Applications of Nanotechnology in the Polymer and Textile Fields Von der Fakultät Chemie der Universität Stuttgart zur Erlangung der Würde eines Doktors der Naturwissenschaften (Dr.rer.nat.) genehmigte Abhandlung Vorgelegt von Master-Chem Wael Sabry Mohamed aus Kairo - Ägypten Hauptberichter: Prof. Dr. Dr. h.c. Franz Effenberger Mitberichter: Prof. Dr. rer. nat. Karl Bredereck Tag der mündlichen Prüfung: 28.September 2009 Universität Stuttgart Institut für Polymerchemie Lehrstuhl für Makromolekulare Stoffe und Faserchemie 2009 TO THE SPIRIT OF MY FATHER II First and foremost, I would like to present my sincere thanks to my advisor, Prof. Dr. Dr. h.c. Franz Effenberger, for all of his friendly support and guidance throughout my education at Stuttgart University. Words cannot express how much I have gained his wisdom, as well as from the many learning opportunities he afforded me during my tenure. Additionally, I would like to thank Dr. Michael Schweizer, for without his insight, patience, and helpful suggestions that have shaped my development as a scientist, this thesis would not have been possible. I would like also to express my sincere thanks and gratitude to Dr. Gabriele Hardtmann for her encouragement and support throughout my studying years at Stuttgart University. Dr. Manuella Frick for her enormous helping. Dr. Anette Hoffmann-Frey for her friendly interesting. Dr. Gutmann for support in the melt spinning. Dr. F. Harmanutz and Mrs. Müller for the manufacturing of X-rays. Mr. Jan Pigorsch for assistance with laboratory work. Mrs. Segel for measuring the mechanical properties. Mrs. Henzler and Mr. Hageroth for the investigation by SEM. Mr. Wölfl for melting intercalating process. All of my colleagues in the institute for polymer chemistry and institute for textile and chemical fibres (Denkendorf) for the pleasant working climate and good cooperation. III I would like to express my sincere thanks and gratitude to Egyptian Government for the financial support and I would like also to extend my gratitude to the Egyptian Cultural Counsellor and all members of the Egyptian Culture Office in Berlin for their interest and enormous helping IV Abstract Intercalated modification of Montmorillonite clay (MMT) with three different amino acids - Alanine, Leucine, and Phenylalanine - in the presence of hydrochloric acid followed by surface modification by phenyl triethoxy silane coupling agent to produce double modified montmorillonite clay which is characterized by X-ray diffraction (XRD) and Thermogravimetric analysis (TGA). The data show an increase in d- spacing of modified clay as a result of cationic exchange. The ability of clay to make glucose and fructose absorption was kinetically studied and also the swelling degree of the clays was determined. Double modified MMT clay was used in the preparation of Polyacrylate / clay nanocomposites by using an in situ redox emulsion polymerization of polyglycidylmethacrylate (PGMA) and polymethylmethacrylate (PMMA). The structure and properties of the prepared nanocomposites were achieved by XRD, TGA, and SEM. The results show that all weight loses temperatures for the nanocomposite samples are higher than that of pure polymer in both PGMA and PMMA. It is also obvious that the increasing in the clay content plays an effective role in the increasing of thermal stability of these materials. SEM shows that the clay is more homogenously dispersed in PMMA than in PGMA matrix. Polyolefin nanocomposites were synthesized by using Na-MMT, Leucine-MMT and DM-MMT clay by solution polymerization method using anhydrous xylene solvent in case of polypropylene and using a co-solvent of xylene and benzonitrile (80:20wt %) in case of polyethylene. The structure and properties of the prepared nanocomposites were examined by XRD, TGA and SEM. The results show that a homogenous dispersion of MMT clay in the polymer matrix is observed only in the case of PP/DM-MMT up to 10%DM-MMT weight percentage. The grafting emulsion polymerization of vinyl monomers onto cotton was carried out in the presence of double-modified montmorillonite clay. The obtained results show that grafting with glycidyl methacrylate/montmorillonite gave a higher rate of grafting than grafting with methyl methacrylate/montmorillonite in all clay percentages, and also, the grafting yield of glycidyl methacrylate monomer onto cotton in the presence of montmorillonite clay had a higher value than that in the absence of the clay for all factors studied. Cotton grafted with glycidyl methacrylate/ montmorillonite with a graft yield of about 50% was prepared according to the emulsion polymerization technique V and was treated with different concentrations of dibutylamine solutions ranging from 1 to 4%. The obtained samples were characterized according to nitrogen content, thermal stability, scanning electron microscopy, mechanical