Emulsions, Foams, Suspensions, and Aerosols: Microscience and Applications

This is the first book to provide an integrated introduction to the nature, formation and occurrence, stability, propagation, and uses of the most common types of colloidal dispersion in the process–related industries. The primary focus is on the applications of the principles, paying attention to practical processes and problems. This is done both as part of the treatment of the fundamentals, where appropriate, and also in the separate sections devoted to specific kinds of industries. Throughout, the treatment is integrated, with the principles of colloid and interface science common to each dispersion type presented for each major physical property class, followed by separate treatments of features unique to emulsions, foams, or suspensions. The first half of the book introduces the fundamental principles, introducing readers to suspension formation and stability, characterization, and flow properties, emphasizing practical aspects throughout. The following chapters discuss a wide range of industrial applications and examples, serving to emphasize the different methodologies that have been successfully applied. The author assumes no prior knowledge of colloid chemistry and, with its glossary of key terms, complete cross–referencing and indexing, this is a must–have for graduate and professional scientists and engineers who may encounter or use emulsions, foams, or suspensions, or combinations thereof, whether in process design, industrial production, or in related R&D fields.

Preface XV About the Author XVII Acknowledgements XIX 1 Introduction 1 1.1 From the Colloidal State to Nanotechnology 1 1.1.1 Microscience, Colloids, Nanoscience and Nanotechnology 4 1.2 Classification of Emulsions, Foams, Suspensions and Aerosols 6 1.2.1 Emulsions 6 1.2.2 Foams 9 1.2.3 Suspensions 11 1.2.4 Aerosols 14 1.2.5 Hybrids 17 1.3 Characterization and Stability 17 References 18 2 Dispersion and Dispersed Species Characterization 23 2.1 Introduction 23 2.2 Surface Area, Surfaces, Porosity and Permeability 23 2.2.1 Surface Area 23 2.2.2 Surfaces 27 2.2.3 Porosity 28 2.2.4 Permeability 29 2.3 Size and Size Distribution 30 2.3.1 Microscopy 31 2.3.2 Filtration and Sieving 36 2.3.3 Radiation Scattering 38 2.3.4 Ultramicroscopy 42 2.3.5 Other Techniques 42 2.4 Conductivity 43 2.4.1 Dispersed Phase Identification 43 2.4.2 Sensing Zone Techniques 44 2.4.3 Conductivity of Dispersions 45 2.5 Sedimentation, Creaming and Centrifugation 46 2.5.1 Sedimentation and Creaming 46 2.5.2 Centrifugation and Ultracentrifugation 53 2.6 Characterization of Emulsions 56 2.6.1 Appearance and Emulsion Type 56 2.6.2 Experimental Assessment of Emulsion Stability 58 2.6.3 Composition 59 2.7 Characterization of Foams 60 2.7.1 Appearance and Foam Type 60 2.7.2 Experimental Assessment of Foam Stability 62 2.8 Characterization of Suspensions 66 2.8.1 Chemical and Surface Analysis 66 2.8.2 Experimental Assessment of Suspension Stability 66 2.9 Characterization of Aerosols 67 2.9.1 Aerosol Composition, Concentration, Size and Charge 67 2.9.2 Aerosol Processes and Stability 74 References 78 3 Interfacial Energetics 85 3.1 Surface Area 85 3.2 Surface and Interfacial Tensions 86 3.2.1 Principles 86 3.2.2 Equation of Young–Laplace 94 3.2.3 Measurement 94 3.2.3.1 Capillary Rise 95 3.2.3.2 Wilhelmy Plate 96 3.2.3.3 du Noüy Ring 97 3.2.3.4 DropWeight and Volume Methods 98 3.2.3.5 Drop Shape Methods 98 3.2.3.6 Oscillating Jet Method 98 3.2.3.7 Spinning Drop Method 101 3.2.3.8 Maximum Bubble or Droplet Pressure Method 102 3.2.3.9 Microfluidic Methods 103 3.2.4 Experimental Results for Dispersions 103 3.3 Pressure and Curved Surfaces 106 3.4 Contact Angle andWettability 107 3.5 Surfactants and Micelles 114 3.5.1 Surface Activity 114 3.5.1.1 Retardation of Evaporation by Monolayers 117 3.5.2 Classification and Analysis of Surfactants 118 3.5.3 Micelles 120 3.5.4 Surface Elasticity 