Arab Republic of EgyptNational Research Centre (NRC)

Ali Hebeish

Achievements in Chemistry of Fibrous and Nonfibrous

Textile Materials

Science-Based Technological Innovations For Textile Development

NRC, Cairo, March 2014

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Arab Republic of EgyptNational Research Centre (NRC)

Ali Hebeish

Achievements in Chemistry of Fibrous and Nonfibrous

Textile Materials

Science-Based Technological Innovations For Textile Development

50 years of research 587 papers

NRC, Cairo, March 2014

ii

Preface

Textile manufacturing industry is complex because of the

wide variety of substrates (fibers), process, machinery and

components used and finishing steps undertaken. Processing of

textile fabrics made, for example,from cotton fibers involves,

inter alia, mechanical processes, notably, spinning to convert the

fibers to yarns and weaving or knitting for conversion of the

spun yarns to woven or knitted fabrics. On the other hand,

chemical processes (often called finishing) of the fabrics

comprise desizing, scouring, bleaching, mercerizing, dyeing,

printing and final finishing. Sizing agents and sizing of the

fabric yarns in the warp direction mayalso be placed among

chemical processing because they involve much chemistry.

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Hence, making up modern fabrics is an intricate and complex

process. These fabrics are further processed into apparel, home

furnishings and industrial goods which, indeed, represent the

three well-known categories of textile products at the market,

viz. apparel, domestic textiles and technical textiles,

respectively.

Success in the textile fields is the end–product of an ability

to bring into focus a body of knowledge which entails the proper

use of men, materials and machinery. Of all the decisions made

in textile processing none is more important than the decision of

why, how and with what the fabric is to be processed chemically

for higher performance and competition without harming the

human and environmental health. Modulation of textile

chemistry and chemical technology along with harnessing of

nanotechnology and biotechnology are exercised in our work to

help accomplish such a decision and solve problems associated

therewith. Advancing insight into structural features and

reactivity of substrates (fibres) created novel types of materials

Our work details with the chemistry of polymers used in

fibrous textiles such as cotton, wool, bast fibers, polyester and

polyamide, as well as nonfibrous textiles commonly known as

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textile auxiliaries and finishes. However, the work is much

devoted to cotton cellulose and auxiliaries and finishes used in

cotton chemical processing. This is because cotton is the most

important textile fibers and there is a great demand all-over the

world for cotton fabrics which exhibit improved multi-

functional characteristics. Easy care and flame retardancy,

antimicrobial and UV- protection are some of the improved

properties which caught imagination of consumers. By and large

research outputs of the work in question form the fundamental

and practical bases for achieving multifunctionalized cotton

products. In combination with this are the numerous derivatives

of nonfibrous materials which were thoroughly investigated in

current work with respect to their synthesis, characterization and

applications particularly in the textile field. Of these materials

mention is made of the following: starch, carboxymethyl

cellulose (CMC), chitosan and cyclodextrin along with

harnessing nanotechnology and biotechnology for development

of functional finishes for development of smart cotton products.

Emphasis is also placed on chemical routes for environmental

protection through energy and materials conservation. The latter

could be achieved via establishment of combined wet processes,

enhancement of cotton reactivity and/or cotton susceptibility

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towards dyeing and finishing, synthesis of reactive carboxylates

as permanent finishes to substitute the conventional ones used in

temporarily finishing and recycling of water soluble starch sizes

using the ultrafiltration technology. It is as well to emphasize

that we have succeeded to synthesize and characterize

nonfibrous materials loaded with nanometalic particles using

world-class facilities. These materials acquire great potentiality

in production of medical textiles.

