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Food Emulsions
Principles, Practices, and Techniques
Second Edition

Copyright 2005 by CRC Press

2023_series 11/4/04 1:57 PM Page 1

CRC Series in
CONTEMPORARY FOOD SCIENCE
Fergus M. Clydesdale, Series Editor
University of Massachusetts, Amherst

Published Titles:
New Food Product Development: From Concept to Marketplace
Gordon W. Fuller
Food Properties Handbook
Shafiur Rahman
Aseptic Processing and Packaging of Foods: Food Industry Perspectives
Jarius David, V. R. Carlson, and Ralph Graves
Handbook of Food Spoilage Yeasts
Tibor Deak and Larry R. Beauchat
Getting the Most Out of Your Consultant: A Guide to Selection
Through Implementation
Gordon W. Fuller
Food Emulsions: Principles, Practice, and Techniques
David Julian McClements
Antioxidant Status, Diet, Nutrition, and Health
Andreas M. Papas
Food Shelf Life Stability
N.A. Michael Eskin and David S. Robinson
Bread Staling
Pavinee Chinachoti and Yael Vodovotz
Food Consumers and the Food Industry
Gordon W. Fuller
Interdisciplinary Food Safety Research
Neal M. Hooker and Elsa A. Murano
Automation for Food Engineering: Food Quality Quantization and Process Control
Yanbo Huang, A. Dale Whittaker, and Ronald E. Lacey
Introduction to Food Biotechnology
Perry Johnson-Green
The Food Chemistry Laboratory: A Manual for Experimental Foods, Dietetics,
and Food Scientists, Second Edition
Connie M. Weaver and James R. Daniel
Modeling Microbial Responses in Food
Robin C. McKellar and Xuewen Lu
Food Emulsions: Principles, Practice, and Techniques, Second Edtition
David Julian McClements

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2023_title 10/25/04 12:27 PM Page 1

Food Emulsions
Principles, Practices, and Techniques
Second Edition

David Julian McClements

CRC PR E S S
Boca Raton London New York Washington, D.C.

Copyright 2005 by CRC Press

2023 disclaimer.fm Page 1 Thursday, November 4, 2004 1:05 PM

Library of Congress Cataloging-in-Publication Data

McClements, D. J.
Food emulsions : principles, practice, and techniques / David Julian
McClements. 2nd ed.
p. cm.
Includes bibliographical references and index.
ISBN 0-8493-2023-2 (alk. paper)
1.
Emulsions. 2. Food. I. Title.
TP156.E6M35 2004
664dc22

2004054209

This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with
permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts have been made to publish
reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials
or for the consequences of their use.
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Visit the CRC Press Web site at www.crcpress.com

2005 by CRC Press
No claim to original U.S. Government works
International Standard Book Number 0-8493-2023-2
Library of Congress Card Number 2004054209
Printed in the United States of America 1 2 3 4 5 6 7 8 9 0
Printed on acid-free paper

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Dedication
This book is dedicated to my wife Jayne and daughter Isobelle.

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Preface
A wide variety of food products, both natural and manufactured, exist either partly or
wholly as emulsions, or have been in an emulsified form sometime during their production. Common examples of these food emulsions include milk, flavored milks, creams,
whipped cream, butter, yogurt, cheese, salad dressings, mayonnaise, dips, coffee whitener,
ice cream, desserts, soups, sauces, margarine, infant formula, and fruit beverages. Even
though these products differ widely in their appearances, textures, tastes, and shelf lives
they all consist (or once consisted) of small droplets of one liquid dispersed in another
liquid. Consequently, many of their physicochemical and sensory properties can be understood by applying the fundamental principles, concepts, and techniques of a discipline
known as emulsion science. Knowledge of this discipline is also essential for the rational
development of ingredients capable of encapsulating, protecting, and delivering functional
food components, such as flavors, antioxidants, vitamins, antimicrobials, and bioactive
lipids. It is for these reasons that anybody working in the food industry with these types
of products should have at least an elementary understanding of emulsion science.
The primary objective of this book is to present the basic principles, concepts, and
techniques of emulsion science and show how they can be used to better understand,
predict, and control the properties of a wide variety of food products and functional
ingredients. Rather than describing the specific methods and problems associated with
the creation of each particular type of emulsion-based food product, I have concentrated
on an explanation of the basic concepts of emulsion science, as these are applicable to all
types of food emulsions. In particular, this book focuses on developing a fundamental
understanding of the major factors that determine the stability, texture, appearance, and
flavor of food emulsions. Having said this, the second edition of this book does contain
a final chapter that demonstrates the practical use of emulsion science by using it to
understand the formulation, formation, and physicochemical properties of some real food
emulsions (beverages, dairy emulsions, and dressings).
The second edition of the book has been revised and expanded considerably to reflect
recent developments in the field of food emulsions and to provide a more accurate, comprehensive, and up-to-date discussion of the most important topics relevant to the field. In
particular, the chapter on emulsion ingredients has been revised extensively to provide a
detailed discussion of the origin, properties, and characteristics of the different kinds of
functional ingredients (emulsifiers, surfactants, lipids, texture modifiers, and so on) that can
be used to produce food emulsions. The second edition also contains two additional chapters. The Appearance and Flavor chapter in the first edition has been divided into two separate
chapters in the second edition to reflect the considerable advances that have been made in
these two important areas. In addition, a chapter on practical applications of emulsion
science in the food industry has been included in the second edition, which highlights the
importance of emulsion science for understanding, controlling, and improving the quality
of dairy products, beverage emulsions, and dressings.

