Characterization of Cereals and Flours doc

Characterization
of
Cereals
and
Flours
Properties,
Analysis,
and
Applications
edited
by
Gonul
Kaletung
The
Ohio
State
University
Columbus,
Ohio,
U.S.A.
Kenneth
J.
Breslauer
Rutgers
University
Piscataway,
New
Jersey,
U.S.A.
MARCEL
MARCEL

DEKKER,
INC.
NEW
YORK
•
BASEL
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
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Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
FOOD
SCIENCE
AND
TECHNOLOGY
A
Series
of
Monographs,
Textbooks,
and
Reference
Books
EDITORIAL
BOARD
Senior
Editors
Owen
R.
Fennema
University
of
Wisconsin-Madison
Y.
H. Hui
Science
Technology
System

Marcus
Karel
Rutgers
University
(emeritus)
Pieter
Walstra
Wageningen
University
John
R.
Whitaker
University
of
California-Davis
Additives
P.
Michael
Davidson
University
of
Tennessee-Knoxville
Dairy
science
James
L.
Steele
University
of
Wisconsin-Madison

Flavor
chemistry
and
sensory
analysis
John
H.
Thorngate
III
University
of
California-Davis
Food
engineering
Daryl
B.
Lund
University
of
Wisconsin-Madison
Food
proteins/food
chemistry
Rickey
Y.
Yada
University
of
Guelph
Health

and
disease
Seppo
Salminen
University
of
Turku,
Finland
Nutrition
and
nutraceuticals
Mark
Dreher
Mead
Johnson
Nutntionals
Phase
transition/food
microstructure
Richard
W.
Hartel
University of
Wisconsin-Madison
Processing
and
preservation
Gustavo
V.
Barbosa-Canovas

Washington
State
University-Pullman
Safety
and
toxicology
Sanford
Miller
University
of
Texas-Austin
1
Flavor
Research
Principles
and
Techniques,
R.
Teranishi,
I.
Horn-
stein,
P
Issenberg,
and E. L.
Wick
2.
Principles
of
Enzymology

for the
Food
Sciences,
John
R.
Whitaker
3.
Low-Temperature
Preservation
of
Foods
and
Living
Matter,
Owen
R.
Fennema,
William
D
Powne,
and
Elmer
H
Marth
4.
Principles
of
Food
Science
Part

I.
Food
Chemistry,
edited
by
Owen
R
Fennema
Part
II
Physical
Methods
of
Food
Preservation,
Marcus
Karel,
Owen
R
Fennema,
and
Daryl
B
Lund
5.
Food
Emulsions,
edited
by
Stig

E.
Fnberg
6.
Nutritional
and
Safety
Aspects
of
Food
Processing,
edited
by
Steven
R.
Tannenbaum
7.
Flavor
Research.
Recent
Advances,
edited
by R
Teranishi,
Robert
A,
Flath,
and
Hiroshi
Sugisawa
8

Computer-Aided
Techniques
in
Food
Technology,
edited
by
Israel
Saguy
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
9.
Handbook
of
Tropical
Foods,
edited
by
Harvey
T.
Chan
10.
Antimicrobials
in
Foods,
edited
by
Alfred
Larry
Branen
and P.

Michael
Davidson
11.
Food
Constituents
and
Food
Residues:
Their
Chromatographic
Determination,
edited
by
James
F.
Lawrence
12.
Aspartame:
Physiology
and
Biochemistry,
edited
by
Lewis
D.
Stegink
and L. J.
Filer,
Jr.
13.

Handbook
of
Vitamins:
Nutritional,
Biochemical,
and
Clinical
Aspects,
edited
by
Lawrence
J.
Machlin
14.
Starch
Conversion
Technology,
edited
by G. M. A. van
Beynum
and J.
A
Roels
15.
Food
Chemistry:
Second
Edition,
Revised
and

Expanded,
edited
by
Owen
R.
Fennema
16.
Sensory
Evaluation
of
Food:
Statistical
Methods
and
Procedures,
Mi-
chael
O'Mahony
17.
Alternative
Sweeteners,
edited
by Lyn
O'Brien
Nabors
and
Robert
C.
Gelardi
18.

Citrus
Fruits
and
Their
Products:
Analysis
and
Technology,
S. V.
Ting
and
Russell
L,
Rouseff
19.
Engineering
Properties
of
Foods,
edited
by M. A. Rao and S. S. H.
Rizvi
20.
Umami:
A
Basic
Taste,
edited
by
Yojiro

Kawamura
and
Morley
R.
Kare
21.
Food
Biotechnology,
edited
by
Dietnch
Knorr
22.
Food
Texture:
Instrumental
and
Sensory
Measurement,
edited
by
Howard
R.
Moskowitz
23.
Seafoods
and
Fish
Oils
in

Human
Health
and
Disease,
John
E.
Kinsella
24.
Postharvest
Physiology
of
Vegetables,
edited
by J.
Weichmann
25.
Handbook
of
Dietary
Fiber:
An
Applied
Approach,
Mark
L.
Dreher
26.
Food
Toxicology,
Parts

A and B,
Jose
M.
Concon
27.
Modern
Carbohydrate
Chemistry,
Roger
W.
Binkley
28.
Trace
Minerals
in
Foods,
edited
by
Kenneth
T.
Smith
29.
Protein
Quality
and the
Effects
of
Processing,
edited
by R.