NRC, Cairo, March 2014 Ali Hebeish

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Table of Contents

Preface iiiSynopsis 1Achievements Within Environmental Scene 6

1. Chemistry of Fibrous Textile Materials 8

1.1. Cellulose

81.1.1. Degradative Treatments 101.1.1.1. Thermal Treatments 101.1.1.2. Hypochlorite, Chlorite and

Persulphate Treatments 121.1.1.3. Acid Treatments 141.1.1.4. Gamma Radiation 141.1.1.5. Pretreatment 141.1.2. Mechanisms of degradation of Cotton

and Effects of Mercerization-Stretching upon the Course of these Mechanisms 16

1.1.2.1. Effect of different Degradative Treatments on Cotton and Slack Mercerized-Restretched Cottons 17

1.1.2.2. Infrared spectroscopy and X-ray Analysis 19

1.1.2.3. Structural Differences Between Scoured Cotton and Slack Mercerized- Restretched Cottons 20

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1.1.2.4. Characterization of Microstrucural Differences Between Scoured Cotton and Slack Mercerized-Restretched Cottons 20

1.1.2.4.1. Reproducibility of the Reaction 211.1.2.4.2. Microstructure of DEAE Cottons

versus unmodified cottons 221.1.2.4.3. Microstructural Differences Among

Scoured and Mercerized Cottons 221.1.2.4.4. Nature of Accessible Regions 231.1.2.4.5. Selective Accessibility 241.1.3. Chemical Reactions Involved in

Functional-ization of Cellulose 251.1.4. Vinyl Graft Copolymerization 261.1.4.1. Nature of the substrate 271.1.4.2. Initiation System 291.1.5. Colouration 301.1.5.1. Dyeing of Cotton Cellulose 311.1.5.2. Dyeing of Chemically Modified

Celluloses 321.1.5.3. Printing of Cotton Fabrics 331.1.5.4. Heat Transfer Printing 341.1.6. Easy Care Cotton Finishing 351.1.6.1. Soiling and Soil Release 361.1.6.2. Output of Research Pertaining to

Soiling and Soil Release 381.1.7. Biotechnology for Development of Wet

Processing of Cotton Based Textiles 391.1.7.1. Establishment of Biotreatment

Appropriate for Processing of Cotton-Based Textiles

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1.1.7.2. Establishment of Optimal Conditions for Bioscouring 42

1.1.7.3. New Development in Scouring and Bleaching 43

1.1.7.4. Most Appropriate Strategy for Bioscouring 43

1.1.7.5. Approaches for Application of Enzymatic Treatment and Reactive Dyeing 44

1.1.7.6. Innovative Technology for Multifunctionalization of Cotton Fabrics 45

1.2. Wool

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1.3. Polyamide

491.3.1. Polyamide Copolymers 501.3.2. Reaction with Cyanuric Chloride and

its Derivatives 501.3.4. Factors Affecting Dyeing 511.3.5. Improved Dyeability 521.3.6. Fading Characteristics 52

1.4. Polyester

551.4.1. Graft Copolymerization onto PET 561.4.2. Properties of PET Graft Copolymers 601.4.3. Dyeing of PET and Modified PET 61

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1.4.3.1. Improved Dyeing by Vinyl Grafts 621.4.3.2. Low Temperature Dyeing 621.4.3.3. pH Control 631.4.3.4. Fading Characteristics 631.4.3.5. Heat Transfer Printing

642. Chemistry of Nonfibrous

Textile Materials 65

2.1. Starch 65

2.1.1. Gelatinization of Starch 662.1.2. Starch Copolymers 672.1.3. Starch Composites 692.1.4. Starch hybrids 712.1.4.1. Development of New Starch Hybrids

through Successive Polymerization and Etherification 71

2.1.4.2. New Starch Hybrids via Etherification of Poly (Acrylamide)- Starch Copolymers with Acrylamide 72

2.1.4.3. New Route for Novel Polycarboxylic Starch Hybrid 72

2.1.5. Oxidation of starch 732.1.6. Starch Ethers 762.1.6.1. Cyanoethyl Starch 762.1.6.2. Carboxymethyl Starch (CMS) 782.1.7. Starch Phosphate Monoesters 802.1.8. Reactive Starches 812.1.9. Multimodification of starch for

development of new materials 822.2. Chitosan 84

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2.2.1. Acid Hydrolysis 862.2.2. Oxidation 862.2.3. Carboxymethylation 872.2.4. Carbamoylethylation 882.2.5. Acrylamidomethylation 882.2.6. Graft Copolymerization of

