Bioactive Compounds Conclusions... 29

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1 Contents 1. Biorefining and the Pulp and Paper Industry Introduction Biomass for Chemicals and Bioproducts Intracellular and Storage Materials Proteins Starch and Fructans Chlorophyll and Other Pigments Plant Cell Wall Components Cellulose Noncellulosic Polysaccharides Lignin Tannin and Other Polyphenols Lipids Cutin and Suberin Oil Crops Terpenes Possibilities of Biorefining Implementation into the Pulp Industry Lignin Separation of Lignin Degradation Products of Polysaccharides Black Liquor as a Feedstock for Synthesis Gas Separation of Hemicelluloses Fine and Speciality Chemicals xi

2 Pulp Production and Processing: From Papermaking to High-Tech Products Bioactive Compounds Conclusions Pulping Fundamentals and Processing Introduction to Pulping Mechanical Pulping Semichemical Pulping Chemical Pulping Kraft Pulping Processes General Description Kraft Pulping Parameters Kraft Pulping Technology Sulfite Pulping Organosolv Pulping Conclusions or Future Trends Chemical Pulp Bleaching General Aspects Optical Properties of Pulp Residual Lignin and Other Oxidisable Structures Oxygen Delignification Chemistry of Oxygen Delignification Process Description and Variables Kinetics of Oxygen Delignification Process Technology and Equipment Chlorine Dioxide Bleaching Reactions and Factors in Chlorine Dioxide Bleaching Kinetic Dependencies of Chlorine Dioxide Bleaching Technology of Chlorine Dioxide Bleaching Reactions in the Extraction Stages Peroxide Bleaching xii

3 Contents Chelating Stages Reactions and Factors in Hydrogen Peroxide Bleaching Process Variables and Technology of Peroxide Bleaching Kinetics of Peroxide Bleaching Peracetic Acid in Pulp Bleaching Ozone Bleaching Chemistry and Technology Xylanases and Laccases in Pulp Bleaching Conclusions Oxygen Bleaching Introduction Advantages and Disadvantages of Oxygen Delignification Oxygen Production Delignification Chemistry Lignin Reactions Carbohydrate Reactions The Role of Hexenuronic Acids in Oxygen Delignification Mass Transfer and Reaction Kinetics Oxygen Delignification Technology Double-stage Medium-consistency Oxygen Delignification Systems Process Variables Pulp Washing Incoming Kappa Number Time and Temperature Reaction Pressure Oxygen Charge Alkali Charge Magnesium Charge Consistency xiii

4 Pulp Production and Processing: From Papermaking to High-Tech Products 4.8 Impact of Oxygen Delignification on Bleaching Effluent Quality Chemistry and Physics of Cellulose and Cellulosic Substances Introduction Basic Chemistry of Cellulose Supermolecular and Hypermolecular Characteristics of Cellulose and Lignocellulose Materials Water and Cellulose/Cellulosic Substances Liquid Crystalline Cellulose Suspensions Wet-web Strength and Wet Strength of Cellulosic Materials Interactions in Cellulosic Fibrous Slurries using Enthalpiometric Measurements Interpretation of Enthalpiometric Observations Existence of Water Inclusions among Cellulosic Chains Hydrogel Structure of Cellulose H-bond Ability and Hydration Bonding/Antibonding Concept Rheosedimentation Thermoresponsive Hydrated Macro-, Micro- and Submicroreticular Systems of Cellulose Swelling Conclusions Physico-chemical Characterisation of Cellulose from the Broussonetia papyrifera Bark and Stem, and Eucommia Ulmoides Oliver Stem Introduction Experimental Materials Isolation of Cellulose Structural Characterisation of Cellulose Results and Discussion xiv

5 Contents Yield of Cellulose Sugar Component Analysis Intrinsic Viscosity, Viscosity Average Degrees of Polymerisation and Molecular Weight Fourier Transform-infrared Spectra Cross Polarisation/Magic Angle Spinning 13 C Solid-state Nuclear Magnetic Resonance Spectra Thermal Analysis Conclusions Cellulose Fibres in the Papermaking Process Paper and Papermaking Raw Materials Suitability of Cellulose Fibres for Papermaking Are All Types of Fibres Equally Suitable for Papermaking? Papermaking Properties of Cellulose Fibres Chemical Composition Morphological Features of Fibres Fibre Length and Fines Cell Wall Thickness and Fibre Coarseness Wet Fibre Properties Dry Fibre Properties Effects of Drying Stress (Jentzen Effect) What happens to Cellulosic Fibres during Papermaking? Cellulose Fibres in the Slushing and Deflaking Processes Swelling of Fibres Cellulose Fibres in the Refining Process Refining Effects on Fibres Removal of the Primary Fibre Wall External Fibrillation Internal Fibrillation Fibre Shortening xv

