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SPRINGER BRIEFS IN MOLECULAR SCIENCE
BIOBASED POLYMERS

Merin Sara Thomas


Rekha Rose Koshy
Siji K. Mary
Sabu Thomas
Laly A. Pothan

Starch, Chitin and


Chitosan Based
Composites and
Nanocomposites

123
SpringerBriefs in Molecular Science

Biobased Polymers

Series editor
Patrick Navard, CNRS/Mines ParisTech, Sophia Antipolis, France
Published under the auspices of EPNOE*Springerbriefs in Biobased polymers
covers all aspects of biobased polymer science, from the basis of this field starting
from the living species in which they are synthetized (such as genetics, agronomy,
plant biology) to the many applications they are used in (such as food, feed,
engineering, construction, health, …) through to isolation and characterization,
biosynthesis, biodegradation, chemical modifications, physical, chemical, mechan-
ical and structural characterizations or biomimetic applications. All biobased
polymers in all application sectors are welcome, either those produced in living
species (like polysaccharides, proteins, lignin, …) or those that are rebuilt by
chemists as in the case of many bioplastics.
Under the editorship of Patrick Navard and a panel of experts, the series will
include contributions from many of the world’s most authoritative biobased
polymer scientists and professionals. Readers will gain an understanding of how
given biobased polymers are made and what they can be used for. They will also be
able to widen their knowledge and find new opportunities due to the multidisci-
plinary contributions.
This series is aimed at advanced undergraduates, academic and industrial
researchers and professionals studying or using biobased polymers. Each brief will
bear a general introduction enabling any reader to understand its topic.
*EPNOE The European Polysaccharide Network of Excellence (www.epnoe.eu)
is a research and education network connecting academic, research institutions and
companies focusing on polysaccharides and polysaccharide-related research and
business.

More information about this series at http://www.springer.com/series/15056


Merin Sara Thomas Rekha Rose Koshy

Siji K. Mary Sabu Thomas


Laly A. Pothan

Starch, Chitin and Chitosan


Based Composites
and Nanocomposites

123
Merin Sara Thomas Siji K. Mary
Department of Chemistry Department of Chemistry
C.M.S. College C.M.S. College
Kottayam, Kerala, India Kottayam, Kerala, India

and and

Department of Chemistry Department of Chemistry


Mar Thoma College Bishop Moore College
Thiruvalla, Kerala, India Mavelikara, Kerala, India

Rekha Rose Koshy Sabu Thomas


Department of Chemistry International and Interuniversity Centre for
C.M.S. College Nanoscience and Nanotechnology
Kottayam, Kerala, India Mahatma Gandhi University
Kottayam, Kerala, India
and
Laly A. Pothan
Department of Chemistry Department of Chemistry
Bishop Moore College C.M.S. College
Mavelikara, Kerala, India Kottayam, Kerala, India

and

Department of Chemistry
Bishop Moore College
Mavelikara, Kerala, India

ISSN 2191-5407 ISSN 2191-5415 (electronic)


SpringerBriefs in Molecular Science
ISSN 2510-3407 ISSN 2510-3415 (electronic)
Biobased Polymers
ISBN 978-3-030-03157-2 ISBN 978-3-030-03158-9 (eBook)
https://doi.org/10.1007/978-3-030-03158-9

Library of Congress Control Number: 2018960176

© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2019


This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission
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The use of general descriptive names, registered names, trademarks, service marks, etc. in this
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the relevant protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in this
book are believed to be true and accurate at the date of publication. Neither the publisher nor the
authors or the editors give a warranty, express or implied, with respect to the material contained herein or
for any errors or omissions that may have been made. The publisher remains neutral with regard to
jurisdictional claims in published maps and institutional affiliations.

This Springer imprint is published by the registered company Springer Nature Switzerland AG
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
Contents

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2 Processing Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1 Starch Based Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.1 Solution Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.2 Compression Moulding . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1.3 Twin Screw Extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.1.4 Thermal Moulding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.1.5 Melt Blending . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2 Processing Techniques of Chitin and Nano Chitin Based
Composite Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.2.1 Solution Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.2.2 Extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.3 Freeze-Drying Method . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.3 Processing Techniques of Chitosan Based Composites . . . . . . . . . 16
2.3.1 Physical Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.3.2 Polyelectrolyte Complexes . . . . . . . . . . . . . . . . . . . . . . . . 16
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3 Properties of Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.1 Thermal Properties of Composites . . . . . . . . . . . . . . . . . . . . . . . . 19
3.1.1 Thermal Properties of Starch Based Composites . . . . . . . . 19
3.1.2 Thermal Properties of Chitin Based Composites . . . . . . . . 20
3.1.3 Thermal Properties of Chitosan Based Composites . . . . . . 23

