Starch chemistry and technology (Food Science and Technology International Series)

STARCH: CHEMISTRY AND TECHNOLOGY

Third Edition


Food Science and Technology
International Series
Series Editor
Steve L. Taylor
University of Nebraska – Lincoln, USA

Advisory Board
Ken Buckle
The University of New South Wales, Australia
Mary Ellen Camire
University of Maine, USA
Roger Clemens
University of Southern California, USA
Hildegarde Heymann
University of California – Davis, USA
Robert Hutkins
University of Nebraska – Lincoln, USA
Ron S. Jackson
Quebec, Canada
Huub Lelieveld
Bilthoven, The Netherlands
Daryl B. Lund
University of Wisconsin, USA
Connie Weaver
Purdue University, USA

Ron Wrolstad
Oregon State University, USA

A complete list of books in this series appears at the end of this volume


Starch: Chemistry
and Technology

Third Edition
Edited by
James BeMiller and Roy Whistler

AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK
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Second edition 1984
Third edition 2009
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Contents

Preface to the Third Edition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xvii
List of Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .xix

1

History and Future of Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
I. History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1. Early History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. 1500–1900 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. 1900–Present. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
II. Development of Specialty Starches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1. Waxy Corn Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2. High-amylose Corn Starch. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3. Chemically Modified Starches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4. Other Naturally Modified Corn Starches . . . . . . . . . . . . . . . . . . . . . . . . 6
III. Other Products from Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1. Sweeteners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2. Ethanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3. Polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4. Organic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5. Amino Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
IV. Future of Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1. Two New Starches for Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2. Present American Companies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
V. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

2

Economic Growth and Organization of the US Corn Starch Industry . . . . . . 11
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
II. Extent and Directions of Market Growth . . . . . . . . . . . . . . . . . . . . . . . . . 11
III. High-fructose Syrup Consumption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
IV. Fuel Alcohol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

V. Technical Progress . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
VI. Plant Location . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
VII. Industry Organization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
VIII. Effects of Corn Price Variability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
IX. International Involvement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
X. Future Industry Prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
XI. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20


vi Contents

3

Genetics and Physiology of Starch Development . . . . . . . . . . . . . . . . . . . . . . 23
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
II. Occurrence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
1. General Distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2. Cytosolic Starch Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3. Starch Formed in Plastids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
III. Cellular Developmental Gradients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
IV. Non-mutant Starch Granule Polysaccharide Composition . . . . . . . . . . . . 28
1. Polysaccharide Components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2. Species and Cultivar Effects on Granule Composition . . . . . . . . . . . . 30
3. Developmental Changes in Granule Composition . . . . . . . . . . . . . . . 31
4. Environmental Effects on Granule Composition . . . . . . . . . . . . . . . . 32
V. Non-mutant Starch Granule and Plastid Morphology . . . . . . . . . . . . . . . 33
1. Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2. Species and Cultivar Effects on Granule Morphology . . . . . . . . . . . . 33
3. Developmental Changes in Average Starch Granule Size . . . . . . . . . . 34
4. Formation and Enlargement of Non-mutant Granules . . . . . . . . . . . 34

VI. Polysaccharide Biosynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
1. Enzymology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2. Compartmentation and Regulation of Starch Synthesis and
Degradation in Chloroplasts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3. Compartmentation and Regulation of Starch
Synthesis in Amyloplasts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
VII. Mutant Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
1. Waxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2. Amylose-extender . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
3. Sugary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4. Sugary-2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
5. Dull . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
6. Amylose-extender Waxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
7. Amylose-extender Sugary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
8. Amylose-extender Sugary-2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
9. Amylose-extender Dull . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
10. Dull Sugary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
11. Dull Sugary-2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
12. Dull Waxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
13. Sugary Waxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
14. Sugary-2 Waxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
15. Sugary Sugary-2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
16. Amylose-extender Dull Sugary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
17. Amylose-extender Dull Sugary-2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
18. Amylose-extender Dull Waxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
19. Amylose-extender Sugary Sugary-2 . . . . . . . . . . . . . . . . . . . . . . . . . . 66
20. Amylose-extender Sugary Waxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
21. Amylose-extender Sugary-2 Waxy. . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
22. Dull Sugary Sugary-2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
23. Dull Sugary Waxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67

24. Dull Sugary-2 Waxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68


Contents vii

25. Sugary Sugary-2 Waxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
26. Amylose-extender Dull Sugary Waxy . . . . . . . . . . . . . . . . . . . . . . . . . 68
VIII. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
IX. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4

Biochemistry and Molecular Biology of Starch Biosynthesis . . . . . . . . . . . . . 83
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
II. Starch Synthesis in Plants: Localization . . . . . . . . . . . . . . . . . . . . . . . . . . 84
1. Leaf Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
2. Starch in Storage Tissues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
III. Enzyme-catalyzed Reactions of Starch Synthesis in Plants and Algae
and Glycogen Synthesis in Cyanobacteria . . . . . . . . . . . . . . . . . . . . . . . . . 85
IV. Properties of the Plant 1,4-α-Glucan-Synthesizing Enzymes . . . . . . . . . . . 87
1. ADP-glucose Pyrophosphorylase: Kinetic Properties and
Quaternary Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2. Relationship Between the Small and Large Subunits: Resurrection
of ADPGlc PPase Catalysis in the Large Subunit . . . . . . . . . . . . . . . . 91
3. Phylogenetic Analysis of the Large and Small Subunits . . . . . . . . . . . 95
4. Crystal Structure of Potato Tuber ADPGlc PPase . . . . . . . . . . . . . . . . 95
5. Supporting Data for the Physiological Importance of Regulation
of ADPGlc PPase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
6. Differences in Interaction Between 3PGA and Pi in Different
ADPGlc PPases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
7. Plant ADPGlc PPases can be Activated by Thioredoxin . . . . . . . . . . 107

