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CHEMICAL MODIFICATION OF STARCH AND PREPARATION OF STARCH-
BASED NANOCOMPOSITES
A Dissertation
Presented to
The Graduate Faculty of The University of Akron
In Partial Fulfillment
of the Requirements for the Degree
Doctor of Philosophy
Lin Song
August, 2010
CHEMICAL MODIFICATION OF STARCH AND PREPARATION OF STARCH-
BASED NANOCOMPOSITES
Lin Song
Dissertation
Approved: Accepted:
Advisor Department Chair

Dr. Chang Dae Han Dr. Sadhan C. Jana
Committee Member Dean of the College

Dr. Mark D. Soucek Dr. Stephen Z.D. Cheng
Committee Member Dean of the Graduate School

Dr. Sadhan C. Jana Dr. George R. Newkome
Committee Member Date

Dr. Li Jia
Committee Member
Dr. Peter L. Rinaldi
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ABSTRACT
A series of chemically modified starches were synthesized in the present study: (1)
a starch modified with an anionic group and benzoyl group; (2) a starch modified with an
anionic group and hexanoyl group; (3) a starch modified with a cationic group and
benzoyl group; and (4) a starch modified with a cationic group and hexanoyl group. The
glass transition temperatures of the modified starches were found to be lower than that of
natural starch. The modified starches synthesized in the present study are found to be
hydrophobic and can biodegrade in composting. Blends of a modified starch and
poly(ethylene-co-vinyl alcohol) (EVOH) were prepared by melt blending. Phase
diagrams of the blends exhibited a lower critical solution temperature. The DSC
thermograms of the blends showed a single glass transition temperature and melting point
depression. The crystallization of EVOH in the blends was interrupted by the hydrogen
bonds formed between the hydroxyl groups in the modified starch and EVOH. The
crystalline structure of EVOH in the blends had an orthorhombic lattice in the quenched
specimen and evolved into a monoclinic lattice when the annealing temperature was
increased. The nanocomposites based on a modified starch and EVOH were prepared.
Natural clay (montmorillnite, MMT) and two commercial organoclays (Cloisite 30B and
Cloisite 15A) were employed to investigate how the functional groups in the modified
starch influence the dispersion characteristics of nanocomposites. Anionically modified
starch was found to be very effective in exfoliating organoclay aggregates due to the
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presence of ionic interaction, as determined by Fourier transmission infrared (FTIR)
spectroscopy, between the anionic group in the modified starch and positively charged N+
in the surfactant residing at the surface of an organoclay. For the nanocomposites based
on a cationically modified starch and EVOH, the preparation methods had a large
influence on the dispersion characteristics of the nanocomposites. The aggregates of
MMT have a very high degree of dispersion characteristics in the nanocomposites
prepared by solution blending but poor dispersion characteristics in the nanocomposites
prepared by melt blending. FTIR spectroscopy has indicated that the ionic interaction
between the cationic group in a modified starch and negatively charged surface of silicate
sheets of MMT could be formed in the nanocomposites prepared by solution blending but
not in the nanocomposites prepared by melt blending. Wide-angle X-ray diffraction
(WAXD) has indicated that the crystalline structure of EVOH in the nanocomposites
containing exfoliated aggregates of organoclay Cloisite 30B takes orthorhombic lattice in
both quenched and annealed specimens, which is different from that of neat EVOH. We
ascribe the difference in the crystalline structure of EVOH in the EVOH-containing
nanocomposites and in neat EVOH to the formation of hydrogen bonds between the
hydroxyl groups in EVOH and the hydroxyl groups in the surfactant residing at the
surface of Cloisite 30B. We have found that an improvement in the tensile properties of
nanocomposites can only be obtained if the nanocomposites have a very high degree of
dispersion of the aggregates of clay, and there is strong attractive interaction between the
clay and the matrix.
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ACKNOWLEDGEMENTS
I would like to express my sincere gratitude to my advisor, Professor Chang Dae
Han, for his advice, patience and support throughout this study. I am proud of having
worked on this dissertation under his guidance.
I would like to extend my gratitude to the committee members, Professors Mark D.
Soucek, Sadhan Jana, Li Jia and Peter L. Rinaldi, for their helpful advices and comments
on the draft of this dissertation.
This dissertation is dedicated to my parents and my wife for their understanding and
love.
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TABLE OF CONTENTS
Page
LIST OF FIGURES………………………………..……………………………….….....ix
LIST OF TABLES…………………………………..…………………………….….…xvi
LIST OF SCHEMES…………………………………………………………………...xvii
CHAPTER
I. INTRODUCTION .………………………………………………………….………....1
II. LITERATURE REVIEW .…………………………………………………….…..…..8
2.1 Introduction to Natural Starch …………………………………….……….…..…8
2.2 Previous Research on Chemical Modification of Starch…………...…………....17
2.3 Thermoplastic Starch (TPS)………………………………………….………..…43
2.4 Previous Research on the Nanocomposites based on Starch………………...…..47
III. EXPERIMENTAL…………...…………………………………………..……..…...51
3.1 Synthesis of Chemically Modified Starch…………………………………….....51
3.2 Preparation of Blends and Nanocomposites based on Modified Starch…….…...54
3.3 Characterization Methods……………………...…………………………….…..55
IV. CHARACTERIZATION OF CHEMICALLY MODIFIED STARCH…….….…...60
4.1 Structure Characterization and Determination of Degree of Substitution

(DS) of Chemically Modified Starch…………………………...……………......60
4.2 Moisture Resistance of Chemically Modified Starch………..…………...……...66
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4.3 Thermal Behavior of Chemically Modified Starch…………….………………..68
4.4 Biodegradability of Chemically Modified Starch…………..……...…………….72
4.5 Concluding Remarks……………………………………………………………..74
V. BLENDS OF MODIFIED STARCH AND EVOH……………………...………......76
5.1 Miscibility of Blends based on Modified Starch and EVOH

Characterized by Phase Diagrams………………………………………………76
5.2 Hydrogen Bonding in Blends based on Modified Starch and EVOH

Characterized by DSC and FTIR…….………………………………….………77
5.3 Crystallization of EVOH in Blends based on Modified Starch

and EVOH…………………………..…………………………………………...89
5.4 Mechanical Properties of Blends based on EVOH and Modified Starch……….93
5.5 Concluding Remarks……………………………………………………..….…..98
VI. NANOCOMPOSITES BASED ON MODIFIED STARCH..…………...………...100
6.1 Introduction………………………………………………………………….....100
6.2 Nanocomposites based on Neat EVOH………………………………….….…103
6.3 Nanocomposites containing Anionically Modified Starch….………….…..….107
6.4 Nanocomposites containing Cationically Modified Starch…...……………….116
6.5 Crystallization and Crystalline Structures of EVOH in Nanocomposites..........133
6.6 Mechanical Properties of Nanocomposites………….………………...……….141
6.7 Concluding Remarks…………………………………………………………...147
VII. CONCLUSIONS AND RECOMMENDATIONS….………………………...…..150
7.1 Conclusions………………………………………………………………….....150
7.2 Recommendations………………………………………………………….…. 153
REFERENCES ………………………………………………………………………...155
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APPENDICES………………………………………………………………………….170
APPENDIX A. 1H-NMR SPECTRA OF CHEMICALLY MODIFIED

STARCH…………………………….……………………………171
APPENDIX B. FTIR SPECTRA OF CHEMICALLY MODIFIED STARCH…...174
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LIST OF FIGURES
Figure Page
1.1 Different types of dispersion of layered silicates in polymeric matrix…………...…..3
2.1 Chemical structures of amylose and amylopectin…………………...…………...…..9
2.2 Single helix structure of amylose molecule……………………………………..…..10
2.3 Structure of branched amylopectin……………………………………………….…11
2.4 Two major types of crystalline structure in the natural starch granules:
A-type and B-type……………………………………………………………….…..13
2.5 Vh-type crystalline structure of starch……………………………………………....13
2.6 X-ray diffraction patterns of A-, B-, and Vh-type of starch……………………...…14
2.7 Schematic representation of the granule architecture of natural starch…………..…15
2.8 Hydrolysis profiles of starch treated by sulfuric acid: (▼) Waxy Maize;
(▽) Potato; (〇) Normal Maize; (□) AE Waxy Maize; and (●) Hylon VII.……...…22
2.9 DSC thermograms of waxy rice starch under acid hydrolysis (the number
next to each curve indicates the duration of hydrolysis in days) ………………...…23
2.10 Thermal stability of amylose esters……………………………………………..…32
2.11 XRD patterns of starch esters……………………………………………………...34
2.12 Crystallization of fatty acid chains within the starch esters……………………..…34
2.13 Water uptakes of starch esters versus time: (■) OCST 1.8; (◆) OCST 2.7; (▲)
DODST 2.7; (▼) OCDST 1.8; and (●) OCDST 2.7..………………….……..…..36
2.14 Stress-strain curves of potato starch with different amounts

of water content (the water contents (wt %) are indicated on the figures)………...44
ix
2.15 X-ray diffraction diagrams of (top) granular waxy maize starch and (bottom)
TPS materials stored at various temperatures and humidity. From bottom
to top: quenched and stored for 2 weeks; stored at 40% relative humidity (RH)
for 2 weeks; stored at 60% RH for 2 weeks; stored at 70% RH for 8 months;
and stored at 90% RH for 2 weeks.……………………………………………..….46
2.16 Effect of Cloisite Na+ on the XRD patterns of TPS nanocomposites: (a) Cloisite
Na+; (b) TPS/Cloisite Na+(97.5/2.5 wt %); (c) TPS/Cloisite Na+(95.0/5.0 wt %);
(d) TPS/Cloisite Na+(90.0/10.0 wt %); and (e) TPS.…………............................…48
2.17 TEM image of TPS nanocomposite containing 5 wt % of MMT…………...……..48
4.1 FTIR spectra of (a) natural starch (NS), (b) starch modified with anionic group
and benzoyl group (AS-B), and (c) starch modified with anionic group and
hexanoyl group (AS-LF).………………………………...…………………..……...61
4.2 FTIR spectra of (a) natural starch (NS), (b) starch modified with cationic group
and benzoyl group (CS-B), and (c) starch modified with cationic group and
hexanoyl group (CS-LF)………………... …………………………………..……...62
4.3 1H-NMR spectra of a starch modified by hexanoyl group……………………….…65
4.4 Moisture absorption of modified starch: (●) NS; (■) AS; (▲) CS; (▼) AS-LF;
(◆) AS-B; (□) CS-LF; and (〇) CS-B….……..…………………...………………..66
4.5 Thermal degradation temperatures of chemically modified starches…………..…...68
4.6 DSC thermograms of (a) AS, (b) AS-LF, and (c) AS-B………………………….…71
4.7 DSC thermograms of (a) CS, (b) CS-B, and (c) CS-LF………………………...…..71
4.8 Weight loss of modified starch during composting: (●) NS; (■) CS-LF;
(▲) LD-PE; (▼) CS-B; (◆) AS-LF; and (□) AS-B……...……………………..…73
5.1 Phase diagrams of the blends of a modified starch and EVOH: (●) (AS-B)/EVOH
blend; (〇) (AS-LF)/EVOH blend; (▼) (CS-B)/EVOH blend; and (▽) (CS-LF)/
EVOH blend………….…….………………..…………...………………………....77
5.2 DSC thermograms of the blends of (AS-B)/EVOH: (a) neat EVOH; (b) blend
of 20/80 (AS-B)/EVOH; (c) blend of 40/60 (AS-B)/EVOH; (d) blend of
70/30 (AS-B)/EVOH; and (e) neat AS-B…………………………….......................79
x
5.3 DSC thermograms of the blends of (AS-LF)/EVOH: (a) neat EVOH; (b) blend
of 20/80 (AS-LF)/EVOH; (c) blend of 40/60 (AS-LF)/EVOH; (d) blend
of 70/30 (AS-LF)/EVOH; and (e) neat AS-LF……………….…………..……..…..79
5.4 DSC thermograms of the blends of (CS-B)/EVOH: (a) neat EVOH; (b) blend
of 20/80 (CS-B)/EVOH; (c) blend of 40/60 (CS-B)/EVOH; (d) blend
of 70/30 (CS-B)/EVOH; and (e) neat CS-B………………….………..………..…..80
5.5 DSC thermograms of the blends of (CS-LF)/EVOH: (a) neat EVOH; (b) blend
of 20/80 (CS-LF)/EVOH; (c) blend of 40/60 (CS-LF)/EVOH; (d) blend
of 70/30 (CS-LF)/EVOH; and (e) neat CS-LF……………………………………...80
5.6 DSC thermograms in the glass transition region for the blends of
(AS-B)/EVOH: (a) neat EVOH; (b) blend of 20/80 (AS-B)/EVOH;
(c) blend of 40/60 (AS-B)/EVOH; (d) blend of 70/30 (AS-B)/EVOH;
and (e) neat AS-B……………………………………………………………………83
(AS-LF)/EVOH: (a) neat EVOH; (b) blend of 20/80 (AS-LF)/EVOH;
(c) blend of 40/60 (AS-LF)/EVOH; (d) blend of 70/30 (AS-LF)/EVOH;
and (e) neat AS-LF………………………………………………………………...…83
(CS-B)/EVOH: (a) neat EVOH; (b) blend of 20/80 (CS-B)/EVOH;
(c) blend of 40/60 (CS-B)/EVOH; (d) blend of 70/30 (CS-B)/EVOH;
and (e) neat CS-B……………………………………………………………..……..84
(CS-LF)/EVOH: (a) neat EVOH; (b) blend of 20/80 (CS-LF)/EVOH;
(c) blend of 40/60 (CS-LF)/EVOH; (d) blend of 70/30 (CS-LF)/EVOH;
and (e) neat CS-LF……………………………………………………………..........84
5.10 FTIR spectra in the hydroxyl group stretching region for: (a) neat EVOH;
(b) neat modified starch AS-B; and (c) blend of 70/30 (AS-B)/EVOH………..….87
(b) blend of 70/30 (AS-LF)/EVOH; and (c) neat modified starch AS-LF…....…...87
(b) blend of 70/30 (CS-B)/EVOH; and (c) neat modified starch CS-B…………....88
(b) blend of 70/30 (CS-LF)/EVOH; and (c) neat modified starch CS-LF………....88
xi
5.14 WAXD patterns of neat EVOH at different annealing temperatures (oC):
(1) 143; (2) 123; (3) 103; (4) 83; and (5) quench. Annealing period was for 3 h,
and the specimen was quenched by liquid nitrogen………………………………..90
5.15 WAXD patterns for a 70/30 (AS-B)/EVOH blend at different

annealing temperatures (oC): (1) 145; (2) 125; (3) 105; and (4) quench……...…..91
5.16 WAXD patterns for a 70/30 (AS-LF)/EVOH blend at different

annealing temperatures (oC): (1) 130; (2) 110; (3) 90; (4) 70; and (5) quench.…...91
5.17 WAXD patterns for a 70/30 (CS-B)/EVOH blend at different

annealing temperatures (oC): (1)143; (2)123; (3)103; and (4) quench……..……...92
5.18 WAXD patterns for a 70/30 (CS-LF)/EVOH blend at different

annealing temperatures (oC): (1) 132; (2) 112; (3) 92; (4) 72; and (5) quench..…..92
5.19 Tensile properties of (AS-B)/EVOH blends: (a) tensile strength;

(b) Young’s modulus; and (c) elongation at break.…………………...……….…..94
5.20 Tensile properties of (AS-LF)/EVOH blends: (a) tensile strength;

(b) Young’s modulus; and (c) elongation at break……………………...….……...95
5.21 Tensile properties of (CS-B)/EVOH blends: (a) tensile strength;

(b) Young’s modulus; and (c) elongation at break…………………….…………..96
5.22 Tensile properties of (CS-LF)/EVOH blends: (a) tensile strength;

(b) Young’s modulus; and (c) elongation at break…………………….………..…97
6.1 XRD patterns for: (a) Cloisite 15A; (b) MMT; and (c) Cloisite 30B……………...104
6.2 XRD patterns for: (a) EVOH/Cloisite 15A nanocomposite; (b) EVOH/
Cloisite 30B nanocomposite; and (c) EVOH/MMT nanocomposite……….……...105
6.3 TEM images for: (a) EVOH/MMT nanocomposite; (b) EVOH/Cloisite 15A
nanocomposite; and (c) EVOH/Cloisite 30B nanocomposite, in which the
dark areas represent the clay, and the grey/white areas represent
the polymer matrix………………………………………………………………....106
6.4 XRD patterns for: (a) (AS-B)/EVOH/Cloisite 15A nanocomposite;

(b) (AS-B)/EVOH/Cloisite 30B nanocomposite; and (c) (AS-B)/EVOH/MMT
nanocomposite………………………………………………………………….….107
6.5 TEM images for: (a) AS-B/EVOH/Cloisite 30B nanocomposite;

(b) (AS-B)/EVOH/Cloisite 15A nanocomposite; and (c) (AS-B)/EVOH/MMT
nanocomposite………………………………………………………………….….108
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6.6 FTIR spectra for: (a) (AS-B)/EVOH blend; (b) (AS-B)/EVOH/Cloisite 30B
nanocomposite; (c) (AS-B)/EVOH/Cloisite 15A nanocomposite;
and (d) (AS-B)/EVOH/MMT nanocomposite…….…………………………….....109
6.7 Carboxylate group stretching region for FTIR spectra shown in Figure 6.6
for: (a) (AS-B)/EVOH blend; (b) (AS-B)/EVOH/Cloisite 30B nanocomposite;
(c) (AS-B)/EVOH/Cloisite 15A; and (d) (AS-B)/EVOH/MMT nanocomposite.....111
6.8 XRD patterns for: (1) (AS-LF)/EVOH/Cloisite 15A nanocomposite;

(2) (AS-LF)/EVOH/MMT nanocomposite; and (3) (AS-LF)/EVOH/Cloisite 30B
nanocomposite……………………………………………………………………..112
6.9 TEM images for: (a) (AS-LF)/EVOH/Cloisite 30B nanocomposite;

(b) (AS-LF)/EVOH/Cloisite 15A nanocomposite; and (c) (AS-LF)/EVOH/MMT
nanocomposite……………………………………………………………………..113
6.10 FTIR spectra at carboxyl group stretching region for: (a) (AS-LF)/EVOH blend;
(b) (AS-LF)/EVOH/Cloisite 30B nanocomposite; (c) (AS-LF)/EVOH/
Cloisite 15A; and (d) (AS-LF)/EVOH/MMT nanocomposite……………………115
6.11 XRD patterns for: (a) (CS-B)/EVOH/MMT nanocomposite; (b) (CS-B)/EVOH/

Cloisite 30B nanocomposite; and (c) (CS-B)/EVOH/Cloisite 15A
nanocomposite. The nanocomposites were prepared by melt blending…………116
6.12 TEM images for: (a) CS-B/EVOH/Cloisite 15A nanocomposite; (b) CS-B/
EVOH/Cloisite 30B nanocomposite; and (c) CS-B/EVOH/MMT
nanocomposite. The nanocomposites were prepared by melt blending……........117
6.13 XRD patterns for: (a) (CS-LF)/EVOH/MMT nanocomposite; (b) (CS-LF)/

EVOH/Cloisite 30B nanocomposite; and (c) (CS-LF)/EVOH/Cloisite 15A
nanocomposite. The nanocomposites were prepared by melt blending………....118
6.14 TEM images for: (a) (CS-LF)/EVOH/Cloisite 15A nanocomposite; (b) (CS-LF)/
EVOH/Cloisite 30B nanocomposite; and (c) (CS-LF)/EVOH/MMT
nanocomposite. The nanocomposites were prepared by melt blending…………119
6.15 XRD patterns for: (a) (CS-B)/Cloisite 30B nanocomposite; (b) (CS-B)/MMT
nanocomposite; and (c) (CS-B)/Cloisite 15A nanocomposites. The
nanocomposites were prepared by solution blending……..……………………...120
6.16 TEM images for: (a) (CS-B)/Cloisite 30B nanocomposite; (b) (CS-B)/MMT
nanocomposite; and (c) (CS-B)/Cloisite 15A nanocomposite. The
nanocomposites were prepared by solution blending……………..……………...121
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6.17 XRD patterns for: (a) (CS-LF)/Cloisite 30B nanocomposite; (b) (CS-LF)/MMT
nanocomposite; and (c) (CS-LF)/Cloisite 15A nanocomposite. The
nanocomposites were prepared by solution blending……………………..……...122
6.18 TEM images for: (a) (CS-LF)/Cloisite 30B nanocomposite; (b) (CS-LF)/MMT
nanocomposite; and (c) (CS-LF)/Cloisite 15A nanocomposite. The
nanocomposites were prepared by solution blending…..……………….……..…122
6.19 FTIR spectra in the C-N+ stretching mode region of nanocomposites based on
cationically modified starch prepared by solution blending: (a) neat CS-B;
(b) (CS-B)/MMT nanocomposite; (c) (CS-B)/Cloisite 15A nanocomposite;
and (d) (CS-B)/Cloisite 30B nanocomposite…………………………..……...….124
6.20 FTIR spectrum in the C-N+ stretching mode region of nanocomposites

based on cationically modified starch prepared by melt blending:
(a) (CS-B)/EVOH blend; (b) (CS-B)/EVOH/Cloisite 15A nanocomposite;
(c) (CS-B)/EVOH/Cloisite 30B nanocomposite; and (d) (CS-B)/EVOH/MMT
nanocomposite. ………………………………………………………………......127
6.21 Structure of MMT…………………………………………………………….…..128
6.22 Structure of MMT: (a) side view of layers in MMT; (b) top view
of tetrahedral layers of MMT; (c) the ditrigonal cavity formed among 6
oxygen atoms in tetrahedral layers of MMT; and (d) coordination polyhedron
formed by ditrigonal cavities of two consecutive layers of oxygen atoms.
In (b), (c) and (d), only oxygen atoms are shown as black spots………………....130
6.23 Schematic of silicates layer in MMT with exchangeable cations:

(a) top view and (b) side view…………………………………………………….131
6.24 Schematic of electrolytic dissociation of ditrigonal cavity and the cations

on the surface of silicates in MMT…………………………………………….…132
6.25 DSC thermograms for: (a) AS-B/EVOH/Cloisite 15A nanocomposite;

(b) (AS-B)/EVOH/Cloisite 30B nanocomposite; (c) (AS-B)/EVOH/MMT
nanocomposite; (d) blend of (AS-B)/EVOH; (e) (AS-B)/Cloisite 30B
nanocomposite; (f) (AS-B)/Cloisite 15A nanocomposite; and (g) neat AS-B..….134
6.26 WAXD patterns for (AS-B)/EVOH/Cloisite 15A nanocomposite at different

annealing temperatures (oC): (1) 153; (2) 133; (3) 113; and (4) quench.…….…..137
6.27 WAXD patterns for (AS-B)/EVOH/Cloisite 30B nanocomposite at different

annealing temperatures (oC): (1) 151; (2) 131; (3) 111; and (4) quench………....137
xiv
6.28 WAXD patterns for (AS-B)/EVOH/MMT nanocomposite at different
annealing temperatures (oC): (1) 146; (2) 126; (3) 106; and (4) quench…………138
6.29 WAXD patterns for (CS-B)/EVOH/Cloisite 15A nanocomposite at different

annealing temperatures (oC): (1) 143; (2) 123; (3) 103; and (4) quench…………139
6.30 WAXD patterns for (CS-B)/EVOH/Cloisite 30B nanocomposite at different

annealing temperatures (oC): (1) 144; (2) 124; (3) 104; and (4) quench….…...…140
6.31 WAXD patterns for (CS-B)/EVOH/MMT nanocomposite at different

annealing temperatures (oC): (1) 144; (2) 124; (3) 104; and (4) quench…….…...140
6.32 Tensile properties of the nanocomposites based on AS-B and EVOH:

(a) tensile strength; (b) Young’s modulus; and (c) elongation at break.
(●) (AS-B)/EVOH blend; (□) (AS-B)/EVOH/Cloisite 30B nanocomposite;
(△) (AS-B)/EVOH/Cloisite 15A nanocomposite; and (▽) (AS-B)/
EVOH/MMT nanocomposite..…………………..………………………………..142
6.33 Tensile properties of the nanocomposites based on AS-LF and EVOH:

(●) (AS-LF)/EVOH blend; (□) (AS-LF)/EVOH/Cloisite 30B nanocomposite;
(△) (AS-LF)/EVOH/Cloisite 15A nanocomposite; and (▽) (AS-LF)/
EVOH/MMT nanocomposite…....………………………………………………..143
6.34 Tensile properties of the nanocomposites based on CS-B and EVOH:

(●) (CS-B)/EVOH blend; (□) (CS-B)/EVOH/Cloisite 30B nanocomposite;
(△) (CS-B)/EVOH/Cloisite 15A nanocomposite; and (▽) (CS-B)/
EVOH/MMT nanocomposite..................................................................................144
6.35 Tensile properties of the nanocomposites based on CS-LF and EVOH:

(●) (CS-LF)/EVOH blend; (□) (CS-LF)/EVOH/Cloisite 30B nanocomposite;
(△) (CS-LF)/EVOH/Cloisite 15A nanocomposite; and (▽) (CS-LF)/
EVOH/MMT nanocomposite..................................................................................145
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LIST OF TABLES
Table Page
1.1 Bond energy and relative strength of different intermolecular forces …………....….5
2.1 The transition temperatures of starch esters…………...………………..………...…30
2.2 The tensile properties of starch esters………………………………………….....…33
2.3 XRD results of TPS/clay nanocomposites…………………..………….……..….…49
2.4 Tensile properties of TPS/Cloisite 30B and TPS/MMT nanocomposites……......…50
4.1 Peak assignments in the FTIR spectra of the chemically modified starches…….….63
4.2 Degree of substitution of chemically modified starches……………………….…....66
5.1 Melting points and the degree of crystallinity of the blends of EVOH and
a modified starch……………………………………………………………..…...…81
5.2 Glass transition temperatures of EVOH/modified starch blends……………….…...85
6.1 The changes in the thermal properties of nanocomposites….………………….….135
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LIST OF SCHEMES
Scheme Page
2.1 Chemical structure of amylopectin and amylose……………………...…..……..….18
2.2 Proton-catalyzed hydrolysis of starch……………………………………………….21
2.3 Alkaline degradation of starch……………………………………………………....25
2.4 Nitration of starch………………………………………………………………...…27
2.5 Acrylation by carboxylic acid chloride…………………………………………...…30
2.6 Alkylation of starch having various side chains………………………………….....37
2.7 Reaction between starch and ethylene oxide or propylene oxide………………...…39
2.8 Quaternary ammonium starch ester……………………………………….….……..41
2.9 Iminoalkyl starch ether…………………………………………………………...…41
2.10 Aminoethylated starch ether……………………………………………...…….….42
2.11 Tertiary aminoalkyl starch ether…………………………………………..…….…42
6.1 Chemical structures of the modified starches……………………...………........…102
6.2 Chemical structures of the surfactant MT2EtOH residing at the surface of

Cloisite 30B and the surfactant 2M2HT residing at the surface of Cloisite 15A ....103
xvii
CHAPTER I
INTRODUCTION
Increasing interest has been cast upon the research of biopolymers because of the
environmental pressure of using lesser amounts of synthetic petroleum-based polymers.
Most petroleum-based polymeric products are not biodegradable. It usually takes several
decades, even centuries, for nature to decompose these polymeric materials. Much
energy and effort spent on the landfill of polymeric wastes could be saved by using
biodegradable polymer products. Besides environmental pressure, exhausting petroleum
resources also drive the researchers to look for alternative resources for polymer
materials. Biopolymeric products manufactured from natural resources, such as starch
and cellulose, can offer the polymer industry inexhaustible and green resources. Natural
starch, as one of the most abundant natural resources for polymer materials, is
inexpensive and biodegradable. With necessary modification and processing, starch can
be used as ideal “green” polymer material that comes from nature and readily goes to
nature. Judicious chemical modifications can be made on starch because of its abundant
hydroxyl groups.
Research showed that all natural starches have granular structure containing
semicrystalline lamellae.1 Both the glass transition temperature and the melting
temperature of pure, dry starch are higher than its thermal decomposition temperature.
Thus, the starch can only be processed as thermoplastic materials in the presence of
1
plasticizers and under the action of heat and shear. Many low-molecular-weight
materials have been used as plasticizers, such as water, glycerol, sorbitol, amine, etc. to
produce thermoplastic starch (TPS).
Water, among all the plasticizers, is the most effective. However, TPS containing
low-molecular-weight plasticizers has inevitable shortcomings. The abundant hydroxyl
groups on the molecules render the starch hydrophilic. The low moisture resistance of
starch limits its use for thermoplastic processing. Additionally, the content of plasticizers,
such as water, in the starch continuously changes because of the plasticizer’s migration,
evaporation, and the starch’s moisture absorption. The physical and mechanical
properties of starch are very sensitive to the content of plasticizers.
Chemical modification is an alternative approach to making starch thermoplastic.
Side chains can be introduced into the starch molecules through chemical reactions
between the hydroxyl groups and functional groups. The side chains interrupt the
hydrogen bonds between the hydroxyl groups of starch and destroy the granular
semicrystalline structure of natural starch. The mobility of starch molecules is enhanced
so that the glass transition temperature and the melting temperature can be lowered.
Furthermore, the decreasing number of available hydroxyl groups and the introduction of
hydrophobic functional groups make the starch hydrophobic.
When a thermoplastic polymer is mixed with layered silicates, the state of
dispersion of aggregation of layered silicates in nanocomposites is schematically shown
in Figure 1.1.
2
Figure 1.1. Different types of dispersion of layered silicates in polymeric matrix.
In the past two decades, the preparation of polymer-based nanocomposites, using
nanoclay, has been a very active research area.2 For the majority of industrial
applications, the ultimate goal for the preparation of nanocomposites is to achieve
exfoliation of the aggregates of layered silicates. The layered silicates consist of platelets
of approximately 1 nm thick and a large aspect ratio (about 1000). From the point of
view of obtaining enhanced physical and mechanical properties of nanocomposites, large
surface areas of exfoliated nanocomposites are highly desirable. Obviously, exfoliated
layered silicates in a polymeric matrix will enhance the available surface areas. Thus,
exfoliation is preferred to intercalation.
It is known that the layered silicates of natural clay are hydrophilic3,4 and do not
have any chemical affinity with hydrophobic synthetic polymers. This is the reason why
so much effort has been placed on providing organophilic surfaces of layered silicates
through chemical modification. The chemical affinity between a surfactant residing at
the surface of an organoclay and the polymeric matrix can give rise to highly dispersed
3
(exfoliated) organoclay nanocomposites. The extent of dispersion of the aggregates of
layered silicates in a polymeric matrix is usually determined by: (1) the chemical
structure of a surfactant residing at the surface of layered silicates; (2) the chemical
structure and the architecture of polymer matrix; (3) the molecular weight of polymer
matrix; (4) the extent of functionality in polymer matrix; (5) the location(s) of the
functionalization; and (6) the gallery distance of layered silicates. Such factors affecting
the dispersion of the aggregates of layered silicates in a polymer are determined by the
nature of chemical interaction between the surface of the layered silicates and polymer.
The preparation of starch-based nanocomposites using montmorillonite (MMT) or
organoclay began several years ago.5,6 It was assumed that the hydrophilic starch would
be compatible with hydrophilic MMT. However, so far researches have only observed a
rather poor dispersion of the aggregates of MMT or organoclay in starch, as determined
by X-ray diffraction (XRD) and/or transmission electron microscopy (TEM). The details
of this research will be discussed in the next chapter. The reasons for the poor dispersion
of aggregates of clay in starch lie in the fact that the assumed attractive interaction
between starch and clay is very weak, and the mobility of amylose and amylopectin
molecules in starch is very low, owing to very high molecular weights and intense
hydrogen bonds, making them difficult to approach the gallery of the layered silicates.
Strong attractive interaction between the layered silicates and the polymer matrix
must be provided in order to achieve a high degree of dispersion (exfoliation) of
aggregates of clay in nanocomposites. In this regard, strong intermolecular forces must
be introduced. Some well-known specific interactions include ionic interactions, ion-
dipole interactions, hydrogen bonding, and dipole-dipole interactions. Table 1.1 gives a
4
summary of bond energy and the relative strength of such intermolecular forces. It can
be concluded that ionic interaction provides the strongest intermolecular forces.
Table 1.1. Bond energy and relative strength of different intermolecular forces7
Type of interaction Bond energy (kJ/mol) Relative strength

Ionic attraction 850-1700 1000
Ion-dipole interaction 500-700 600
Hydrogen bonding 50-170 100
Dipole-dipole interaction 2-8 10
van der Waals interaction less than 1 1
Once a strong interaction, such as ionic interaction, is introduced between starch
and clay, a high degree of dispersion (exfoliation) of aggregates of clay can be expected.
On the other hand, the substitution of hydroxyl groups by other functional groups can
also effectively enhance the mobility of starch molecular chains.
A biodegradable polymeric product based on modified starch, having comparable
physical and mechanical properties, can potentially replace the synthetic petroleum-based
polymeric materials, such as low-density polyethylene (LDPE), which is widely used in
the current market in such applications as grocery bags, garbage bags, baby diapers, and
food packaging materials. The present research was to prepare polymer blends and
nanocomposites based on chemically modified starch. Through our research, we can find
a way of making use of natural starch as thermoplastic polymer materials. Moreover,
from a fundamental point of view, the research of blends and nanocomposites based on
modified starch is still a new field. Few previous researchers have ever done such a
study, and there was no good dispersion of nanoclay (intercalation at best) ever reported.
5
In the first part of this dissertation, we present the synthesis of modified starches
having different functional groups, such as acetate sodium, trimethylammonium chloride,
hexanoyl group, and benzoyl group. The role of hexanoyl group and benzoyl group on
the starch is to lower the number of hydroxyl group so that the hydrogen bonds present in
starch can be destroyed. Then the mobility of starch molecules is enhanced, and the glass
transition temperature is lowered. Furthermore, the hydrophobic functional group can
make a chemically modified starch hydrophobic. The role of sodium acetate and
trimethylammonium chloride is to introduce ionic groups into the starch molecules. The
ionic group in starch molecules can form ionic interaction with the aggregates of
nanoclay so that a high degree of dispersion of silicate sheets can be obtained in
nanocomposites.
In the second part of this dissertation, we present experimental results for the
blends of modified starch and poly(ethylene-co-vinyl alcohol) (EVOH). The miscibility
between a modified starch and EVOH was investigated. Miscible blends of a modified
starch and EVOH were obtained at specific compositions. The FTIR spectra show the
presence of the hydrogen bonds between a modified starch and EVOH. We ascribed the
hydrogen bonds between modified starch and EVOH to the reason of high miscibility in
blends. In addition, the crystallization and crystalline structure of EVOH in the blends
with the interference of hydrogen bonds were investigated.
In the third part of this dissertation, we present the dispersion characteristics of the
nanocomposites based on miscible blends of a modified starch and EVOH. We
investigated the dispersion characteristics of the nanocomposites, using X-ray diffraction
(XRD) and transmission electron microscopy (TEM). Natural clay (MMT) and
6
organoclays (Cloisite 30B and Cloisite 15A) that were treated by surfactants were
employed in the present study. We also took effort to find out how the degree of
dispersion of clay aggregates depends on the functional groups in a modified starch
molecules and the surfactant residing at the surface of organoclay.
In the fourth part of this dissertation, we present the crystallization and crystalline
structure of EVOH in the nanocomposites prepared. We found that the degree of
dispersion of clay aggregates and the surfactant residing at the surface of clay have a
profound influence on the crystallization and crystalline structure of EVOH. The tensile
properties were investigated, including tensile strength, Young’s modulus, and elongation
at break, of miscible blends of a modified starch and EVOH, and nanocomposites based
on such blends.
7
CHAPTER II
LITERATURE REVIEW
2.1 Introduction to Natural Starch
Starch is a carbohydrate material that can be hydrolyzed into small molecules by
specific enzymes during animal metastasis, generating biological energy for animals.
Many plants, in their fruits, seeds, tubers or rhizomes, grow with starch. Potato, corn,
wheat and rice are major resources for production of starch worldwide.
2.1.1 Compositions of Natural Starch
Starch contains two major components: one is amylose, which is a linear polymer,
and the other is amylopectin, which is a highly branched polymer. The repeat units in
both amylose and amylopectin are identical (so-called α-D-glucosyl residues) but
connected in different ways, as given in Figure 2.1. Most starch contain 20―30 wt % of
amylose, although some waxy starches contain very little amylose.
In amylose, α-D-glucosyl residues are linked by an α[1→4] bond. Typically, the
molecular weights of extracted amylose are in the order of 105―106 g/mol.8 Amylose
generally is recognized as linear macromolecule. However, it has been reported that
there is a slight degree of branching (9―20 branch points per molecule) in amylose from
various botanical sources.9 The length of side chains ranges from 4 to over 100 repeat
8
OH
OH O
O OH
OH
O HO OH
OH
O O OH
OH O OH OH OH
OH
acetal OH 6
O O O 5 O O
HO 4 1 OH
O O O O
3
2
HO OH HO OH HO OH HO OH HO OH
anomeric carbon
amylopectin n
OH OH OH
6
O 5 O O hemiacetal
HO 4 1 OH
O O
3
2
HO OH HO OH HO OH
amylose
Figure 2.1. Chemical structures of amylose and amylopectin.
units.9,10 There is no effective way of separating the branched amylose from the linear
amylose.
Side chains on branched amylose form small clusters rather than a random comb
structure. Note that amylopectin also forms clusters by its branched side chains, which
will be elaborated on later. Branched amyloses still have properties, such as iodine
binding capability, which amylopectin does not have.9 In aqueous solutions, amylose
molecules can form extended chains with a hydrodynamic radius of 7―22 nm.11 In
natural starch, the amylose molecules tend to have a rather stiff left-handed single helical
9
structure or form an even stiffer parallel double left-handed helix.11 The helix consists of
six α-D-glucosyl residues per turn with a pitch of 0.8 nm. Figure 2.2 shows a single helix
structure of amylose molecule.
On each of the glucose residues, hydroxyl groups connecting with carbons on
position 2 and 6 (C2 and C6) point outward of the helix, while the hydroxyl group
connecting with carbon on position 3 (C3) points inward of the helix, which makes the
inner surface of the helix more hydrophobic than the outer surface. Thus, amylose with a
helix structure can hold the hydrocarbon portion of glycerides and fatty acid in its helix
cavity to form a V-helix complex. The distinct capability of amylose to bind with iodine
is also by holding iodine ions in its hydrophobic helix cavity.
Figure 2.2. Single helix structure of amylose molecule.
10
Amylopectin is a highly branched component of starch. The α-D-glucosyl residues
are mainly linked by α[1→4] bonds but with 5－6% of α[1→6] bonds at the branch
points. Its molecular weight ranges 107―109 g/mol. The amylopectin molecular chains
can be classified into three categories by their ways of connecting with each other: the C
chain carries the sole reducing end of the molecule; the A chain (unbranched) is only
linked to the rest of the molecule through its potential reducing end; and the B chains
carry one or more A chains and/or B chains. Figure 2.3 shows a schematic describing
this classification.
Figure 2.3. Structure of branched amylopectin.
In most experiments, the C chain is not distinguished from B chains. According to
their positions in the cluster structure, B chains are further subdivided: B1 is a short chain,
being components of only one cluster while B2, B3, etc. are long chains that span over
two, three, or more clusters, thereby interconnecting them.
11
The branching points on the amylopectin molecules are not randomly distributed
but periodically clustered. The distance between two clusters on the same B chains is 22
α-D-glucosyl residues on average. Most short chains (the average degree of
polymerization ranges from 14 to 18) are organized within clusters, while long chains
(the average degree of polymerization is more than 55) usually span more than one
cluster. The molar ratio of short to long chains, influenced by the source of starch, varies
from 5 in potato starch amylopectin to 8―10 in cereal amylopectin. The distribution of
chain length in amylopectin critically influences the inner assembly structure of starch
granules and the interaction with the water or solvent.
2.1.2 Structures of Natural Starch
As described above, the linear polysaccharide chains tend to have helix structure
either left-handed or right-handed. The left-handed form is energetically preferred to the
right-handed form.11 There are two ways the helical molecule is packed in the crystalline
phases of starch: A-type and B-type, as shown in Figure 2.4.
In A-type crystalline structure, these helices are packed in a monoclinic unit cell (a
= 2.124 nm, b = 1.172 nm, c = 1.069 nm, γ= 123O);11,12 in the B-type structure, the
helices are packed in a hexagonal unit cell (a = b = 1.85 nm, c = 1.04 nm).12 In both
A- and B-type crystals, the helices are packed parallel.
Besides A-type and B-type crystalline structures in natural starches, previous
researchers12 also found Vh-type crystalline structure in starch complex formed between
the single helix of amylose molecules with compounds, such as iodine, dimethyl
12
Figure 2.4. Two major types of crystalline structure in the natural starch granules: A-type
and B-type.13 (Reprinted with permission from Elsevier.)
sulfoxide (DMSO), alcohol, and fatty acid. In such complexes, iodine atoms or the
hydrocarbon part of alcohol or fatty acid are held by the hydrophobic inner surface in the
helix, as given in Figure 2.5. Then these complexes are packed parallel in an
orthorhombic unit cell.
Figure 2.5. Vh-type crystalline structure of starch.13 (Reprinted with permission from
Elsevier.)
13
Figure 2.6 shows the typical X-ray diffraction patterns for the three crystalline
structures described above. In the natural starch source, A-type crystalline is found
mainly in cereal starch, and B-type is in tuber and amylose rich starches.14,15 The Vh-
type crystal is rarely observed in natural starch.16 X-ray diffraction results also showed
that in some natural starch there is a mixture of A-type and B-type crystalline phases,
called C-type, mostly found in legume starches and cereal grown under specific
conditions of temperature and hydration.
In natural starch, polysaccharide chains are packed in granules. Their size varies
1 to 100 μm. The organization of crystalline and amorphous phases in granules can be
observed by acid hydrolysis. Crystalline phase is believed to be more resistant to acid
hydrolysis than amorphous phase. A schematic representation of the granule architecture
is given in Figure 2.7. The layered concentric shell, the so-called “growth ring”, was
observed. These shells, with the thickness of 120－400 nm,17,18 consist of alternating
amorphous and semi-crystalline layers.
Figure 2.6. X-ray diffraction patterns of A-, B-, and Vh-type of starch.13 (Reprinted with
permission from Elsevier.)
14
Figure 2.7. Schematic representation of the granule architecture of natural starch.18
(Reprinted with permission from Elsevier.)
2.1.3 Gelatinization, Glass Transition, and Retrogradation of Starch
Gelatinization of starch is usually known as the disruption of the crystalline
structure and ultimately the destruction of the starch granular structure when heat and
water (or other effective solvents) are applied. In the presence of excessive water
(usually > 90 wt %), starch granules start to swell because the amylose molecules are
preferentially solubilised in the water. Below a characteristic temperature known as
gelatinization temperature, the crystalline region, mainly composed of high molecular
weight and branched amylopectin molecules, still maintains its integrity. Above the
gelatinization temperature, the crystalline region starts to lose its order and swell
irreversibly.19 If approximately treating starch granules as a polymer network, the
swelling of the starch before the occurrence of gelatinization can be considered as a
reversible equilibrium. In this equilibrium, the affinity between the polymer network and
the solvent generates osmotic pressure (favoring the swelling), which is equal to the
restoring force (disfavoring the swelling), from the stiffness of polymer network.
Obviously, enhancing the temperature or choosing the solvent that has a high affinity
15
with starch will increase swelling. Swelling above the gelatinization temperature is
profoundly irreversible.
The glass transition temperature (Tg) of dry starch is experimentally inaccessible,
because its degradation temperature is higher than Tg. The addition of water has a very
strong plasticizing effect, causing a remarkable depression in Tg.20 Since the Tg of starch
is considerably influenced by the water content, the mechanical properties are also
affected by it. Due to the evaporation and migration of water, the water content in starch
keeps changing, causing difficulty in maintaining steady mechanical properties of the
starch materials. Other non-volatile plasticizers have been used. Many studies were
carried out on low molecular-weight compounds, such as glycerol and sorbitol.21-25
Retrogradation is another characteristic behavior of natural starch granules while
interacting with water. If the gelatinized starch/water mixture is cooled to room
temperature, there will be a strong driving force for starch to crystallize. Then water will
normally be driven out of the starch (phase separation). This process, which occurs upon
cooling, is known as retrogradation. Obviously, the thermodynamic force for
crystallization will be different between amylose and amylopectin because of their highly
different conformations of molecular structure. The former has very long molecular
chains, which make the formation of crystalline phase harder than the branched
amylopectin having abundant short linear molecular chains.26 If a concentrated aqueous
amylose solution is cooled to room temperature, a very rapid phase separation will be
observed. The clear solution turns to opaque very fast, indicating the appearance of the
polymer aggregates. The size of the aggregates is larger than the wavelength of the light.
When the concentration of amylose solution reaches to a certain level (greater than 1―2
16
wt %), an elastic gel is observed after a sudden temperature drop. Double helices were
observed in the initial aggregates.27 It was reported that the rate of crystallization of
amylose was very low, as observed by X-ray diffraction.28,29
When a concentrated amylopectin/water mixture was quenched to room
temperature or below, a slow crystallization of amylopectin was observed by X-ray
diffraction.30,31 This crystallization is associated with the development of stiffness of the
material. The crystallinity could reach up to 30%, comparable to that found in the natural
starch granules. It was also reported that the longer the chain of amylopectin and the
more abundance of short chain fraction, the greater tendency the amylopectin will have to
retrograde and crystallize from aqueous solution.30-34
2.2 Previous Research on the Chemical Modification of Starch
Various types of chemical reactions can occur on different sites in the molecular
chains of starch, resulting in different properties and molecular assembly.
2.2.1 Reactive Positions on the Molecular Chains of Starch
The chemical reactivity of starch is controlled by the reactivity of its glucose
residues. Scheme 2.1 shows the molecular structure and reactive sites of amylose and
amylopectin. On every glucose residue, there are six carbons (referred as C1, C2, C3 . . . ,
etc.). Generally, there are two terminal hydroxyl groups at the ends of the molecular
chains at C1 and C4, as shown in Scheme 2.1. In each glucose residue of amylose, there
are two secondary hydroxyl groups at C2 and C3, as well as one primary hydroxyl group
at C6. In amylopectin, each branch point decreases the number of primary hydroxyl
17
groups by one and simultaneously increases the number of secondary hydroxyl groups at
C4 by one.
Scheme 2.1. Chemical structure of amylopectin and amylose.
OH
OH O
O OH
OH
O HO OH
OH
O O OH
OH O OH OH OH
OH
acetal OH 6
O O O 5 O O
HO 4 1 OH
O O O O
3
2
HO OH HO OH HO OH HO OH HO OH
anomeric carbon
amylopectin n
OH OH OH
6
O 5 O O hemiacetal
HO 4 1 OH
O O
3
2
HO OH HO OH HO OH
amylose
All available hydroxyl groups of amylose and amylopectin are capable of being
oxidized and reduced, as well as participating in the formation of hydrogen bonds. These
hydroxyl groups may form salts and participate in the formation of ethers and esters. The
starch esters may be formed with inorganic, as well as organic acids.
18
The macrostructure of starch also has an impact on its reactivity. Inter- and
intramolecular hydrogen bonding decrease the solubility of the material and limit the
accessibility of potential reaction sites to the reagents used.35 Entanglement of amylose
and amylopectin chains may also be a factor. These circumstances do not change the
reactivity of starch in the qualitative sense but may have serious quantitative impact.
Hence, the selection of the reagents and reaction conditions require special consideration.
The granular character of native starch also influences the reactivity of starch.
Depending on the penetrating ability of the reagent, the reaction of starch proceeds either
on the granule surface or in its interior.35,36 Moreover, the capillaries between granules,
together with the polar character of the granule surface, make starch a good, porous
absorbent. Many reagents undergo inclusion in the capillaries, forming starch capillary
complexes.36
Since humans started using starch, not only as a food but also as various applied
materials, chemical modification has been a major way of obtaining desirable properties
and adding special value to the natural starch. We do not intend to cover all types of the
chemical modifications reported. Instead, several major chemical modifications, mainly
involving hydroxyl reaction and acidic/basic hydrolysis, will be described below. It is
interesting to note that some chemical modifications that were mainly used in food
related practices may also be used to obtain thermoplastic materials.
2.2.2 Acidic Hydrolysis of Natural Starch
Because of its polyacetal structure, starch is very sensitive to protonic acids that
readily catalyze the hydrolysis of starch. Even very small amounts of weak organic acids,
19
in the form of complexes within the amylose helix, produce visible decreases in the
viscosity of starch gels.37,38 Potato starch contains some phosphate ester groups as metal
salts. These phosphate esters can be decationized and turned into acids that finally
catalyze the hydrolysis, producing the so-called hydrogenated starch. Although this
acidic group occurs on only one of every 30－200 glucose units, it is sufficient to make
this starch unstable during storage. Slightly hydrolyzed starch has low viscosity and
good gel-forming ability. More extended hydrolysis has been used to produce adhesives.
Finally, oligo- and monosaccharides were achieved with further extended hydrolysis.39
Scheme 2.2 shows the hydrolysis pathway that starts with a fast, reversible
protonation at either the oxygen atoms on the pyranose ring and/or the oxygen atoms of
the glycosidic bonds. This step is followed by the slow breakage of the respective C-O
bond. The resulting carbocations rapidly accept a water molecule from the solution. It
was shown that both mechanisms operate in parallel, and that particular reaction
conditions give priority to one of them.
Acid-catalyzed hydrolysis of starch was reported as a unimolecular process
resembling the hydrolysis of simple glycosides and led to glucoses as a single, acid-stable
product.40 The hydrolysis of starch catalyzed by acid was usually accompanied by
reversion. The primary hydrolysis products could be repolymerized. In addition, both
this repolymerization and decomposition depended on the reaction time, temperature,
concentration, and pH.
Hydrolysis reaction follows the slow penetration of acid into starch granules, which
may differentiate the hydrolyzing ability of various acids. Hydrochloric acid has always
20
Scheme 2.2. Proton-catalyzed hydrolysis of starch.
H
HO O HO O HO O
O H O
H O
O fast O fast O
OH OH OH
H
HO HO HO
H
HO O HO O
HO O
O O
O OH
O OH OH
OH
HO HO
HO
proven to be the most effective catalyst.41 Electron microscopy of acid-hydrolyzed starch
granules indicates that the amorphous regions of granules accept the catalyzing acid
first.42 In contrast, the crystalline regions hydrolyze much more slowly. It is reported
that all starches exhibit a two-stage hydrolysis pattern.40 Figure 2.8 gives the hydrolysis
profiles of various starches treated by sulfuric acid. The two-stage process is evident.
The faster stage corresponds to the hydrolysis of the more amorphous parts of the starch
granule. During the second stage, the crystalline material is slowly degraded. This is
consistent with the observation that hydrolysis increases the crystallinity of the starch
granules.43 There are two hypotheses proposed to account for the slower hydrolysis rate
of the crystalline parts of the starch.44,45 First, the dense packing of starch chains within
the starch crystallites does not readily allow the penetration of protonic cation into the
regions. Second, acid hydrolysis of a glucosidic bond may require a change in
21
Figure 2.8. Hydrolysis profiles of starch treated by sulfuric acid: (▼) Waxy Maize; (▽)
Potato; (〇) Normal Maize; (□) AE Waxy Maize; and (●) Hylon VII.46 (Reprinted with
conformation (from chair to half-chair) of the D-glucose unit, and the crystalline structure
immobilizes the conformation, making this transition sterically difficult. Furthermore,
the differences of the rate and the extent of hydrolysis have been attributed to differences
in granular size, the extent of starch chain interactions (within the amorphous and
crystalline regions of the granule), and starch composition (the extent of phosphorylation,
amylose content, and lipid-complexed amylose chains).
The hydrolysis of starch initially results in the formation of amylodextrin paste that
still develops a strong blue stain with iodine.47 Then it turns into a complex of dextrin
and maltose. The gelatinization temperature and the breadth of the gelatinization
endotherm have been shown to increase on acid hydrolysis as shown in Figure 2.9.30
22
Figure 2.9. DSC thermograms of waxy rice starch under acid hydrolysis (the number
next to each curve indicates the duration of hydrolysis in days).30 (Reprinted with
Since acid hydrolysis preferentially attacks the amorphous regions in the granule, the
crystalline regions are decoupled from and no longer destabilized by the amorphous
parts.18 Consequently, the starch crystallites of the acid-treated starches melt at a higher
temperature, and the transition temperature range is broader.48,49 The studies on normal
and waxy barley starch lintner residues suggested that the higher transition temperature
might be due to longer amylopectin double helices than in the unhydrolyzed amylopectin
molecules, whereas the branch points might reduce the length of the helix.50,51
23
As described above, the hydrolysis of starch resulting from protonic acid mainly
involves the oxygen atoms on the pyranose ring or glycosidic bonds. The acidic
hydrolysis results in more primary hydroxyl groups and short molecular chains. The
three hydroxyl groups on the pyranose are not involved in the acidic hydrolysis. This is
in contrast to the chemical reaction between starch and acryl acids (described later) and is
a very important way to functionalize starch by adding functional group onto starch
molecular chains.
2.2.3 Reactions of Natural Starch Under Basic Conditions
The behavior of starch with base depends on the type of base, its concentration,
either the presence or absence of oxygen, and the temperature and time of the reaction.
The term “degradation” is a better word to describe the reaction of starch under basic
conditions.
Diluent aqueous alkali solution (0.1－0.4 wt %) at room temperature caused the
swelling of starch granules and the liberation of proteins and lipids present in the starch.52
It was reported that starch gelatinization was retarded by hydroxyl anions, especially in
the presence of salts and that the gelatinization temperature increases with anion
concentration.53
Scheme 2.3 shows reaction pathways in the alkaline degradation of starch. Various
carboxylic acids (formic, acetic, glycolic, lactic, 2-hydroxybutanoic, 2-hydroxyl-2-
methylpropanoic, and 2-hydroxypentanoic acids) were isolated from alkali-degraded
starch.54 They constituted 41－46 wt % of the starting material. The alkaline
24
Scheme 2.3. Alkaline degradation of starch.
OH H
O OH H OH
O O
R H H
O R R H
OH O O O
HO
HO OH O HO OH O
OH H OH H
O O
R CH 2 OH CH 2 OH
O
HO O HO O
OH H OH H
Benzylic acid
O O
rearrangement
COO
CH 2 OH CH 2 OH
O O HO
COO
COO
H C H
CH 2 OH
H C OH
CH 2 OH
degradation of starch under anaerobic conditions is a slow process that increases with the
concentration of alkali.52 Part of the starch undergoes degradation with diluted aqueous
alkali, whereas other parts are resistant, even to concentrated alkali solutions. It has been
reported that these proportions of the alkali-resistant part may be changed by treatment of
starch with acids, heat, or by grinding.55 Moreover, viscosity measurements showed that
the rate of alkali degradation was faster during the initial stages.44,55 These findings
suggest that starch undergoes selective degradation and that these reaction sites are
hindered inside the starch matrix. Since the degradation of starch is considered to
25
progress from the reducing end of the macromolecular chains, the reducing-terminal
glucose units, even in branched structures are split off, indicating that, not only amylose
but also amylopectin is alkali labile.
In air, the reaction retains its unimolecular character, but it proceeds faster and is
accelerated by phosphate and acetate ions.56 The degradation just described is further
assisted by oxidation. Starch can also be degraded by treatment with hydrolyzing salts
formed from strong bases and weak acids, i.e., sodium carbonate, sodium
hydrogencarbonate, sodium borate, hydrogenphosphates, and alumina blended with
sodium oxide.57
2.2.4 Esterification
Starch readily forms esters with organic and inorganic reagents because of its
hydroxyl groups on each glucose residue. One, two, or all three hydroxyl groups of the
starch glucose units may be involved in esterification. The selectivity of these groups in
esterification is affected by the reagent, reaction conditions, and the degree of chain
branching in the amylopectin component.36,58 The reactions usually proceed in
suspension. With granular starch, such reactions take place, first on the granular surface.
After the reagents penetrate the granules, the reaction occurs in both the amorphous
region and crystalline region of the granule interiors.
(a) Nitration
The study of nitration of starch initially was inspired by the great success of
cellulose nitrates. The chemical similarity of cellulose and starch motivated the studies
of starch esterified with nitric acid. Scheme 2.4 shows the starch of nitration.
26
Scheme 2.4. Nitration of starch.
NO2
OH O
O O
O -
O O
+ H N
O O O O
OH O
OH O
O 2N NO2
starch nitrate
O
N
OH O
O O
- O
O + H O N O
O O
OH O
OH O N
N
O
O
starch nitrite
Significant differences were reported in the viscosities of solutions of esterified
cellulose and starch having the same degree of nitration.59 Increasing the concentration
of nitric acid and maintaining a low reaction temperature was crucial to achieving a high
degree of esterification and a high overall yield.60 Impurities in native starch, such as
proteins and lipids, should be removed prior to nitration to avoid contamination by their
nitration. This can be achieved by the preliminary treatment of starch with a solution of
1.5－2 wt % aqueous sodium hydroxide.61
Nitration also occurred with a mixture of nitric and phosphoric acid to produce a
material having 13.0% nitrogen content, which means an almost completely trinitrated
starch (fully substituted starch has 14.14% of nitrogen content).62 This method of
nitration inhibits acid-hydrolytic degradation of the starch structure.
27
It was shown that nitration with nitric acid alone gives a methanol-soluble product.
Nitration with mixtures of nitric and sulfuric acids gave products partially soluble in
methanol.63 The insoluble portion consisted of amylopectin nitrates. The highest degree
of esterification occurs when either gaseous or liquid nitric anhydride was used and also
in the presence of sodium fluoride in chloroform, which allows the reaction to proceed at
a temperature close to ambient.
Amylopectin nitrate is more viscous than amylose nitrate.64 Solid esters are pure
white, soluble in concentrated sulfuric acid, and also more hygroscopic than esterified
cellulose. Their stability was high, and their density exceeded that of the cellulose
esters.62,64 Amylose nitrate is more stable than amylopectin nitrate, and the latter is more
stable than starch nitrate. Isolated starch nitrate could also be protected from hydrolysis
by washing the crude isolated product with a solution of 50－90 wt % ethanol or by
washing reacting acids out with a stream of water. Isolated starch nitrate could also be
protected by boiling crude starch nitrate in water under pressure and eventually either by
the addition of sodium carbonate or by boiling in ethanol. Nevertheless, the extent of
acid hydrolysis upon nitration is significant. Starch nitrate is actually an ester of an
oligosaccharide of 6－7 glucose units and even maltose octanitrate.35 The nitrated starch
was mainly used as an explosive when the nitrogen content was higher than 9%.62
(b) Acylation by carboxylic acid chloride
In the acylation of starch, it was seen that anhydrides, carboxylic acid, and
carboxylic acid chloride could all be used to react with hydroxyl groups. However,
previous research showed that the reactivity of carboxylic acid and its anhydride usually
28
are very low.35,65 The reaction has to be catalyzed by mineral acids, such as sulfuric acid
and perchlorate acid, but the results of acylation were influenced by hydrolysis of the
esters in the acidic reaction medium. Thus, some metal oxide or metal hydroxide, for
example MgO or Mg(OH)2, must also be added to control the acidity of the reaction
mixture.63
Carboxylic acid chlorides were more often used in the acylation of starch as its
reactivity is stronger than carboxylic acid. Thus, when starch with higher fatty acid esters
is desired, especially with a high degree of substitution, the acyl chlorides were used.
Scheme 2.5 shows the reaction. Pyridine was proven to be a very effective catalyst in the
acylation starch with acyl chlorides.66,67 The first reason for its effectiveness lies in the
fact that the long pair electron on the nitrogen atom can accelerate the breakage of acetyl
chloride bond. Moreover, pyridine, acting like tertiary amines, is a good acceptor of
hydrochloric acid produced during the esterfication. In some research, esterification was
even conducted using pyridine as a suspension medium without any other solvents.67-69
Other catalysts, such as quioline and triethyamine, were also used. Starches having long-
chain fatty acid esters with various chain lengths have been obtained, ranging from starch
having butanoic acid ester (four carbons on the fatty acid chain) to starch having
octadecanoic acid ester (eighteen carbons on the fatty acid chain).66,67,70,71 The thermal
and mechanical properties of these starch esters were examined. The relationship
between the properties of starch esters and the side-chain length and degree of
substitution was researched. The resulting starch esters are hydrophobic, thermoplastic
materials that can be shaped, handled, and processed with much greater ease than the
native starch.
29
Scheme 2.5. Acrylation by carboxylic acid chloride.
OH
OH
O
O
O O
O Pyridine
+ Cl C(CH 2 ) n CH 3 O
O HO O
HO OH
(CH 2 ) n CH 3
O
Table 2.1 lists transition temperatures of some starch long-chain fatty acid
esters.66,68,72 It is known that the Tg and Tm of dry native starch cannot be determined,
because they lie above the decomposition temperature. The transition temperatures of
starch esters were dramatically lowered through chemical modification. This can be
explained by the plasticization introduced by ester groups. On the other hand,
esterification of long-chain fatty acid reduces the number of hydroxyl groups and
interferes with the hydrogen bonding. The crystalline phase presented in the native starch
was destroyed by the side chains. The mobility of amylose and amylopectin molecules
was enhanced. Previous research showed that the increase of side-chain length has
resulted in a depression of glass transition temperature.67 This behavior can be explained
by the increase of free volume of the polymer resulting from the increasing size of bulky
Table 2.1. The transition temperatures of starch esters66,68,72
Starch esters Tg (oC) Tm (oC)