Dixon
Phillips
and
John
W.
Finley
30.
Adulteration
of
Fruit
Juice
Beverages,
edited
by
Steven
Nagy,
John
A.
Attaway,
and
Martha
E.
Rhodes
31.
Foodborne
Bacterial
Pathogens,
edited
by
Michael

P.
Doyle
32.
Legumes.
Chemistry,
Technology,
and
Human
Nutrition,
edited
by
Ruth
H.
Matthews
33.
Industrialization
of
Indigenous
Fermented
Foods,
edited
by
Keith
H
Steinkraus
34.
International
Food
Regulation
Handbook.

Policy
•
Science
•
Law,
edited
by
Roger
D.
Middlekauff
and
Philippe
Shubik
35.
Food
Additives,
edited
by A
Larry
Branen,
P
Michael
Davidson,
and
Seppo
Salminen
36.
Safety
of
Irradiated

Foods,
J. F
Diehl
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
37
Omega-3
Fatty
Acids
in
Health
and
Disease,
edited
by
Robert
S.
Lees
and
Marcus
Karel
38.
Food
Emulsions:
Second
Edition,
Revised
and
Expanded,
edited
by

Kare
Larsson
and
Stig
E.
Fnberg
39
Seafood
Effects
of
Technology
on
Nutrition,
George
M
Pigott
and
Barbee
W.
Tucker
40
Handbook
of
Vitamins:
Second
Edition,
Revised
and
Expanded,
edited

by
Lawrence
J.
Machlin
41.
Handbook
of
Cereal
Science
and
Technology,
Klaus
J.
Lorenz
and
Karel
Kulp
42
Food
Processing
Operations
and
Scale-Up,
Kenneth
J.
Valentas,
Leon
Levine,
and J.
Peter

Clark
43.
Fish
Quality
Control
by
Computer
Vision,
edited
by L F. Pau and R.
Olafsson
44.
Volatile
Compounds
in
Foods
and
Beverages,
edited
by
Henk
Maarse
45.
Instrumental
Methods
for
Quality
Assurance
in
Foods,

edited
by
Daniel
Y C
Fung
and
Richard
F.
Matthews
46
Listena,
Listenosis,
and
Food
Safety,
Elliot
T
Ryser
and
Elmer
H
Marth
47
Acesulfame-K,
edited
by D G
MayerandF.H
Kemper
48
Alternative

Sweeteners.
Second
Edition,
Revised
and
Expanded,
ed-
ited
by Lyn
O'Brien
Nabors
and
Robert
C
Gelardi
49
Food
Extrusion
Science
and
Technology,
edited
by
Jozef
L
Kokini,
Chi-Tang
Ho, and
Mukund
V.

Karwe
50.
Sunmi
Technology,
edited
by
Tyre
C
Lamer
and
Chong
M Lee
51
Handbook
of
Food
Engineering,
edited
by
Dennis
R
Heldman
and
Daryl
B
Lund
52
Food
Analysis
by

HPLC,
edited
by Leo M L.
Nollet
53
Fatty
Acids
in
Foods
and
Their
Health
Implications,
edited
by
Chmg
Kuang
Chow
54
Clostndium
botulmum:
Ecology
and
Control
m
Foods,
edited
by
Andreas
H W

Hauschild
and
Karen
L.
Dodds
55
Cereals
in
Breadmaking:
A
Molecular
Colloidal
Approach,
Ann-Charlotte
Eliasson
and
Kare
Larsson
56
Low-Calorie
Foods
Handbook,
edited
by
Aaron
M
Altschul
57
Antimicrobials
in

Foods
Second
Edition,
Revised
and
Expanded,
edited
by P
Michael
Davidson
and
Alfred
Larry
Branen
58
Lactic
Acid
Bacteria,
edited
by
Seppo
Salmmen
and
Atte
von
Wnght
59
Rice
Science
and

Technology,
edited
by
Wayne
E.
Marshall
and
James
I
Wadsworth
60
Food
Biosensor
Analysis,
edited
by
Gabnele
Wagner
and
George
G
Guilbault
61.
Principles
of
Enzymology
for the
Food
Sciences
Second

Edition,
John
R.
Whitaker
62.
Carbohydrate
Polyesters
as Fat
Substitutes,
edited
by
Casimir
C
Akoh
and
Barry
G
Swanson
63.
Engineering
Properties
of
Foods
1
Second
Edition,
Revised
and
Expanded,
edited

by M. A Rao and S S H
RIZVI
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
64
Handbook
of
Brewing,
edited
by
William
A
Hardwick
65
Analyzing
Food
for
Nutrition
Labeling
and
Hazardous
Contaminants,
edited
by Ike J
Jeon
and
William
G
Iktns
66
Ingredient

Interactions
Effects
on
Food
Quality,
edited
by
Amlkumar
G
Gaonkar
67
Food
Polysaccharides
and
Their
Applications,
edited
by
Alistair
M
Stephen
68
Safety
of
Irradiated
Foods
Second
Edition,
Revised
and

