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ISOLATION AND CHARACTERIZATION OF NANOCELLULOSE FROM
EMPTY FRUIT BUNCH FIBER FOR NANOCOMPOSITE APPLICATION
NURUL SAADIAH BINTI LANI
A thesis submitted in fulfilment of the

requirements for the award of the degree of
Master of Engineering (Chemical)
Faculty of Chemical Engineering

Universiti Teknologi Malaysia
AUGUST 2014
iii
To my wonderful families especially to my beloved mother and father
ACKNOWLEDGEMENTS
First and foremost, I would like to extend my heartfelt gratitude to my

supervisor, Dr Norzita Ngadi for giving me an opportunity to complete this thesis
under her supervision. I am very grateful to receive her constant guidance and time
throughout my journey in completing this research.
Furthermore, I also would like to show my appreciation to all my friends and

others who have provided assistance at various occasions as well as their useful
views and opinions regarding my postgraduate research.
Last but not least, I would also like to take this opportunity to thank my
parents for financially and morally supporting me in completing this research.
ABSTRACT
Nowadays, the demands for plastics materials are increasing rapidly.

Nevertheless, most of these products are non-environmentally friendly and nonbiodegradable. About 60 to 100 million gallons of petroleum are needed to produce
plastics every year around the world. Therefore, there has been growing interest in
developing biobased products that can offer favorable environmental advantages.
The purpose of this study is to isolate nanocellulose from empty fruit bunch (EFB)
fiber and to investigate reinforcing effect of nanocellulose in poly(vinyl alcohol)
(PVA)/starch blend films.
The optimization of acid hydrolysis conditions for
nanocellulose yield with response surface methodology (RSM) was also investigated.
Cellulose and nanocellulose fibers were successfully extracted by using alkali
treatment and acid hydrolysis, respectively. Subsequently, a series of PVA/starch
film with different content of nanocellulose were prepared by solution casting
method. The isolated nanocellulose displayed a relatively high crystallinity, which
were around 73% that consisted of rod like nanoparticles with the diameter of 4 to 15
nm. Analysis of the RSM result revealed that high nanocellulose yield (83.42%) was
obtained when the sulfuric acid concentration, hydrolysis time and reaction
temperature were set at 58 wt%, 43 minutes and 35 C, respectively. PVA/starch
films reinforced with nanocellulose fiber possessed significantly improved properties
compared to the film without reinforcement. From the results, PVA/starch films
with the addition of 5% (v/v) of nanocellulose suspension exhibited the best
combination of properties. This nanocomposite was found to have tensile strength
about 5.694 MPa and the elongation at break about 481.85%. In addition, this
nanocomposite had good water resistance (19.71% ) and biodegradability (47.73%).
It can be concluded that the nanocellulose obtained in this study can be an excellent
reinforcing material in PVA/starch blend film.
ABSTRAK
Pada masa kini, permintaan untuk bahan plastik semakin meningkat dengan
pantas. Walau bagaimanapun, kebanyakan produk ini tidak mesra alam dan tidak
terurai. Kirakira 60 hingga 100 juta gelen petroleum diperlukan untuk membuat
plastik setiap tahun di seluruh dunia. Justeru itu, terdapat minat yang semakin
meningkat dalam membangunkan penggunaan produk berasaskan bio yang
mempunyai kebaikan untuk alam sekitar. Tujuan kajian ini adalah untuk
mengasingkan nano selulosa dari serat tandan buah kosong dan mengkaji kesan
pengukuhan mereka dalam filem polivinil alkohol (PVA)/kanji. Pengoptimuman
keadaan hidrolisis asid untuk menghasilkan nano selulosa dengan menggunakan
kaedah gerak balas permukaan (RSM) juga dilakukan. Serat selulosa dan nano
selulosa telah berjaya diekstrak dengan menggunakan rawatan alkali dan hidrolisis
asid. Selepas itu, satu siri filem PVA/kanji dengan kandungan nano selulosa yang
berbeza disediakan dengan menggunakan kaedah tuangan larutan. Nano selulosa
yang telah diasingkan meunujukkan penghabluran yang secara relatifnya tinggi, iaitu
kira-kira 73% dan mempunyai bentuk seperti rod dengan diameter dari 4 hingga 15
nm. Analisis keputusan RSM mendedahkan bahawa hasil nano selulosa (83.42%)
adalah tinggi apabila kepekatan asid sulfurik, masa hidrolisis dan suhu tindak balas
diletak masing-masing pada 58 wt%, 43 minit dan 35 C. Filem PVA/kanji yang
diperkukuhkan dengan gentian nano selulosa mempunyai ciri-ciri penambahbaikan
yang ketara berbanding filem tanpa pengukuh. Daripada keputusan, filem PVA/kanji
dengan tambahan 5% (v/v) ampaian nano selulosa meunujukkan kombinasi ciri-ciri
yang terbaik. Nano komposit ini didapati mempunyai kekuatan tegangan pada kirakira 5.694 MPa dan pemanjangan pada takat putus adalah 481.85%. Sebagai
tambahan, nano komposit ini mempunyai rintangan air (19.71%) dan biodegradasi
(47.73%) yang baik. Kesimpulannya, nano selulosa yang diperoleh dalam kajian ini
boleh menjadi bahan pengukuh yang sangat baik untuk filem adunan PVA/kanji.
TABLE OF CONTENTS
CHAPTER
TITLE
PAGE
DECLARATION
ii
DEDICATION
iii
ACKNOWLEDGEMENTS
iv
ABSTRACT
ABSTRAK
vi
TABLE OF CONTENTS
vii
LIST OF TABLES
xi
LIST OF FIGURES
xiii
LIST OF ABBREVIATIONS
xvi
LIST OF SYMBOLS
xix
LIST OF APPENDICES
xx
INTRODUCTION
1.1
Background of Study
1.2
Problem Statement
1.3
Objectives of Study
1.4
Scopes of Study
1.5
Research Hypothesis
1.6
Significant of Study
LITERATURE REVIEW
2.1
Nanotechnology
2.2
Composite
11
viii
2.2.1 Matrix
12
2.2.2 Reinforcement
15
Polyvinyl Alcohol
18
2.3.1 Physical Properties
18
2.3.2 Composite based on Polyvinyl Alcohol
19
Starch
22
2.4.1 Composite based on Starch
24
2.5
PVA/Starch Blend
26
2.6
Natural Fiber
29
2.6.1 Chemical Composition
33
2.6.2 Physical Structure
36
2.7
Empty Fruit Bunch Fiber
38
2.8
Extraction of Cellulose
40
2.8.1 Bleaching Process
40
2.8.2 Alkali Treatment
41
Nanocellulose Fiber
42
2.9.1 Isolation of Nanocellulose Fiber
46
2.9.1.1 Acid Hydrolysis
47
2.3
2.4
2.9
2.9.2 Nanocellulose Reinforced Composite
50
2.10
Nanocomposite based on PVA/Starch
53
2.11
Response Surface Methodology
56
METHODOLOGY
58
3.1
Introduction
58
3.2
Materials
60
3.2.1 Polyvinyl Alcohol
60
3.2.2 Starch
60
3.2.3 Natural Fiber
60
3.2.4 Other Chemicals
61
3.3
61
3.4
Isolation of Nanocellulose Fiber
62
3.5
Characterization of Fiber
62
62
3.5.2 Fourier Transform Infrared Spectroscopy
65
ix
3.5.3 XRay Diffraction (XRD)
65
3.5.4 Thermogravimetric Analysis (TGA)
66
3.5.5 Field Emission Scanning Electron Microscope

(FESEM)
66
3.6
3.7
66
Optimization on Nanocellulose Yield
67
3.6.1 Screening Test
67
3.6.2 Statistical Design
67
PVA/Starch Filled with Nanocellulose Fiber

Film Preparation
68
Characterization of Nanocomposite
69
3.8.1 XRay Diffraction (XRD)
69
3.8.2 Scanning Electron Microscopy (SEM)
70
3.8.3 Mechanical Test
70
3.8.4 Water Absorption Test
71
3.8.5 Soil Burial Degradation Test
72
Comparative Study
72
RESULTS AND DISCUSSION
73
4.1
Introduction
73
4.2
Characteristics of Fibers
74
74
4.2.2 Fourier Transform Infrared Spectroscopy
76
4.2.3 XRay Diffraction
78
4.2.4 Thermogravimetric Analysis
81
3.8
3.9
3.5.5 Transmission Electron Microscope (TEM)
4.2.5 Field Emission Scanning Electron Microscopy 83
4.3
4.2.6 Transmission Electron Microscopy
86
87
4.3.1 Screening of Hydrolysis Conditions
88
4.3.1.1 Effect of Acid Concentration
88
4.3.1.2 Effect of Hydrolysis Time
90
4.3.1.3 Effect of Reaction Temperature
91
4.3.2 Response Surface Methodology

4.3.2.1 Statistical Analysis
92
93
x
4.3.2.2 Verification of Predicted Model
4.4
4.5
4.6
97
Characteristics of PVA/Starch Blend Film
98
4.4.1 Mechanical Properties
98
4.4.2 Water Absorption
101
4.4.3 Biodegradation Properties
104
Characteristics of PVA/Starch Nanocomposite
105
4.5.1 Mechanical Properties
105
4.5.2 Water Absorption
108
4.5.3 Biodegradation Properties
109
Comparative Study
111
CONCLUSIONS AND RECOMMENDATIONS
115
5.1
Conclusions
115
5.2
Recommendations
117
REFERENCES
119
Appendices AG
140166
LIST OF TABLES
TABLE NO.
TITLE
PAGE
2.1
Packaging applications of nanomaterials
11
2.2
Main characteristics of thermosets and thermoplastics
13
2.3
Physical properties of polyvinyl alcohol
19
2.4
Rate of glucose production and percentage of starch

hydrolysis from each PVA/starch substrate
28
2.5
Characteristics of natural fibers
32
2.6
Chemical composition of some typical cellulose

containing materials
33
2.7
Nutrient content of EFB
39
2.8
Comparison between nanocrystal and MFC
43
2.9
Preparation of nanocellulose from different sources

and isolation methods
45
Characteristics of NR and NR/CW nanocomposite

films reinforced with 2.5 and 7.5wt%
52
3.1
The parameter values for screening test
67
3.2
The composition of PVA, starch, glycerol and

nanocellulose fiber
69
2.10
xii
4.1
Chemical composition of the EFB fiber in different

stages
75
Effect of sulfuric acid concentration on the yield of

nanocellulose
88
Effect of different hydrolysis time on the yield of

nanocellulose
90
Effect of different reaction time on the yield of

nanocellulose
91
4.5
Code and level of factors chosen for RSM design
92
4.6
Experimental design and results
93
4.7
Analysis of variance (ANOVA) for nanocellulose yield
94
4.8
Regression coefficients and p value of second-order

polynomial model for nanocellulose yield
95
Experimental value using optimum conditions for

nanocellulose yield
97
Water absorption of pure PVA, PVA/starch,

PVA/starch/cellulose and
PVA/starch/nanocellulose composite
112
4.2
4.3
4.4
4.9
4.10
LIST OF FIGURES
FIGURE NO.
TITLE
PAGE
2.1
Classification of matrices
12
2.2
Types of reinforcement in composites
15
2.3
Production of starches and starch derivatives
23
2.4
Possible hydrogen bond formation between starch

and PVA
26
2.5
SEM of fracture of (a) starch film (b) starch/PVA film
28
2.6
Schematic representation of plant biofiber

classification
30
Capacity, production, import, export and demand of

natural fibers in Asian region
31
2.8
Chemical structure of cellulose
34
2.9
Structure of natural fiber
36
2.10
(a) EFB; (b) EFBF
39
2.11
Schematic structure and TEM image of (a) cellulose

nanocrystal and (b) microfibrillated cellulose
44
2.12
The main steps involved in the preparation of cellulose
46
2.13
SEM of fractured surface of TPS reinforced (a) 0 wt%

and (b) 20 wt%
53
2.7
xiv
3.1
Flowchart of laboratory work
59
4.1
Photograph of (a) EFB fiber, (b) cellulose fiber, and

(c) nanocellulose fiber
74
FTIR spectra of (a) untreated fiber, (b) cellulose, and

(c) nanocellulose
76
X-ray diffraction patterns for (a) untreated fiber,

(b) cellulose, and (c) nanocellulose
79
Thermogravimetric curves of (a) untreated fiber,

(b) cellulose, and (c) nanocellulose
81
FESEM images raw EFB fiber at (a) 80 (b) 1000

(c) 8000 and 80000 magnification level
83
FESEM images cellulose fiber at (a) 80 (b) 1000

84
FESEM images nanocellulose fiber at (a) 80 (b) 1000

84
4.8
TEM image of nanocellulose from EFB fiber
86
4.9
Pareto chart showing the standardized effect of

independent variables and their interaction on the
nanocellulose yield
96
Tensile strength and elongation at break for PVA/starch

blend films
98
Surface morphology of (a) pure PVA fim (b) 70:30

PVA/starch blend film and (c) 50:50 PVA/starch blend
film
100
Percentage of water absorption capacity for PVA/starch

blend films
101
4.13
Xray diffraction pattern of the composite films
103
4.14
Degradability of PVA/starch blend films in the soil

burial test
104
4.2
4.3
4.4
4.5
4.6
4.7
4.10
4.11
4.12
xv
4.15
4.16
4.17
4.18
4.19
4.20
The dependence of the tensile strength and elongation

at break on the nanocellulose content
106
SEM image of the surface of (a) PVA/starch blend film,

(b) PVA/starch reinforced with 5% (v/v) nanocellulose
film and (c) PVA/starch reinforced with 20% (v/v)
nanocellulose film
107
Percentage of water absorption capacity for

PVA/starch reinforced with nanocellulose fiber at
different amount
118
Degradability of PVA/starch nanocomposite films in

the soil burial test
110
Mechanical properties of pure PVA, PVA/starch,

PVA/starch/cellulose and PVA/starch/nanocellulose
composite.
111
Degradation properties of pure PVA, PVA/starch,

PVA/starch/cellulose and PVA/starch/nanocellulose
composite.
112
LIST OF ABBREVIATION
AFM
Atomic Force Microscope
AOX
Adsorbable Organic Halide
AMG
Amyloglycoside
ANOVA
Analysis of Variance
ASTM
American Society for Testing and Materials
BCC
Bamboo Cellulose Crystal
Ca
Calcium
CBN
Cassava Bagasse Cellulose Nanofiber
CCD
Central Composite Design
CMC
Carboxymethyl cellulose
COD
Chemical Oxygen Demand
CW
Cellulose Whisker
DMA
Dynamic Mechanical Analyzer
EMC
Equilibrium Moisture Content
EFB
Empty Fruit Bunch
FESEM
Field Emission Scanning Electron Microscope
FMP
Fish Myofibrillar Protein
xvii
FTIR
Fourier Transform Infrared
JNF
Jute Nanofibril
KBr
Potassium Bromide
KOH
Potassium Hydroxide
LDPE
Low Density Polyethylene
MFC
Microfibrillated Cellulose
Mg
Magnesium
MMC
Metal Matrix Composite
MS
Mean Square
NaCIO2
Sodium Chlorite
NaOH
Sodium Hydroxide
NFC
Nanofibril Cellulose
NR
Natural Rubber
OPT
Oil Palm Trunk
OPF
Oil Pam Frond
PALF
Pineapple Leaf Fiber
PFF
Presses Fruit Fiber
PHB
Poly-3-hydroxybutyrate
POME
Palm Oil Mill Effluent
PP
Polypropylene
PVA
Polyvinyl Alcohol
PU
Polyurethane
xviii
RSM
SEM
Scanning Electron Microscope
SiO2
Silicon Dioxide
SPI
Soy Protein Isolate
SPU
Segmented Polyurethane
TEM
Transmission Electron Microscope
TPS
Thermoplastics Cassava Starch
WAC
Water Absorption Capacity
WVP
Water Vapor Permeability
WVTR
Water Vapor Transmission Rate
XRD
XRay Diffraction
LIST OF SYMBOLS
Ea
Activation energy
kg/m3
kilogram per cubic meter
mL
milliliter
mg/L
milligram per liter
MPa
megapascal
macrometer
w/v
weight per volume
degree celcius
percentage
LIST OF APPENDICES
APPENDIX
TITLE
PAGE
Calculation of chemical composition of fiber
140
Calculation of crystallinity index of fiber
142
Images of nanocellulose suspension at different

hydrolysis conditions
143
Intensity of particle size distribution
145
Experimental data of tensile strength
152
Experimental data of water absorption
160
Experimental data of degradation rate
165
CHAPTER 1
INTRODUCTION
1.1
Background of Study
In recent years, many researchers have shown considerable interest for the
incorporation of nanocellulose fibers as reinforcement. The applications of nanoscale
particles in composite processing are also expected to have achieved a significant
improvement on the environmental issue as this nanocellulose reinforcement could
develop a more biodegradable plastic. This is due to the fact that the usage of non
biodegradable plastics nowadays contributes to about one quarter of all domestic
trash in landfill sites. Moreover, the process to manufacture plastics are often
involves the use of toxic and environmentally harmful chemicals. Therefore, it is
quite important to develop composites that can be easily and completely degraded
and also produced from renewable resources.
2
Polyvinyl alcohol (PVA) has been considered as a suitable source of
materials for the composite production because of its benefits of being nontoxic and
highly durable. Besides that, PVA is a synthetic polymer that can be fully
biodegradable in the environment. However, the applications of PVA materials are
limited due to their high cost and slow degradation process especially under
anaerobic condition (Takasu et al., 2002). To overcome these limitations, PVA is
often blended with other cheap and biodegradable polymers.
By blending with other renewable polymers, it will improve PVAs

biodegradation rate and lowers the overall cost. Among the different types of
biopolymer available, starch is well known as the most abundant raw materials and
relatively cheap. Previous studies have reported that blending of PVA and starch can
enhance their tensile strength, elongation and toughness (Guohua et al., 2006; Mao et
al., 2002; Rahman et al., 2010; Russo et al., 2009; Sin et al., 2010). In addition,
starch has been successfully blended with PVA due to the presence of hydroxyl
groups in both PVA and starch molecules, which tend to form strong hydrogen
bonding and relatively good compatibility of PVA and starch (Tang and Alavi,
2011). However, the major disadvantages of these PVA/starch blends are particularly
poor water barrier properties, generally attributed to the very large number of
hydroxyl groups along with their intrinsic hydrophilicity. Therefore, several studies
have proposed the incorporation of fillers in a nanoscale size into PVA/starch blends
in order to improve their water barrier properties.
Most of the attention so far has focused on the preparation of nanoparticles

from natural fibers. Natural fibers has attracted growing interest because of their
unique characteristics, including low cost, lower density, high specific strength, good
thermal properties and biodegradable.Oil palm empty fruit bunch (EFB) fiber is a
natural fiber which has great relevance to Malaysia, as a large quantity of the
biomass is generated by oil palm industries. In 2012, it is estimated that around
18.79 million tons of crude palm oil and 70 million tons of biomass residue are
produced in the oil palm industry in Malaysia (Aljuboori, 2013). In addition, the
total crop of fresh fruit bunch is approximately 92.78 million tons per year, which
3
generate more than 20 million tons of EFB(Wan-Razali et al.,2012). Approximately
only 10% of the EFB is used and the rest are abundant.This residue may cause many
environmental problems. Therefore, there is huge potential for EFB to be exploited
in the production of high value-added products, which not only complies with zerowaste strategy but also generated additional profits for the palm oil industry.
Therefore in this study, cellulose was extracted from palm oil empty fruit
bunch (EFB) fiber via alkali treatment method while the isolation of nanocellulose
was done by acid hydrolysis method. A large number of treatments to extract
highlypurified cellulose fibers have already been reported. The most common
treatment is mercerization method, which is also known as alkali treatment. The
important point to note regarding alkali treatment is their capability to remove certain
amount of noncellulosic impurities on the fiber surface by disrupting the hydrogen
bonding in the network structure (Li et al., 2007).
Meanwhile, a comprehensive research and review article dealing with

isolation of cellulose fiber in nanoscale size by sulfuric acid hydrolysis was
published by many researchers (Araki et al., 1999; Cho and Park, 2011; Fahma et al.,
2011; Luduena et al., 2011; Mandal and Chakrabarty, 2011; Morais et al., 2012;
Morn et al., 2008; Revol et al., 1992; Rosa et al., 2012). Controlled acid hydrolysis
of native cellulose fibers disrupts the fibers which can then be dispersed into their
constituent rodshaped elementary crystalline microfibrils.During acid hydrolysis,
the amorphous regions in native cellulose are more accessible to acid and more
susceptible to hydrolytic action than the crystalline domains. Therefore, acid
hydrolysis of cellulose is a wellknown process used to remove amorphous regions.
4
Subsequently, nanocellulose that are isolated from EFB fiber was used as
reinforcement in composite films. In this study, two series of PVA and starch blend
films were prepared and characterized. The first series was based on only PVA and
starch in different ratios, as follows: 80% PVA/20% starch, 70% PVA/30% starch,
60% PVA/40% starch, 50% PVA/50% starch, and 40% PVA/60% starch. The
second series contain5, 10, 15 and 20% (v/v) of nanocellulose suspension with
respect to the volume of PVA and starch solution. The ratio between PVA and starch
was chosen based on mechanical properties, water absorption and biodegradation
properties that yield optimum results in the first series.
1.2
Problem Statement
Nowadays, the demands of plastics materials are increasing rapidly. The

application of plastics materials includes aeronautics, building and construction,
electronic device, packaging, automotives and medical devices. However, most of
these products are non-environmentally friendly and nonbiodegradable. Moreover,
all these plastics residues are mainly discarded into the landfill and frequently the
causes of pollution as well. The high usages of plastics are leading to serious
environmental pollution, a problem that has to be faced by all societies.
Nevertheless, there is an alternative to reduce the environmental problems

