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PREPARATION AND CHARACTERIZATION OF BIODEGRADABLE POLY LACTIC ACID (PLA) COMPOSITES WITH OIL PALM EMPTY FRUIT BUNCH (EFB) FIBER

ABU KASHEM MOHAMMAD MOSHIUL ALAM

Thesis submitted in fulfillment of the requirements For the award of the degree of Master of Engineering in Chemical

Faculty of Chemical and Natural Resources Engineering UNIVERSITY MALAYSIA PAHANG

APRIL 2012

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ABSTRACT Application of natural fibers as reinforcing material of polymer matrix is the prime attention in this research. Oil palm empty fruit bunch (EFB) fiber has been considered as reinforcing material of Poly lactic acid (PLA) for preparation of EFB/PLA biocomposites. The limitation in the broad use of EFB fiber in PLA matrix is poor compatibility between fibers and matrix due to presence of non cellulosic components and the hydroxyl groups of cellulose. Moreover, the hydroxyl groups form hydrogen bonds inside the macromolecule itself (intra-molecular) and also with hydroxyl groups from moist air that restrict the fiber matrix adhesion and also bring about dimensional changes in the fiber. These limitations has been successfully overcome by removing the non cellulosic components, altering the fiber surface, through conventional alkali (ALK) and non conventional ultrasound (ULS) pre-treatment methods. The Pretreatment were conducted with variation of sodium hydroxide (NaOH) concentration, soaking or exposing time and treatment temperature. Fiber characterization was done by the single fiber strength, FTIR spectrum, SEM and TGA-DTG thermal analysis. The ULS EFB fiber was given best properties compare to ALK EFB fiber at mild treatment conditions. The treatment parameters were optimized on the basis of that treated EFB/PLA composites mechanical properties and by using Design Expert Software. Optimization of fiber loading was carried out by 10 wt%, 20wt%, 30 wt% and 40wt% raw EFB fiber, composite was prepared by extrusion with PLA followed by injection molding. The composites properties were examined by mechanical tests such as tensile strength (TS), tensile modulus (TM), elongation at break (EB) and impact strength (IS). It was found that 30wt% EFB fiber incorporated composite represented good TS, TM, EB and IS. By considering these mechanical properties, 30wt% EFB was considered as optimum loading in EFB/ PLA composite. Beside this comparative analysis was done for 30wt% EFB fiber incorporated raw EFB/PLA, ALKEFB/PLA and ULSEFB/PLA composites. This comparison was carried out by the analysis of melt flow index (MFI), mechanical properties (TS, TM, EB, IS), kinetic property (activation energy, Ea) by TGA-DTG data and crystallinity index (IDSC) by DSC thermograms. The ULSEFB/PLA composite was shown better properties, such as higher MFI (3.55 g/10min), mechanical strength (TS= 63MPa, TM=2468 MPa, IS=18.67 J/m2), crystallinity index (IDSC=43.12) and lower activation energy (Ea=69.73 kJ/mol), compare to ALKEFB/PLA composite. Moreover, these properties were obtained when the ULSEFB fiber was treated at lower NaOH concentration (3 wt%) and treatment temperature (800C) at 90 minutes exposing time. The ULSEFB/PLA composite properties were increased by treating that ULSEFB fiber with HBPE as coupling agent in ULSEFB/HBPE/PLA composite. It shows highest MFI (4.15 g/10min) and mechanical properties (TS=66.78 MPa, TM=2629MPa, IS=19.33), greater thermal stability, highest crystallinity index (IDSC=45.13) and lowest activation energy (Ea=67.89 kJ/mol) among all composites.