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It is a great pleasure to acknowledge the contributions of all those who helped bring
this book to fruition. I could never have completed this book without the love, support,
and understanding of my wife Jayne, my daughter Isobelle, and my family. I must also
thank all of my students, Post-Docs, and coworkers who have been a continual source of
stimulating ideas and constructive criticism, and my teachers for providing me with the
academic foundations on which I have attempted to build. I also thank all of the scientists
who have helped me put together this new edition of the book by providing useful
comments on the text or by providing figures that demonstrate useful and important
concepts, including Dr. Marc Anton, Prof. John Coupland, Dr. Julia DesRocher, Prof. Eric
Dickinson, Mr Robert Engel, Prof. Douglas Goff, Prof. Yoshinori Mine, Dr. Luis Pugnaloni,
Prof. Helmar Schubert, Prof. Pieter Walstra, and Dr. Peter Wilde. Finally, I thank all those
at CRC Press for their help in the preparation of this book.

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About the Author

Dr. David Julian McClements has been an Assistant or Associate Professor at the Department of Food Science at the University of Massachusetts since 1994. He received a B.Sc.
(Hons) in Food Science (1985) and a Ph.D. in Ultrasonic Characterization of Fats and Emulsions
(1989) at the University of Leeds (United Kingdom). He then did Post Doctoral Research
at the University of Leeds, University of California (Davis), and the University College
Cork (Ireland), before starting at the University of Massachusetts.
Dr. McClements has coauthored a book entitled Advances in Food Colloids with
Prof. Eric Dickinson, coedited a book entitled Developments in Acoustics and Ultrasonics
with Dr. Malcolm Povey, and is the sole author of the first edition of Food Emulsions:
Principles, Practice and Techniques. In addition, he has published over 220 scientific articles
as journal manuscripts, book chapters, encyclopedia entries, and conference proceedings.
Dr. McClements has received awards from the American Chemical Society and Institute
of Food Technologists in recognition of his scientific achievements.

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Contents
Chapter 1 Context and background
1.1 Emulsion science in the food industry
1.1.1 Development of a more rigorous scientific approach
to understanding food emulsion properties
1.1.2 Development of new analytical techniques
to characterize food properties
1.2 General characteristics of food emulsions
1.2.1 Definitions
1.2.2 Mechanisms of emulsion instability
1.2.3 Ingredient partitioning in emulsions
1.2.4 Dynamic nature of emulsions
1.2.5 Complexity of food emulsions
1.3 Emulsion properties
1.3.1 Disperse phase volume fraction
1.3.2 Particle size distribution
1.3.3 Interfacial properties
1.3.4 Droplet charge
1.3.5 Droplet crystallinity
1.3.6 Droplet interactions
1.4 Hierarchy of emulsion properties
1.5 Understanding food emulsion properties
1.5.1 Factors influencing topics and directions of research
1.5.2 General approaches used to study food emulsions
1.6 Overview and philosophy
Chapter 2 Molecular characteristics
2.1 Introduction
2.2 Forces of nature
2.3 Origin and nature of molecular interactions
2.3.1 Covalent interactions
2.3.2 Electrostatic interactions
2.3.3 van der Waals interactions
2.3.4 Steric overlap interactions
2.4 Overall intermolecular pair potential
2.5 Molecular structure and organization is determined by a balance
of interaction energies and entropy effects
2.6 Thermodynamics of mixing
2.6.1 Potential energy change on mixing
2.6.2 Entropy change on mixing