caused by plastics. For example, the production and application of biodegradable
composites based on biodegradable resources such as natural fiber can be pursued to
provide benefits to the environment with respect to the degradability. However,the
most serious concerned problem with natural fibers is its hydrophilic nature, which
tends to prevent better dispersion of the fibers into the matrix. Therefore, to
overcome this challenge, fiber treatment process is one of the common alternatives
that can be used to modify the fiber surface topology.
5
The need for PVA composites has never been as prevalent as it currently is.
PVA offers high tensile strength and flexibility as well as excellent film forming.
However, this synthetic polymer has important drawback that need to be addressed,
which is their degradation rate. Therefore, blending with starch would help to
improve the biodegradable properties. In the meantime, nanoreinforced starch/PVA
blends are not widely studied compared to starch nanocomposites and PVA
nanocomposites.Furthermore, most of the previous studies have investigated the use
of nanofillers such as nano silicon dioxide (Xiong et al., 2008; Abbasi, 2012),
montmorillonite clay (Ardakani and Nazari, 2010; Spiridon et al., 2008), sodium
montmorillonite clay (Taghizadeh et al., 2012) and nanoparticles of poly(methyl
methacrylatecoacrylamide) (Yoon et al., 2012). However, these nanoparticles had
no significant influence on biodegradability of films. For that reason, this research
was conducted for the purpose of improvement in the properties of PVA and starch
blend by using nanocellulose from EFB fiber as reinforcement.
1.3
Objective of Study
The objectives of this study are:
i. To extract and characterize cellulose and nanocellulose from oil palm empty
fruit bunch fiber
ii. Toperform an optimization study on nanocellulose yield
iii. To study the effect of varying the PVA, starch and nanocellulose content on
the composites properties
iv. To compare the properties of composites between pure PVA film,
PVA/starch blend film, PVA/starch reinforced with cellulose composite
film and PVA/starch reinforced with nanocellulose composite film.
6
1.4
Scope of Study
Once the objective is decided, it is necessary to determine the scopes that will
limit the range of the study. This study was firstly focused on the extraction of
cellulose from empty fruit bunch fiber. The cellulose from empty fruit bunch fiber
was extracted by using alkaline method, whereby the experimental conditions were
fixed according to the method used by Moranet al. (2008). Meanwhile, the
nanocellulose was isolated from obtained cellulose by using acid hydrolysis method,
whereby the hydrolysis conditions were fixed at 60wt% sulfuric acid solutions and
reaction temperature at about 45C with hydrolysis time of 30 minutes under strong
agitation (Moranet al., 2008). After that, the extracted cellulose and nanocellulose
were characterized by using Fourier transform infrared spectroscopy (FTIR), field
emission scanning electron microscopy (FESEM), x-ray diffraction (XRD) and
thermogravimetric
analysis
(TGA).
Furthermore,
the
nanodimensions
of
nanocellulose were determined using a transmission electron microscope (TEM).
For the optimization study, the central composite design (CCD) method was
used to determine the relationshipbetween hydrolysis conditions on maximum yield
of nanocellulose.Prior to optimization study, a preliminary screening test was
conducted to determine trends in the yields of nanocellulose. The yield of
nanocellulose was measured as a function of acid concentration, hydrolysis time and
reaction temperature, whereby the sulfuric acid concentration in the range of 4585
wt%, hydrolysis time from 30 to 90 minutesand reaction temperature between 25 and
65Cwere used as hydrolysis conditions.
The third part of this study covered the production of PVA/starch blend films.
The starch used in the blend was a corn starch, whereby corn starch has higher
amylose content compared to other types of starch, around 28%.High amylose
content in starch is known to produce films with better mechanical properties (Yun
and Yoon, 2010). This experiments were done by mixing PVA with starch by
varying the blend ratio of PVA:starch, which is 80:20, 70:30, 60:40, 50:50 and
7
40:60. Glycerol was used as a plasticizer, in which it was added to the mixed solution
at a 30 wt% ratio based on total weight of starch and PVA (Yao et al., 2011). The
mixing temperature and time were fixed at 97C and 2 hours, respectively (Rahman
et al., 2010). The effect of varying the PVA and starch content on the composites
properties was analyzed according to their mechanical properties, water absorption
and biodegradation properties.
The effectiveness of the nanocellulose fibers as reinforcementwas tested in

the PVA/starch blend solutions. In this study, content of nanocellulose was varied
from 0 to 20% (v/v) of nanocellulose suspension with respect to the volume of PVA
and starch solution. Nanocomposite films reinforced with nanocellulose fibers were
characterized according to their mechanical properties and water absorption while
the biodegradation of films were carried out by using the soil burial test.
In the comparative study, 5% (v/v) cellulose reinforced PVA/starch

composite was produced. Therefore, a comparison was made between pure PVA
film, PVA/starch blend film, 5% (v/v) cellulose reinforced PVA/starch composite
and 5% (v/v) nanocellulose reinforced PVA/starch nanocomposite based on their
mechanical properties, water absorption and degradation properties.
1.5
Research Hypothesis
Nanocellulose can be successfully isolated from empty fruit bunch fiber by

acid hydrolysis and their incorporation as reinforcement can result in an
improvement in polyvinyl alcohol/starch blend film.
8
1.6
Significance of Study
The finding of the research is important to discover the performance of

nanocellulose fiber as reinforcing materials in polymer composites due to their large
surface area and the nanoscale dimensions. Therefore, it can provide the
opportunity for nanoengineered materials in composite processing that could have
not achieved from conventional materials.
Apart from that, this research will also contribute on improving the properties
and biodegradation of nanocomposite. Their good mechanical performance showed
the potential replacement to glass fiber composite in the emerging advanced
composite market. It may give the plastics industry a more economic solution in
managing the environmental problems caused by conventional synthetic plastics.
CHAPTER 2
LITERATURE REVIEW
2.1
Nanotechnology
Recently, nanotechnologies along with bioproduct have attracted significant

scientific attention due to their environmental advantages, together with the
manufacture of new products with enhanced properties. Nanotechnology is defined
as the manufacture and use of materials which have at least one of its dimensions is
lower than 100nm. When compared between nanoparticles and their microscale
counterpart, nanoparticles have larger surface area and more surface atoms. The
concept of nanotechnology was first introduced by Richard Feynman at a meeting of
the American Physical Society in 1959 (Khademhosseinin and Langer, 2006). Since
then, many researchers have investigated the use of nanotechnology in industrial
field.
There are great numbers of potential applications of nanotechnology within

different industrial. These applications includes pharmaceutical applications, water
treatment industry, new materials for electronics, composites for construction and
industrial coating, fields of consumer goods such as food industry, household,
textiles, cosmetics, agriculture sector and sports. Some water treatment devices
10
incorporating nanotechnology offer an effective and reliable method to develop in
water treatment industry. In addition, nanotechnology has the potential to make
construction faster, cheaper, safer and more varied.
Nanotechnology has been widely used in the medical field for diagnostic,
drug delivery and tissue engineering application. As indicated by Cherian et al.
(2011), the produced nanocellulose and its composites have been utilized for
applications in medical field. These include cardiovascular implants, scaffolds for
tissue engineering, repair of articular cartilage, vascular grafts, urethral catheters,
mammary prostheses, penile prostheses, adhesion barriers and artificial skin.
Furthermore, the developed material can also be used for construction of nonlatex
condoms, breathable wound dressing, surgical gloves, surgical gowns or drapes,
medical bags, organ retrieval bags and medical disposables.
The uses of nanotechnology in food packaging have developed over the

centuries. Nanotechnology can be applied in the production, processing, safety and
packaging of food. Packaging is used to keep the product from surrounding and to
maintain the food product quality.
The levels of chemical migration from the
packaging have to be lower than control safe level (Barnes et al., 2007), or otherwise
the food might be contaminate and consequently risk the consumer safety.
Moreover, another issue and consideration is the severe problems created by food
packages to the environment. Table 2.1 gives an overview of the applications of
nanomaterials in food packaging materials (Bradley et al., 2011).
11
Table 2.1: Packaging applications of nanomaterials (Bradley et al., 2011)
Application
Features
Incorporating nanomaterials into the packaging to improve
Nanocomposites
physical performance, durability, barrier properties,

biodegradation
Incorporating nanomaterials onto the packaging surface,
Nanocoatings
either the inside or the outside surface, or a sandwiched as a

layer in a laminate, to improve especially the barrier
properties
Surface biocides
Incorporating nanomaterials with antimicrobial properties

acting on the packaging surface
Incorporating nanomaterials with antimicrobial or other
Active packaging
properties with intentional release into and consequent

effect on the packaged food
Intelligent
Incorporating nanosensors to monitor and report on the
packaging
condition of the food.
2.2
Composite
Composites can be defined as engineered materials that consists two or more

constituents, whereby each of them exhibit different chemical composition and
physical structure and are essentially insoluble in each other. They have been widely
used in numerous industrial applications such as transportation, infrastructure,
construction, electrical, aircraft and aerospace, etc. One of the main advantages of
composites is the ability to choose the materials and manufacturing method to meet
the design requirement of an application.
There are two types of constituent
materials, which are known as matrix and reinforcement components
12
2.2.1
Matrix
The matrix in the material surrounds and supports the reinforcement

component by retaining their shape and relative positions as well as helping to
protect the reinforcement from environmental damage (Baker et al., 2004). Figure
2.1 shows the classification of matrices in composite materials.
Matrices
Polymer
matrix
materials
Thermosets
Metal
matrix
materials
Ceramic
matrix
materials
Carbon and
Graphic matrix
materials
Thermoplastics
Figure 2.1: Classification of matrices (Baker et al., 2004)
Polymers are one of the most popular matrix materials widely used in
composites.
The main advantages of using polymer as a matrix because the
fabrication methods involve are simple and relatively low cost, as it does not require
high temperatures and high pressures (Matthews and Rawlings, 1999). Polymers,
which are also known as macromolecules, are large molecules that are composed by
repetitive linking of many smaller units called monomers. A typical polymer may
include tens of thousands of monomers. The two most common classifications of
polymers are thermoset and thermoplastic materials.
One important difference
between those two polymers is that the thermosets become hard when subjected to
above a particular temperature and pressure or addition of appropriate chemical
agents, whereas thermoplastics becomes soft and are able to be shaped and molded
upon heating (Chawla, 1998; Matthews and Rawlings, 1999).
Examples of
13
thermosets include epoxy, vinyl ester and unsaturated polyester, while for
thermoplastic polymers include polyethylene, polypropylene, polyvinyl chloride,
nylon and acrylics. The main characteristics of thermosets and thermoplastics are
summarized in Table 2.2 (Baker et al., 2004).
Table 2.2: Main characteristics of thermosets and thermoplastics (Baker et al., 2004)
Thermosets
Undergoes chemical changes when

cured
Low strain to failure
Low fracture energy
Processing is irreversible
Very low viscosity possible
Absorbs moisture
Highly resistant to solvents
Thermoplastics
Nonreacting, no cure required
High strain to failure
High fracture energy
Very high viscosity
Processing is reversible
Absorbs little moisture
Limited resistance to organic
solvents, in some cases
Metal matrix composite (MMC) is made by dispersing a reinforcing

material into a metal matrix. Many different metals have been employed in MMC
such as aluminium (Tjong and Ma, 1997; Ding et al., 2003; Urea et al., 2004),
magnesium (Lim et al., 2003; Wang et al., 2007; Wang et al., 2010), titanium
(Gundel and Wawner, 1997; Thomas and Winstone, 1999), copper (Korb et al.
,2002; Luo et al., 2007) and superalloy (Mamalis et al., 1981; Nardone, 1994),
reinforced with most usually SiC or Al2O3 either in the form of continuous and
discontinuous fibers, short fibers, whiskers or particles. Composites, consisting of a
metal as matrix have been widely used in automotive and aerospace industry because
of their high temperature mechanical properties and are able to reduce weight by
approximately 25% (Iuliano et al., 1998).
However, there are some of the
disadvantages of MMCs compared to polymer matrix composites, which are

expensive production system, relatively immature technology, complex fabrication
method and limited experience of services dedicated to production.
14
Warren (1992) defined ceramics as a solid, crystalline and inorganic materials
which composed by nonmetallic compounds or mixture of such compounds. Their
chemical bonding is generally a hybrid of ionic and covalent, whereby their ionic
bonds and some covalent bonds are very strong. Ceramic materials have a very high
melting point and temperature stability, and therefore have emerged as a very best
candidate for high temperature applications compared to metal matrix material.
Apart from this, ceramic materials are also known for its good corrosion resistance,
excellent wear resistance and high compressive strength (Warren, 1992; Chawla,
2003). These properties make them suitable in a broad field of applications such as
gas sensor, thermal barriers, gas turbine, aircraft brakes, turbine nozzles and high
temperature superconductor (Ohnabe et al., 1999).
However, the manufactured
composites by ceramic matrix materials would present poor mechanical properties,

as they do not deform plastically under tensile and impact loading.
Carbon materials exhibit high corrosion resistant and more lightweight

compared to those of metals (Chung, 2003) and thus, make it suitable to employ in
the preparation of thermal conductive composites. As their sublimation temperature
is high, they are becoming increasingly useful as matrix for very high temperature
composite applications. Another matrix material that capable of withstanding very
high temperatures under ablative environment and inert atmosphere is graphite
(Kelly, 1989). The compatibilization of carbon or graphite matrix with their own
filler provides composites, which have been known as carboncarbon composites.
Despite its many benefits, these composites have very low oxidation resistance, high
fabrication cost and insufficient engineering data base (Chung, 1994).
All these types of matrix materials have their own advantages and
disadvantages. Of these, polymer matrix composite is very popular due to their low
cost and simple fabrication methods. Other desirable properties include their light
weight, superior mechanical properties and ease of forming make them the preferred
and ideal material for many engineering applications.
15
2.2.2
Reinforcement
The reinforcement materials are used to improve the overall physical and
mechanical properties of composites. Furthermore, they also provide the strength
and rigidity to matrix as well as enhancing its heat, conductivity and corrosion
resistance. The strength and stiffness of reinforcement is generally higher than the
matrix. Reinforcement in a composite can be present in a number of different forms,
classified according to their shape, aspect ratio, direction and geometric arrangement
as shown in Figure 2.2.
Reinforcements
Fibers
Filled
Particle filled
Whiskers
Flake
Particulates
Microspheres
Solid
Hollow
Figure 2.2: Types of reinforcement in composites (Gupta, 2005)
The utilization of fibers as reinforcing agents has been widely used in

engineering applications as they provides the structural performance required of the
composites. Fibers can be classified into a large class comprising both natural and
synthetic materials, and each material has its own properties. Synthetic fibers such
as glass fiber, aramid and carbon have many advantages, including high strength and
good heat resistance. However, these kinds of fibers have caused in environmental
problems due to their partial combustibility and nonbiodegradable properties
(Shanks et al., 2004). Therefore, extensive research has been reported to replace
16
synthetic fibers by natural fibers and use them as reinforcement such as kenaf fiber
(Nishino et al., 2003; Zampaloni et al., 2007; Ochi, 2008), empty fruit bunch fiber
(Khalid et al., 2008; Tan et al., 2011), jute fiber (Mansur and Aziz, 1982; Liu et al.,
2009), pineapple leaf fiber (Mangal et al., 2003; Arib et al., 2006), sisal fiber
(Prasantha-Kumar et al., 2000; Fung et al., 2003) and others. Apart from this, fibers
reinforced composites can be divided in terms of its influences by its length, shape,
volume fraction, orientation and composition of the fibers.
Filledcomposite are a kind of the most widely used composites materials,

which are prepared by combination of matrix and filler materials. The filler material
will replace a portion of the matrix and therefore, leads to great improvement of
selected mechanical properties of the matrix resin and achieve the desired
performance of composites.
Microspheres are spherical particles with typical
diameters between 10 and 150 m (Berthelot, 1999). The advantages offered by

microspheres include increase smoothness, abrasion resistance, and chemical
resistance (Murphy, 2001), with smallest ratio of surface area to volume and low oil
absorption. Microspheres can be characterized into two types according to their
form, which are solid and hollow. These solid and hollow microspheres can be made
of glass, carbon or ceramic. Compared to solid, hollow microspheres have a much
lower density. However, the major problems associated with the use of hollow
microspheres refer to the fact that their resistance to crushing is very low, thus
making manufacturing process possible at low pressure (Berthelot, 1999).
Whiskers typically have a rodlike highly crystalline nanoparticles and due

its crystal structure, a whiskers exhibit outstanding tensile strength and a very close
to the binding force of adjacent atoms. Furthermore, the whiskers were very short,
with a small diameter and thus very low degree of internal defects such as
dislocations can occur (Yu et al., 2000). In particular, it has been noted that the
incorporation of whisker as reinforcement can influence the strength and stiffness, as
well as fracture toughness. However, whiskers are brittle and tend to break up into
shorter lengths during processing. This reduces their reinforcement efficiency and
makes the much higher cost o whisker reinforcement. Another disadvantage of using
17
whisker reinforcement is that whiskers tend to become oriented by some processes,
such as rolling and extrusion, producing composites with different properties in
different directions.
Meanwhile, there are three main types of flakes used as reinforcement in

composites, which are glass flakes, mica flakes and metal flakes. The excellent
moisture, gas and chemical transport barrier properties of composites are achieved by
the distribution of the flakes in the matrix (Mukhopadhyay, 2001). Metal flakes
conduct electricity and heat well due to the fact that they are in close contact with
each other in matrix, whereas glass and mica flakes have generally good electrical
and heat resistance.
Disadvantages of these types of reinforcement are their
difficulty to be oriented and only a limited number of materials are available for use.
In addition, they fall short of expectations because lack of control of size, shape and
show defects in the end product (Gupta, 2005).
Particulates reinforced composites are known as the dispersion of particles of

one material in a matrix of another material (Srinivasan, 2010). They present several
advantages such as lower density, higher thermal conductivity and elastic modulus,
higher resistance to electricity, and improved strength and hardness as well as
toughness.
Generally, the strength of particulates reinforced composites are
influenced by particles size, interparticles distance and volume fraction of the

composites. In another study, Akovali (2001) stated that the various effects of
particulates on the matrix have been due to the differences in properties between
them. Addition of ductile particles in a brittle matrix has resulted in an increase in
toughness meanwhile, hard particles dispersed in a ductile matrix increase strength
and stiffness.
However, the use of particulates reinforced composite is limited
because of the micro damage nucleation mechanism during the early stage of
deformation process including cracking of particles, fracture of matrix and interfacial
debonding between particles and matrix (Chen et al., 2003; Tohgo and Itoh, 2005).
18
In comparison to other reinforcements, natural fibers have received
increasing attention both by the academic sector and the industry because of their
advantages. They are renewable resources, cheaper, pose no health hazards and also
provide a solution to environmental pollution by finding new uses for waste
materials. Furthermore, the cellulose whiskers obtained from natural fibers have
become one of the new classes of materials which seem to have a very good
reinforcing effect on the final properties of composites.
2.3
Polyvinyl Alcohol
2.3.1
Physical Properties
Polyvinyl alcohol (PVA) is manufactured by the hydrolysis of polyvinyl

acetate in the reaction as shown in Equation 2.1.
CH2 CH CH2 CH
OAc
NaOH
H2O
CH2 CH CH2 CH
OAc
OH
+ NaOAc
OH
(2.1)
The percentage of hydrolysis of PVA refers to the amount of the acetate

groups converted to hydroxyl groups in the reaction. Therefore, higher degree of
hydrolysis means that the fewer acetate groups remain in the molecules. The degree
of hydrolysis of PVA influences the PVA polymer properties such as its degree of
polymer crystallinity and the solubility of PVA in water. In addition, the physical
properties and biodegradability of PVA also depends on the degree of hydrolysis
(Bohlmann, 2005).
19
PVA is an odorless and white colored granular powder. This polymer can be
soluble in hot water but not in the cold water. Generally, PVA is used in many
applications by dissolving PVA in water solutions. PVA also offers various benefits
over the other polymers, such as high mechanical strength and tear resistance.
Furthermore, PVA polymer has very good adhesion to waterabsorbent and porous
surfaces. Table 2.3 shows the physical properties of polyvinyl alcohol.
Table 2.3: Physical properties of polyvinyl alcohol (Durairaj and Sittaramane, 2012)
Form
Color
Hydrolysis, mole %
Saponification Number
Residual polyvinyl acetate, weight %
Viscosity, mPa.s
Solution pH
Volatiles, % max
Ash (as Na2O), % max
Bulk density, kg/m3
Specific gravity
Resin density, kg/m3
Specific volume, m3/kg
Refractive index
Hardness, Shore unplasticized
Specific heat, J kg/K
2.3.2
Granular
White
99.0 99.8
3 12
0.5 1.8
27 33
5.0 7.0
5
1.0
400 432
1.30
1294
7.7 10-4
1.54
> 100
1674
Composite based on Polyvinyl Alcohol
As indicated by Masuhiro et al. (1994), PVA is well known as a water

processable polymer. Nowadays, the use of PVA particularly in commercial industry
has arisen worldwide. This is due to their unique chemical and physical properties,
as well as being nontoxic, highly crystalline, and watersoluble polymer and has
good filmforming and high hydrophilic properties. However, PVA as a soluble
20
polymer has not been successful to be used in the treatment of wastewaters. Thus, it
has to be converted to a completely insoluble material with high mechanical
properties.
PVA is highly recognized as a biodegradable polymer, whereby

microorganisms and enzymes consume a substance in the natural environment, as
presented by Chiellini et al. (1999). Due to its biodegradability nature, PVA is
suitable to be used as biomaterials to replace the current synthetic packaging
materials, thus can be able to reduce the environmental impacts caused by non
biodegradable plastics.
In addition, PVA is a hydrophilic polymer.
This
characteristic makes them ideal candidates for the production of hydrogel in the
pharmaceutical field typically as drug delivery medium. PVA hydrogel has high
degree of swelling with low selectivity of drugs and bioactive agents (Constantin et
al., 2004). However, the main disadvantage of PVA is their price which is quite
expensive. Therefore, PVA can be blended with others natural polymers such as
starch, cellulose, chitin and chitosan, soy protein, wheat protein, egg protein, lignin
and sodium alginate, in order to reduce the materials costs, and thus make PVA more
economical to use.
Starch is one of the most widely used in blends with PVA as PVA/starch
blend would increase biodegradability of PVA. It has been scientifically proven
through extensive worldwide studies by many researchers (Ishigaki et al., 1999;
Russo et al., 2009; Tudorachi et al., 2000; Yun et al., 2008). Similarly, Azahari et
al. (2011) highlighted that the degradable properties of composite increases with
increasing in starch content whereas for the strength of composite it significantly
decreased. As reported by Sreekumar et al. (2012), they concluded that the best
compatibility between PVA and starch was recorded at blend ratio of 70:30. The
degree of compatibility was, however, decreased by increasing the starch content. An
earlier study by the same researchers, Sreekumar et al. (2012) have demonstrated the
effects of glycerol content on the properties of PVA/starch blend. On another study,
the influence of different types of plasticizers on the thermal and surface
characteristics of PVA/starch blend was investigated by Sreedhar et al. (2006)
21
Besides starch, cellulose also has been considered as a suitable blend material
with PVA. Blend films of PVA with carboxymethyl cellulose (CMC) in different
compositions was prepared by ElSayed et al. (2011).
A good compatibility
between PVA and CMC was observed in all samples. In addition, the thermal
stability of PVA increases with the CMC content in the blend films. Another study
of PVA/cellulose blend composite was done by Zhang et al. (2011). This study
evaluated the physiochemical properties of PVA composites by modifying the
cellulose through mechanochemical treatment. It was found that the cellulose treated
gave an improvement in tensile strength, elongation at break and thermal stability as
well as biodegradability rate.
Srinivasa et al. (2003) in their paper successfully have proven the ability to
prepare the PVA/chitosan blend films with optimum blend ratio of 20/80. In another
study, PVA/chitosan film were prepared by Pei et al. (2007) using the casting/solvent
evaporation method. Remarkable improvement of the light transmittance and water
vapor evaporation control was observed by them compared with the single layer
films. Blending of PVA with chitosan has been suggested as a promising approach
for a variety of pharmaceutical applications. Yang et al. (2007) reported that the risk
of complications using urethral catheters can be reduced by coating the surface of
segmented polyurethane (SPU) catheters with a PVA/chitosan blending hydrogel
while Matthew et al. (2007) used PVA/chitosan blending hydrogel for cell culture.
As reported by anl et al. (2008), blend microspheres of PVA and chitosan have
potential for oral delivery system.
Charernsriwilaiwat et al. (2012) meanwhile
reported that chitosan blended with PVA nanofibre mat was able to use as wound
dressing material.
Limpan et al. (2010) in their research have used fish myofibrillar protein
(FMP), blended together with PVA in the production of biodegradable blend films.
In this study, Limpan and his research team has demonstrated the effects of the
addition of PVA blending on the properties of FMP films. The addition of PVA at a
certain level could improve the mechanical properties, whereby their tensile
properties and elongation at break increases, whereas for their appearances, it
22
significantly lowered the redness and yellowness.
As investigated by Su et al.
(2010), PVA films were prepared by blending with soy protein isolate (SPI) and
glycerol as plasticizer.
The aim of this study was to investigate the moisture
sensitivity of films by carried out the water vapor permeability (WVP) and moisture
sorption tests. Results reveal that the WVP increases, while equilibrium moisture
content (EMC) decreases with increase in PVA content.
The application of nanocellulose particles in the PVA film was investigated