starch having butanoic acid ester 65 ―
starch having pentanoic acid ester 63 124
starch having hexanoic acid ester 50 91
starch having octanoic acid ester (OCST) − 50/40 ―
starch having dodecanoic acid ester (DODST) − 56/25 ―
30
flexible side-chain groups. It should be noted that some starch esters have two glass
transition temperatures, and this behavior can only be found during the first scan in the
DSC. In the second scan, only one glass transition was observed at a temperature close to
the larger transition observed in the first scan. So far, there is no systematic research or
conclusive explanation on this behavior. A possible suggestion is that these two glass
transition temperatures correspond to two components of starch esters, amylose ester and
amylopectin ester.66 As the unmodified two components in native starch (amylose and
amylopectin are incompatible, located in different granule regions), they remain to be
incompatible after esterification. Since amylopectin has a branched structure, it must
have a higher glass transition temperature than amylose, which applies accordingly to
their esters.
Previous studies also showed that decomposition temperature was increased after
esterification.67,68 Figure 2.10 shows the thermal stability of starch esters.67 This greater
thermal stability of starch ester is due to the reduced amount of the remaining hydroxyl
groups after esterification. The amylose esters have similar results in thermal stability.70
The study also showed that the main mechanism of starch thermal decomposition is the
dehydration among the hydroxyl groups on the starch molecules.73 The internal
plasticization provided by the bulky flexible side groups also profoundly affects the
mechanical properties of starch esters. The starch esters with a high degree of
substitution behave like typical thermoplastic materials, showing tensile strength and
high elongation at break. The side-chain length and the degree of substitution both play
important roles in the tensile strength and elongation at break.
31
Figure 2.10. Thermal stability of amylose esters.67 (Reprinted with permission from
John Wiley & Sons.)
Table 2.2 lists the mechanical properties of some starch esters.66,70,72 First, it is
shown that the tensile strength decreases as DS gets higher, whereas the elongation at
break increases with the DS. On the other hand, the increase of the side chain length
results in lower tensile strength and higher elongation at break once the DS remains
consistent. It seems that the longer side chain provides more intensive plasticization to
the final materials. However, there is a reversal trend on the mechanical properties.
When the side chain length increases to 18 carbons, the starch ester has higher tensile
strength and lower elongation at break than starch esters with shorter side chains (such as
8 carbons and 12 carbons). This behavior must be attributed to the partial crystallization
of 18-carbon side chain. The crystalline phase in the material usually contributes to the
32
Table 2.2. The tensile properties of starch esters66,70,72
Starch esters (DS) Tensile strength Elongation at break

(MPa) (%)
starch having butanoic acid ester (2.7) 15.9 36.7

starch having pentanoic acid ester (2.7) 12.7 20
starch having hexanoic acid ester (2.7) 5.48 74.9
starch having octanoic acid ester (2.7) 0.7 380
starch having octanoic acid ester (1.8) 3.1 9
starch having dodecanoic acid ester (2.7) 0.7 1500
starch having octadecanoic acid (2.7) 1.9 10
starch having octadecanoic acid (1.8) 3.7 9
high tensile strength and low elongation at break. The results of DSC and X-ray
diffraction already proved the presence of the side chain crystalline in starch esters.67,71
A complete loss of native crystallinity after substitution of hydroxyl groups by a fatty
acid chain is observed by XRD as Figure 2.11 shows. The large diffraction peak between
9.9 and 10.5 increases when the length of fatty acid chains grafted on the starch is
increased up to 18 carbons. These two diffraction peaks were attributed to the fatty acid-
amylose complex as shown in Figure 2.11. It is seen that there is an optimum side-chain
length, which can provide effective plasticization and desirable mechanical properties.
Figure 2.12 schematically displays the crystallization of fatty acid groups on the starch.
Sagar et al.66 have reported on the long-chain fatty acid starch esters, and the DSC
thermograms also indicated the presence of some crystallinity. It was also found that the
crystalline structure did not reappear in the second scan during the measurement of DSC.
However, annealing at a temperature above the glass transition temperature and below
the melting point led to the reappearance of endotherms of starch esters.
33
Figure 2.11. XRD patterns of starch esters.71 (Reprinted with permission from
Wiley-VCH.)
Figure 2.12. Crystallization of fatty acid chains within the starch esters.71 (Reprinted
with permission from Wiley-VCH.)
34
Since the long-chain fatty acid groups lead to the loss of the hydrophilic character
of starch, the water uptake of starch esters will reflect the hydrophobicity. Figure 2.13
shows the diagram of water uptake of starch esters versus time.70 The DS is the main
factor affecting the water uptake. It shows that starch esters, such as the octanoated and
the octadecanoated with a degree of substitution 1.8, have significantly higher water
absorption compared to the corresponding esters with a degree of substitution of 2.7.
Even so, the maximum increase does not exceed 4 wt %, indicating essentially
hydrophobic materials. The length of fatty acid groups has a minor effect on the water
uptake. Dodecanoated and octadecanoated starch esters having DS = 2.7 demonstrate a
similar behavior, which is different from that of octanoated esters. The latter has a very
small water absorption, which seems to grow steadily without reaching a plateau as in the
case with esters having DS = 1.8. This behavior could be attributed to the lower chain
length of the ester, which cannot effectively hinder the unreacted hydroxyl groups to
absorb water. Besides being catalyzed by pyridine in organic solvents, such as dioxane
and toluene, the same long side-chain starch esters could be produced in a organic
solvent-absence method.67,68,70 In this method, starch was first treated by formic acid
prior to reacting with long-chain fatty acid chloride. The highly reactive formic acid
reacts with hydroxyl groups on the starch, producing formate starch esters. The initial
reaction decreases the number of hydroxyl groups and interferes with the strong hydrogen
bonding among the starch molecules. The remaining hydroxyl groups in formate starch
ester are more accessible to the fatty acid chloride that was added immediately after the
initial reaction, without interruption. In each of the steps, the reagents formic acid and
fatty acid chloride were in excess. This one-pot process was conducted under a stream of
35
Figure 2.13. Water uptakes of starch esters versus time: (■) OCST 1.8; (◆) OCST 2.7;
(▲) DODST 2.7; (▼) OCDST 1.8; and (●) OCDST 2.7.70 (Reprinted with permission
from John Wiley & Sons.)
nitrogen gas that drew the hydrochloric acid away from the reaction system. The formate
group is inherently unstable and removed at the end of the reaction, giving rise to pure
starch long-chain fatty acid ester. Starch esters can be obtained with minimum
degradation during the reaction. However, compared with those of the catalyzed
esterification, the degree of substitution (DS) of starch esters cannot be higher than 2.
Moreover, the results indicated that the DS of starch ester dramatically diminished with
an increase in the fatty acid chain length, because the longer fatty acid has less
accessibility to the hydroxyl groups in the absence of solvent.
36
2.2.5 Etherification
(a) Alkylation with alkyl and benzyl halides and sulfates
The hydroxyl groups of the glucose residues in starch, exhibiting reactivity typical
for alcohols, could undergo conversion into ethers by various alkylation agents. Methyl
and ethyl starch ethers were produced by using methylating and ethylating agents,
dimethyl sulfate, and diethyl sulfate.74-76 The reactions took place in dimethyl sulfoxide
(DMSO) with the addition of aqueous NaOH. The degree of substitution of the reaction
products could be very high. The infrared spectra of the products had little absorption at
3400－3600 cm−1, indicating that nearly all of the hydroxyl groups had been converted
into ether groups.77
More often, starch ethers with various side chains were produced through
reactions with alkyl halides. Scheme 2.6 shows the reaction of alkylation of starch with
various side chains. Early reports78 showed that starch ethers could be produced by
blending starch with alkyl halide in the presence of such desiccating agents as CaCl2.
Higher alkyl halides react with starch in aqueous alkali, but the use of high pressure is
recommended.63 Research indicated that methylation of starch may retain the granular
Scheme 2.6. Alkylation of starch having various side chains.
OH OH
O O
O A queous N aO H O
+ Cl CH2 R
O O
HO OH HO O
R= H CH3 ,
OH , ,
37
structure of the product, although the alkylation was uniform throughout the granule
interior.79,80 The addition of sodium phosphate inhibits gelatinization of starch granules
and has been used in the preparation of granular methyl starch ether with a degree of
substitution above 2.77
So far, there has been no report regarding alkyl starch ethers as thermoplastics.
This is partly because long-chain alkyl groups can hardly be attached to the starch by
alkyl halide, in contrast to the long-chain fatty acid chloride esterification of starch. The
reactivity of alkyl halide was highly limited by its length.65
Besides the alkyl starch ethers, the benzyl group could also be added onto starch
through the reaction between starches with benzyl chloride.81,82 Presently, benzyl starch
ether is not widely used, but there are possibilities for future use in the industry. The
benzyl group provides hydrophobicity to the products that can be used as molding
powder, resin additive, and detergent component. Moreover, research showed good
miscibility between benzyl starch and certain synthetic polymers, such as poly(vinyl
acetate), polystyrene, polyurethane, etc.83-85 Such polymer composites, copolymerized
or blended, show good tensile strength, high softening temperature, increased flexibility,
and more importantly, biodegradability. Benzyl starch could be a potential choice for
TPS, because the benzene ring could effectively provide hydrophobicity to the materials
and interfere with the hydrogen bonding between hydroxyl groups to mobilize the starch
molecules. The benzene ring could also act as an internal plasticizer, similar to long-
chain fatty acid groups. So far, the reported benzyl starch had only low DS (less than
0.5).81 In the future, benzyl starch having high DS should be synthesized to obtain
thermoplastic characters.
38
(b) Alkylation with epoxide compounds
Etherification of starch by epoxides (also referred to as alkylene oxides) can occur
without the addition of alkali. Alkylene oxides of complicated structures provided novel
opportunities for starch modifications. The asymmetrical epoxide group is very reactive
because of its highly strained three-membered oxide ring with bond angles of 60o.36
Opening of the asymmetrical epoxide ring occurs by attacking at the sterically less
hindered end of epoxide to produce 2-hydroxylalkyl starch ether.86 Scheme 2.7 shows
the reaction between hydroxyl groups on the starch and the expoxides.
Scheme 2.7. Reaction between starch and ethylene oxide or propylene oxide.
OH
O
O
OH O
O HO O
O Aqueous NaOH
+
O or O OH
HO OH O or
OH
O
O
O O
HO
OH
Ethylene oxide could etherify starch in granular form by pressurized hot air
through dried starch containing 10 wt % or less of moisture.58 The reaction rate
increased with temperature and with the concentration of absorbed ethylene oxide.
Hydroxylethylation of starch increases the water-binding capacity when compared with
the untreated starch.87 Hydroxyethyl starch is one of the most frequently used blood
plasma substitutes and is also used in oil drilling. Studies about the substitution pattern
39
of hydroxyethyl starch showed that most of the substituents (above 80%) were located on
the oxygen atom at 2-position (O-2), and the remaining hydroxyethyl groups were found
almost exclusively on the oxygen atom at 6-position (O-6).58,88 Only traces of
etherification at 3-position (O-3) took place.
The reaction of propylene oxide with starch under alkaline conditions is a
nucleophilic substitution, as Scheme 2.7 shows. The hydroxypropyl groups are
predominantly located at O-2 position on the glucose residues. The possible reason for
the higher reactivity of the oxygen atom at 2 position over the other two positions
(oxygen at 6 and 3) is the higher relative acidity of the O-2 due to its proximity to the
anomeric center.89 There are two ways of hydroxypropylation of starch, depending on
the desirable DS. When low DS (lower than 0.25) is desirable, starch is slurried in
aqueous NaOH.90 Propylene oxide is added based on the starch dry weight. The
preparation of hydroxypropyl starch with a high DS is industrially carried out in a
semidry state. Starch is first sprayed with aqueous NaOH until it contains 20% moisture.
Then the alkali starch is stirred in a closed reactor with gaseous propylene oxide of an
excess amount.89
Introduction of hydroxypropyl groups has affected the biodegradability of starch.
Research on the hydroxypropyl starch showed that the substitution of hydroxypropyl
groups decreased the extent of enzymatic hydrolysis of modified starch with increasing
DS.90
40
(c) Cationization
Cationic starches are important industrial derivatives in which starch is given a
positive ion by introducing ammonium, amino, and imino groups. Etherification by
different aminoalkyl agents, such as 2-diethylaminoethyl chloride, 2,3-(epoxypropyl)
trimethylammonuim chloride, (4-chlorobutene-2)-trimethylammonium chloride, etc., is a
major way of producing cationic starches.36 Schemes 2.8－2.11 show their structures
and the reactions with starch.
Scheme 2.8. Quaternary ammonium starch ester.
+ +
OH
H2C CHCH2N(CH3)3 Cl + NaCl
Cl CH2CH CH2N(CH3)3 Cl + NaOH
O
2,3-(epoxypropyl)trimethylammonuim chloride
+ +
H2C CHCH2N(CH3)3 Cl 50 oC
Starch OH + Starch O CH2CHCH2N(CH3)3 Cl
O Aqueous NaOH
OH
Quaternary ammonium starch ether
Scheme 2.9. Iminoalkyl starch ether.
R NH R
OH
Starch OH + N C N Starch O C N
R R
Iminoalkyl starch ether
41
Scheme 2.10. Aminoethylated starch ether.
H2C CH2
Starch OH + N CCl4 and benzene
Starch O CH2CH2NH2
H
Aminoethylated starch ether
Scheme 2.11. Tertiary aminoalkyl starch ether.
+
OH (C2H5)N CH2
ClCH2CH2N(CH2CH3)2 Cl
H 2C
2-diethylaminoethyl chloride
+
(C2H5)N CH2
Starch OH + Cl Starch O CH2CH2N(CH2CH3)2
H 2C
H +
O HCl
Starch CH2CH2N(CH2CH3)2 Starch O CH2CH2N(CH2CH3)2 Cl
Tertiary aminoalkyl starch ether
So far, all of the research on cationic starch is still concentrated on its
gelatinization behavior, pasting properties, and solubility. There are no reports about the
thermal or mechanical properties of cationic starch, except one report about cationic
starch that was used to modify clay as compatibilizer in the production of
nanocomposites (described later). Cationic starches are mainly used in the manufacture
of paper. They are employed as wet-end additives during the formation of paper to
improve the retention and drainage rate of the pulp and strength of the finished sheets.
42
2.3 Thermoplastic Starch (TPS)
Recently, there has been much interest in the research of thermoplastic starch
because of its biodegradability and bio-sustainable source. Both the glass transition
temperature (Tg) and the melting temperature (Tm) of natural, dry starch are higher than
its thermal decomposition temperature.91 The obstacle of using starch in plastics is its
brittle nature due to its relatively high Tg and lack of a sub-Tg main-chain relaxation.
Moreover, brittleness increases with time because of the free volume relaxation and
retrogradation.91 Thus, unlike other synthetic thermoplastic polymers, starch can only be
processed into a thermoplastic material by providing plasticization to starch molecules.
In the previous section, several basic chemical modifications of starch were
described. Various novel functional groups could be attached onto the starch through
such chemical modifications, depending on the desired properties. However, so far only
starch modified with long-chain fatty acid esters groups were systematically studied as a
thermoplastic material and showed some promising results (reduced Tg and Tm, increased
elongation at break and flexibility). Currently, most thermoplastic starches are produced
by the addition of low-molecular-weight plasticizers, such as water, glycerol, sorbitol,
urea, amide, sugars, quaternary amine, etc.15,23,92-94
Water, due to its strong affinity with hydroxyl groups on starch, is a very effective
plasticizer for thermoplastic starch. Compared with the preparation of gels or food
related products, the preparation of thermoplastic starch products require a relatively low
amount of water.95 In most cases, the water content is less than 20 wt % during
processing.15,96 Usually, a small amount of glycerol is used together with water.
Because glycerol enhances the boiling point of water, the migration and evaporation of
43
water inside the starch could be hindered.23,97 The thermoplastic properties of potato
starch with water and glycerol prepared by extrusion were studied.94 The samples
containing less than 9 wt % of water were glasslike and had an elastic modulus of 400
MPa.98 The viscoelastic behavior of thermoplastic starch highly depends on the water
content and typically shows three regions: a glassy region when the water content is
lower than 9 wt %, followed by a glass-to-rubber transition, then a rubbery region when
water is between 9 and 15 wt %, and finally, the viscous gel-like region with the water
content higher than 15 wt %.94 Figure 2.14 shows the stress-strain curve of TPS with
different amounts of water as a plasticizer.94
Figure 2.14. Stress-strain curves of potato starch with different amounts of water content
(the water contents (wt %) are indicated on the figures).94 (Reprinted with permission
from Elsevier.)
The structure of TPS plasticized by water was also studied.98 The extrudates of
TPS with water seemed to be translucent, suggesting that the granular structure of starch
44
was destroyed during extrusion. X-ray diffraction results proved the disappearance of the
native crystallinity of starch. Granular waxy maize starch showed A-type crystalline
structure on the X-ray diffraction curve. After being plasticized by water and extruded,
the X-ray diffraction results showed the amorphous morphology and a small amount of
B-type crystallinity. Thermal analysis indicated that the glass transition temperature of
the starch decreased appreciably with an increase in water content. The Tg of TPS (potato
starch) was decreased from 59 oC with 5 wt % of water content to –10 oC with 20 wt %
of water content.94 Other research on the starch/glycerol/water blends found that the Tg
of the TPS depends on the water contents almost linearly when the glycerol content is
fixed.99 Moreover, the amount of glycerol (higher than 14 wt %) only slightly affects the
Tg.
Since the thermal behavior and mechanical properties of TPS are very sensitive to
the water content, the major drawback of the TPS-based materials is the decline of the
material properties with time because of the migration and evaporation of the water
inside the starch, or the absorbing water by hydrophilic starch from the
atmosphere.93,95,98 Furthermore, studies also found the time-dependent post-
crystallization of starch in the presence of water and glycerol during storage. Figure 2.15
shows X-ray diffraction curves of TPS containing water stored at various periods and
under different humidity values.98 The problem of the decline in material properties with
time is at least in part due to the reorganization and crystallization of the amylose and
amylopectin molecules. Naturally, it is limited to the use of materials manufactured only
from TPS because of its poor water resistance. Thus, blending TPS with other polymers
would be helpful to enhance the overall water resistance.
45
Figure 2.15. X-ray diffraction patterns of (top) granular waxy maize starch and (bottom)
TPS materials stored at various temperatures and humidity. From bottom to top:
quenched and stored for 2 weeks; stored at 40% relative humidity (RH) for 2 weeks;
stored at 60% RH for 2 weeks; stored at 70% RH for 8 months; and stored at 90% RH for
2 weeks.98 (Reprinted with permission from John Wiley & Sons.)
46
2.4 Previous Research on the Nanocomposites based on Starch
The research on the starch-based nanocomposites began several years ago. The
most intensive research has been focused on organically modified silicates. Improved
properties, such as gas barrier, mechanical stiffness, and thermal stability, could be
achieved. Many reports have been published on starch-base nanocomposites.5,6,100-103
However, none of them achieved a high degree of exfoliation. Because both starch and
natural clay (montmorillnite, MMT) are hydrophilic, it was assumed that these
compounds would have high affinity with each other. But according to the X-ray
diffraction studies,6,104 it seems that mainly those low molecular-weight plasticizers such
as glycerol are intercalated, resulting in a low degree of exfoliation.102,105 Figure 2.16
shows X-ray diffraction (XRD) patterns, and Figure 2.17 shows TEM images of
TPS/MMT (the counter ion on the surface of layered silicates is Na+) nanocomposites
with various amounts of MMT in which TPS was plasticized by glycerol and water.103
o
The XRD patterns indicate that the peak around 7.85 of MMT shifted to
4.5o－5.0o regardless of the clay content, suggesting the intercalated nanocomposites.
One can observe agglomerates of MMT from the TEM images given in Figure 2.17.
Other research groups also showed similar results.5,104,106-109 So far, there is no
publication reported on exfoliated nanocomposites based on starch.
Table 2.3 lists the XRD results of various TPS/clay (treated and untreated)
nanocomposites. It is seen in Table 2.3 that only intercalation was achieved in TPS/clay
nanocomposites regardless of whether MMT or organoclay was used.
47
Figure 2.16. Effect of Cloisite Na+ on the XRD patterns for TPS nanocomposites: (a)
Cloisite Na+; (b) TPS/Cloisite Na+(97.5/2.5 wt %); (c) TPS/Cloisite Na+(95.0/5.0 wt %);
(d) TPS/Cloisite Na+(90.0/10.0 wt %); and (e) TPS.103 (Reprinted with permission from
Kluwer Academic Publishers.)
Figure 2.17. TEM image of TPS nanocomposite containing 5 wt % of MMT.103

