Surfactants and Block Copolymers:
Structure-Performance Relationships
Synopsis:
Surfactants find numerous applications in chemical
process industries, in the formulation of pharmaceuticals, household products,
and agricultural chemicals, in mineral processing technologies, and in
food processing industries. Naturally occurring surfactants in plants,
animals, and humans have important biological or physiological functions.
The research activity in the field of surfactants has experienced enormous
growth during the last twenty five years. More than one thousand
research articles are published annually and many scientific journals are
devoted to the study of surfactants.
The wide-spread applications of surfactants
originate from the intrinsic duality in their molecular characteristics,
namely, they are composed of a polar head group that likes water and a
non-polar tail group that dislikes water. Numerous variations are
possible in the types of the head groups and tail groups. This
variety in the molecular structure of the surfactants allows for extensive
variation in their solution and interfacial properties.
One would naturally like to discover the link
between the molecular structure of the surfactant and its self-assembling
and solution properties so that surfactants can be synthesized or selected
specifically for a given application. This course is designed to
address this need.
Who Should Attend:
This course is designed for industrial researchers
and practitioners interested in surfactants, block copolymers and their
applications. Depending on the interest of the audience, the topics and
the extent of coverage can be varied from the description given below.
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Topics Covered:
Surfactants and Block
Copolymers:
Structure-Performance Relationships
* INTRODUCTION TO SURFACTANTS
Classification of Surfactants
Introduction to Block Copolymers
Phenomenon of Self-Assembly
Critical Micelle Concentration
Aggregate Shapes
* PRINCIPLES OF SELF-ASSEMBLY
Closed and Continuous Association
Pseudo-Phase Model
Estimation of Critical Micelle
Concentration
Estimation of Micelle Size
Size Dispersion of Micelles
Concentration Dependence of
Micelle Size
Micelle Charge
Concentration of Surfactant
Monomer Beyond CMC
Sphere-to-Rod Transition
Sphere-to Bilayer Transition
* MOLECULAR PACKING AND SELF-ASSEMBLY
Packing Requirements
Packing Parameter
Principle of Opposing Forces
of Tanford
Packing Parameter Model
Predicting Type of Self-Assembly
* SURFACTANTS IN AQUEOUS SOLUTIONS
Why Molecules Aggregate ?
What Factors Control Aggregate
Size and Shape?
Determining Molecular Constants
for Surfactants
Influence of Head Groups on
Aggregation Behavior
Influence of Tail Groups on
Aggregation Behavior
Influence of Ionic Strength
on Aggregation Behavior
Influence of Temperature on
Aggregation Behavior
Transition from Spherical to
Rod-like Micelles
Formation of Vesicles
* SURFACTANT MIXTURES
Ideal and Non-Ideal Mixed Micelles
Regular Solution Model
Size and Composition Distribution
of Aggregates
How Surfactant Composition Affects
Mixture Behavior ?
Nonionic Hydrocarbon-Nonionic
Hydrocarbon Surfactant Mixtures
Ionic Hydrocarbon-Ionic Hydrocarbon
Surfactant Mixtures
Ionic Hydrocarbon-Nonionic Hydrocarbon
Surfactant Mixtures
Anionic Hydrocarbon-Cationic
Hydrocarbon Surfactant Mixtures
Anionic Fluorocarbon-Nonionic
Hydrocarbon Surfactant Mixtures
Anionic Hydrocarbon-Anionic
Fluorocarbon Surfactant Mixtures
Origin of Ideal and Non-Ideal
Mixing Behavior
* SURFACTANTS IN NON-POLAR SOLVENTS
Differences Between Water and
Non-Polar Solvents
Why Molecules Would Aggregate
?
Types of Aggregates
Size Distribution of Aggregates
Question of Existence of a CMC
Influence of Surfactant Molecular
Structure
Influence of Temperature
Influence of Solvent Polarity
* SURFACTANTS IN POLAR ORGANIC SOLVENTS
Types of Polar Solvents
Why Surfactants Would Aggregate
?