126 3.5.5 Polymeric Surfactants 129 3.6 Applications of Surface Activity 129 3.6.1 Surfactants and Emulsification 129 3.6.2 Surfactants and Foaming 132 3.6.3 Surfactants and Flotation 133 3.6.4 Surfactants and Suspensions 134 3.6.5 Surfactants andWetting 134 3.6.6 Surfactants and Detergency 135 3.7 Other Lyophilic Colloids: Microemulsions 138 References 142 4 Electrokinetics 147 4.1 Charged Interfaces 147 4.2 Electric Double Layer 149 4.3 Electrokinetic Phenomena 151 4.3.1 Electrophoresis 154 4.3.2 Point of Zero Charge and Isoelectric Point 158 4.3.3 Electrodialysis 159 4.4 Electrostatic Properties in Non–aqueous Media 160 References 161 5 Colloid Stability 163 5.1 Introduction 163 5.2 Electrostatic and Dispersion Forces 165 5.2.1 Repulsive Forces 165 5.2.2 Dispersion Forces 167 5.3 DLVO Theory and Practice 168 5.3.1 Theory 168 5.3.2 Practical Guidelines 174 5.3.3 Schulze–Hardy Rule 176 5.3.4 Peptization 178 5.4 Hydration and Steric Effects 178 5.4.1 Steric Stabilization 180 5.5 Additional Stabilizing Influences 183 5.5.1 Other Stabilizing Influences for Suspension Stability 183 5.5.2 Other Influences on Emulsion Stability 184 5.5.3 Other Influences on Foam Stability 187 5.6 Kinetics 189 5.7 Destabilization of Colloids 195 5.7.1 Aggregation and Flocculation 195 5.7.2 Structures in Flocculation 196 5.7.3 Bridging Flocculation 198 5.7.4 Agglomeration Flocculation 200 5.7.5 Depletion Flocculation 200 5.7.6 Filtration 200 5.7.7 Foam Stability in the Presence of Oil 201 5.7.7.1 Adsorption of Stabilizing and Destabilizing Components 202 5.7.7.2 Spreading and Entering Coefficients 202 5.7.7.3 Emulsification and Imbibition Models 202 5.7.7.4 Pseudoemulsion Film Model 203 References 204 6 Colloid Rheology 209 6.1 Introduction 209 6.2 Principles 210 6.3 Measurement 213 6.3.1 Tube Methods 215 6.3.2 Rotational Methods 219 6.3.3 Other Methods 222 6.4 Non–Newtonian Flow Properties 224 6.4.1 Pseudoplasticity 225 6.4.2 Dilatancy 229 6.4.3 Plasticity/Pseudoplasticity with Yield Stress 229 6.4.4 Thixotropy 230 6.4.5 Rheopexy 232 6.4.6 Viscoelasticity 233 6.4.7 Rheomalaxis 233 6.4.8 Summary 234 6.5 Other Viscosity Nomenclature and Parameters 234 6.5.1 Viscosity Nomenclature 234 6.5.2 Other Viscosity Parameters 234 6.5.3 Experimental Considerations 237 6.6 Dispersion Rheology 238 6.6.1 Einstein’s Equation 238 6.6.2 Virial Expansions 241 6.6.3 Other Empirical Equations 243 6.6.4 Dispersed Phase Size and Polydispersity 243 6.6.5 Additional Considerations for Emulsions and Foams 244 6.6.6 Other Equations 247 6.7 Surface Rheology 248 6.8 Flow in Pipelines and Constraining Media 250 6.8.1 Applications in Pipeline Flow 250 6.8.2 Applications in Porous Media 252 References 254 7 Preparation, Inhibition and Destruction of Dispersions 259 7.1 Introduction 259 7.2 Preparation 260 7.2.1 Preparation of Emulsions 260 7.2.2 Preparation of Foams 269 7.2.3 Preparation of Suspensions 271 7.2.4 Preparation of Aerosols 275 7.2.5 Ostwald Ripening 277 7.2.6 Size Fractionation 278 7.3 Destruction and/or Inhibition 279 7.3.1 Demulsification 279 7.3.2 Antifoaming and Defoaming 283 References 285 8 Introduction to Practical and Industrial Applications 291 8.1 General Uses 291 8.2 Emulsions 292 8.3 Foams 295 8.4 Suspensions 297 8.5 Aerosols 297 8.6 Hazards 300 References 303 9 Applications in the Environment 307 9.1 Introduction 307 9.2 Rocks, Sediments and Soils 307 9.2.1 Magmas 307 9.2.2 Aquatic Suspensions 307 9.2.3 Soils 310 9.3 Environmental Soil Remediation 311 9.4 Water andWastewater Treatment 313 9.5 Spills and Other Hazards 315 9.6 Environmental Foam Blankets 318 9.7 Environmental Aerosols 319 9.7.1 Clouds 321 9.7.2 Atmospheric Aerosols and Climate 323 9.7.3 Aerosol Treatment 324 References 324 10 Mining and Mineral Processing Applications 329 10.1 Introduction 329 10.2 Hydraulic Mining and Hydrotransport 329 10.3 Mineral Flotation 331 10.3.1 Carrier, Emulsion and Floc Flotation 343 10.4 Tailings and Tailings Ponds 344 