Expanded,
J
F
Diehl
69
Nutrition
Labeling
Handbook,
edited
by
Ralph
Shapiro
70
Handbook
of
Fruit
Science
and
Technology
Production,
Composition,
Storage,
and
Processing,
edited
by D K
SalunkheandS
S
Kadam
71

Food
Antioxidants
Technological,
Toxicological,
and
Health
Perspec-
tives,
edited
by D L
Madhavi,
S S
Deshpande,
and D K
Salunkhe
72
Freezing
Effects
on
Food Quality,
edited
by
Lester
E
Jeremiah
73
Handbook
of
Indigenous
Fermented

Foods
Second
Edition,
Revised
and
Expanded,
edited
by
Keith
H
Stemkraus
74
Carbohydrates
in
Food,
edited
by
Ann-Charlotte
Eliasson
75
Baked Goods Freshness Technology, Evaluation,
and
Inhibition
of
Staling,
edited
by
Ronald
E
Hebeda

and
Henry
F
Zobel
76
Food Chemistry Third Edition,
edited
by
Owen
R
Fennema
77
Handbook
of
Food
Analysis
Volumes
1 and 2,
edited
by Leo M L
Nollet
78
Computerized Control Systems
in
the
Food Industry,
edited
by
Gauri
S

Mittal
79
Techniques
for
Analyzing
Food Aroma,
edited
by Ray
Marsili
80
Food
Proteins
and
Their
Applications,
edited
by
Srimvasan
Damo-
daran
and
Alam
Paraf
81
Food Emulsions Third Edition, Revised
and
Expanded,
edited
by
Stig

£
Fnberg
and
Kare
Larsson
82
Nonthermal
Preservation
of
Foods,
Gusfavo
V
Barbosa-Canovas,
Usha
R
Pothakamury,
Ennque
Palou,
and
Barry
G
Swanson
83
Milk
and
Dairy Product Technology,
Edgar
Spreer
84
Applied Dairy Microbiology,

edited
by
Elmer
H
Marth
and
James
L
Steele
85
Lactic
Acid
Bacteria
Microbiology
and
Functional
Aspects Second
Edition,
Revised
and
Expanded,
edited
by
Seppo
Salmmen
and
Atte
von
Wnght
86

Handbook
of
Vegetable Science
and
Technology Production,
Composition,
Storage,
and
Processing,
edited
by D K
Salunkhe
and
S S
Kadam
87
Polysacchande
Association Structures
in
Food
edited
by
Reginald
H
Walter
88
Food
Lipids
Chemistry, Nutrition,
and

Biotechnology,
edited
by
Casimir
C
Akoh
and
David
B Mm
89
Spice Science
and
Technology,
Ken//
Hirasa
and
Mitsuo
Takemasa
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
90
Dairy
Technology
Principles
of
Milk
Properties
and
Processes,
P
Walstra,

T J
Geurts,
A
Noomen,
A
Jellema,
and M A J S van
Boekel
91
Coloring
of
Food,
Drugs,
and
Cosmetics,
Gisbert
Otterstatter
92
Listens,
Listeriosis,
and
Food
Safety
Second
Edition,
Revised
and
Expanded,
edited
by

Elliot
T
Ryser
and
Elmer
H
Marth
93
Complex
Carbohydrates
in
Foods,
edited
by
Susan
Sungsoo
Cho,
Leon
Prosky,
and
Mark
Dreher
94
Handbook
of
Food
Preservation,
edited
by M
Shafiur

Rahman
95
International
Food
Safety
Handbook
Science,
International
Regula-
tion,
and
Control,
edited
by
Kees
van der
Heijden,
Maged
Younes,
Lawrence
Fishbein,
and
San
ford
Miller
96
Fatty
Acids
in
Foods

and
Their
Health
Implications
Second
Edition,
Revised
and
Expanded,
edited
by
Ching
Kuang
Chow
97
Seafood
Enzymes
Utilization
and
Influence
on
Postharvest
Seafood
Quality,
edited
by
Norman
F
Haard
and

Benjamin
K
Simpson
98
Safe
Handling
of
Foods,
edited
by
Jeffrey
M
Farber
and
Ewen
C D
Todd
99
Handbook
of
Cereal
Science
and
Technology
Second
Edition,
Re-
vised
and
Expanded,

edited
by
Karel
Kulp
and
Joseph
G
Ponte,
Jr
100
Food
Analysis
by
HPLC
Second
Edition,
Revised
and
Expanded,
edited
by Leo M L
Nollet
101
Surimi
and
Surimi
Seafood,
edited
byJae
W

Park
102
Drug
Residues
in
Foods
Pharmacology,
Food
Safety,
and
Analysis,
Nickos
A
Botsoglou
and
Dimitnos
J
Fletouns
103
Seafood
and
Freshwater
Toxins
Pharmacology,
Physiology,
and
Detection,
edited
by
Luis