perbandingan telah dilakukan terhadap gentian EFB yang mengandungi 30wt% serat dan PLA. TM.13%) dan tenaga pengaktifan terendah (Ea = 67. pengubahsuaian permukaan serat melalui kaedah pra-rawatan alkali konvensional dan ultra-bunyi bukan konvensional. TM = 2468 MPa. kestabilan terma yang lebih baik. Sifat-sifat komposit telah dianalisa melalui ujian mekanikal seperti kekuatan tegangan (TS). IS). Dengan mengambil kira sifat-sifat mekanik ini. Komposit ULSEFB / PLA telah menunjukkan sifat yang lebih baik. . ALK EFB / PLA dan ULS EFB / PLA komposit. Parameter rawatan telah dioptimumkan berdasarkan sifat mekanikal komposit EFB/PLA dan menggunakan perisian Design Expert. IS= 18. imbasan SEM dan terma TGA-DTG. tenaga pengaktifan lebih rendah (Ea = 69. 20wt%. EB dan IS. EFB 30wt% dianggap sebagai muatan yang optimum dalam komposit EFB / PLA. Pra-rawatan telah dijalankan dengan kepelbagaian tahap kepekatan natrium hidroksida (NaOH). Serat tandan kelapa sawit kosong (EFB) merupakan bahan penguat kepada asid polilaktik (PLA) bagi penyediaan biokomposit EFB/PLA.15 g/10min) dan sifat mekanik (TS = 66.12%). Selain itu. Sifat-sifat komposit ULSEFB / PLA meningkat dengan perawatan ULSEFB serat dengan HBPE sebagai agen gandingan pada komposit ULSEFB / HBPE / PLA. tempoh rendaman atau masa pendedahan dan suhu rawatan. 30wt% dan 40wt%. spektrum FTIR. sifat kinetik (tenaga pengaktifan. iaitu nilai yang tinggi bagi MFI (3. Perbandingan komposit dilakukan melalui analisis indeks pengaliran leburan (MFI).33 J/m2). IS = 19.Pengoptimuman muatan serat dijalankan dengan peratusan berat kandungan gentian EFB yang berbeza iaitu 10wt%. modulus tensil (TM). sifat mekanik (TS. berbanding dengan komposit ALKEFB / PLA. komposit telah disediakan oleh kisaran campuran dengan PLA diikuti oleh pembentukan acuan. kesesuaian antara serat dan matrik plastik adalah terhad disebabkan kehadiran komponen yang bersifat bukan selulosik dan terdiri daripada kumpulan hidroksil pada struktur selulosa. Didapati bahawa gentian EFB 30wt% gabungan komposit menunjukkan sifat yang baik bagi sifat-sifat TS. kekuatan mekanikal (TS = 63MPa. Faktorfaktor yang menghadkan lekatan ini dapat diatasi melalui penyingkiran bahan yang tidak bersifat selulosa. Tambahan lagi. Dalam penggunaan serat EFB di dalam matrik PLA. EB. TM. penghabluran indeks (IDSC = 43.89 kJ / mol) di antara kesemua komposit.. indeks penghabluran tertinggi (IDSC = 45.73 kJ / mol). kumpulan hidroksil menbemtuk ikatan hidrogen di dalam makromolekul itu dan kehadiran kumpulan hidroksil kesan dari kelembapan udara menghadkan lekatan antara seratmatrik yang akhirnya menyebabkan perubahan dimensi pada serat tersebut. Serat ULS EFB menunjukkan sifat yang terbaik berbanding dengan ALK EFB dengan keadaan rawatan yang sederhana.67 J/m2). Pencirian serat telah dijalankan melalui kaedah analisis kekuatan gentian tunggal. Ia menunjukkan MFI tertinggi (4. Ea) menggunakan TGA-DTG dan indeks penghabluran (IDSC) oleh DSC termogram.78 MPa. Manakala. TM = 2629MPa.vii ABSTRAK Aplikasi fiber semulajadi sebagai bahan penguat matrik plastik menjadi perhatian utama dalam kajian ini.55 g/10min). Selain analisis ini. sifat-sifat ini telah diperolehi apabila ULSEFB serat dirawat pada kepekatan NaOH yang lebih rendah (3%) dan suhu rawatan (80˚C) selama 90 minit bagi masa pendedahan. pemanjangan pada takat putus (BP) dan kekuatan kesan (IS).

3.2 Introduction Natural Fiber and Its Source 2.1 2.1 1.3 Treatment of Fiber 2.4 Introduction Problem Statement Objectives Scope of Study LITERATURE REVIEW 8 8 9 10 15 15 17 INTRODUCTION 1 6 6 7 ii iii iv v Vi xv xviii xxiv xxv CHAPTER 2 2.2 Oil Palm Empty Fruit Bunch (EFB) Morphology and properties of EFB 2.2.1 2.2.2 1.1 2.3 1.2 Alkali Treatment Of Natural Fibers Ultrasonic Treatment .viii TABLE OF CONTENTS SUPERVISOR’S DECLARATION STUDENT’S DECLARATION ACKNOWLEDGEMENTS ABSTRACT ABSTRAK LIST OF TABLES LIST OF FIGURES LIST OF SYMBOLS LIST OF ABBREVIATIONS CHAPTER 1 1.3.

1 2.2 2.4.1 Extrusion .3.3 Effect of Oil Palm EFB Fiber Loading on Composite Mechanical Properties Effect of Fiber Size on Mechanical Properties of Oil Palm EFB Fiber Composites Effect of Fiber Treatment on Mechanical Properties of Oil ) Palm EFB Fiber Composites Thermal Properties of Oil palm EFB Fiber Reinforced Polymer Composites 2.6 Oil Palm Empty Fruit Bunch (EFB) Fiber Reinforced Polymer Composites 2.8 Natural Fiber Reinforced Poly Lactic Acid Composites Processing Methods 2.2 Mechanism of Reinforcement Factors Controlling Performance of Fiber Reinforced Composites (i) (ii) (iii) (iv) (v) (vi) Dispersion of Fiber in to Matrix Thermal Stability of the Fiber Hydrophilic Nature of Natural Fiber Critical Fiber Length Fiber Orientation Fiber Volume Fraction 2.7 2.6.3.4.4 2.5 Coupling Agent Pre-Treatment of Fiber with Coupling Agents 19 23 24 Thermosets Thermoplastics Biodegradable Plastics Poly (lactic acid) 24 25 27 29 33 33 34 34 35 35 36 36 37 37 38 39 39 41 42 43 44 48 48 Natural Fiber Reinforced Plastics 2.3 2.2 Physical Properties of EFB Fiber Composites Mechanical Properties of Oil Palm EFB Fiber Composites (i) (ii) (iii 2.4 Matrix 2.6.6.8.3 2.5.4 2.1 2.4.4.1 2.ix 2.5.