(Reprinted with permission from Kluwer Academic Publishers.)
48
Table 2.3. XRD results of TPS/clay nanocomposites5,104,106-109
XRD peak XRD peak XRD peak position

position (2θ) of position (2θ) (2θ) layered
layered silicates layered silicates silicates in the
Sample code before treatment after treatment nanocomposites
TPS/Cloisite-Na+ 7.85 N/A 4.68
TPS/Cloisite-30B 7.85 4.73 4.30
TPS/MMT(treated by 8.75 7.06 4.24
ethanolamine)
TPS/MMT (treated by 5.975 5.590 5.015
chitosan)
TPS/MMT(treated by 7.3 3.6 3.6
cationic starch
Another way of improving the chemical affinity between starch and clay is to
modify the starch by the introduction of functional groups. Presently, there are very few
studies reported on such an approach. Two studies reported on chemically modified
starch-based nanocomposites.101,110 Oxidized starch by hydrogen peroxide and
acetylated starch were produced. However, neither of them exhibited good dispersion of
clay. Only a low degree of intercalation of layered silicates was observed by XRD, and
the experimental results can be explained as follows. (1) The amylose and amylopectin
in starch were stiff molecules, and such modifications could not effectively enhance the
mobility of molecules. It was very difficult for them to diffuse into the gallery of the
layered silicates exfoliating the aggregates of MMT. (2) Both modifications have mainly
introduced carbonyl or carboxyl groups into starch, which could have formed hydrogen
bonding, that apparently was not strong enough to exfoliate the aggregates of MMT.
Efforts on dispersion of clay in TPS nanocomposites are still underway, and
enhanced mechanical properties, gas barrier, and improved thermal stability have been
reported in various publications.5,6,103,104,107,108 Table 2.4 gives a summary of the
49
Table 2.4. Tensile properties of TPS/Cloisite 30B and TPS/MMT nanocomposites103
Blend composition Tensile strength Elongation at break

(MPa) (%)
TPS 97.5/MMT 2.5 wt % 2.79 48.9
TPS 95/MMT 5.0 wt % 3.32 57.2
TPS 90/MMT 10.0 wt% 3.20 52.0
TPS 97.5/Cloisite 30B 2.5 wt % 2.75 45.7
TPS 95/Cloisite 30B 5.0 wt % 2.80 44.5
TPS 90/Cloisite 30B 10.0 wt % 3.00 45.7
TPS 100 wt % 2.61 47.0
mechanical properties of TPS/MMT and TPS/Cloisite 30B nanocomposites.103 It is seen
that the tensile properties of TPS/MMT are increased with increasing content of MMT. It
should be noted that the TPS/MMT nanocomposite showed higher tensile strength than
the TPS/Cloisite 30B nanocomposite. As far as the dispersion of clay in TPS is
concerned, Cloisite 30B would be a poor example of modification of MMT. Because the
hydrophobic functional groups introduced into the Cloisite 30B decreased the chemical
affinity between Cloisite 30B and TPS, it resulted in lower intercalation of layered
silicates in comparison with TPS/MMT nanocomposites.
50
CHAPTER III
EXPERIMENTAL
3.1 Synthesis of Chemically Modified Starch
Starch employed in this study is a cornstarch purchased from Sigma-Aldrich
Chemical Company. Other chemicals used for the synthesis were purchased from Sigma-
Aldrich Chemical Company, and they were used as received without further purification.
Natural clay (montmorillonite, MMT) and two commercial organoclays (Cloisite 30B
and Cloisite 15A) used in the preparation of nanocomposites were provided by Southern
Clay Products. EVOH contained 27 mol % of ethylene units.
3.1.1 Synthesis of Anionically Modified Starch with Hexanoyl Group (AS-LF)
5 g of natural starch (NS) was added to a flask containing 150 ML isopropyl
alcohol. The reaction mixture was vigorously stirred at room temperature for 60 min
upon the addition of aqueous NaOH solution (10 ML, 5%). Sodium chloroacetate with a
predetermined amount (based on the desired DS) was then added into the reaction
mixture, and the temperature of the reactor was raised to 55 oC. The reaction was
stopped after 6 h by pouring the reaction mixture into a beaker containing ethanol. The
modified starch was precipitated from the ethanol. Then the product was filtered off.
The anionically modified starch (AS) was stirred in anhydrous ethanol for at least 24 h
and dried in a vacuum oven at 50 oC for 24 h.
51
5 g of dried AS was added to a flask containing 80 ML pyridine. The suspension
was vigorously stirred at 115 oC for 60 min. The reaction system was connected to a
condenser cooled by water. Hexanoyl chloride with a predetermined amount (based on
desired DS) was added dropwise into the reaction mixture, and the temperature of the
reactor was kept at 115 oC for 6 h. The reaction mixture was poured into a beaker
containing ethanol. The product (AS-LF) was precipitated from the ethanol and filtered
off. The product was stirred in anhydrous ethanol for at least 24 h and dried in a vacuum
oven at 60 oC for 24 h.
3.1.2 Synthesis of Anionically Modified Starch with Benzoyl Group (AS-B)
5 g of dried AS was added to a flask containing 80 ML pyridine. The suspension
was vigorously stirred at 115 oC for 60 min. The reaction system was connected with a
condenser cooled by water. Benzoyl chloride with a predetermined amount (based on
reaction was kept at 115 oC for 6 h. The reaction mixture was poured into a beaker
containing ethanol. The product (AS-B) was precipitated from the ethanol and filtered
3.1.3 Synthesis of Cationically Modified Starch with Hexanoyl Group (CS-LF)
5 g of natural starch was added to a flask containing 100 ML aqueous NaOH
solution (5%). The reaction mixture was vigorously stirred at room temperature for 60
min. Then glycidyltrimethylammonium chloride with a predetermined amount (based on
52
the desired DS) was added dropwise into the reaction mixture, and the temperature of the
reaction was raised to 60 oC. The reaction was stopped after 6 h by pouring the reaction
mixture into a beaker containing ethanol. The product (CS) was precipitated from the
ethanol and filtered off. The CS was stirred in anhydrous ethanol for at least 24 h and
dried in a vacuum oven at 50 oC for at least 24 h.
5 g of CS was added to a flask containing 80 ML pyridine. The suspension was
vigorously stirred at 115 oC for 60 min. The reaction system was connected with a
condenser cooled by water. Hexanoyl chloride with a predetermined amount (based on
containing ethanol. The product (CS-LF) was precipitated from the ethanol and filtered
3.1.4 Synthesis of Cationically Modified Starch with Benzoyl Group (CS-B)
5 g of CS was added to a flask containing 80 ML pyridine. The suspension was
vigorously stirred at 115 oC for 60 min. The reaction system was connected with a
condenser cooled by water. Benzoyl chloride with a predetermined amount (based on
containing ethanol. The product (CS-B) was precipitated from the ethanol and filtered
off. The product was stirred in anhydrous ethanol for 24 h and dried in a vacuum oven at
100 oC for 12 h.
53
3.2 Preparation of Blends and Nanocomposites based on Modified Starch and
EVOH
Solution Blending of Blends of Modified Starch and EVOH A predetermined amount
of modified starch and EVOH were dissolved into dimethyl sulfoxide(DMSO) at a mildly
elevated temperature (around 60 oC). A magnetic stirrer was used to facilitate the
dissolution. A transparent and yellowish solution was obtained after total dissolution of
polymers. The solution was put into a hood, allowing the evaporation of the solvent.
Then the mixture was put into a vacuum oven at 100 oC until no weight changes were
detected.
Solution Blending of Nanocomposites based on Modified Starch A predetermined
amount of modified starch was dissolved in tetrahydrofuran (THF) upon heating. 5 wt %
of organoclay (or MMT) was pre-dispersed in THF (a co-solvent THF/water, 10/1 v/v
was used to disperse MMT) by ultrasonic bath for 30 min, and then it was added slowly,
while stirring, into the polymer solution. The mixture of modified starch and organoclay
was stirred constantly for 2 days at an ambient temperature, allowing the evaporation of
the solvent. Then the mixture were put into a vacuum oven at 100 oC until no weight
changes were detected.
Melt Blending of Blends and Nanocomposites Melt blending was performed by a
twin-screw mini compounder (Haake Instruments). 5.5 g of polymer mixture, including a
modified starch, EVOH, and 5 wt % of nanoclay, were fed to the compounder, which had
been preheated to 185 oC. The compounder was run in a closed-loop mode, and the melt
54
blending was performed by the twin-screw extruding in the compounder before discharge
into a circular die. An external nitrogen supply prevented possible oxidation. For other
characterization purposes, the nanocomposites were hot-compression molded when
needed.
3.3 Characterization Methods
Proton Nuclear Magnetic Resonance (1H-NMR) Spectroscopy 1H-NMR spectra were
obtained with a Varian Gemini 300 MHz NMR spectrometer. Solid samples were
solubilised in deuterated dimethyl sulfoxide (DMSO-d6) and placed in 5 mm NMR tube.
The spectra were collected at 25 oC over a spectra width of 4796 Hz using a 90o pulse.
The acquisition time was 1.98 s, the relaxation delay (d1) was 5 s (the relaxation time (T1)
of anomeric proton was measured to be 0.9 s), and 16 scans were accumulated. Data
were processed with 0.5 Hz exponential line broadening and zero filled to 131,072 points
before Fourier transformation.
Differential Scanning Calorimetry (DSC) The thermal transition temperatures of a
modified starch, EVOH, blends, and nanocomposites prepared in the present research
were determined by differential scanning calorimetry (DSC) (TA instruments). All DSC
runs were made under a nitrogen atmosphere with heating rates of 10 oC/min. Indium
and zinc were used to calibrate the temperature and the heat of fusion.
Optical Microscopy The phase separation of blends of modified starch and EVOH was
observed by an optical microscope equipped with a hot stage (Instec) and a digital camera
55
(Spot insight 2, Diagnostic Instrument). Specimens were cast from 1 wt % solution of
polymer mixtures on a slide glass to obtain a film of about 2－3 μm in thickness, which
was then first dried in a fume hood and subsequently in a vacuum oven. The heating rates
employed were 0.5 oC/min. Images of single phase and separated phase were obtained by
digital camera. At each weight fraction of EVOH, at least 5 samples were measured for
determining the cloud point of the mixture, and an average value was obtained from the
repeated measurements.
Fourier Transform Infrared (FTIR) Spectroscopy Using a Fourier transform infrared
spectrometer (Perkin Elmer), FTIR spectra were obtained at room temperature for
modified starches, blends of a modified starch and EVOH, and nanocomposites based on
a modified starch with mode of attenuated total reflectance (ATR). Spectral resolution
was maintained at 4 cm−1. Specimens were grinded into fine powders and slowly dried
for 24 h in a fume hood until the solvent and moisture evaporated, and they were then
stored in a vacuum oven until use.
Wide Angle X-ray Diffraction (WAXD) WAXD experiments were conducted at room
temperature on the films, which were hot pressed by compression molding, using a
General Electric X-ray generator (Model XRD-6) operated at 30 kV and 30 mA (Ni-
filtered Cu Kα radiation). For annealed specimens, the films were first heated at 200 oC
for 5 min and then immediately transferred to a vacuum oven in which the temperature
was regulated at an annealing temperature. The samples were annealed for at least 3 h
and quenched by liquid nitrogen before the WAXD measurements began.

56
X-ray Diffraction (XRD) Using a Rigaku X-ray generator operated at 40 kV and 150
mA, X-ray diffraction patterns were obtained to determine the mean interlayer spacing of
the (001) plane (d001) for the natural clay or organoclays, and their nanocomposites. The
X-ray beam was monochromatized to Cu Kα with a graphite crystal. The range of 2θ
scanning of X-ray intensity employed was 1.5–10 degrees.
Transmission Electron Microscopy (TEM) TEM images of specimens were taken at
room temperature. The ultrathin sectioning (around 100 nm) was performed by
ultramicrotomy at room temperature for the clay (or organoclay) nanocomposites. A
transmission electron microscope (JEM1200EX 11, JEOL) operated at 120 kV was used
to obtain images of nanocomposite specimens.
Thermogravometric Analysis (TGA) The thermal degradation temperature of
polymers was determined by a thermogravometric analyzer (TGA 2050, TA Instrument).
All TGA data was obtained under a nitrongen atmosphere at a heating rate of 10 oC/min,
and the thermal degradation temperature was determined at the point of 90 wt % of the
original weight.
Tensile Test The tensile test of the blends and nanocomposites based on a modified
starch was performed by a tensile tester (Instron, Model 5567), following the ASTM
standard, D638-00. The load cell used for the tensile test was an Instron static load cell
with a 10 kN capacity. A cross-head speed of 5 mm/min was used for the test. The
57
upper yield stress on the stress-strain curve was considered as the tensile strength. For all
the results reported in this dissertation, at least 3 replicates of specimens were tested, and
an average value of the measured values was used. All specimens for tensile testing were
compounded by a twin-screw mini compounder (Haake Instruments) and hot compressed
into films with uniform thickness. Then the films were cut into dumbbell shape for the
tensile test. The thickness and length of the specimens were accurately measured before
use.
Hydrophilicity Test Saturated aqueous sodium chloride solution was prepared, and it
was put into a sealable chamber. The ambient temperature of this chamber was kept
around 20 °C. In this way, the constant relative humidity (74%) was obtained in the
chamber. Dried, chemically modified starch samples were put into the chamber after
being accurately weighed. Then the samples were weighed every two days until the
weight did not change further.
Biodegradability Test Materials that were to be characterized for their biodegradability
include NS (the positive control), modified starches employed in the present study, and
LDPE (the negative control). Since dry natural starch is not processable, it was premixed
with 10 wt % of glycerol (acting as plasticizer) by mini twin-screw compounder. All
materials were molded between two Teflon sheets into thin films (25×50×1 mm ) by
applying a 250 kg/cm2 pressure using a preheated hydraulic press, and accurately
weighted by digital balance. Every sample had 10 duplicates with the same size and
weight. The compost was offered by KB Compost Services, Inc. The composition of the
compost was (approximate dry weight): 5% animal dung; 10% sawdust; 10% shredded
58
paper; 10% food waste; 20% shredded leaves; and 45% garden soil. The compost was
fully shredded and sifted to remove large clumps. The moisture content of the compost
was maintained by periodic spraying of water. To avoid anaerobic condition, the
compost was aerated by turning at least 3 times a week. All samples were buried inside
the compost at a depth of at least 1.5 feet. One duplicate of each sample was dug out
every two weeks and weighed after thorough washing with water and drying in a vacuum
oven until it reached a constant weight. The weight loss (Wloss) was calculated by:
Winitial − Wweighted
Wloss = × 100%
Winitial
59
CHAPTER IV
CHARACTERIZATION OF CHEMICALLY MODIFIED STARCH
4.1 Structure Characterization and Determination of Degree of Substitution (DS)
of Chemically Modified Starch
As described in Chapter II, there are three hydroxyl groups in each repeat unit of
starch molecules. Chemical modification explored in the present study is to substitute
these hydroxyl groups with functional groups, such as anionic groups, cationic groups,
hexanoyl groups, or benzoyl groups. The rationale behind this modification was as
follows. (1) Because of ionic interaction between the modified starch and clay, starch
having anionic or cationic groups can have higher compatibility with organoclay or
natural clay. (2) Because the granular semicrystalline structure of natural starch was
destroyed by the interruption of functional groups, starch having hexanoyl groups or
benzoyl groups can have higher molecular mobility than natural starch. (3) Because the
hexanoyl groups or benzoyl groups are hydrophobic, starch having hexanoyl groups or
benzoyl groups can have lower affinity with water than natural starch.
Figures 4.1 and 4.2 give the FTIR spectra of the modified starches synthesized in
the present study. Following the FTIR spectra, Table 4.1 lists the major absorbance
bands shown in the FTIR spectra for the functional groups in the modified starches.
The FTIR spectra of natural starch (NS) show a very broad and strong band at
3263 cm−1, suggesting strong hydrogen bonds in natural starch. These hydrogen bonds
60
Absorbance (arb. unit)
(1)
(a) (2)
(1)
(b)
(c)
(2) (1)
4000 3000 2000 1000

−1
Wavenumber (cm )
Figure 4.1. FTIR spectra of (a) natural starch (NS), (b) starch modified with anionic
group and benzoyl group (AS-B), and (c) starch modified with anionic group and
hexanoyl group (AS-LF). (Arrow (1) points to the absorbance of the hydrogen-bonded
−OH group, and arrow (2) points to the absorbance of the free −OH group.)
61
(1)
(a)
(2) (1)
(b)
(c)
(2) (1)
4000 3000 2000 1000

−1
Wavenumber (cm )
Figure 4.2. FTIR spectra of (a) natural starch (NS), (b) starch modified with cationic
group and benzoyl group (CS-B), and (c) starch modified with cationic group and
hexanoyl group (CS-LF). (Arrow (1) points to the absorbance of the hydrogen-bonded
−OH group, and arrow (2) points to the absorbance of the free −OH group.)
62
Table 4.1. Peak assignments in the FTIR spectra of the chemically modified starches
Bond Peak
hydrogen-bonded v (O−H) 3263 cm−1 in NS, 3410 cm−1 in AS-B, 3456 cm−1 in
AS-LF, 3401 cm−1 in CS-B, and 3422 cm−1 in CS-LF
free v (O−H) 3566 cm−1 in AS-B, 3589 cm−1 in AS-LF, 3559 cm−1
in CS-B, and 3577 cm−1 in CS-LF
v (C=O) 1737 cm−1 in AS-B and CS-B, 1743 cm−1 in AS-LF

and CS-LF
v (COO−Na+) 1595 cm−1 in AS-B and AS-LF
v (C−H) in CH2 or CH3 2854 cm−1 and 2956 cm−1 in AS-LF and CS-LF
δ (C−H) in −N+(CH3)3 1470 cm−1 in CS-B and CS-LF
v (C−N+) in −N+(CH3)3 957 cm−1, 911 cm−1, and 872 cm−1 in CS-B and
CS-LF
are present in the granular structure of natural starch, in both the amorphous and
crystalline phases. As described in Chapter II, the mobility of starch molecular chains is
very low (its glass transition temperature is higher than its thermal degradation
temperature), which was partly resulting from the strong hydrogen bonds present among
molecules. (The other reasons could include high molecular weight and microscopically
granular structure of natural starch.)
The FTIR spectra of the modified starches synthesized in the present study include
a starch modified with anionic group and benzoyl group (AS-B), a starch modified with
anionic group and hexanoyl group (AS-LF), a starch modified with cationic group and
benzoyl group (CS-B), and a starch modified with cationic group and hexanoyl group
(CS-LF). They show that the absorbance band of hydrogen-bonded −OH group was
63
lowered and shifted to a higher wavenumber, suggesting that the hydrogen bonds in a
modified starch were drastically decreased as compared with natural starch. Furthermore,
the absorbance band of free −OH group was observed in the FTIR spectra of a modified
starch. The substitution of hydroxyl groups in a modified starch by other functional
groups decreased the total number of hydroxyl group so that the strong hydrogen bonds
were weakened. Additionally, the presence of functional groups, such as hexanoyl
groups or benzoyl groups, interfere with the hydrogen bonds present between the
available hydroxyl groups. That is the reason why we can observe the absorbance peaks
of free −OH groups in a modified starch.
Qualitatively, we have shown above that chemical modification decreased the total
number of hydroxyl groups in the starch molecules. The hydrogen bonds present in
starch molecules were decreased, upon chemical modification, because of the lowered
number of available hydroxyl groups. However, the number of hydroxyl groups
substituted by functional groups and the number of hydroxyl groups available in a starch
should be determined quantitatively. The values of degree of substitution (DS) indicate
that the number of hydroxyl groups substituted in each repeat unit of a starch molecule
ranges from 0 to 3. The DS of modified starches were determined from the 1H-NMR
spectra of a modified starch by equations 4.1 to 4.4:
DSanionic = Amethylene / 2Aanomeric (4.1)
DScationic = Amethyl/ 9Aanomeric (4.2)
DShexanoyl = Amethyl / 3Aanomeric (4.3)
DSbenzoyl = Abenzoyl / 5Aanomeric (4.4)
64
in which A stands for the integrated area of chemical shift found from the 1H-NMR
spectra for specific functional groups. Figure 4.3 gives the 1H-NMR spectra, showing
how the DS of hexanoyl group was determined. The peak locating at 5.1 ppm is the
chemical shift of anomeric proton in the glycosidic ring.111 The peaks locating around
1.1 ppm are the chemical shift of methyl protons in hexanoyl group. The numbers under
both of those two peaks denote the integrated peak area (Aanomeric and Amethyl). The value
of DS for all modified starches were determined in the same way. Table 4.2 lists the
values of DS for the four chemically modified starches.
H OH
H
a
O O H
H H b
Intensity (arb. unit)
H O b
H
OH O
C Hb
O Hb
1.0 3.67
10 9 8 7 6 5 4 3 2 1 0
Chemical shift (ppm)
Figure 4.3. 1H-NMR spectra of a starch modified by hexanoyl group.
65
Table 4.2. Degree of substitution of chemically modified starches
Sample code DSa1 DSa2
AS-B 0.03 1.3

