Stimuli-Responsive Super Absorbent Copolymers for Industrial Waste Treatment

147 Pages·2010·1.53 MB·English

EG1200358
Stimuli-Responsive Super Absorbent
Copolymers for Industrial Waste Treatment
By
Doaa Mostafa Ebrahem Abo-Elkher
AL-Azhar University
B.sc (2004)
A Thesis Submitted in Partial Fulfillment
For
The requirement of the Master Degree
In Chemistry
Department of Chemistry
Faculty of Science
Helwan University
2009
EG1200358
Stimuli-Responsive Super Absorbent
Copolymers for Industrial Waste Treatment
By
Doaa Mostafa Ebrahem Abo-Elkher
AL-Azhar University
B.sc (2004)
This Thesis in Partial Fulfillment of the
Requirement for the Master Degree
In Chemistry
Under the Supervision of:
Prof. Dr. Ahmed Mohammed Ramadan
Professor of Chemistry
Chemistry Department
Faculty of Science
Helwan University
Prof. Dr. El-Sayed Ahmed Abdel Aziz Hegazy
Professor of Radiation Chemistry
Polymer Chemistry Department
National Center for Radiation Research and Technology
Atomic Energy Authority
Prof. Dr. Horia Mahmoud Mahmoud Nizam El-Din
Professor of Radiation Chemistry
Polymer Chemistry Department
National Center for Radiation Research and Technology
Atomic Energy Authority
Dr. . Nevien Abdel Atti Said Ahmed Khalifa
Chemistry Department
Faculty of Science
Chemistry Department
Helwan University
2009
EG1200358
ACKNOWLEDGMENT
The author would like to thank the Prof Dr. Ahmed Mohammed
Ramadan, professor of Chemistry, Chemistry Department, Faculty of
Science, Helwan University, for his capable supervision, encouragement,
interest and useful discussion throughout this work.
Deepest gratitude is owed to Prof. Dr. El-Sayed Ahmed Abdel Aziz
Hegazy, professor of Radiation Chemistry, the Chairman of the National
Center for Radiation Research and Technology, for suggesting the topic
of this work, his keen enthusiasm, sincere guidance and continuous
supervision throughout this work.
Deepest gratitude is owed to Prof. Dr. Horia Mahmoud Mahmoud
Nizam El-Din, professor of Radiation Chemistry, National Center for
Radiation Research and Technology, for suggesting the topic of this
work, her keen enthusiasm, sincere guidance and continuous supervision
that made this work possible.
Great thanks are due to Assist. Prof. Dr. Nevien Abdel Atti Said
Ahmed, Chemistry Department, Faculty of Science, Helwan University, for
her capable supervision, throughout this work.
Finally, thanks are expressed to the Head of Polymer Chemistry
Department and for my colleagues in the Polymer Chemistry Department.
EG1200358
I
List of Tables
Table 1: Thermal Stability Expressed as Weight Loss and
Temperatures of the Maximum Rate of Reaction for AAc/MAC 55
Hydrogels Prepared at 20 kGy of Gamma Irradiation
Table 2: Antimicrobial resistance against different types of bacteria
101
(inhibition zones) of PVA/PEG hydrogels of different ratios
Table 3: Metal contents of PVA and PVA/PEG hydrogels of
different ratios loaded with nickel metal from solutions of different 109
concentrations as determined by (EDX)
Table 4 : Metal contents of PVA and PVA/PEG hydrogels of
different ratios loaded with Chromium metal from solutions of 109
different concentrations as determined by (EDX)
EG1200358
II
List of Figures
Figure 1: Effect of comonomer ratio on gel fraction for
hydrogels formed by gamma irradiation copolymerization at a 52
dose of 20 kGy
Figure 2: IR spectra of hydrogels based on pure monomers and
53
AAc/MAc comonomers
Figure 3: Initial TGA thermograms for hydrogels formed by
gamma irradiation copolymerization of different mixtures of
55
acrylic acid (AAc) and methacrylic acid (MAc) monomers at a
dose of 20 kGy
Figure 4: Rate of reaction curves for hydrogels formed by
gamma irradiation copolymerization of different mixtures of
57
acrylic acid (AAc) and methacrylic acid (MAc) monomers at a
dose of 20 kGy
Figure 5: Swelling kinetic of hydrogels formed by gamma
