Introduction to Interfaces and Colloids, An: The Bridge to Nanoscience (Second Edition)

CONTENTS
Preface to Second Edition
Preface to First Edition
1. INTRODUCTION
	A. Interfaces
	B. Colloids
	C. The bridge to nanoscience
		1. What is “nanoscience?”
		2. Nanostructures and assemblies
		3. Generic nanoscience
		4. New tools of generic nanoscience
		5. The plan
2. FLUID INTERFACES AND CAPILLARITY
	A. Fluid interfaces: Young’s Membrane Model
		1. The thinness of interfaces
		2. Definition of surface tension
	B. The surface tension of liquids
		1. Pure liquids
		2. Temperature dependence of surface tension
		3. Surface tension of solutions
	C. Intermolecular forces and the origin of surface tension
		1. Van der Waals forces
		2. Surface tension as “unbalanced” intermolecular forces; the Hamaker constant
		3. Pressure deficit in the interfacial layer; Bakker’s Equation
		4. Components of the surface tension
	D. Interfacial tension
		1. Experimental interfacial tension
		2. Combining rules for interfacial tension
	E. Comment on dynamic surface tension
	F. Capillary hydrostatics: the Young-Laplace Equation
		1. Capillary pressure: pressure jump across a curved fluid interface
		2. The curvature of a surface
		3. Derivation of the Young-Laplace Equation
		4. Boundary conditions for the Young-Laplace Equation
	G. Some solutions to the Young-Laplace Equation
		1. Cylindrical surfaces; meniscus against a flat plate
		2. Axisymmetric and other surfaces
		3. Non-dimensionalization of the Young-Laplace Equation; the Bond Number
		4. Saddle-shaped surfaces: Gaussian vs. Hermitian curvature
	H. The measurement of surface and interfacial tension
		1. Geometric vs. force methods
		2. Capillary rise
		3. Sessile drop and pendant drop (or captive or pendant bubble)
		4. Du Noüy ring detachment
		5. Wilhelmy slide
		6. Langmuir film balance
		7. Drop weight (or volume)
		8. Maximum bubble pressure and dynamic surface tension
		9. The pulsating bubble “surfactometer”
		10. Elliptical (vibrating) jet
		11. Contracting circular jet
		12. Problems with interfacial tension measurement
		13. Spinning drop method
	I. Forces on solids in contact with liquids: capillary interactions
		1. Liquid bridges
		2. Shared menisci
	J. Effect of curvature on the equilibrium properties of bulk liquids: the Kelvin Effect
		1. The vapor pressure of small droplets and liquids in pores
		2. The effect of curvature on boiling point
		3. Capillary condensation
		4. Homogeneous nucleation
	K. Thin liquid films
		1. Disjoining pressure and its measurement
		2. The molecular origin of disjoining pressure
		3. The disjoining pressure isotherm
		4. The augmented Young-Laplace Equation
	SOME FUN THINGS TO DO: CHAPTER 2
3. THERMODYNAMICS OF INTERFACIAL SYSTEMS
	A. The thermodynamics of simple bulk systems
		1. Thermodynamic concepts
		2. The simple compressible system
	B. The simple capillary system
		1. The work of extension
		2. Heat effects; abstract properties; definition of boundary tension
	C. Extension to fluid-solid interfacial systems
		1. The work of area extension in fluid-solid systems
		2. Compound interfacial systems; Young’s equation
	D. Multicomponent interfacial systems
		1. The Gibbs dividing surface and adsorption
		2. Immiscible interfacial systems
		3. The measurement of adsorption
		4. The phase rule; descriptive equations for binary interfacial systems
	E. The Gibbs Adsorption Equation
	F. Surface tension of solutions
		1. Ideal-dilute capillary systems
		2. Moderately dilute capillary systems
	G. Surface active agents (surfactants) and their solutions
		1. The structure of different types of surface active agents
		2. Solutions of non-electrolyte surfactants
		3. Solutions of electrolyte surfactants
	H. Self-assembly of surfactant monomers in solution
		1. Formation of micelles: critical micelle concentration (CMC)
		2. Solubilization
	I. Micelle morphology, other self-assembled structures, and concentrated surfactant solutions
		1. Micellar shape and the Critical Packing Parameter (CPP)
		2. Beyond micelles: other self-assembled structures
		3. Concentrated surfactant solutions; liquid crystalline mesophases
		4. Kinetics of micellization and other self-assembly processes
	J. Dynamic surface tension of surfactant solutions
		1. Diffusion-controlled adsorption