1 3.4 .4.2 Fiber 3.2.3 Chemicals 51 51 51 52 52 52 52 53 53 53 54 54 55 55 58 58 58 59 59 59 59 59 60 60 3.7 3.4.1 Flow Chart of Methodology 3.4.4.3 Methods 3.3 3.3.8 3.9 Fourier Transformation Infrared Spectroscopy (FTIR) Scanning Electron Microscopy (SEM) Density Measurement Single Fiber Tensile Testing Melt Flow Index (MFI) Tensile Testing of Composites Impact Testing Thermogravimetric Analysis (TGA) Differential Scanning Calorimetry (DSC) Analysis 3.2 CHAPTER 3 3.1 3.2 Materials Processing 3.1 Matrix 3.8.4.5 3.3.3 Fiber Treatment (i) (ii) (iii) Alkali treatment of EFB fiber Ultrasonic treatment of EFB fiber Hyper Branched Polyester (HBP) Treatment of EFB Fiber 3.3.2 Injection Molding MATERIALS AND EXPERIMENTAL METHODS 49 Introduction Materials 3.5 Response Surface Method (RSM) For Optimization of EFB Fiber Treatment Parameters Characterization and Testing of Fiber and Composites 3.4.4 Composites Fabrication 3.2.2.x 2.4.4.3.3.4 3.2 3.4.6 3.

2 4.1.2 Optimization of Alkali Treatment Parameters of Oil Palm EFB Fiber Optimization of Ultrasound Treatment Parameters of Oil Palm EFB Fiber 4.4 4.1 4.6 Mechanical Properties of Alkali Treated EFB/PLA Composites (i) (ii) (iii) Effect of NaOH Concentration on Mechanical Properties ALKEFB/PLA Composites Effect of Soaking Time on Mechanical Properties of ALKEFB/PLA Composites Effect of Temperature on Mechanical Properties of ALKEFB/PLA Composites 87 87 89 92 94 94 4.2.7 Thermogravimetric Analysis (TGA) of Oil Palm EFB Fiber (i) TGA Curves Analysis of Raw EFB Fiber and Alkali Treated .2 Effect Of Alkali Treatment On The Compatibility And Mechanical Properties Of Oil Palm Empty Fruit Bunch (EFB) Fiber Reinforced Polylactic Acid Composites 4.1 Optimization of EFB Fiber Treatment Parameters Using Response Surface Method (RSM) 4.5 Effect of NaOH Concentration on Single Fiber Strength of ALKEFB Fiber Effect of Soaking Time on Single Fiber Strength of ALKEFB Fiber Effect of Treatment Temperature on Single Fiber Strength of ALKEFB Fiber 77 78 78 78 80 82 83 85 Composite Melt Flow Index (MFI) Mechanical Properties of Raw EFB Fiber Incorporated PLA Composites 4.2.2.2.xi CHAPTER 4 RESULTS AND DISCUSSION 62 62 70 77 4.2.1 4.3 Mechanism of Alkali Treatment SEM of Raw and Alkali Treated EFB Fiber Single Fiber Strength of ALKEFB Fiber (i) (ii) (iii) 4.2.1.2.

2.8 EFB (ALKEFB) Fiber Effect of NaOH Concentration on Thermal Stability of ALKEFB Fiber Effect of Soaking Time on Thermal Stability of ALKEFB Fiber Effect of Treatment Temperature on Thermal Stability of ALKEFB Fiber 95 96 97 98 Differential Thermal Analysis (DTG) of Raw EFB and Alkali Treated EFB (ALKEFB) Fiber (i) (ii) (iii) (iv) DTG Curves of Raw EFB and ALK EFB Fibers Effect of NaOH Concentration on Activation Energy of Raw and ALKEFB Fiber Effect of Soaking Time on Activation Energy of ALKEFB Fiber Effect of Treatment Temperature on Activation Energy of ALKEFB Fiber 98 99 100 101 102 102 103 103 104 105 4.xii (ii) (iii) (iv) 4.10 Differential Thermal Analysis (DTG) of Raw EFB/PLA and Alkali Treated ALKEFB/PLA Composites (i) (ii) (iii) Effect of NaOH Concentration on Activation Energy of ALKEFB/PLA Composites Effect of Soaking Time on Activation Energy of ALK EFB/PLA Composites Effect of Treatment Temperature on Activation Energy of ALKEFB/PLA Composites 106 107 108 108 4.9 Thermogravimetric Analysis (TGA) of EFB/PLA Composites (i) (ii) (iii) (iv) TGA Curves Analysis of Alkali Treated EFB/PLA Composites Effect of NaOH Concentration on Thermal Stability of ALK EFB/PLA Composites Effect of Soaking Time on Thermal Stability of ALKEFB/PLA Composites Effect of Treatment Temperature on Thermal Stability of ALKEFB/PLA Composites 4.2.11 Differential Scanning Calorimetric (DSC) Analysis of ALK EFB/PLA Composites (i) (ii) Effect of NaOH Concentration on DSC Thermograms of ALKEFB/PLA Composites Effect of Soaking Time on DSC Thermograms of ALK EFB/PLA Composites 109 110 .2.2.

