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E-grāmata: Emulsion Formation and Stability

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Emulsion Formation and StabilityPalielināt
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Eight papers from the Fifth World Congress on Emulsions, held in Lyon, France in October 2010 explore emulsification techniques, the production of nanoparticles for biomedical applications, and the application of rheological techniques for studying the interaction between the emulsion droplets. The topics include emulsion formation in membrane and microfluidic devices, adsorption characteristics of ionic surfactants at a water/hexane interface obtained by the profile analysis technique and the oscillating drop and bubble analyzer, measuring techniques applicable to investigating emulsion formation during processing, emulsion in roto-stator mixes, and the rheology and stability of sterically stabilized emulsions. Annotation ©2013 Book News, Inc., Portland, OR (booknews.com)

Highlighting recent developments as well as future challenges, this volume covers such topics as emulsions, nano-emulsions, nano-dispersions and novel techniques for their investigation. It also considers the fundamental approach in areas such as controlled release, drug delivery and various applications of nanotechnology.

Recenzijas

About the editor:

"Dr. Tadros is a very well recognized individual in the surface chemistry community and is known to write well." (Prof. Krister Holmberg, Chalmers University, Goteborg, Sweden)

"The author is a well-known scientist in this field with a long experience in colloid science." (Henkel KGaA, Dusseldorf, Germany)

"Dr. Tadros is well-known in the field of colloid science. High quality can be expected." (University of Bayreuth, Germany)

"Professor Tadros is a well-known expert on the topic. Because of his industrial experience it might be possible to close the gap between fundamentals and the relevance and applications in the practice." (Dr. Oetter, BASF AG, Ludwigshafen, Germany)

"Dr. Tadros is a well-known scientist in emulsion and rheology science who can write about fundamentals and applications of surfactants." (Yokohama National University, Japan)