6 Pulp Production and Processing: From Papermaking to High-Tech Products Creation of New Surfaces and Fines Partial Dissolution of the Fibre Wall Increase in Fibre Conformability Effects on Pulp Properties Cellulose Fibres in the Dewatering and Drying Processes Conclusions Cellulose Esters - From Traditional Chemistry to Modern Approaches and Applications Introduction Cellulose Esters: Heterogeneous or Cvasi-homogeneous Processes Cellulose Esters: Homogeneous Processes Dissolution of Cellulose Nonderivatising Solvents Aqueous Nonderivatising Solvents Nonaqueous Nonderivatising Solvents Derivatising Solvents Homogeneous Esterification of Cellulose Cellulose Esters in Nanotechnology Conclusions Lyocell Processes and Products Overview Reasons for a New Cellulose Fibre Lyocell/TENCEL Outline Profile TENCEL Development Timescale Process Description Pulp and Premix xvi

7 Contents Dissolution Stage Solution Transport Filtration Spinning Fibre Washing Fibre Treatments Fibre Drying Crimping, Cutting and Baling Solvent Recovery Fibre Properties Environmental Factors Key Technological Factors Air Gap Spinning Safe Control of Reactions between Cellulose and N-methylmorpholine-N-oxide Chemical Reactions occurring in the Process Practical Solutions for Control of the Cellulose Reaction with N-methylmorpholine-N-oxide Cellulose Solution Temperature Control Pressure Relief to Accommodate an Exothermic Reaction Operation of Pumps used to Transport the Cellulose Solution Wood Pulp Requirements Control and Manipulation of Fibrillation Background What is Fibrillation? Approaches to Manipulation of Fibrillation Fibre Modification TENCEL A TENCEL LF xvii

8 Pulp Production and Processing: From Papermaking to High-Tech Products 9.9 Dyeing and Finishing Technology Manipulation of Fibrillation Using Fibrillation to give Peach Touch Fabrics Processing Routes to Making Peach Touch Fabrics Machinery Selection and Process Methodology Garment Processing Piece Dyeing Dyeing/Finishing Routes that Avoid Fibrillation TENCEL Conversion to Yarns and Fabrics TENCEL in Nonwovens TENCEL in Papers Conclusions Functional Cellulose Microspheres Introduction Challenges in the Dissolution of Cellulose Conventional Solvents Green Cellulose Solvents Pretreatments of Cellulose Fibres Preparation of the Microspheres using a Green Solvent Sodium Hydroxide-urea-water System Techniques for the Preparation of Microspheres Tailoring of Cellulose Microspheres using Physico-chemical Design Applications of Cellulose Microspheres Chromatography Protein Immobilisation Drug Loading and Release Conclusions Processing Cellulose Fibres to the Micron and Nanoscale Introduction xviii

9 Contents 11.2 Ultrastructure and Morphology of Cellulose Fibres Processing of Micro- and Nanocelluloses Processing of Microcrystalline Cellulose Processing of Cellulose Nanocrystals Processing of Micro/Nanofibrillated Cellulose Pretreatments Morphological Properties of Nanocelluloses Industrial Production of Micro- and Nanocelluloses Examples of Nanocellulose-based Materials Foams and Aerogels Films and Nanopapers Polymeric Nanocomposites Conclusions and Future Optical Properties of Cellulose Esters and Applications to Optical Functional Films Optical Properties of Polymeric Materials Wavelength Dispersion of Orientation Birefringence Orientation Birefringence of Cellulose Esters Advanced Methods to Control Orientation Anisotropy Conclusions Antibacterial Fibres A Brief Introduction Bacteria and Antibacterial Substances Cellulose as an Antibacterial Material Classification of Antibacterial Materials Fabrication of Leaching Materials Silver Triclosan Controlled Release of Antibacterial Substances xix

10 Pulp Production and Processing: From Papermaking to High-Tech Products Leaching Natural Compounds Fabrication of Contact-active Materials Grafting of Polymers Adsorption of Polymers Other Approaches Testing of Antibacterial Fibres Available Standard Methods American Association of Textile Chemists and Colourists Standards Japanese Industry Standards American Society for Testing and Materials International Standards International Organization for Standardization Technical Association of the Pulp and Paper Industry SCAN Methods Methods for Contact-active Materials Final Remarks Recent Advances in the Processing of Biomass Feedstocks for Biohydrogen Production Introduction Biomass Pretreatment for Biohydrogen Production Biohydrogen Production with Processing of Sugar-rich and Mixed-composition Biomass Biohydrogen Production with Processing of Lignocellulosic Biomass Conclusions Abbreviation Index xx