8. Characterization of ADPGlc PPases from Different Sources . . . . . . . 108
9. Identification of Important Amino Acid Residues Within the
ADPGlc PPases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
10. Starch Synthase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
11. Branching Enzyme . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
12. Other Enzymes Involved in Starch Synthesis . . . . . . . . . . . . . . . . . . . 136
V. Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
VI. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139

5

Structural Features of Starch Granules I . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
II. Granule Architecture. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
1. An Overview of Granule Structure . . . . . . . . . . . . . . . . . . . . . . . . . . 153
2. Molecular Organization of Crystalline Structures . . . . . . . . . . . . . . 153
3. Crystalline Ultrastructural Features of Starch . . . . . . . . . . . . . . . . . 158
4. The Supramolecular Organization of Starch Granules . . . . . . . . . . . 160
III. The Granule Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
1. Starch Granule Surface and Chemistry and Composition . . . . . . . . 168
2. Surface-Specific Chemical Analysis . . . . . . . . . . . . . . . . . . . . . . . . . 169
IV. Granule Surface Imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
1. Granule Imaging by SEM Methods . . . . . . . . . . . . . . . . . . . . . . . . . 170
2. Principles of AFM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
3. Sample Preparation for AFM Imaging of Granular Starch . . . . . . . . 172
4. Surface Detail and Inner Granule Structure Revealed by AFM . . . . . 173
5. Interpretation of AFM Images with Respect to Granule Structure . . 175


viii Contents

V.
VI.
VII.
VIII.
IX.

6. Discussion of Granule Surface Imaging by Scanning Probe
Microscopy (SPM). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
7. Future Prospects of SPM of Starch . . . . . . . . . . . . . . . . . . . . . . . . . . 179
A Hypothesis of Starch Granule Structure: The Blocklets Concept . . . . . 180
Location and State of Amylose Within Granules. . . . . . . . . . . . . . . . . . . 184
Surface Pores and Interior Channels of Starch Granules . . . . . . . . . . . . . 186
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188

6

Structural Features of Starch Granules II . . . . . . . . . . . . . . . . . . . . . . . . . . 193
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
II. General Characteristics of Starch Granules. . . . . . . . . . . . . . . . . . . . . . . 194
1. Granule Shapes, Sizes and Distributions . . . . . . . . . . . . . . . . . . . . . . 194
2. Porous Structures of Starch Granules . . . . . . . . . . . . . . . . . . . . . . . . 195
3. Shapes of Gelatinized Starch Granules . . . . . . . . . . . . . . . . . . . . . . . 200
III. Molecular Compositions of Starch Granules . . . . . . . . . . . . . . . . . . . . . 201
1. Amylopectin and Amylose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
2. Intermediate Material and Phytoglycogen . . . . . . . . . . . . . . . . . . . . . 202
3. Lipids and Phospholipids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
4. Phosphate Monoesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
IV. Structures of Amylose and Amylopectin . . . . . . . . . . . . . . . . . . . . . . . . . 205

1. Chemical Structure of Amylose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
2. Single Helical Structures (V-Complexes) of Amylose . . . . . . . . . . . . . 208
3. Double Helical Structures of Amylose . . . . . . . . . . . . . . . . . . . . . . . . 211
4. Chemical Structure of Amylopectin . . . . . . . . . . . . . . . . . . . . . . . . . . 212
5. Cluster Models of Amylopectin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
6. Effects of Growing Temperature and Kernel Maturity on
Starch Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
V. Locations of Molecular Components in the Granule . . . . . . . . . . . . . . . 225
VI. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227

7

Enzymes and Their Action on Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
II. Amylases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
1. Action of Endo-Acting α-Amylases . . . . . . . . . . . . . . . . . . . . . . . . . . 238
2. Action of Exo-Acting β-Amylases . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
3. Amylases Producing Specific Maltodextrin Products . . . . . . . . . . . . . 246
4. Action of Isoamylases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
5. Archaebacterial Amylases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
6. Action of Cyclomaltodextrin Glucanosyltransferase . . . . . . . . . . . . . 250
III. Relation of Structure with Action of the Enzymes . . . . . . . . . . . . . . . . . . 253
1. Relation of Structure with Action of Endo-Acting α-Amylases. . . . . . 253
2. Structure and Action of Soybean β-Amylase . . . . . . . . . . . . . . . . . . . 257
3. Structure and Action of Glucoamylases . . . . . . . . . . . . . . . . . . . . . . . 257
4. Specific Amino Acids at the Active-Site Involved in Catalysis
and Substrate Binding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
5. Structure and Function of Domains in Amylolytic Enzymes . . . . . . . . 262
IV. Mechanisms for the Enzymatic Hydrolysis of the Glycosidic Bond . . . . . 264
V. Action of Amylases on Insoluble Starch Substrates. . . . . . . . . . . . . . . . . 267

Contents ix

VI.
VII.

VIII.

IX.

1. Action of α-Amylases on Amylose-V Complexes and
Retrograded Amylose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
2. Action of Amylases with Native Starch Granules . . . . . . . . . . . . . . . . 269
Inhibitors of Amylase Action. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
Action of Phosphorylase and Starch Lyase . . . . . . . . . . . . . . . . . . . . . . . 276
1. Plant Phosphorylase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
2. Starch Lyase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
Enzymic Characterization of Starch Molecules . . . . . . . . . . . . . . . . . . . . 278
1. Determination of the Nature of the Branch Linkage in Starch . . . . . . 279
2. Identification and Structure Determination of Slightly
Branched Amyloses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
3. Formation of β-Amylase Limit Dextrins of Amylopectin and
Determination of their Fine Structure . . . . . . . . . . . . . . . . . . . . . . . . 282
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284

8

Structural Transitions and Related Physical Properties of Starch. . . . . . . . . 293
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293