		2. Finite adsorption-desorption kinetics
	K. Insoluble (Langmuir) monolayers
		1. Formation of monolayers by spontaneous spreading
		2. Hydrodynamic consequences of monolayers: Gibbs elasticity
		3. π-A isotherms of insoluble monolayers
		4. Langmuir-Blodgett films
		5. Transport properties of monolayers
	L. The thermodynamics of fluid-solid interfacial systems revisited
		1. The concept of interfacial energy and its measurement in fluid-solid systems
		2. Adsorption of non-polymeric molecules at the solid-liquid interface
		3. Experimental measurement of small molecule solid-liquid adsorption
		4. Adsorption of polymers at the solid-liquid interface
	SOME FUN THINGS TO DO: CHAPTER 3
4. SOLID-FLUID INTERACTIONS
	A. Wettability and the contact angle: Young’s Equation
		1. Importance of wetting; definition of contact angle
		2. Young’s Equation revisited; classification of wetting and contact angle values
	B. Contact angle hysteresis
		1. Origins of hysteresis: roughness and heterogeneity
		2. Complexity of real surfaces: texture and scale
		3. Wenzel Equation for rough surfaces
		4. Cassie and Cassie-Baxter analysis of heterogeneous surfaces; composite surfaces and ultra-hydrophobicity
		5. Electro-wetting
		6. The dynamic contact angle; Tanner’s Law
	C. Methods for measuring the contact angle
		1. Optical or profile methods: contact angle goniometry
		2. Force methods: contact angle tensiometry
		3. Dynamic contact angle measurement
		4. Measurement of the thermodynamically preferred (most stable) contact angle, θ0
	D. Relation of wetting behavior to solid surface energy and chemical constitution
		1. Zisman Plots; the critical surface tension
		2. The wettability series
		3. Contact angle titrations
		4. Thermodynamics of solid-liquid contact: work of adhesion, work of wetting and work of spreading; the Young-Dupré Equation
		5. The promotion or retardation of wetting: practical strategies
	E. Spreading of liquids on solid surfaces
		1. Criteria for spontaneous spreading; spreading morphology
		2. Temperature effects of wetting; heats of immersion and temperature-dependent wetting transitions
		3. The kinetics of spreading on smooth surfaces
		4. Spreading agents; superspreaders
	F. The relationship of wetting and spreading behavior to adhesion
		1. Definition of adhesion; adhesion mechanisms
		2. The “Laws of Molecular Adhesion”
		3. “Practical adhesion” vs. “thermodynamic adhesion”
		4. The importance of wetting (contact angle) to practical adhesion
		5. Optimization of thermodynamic contact adhesion
		6. Acid-base effects in adhesion
		7. Contact mechanics; the JKR method
		8. Biomemetic adhesion: mussels, barnacles and geckos
	G. Heterogeneous nucleation
	H. Processes based on wettability changes or differences
		1. Detergency
		2. Flotation
		3. Selective or “spherical” agglomeration
		4. Offset lithographic printing
	I. Wicking flows (capillary action) and absorbency
		1. Wicking into a single capillary tube
		2. Wicking in porous media
		3. Practical strategies for promoting absorbency
		4. Immiscible displacement
		5. Mercury porosimitry
		6. Motion of liquid threads
		7. Surface wicking; spreading over rough or porous surfaces
	J. Particles at interfaces
		1. Particles at solid-fluid interfaces: effects on wetting and spreading
		2. The disposition of particles at fluid interfaces
		3. Particle-assisted wetting
		4. Pickering emulsions
		5. Armored bubbles and liquid marbles
		6. Janus particles and nanoparticles at fluid interfaces
		7. Bijels
	K. The description of solid surfaces
		1. Solid surface roughness
		2. Fractal surfaces
		3. Surface texture
		4. Measurement of surface roughness and texture by stylus profilometry
	L. Optical techniques for surface characterization
		1. Optical microscopy
		2. Optical profilometry
		3. Confocal microscopy
		4. Electron microscopy
		5. Near-field scanning optical microscopy (NSOM)
	M. Scanning probe microscopy (SPM)
		1. Scanning Tunneling Microscopy (STM)
		2. Atomic Force Microscopy (AFM)
	N. Surface area of powders, pore size distribution
	O. Energetic characterization of solid surfaces: Inverse Gas Chromatography (IGC)
	SOME FUN THINGS TO DO: CHAPTER 4
5. COLLOIDAL SYSTEMS: PHENOMENOLOGY AND CHARACTERIZATION
	A. Preliminaries
