Colloids and the Depletion Interaction (Lecture Notes in Physics, 1026)

✍ Scribed by Henk N.W. Lekkerkerker, Remco Tuinier, Mark Vis

• Publisher: Springer
• Year: 2024
• Tongue: English
• Leaves: 400
• Edition: 2
• Category: Library

✦ Synopsis

This open access book provides a detailed exploration of the phase behaviour of, and interfacial properties in, complex colloidal mixtures (e.g., clay, milk, blood). Insights into colloids have been at the heart of many innovations in different industries. The big question underlying these innovations is how can colloidal systems be formulated and designed towards the desired properties? To do this, the forces between the colloidal particles need to be controlled. Adding depletants (non-adsorbing polymers or small colloids) is key to controlling the attractive interactions. Colloids and the Depletion Interaction provides the qualitative insights and quantitative tools to understand and predict such forces in colloidal dispersions. It offers a concise introduction to the history and fundamentals of the depletion interaction in, and phase behaviour of, colloidal dispersions.

Why does adding polymers lead to attractive forces between colloidal particles? What determines the phase stability of multi-component colloidal systems? These include colloid―polymer mixtures, binary colloidal mixtures, and anisotropic particles such as clay platelets, cubes and rod-like viruses. Conceptual explanations are accompanied by experimental and computer simulation results throughout. Illustrations of depletion effects in colloid science, biology and technology demonstrate its wider significance. The concluding outlook provides the scope of challenges and possibilities in this exciting field of science.

This second updated and enlarged edition contains 12 Chapters. It is an ideal book for advanced undergraduates and graduate students in physical chemistry, chemical engineering and soft matter physics. Besides providing a fundamental understanding of depletion interactions in colloidal mixtures, it gives background information on colloidal stability and phase behaviour in general. For experienced scientists and engineers working on mixtures of colloids and non-adsorbing (bio)polymers or colloidal particles, this book serves as a reference for understanding depletion interactions in systems of their specific interest.