II. Starch Structure, Properties and Physical Methods of Analysis . . . . . . . . 295
1. Ordered and Amorphous Structural Domains (See Also
Chapters 5 and 6) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
2. Physical Properties of Starch in Water . . . . . . . . . . . . . . . . . . . . . . . . 301
III. State and Phase Transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
3. Glass Transitions of Amorphous Structural Domains . . . . . . . . . . . . 311
4. Annealing and Structural Modifications by Heat–Moisture
Treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
5. Melting Transitions of Crystallites in Granular Starch . . . . . . . . . . . . 323
6. Gelation and Retrogradation of Starch and its Polymeric
Components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
7. Phase Transitions and Other Properties of V-Structures . . . . . . . . . . 354
IV. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359

9

Corn and Sorghum Starches: Production . . . . . . . . . . . . . . . . . . . . . . . . . . 373
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 374
II. Structure, Composition and Quality of Grain . . . . . . . . . . . . . . . . . . . . . 375
1. Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
2. Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
3. Grain Quality. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385
III. Wet-milling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
1. Grain Cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
2. Steeping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
3. Milling and Fraction Separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
4. Starch Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421
5. Product Drying, Energy Use and Pollution Control . . . . . . . . . . . . . . 421
6. Automation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
IV. The Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423

1. Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
2. Sweeteners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
3. Ethanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
4. Corn Oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
5. Feed Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 426


x Contents

V. Alternative Fractionation Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . 427
VI. Future Directions in Starch Manufacturing . . . . . . . . . . . . . . . . . . . . . . . 429
1. Continued Expansion into Fermentation Products . . . . . . . . . . . . . . 429
2. Biosolids as Animal Food . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
3. Processing of Specific Hybrids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430
4. New Corn Genotypes and Phenotypes via Biotechnology and
Genetic Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430
5. Segregation of the Corn Starch Industry . . . . . . . . . . . . . . . . . . . . . . 430
VII. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431
10

Wheat Starch: Production, Properties, Modification and Uses . . . . . . . . . . 441
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 442
II. Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 442
III. Industrial Processes for Wheat Starch Production . . . . . . . . . . . . . . . . . 444
1. Conventional Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446
2. Hydrocyclone Process (Dough–Batter) . . . . . . . . . . . . . . . . . . . . . . . 448
3. High-pressure Disintegration Process . . . . . . . . . . . . . . . . . . . . . . . . 450
IV. Properties of Wheat Starch and Wheat Starch Amylose and
Amylopectin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
1. Large Versus Small Granules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 452

2. Fine Structures of Amylose and Amylopectin . . . . . . . . . . . . . . . . . . . 457
3. Partial Waxy and Waxy Wheat Starches . . . . . . . . . . . . . . . . . . . . . . 465
4. High-amylose Wheat Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 470
5. A Unique Combination of Properties . . . . . . . . . . . . . . . . . . . . . . . . 471
V. Modification of Wheat Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
1. Crosslinking. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
2. Substitution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 478
3. Dual Derivatization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479
4. Bleaching, Oxidation and Acid-thinning . . . . . . . . . . . . . . . . . . . . . . 480
VI. Uses of Unmodified and Modified Wheat Starches . . . . . . . . . . . . . . . . 481
1. Role in Baked Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
2. Functionality in Noodles and Pasta . . . . . . . . . . . . . . . . . . . . . . . . . . 485
3. Other Food Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
4. Industrial Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 489
VII. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 491

11

Potato Starch: Production, Modifications and Uses . . . . . . . . . . . . . . . . . . 511
I. History of Potato Processing in The Netherlands . . . . . . . . . . . . . . . . . . 512
II. Starch Production. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
1. World Starch Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
2. Potato Starch Production in Europe . . . . . . . . . . . . . . . . . . . . . . . . . 514
III. Structure and Chemical Composition of the Potato . . . . . . . . . . . . . . . . 515
1. Formation and Morphology of the Tuber . . . . . . . . . . . . . . . . . . . . . 515
2. Anatomy of the Tuber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 516
3. Chemical Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 518
4. Differences Between Commercial Starches . . . . . . . . . . . . . . . . . . . . 519
5. New Development: The All-amylopectin Potato . . . . . . . . . . . . . . . . 521
IV. Potato Starch Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 522

1. Grinding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525


Contents xi

V.

VI.

VII.
VIII.

2. Potato Juice Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
3. Fiber Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
4. Starch Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
5. Starch Refinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 529
6. Sideline Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 530
7. Removal of Water from the Starch . . . . . . . . . . . . . . . . . . . . . . . . . . 532
8. Starch Drying and Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 533
Potato Protein . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 534
1. Environmental Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 534
2. Protein Recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535
3. Properties and Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535
Utilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535
1. Substitution (See Also Chapters 17 and 20) . . . . . . . . . . . . . . . . . . . 535
2. Converted Starches (See Also Chapters 17 and 20) . . . . . . . . . . . . . 536
3. Crosslinked Starches (See Also Chapters 17 and 20). . . . . . . . . . . . . 536
4. The Preference for Potato Starch in Applications . . . . . . . . . . . . . . . 537
Future Aspects of Potato Starch Processing . . . . . . . . . . . . . . . . . . . . . . 538
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 538

12

Tapioca/Cassava Starch: Production and Use . . . . . . . . . . . . . . . . . . . . . . . 541
I. Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 541
II. Processing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 545
III. Tapioca Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 550
IV. Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 555
V. Food Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 556
VI. Industrial Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 563
VII. Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 564
VIII. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 564

13

Rice Starches: Production and Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 569
I. Rice Production and Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 569
1. Rice Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 569
2. Rice Milling and Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 570
II. Uses of Milled Rice and Rice By-products . . . . . . . . . . . . . . . . . . . . . . . . 571
1. Milled Rice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 571
2. By-products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 572
III. Preparation of Rice Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573
1. Traditional Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573
2. Mechanical Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 574
IV. Properties of Rice Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 574
1. General Properties Unique to Rice Starch . . . . . . . . . . . . . . . . . . . . . 574
2. Pasting Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575
V. Factors Affecting Rice Starch Properties . . . . . . . . . . . . . . . . . . . . . . . . . 575
1. Rice Variety: Common Versus Waxy. . . . . . . . . . . . . . . . . . . . . . . . . . 575