properties, water absorption, and colour strength according to acid, basic, and reactive dyes. Polypropylene and nanocomposites polypropylene fibres were successfully prepared via melt spinning process. The prepared fibres were characterized according to thermal stability, scanning electron microscopy, mechanical properties, water absorption, and colour strength according to acid and disperse dyes. VI Table of Contents Chapter 1: Introduction and Objectives 1 1.1. Nanotechnology 1 1.1.1. Nanoscale systems and their properties 2 1.2. Nanocomposites 2 1.2.1. Types of Composite materials 2 1.2.2. The classification of nanocomposites 3 1.2.3. Nanoeffect 4 1.2.4. Polymer-Clay Nanocomposites 5 1.2.5. Applications of nanocomposites in Textile field 8 1.3. Objective of the study 8 Chapter 2: Clay Structure and Modification 10 2.1. Crystal Structure of Layered Silicate 11 2.1.1. Montmorillonite (MMT) 14 2.2. Modification of the Clay 16 2.2.1. Cation Exchange Process 16 2.2.2. Cation Exchange Capacity 17 2.2.3. Surface Charge Density 18 2.2.4. Types of Clay Modifications 18 A) Interlayer modification 18 Ι) Amino acids 18 II) Alkylammonium ions 19 B) Surface and edges modification 19 Chapter 3: Polymer Layered Silicate Nanocomposites (PLSN) 21 3.1. Polymer Matrices Used in Layered Silicate Nanocomposites 21 3.1.1. Vinyl Polymers 21 3.1.2. Polyolefin 22 3.2. Morphology of Polymer Layered Silicate Nanocomposites 22 3.2.1. Intercalated 22 3.2.2. Exfoliated 23 3.2.3. Flocculated 25 3.2.4. Intercalated-Exfoliated mix VII 26 3.3. Synthesis of Polymer Layered Silicate Nanocomposites 26 3.3.1. In-Situ Polymerization 26 3.3.2. Solution Mixing 29 3.3.3. Melt Intercalation 33 3.4. Characterization of Polymer Layered Silicate Nanocomposites 34 3.4.1. Wide Angle X-ray Diffraction (WAXD) 34 3.4.2. Transmission Electron Microscopy (TEM) 36 3.4.3. Rheology 36 3.5. Properties of Polymer Layered Silicate Nanocomposites 37 3.5.1. Young’s modulus 37 3.5.2 Flexural modulus 38 3.5.3 Thermal degradation 38 3.5.4 Heat Distortion Temperature (HDT) 39 3.5.5 Barrier property improvements 40 Chapter 4: Grafting of Vinyl Monomers Nanocomposites onto Cotton Fabric 41 4.1. Cotton Fabric 41 4.1.1. Chemical Composition 41 4.1.2. Cotton Morphology 44 4.1.3. Cellulose Chemistry and Reactions 45 4.2. Grafting 47 4.2.1. Grafting Method 47 4.2.1.1. Grafting Initiated by Chemical Technique 47 4.2.1.1.1. Free-radical grafting 47 4.2.1.1.2. Grafting through living polymerization 48 4.2.1.1.3. Ionic grafting 50 4.2.1.2. Grafting Initiated by Radiation Technique 50 4.2.1.2.1. Free-radical grafting 50 4.2.1.2.2. Ionic grafting 51 4.2.1.3. Photochemical grafting 52 4.2.1.4. Plasma radiation induced grafting 52 4.2.1.5. Enzymatic grafting 53 VIII Chapter 5: Fibre Reinforcement Polypropylene / Montmorillonite 54 Nanocomposite 5.1. Polypropylene Based Nanocomposites 55 5.2. Processing Of PP/MMT Filament 56 5.2.1. Introduction to Spinnability Criteria 56 5.2.2. Melt Spinning Processing Techniques 59 5.2.2.1. Fibre Melt-spinning Principles 59 5.2.2.2. Film Extrusion-Calendering 59 Chapter 6: Experimental Part 61 6.1. Materials 61 6.2. Methods 62 6.2.1. Modification of MMT Clay 62 6.2.1.1. Intercalated Modification of MMT with Amino Acids 62 6.2.1.2. Surface Modification of MMT with Silane Coupling Agent 62 6.2.1.3. Double Modification of MMT with Amino acid and Silane 62 Coupling Agent 6.2.2. The Swelling Degree 62 6.2.3. Glucose and Fructose Absorption Studies 63 6.2.3.1. Preparation of Calibration Curve 63 6.2.4. Preparation of Nanocomposites 63 6.2.4.1. Preparation of Polyacrylate / MMT Nanocomposites by In Situ 63 Emulsion Polymerization 6.2.4.2. Preparation of Polypropylene / Montmorillonite Nanocomposite 63 by Solution Polymerization 6.2.4.3. Preparation of Polyethylene / Montmorillonite Nanocomposite 64 by Solution Polymerization 6.2.4.4. Preparation of Polypropylene / Montmorillonite Nanocomposite 64 by Direct Melt Spinning Intercalation Method 6.2.5. Polypropylene / Montmorillonite Fibre Production Method 64 6.2.6. Grafting Polymerization Procedure 65 6.2.7. Dyeing Methods 65 6.2.8. Water Absorption 66 6.3. Characterization 67 IX Chapter 7:Modifications, Characterizations and Applications of 68 Montmorillonite Nanoparticles 7.1. Introduction 68 7.2. Modification of Montmorillonite Clay 69 7.3. Characterization of Montmorillonite Clay 71 7.3.1. Thermal Gravimetric Analysis (TGA) 71 7.3.2. Morphology of MMT Clay by Scanning Electron Microscope(SEM) 72 7.4. Applications of Montmorillonite Clay 72 7.4.1. The Swelling Degree 72 7.4.2. Sugar Absorption Study 73 7.5. Conclusion 75 Chapter 8: Synthesis and Characterization of some Polyacrylate / 75 Montmorillonite Nanocomposites by In Situ Emulsion Polymerization using Redox Initiation System 8.1. Introduction 75 8.2. Structures and Properties of nanocomposites 76 8.2.1. Thermal Gravimetric Analysis (TGA) 76 8.2.2.