Preface xi
List of Contributors
xiii
1 Emulsion Formation, Stability, and Rheology
1(76)
Tharwat F. Tadros
1.1 Introduction
1(3)
1.1.1 Nature of the Emulsifier
1(1)
1.1.2 Structure of the System
2(1)
1.1.3 Breakdown Processes in Emulsions
3(1)
1.1.4 Creaming and Sedimentation
3(1)
1.1.5 Flocculation
4(1)
1.1.6 Ostwald Ripening (Disproportionation)
4(1)
1.1.7 Coalescence
4(1)
1.1.8 Phase Inversion
4(1)
1.2 Industrial Applications of Emulsions
4(1)
1.3 Physical Chemistry of Emulsion Systems
5(1)
1.3.1 The Interface (Gibbs Dividing Line)
5(1)
1.4 Thermodynamics of Emulsion Formation and Breakdown
6(2)
1.5 Interaction Energies (Forces) between Emulsion Droplets and Their Combinations
8(6)
1.5.1 van der Waals Attraction
8(1)
1.5.2 Electrostatic Repulsion
9(3)
1.5.3 Steric Repulsion
12(2)
1.6 Adsorption of Surfactants at the Liquid/Liquid Interface
14(12)
1.6.1 The Gibbs Adsorption Isotherm
14(3)
1.6.2 Mechanism of Emulsification
17(12)
1.6.3 Methods of Emulsification
29
1.6.4 Role of Surfactants in Emulsion Formation
22(1)
1.6.5 Role of Surfactants in Droplet Deformation
22(4)
1.7 Selection of Emulsifiers
26(9)
1.7.1 The Hydrophilic-Lipophilic Balance (HLB) Concept
26(3)
1.7.2 The Phase Inversion Temperature (PIT) Concept
29(2)
1.7.3 The Cohesive Energy Ratio (CER) Concept
31(1)
1.7.4 The Critical Packing Parameter (CPP) for Emulsion Selection
32(3)
1.8 Creaming or Sedimentation of Emulsions
35(5)
1.8.1 Creaming or Sedimentation Rates
36(1)
1.8.2 Prevention of Creaming or Sedimentation
37(3)
1.9 Flocculation of Emulsions
40(4)
1.9.1 Mechanism of Emulsion Flocculation
40(1)
1.9.1.1 Flocculation of Electrostatically Stabilized Emulsions
41(1)
1.9.1.2 Flocculation of Sterically Stabilized Emulsions
42(1)
1.9.2 General Rules for Reducing (Eliminating) Flocculation
43(1)
1.10 Ostwald Ripening
44(1)
1.11 Emulsion Coalescence
45(3)
1.11.1 Rate of Coalescence
46(1)
1.11.2 Phase Inversion
47(1)
1.12 Rheology of Emulsions
48(5)
1.12.1 Interfacial Rheology
48(1)
1.12.1.1 Interfacial Tension and Surface Pressure
48(1)
1.12.1.2 Interfacial Shear Viscosity
49(1)
1.12.2 Measurement of Interfacial Viscosity
49(1)
1.12.3 Interfacial Dilational Elasticity
50(1)
1.12.4 Interfacial Dilational Viscosity
51(1)
1.12.5 Non-Newtonian Effects
51(1)
1.12.6 Correlation of Emulsion Stability with Interfacial Rheology
51(1)
1.12.6.1 Mixed Surfactant Films
51(1)
1.12.6.2 Protein Films
51(2)
1.13 Bulk Rheology of Emulsions
53(4)
1.13.1 Analysis of the Rheological Behavior of Concentrated Emulsions
54(3)
1.14 Experimental ηr - φ Curves
57(2)
1.14.1 Experimental ηr - φ Curves
58(1)
1.14.2 Influence of Droplet Deformability
58(1)
1.15 Viscoelastic Properties of Concentrated Emulsions
59(18)
1.15.1 High Internal Phase Emulsions (HIPEs)
61(5)
1.15.2 Deformation and Breakup of Droplets in Emulsions during Flow
66(7)
References
73(4)
2 Emulsion Formation in Membrane and Microfluidic Devices
77(22)
Goran T. Vladisavljevic
Isao Kobayashi
Mitsutoshi Nakajima
2.1 Introduction
77(1)
2.2 Membrane Emulsification (ME)
78(4)
2.2.1 Direct Membrane Emulsification
78(1)
2.2.2 Premix Membrane Emulsification
79(1)
2.2.3 Operating Parameters in Membrane Emulsification
80(1)
2.2.4 Membrane Type
80(1)
2.2.4.1 Surfactant Type
80(1)
2.2.4.2 Transmembrane Pressure and Wall Shear Stress
81(1)
2.3 Microfluidic Junctions and Flow-Focusing Devices
82(3)
2.3.1 Microfluidic Junctions
82(1)
2.3.2 Microfluidic Flow-Focusing Devices (MFFD)
83(2)
2.4 Microfluidic Devices with Parallel MicroChannel Arrays
85(4)
2.4.1 Grooved-Type MicroChannel Arrays
86(2)
2.4.2 Straight-through Microchannel Arrays
88(1)
2.5 Glass Capillary Microfluidic Devices
89(4)
2.6 Application of Droplets Formed in Membrane and Microfluidic Devices
93(1)
2.7 Conclusions
93(6)
Acknowledgments
94(1)
References
94(5)
3 Adsorption Characteristics of Ionic Surfactants at Water/Hexane Interface Obtained by PAT and ODBA
99(10)
Nenad Mucic
Vincent Pradines
Aliyar Javadi
Altynay Sharipova
Jurgen Kragel
Martin E. Leser
Eugene V. Aksenenko
Valentin B. Fainerman
Reinhard Miller
3.1 Introduction
99(1)
3.2 Experimental Tools
99(2)
3.3 Theory
101(1)
3.4 Results
102(5)
3.5 Summary
107(2)
Acknowledgments
107(1)
References
107(2)
4 Measurement Techniques Applicable to the Investigation of Emulsion Formation during Processing
109(18)
Nima Niknafs
Robin D. Hancocks
Ian T. Norton
4.1 Introduction
109(3)
4.2 Online Droplet Size Measurement Techniques
112(9)
4.2.1 Laser Systems
112(3)
4.2.2 Sound Systems
115(1)
4.2.3 Direct Imaging
115(3)
4.2.4 Other Techniques
118(3)
4.3 Techniques Investigating Droplet Coalescence
121(2)
4.4 Concluding Remarks
123(4)
References
125(2)
5 Emulsification in Rotor-Stator Mixers
127(42)
Andrzej W. Pacek