2. Protein Content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576
3. Method of Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576
4. Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 577
VI. Rice Starch Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 577
VII. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 578


xii Contents

14

Rye Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
II. Isolation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
1. Industrial . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
2. Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
III. Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
IV. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
V. Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
1. Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
2. Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 583
3. X-Ray Diffraction Patterns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
4. Gelatinization Behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
5. Retrogradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
6. Amylose–Lipid Complex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
7. Swelling Power and Amylose Leaching. . . . . . . . . . . . . . . . . . . . . . . . 584
8. Rheology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585
9. Falling Number . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
VI. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586

15

Oat Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
II. Isolation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
1. Industrial . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 590
2. Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 590
III. Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
IV. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
V. Properties of Oat Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
1. Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
2. Chemical Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 592
3. X-Ray Diffraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 594
4. Gelatinization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 594
5. Retrogradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 595
6. Swelling Power and Amylose Leaching. . . . . . . . . . . . . . . . . . . . . . . . 596
7. Rheological Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 597
VI. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598

16

Barley Starch: Production, Properties, Modification and Uses. . . . . . . . . . . 601
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
II. Barley Grain Structure and Composition . . . . . . . . . . . . . . . . . . . . . . . . 602
III. Barley Starch. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
1. Isolation and Purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
2. Chemical Composition of Barley Starch . . . . . . . . . . . . . . . . . . . . . . 605
3. Granule Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607
4. X-Ray Diffraction and Relative Crystallinity . . . . . . . . . . . . . . . . . . . . 607
5. Gelatinization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607

6. Swelling Factor and Amylose Leaching . . . . . . . . . . . . . . . . . . . . . . . 610
7. Enzyme Susceptibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 612
8. Acid Hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 613
9. Pasting Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 615


Contents xiii

IV.
V.
VI.
VII.

10. Retrogradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 618
11. Freeze–Thaw Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 619
12. Chemical Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 619
13. Physical Modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 621
Resistant Barley Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 621
Production and Uses of Barley Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . 623
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 625
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 625

17

Modification of Starches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629
II. Cationic Starches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 632
1. Dry or Solvent Cationization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633
2. Polycationic Starches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 634
3. Amphoteric Starch or Starch-containing Systems . . . . . . . . . . . . . . 635

4. Cationic Starches with Covalently-reactive Groups . . . . . . . . . . . . . 636
III. Starch Graft Polymers (See Also Chapter 19) . . . . . . . . . . . . . . . . . . . . . 637
IV. Oxidation of Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 638
V. Starch-based Plastics (See Also Chapter 19). . . . . . . . . . . . . . . . . . . . . . 640
VI. Encapsulation/Controlled Release . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642
VII. Physically Modified Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
1. Granular Cold-Water-Swellable (CWS) and Cold-Water-Soluble
Starch (Pregelatinized Granular Starch) . . . . . . . . . . . . . . . . . . . . . . 644
2. Starch Granule Disruption by Mechanical Force . . . . . . . . . . . . . . . 646
VIII. Thermal Treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 646
IX. Enzyme-catalyzed Modifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 647
X. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 648

18

Starch in the Paper Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 657
I. Introduction to the Paper Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 658
II. The Papermaking Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
III. Starch Consumption by the Paper Industry . . . . . . . . . . . . . . . . . . . . . . 662
IV. Starches for Use in Papermaking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663
1. Current Use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663
2. Recent Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665
V. Application Requirements for Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . 666
1. Viscosity Specifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 666
2. Charge Specifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 668
3. Retrogradation Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 669
4. Purity Requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 671
VI. Dispersion of Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 672
1. Delivery to the Paper Mill . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 672
2. Suspension in Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 673

3. Dispersion Under Atmospheric Pressure . . . . . . . . . . . . . . . . . . . . . 674
4. Dispersion Under Elevated Pressure . . . . . . . . . . . . . . . . . . . . . . . . . 674
5. Chemical Conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
6. Enzymic Conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 677
VII. Use of Starch in the Papermaking Furnish . . . . . . . . . . . . . . . . . . . . . . . 681
1. The Wet End of the Paper Machine . . . . . . . . . . . . . . . . . . . . . . . . . 681


xiv Contents

VIII.

IX.

X.

XI.
XII.
XIII.
XIV.

2. Flocculation of Cellulose Fibers and Fines . . . . . . . . . . . . . . . . . . . . . 681
3. Adsorption of Starch on Cellulose and Pigments . . . . . . . . . . . . . . . 682
4. Retention of Pigments and Cellulose Fines . . . . . . . . . . . . . . . . . . . . 683
5. Sheet Bonding by Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 684
6. Wet-end Sizing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685
7. Starch Selection for Wet-end Use . . . . . . . . . . . . . . . . . . . . . . . . . . . 687
Use of Starch for Surface Sizing of Paper . . . . . . . . . . . . . . . . . . . . . . . . 688
1. The Size Press in the Paper Machine . . . . . . . . . . . . . . . . . . . . . . . . . 688
2. The Water Box at the Calender . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 693

3. Spray Application of Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 693
4. Starch Selection for Surface Sizing. . . . . . . . . . . . . . . . . . . . . . . . . . . 693
Use of Starch as a Coating Binder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 695
1. The Coater in the Paper Machine . . . . . . . . . . . . . . . . . . . . . . . . . . . 695
2. Starch Selection for Paper Coating . . . . . . . . . . . . . . . . . . . . . . . . . . 698
Use of Starch as Adhesive in Paper Conversion . . . . . . . . . . . . . . . . . . . . 700
1. Lamination of Paper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 700
2. The Corrugator for Paperboard . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 700
3. Starch Selection for Use in Corrugation and Lamination. . . . . . . . . . 702
Use of Starch in Newer Specialty Papers . . . . . . . . . . . . . . . . . . . . . . . . . 703
Environmental Aspects of Starch Use in the Paper Industry . . . . . . . . . . 703
Starch Analysis in Paper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 705
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 706