M
Botana
104
Handbook
of
Nutrition
and
Diet,
Babasaheb
B
Desai
105
Nondestructive
Food
Evaluation
Techniques
to
Analyze
Properties
and
Quality,
edited
by
Sundaram
Gunasekaran
106
Green
Tea
Health
Benefits

and
Applications,
Yukihiko
Hara
107
Food
Processing
Operations
Modeling
Design
and
Analysis,
edited
by
Joseph
Irudayaraj
108
Wine
Microbiology
Science
and
Technology,
Claudio
Delfini
and
Joseph
V
Formica
109
Handbook

of
Microwave
Technology
for
Food
Applications,
edited
by
Ashim
K
Datta
and
Ramaswamy
C
Anantheswaran
110
Applied
Dairy
Microbiology
Second
Edition,
Revised
and
Expanded,
edited
by
Elmer
H
Marth
and

James
L
Steele
111
Transport
Properties
of
Foods,
George
D
Saravacos
and
Zachanas
B
Maroulis
112
Alternative
Sweeteners
Third
Edition,
Revised
and
Expanded,
edited
by Lyn
O'Bnen
Nabors
113
Handbook
of

Dietary
Fiber,
edited
by
Susan
Sungsoo
Cho and
Mark
L
Dreher
114
Control
of
Foodborne
Microorganisms,
edited
by
Vijay
K
Juneja
and
John
N
Sofos
115
Flavor,
Fragrance,
and
Odor
Analysis,

edited
by Ray
Marsili
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
116.
Food
Additives:
Second
Edition,
Revised
and
Expanded,
edited
by A.
Larry
Branen,
P.
Michael
Davidson,
Seppo
Salminen,
and
John
H.
Thorngate,
III
117.
Food
Lipids:
Chemistry,

Nutrition,
and
Biotechnology:
Second
Edition,
Revised
and
Expanded,
edited
by
Casimir
C.
Akoh
and
David
B. Min
118.
Food
Protein
Analysis:
Quantitative
Effects
on
Processing,
R.
K.
Owusu-Apenten
119.
Handbook
of

Food
Toxicology,
S. S.
Deshpande
120.
Food
Plant
Sanitation,
edited
by Y. H.
Hui,
Bernard
L.
Brumsma,
J.
Richard
Gorham,
Wai-Kit
Nip,
Phillip
S.
Tong,
and
Phil
Ventresca
121.
Physical
Chemistry
of
Foods,

Prefer
Walstra
122.
Handbook
of
Food
Enzymology,
edited
by
John
R.
Whitaker,
Alphons
G,
J.
Voragen,
and
Dominic
W.
S.
Wong
123.
Postharvest
Physiology
and
Pathology
of
Vegetables:
Second
Edition,

Revised
and
Expanded,
edited
by
Jerry
A.
Bartz
and
Jeffrey
K.
Brecht
124.
Characterization
of
Cereals
and
Flours:
Properties,
Analysis,
and Ap-
plications,
edited
by
Gonul
Kaletung
and
Kenneth
J
Breslauer

125.
International
Handbook
of
Foodborne
Pathogens,
edited
by
Marianne
D.
Miliotis
and
Jeffrey
W.
Bier
Additional
Volumes
in
Preparation
Handbook
of
Dough
Fermentations,
edited
by
Karel
Kulp
and
Klaus
Lorenz

Extraction
Optimization
in
Food
Engineering,
edited
by
Constantina
Tzia
and
George
Liadakis
Physical
Principles
of
Food
Preservation:
Second
Edition,
Revised
and
Expanded,
Marcus
Karel
and
Daryl
B.
Lund
Handbook
of

Vegetable
Preservation
and
Processing,
edited
by Y. H.
Hut,
Sue
Ghazala,
Dee M.
Graham,
K. D.
Murrell,
and
Wai-Kit
Nip
Food
Process
Design,
Zacharias
B.
Maroulis
and
George
D.
Sara-
vacos
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
To my parents, Nevin and Fethi Kaletunc
¸

,
Janet and George Plum,
my husband, Eric,
and my son, Barıs
¸
,
for their support and encouragement
Go
¨
nu
¨
l Kaletunc
¸
To my wife, Sherrie Schwab,
and my two sons, Danny and Jordan Breslauer,
for their patience, support, and special spirit for life
Kenneth J. Breslauer
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
Preface
Cereal-based foods comprise a substantial portion of the world’s food supply,
despite regional, economical, and habitual differences in consumption. In the
human diet, cereals are considered excellent sources of fiber and nutrients (e.g.,
starches, proteins, vitamins, and minerals). In many developing countries, cereals
provide as much as 75% of human dietary energy. In 1992, the U.S. Department
of Agriculture emphasized the importance of cereal-based foods in the human
diet by introducing the Food Guide Pyramid. This graphical guideline organizes
foods into five groups and recommends daily consumption of 6–11 servings of
bread, cereals, rice, and pasta (two to three times more than the number of serv-
ings for other food groups), thereby stressing the relative significance of the
grains group. As economical and abundant raw materials, cereals have long been