3 Effect of Ultrasonic Treatment on EFB Fiber and Study of Ultrasound 113 Treated EFB Fiber Reinforced PLA Composites 4.1 4.3.4 113 114 Effect of NaOH Concentration on Single Fiber Strength of 114 ULSEFB Fiber Effect of Exposing Time on Single Fiber Strength of 116 ULSEFB Fiber Effect of Treatment Temperature on Single Fiber Strength of 118 ULSEFB Fiber 120 122 122 123 123 124 124 125 126 127 128 128 131 134 136 FTIR Analysis of Raw EFB and ULSEFB Fiber ULSEFB Fiber Density (i) (ii) (iii) Effect of NaOH Concentration on Density of ULSEFB Fiber Effect of Exposing Time on Density of ULSEFB Fiber Effect of Treatment Temperature on Density of ULSEFB Fiber 4.3.3 4.7 Melt Flow Index (MFI) of Different ULSEFB/PLA Composites ULSEFB/PLA Composites Mechanical Properties (i) (ii) (iii) Effect of NaOH Concentration on Mechanical Properties of ULSEFB/PLA Composites Effect of Exposing Time on Mechanical Properties of ULSEFB/PLA Composite Effect of Treatment Temperature on Mechanical Properties of ULSEFB/PLA Composite 4.5 ULSEFB/PLA Composites Density (i) (ii) (iii) Effect of NaOH Concentration on Density of ULSEFB/PLA Composites Effect of Exposing Time on Density of ULS EFB/PLA Composites Effect of Treatment Temperature on Density of ULSEFB/PLA Composites 4.3.3.8 Thermogravimetric Analysis (TGA) of Ultrasound Treated EFB (ULS EFB) Fiber .3.3.xiii (iii) Effect of Treatment Temperature on DSC Thermograms of ALKEFB/PLA Composites 111 4.3.2 SEM Raw EFB and Ultrasound Treated ULSEFB Fiber Single Fiber Strength of Ultrasound Treated EFB (ULSEFB) Fiber (i) (ii) (iii) 4.3.6 4.

4 Effect of Hyper Branched Polyester (HBPE) Coupling Agent on ULS 154 EFB/PLA Composite .3.11 Differential Thermal Analysis (DTG) of ULSEFB/PLA Composites 146 (i) (ii) (iii) Effect of NaOH Concentration on Activation Energy of ULSEFB/PLA Composites Effect of Exposing Time on Activation Energy of ULSEFB/PLA Composites Effect of Treatment Temperature on Activation Energy of ULSEFB/PLA Composites 147 148 149 149 4.10 Thermogravimetric Analysis (TGA) of ULSEFB/PLA Composites (i) (ii) (iii) Effect of NaOH Concentration on Thermal Stability of ULSEFB/PLA Composites Effect of Exposing Time on Thermal Stability of ULSEFB/PLA Composites Effect of Treatment Temperature on Thermal Stability of ULSEFB/PLA Composites 4.3.3.xiv (i) (ii) (iii) (iv) 4.9 TGA Curves Analysis of Raw EFB and ULSEFB Fibers Effect of NaOH Concentration on Thermal Stability of ULSEFB Fibers Effect of Exposing Time on Thermal Stability of ULSEFB Fibers Effect of Treatment Temperature on Thermal Stability of ULSEFB Fibers 136 137 138 138 139 140 141 142 143 144 144 145 Differential Thermal Analysis (DTG) Of Raw EFB And ULSEFB Fibers (i) (ii) (iii) Effect of NaOH Concentration on Activation Energy of ULSEFB Fibers Effect of Exposing Time on Activation Energy of ULSEFB Fibers Effect of Treatment Temperature on Activation Energy of ULSEFB Fibers 4.12 Differential Scanning Calorimetric (DSC) Analysis of ULSEFB/PLA Composites (i) (ii) (iii) Effect of NaOH Concentration on DSC Thermograms of ULSEFB/PLA Composites Effect of Exposing Time on DSC Thermograms of ULSEFB/PLA Composites Effect of Treatment Temperature on DSC Thermograms of ULSEFB/PLA Composites 150 151 152 4.3.