Acrylamide Onto Chitosan and Hydrolyzed Chitosan 88

2.2.7. Utilization of Tailored Chitosan Adducts as Chemical Finishes 89

2.2.8. Synthesis and Application of Chitosan-O-PEG Graft Copolymer 90

2.2.9. Synthesis and Application of Chitosan-N-PEG Graft Copolymer 91

2.2.10. Performance Properties of Chitosan-O-PEG and Chitosan-N- PEG Copolymers 92

2.3. Carboxymethyl Cellulose (CMC)92

2.4. Nanotechnology for Development of Functional Finishes

972.4.1. Synthesis and Characterization of

Silver Nanoparticles 992.4.2. Bio-synthesis of Silver Nanoparticles 10 02.4.3. Ultra-Fine Characteristics of Starch

Nanoparticles 1022.4.4. Concurrent Formation of Nanosized

Particles of Both Starch and Silver with Emphasis on Their Nanostructural Features 103

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2.4.5. More Insight on Characterization of Nano-sized Particles of Silver Powder and Their Evaluation for Different Medical applications 104

2.4.6. Development of New system based on Crosslinked Starch Nanoparticles for Drug (diclofenac sodium) Delivery 105

2.4.7. Modulation of the Nano-structural Characteristics of Cellulose Nanowhiskers 106

2.4.8. Development of Cellulose Nanowhiskers – Polyacrylamide Copolymer as Highly Functional Precursor in Synthesis of Nanometal Particles 107

2.4.9. Synthesis, Characterization and Application of Nanosized Carbamoylethyl Cellulose Whiskers 108

2.4.10. Processing and Properties of Novel Hybrid Nanogels 109

2.4.11. Carboxymethyl Cellulose (CMC) Hydrogel Containing Metallic Nanoparticles

1112.4.12. Cyclodextrin Copolymers–Nanosized

Composites for Production of Smart Cotton Textiles

1132.4.12.1. β-Cyclodextrin-Poly(acrylic acid)

Graft Copolymer as Green Precursor for Synthesis of Silver Nanoparticles 114

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2.4.12.2. Reactive Preformed Polymers 1162.4.12.3. Cotton Cellulose Bearing Cationized

Groups, Triazinyl -β-Cyclodextrin Moieties and PAA Moieties for Incorporation of AgNPs and Perfume 116

2.4.12.4. In Situ Formation of AgNPs 1172.4.13. Development of Silver-Containing

Nano-cellulosics for Effective Water Disinfection 118

2.4.14. Nanotechnology in Textile with Contribution to Pigment Printing 119

3. Chemical Routes for Environment Protection Via Energy and Material Saving

1223.1. Combined processes 1233.1.1. Combined pretreatment 1233.1.2. Combined dyeing and finishing 1243.2. Improving Chemical Reactivity of

Cotton 1243.2.1. Acrylamidomethylated Cotton

(AMC) 1243.2.2. Cotton Bearing Aromatic Amino

Groups: 1253.2.3. Cellulose Carbamate 1253.2.4. Other Modified Cottons 1253.2.5. Heat Transfer Printing 1253.3. Enhancement of Reactive Dye

Fixation 1253.4. Reactive carbohydrate polymeric

products126

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3.5. New Reclaimable sizes for Improved High Speed Weaving and Reduced Pollution.. 127

3.5.1. Recycling of Water-Soluble Starch Sizes 127

3.5.2. Introduction of Ultrafiltration Technology to Textile Industry in Egypt

1283.6. Multifunctionalization of Cotton 131

4. Conclusion132

5. Innovation141

6. References147

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