v
vi Contents

3.2 Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24


3.2.1 Mechanical Properties of Starch Based Composites . . . . . . 24
3.2.2 Mechanical Properties of Chitin Based Composites . . . . . . 25
3.2.3 Mechanical Properties of Chitosan Based Composites . . . . 29
3.3 Morphological Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.3.1 Morphological Analysis of Starch Based Composites . . . . . 31
3.3.2 Morphological Analysis of Chitin Based Composites . . . . . 31
3.3.3 Morphological Analysis of Chitosan Based Composites . . . 34
3.4 Barrier Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4 Applications of Polysaccharide Based Composites . . . . . . . . . . . . . . 43
4.1 Packaging Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4.2 Water Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.3 Biosensor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4.4 Biomedical Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.4.1 Biomedical Applications of Starch Based Composites . . . . 49
4.4.2 Biomedical Applications of Chitin Based Composites . . . . 50
4.4.3 Biomedical Application of Chitosan Based Composites . . . 51
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
Abbreviations

AFM Atomic force microscopy


AuNPs Gold nanoparticles
Au@CDs-CS/GCE Gold@carbon dots-chitosan-modified glassy carbon
electrode
B.mori Bombyx mori
CA Citric acid
CCNGs Curcumin-loaded chitin nanogels
CF Coir fiber
CHNC Chitin nanocrystals
CHNF Chitin nanofibers
ChOx Cholesterol oxidase
CMC Carboxymethyl cellulose
CNT Carbon nanotube
CNF Cellulose nanofiber
CNP Chitin nanoparticle
CNW Chitin nanowhiskers
Cr(VI) Chromium
CS Chitosan
CZB Chitosan hydrogel/nano zinc oxide composite bandages
a-chitin Alpha chitin
b-chitin Beta chitin
°C Degree Celsius
DMA Dynamic mechanical analysis
DSC Differential scanning calorimetry
dTG Derivative thermogram
ECM Extracellular matrix
E.coli Escherichia coli
EM Elastic modulus
ENR Epoxidized natural rubber
Fe3O4 Magnetite

vii
viii Abbreviations

c-Fe2O3 Maghemite
GeO2 Germanium dioxide
GPa Giga pascal
GPS Glycerol-plasticized potato starch
H Gelatinization enthalpy
HA Hydroxyapatite
ITO Indium tin oxide
L. monocytogenes Listeria monocytogenes
MC3T3-E1 Mouse osteoblastic cells
MgG Magnesium gluconate
MgO Magnesium oxide
MMT Montmorillonite
MPa Mega pascal
MTT 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium
bromide
MWCNT Multi-walled carbon nanotubes
µm Micrometer
N-chitin Nano chitin gel
NFC Nanofibrillar cellulose
NIH-3T3 Mouse embryo fibroblast cell line
nm Nanometer
NP Nanoparticles
OPEFB Oil palm empty fruit bunch
PCC Chitin-coated with polyaniline
PCL Polycaprolactone
PEGDA Polyethylene glycol diacrylate
PEO Poly(ethylene oxide)
PHBV Poly(3-hydroxybutyrate-co-3-hydroxyvalerate
PHF Pea hull fiber
PHFNW Cellulose nanowhiskers from pea hull fiber
PLA Polylactic acid
PLGA Poly(lactic-co-glycolic acid)
PMMA Polymethylmethacrylte
PS/GO-n Glycerol-plasticized pea starch/graphene oxide
PVA Polyvinylalcohol
PVP Poly(N-vinylpyrrolidone)
RCB Bleached rice hull
RH Rice hull
RHNF Cellulose nanofibrils extracted from rice hull
S/CHNC Starch/Chitin nanocrystal
S/CHNF Chitin nanofiber-reinforced starch matrix
SCB Sugarcane baggase
SEM Scanning electron microscope
ST Starch
SiO2 Silicon dioxide
Abbreviations ix

SPI Soy protein isolate


Tc Crystallization temperature
TEC Tri Ethyl Citrate
TEOG Germanium tetraethoxide
TEM Transmission electron microscope
TEMPO 2, 2, 6, 6-tetramethyl-piperidinyl-1-oxyl
TGA Thermogravimetric analysis
TiO2 Titanium dioxide
To Onset temperature
Tp Peak temperature
TPS Thermoplastic starch
WPI Whey protein isolate
wt% Weight percentage
WVP Water vapour permeability
WVTR Water vapour transmission rate
w/w% Weight/weight percent
ZnO Zinc oxide
ZrO2 Zirconium dioxide
Chapter 1
Introduction