5.3 FTIR Analysis of ULSEFB/PLA and ULSEFB/HBPE/PLA Composites Melt Flow Index (MFI) of ULSEFB/PLA and ULSEFB/HBPE/PLA Composites Mechanical Properties of ULSEFB/PLA and ULSEFB/HBPE/PLA Composites 154 155 155 159 159 159 163 166 167 167 4.5.1 4.3 4.4.1 CONCLUSION 5.2 Recommendations and Future Work REFERENCES APPENDIX A List of Publications 169 170 171 185 .5 Comparative Assessment of Composites Properties 4.2 4.6 CHAPTER 5 Comparative Melt Flow Index (MFI) of Raw EFB/PLA and Treated EFB/PLA Composites Comparative Mechanical Properties of Raw EFB/PLA and Treated EFB/PLA Composites Comparative FTIR Analysis of Raw EFB and Treated EFB incorporated PLA Composites Comparative TGA analysis of Raw EFB/PLA and Treated EFB/PLA Composites Comparative DTG Analysis of Raw EFB/PLA and Treated EFB/PLA Composites Comparative DSC analysis of Raw EFB/PLA and Treated EFB/PLA composites CONCLUSION AND RECOMENDATIONS 5.2 4.xv 4.4 4.4.4.5 4.5.5.1 4.5.5.

5 3.3 Title Chemical composition of OPF Physico-mechanical properties of OPF List of Chemicals Processing parameters for Extrusion and Injection molding of composites Independent variables (concentration.10 4.2 3. 2.6 4.13 57 58 63 64 69 70 71 76 76 96 97 97 100 101 102 .4 4.2 4.9 4.2 3.3 4.1 2.4 56 3.11 4.5 4.8 4. time and temperature) levels for response surface study prior to ultrasonic treatment of oil palm EFB fiber Experimental layout of 23 full factorial central composite designs for ALK EFB/PLA Composites Experimental layout of 23 full factorial central composite designs for ULS EFB/PLA composites Experimental layout and results of 23 full factorial central composite design (ALKEFB/PLA composites) ANOVA for Response Surface Quadratic Model Response: TS (MPa) of ALK EFB/PLA composite Results of operating conditions with experimental design in confirmation run Experimental layout and results of 23 full factorial central composite design (ULS EFB/PLA composites) ANOVA for Response Surface Quadratic Model Response: TS (MPa) of ULS EFB/PLA composite Predected optimum values for Ultrasonic treatment of EFB fiber Results of operating conditions with experimental design in confirmation run Effect of NaOH concentration on the thermal stability ALK EFB fiber Effect of soaking time on the thermal stability of ALK EFB fiber Effect of treatment temperature on the thermal stability of ALK EFB fiber Effect of NaOH concentration on DTG curves and activation energy of ALK EFB fiber Effect of soaking time on DTG curves and activation energy of ALK EFB fiber Effect of treatment temperature on DTG curves and activation Page 12 13 52 55 56 3.1 3.xvi LIST OF TABLES Table No.7 4.6 4.1 4. time and temperature) levels for response surface study prior to Alkali treatment of oil palm EFB fiber Independent variables (concentration.12 4.

24 4.25 4.21 4.31 Effect of NaOH concentration on thermal stability of ALK EFB/PLA composite Effect soaking time on thermal stability of ALKEFB/PLA composite Effect of treatment temperature on the thermal stability of ALKEFB/PLA composite Effect of NaOH concentration on DTG curves and activation energy of ALK EFB/PLA composite Effect of soaking time on DTG curves and activation energy of ALK EFB/PLA composite Effect of treatment temperature on DTG curves and activation energy of ALK EFB/PLA composite Effect of NaOH concentration on the DSC thermogram of ALK EFB/PLA composites Effect of soaking time on the DSC thermogram of ALK EFB/PLA composites Effect of treatment temperature on the DSC thermogram of ALK EFB/PLA composites Summary of FT-IR spectra for Raw EFB and ULS EFB fiber Effect of NaOH concentration on thermal stability ULS EFB fiber Effect of exposure time on thermal stability ULS EFB fiber Effect of treatment temperature on thermal stability of ULS EFB fiber Effect of NaOH concentration on DTG curves and activation energy of ULS EFB fiber Effect of exposing time on DTG curves and activation energy of ULS EFB fiber Effect of treatment temperature on DTG curves and activation energy of ULS EFB fiber Effect of NaOH concentration on thermal stability of ULSEFB/PLA composite Effect of Exposing time on thermal stability of ULSEFB/PLA composite 103 104 104 106 107 108 110 111 112 121 137 138 139 141 142 143 144 145 .29 4.16 4.18 4.20 4.23 4.22 4.28 4.30 4.15 4.26 4.xvii energy of ALK EFB fiber 4.17 4.14 4.27 4.19 4.

