Fabrication Of Innovative Biopolymer Nanocomposites Thin Films For Degradable Food Bags / Amal Abdullah Mahmoud Ibrahim Elhussieny

Supervisor:

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
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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
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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 ……

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
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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.

Text in English, abstracts in English.