AS-LF 0.03 1.2
CS-B 0.1 1.7
CS-LF 0.03 1.6
a DS
1 is the degree of substitution of ionic group in modified starch, and DS2 is the degree
of substitution of hexanoyl groups or benzoyl groups in modified starch.
4.2 Moisture Resistance of Chemically Modified Starch
Figure 4.4 shows how much moisture was absorbed by a modified starch over time
in an environment having a constant humidity (75%). It is seen that natural starch and
60
50
Absorbed Moisture (wt %)
40
30
20
10
0 2 4 6 8 10 12 14 16 18 20 22 24
Period (day)
Figure 4.4. Moisture absorption of modified starches: (●) NS; (■) AS; (▲) CS;
(▼) AS-LF; (◆) AS-B; (□) CS-LF; and (〇) CS-B.
66
the starches modified with ionic groups (AS or CS) are very hydrophilic. Their moisture
absorption could reach up to an equilibrium value of 50 wt %. Natural starch has a strong
affinity with water due to its abundant hydroxyl groups. As we described in Chapter II,
the mechanical properties of natural starch-based products keep changing because the
product absorbs water from its ambient environment due to a strong affinity with water.
Furthermore, its high water content limits the use of starch as a conventional
thermoplastic material. Figure 4.4 shows that the starches modified with ionic groups
(AS or CS) have even higher moisture absorption than natural starch, suggesting that both
AS and CS are more hydrophilic than natural starch. It should be noted in Table 4.2 that
the values of DS of AS and CS are around 0.1, which means that only a very small
amount of hydroxyl groups in starch was substituted by ionic groups. Considering that
the ionic groups are more hydrophilic than hydroxyl groups, it is understandable that the
starch modified with ionic groups have a higher affinity with water than natural starch.
Besides moisture absorption, we have found that both AS and CS are soluble in cold
water, while natural starch is not, which also suggests a higher affinity of AS and CS with
water.
On the other hand, Figure 4.4 shows that the starch modified with hexanoyl groups
or benzoyl groups have very low moisture absorption. We can see that starch was
changed from hydrophilic to hydrophobic material through the chemical modification in
the present study. The substitution of functional groups decreased the number of
hydroxyl groups. It was well known that hydroxyl groups have a strong affinity with
water. Additionally, the hydrophobic substituents limit the access of available hydroxyl
group to moisture.
67
4.3 Thermal Behavior of Chemically Modified Starch
Thermal Stability of Chemically Modified Starch
The thermal stability of chemically modified starch was characterized by
thermogravimetric analysis (TGA) in a nitrogen atmosphere. Figure 4.5 shows how the
thermal degradation temperature of a starch was changed by chemical modification. The
thermal degradation temperature is defined by the temperature at which the weight loss of
a sample reaches 10 wt % in the weight loss versus temperature curves obtained from
TGA measurements.
Thermal Degradation Temperature (oC)
400
NS NS
AS-LF AS-B CS-LF
CS-B
300
CS
200 AS
100
Starch samples
Figure 4.5. Thermal degradation temperatures of chemically modified starches.
It is worth noting that the thermal degradation temperature of starch greatly
decreased from 330 oC (natural starch) to around 200 oC after modification with ionic
groups (AS or CS). Previous studies73 on the thermal stability of starch showed that the
68
thermal weight loss of starch started with the intra- and intermolecular dehydration
among hydroxyl groups and then was followed by decomposition and depolymerization
at a higher temperature. In both AS and CS, only a very small amount of hydroxyl
groups were substituted by ionic groups. The intra- and intermolecular dehydration
among hydroxyl groups would not be hindered by the substitution of ionic groups.
Moreover, the substitution of ionic groups destroyed the granular structure of natural
starch and made abundant hydroxyl groups more easily accessible to each other for the
dehydration.
On the other hand, Figure 4.5 shows that the thermal degradation temperatures of
the starches modified with hexanoyl groups or benzoyl groups (AS-B, AS-LF, CS-B, or
CS-LF) were almost not changed. In these modified starches, the DS of hexanoyl groups
or benzoyl groups is around 2, suggesting that out of three hydroxyl groups on each
repeat unit, two hydroxyl groups were substituted. The decreased total number of
hydroxyl groups in the modified starch has lowered the possibility of having dehydration
among the available hydroxyl groups. Furthermore, the hexanoyl groups or the benzoyl
groups interfered with the accessibility of hydroxyl groups.
Glass Transition Temperature
As described in the previous chapter, the glass transition temperature of dried
natural starch cannot be practically measured, because it is higher than the thermal
decomposition temperature. It is necessary to lower the glass transition temperature of a
starch below its thermal decomposition temperature so that we can possibly process
starch as a conventional thermoplastic material. Thermoplastic starch can be prepared in
two ways: one is by the addition of low-molecular-weight plasticizer, and the other is by
69
chemical modification. In this dissertation, side groups such as hexanoyl groups and
benzoyl groups were attached into a starch through chemical reaction with hydroxyl
groups. Figures 4.6 and 4.7 give the DSC thermograms of the modified starches
synthesized in this study. For starches modified only with ionic groups (AS or CS), there
was no discernible glass transition temperature found in the DSC thermograms. For
starches modified with multiple functional groups (AS-B, AS-LF, CS-B, or CS-LF), we
can clearly observe the glass transition temperature in the DSC thermograms. The
introduction of hexanoyl groups or benzoyl groups into a starch destroyed the
semicrystalline granular structure and the hydrogen bonds formed between the hydroxyl
groups. Hence, the mobility of starch was enhanced. In addition, the introduction of
functional groups into a starch have increased the free volume of the modified starch.
Thus, the glass transition temperature of a starch was lowered and it became discernible
in the DSC measurements. On the other hand, for a starch modified only with ionic
groups (AS or CS), the DS of ionic groups was around 0.1. Only a very small amount of
hydroxyl groups was substituted by the ionic groups. There still are very strong
hydrogen bonds in both AS and CS, which limit the mobility of the starch molecules.
Thus, the glass transition temperature of AS or CS was not discernible in the DSC
thermograms.
70
90 (c)
45 (b)
Endotherm
(a)
0 50 100 150 200

Temperature (oC)
Figure 4.6. DSC thermograms of (a) AS, (b) AS-LF, and (c) AS-B.
(c)
44
(b)
Endotherm
92
(a)
0 50 100 150 200 250

Temperature (oC)
Figure 4.7. DSC thermograms of (a) CS, (b) CS-B, and (c) CS-LF.
71
It should be noted that there was no melting peak on the DSC thermograms of
modified starches, indicating an amorphous morphology in the modified starches. The
modification by functional groups destroyed the semicrystalline granular structure of
natural starch. Furthermore, the bulky side chains in the starch molecules after
modification decreased the irregularity of starch molecules so that it was hard for
modified starch to crystallize.
4.4 Biodegradability of Chemically Modified Starch
Biodegradable material can be defined as a material that has a proven capability to
decompose in a specific environment within a period through natural biological processes
into non-toxic carbonaceous soil, water, carbon dioxide, or methane. Apparently, natural
starch is a biodegradable material. In this dissertation, natural starch has been chemically
modified by various functional groups, including ionic groups, hexanoyl groups, and
benzoyl groups. Whether or not these chemically modified starches are still
biodegradable crucially dictates their potential applications. Biodegradation represents a
complex phenomenon brought about by the actions of naturally occurring
microorganisms, such as bacteria, fungi, and algae. As biodegradation proceeds, it
produces carbon dioxide, water, and/or methane. Biodegradability can be characterized
by monitoring the change of such properties as thickness, transparency, weight, tensile
strength, and molecular weight/distribution of molecular weight of a material or the
production of by-products (e.g., carbon dioxide and methane) during the biodegradation.
It must be noted that a specific time frame should be added to any characterization of
biodegradability.
72
In this dissertation, composting environment was built for the characterization of
biodegradability of the modified starches. Composting is one of the most important
waste management strategies, and natural starch is readily biodegradable in a composting
environment. The weight loss of samples during composting will indicate biodegradation.
Thus, the biodegradability of natural starch and the modified starches can be
quantitatively evaluated by measuring the weight loss of samples against time. Figure
4.8 shows the weight loss of the modified starches during composting against time. For
natural starch (the positive control in our research), we can see from Figure 4.8 that it
degraded very fast in composting. After 6 weeks, natural starch completely degraded.
For LDPE (the negative control in our research), we cannot find any weight loss during
the whole testing period, suggesting no degradation during composting.
100
80
Weight loss (%)
60
40
20
0 2 4 6 8 10 12 14 16 18
Composting period (week)
Figure 4.8. Weight loss of the modified starch during composting: (●) NS; (■) CS-LF;
(▲) LDPE; (▼) CS-B; (◆) AS-LF; and (□) AS-B.
73
For the modified starches synthesized in the present study, we can clearly find
weight loss during composting, suggesting biodegradability of a modified starch. In
Figure 4.8, we can observe that the degradation of natural starch is faster than the
modified starches, suggesting that the biodegradability of natural starch is higher than
modified starches. It is interesting to observe that the modified starches having cationic
functional groups (CS-LF and CS-B) have different degradation patterns from the
modified starches having anionic functional groups (AS-LF and AS-B).
4.5 Concluding Remarks
A series of chemically modified starches has been synthesized in the present study.
The hydroxyl groups in starch molecules were substituted by ionic groups (acetate
sodium or trimethylammonium chloride) and hydrophobic groups (hexanoyl group or
benzoyl group). The FTIR spectra showed that the hydrogen bonds present in natural
starch were weakened by the chemical modification. Through the calculation from the
1
H-NMR spectra, the degree of substitution of the modified starch prepared was
determined.
The modified starches, including AS-B, AS-LF, CS-B, and CS-LF, were
characterized by DSC. The DSC thermograms showed that the chemical modification
has lowered the glass transition temperature of starch. Additionally, there was no melting
peak in the DSC thermograms of modified starches, suggesting an amorphous
morphology in the modified starches.
The thermal stability of the modified starches was characterized by TGA. When
starch was modified only with ionic groups, the thermal degradation temperature of
74
starch was largely decreased from over 300 oC to around 200 oC. On the other hand, the
starches modified with both ionic groups and hydrophobic groups have a higher thermal
degradation temperature than the starch modified only with ionic groups.
Natural starch is known to be very hydrophilic, which limits its use in conventional
thermoplastic processing. The substitution of hydrophobic groups (hexanoyl groups or
benzoyl groups) decreased the hydrophilicity of starch. We characterized the moisture
absorbance of the modified starches in an environment having constant humidity over
time. The results showed that the chemical modification has changed the starch from
hydrophilic to hydrophobic.
We also investigated whether or not the biodegradability of a starch was influenced
by the chemical modification. The weight loss of a modified starch during composting in
a given period clearly has shown biodegradability of the modified starch. However, the
weight loss of a modified starch is slower than natural starch, suggesting that the
biodegradability of modified starches is lower than natural starch.
75
CHAPTER V
BLENDS OF MODIFIED STARCH AND EVOH
5.1 Miscibility of Blends Based on Modified Starch and EVOH Characterized by
Phase Diagrams
In this dissertation, blends of a chemically modified starch (including AS-LF, AS-B,
CS-LF, or CS-B) and EVOH were prepared. There is plenty of literature reporting on the
mechanical properties, biodegradability, processability, thermal behavior of blends of
natural starch and EVOH. However, few of them discussed the phase behavior of blends
of starch, and EVOH. So far, there is no literature reporting on the blends of chemically
modified starch and EVOH. The purpose of this study was to prepare miscible blends of
a modified starch and EVOH so that exfoliated organoclay nanocomposites could be
prepared. Moreover, miscible blends can effectively improve their mechanical properties
of blend. Using an optical microscope equipped with a programmable heating system,
the phase behavior of a blend can be observed at a specific temperature and composition.
Figure 5.1 gives phase diagrams of blends based on a modified starch and EVOH.
It is seen that all blend specimens exhibit a lower critical solution temperature (LCST).
The blends containing a starch modified by hexanoyl groups (AS-LF or CS-LF) and a
starch modified by benzoyl groups (AS-B or CS-B) have a critical temperature at the
same blend composition (0.6 weight fraction of EVOH). The former (AS-LF or CS-LF)
has a higher critical temperature than the latter (AS-B or CS-B).
76
Temperature (oC) 300
200
100
0
0.0 0.2 0.4 0.6 0.8 1.0
EVOH (wt fraction)
Figure 5.1. Phase diagrams of the blends of a modified starch and EVOH: (●) (AS-B)/
EVOH blend; (〇) (AS-LF)/EVOH blend; (▼) (CS-B)/EVOH blend; and (▽) (CS-LF)/
EVOH blend.
5.2 Hydrogen Bonding in Blends based on Modified Starch and EVOH
Characterized by DSC and FTIR
The blends based on a modified starch and EVOH were prepared by melt blending.
The modified starches include AS-B, AS-LF, CS-B, and CS-LF, the thermal behavior and
the biodegradability of which were summarized in Chapter IV. EVOH used in the
present study contains 27 mol % ethylene.
It should be noted that EVOH is a semicrystalline polymer. Previous results112,113
showed that the vinyl alcohol content in the crystalline phase is essentially equal to that
77
in the bulk sample. EVOH employed in the present study contains 73 mol % of vinyl
alcohol, suggesting that most of the crystalline phase was contributed by the vinyl alcohol
component. Because the vinyl alcohol groups in EVOH can form hydrogen bonds with
the hydroxyl groups in a modified starch, we might expect to find that the crystallization
of EVOH will be interrupted by the presence of the starch in the blend of EVOH and the
modified starches.
Figures 5.2 to 5.5 give the DSC thermograms of the blends of EVOH and a
modified starch for different compositions. Several common features in the DSC
thermograms are worth noting as follows. (1) Endothermic peaks were found on every
DSC thermogram of the blends of EVOH and a modified starch, which indicate that the
crystalline phase was present in the blends. Because the modified starch was an
amorphous material, we ascribed the crystallization in the blends to the presence of
EVOH. (2) The melting point of the crystalline phase in the blends decreases with an
increasing amount of modified starch. (3) The melting enthalpy of the crystalline phase
in the blends decreases with increasing amount of modified starch. The melting point
depression in the blends suggests that the crystallization of EVOH was interrupted. The
imperfection of the crystalline phase in the blend was increased because of the
interruption induced by the modified starch. We ascribe this interruption to the formation
of hydrogen bonds between the hydroxyl groups in a modified starch and the vinyl
alcohol groups of EVOH. On the other hand, the decreased melting enthalpy of the
crystalline phase with increasing amount of modified starch in a blend, shown in Figures
5.2 to 5.5, clearly indicates that the crystallinity of the blend is decreased as the weight
fraction of modified starch is increased.
78
(a)
Endotherm (b)
(c)
(d)
(e)
0 50 100 150 200

o
Temperature ( C)
Figure 5.2. DSC thermograms of the blends of (AS-B)/EVOH: (a) neat EVOH; (b) blend
of 20/80 (weight ratio) (AS-B)/EVOH; (c) blend of 40/60 (AS-B)/EVOH; (d) blend of
70/30 (AS-B)/EVOH; and (e) neat AS-B.
(a)
Endotherm
(b)
(c)
(d)
(e)
0 50 100 150 200

o
Temperature ( C)
Figure 5.3. DSC thermograms of the blends of (AS-LF)/EVOH: (a) neat EVOH; (b)
blend of 20/80 (AS-LF)/EVOH; (c) blend of 40/60 (AS-LF)/EVOH; (d) blend of 70/30
(AS-LF)/EVOH; and (e) neat AS-LF.
79
(a)
(b)
Endotherm
(c)
(d)
(e)
0 50 100 150 200

Temperature (o C)
Figure 5.4. DSC thermograms of the blends of (CS-B)/EVOH: (a) neat EVOH; (b) blend
of 20/80 (CS-B)/EVOH; (c) blend of 40/60 (CS-B)/EVOH; (d) blend of 70/30 (CS-B)/
EVOH; and (e) neat CS-B.
(a)
Endotherm
(b)
(c)
(d)
(e)
0 50 100 150 200

Temperature (oC)
Figure 5.5. DSC thermograms of the blends of (CS-LF)/EVOH: (a) neat EVOH; (b)
blend of 20/80 (CS-LF)/EVOH; (c) blend of 40/60 (CS-LF)/EVOH; (d) blend of 70/30
(CS-LF)/EVOH; and (e) neat CS-LF.
80
The values of melting point Tm and the degree of crystallinity of the blends are
summarized in Table 5.1. Two points should be addressed in the calculation of the
degree of crystallinity in the blends. First, since we calculated the degree of crystallinity
of a blend using melting enthalpy determined from the DSC thermograms, we had to
determine the melting enthalpy of neat EVOH ( ΔH m0 ). However, since ΔH m0 could not
be determined experimentally, we estimated ΔH m0 from the enthalpies of completely
crystallized poly(vinyl alcohol) (PVA), ΔH PVA

0
(156.14 J/g)114, and polyethylene (PE),
ΔH PE
0
(290 J/g)115, by
ΔH m0 = αΔH PVA
0
+ βΔH PE
0
(5.1)
where α and β are the weight fractions of the vinyl alcohol component and the ethylene
Table 5.1. Melting points and the degree of crystallinity of blends of EVOH and
modified starch
Weight ratio Melting Point Tm Degree of crystallinity

(oC) (wt %)
EVOH n/a 184 58.3
AS-B/EVOH 2/8 179 49.7
4/6 172 40.1
7/3 162 23.2
AS-LF/EVOH 2/8 180 45.2
4/6 174 36.8
7/3 166 20.7
CS-B/EVOH 2/8 178 50.2
4/6 173 41.3
7/3 164 24.3
CS-LF/EVOH 2/8 177 43.2
4/6 172 32.7
7/3 163 21.6
81
component in EVOH, respectively. In this study EVOH had 73 mol % (α = 0.81) of
vinyl alcohol and 27 mol % (β = 0.19) of ethylene. Thus, we have calculated the value of
ΔH m0 to be 181.6 J/g. The second point that should be addressed is that the degree of
crystallinity calculated is the percentage of the crystalline phase in a crystallizable
material (EVOH) instead of the entire sample (a blend of a modified starch and EVOH).
Thus, the degree of crystallinity (%) of a blend was calculated from:
C = 100ΔH m (ΔH m0 WEVOH ) (5.2)
where ΔH m is the melting enthalpy of the crystalline phase in a blend determined from
the DSC thermograms, and WEVOH is the weight fraction of EVOH in a blend sample.
The increasing imperfection of the crystalline phase (indicated by melting point
depression) and the decreasing degree of crystallinity (indicated by decreasing melting
enthalpy) in a blend with increasing weight fraction of a modified starch suggest the
presence of strong interactions between the modified starch and EVOH. We ascribe this
interaction to the formation of hydrogen bonds between the two components in a blend.
This strong interaction not only interrupts the crystallization of EVOH in the blend, but
also enhances the miscibility of the blend. It is seen in the DSC thermograms that only
one glass transition temperature is observed on each DSC thermogram over the entire
composition of a blend.
Figures 5.6 to 5.9 give the DSC thermograms in the glass transition region for all
blends. It should be noted in Figures 5.6 to 5.9 that the vertical bar denotes glass
82
(a)
(b)
Endotherm (c)
(d)
(e)
0 50 100 150
Temperature (o C)
Figure 5.6. DSC thermograms in the glass transition region for the blends of (AS-B)/
EVOH: (a) neat EVOH; (b) blend of 20/80 (AS-B)/EVOH; (c) blend of 40/60 (AS-B)/
EVOH; (d) blend of 70/30 (AS-B)/EVOH; and (e) neat AS-B.
(a)
(b)
Endotherm
(c)
(d)
(e)
0 50 100 150
Temperature (oC)
Figure 5.7. DSC thermograms in the glass transition region for the blends of (AS-LF)/
EVOH: (a) neat EVOH; (b) blend of 20/80 (AS-LF)/EVOH; (c) blend of 40/60 (AS-LF)/
EVOH; (d) blend of 70/30 (AS-LF)/EVOH; and (e) neat AS-LF.
83
(a)
(b)
Endotherm
(c)
(d)
(e)
0 50 100 150
Temperature ( o C)
Figure 5.8. DSC thermograms in the glass transition region for the blends of (CS-B)/
EVOH: (a) neat EVOH; (b) blend of 20/80 (CS-B)/EVOH; (c) blend of 40/60 (CS-B)/
EVOH; (d) blend of 70/30 (CS-B)/EVOH; and (e) neat CS-B.
(a)
(b)
Endotherm
(c)
(d)
(e)
0 50 100 150
Temperature (oC)
Figure 5.9. DSC thermograms in the glass transition region for the blends of (CS-LF)/
EVOH: (a) neat EVOH; (b) blend of 20/80 (CS-LF)/EVOH; (c) blend of 40/60 (CS-LF)/
EVOH; (d) blend of 70/30 (CS-LF)/EVOH; and (e) neat CS-LF.
84
transition temperature Tg, the arrow pointing upward denotes the onset of glass transition
Tgi, and the arrow pointing downward denotes the final point of the glass transition
temperature Tgf. All the values were determined by Universal Analysis 2000 (TA
Instruments). The following observations are worth noting in the DSC thermograms.
First, only one glass transition temperature can be found on each DSC thermogram of a
blend, suggesting that the modified starches (including AS-B, AS-LF, CS-B, and CS-LF)
are miscible with EVOH (within the size scale, which DSC can detect). The values of Tg
of the four blend systems are summarized in Table 5.2. Second, the blend composition
has a significant influence on the width of the glass transition of each blend system,
namely, the width of glass transition (ΔwTg = Tgf − Tgi) decreases with increasing weight
fraction of a modified starch, as summarized in Table 5.2. Note that the value of ΔwTg of
Table 5.2. Glass transition temperatures of EVOH/modified starch blends
Weight ratio Tg (oC) ΔwTg

EVOH n/a 63 41
(AS-B)/EVOH 2/8 71 44
4/6 79 40
7/3 85 26
10/0 90 15
(AS-LF)/EVOH 2/8 60 42
4/6 57 40
7/3 50 25
10/0 45 16
(CS-B)/EVOH 2/8 72 43
4/6 80 27
7/3 83 20
10/0 92 18
(CS-LF)/EVOH 2/8 61 43
4/6 58 30
7/3 52 25
10/0 44 18
85
neat EVOH is higher than that of neat modified starch, which might be explained by the
fact that the self-association in EVOH is stronger than that in a modified starch. When a
modified starch was introduced into neat EVOH, the hydrogen bonds between EVOH
and a modified starch decreased the self-association of EVOH. In other words, the
hydrogen bonds between a modified starch and EVOH in a blend is favored over the
hydrogen bonds in self-association of neat EVOH.
FTIR spectroscopy was used to evaluate the strength of hydrogen bonding in a
modified starch, neat EVOH, and between a modified starch and EVOH in a given blend.
Figures 5.10 to 5.13 give the FTIR spectra of the blends based on a modified starch and
EVOH. In the FTIR spectra of neat EVOH, a broad and strong absorption band centered
at 3349 cm−1 is ascribed to the stretching vibration of the hydrogen-bonded hydroxyl
group, suggesting strong self-association present in EVOH. From the FTIR spectra of
four modified starches (AS-B, AS-LF, CS-B, and CS-LF) we made the following
observations. (1) The absorption band located at 3550 cm−1 is ascribed to the free
hydroxyl group in a modified starch. (2) A weak but broad absorption ranging from
3220 cm−1 to 3500 cm−1 (centered at 3470 cm−1) is ascribed to the hydrogen-bonded
hydroxyl groups in a modified starch. Some investigations116 reported that the difference
in wavenumbers between the absorption bands of hydrogen-bonded and free hydroxyl
groups could be used as a measure of the relative strength of the hydrogen bonds. Thus,
it is clearly seen in Figures 5.10 to 5.13 that the hydrogen bonding in neat EVOH is
stronger than that in a modified starch. In the FTIR spectra of the blends of EVOH and a
modified starch, we find that the absorption band of the hydrogen-bonded hydroxyl
86
(a) −OH −OH
(b)
free −OH −OH −OH
(c)
3800 3600 3400 3200 3000 2800

−1
Wavenumber (cm )
Figure 5.10. FTIR spectra in the hydroxyl group stretching region for: (a) neat EVOH; (b)
neat modified starch AS-B; and (c) blend of 70/30 (AS-B)/EVOH.
−OH −OH
(a)
free −OH
(b)
(c)
free −OH
3800 3600 3400 3200 3000 2800

−1
Wavenumber (cm )
blend of 70/30 (AS-LF)/EVOH; and (c) neat modified starch AS-LF.
87
(a) −OH −OH
(b)
free −OH
(c)
3800 3600 3400 3200 3000 2800

−1
Wavenumber (cm )
blend of 70/30 (CS-B)/EVOH; and (c) neat modified starch CS-B.
(a)
−OH −OH
(b)
free −OH
(c)
3800 3600 3400 3200 3000 2800

