TY - BOOK AU - Amal Abdullah Mahmoud Ibrahim Elhussieny TI - Fabrication Of Innovative Biopolymer Nanocomposites Thin Films For Degradable Food Bags / U1 - 620 PY - 2018/// KW - Nano- Science & Technology KW - NULIB KW - Dissertation, Academic N1 - Thesis (M.A.)—Nile University, Egypt, 2018; "Includes bibliographical references"; Contents: Dedication………………………………………………………………………….. iv Acknowledgments……………………………………………………………………v Table of Content……………………………………………………………………..vi Nomenclature………………………………………………………………………..vii List of Tables …………………………………………………………………..…..viii List of Figures ………………………………………………………………………ix Abstract ……………………………………………………………….……………xvi Chapter (1) Introduction………..…………………………………………………1-6 1.1.Background ………………………………………………………….……… 2 1.2.Natural bio-polymer………………………………..……………….…………5 1.3.Scope of objective ………………………….…………………………………5 Chapter (2) Literature review…………...…………………………………………7-22 2.1. Natural polymers……………………………………………………….8 2.2. Composites………………………………………………………………… 9 2.3. Chitin and chitosan ……………………………………………….10 2.4. Cellulose…………………………………………………………..12 2.4.1. Rice straw ………………………………………………………13 2.5. Extraction methods of pure chitosan…………………………………….14 2.6. Preparation methods of chitosan composites…………………….16 2.6.1. Chitin fiber and chitin whisker as reinforced materials…………17 2.6.2. Cellulosic fibers and cellulosic nanofibers extracted from rice straw waste as reinforced materials..................................................…...19 2.6.3. Chitosan /cellulose composites………………………………………...20 2.7. Summary…………………………………………………………………….22 Chapter (3) Material and methods……..…………………………………………23-43 vii 3.1. Materials…………………………………………….………..…………………24 3.2.1. Method of preparation…………………….………………...………………25 3.2.1.1 Simple collection and preparation…………………………………………27 3.2.1.2. Deproteinization (DP) of shrimp shell waste…………………..………….28 3.2.1.3. Demineralization (DM) of shrimp shell waste…………………………….29 3.2.1.4. Deacetylation (DD) of shrimp shell waste………….…….…………….…30 3.2.1.5. Preparation of chitosan thin films…………………...…………………….31 3.2.2. Extraction of chitosan (CS) from shrimp shells waste with different degrees of deacetylation…………………………………………………………………………32 3.2.2.1. Preparation of chitosan (CS) thin film……………………….…………...32 3.2.3. Nano-chitosan(NCS) synthesis and optimization…………….…………..…33 3.2.3.1. Preparation of nano chitosan (NCS) thin films………………………..34 3.2.4. Extraction of chitin whisker (WH)……………………………………….....34 3.2.5. Extraction of Rice straw fibre (RS) and nano fibres (NRS) from Rice Straw waste…………………………………………………………………………………35 3.2.6. Preparation of nano rice straw fibers (NRS)…………………….…………..35 3.2.6. Preparation of CS composites thin films…………………………….……...36 3.2.7. Preparation of NCS composites thin films…………………………….…….36 3.3. Characterization of powders and fabricated thin films……………………….....37 3.3.1. Nuclear magnetic resonance (1HNMR) for chitosan powder……………….37 3.3.2. Fourier transformation Infrared (FT-IR) for powder and thin films………..37 3.3.3. X-ray diffraction (XRD) for powders and thin films……………….……….38 3.3.4. The particle size analysis for powders…………………………..…...………38 3.3.5. Mechanical Test for thin films……………………………..………..….……38 3.3.6. Nanoindentation for nano thin films………………………….....……..…....41 3.3.7. Cryogenic scanning electron microscopy (SEM) for thin films……….…….42 3.3.8. Thermal gravimetric analysis (TGA) for powders and thin films……...…….42 3.3.9. In-soil degradation test for thin films………………………...……………….42 3.3.10. Swelling and solubility test for thin films…………………..……………....43 3.3.11. Statistical analysis for thin films………………..…………………………..43 Chapter (4) Results and discussion……..………………………………………44-43 4. Results and discussion for extracted chitosan powder with mechanical and chemical methods……………………………………………………………………46 4.1.1HNMR of grounded and non-grounded chitosan powders…………………..46 4.2. Fourier transformation Infrared (FT-IR) Spectra of grounded and nongrounded chitosan powder…………………………………………………………………...…47 4.3.1HNMR of extracted non- grounded chitosan powder with three different degree of deacetylation………………………………………………………………………50 viii 5. Results and discussion for chitosan and nanochitosan composites with rice straw and nano-rice straw fibers…………………………………………………………...51 5.1. Fourier transformation Infrared (FT-IR) Spectra of chitosan, nanochitosan with rice straw and nanorice straw thin films ……………………………………………52 5.2. X-ray diffraction of rice straw and nanorice straw composites thin film…….54 5.3. Particle size analysis of nanochitosan and nanorice straw powders………….56 5.4. Mechanical properties of chitosan thin film composites………………………..57 5.5. Nano indentation for nano chitosan nanorice straw composites thin films……..59 5.6. Scanning electron microscopy (SEM) of rice straw and nanorice straw composites thin films………………………………………………………………...61 5.7. Thermogravimetric analysis (TGA) of chitosan and nanochitosan composites..63 5.8. In-soil Degradation test of chitosan and nano chitosan composites…………….65 5.9. Swelling and solubility tests of chitosan composites thin films……………..