used for the production of a wide range of food and nonfood products, including
breads, cookies, pastas, breakfast cereals, snack foods, malted cereals, pharma-
ceuticals, and adhesives.
The improvement and development of cereal products and processes re-
quire an understanding of the impact of processing and storage conditions on the
physical properties and structure of pre- and postprocessed materials. In this
book, we focus on techniques used to characterize the influence on the physical
properties of cereal flours of several cereal processing technologies, including
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
baking, pasta extrusion, and high-temperature extrusion, as well as cookie and
cracker production. This text facilitates viewing the impact of various cereal pro-
cessing technologies on cereal flours from three complementary perspectives:
characterization of thermal, mechanical, and structural properties. Establishing
quantitative relationships among the various physical observables and between
the physical properties and the sensory attributes of end products should provide
a rapid and objective means for assessing the quality of food materials, with the
overall goal of improving this quality. To this end, a fourth perspective is also
included: namely, sensory end-product attributes of significance to the consumer.
In several chapters, in fact, correlations between sensory attributes and physical
properties are reported.
Cereal processing consists basically of mixing cereal flours with water,
followed by heating to various temperatures, cooling, and storing. Consequently,
for the purpose of improving processing, it would be most useful if one could
predict the physical properties of pre- and postprocessed cereal flours when sub-
jected to varied processing and storage conditions. Part I of this book, which
includes Chapters 1 through 5, focuses on discussions of thermal analysis tech-
niques to assess the impact of various cereal processing conditions on the physical
properties of cereal flours in high-temperature extrusion, cookie manufacturing,
and baking.
Chapters 1, 2, and 3 describe thermally induced transitions (glass, melting,

gelatinization) in cereal flours as a function of conditions relevant to cereal pro-
cessing technologies. Chapter 4 addresses the influence of moisture on the pro-
cessing conditions and the physical properties of the product. The final chapter
of Part I (Chapter 5) focuses on the utilization of a database created from the
studies described in the previous chapters to establish state diagrams that define
the state of the cereal flour prior to, during, and after processing. This chapter
also describes the application of such state diagrams to map the path of processes,
to assess the impact of processing conditions, and, ultimately, to design pro-
cessing conditions that achieve desired end-product attributes.
Part II includes Chapters 6 through 10 and focuses on the characterization
of mechanical properties of cereal flours, prior to, during, and after processing.
Chapter 6 reports on the assessment of the stability of cereal flours in terms of
caking or loss of flowability as a result of moisture sorption or exposure to ele-
vated temperatures during storage. Chapter 7 covers the rheological characteris-
tics of cereal flours during processing and their relation to end-product physical
properties such as expansion of extrudates. Chapters 8 and 9 describe the mechan-
ical properties of postprocessed cereal flours as a function of processing condi-
tions, additives, and postprocessing storage conditions in relation to pasta drying,
textural attributes, and shelf life of extruded products. Mechanical properties of
biopolymers change as their physical state is altered during processing or storage.
Chapter 10 focuses on the application of this information in product and process
development.
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
The third and final part includes studies exploring the microscopic determi-
nants of macroscopic properties. These studies employ techniques such as light
and electron microscopy and nuclear magnetic resonance (NMR) spectroscopy.
Chapters in this part focus on the development of correlations between the micro-
scopic structural features of pre- and postprocessed food biopolymers and their
macroscopic physical properties. Chapter 11 describes how image analysis tech-
niques can be used to evaluate macrostructures created in expanded extrudates

as a function of formulation and processing conditions. The cell structure and
cell size distribution in these products are responsible for the characteristic crispy
texture of cereal products.
Macroscopic observables do not reveal whether an observed order–disorder
transition reflects a change in the overall structure or whether the transition is
specific for local structural domains. As with all food materials, compositional
and microstructural heterogeneity are intrinsic characteristics of pre- and postpro-
cessed cereal flours. Consequently, it is most useful to characterize chemical and
structural composition at a microscopic level. Chapter 12 focuses on the use of
microscopy as a tool to gain such information about structural organization, as
well as the distribution of various domains within proteins, starches, and other
components in pre- and postprocessed cereal flours. Chapters 13 and 14 focus
on probing the relationships between structure, dynamics, and function using
NMR and phosphorescence spectroscopy. Due to the noninvasive character of
NMR and the richness of its information content, its use to study pre- and postpro-
cessed cereal biopolymers has increased in the past decade. Such NMR studies
range from structural characterization of starch granules to observations of
changes in water mobility in staling bread. Phosphorescence spectroscopy is a
promising emerging technique for studying the molecular dynamics of the glassy
state in which the mobility is very limited. Chapter 15 is devoted to two converg-
ing lines of starch research with implications for the cereal processing industry.
Chemical studies link the molecular characterization of starch granules and
starch-bound proteins to the properties of starch-based products. Biochemical and
genetic studies provide information on starch modification and biosynthesis with
the ultimate objective being to enhance the starch yield and quality.
All of the chapters in this book are designed
1. To develop a fundamental understanding of the influence of processing
on cereal flours by creating a database via systematic studies of the
physical properties of pre- and postprocessed cereal flours
2. To demonstrate how this knowledge can be used as a predictive tool

for evaluating the performance of cereal flour during processing, and,
ultimately, for adjusting, in a rational fashion, the formulation of raw
materials and processing parameters so as to achieve desired end-
product attributes
This book bridges the gap between basic knowledge and application. We be-
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
lieve it will prove to be a comprehensive and valuable teaching text and ref-
erence book for students and practicing scientists, in both academia and in-
dustry.
Go
¨
nu
¨
l Kaletunc
¸
Kenneth J. Breslauer
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
Contents
Preface
Contributors
PART I. THERMAL ANALYSIS
1. Calorimetry of Pre- and Postextruded Cereal Flours
Go
¨
nu
¨
l Kaletunc
¸
and Kenneth J. Breslauer
2. Application of Thermal Analysis to Cookie, Cracker,