✦ Table of Contents

Preface to the Second Edition
References
Preface to the First Edition
Contents
Symbols
Greek
Latin
1 Introduction
1.1 Colloids
1.2 Colloidal Interactions
1.2.1 Van der Waals Attraction
1.2.2 Double Layer Interaction
1.2.3 DLVO Interaction
1.2.4 Influence of Attached Polymers
1.2.5 Depletion Interaction
1.3 Historical Overview on Depletion
1.3.1 Early Interest in Unbalanced Forces
1.3.2 Experimental Observations on Depletion Before the 1950s
1.3.3 1950–1969
1.3.4 1970–1982
1.3.5 1983–1999
1.3.6 2000–2022
1.4 Outline
2 Depletion Interaction
2.1 Depletion Interaction Due to Penetrable Hard Spheres
2.1.1 Depletion Interaction Between Two Flat Plates
2.1.2 Depletion Interaction Between Two Spheres
2.1.3 Depletion Interaction Between a Sphere and a Plate
2.1.4 Derjaguin Approximation
2.2 Depletion Interaction Due to Ideal Polymers
2.2.1 Depletion Interaction Between Two Flat Plates
2.2.2 Interaction Between Two Spheres
2.3 Depletion Interaction Due to Colloidal Hard Spheres
2.3.1 Concentration Profiles Near a Hard Wall and Between Two Hard Walls
2.3.2 Depletion Interaction Between Two Flat Plates
2.3.3 Depletion Interaction Between Two (Big) Spheres
2.4 Depletion Interaction Due to Colloidal Hard Rods
2.4.1 Depletion Interaction Between Two Flat Plates
2.4.2 Interaction Between Two (Big) Colloidal Spheres Using the Derjaguin Approximation
2.5 Depletion Interaction Due to Thin Colloidal Hard Discs
2.5.1 Depletion Interaction Between Two Flat Plates
2.5.2 Interaction Between Two (Big) Colloidal Spheres Using the Derjaguin Approximation
2.6 Measurements of Depletion Interactions
2.6.1 Atomic Force Microscope
2.6.2 Total Internal Reflection Microscopy
2.6.3 Optical Tweezers
2.6.4 Scattering and Microscopy
3 Phase Transitions of Hard Sphere–Depletant Mixtures—The Basics
3.1 Introduction: The Colloid–Atom Analogy
3.2 The Hard-Sphere Fluid–Crystal Transition
3.2.1 Hard-Sphere Fluid
3.2.2 Hard-Sphere Crystal
3.2.3 Fluid–Crystal Coexistence
3.3 Free Volume Theory of Hard Spheres and Depletants
3.3.1 System
3.3.2 Thermodynamics
3.3.3 Scaled Particle Theory
3.3.4 Phase Diagrams
4 Phase Separation and Long-Lived Metastable States in Colloid–Polymer Mixtures
4.1 Experimental State Diagrams of Model Colloid–Polymer Mixtures
4.2 Phase Behaviour of Colloid–Ideal Polymer Mixtures
4.3 Mixtures of Spheres and Interacting Polymer Mixtures
4.3.1 Characteristic Length Scales in Polymer Solutions
4.3.2 Depletion Thickness
4.3.3 Osmotic Pressure of Polymer Solutions
4.3.4 Generalised Free Volume Theory Phase Behaviour
4.4 Phase Separation Kinetics and Long-Lived Metastable …
4.4.1 q > 0.3
4.4.2 q < 0.3
5 The Interface in Demixed Colloid–Polymer Dispersions
5.1 Interfacial Tension Measurements
5.1.1 The Spinning Drop Method
5.1.2 The Meniscus Method
5.2 Prediction of Interfacial Properties Using Free Volume Theory
5.2.1 Interfacial Tension
5.2.2 Interfacial Density Profiles
5.3 Some Dynamic Properties of the Colloidal Gas–Liquid Interface
5.3.1 Thermal Capillary Waves
5.3.2 Droplet Coalescence
6 Phase Behaviour of Colloidal Binary Hard Sphere Mixtures
6.1 Introduction to Binary Mixtures of Hard Spheres
6.2 Free Volume Theory for Binary Hard Sphere Mixtures
6.2.1 Simple FVT Extension for a Binary Hard Sphere Mixture
6.2.2 Rigorous FVT Approach for a Binary Hard Sphere Mixture
6.3 Phase Behaviour of Mixed Suspensions of Large and Small Spherical Colloids
6.3.1 Phase Separation in Binary Mixtures Differing Only in Diameter
6.3.2 Mixtures of Latex Particles and Micelles
7 Phase Behaviour of Colloidal Hard Spheres Mixed with Hard Rod-Like Colloids
7.1 Introduction
7.2 Free Volume Theory for Sphere–Rod Mixtures: Simple Extension
7.2.1 Free Volume Fraction
7.2.2 Osmotic Pressure of a Dispersion of Rods
7.2.3 Phase Behaviour Predictions of Simple FVT Theory
7.3 Phase Behaviour of Colloidal Sphere–Rod Mixtures. Experiment
7.4 Free Volume Theory for Sphere–Rod Mixtures: A Rigorous Approach
8 Phase Behaviour of Colloidal Rods Mixed with Depletants
8.1 Experimental Observations with Rod-Like Particle Dispersions
8.2 Onsager Theory of the Isotropic–Nematic Transition
8.2.1 Long Hard Rods
8.2.2 Charged Rods
8.3 Scaled Particle Theory of the Isotropic–Nematic Transition
8.4 Isotropic–Nematic Phase Behaviour of Rods Mixed …
8.5 Experimental Phase Behaviour of Rod–Polymer Mixtures
8.5.1 Stiff and Semiflexible Virus Particles Mixed with Polymer
8.5.2 Cellulose Nanocrystals Mixed with Nonadsorbing Polymers
8.5.3 Sterically Stabilised Colloidal Boehmite Rods Mixed with Polymer
8.6 Phase Diagrams of Rod/polymer Mixtures Including Highly Ordered Phases
8.6.1 Full Phase Diagrams of Hard Spherocylinders
8.6.2 Phase Behaviour of Rod–Polymer Mixtures Including Highly Ordered Phases
8.6.3 Comparison with Experiments
9 Phase Behaviour of Colloidal Platelet–Depletant Mixtures
9.1 Introduction to Colloidal Platelets
9.2 Phase Diagram of Hard Colloidal Platelets
9.2.1 Computer Simulations
9.2.2 Theoretical Account
9.3 Phase Behaviour of Hard Platelet–Penetrable Hard Sphere Mixtures
9.4 Experimentally Observed Phase Behaviour of Mixtures …
9.4.1 Sterically Stabilised Gibbsite Platelets Mixed with Polymers
9.4.2 Mixtures of Magnesium Aluminide Layered Double Hydroxide Platelets and Polymers
9.4.3 Gibbsite Plate—Silica Sphere Mixtures
9.4.4 Mixtures of Zirconium Phosphate Platelets and Silica Spheres
9.4.5 Effect of Added Silica Nanoparticles on the Nematic Liquid Crystal Phase Formation in Beidellite Suspensions
10 Phase Behaviour of Colloidal Cubes Mixed with Depletants
10.1 Introduction to Colloidal Cubes
10.2 Equations of State of Hard Colloidal Superballs
10.2.1 Second (Osmotic) Virial Coefficient of Superballs
10.2.2 Fluid Phase State of Superballs
10.2.3 Solid Phase States of Superballs
10.3 Phase Behaviour of Hard Colloidal Superballs
10.4 Theory for the Phase Behaviour of Colloidal Superballs Mixed with Polymers
10.4.1 Free Volume Theory
10.4.2 Free Volume Fraction
10.5 Phase Diagrams of Mixtures of Hard Superballs and Polymers …
10.6 Phase Stability of Cubes Mixed with Polymers: Experiments
11 Further Manifestations of Depletion Effects
11.1 Macromolecular Crowding
11.2 Depletion Interactions and Protein Crystallisation
11.3 Shape and Size Selection
11.4 Directing Colloidal Self-assembly Using Surface Microstructures
11.5 Dynamic Depletion Effects
12 Epilogue
A Thermodynamic Quantification of Phase Transitions and Equilibria
A.1 Relation Between Helmholtz Energy, (Osmotic) Pressure and Chemical Potential
A.2 Thermodynamics of Phase Transitions of Colloidal Dispersions
B Statistical Mechanical Derivation[3pt] of the Free Volume Theory
C Configurational Integrals[3pt] for a Columnar Phase of Colloidal Hard[3pt] Platelets