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2.6.3 Overall free energy change on mixing

2.6.4 Complications
2.7 Molecular conformation
2.8 Compound interactions
2.8.1 Hydrogen bonds
2.8.2 Hydrophobic interactions
2.9 Computer modeling of liquid properties
2.9.1 Monte Carlo techniques
2.9.2 Molecular dynamics techniques
2.10 Measurement of molecular characteristics
Chapter 3 Colloidal interactions
3.1 Introduction
3.2 Colloidal interactions and droplet aggregation
3.3 van der Waals interactions
3.3.1 Origin of van der Waals interactions
3.3.2 Modeling van der Waals interactions
3.3.3 General features of van der Waals interactions
3.4 Electrostatic interactions
3.4.1 Origins of electrostatic interactions
3.4.2 Modeling electrostatic interactions
3.4.3 General characteristics of electrostatic interactions
3.5 Steric interactions
3.5.1 Origin of steric interactions
3.5.2 Modeling steric interactions
3.5.3 General characteristics of steric interactions
3.6 Depletion interactions
3.6.1 Origin of depletion interactions
3.6.2 Modeling of depletion interactions
3.6.3 General characteristics of depletion interactions
3.7 Hydrophobic interactions
3.7.1 Origin of hydrophobic interactions
3.7.2 Modeling hydrophobic interactions
3.7.3 General characteristics of hydrophobic interactions
3.8 Hydration interactions
3.8.1 Origin of hydration interactions
3.8.2 Modeling hydration interactions
3.8.3 General characteristics of hydration interactions
3.9 Thermal fluctuation interactions
3.9.1 Origin of thermal fluctuation interactions
3.9.2 Modeling thermal fluctuation interactions
3.9.3 General characteristics of fluctuation interactions
3.10 Nonequilibrium effects
3.10.1 Molecular rearrangements at the interface
3.10.2 Hydrodynamic flow of continuous phase
3.10.3 GibbsMarangoni effect
3.11 Total interaction potential
3.11.1 van der Waals and steric
3.11.2 van der Waals, steric, and electrostatic
3.11.3 van der Waals, steric, electrostatic, and hydrophobic
3.11.4 van der Waals, steric, electrostatic, and depletion

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3.12 Measurement of colloidal interactions

3.13 Prediction of colloidal interactions in food emulsions
Chapter 4 Emulsion ingredients
4.1 Introduction
4.2 Fats and oils
4.2.1 Molecular structure and organization
4.2.2 Bulk physicochemical properties
4.2.3 Fat crystallization
4.2.4 Chemical changes
4.2.5 Selection of an appropriate lipid
4.3 Water
4.3.1 Molecular structure and organization
4.3.2 Bulk physicochemical properties
4.3.3 Influence of solutes on the organization of water molecules
4.3.4 Influence of solutes on the physicochemical properties
of solutions
4.3.5 Selection of an appropriate aqueous phase
4.4 Emulsifiers
4.4.1 Surfactants
4.4.2 Amphiphilic biopolymers
4.4.3 Selection of an appropriate emulsifier
4.5 Texture modifiers
4.5.1 Thickening agents
4.5.2 Gelling agents
4.5.3 Commonly used texture modifiers
4.5.4 Selection of an appropriate texture modifier
4.6 Other food additives
4.6.1 pH control
4.6.2 Minerals
4.6.3 Sequestrants (chelating agents)
4.6.4 Antioxidants
4.6.5 Antimicrobial agents
4.6.6 Flavors
4.6.7 Colorants
4.6.8 Weighting agents
4.6.9 Fat replacers
4.7 Factors influencing ingredient selection
Chapter 5 Interfacial properties and their characterization
5.1 Introduction
5.2 General characteristics of interfaces
5.2.1 Interfaces separating two pure liquids
5.2.2 Interfaces in the presence of solutes
5.3 Adsorption of solutes to interfaces
5.3.1 Definition of surface excess concentration
5.3.2 Relationship between adsorbed and bulk
solute concentrations
5.3.3 Stipulating interfacial properties of surface-active solutes
5.3.4 Adsorption kinetics