and Pretzel Manufacturing
James Ievolella, Martha Wang, Louise Slade,
and Harry Levine
3. Utilization of Thermal Properties for Understanding Baking and
Staling Processes
Ann-Charlotte Eliasson
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
4. Plasticization Effect of Water on Carbohydrates in Relation to
Crystallization
Yrjo
¨
Henrik Roos and Kirsi Jouppila
5. Construction of State Diagrams for Cereal Processing
Go
¨
nu
¨
l Kaletunc
¸
PART II. MECHANICAL PROPERTIES
6. Powder Characteristics of Preprocessed Cereal Flours
G. V. Barbosa-Ca
´
novas and H. Yan
7. Rheological Properties of Biopolymers and Applications to
Cereal Processing
Bruno Vergnes, Guy Della Valle, and Paul Colonna
8. Stress and Breakage in Formed Cereal Products Induced by
Drying, Tempering, and Cooling
Betsy Willis and Martin Okos

9. Textural Characterization of Extruded Materials and Influence
of Common Additives
Andrew C. Smith
10. Utilization of Rheological Properties in Product and Process
Development
Victor T. Huang and Go
¨
nu
¨
l Kaletunc
¸
PART III. STRUCTURAL CHARACTERIZATION
11. Characterization of Macrostructures in Extruded Products
Ann H. Barrett
12. Understanding Microstructural Changes in Biopolymers Using
Light and Electron Microscopy
Karin Autio and Marjatta Salmenkallio-Marttila
13. NMR Characterization of Cereal and Cereal Products
Brian Hills, Alex Grant, and Peter Belton
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
14. Phosphorescence Spectroscopy as a Probe of the Glassy State in
Amorphous Solids
Richard D. Ludescher
15. Starch Properties and Functionalities
Lilia S. Collado and Harold Corke
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
Contributors
Karin Autio VTT Biotechnology, Espoo, Finland
G. V. Barbosa-Ca
´

novas Department of Biological Systems Engineering,
Washington State University, Pullman, Washington, U.S.A.
Ann H. Barrett Combat Feeding Program, U.S. Army Natick Soldier Center,
Natick, Massachusetts, U.S.A.
Peter Belton School of Chemical Sciences, University of East Anglia, Nor-
wich, U.K.
Kenneth J. Breslauer Department of Chemistry and Chemical Biology, Rut-
gers University, Piscataway, New Jersey, U.S.A.
Lilia S. Collado Institute of Food Science and Technology, University of the
Philippines Los Ban
˜
os, College, Laguna, Philippines
Paul Colonna Plant Products Processing, Institut National de la Recherche
Agronomique, Nantes, France
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
Harold Corke Department of Botany, The University of Hong Kong, Hong
Kong, China
Guy Della Valle Plant Products Processing, Institut National de la Recherche
Agronomique, Nantes, France
Ann-Charlotte Eliasson Department of Food Technology, Center for Chemis-
try and Chemical Engineering, Lund University, Lund, Sweden
Alex Grant Institute of Food Research, Norwich, U.K.
Brian Hills Institute of Food Research, Norwich, U.K.
Victor T. Huang General Mills, Inc., Minneapolis, Minnesota, U.S.A.
James Ievolella* Nabisco, Kraft Foods, East Hanover, New Jersey, U.S.A.
Kirsi Jouppila Department of Food Technology, University of Helsinki, Hel-
sinki, Finland
Go
¨
nu

¨
l Kaletunc
¸
Department of Food, Agricultural, and Biological Engi-
neering, The Ohio State University, Columbus, Ohio, U.S.A.
Harry Levine Nabisco, Kraft Foods, East Hanover, New Jersey, U.S.A.
Richard D. Ludescher Department of Food Science, Rutgers University, New
Brunswick, New Jersey, U.S.A.
Martin Okos Department of Agricultural and Biological Engineering, Purdue
University, West Lafayette, Indiana, U.S.A.
Yrjo
¨
Henrik Roos Department of Food Science, Food Technology, and Nutri-
tion, University College Cork, Cork, Ireland
Marjatta Salmenkallio-Marttila VTT Biotechnology, Espoo, Finland
Louise Slade Nabisco, Kraft Foods, East Hanover, New Jersey, U.S.A.
* Retired.
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
Andrew C. Smith Institute of Food Research, Norwich, U.K.
Bruno Vergnes Centre de Mise en Forme des Materiaux (CEMEF), Ecole des
Mines de Paris, Sophia-Antipolis, France
Martha Wang Nabisco, Kraft Foods, East Hanover, New Jersey, U.S.A.
Betsy Willis School of Engineering, Southern Methodist University, Dallas,
Texas, U.S.A.
H. Yan Department of Biological Systems Engineering, Washington State Uni-
versity, Pullman, Washington, U.S.A.
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
1
Calorimetry of Pre- and
Postextruded Cereal Flours