−1
Wavenumber (cm )
blend of 70/30 (CS-LF)/EVOH; and (c) neat modified starch CS-LF.
88
groups is shifted to around 3220 cm−1. The difference in wavenumbers between the
absorption bands of the hydrogen-bonded hydroxyl groups and the free-hydroxyl groups
is found to be larger in the blends of EVOH and a modified starch than in a modified
starch or in neat EVOH. Thus, the hydrogen bonding between EVOH and a modified
starch in a blend is stronger than that in self-association of neat EVOH.
5.3 Crystallization of EVOH in Blends based on Modified Starch and EVOH
Wide-angle X-ray diffraction (WAXD) was used to investigate whether or not the
crystalline structure of EVOH was influenced by the hydrogen bonding between EVOH
and a modified starch in a blend. Previous research113,117 reported that the crystalline
structure was largely affected by the amount of vinyl alcohol groups in EVOH. The
crystalline structure takes orthorhombic lattice when the amount of vinyl alcohol groups
is lower than 20 mol %, and takes monoclinic lattice when the amount of vinyl alcohol
groups is higher than 20 mol %. It was also found that the composition-dependence of
crystalline structure described above is only valid for slow crystallized samples. Thermal
history also has an influence on the crystalline structures of EVOH. The literature112,118
showed that various cooling rates or crystallization temperatures could induce a change in
crystalline lattice between monoclinic lattice and orthorhombic lattice.
Figure 5.14 gives WAXD patterns of neat EVOH samples at various annealing
temperatures. It is clearly seen that the diffraction patterns of EVOH are largely
influenced by crystallization temperature. The quenched sample has a pattern
characteristic of an orthorhombic lattice, with the (110) reflection peak being located at
89
monoclinic lattice group

(1)
(2)
(3)
(4)
(5)
orthohombic lattice group
16 17 18 19 20 21 22 23 24 25
2θ (degree)
Figure 5.14. WAXD patterns of neat EVOH at different annealing temperatures (oC):
(1) 143; (2) 123; (3) 103; (4) 83; and (5) quench. Annealing period was for 3 h, and the
specimen was quenched by liquid nitrogen.
20.5o (2θ). With increasing crystallization temperature, the (110) reflection peak is
broadened and split into two monoclinic reflection (110) and (110) peaks. This change in
the crystallization morphology was not observed during a typical temperature scan of the
samples, even at the relatively slow ramp speed of 5 oC/min, because of its rather slow
crystallization kinetics.
The change in crystalline morphology described above in neat EVOH has been
reported.112,118 Figures 5.15 to 5.18 give WAXD patterns of the blends based on EVOH
and a modified starch, crystallizing at various temperatures. The reflection peaks shown
in the WAXD patterns of the blends are ascribed to the crystalline phase of EVOH in the
blend (the modified starch is amorphous). Referring to Figures 5.15 to 5.18, it is shown
90
Intensity (arb. unit) (1)
(2)
(3)
(4)
16 17 18 19 20 21 22 23 24 25
2θ (degree)
Figure 5.15. WAXD patterns for a 70/30 (AS-B)/EVOH blend at different annealing
temperatures (oC): (1) 145; (2) 125; (3) 105; and (4) quench.
(1)
(2)
(3)
(4)
(5)
16 17 18 19 20 21 22 23 24 25
2θ (degree)
Figure 5.16. WAXD patterns for a 70/30 (AS-LF)/EVOH blend at different annealing
temperatures (oC): (1) 130; (2) 110; (3) 90; (4) 70; and (5) quench.
91
(1)
(2)
(3)
(4)
16 17 18 19 20 21 22 23 24 25
2θ (degree)
Figure 5.17. WAXD patterns for a 70/30 (CS-B)/EVOH blend at different annealing
temperatures (oC): (1) 143; (2) 123; (3) 103; and (4) quench.
(1)
(2)
(3)
(4)
(5)
16 17 18 19 20 21 22 23 24 25
2θ (degree)
Figure 5.18. WAXD patterns for a 70/30 (CS-LF)/EVOH blend at different annealing
temperatures (oC): (1) 132; (2) 112; (3) 92; (4) 72; and (5) quench.
92
that the change in the crystalline morphology in a blend with increasing crystallization
temperature is similar to that in neat EVOH (see Figure 5.14).
5.4 Mechanical Properties of Blends based on EVOH and Modified Starch
Figures 5.19 to 5.22 give the tensile properties (tensile strength, Young’s modulus,
and elongation at break) of the blends based on a modified starch and EVOH. The
dashed line in the figures denotes a linear additive rule as a reference. For the tensile
properties of the blend based on modified starch and EVOH, it is worth noting that all
(AS-B)/EVOH blends, (AS-LF)/EVOH blends, (CS-B)/EVOH blends, and (CS-LF)/
EVOH blends exhibit a positive deviation from linearity for the tensile properties versus
composition plots. Then the tensile properties of blends are enhanced over those of the
constituent components. These synergistic effects obtained in the blends suggest an
enhanced miscibility between the modified starch and EVOH. Usually, the synergistic
effects for tensile properties have been found in miscible blends in which the
densification of the blends occurred due to the specific interaction. We ascribed the
apparent miscibility of the blends to the formation of hydrogen bonds between the
hydroxyl groups in a modified starch and the hydroxyl group in vinyl alcohol units of
EVOH. In the previous section, the attractive interaction between a modified starch and
EVOH in the blends have been characterized by FTIR spectroscopy and DSC.
93
140 7.0
(a) (b)
Tensile strength (MPa)
Young's modulus (GPa)

6.5
120
6.0
100
5.5
80
5.0
60 4.5
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
EVOH (wt fraction) EVOH (wt fraction)
60
(c)
50
Elongation at break (%)
40
30
20
10
0
0.0 0.2 0.4 0.6 0.8 1.0
EVOH (wt fraction)
Figure 5.19. Tensile properties of (AS-B)/EVOH blends: (a) tensile strength; (b)
Young’s modulus; and (c) elongation at break.
94
140 7
(a) (b)
120
Young's Modulus (GPa)

100
5
80
4
60
40 3
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
60
(c)
50
Elongation at Break (%)
40
30
20
10
0
0.0 0.2 0.4 0.6 0.8 1.0
EVOH (wt fraction)
Figure 5.20. Tensile properties of (AS-LF)/EVOH blends: (a) tensile strength; (b)
95
140 7.0
(a) (b)

120 6.5
100 6.0
80 5.5
60 5.0
40 4.5
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
60
(c)
50
40
30
20
10
0
0.0 0.2 0.4 0.6 0.8 1.0
EVOH (wt fraction)
Figure 5.21. Tensile properties of (CS-B)/EVOH blends: (a) tensile strength; (b)
96
140 7.0
(a) (b)
6.5

120
6.0
100 5.5
5.0
80
4.5
60
4.0
40 3.5
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
60
(c)
50
40
30
20
10
0
0.0 0.2 0.4 0.6 0.8 1.0
EVOH (wt fraction)
Figure 5.22. Tensile properties of (CS-LF)/EVOH blends: (a) tensile strength; (b)
Young’s modulus; and (c) elongation at break
97
A series of chemically modified starch synthesized in the present study was blended
with EVOH (having 27 mol % of ethylene component). The miscibility between the
modified starch and EVOH was characterized by phase diagrams. The blends of a
modified starch and EVOH was characterized by DSC. The DSC thermograms have
shown a single glass transition temperature, suggesting a good miscibility between the
modified starch and EVOH. We ascribed the miscibility in the blends to the formation of
the hydrogen bonds between the hydroxyl groups in EVOH and a modified starch.
Additionally, the DSC thermograms have shown a melting point depression and a
decreasing melting enthalpy with the increase of the composition of the modified starch
in the blends, suggesting that the crystallization of EVOH was interrupted by the
modified starch. We also ascribed this interruption to the formation of the hydrogen
bonds between a modified starch and EVOH. The FTIR spectra of the blends have
shown a broad absorbance band of the hydrogen-bonded hydroxyl groups, which was
located at a lower wavenumber than the absorbance band of hydrogen-bonded hydroxyl
groups in neat EVOH, suggesting that the hydrogen bonds formed between a modified
starch and EVOH in the binary blends are favored over the hydrogen bonds due to self-
association in neat EVOH.
Furthermore, the crystalline structure of EVOH in the blends of a modified starch
and EVOH was characterized by WAXD. In neat EVOH, the crystalline structure of
EVOH takes orthorhombic lattice in the quenched specimen and evolves into monoclinic
lattice as the crystallization temperature is increased. The WAXD patterns have shown
that the crystalline structure of EVOH in the blends of a modified starch and EVOH did
98
not change from that of neat EVOH. The tensile properties of blends of a modified starch
and EVOH are found to have a positive deviation from linearity over the entire blend
composition, indicating that the blends are miscible.
99
CHAPTER VI
NANOCOMPOSITES BASED ON MODIFIED STARCH
6.1 Introduction
The research on nanocomposites started in the early 1990s by the publication about
nylon 6 of Toyota scientists.119-121 A very high degree of dispersion of organoclay
aggregates will generate large surface areas, which is supposed to significantly enhance
the mechanical properties of nanocomposites. Furthermore, a high degree of dispersion
of nanoclay aggregates also was reported to have a profound influence on the
morphology of the polymer matrix due to its enhanced surface areas.122 On the other
hand, highly dispersed organoclay nanocomposites have been found to increase heat
distortion temperature and the gas barrier properties.119,123-127
To achieve a high degree of dispersion of nanoclay aggregates, a fundamental issue
should be addressed about compatibility between a polymer matrix and clay. During the
last two decades, much effort has been spent on the modification of the surface of natural
clay by developing surfactants. However, there is no universal surfactant that enables
one to achieve a high degree of dispersion of nanocomposites based on any polymer
matrix. One has to modify either the chemical structure of the polymer matrix or the
chemical structure of a surfactant residing at the surface of the nanoclay to obtain the
desired compatibility between the polymer matrix and nanoclay.
100
Han et al.128-134 have reported on successful research results on the preparation of a
high degree of dispersion of nanocomposites. They found exfoliated nanoclay
(evidenced by TEM and XRD) in nanocomposites by introducing functional group(s) into
a polymer matrix. In those studies, natural clay (MMT) and two commercial organoclays
(Cloisite 30B and Cloisite 15A) were employed. The specific interactions, including
hydrogen bonding, ionic interaction, or ion-dipole interaction, between the functional
group(s) in a polymer matrix and the layered silicates of nanoclay were confirmed by
FTIR spectroscopy, UV-vis spectroscopy, and solid-state NMR spectroscopy. They
established guidelines for the preparation of nanocomposites with a high degree of
dispersion.
The research on the starch-based nanocomposites began several years ago.5,6 Since
then, many reports have been published on starch-based nanocomposites.100-110 However,
all XRD patterns and TEM images have shown quite a low degree of dispersion of
nanoclay aggregates.
In this dissertation, we prepared and characterized the nanocomposites based on the
chemically modified starch. To investigate how functional groups in a modified starch
affect the dispersion characteristics of nanocomposites, a series of chemically modified
starches has been synthesized with the chemical structures, as shown in Scheme 6.1. In
Chapter IV we presented the chemical structures, thermal behavior, biodegradability, and
hydrophobicity of these chemically modified starches, and in Chapter V we presented the
miscibility of the blends based on a chemically modified starch and EVOH. As described
in Chapter IV, we attached the hexanoyl groups or benzoyl groups into starch molecules
to lower the glass transition temperature and enhance the hydrophobicity of starch.
101
Scheme 6.1. Chemical structures of the modified starches.
(CH2)4CH3
O
O
O
(CH2)4CH3 O
O O
O
O
O
O O
OH O
O O O
O
O O O OH
O O
OH OH
O
O OH
O
Cl OH
O O H3C N CH3 Cl
ONa ONa CH3 H3C N CH3
CH3
AS-LF AS-B CS-LF
CS-B
On the other hand, from the point of view of preparing nanocomposites, we
attached ionic groups (acetate sodium for anionic group or trimethylammonium chloride
for cationic group) into the starch molecules with the expectation that the attached ionic
groups may have ionic interactions with layered silicates of clay. Specifically, the
cationic groups attached onto a starch are expected to have ionic interaction with the
negatively charged surface of natural clay (MMT). Note that the counter ion residing at
the surface of layered silicates in MMT is Na+. And the anionic groups are expected to
have ionic interaction with the positively charged N+ in the surfactant (MT2EtOH for
Cloisite 30B and 2M2HT for Cloisite 15A) residing at the surface of organoclay. The
chemical structures of the surfactants are shown in Scheme 6.2. In the chemical structure
of MT2EtOH, N+ denotes quaternary ammonium chloride, and T denotes tallow
102
consisting of ca. 65% C18, ca. 30% C16, and ca. 5% C14. In the chemical structure of
2M2HT, N+ denotes quaternary ammonium chloride, and HT denotes hydrogenated
tallow consisting of ca. 65% C18, ca. 30% C16, and ca. 5% C14.
Scheme 6.2. Chemical structures of the surfactant MT2EtOH residing at the surface of
Cloisite 30B and the surfactant 2M2HT residing at the surface of Cloisite 15A.
CH2CH2OH CH3
CH3 N T CH3 N HT
CH2CH2OH HT
MT2EtOH 2M2HT
The dispersion characteristics of the nanocomposites prepared in the present study
were investigated using X-ray diffraction (XRD) and transmission electron microscopy
(TEM). The presence of ionic interactions between a modified starch and nanoclay was
investigated using Fourier transform infrared (FTIR) spectroscopy. The mechanical
properties of nanocomposites prepared were also measured.
6.2 Nanocomposites based on Neat EVOH
Figure 6.1 gives the XRD patterns for nanoclays used in this study, which include
MMT, Cloisite 30B, and Cloisite 15A. Note in Figure 6.1 that MMT has a gallery
distance (d001 spacing) of 1.1 nm, while Cloisite 30B and Cloisite 15A, due to the
presence of a surfactant, have a larger gallery distance, 1.9 nm and 3.1 nm, respectively.
103
3.1 nm

(a)
1.1 nm
1.9 nm (b)
(c)
2 3 4 5 6 7 8 9 10
2θ (degree)
Figure 6.1. XRD patterns for: (a) Cloisite 15A; (b) MMT; and (c) Cloisite 30B.
The goal of this research was to investigate how the functional group(s) attached
onto starch might affect the dispersion characteristics of organoclay (or natural clay)
aggregates by specific interactions. Thus, before characterizing the dispersion
characteristics of nanocomposites based on a mixture of a modified starch and EVOH,
the dispersion of nanocomposites based on neat EVOH should be investigated. Figure
6.2 gives XRD patterns for nanocomposites based on neat EVOH. It is worth noting that
the XRD patterns for EVOH/MMT nanocomposite and EVOH/Cloisite 15A
nanocomposite show little difference from the XRD patterns for Cloisite 15A and MMT,
suggesting that both nanocomposites have a very poor dispersion of nanoclay aggregates.
This is not surprising, because no attractive interaction can be expected between neat
EVOH and the surface of MMT or a surfactant residing at the surface of Cloisite 15A.
104
3.2 nm
(a)
2.3 nm
(b)
1.2 nm
(c)
2 3 4 5 6 7 8 9 10
2θ (degree)
Figure 6.2. XRD patterns for: (a) EVOH/Cloisite 15A nanocomposite; (b) EVOH/
Cloisite 30B nanocomposite; and (c) EVOH/MMT nanocomposite.
On the other hand, the EVOH/Cloisite 30B nanocomposite has a d001 spacing of 2.3 nm,
an increase of 0.4 nm over the d001 spacing of Cloisite 30B, suggesting that the
nanocomposite might have intercalated Cloisite 30B aggregates.
Figure 6.3 shows TEM images for the nanocomposites based on neat EVOH.
Both XRD patterns and TEM images indicated that there is no high degree of dispersion
of organoclay aggregates in neat EVOH. The preparation of nanocomposites based on
EVOH has previously been reported.132 In that study, EVOH had 53 mol % of vinyl
alcohol, while in the present study EVOH has 79 mol % of vinyl alcohol. The XRD
results showed that the d001 spacing of EVOH/Cloisite 30B nanocomposite has increased
by 1.69 nm over the d001 spacing of Cloisite 30B. Although there are hydroxyl groups on
both EVOH and the surfactant residing at the surface of Cloisite 30B, the hydrogen
105
(a) (b)
200 nm 200 nm
(c)
200 nm
Figure 6.3. TEM images for: (a) EVOH/MMT nanocomposite; (b) EVOH/Cloisite 15A
nanocomposite; and (c) EVOH/Cloisite 30B nanocomposite, in which the dark areas
represent the clay, and the grey/white areas represent the polymer matrix.
bonding between them was believed to be hindered, because the attractive interaction
within EVOH molecules was very strong.132 The above observations led us to conclude
that the EVOH employed in the present study could not have a high degree of dispersion
of organoclay aggregates.
106
6.3 Nanocomposites containing Anionically Modified Starch
Figure 6.4 gives XRD patterns for the nanocomposites based on the (AS-B)/EVOH
blend. It is worth noting that the nanocomposites containing organoclay (Cloisite 30B or
Cloisite 15A) show featureless XRD patterns, suggesting that organoclay aggregates
might have been highly dispersed. On the other hand, the nanocomposite containing
MMT has a d001 spacing of 1.3 nm, which is slightly higher than the d001 spacing of MMT
(1.1 nm). This is not surprising because there is no attractive interaction expected
between AS-B and the surface of MMT.
Figure 6.5 shows TEM images for the nanocomposites based on the (AS-B)/EVOH
blend, and Cloisite 15A, Cloisite 30B, or MMT. It is clearly seen in Figure 6.5 that both
the (AS-B)/EVOH/Cloisite 30B and (AS-B)/EVOH/Cloisite 15A nanocomposite have a

(a)
(b)
1.3 nm
(c)
2 3 4 5 6 7 8 9 10
2θ (degree)
Figure 6.4. XRD patterns for: (a) (AS-B)/EVOH/Cloisite 15A nanocomposite;

(b) (AS-B)/EVOH/Cloisite 30B nanocomposite; and (c) (AS-B)/EVOH/MMT
nanocomposite.
107
(a) (b)
200 nm 200 nm
(c)
200 nm
Figure 6.5. TEM images for: (a) (AS-B)/EVOH/Cloisite 30B nanocomposite;

(b) (AS-B)/EVOH/Cloisite 15A nanocomposite; and (c) (AS-B)/EVOH/MMT
nanocomposite.
very high degree of dispersion of organoclay aggregates in the matrix, whereas the
(AS-B)/EVOH/MMT nanocomposite has large MMT aggregates, indicating a poor
dispersion of the nanocomposites.
Both XRD patterns and TEM images shown above indicate that both the (AS-B)/
EVOH/Cloisite 30B and (AS-B)/EVOH/Cloisite 15A nanocomposites have a high degree
of dispersion of organoclay aggregates, whereas the (AS-B)/EVOH/MMT nanocomposite
108
has a very poor dispersion of MMT aggregates. Note that the surfactant residing at the
surface of Cloisite 30B or Cloisite 15A have positively charged N+, and AS-B has
anionic functional group −COO−. Thus, the high degree of dispersion of organoclay
aggregates (so-called exfoliation of layered silicates) might have resulted from the ionic
interaction between N+ at the surface of the organoclay and −COO− in the modified
starch. It is well established that the ionic interaction is much stronger, although not as
strong as covalent bonding, than the hydrogen bonding.
To directly probe evidence of the ionic interaction between −COO− and N+, FTIR
spectroscopy was employed. Figure 6.6 gives the FTIR spectra for (a) (AS-B)/EVOH
blend, (b) (AS-B)/EVOH/Cloisite 30B nanocomposite, (c) (AS-B)/EVOH/Cloisite 15A
nanocomposite, and (d) (AS-B)/EVOH/MMT nanocomposite.

(d)
(c)
(b)
(a)
4000 3000 2000 1000

−1
Wavenumber (cm )
Figure 6.6. FTIR spectra for: (a) (AS-B)/EVOH blend; (b) (AS-B)/EVOH/Cloisite 30B
nanocomposite; (c) (AS-B)/EVOH/Cloisite 15A nanocomposite; and (d) (AS-B)/EVOH/
MMT nanocomposite.
109
Figure 6.7 gives the carboxyl group stretching region for the same FTIR spectra
shown in Figure 6.6. In reference to Figure 6.7, the absorbance band at 1737 cm−1 is
attributed to the stretching of carbonyl groups (C=O) in the benzoyl ester group in a
modified starch. The absorbance band at 1594 cm−1 in the spectra of the AS-B/EVOH
−
blend is attributed to asymmetric stretching carboxylate group (−COO ) in the AS-B. It
is seen that the absorbance band of carboxylate group is shifted to 1572 cm−1 for the
nanocomposites containing a high degree of dispersion of Cloisite 30B or Cloisite 15A
aggregates. There is no shift in the absorbance band of carboxylate group for the
nanocomposite containing MMT aggregates. Previous studies133,135,136 reported that the
absorbance band of carboxylate group was shifted to a lower wavenumber when ionic
interactions were present between the carboxylate groups and other positively charged
groups. Yano and coworkers135,136 reported that in the binary blends of sodium and zinc
salt ionomers of poly(ethylene-co-methacrylate) (PEMMA), the absorbance band of
asymmetric stretching of carboxylate groups was found at 1569 cm−1 when carboxylate
groups bridged sodium and zinc cations. Zha et al.133 reported that in the preparation of
nanocomposites based on synthetic polymers (homopolymer or block polymer)
end-functionalized by carboxylate sodium salt, the absorbance band of asymmetric
stretching of carboxylate groups was found at 1570 cm−1 because of the ionic interaction
between the carboxylate groups and the N+ in the surfactant residing at the surface of
Cloisite 30B. Thus, it is reasonable to state that the absorbance band at 1572 cm−1 found
in Figure 6.7 is asymmetric stretching of carboxylate group, while having ionic
interaction with N+ in the surfactant residing at the surface of Cloisite 30B or Cloisite
110
O
C
(1)
(1) O
(3)
(d)
O (2)
(c) O C
O Na
(2)
(b) N
(3) O
(a) (3)
O C
O Na
1800 1700 1600 1500 1400

−1
Wavenumber (cm )
Figure 6.7. Carboxylate group stretching region for the FTIR spectra shown in Figure 6.6
for: (a) (AS-B)/EVOH blend; (b) (AS-B)/EVOH/Cloisite 30B nanocomposite; (c)
(AS-B)/EVOH/Cloisite 15A; and (d) (AS-B)/EVOH/MMT nanocomposite.
15A. On the other hand, since there are no functional groups on the surface of MMT, the
absorbance band of asymmetric stretching of carboxylate groups on a modified starch did
not shift along the spectra of the (AS-B)/EVOH/MMT nanocomposite, because there was
no ionic interaction present.
The XRD patterns and TEM images indicated that both (AS-B)/EVOH/Cloisite 30B
and (AS-B)/EVOH/Cloisite 15A nanocomposites have a high degree of dispersion of
organoclay aggregates. We ascribed this observation to the presence of the ionic
interaction between the positively charged N+ residing at the surface of organoclay,
Cloisite 30B or Cloisite 15A, and the negatively charged carboxylate groups attached
onto the main chain of a modified starch. The FTIR spectra showed that the absorbance
111
band of carboxylate groups was shifted to a lower wavenumber, indicative of the
presence of the ionic interaction occurring on the carboxylate groups. On the other hand,
the (AS-B)/EVOH/MMT nanocomposite has a poor dispersion of MMT aggregates.
There is no attractive interaction formed between the AS-B and MMT in the
nanocomposite.
The dispersion of nanoclay (Cloisite 30B, Cloisite 15A, or MMT) aggregates in the
nanocomposites based on the blends of (AS-LF)/EVOH was also characterized. It should
be noted that the anionic moiety in the AS-LF also has a carboxylate group, which is the
same as in the AS-B. Figure 6.8 shows XRD patterns for the nanocomposites based on
the blends of (AS-LF)/EVOH. It can clearly be seen that the aggregates of clay have
similar dispersion characteristics in the (AS-LF)/EVOH blend as in the (AS-B)/EVOH

(1)
1.4 nm
(2)
(3)
2 3 4 5 6 7 8 9 10
2θ (degree)
Figure 6.8. XRD patterns for: (1) (AS-LF)/EVOH/Cloisite 15A nanocomposite;
(2) (AS-LF)/EVOH/MMT nanocomposite; and (3) (AS-LF)/EVOH/Cloisite 30B
nanocomposite.
112
blend. Featureless XRD patterns for (AS-LF)/EVOH/Cloisite 30B and (AS-LF)/EVOH/
Cloisite 15A nanocomposite indicate a high degree of dispersion of organoclay
aggregates in the respective blends. On the other hand, the (AS-LF)/EVOH/MMT
nanocomposite has a d001 spacing of 1.4 nm, which is 0.3 nm higher than the d001 spacing
of MMT (1.1 nm) (see Figure 6.1) and only 0.1 nm higher than the d001 spacing of the
(AS-B)/EVOH/MMT nanocomposite (1.3 nm), given in Figure 6.4.
Figure 6.9 gives TEM images of the nanocomposites based on (AS-LF)/EVOH
blends, and Cloisite 30B, Cloisite 15A, or MMT. It is clearly seen that both (AS-LF)/
(a) (b)
200 nm 200 nm
(c)
200 nm
Figure 6.9. TEM images for: (a) (AS-LF)/EVOH/Cloisite 30B nanocomposite;

(b) (AS-LF)/EVOH/Cloisite 15A nanocomposite; and (c) (AS-LF)/EVOH/MMT
nanocomposite.
113
EVOH/Cloisite 30B and AS-LF/EVOH/Cloisite 15A nanocomposites have a very high
degree of dispersion of organoclay aggregates in the matrix, whereas the (AS-LF)/
EVOH/MMT nanocomposite has large clay aggregates, indicating a poor dispersion of
MMT aggregates.
The XRD patterns and TEM images shown above suggest that organoclay
aggregates (Cloisite 30B or Cloisite 15) have a high degree of dispersion in the
nanocomposites based on the (AS-LF)/EVOH blend, whereas MMT aggregates have a
very poor dispersion in the (AS-LF)/EVOH/MMT nanocomposite.
Figure 6.10 gives the FTIR spectra in carboxylate group stretching region for the
nanocomposites based on the (AS-LF)/EVOH blend, and Cloisite 15A, Cloisite 30B, or
MMT. The absorbance band at 1743 cm−1 was designated to the stretching of carbonyl
group (C=O) in the hexanoyl group, contrasting to the absorbance band at 1737 cm−1
designated to the same carbonyl group (C=O) in the benzoyl ester group, shown in Figure
6.7. In the FTIR spectra of the (AS-LF)/EVOH blend shown in Figure 6.10, the
absorbance band at 1594 cm−1 was designated to asymmetric stretching of the
carboxylate group (−COO−) in the AS-LF. Similar to that observed in Figure 6.7, the
absorbance band of carboxylate group shifted to a lower wavenumber in the
nanocomposites containing Cloisite 30B or Cloisite 15A with a high degree of dispersion,
indicating the presence of the ionic interaction between the carboxylate groups (−COO−)
and N+ residing at the surface of Cloisite 30B or Cloisite 15A. On the other hand, the
spectra of the (AS-LF)/EVOH/MMT nanocomposite show that the absorbance band of
carboxylate group has not changed at all, suggesting no ionic interaction in the
nanocomposite.
114
O C C C
(1) C C C
(1)
Absorbance (arb. unit) O
(3) (d)
O
(2)
(c) O C
O Na
(2) (b) N
(a)
O
(3)
O C
(3) O Na
1800 1700 1600 1500 1400

−1
Wavenumber (cm )
Figure 6.10. FTIR spectra at carboxyl group stretching region for: (a) (AS-LF)/EVOH
blend; (b) (AS-LF)/EVOH/Cloisite 30B nanocomposite; (c) (AS-LF)/EVOH/Cloisite
15A nanocomposite; and (d) (AS-LF)/EVOH/MMT nanocomposite.
The dispersion characteristics of the nanoclay aggregates in the blends based on the
anionically modified starch and EVOH have been characterized by XRD and TEM. It
was found that the aggregates of organoclay (Cloisite 30B or Cloisite 15A) have a high
degree of dispersion, whereas the aggregates of MMT have a very poor dispersion in the
anionically modified starch. We ascribed the high degree of dispersion of organoclay
aggregates in nanocomposites based on anionically modified starch to the presence of the
−
ionic interaction between the negatively charged carboxylate group (−COO ) in the
modified starch and the positively charged N+ in the surfactant residing at the surface of
organoclay. This ionic interaction was confirmed by FTIR spectroscopy.
115
6.4 Nanocomposites containing Cationically Modified Starch
Figure 6.11 gives XRD patterns for the nanocomposites based on the blends of
cationically modified starch (CS-B) and EVOH, and Cloisite 15A, Cloisite 30B, or MMT.
It is seen in Figure 6.11 that the nanocomposite containing Cloisite 15A has the d001
spacing of 3.2 nm, and the nanocomposite containing Cloisite 30B has the d001 spacing of
2.2 nm. It is worth noting that both nanocomposites containing either Cloisite 15A or
Cloisite 30B have a d001 spacing only slightly higher than the d001 spacing of organoclay
shown in Figure 6.1, suggesting that the dispersion characteristics of the organoclay
aggregates in the polymer matrix would be low. This observation is not surprising
because sufficiently strong attractive interaction is not expected between the cationically
modified starch and the organoclay.