irradiation copolymerization of different mixtures of acrylic
59
acid (AAc) and methacrylic acid (MAc) monomers at a dose of
20 kGy
Figure 6: Initial swelling kinetics as a function of time for: ((cid:122))
PAAc, ((cid:100)) Ac/MAc (70/30), ((cid:132)) AAc/MAc (50/50), ((cid:161))
60
AAc/MAc (30/70), ((cid:83)) MAc (100) hydrogels formed by
gamma irradiation at a dose of 20 kGy
Figure 7: Swelling behaviour as a function of temperature for
hydrogels formed by gamma irradiation of acrylic acid (AAc)
and methacrylic acid (MAc) monomers at a dose of 20 kGy: 62
((cid:122)) AAc (100), ((cid:100)) AAc/MAc (70/30), ((cid:132)) AAc/MAc
(50/50), ((cid:161)) AAc/MAc (30/70), ((cid:83)) MAc (100)
EG1200358
III
Figure 8: Swelling behaviour as a function of temperature for
hydrogels formed by gamma irradiation of acrylic acid (AAc)
and methacrylic acid (MAc) monomers at a dose of 20 kGy:
63
((cid:122)) AAc (100), ((cid:100)) AAc/MAc (70/30), ((cid:132)) AAc/MAc
(50/50), ((cid:161)) AAc/MAc (30/70), ((cid:83)) MAc (100)
Figure 9: Swelling behaviour as a function of pH values for
hydrogels formed by gamma irradiation of acrylic acid (AAc)
and methacrylic acid (MAc) monomers at a dose of 20 kGy: 65
((cid:122)) AAc (100), ((cid:100)) AAc/MAc (70/30), ((cid:132)) AAc/MAc
(50/50), ((cid:161)) AAc/MAc (30/70), ((cid:83)) MAc (100)
Figure 10: Swelling behaviour as a function of pH values for
hydrogels formed by gamma radiation of acrylic acid (AAc)
and methacrylic acid (MAc) monomers at a dose of 20 kGy: 66
((cid:122)) AAc (100), ((cid:100)) AAc/MAc (70/30), ((cid:132)) AAc/MAc
(50/50), ((cid:161)) AAc/MAc (30/70), ((cid:83)) MAc (100)
Figure11: Basic dye uptake after one hour by AAc/MAc
hydrogels of different compositions from dye solutions of 68
different concentrations
Figure12: Basic dye uptake after seven hour by AAc/MAc
hydrogels of different compositions from dye solutions of 69
different concentrations
Figure13: Direct dye uptake after one hour by AAc/MAc
hydrogels of different compositions from dye solutions of 70
different concentrations
Figure 14: Direct dye uptake after seven hour by AAc/MAc
hydrogels of different compositions from dye solutions of 71
different concentrations
Figure 15: Effect of PVA/PEG ratio on the gel fraction
75
different doses
Figure 16: Effect of PVA/PEG ratio on the gel fraction by
77
using different solvent volumes
EG1200358
IV
Figure 17: IR spectra for hydrogels based on pure PVA and
PVA/PEG of different compositions synthesized at dose of 20 79
kGy of (cid:534)-radiation
Figure 18: TGA thermograms for PVA/PEG hydrogels of
different ratios. Preparation conditions: Dose, 20 kGy; solvent 81
volume, 10 ml
Figure 19: Rate of reaction curves for PVA/PEG hydrogels of
different ratios. Preparation conditions: Dose, 20 kGy; solvent 83
volume, 10 ml
Figure 20: Swelling-time dependency of PVA and PVA/PEG
85
hydrogels prepared at a dose of 20 kGy of gamma radiation
Figure 21: Effect of temperature on the equilibrium swelling of
PVA/PEG hydrogels of different ratios prepared at a dose of 20 86
kGy of gamma radiation
Figure 22: Effect of pH value on the equilibrium swelling of
PVA/PEG hydrogels of different ratios prepared at a dose of 20 88
kGy of gamma radiation
Figure 23: Chlortetracycline HCl uptake by PVA/PEG
hydrogels of different ratios at room temperature and neutral
90
medium. All hydrogels were prepared at a constant dose of 20
kGy of gamma radiation and drug concentration = 0.03 mg/l
Figure 24: Chlortetracycline HCl uptake by PVA/PEG
hydrogels of different ratios at room temperature and neutral
91
medium. All hydrogels were prepared at a constant dose of 20
kGy of gamma radiation and drug concentration = 0.08 mg/l
Figure 25: Chlortetracycline HCl release from PVA/PEG
hydrogels of different ratios at room temperature and pH of 3.