19

Starch in Polymer Compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 715
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 715
II. Starch Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 717
III. Granular Starch Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 719
IV. Starch in Rubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 724
V. Starch Graft Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 726
VI. Thermoplastic Starch Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 731
VII. Starch Foams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735
VIII. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 737

20

Starch Use in Foods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 745
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 746

1. First Enhancement of Starch for Foods . . . . . . . . . . . . . . . . . . . . . . . 747
2. Modern Use of Starch in Foods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 747
3. Development of Crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 747
4. Development of Monosubstitution . . . . . . . . . . . . . . . . . . . . . . . . . . 747
5. ‘Instant’ Starches. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 748
6. Improvement of Starch Sources (See Also Chapter 3) . . . . . . . . . . . . 748
II. Functions of Starch in Food Applications . . . . . . . . . . . . . . . . . . . . . . . . 748
1. Starch Structures Relevant to Foods . . . . . . . . . . . . . . . . . . . . . . . . . 749
2. Gelatinization and Pasting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 749
3. Changes During Cooking. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 750
III. Impact of Processing and Storage on Foods
Containing Cooked Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 751
1. Concentration During Cooking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 751
2. Effects of Time and Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . 751


Contents xv

IV.

V.

VI.

VII.

3. Effects of Shear . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 752
4. Comparison of Food Processing Equipment . . . . . . . . . . . . . . . . . . 753
5. Impact of Processing and Storage . . . . . . . . . . . . . . . . . . . . . . . . . . 754
6. Changes that Occur During Cooling, Storage and Distribution . . . . 754

7. Recommended Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 755
Modified Food Starches (See Also Chapter 17) . . . . . . . . . . . . . . . . . . . 756
1. Why Starch is Modified . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 756
2. Derivatizations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 756
3. Conversions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 760
4. Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 761
5. Physical Modifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 762
6. Native Starch Thickeners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 767
Starch Sources (See Also Chapters 9–16) . . . . . . . . . . . . . . . . . . . . . . . . 767
1. Dent Corn . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 768
2. Waxy Corn . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 768
3. High-amylose Corn . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 769
4. Tapioca . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 770
5. Potato . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 770
6. Wheat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 770
7. Sorghum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 771
8. Rice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 771
9. Sago. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 772
10. Arrowroot . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 772
11. Barley . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 772
12. Pea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 772
13. Amaranth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 773
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 773
1. Canned Foods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 774
2. Hot-filled Foods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 775
3. Frozen Foods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 775
4. Salad Dressings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 776
5. Baby Foods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 777
6. Beverage Emulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 777
7. Encapsulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 777

8. Baked Foods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 778
9. Dry Mix Foods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 778
10. Confections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 778
11. Snacks and Breakfast Cereals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 779
12. Meats. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 780
13. Surimi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 781
14. Pet Food . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 781
15. Dairy Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 781
16. Fat Replacers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 782
Interactions with Other Ingredients . . . . . . . . . . . . . . . . . . . . . . . . . . . . 783
1. pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 783
2. Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 783
3. Sugars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 784
4. Fats and Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 784


xvi Contents

5. Proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 785
6. Gums/hydrocolloids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 786
7. Volatiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 786
8. Amylolytic Enzymes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 786
VIII. Resistant Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 787
IX. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 788
21

Sweeteners from Starch: Production, Properties and Uses . . . . . . . . . . . . . 797
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 797
1. History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 797
2. Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 799

3. Regulatory Status. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 800
II. Production Methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 800
1. Maltodextrins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 800
2. Glucose/corn Syrups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 802
3. High-fructose Syrups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 808
4. Crystalline Fructose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 813
5. Crystalline Dextrose and Dextrose Syrups . . . . . . . . . . . . . . . . . . . . 813
6. Oligosaccharide Syrups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 815
III. Composition and Properties of Sweeteners from Starch . . . . . . . . . . . . . 817
1. Carbohydrate Profiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 817
2. Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 818
3. Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 819
4. Browning Reaction and Color . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 821
5. Fermentability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 822
6. Foam Stabilization and Gel Strength . . . . . . . . . . . . . . . . . . . . . . . . 823
7. Freezing Point Depression . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 824
8. Boiling Point Elevation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 824
9. Gelatinization Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 824
10. Humectancy and Hygroscopicity . . . . . . . . . . . . . . . . . . . . . . . . . . . 825
11. Crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 826
12. Sweetness. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 827
13. Selection of Sweeteners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 828
IV. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 829

22

Cyclodextrins: Properties and Applications . . . . . . . . . . . . . . . . . . . . . . . . . 833
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 833
II. Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 835
III. Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 837

IV. Toxicity and Metabolism. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 838
V. Modified Cyclodextrins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 840
1. Hydroxyalkylcyclodextrins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 840
VI. Complex Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 842
VII. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 845
VIII. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 848