		1. Definition and classification of colloids
		2. General properties of colloidal dispersions
		3. Dense vs. dilute dispersions
	B. Mechanisms of lyophobic colloid instability
		1. Phase segregation: the “phoretic processes”
		2. Thermodynamic criteria for stability
		3. Aggregation
		4. Coalescence
		5. Particle size disproportionation
	C. Preparation of colloid particles and colloidal dispersions
		1. Classification of preparation strategies for lyophobic colloids
		2. Top-down strategies
		3. Bottom-up strategies
	D. Morphology of colloids: particle size, size distribution, and particle shape
		1. Description of particle size distributions
		2. Distributions based on different size variables and weighting factors
		3. Normal (Gaussian) and log-normal (log-Gaussian) distributions
		4. Particle shape
	E. Sedimentation and centrifugation
		1. Individual particle settling: Stokes’ Law
		2. Multi-particle, wall and charge effects on sedimentation
		3. Differential sedimentation; particle size analysis
		4. Centrifugation
	F. Brownian motion; sedimentation-diffusion equilibrium
		1. Kinetic theory and diffusion
		2. Brownian motion
		3. Sedimentation (centrifugation) – diffusion equilibrium
		4. Practical retrospective regarding sedimentation and other phoretic processes
	G. Measurement of particle size and size distribution: overview
		1. Classification of methods
		2. Microscopy
	H. Light scattering
		1. Classical (static) light scattering
		2. Rayleigh scattering
		3. Turbidity
		4. Rayleigh-Gans-Debye (RGD) scattering
		5. Guinier plots, Low-Angle Laser Light Scattering (LALLS)
		6. Light scattering from solutions; Zimm Plots
		7. Mie scattering
		8. Fraunhofer diffraction; laser diffraction
		9. Inelastic scattering: absorbance; the Raman effect
		10. Scattering from denser dispersions
		11. Small angle X-ray scattering (SAXS) and small angle neutron scattering (SANS)
		12. Dynamic Light Scattering (Photon Correlation Spectroscopy)
		13. Dynamic light scattering from denser dispersions
	I. Aperture, chromatographic and acoustic methods for particle sizing
		1. Aperture (one-at-a-time) methods
		2. Chromatographic methods
		3. Acoustic methods
	SOME FUN THINGS TO DO: CHAPTER 5
6. ELECTRICAL PROPERTIES OF INTERFACES
	A. Origin of charge separation at interfaces
		1. Overview
		2. Preferential adsorption/desorption of lattice ions
		3. Specific adsorption of charged species
		4. Ionization of surface functional groups
		5. Isomorphic substitution
		6. Accumulation/depletion of electrons
		7. Interface charging in non-aqueous systems
	B. Electric double layer formation and structure
		1. The Helmholtz model; electrostatic units
		2. The Gouy-Chapman Model; Poisson-Boltzmann Equation
		3. Boundary conditions to the Poisson-Boltzmann Equation
		4. Double layers at spherical and cylindrical surfaces
		5. The free energy of double layer formation
		6. The Stern Model; structure of the inner part of the double layer
		7. The mercury solution interface; electrocapillarity and refinements to the double layer model
		8. Electrowetting
		9. Oriented dipoles at the interface: the χ-potential
	C. Electrostatic characterization of colloids by titration methods
		1. Colloid titrations
		2. Potentiometric titrations
		3. Conductometric titrations
		4. Donnan equilibrium and the suspension effect
	D. Electrokinetics
		1. The electrokinetic effects: overview
		2. Electro-osmosis: the zeta potential and its interpretation
		3. Streaming current and potential: relationship to zeta potential
		4. Electrokinetic measurements; micro-electrophoresis
		5. Relationship of zeta potential to electrophoretic mobility
		6. Electrokinetic titrations and electro-viscosity effects
		7. Electro-acoustic measurements
	E. Dielectrophoresis and optical trapping
		1. Dielectrophoresis
		2. Isomotive DEP
		3. Electro-rotation and traveling wave dielectrophoresis
		4. Optical trapping; laser tweezers
	SOME FUN THINGS TO DO: CHAPTER 6
7. INTERACTION BETWEEN COLLOID PARTICLES
	A. Overview and rationale
	B. Long-range van der Waals interactions
		1. The Hamaker (microscopic) approach
		2. Retardation
		3. The Lifshitz (macroscopic) approach
		4. Measurement of Hamaker constants
	C. Electrostatic interactions; DLVO theory
		1. Electrostatic repulsion between charged flat plates