33 4.36 4.35 4.xviii 4.38 4.37 4.34 4.40 4.39 4.32 4.41 Effect of treatment temperature on thermal stability of ULS EFB/PLA composite Effect of NaOH concentration on DTG curves and activation energy of ULS EFB/PLA composite Effect of exposing time on DTG curves and activation energy of ULS EFB/PLA composite Effect of treatment temperature on the DTG curves and activation energy of ULS EFB/PLA composite Effect of NaOH concentration on DSC thermograms of ULSEFB/PLA composite Effect of exposing time on DSC thermograms of ULSEFB/PLA composite Effect of treatment temperature on DSC thermograms of ULSEFB/PLA composite Comparative thermal stability of Raw EFB/PLA and Treated EFB/PLA composites Comparative DTG curves analysis of EFB/PLA composites Comparative DSC curves analysis of EFB/PLA composites 145 147 148 149 151 152 153 166 167 168 .

7 4.4 2.xix LIST OF FIGURS Figure No 2.9 4.1 2.1 4.10 4.3 2.5 2.6 4.11 4.12 4.5 4.13 Title View of EFB wastes piled up in a palm oil mill premise SEM images of transverse sections of OPF Structure of cellulose Structure of hemicellulose Structure of Lignin Structure of hyper branched polyester (HBPE) Preparation of high molecular weight PLA Normal probability plot of residual for TS Plot of residual against predicted responseTS 3D surface of TS from the model equation: effect of NaOH concentration and Time 3D surface of TS from the model equation: effect of NaOH concentration and Temperature.3 4. 3D surface of TS from the model equation: effect of Time anTemperature Normal probability plot of residual for TS Plot of residual against predicted response TS 3D surface of TS from the model equation: effect of NaOH concentration and Time 3D surface of TS from the model equation: effect of NaOH concentration and Temperature 3D surface of TS from the model equation: effect of Time and Temperature SEM of Raw EFB and alkali treated (ALKEFB) fiber Effect of NaOH concentration on tensile strength of ALKEFB single fiber Effect of NaOH concentration on tensile modulus of ALKEFB single fiber Page 10 11 13 14 15 23 31 66 66 67 68 68 73 73 74 75 75 78 78 79 .8 4.6 2.2 2.4 4.2 4.7 4.

19 4.30 4.33 Effect of NaOH concentration on elongation at break of ALKEFB single fiber Effect of soaking time on tensile strength of ALKEFB single fiber Effect of soaking time on tensile modulus of ALKEFB single fiber Effect of soaking time on elongation at break of ALKEFB single fiber Effect of treatment temperature on tensile strength of ALKEFB single fiber Effect of treatment temperature on tensile modulus of ALKEFB single fiber Effect of treatment temperature on elongation at break of ALKEFB single fiber MFI of Virgin PLA.22 4.27 4.17 4. raw EFB/PLA and different ALKEFB/PLA composites Tensile strength of virgin PLA and raw EFB/PLA composites Tensile modulus of virgin PLA and raw EFB/PLA composites Elongation at break of virgin PLA and raw EFB/PLA composites Impact strength of virgin PLA and raw EFB/PLA composites Effect of NaOH concentration on tensile strength of ALKFB/PLA composite Effect of NaOH concentration on tensile modulus of ALK EFB/PLA composite Effect of NaOH concentration on elongation at break of ALK EFB/PLA composite Effect of NaOH concentration on impact strength of ALK EFB/PLA composite Effect of soaking time on tensile strength of ALKEFB/PLA composite Effect of soaking time on tensile modulus of ALKEFB/PLA composite Effect of soaking time on elongation at break of ALKEFB/PLA composite Effect of soaking time on impact strength of ALKEFB/PLA 80 80 81 81 82 83 83 84 85 86 86 87 88 88 89 89 90 91 91 92 .31 4.xx 4.29 4.32 4.15 4.16 4.26 4.18 4.14 4.20 4.25 4.23 4.24 4.28 4.21 4.

39 4. Raw EFB/PLA and ALKEFB/PLA composites at optimum alkali treatment conditions DTG curves of virgin PLA.40 4. Raw EFB/PLA and ALK EFB/PLA composites at optimum alkali treatment conditions ln[ln(1/y)] versus 1/T(K) for decomposition stage of ALK EFB/PLA composite DSC Thermograms of PLA and ALKEFB/PLA composites SEM of (a) Raw EFB (b) Alkali treated EFB fiber (ALK EFB) (c) Ultrasound treated EFB fiber (ULS EFB) Effect of NaOH concentration on tensile strength of ULS Single EFB fiber Effect of NaOH concentration on tensile modulus of ULS Single EFB fiber Effect of NaOH concentration on elongation at break of ULS treated Single EFB fiber Effect of exposing time on tensile strength of ULS treated Single EFB fiber Effect of exposing time on tensile modulus of ULS treated Single EFB fiber Effect of exposing time on elongation at break of ULS treated 92 93 93 94 95 98 99 100 102 105 106 109 113 115 115 116 117 117 118 .51 4.48 4.34 4.52 Effect of treatment temperature on tensile strength of ALKEFB/PLA composite Effect of treatment temperature on tensile modulus of ALKEFB/PLA composite Effect of treatment temperature on Elongation at break of ALKEFB/PLA composite Effect of treatment temperature on impact strength of ALKEFB/PLA composite TGA curves of Raw EFB and different ALKEFB fibers DTG curves of Raw EFB and different ALKEFB fibers ln[ln(1/y)] versus 1/T(K) for the second stage decomposition of raw EFB SEM and EDX raw EFB fiber TGA curves of Virgin PLA.xxi composite 4.49 4.46 4.36 4.37 4.38 4.42 4.43 4.35 4.41 4.44 4.50 4.47 4.45 4.