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5.4

5.5

5.6

5.7

5.8

5.9

Electrical characteristics of interfaces

5.4.1 Origin of interfacial charge
5.4.2 Ion distribution near a charged interface
5.4.3 Factors influencing interfacial electrical properties
of emulsions
5.4.4 Characterization of interfacial electrical properties
Interfacial composition and its characterization
5.5.1 Factors influencing interfacial composition
5.5.2 Characterization of interfacial composition in emulsions
Interfacial structure
5.6.1 Factors influencing interfacial structure
5.6.2 Characterization of interfacial structure in emulsions
Interfacial tension and its measurement
5.7.1 Factors influencing interfacial tension
5.7.2 Characterization of interfacial tension
Interfacial rheology
5.8.1 Factors influencing interfacial rheology
5.8.2 Characterization of interfacial rheology
Practical implications of interfacial phenomena
5.9.1 Properties of curved interfaces
5.9.2 Contact angles and wetting
5.9.3 Capillary rise and meniscus formation
5.9.4 Interfacial phenomenon in food emulsions

Chapter 6 Emulsion formation

6.1 Introduction
6.2 Overview of homogenization
6.3 Flow profiles in homogenizers
6.4 Physical principles of emulsion formation
6.4.1 Droplet disruption
6.4.2 Droplet coalescence
6.4.3 The role of the emulsifier
6.5 Homogenization devices
6.5.1 High-speed mixers
6.5.2 Colloid mills
6.5.3 High-pressure valve homogenizers
6.5.4 Ultrasonic homogenizers
6.5.5 Microfluidization
6.5.6 Membrane and microchannel homogenizers
6.5.7 Homogenization efficiency
6.5.8 Comparison of homogenizers
6.6 Factors that influence droplet size
6.6.1 Emulsifier type and concentration
6.6.2 Energy input
6.6.3 Properties of component phases
6.6.4 Temperature
6.7 Demulsification
6.7.1 Nonionic surfactants
6.7.2 Ionic surfactants
6.7.3 Biopolymer emulsifiers

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6.8

6.7.4 General methods of demulsification

6.7.5 Selection of most appropriate demulsification technique
Future developments

Chapter 7 Emulsion stability

7.1 Introduction
7.2 Thermodynamic and kinetic stability of emulsions
7.2.1 Thermodynamic stability
7.2.2 Kinetic stability
7.3 Gravitational separation
7.3.1 Physical basis of gravitational separation
7.3.2 Methods of controlling gravitational separation
7.3.3 Experimental characterization of gravitational separation
7.4 General features of droplet aggregation
7.4.1 Dropletdroplet encounters
7.4.2 Film thinning
7.4.3 Thin film formation
7.4.4 Film rupture
7.5 Flocculation
7.5.1 Physical basis of flocculation
7.5.2 Methods of controlling flocculation
7.5.3 Structure and properties of flocculated emulsions
7.5.4 Experimental measurement of flocculation
7.6 Coalescence
7.6.1 Physical basis of coalescence
7.6.2 Methods of controlling coalescence
7.6.3 Factors affecting coalescence
7.6.4 Measurement of droplet coalescence
7.7 Partial coalescence
7.7.1 Physical basis of partial coalescence
7.7.2 Methods of controlling partial coalescence
7.7.3 Experimental characterization of partial coalescence
7.8 Ostwald ripening
7.8.1 Physical basis of Ostwald ripening
7.8.2 Methods of controlling Ostwald ripening
7.8.3 Experimental characterization of Ostwald ripening
7.9 Phase inversion
7.9.1 Physical basis of phase inversion
7.9.2 Methods of controlling phase inversion
7.9.3 Characterization of phase inversion
7.10 Chemical and biochemical stability
Chapter 8 Emulsion rheology
8.1 Introduction
8.2 Rheological properties of materials
8.2.1 Solids
8.2.2 Liquids
8.2.3 Plastics
8.2.4 Viscoelastic materials

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8.3

8.4

8.5
8.6

8.7

Measurement of rheologic properties

8.3.1 Simple compression and elongation
8.3.2 Shear measurements
8.3.3 Empirical techniques
Rheologic properties of emulsions
8.4.1 Dilute suspensions of rigid spherical particles
8.4.2 Dilute suspensions of fluid spherical particles
8.4.3 Dilute suspensions of rigid nonspherical particles
8.4.4 Dilute suspensions of flocculated particles
8.4.5 Concentrated suspensions of nonflocculated particles
in the absence of long-range colloidal interactions
8.4.6 Suspensions of nonflocculated particles with repulsive
interactions
8.4.7 Concentrated suspensions with attractive interactions:
flocculated systems
8.4.8 Emulsions with semisolid continuous phases
Computer simulation of emulsion rheology
Major factors influencing emulsion rheology
8.6.1 Disperse phase volume fraction
8.6.2 Rheology of component phases
8.6.3 Droplet size
8.6.4 Colloidal interactions
8.6.5 Droplet charge
Future Trends