Concern about the depletion of natural resources and environment pollution, caused
by petroleum-based plastics, has drawn attention to the development of environ-
ment friendly polymer composites and nanocomposites, for applications in food,
cosmetics, and pharmaceutical industries. Natural polymers are much more attrac-
tive than artificial polymers for the preparation of composites, due to their “green”
characteristics, such as biodegradability, biocompatibility, renewability, and sustain-
ability (Lu et al. 2013). Biopolymers, like polysaccharides (starch, cellulose, chitin
and chitosan) and proteins (soy protein, wheat protein, casein, and gelatin) obtained
from the nature, are the most viable alternative for producing green materials in the
near future. Polysaccharides, a class of natural macromolecules, have the tendency
to be extremely bioactive, and are generally derived using different biotechnologi-
cal approaches from agricultural feedstock or crustacean shell wastes (Anitha et al.
2014).
Naturally occurring polymers perform a diverse set of functions in their native
setting. Polysaccharides function in membranes and intracellular communication, in
recognition events at the cell surface, as cell wall structures, as capsular layers or pro-
tective barriers around cells, as emulsifiers, as adhesives, and as sequestering agents
for water, nutrients and metals for cells. The benefits of using naturally occurring
polymers for material applications are many. For example, environmental compati-
bility would be enhanced since no environmental burdens would be introduced due
to their use. In addition, the utilization of renewable resources provides an incentive
to extend nonrenewable petrochemical supplies (Kaplan et al. 1998). Here we are
discussing the use of starch, chitin and chitosan as fillers in polymer composites and
nanocomposites.

© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2019 1


M. S. Thomas et al., Starch, Chitin and Chitosan Based Composites
and Nanocomposites, Biobased Polymers,
https://doi.org/10.1007/978-3-030-03158-9_1
2 1 Introduction

1.1 Starch

Polysaccharides are good candidates for biodegradable films. Starch is considered


as the most promising among them due to its abundance, low cost, biodegradability
and renewability. Starch based composites and nanocomposites are now considered
to be next generation “green” materials, because of its capability to be converted
into thermoplastic materials (Tang and Alavi 2011; Gironès et al. 2012; Lopez et al.
2014). In biocomposites, starch can be used either as the continuous polymeric phase
(matrix) or the dispersed phase (filler) or both. Nano reinforced starch based compos-
ites generally exhibit enhanced mechanical and thermal properties when nanofillers
are well dispersed (Yu et al. 2009; Kaushik et al. 2010; da Silva et al. 2015; Li et al.
2015; González et al. 2015; Cao et al. 2008; Salehudin et al. 2014; Tang and Alavi
2011).
Starch consists of linear polysaccharide amylose and highly branched polysaccha-
ride (Fig. 1.1). Depending on the source, starch generally contains 20–25% amylose
and 75–80% amylopectin. Amylose is a semicrystalline biopolymer and is soluble
in hot water, while amylopectin is highly crystalline and is insoluble in hot water.
Starch based biodegradable composites have drawn considerable attention of the
scientific community over the last two decades due to their potential applications
in many industries including food and medicine. However, in comparison with con-
ventional synthetic materials, starch based biodegradable products exhibit many dis-
advantages such as poor resistance to water, brittleness and poor elasticity. All of
these disadvantages can be attributed to the highly hydrophilic characteristics of
starch. One of the effective methods to improve the above mentioned detriments is
to incorporate various fillers. The use of natural fibers and nano reinforcements for
the elaboration of composites and nanocomposites is an effective way to improve
properties of thermoplastic starch (Babu et al. 2013; Orue et al. 2014).

Fig. 1.1 Structure of amylose and amylopectin in starch. Reprinted with permission from Zia et al.
(2016). Copyright Elsevier
1.1 Starch 3

Fig. 1.2 Molecular structure of chitin. Reprinted with permission from Visakh and Thomas (2010).
Copyright Springer

Polysaccharides based on chitin and chitosan have received much attention in


recent years as new functional biomaterials with potential applications in various
fields. Chitin is the second most ubiquitous natural polysaccharide after cellulose
on earth and is composed of β(1 → 4)-linked 2-acetamido-2-deoxy-β- D-glucose
(N-acetylglucosamine). It has acetamide groups (−NHCOCH3 ) at the C2 positions
(Fig. 1.2).
Chitins are present as the main components in crab and shrimp shells, in the outer
skins or cuticles of other arthropods, and in the molluscan shell of squid (so-called
squid pen), coexisting with proteins and certain minerals (Boonurapeepinyo et al.
2011; Tzoumaki et al. 2011; Ifuku and Saimoto 2012). Figure 1.3 shows the scheme
of the hierarchical organization in arthropod exoskeleton (H. americanus, American
lobster), which reveals different structural levels.
Two types of chitin crystal are known, α- and β-chitins. Most natural chitins have
the α-type crystal structure, while the β-type chitin is present in squid pens and tube-
worms. In α-chitins, all molecular chains are arranged in an antiparallel mode with
strong intermolecular hydrogen bonding. On the other hand, β-chitins have a parallel
chain packing mode. Especially, the intermolecular forces in squid pen β-chitins are
weaker than those in α-chitins, and this makes squid pen β-chitins more suscepti-
ble to enzymatic degradations or chemical reactions. The lateral dimensions of the
crystalline fibrils of chitins range from 2.5 to 25 nm, depending on their biologi-
cal origins (Fan et al. 2008b). Most of the naturally occurring polysaccharides e.g.
cellulose, dextrin, pectin, alginic acid, agar, agarose and carrageenans are neutral or
acidic in nature, whereas, chitin is an example of highly basic polysaccharide. Their
unique properties include optical structural characteristics, ability to form films and
4 1 Introduction