Go
¨
nu
¨
l Kaletunc
¸
The Ohio State University, Columbus, Ohio, U.S.A.
Kenneth J. Breslauer
Rutgers University, Piscataway, New Jersey, U.S.A.
I. INTRODUCTION
Extrusion processing is widely utilized in the food and feed industries for the
manufacture of value-added products. Extrusion processing is a versatile technol-
ogy producing a wide range of products, including confectionery products, pasta,
ready-to-eat (RTE) cereals, flat bread, snack products, texturized proteins, and
pet foods. A broad range of operating parameters is used to manufacture products
with a large variety of structures and textures, ranging from high moisture (up
to 75%)–low temperature (as low as 50°C)–low shear in texturized vegetable
and pasta production to low moisture (as low as 11%)–high temperature (as high
as 180°C)–high shear in breakfast cereal and snack production.
High-temperature extrusion processing finds wide application in the food
industry for the preparation of breakfast cereals and snack foods. Starch-and
protein-based cereal flours are frequently encountered as major components of
the raw material mixtures. Rice, wheat, oat, corn, and mixed grain cereal flours
or meals are commonly utilized for extrusion processing. During extrusion, as a
result of shear and high temperatures, usually above 140°C, cereal flours are
transformed into viscoelastic melts. Upon extrusion, the melt expands and cools
rapidly due to vaporization of moisture, eventually settling into an expanded solid
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
foam. Because extrusion processing is associated with thermal manipulation
(mainly heating and some cooling for unexpanded materials) of the materials,

thermal characterization of cereal flours and their biopolymer components will
lead to data that can be related directly to the processing protocols. Furthermore,
thermal characterization of extruded products as a function of storage conditions
(relative humidity–temperature) allows evaluation of the impact of such treat-
ment.
In this chapter, we review the characterization by calorimetry of thermally
induced conformational changes and phase transitions in pre- and postextruded
cereal flours and the use of calorimetric data to elucidate the macromolecular
modifications that these materials undergo during extrusion processing. The use
of calorimetric data as a tool to evaluate the impact of formulation, processing,
and storage on end-product attributes will be demonstrated.
II. CALORIMETRY
Differential scanning calorimetry (DSC) is a thermal analysis technique that de-
tects and monitors thermally induced conformational transitions and phase transi-
tions as a function of temperature. A pair of matching crucibles or sample pans,
one containing the sample and one serving as reference, are heated in tandem.
As a crucible is heated, its temperature increases, depending on the heat capacity
of the contents of the crucible. At temperatures where an endothermic transition
occurs, the thermal energy supplied to the crucible is consumed by that transition
and the temperature of the sample cell lags behind the reference cell temperature.
Conversely, the reference cell temperature lags when an exothermic transition
occurs in the sample. A temperature difference between the cells results in heat
flow between the cells. DSC measures the differential heat flow between the
sample and reference crucibles as a function of temperature at a fixed heating
rate. DSC thermograms are normalized to yield the specific heat capacity (C
p
)
as a function of temperature (1).
At temperatures where crystalline regions of cereal flour components
undergo order–disorder transitions, peaks are observed in the heat flow vs. tem-

perature diagrams, either as heat absorption (endotherm) or as heat release (exo-
therm). Endotherms are typically associated with the melting of mono-, di-,
oligo-, and polysaccharides, denaturation of proteins, and gelatinization of starch.
Exotherms are observed for crystallization of carbohydrates and aggregation of
denatured proteins. When both crystalline and amorphous structures are present,
which is typical in cereal flours, an additional transition is observed prior to the
exothermic and endothermic transitions. This transition, known as a glass transi-
tion, is associated with amorphous materials or amorphous regions of partially
crystalline materials. With DSC, the glass transition is observed as a sharp de-
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
crease of the heat capacity on cooling and a sudden increase in heat capacity on
heating. A typical DSC thermogram, displaying glass, endothermic, and exother-
mic transitions, is given in Figure 1.
The glass transition temperature indicates a change in the mobility of the
molecular structure of materials. Because cooperative motions in the molecular
structure are frozen below the glass transition temperature, for partially crystal-
line materials exothermic and endothermic events are not observed until the glass
transition is completed. Slade and Levine (2) discussed in detail that crystalliza-
tion (exothermic event) can occur only in the rubbery state and the overall rate
of crystallization (net rate of nucleation and propagation) in polymer melts is
maximized at a temperature midway between the glass transition and melting
temperatures. Furthermore, it has been demonstrated that for partially crystalline
polymers the ratio of the melting to glass transition temperatures (T
m
/T
g
) varies
from 0.8 to greater than 1.5. This ratio is shown to correlate with the glass-
forming tendency and crystallizability of the polymers, because it predicts the
relative mobilities of polymers at T

g
and at T ϾϾ T
g
. More specifically, polymers
with T
m
/T
g
ϾϾ 1.5 readily crystallize, while the polymers with T
m
/T
g
ϽϽ 1.5 have
a high glass-forming tendency. Food biopolymers such as gelatin, native starch,
and dimers or monomers such as galactose and fructose are reported to exhibit
behavior similar to synthetic polymers with T
m
/T
g
ϽϽ 1.5, which demonstrates a
large free-volume requirement and thus a large temperature increase required for
mobility.
Figure 1 Typical DSC curve for partially crystalline materials.
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
In DSC thermograms similar to the one in Figure 1, the glass transition is
detectable by a step change of the heat capacity. Although T
g
can be observed
experimentally by measuring physical, mechanical, or electrical properties, it is
important to point out that DSC alone supplies thermodynamic information about