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 853


Preface to the Third
Edition

Work towards production of the third edition of Starch: Chemistry and Technology
was begun by Professor Roy L. Whistler and myself, but shortly thereafter Professor
Whistler was unable to continue with the project. I was pleased to be able to see this
edition through to completion.
Many developments have occurred in the world of starch chemistry, genetics, biochemistry, molecular biology and applications since the second edition was published
in 1984. This edition, like the previous two editions, covers the isolation processes,
properties, functionalities and uses of the most commonly used starches, viz., normal
maize/corn, waxy maize, high-amylose maize, cassava (tapioca), potato and wheat
starch, with emphases on those aspects of production, properties and uses that are
unique to each; but not in single chapters. It also covers those starches that are generally available in only limited or potentially limited amounts, viz., rice (including
waxy rice, but not all varieties of rice), sorghum, barley (including waxy barley), oat
and rye starches. Chapters on the latter three starches are new to this edition. Not
included are other starches that may be isolated from plants that are grown in limited
areas and may be localized commercial products. These include amaranth, arrowroot,
banana, canna, kuzu, millet, mung bean, pea (smooth and wrinkled), quinoa, sago,
sweet potato and taro starch, except that some are mentioned in the chapter on starch
use in foods and two are mentioned in the first chapter. Where available, many of

these starches are available as flours, rather than pure starch. There has been an interest in small granule starch that can be obtained from cattail roots, dasheen tubers,
and the seeds of amaranth, canary grass, catchfly, cow cockle, dropwort, pigweed and
quinoa. None of these are covered except as noted above. However, properties and
uses of small granule wheat starch are covered in the chapter on wheat starch.
All chapters/subjects that were also in the previous edition have been updated.
Chapters have been added on the biochemistry and molecular biology of starch biosynthesis, structural transitions and related physical properties of starch, and cyclodextrins. There are two chapters on the structural features of starch granules that
present not only advances in understanding the organization of starch granules, but
also advances in understanding the fine structures of amylose and amylopectin, both
of which are based on techniques that have been developed since 1984.


xviii Preface to the Third Edition

The chapter on corn and sorghum starch production not only thoroughly covers
advances in understanding and in carrying out the wet-milling process, but also alternative corn kernel fractionation techniques, the relationship of starch production to
other products from corn grain and future directions.
The greatly enlarged chapter on wheat starch presents advances in its production,
the differences between large and small granules, the fine structures of wheat starch
amylose and amylopectin, genetic and chemical modification of wheat starch, and its
functionalities and uses, especially in food products.
The past two decades have also seen a considerable enlargement and maturation
of the cassava (tapioca) starch industry that is reflected in another larger chapter,
which also compares the characteristics of tapioca/cassava starch with those of other
starches. The chapter on potato starch has also been considerably updated, especially from a processing standpoint. The latter chapter contains a discussion of allamylopectin potato starch.
Because consumers have become more mindful of what is in their diet, and
because in the European Economic Community chemically-modified starches must
be labeled as such, there has developed an interest in starches that have only been
heated to achieve the process tolerance and short texture of a lightly-crosslinked
starch. Such developments in modifying the properties of starch without chemical
derivatization are discussed in two chapters.

Also greatly enlarged and updated is the thorough chapter on the applications of
starch products in the paper industry.
James N. BeMiller
West Lafayette, Indiana USA
May 2008


List of Contributors

Karin Autio, VTT Biotechnology and Food Research,VTT, Finland (Chapter 14, 15)
Paul M. Baldwin, Centre de Recherches Agro-Alimentaires, INRA, Nantes, France
(Chapter 5)
Sukh D. Bassi, MGP Ingredients Inc., Atchison, Kansas, USA (Chapter 10)
Costas G. Biliaderis, Department of Food Science and Technology, Aristotle
University, Thessaloniki, Greece (Chapter 8)
Charles D. Boyer, Department of Horticulture, Oregon State University, Corvallis,
Oregon (Chapter 3)
William F. Breuninger, National Starch and Chemical Company, Bridgewater, New
Jersey, USA (Chapter 12)
Chung-wai Chiu, National Starch and Chemical Co., Bridgewater, New Jersey
(Chapter 17)
Steven R. Eckhoff, Department of Agricultural Engineering University of Illinois,
Urbana, Illinois, USA (Chapter 9)
Ann-Charlotte Eliasson, Department of Food Technology, Lund University, Lund,
Sweden (Chapter 14, 15)
Paul L. Farris, Department of Agricultural Economics, Purdue University, West
Lafayette, Indiana USA (Chapter 2)
Daniel J. Gallant, Centre de Recherches Agro-Alimentaires, INRA, Nantes, France
(Chapter 5)
Douglas L. Garwood, Golden Harvest Seeds, Stonington, Illinois (Chapter 3)

Hielko E. Grommers, AVEBE U.A., P.O. Box 15, 9640 AA, Veendam, The
Netherlands (Chapter 11)
Allan Hedges, Consultant, Crown Point, Indiana USA (Chapter 22)
Larry Hobbs, (Chapter 21)
Ratnajothi Hoover, Department of Biochemistry, Memorial University of
Newfoundland, St. John’s, Canada (Chapter 16)
Jay-lin Jane, Department of Food Science and Human Nutrition and the Center for
Crops Utilization Research, Iowa State University, Ames, Iowa, USA (Chapter 6)
Gerald D. Lasater, MGP Ingredients Inc., Atchison, Kansas, USA (Chapter 10)
Clodualdo C. Maningat, MGP Ingredients Inc., Atchison, Kansas, USA (Chapter 10)
William R. Mason, Formerly of National Starch and Chemical Co., Bridgewater,
New Jersey, USA (Chapter 20)
Hans W. Maurer, Highland, Maryland 20777 (Chapter 18)


xx List of Contributors

Cheryl R. Mitchell, Creative Research Management, Stockton, California, USA
(Chapter 13)
Serge Pérez, Centre de Recherches sur les Macromolécules Végétales (affiliated with
the Université Joseph Fourier, Grenoble), CNRS, Grenoble, France (Chapter 5)
Kuakoon Piyachomkwan, National Center for Genetic Engineering and
Biotechnology, Pathumthani, Thailand (Chapter 12)
Jack Preiss, Department of Biochemistry and Molecular Biology, Michigan State
University, East Lansing, Michigan, 48824, USA (Chapter 4)
John F. Robyt, Laboratory of Carbohydrate Chemistry and Enzymology, Department
of Biochemistry, Biophysics, and Molecular Biology, Iowa State University,
Ames, Iowa, 50011, USA (Chapter 7)
Deborah Schwartz, Corn Refiners Association, Inc., Washington, D.C. (Chapter 1)
Paul A. Seib, Department of Grain Science and Industry, Kansas State University,