Fig. 1.3 Scheme of the hierarchical organization in arthropod exoskeleton (H. americanus, Amer-
ican lobster), which reveals different structural levels. Reprinted with permission from Salaberria
et al. (2015b). Copyright Elsevier

chelate metal ions (Visakh and Thomas 2010). Chitin has great potential to be used in
the fabrication of implant devices, wound dressing materials, drug delivery systems,
and regenerative medical components for bones and other medical materials, due to
its high crystallinity, high strength, and biocompatibility (Fan et al. 2008b). Com-
mercially chitin and chitosan are of great importance owing to their relatively high
percentage of nitrogen (6.89%) compared to synthetically substituted cellulose. The
following three steps in chronological order of the process are needed to produce
chitin from crustacean shells: deproteinization (i) removal of residual proteins by
chemical (NaOH) or enzymatic hydrolysis; (ii) demineralization—removal of min-
eral salts by acid treatment; and finally (iii) removal of lipids and pigments by typical
bleaching treatments. In some cases, when the raw material is rich in minerals, it
is preferable that the demineralization operation precedes the deproteinization pro-
cess. After this, purified chitin could be: (i) dried and cracked into powders or small
flakes; or (ii) kept wet in suspension. Figure 1.4 shows a schematic illustration of the
conventional process of the chitin isolation from shell wastes.
Chitin nano-objects can be obtained by two approaches: top-down and bottom-up.
As chitin fibrils are composed of two regions, i.e. crystalline and amorphous, chitin
can be turned in nanocrystals, nanofibers and nanowhiskers via top-down method.
This approach breaks down the chitin fibrils from native chitin into nanofibrils. Acid
hydrolysis (Fan et al. 2008a), 2,2,6,6-tetramethyl-piperidinyl-1-oxyl (TEMPO)-
mediated oxidation (Fan et al. 2008b), grinding and high-pressure homogenizing
(Lu et al. 2013) are some representative techniques of this approach. The isola-
tion of these nano-size chitin using: (i) acid conditions results in chitin nanocrystals
(CHNC), which are rod like in appearance with low aspect ratio, (ii) mechanical
treatments/disintegration results in chitin nanofibers (CHNF), which are fibrillar in
appearance with high aspect ratio, and have lower crystallinity than CHNC. Chitin
1.1 Starch 5

Fig. 1.4 Illustrative scheme of the extraction process of chitin from shell wastes. Reprinted with
permission from Salaberria et al. (2015a). Copyright Elsevier

nano-whiskers (CNW) of slender parallelepiped rods have been successfully pre-


pared from chitin, using dilute acid hydrolysis at high temperature, followed by
repeated mechanical treatment. This has been recently explored in nanotechnology
applications (Mincea et al. 2012; Muzzarelli 2011). CNWs have many excellent
properties, including biodegradability, biocompatibility, renewability, and antibac-
terial properties. On the other hand, self-assembled chitin nano-objects have been
produced by regeneration from chitin solutions or gels via the bottom-up approach.
6 1 Introduction

Fig. 1.5 Structure of chitin and chitosan. Reprinted with permission from Jayakumar et al. (2010).
Copyright Elsevier

1.2 Chitosan

Chitosan, a highly versatile naturally occurring polymer, is a derivative of chitin, a


structural element found in the exoskeleton of crustaceans. Chitosan is obtained by
the deacetylation of chitin. Figure 1.5 shows the structure of chitin and chitosan.
A higher degree of deacetylation corresponds to a higher percentage of positively
charged primary amines and an overall higher charge density. Commercially available
chitosan results from alkaline deacetylation of chitin. It is an attractive biocompatible,
biodegradable and nontoxic natural biopolymer that exhibits excellent film-forming
ability. Chemically, chitosan is a linear polysaccharide composed of glucosamine
and N-acetyl glucosamine units linked by β(1-4) glycosidic bonds (Levengood and
Zhang 2014). There are many forms of pure chitosan, which differ by their degrees of
deacetylation (DD) and molecular weights. The degree of deacetylation represents
the glucosamine to N-acetyl-glucosamine ratio. Both the degree of deacetylation and
the molecular weight have a strong influence on other physicochemical properties of
chitosan including crystallinity, solubility, and degradation (Levengood and Zhang
2014). An important property of chitosan is the ease with which it can be function-
alized due to the presence of reactive primary amines and primary and secondary
hydroxyl groups.
References 7