3.2 nm
(c)
2.2 nm
(b)
1.2 nm (a)
2 3 4 5 6 7 8 9 10
2θ (degree)
Figure 6.11. XRD patterns for: (a) (CS-B)/EVOH/MMT nanocomposite; (b) (CS-B)/
EVOH/Cloisite 30B nanocomposite; and (c) (CS-B)/EVOH/Cloisite 15A nanocomposite.
The nanocomposites were prepared by melt blending.
116
The XRD patterns further indicate that the nanocomposite containing MMT has a
d001 spacing of 1.2 nm, only 0.1 nm higher than the d001 spacing of MMT, suggesting that
the dispersion characteristics of MMT aggregates in the cationically modified starch
would also be very low.
Figure 6.12 gives TEM images for the nanocomposites based on the (CS-B)/EVOH
blend and Cloisite 15A, Cloisite 30B, or MMT. It is clearly seen in Figure 6.12 that all
(a) (b)
200 nm 200 nm
(c)
200 nm
Figure 6.12. TEM images for: (a) (CS-B)/EVOH/Cloisite 15A nanocomposite;

(b) (CS-B)/EVOH/Cloisite 30B nanocomposite; and (c) (CS-B)/EVOH/MMT
nanocomposite. The nanocomposites were prepared by melt blending.
117
nanocomposites have large clay aggregates, indicating the presence of poor dispersion of
clay aggregates, which is consistent with the speculation made above in reference to
Figure 6.11. Figure 6.13 gives XRD patterns for the nanocomposites based on the
(CS-LF)/EVOH blend. As can be seen in Figure 6.13, the nanocomposites based on the
(CS-LF)/ EVOH blend and Cloisite 15A, Cloisite 30B, or MMT have d001 spacings of 3.5,
2.2, and 1.2 nm, respectively, only slightly higher than the d001 spacing of clay, which
suggests that the dispersion of clays in CS-LF would be poor. Figure 6.14 gives the TEM
images for the nanocomposites based on the (CS-LF)/EVOH blend. It is clearly seen that
all nanocomposites have large clay aggregates. The results of XRD patterns and TEM
3.5 nm
(c)
2.2 nm
(b)
1.2 nm
(a)
2 3 4 5 6 7 8 9 10
2θ (degree)
Figure 6.13. XRD patterns for: (a) (CS-LF)/EVOH/MMT nanocomposite; (b) (CS-LF)/
EVOH/Cloisite 30B nanocomposite; and (c) (CS-LF)/EVOH/Cloisite 15A
118
(a) (b)
200 nm 200 nm
(c)
200 nm
Figure 6.14. TEM images for: (a) (CS-LF)/EVOH/Cloisite 15A nanocomposite;

(b) (CS-LF)/EVOH/Cloisite 30B nanocomposite; and (c) (CS-LF)/EVOH/MMT
images given in Figures 6.11 to 6.14 indicate that the aggregates of both organoclays
(Cloisite 30B and Cloisite 15A) and natural clay (MMT) have a poor dispersion in the
cationically modified starch (CS-LF and CS-B).
Figure 6.15 gives XRD patterns for the nanocomposites based on the cationically
modified starch CS-B prepared by solution blending. It is worth noting that the
119
3.3 nm
(c)
(b)
2.2 nm
(a)
2 3 4 5 6 7 8 9 10
2θ (degree)
Figure 6.15. XRD patterns for: (a) (CS-B)/Cloisite 30B nanocomposite; (b) (CS-B)/
MMT nanocomposite; and (c) (CS-B)/Cloisite 15A nanocomposites. The
nanocomposites were prepared by solution blending.
nanocomposites containing Cloisite 15A or Cloisite 30B have the d001 spacings of 3.3 nm
or 2.2 nm, both slightly higher than the d001 spacing of Cloisite 15A and Cloisite 30B (see
Figure 6.1), which suggests that a poor dispersion of organoclay aggregates in the
nanocomposites would be expected. On the other hand, the nanocomposite containing
MMT has featureless XRD patterns shown in Figure 6.15, indicating that the dispersion
characteristic of layered silicates of MMT in the CS-B would be good. Figure 6.16 gives
TEM images for the nanocomposites based on CS-B, and Cloisite 15A, Cloisite 30B, or
MMT. It can be clearly seen in Figure 6.16 that there are large clay aggregates in the
nanocomposites containing Cloisite 15A or Cloisite 30B, indicating poor dispersion of
120
(a) (b)
200 nm 200 nm
(c)
200 nm
Figure 6.16. TEM images for: (a) (CS-B)/Cloisite 30B nanocomposite; (b) (CS-B)/MMT
nanocomposite; and (c) (CS-B)/Cloisite 15A nanocomposite. The nanocomposites were
prepared by solution blending.
clay aggregates in the CS-B, which is consistent with the XRD patterns shown in Figure
6.15. On the other hand, the TEM image for the nanocomposite containing MMT given
in Figure 6.16 shows a very high degree of dispersion of MMT aggregates in the CS-B
matrix.
Figure 6.17 gives XRD patterns, and Figure 6.18 gives TEM images for the
nanocomposites based on CS-LF which were prepared by solution mixing. It can be seen
121
3.4 nm
(c)
(b)
2.4 nm (a)
2 3 4 5 6 7 8 9 10
2θ (degree)
Figure 6.17. XRD patterns for: (a) (CS-LF)/Cloisite 30B nanocomposite; (b) (CS-LF)/
MMT nanocomposite; and (c) (CS-LF)/Cloisite 15A nanocomposite. The
(a) (b)
200 nm 200 nm
(c)
200 nm
Figure 6.18. TEM images for: (a) (CS-LF)/Cloisite 30B nanocomposite; (b) (CS-LF)/
MMT nanocomposite; and (c) (CS-LF)/Cloisite 15A nanocomposite. The
122
that the dispersion characteristics of clay aggregates in the nanocomposites based on the
CS-LF is similar to that of the nanocomposites based on the CS-B (see Figure 6.16),
namely, the aggregates of Cloisite 30B or Cloisite 15A have a poor dispersion in the
CS-LF matrix, whereas the aggregates of MMT have a good dispersion in the CS-LF
matrix.
In summary, we have observed that both organoclays, Cloisite 15A and Cloisite
30B, have poor dispersion characteristics in the nanocomposites based on cationically
modified starch, which were prepared by melt blending or solution blending. The poor
dispersion characteristics of the organoclay aggregates resulted from poor compatibility
between the layered silicates and the modified starch, which is attributed to insufficient
strength of attractive interactions between the surfactant residing at the surface of an
organoclay and the cationically modified starch. On the other hand, the experimental
results show poor dispersion characteristics of MMT aggregates in the nanocomposite
based on a cationically modified starch prepared by melt blending, whereas MMT
aggregates have a high degree of dispersion in the nanocomposite based on the same
cationically modified starch, which was prepared by solution blending. The above
observation points out that the preparation methods of nanocomposites have a significant
influence on the dispersion characteristics of MMT aggregates in a cationically modified
starch. The high degree of dispersion characteristics of MMT aggregates in the
nanocomposite based on a cationically modified starch, which was prepared by solution
blending, can be attributed to the presence of the ionic interaction between the positively
charged −N+(CH3)3 in the modified starch and the negatively charged surface of layered
silicates of MMT.
123
Figure 6.19 gives the FTIR spectra in C-N+ stretching mode of the
nanocomposites based on the cationically modified starch (CS-B) prepared by solution
blending. In the FTIR spectra of neat CS-B shown in Figure 6.19, the absorbance band at
957 cm−1 was designated to the asymmetric C-N+ stretching mode vas(C-N+), whereas the
absorbance bands locating at 911 cm−1 and 872 cm−1 were designated to the symmetric
C-N+ stretching modes vs(C-N+). As shown in Figure 6.19, the absorbance bands of
vs(C-N+) were shifted to higher wavenumbers of 923 cm−1 and 884 cm−1 from 911 cm−1
and 872 cm−1, respectively, in the nanocomposite having a high degree of dispersion of
MMT aggregates. On the other hand, there is no shift in the absorbance bands of vs(C-N+)
in nanocomposites containing organoclays (Cloisite 15A or Cloisite 30B).
vas(C-N+)
vs(C-N+)
Starch O CH3
C C C N CH3
(d)
OH CH3
(c)
(b)
(a)
1000 950 900 850 800

−1
Wavenumber (cm )
Figure 6.19. FTIR spectra in the C-N+ stretching mode region of the nanocomposites
based on cationically modified starch prepared by solution blending: (a) neat CS-B; (b)
(CS-B)/MMT nanocomposite; (c) (CS-B)/Cloisite 15A nanocomposite; and (d) (CS-B)/
Cloisite 30B nanocomposite.
124
The number of absorbance bands of vs(C-N+) and their wavenumbers in infrared
spectroscopy or Raman spectroscopy were found to be very sensitive to the conformation
of O-C-C-N+ group.137-139 In the trans-conformation of the O-C-C-N+ group, the
absorbance bands of vs(C-N+) were reported to be at 925 cm−1 and 875 cm−1.139,140 In
gauche conformation, the absorbance bands of vs(C-N+) were observed at 905 cm−1 and
860 cm−1.139,140 Previous researchers137,141 reported that the gauche conformation of
O-C-C-N+ group in choline-containing structures is more stable than trans-conformation
in general. Thus, the gauche-conformation was reported to be dominant in choline
group.137,141-144 However, the trans-conformation becomes more stable than the gauche
conformation in some crystals or specific structures, which is attributable to specific
intermolecular interactions.137 In the investigation of thin silica film covered by a
1,2-dimyristoyl-sn-glycero-3-phosphocholine bilayer, infrared spectroscopy results
showed that O-C-C-N+ group preferably had the trans-conformation due to the ionic
interaction between the positively charged C-N+ and the negatively charged silicate
surface.140,145 Other research groups138 also reported on a conformation change of
O-C-C-N+ group arising from ionic interactions between the positively charged
O-C-C-N+ group and the negatively charged acid moiety in bisdesmosidic triterpenoid
glycosides, and infrared spectroscopy was used to confirm the interaction.
Thus, the shift in the absorbance bands of vs(C-N+) to higher wavenumbers in
nanocomposites containing MMT aggregates shown in Figure 6.19 can reasonably be
explained by the ionic interaction between the C-N+ in the modified starch and the
negatively charged surface of layered silicates in MMT aggregates. On the other hand, in
125
nanocomposites containing organoclays (Cloisite 15A or Cloisite 30B), the fact that there
is no shift in vs(C-N+) to higher wavenumbers in the FTIR spectra indicates that the
conformation of O-C-C-N+ has not changed, suggesting that no ionic interaction occurred
on the C-N+ group in the modified starch CS-B.
So far, XRD patterns and TEM images showed that MMT aggregates have a high
degree of dispersion characteristics in the nanocomposites based on the cationically
modified starch (CS-B), which was prepared by solution blending. We ascribed the high
degree of dispersion characteristics observed to the ionic interactions between the
positively charged −N+(CH3)3 and negatively charged surface of silicates in MMT,
which was confirmed by the FTIR spectra in the C-N+ stretching mode shown in Figure
6.19.
One might ask why the nanocomposite based on the same cationically modified
starch (CS-B) but prepared by melt blending, has poor dispersion characteristics of MMT
aggregates (refer to Figures 6.11 and 6.12). To answer the question, let us first show the
FTIR spectra in the C-N+ stretching mode region for the nanocomposites based on the
cationically modified starch, which were prepared by melt blending, as shown in Figure
6.20.
As described above in reference to Figure 6.19, the absorbance bands at 911 cm−1
and 872 cm−1 are ascribed to the symmetric stretching mode of C-N+(vs(C-N+)) in a
modified starch (CS-B). On the other hand, referring to Figure 6.20, the absorbance
bands of vs(C-N+) in the nanocomposites containing Cloisite 15A or Cloisite 30B have
not changed, indicating that no interaction occurred on the C-N+ group in a modified
126
vas(C-N+)
vs(C-N+)
Starch O CH3
C C C N CH3
(d)
OH CH3
(c)
(b)
(a)
1000 950 900 850 800

−1
Wavenumber (cm )
Figure 6.20. FTIR spectrum in the C-N+ stretching mode region of nanocomposites
based on the cationically modified starch prepared by melt blending: (a) neat (CS-B)/
EVOH mixture; (b) (CS-B)/EVOH/Cloisite 15A nanocomposite; (c) (CS-B)/EVOH/
Cloisite 30B nanocomposite; and (d) (CS-B)/EVOH/MMT nanocomposite.
starch (CS-B). We further find from Figure 6.20 that the absorbance bands of vs(C-N+) in
the nanocomposite containing MMT have not changed, indicating that the proposed ionic
interaction between the positively charged −N+(CH3)3 in a modified starch (CS-B) and
the negatively charged surface of silicates in MMT aggregates have not occurred in the
nanocomposite prepared by melt blending. Thus, MMT aggregates have poor dispersion
characteristics in the nanocomposite prepared by melt blending, as has been described in
reference to Figures 6.11 to 6.14.
One might ask another question as to why the positively charged −N+(CH3)3 in a
cationically modified starch can form ionic interaction with the negatively charged
127
surface of silicates in MMT aggregates in the nanocomposite prepared by solution
blending, but fails to form ionic interaction with the same MMT in the nanocomposite
prepared by melt blending. We hasten to point out that water was used as the co-solvent
in the preparation of nanocomposites via solution blending. To answer the question
posed above, let us examine the chemical structure of MMT and the origins of the
negative charge at the surface of silicates in MMT.
Figure 6.21 gives schematic of the chemical structure of MMT.146 It should be
noted that the exchangeable cations in the interlayers of MMT are not quite accurately
shown in Figure 6.21. We will elaborate on this later. Referring to Figure 6.21, the
crystal lattice of MMT consists of layers made up of two tetrahedrally coordinated silicon
atoms fused to an edge-shared octahedral sheet of either aluminum or magnesium
hydroxide. The layer thickness is approximately 1 nm, and the lateral dimensions of
these layers vary from 30 nm to several microns.146 Normally, the net negative charge of
layers in MMT aggregates is generated either by tetrahedral substitution (silicon atoms in
Figure 6.21. Structure of MMT.146 (Reprinted with permission from Elsevier.)
128
tetrahedral sheet were substituted by aluminum atoms) or by octahedral substitution (in
octahedral sheet, Al3+ was replaced by Mg2+ or by Fe2+, or Mg2+ was replaced by
Li+).147 The negative surface charge of the layers in pristine MMT mainly resulted from
octahedral substitution.146,147 Figure 6.22 shows schematics of MMT layers from (a) the
side view and (b) the top view.
From the side view of the silicate layers in MMT aggregates shown in Figure
6.22(a), we can see that the tetrahedral layer consists of two consecutive layers of oxygen
atoms. In each layer of oxygen atoms, every six oxygen atoms form a cavity with a
diameter of 0.26 nm, shown in Figure 6.22(b).148 Normally, the electron orbital of 6
oxygen atoms in such a form as the cavity shown in Figure 6.22(b) will give rise to a
character of weak Lewis base,148 without considering the positive charge deficiency
resulted from octahedral substitution. With octahedral substitution, the resulted negative
charge will be distributed among oxygen atoms in cavities bonded to substituted
octahedral metal cations. Then the Lewis base behavior of the ditrigonal cavity is
reinforced and becomes sufficient to form complexes with those exchangeable cations.
Furthermore, ditrigonal cavities in two consecutive layers are preferable to superpose, as
shown in Figure 6.22(d), by rotation with a specific degree.147,148 Thus, the
exchangeable cations reside in the gallery of layered silicates in MMT by being housed
into such polyhedron structures. Figure 6.23 gives a schematic illustrating how
exchangeable cations reside at the surface of silicate layers in MMT.
Now we know that the negative charge resulted from octahedral substitution is
located at so-called ditrigonal cavities formed by oxygen atoms at the surface of silicate
129
a
b c d
Figure 6.22. Structure of MMT: (a) side view of layers in MMT; (b) top view of
tetrahedral layers of MMT; (c) the ditrigonal cavity formed among 6 oxygen atoms in
tetrahedral layers of MMT; and (d) coordination polyhedron formed by ditrigonal cavities
of two consecutive layers of oxygen atoms. In (b), (c), and (d), only oxygen atoms are
shown as black spots.148 (Reprinted with permission from Springer.)
130
a
cationically modified starch
Figure 6.23. Schematic of silicates layer in MMT with exchangeable cations: (a) top
view and (b) side view.
layers. Due to the electrostatic force, Na+ is absorbed at the surface of the silicate layer
and occupies the negatively charged cavities. Then the reason why there is no ionic
interaction between the positively charged −N+(CH3)3 in the modified starch (CS-B) and
the negatively charged surface of layered silicates in MMT in melt-blended
nanocomposites based on the (CS-B)/EVOH blend can be explained as follows: although
the surface of layered silicates is negatively charged, it is covered by a layer of positively
charged Na+. When the polymer molecules containing cationic moiety (cationically
modified starch in the present study) migrate into a gallery of layered silicates in MMT
aggregates, the presence of Na+ on the surface of silicates prevent the cationic moiety
131
from going close to the negatively charged ditrigonal cavities. Thus, the ionic interaction
could not be formed between the −N+(CH3)3 in the modified starch and negatively
charged ditrigonal cavities.
On the other hand, the ionic interaction between −N+(CH3)3 in the modified starch
(CS-B) and negatively charged ditrigonal cavities was found in nanocomposites prepared
by solution blending. It should be noted that water was used as a co-solvent in solution
blending. Because of its high hydrophilicity, the layered silicates of MMT change its
aggregation dramatically with the addition of water.147-149 When the dry MMT is
exposed to water, water molecules penetrate into the interlayer space of MMT. Because
of the high polarity of water, the negatively charged ditrigonal cavity at the surface of
silicates and the exchangeable cations will be hydrated.148,150-152 In this process, the
exchangeable cations move out of the ditrigonal cavities.147,148,152 The dissociation of an
ionic pair between the ditrigonal cavities and the exchangeable cations is schematically
shown in Figure 6.24.
Now we can explain why the ionic interaction between the positively charged
−N+(CH3)3 in the modified starch (CS-B) and the negatively charged surface of layered
silicates can be found in nanocomposites prepared by solution blending. The electrolytic
cationically modified starch
Figure 6.24. Schematic of electrolytic dissociation of ditrigonal cavity and the cations on
the surface of silicates in MMT.
132
dissociation of an ionic pair between the ditrigonal cavities and the exchangeable cations
resulted from water makes the negatively charged surfaces of silicates more accessible to
the positively charged −N+(CH3)3 in a modified starch. Then the ionic interaction can be
formed between the −N+(CH3)3 in the modified starch and negatively charged ditrigonal
cavities at the surface of silicates in MMT. Furthermore, some researchers148,149 reported
that the hydration of MMT in water increases the gallery distance of layered silicates.
The extent of hydration depends on the nature of the cations residing at the surface of
MMT aggregates. For Wyoming MMT saturated with Na+ residing at the surface of
layered silicates, the d001 spacing can be increased from 0.96 nm (without water) to 1.88
nm due to the increase of water partial pressure in the environment.148 The increase of
gallery distance of layered silicates in MMT resulted from water obviously helps achieve
a high degree of dispersion of MMT in a polymer matrix. However, it should be noted
that the strong attractive interaction between a polymeric matrix and the layered silicates
is the key factor in achieving a high degree of dispersion of MMT aggregate, not the
gallery distance of layered silicates.132,133
6.5 Crystallization and Crystalline Structures of EVOH in Nanocomposites
Figure 6.25 gives the DSC thermograms for the nanocomposites based on an
anionically modified starch AS-B or the (AS-B)/EVOH blend. It is worth noting that in
the nanocomposites containing organoclay, such as Cloisite 30B and Cloisite 15A, the
glass transition temperature has increased, from 85 oC ((AS-B)/EVOH blend) to
91 oC ((AS-B)/EVOH/Cloisite 30B nanocomposite) and 93 oC ((AS-B)/EVOH/
133
93 (a)
(b)
91
(c)
Endotherm
86
(d)
85 (e)
98 (f)
(g)
108
90
0 50 100 150 200

Temperature (oC)
Figure 6.25. DSC thermograms for: (a) (AS-B)/EVOH/Cloisite 15A nanocomposite; (b)
(AS-B)/EVOH/Cloisite 30B nanocomposite; (c) (AS-B)/EVOH/MMT nanocomposite; (d)
(AS-B)/EVOH blend; (e) (AS-B)/Cloisite 30B nanocomposite; (f) (AS-B)/Cloisite 15A
nanocomposite; (g) neat AS-B.
Cloisite 15A nanocomposite), and from 90 oC (neat AS-B) to 108 oC ((AS-B)/Cloisite
30B nanocomposite) and 98 oC ((AS-B)/Cloisite 15A nanocomposite). The increase in
the glass transition temperature was also observed in the nanocomposites based on neat
AS-LF and the (AS-LF)/EVOH blend, and Cloisite 30B or Cloisite 15A. The values of
glass transition temperatures determined from DSC thermograms are summarized in
Table 6.1. For the nanocomposites containing MMT, the glass transition temperature has
hardly changed. In previous sections, we have shown that the aggregates of Cloisite 15A
or Cloisite 30B have a high degree of dispersion (evidenced by XRD patterns and TEM
images) in the nanocomposites based on an anionically modified starch due to the ionic
134
Table 6.1. The changes in the thermal properties of nanocomposites*
Sample code ΔT g ΔTm ΔC