by Ibrahim et al. (2010).
In their study, they have demonstrated the uses of
nanocellulose particles from cotton linter and linen in a PVA film. The mechanical
properties of PVA matrix such as tensile strength and percentage elongation at break
increased with the addition of nanocellulose particles. In term of biodegradability
property, the resulted PVA/nanocellulose films can be easily degraded in natural
condition. As investigated by Cho and Park (2011), it can be concluded that the
tensile modulus and strength of PVA nanocomposite increases with increasing in
nanocellulose content and then, decreased upon reaching 7 wt%. In reference to Li
et al. (2012), incorporation of nanocrystalline cellulose has been reported to improve
the storage modulus of PVA composites compared to pure PVA.
2.4
Starch
Starch is the most popular carbohydrate in green plants, where it can be

categorized as renewable, biodegradable, ready availability, and low cost agro
polymer. Characteristics of starch such as shape and size of starch granules, and the
composition of starch granules depends on the sources of starch from. Sources for
industrial production of starch are plant seeds, roots and tubers. A large number of
synthesis methods for producing starch have already reported. It is wellknown that
it has five basic process steps, which are cleaning, steeping, grinding, separation and
isolation of finished products.
23
Commercial starch is industrially produced through dry and wet milling
process.
Among the two milling process, wet milling process appears to be a
promising method. This is because the adhesion between starch and protein occurred
in the dry milling process. The presence of this protein also caused this process not
suitable for hydrolysate manufacture and consequently increased refining cost
(Zobel, 1992). The wet milling process was found to produce not only native starch
as final products, but also a range of starch derivatives. Figure 2.3 shows wet milling
processes in a diagrammatic form.
Agricultural inputs containing

carbohydrates
Milling
processes
Starch slurry
Drying
Chemical modification
Hydrolysis and
subsequent processes
Native starches
Modified starches
Maltodextrins/glucose
syrups/fructose
Figure 2.3: Production of starches and starch derivatives (Zobel, 1992)
The commercial starches can be divided into three groups.
First group
comprises the tuber (potato), root (tapioca, arrowroot and sweet potato), and pith
(sago) starches. The second group comprises the common cereal starches (corn,
wheat, sorghum and rice). These two groups are distinctly different from each other
with respect to chemical composition and physical properties.
The third group
comprises the waxy starches (waxy maize, waxy sorghum and waxy rice).
24
The biodegradable starches used in most of the applications like paper
making, bioplastics, detergents and cosmetics, drilling industry, paint and ink
industry, textile industry, and water treatment industry. The use of starch in paper
making industry aims providing a better strength of paper and as a component of
coating formulations. Native starch and their derivatives may also play a role as
drilling aids and flocculant aids in drilling industry and water treatment industry,
respectively. Furthermore, there has been a growing interest in the use of starch by
paint manufacturer to act as rheological control agents.
2.4.1
Composite Based on Starch
Starch generates a great interest and it is considered as a promising

alternative to synthetic polymers for composite applications. However, the use of
starch has been limited in composites industrial because of problems related to
performance such as low resistance to mechanical stresses and humidity. Therefore,
several strategies have been investigated in order to open new possibilities for
improving these mechanical and barrier properties. These strategies include the
chemical modification of starch, blending with synthetic or natural polymers, and
addition of filler in association with starch.
Guohua et al. (2006) in their study successfully have proven the ability to
prepare blend films by mixing corn starch and methylatedcornstarch with PVA. It
is reported that methylation, as one of the etherification method, is found to be the
most effective treatment compared to other modification methods such as
esterification, oxidation and crosslinking. As a result, it was found that methylated
cornstarch/PVA film had higher water resistance and tensile strength than the native
starch/PVA film. Another study regarding chemical modification of starch has been
carried out by Yun et al. (2008). In this study, starches were crosslinked with
sodium trimetaphosphate and sodium tripolyphosphate under alkaline condition to
25
produce chemically modified starches. It was found that the chemically modified
starch film had higher tensile strength and elongation comparable to that of native
starch film.
On another study, Wang et al. (2009) have modified starch by
esterification method. The modified starches were then blended with natural rubber
latex and the composite obtained were characterized. The morphological studies
revealed that there is good interaction between rubber and modifiedstarch, leading
to improved thermal stability and mechanical properties of composites.
The
preparation of composites based on oxidized starch has been conducted by PalmaRodrguez et al. (2012), whereby the oxidation of starch to improve the mechanical
and barrier properties of composite has been well documented.
It has been proven by Godbole et al. (2003) which indicated that by blending
starch
and
poly3hydroxybutyrate
(PHB),
whereby
this
composite
has
advantageous for cost reduction comparable to the virgin PHB. This point is also
supported by Thir et al. (2006), which stated that incorporation of starch into PHB
led to a higher degradation rate. Besides PHB, starch has been successfully blended
with various synthetic polymers such as poly(caprolactone) (Singh et al., 2003;
Rosa et al., 2005), poly(-lactide) (Chen et al., 2007; Kozlowski et al., 2007),
polycaprolactone (Averous et al., 2000; Koenig and Huang, 1995; Spvek et al.,
2007), polypropylene (Ramis et al., 2004) and low density polyethylene (Ning et al.,
2007; Thakore et al., 1999). A biodegradable blend film from rice starchchitosan by
casting film solution on leveled trays has been prepared by Bourtoom and Chinnan
(2008). The results of the investigation revealed that the rice starchchitosan blend
film was better than starch film in tensile strength, water vapor permeability, lighter
color and yellowness, elongation at break and solubility.
A study conducted by Teixera et al. (2009) investigated the characterization

of composite based thermoplastics cassava starch reinforced with cassava bagasse
cellulose nanofibrils.
A remarkable improvement of the water uptake with the
incorporation of cassava bagasse cellulose nanofibrils in the thermoplastic starch

matrices was observed and this can be explained due to the decrease of its
hydrophilic character. Another study of starch based nanocomposites was done by
26
Liu et al. (2010). The improvement of the tensile strength and Youngs modulus of
bamboo cellulose crystal (BCC) reinforced starch biocomposite have been obtained.
Girons et al. (2012) in their research have used natural strands as reinforcement in
thermoplastic starch, whereby the addition of sisal or hemp strands has been shown
to have a positive effect in both the storage and Youngs modulus of composite.
2.5
PVA/Starch Blend
Tang and Alavi (2011) mentioned that both starch and polyvinyl alcohol are
polar substances that is comprised of hydroxyl groups in their chemical structure, and
due to its polar nature, the hydroxyl groups of the PVA and starch are able to form
intermolecular and intramolecular hydrogen bonds that result improvement in their
miscibility. Figure 2.4 shows possible hydrogen bond formation between starch and
PVA.
PVA
Starch
PVA
Figure 2.4: Possible hydrogen bond formation between starch and PVA (Tang and
Alavi, 2011)
27
Sin et al. (2010) in their study have concluded that the PVA and starch are
reactively compatible. It is evident from the results of binding energies, vibrational
frequencies and solubility analysis as well as experimental infrared spectroscopy.
The study summarized four main points, which describes the nature of hydrogen
bonding effects between PVA and starch. The first point is the binding energies data
has shown the negative values which exhibits that PVAstarch is a stable compound.
Secondly, PVAstarch blend showed a stable and compatible compound system due
to the solubility parameters and the results are very close to each other. Thirdly, the
hydroxyl group shifts to lower wavenumbers can be observed from vibrational
frequencies analysis due to the formation of hydrogen bond. Lastly, by performing
experimental infrared spectroscopy, it has shown that increment of the wavenumbers
of the specimens indicate that PVA and starch interact in a harmonize manner and
the blending is compatible.
In general, it is noted that the main shortcomings of composites based PVA is

their low degradation rate. This point was supported by Guohua et al. (2006) where
they concluded that the rapid degradation occurred in the starch/PVA film compared
to pure PVA film. However, it was found that the tensile strength decreased with the
addition of starch, and then it was almost constant upon reaching 35% of starch
percentage in matrix film. In contrast, increasing starch percentage in film matrix
caused the percentage of water absorption to increase.
Similar findings were
reported by Yun et al. (2008) in their paper which studies the biodegradability of
starch/PVA blend films. As seen in the result of degradation test, it can be observed
that PVA films had higher resistance against degradation, exhibited approximately
8% degradation, compared to starch/PVA blend films which were degraded about
80%. In a research by Russo et al. (2009), it was observed that rate of glucose
production and percentages of starch hydrolysis are decreased with the addition of
PVA, as shown in Table 2.4.
28
Table 2.4: Rate of glucose production and percentage of starch hydrolysis from each
PVA/starch substrate (Russo et al., 2009)
Rate of Glucose Production
Percentage of Starch
(g/mL h)
Hydrolysis
100:0
392
100
90:10
268
98
75:25
224
92
50:50
76
79
0:100
Substrate
On another study, Mao et al. (2002) examined the effect of PVA on the
mechanical properties and morphology of the starch film. In this study, the tensile
strength of starch film was increased when PVA is to be blended from 1.8 to 4 MPa
The same trend from addition of fiber content can also be found for the elongation at
break, whereby the elongation at break for starch film without PVA was 113% and
after addition of PVA, the percentage of elongation had increased up to 150%. In the
SEM image shown in Figure 2.5, many exposed starch granules can be seen on the
surface of starch film, which disappeared after incorporating PVA.
(a)
(b)
Figure 2.5: SEM of fracture of (a) starch film (b) starch/PVA film (Mao et al., 2002)
29
Rahman et al. (2010) have investigated the thermal behavior of cassava
starch filled with glycerol plasticized polyvinyl alcohol blend films. The blend films
were then analyzed using thermogravimetry and differential scanning calorimetry
methods. Results from differential calorimetry analysis showed that the onset and
endpoint temperature decreases with increasing in the amount of PVA in films. A
thermogravimetry degradation of PVA/starch blend can be divided into three phases
which are phase 1 is the vaporization of volatiles, phase 2 is the rapid decomposition
dehydration and elimination degradants and phase 3 is the formation of carbonaceous
residues. In addition, thermogravimetry kinetics analysis showed that the activation
energy (Ea) of PVA/starch blends is higher than their original components.
Therefore, it can be concluded that blending of PVA and starch exhibited good
thermal attack resistance due to the thermal stability of the blends is higher than PVA
and starch.
2.6
Natural Fiber
Synthetic fibers such as aramid, carbon and glass have been extensively used
in many applications owing to its high strength and heat resistance. However, these
kinds of fibers have resulted in environmental problems due to their partial
combustibility, difficulty to recycle and nonbiodegradable (Shanks et al., 2004).
Therefore, natural fibers have been used to replace the existing synthetic fibers. A
broad classification of plant fibers is presented schematically in Figure 2.6.
30
Plant Biofibers
NonWood
Trunk/Stem
/Frond
Straw
Bast
Examples:
Rice,
wheat, corn
straw
Examples:
Oil palm,
coconut tree,
date palm,
banana stem
Leaf
Wood
Seed/
Fruit
Examples:
Henequeen,
sisal,
pineapple
leaf fiber
Examples:
Kenaf, flax,
jute, hemp
Grass
Examples:
Bamboo
fiber,
elephant
grass
Examples:
Cotton, coir,
EFB, Palm
pressed fiber,
jatropha,
cocoa
Examples:
Recycled
wood fibers
(newspaper,
magazine
fiber)
Examples:
Soft and
hard woods
(pine, teak,
rubber
wood)
Figure 2.6: Schematic representation of plant biofibers classification (AbdulKhalil

et al., 2011).
Plant fibers can be categorized in two categories which are wood and non
wood biofibers. The most widely known wood derivatives are wood flour and fibers.
Wood flour can be easily and cheaply obtained from sawmill wastes and it is usually
used after proper sieving. Wood fibers are produced from wood waste by thermo
mechanical processes (LaMantia and Morreale, 2011). On the other hand, non
wood biofibers are classified depending on their sources including stem, straw, bast,
leaf, seed and grass (AbdulKhalil et al., 2011). Bast and stem fibers are the fibrous
bundles in the inner bark of the plan stem running the length of the stem, while leaf
fibers run the length of leaves. Seed and fruit fibers are collected from the seeds or
seed cases and from the fruit of the plant, respectively.
31
Natural fibers have the benefits of having marketing appeal and being
versatile in many applications, varying from yarn and textiles; rope, twines and nets;
nonwoven matrices; paper and board products, packaging; building and
construction materials; composites and automotives parts (Taj et al., 2007). The use
of natural fibers in the building industry is mostly economical and technical, whereby
these fibers exhibiting higher insulation properties compared to current materials.
Natural fiber composites market is divided into two segments, which are wood fiber
and non-wood fiber.
Automotive is the largest segment for non-wood fibers,
whereas construction is for woof fibers.
Demand for natural fiber composites
expected to be high in automotive and construction applications for the next few
years. Year wise details of capacity, production, import, export and demand for
natural fibers in Asian region are shown in Figure 2.7 (Markus, 2012).
Figure 2.7: Capacity, production, import, export and demand of natural fibers in
Asian region (Markus, 2012)
32
As shown in Figure 2.7, it was observed that the imports have been increasing
due to rapid growth in demand of natural fibers and its limited domestic availability.
Import dependency, which was at 55% in 2005 to 2006, has increased to 73% in
2010 to 2011. Therefore, it can be concluded that the use of natural fibers has
attracted much attention for environmental protection and sustainable development
as well as their ability to obtain wide commercial applications. The utilization of
these natural fibers has attracted growing interest because of their unique
characteristics, including low cost, lower density, high specific strength, good
thermal properties and biodegradability. In addition, natural fibers have flexibility
and therefore are less susceptible to fracture during processing (Bledzki and Gassan,
1999) and could avoid any abrasion towards processing equipment (Bhatnagar and
Sain, 2005). Characteristics of some natural fibers, including its density, diameter
and mechanical properties are summarized in Table 2.5.
Table 2.5: Characteristics of natural fibers (Faruk et al., 2012)

Tensile
Strength
(MPa)
400
Youngs
Modulus
(GPa)
12
Elongation
at Break
(%)
3-10
Bagasse
290
17
1.25
Bamboo
140-230
11-17
0.6-1.1
Flax
345-1035
27.6
2.7-3.2
1.5
690
70
1.6
1.48
393-773
26.5
1.5-1.8
1.3
Kenaf
930
53
1.6
Sisal
511-635
9.4-22
2.0-2.5
1.5
Ramie
560
24.5
2.5
1.5
Oil palm
248
3.2
25
0.7-1.55
Pineapple
400-627
1.44
14.5
0.8-1.6
175
4-6
30
1.2
500-1150
11.8
3.7-4.3
1.4
Fibers
Abaca
Hemp
Jute
Coi
Curaua
Density
(g/cm3)
1.5
33
2.6.1
Chemical Composition
Chemical composition of some typical plant biofiber has been given by

Mohanty et al. (2002) as shown in Table 2.6. Natural fibers are mainly composed of
cellulose, hemicelluloses and lignin. Pectin, pigments and extractives can be found in
lower quantities. The presences of noncellulosic substances such as lignin and
hemicelluloses that cover the cellulose inside have important effects on the final
properties of the fibers.
Table 2.6: Chemical composition of some typical cellulose containing materials

(Mohanty et al., 2002)
Type of
biofiber
Wood
Sources
Hardwood
Softwood
Extract
28
2529
2531
15
40
30
20
10
3243
1020
4349
Corn Cobs
45
53
15
Corn Stalks
35
25
35
Cotton
95
0.4
EFB
50
30
17
Flax (retted)
71
21
Flax (unretted)
63
12
13
Hemp
70
22
Henequen
78
48
13
Istle
73
48
17
Jute
71
14
13
Kenaf
36
21
18
Ramie
76
17
Sisal
73
14
11
Sunn
80
10
Wheat Straw
30
50
15
Coir
Wood
Lignin
1624
4044
Bagasse
Non
Composition (%)
Cellulose Hemicellulose
4347
2535
34
Cellulose is a natural polysaccharide, where Dglucopyranose rings are
connected to each other with (1 4)glycosidic linkages, as can be seen in Figure
2.8. According to Kadla and Gilbert (2000), the crystal packing direction and the
physical properties of cellulose are influenced by the presence of three hydroxyl
groups, which are secondary OH at carbon 2 and carbon 3, and primary OH at carbon
6 positions. These hydroxyl groups display different reactivities from each other and
are able to form hydrogen bonds. Cellulose is the main component of all plant
materials and synthesized through photosynthesis process. Therefore, cellulose is
considered as the most common and most abundant organic polymer on earth since
they are renewable natural resources that are being constantly produced.
OH
OH
CH2OH
H
H
O
O
CH2OH
H
H
OH
CH2OH
H
O
H
OH
OH
O
H
CH2OH
n
OH
Figure 2.8: Chemical structure of cellulose (Mohanty et al., 2002)
Celluloses in natural fibers come in four types of cellulose that are classified
as type , , , V and V, which can be determine the mechanical properties of
cellulose (Zimmerman et al., 2005). Among these types of celluloses, type I was
found to has outstanding mechanical properties.
The main difference between
cellulose I and cellulose II is their chain orientation, whereby cellulose I have

parallel chains, in contrast to the antiparallel chains of cellulose II (Lennholm and
Iversen, 1995).
35
In reference to Moran et al. (2008), hemicelluloses are composed of a
combination of various 5- and 6- carbon ring sugars and they are comprised of a
group of polysaccharides such as xylose, mannose and glucose. It forms a highly
branched random structure and it is mainly amorphous.
When comparing the
hemicellulose and cellulose, three important differences are noticed in terms of their
structure and properties (John and Anandjiwala, 2008). Firstly, it was noticed that
hemicelluloses consists of different types of sugar units while cellulose consists of
only 1,4Dglucopyranose units. Secondly, increased noncrystalline nature of
hemicellulose was reported and considerable degree of chain branching was obtained
due to presence of pendant side groups, whereas cellulose is a uniform and linear
polymer. Thirdly, hemicelluloses have lower degree of polymerization with around
50300, compared to cellulose that has a very high degree of polymerization which
is 10100 times higher than that of hemicellulose.
Lignin is a complex hydrocarbon and totally amorphous in nature, which

contains both aliphatic and aromatic constituents such as guaiacyl, syringyl and
phenylpropane. In addition, they usually cannot dissolve in most solvents and much
more difficult to break down to monomeric units. In general, lignin consists of five
hydroxyl and five methoxyl groups per building unit. It is believed that the structural
units of lignin molecule are derivatives of 4hydroxyl3 methoxy phenylpropane.
Lignin is categorized as a thermoplastic polymer with glass transition and melting
temperature are 90 and 170 C, respectively. It is not undergo in acid hydrolysis, but
can be soluble in alkali solution at high temperature.
In addition, it is readily
oxidized and easily condensable with phenol (Mohanty et al., 2005).
36
2.6.2
Physical Structure
John and Anandjiwala (2008) in their paper stated that the cell wall in a fiber
is not a homogenous membrane and each fiber has a complex and layered structure.
Primary wall is thin, which is the first layer deposited during cell growth encircling a
secondary wall and it is typically composed of cellulose microfibrils and
interpenetrating matrix of hemicelluloses and pectins. Secondary walls are derived
from the primary walls by the thickening and inclusion of lignin into the cell wall
matrix and they occur inside the primary wall (Bhatnagar and Sain, 2005).
In
addition, secondary wall consisting of three layers and the thick middle layer play a
major role in governing the mechanical properties of the fiber. The middle layer
consists of a series of helically wound cellular microfibrils formed from long chain
cellulose molecules.
Secondary wall S3
Helically
arranged
crystalline
microfibrils
of cellulose
Lumen
Secondary wall S2
Spiral angle
Secondary wall S1
Primary wall
Amorphous
region mainly
consisting of lignin
and hemicelluloses
Disorderly arranged
crystalline cellulose
microfibrils networks
Figure 2.9: Structure of natural fiber (John and Anandjiwala, 2008)
37
The physical structure of a fiber is associated with the degree of crystallinity,
their orientation to the fiber axis and the size of the crystals, as presented by Reddy
and Yang (2005). The degree of crystallinity can be defined as the amount of
crystalline cellulose present in a cellulosic fiber. It could be noticed that the lower
degree of crystallinity reduces the strength of fibers, but increased elongation and
higher moisture regain and more available sites for chemical reactions. The increase
in the elongation properties can be explained by the more amorphous region,
whereby molecules in these regions can align themselves to become more oriented to
the fiber axis without rupture, whereas molecules in crystalline regions cannot move
easily and subsequently tend to be brittle.
In addition, easily and unlimited
accessibility to water and chemicals in amorphous region are due to the lots of void
space between molecules in these region.
Besides that, the smaller size of crystals also contributed to higher