		2. Electrostatic interactions between curved surfaces; the Derjaguin approximation
		3. DLVO theory: electrocratic dispersions
		4. Jar testing, the Schulze-Hardy Rule and agreement with theory
		5. The Hofmeister series; ion speciation and ionic specific adsorption
		6. Repeptization
		7. Interaction between dissimilar surfaces: hetero-aggregation
		8. Further limitations of DLVO theory for electrocratic colloids
	D. Kinetics of aggregation
		1. Classification of aggregation rate processes and nomenclature
		2. Smoluchowski theory of diffusion-limited (rapid) aggregation
		3. The hydrodynamic drainage effect
		4. Orthokinetic (shear-flow-induced) aggregation
		5. Reaction-limited (slow) aggregation; the stability ratio W
		6. Secondary minimum effects
		7. Kinetics of hetero-aggregation
		8. Measurement of early-stage aggregation kinetics (W)
		9. Surface aggregation
		10. Electrostatic stabilization and aggregation rates in apolar media
	E. Steric stabilization and other colloid-polymer interactions
		1. Polymer adsorption and steric stabilization
		2. Thermodynamic considerations: enthalpic vs. entropic effects
		3. Fischer theory
		4. Steric repulsion plotted on DLVO coordinates
		5. Electro-steric stabilization
		6. Bridging flocculation
		7. Depletion flocculation
	F. The kinetics (and thermodynamics) of flocculation
	G. Other non-DLVO interaction forces
	H. Aggregate structure evolution; fractal aggregates
		1. Stages of the aggregation process
		2. Fractal aggregates
		3. The effect of particle size on aggregation phenomena; coating by nanoparticles
	SOME FUN THINGS TO DO: CHAPTER 7
8. RHEOLOGY OF DISPERSIONS
	A. Rheology: scope and definitions
	B. Viscometry
		1. Newton’s Law of viscosity
		2. Measurement of viscosity
	C. The viscosity of colloidal dispersions
		1. Dilute dispersions; Einstein theory
		2. Dilute dispersions of non-spherical particles
		3. Denser dispersions of non-interacting particles
	D. Non-Newtonian rheology
		1. General viscous behavior of dispersions of non-interacting particulates
		2. Flocculated systems
		3. Fluids with a yield stress
		4. Time-dependent rheology
		5. Viscoelasticity
	E. Electroviscous effects
	F. Microrheology
	SOME FUN THINGS TO DO: CHAPTER 8
9. EMULSIONS AND FOAMS
	A. General consideration of emulsions
		1. Classification of emulsions
		2. Emulsifiers and emulsion stability
		3. Thermodynamics of emulsification/breakdown
		4. Preparation of emulsions
	B. O/W or W/O emulsions?
		1. Rules of thumb
		2. The hydrophile-lipophile balance (HLB) and related scales
		3. High internal phase emulsions, HIPEs
		4. Double (or multiple) emulsions
		5. Water-in-water (W/W) emulsions
	C. Application of emulsions
		1. Formation/breaking in situ
		2. Demulsification
	D. Microemulsions
		1. Distinction between microemulsions and macroemulsions
		2. Phase behavior of microemulsion systems
		3. Ultra-low interfacial tension
		4. Interfacial film properties in microemulsion systems
	E. General consideration of foams
		1. Nature and preparation of foams
		2. Stages in foam lifetime
		3. Stability mechanisms
		4. Foam behavior and foaming agents
		5. Antifoam action
		6. Froth flotation
		7. Foaming in non-aqueous media; general surface activity near a phase split
		8. Aphrons
	SOME FUN THINGS TO DO: CHAPTER 9
10. INTERFACIAL HYDRODYNAMICS
	A. Unbalanced forces at fluid interfaces
		1. Unbalanced normal forces
		2. Tangential force imbalances: the Marangoni effect
		3. Boundary conditions at a fluid interface
	B. Examples of Interfacial Hydrodynamic Flows
		1. The breakup of capillary jets
		2. Steady thermocapillary flow
		3. The motion of bubbles or drops in a temperature gradient
		4. Marangoni instability in a shallow liquid pool – Bénard cells
	C. Some Practical Implications of the Marangoni Effect
		1. Marangoni effects on mass transfer
		2. Marangoni drying
		3. Marangoni patterning
	D. The Effect of Surface Active Agents
		1. Gibbs elasticity
		2. The boundary conditions describing the effects of surfactants
		3. The effect of surfactants on bubble or droplet circulation
		4. The effect of surfactants on the stability of a pool heated from below
	SOME FUN THINGS TO DO: CHAPTER 10
Appendix 1: PHYSICAL CONSTANTS
Appendix 2: EXERCISES
Appendix 3: THE TOP TWELVE
Index