…67 5.10. Statistical analysis of chitosan and nano chitosan composites thin films……..69 6. Results and discussion for chitosan and nanochitosan composites reinforced with chitin fibers and chitin whisker………………………………………………………73 6.1. Fourier transformation Infrared (FT-IR) Spectra for chitin powder…………….75 6.2. Fourier transformation Infrared (FT-IR) Spectra of chitosan, nanochitosan with chitin fibers and chitin whisker thin films…………………………………………...75 6.3. X ray diffraction (XRD) of powders and composites thin films……………...78 6.4. Particle size of chitin whisker………………………………………………….80 6.5. Mechanical test of chitosan composites thin films………………………….…80 6.6. Nano indentation for nano chitosan composites reinforced with chitin fibers and chitin whisker thin films…………………………………………………………...82 6.7. Crayon Scanning Electron Microscope (C-SEM) of chitosan composites films reinforced with chitin and chitin whisker…………………………………………..84 6.8. Thermogravimetric analysis (TGA) of chitosan composites reinforced with chitin fibers and chitin whisker thin films……………………………………………………………………….…………85 6.9. In- Soil Degradation test of chitosan and nano chitosan composites reinforced with chitin fibers and chitin whisker thin films……………………………………...88 6.10. Swelling and solubility tests of chitosan composites reinforced with chitin fibers and chitin whisker thin films…………………………………………………………90 6.11. Statistical analysis of chitosan and nano chitosan composites reinforced with chitin fibers and chitin whisker thin films…………………………………………...91 7. Conclusion……………………………………………………………….……….97 8. Reference …… N2 - Abstract: The currently used carrier bags are synthesized from polyethylene, which is based on a petroleum-based material (non-renewable source); need a several hundred years to decompose. Estimates of the number of plastic bags used annually worldwide vary in the range of 100 million to a trillion according to a New York Times article and only a small portion of these bags is recycled, and plenty are left to enter the waste stream. Because the production of such a huge number of bags is associated with a long time to decompose, the plastic bags that are thrown away create several ecological problems. Carrier bags based on natural materials such as natural bio-polymers composites do not pose environmental hazards. Moreover, there are continuous efforts to spread the use of bio-composite materials for various manufacturing purposes such as carrier bags production due to their biodegradability, low carbon emissions, low cost, and being from non-petroleum-based sources. The aim of this research is to investigate the physical, mechanical, chemical, and thermal properties of the nanocomposite films from natural polymers and determine their potential use as carrier bags. The potential use of chitosan films as a replacement to synthetic polymers in packaging industry applications is receiving huge attention by both the academic and industrial sectors due to its biodegradability and antimicrobial properties. In this study, the effect of different reaction times during the chemical transformation of chitosan to a natural polymer was explored. Furthermore, the current work focuses on the preparation of chitosan and nano-chitosan with various methods since the particle size of chitosan has a significant influence on the previously mentioned properties. In addition, reinforcement of the chitosan with natural fillers was studied. The purpose of using the fillers was to overcome the limitations in the physical and mechanical properties of chitosan and nano-chitosan. The addition of several fillers such as cellulose fibres, nano-cellulose fibres extracted from rice straw waste, chitin fibres and chitin whisker extracted from shrimp shell waste with different wt. % is considered in this research and finally the properties of xvii the prototype are compared to Egyptian synthetic plastic bags properties. Additionally, a statistical analysis was performed to define the most desirable type and concentration of filler for the reinforcement application. Experimental results showed that cellulose fibres, nano-cellulose fibres and chitin whisker with 25wt. % significantly enhanced the yield strength, fracture strength, and young`s modulus of chitosan in comparison with the unreinforced polymer. Thermal degradation temperature of the chitosan was improved by adding all fillers to chitosan composites which indicates that the nano composite thin films can compete with current thermoplastic synthetic polymers. Chitin fibres and nano-cellulose fibres improved the degradation rate of composites compared to pure chitosan. All fillers decreased the degree of swelling and solubility, which indicated the enhancement of composites physical properties upon adding the fillers ER -