Manhattan, Kansas, USA (Chapter 10)
Jack C. Shannon, Department of Horticulture, The Pennsylvania State University,
University Park, Pennsylvania (Chapter 3)
Daniel Solarek, National Starch and Chemical Co., Bridgewater, New Jersey
(Chapter 17)
Klanarong Sriroth, Department of Biotechnology, Kasetsart University, Bangkok,
Thailand (Chapter 12)
Do A. van der Krogt, AVEBE U.A., P.O. Box 15, 9640 AA, Veendam, The
Netherlands (Chapter 11)
Thava Vasanthan, Department of Agricultural, Food and Nutritional Sciences,
University of Alberta, Edmonton, Canada (Chapter 16)
Stanley A. Watson, Ohio Agricultural Research and Development Center The Ohio
State University, Wooster, Ohio, USA (Chapter 9)
Roy L. Whistler, Whistler Center for Carbohydrate Research, Purdue University,
West Lafayette, Indiana (Chapter 1)
J. L. Willett, Plant Polymer Research, National Center for Agricultural Utilization
Research, Agricultural Research Service, US Department of Agriculture, Peoria,
Illinois, USA (Chapter 19)
Kyungsoo Woo, MGP Ingredients Inc., Atchison, Kansas, USA (Chapter 10)


1

History and
Future of Starch
Deborah Schwartz1 and Roy L. Whistler2
1
2

Corn Refiners Association, Inc., Washington, D.C.

Whistler Center for Carbohydrate Research, Purdue University, West Lafayette, Indiana

I. History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Early History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2. 1500–1900. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3. 1900–Present . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
II. Development of Specialty Starches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Waxy Corn Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2. High-amylose Corn Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3. Chemically Modified Starches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4. Other Naturally Modified Corn Starches . . . . . . . . . . . . . . . . . . . . . . . .
III. Other Products from Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Sweeteners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2. Ethanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3. Polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4. Organic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5. Amino Acids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
IV. Future of Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Two New Starches for Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2. Present American Companies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
V. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1
1
2
4
5
5
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6

6
6
6
7
8
8
8
9
9
9
10

I. History
1. Early History
Humans and their ancestors have always eaten starchy foods derived from seeds,
roots, and tubers. It is fascinating to read the known history of crops and especially
to follow the very early agricultural production of grain crops such as barley, rice,
wheat and corn, with the latter having become the major source of isolated starch.
Trace amounts of rice found in underground excavations along the middle region of
the Yangtze River in Hubei and Hunan provinces have been radioactive carbon dated
to a medium age of 11 5000 by a team of Japanese and Chinese archaeologists.1 This
Starch: Chemistry and Technology, Third Edition
ISBN: 978-0-12-746275-2

Copyright © 2009, Elsevier Inc.
All rights reserved


2 History and Future of Starch

predates the previous earliest known site for domestication of barley in China, indicated as 10 000 years ago.1
Corn (see Chapter 9), the only important cereal crop indigenous to the Americas,
probably originated in Mexico, the oldest record (dating back 7000 years) being
found in Mexico’s valley of Tehuacan.2 By 5000 BC, the teosinte plant must have
interbred with the original corn plant to give the female inflorescence a degree of
specialization that precluded the possibility of natural seed dissemination with the
positive requirement that human activity was required for continuing survival. Corn
apparently spread rapidly throughout the Americas, as far as the regions that are now
Argentina and Canada.
Wheat (see Chapter 10) is the number one food grain consumed by humans, and
its production leads all crops, including rice and corn. Wheat is a cool-season crop,
but it flourishes in many different agroclimate zones. It is believed to have originated
in the fertile crescent of the Middle East, where radiocarbon dating places samples
at, or before, 6700 BCE, with wheat grains existing in the Neolithic site of Jarno,
Northern Iraq.3
The practical use of starch products and, perhaps of starch itself, developed when
Egyptians, in the pre-dynastic period, cemented strips of papyrus together with starch
adhesive made from wheat. Early documents were lost, but Caius Plinius Secundus,
Pliny the Elder, 23–74 AD (who died in the eruption of Vesuvius), described documents made by sizing papyrus with modified wheat starch to produce a smooth
surface. The adhesive was made from fine ground wheat flour boiled with diluted
vinegar. The paste was spread over papyrus strips, which were then beaten with a
mallet. Further strips were lapped over the edges to give a broader sheet. Pliny stated
that the 200-year-old sheets which he observed were still in good condition. Pliny
also described the use of starch to whiten cloth and to powder hair. Chinese paper
documents of about the year 312 are reported to contain starch size.4 At a later date,
Chinese documents were first coated with a high fluidity starch to provide resistance
to ink penetration, then covered with powdered starch to provide weight and thickness. Starches from wheat and barley were common at that time.
A procedure for starch production was given in some detail in a Roman treatise
by Cato in 184 BCE.5 Grain was steeped in water for ten days and then pressed. Fresh
water was added. Mixing and filtration through linen cloth gave a slurry from which

the starch was allowed to settle. It was washed with water and finally dried in the sun.