accessibility to water and other chemicals. This could be attributed to more surface
area of the fibers, which increase the ability of a fiber to absorb water or chemicals.
Another possible reason for this kind of behavior may be related to the decreased
distance between layers of cellulose and thus increasing the capillary effect in the
fibers. Orientation of the crystalline regions to the fiber axis also influences the
strength of the fiber. The orientation of crystals in the fiber is characterized from the
Xray diffraction analysis. The lower degree of orientation resulted in a decrease in
strength properties. The lower strength in fiber could be due to the stress placed
upon the fibers may not be in the direction of the strong crystalline regions (Reddy
and Yang, 2005).
38
2.7
Empty Fruit Bunch Fiber
Oil palm tree, which is belongs to the species Elaeis guineensis under the
family Palmacea was first introduced to Southern Asia in 1948. Oil palm is very
important to economy in Malaysia. Currently, about 60% or 3.5 million hectares of
the countrys land are under oil palm cultivation. In addition, Malaysia is known as
one of the largest producer and exporter of oil palm in the world, whereby Malaysia
accounts for 39% of world oil palm production and 44% of world exports.
Empty fruit bunch (EFB) is one of the lignocellulosic materials, which has
great relevance to Malaysia, as a large quantity of the biomass is generated by oil
palm industries. More than 11.9 million tons of oils and 100 million tons of biomass
are produced in the oil palm industry in Malaysia. The biomass from oil palm
residue include the oil palm trunks (OPT) and fronds (OPF), kernel shell, EFB,
presses fruit fiber (PFF) and palm oil mill effluent (POME). In addition, the total
crop of fresh fruit bunch is more than 30 million tons per year, which generate more
than 10 million tons of EFB. Only 10% of the EFB is used and the rest are abundant
(Hariharan and AbdulKhalil, 2005).
These considerable volumes of organic waste, which are produced on a

continuous basis, require effective removal procedures adapted to the nature of the
by-product. Traditionally, EFB has been burnt in simple incinerator and their ash
recycled into the plantation as fertilizer. However, due to the pollution problem,
incineration of EFB has been discouraged. Alternatively EFB can be composted and
returned to the plantation, or returned directly as mulch. EFB is a good source of
organic matter and plant nutrients. It is claimed that using the EFB as mulch has
several advantages for the nutritional sustainability of the plantation. Mulch benefits
crop production because it releases nutrients slowly to the soil via microorganisms
therefore effectively recycling the plant nutrients. Table 2.7 shows some typical
nutrient content of EFB, expressed as a percentage of the dry matter (Menon et al,
2003).
39
Table 2.7: Nutrient content of EFB (Menon et al, 2003)
Element
Percentage of Dry Matter
Potassium, K
2.24
Nitrogen, N
0.44
Phosphorus, P
0.14
Calcium, Ca
0.36
Magnesium, Mg
0.36
Two sources of oil palm tree to obtain oil palm fibers are EFB and mesocarp.
Fibers from EFB are most commonly used for composite materials and various other
applications compared to those from mesocarp. This is due to their property which
consist of a bunch of fibers, and thus readily available as well as being low cost. EFB
fiber are extracted by retting process from EFB whereas mesocarp fibers are waste
materials left after the oil extraction that needs cleaning process before its final
usage. EFB and the EFB fiber are shown in Figure 2.10 (Hassan et al., 2010).
Figure 2.10: (a) EFB (b) EFB fiber (Hassan et al., 2010)
40
2.8
2.8.1
Bleaching Process
Bleaching is a chemical treatment employed for the removal of coloring

matter from lignocellulosic fibers and it has been developed in various industries,
especially in textile and paper and pulp industries. Actually, cellulose and most other
fiber forming polymers are white in their natural state. However, the impurities of
fibers may absorb light causing the fibers to have a creamy, yellowish and dull
appearance. Therefore, fibers usually required bleaching in order to remove the
inherent color. The source of natural color is organic compounds with conjugated
double bonds. During the process of whitening, bleaching chemicals attack the
chromophore, most likely destroying the one or more double bonds with in this
conjugated system.
In the meantime, another purpose of bleaching is to improve the cleanliness

of the fiber by removing extractives. It has been proven by Mehta et al. (2004)
which indicated that the characteristics absorption peak of lignin and hemicelluloses
in fiber treated sodium chlorite and sodium hydroxide was significantly weaken
compared to that in the fiber without sodium chlorite process, suggesting that lignin
and hemicelluloses were partially removed during process of bleaching. The light
absorption of fiber is mainly associated with its lignin component. To reach an
acceptable brightness level, lignin should thus either be removed from the fiber or
alternatively, freed from strongly light-adsorbing groups as completely as possible.
The bleaching is carried out in a number of consecutive stages in which

natural fibers are treated with bleaching agents. Bleaching agents is further classified
into oxidative bleaching agents and reductive bleaching agents. Natural fibers are all
generally bleached with oxidative methods using chemicals such as sodium
hypochlorite, sodium chlorite or hydrogen peroxide. An oxidizing bleach work by
41
breaking the double bond, meanwhile double bond is converted into single bond in
case of reductive bleaching.
Sodium chlorite is one of the most commonly used bleaching agents and it is
an oxidant particularly adapt for cellulosic, either natural or man-made and synthetic
fiber bleaching such as polyamidic, acrylic or polyester. A bleaching treatment using
a sodium chlorite solution is a popular technique at the laboratory scale to remove
lignin from plants. Lignin is rapidly oxidized by chlorine and chlorites. Lignin
oxidation leads to lignin degradation and to dissolution in an alkaline medium
(Bhatnagar and Sain, 2005). The sodium chlorite bleaching has the advantages of
high brightness degree compared to other bleaching agents.
In addition, the
degradation of fiber can be considered to be negligible whereby their weight loss was
very low, between 1 and 3%. It was even contributed to the very low chemical
oxygen demand (COD) and adsorbable organic halide (AOX) discharge number and
therefore has far less environmental impact of wastewater.
2.8.2
Alkali Treatment
The cell wall structure of the fiber cylinder is built up from cellulose
molecules which are extremely hydrophilic. The magnitude of this swelling effect is
very dependent upon the fiber structure. Natural fibers are usually soaked in sodium
hydroxide solution in order to swell the cell wall to enable chemical molecules to
penetrate through the crystalline region of the cellulose (Bhatnagar, 2004). Alkali
soaking increased fiber swelling, increased internal bonding, enhanced the pliability
of the fibers, as well as increased the potential bonding areas between fibers.
42
In addition, the important point to note regarding alkali treatment is their
capability to removes certain amount of noncellulosic impurities on the fiber
surface by disrupting the hydrogen bonding in the network structure. In a research
by Ben-Sghaier et al. (2012), natural stalk Agave Americana L. fiber was treated
with alkali and their study confirmed that NaOH treatment seems to be effective in
the removal of lignin and hemicellulose components. Evidence of noncellulosic
components loss can also be observed in the morphological analysis, whereby there
in no precipitated lignin and other of noncellulosic material on the treating fiber
surface. Similar study was done in more detailed for natural stalk bark fiber by Li et
al. (2012). It was found that the fineness, length and crystallinity of the fiber were
decreased by treating fiber with NaOH and higher improvement in the strength of
fiber was noted for higher NaOH content.
2.9
Nanocellulose Fiber
Xia et al. (2003) defined nanocellulose fibers as fibers with a diameter below
100 nm and have a high aspect ratio, whereby typical dimensions are found to be 5
20 nm width and up to 2000 nm long. Nanocelluloses are known to exhibit thick and
high viscosity under normal conditions, but become thin and the viscosity is also lost
upon introduction of the shearing forces. When the shearing forces are removed,
they regain much of its original state. This property is known thixotropy. Moreover,
it is wellknown that nanocellulose has outstanding mechanical properties, including
a high stiffness and high Youngs modulus.
In addition to their exceptional
mechanical properties, nanocellulose fibers have been shown to be able to act as a

barrier material.
43
As mentioned by AziziSamer et al. (2005), there are two types of
nanocellulose that can be obtained from natural fibers, which are cellulose
nanocrystals and microfibrillated cellulose (MFC). These kinds of nanocelluloses
are categorized depending on their production process. Cellulose nanocrystals, also
known as cellulose nanowhiskers, are prepared by acid hydrolysis of native
celluloses and successive mechanical agitation of the acidhydrolyzed residues in
water to obtain stiff rodlike nanocrystals. MFC resulting from disintegration of
cellulose fibers under high shearing and impact forces are shaped like nanofibrils
with diameter lower than 100 nm but length close to micrometer. This process
always involves a homogenization process. The main differences between cellulose
nanocyrstals and MFC are summarized in Table 2.8, while Figure 2.11 shows
schematic structure and TEM image of cellulose nanocrystal and MFC, respectively.
Table 2.8: Comparison between nanocrystal and MFC (Dufresne, 2012)

Microfibrillated Cellulose
Cellulose Nanocrystal
Long fibrils
Whiskers relatively short
Amorphous and crystalline phase
Mostly crystalline
Produce by mechanical or chemi
Produce by chemical process
mechanical process
No self assembly
Self assembly possible
High yield
Lower yield from pulp
44
B
Figure 2.11: Schematic structure (Pkk et al., 2007) and TEM image (Klemm et
al., 2011) of (a) cellulose nanocrystal and (b) microfibrillated cellulose
Besides the isolation method, the morphology and physiochemical properties

of nanocellulose such as size, dimensions, shape, thermal stability and crystallinity
are strongly influenced by many factors, including the chemical composition of
fibers, internal fiber structure, microfibril angle, cell dimensions and defects, which
differ from different parts of a plant as well as from different plants. Consequently,
the properties of composite reinforced with nanocellulose fibers are also depend on
their cellulose types and nature of the cellulose source, because each type of
cellulose has its crystalline organization, which can determine the final properties of
composites (Luduena et al., 2013).
Properties of nanocellulose from different
sources and isolation methods are summarized in Table 2.9.
Table 2.9: Properties of nanocellulose from different sources and isolation methods
Source
Method
Diameter (nm)
Crystallinity index (%)
Reference
100112
76.39
Dai et al. (2013)
Hemp fiber
Sonication-assisted oxidation hydrolysis
Sugarcane bagasse
High pressure homogenization
1020
36
Li et al. (2012)
EFB fiber
High pressure homogenization
540
69
Jonoobi et al. (2011)
Rice straw
Grinding treatment
1235
76
Abe and Yano (2009)
Jute fiber
TEMPO-mediated oxidation
310
69.72
Cao et al. (2012)
Bamboo fiber
High intensity ultrasonication
3080
73.62
Chen et al. (2011)
Flax fiber
Mechanical treatment
1060
59
Bhatnagar and Sain (2005)
Isora fiber
Steam explosion
4080
90
Chirayil et al. (2014)
Pineapple leaf fiber
Steam explosion
20 60
61.25
Cherian et al. (2010)
Banana fiber
Steam explosion
58
73.62
Cherian et al. (2008)
Kenaf fiber
Acid hydrolysis
1215
81.8
Zainuddin et al. (2013)
Pandanus fiber
Acid hydrolysis
32184
40.13
Chenampulli et al. (2013)
Cotton linter
Acid hydrolysis
20179
90.45
Morais et al. (2013)
Mulberry
Acid hydrolysis
2040
73.4
Li et al. (2009)
Rice husk
Acid hydrolysis
614
79
Rosa et al. (2012)
Sisal fiber
Acid hydrolysis
1843
75
Moran et al. (2008)

45
46
2.9.1
As mentioned earlier, there are two methods to produce nanocellulose which

are by acid hydrolysis and homogenization process. Figure 2.12 shows the main
steps involved in preparation of cellulose nanocrystal and microfibrillated cellulose.
The initial steps to prepare nanocellulose is generally involves fiber treatment, which
are alkaline and bleaching treatment.
During treatment step, the removal of
impurities such as lignin, hemicelluloses, wax and oils covering the external surface
of the fiber wall take place.
Consequently, the native cellulose structure will
depolymerizes, defibrillates the external cellulose microfibrils and exposes short

length crystallites (Abraham et al., 2011). The bleached fibers are then ready to be
hydrolyzed (acid hydrolysis) or disintegrated (mechanical shearing at high pressure).
Milled Fibers
Alkali Treatment (80C)

NaOH 4% (wt/wt)
Bleaching Treatment (80C)
NaClO2/Acetate buffer (pH=4.8)
Hydrolysis
Mechanical
Homogenization
Dialysis
Defibrilation
Nanocrystal
MFC
Figure 2.12: The main steps involved in the preparation of cellulose nanoparticles
(AziziSamer et al., 2005)
47
Recently, many studies were done to develop a simple process to obtain
nanocellulose by modifying the existing methods. Abraham et al. (2011) in their
research have used steam explosion technique along with mild chemical treatment.
These processes involved typical steps such as alkaline treatment, bleaching
treatment and acid hydrolysis, but a very mild concentration of the chemicals was
utilized.
It is reported that this methods was able to overcome toxicity of the
chemicals and degradation of cellulose are completely varnished. Another studies

regarding the nanocellulose production method was conducted by BilbaoSainz et al.
(2011),
whereby
nanofibrils
cellulose
(NFC)
is
prepared
by
2,2,6,6
tetramethylpiperidine1oxyradical (TEMPO)mediated oxidation of natives

cellulose followed by mechanical disintegration of the oxidized celluloses in water.
2.9.1.1 Acid Hydrolysis
Generally, sulfuric and hydrochloric acid are widely used in preparation of

nanocellulose via acid hydrolysis. However, sulfuric acid offers more benefits than
hydrochloric acids. Araki et al. (1998) found that hydrochloric acids are difficult to
disperse and their aqueous suspension tends to flocculate if the nanocellulose is
prepared by hydrolysis in hydrochloric acids. On the other hand, when the sulfuric
acid is used as a hydrolyzing agent, charged surface sulfate ester is yielded due to the
reaction of sulfuric acid and surface hydroxyl groups of cellulose and therefore
making the nanocellulose to easily be dispersed in water (Revol et al., 1992).
Besides that, the suspension obtained from sulfuric acid hydrolysis and
hydrochloric acid shows differences in rheological behavior.
The sulfuric acid
treated suspension has shown no timedependent viscosity, whereas the hydrochloric

acid treated suspension showed a thixotropic behavior at concentrations above 0.5%
(w/v) and antithixotropic behavior at concentrations below 0.3%. Studies by Araki
et al. (1999) have demonstrated the posttreatment of nanocellulose generated by
48
hydrochloric acid hydrolysis with sulfuric acid.
Nanocellulose generated from
hydrochloric acid and then treated with sulfuric acid had the same particle size as
those directly obtained from sulfuric acid hydrolysis. In morphology behavior of the
particles, spherical nanocellulose was obtained from combinations of sulfuric acid
and hydrochloric acid during hydrolysis step. These spherical nanocelluloses have
shown improvement in thermal stability compared to the rodlike nanocellulose due
to the fewer sulfate groups on their surfaces.
During acid hydrolysis, the amorphous regions in native cellulose are more
accessible to acid and more susceptible to hydrolytic action than the crystalline
domains. Therefore, acid hydrolysis of cellulose is a wellknown process used to
remove amorphous regions.
Treating cellulose with sulfuric acid involves the
esterification of hydroxyl groups by sulfate ions. Moreover, the introduction of

sulfate groups produces a negative charge on the surface of the crystallites. This
anionic stabilization via the attraction/repulsion forces of electrical double layers is
probably the reason for the stability of colloidal suspensions of crystallites (Lu and
Hsieh, 2010).
Several studies have been reported where nanocellulose were identified and
separated from various sources by acid hydrolysis. Morn et al. (2008) indicated
about the use of sulfuric acid hydrolysis to produce nanocellulose from sisal fibers
with an average diameter of 30.9 12.5 nm. Mandal and Chakrabarty (2011) have
obtained nanocellulose from waste sugarcane bagasse in the form of a stable
dispersion where the surface anionic charges help to bring forth the necessary
stabilization of nanocellulose. Rosa et al. (2012) studied the hydrolysis of rice husk
cellulose using acid hydrolysis and reported that it was possible to isolate needle-like
structure of nanocellulose with size varying from 6 to 14 nm and 100400 nm in
length. Morais et al. (2012) found that nanocellulose from raw cotton linter with an
aspect ratio of 19, crystallinity of 91% and high hydrophilicity were obtained after
applying sulfuric acid hydrolysis. It has also been reported that the nanocellulose
isolated by the acid hydrolysis has shown a great potential for application in
reinforcing polymer (Cho and Park, 2011; Liu et al., 2010; Teixera et al., 2009)
49
The hydrolysis conditions such as acid concentration, temperature and
reaction time are known to affect the properties of the resulting nanocellulose. In
most of the works, the concentration of sulfuric acid is kept in the range of 60 65
wt%. Lu et al. (2005) investigated starch films reinforced with cellulose crystallites
prepared from cottonseed linter with 64 wt%. Habibi and Dufresne (2008) used 65
wt% sulfuric acid to prepare the nanocrystals from ramie fibers meanwhile Morn et
al. (2008) isolated nanocellulose from sisal fibers with 60 wt%. On another study,
Ioelovich (2012) evaluated several different acid concentrations, ranging from 50 to
about 68 wt%, which concluded that the optimal condition of the acidic treatment for
isolation of nanocrystalline cellulose is in the range of 5760 wt%. When
concentration of sulfuric acid is less than 50 wt%, the microscale particles are
isolated. On the other hand, when acid concentration is higher than 63 wt%, the
cellulose completely dissolved and the amorphous particles are formed with
decreased yield instead of nanocrystalline. However, Das et al. (2009) in their paper
successfully have proven the ability to obtain very fine structured MCC particles
from cotton, with the size of 1525 nm, by using 3047 wt% concentration of
sulfuric acid.
With a sulfuric acid concentration of 63.5 wt%, it was possible to produce

nanocellulose with a length between 200 and 400 nm and a width less than 10 nm in
approximately 2 hours and with a yield of 30% of initial weight (Bondeson et al.,
2006).
In a research by Martinez-Sanz et al. (2011), the length of cellulose
nanowhiskers from bacterial cellulose has been found to decrease when applying a
relatively long hydrolysis time compared to a 2 hours treatment. It was observed that
short times, which are typically applied for extraction of plant nanocellulose, are not
enough to digest the amorphous domains of the material. A study conducted by
Fahma et al. (2010) concluded that the optimal hydrolysis time was found to be
around 60 minutes to isolate nanocellulose from oil palm empty fruit bunch fiber.
Another study of the effect of hydrolysis time on the nanocellulose properties was
done by Kargarzadeh et al. (2012). It was found that the nanocellulose showed an
increased crystallinity when the reaction time was increased to 40 minutes.
50
These optimized parameters in the hydrolysis process would have been
different if the cellulose had come from different sources or had been pre-treated in
different ways before hydrolysis. However, reports on the relationships between the
hydrolysis conditions of the nanocellulose and the performance of the
nanocomposites were limited. A study by Chen et al. (2009) have demonstrated the
effects of hydrolysis time on the structure and properties of the pea hull fiber derived
nanowhiskers and those of the corresponding pea starch nanocomposite films. It was
found that 8 hours was the most suitable time for hydrolysis of pea hull fibers with
sulfuric acid in order to improve the elongation at break of the resulting
bionanocomposite films.
2.9.2
Nanocellulose Reinforced Composite
Nanocomposites, consisting of a polymeric matrix and nanosized elements as

reinforcement have attracted significant scientific attention because of their high
mechanical performance. A large variety of nanocomposites have been prepared
using biobased materials as a matrix and nanoreinforcement, so that it can reduce
the dependence on nondegradable products and move to a sustainable materials
basis.
Studies by Roohani et al. (2008) have prepared the nanocomposites from

copolymers of polyvinyl alcohol and polyvinyl acetate reinforced with cellulose
whiskers. The addition of cellulose whiskers up to 12 wt% to polyvinyl alcohol
copolymers resulted in increasing the tensile modulus, tensile strength and yield
stress compared to neat PVA. Furthermore, the effect of cellulose whiskers on the
strain at break can be seen, whereby this property decreased from 29.5% for the
unfilled matrix down to 9.1% for the nanocomposites film reinforced with 12 wt% of
cotton whiskers.
51
Bhatnagar and Sain (2005) have performed a research on preparation of
nanofiberreinforced film, whereby the nanofibers reinforcement content was 10% in
90% PVA. Cellulose nanofibers used in this study are obtained from various sources
such as flax bast fibers, hemp fibers, kraft pulp and rutabaga. Optical microscopy
analysis showed that the morphology was the same for the nanofiberreinforced film
and pure polymer film. However, when comparing films in terms of mechanical
performance, it was noticed that even 10% nanofibers provide a remarkable
reinforcing potential. Tensile strength of the nonreinforced pure PVA film was
found to be at 69 MPa. When 10% nanofibers were used as reinforcement, tensile
strength of the film increased to 102 MPa, 111 MPa, 178 MPa and 76 MPa for kraft
pulp, hemp, rutabaga and flax, respectively. The increase in tensile strength could be
due to the strong interface bonding between hydroxyl groups of nanofibers with
hydrophilic polymer. In addition, four to fivefold increase in Youngs modulus was
observed in nanofiberreinforced composite films compared to nonreinforced
polymer.
Preparation of nanocomposites by using nanocellulose fiber as the

reinforcement in PVA matrix was also investigated by Lu et al. (2008). A type of
nanocellulose used in this study is microfibrillated cellulose (MFC), which was
separated from kraft pulp by a mechanical process.
From dynamic mechanical
analysis (DMA), it can be seen that the storage modulus of MFC reinforced PVA
composite film are higher than that of pure PVA in the glass state, but a more
significant increase in modulus was observed above the glass transition temperature.
Both tensile strength and modulus of MFC/PVA films increased continuously as
plateau is reached at 10 wt% MFC.
Bras et al. (2010) in their paper successfully proved the ability to isolate
cellulose whisker (CW) from bleached sugar cane bagasse kraft pulp by acid
hydrolysis. These cellulose whiskers were then used as reinforcing elements in the
natural rubber (NR) matrix. Table 2.10 summaries the characteristics of natural
rubber nanocomposites with the addition of cellulose whiskers up to 7.5%. As a
result of effect of cellulose whiskers loading to the rubber matrix, it can be concluded
52
that the significant improvement of nanocomposite properties was observed with the
addition of cellulose whiskers. The increase in moisture sorption and water vapor
permeability could be explained due to the hydrophilic nature of cellulose whiskers.
More rapid disintegration of nanocomposites reinforced with cellulose whiskers than
that neat rubber film is observed probably because cellulose component in the
nanocomposites films is consumed by the microorganisms faster than rubber leading
to increased porosity, void formation and the loss of the integrity of the rubber
matrix. Consequently, the rubber matrix will be broken down into smaller particles.
Table 2.10: Characteristics of NR and NR/CW nanocomposites films reinforced

with 2.5 and 7.5 wt% (Bras et al., 2010)
0 wt% CW
2.5wt% CW
7.5wt% CW
Tensile Strength (MPa)
0.3
0.4
0.5
Tensile Modulus (MPa)
0.3
2.0
4.0
Moisture Sorption (%)
2.3
9.8
Water Vapor Permeability (x10-12)
0.4
0.6
5.0
Weight Loss in Soil for 4 weeks (%)
18
59
63
Cassava bagasse cellulose nanofibers (CBN) reinforced thermoplastics

cassava starch (TPS) nanocomposite has been prepared by Teixera et al. (2009). The
presence of CBN as reinforcement significantly influenced the surface of
nanocomposites which display rougher and more structure surface compared to
smooth surface for unreinforced TPS matrix, as shown in Figure 2.13. It was also
reported that the unreinforced TPS matrix is found to absorb more water than the
CBNreinforced nanocomposites and this phenomenon was ascribed to the
decreasing of hydrophilic TPS matrix. Moreover, adding CBN to TPS resulted in
increasing the mechanical properties from tensile tests, such as tensile strength, strain
at break and tensile modulus.
53
Figure 2.13: SEM of fractured surface of TPS reinforced (A) 0 wt% and (B) 20 wt%
(Teixera et al., 2009).
2.10
Nanocomposite based on PVA/Starch
As described in some reviews, nanoparticles filled PVA/starch blend is

presently the subject of much attention because of their unique properties. Very
limited studies have been reported concerning the PVA/starch blend composite filled
with nanoparticles. Nano silicon dioxide (nanoSiO2) is one of the nanofiller which
is the most commonly used in PVA/starch blend due to their ability to improve the
properties of blend film. Another types of reported works have investigated the used
of different types of nanofiller such as montmorillonite clay (Ardakani and Nazari,
2010; Spiridon et al., 2008), sodium montmorillonite clay (Taghizadeh et al., 2012),
nanoparticles of poly(methyl methacrylatecoacrylamide) (Yoon et al., 2012), and
nanocellulose (Ibrahim et al., 2010; Das et al., 2011).
54
In a research by Xiong et al. (2008), nanoSiO2 filled PVA/starch films were
prepared by the coating method, which were exposed to physical and
biodegradability test.
The crystallinity of the nanoSiO2 filled PVA/starch film
decreased to 32.97% when compared to 41.2% for a non-filled PVA/starch film.