60 4.54 4.53 4.xxii Single EFB fiber 4.57 4.69 4.59 4.70 4.61 4.55 4.66 4.58 4.64 4.65 4.56 4.71 Effect of treatment temperature on tensile strength of ULS treated Single EFB fiber Effect of treatment temperature on tensile modulus of ULS treated Single EFB fiber Effect of treatment temperature on elongation at break of ULS treated Single EFB fiber FT-IR spectrum of Raw EFB and Ultrasound treated EFB fiber Effect of NaOH concentration on density of ULS EFB fiber Effect of exposing time on density of ULS EFB fiber Effect of treatment temperature on density of ULS EFB fiber Effect of NaOH concentration on density of ULS EFB/PLA composite Effect of exposing time on density of ULS EFB/PLA composite Effect of treatment temperature on density of ULS EFB/PLA composite Melt flow index of virgin PLA. raw EFB/PLA and different ULS EFB/PLA composites Effect of NaOH concentration on tensile strength of ULS EFB/PLA composites Effect of NaOH concentration on tensile modulus of ULS EFB/PLA composite Effect of NaOH concentration on elongation at break of ULSEFB/PLA composites Effect of NaOH concentration on impact strength of ULSEFB/PLA composites Effect of exposing time on tensile strength of ULSEFB/PLA composites Effect of exposing time on tensile modulus of ULSEFB/PLA composites Effect of exposing time on elongation at break of ULSEFB/PLA composites Effect of exposing time on impact strength of ULSEFB/PLA composites 119 119 120 121 122 123 124 125 126 126 127 129 129 130 130 132 132 133 133 .63 4.62 4.67 4.68 4.

88 4.87 4.84 4.73 4.86 4.76 4.89 Effect of treatment temperature on tensile strength of ULSEFB/PLA composites Effect of treatment temperature on tensile modulus of ULSEFB/PLA composites Effect of treatment temperature on elongation at break of ULSEFB/PLA composites Effect of treatment temperature on impact strength of ULSEFB/PLA composites TGA curves of Raw EFB and ULS EFB fiber at optimum ultrasonic treatment conditions DTG curves of Raw EFB and ULS EFB at optimum treatment conditions ln[ln(1/y)] versus 1/T(K) for the decomposition of 3% NaOH treated ULS EFB fiber TGA curves of Raw EFB/ PLA and ULS EFB/PLA composites at optimum treatment conditions DTG curves of Raw EFB/PLA and ULS EFB/PLA composites at optimum treatment conditions ln[ln(1/y)] versus 1/T(K) for decomposition stage of 800C temperature treated ULS EFB/PLA composite DSC thermograms of Raw EFB/PLA and ULS EFB/PLA composites with optimum treatment conditions FTIR analysis of ULSEFB/PLA and HBPE treated ULS EFB incorporated (ULSEFB/HBPE/PLA) PLA composites MFI of ULSEFB/PLA and HBPE treated ULS EFB incorporated ULSEFB/HBPE/PLA composites Tensile strength of ULSEFB/PLA and ULSEFB/HBPE/PLA composites Tensile modulus of ULSEFB/PLA and ULSEFB/HBPE/PLA composites Elongation at break of ULSEFB/PLA and ULSEFB/HBPE/PLA composites Impact strength of ULSEFB/PLA and ULSEFB/HBPE/PLA composites SEM of ultrasound treated EFB/PLA (ULSEFB/PLA) and HBPE treated ULSEFB/PLA (ULSEFB/HBPE/PLA) composites 134 135 135 136 137 140 140 143 146 147 150 154 155 156 156 157 157 158 .78 4.77 4.81 4.75 4.80 4.79 4.85 4.72 4.xxiii 4.83 4.74 4.82 4.