References

Anitha A, Sowmya S, Kumar PTS, Deepthi S, Chennazhi KP, Ehrlich H, Tsurkan M, Jayakumar R
(2014) Chitin and chitosan in selected biomedical applications. Prog Polym Sci 39:1644–1667.
https://doi.org/10.1016/j.progpolymsci.2014.02.008
Babu RP, O’Connor K, Seeram R (2013) Current progress on bio-based polymers and their future
trends. Prog Biomater 2:8. https://doi.org/10.1186/2194-0517-2-8
Boonurapeepinyo S, Jearanaikoon N, Sakkayawong N (2011) Reactive Red (RR141) solution
adsorption by nanochitin particle via XAS and ATR-FTIR techniques. Int Trans J Eng Manag
Appl Sci Technol 2:461–470
Cao X, Chen Y, Chang PR, Muir AD, Falk G (2008) Starch-based nanocomposites rein-
forced with flax cellulose nanocrystals. Express Polym Lett 2:502–510. https://doi.org/10.3144/
expresspolymlett.2008.60
da Silva JBA, Nascimento T, Costa LAS, Pereira FV, Machado BA, Gomes GV, Druzian JI (2015)
Effect of Source and Interaction with Nanocellulose Cassava Starch, Glycerol and the properties
of films bionanocomposites. Mater Today Proc 2:200–207. https://doi.org/10.1016/j.matpr.2015.
04.022
Fan Y, Saito T, Isogai A (2008a) Chitin nanocrystals prepared by TEMPO-mediated oxidation of
α-chitin. Biomacromol 9:192–198. https://doi.org/10.1021/bm700966g
Fan Y, Saito T, Isogai A (2008b) Preparation of chitin nanofibers from squid Pen β-chitin by simple
mechanical treatment under acid conditions. Biomacromol 9:1919–1923. https://doi.org/10.1021/
bm800178b
Gironès J, López JP, Mutjé P, Carvalho AJFD, Curvelo AADS, Vilaseca F (2012) Natural fiber-
reinforced thermoplastic starch composites obtained by melt processing. Compos Sci Technol
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González K, Retegi A, González A, Eceiza A, Gabilondo N (2015) Starch and cellulose nanocrystals
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2015.08.034
Chapter 2
Processing Techniques

2.1 Starch Based Composites

2.1.1 Solution Casting

Solution casting is one of the most common processing techniques for the prepa-
ration of starch based bionanocomposite. Solution casting is an easy method for
homogeneous dispersion of starch and reinforcement using water as the solvent.
Sreekumar et al. prepared nano TiO2 filled starch/PVA composite by solution cast-
ing method (Sreekumar et al. 2012). Initially the suspension of nano TiO2 in distilled
water at various concentrations of nano TiO2 (i.e. 0.5, 1, and 2 wt% with respect to
the total polymer content) were prepared using ultrasonicator using the dispersing
agent span 60. The suspension was ultrasonicated for 1 h and then added slowly to
starch/PVA solution (1:1) containing 3.5 g of glycerol while stirring continuously.
Composite films were obtained.
Almasi et al. prepared citric acid (CA) modified starch-carboxymethyl cellulose
(CMC)-montmorillonite (MMT) bionanocomposite films by casting method (Almasi
et al. 2010). Starch in distilled water was mixed with glycerol and CA at room
temperature (25 °C) for 5 min. Suspension was agitated by magnetic stirrer. Starch
CMC was solubilized in 75 mL of water at 75 °C for 10 min. On the other hand,
montmorillonite (MMT) was dispersed in distilled water by sonication. The clay
dispersion was added to the aqueous dispersion of starch. CMC and starch-MMT
solution were mixed together and stirred. Dried films were then prepared by casting.
Chang et al. prepared glycerol plasticized potato starch (GPS) reinforced with
chitin nanoparticle (CNP) by casting and evaporation method. At low loading levels,
CNP were uniformly dispersed in the GPS matrix and had good interaction between
the filler and matrix, which led to improvements in tensile strength, storage modulus,
glass transition temperature, and water vapor barrier properties of the GPS/CNP
composites. However, at higher loading (greater than 5 wt.%), aggregation of CNP
had a negative effect on these properties (Chang et al. 2010).
© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2019 9
M. S. Thomas et al., Starch, Chitin and Chitosan Based Composites
and Nanocomposites, Biobased Polymers,
https://doi.org/10.1007/978-3-030-03158-9_2
10 2 Processing Techniques