Chapter 9 Emulsion flavor

9.1 Introduction
9.1.1 Physicochemical processes
9.1.2 Physiologic processes
9.1.3 Psychologic processes
9.1.4 General aspects
9.2 Flavor partitioning
9.2.1 Partitioning between a homogenous liquid and a vapor
9.2.2 Influence of flavor ionization
9.2.3 Influence of flavor binding on partitioning
9.2.4 Influence of surfactant micelles on partitioning
9.2.5 Partitioning in emulsions in the absence of
an interfacial membrane
9.2.6 Partitioning in emulsions in the presence of
an interfacial membrane
9.3 Flavor release
9.3.1 Overview of physicochemical process of flavor release
9.3.2 Release of nonvolatile compounds (taste)
9.3.3 Release of volatile compounds (aroma)
9.4 Emulsion mouthfeel
9.5 Measurement of emulsion flavor
9.5.1 Analysis of volatile flavor compounds
9.5.2 Analysis of nonvolatile flavor compounds
9.5.3 Sensory analysis
9.6 Overview of factors influencing emulsion flavor
9.6.1 Disperse phase volume fraction

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9.7

9.6.2 Droplet size

9.6.3 Interfacial characteristics
9.6.4 Oil phase characteristics
9.6.5 Aqueous phase characteristics
Concluding remarks and future directions

Chapter 10 Appearance
10.1 Introduction
10.2 General aspects of optical properties of materials
10.2.1 Interaction of light with matter
10.2.2 Human vision
10.2.3 Quantitative description of appearance
10.3 Mathematical modeling of emulsion color
10.3.1 Calculation of scattering characteristics of emulsion droplets
10.3.2 Calculation of spectral transmittance or reflectance
of emulsions
10.3.3 Relationship of tristimulus coordinates to spectral
reflectance and transmittance
10.3.4 Influence of polydispersity
10.3.5 Numerical calculations of emulsion color
10.3.6 Influence of measurement cell
10.4 Measurement of emulsion color
10.4.1 Spectrophotometric colorimeters
10.4.2 Trichromatic colorimeters
10.4.3 Light scattering
10.4.4 Sensory analysis
10.5 Major factors influencing emulsion color
10.5.1 Droplet concentration and size
10.5.2 Relative refractive index of droplets
10.5.3 Colorant type and concentration
10.5.4 Factors affecting color of real food emulsions
10.6 Concluding remarks and future directions
Chapter 11 Characterization of emulsion properties
11.1 Introduction
11.2 Testing emulsifier effectiveness
11.2.1 Emulsifying capacity
11.2.2 Emulsion stability index
11.3 Microstructure and droplet size distribution
11.3.1 Microscopy
11.3.2 Static light scattering
11.3.3 Dynamic light scattering and diffusing wave spectroscopy
11.3.4 Electrical pulse counting
11.3.5 Sedimentation techniques
11.3.6 Ultrasonic spectrometry
11.3.7 Nuclear magnetic resonance
11.3.8 Neutron scattering
11.3.9 Dielectric spectroscopy
11.3.10 Electroacoustics
11.4 Disperse phase volume fraction
11.4.1 Proximate analysis

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11.4.2 Density measurements

11.4.3 Electrical conductivity
11.4.4 Alternative techniques
11.5 Droplet crystallinity
11.5.1 Dilatometry
11.5.2 Nuclear magnetic resonance
11.5.3 Thermal analysis
11.5.4 Ultrasonics
11.6 Droplet charge
11.6.1 Particle electrophoresis
11.6.2 Electroacoustics
11.7 Droplet interactions
Chapter 12 Food emulsions in practice
12.1 Introduction
12.2 Milk and cream
12.2.1 Composition
12.2.2 Microstructure
12.2.3 Production
12.2.4 Physicochemical properties
12.2.5 Dairy products
12.3 Beverage emulsions
12.3.1 Composition
12.3.2 Microstructure
12.3.3 Production
12.3.4 Physicochemical properties
12.4 Dressings
12.4.1 Composition
12.4.2 Microstructure
12.4.3 Production
12.4.4 Physicochemical properties
References

Copyright 2005 by CRC Press