This is possibly a result of the hydrogen bond formation between nanoSiO2 and
PVA/starch, which disturbs the parallel direction of the PVA/starch chains. In
addition, the small sizes of nanoSiO2 make it easier to disperse into the
macromolecular chains. Therefore, it was difficult for the remaining residual stress
to generate induced crystallization during processing and the crystallinity of the film
decreased.
The tensile strength, breaking elongation and transmittance of the
nanocomposite films were increased up to 79.4%, 18% and 15%, respectively.

These results indicate that the nanoSiO2 has a great potential to improve the
miscibility and compatibility between PVA and starch. Furthermore, the
incorporation of nanoSiO2 in the PVA/starch films has resulted in a decrease of its
water absorption properties due to their network structure which prevented the water
molecules from dissolving.
This study was then elaborated by the same researchers, whereby Xiong et al.
(2008) studied the effects of different content of nanoSiO2 on the performance of
PVA/starch blend films. According to experimental data of this study, it was found
that the tensile strength increases with increasing in nanoSiO2 content. The degree
of tensile strength was, however, decreased upon reaching 2.5% of nanoSiO2
content. Results also revealed that the tensile strength kept decreasing with the
increase in nanoSiO2 content. Similar trend can be seen in the water absorption of
the films, whereby the absorption decreased with an increase in nanoSiO2 content,
then a further increase in the amount of nanoSiO2 content from 3 to 5% results in
the increase of water absorption value.
55
Abbasi (2012) in his paper successfully proved the ability of nanoSiO2 to
enhance the properties of PVA/starch blend films. With increasing amount of nano
SiO2 in blend solution, the weight loss and water absorption of these systems
decreased as well as the rate of glucose production and rate of starch hydrolysis. On
another note, Yao et al. (2011) indicated that the crystal structure of the films was
found to increase with increasing the content of nanoSiO2. The analysis of SEM
revealed that the cross section of PVA/starch film is lamellar, whereas the
PVA/starch film consisting nanoSiO2 showed a clear microporous structure,
indicating that the gel network structure was formed by combining nanoSiO2 with
PVA/starch.
This result suggests that the permeation of nanoSiO2 into the
molecular chains of PVA and starch occurred due to the plenty of hydroxyl groups
on the nanoSiO2 surface, and hence the gel network structure formed. Also it can
be observed that the increasing of nanoSiO2 content does not provide sufficient
improvement in the biodegradability of the films.
Another studies regarding the nanocomposites based PVA/starch blend films

was conducted by Ardakani and Nazari (2010) whereby the tensile strength and
modulus were increased in the clay content up to 4 wt%, followed by leveling off the
tensile strength after the best amount of clay content was achieved. This point was
supported from TEM analysis of nanocomposite films. For 4 wt% of clay content,
an intercalative/exfoliated structure can be observed, indicating that the clay particles
are well dispersed throughout the polymer matrix, whereas increasing the clay
content to 8 wt% may lead to the agglomerations of platelets. Taghizadeh et al.
(2012) published a literature which indicated that the increase of nanoparticles of
sodium montmorillonite clay leads to the decrease of weight loss, water absorption,
rate of glucose production and rate of starch hydrolysis.
In recent times, very limited studies have been reported concerning the
nanocellulose fiber filled PVA/starch blend films. Das et al. (2011) in their research
have used different loading of jute micro/nanofibrils (JNF) as reinforcement filler in
the PVA/starch films. It was reported that the tensile strength of nanocomposite
films increased steadily with the addition of nanocellulose content. The same goes
56
for the percentage strain of the biocomposite films. However, when the 15 wt% of
nanocellulose was added, the presence of the nanocelluloses adversely affects the
percentage strain of nanocomposite. In addition, the most uniform and homogenous
dispersion without any aggregation can be seen in nanocellulose loading of 10 wt%.
From this point of view, nanocellulose content of 10 wt% can be considered as the
best nanocellulose loading in the PVA/starch biocomposites films.
2.11
Response Surface Methodology (RSM) is a statistical and mathematical

technique to identify an appropriate experimental design for the optimization
process. RSM indicates the correlation between the control input variables and
response surface obtained. Optimization process using RSM is a faster approach
method to identify the optimum condition compared with conventional time
consuming one-factor-at-a-time approach. This technique is helpful to reduce the
number of experiments, so it is easier to arrange and interpret in comparison to
others. Since the discovery of the best value is beyond the available resources of the
experiments, then response surface methods are used to at least gain a better
understanding of the overall response system.
A Central Composite Design (CCD) of RSM is one of the most commonly

employed to design the experiments, especially for fitting quadratic polynomial
equation. This method facilitates to optimize the effective parameter to acquire
sufficient process response with a minimum number of experiments. CCD with full
24 factorial designs (four factors each at two levels) usually used to identify the effect
on independent variables on the response.
57
The significant of the fitted model can be checked by analysis of variance
(ANOVA) suing Fisher F-test. The ANOVA is a collection of statistical procedures
for analysis of responses from experiments.
The F-value is a measurement of
variance of data about the mean based on the ratio of mean square (MS) of group
variance due to error and it is known as F-calculated. Then, the null hypothesis is
rejected when the F-calculated is exceeds the critical value (F-tabulated) from the
table at a significance level of .
The fit of the model can be checked by the coefficient of determination (R2),
whereby a larger value of R2 indicates a good agreement between experimental data
and predicted value. The p-value is also important, whereby it is serves as a tool to
check the significance of each coefficient.
For the regression coefficients of
independent variables, both the magnitude and sign are important. The sign indicates
the direction of the proportionality coefficient in relation to the response, whereby a
positive sign means that the independent variable is directly proportional to the
response while a negative sign means the opposite.
CHAPTER 3
METHODOLOGY
3.1
Introduction
This chapter describes the details of the experiment work done in this study.
There are three major stages of experimental work involved in this study; (i)
extraction of cellulose, (ii) isolation of nanocellulose fiber and (iii) preparation of
composite film. The work was started with the extraction of cellulose from empty
fruit bunch (EFB) fiber via alkaline treatment. The experiment then was continued
with the isolation of nanocellulose via acid hydrolysis method. Then, the cellulose
and nanocellulose obtained was characterized using FTIR, XRD, TGA, FESEM and
TEM. The optimization process employed Response Surface Methodology (RSM)
model to get the optimum hydrolysis conditions for nanocellulose yield. Meanwhile,
composite film was prepared by solution casting method. The effect of blend ratio
on the compatibility of PVA /starch blend has been done.
Subsequently, the
performance of the nanocellulose as a reinforcement in blend film was also

investigated. Lastly, comparison was made between pure PVA film, PVA/starch
blend film, cellulose reinforced PVA/starch film and nanocomposite reinforced
PVA/starch film. Figure 3.1 shows the flowchart of the experimental work, which
involves a series of steps that were performed in this study.
59
Sample preparation
(wash, dry, grind)
Characterize Fiber
Chemical
composition
FTIR
XRD
TGA
FESEM
TEM
Extraction of
cellulose via alkali
method
Isolation of
nanocellulose via
acid hydrolysis
Optimization on
nancellulose using
RSM
Preparation of
composite via casting
method
Variables:
Acid concentration
Hydrolysis time
Reaction temperature
Varying PVA
and starch ratio
Response:
Yield of
nanocellulose
Varying nanocellulose
content
Characterize composite
X-ray diffraction
Morphology analysis
Tensile strength
Water absorption
Biodegradability
Comparative study
Figure 3.1: Flowchart of laboratory work
60
3.2
Materials
3.2.1
Polyvinyl Alcohol (PVA)
In this study, polyvinyl alcohol with degree of hydrolysis about 88% was
purchased from Fluka. The general characteristics of this polymer include an ester
value of 140 mg KOH/g, residual acetyl content of about 10.8 wt% and max ash
content of 0.5%.
3.2.2
Starch
The starch used in the blend film was a corn starch and it was purchased from
local market.
3.2.3
Natural Fiber
Palm oil empty fruit bunch (EFB) fibers were collected from Kulai, Johor and
were used as reinforcement in PVA/starch blend films. As received, the fibers were
preconditioned prior to cellulose extraction.
The fibers were first washed with
distilled water for several times and dried in an oven for 24 hours. Then the fibers
were cut to length of approximately 45 cm and subsequently ground into fine
powder using a grinder.
61
3.2.4
Other Chemicals
Other chemicals used in this study were sodium chlorite, sodium sulfite,
sodium hydroxide, acetic acid, sulfuric acid and glycerol. All the chemicals are
reagent grade and were used as received from MD Interactive Sdn Bhd.
3.3
A 0.7% (w/v) sodium chlorite solution was prepared and then acetic acid was
added to acidify the NaClO2 solution until the pH reached to 4. The fibers were
boiled in NaClO2 solution for 2 hours at 7080 C whereby the ratio of fiber to
NaClO2 solution was set to 1:50. The bleaching process was repeated for four or five
times until the fiber became white and then were filtered. After being filtered, the
residue were washed for several times with distilled water and dried in air. The
bleached cellulose obtained were heated to about 70 to 80 C in 5% (w/v) sodium
sulfite solution for 2 hours. The fibers were filtered, washed and dried in air. After
being dried, the fibers were treated in 17.5% (w/v) sodium hydroxide solution for 2
hours. The residue were washed for several times with distilled water and dried in
air. This procedure was followed from the works of Moran et al. (2008).
62
3.4
After alkali treatment of fibers, the cellulose materials were hydrolyzed in 60

wt% sulfuric acid solution under strong agitation at 45 C for 30 minutes (Moran et
al., 2008). Then, cold water was added to stop the reaction. The diluted suspension
was then centrifuged at 11000 rpm for 10 minutes to obtain the precipitate. This
process was repeated until the pH of the suspension reached to pH 5. Then, the
dialysis was carried out for 3 days (Fahma et al., 2010).
Subsequently, the
suspension was dried in an oven at 65 C overnight.
3.5
Characterization of Fiber
3.5.1
Holocellulose content was determined by a modified sodium chlorite method

according to Browning (1967). A sample of approximately 3 g of EFB fiber was
weighted and placed in an Erlenmeyer flask with 160 mL of distilled water, 0.5 mL
of acetic acid and 1.5 g of sodium chlorite. This mixture was then heated in water
bath for 1 hour at 75 C. An additional 0.5 mL of acetic acid and 1.5 g of sodium
chlorite were added to the mixture for every 1 hour for up to three hours. The
mixture was cooled down at a temperature below 10 C by placing the flask in an ice
bath. After the mixture has cooled down, the mixture was filtered. The residue was
then washed with acetone, ethanol and water consecutively. The remaining residue
which is known as holocellulose was transferred to the crucible and subsequently
weighed after it was left in oven at 105 C overnight. Equation 3.1 shows the
calculation for holocellulose content.
63
Holocellulose content = W2 W1
(3.1)
where W1 is the weight of empty crucible and W2 is the weight of the crucible
containing the dry residue.
The cellulose content was determined by further treatment of holocellulose

with sodium hydroxide solution in order to remove hemicelluloses, as specified in
ASTM Standard Test D1103-55T. Sodium hydroxide solution at concentration of
17.5% was first prepared. The obtained holocellulose was added to 10 mL of the
prepared sodium hydroxide solution. The samples were stirred with a glass rod in
order to ensure that the samples were completely soaked in sodium hydroxide
solution. A 10 mL of sodium hydroxide solution was then added to the mixture
every 5 minutes for half an hour, whereby the temperature of the mixture was kept
constant at 20 C. Then, 33 mL of distilled water was added to the mixture and let it
stand for one hour. Finally, the mixture was filtered and washed with 100 mL of
8.3% sodium hydroxide, 200 mL of distilled water, 15 mL of acetic acid and again
with an excess amount of water. The remaining residue which is known as
cellulose was transferred to the crucible followed by weighing the crucible after it
was dried in oven at 105 C for 24 hours. The percentage of cellulose was calculated
using equation 3.2.
Percentage of -cellulose =
W4 W3
100%
W5
(3.2)
where W3 is the weight of empty crucible, W4 is the weight of the crucible

containing the dry residue and W5 is the weight of EFB fiber (3 g).
64
Hemicellulose content was calculated as the difference between the value of
holocellulose and cellulose. Meanwhile, lignin content was determined according
to the ASTM Standard Test D1106-56. Approximately 3 g of fibers were frequently
stirred with 15 mL of 72% sulfuric acid solution for two and half hour at room
temperature. Then 200 mL of distilled water was added and the mixture was boiled
for 2 hours. After being boiled, the mixture was allowed to cool to room temperature
for 24 hours. Subsequently, the mixture was filtered and the residue was washed
with hot water to remove acid. The residue which is known as lignin was transferred
to the crucible and subsequently weighed after it was left in oven at 105 C
overnight.
The percentage of hemicelluloses and lignin was calculated using
equations 3.3 and 3.4, respectively.
Percentage of hemicellulose =
Percentage of lignin =
W6 W7
100%
W5
W8 W9
100%
W5
(3.3)
(3.4)
where W5 is the weight of EFB fiber (3 g), W6 is the weight of holocellulose, W7 is

the weight of cellulose , W3 is the weight of empty crucible and W9 is the weight
of the crucible containing the dry residue.
65
3.5.2
Fourier Transform Infrared Spectroscopy (FTIR)
In this study, FTIR spectra of raw EFB, cellulose and nanocellulose fibers
were obtained by using Spectrum One-Perkin Elmer with software spectrum v5.02
(Polymer Analysis Lab, Faculty of Chemical Engineering, UTM). The fibers were
crushed into small particles and then blended with potassium bromide (KBr)
followed by pressing the mixture into ultrathin pellets. In this analysis, ratio of
fiber to KBr was approximately 1:99. A total of 100 scans were recorded in the
range 3704000 cm-1 with a resolution of 2 cm-1 for each sample.
3.5.3
XRay Diffraction (XRD)
Xray Diffraction (XRD) is a versatile and nondestructive analysis that

reveals information about the type and nature of crystalline phases present in the
samples as well as the degree of crystallinity and amount of amorphous content. The
XRD patterns for untreated, cellulose and nanocellulose fibers were measured by
using Nifilter Cu K radiation, with a wavelength of 0.1541 nm at 40 kV and 40
mA (Tang et al., 2014). Powder samples were scanned in 2 range varying from 10
to 50. Equation 3.5 was used to calculate the crystallinity index of the fibers.
Crystallinity index =
I 200 I am
100%
I 200
(3.5)
where I200 is the height of the 200 peak, which represents both crystalline and
amorphous material while Iam is the lowest height between the 200 and 110 peaks,
which represents amorphous material.
66
3.5.4
Thermogravimetric Analysis (TGA)
In this study, thermogravimetric analysis was carried out from 50 to 900 C at

a heating rate of 10 C/min. Approximately 10 to 20 mg of each sample was heated
under a nitrogen atmosphere with a gas flow of 20 mL/min in order to prevent any
thermoxidative degradation.
3.5.5
Field Emission Scanning Electron Microscope (FESEM)
A JEOL JSM7600F field emission scanning electron microscope with EDX

system (Microelectronic and NanotechnologyShamsuddin Research Centre,
UTHM) was used at voltage of 2 kV to investigate the morphology of the fibers. To
perform the FESEM analysis, the fibers were first coated with a thin layer of gold by
sputtering before the FESEM imaging take place.
3.5.6
Transmission Electron Microscopy (TEM)
TEM images were obtained using a JEM2100 transmission electron

microscope (Nanochemistry Laboratory, Ibnu Sina Institute for Fundamental Science
Studies, UTM) operated at 120 kV. For TEM sample preparation, the nanocellulose
particles were deposited on a carboncoated grid by placing a drop of a very dilute
cellulose nanofiber suspension on the grid and then allowed to dry in order to
evaporate the liquid.
67
3.6
3.6.1
Screening Test
In this study, the screening test was started with different acid concentrations
in the range of 45 to 85 wt%, under constant reaction temperature (45 C) and
hydrolysis time (30 minutes). In another hydrolysis experiment, hydrolysis was
performed for 30, 45, 60, 75 and 90 minutes, by using 60 wt% acid sulfuric solutions
at the temperature of 45 C in order to study the effects of time. Meanwhile, the
reaction temperature was varied at 25, 35, 45, 55, 65 C with an acid concentration of
60 wt% and the reaction time of 30 minutes to understand the effect of changes of
temperature on the yield of nanocellulose. The parameter values for this screening
test are summarized in Table 3.1.
Table 3.1: The parameter values for screening test

Acid
Concentration (wt%)
Hydrolysis
Time (min)
Reaction
Temperature (C)
45, 55, 65, 75, 85

60
60
30
30, 45, 60, 75, 90
30
45
45
25, 35, 45, 55, 65
3.6.2
Statistical Design
Response Surface Methodology (RSM) was used to investigate the effect of

different factors regarding the isolation of nanocellulose fibers. Three variables and
one response were used.
The variables investigated are acid concentration,
hydrolysis time and reaction temperature. Independent variables were studied at
68
different levels; low (-1), medium (0) and high (+1), whereby the level values for
each variable of the experimental design were selected according to previous
screening test results. The yield of nanocellulose was calculated using equation 3.6.
Yield of nanocellulose =
m
100
(3.6)
where m is the volume of nanocellulose obtained after acid hydrolysis and is the
percentage of nanocellulose (for particle with size less than 20 nm). The size of
nanocellulose was obtained from analysis with nano-size analyzer.
3.7
PVA/Starch Reinforced with Nanocellulose Fiber Film Preparation
An aqueous solution containing PVA, starch, glycerol and nanocellulose fiber

were used to cast the film. The PVA and starch solution was prepared by stirring
PVA powder first in 100 mL distilled water at 97 C, since PVA requires at least 90
C to be dissolved in water. After that, starch was added and the mixture was again
heated and stirred at 97 C for 30 minutes (Rahman et al., 2010). Glycerol was
added to the mixed solution at a 30 wt% ratio based on total weight of starch and
PVA (Das et al., 2011). A solution of 5 g mixed polymer were cast on Petridish
plate and dried at room temperature for 2 days. After the film was completely dried,
the film was peeled off from the plate. The composition of PVA, starch and glycerol
for the preparation of the films is shown in Table 3.2.
69
Table 3.2: The composition of PVA, starch and glycerol
Sample
PVA/Starch
PVA (g)
Starch (g)
Glycerol (g)
Water (mL)
PS100
100:0
10
3.0
100
PS82
80:20
3.0
100
PS73
70:30
3.0
100
PS64
60:40
3.0
100
PS55
50:50
3.0
100
PS46
40:60
3.0
100
The PVA/starch nanocomposites were prepared by the addition of a

nanocellulose fiber to the plasticized PVA/starch solutions. The ratio between PVA
and starch is chosen based on tensile strength and water absorption properties that
yield optimum results in the previous experiment. Five sets of nanocomposites with
a nanocellulose content of 5, 10, 15 and 20% (v/v) with respect to the volume of
PVA and starch solution were prepared. The solutions were cast on Petridish plate
and dried at room temperature for 2 days. After the film was completely dried, the
film was peeled off from the plate.
3.8
Characterization of Composite
3.8.1
XRay Diffraction (XRD)
The XRD patterns for PVA, starch and PVA/starch film were measured by
using Nifilter Cu K radiation, with a wavelength of 0.1541 nm at 40 kV and 40
mA (Tang et al., 2014). Composite films were scanned in 2 range varying from 10
to 50.
70
3.8.2
Scanning Electron Microscopy (SEM)
The surface morphology of the film samples were investigated by using a