2. 1500–1900
In the Middle Ages the manufacture of wheat starch became an important industry
in Holland, and Dutch starch was considered to be of high quality. An early form
of starch modification practiced in this period involved the starch being slightly
hydrolyzed by vinegar. At that time, starch found its principal use in the laundry for
stiffening fabrics and was considered a luxury suitable for the wealthy. During the
mid-1500s, starch was introduced into England during the reign of Queen Elizabeth,
who is said to have appointed a special court official for laundry starching. The custom of powdering the hair with starch appears to have become popular in France in


I. History 3

the sixteenth century, and by the end of the eighteenth century, the use of starch for
this purpose was generally practiced.
In the eighteenth century, more economical sources of starch than wheat were
being sought. In 1732, the Sieur de Guife recommended to the French government
that potatoes be used to manufacture starch. The potato starch industry in Germany
dates from 1765 (see Chapter 11).
The nineteenth century witnessed an enormous expansion of the starch industry,
due largely to demands of the textile, color printing and paper industries, and to the
discovery that starch can be readily converted into a gum-like product known as
dextrin. In the early 1800s, gum substitutes from starch were first made. A textile
mill fire in 1821, however, is generally credited with the founding of the British gum
industry. After the blaze was extinguished, one of the workmen noticed that some of
the starch had been turned brown by the heat and dissolved easily in water to produce
a thick, adhesive paste. The roasting of new starch was repeated, and the product was
shown to have useful properties. Commercial dextrins were made in Germany in
1860 by an acid process. An American patent for dextrin manufacture that appeared

in 1867 incorporated roasting of starch after it had been moistened with acid.
The early 1800s also saw development of the basic technology which would lead
to today’s starch-derived sweetener industry. The discovery that starch could be transformed into a sweet substance by heating with dilute acid was made in 1811 by the
Russian chemist G.S.C. Kirchoff, who was trying to develop a substitute for the gum
arabic that was then used as a soluble binder for clay. The first American facility to
produce starch syrups was established in 1831. In 1866, production of D-glucose
(dextrose) from starch was realized. A number of glucose manufacturing plants were
built in Europe in the 1800s. Manufacture of crystalline dextrose began in 1882.
The first American starch plant, a wheat starch production facility, was started
by Gilbert in Utica, New York in 1807. It was converted to a corn starch production facility in 1849. Industrial production of corn starch in the United States had
begun in 1844, when the Wm. Colgate & Co. starch plant in Jersey City, New
Jersey, switched from manufacture of wheat starch to manufacture of corn starch
using a process developed by Thomas Kingsford in 1842, in which crude starch was
extracted from corn kernels using an alkaline steep. In 1848, Kingsford started his
own firm in Oswego, New York. By 1880, this firm had grown to be the largest company of its kind in the world. Other US wheat starch plants began operating in this
period, but within a few years all were converted to corn starch plants.
In 1820, the production of potato starch had begun in Hillsborough County, New
Hampshire. Potato starch use grew rapidly until 1895, at which time 64 factories
were operating. They manufactured 24 million pounds (11 million kg) of starch
annually during the production season, which lasted about three months. Rice starch
manufacture began in the United States in 1815. However, production did not expand
significantly, and the little rice starch used was mainly imported.
By 1880 there were 140 US plants producing corn, wheat, potato and rice starches.
By 1900 the number of American starch facilities had decreased to 80, producing
240 million pounds (110 million kg) per year. Although a number of small plants
continued to be built they could not compete and, in 1890, a consolidation took place


4 History and Future of Starch

to form the National Starch Manufacturing Company of Kentucky, representing 70%
of the corn starch capacity. Although National Starch Manufacturing did not perform
well, in the 1890s a number of glucose manufacturers tried to relieve their problems
through similar consolidations. In 1897, six of the country’s seven glucose factories
were consolidated and became known as the Glucose Sugar Refining Company. In
1899, some of the remaining independent firms formed the United Starch Company.

3. 1900–Present
In 1900, the United Starch Company and the National Starch Manufacturing
Company joined forces to form the National Starch Company of New Jersey. In 1902,
Corn Products Company, representing 80% of the corn starch industry with a daily
grind of 65 000 bushels (1800 tons), was formed by union of the National Starch
Company of New Jersey, the Glucose Sugar Refining Company, the Illinois Sugar
Refining Company, and the Charles Pope Glucose Company. In 1906, Corn Products
Company and the National Starch Company merged to become Corn Products
Refining Company, with a daily grinding capacity of 140 000 bushels (3900 tons).
This was soon reduced to 110 000 bushels (3100 tons), or 74% of the US total. The
Corn Products Refining Company is known today as Corn Products International, Inc.
Many of today’s US starch companies also have their roots in the early 1900s.
In 1906, the Western Glucose Company was incorporated; in 1908, it became the
American Maize-Products Company, which was purchased by Cerestar in 1996, then
Cargill gained complete control of Cerestar in 2002. The Clinton Sugar Refining
Company began as a subsidiary of the National Candy Company in 1906. It underwent a series of ownership and name changes, beginning with the Clinton Corn
Syrup Refining Company. The plant in Clinton, Iowa was acquired by Archer Daniels
Midland Co. in 1982. The A.E. Staley Manufacturing Company was organized in 1906
and began with corn starch production in Decatur, Illinois. In 1903, the J.C. Hubinger
Brothers Company began corn starch production in a factory in Keokuk, Iowa. This
firm was purchased by Roquette in 1991 and became Roquette America, Inc. Douglas
& Company was organized and began corn starch production in a plant in Cedar
Rapids, Iowa in 1903. In 1920, the company was purchased by Penick & Ford, Ltd. It

became Penford Products Company in 1998. A facility built by Piel Brothers Starch
Company was organized in 1903. Its plant in Indianapolis, Indiana became the core
of the starch business of National Starch and Chemical Corporation upon its acquisition by National Adhesives Corporation in 1939 and reorganization as National Starch
Products, Inc. A number of other companies, including Union Starch, Huron Milling
Company, Keever Starch Company, Anheuser-Busch, and Amstar Corporation operated starch facilities during the period from 1902 through the 1970s, but then either
stopped production or sold the facility. A surplus government grain alcohol plant in
Muscatine, Iowa was acquired after World War II by the Grain Processing Company
and was modified to produce commercial starch in addition to ethanol.
Archer Daniels Midland Company and Cargill, Inc. both entered the starch industry through purchase of plants that were originally built by entrepreneurs in Cedar
Rapids, Iowa. The Corn Starch & Syrup Company was acquired by Cargill in 1967