93
All hydrogels were prepared at a constant dose of 20 kGy of
gamma radiation and drug concentration = 0.08 mg/l
EG1200358
V
Figure 26: Chlortetracycline HCl release from PVA/PEG
hydrogels of different ratios at room temperature and pH of 7.
94
All hydrogels were prepared at a constant dose of 20 kGy of
gamma radiation and drug concentration = 0.08 mg/l
Figure 27: Chlortetracycline HCl release from PVA/PEG
hydrogels of different ratios at room temperature and pH of 9.
95
All hydrogels were prepared at a constant dose of 20 kGy of
gamma radiation and drug concentration = 0.08 mg/l
Figure 28: Antimicrobial activity against Escherichia Coli
(inhibition zone) for pure PVA and PVA/PEG hydrogels of 97
different ratios
Figure 29: Antimicrobial activity against Escherichia Coli
98
(inhibition zone) for PVA/PEG hydrogels of different ratios
Figure 30: Antimicrobial activity against Staphylococcus
(inhibition zone) for pure PVA and PVA/PEG hydrogels of 99
different ratios
Figure 31: Antimicrobial activity against Staphylococcus
100
(inhibition zone) for PVA/PEG hydrogels of different ratios
Figure 32: Energy dispersive x-ray (EDX) spectra of PVA and
PVA/PEG hydrogels of different ratios loaded with nickel 103
metal from solution concentration of 100 mg/l
Figure 33: Energy dispersive x-ray (EDX) spectra of PVA and
PVA/PEG hydrogels of different ratios loaded with nickel 104
metal from solution concentration of 250 mg/l
Figure 34: Energy dispersive x-ray (EDX) spectra of PVA and
PVA/PEG hydrogels of different ratios loaded with chromium 105
metal from solution concentration of 250 mg/l
Figure 35: Energy dispersive x-ray (EDX) spectra of PVA and
PVA/PEG hydrogels of different ratios loaded with chromium 106
metal from solution concentration of 100 mg/l
EG1200358
VI
Figure 36: Metal contents of PVA and PVA/PEG hydrogels of
different ratios loaded with nickel metal from solutions of
107
different concentrations as determined by Energy dispersive x-
ray (EDX)
Figure 37: Metal contents of PVA and PVA/PEG hydrogels of
different ratios loaded with Chromium metal from solutions of
108
different concentrations as determined by Energy dispersive x-
ray (EDX)
EG1200358
VII
Contents
Page
List of Tables I
List ofFigures II
Abstract 1
Aim of the Work 3
CHAPTER I
INTRODUCTION AND LITERATURE REVIEW
1.1. Interaction of Ionizing Radiation with Polymeric Materials 5
1.1.1. Sources of Ionizing Radiation 5
1.1.2. Interaction of Radiation with Polymeric Materials 5
1.1.3. Radiation Crosslinking and Degradation of Polymers 7
1.2. Hydrogels 9
1.2.1. Classification of Hydrogels 10
1.2.1.1. According to Method of Preparation 11
1.2.1.2. According to Charge 12
1.2.2. Synthesis of Hydrogels 16
1.2.2.1. Physical Crosslinking 19
1.2.2.2. Polyelectrolyte Complexation 20
1.2.2.3. Hydrogen Bonding 21
1.2.2.4. Chemical Crosslinking 21
1.2.2.5. Ionizing Radiation 22
1.2.3. Applications of Hydrogels 29
1.2.3.1. Responsive Hydrogels 29
1.2.3.2. Drug Delivery Hydrogels 30
1.2.3.3. Biomaterial Hydrogels 32
1.2.3.4. Applications in Agriculture 36
1.2.3.5. Wastewater Treatments 37
CHAPTER II
MATERIALS AND MEHODS
2.1 Materials 40
2.1.1. Monomers 40
2.1.2. Polymers 40
2.1.3. Buffer stuff 40
2.1.4. Dyestuffs 41
2.2. Methods 42
2.2.1. Preparation of AAc/MAc Copolymer Hydrogels 42