10.5 Dust–Suppressing Foam Blankets 348 References 348 11 Petroleum Industry Applications 351 11.1 Introduction 351 11.2 Oilwells, GasWells and NearWells 353 11.2.1 Drilling and Completion Fluids 353 11.2.2 Well Stimulation: Fracturing and Acidizing 355 11.2.3 GasWell Unloading 357 11.3 Reservoirs 358 11.3.1 Primary and Secondary Oil Recovery 358 11.3.2 Enhanced (Tertiary) Oil Recovery 360 11.3.2.1 Chemical, Microemulsion and Macroemulsion Flooding 361 11.3.2.2 Foam Injection Processes 365 11.4 Surface Operations 368 11.4.1 Surface Treatment 368 11.4.2 Oil Sands Processing 370 11.4.3 Pipeline Transportation 372 11.4.4 Upgraders and Refineries 374 References 374 12 Manufacturing and Materials Science Applications 383 12.1 Introduction 383 12.2 Wood Processing and Papermaking 383 12.3 Inks and Printing 386 12.4 Emulsions for Road Paving 387 12.5 Metalworking 388 12.6 Cleaning Processes 389 12.6.1 Detergency 389 12.6.2 De–inking 392 12.7 Surface Coatings Including Paints 394 12.8 Polymer Synthesis 397 12.9 Ceramics Manufacture 398 12.9.1 Aerogels and Xerogels 398 12.10 Firefighting Foams 399 12.11 Other Applications 401 References 401 13 Food Product and Agricultural Applications 405 13.1 Introduction to Food Colloids 405 13.2 Stabilizing Agents 406 13.3 Preparation 408 13.4 Stability 409 13.5 Protein–Stabilized Emulsions 410 13.5.1 Ice Cream 414 13.5.2 Cream Liqueurs 416 13.6 Non–protein–Stabilized Emulsions 416 13.6.1 Carbonated Soft Drinks 418 13.7 Foam Food Products 419 13.7.1 Baked Products 420 13.7.2 Foam Toppings 421 13.7.3 Champagne and Beer Foams 422 13.7.4 Coffee Beverage Foam 423 13.7.5 Undesirable Food Foams 424 13.8 Other Food Colloids 425 13.8.1 Food Suspensions 425 13.8.2 Food Aerosols 425 13.8.3 Mixed Food Colloids 426 13.9 Introduction to Agricultural Colloids 427 References 429 14 Biological and Medical Applications 433 14.1 Introduction 433 14.2 Vesicle Carriers 438 14.3 Polymer Coatings 439 14.4 Emulsion Carriers 441 14.5 Colloids in Diagnostics 444 14.6 Smart Materials in Medicine 445 References 446 15 Personal Care Product Applications 449 15.1 Introduction 449 15.2 Detergents, Shampoos and Conditioners 449 15.3 Cosmetic Skin Care Products 452 15.4 Other Personal Care Products 458 15.4.1 Aerosol Sprays and Foams 459 References 461 16 Emerging Areas in Emulsions, Foams, Suspensions and Aerosols 463 16.1 Introduction 463 16.2 Microscopy, Supermicroscopy and Nanoscopy 463 16.3 Combatting Terror Agents 465 16.4 Smart Colloids and Smart Materials 467 16.5 Nanomaterials and Nanodispersions 471 16.5.1 Nanosheets, Nanotubes and Nanowires 472 16.5.2 Other “Nano” Applications 474 16.6 Nanoscience Phenomenology and Biomimetics 477 16.6.1 Reflective and Antireflective Surfaces 477 16.6.2 Adhesive Surfaces 477 16.6.3 Wetting and Slip on Surfaces 478 16.6.4 Nanomechanics 478 References 479 Index 483

Dr. Laurier L. Schramm is President and CEO of the Saskatchewan Research Council (SRC). He is also an Honorary Member of the Engineering Institute of Canada and an adjunct professor of Chemical and Petroleum Engineering at the University of Calgary. Prior to joining SRC, Dr. Schramm held a variety of professional and managerial positions with the Alberta Research Council, Petroleum Recovery Institute, and Syncrude Canada Ltd. His main research interests are in the applications of colloid, interface, and petroleum science. He has received major national awards for his research, and is best known for his basic and applied research involving petroleum industry applications of suspensions, emulsions, foams, and surfactants. He holds 17 patents, has published nine books, over 400 other scientific publications and proprietary reports, and has given over 160 national and international scientific and technical presentations. Many of his inventions have been adopted into commercial practice. He has also served on numerous Boards of Directors and national and international expert advisory panels.