El Miri et al. prepared bionanocomposite films of carboxymethyl cellulose


(CMC)/Starch (ST) polysaccharide matrix reinforced with cellulose nanocrystals
(CNC) using solution casting method (El Miri et al. 2015). The CNC were extracted
from sugarcane bagasse (SCB) via sulphuric acid hydrolysis process. The loading
levels of CNC in CMC/ST-CNC bionanocomposite films were fixed at 0.5, 2.5 and
5.0 wt%. Enhancement in properties of composite film occurs due to strong interfa-
cial adhesion generated from the hydrogen bonding between the functional groups
that are present in the components CMC, starch and CNC. Figure 2.1 shows the
visual observations of the bionanocomposite films.
Fabrication of pea starch (PS)/cellulose nanowhiskers from pea hull fiber
(PHFNW) were done by solution casting and evaporation method. PHFNW dis-
persions were prepared and coded as PHFNW-t, where t was the hydrolysis time.
For example, PHFNW-8 means the nanowhiskers were hydrolysed from PHF by
sulphuric acid for 8 h. A series of pea hull fiber-derived nanowhiskers (PHFNW-t)
was successfully extracted from pea hull fibers (PHF) by sulphuric acid hydrolysis
with different hydrolysis times (t). The PHFNW-t was then blended with pea starch
(PS) to prepare PS/PHFNW-t bionanocomposite films. Compared to the neat PS
film and the PS/PHF (t  0 h) film, the PS/PHFNW-t nanocomposite films showed
higher ultraviolet absorption, transparency, tensile strength, elongation at break, and
water-resistance (Chen et al. 2009).
Tape casting (De Moraes et al. 2013) is another method that is used for the prepa-
ration of thin films. The starch–glycerol–fiber suspensions were prepared as sketched
in Fig. 2.2a. Tape casting technique allows the spreading of a suspension on large sup-
ports, controlling the thickness by an adjustable blade at the bottom of the spreading
device. Drying of the films can be carried-out on the support itself, under controlled
conditions. Cellulose fiber reinforced starch biocomposite films were prepared by
this method. The obtained films were homogeneous, without bubbles or defects and
were easy to handle, as shown qualitatively in Fig. 2.3.

Fig. 2.1 Digital images of


CMC/ST, CMC/ST-CNC
films%. Reprinted with
permission from El Miri
et al. (2015). Copyright
Elsevier
2.1 Starch Based Composites 11

Fig. 2.2 a Summary of the process used to prepare cellulose fibers–starch films by tape-casting,
b.1 Picture of the support for the spread suspension in the discontinuous (manual) tape-casting
device, b.2 Sketch of the acrylic plate, and c Picture of a doctor blade device (De Moraes et al.
2013). Reprinted with permission from De Moraes et al. (2013). Copyright Elsevier

2.1.2 Compression Moulding

Orue et al. prepared composites based on thermo plastic starch (TPS) and cellulose
nanofibers by compression moulding method. Cellulose nanofibers were extracted
by chemical treatments from sisal fibers. TPS composition with the best mechanical
12 2 Processing Techniques

Fig. 2.3 Image of a large dimension film prepared by tape-casting, with 3 g starch/100 g of sus-
pension, 0.20 g glycerol/g dry starch and 0.30 g fiber/g dry starch %). Reprinted with permission
from De Moraes et al. (2013). Copyright Elsevier

property was observed for 60 g starch with glycerol to water ratio of 0.25. The
addition of cellulose nanofibers to TPS matrix improved the mechanical properties.
Maximum improvement was observed when 0.5 wt% of nanofibers of cellulose was
added to TPS matrix. At higher nanofiber contents, the dispersion of reinforcements
in the matrix seemed not to be good enough and agglomerations could be generated
where film started to break (Orue et al. 2014).

2.1.3 Twin Screw Extrusion

The extruder barrel was equipped with two atmospheric vents and vacuum ventilation
in order to remove the vaporized water from the material. Feeding of the materials
was done manually due to the small amounts of the prepared pre-mixes. The extrusion
set-up together with the screw configuration and the temperature profile is shown
in Fig. 2.4. Before extrusion, premixes of starch, sorbitol, stearic acid and cellulose
nanofibers were made. The extruded material was compression moulded into thin
films (Hietala et al. 2013) (Fig. 2.5).
Nascimento et al. used the method of melt extrusion for the preparation of rice
hull (RH), bleached rice hull (RCB) and cellulose nanofibrils from rice hull (RHNF)
reinforced thermoplastic starch films. The mixture was fed to the extruder first to
obtain pellets of gelatinized material. These pellets were then re-extruded for bet-
ter homogenization. The second batch of pellets was fed to the extruder for film
manufacturing by blowing.
2.1 Starch Based Composites 13

Fig. 2.4 Extrusion set-up used in the compounding of TPS/CNF composites %). Reprinted with
permission from Hietala et al. (2013). Copyright Elsevier

Fig. 2.5 Visual appearance of TPS and TPS/CNF films %). Reprinted with permission from Hietala
et al. (2013). Copyright Elsevier

2.1.4 Thermal Moulding

Lomelí Ramírez et al. (2011) prepared coir fiber reinforced cassava starch based
composites by thermal moulding using glycerol as the plasticizer. With the help of
a mixer, the coir fibers were well dispersed in the matrix starch. The quantity of
coconut fibers used to prepare the composites were 5, 10, 15, 20, 25 and 30% (Souza
et al. 2012). Figure 2.6a, b shows photographs of cassava starch–glycerol composites
with 5 and 30% coir fibers as observed under a stereomicroscope.