(oC) (oC) (100%)
Nanocomposites based on blends
AS-B/EVOH/Cloisite 30B 6 14 16.3
AS-B/EVOH/Cloisite 15A 8 8 7.1
AS-B/EVOH/MMT 1 1 1.2
AS-LF/EVOH/Cloisite 30B 7 16 18.7
AS-LF/EVOH/Cloisite 15A 10 7 5.6
AS-LF/EVOH/MMT 2 0 − 0.7
CS-B/EVOH/Cloisite 30B 1 2 0.7
CS-B/EVOH/Cloisite 15A 0 1 1.3
CS-B/EVOH/MMT 1 1 1.1
Nanocomposites based on neat starch
AS-B/Cloisite 30B 8 n/a n/a
AS-B/Cloisite 15A 18 n/a n/a
AS-B/MMT 0 n/a n/a
AS-LF/Cloisite 30B 12 n/a n/a
AS-LF/Cloisite 15A 9 n/a n/a
AS-LF/MMT 1 n/a n/a
CS-B/Cloisite 30B 2 n/a n/a
CS-B/Cloisite 15A 1 n/a n/a
CS-B/MMT 14 n/a n/a
*
The values listed in the table above are the difference between nanocomposites and
their blends or neat materials. The thermal properties of blend and neat material samples
were listed in Tables 5.1 and 5.2.
interaction between the negatively charged carboxylate group in a modified starch and
the positively charged N+ in the surfactant residing at the surface of organoclay. On the
other hand, MMT has quite poor dispersion characteristics in the matrix, because there is
no strong attractive interaction formed between MMT and the matrix.
In the nanocomposites based on the blends of an anionically modified starch and
EVOH, the reason for the observed increase in glass transition temperature lies in the
135
strong attractive interaction between the modified starch and silicates. However, the
possibility of forming attractive interaction between EVOH and the surfactant residing at
the surface of organoclay cannot be ruled out. The surfactant residing at the surface of
Cloisite 30B has hydroxyl groups which can form hydrogen bonding with EVOH.
Figures 6.26 to 6.28 give WAXD patterns of the nanocomposites based on
anionically modified starch (AS-B) and EVOH, and Cloisite 15A, Cloisite 30B, or MMT.
Referring to Figures 6.26 and 6.28, for nanocomposites containing Cloisite 15A or MMT,
the crystalline structure of EVOH in quenched samples takes orthorhombic lattice (the
single (110) reflection peak on WAXD patterns) and evolves into monoclinic lattice (the
(110) and (110) reflection peaks on WAXD patterns) as the crystallization temperature
was increased, which is similar to that of EVOH in the blends with a modified starch (see
Chapter V). On the other hand, referring to Figure 6.27 for the WAXD patterns for the
nanocomposite containing Cloisite 30B, we find that the crystalline structure of EVOH
takes orthorhombic lattice in quenched samples and does not evolve into monoclinic
lattice as the crystallization temperature is increased, which is different from that of
EVOH in the blends with a modified starch (see Chapter V). One should keep in mind
that both Cloisite 30B and Cloisite 15A have a very high degree of dispersion
characteristics in the nanocomposites based on AS-B and EVOH, whereas MMT has
poor dispersion characteristics in the nanocomposite, as described in Section 6.3.
For EVOH in the nanocomposites prepared in the present study, the interaction
between the hydroxyl groups in EVOH and the surfactant residing at the surface of
silicate sheets of Cloisite 30B could change the vinyl alcohol content on the molecules of
EVOH locally (in the vicinity of silicate sheets, but silicate sheets are exfoliated and
136
monoclinic lattice group

(1)
(2)
(3)
(4)
orthohombic lattice group
16 17 18 19 20 21 22 23 24 25
2θ (degree)
Figure 6.26. WAXD patterns for (AS-B)/EVOH/Cloisite 15A nanocomposite at different
annealing temperatures (oC): (1) 153; (2) 133; (3) 113; and (4) quench.
(1)
(2)
(3)
(4)
16 17 18 19 20 21 22 23 24 25
2θ (degree)
Figure 6.27. WAXD patterns for (AS-B)/EVOH/Cloisite 30B nanocomposite at different
137
(1)
(2)
(3)
(4)
16 17 18 19 20 21 22 23 24 25
2θ (degree)
Figure 6.28. WAXD patterns for (AS-B)/EVOH/MMT nanocomposite at different

highly dispersed all over the sample), and the crystalline structure predominantly takes
orthorhombic lattice groups. Furthermore, due to the rigid nature of silicate sheets
(compared with flexible polymer chains), the local change of vinyl alcohol content due to
the interaction between EVOH and silicate sheets does not vary with temperature nor the
hydrogen bonds between EVOH and the surfactant. That is the reason why a
transformation of crystalline structure of EVOH from orthorhombic lattice into
monoclinic lattice does not occur in the nanocomposite containing Cloisite 30B.
On the other hand, in the nanocomposites containing Cloisite 15A, its surfactant
does not have hydroxyl groups, and there is no attractive interaction between the silicate
138
sheets and EVOH. Thus, the crystalline structure of EVOH is quite the same as that of
neat EVOH.
Figures 6.29 to 6.31 give WAXD patterns for the nanocomposites based on the
cationically modified starch (CS-B) and EVOH, and Cloisite 15A, Cloisite 30B, or MMT.
One should keep in mind that the aggregates of Cloisite 15A, Cloisite 30B, and MMT
have a poor dispersion in the melt-blended nanocomposites based on the CS-B and
EVOH, as described in Section 6.4. Referring to Figures 6.29 and 6.31, the
nanocomposites containing Cloisite 15A or MMT have the similar crystalline structure of
EVOH to that of neat EVOH under different annealing temperatures, namely, the
crystalline structure of EVOH takes orthorhombic lattice in quenched sample and evolves
(1)
(2)
(3)
(4)
16 17 18 19 20 21 22 23 24 25
2θ (degree)
Figure 6.29. WAXD patterns for (CS-B)/EVOH/Cloisite 15A nanocomposite at different

139
(1)
(2)
(3)
(4)
16 17 18 19 20 21 22 23 24 25
2θ (degree)
Figure 6.30. WAXD patterns for (CS-B)/EVOH/Cloisite 30B nanocomposite at different
(1)
(2)
(3)
(4)
16 17 18 19 20 21 22 23 24 25
2θ (degree)
Figure 6.31. WAXD patterns for (CS-B)/EVOH/MMT nanocomposite at different

140
into monoclinic lattice as the crystallization temperature is increased. Referring to Figure
6.30, the nanocomposite containing Cloisite 30B also has the similar crystalline structure
of EVOH to that of neat EVOH. Although there are hydroxyl groups in the surfactant
residing at the surface of Cloisite 30B aggregates, which might form hydrogen bonds
with EVOH, the poor dispersion characteristics of Cloisite 30B aggregates limit the
contact area between the silicate sheets and EVOH.
6.6 Mechanical Properties of Nanocomposites
Figures 6.32 to 6.35 give the tensile properties (tensile strength, Young’s modulus,
and elongation at break) of the nanocomposites based on a modified starch and EVOH,
and Cloisite 15A, Cloisite 30B, or MMT. In Chapter V, we have presented the tensile
properties of the blends based on a modified starch and EVOH (see Figures 5.19 to 5.22).
For the tensile properties of the nanocomposites based on an anionically modified
starch (AS-B or AS-LF) and EVOH, it is worth noting that the tensile strength and
Young’s modulus are enhanced in the nanocomposites containing organoclays (Cloisite
15A or Cloisite 30B), whereas the elongation at break is decreased in the same
nanocomposites. On the other hand, the tensile properties (tensile strength, Young’s
modulus, and elongation at break) of the nanocomposite containing MMT have not
changed much as compared with those of blends. The difference in the tensile properties
between the nanocomposites containing organoclay and the one containing MMT may be
explained as follows. The improved mechanical properties may be attributable to the
presence of the attractive interaction and large surface areas between the silicate sheets
and the matrix. In the nanocomposites containing an organoclay, the ionic interaction
141
140 7.0
130
(a) (b)
6.5
Young's modulus (GPa)

120
110 6.0
100
90 5.5
80
5.0
70
60 4.5
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
60
(c)
50
40
30
20
10
0
0.0 0.2 0.4 0.6 0.8 1.0
EVOH (wt fraction)
Figure 6.32. Tensile properties of the nanocomposites based on AS-B and EVOH: (a)
tensile strength; (b) Young’s modulus; and (c) elongation at break. (●) (AS-B)/EVOH
blend; (□) (AS-B)/EVOH/Cloisite 30B nanocomposite; (△) (AS-B)/EVOH/Cloisite 15A
nanocomposite; and (▽) (AS-B)/EVOH/MMT nanocomposite.
142
140 7.5
(a) 7.0 (b)

120
6.5
100 6.0
5.5
80 5.0
4.5
60
4.0
40 3.5
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
60
(c)
50
Elongation at Break (%)
40
30
20
10
0
0.0 0.2 0.4 0.6 0.8 1.0
EVOH (wt fraction)
Figure 6.33. Tensile properties of the nanocomposites based on AS-LF and EVOH: (a)
tensile strength; (b) Young’s modulus; and (c) elongation at break. (●) (AS-LF)/EVOH
blend; (□) (AS-LF)/EVOH/Cloisite 30B nanocomposite; (△) (AS-LF)/EVOH/Cloisite
15A nanocomposite; and (▽) (AS-LF)/EVOH/MMT nanocomposite.
143
140 7.0
(a) (b)
120

6.5
100 6.0
80 5.5
60 5.0
40 4.5
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
60
(c)
50
40
30
20
10
0
0.0 0.2 0.4 0.6 0.8 1.0
EVOH (wt fraction)
Figure 6.34. Tensile properties of the nanocomposites based on CS-B and EVOH: (a)
tensile strength; (b) Young’s modulus; and (c) elongation at break. (●) (CS-B)/EVOH
blend; (□) (CS-B)/EVOH/Cloisite 30B nanocomposite; (△) (CS-B)/EVOH/Cloisite 15A
nanocomposite; and (▽) (CS-B)/EVOH/MMT nanocomposite.
144
140 7
(a) (b)
120

100
5
80
4
60
40 3
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
60
(c)
50
40
30
20
10
0
0.0 0.2 0.4 0.6 0.8 1.0
EVOH (wt fraction)
Figure 6.35. Tensile properties of the nanocomposites based on CS-LF and EVOH: (a)
tensile strength; (b) Young’s modulus; and (c) elongation at break. (●) (CS-LF)/EVOH
blend; (□) (CS-LF)/EVOH/Cloisite 30B nanocomposite; (△) (CS-LF)/EVOH/Cloisite
15A nanocomposite; and (▽) (CS-LF)/EVOH/MMT nanocomposite.
145
between the negatively charged carboxylate groups in a modified starch and the
positively charged N+ in the surfactant residing at the surface of an organoclay exfoliated
the layered silicates, yielding nanometer-sized platelets. These nanometer-sized platelets
brought large surface areas in contact with the matrix. The attractive interaction between
the silicate sheets and polymer molecules acts like a cross-linking point in the
nanocomposites. From the point of view of tensile properties in the nanocomposites
under the tensile tests, the stress is much more efficiently transferred from the polymer
matrix to the inorganic silicate sheets through the attractive interactions, resulting in
higher tensile strength and modulus. Referring to Figures 6.32 to 6.33, we find that the
nanocomposite containing Cloisite 30B has higher tensile strength and Young’s modulus
than the nanocomposite containing Cloisite 15A. On the other hand, for the
nanocomposite containing MMT, which has no functional groups to form attractive
interaction with the matrix, the tensile properties of the nanocomposite were not
improved as compared with those of the blend based on the same matrix.
On the other hand, referring to Figures 6.34 and 6.35, the tensile properties of the
nanocomposites based on a cationically modified starch (CS-B or CS-LF) and EVOH
were not improved by the addition of nanoclays (Cloisite 15A, Cloisite 30B, or MMT).
In the previous section, we have shown that the nanocomposites based on a cationically
modified starch and EVOH have poor dispersion characteristics of the aggregates of
Cloisite 15A, Cloisite 30B, or MMT.
146
Nanocomposites based on a modified starch and EVOH were prepared in the
present study. The starch was modified with ionic groups (acetate sodium group or
trimethylammonium chloride group) and hydrophobic groups (hexanoyl group or benzoyl
group). The rationale behind the approach was to introduce ionic interaction between the
modified starch and nanoclay, so that the nanocomposites could have a high degree of
dispersion of nanoclay aggregates.
The dispersion characteristics of nanocomposites based on the anionically modified
starch (AS-B or AS-LF) or the cationically modified starch (CS-B or CS-LF) were
investigated by XRD and TEM. For the nanocomposites based on AS-B or AS-LF, the
experimental results have shown that organoclay aggregates (Cloisite 30B and Cloisite
15A) have a high degree of dispersion characteristics, whereas natural clay (MMT)
aggregates have very poor dispersion characteristics. We have ascribed the high degree
of dispersion of organoclay aggregates in nanocomposites based on the anionically
modified starch and EVOH to the ionic interaction formed between the negatively
charged carboxylate groups (−COO−) in the modified starch and positively charged N+ in
a surfactant (MT2EtOH or 2M2HT) residing at the surface of layered silicates of
organoclays. The FTIR spectra of nanocomposites confirmed the presence of ionic
interaction in the nanocomposites. On the other hand, there is no functional group
residing at the surface of MMT to form any specific attractive interaction with the matrix
in the nanocomposites, which we ascribed to the poor dispersion characteristics of MMT
aggregates.
147
For the nanocomposites based on the cationically modified starch (CS-B or CS-LF)
and EVOH, the experimental results have shown that both organoclays (Cloisite 30B or
Cloisite 15A) and natural clay (MMT) gave rise to poor dispersion characteristics in
nanocomposites. We have interpreted the results by presenting evidence that no
attractive interaction existed between the clay and the cationically modified starch.
However, we have learned that the nanocomposite based on the same cationically
modified starch, which was prepared by solution blending, has a very high degree of
dispersion of MMT aggregates. We ascribed the high degree of dispersion of MMT
aggregates in the nanocomposite to the ionic interaction between the negatively charged
surface of MMT and positively charged −N+(CH3)3 in the modified starch. The FTIR
spectra confirmed the presence of ionic interaction in the nanocomposite. Then we
explained why ionic interactions existed between the MMT and cationically modified
starch in the nanocomposites prepared by solution blending.
The nanocomposites prepared in the present study were characterized by DSC and
WAXD. The glass transition temperature was increased in those nanocomposites which
have a high degree of dispersion of organoclay aggregates. We ascribed the increased
glass transition temperature to the ionic interaction between the aggregates of organoclay
and matrix in the nanocomposites. The DSC thermograms showed that the melting point
and melting enthalpy of EVOH in the nanocomposites containing the aggregates of
Cloisite 30B were increased, suggesting that the dispersion characteristics of the
organoclay influenced the crystallization of EVOH in the nanocomposites. The WAXD
patterns have shown that in the nanocomposites containing exfoliated Cloisite 30B, the
crystalline structure of EVOH takes orthorhombic lattice in the quenched and annealed
148
samples at various annealing temperatures. In the nanocomposites based on EVOH and a
modified starch, and Cloisite 15A or MMT, the crystalline structure of EVOH was found
to be similar to that of neat EVOH. We ascribed the difference in crystallization and the
crystalline structure of EVOH between the nanocomposite containing Cloisite 30B and
the nanocomposites containing other clays (Cloisite 15A and MMT) to the presence of
hydrogen bonds formed between the hydroxyl group in EVOH and the hydroxyl group in
the surfactant (MT2EtOH) residing at the surface of silicate sheets of Cloisite 30B.
The tensile properties of the nanocomposites prepared in the present study were
characterized. We have found that an improvement in the tensile properties of the
nanocomposites based on a modified starch and EVOH can only be obtained if the clay
has a very high degree of dispersion in the nanocomposites, and strong attractive
interaction is present between the silicate sheets of clay and the matrix.
149
CHAPTER VII
CONCLUSIONS AND RECOMMENDATIONS
7.1 Conclusions
In this dissertation, we have synthesized four chemically modified starches
functionalized by ionic and hydrophobic groups: (1) a starch modified with anionic group
and benzoyl group (AS-B); (2) a starch modified with anionic group and hexanoyl group
(AS-LF); (3) a starch modified with cationic group and benzoyl group (CS-B); and (4) a
starch modified with cationic group and hexanoyl group (CS-LF). Subsequently, the
degree of substitution (DS) of the modified starches was determined by calculations from
the 1H-NMR spectra. The FTIR spectra have indicated that the strength of hydrogen
bonds in starch was weakened by chemical modification. The thermal stability of the
modified starches was also characterized. We have found that the thermal degradation
temperature was drastically decreased from over 300 oC to below 200 oC for the starches
modified only by ionic groups. However, when a starch was modified by both ionic and
hydrophobic groups, the thermal degradation temperature was increased, because the
number of hydroxyl groups in the starch was decreased. The glass transition temperature
of dried natural starch could not be determined because it is higher than the thermal
degradation temperature. We have found that the glass transition temperature of the
modified starch was decreased to below 100 oC, which would be useful for processing
starch as a thermoplastic material. The chemical modification destroyed the granular
150
semicrystalline structure and the hydrogen bonds in natural starch, consequently
increasing the mobility of starch molecules. No melting peak was found in the DSC
thermograms of the modified starches, suggesting that the modified starches are
amorphous.
Because of the chemical modification employed, we have changed starch from
hydrophilic to hydrophobic. The composting tests conducted showed that the chemically
modified starches have good biodegradability. However, the rate of weight loss of the
modified starches during compositing was slower than natural starch, suggesting that the
biodegradability of starch was lowered by chemical modification.
We also prepared the blends based on a modified starch and EVOH. Phase
diagrams of the modified starch/EVOH blends were obtained, and the blends exhibited
LCST. The DSC thermograms of the blends of a modified starch and EVOH showed a
single glass transition temperature, suggesting a good miscibility between the modified
starch and EVOH. We ascribed the miscibility of the blends to the presence of hydrogen
bonds, which were formed between the modified starch and EVOH, as confirmed by
FTIR spectroscopy. The DSC thermograms of the blends of a modified starch and
EVOH also showed that the melting point and melting enthalpy of EVOH were decreased,
suggesting that the crystallization of EVOH was interrupted. We ascribed the
interruption of crystallization to the presence of hydrogen bonds between the modified
starch and EVOH. The FTIR spectra showed that the hydrogen bonds formed between
the modified starch and EVOH was favored over the hydrogen bonds by self-association
within neat EVOH. In neat EVOH, the WAXD patterns have shown that the crystalline
structure of EVOH takes orthorhombic lattice in the quenched specimens and evolves
151
into monoclinic lattice when annealing temperature was increased. We have found that
the crystalline structure of EVOH in the blends of a modified starch and EVOH is similar
to that of neat EVOH, suggesting that the hydrogen bonds between the modified starch
and EVOH do not influence the crystalline structure of EVOH. Synergistic effects were
observed in the tensile properties of the blends of a modified starch and EVOH, owing to
a good miscibility between the modified starch and EVOH.
Nanocomposites were prepared based on a modified starch and EVOH. The
nanoclay employed in the preparation of nanocomposites include natural clay (MMT)
and two commercial organoclays (Cloisite 30B and Cloisite 15A). We have found that in
the nanocomposites based on the anionically modified starch (AS-B or AS-LF), the
aggregates of an organoclay have a very high degree of dispersion, whereas the
aggregates of MMT have poor dispersion characteristics. We ascribed the experimental
observations to the ionic interaction formed between the modified starch and the
organoclay. The FTIR spectra of the nanocomposites prepared have confirmed the
presence of ionic interaction between the negatively charged carboxylate groups in a
modified starch and positively charged N+ in a surfactant residing at the surface of
organoclay.
We have found poor dispersion characteristics of both organoclays (Cloisite 30B
and Cloisite 15A) and MMT in the nanocomposites based on the cationically modified
starch, when the nanocomposites were prepared by melt blending. In the nanocomposites
prepared by solution blending, we have found that MMT aggregates have a very high
degree of dispersion in the cationically modified starch. The FTIR spectra showed that
152
ionic interaction existed between the positively charged −N+(CH3)3 in the modified starch
and negatively charged surface of MMT aggregates.
To investigate how the dispersion characteristics of nanoclay aggregates might
influence the morphology and crystalline structure of nanocomposites, we characterized
the nanocomposites prepared by DSC and WAXD. The DSC thermograms have shown
that the glass transition temperature was increased in the nanocomposites having a high
degree of dispersion of organoclay aggregates. The WAXD patterns have shown that the
crystalline structure of EVOH in the nanocomposites containing exfoliated Cloisite 30B
takes orthorhombic lattice in both the quenched and annealed samples. On the other hand,
the crystalline structure of EVOH in the nanocomposites containing Cloisite 15A and
MMT is similar to that of neat EVOH.
The tensile properties of the nanocomposites were also measured. We have found
that an improvement in the tensile properties of the nanocomposites based on a modified
starch and EVOH could only be obtained when the nanoclay aggregates have a very high
degree of dispersion in the nanocomposites, which was attributable to the presence of
strong attractive interaction between the silicate sheets of clay and the matrix.
7.2 Recommendations
The present study has shown that the rate of biodegradation of a chemically
modified starch was lowered as compared to that of natural starch. The weight loss
during composting showed two different patterns between the cationically modified
starch and the anionically modified starch, suggesting that the functional groups might
have changed the biodegradation mechanism of starch. It is recommended that an
153
investigation be undertaken to find out the mechanism(s) of biodegradation of chemically
modified starch during composting.
We have found that the modified starch synthesized in the present study is miscible
with EVOH. It is recommended that an investigation be undertaken to find out what
degree of substitution of modified starch and the vinyl alcohol content in EVOH might
influence miscibility between the modified starch and EVOH.
The biodegradable starch-based material is a potential candidate for the replacement
of petroleum-based synthetic packaging materials widely used in the current market. We
recommended that the processability of modified starch be investigated.
154
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169
APPENDICES
170
APPENDIX A
1
H-NMR SPECTRA OF CHEMICALLY MODIFIED STARCH
AS-B
171
AS-LF
CS-B
172
CS-LF
173
APPENDIX B
FTIR SPECTRA OF CHEMICALLY MODIFIED STARCH
AS-B
174
AS-LF
CS-B
175
CS-LF
176

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CHEMICAL MODIFICATION OF STARCH AND PREPARATION OF STARCH-

The Graduate Faculty of The University of Akron

of the Requirements for the Degree

Advisor Department Chair

Committee Member Dean of the College

Committee Member Dean of the Graduate School

Committee Member Date

hydrophobic and can biodegrade in composting. Blends of a modified starch and

poly(ethylene-co-vinyl alcohol) (EVOH) were prepared by melt blending. Phase

starch influence the dispersion characteristics of nanocomposites. Anionically modified

influence on the dispersion characteristics of the nanocomposites. The aggregates of

MMT have a very high degree of dispersion characteristics in the nanocomposites

prepared by solution blending but poor dispersion characteristics in the nanocomposites

not in the nanocomposites prepared by melt blending. Wide-angle X-ray diffraction

containing exfoliated aggregates of organoclay Cloisite 30B takes orthorhombic lattice in

ascribe the difference in the crystalline structure of EVOH in the EVOH-containing

clay and the matrix.

I would like to express my sincere gratitude to my advisor, Professor Chang Dae

worked on this dissertation under his guidance.

I would like to extend my gratitude to the committee members, Professors Mark D.

on the draft of this dissertation.

II. LITERATURE REVIEW .…………………………………………………….…..…..8

2.1 Introduction to Natural Starch …………………………………….……….…..…8

2.2 Previous Research on Chemical Modification of Starch…………...…………....17

2.3 Thermoplastic Starch (TPS)………………………………………….………..…43

2.4 Previous Research on the Nanocomposites based on Starch………………...…..47

3.1 Synthesis of Chemically Modified Starch…………………………………….....51

3.2 Preparation of Blends and Nanocomposites based on Modified Starch…….…...54

3.3 Characterization Methods……………………...…………………………….…..55

IV. CHARACTERIZATION OF CHEMICALLY MODIFIED STARCH…….….…...60

4.1 Structure Characterization and Determination of Degree of Substitution

4.2 Moisture Resistance of Chemically Modified Starch………..…………...……...66

4.4 Biodegradability of Chemically Modified Starch…………..……...…………….72

4.5 Concluding Remarks……………………………………………………………..74

V. BLENDS OF MODIFIED STARCH AND EVOH……………………...………......76

5.1 Miscibility of Blends based on Modified Starch and EVOH

5.2 Hydrogen Bonding in Blends based on Modified Starch and EVOH

5.3 Crystallization of EVOH in Blends based on Modified Starch

5.4 Mechanical Properties of Blends based on EVOH and Modified Starch……….93

5.5 Concluding Remarks……………………………………………………..….…..98

VI. NANOCOMPOSITES BASED ON MODIFIED STARCH..…………...………...100

6.2 Nanocomposites based on Neat EVOH………………………………….….…103

6.3 Nanocomposites containing Anionically Modified Starch….………….…..….107

6.4 Nanocomposites containing Cationically Modified Starch…...……………….116

6.5 Crystallization and Crystalline Structures of EVOH in Nanocomposites..........133

6.6 Mechanical Properties of Nanocomposites………….………………...……….141

6.7 Concluding Remarks…………………………………………………………...147

VII. CONCLUSIONS AND RECOMMENDATIONS….………………………...…..150

7.2 Recommendations………………………………………………………….…. 153

APPENDIX A. 1H-NMR SPECTRA OF CHEMICALLY MODIFIED

APPENDIX B. FTIR SPECTRA OF CHEMICALLY MODIFIED STARCH…...174

1.1 Different types of dispersion of layered silicates in polymeric matrix…………...…..3

2.1 Chemical structures of amylose and amylopectin…………………...…………...…..9

2.2 Single helix structure of amylose molecule……………………………………..…..10

2.3 Structure of branched amylopectin……………………………………………….…11

2.5 Vh-type crystalline structure of starch……………………………………………....13

2.6 X-ray diffraction patterns of A-, B-, and Vh-type of starch……………………...…14

2.7 Schematic representation of the granule architecture of natural starch…………..…15

2.10 Thermal stability of amylose esters……………………………………………..…32

2.11 XRD patterns of starch esters……………………………………………………...34

2.12 Crystallization of fatty acid chains within the starch esters……………………..…34

2.14 Stress-strain curves of potato starch with different amounts

2.17 TEM image of TPS nanocomposite containing 5 wt % of MMT…………...……..48