96 4. EFB and EFB/PLA composites Schematic illustration for the probable reaction sites of PLA and cellulose of EFB fibres Schematic illustration for the probable reaction sites of PLA and HBPE grafted cellulose of EFB fibres 159 161 162 162 163 163 165 165 .91 4.95 4.94 4.97 Comparative MFI of raw EFB/PLA and treated EFB/PLA composites Comparative tensile strength of raw EFB/PLA and treated EFB/PLA composites Comparative tensile modulus of raw EFB/PLA and treated EFB/PLA composites Comparative elongation at break of raw EFB/PLA and treated EFB/PLA composites Comparative impact strength of raw EFB/PLA and treated EFB/PLA composites Comparative FTIR spectra of PLA.90 4.93 4.xxiv 4.92 4.

xxv LIST OF SYMBOLS Ea IDSC Tc y Z R Tg ∆H β Tm µm Tmax Activation Energy (kJ/mol) % Crystallinity determined by DSC Crystallization Temperature (⁰C) Fraction of materials not been decomposed Frequency factor Gas constant (J/mol K) Glass Transition Temperature (⁰C) Heat of fusion (J/g) Heating Rate (⁰C/min) Melting Temperature (⁰C) Micrometer Temperature at maximum reaction rate (⁰C) .

xxvi LIST OF ABBREVIATIONS ALK ASTM DSC DTG EB EFB EDX ENR ETP GPa HBP HBPEA HMDI IS MPa MA MCC MFI NFRPC OPF Alkali American Standard Testing Method Differential scanning calorimetri Differential thermo gravimetry Elongation at break Empty fruit bunch Energy dispersive X-ray Epoxidized Natural Rubber Engineering thermoplastics Giga Pascals Hyper branched polyester Hyper branched polyester amide Hexamethylene diisocyanate Impact strength Mega Pascals Methyl acrylate Microcrystalline cellulose Melt flow index Natural fiber reinforced polymer composites Oil palm fiber .

xxvii PF PLA PP SEM TDI TGA THF TM TPM TS ULS UTS UV Phenol formaldehyde Poly(lactic acid) Poly(propylene) Scanning electron microscopic Toluene diisocynate Thermo gravimetric analysis Tetra hydrofuran Tensile moldulus 3-(trimethoxysilyl)-propylmethacrylate Tensile strength Ultrasound Ultimate tensile strength Ultra-violet .

Singh. in terms of renewable. coconut etc.. 2008) . use of natural polymers is not new.CHAPTER 1 INTRODUCTION 1. sustainable and triggered biodegradable. sisal. Due to environmental awareness. silk. Similarly. etc. recyclable.1 INTRODUCTION In recent years there has been an expanding search for new materials with high performance at affordable costs.2008. (Satyanarayana et al. Several lignocellulosic fibers such as jute. The use of natural polymers was superseded in the 20th century as a wide-range of synthetic polymers was developed based on raw materials from low cost petroleum. since bamboo. These examples give emphasis to the development of new materials based on renewable materials. straw. have been used from historical times. pineapple. paper. In recent years it has found that the demand of these materials increasing on a commercial scale... increased attention has been paid to the use of natural polymers and lignocellulosic fibers. are source of raw materials in plastic industries. However. The reasons for this . since the 1990s. this search particularly emphasis on environment friendly materials.2008. Zheng et al. These fibers have established their potentiality as reinforcing fillers in many polymers to develop new composite materials.. In this perception composite materials make from renewable resources are very prospective in the field of composite science. et al.

such as being less abrasive to tooling and not causing as many respiratory problems for workers (Kandachar. sidings. Many window and door manufacturers are considering natural fiber . through modern instruments at different levels. 2009). the use of large volumes of polymer-based synthetic fiber composites in different sectors in spite of their high cost has led to disposal problems. These materials thus form inexpensive “new or secondary resources”. Brazil and some of the African countries have national projects for the utilization of their agro wastes such as coconut based materials. 2002 and Sanadi. wastes from rubber and palm oil industries. Philippines. Several countries such as India. along with their long durability (Bledzki and Gassan 1999. These factors have greatly increased the understanding and development of new materials such as biocomposites (Kestur et al. rice husk. 2004). several countries have already approved laws for the reduction of such environmentally abusive materials. etc. Lignocellulosic fibers have some unique attributes. triggering greater efforts to find materials based on natural resources in view of the latter’s ecofriendly attributes. Indonesia.. Natural fiber reinforced polymer composites are used in cars behind the vinyl carpeting on the doors.2 include: (a) growing interest in reducing the environmental impact of polymers or composites (b) finite petroleum resources. Synthetic polymer-based composite materials are now well established all over the world for a wide variety of applications because of their high specific strength and modulus compared to conventional materials such as metals and alloys. However. Natural fibers are sourcing of organic materials also a source for carbon and a host of other useful materials and chemicals. and roof tiles. Residential construction applications include windows. particularly for the production of “green” materials. consoles and seat backs. which could make them more valuable for extensive utilization (Rijswijk and Brouwer. Furthermore. the use of natural fiber based composites has spread to various sectors. including aircraft. because they are inexpensive and have load bearing capacity. Malaysia. and hence better understanding of their structure–property correlations. 2002). decreasing pressures for the dependence on petroleum products with increasing interest in maximizing the use of renewable materials and (c) the availability of improved data on the properties and morphologies of natural materials such as lignocellulosic fibers. Marikarian 2008). construction. In fact.. grain and fruit storage and footwear.