JEOL JSM6390LV scanning electron microscope, with the accelerating voltage of
50 kV. All specimens were coated with gold and then observed.
3.8.3
Mechanical Test
Mechanical tests were performed on the composite films for obtaining the
tensile strength and elongation at break. Maximum tensile strength is the largest
stress that a film is able to sustain against applied tensile stress before the film tears
meanwhile elongation at break is the maximum percentage change in the original
film length before breaking.
The tensile strength and elongation at break of the composite films were
measured on the 2.5 kN Lloyd tensile tester according to the ASTM D882. The test
was conducted at Polymer Analysis Lab, Faculty of Chemical Engineering, UTM.
Samples with rectangular shape were cut into 60 mm 13 mm strips from the films.
The cut films were conditioned at the temperature and relative humidity of 23 2C
and 50 10%, respectively for more than 40 hours prior to measurement of
mechanical properties in order to provide adequate air circulation on all sides of the
composite films (Procedure A of Practice ASTM D618).
Tensile testing was
conducted at a cross-head speed of 10 mm/minute and a gauge length of 40 mm. Six

samples were tested for each set and averaged. The maximum tensile strength and
elongation at break were calculated using equations 3.7 and 3.8, respectively.
71
Maximum tensile strength =
Elongation at break =
N
A
L
100%
(3.7)
(3.8)
where N is the maximum load recorded, A is the cross section area, L is the length at
break and is the initial gauge length
3.8.4
Water Absorption Test
The water absorption capacity of the composite films was measured by

drying the film in a vacuum oven at 50 C for 24 hours. Then, the film was cooled in
desiccator and immediately weighted. The conditioned film was fully immersed in
distilled water for 5 minutes. Subsequently, the remaining water on the surface of
film was removed by using filter paper and immediately weighted (Xiong et al.,
2008). All measurements were performed for four specimens and averaged. The
water absorption capacity was calculated using equation 3.9.
Water absorption capacity =
WA WI
100%
WI
(3.9)
where WA is the weight of film after being immersed in distilled water and WI is the
initial dry weight of the film.
72
3.8.5
Soil Burial Degradation Test
Soil burial degradation was performed as described by Yoon et al. (2012)

with a slight modification. The films were cut into 50 mm 50 mm strips and then
were weighted. Then the test was carried out by burying the films in the soil placed
in a flower pot at the depth of 5 cm. The humidity, temperature and moisture values
was negligible and does not require any adjustment in order to provide a realistic
environment, where soil humidity, temperature and type and amount of
microorganisms are in less control and change with weather. At a 15 day interval, the
films were taken out carefully from the soil. The remaining soil on the surface of the
film was removed and then weighted. The degradation rate in the soil burial test was
determined by calculating the weight loss of the films with time using equation 3.10.
Degradation rate =
WI WH
100%
WI
(3.10)
where WH is the dry weight of the specimen after being buried in the soil and W I is
the initial dry weight of the specimen.
3.9
Comparative Study
In this section, cellulose reinforced PVA/starch composite film was prepared

in order to compare the characteristics between pure PVA film, PVA/starch blend
film, cellulose reinforced PVA/starch composite film and nanocellulose reinforced
PVA/starch composite film. The same procedure was applied for the preparation of
cellulose reinforced PVA/starch composite film.
CHAPTER 4
RESULTS AND DISCUSSION
4.1
Introduction
This chapter presents and discusses the research findings from the analyses
conducted in Chapter 3. The results are divided into five sections. This chapter
begins with a discussion of the properties of fiber before and after being subjected to
alkali treatment and acid hydrolysis.
It is then followed by the effects of the
hydrolysis conditions on the yield of nanocellulose and the results obtained through
response surface methodology (RSM) are also explained in Section 4.2. The third
and fourth section presents the properties of PVA/starch composite and
nanocomposites, respectively.
Finally, overall comparison is made between
composite and nanocomposite film.
74
4.2
Characteristics of Fibers
Figure 4.1a shows the raw material used in this study, which is palm oil EFB
fiber while Figure 4.1b shows the cellulose fiber obtained after alkali treatment.
Subsequently, nanocellulose fiber (Figure 4.1c) was produced by acid hydrolysis
method.
Figure 4.1: Photograph of (a) EFB fiber, (b) cellulose fiber, and (c) nanocellulose
fiber
4.2.1
The content of the three major components, which is cellulose,

hemicelluloses and lignin, of the EFB fiber before treatment and after each stage of
treatments is summarized in Table 4.1.
75
Table 4.1: Chemical composition of the EFB fiber in different stages
-Cellulose (%)
Hemicellulose (%)
Lignin (%)
Untreated fiber
47.80
18.07
15.55
Cellulose fiber
92.30
5.23
2.15
Nanocellulose fiber
93.03
5.03
1.60
Materials
From the data, it was found that cellulose content was increased
significantly from 47.80% to 92.30% for untreated and treated cellulose fiber,
respectively.
Meanwhile, the cellulose content in nanocellulose fiber was
increased slightly to 93.03% and hence may indicate a case whereby experimental
errors have occurred. On the other hand, the original EFB fibers have recorded the
highest percentage of hemicelluloses, which is 18.07%.
When the fibers were
subjected to alkaline treatment, the hemicelluloses percentage of cellulose fibers

decreased to 5.23%. A decrease of not more than 0.2% of the hemicelluloses content
resulted in nanocellulose fiber.
The same trend can also be observed for the
percentage of lignin, whereby the lignin content decreased from 15.55% to 2.15%
when treated with sodium hydroxide followed by acid hydrolysis treatment (1.60%).
The decrement in the percentage of lignin and hemicellulose was a result of

the swelling of the cell wall during alkaline treatment which causes the noncellulosic materials gets dissolved (Joshy et al., 2008). Another possible explanation
for this decrement in lignin and hemicellulose percentage is the disruption of the
hydrogen bonding in the network structure by sodium hydroxide solution (Bhatnagar,
2004). In addition, the EFB fibers were also subjected to a number of consecutive
stages of bleaching process to ensure that most of the lignin would be removed from
this fiber. Sodium chlorite and acetic acid were applied to the fiber so that lignin
would be rapidly oxidized by chlorine and chlorites. Lignin oxidation leads to lignin
degradation and therefore allowing for efficient removal of lignin (Bhatnagar and
Sain, 2005; Jonoobi et al., 2011). Further treatment using sulfuric acid was also able
to remove lignin and hemicelluloses due to the ability of sulfuric acid to dissolve
amorphous region effectively.
76
4.2.2
Fourier Transform Infrared Spectroscopy
The FTIR spectra of the untreated, cellulose and nanocellulose fibers are
shown in Figure 4.2.
Figure 4.2: FTIR spectra of (a) untreated fiber, (b) cellulose, and (c) nanocellulose
As shown in Figure 4.2, all samples presented two main regions of

absorbance; the first one at low wavelengths (5001750 cm-1) and the second one at
higher wavelengths (28003500 cm-1). This observation is in agreement with the
study done by Moran et al. (2008). The absorption peak located in the range 3300
3450 cm-1 and 28902900 cm-1 in all samples are attributed to the hydroxyl group
and aliphatic saturated CH stretching vibration, respectively (Cherian et al., 2008;
Khalil et al., 2001; Moran et al., 2008). The peaks appearing from 1330 to 1360 cm1
is due to the bending vibration of the CH and CO groups in the polysaccharide
77
aromatic rings in cellulose, hemicelluloses and lignin (Troedec et al., 2008).
Meanwhile, stretching of CO and OH was reflected by peaks appearing in the
region 10501070 cm-1 (Nacos et al., 2006) and the peak at 1055 cm-1 arises could be
due to the COC pyranose ring stretching vibration in all samples (Mandal and
Chakrabarty, 2011).
Stretching vibrations of C=C bonds in the lignin are found in the 16081623
cm-1, whereby the peak at 1623 cm-1 is caused by vibrations of C=C bonds in the
benzene stretching ring. Meanwhile, the vibration of the aromatic rings can be seen
at 1608 cm-1 in the spectra of the untreated fiber, which is attributed to the C=C
stretching of the carboxyl groups (Nacos et al., 2006). In addition, lignin presented
characteristic peak at 1432 cm-1 was due to the presence of methoxyOCH3 while
the vibration peak at 1259 cm-1 has been related to the COC stretching of the arylalkyl ether (Yang et al., 2007). Disappearance of all these peaks from the spectra of
the treated fibers can be ascribed to treatment of the EFB fibers with sodium chlorite
followed by sodium hydroxide as these treatments are known to remove most of the
lignin from the EFB fibers.
Furthermore, the most noticeable difference between spectra of the untreated

fiber and those of the chemically treated ones is disappearance of the vibration peak
observed at 1736 cm -1 from the spectra of the alkali treated fibers. This peak is also
absent in the sulfuric acid hydrolysed cellulose. The peak observed at 1736 cm
-1
in
the spectra of the untreated fibers is likely to be associated to the C=O stretching in
the acetyl and uronic ester groups of hemicelluloses or the ester carbonyl groups in
the p-coumaric units of the lignin. Another possibility is that carboxyl or aldehyde
absorption could be arising from the opened terminal glycopyranose rings or
oxidation of the COH groups (Alemdar and Sain, 2007; Jonoobi et al., 2011). This
peak has disappeared from the spectra of cellulose fibers and it is believed to be due
to removal of hemicellulose by the bleaching and alkali treatment.
78
By comparing the spectra of the untreated and treated EFB fibers, the peak
presents at 1646 cm-1 corresponding to the treated fibers are related to the absorption
of water by cellulose. Appearance of this peak in the spectra of the cellulose fibers is
probably due to reaction of sodium hydroxide with the hydroxyl groups of celluloses
and subsequent formation of water molecules (Troedec et al., 2008). As pointed out
by Abraham et al. (2011), even though the treated fibers were subjected to the drying
process, the water adsorbed in the cellulose molecules is very difficult to be extracted
due to the cellulose-water interaction.
From the FTIR analysis, it has been concluded that almost all the lignin and
hemicelluloses were removed after the process of bleaching and alkali treatment.
This arises from the absence of the absorption bands in between 15001600 cm-1 and
17301740 cm-1, which relates to the lignin and hemicelluloses components,
respectively. In addition, it was found that the spectra of nanocellulose resembles to
that of cellulose. Therefore, it can be stated that the cellulose and nanocellulose
obtained in this study were almost pure, which contains a very small amounts of
lignin and other non-cellulosic substances.
4.2.3
XRay Diffraction
The X-ray diffractogram of the untreated EFB fiber, cellulose and

nanocellulose are shown in Figure 4.3.
79
I110
Iam
I200
Figure 4.3: X-ray diffraction patterns for (a) untreated fiber, (b) cellulose, and (c)
nanocellulose
As can be seen, all the three samples had diffraction peaks at around 2=22
(for 200 plane) and 2=14 (for 110 plane), representing the presence of crystalline
and amorphous cellulose structure, respectively. The crystallinity index of untreated
EFB fiber, which was calculated by Segal formula (Segal et al., 1959), was
approximately 38% while that of cellulose fiber was estimated 63%.
For
comparison, the cystallinity index of cellulose from EFB fiber in previously

published studies, was found to be around 55% (Fahma et al., 2010), 59% (Rozana,
2011) and 61% (Jonoobi et al., 2011). Therefore, it can be concluded that the
bleaching process with sodium chlorite followed by treatment with sodium
hydroxide, as employed in this study, is suitable in order to obtain cellulose fibers
with high crystallinity. In addition, the crystallinity of cellulose obtained was higher
than that of the untreated fiber can be explained due to the high removal efficiency of
non-cellulosic components from the fibers, which are generally amorphous
(Abraham et al., 2011; Jonoobi et al., 2011).
80
As stated in the literature, cellulose in natural fibers comes in four types of
cellulose that are classified as type I, II, III and IV. It is interesting to note that the
untreated EFB fiber shows typical cellulose I structure, based on the fact that there is
no doublet in the main peak at 2=22 (Bhatnagar and Sain, 2005; Klemm et al.,
2005). After treating the EFB fiber with sodium hydroxide, the crystalline peak
appears as a doublet at 2=22 and 2=23, representing transformation of native
cellulose from cellulose I to cellulose II. A significant variation in the diffraction
pattern of untreated and cellulose fibers can be explained by the replacement of OH
groups by ONa groups during alkaline treatment. Subsequent rinsing with water will
remove the linked Na-ions and thus causing the cellulose to be converted to a new
crystalline structure, which is cellulose II (John and Anandjiwala, 2007).
On the other hand, there is also a significantly different between untreated

fiber and nanocellulose fiber for their crystallinity index. Nanocellulose fiber shows
the highest value of crystallinity, which is approximately 73%. By comparing the
results, nanocellulose from EFB fiber obtained in this study exhibited higher
crystallinity than those produced by Fahma et al. (2010) and Jonoobi et al. (2011),
which is around 59 and 69%, respectively. According to the Jonoobi et al. (2011),
the higher crystallinity of nanofiber was due to the peeling reactions that take place
in the amorphous areas during the hydrolysis process. Because of the ability of
sulfuric acid to penetrate into the amorphous region, the glycosidic bonds were
cleaved under hydrolytic conditions and finally releasing individual crystallites
(Dufresne, 2012; Li et al., 2009).
The crystallinity index of fiber may affected the final properties of the
composite, whereby the higher crystallinity value of the nanocellulose compared to
the raw and cellulose EFB fiber could be more effective in providing better
reinforcement for composite materials. Therefore, the high crystalline fiber might be
expected to improve the properties of the composite.
81
4.2.4
Thermogravimetric Analysis
The decomposition of hemicelluloses, lignin and cellulose at different

temperature are strongly influenced by the differences in their chemical structures.
According to Lee et al. (2004), thermal degradation of lignocellulosic materials starts
with an early decomposition of hemicelluloses, followed by the early pyrolysis of
lignin, depolymerization of cellulose, active flaming combustion and char oxidation.
The thermogravimetric (TG) curves of the EFB fibers before and after treatments are
shown in Figure 4.4.
Figure 4.4: Thermogravimetric curves of (a) untreated fiber, (b) cellulose, and (c)
nanocellulose
As seen in Figure 4.4, all the TG curves showed the small weight loss from
50 to 100 C corresponding to the mass loss of water or low molecular weight
compound remaining from the isolation procedures (Moran et al., 2008). The figure
also showed that the raw EFB fiber started to degrade at around 240 C due to the
early decomposition of hemicelluloses.
Meanwhile, the onset of the thermal
degradation of cellulose fiber occurs at a higher temperature than raw fiber, which is
around 340 C. This trend of a rise in decomposition temperature can be explained
82
due to removal of hemicelluloses, pectin and lignin in the cellulose obtained after the
chemical treatments.
For nanocellulose fibers, the onset temperature of degradation was found to

take place at 180C. The reasons for this kind of behaviour was related to the
introduction of sulfate group content into the crystal of cellulose during acid
hydrolysis process and therefore reduces the thermal stability of nanocellulose
(Mandal and Chakrabarty, 2011).
According to Kargazadeh et al. (2012), the
presence of sulfate group in nanocellulose can be identified from FTIR spectra,

whereby the peak at around 1100 cm-1 is composed mostly of a SO4 stretching.
Unfortunately, this peak may be lost in the peak from the CO groups in
polysaccharides aromatic ring.
Furthermore, the lower initial temperature of
decomposition of nanocellulose compared to those of raw EFB and cellulose fiber

could also due to the smaller particle size of nanocellulose and caused more free end
chains, whereby the end chains started the decomposition at lower temperature
(Krishnamachari et al., 2011).
From Figure 4.4, it also can be observed that the degradation behaviour of
nanocellulose showed a different mechanism from that of raw EFB and cellulose
fiber. This is manifested by the presence of two different curves that has a different
slope. The lower temperature stage showing a curve in the temperature range from
140 to 290 C is related to the degradation of highly sulfated amorphous regions,
whereas the higher temperature stage showing a curve in the temperature range of
290395 C was due to the breakdown of unsulfated crystal interior (Mandal and
Chakrabarty, 2011).
83
4.2.5
Field Emission Scanning Electron Microscopy
Figures 4.5, 4.6 and 4.7 show the FESEM images of untreated EFB fibers,
cellulose fibers and nanocellulose fibers, respectively.
Meanwhile, the dashed
rectangles in (a), (b) and (c) correspond to the image in (b), (c), and (d), respectively.
Figure 4.5: FESEM images of raw EFB fiber at (a) 60 (b) 1000 (c) 8000 and (d)
80000 magnification level
84
Figure 4.6: FESEM images of cellulose fiber at (a) 60 (b) 1000 (c) 8000 and (d)
80000 magnification level
Figure 4.7: FESEM images of nanocellulose fiber at (a) 60 (b) 1000 (c) 8000
and (d) 80000 magnification level
85
As shown in Figures 4.5a and 4.6a, it can be seen that the cellulose fiber
bundles in the untreated EFB fibers was separated extensively into individual
cellulose fibers after alkali treatment. A change in the fibril structure could also
represent the removal of noncellulosic components as hemicelluloses and lignin
shield surrounds cellulose. The cementing components present in the raw EFB fibers
get dissolved during alkali treatment and thus, enabling the separation of cellulose
into individual microsized fibers. The removal of hemicelluloses and lignin can
also be observed, whereby the noncellulosic components that covered the raw EFB
fiber (Figure 4.5b) were disappeared in the alkalitreated fiber (Figure 4.6b).
Meanwhile, Figure 4.6c clearly showed that the alkali treated fiber had well
aligned pattern of cellulose microfibrils and became more structured, which could
not be seen in the raw EFB fibers (Figure 4.5c). In addition, the surface of the
treated fibers looks smoother than that in the untreated one, as seen in Figures 4.5d
and 4.6d. The cleaner surface of treated fibers was noticed due to the removal of
hemicelluloses and lignin, whereby these two components were black in color
(Kabir, 2012).
On the other hand, it was found that the FESEM image of nanocellulose, as
observed in Figure 4.7a, showed a very different morphology. This could be due to
their drying effect in conventional oven, whereby the dried nanocellulose fibers
formed a platelike structure with different sizes. The appearance of pores on the
fiber surface of nanocellulose can be explained by the removal of some fatty
substance form the fiber surface. Furthermore, ovendried nanocellulose fiber also
exhibited a smooth surface as untreated and alkali treated fiber.
86
4.2.6
Transmission Electron Microscopy
Figure 4.8 shows the TEM micrograph of a dilute suspension of

nanocellulose from EFB fiber produced by acid hydrolysis.
Figure 4.8: TEM image of nanocellulose from EFB fiber
87
The analysis of the TEM micrograph revealed that the aqueous suspension of
nanocellulose fiber consisting of rod like nanoparticles, whereby there were some
nanoparticles are agglomerated in the forms of bundles while some of them were
well separated. According to Othman et al. (2012), agglomeration is generally due
to the Van der Waals attraction forces between nanoparticles.
Moreover, it can be seen that the diameter of the nanocellulose fiber was
found to be in the range of 415 nm. Interestingly, the diameter of the nanocellulose
obtained in this study was smaller than those produced by an acid hydrolysis from
different sources such as cotton linter (14.6 3.9 nm) by Roohani et al. (2008),
microcrystalline cellulose (28 9 nm) by BilbaoSainz et al. (2011) and sisal fiber
(30.9 12.5 nm) by Moran et al. (2008) as well as those produced by mechanical
treatment originating from rutabaga fiber (Bhantnagar and Sain, 2005), bamboo fiber
(Chen et al., 2011) and rubberwood (Jonoobi et al., 2011), for which the range of
diameter have been reported as 520 nm, 3080 nm and 1090 nm, respectively.
4.3
The optimization study was started with a screening experiment, whereby the
effects of acid concentration, hydrolysis time and reaction temperature on the yield
of nanocellulose were investigated by single-factor experiment.
Subsequently,
response surface methodology (RSM) was used to further investigate the optimal
conditions for these factors on nanocellulose yield.
88
4.3.1
Screening of Hydrolysis Conditions
The hydrolysis conditions were found to have a significant impact on the

efficiency of acid hydrolysis and thus to the yield of nanocellulose. Thus, in this
study, sulfuric acid concentration, hydrolysis time and the reaction temperature were
taken into consideration when determining the yield of nanocellulose. In reference to
Fan and Li (2012), the impact level of these three factors was in the following order:
sulfuric acid concentration > hydrolysis time > reaction temperature.
4.3.1.1 Effect of Acid Concentration
Hydrolysis of EFB cellulose fiber was carried out at various concentration of

acid, which was from 45 to 85 wt%. A preliminary study on the effect of sulfuric
acid concentration in acid hydrolysis was conducted at 45 C for 30 minutes and the
yield of nanocellulose and observation of the suspension are given in Table 4.2.
Table 4.2: Effect of sulfuric acid concentration on the yield of nanocellulose

Acid concentration
(wt%)
45
Yield (mL)
Observation*
White suspension, with large fiber particle
55
50
White suspension
65
Light yellow suspension
75
2.3
Black suspension
85
1.8
Black suspension
* refer to Appendix C
89
As shown in Table 4.2, the yield that was obtained when acid hydrolysis was
carried out at sulfuric acid of 45 wt% was not measured because the cellulose was
not completely dissolved in sulfuric acid solution even after acid hydrolysis process
was completed. The existence of such large agglomerate and poorly dispersed fibers
in suspension indicated that the nanoscale particles could not be formed at very low
acid concentration.
The yield of nanocellulose with 55 wt% sulfuric acid was recorded to be

around 50 mL and then it was drastically decreased from 50 to 5 mL when the acid
concentration increased from 55 to 65 wt%. The yield of nanocellulose were kept
decreasing with further increasing in acid concentration. Increasing of sulfuric acid
concentration to more than 65 wt% caused the cellulose to be fully dissolved.
According to Camacho et al. (1996), the cellulose that has been dissolved in high
concentration of sulfuric acid solution cannot be regenerated after being diluted with
water. This is because the cellulose is rapidly depolymerized in acidic conditions,
thus resulting to the formation of water-soluble oligomers.
Also it can be observed that the white suspension of nanocellulose was

gradually changed into light yellow as the sulfuric acid concentration was increased.
The possible reasons for the changing colors of suspension are due to the some
coloring matter which existed in glucose. Cellulose molecules can be broken down
into glucose by treating it with sulfuric acids at high concentrations (Fan and Li,
2012). Consequently, with further increase of the concentration of the sulfuric acid
has changed the color of suspension to black due to the incomplete combustion of
cellulose fibers.
Therefore, a black residue of char was produced, which is
composed primarily of carbon, as acid removes hydrogen and oxygen by the action
of heat (Yu et al., 2012).
90
4.3.1.2 Effect of Hydrolysis Time
The effect of hydrolysis time was investigated for the time of 30, 45, 60, 75
and 90 minutes, by using 60 wt% acid sulfuric solutions at the temperature of 45 C.
Table 4.3 presents the yield of nanocellulose against hydrolysis time.
Table 4.3: Effect of different hydrolysis time on the yield of nanocellulose

Hydrolysis Time
(min)
Yield of
Nanocellulose (mL)
Observation*
30
14.7
White suspension
45
8.3
Light yellow suspension
60
5.1
Yellowish brown suspension
75
2.5
Black suspension
90
1.9
Black suspension
* Refer to Appendix C
From the result, the highest value of nanocellulose yield was found to be 14.7
mL at hydrolysis time of 30 minute.
Also it was found that the yield of
nanocellulose was continuously decreased with the increase in the hydrolysis time.
When the reaction time was increased, it can be observed that the color of the
suspension changed from light yellow to yellowish brown and subsequently to black
as the hydrolysis time was continued to extent to 75 minutes and above.
Fan and Li (2012) stated that the longer hydrolysis time led to the reduction
of acid hydrolysis efficiency and thus, reducing the yield of nanocellulose.
Furthermore, prolonged acid hydrolysis was not only removed the amorphous region
but also leaving the crystalline region to be accessible for hydrolytic attack. In
general, the yield of nanocellulose was decreased as parts of the crystalline regions
were hydrolyzed (Sadeghifar et al., 2011). In another study, Dong et al. (1998)
91
indicated that too long hydrolysis time decreased the dimensions of the resulting
nanocellulose and also to the yield.
4.3.1.3 Effect of Reaction Temperature
The effect of temperature on the yield of nanocellulose is shown in Table 4.4.