Steven Hall
Michael Cooke
Adam J. Kowalski
5.1 Introduction
127(1)
5.2 Classification and Applications of Rotor-Stator Mixers
128(10)
5.2.1 Colloid Mills
129(1)
5.2.2 In-Line Radial Discharge Mixers
130(1)
5.2.3 Toothed Devices
131(1)
5.2.4 Batch Radial Discharge Mixers
132(1)
5.2.5 Design and Arrangement
133(3)
5.2.6 Operation
136(2)
5.3 Engineering Description of Emulsification/Dispersion Processes
138(14)
5.3.1 Drop Size Distributions and Average Drop Sizes
138(2)
5.3.2 Drop Size in Liquid-Liquid Two-Phase Systems - Theory
140(1)
5.3.3 Maximum Stable Drop Size in Laminar Flow
141(1)
5.3.4 Maximum Stable Drop Size in Turbulent Flow
142(1)
5.3.5 Characterization of Flow in Rotor-Stator Mixers
143(1)
5.3.5.1 Shear Stress
143(1)
5.3.5.2 Average Energy Dissipation Rate
144(1)
5.3.5.3 Power Draw
144(1)
5.3.6 Average Drop Size in Liquid-Liquid Systems
145(2)
5.3.7 Scaling-up of Rotor-Stator Mixers
147(5)
5.4 Advanced Analysis of Emulsification/Dispersion Processes in Rotor-Stator Mixers
152(11)
5.4.1 Velocity and Energy Dissipation Rate in Rotor-Stator Mixers
153(1)
5.4.1.1 Batch Rotor-Stator Mixers
154(3)
5.4.1.2 In-Line Rotor-Stator Mixers
157(3)
5.4.2 Prediction of Drop Size Distributions during Emulsification
160(3)
5.5 Conclusion
163(6)
Nomenclature
163(2)
References
165(4)
6 Formulation, Characterization, and Property Control of Paraffin Emulsions
169(30)
Jordi Esquena
Jon Vilasau
6.1 Introduction
169
6.1.1 Industrial Applications of Paraffin Emulsions
170(1)
6.1.2 Properties of Paraffin
170(2)
6.1.3 Preparation of Paraffin Emulsions
172
6.2 Surfactant Systems Used in Formulation of Paraffin Emulsions
74(104)
6.2.1 Phase Behavior
175(3)
6.3 Formation and Characterization of Paraffin Emulsions
178
6.4 Control of Particle Size
82(103)
6.5 Stability of Paraffin Emulsions
185(10)
6.5.1 Stability as a Function of Time under Shear (Orthokinetic Stability)
185(1)
6.5.2 Stability as a Function of Freeze-Thaw Cycles
186(3)
6.5.3 Stability as a Function of Electrolytes
189(6)
6.6 Conclusions
195(4)
Acknowledgments
196(1)
References
196(3)
7 Polymeric O/W Nano-emulsions Obtained by the Phase Inversion Composition (PIC) Method for Biomedical Nanoparticle Preparation
199(10)
Gabriela Calderd
Conxita Solans
7.1 Introduction
199(1)
7.2 Phase Inversion Emulsification Methods
200(1)
7.3 Aspects on the Choice of the Components
201(1)
7.4 Ethylcellulose Nano-Emulsions for Nanoparticle Preparation
202(2)
7.5 Final Remarks
204(5)
Acknowledgments
205(1)
References
205(4)
8 Rheology and Stability of Sterically Stabilized Emulsions
209(38)
Tharwat F. Tadros
8.1 Introduction
209(1)
8.2 General Classification of Polymeric Surfactants
210(2)
8.3 Interaction between Droplets Containing Adsorbed Polymeric Surfactant Layers: Steric Stabilization
212(14)
8.3.1 Mixing Interaction Gmix
213(1)
8.3.2 Elastic Interaction Gel
214(12)
8.4 Emulsions Stabilized by Polymeric Surfactants
226
8.4.1 W/O Emulsions Stabilized with PHS-PEO-PHS Block Copolymer
229
8.5 Principles of Rheological Techniques
220(6)
8.5.1 Steady State Measurements
220(1)
8.5.1.1 Bingham Plastic Systems
221(1)
8.5.1.2 Pseudoplastic (Shear Thinning) System
222(1)
8.5.1.3 Herschel-Bulkley General Model
222(1)
8.5.2 Constant Stress (Creep) Measurements
222(1)
8.5.3 Dynamic (Oscillatory) Measurements
223(3)
8.6 Rheology of Oil-in-Water (O/W) Emulsions Stabilized with Poly(Vinyl Alcohol)
226(21)
8.6.1 Effect of Oil Volume Fraction on the Rheology of the Emulsions
226(3)
8.6.2 Stability of PVA-Stabilized Emulsions
229(7)
8.6.3 Emulsions Stabilized with an A-B-A Block Copolymer
236(4)
8.6.4 Water-in-Oil Emulsions Stabilized with A-B-A Block Copolymer
240(5)
References
245(2)
Index 247
After finishing his PhD at Alexandria University, Tharwat Tadros was appointed lecturer in Physical Chemistry (1962-1966) at the same University. Between 1966 and 1969, he spent a sabbatical at the Agricultural University of Wageningen and T.N.O in Delft, the Netherlands. Thereafter he worked at I.C.I. and ZENECA until 1994, where he researched various fields of surfactants, emulsions, suspensions, microemulsions, wetting spreading and adhesion, and rheology. During that period he was also appointed visiting professor at Imperial College London, Bristol University and Reading University. In 1992, he was elected President of the International Association of Colloid and Interface Science. Since leaving ZENECA, Dr Tadros has worked as a consultant for various industries and also given several courses in his specialized field. He is the recipient of two medals from the Royal Society of Chemistry in the UK, and has more than 250 scientific papers to his name.
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