging applications.

Keywords: Composite, Cellulose, Polylactic Acid, Permeability, Differential Scanning Calorimetry

INTRODUCTION

Biocomposite packaging materials are one of the alternative solutions for today’s issues of petroleum shortage and
non-degradable petroleum based packaging. Many researchers are putting their effort on the development of
biobased composite by incorporating the natural fibers in biopolymer matrices like poly lactic acid (PLA), poly
hydroxybutyrate (PHB) and poly vinyl alcohol (PVA). Biopolymers are proven to perform better even with small
addition of natural fibers compared to the conventional petroleum based polymers. For instance, it is found that the
composite strength of PLA/flax is 50 % better compared to similar PP/flax fibre composites [1]. Polylactic acid
(PLA) is a transparent plastic whose characteristics resemble common petrochemical-based plastics such as
polyethylene and polypropylene. PLA is recently used in food packaging application for short shelf life products
such as candy twist wrap, salad and vegetables bags, label film, and drinking cup. Natural fibers on the other hand
are categorized based on their origin including vegetable, animal and mineral fibers. Natural fibers provide strength,
stiffness, and act as reinforcement in the composite materials [2]. Incorporating natural fibers into polylactic acid is
one of the appealing parts of natural-fiber-reinforced-biocomposite studies and become the field of interest for some
researchers [1,3-8]. They exhibit unique properties, even with small loading of less than 5 % into the biopolymer
matrices, the properties that cannot be obtained with other type of fillers. Kenaf, jute, hemp, pineapple leaf and
ramie are among most of the cellulose fibers that are used as reinforcement in biocomposite. Apart from that, the
natural fibers that are embedded in the polymer matrix also shows some drawback such as reducing the tensile
strength, [9-10], and producing high moisture absorption characteristic to the composite [11]. Although this
drawback occurs in biocomposite film, the fiber content in biopolymer matrix still donates to a promising attribute
which is the improvement in barrier properties. Natural fibers are suggested to provide torturous path to the
permeant molecule to permeate trough a biocomposite materials [12]. Besides imposing more tortuous path to the
permeant, cellulose content in biopolymer also provide higher value of crystallinity which reduce the permeability
of biocomposite film. The limitation in the widespread availability of cellulose reinforced PLA raises interesting and
important questions regarding its intrinsic barrier properties. This study is carried out in order to determine the
KDC-PLA biocomposite reputation as a good barrier film in packaging application from the oxygen gas as oxygen

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 World Engineering Congress 2010, 2nd – 5th August 2010, Kuching, Sarawak, Malaysia
Conference on Advanced Processes and Materials

is known as non-condensable and non-interacting gas permeant that may contribute to the food deterioration in a
package.

MATERIALS AND METHODS

Materials
Commercial PLA 2002D resin (melting temperature of 210 ºC, melt index of (4–8 g/10 min) was purchased from
NatureWorks Co. (USA). Kenaf bast fibre was kindly supplied by Institute of Tropical Forestry and Forest Products
(INTROP), Malaysia.

Preparation of Composite Films

Cellulose was derived from kenaf via chlorination and mercerisation according to ASTM D1104 method. Kenaf
derived cellulose fibers KDC) and polylactic acid (PLA) composite were prepared by melt blending using an
internal mixer at fixed screw speed of 50 rpm and processing condition at 170 °C for 30 min. KDC loading ranging
from 0 – 60 % (dry weight basis) was incorporated in the PLA to produce composites. Each composite was hot
pressed at a temperature of 170 oC for 10 minutes to form films with thickness of 0.30 to 0.35 mm.

Oxygen permeability
Oxygen transmission rates of composite films were obtained using Oxygen Permeability Analyzer model 8000
(Illinois Instrument Inc., USA) with diffusion cell area of ~ 110 cm2. Experimental conditions were as follows:
permeant = O 2 ; carrier gas = N 2 ; temperature = 28 ºC; and relative humidity = 0 %. The samples were first nitrogen
purged at the desired environmental conditions, then exposed to 40 psi of oxygen on the upstream side of the films
and to 40 psi of N 2 on the downstream side of the films. The permeated oxygen carried by the downstream N2 flow
was taken to the detector, which charted the oxygen transmission rate (OTR). The permeability coefficient, P, can be
calculated using the Eq. (1):

𝑉𝑉𝑉𝑉 𝑙𝑙
P= = 𝑂𝑂𝑂𝑂𝑂𝑂. (1)
𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝛥𝛥𝛥𝛥
where P is permeability coefficient (cc.mil/m2/day.psi); OTR is the measured oxygen vapor transmission rate (cc
/m2/day) through a film, 𝑙𝑙 is the mean film thickness (m) and ΔP is the partial oxygen pressure difference across the
two sides of the film (Psi).