2.1.5 Melt Blending

Castaño et al. prepared cellulosic reinforced composite by melt blending. Araucaria


araucana (pehuen) cellulosic husk was employed as the reinforcement in pehuen
thermo plastic starch (TPS). A comparative study of pehuen TPS/poly vinyl alcohol
(PVA)/poly lactic acid (PLA) blends were also done. Incorporation of pehuen husk
14 2 Processing Techniques

Fig. 2.6 Photographs of cassava starch composite a 5% and b 30% coconut fiber. c Panoramic view
of the composite at higher magnification; TPS: thermoplastic starch; CF: coir fiber %). Reprinted
with permission from Lomeli Ramirez et al. (2011). Copyright Elsevier

improved the thermal stability and mechanical properties of the studied composites
considerably, mainly in TPS composites (Castaño et al. 2012).

2.2 Processing Techniques of Chitin and Nano Chitin Based


Composite Films

The possibility of formation of continuous nanocrystal network and the final prop-
erties of nanocomposite material are governed by the processing method.

2.2.1 Solution Casting

Solution casting, also called wet process is a technique which involves the dispersion
or solubilization of chitin in a solvent medium before pouring the solution onto a
2.2 Processing Techniques of Chitin and Nano Chitin Based Composite Films 15

flat surface and drying. The film can be peeled off the flat surface after drying. This
slow process of casting/evaporation are reported to give materials with the highest
mechanical performance. This is attributed to the fact that during slow water evap-
oration rearrangement of nanoparticles is possible due to Brownian motion in the
suspension or solution. Thus they get enough time to interact and connect to form a
percolating network which is the basis of their reinforcing effect. The resulting struc-
ture is completely relaxed and direct contacts between nanocrystals or microfibrils
are then created (Dufresne 2008).

2.2.2 Extrusion

Extrusion being a conventional polymer-processing technique there is growing inter-


est in this technique for nanocomposite processing in industrial applications. The
main challenges of this technique are the feeding of the nanomaterials into the
extruder and obtaining well-dispersed nanocrystals in the polymer matrix since nano-
materials tend to aggregate while drying. Since chitin forms hydrogen bonds when
dried, drying prior to the extrusion is not suitable. Liquid feeding of nanomaterials
together with a suitable processing aid, such as plasticizer or water, is one way to
avoid the drying process and to improve the dispersion of the nanomaterials in the
matrix (Herrera et al. 2016). However, when water or other solvents are used, it is
important to use a co-rotating twin-screw extruder where the steam can be effectively
removed during the processing.

2.2.3 Freeze-Drying Method

The arrangement of nanoparticles in the suspension is first frozen during the freeze-
drying/hot-processing method and during the subsequent hot-processing stage, the
rearrangement of particles is strongly limited because of polymer melt viscosity and
contacts can be made through a limited amount of polymer matrix. However, although
the freeze-drying/hot pressing process limits the possibility of creation of hydrogen
bonds, it is expected that, for high polysaccharide nanoparticles content, some bonds
may still be created. Zheng et al. (2003) prepared nanocomposites with Soy Protein
Isolate (SPI) using freeze drying method. SPI of desired weight and various content
of chitin were mixed and stirred to obtain a homogeneous dispersion. The dispersion
was freeze-dried and 30% glycerol was added. The resulting mixture was hot-pressed
at 20 MPa for 10 min at 140 °C and then slowly cooled to room temperature.
16 2 Processing Techniques

2.3 Processing Techniques of Chitosan Based Composites

2.3.1 Physical Blends

Polymeric composites can be prepared by the physical mixing of two or more


polymers. But it is very difficult to prepare a homogeneous system of chitosan
and polyester because of lack of co-solvents that can accommodate both polymers
(Levengood and Zhang 2014). Mechanical stirring was utilized by Jiang et al.
(2006) to fabricate a homogenous suspension of milled chitosan microparticles in a
solution of PLGA in methylene chloride. Subsequently, composite chitosan-PLGA
microspheres were formed via solvent evaporation and microspheres were fused to
yield scaffolds (Jiang et al. 2006). Melt blending techniques were also adopted for
the preparation of chitosan—polyester composites where heating and compression
of polymer particles results in the formation of a continuous polymer network
(Levengood and Zhang 2014). Combined with leaching of salt particles, melt blend-
ing yields porous scaffolds and in both cases, mechanical strength of the resultant
scaffolds exceeded that of pure chitosan scaffolds (Levengood and Zhang 2014).

2.3.2 Polyelectrolyte Complexes

The electrostatic interactions between charged functional groups chitosan and


anionic macromolecules results in the formation of polyelectrolyte complex (PEC)
networks. Mechanical stirring was utilized by Jiang et al. (2006) to fabricate a
homogenous suspension of milled chitosan microparticles in a solution of PLGA
in methylene chloride. Subsequently, composite chitosan-PLGA microspheres were
formed via solvent evaporation and microspheres were fused to yield scaffolds (Jiang
et al. 2006). Melt blending techniques were also adopted for the preparation of chi-
tosan—polyester composites where heating and compression of polymer particles
results in the formation of a continuous polymer network (Levengood and Zhang
2014).