A temperature ranged from 25 to 65 C with an acid concentration of 60 wt% and the
reaction time of 30 minutes was studied.
Table 4.4: Effect of different reaction time on yield of nanocellulose

Reaction
Temperature (C)
Yield of Nanocellulose
(mL)
Observation*
25
12.3
White suspension
35
13.1
White suspension
45
14.7
White suspension
55
4.2
Black suspension
65
2.2
Black suspension
* Refer to Appendix C
As can be seen, higher yield of nanocellulose was obtained at reaction

temperature of 45 C compared to either temperature of 25 or 35 C. The yield of
nanocellulose slightly increased from 12.3 to 14.7 mL, when the temperature was
increased from 25 to 45 C. However, the yield was decreased to 2.2 mL when the
temperature was increased to 65 C. Similar to the results on the hydrolysis time
variation, the color of suspension became black as the temperature rose to 55 C.
92
According to Ioelovich (2012), the sulfonation process takes a longer time
when the reaction is carried out at low temperature. Therefore, as mentioned earlier,
the longer hydrolysis time led to the reduction of nanocellulose yield (Fan and Li,
2012). Meanwhile, the yield of nanocellulose begins to fall with further increment in
temperature of 45 C. This is due to the decrease in the crystallinity degree of
regenerated cellulose that results from the destruction of crystalline regions.
Therefore, low degree of crystallinity leads to a decrease in yield of nanocellulose
(Dong et al., 1998).
4.3.2
Response Surface Methodology (RSM)
The screening results were analyzed in order to determine the optimum

ranges of values of independent variables in the design. Based on preliminary
screening test results, the concentration of the sulfuric acid would be within the range
of 55 to 65 wt%. Meanwhile, the acceptable ranges of hydrolysis time should be
within 30 to 60 minutes at the reaction temperature of 25 to 45 C. The value of
three parameters (X1, X2 and X3) each at three levels, coded -1, 0 and +1, for low,
middle and high values, respectively are presented in Table 4.5. In addition, the
effect of hydrolysis conditions on the yield of nanocellulose is shown in Table 4.6.
Table 4.5: Code and level of factors chosen for RSM design
Factor
Acid concentration, X1 (wt %)
1
55
0
60
+1
65
Hydrolysis time , X2 (minute)
30
45
60
Reaction temperature, X3 (C)
25
35
45
93
Table 4.6: Experimental design and results
Run
X1
X2
X3
m (mL)
*(%)
Total yield
(mL)
55
30
25
42
33.2
13.944
55
30
45
55
25.1
13.805
55
60
25
30
39.1
11.730
55
60
45
32
33.3
10.656
65
30
25
6.5
86.8
5.642
65
30
45
5.8
60.7
3.521
65
60
25
2.9
100
2.900
65
60
45
2.3
99
2.277
52
45
35
63
11.7
7.371
10
68
45
35
1.0
100
1.000
11
60
20
35
24
33.3
7.992
12
60
70
35
88.1
7.048
13
60
45
18
22
40.6
8.932
14
60
45
52
8.6
100
8.600
15
60
45
35
38
46.1
17.518
16
60
45
35
36
45.2
16.272
* Percentage of nanocellulose whose particle size is less than 20 nm, which is

obtained by analysis with nano-size analyzer (refer to Appendix D)
4.3.2.1 Statistical Analysis
The experimental data were fitted to the second-order polynomial model and
the regression of the obtained equation was evaluated from variance analysis
(ANOVA). The model equation representing the response (Y) was expressed in
terms of coded factor of acid concentration (X1), hydrolysis time (X2) and reaction
temperature (X3) after elimination of other insignificant terms that was derived to
predict the nanocellulose yield is expressed by equation 4.1. The ANOVA was
94
conducted with experimentally observed data to test the significance of the second
order polynomial equation and the test results are presented in Table 4.7.
Y = 586.448 + 19.011X1 0.164X12 0.013X22 0.025X32
(4.1)
Table 4.7: Analysis of variance (ANOVA) for nanocellulose yield

Source
Sum of
Degree of
Squares (SS) Freedom (df)
Mean Square
(MS)
Fvalue
F0.05
Regression (SSR)
340.4389
37.8265
6.222
4.105
Residual
36.4778
6.0796
Total (SST)
376.9167
15
The Fvalue of 6.222 implies that the model is significant, since the
calculated value of Fvalue was higher than the tabulated value of F0.05. The fit of the
model can be checked by the coefficient of determination (R2), which was calculated
to be 0.90322, indicating that the model variation of 90.32% for the response can be
demonstrated by the experimental factors and their interaction. Therefore, the R2
value in this study signifies a good correlation between the predicted and the
experimental values.
The coefficient estimates in the regression model for
nanocellulose yield and the corresponding p-value of the variables are presented in
Table 4.8.
95
Table 4.8: Regression coefficients and p value of second-order polynomial model for
nanocellulose yield
Variables
Coefficient
p-value
Significant
Intercept
-586.448
0.004503
Yes
X1
19.011
0.003047
Yes
X12
-0.164
0.002335
Yes
X2
0.918
0.292886
No
-0.013
0.011451
No
X3
1.958
0.159654
Yes
X32
-0.025
0.022625
Yes
X1X2
0.003
0.825097
No
X1X3
-0.005
0.784974
No
X2X3
0.001
0.885258
No
X2
For the regression coefficients of independent variables, both the magnitude

and sign are important.
The sign indicates the direction of the proportionality
coefficient in relation to the response, whereby a positive sign means that the
independent variable is directly proportional to the response while a negative sign
means the opposite. The acid concentration (X1), hydrolysis time (X2) and the
reaction temperature (X3), along with the interactive term (X1X2 and X2X3) exhibited
positive relationship with the nanocellulose yield, whereas all the other terms showed
negative effect on the yield. Meanwhile, the p-value is also important, whereby it
serves as a tool to check the significance of each coefficient. Table 4.8 clearly
demonstrates that X1 and all the quadratic terms are significant as the p-value is
lower than 0.05. The results obtained from Pareto analysis is illustrated in Figure
4.9.
96
acid concentration (X1)
-5.07196
acid concentration (X12)
-5.04932
time (X22)
-3.59381
temperature (X32)
-3.04608
time (X2)
temperature (X3)
-1.22675
-.424764
X1X3
-.285344
X1X2
.2308566
X2X3
.1505586
p=.05
Standardized Effect Estimate (Absolute Value)
Figure 4.9: Pareto chart showing the standardized effect of independent variables
and their interaction on the nanocellulose yield
As shown in Figure 4.9, the length of bars means the standardized effects of
independent variables and their interactions on the nanocellulose yield. For the
linear term, the acid concentration had the most important effect on the yield of
nanocellulose followed by hydrolysis time and reaction temperature. Significant
impact of acid concentration predicted by Pareto analysis was in agreement with
previous studies of Fan and Li (2012), whereby the main effects of parameters are in
the following order: acid concentration > hydrolysis time > reaction temperature. On
the other hand, the variables such as .X2, X3, X1X2, X1X3 and X2X3 remained inside
the reference line in Figure 4.9, which is due to the lower contribution in prediction
of the nanocellulose yield.
97
4.3.2.2 Verification of Predicted Model
By using response surface and contour plots, the optimum set of operating
variables was found to be at 57.9188 wt% of acid concentration, 42.6619 minutes of
hydrolysis time and 34.5941 C of reaction temperature.
At these optimized
conditions, the maximum yield of nanocellulose was predicted as 16.6839 mL by the

quadratic response surface model. Three replicates experiments were conducted
using the optimized conditions representing the maximum point of the yield of
nanocellulose, whereby the acid concentration, time and temperature was set at 58
wt%, 43 minutes and 35 C, respectively to verify the modeling results. The results
of this experiment are shown in Table 4.9.
Table 4.9: Experimental value using optimum conditions for nanocellulose yield
Run
m (mL)
(%)
Total yield (mL)
37
53.4
19.758
43
43.9
18.877
35
51.0
17.850
From Table 4.9, the average nanocellulose yield found by experiment was
18.828 mL. The result obtained showed a good correlation between predicted and
experimental value and thus verified the predictive model. As a final remark, it was
recommended that the acid hydrolysis clarification condition be 58 wt% acid
concentrations at 35 C for 43 minutes.
98
4.4
Characteristics of PVA/Starch Blend Film
4.4.1
Mechanical Properties
The calculated mechanical properties such as tensile strength and percentage

elongation at break of the PVA films with respect to the amount of starch addition
are presented in Figure 4.10.
tensile
strength
elongation
at break
9
8
7
6
300
250
200
5
4
150
100
50
1
0
Elongation at break (%)
350
10
0
100/0
80/20
70/30
60/40
50/50
PVA/starch weight ratio (g/g)
40/60
Figure 4.10: Tensile strength and elongation at break for PVA/starch blend films
As shown in Figure 4.10, it can be observed that the highest value of tensile
strength recorded was 7.946 MPa at weight ratio of 100:0, which is pure PVA film.
Results also revealed that there was a sharp decrease in tensile strength value from
7.95 to 5.127 MPa when PVA and starch were blended in the weight ratio of 80:20.
By changing the weight ratio of PVA to starch from 70:30 to 40:60, the tensile
strength of the blend films was found to decrease steadily from 3.830 to 2.389 MPa.
99
Besides that, it is also seen that the elongation at break showed a very
different trend as compared to tensile strength. The elongation at break was around
287.25% for neat PVA film, increased gradually to around 305.43% for PVA/starch
blend film in the weight ratio of 80:20, and further increased to around 334.69% for
PVA/starch blend film in the weight ratio of 70:30. After the maximum value, there
was a sudden reduction from 334.69% at weight ratio of 70:30 to 77.71% at weight
ratio of 50:50. Thereafter, the elongation at break decreased slightly from 77.71% to
62.76%.
As can be seen, the pure PVA film presented the highest value of tensile
strength. This is due to the reason that the pure PVA film is susceptible to undergo
large plastic deformation (Veerasamy, 2012). Nevertheless, addition of starch into
the PVA matrix caused the reduction in tensile strength.
As reported in most
previous studies, the tensile strength of the PVA/starch blend films were lower than
that of pure PVA film and decreased with the increase in the amount of starch.
These findings are similar to the results obtained by Ishiaku et al. (2002) and Wu
(2003) on blends of polycaprolactone and starch, as well as study conducted by
Sreekumar et al. (2012) regarding the mechanical properties of PVA and starch.
According to Tudorachi et al., 2000, the reduction in tensile strength was

mainly due to the formation of starch intramolecular hydrogen bond rather than
intermolecular hydrogen bond.
In fact, addition of higher amounts of starch
generally results in an agglomeration of starch and therefore cause starch to not

completely dispersed in the PVA solution (Ooi et al., 2012), which corresponds to
lower tensile strength. This result is in well agreement with that obtained by SEM
analysis. Figure 4.11 shows the surface morphology of the pure PVA film, 70:30
and 50:50 PVA/starch blend films. Based on the SEM images, the surface of pure
PVA film was found to be smooth, meanwhile, a large agglomeration of starch was
observed at the 50:50 blend film compared to 70:30 blend film.
100
Figure 4.11: Surface morphology of (a) pure PVA film, (b) 70:30 PVA/starch blend
film and (c) 50:50 PVA/starch blend film
On the other hand, a slight improvement in percentage of elongation at break

from pure PVA film to 80:20 PVA/starch, and subsequently to 70:30 PVA/starch
blend films may be attributed to the formation of hydrogen bonds between polymer
chains. In addition, it could be said that the low rates of agglomeration between
starch particles and better dispersion of starch in PVA matrix, as can be seen in
Figure 4.11, is vital to improve the elongation at break of the PVA/starch blend
films. Meanwhile, incorporating an extra amount of starch into the blend films
prevents the increment in the percentage of elongation at break, where it can be
related to the stiffening effect of starch.
Another factor to account for this
observation is the relatively low extensibility of starch granules, which will caused a
low percentage of elongation at break even if there is good interfacial bonding
between PVA and starch (Reis et al., 2008).
101
4.4.2
Water Absorption
The absorbed water has been found to influence the properties of composite
and therefore, understanding of mechanism of water absorption in PVA/starch blend
system is needed for application of the material. Figure 4.12 shows the percentage of
water absorption capacity for PVA/starch blend films at different weight ratio, which
conditioned at room temperature.
Water absorption capacity (%)
100
90
80
70
60
50
40
30
20
10
0
100/0
80/20
70/30
60/40
50/50
40/60
PVA/starch weight ratio (g/g)

Figure 4.12: Percentage of water absorption capacity for PVA/starch blend films
The result showed that the percentage of water absorption capacity of pure
PVA was found to be 8.87%. The percentage of water absorption was, however,
increased from 8.87 to 28.91% for 80:20 blend films and subsequently to 49.59% for
70:30 blend films. The percentage of water absorption capacity was continually
increased to 63.02 and 79.04% at a weight ratio of 60:40 and 50:50, respectively.
Again the percentage of water absorption kept increasing gently to 94.18% as the
weight ratio of PVA and starch was 40:60 in the blend.
Therefore, it can be
concluded that the lowest percentage of water absorption between the blend films
102
was achieved when the weight ratio of the blend film was set at 80:20, which is
around 28.91%.
From the results obtained, it can be observed that the pure PVA films
demonstrated lower percentage of water absorption than the PVA/starch films. This
is due to the fact that PVA and starch is highly hydrophilic polymer in nature caused
by the presence of many hydroxyl groups in it and thus capable of forming hydrogen
bonds in water (Yee et al., 2011). As indicated by Mucha et al. (2005), water
absorption occurs almost entirely in the amorphous region of a polymeric system.
Based on the XRD diffractogram shown in Figure 4.13, the crystallinity indexes of
PVA, starch and PVA/starch blend films (70:30 weight ratio) were found to be
50.38, 22.98 and 30.77%, respectively.
Since starch has a lower degree of
crystallinity than PVA, it contains higher amount of water binding sites and
therefore, higher amount of water being absorbed with addition of starch.
103
Intensity (a.u)
1800
1600
1400
1200
1000
800
600
400
200
0
PVA film
10
20
30
40
50
1400
Intensity (a.u)
1200
Starch film
1000
800
600
400
200
0
Intensity (a.u)
10
20
30
1600
1400
1200
1000
800
600
400
200
0
40
50
PVA/starch
blend film
10
20
30
40
2 (degree)
Figure 4.13: Xray diffraction pattern of the composite films
50
104
4.4.3
Biodegradation Properties
The soil burial test of the blend films was conducted in the present study
since this test provide a realistic environment, where soil humidity, temperature, type
and amount of microorganisms are in less control and change with weather. The
results are presented in Figure 4.14. The biodegradation test was carried out for 90
days.
70
Degradation rate (%)
60
50
100/0
40
80/20
30
70/30
60/40
20
50/50
10
40/60
0
0
15
30
45
60
75
90
Time (day)
Figure 4.14: Degradability of PVA/starch blend films in the soil burial test
According to the experimental data of this study, the degradation rate of PVA
film was found to be in the range between 5.8 and 22.41%. The PVA film does not
provide high degradation rate as the films had good resistance against soil burial
degradation. Furthermore, it is clear from the figure that the presence of starch
significantly improved biodegradation of PVA films in soil. It is believed that the
faster disintegration of PVA/starch blend films than that of PVA film was observed
because of the biodegradation rate of starch was higher than PVA. In overall,
increased degradation rate was observed with increasing starch content.
For
105
comparison, PVA/starch blend film in the ratio of 80:20 lost about 42.42% of its
weight after 90 days of exposure while the weight loss of the blend films at a ratio of
70:30 and 40:60 was found to be 59.39 and 62.85%, respectively after the same
period buried in soil.
These results suggested that the growth rate of the
microorganisms was much faster when large amounts of starch were added to the
blend. For all the blend films, a rapid degradation was observed in the first 45 days,
followed by slow degradation until the end of the experiment. The explanation lies
with the initiation of the starch degradation until then the degradation of PVA take
place.
4.5
Characteristics of PVA/Starch Nanocomposite
Polyvinyl alcohol and starch at a weight ratio of 70:30 was selected as the
blending composition in the production of nanocomposites experiment based on the
results from mechanical properties and water absorption test of PVA/starch blend
film. The result from previous experiments revealed that the 70:30 blend film have
the best elongation at break at about 334.69%, with a tolerable tensile strength value
and water absorption capacity of 3.830 MPa and 49.59%, respectively.
4.5.1
Mechanical Properties
Figure 4.15 indicates the effect of nanocellulose content on tensile strength

and elongation at break of the nanocomposite films.
106
10
500
8
7
450
400
350
300
250
200
150
100
50
tensile
strength
elongation
at break
0
0
5
10
15
Nanocellulose content (v/v)
20
Figure 4.15: The dependence of the tensile strength and elongation at break on the
nanocellulose content
From Figure 4.15, it is observed that the tensile strength of the PVA/starch
blend film was 3.830 MPa. When nanocellulose fiber was added into the PVA and
starch solution, the tensile strength was increased along with an increase in
nanocellulose content, and the highest tensile strength occurred at 10% (v/v), which
was around 7.094 MPa. When the nanocellulose content exceeded 10% (v/v), the
tensile strength of the blend film decreased along with an increase in nanocellulose
content, but it was still much higher than that of the unreinforced film.
The same trend from addition of nanocellulose fiber content can also be
found for the elongation at break. It was found that the elongation at break had the
highest value when 5% (v/v) nanocellulose was used during the nanocomposite
preparation, whereby the elongation at break of the nanocomposite film increased by
30.54% in comparison to the unreinforced film.
An addition of 10% (v/v)
nanocellulose content however had deterioration effect for elongation at break as a

sharp decrease was observed from 481.85 to 312.18%. Then, the elongation at break
of the nanocomposite film decreased slowly from 312.18 to 288% along with an
increase in nanocellulose content from 10 to 20% (v/v).
107
The enhancement in tensile strength and elongation at break at low content of
fillers was due to very fine nature of nanocellulose fiber and better dispersion of
nanocellulose through the PVA/starch matrix occurred, as observed in Figure 4.16b.
Meanwhile, according to Das et al. (2011), the remarkable increase in the mechanical
properties indicated the presence of intermolecular interactions between hydroxyl
group present in nanocellulose and PVA components or nanocellulose and starch
components, which disturbs the interchain force of attraction of the PVA/starch. On
the other hand, as more fibers were added into the composites, the fibers were not
homogenously distributed throughout the PVA/starch matrix (Figure 4.16c), thus
decreasing the tensile strength and elongation at break.
Figure 4.16: SEM image of the surface of (a) PVA/starch blend film, (b) PVA/starch
reinforced with 5% (v/v) nanocellulose film and (c) PVA/starch reinforced with 20%
(v/v) nanocellulose film
108
4.5.2
Water Absorption
As mention before, it is very important to control the film water content for
engineering applications that are moisture sensitive such as gas selective membranes
and ion channels.
Therefore, it is an effective way to incorporate appropriate
reinforcement in film, in order to improve the water absorption properties. Figure

4.17 shows the water absorption capacity of PVA/starch/nanocellulose composite
films depended on the amount of nanocellulose loading.
50
45
40
35
30
25
20
15
10
5
0
0
10
15
20
Nanocellulose content (v/v)

Figure 4.17: Percentage of water absorption capacity for PVA/starch reinforced with
nanocellulose fiber at different amount
Comparing the water absorption capacity of PVA/starch blend film and

nanocellulose fiber reinforced PVA/starch composite, it is noted that the percentage
of water absorption of all nanocellulose fiber reinforced films were lower, indicating
that films contain nanocellulose have a good preventive ability against water. This
result illustrates that the water absorption properties was improved by the presence of
nanocellulose fiber in the blend films. The possible reason for this kind of behavior
was related to the hydrophobic properties of fibers (Ramadevi et al., 2012). The
109
water absorption of composite depends on the hydrophilichydrophobic ratio of the
film constituents (Bledzki et al., 2008).
In this study, pretreatment of fibers with alkali solution had reorganized fiber
cellulose bonds by transforming them from cellulose I to cellulose II (Figure 4.3).
According to Sreekala et al. (2002), the cellulose II is more stable crystalline form
than that of cellulose I. Therefore, the fibers became hydrophobic due to their high
crystallinity. Furthermore, the presence of the nanocellulose fibers means that the
pathway for water molecules to diffuse into the composites is altered from the direct
diffusion to a tortuous path, which leads to the improvement in water barrier
properties.
Some differences are observed by increasing nanocellulose content in