Shape and Size Distribution
Critical Micelle Concentration
Aggregate Size Polydispersity
Concentration-Dependent Aggregate
Size
Micelle Formation in Mixed Aqueous-Organic
Solvents
* SOLUBILIZATION
Phenomenon of Solubilization
Relations for Solubilizate Uptake
in Micelles
Why Solubilization Occurs and
What Factors Limit it ?
Solubilization in Ionic Surfactant
Solutions
Solubilization in Micelles of
Poly(ethylene oxide) Surfactants
Solubilization-Induced Rod-to-Sphere
Transition
Solubilization of Binary Hydrocarbon
Mixtures
Solubilization in Mixed Micelles
* MICROEMULSIONS
Microemulsion Formation
Droplet Microemulsions
Bicontinuous Microemulsions
Phase Diagrams
Size and Composition Dispersion
of Droplets
Persistence Length in Bicontinuous
Microemulsions
Calculation of Interfacial Tension
Phase Transitions Between Microemulsion
Systems
Nonionic Microemulsions
Microemulsions With Ionic Surfactants
Use of Cosurfactants
* POLYMER-SURFACTANT INTERACTIONS
Interaction of Nonionic Polymer
with Globular Micelles
Interaction of Nonionic Polymer
with Rod-like Micelles
Interaction of Nonionic Polymer
with Vesicles and Bilayers
Interaction of Nonionic Polymer
with Microemulsions
* BLOCK COPOLYMER AGGREGATES
Structure of Block Copolymers
Aggregation of AB, ABA, BAB,
and ABC Type Block Copolymers
Why Molecules Aggregate ?
What Factors Control Micelle
Size ?
What Factors Determine Amount
of Solubilization ?
Block Copolymer Composition
and Aggregate Shapes
Solution Conditions and Aggregate
Shape
Aggregate Shape Transitions
Induced by Solubilization
Phase Behavior of Block Copolymer-Oil-Water
System
Comparison to Conventional Surfactants
* SOME APPLICATIONS
Chemical Separations
Selective Protein Extraction
Enzymatic Biocatalysis
Deinking of Laser and Xerox
Printed Papers
Use as Environmentally-Benign
Solvent for Product Recovery
Enhanced Oil Recovery
Lubricant Additives
Synthesis and Stabilization
of Nanoparticles
* REVIEW AND CONCLUDING DISCUSSIONS
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Instructor
Professor Nagarajan is Professor of Chemical Engineering at the Pennsylvania
State University. He has pursued a research program focusing on the
fundamentals of surfactant and block copolymer self-assembly over the past
twenty five years. He has formulated many of the predictive models
available in the literature for a variety of self-assembly phenomena.
His research has also concentrated on the development of practical applications
for self-assembled systems. Past and current research projects include:
enhanced oil recovery by surfactant/microemulsion flooding, chemical separations
using emulsion liquid membranes, selective chemical extractions using aqueous
micellar systems, preparation of stable concentrated liquid flavorings
using
surfactant and block copolymer micelles, aggregation of lubricant
additives and additive interactions, separation of proteins and enzymes
using microemulsions, enzymatic biocatalysis in block copolymer microdomains
and in microemulsions, use of block copolymer surfactants for deinking
and recycling of office waste paper, use of block copolymers for integrated
fermentation and product recovery, and applications of surfactants in nanoparticle
synthesis and processing. He is a recipient of the Outstanding Research
Award from the Pennsylvania State Engineering Society, US-France Foundation
Fellowship for sabbatical research in Paris, France, and a CNRS Director
of Research position during the period of sabbatical research in Toulouse,
France. He is on the editorial advisory board of Journal of Colloid
and Interface Science. He has been serving as the Program Chair of
the American Chemical Society Division of Colloid and Surface Chemistry.
He is currently working on a monograph "Surfactant Self-Assembly: A Predictive
Molecular Thermodynamic Approach" which will provide much of the textual
material for the short course.
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