Differential Scanning Calorimetry Measurement

DSC thermograms of neat PLA and KDC-PLA composites were acquired using Perkin Elmer DSC 7 by employing
~ 7 mg of testing material. The DSC equipment was calibrated using indium as a standard and the heating was
performed from 0 to 200 °C at a rate of 10 °C/min. Glass transition onset temperature (T g ), cold crystallization onset
temperature (T c ), melting onset temperature (T m ) and melting enthalpy (ΔH m ) were obtained from the curves. The
percentage of crystallinity (X c ) was calculated using the Eq. (2) below:

∆𝐻𝐻𝑚𝑚 + ∆𝐻𝐻𝑐𝑐
𝑋𝑋𝑃𝑃𝑃𝑃𝑃𝑃 (2)
𝑋𝑋𝑐𝑐 [%] = 𝑐𝑐 . 100
∆𝐻𝐻𝑚𝑚
𝑐𝑐
where ∆𝐻𝐻𝑐𝑐 is the enthalpy of cold crystallisation, ∆𝐻𝐻𝑚𝑚 is the enthalpy of fusion, and ∆𝐻𝐻𝑚𝑚 = 93 Jg-1 is the
enthalpy of fusion of 100 % crystalline PLA [13].

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 World Engineering Congress 2010, 2nd – 5th August 2010, Kuching, Sarawak, Malaysia
Conference on Advanced Processes and Materials

RESULTS AND DISCUSSION

Oxygen permeability
Figure 1 shows a typical oxygen transmission rate (OTR) curves of KDC-PLA biocomposites with various KDC
loading. The incorporation of KDC loadings into PLA matrix reduced the OTR of neat PLA by 77 % which is from
35 to 8 cc/m2/day. The oxygen permeability coefficient, P, can be estimated from the OTR curves obtained (see
Figure 2). The significant result of the data is that the oxygen barrier of the composite film has a much better oxygen
barrier, which is 35 % with only 10 % of incorporated KDC. The permeability coefficient for the 20 % KDC-PLA is
reduced by 42 % as compared to those of the neat PLA. This effect was found to be insignificant for higher loading
of KDC. The maximum reduction in permeability coefficient of 85 % was achieved with 50 % KDC-PLA
biocomposite. On the other hand, no significant reduction in permeability coefficient was observed for 60 % of KDC
loading. The KDC-PLA composite films become less oxygen permeable by increasing the KDC loading. This can
be explained by the blocking effect of the fibers that dispersed and embedded in the polymeric matrix thus
decreasing the area available for diffusion and consequently increase the tortuosity distance path for a solute to cross
a film [9, 14].

50 Neat PLA 10% KDC-PLA

20% KDC-PLA 40% KDC-PLA
40 50% KDC-PLA 60% KDC-PLA
OTR (cc/m2/day)

30

20

10

0
0 100 200 300 400 500 600 700
Time (min)
Figure 1: OTR curves for 0-60 % loading of KDC-PLA composite films.
0.7

0.6
Permeability Coefficient

0.5
(cc.mil/m2/day.psi)

0.4

0.3

0.2

0.1

0.0
0 10 20 40 50 60
KDC loading (%)
Figure 2: Oxygen permeability of KDC-PLA composites as a function of KDC loading

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 World Engineering Congress 2010, 2nd – 5th August 2010, Kuching, Sarawak, Malaysia
Conference on Advanced Processes and Materials

Differential Scanning Calorimetry Analysis

Figure 6 shows the typical DSC thermograms of neat PLA and KDC-PLA biocomposite films. The values of glass
transition onset temperature (T g ), cold crystallization onset temperature (T c ), melting onset temperature (T m ),
melting enthalpy (ΔH m ) and the percentage of crystallinity (X c ) are tabulated in Table 1. The neat PLA is
characterized by T g at 56.0 °C, T c at 96.4 °C and T m at 138.8 °C. Increasing the KDC loadings in composites has
shifted both T g and T c to lower values. The low value of Tc suggests that incorporation of cellulose fibers in PLA
has facilitated the crystallization process. In addition, incorporation of cellulose fibers has produced composites with
higher T m . This can be explained by the restriction in the mobility of polymer chains as the consequences of
interaction at the cellulose matrix interphase. Thus hinder the free rotation of the polymeric chain [9, 15]. Table 1
also shows that the percent of crystallinity (X c ) in the composites is lower than the neat PLA and the percentage are
decreases for composites at higher loading. This implies that addition of KDC fibers produced a negative effect into
the crystallinity of biocomposites.
Normalized heat flow endo up (mW)

Tm
Tc Neat PLA
10% KDC-PLA
30%KDC-PLA
Tg
60% KDC-PLA

0 50 100 150 200

Temperature (°C)
Figure 3: Effect of KDC loading on DSC thermograms of KDC-PLA biocomposite

Composition Tg[°C] Tc[°C] Tm[°C] ΔHm[J·g–1] ΔHc[J·g–1] Xc[%]

Neat PLA 56.0 96.4 138.8 22.0 20.7 45.9
10% KDC-PLA 52.3 87.7 145.0 21.7 14.7 43.5
30% KDC-PLA 51.0 89.1 145.0 18.1 14.4 41.6
60% KDC-PLA 52.1 86.2 144.0 8.3 4.7 34.8
Table 1: DSC results for neat PLA and KDC-PLA biocompsites from the heating run.

CONCLUSIONS

This study suggests that the incorporation of cellulose derived from kenaf fibers into PLA reduces the crystallinity
of composites. Interestingly, the reduction in oxygen permeability of composites has been driven by the blocking
effect of the cellulose fiber itself. This demonstrated the potential of kenaf derived cellulose as a filler in PLA to
enhance the oxygen barrier properties of PLA.

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 World Engineering Congress 2010, 2nd – 5th August 2010, Kuching, Sarawak, Malaysia
Conference on Advanced Processes and Materials

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