PVA/starch blend films during water absorption tests. By comparison, an increment
of water absorption capacity was observed with increasing nanocellulose content,
which possibly due to the poor dispersion of the nanocellulose fiber (Figure 4.16c).
It can be observed that the water absorption of PVA/starch/nanocellulose films
increase from 19.71 to 31.06% with cellulose content from 5 to 20% (v/v). At higher
content of nanocellulose, the dispersion was not homogenous and agglomerates are
formed. In consequences, the effective number of interactions decreases and more
hydroxyl groups are available to promote absorption of water (He et al., 2001).
4.5.3
Biodegradation Properties
Degradability of composites is important when a polymeric system is applied

in daily lives as its weight loss degree has a direct influence on the environment. In
this study, the effect of different amount of nanocellulose fiber on film weight loss
rate is conducted via soil burial test and the results were presented in Figure 4.18.
110
60
50
40
0 (v/v)
5% (v/v)
30
10% (v/v)
20
15% (v/v)
20% (v/v)
10
0
0
20
40
60
Time (day)
80
100
Figure 4.18: Degradability of PVA/starch nanocomposite films in the soil burial test
Results showed that the degradation rate of PVA/starch blend film were
higher than PVA/starch films that contained nanocellulose fiber, whereby the
PVA/starch blend films without the addition of nanocellulose was able to lose its
weight up to 59.39% after being buried for 90 days. It is believed that the faster
disintegration of PVA/starch blend films can be explained by the ability of composite
film to absorb higher amount of water. This is because the water absorbed by the
films caused the microorganisms such as algae, bacteria and fungi to attach and
grow, since the films have become the main energy sources of the microbial growth.
This result is consistent with the result from water absorption test of PVA/starch
nanocomposite films reflected in Figure 4.17 and thus illustrates that the addition of
nanocellulose fiber prevented water to be diffused into the films and the growth of
microorganism occurred slowly.
Furthermore, the study also found that the
degradation rate of PVA/starch nanocomposite after being buried for 90 days is

slightly lower than that of the PVA/starch blend film.
111
4.6
Comparative Study
Based on the results of the study, 5% (v/v) of nanocellulose EFB fibers was
found to be the optimum percentage of reinforcement to make the best composites.
As a comparison, 5% (v/v) cellulose reinforced PVA/starch composite was also
produced. Therefore, a comparison was made between pure PVA, PVA/starch blend
film, 5% (v/v) cellulose reinforced PVA/starch composite and 5% (v/v)
nanocellulose reinforced PVA/starch nanocomposite based on their mechanical
properties, water absorption and degradation properties. These results are presented
in Figure 4.19, Table 4.10 and Figure 4.20, respectively.
500
8
7
tensile strength
450
elongation at break
400
350
300
250
4
200
150
100
50
pure0PVA
3
PVA/starch
5
PVA/starch/
cellulose
7
PVA/starch/
nanocellulose
Figure 4.19: Mechanical properties of pure PVA, PVA/starch, PVA/starch/cellulose

and PVA/starch/nanocellulose composite.
112
Table 4.10: Water absorption of pure PVA, PVA/starch, PVA/starch/cellulose and
PVA/starch/nanocellulose composite
Composite
Pure PVA
8.87
PVA/starch blend film
49.59
PVA/starch/cellulose
58.22
PVA/starch /nanocellulose
19.71
70
60
50
pure PVA
40
PVA/starch
30
PVA/starch/
cellulose
20
PVA/starch/
nanocellulose
10
0
0
15
30
45
60
Time (day)
75
90
Figure 4.20: Degradation properties of pure PVA, PVA/starch, PVA/starch/cellulose

and PVA/starch/nanocellulose composite.
As shown in Figure 4.19, the incorporation of starch in PVA film produced

an increase on percentage of elongation at break but a clear decrease on tensile
strength, which is associated with increased hardness but with decreased ductility of
composite film. Furthermore, it was possible to obtain PVA/starch composite and
PVA/starch nanocomposites films, by using cellulose and nanocellulose fiber as
reinforcement, respectively. However, the incorporation of cellulose produced a
slight decrease on tensile strength and a clear decrease on elongation at break. The
decrease in mechanical properties may be due to the poor compatibility between
matrix and reinforcement material. Meanwhile, an increment could be observed in
113
both tensile strength and percentage of elongation at break by the presence of
nanocellulose. The enhancement in tensile strength and elongation at break by using
nanocellulose as reinforcement was due to very fine nature of nanocellulose fiber and
better dispersion of nanocellulose through the PVA/starch matrix occurred (Figure
4.16).
From Table 4.10, it can be stated that the pure PVA had lower percentage of
water absorption compared to PVA/starch blend film due to the fact that PVA and
starch is highly hydrophilic polymer in nature caused by the presence of many
hydroxyl groups in it and thus capable of forming hydrogen bonds in water (Yee et
al., 2011). The table also shows that the PVA/starch mirocomposites absorbed more
water than the matrix. This trend was unexpected because the addition of cellulose
as reinforcement can have a reduction in water absorption of composite (Ollier et al.,
2013; Soykeabkaew et al. 2012). This is because the hydrophilic nature of fiber had
changed into hydrophobic by alkali treatment, as evidenced by higher crystallinity of
fiber, and thus leading to lower water absorption (Ramadevi et al., 2012).
Meanwhile, significantly better results can be observed in the composites prepared
with the PVA/starch matrix by using nanocellulose fibers as reinforcement. The
lower percentage of water absorption of PVA/starch composite reinforced with
nanocellulose compared to cellulose can be associated with the crystallinity index of
fiber. Based on the previous XRD of fiber (Figure 4.3), it can be seen that the
nanocellulose fiber has higher crystallinity and therefore, reducing the amount of
water being absorbed.
Results from the soil burial test (Figure 4.20) indicated that PVA/starch blend
films has higher rate of degradation due to its ability to absorb more water.
Meanwhile, the incorporation of nanocellulose in PVA/starch matrix however
showed a decreasing in degradation rate. In fact, this is an interesting result in that
although the PVA/starch blend films containing nanocellulose fiber showed a
reduction in their degradation rate, but they all exhibited higher rate of degradation
than pure PVA film. However, there were some unexpected results for cellulose
reinforced PVA/starch composite film, whereby their degradation rate was not
114
consistent with water absorption capacity. As can be seen, PVA/starch reinforced
with cellulose composite film degraded much slower than those composites which
have lower percentage of water absorption. One explanation of this observation is
because of the uncontrollable factors such as the weather, soil humidity, temperature
and type and amount of microorganisms. It could be that the cellulose reinforced
PVA/starch composite film was buried during hot and dry weather, which caused the
soil to have a low water-holding capacity.
Based on the results of this comparison, it can be concluded that the

nanocellulose fiber is promising to be an ideal candidate for the reinforcement of the
PVA/starch composite. This is due to the small size of particles and large surface
area of nanocellulose, thus enabling better interaction between fiber and matrix. A
most attractive of nanocomposite is that they showed a significant enhancement of
the properties even by the addition of small amount of nanocellulose. The observed
decrease in water absorption and enhancement in mechanical properties as well as
the biodegradation properties for PVA/starch nanocomposite are of great interest for
enlarging their use in food packaging, protective coating and other applications
where efficient polymeric barrier are needed.
CHAPTER 5
CONCLUSIONS AND RECOMMENDATIONS
5.1
Conclusion
In this study, cellulose and nanocellulose were successfully extracted from

palm oil EFB fiber. It has been proven that alkali treatment seems to be effective in
the removal of lignin and hemicelluloses components. In addition, the chemical
treatment used in this study was able to achieve improvement in the properties of
cellulose and nanocellulose, compared to that observed in previous studies (Cao et
al., 2012; Chenampulli et al., 2013; Fahma et al., 2010; Jonoobi et al., 2011; Li et
al., 2009). Evidence of noncellulosic components loss can be observed in the FTIR
spectra, whereby there were no main absorption band of lignin and hemicelluloses at
15001600 cm-1 and 17301740 cm-1 after treating with NaOH. Alkali treatment of
the fiber made cell wall swells in order to enable chemical molecules to penetrate
through the crystalline region of the cellulose, thereby causing the cementing
substances like lignin and hemicelluloses to be removed. In addition, FTIR spectra
of nanocellulose was almost the same as that of cellulose.
116
On the other hand, the crystallinity index of the fiber increased after each
treatment. Higher crystallinity value of the fiber is expected to provide better
reinforcement and therefore better properties of the composite films. From field
emission scanning electron microscopy (FESEM) analysis, different morphologies
were observed at every stage of each treatment, whereby the cellulose was able to be
separated into individual microsized fibers after alkali treatment. Meanwhile, the
significant different on morphology of nanocellulose fiber can be seen due to the
major drawback relating to the drying process of the nanocellulose. Transmission
electron microscopy (TEM) observation revealed that acid hydrolysis was able to
produce nanocellulose from EFB fiber with a diameter in the range of 415 nm.
Response surface methodology (RSM) based on a factorial Central

Composite Design (CCD) was carried out via Statistica Software to identify the
optimum condition for nanocellulose yield. The result indicated that the second
order model was adequate for all the independent variables on the response with
R2=0.90322. The linear and quadratic effect of acid concentration was the two most
influential variables.
The optimum yield of nanocellulose (16.6839 mL) was
achieved at acid concentration, hydrolysis time and reaction temperature of 58 wt%,

43 minutes and 35 C, respectively. Three replicates experiments were conducted
using the optimized conditions which representing the maximum point of the yield of
nanocellulose. As a result, the experimental values were in a good agreement with
the values predicted by the models indicating that the model was suitable to optimize
isolation of nanocellulose via acid hydrolysis.
The polyvinyl alcohol (PVA)/starch blend films with different blended ratios
were successfully prepared via solution casting method. The obtained films were
investigated on their mechanical, water absorption and biodegradability properties.
This study showed that the properties of PVA/starch blend films could be adjusted by
varying the blend ratio. The results revealed that 70% PVA and 30% starch was the
best ratio, whereby this blend film had the best elongation at break at about 334.69%,
with a tolerable tensile strength value and water absorption capacity of 3.830 MPa
and 49.59%, respectively.
117
Subsequently, the effectiveness of the nanocellulose fiber as a reinforcement
was tested on the properties of 70:30 PVA/starch ratio. Successful improvements of
nanocellulose reinforced PVA/starch film can be seen in terms of mechanical and
water absorption properties due to the good compatibility between the nanocellulose
and the polymer matrix. Furthermore, the properties of nanocomposite films were
also affected by different nanocellulose content. The reinforcement effect at low
nanocellulose content in the PVA/starch matrix was much stronger because the
excess nanocellulose tended to agglomerate.
The PVA/starch reinforced with
nanocellulose fiber had a tensile strength, elongation at break and water absorption
capacity of approximately 5.694 MPa, 481.85% and 19.71% respectively at an
addition of 5% (v/v) nanocellulose content.
Finally, a comparison was made between pure PVA, PVA/starch blend film,
5% (v/v) cellulose reinforced PVA/starch composite and 5% (v/v) nanocellulose
reinforced PVA/starch nanocomposite.
As a result, PVA/starch reinforced with
nanocellulose composite has owned better performance in mechanical properties,

water absorption and degradation properties. Therefore, it can be concluded that the
nanocellulose fiber is promising to be an ideal candidate for the reinforcement of the
PVA/starch composite
5.2
Recommendations
One of the major challenges in isolating nanocellulose is to obtain dry

nanocellulose fiber while maintaining their nano-scale dimensions. This is because
the agglomeration mechanism was occurred among the nanocellulose particles
during oven drying process. In this process, water evaporation take place over the
nanocellulose surfaces which causes the particles to move closer together by
capillary action followed by vapor diffusion. For that reason, nanocellulose in the
form of a water-based suspension was used to reinforce polymer matrix in this study.
118
Therefore, different drying methods such as spray drying and freeze drying can be
investigated in order to find the suitable method to dry the nanocellulose suspension
without disturbing their nanoscale sizes.
Meanwhile, the optimization study was focused to investigate the effect of

different hydrolysis conditions on nanocellulose yield, whereby high product yield is
an optimum response of the study. However, the different hydrolysis conditions
have resulted in different properties of nanocellulose such as their crystallinity and
thermal stability behavior. Therefore, the properties of nanocellulose after acid
hydrolysis would also be considered as these properties affect the potential of
nanocellulose as reinforcement.
It is well known that both PVA and starch has hydrophilic characteristics that
allows for good compatibility between them.
However, the dispersion of
nanocellulose fibers in the PVA/starch matrix is not very good due to their
incompatibility.
This is because the hydrophilic nature of cellulose fiber had
changed into a more hydrophobic nature by alkali treatment. Therefore, addition of

organic surfactant and compatibilizer are needed in order to improve the dispersion
of nanocellulose in polymer matrix. Furthermore, different type of compatibilizers
can also be investigated as a part of a parametric study to find the effective
compatibilizing agent.
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APPENDIX A
Calculation of chemical composition of fiber
For raw EFB fiber:-
Determination of holocellulose
Weight of empty crucible = 132.257 g

Weight of crucible containing the dry residue = 134.233 g
Holocellulose content = 134.233 132.257
= 1.976 g
Determination of cellulose
-cellulose content = 133.660 132.226
= 1.434 g
Since the initial weight of sample is 3 g, therefore,

Percentage of -cellulose =
1.434
100%
3
= 47.8%
141
Determination of hemicelluloses
Hemicellulose content = Holocellulose content -cellulose content
= 1.976 1.434
= 0.542
Since the initial weight of sample is 3 g, therefore
Percentage of hemicellulose =
0.542
100%
3
= 18.07%
Determination of lignin

Lignin content = 132.706 132.239
= 0.467 g
Since the initial weight of sample is 3 g, therefore,

Percentage of lignin =
0.467
100%
3
= 15.55%
The same calculation was conducted for the chemical composition of cellulose
and nanocellulose fiber.
APPENDIX B
Calculation of crystallinity index of fiber
Raw EFB fiber
Crystallinity index =
I 200 I am
100%
I 200
750 466
100%
750
= 38%
The same calculation was conducted for the crystallinity index of cellulose and
nanocellulose fiber.
APPENDIX C
Images of nanocellulose suspension at different hydrolysis conditions
These images show the nanocellulose suspension that was obtained after
subjected to acid hydrolysis process when:-
1. Acid concentration was varied from 45 to 85 wt% at 45 C for 30 minutes
45wt%
55wt%
65wt%
75wt%
85wt%
144
2. Hydrolysis time was varied from 30 to 90 minutes, by using 60 wt% acid sulfuric
solutions at the temperature of 45 C.
30 min
45 min
60 min
75 min
90 min
3. Reaction temperature was varied from 25 to 65 C with an acid concentration of

60 wt% and the reaction time of 30 minutes
25 C
35 C
45 C
55 C
65 C
145
APPENDIX D
Intensity of particle size distribution
Run 1
25
Intensity (%)
20
15
10
5
0
(Size d.nm)
Run 2
25
Intensity (%)
20
15
10
5
0
Size (d.nm)
Intensity (%)
Intensity (%)
0
3.615
4.187
4.849
5.615
6.503
7.531
8.721
10.1
11.7
13.54
15.69
18.17
21.04
24.36
28.21
32.67
37.84
43.82
50.75
58.77
68.06
78.82
91.28
Intensity (%)
146
Run 3
20
15
10
5
Size (d.nm)
Run 4
25
20
15
10
3.122 3.615 4.187 4.849 5.615 6.503 7.531 8.721

Size (d.nm)
Run 5
30
25
20
15
10
Size (d.nm)
147
Run 6
25
Intensity (%)
20
15
10
5
0.6213
0.7195
0.8332
0.9649
1.117
1.294
1.499
1.736
2.01
2.328
2.696
3.122
3.615
4.187
4.849
5.615
6.503
7.531
8.721
10.1
11.7
13.54
15.69
18.17
21.04
Size (d.nm)
Run 7
40
Intensity (%)
35
30
25
20
15
10
5
0
4.849 5.615 6.503 7.531 8.721 10.1 11.7 13.54 15.69

Size (d.nm)
Run 8
40
Intensity (%)
35
30
25
20
15
10
5
0
10.1
11.7 13.54 15.69 18.17 21.04 24.36 28.21 32.67
Size (d.nm)
148
Run 9
Intensity (%)
30
25
20
15
10
5
0
Size (d.nm)
Run 10
Intensity (%)
30
25
20
15
10
5
0
Size (d.nm)
Intensity (%)
Run 11
20
18
16
14
12
10
8
6
4
2
0
Size (d.nm)
149
Run 12
30
Intensity (%)
25
20
15
10
5
0
Size (d.nm)
Run 13
25
Intensity (%)
20
15
10
5
0
Size (d.nm)
Intensity (%)
Run 14
50
45
40
35
30
25
20
15
10
5
0
1.736 2.01 2.328 2.696 3.122 3.615 4.187 4.849

Size (d.nm)
150
Run 15
30
Intensity (%)
25
20
15
10
5
0
Size (d.nm)
Intensity (%)
Run 16
40
35
30
25
20
15
10
5
0
Size (d.nm)
Verification of predicted model
Run 1
25
Intensity (%)
20
15
10
5
0
Size (d.nm)
151
Run 2
30
25
Intensity (%)
20
15
10
5
0
Size (d.nm)
Intensity (%)
Run 3
18
16
14
12
10
8
6
4
2
0
6.503 7.531 8.721 10.1 11.7 13.54 15.69 18.17 21.04

Size (d.nm)
APPENDIX E
Experimental data of tensile strength
1.
PVA/starch blend film
153
154
155
156
2.
PVA/starch reinforced with cellulose composite film
157
3.
PVA/starch reinforced with nanocellulose composite film
158
159
APPENDIX F
Experimental data of water absorption
1. PVA/starch blend film
161
Film sample
100:0
Initial weight (g)
Final weight (g)
WAC (%)
1.030
1.149
11.55
0.998
1.062
6.41
1.053
1.214
15.29
0.986
1.008
2.23
Average
80:20
8.87
0.929
1.308
40.80
0.955
1.027
7.54
0.947
1.104
16.58
0.972
1.465
50.72
Average
70:30
28.91
0.767
1.240
61.67
0.772
1.070
38.60
0.782
1.210
54.73
0.745
1.068
43.36
Average
60:40
49.59
0.972
1.695
74.38
0.990
1.649
66.57
1.001
1.508
50.65
0.951
1.526
60.46
Average
50:50
63.02
0.826
1.346
62.95
0.861
1.548
79.79
0.892
1.688
89.24
0.859
1.582
84.17
Average
40:60
79.04
0.712
1.483
108.29
0.710
1.230
73.24
0.680
1.331
95.74
0.731
1.458
99.45
Average
94.18
162
Example of calculation of water absorption percentage of blend films
Weight ratio of 100:0
For sample 1,
Initial weight = 1.030 g
Final weight = 1.149 g
1.149 1.030
100%
1.030
= 11.55%
For sample 2,
1.062 0.998
100%
0.998
= 6.41%
For sample 3,
1.214 1.053
100%
1.053
= 15.29%
For sample 4,
1.008 0.986
100%
0.986
= 2.23%
163
Therefore, average for 4 samples of blend films
11.55 6.41 15.29 2.23

4
= 8.87%
The same calculation was conducted for the water absorption capacities of others
blend films.
2. PVA/starch reinforced with cellulose composite film
Film sample
5% (v/v)
Initial weight (g)
Final weight (g)
WAC (%)
1.273
2.134
67.64
1.168
1.721
47.35
1.189
1.803
51.64
1.211
2.013
66.23
Average
58.22
164
3. PVA/starch reinforced with nanocellulose composite film
Film sample
0% (v/v)
Initial weight (g)
Final weight (g)
WAC (%)
0.767
1.240
61.67
0.772
1.070
38.60
0.782
1.210
54.73
0.745
1.068
43.36
Average
5% (v/v)
49.59
0.891
1.032
15.82
0.947
1.174
23.97
0.911
1.086
19.21
0.867
1.039
19.84
Average
10% (v/v)
19.71
1.256
1.578
25.64
0.983
1.310
33.27
0.994
1.209
21.63
1.024
1.213
18.64
Average
15% (v/v)
24.75
1.143
1.354
18.46
1.063
1.386
30.39
1.243
1.502
20.84
0.987
1.325
34.25
Average
20% (v/v)
25.99
0.876
1.213
38.47
0.743
0.989
33.11
0.980
1.254
27.96
1.097
1.368
24.70
Average
31.06
APPENDIX G
Experimental data of degradation rate
1. PVA/starch blend film
Day
100:0
(Initial weight = 0.879 g)
Final
Degradation
weight (g)
Rate (%)
80:20
Final
Degradation
weight (g)
Rate (%)
70:30
Final
Degradation
weight (g)
Rate (%)
15
0.828
5.80
0.810
15.36
0.696
24.43
30
0.763
13.20
0.771
19.44
0.616
34.20
45
0.721
17.97
0.706
26.23
0.523
43.21
60
0.705
19.80
0.592
38.14
0.442
52.01
75
0.689
21.62
0.565
40.96
0.407
55.81
90
0.682
22.41
0.551
42.42
0.374
59.39
Day
60:40
Final
Degradation
weight (g)
Rate (%)
50:50
Final
Degradation
weight (g)
Rate (%)
60:40
Final
Degradation
weight (g)
Rate (%)
15
0.553
26.88
0. 553
34.17
0.775
30.12
30
0.435
30.45
0.435
48.21
0.602
45.72
45
0.374
49.69
0.374
55.48
0.440
60.32
60
0.354
55.09
0.354
57.86
0.431
61.14
75
0.346
56.52
0.346
58.81
0.420
62.13
90
0.342
57.03
0.342
59.29
0.412
62.85
166
Example of calculation of degradation rate at blend ratio of 80:20
Day 15

Degradation rate =
0.957 0.810
100%
0.957
= 15.36%
The same calculation was conducted for the degradation rates of others blend
films.
2. PVA/starch reinforced with cellulose composite film
Day
Final weight (g)
1.093
15
0.871
20.31
30
0.755
30.92
45
0.690
36.87
60
0.654
40.16
75
0.626
42.73
90
0.609
44.28
167
3. PVA/starch reinforced with nanocellulose composite film
0 wt%
5% (v/v)
10% (v/v)
Final
weight (g)
Degradation
Rate (%)
Final
weight (g)
Degradation
Rate (%)
Final
weight (g)
Degradation
Rate (%)
15
0.696
24.43
0.796
23.09
0.706
24.00
30
0.616
34.20
0.683
34.01
0.637
31.43
45
0.523
43.21
0.612
40.87
0.572
38.43
60
0.442
52.01
0.591
42.90
0.506
45.53
75
0.407
55.81
0.574
44.54
0.488
47.47
90
0.374
59.39
0.541
47.73
0.477
48.65
Day
15% (v/v)
20% (v/v)
Final
weight (g)
Degradation
Rate (%)
Final
weight (g)
Degradation
Rate (%)
15
0.604
29.27
0.752
23.73
30
0.542
36.53
0.679
31.14
45
0.508
40.52
0.638
35.29
60
0.457
46.49
0.562
43.00
75
0.421
50.70
0.541
45.13
90
0.406
52.46
0.490
50.30
Day

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ISOLATION AND CHARACTERIZATION OF NANOCELLULOSE FROM

EMPTY FRUIT BUNCH FIBER FOR NANOCOMPOSITE APPLICATION

NURUL SAADIAH BINTI LANI

A thesis submitted in fulfilment of the

Faculty of Chemical Engineering

To my wonderful families especially to my beloved mother and father

First and foremost, I would like to extend my heartfelt gratitude to my

Furthermore, I also would like to show my appreciation to all my friends and

Nowadays, the demands for plastics materials are increasing rapidly.

The optimization of acid hydrolysis conditions for

2.3.1 Physical Properties

2.3.2 Composite based on Polyvinyl Alcohol

2.4.1 Composite based on Starch

2.6.1 Chemical Composition

2.6.2 Physical Structure

Empty Fruit Bunch Fiber

2.8.1 Bleaching Process

2.8.2 Alkali Treatment

2.9.1 Isolation of Nanocellulose Fiber

2.9.1.1 Acid Hydrolysis

2.9.2 Nanocellulose Reinforced Composite

Nanocomposite based on PVA/Starch

Response Surface Methodology

3.2.1 Polyvinyl Alcohol

3.2.3 Natural Fiber

3.2.4 Other Chemicals

Isolation of Nanocellulose Fiber

3.5.1 Chemical Composition

3.5.2 Fourier Transform Infrared Spectroscopy

3.5.4 Thermogravimetric Analysis (TGA)

3.5.5 Field Emission Scanning Electron Microscope

Optimization on Nanocellulose Yield

3.6.1 Screening Test

3.6.2 Statistical Design

PVA/Starch Filled with Nanocellulose Fiber

3.8.1 XRay Diffraction (XRD)

3.8.2 Scanning Electron Microscopy (SEM)

3.8.3 Mechanical Test

3.8.4 Water Absorption Test

3.8.5 Soil Burial Degradation Test

RESULTS AND DISCUSSION

4.2.1 Chemical Composition

4.2.2 Fourier Transform Infrared Spectroscopy

4.2.3 XRay Diffraction

4.2.4 Thermogravimetric Analysis

3.5.5 Transmission Electron Microscope (TEM)

4.2.5 Field Emission Scanning Electron Microscopy 83

4.2.6 Transmission Electron Microscopy

Optimization on Nanocellulose Yield

4.3.1 Screening of Hydrolysis Conditions

4.3.1.1 Effect of Acid Concentration

4.3.1.2 Effect of Hydrolysis Time

4.3.1.3 Effect of Reaction Temperature

4.3.2 Response Surface Methodology

Characteristics of PVA/Starch Blend Film

4.4.1 Mechanical Properties

4.4.2 Water Absorption

4.4.3 Biodegradation Properties

Characteristics of PVA/Starch Nanocomposite

4.5.1 Mechanical Properties

4.5.2 Water Absorption

4.5.3 Biodegradation Properties

CONCLUSIONS AND RECOMMENDATIONS