T
g
(3). The thermodynamic property of interest in DSC measurements is the
change in the heat capacity, which reflects changes in molecular motions. It
should be emphasized that the formation and behavior of the glassy state is a
kinetic phenomenon. However, the rubbery state on the high-temperature side of
the glass transition is at equilibrium and can be described by equilibrium thermo-
dynamics. Equilibrium thermodynamics also can be applied well below the glass
transition temperature because the response of internal degrees of freedom to
external effects is very slow. However, during the glass transition, both intrinsic
and measurement variables occur on the same time scale, the measured quantities
become time dependent, and equilibrium thermodynamics cannot be applied to
analyze the system. The system has a memory of its thermal history, which results
in the occurrence of relaxation phenomena if the heating and cooling rates are
different. It is not possible to get equilibrium values for T
g
and the heat capacity
change at the glass transition by extrapolating to zero scanning rate because these
quantities depend on the thermal history, which includes the scanning rate, an-
nealing temperature, and time.
A complete characterization of the glass transition can be achieved using
several parameters. These parameters, as described by Ho
¨
hne et al. (1), include
the temperatures corresponding to vitrification (T
g, f
) and devitrification (T
g, i
)of
the material upon cooling and heating, extrapolated onset temperature (T

g, e
), heat
capacity change, and the temperature corresponding to the midpoint of the heat
capacity change between the extrapolated heat capacity of the glassy and rubbery
states (T
g,1/2
). The specific heat capacity versus temperature curve derived from
a DSC thermogram of a typical glass transition and the parameters describing
the glass transition are given in Figure 2.
T
g
is also reported as the inflection point of the heat capacity versus temper-
ature curve. The inflection point that corresponds to T
g
is the temperature corre-
sponding to the peak in the dC
p
/dT vs. T curve. However, it should be kept in
mind that the glass transition curve typically has an asymmetric shape and that
the temperature corresponding to the inflection point and (T
g,1/2
) are not the same.
Therefore, it is a good practice to report the approach by which T
g
is defined.
Ho
¨
hne and coauthors (1) indicate that T
g, e
and T

g,1/2
cannot describe the nonequi-
librium nature of the glass transition, especially if the ‘‘enthalpy relaxation
peaks’’ appear in the glass transition curve. However, these authors discuss at
length that the glass transition, although a kinetically controlled parameter, can be
unambiguously defined thermodynamically using a temperature called the fictive
temperature. This thermodynamically defined T
g
is based on the equality of en-
thalpy of the glassy and rubbery states at T
g
. Further discussion of this subject
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
Figure 2 Glass transition.
is beyond the scope of this chapter, and the reader is referred to the book by
Ho
¨
hne et al. (1).
In addition to the conventional linearly increasing temperature protocol uti-
lized in DSC, a recently introduced modulated differential scanning calorimetry
(MDSC) employs a temperature protocol utilizing an oscillating sine wave of
known frequency and amplitude superimposed onto the linear temperature in-
crease applied to the sample and reference pans (4). The MDSC output signal,
heat flow, can be deconvoluted to evaluate the contributions from thermody-
namically reversible (reversing heat flow) and from irreversible or kinetically
controlled transitions (nonreversing heat flow) within the time scale of the
DSC experiment. This attribute enables the separation of overlapping complex
transitions. One of the primary applications of this feature is the separation of
the relaxation endotherm from the glass transition in amorphous materials (5–
8). Figure 3 shows the total heat flow, reversing heat flow, and nonreversing heat

flow deconvoluted from an MDSC experiment carried out with corn flour extru-
date (9). It is apparent from Figure 3 that MDSC is an effective method of charac-
terizing the glass transition of an amorphous extrudate, allowing the separate
characterization of T
g
and endothermic relaxation in one heating cycle.
At plasticizer levels that cause the partial or complete masking of the glass
transition by an endothermic relaxation endotherm, the protocol used to deter-
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.
Figure 3 Glass transition of corn extrudate using MDSC.
mine the glass transition temperature using conventional DSC is to make a partial
scan to just above the glass transition, followed by cooling and a second scan.
The glass transition temperature is determined from the second heating scan (10).
Another benefit of this technique over standard DSC is an increase of resolution
and sensitivity due to the cycling instantaneous heating rates, which enables one
to detect weak transitions. Although the use of MDSC expands the capabilities
of DSC and allows one to measure heat capacities and characterize reversible/
nonreversible thermal transitions, one should remember that the deconvolution
of the total heat flow into reversing and nonreversing components is affected
by experimental parameters. In addition to linear heating rate, the operational
parameter in conventional DSC, MDSC requires the choice of modulation ampli-
tude and modulation period. The selection of the best combination of modulation
parameters, modulation period, and modulation amplitude, and the underlying
linear heating rate for the specific sample under investigation, is critical in the
generation of reliable data and the correct analysis and interpretation of results.
MDSC should be applied with caution for the analysis of melting transitions (due
to the difficulty of maintaining controlled temperature modulation throughout the
Copyright 2003 by Marcel Dekker, Inc. All Rights Reserved.