References

Almasi H, Ghanbarzadeh B, Entezami AA (2010) Physicochemical properties of starch–CMC—


nanoclay biodegradable films. Int J Biol Macromol 46(1):1–5.
Castaño J, Rodríguez-Llamazares S, Carrasco C, Bouza R (2012) Physical, chemical and mechanical
properties of pehuen cellulosic husk and its pehuen-starch based composites. Carbohydr Polym
90:1550–1556. https://doi.org/10.1016/j.carbpol.2012.07.029
Chang PR, Jian R, Yu J, Ma X (2010) Starch-based composites reinforced with novel chitin nanopar-
ticles. Carbohydr Polym 80:421–426. https://doi.org/10.1016/j.carbpol.2009.11.041
References 17

Chen Y, Liu C, Chang PR, Cao X, Anderson DP (2009) Bionanocomposites based on pea starch
and cellulose nanowhiskers hydrolyzed from pea hull fibre: effect of hydrolysis time. Carbohydr
Polym 76:607–615. https://doi.org/10.1016/j.carbpol.2008.11.030
De Moraes JO, Scheibe AS, Sereno A, Laurindo JB (2013) Scale-up of the production of cas-
sava starch based films using tape-casting. J Food Eng 119:800–808. https://doi.org/10.1016/j.
jfoodeng.2013.07.009
Dufresne A (2008) Polysaccharide nano crystal reinforced nanocomposites. Can J Chem
86:484–494. https://doi.org/10.1139/v07-152
El Miri N, Abdelouahdi K, Barakat A, Zahouily M, Fihri A, Solhy A, El Achaby M (2015)
Bio-nanocomposite films reinforced with cellulose nanocrystals: rheology of film-forming
solutions, transparency, water vapor barrier and tensile properties of film. Carbohydr Polym
20(129):156–167. https://doi.org/10.1016/j.carbpol.2015.04.051
Herrera N, Salaberria AM, Mathew AP, Oksman K (2016) Plasticized polylactic acid nanocomposite
films with cellulose and chitin nanocrystals prepared using extrusion and compression molding
with two cooling rates: Effects on mechanical, thermal and optical properties. Compos Part A
Appl Sci Manuf 83:89–97. https://doi.org/10.1016/j.compositesa.2015.05.024
Hietala M, Mathew AP, Oksman K (2013) Bionanocomposites of thermoplastic starch and cellulose
nanofibers manufactured using twin-screw extrusion. Eur Polym J 49:950–956. https://doi.org/
10.1016/j.eurpolymj.2012.10.016
Jiang T, Abdel-Fattah WI, Laurencin CT (2006) In vitro evaluation of chitosan/poly (lactic
acid—glycolic acid) sintered microsphere scaffolds for bone tissue engineering. Biomater
27(28):4894–903. https://doi.org/10.1016/j.biomaterials.2006.05.025
Levengood SL, Zhang M (2014) Chitosan-based scaffolds for bone tissue engineering. J Mater
Chem B 2(21):316. https://doi.org/10.1039/C4TB00027G
Lomelí Ramírez MG, Satyanarayana KG, Iwakiri S, de Muniz GB, Tanobe V, Flores-Sahagun TS
(2011) Study of the properties of biocomposites. Part I. Cassava starch-green coir fibers from
Brazil. Carbohydr Polym 86:1712–1722. https://doi.org/10.1016/j.carbpol.2011.07.002
Orue A, Corcuera MA, Pena C, Eceiza A, Arbelaiz A (2014) Bionanocomposites based on ther-
moplastic starch and cellulose nanofibers. J Thermoplast Compos Mater 29:817–832. https://doi.
org/10.1177/0892705714536424
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Chapter 3
Properties of Composites

3.1 Thermal Properties of Composites

3.1.1 Thermal Properties of Starch Based Composites

Thermal stability of composites depends on the type of reinforcement added to


the starch. Study of thermal stability of glycerol-plasticized pea starch/graphene
oxide (PS/GO-n) biocomposite films with different loading levels of graphene oxide
revealed that an improvement in the stability of biocomposite films can be seen with
an increase of the fillers loading (Li et al. 2011). Thermogravimetric (TG) and deriva-
tive thermogravimetric (DTG) curves of the PS film and PS/GO-n biocomposites are
shown in Fig. 3.1a, b, respectively.
Differential Scanning Calorimetry (DSC) is widely accepted as the most suit-
able method for the evaluation of starch gelatinization and other thermal behaviour.
DSC thermograms facilitate the analysis of starch transition temperatures as well
as transition enthalpies. The enthalpy (H) of a transition has been interpreted as
corresponding to the amount of crystal order in starch suspensions. The reported
DSC results are not always consistent and are sometimes controversial, not only due
to the complexity of the thermal behaviors of starches, but also due to the differing
measurement conditions used. The key factors that affect the measured results are
sample preparation, the type of pan used and the measurement conditions. More
recently, a new technique using high-pressure stainless-steel pans has been devel-
oped, which allows the study of the phase transitions of starch with higher water
content (9–75%) and at higher temperatures (up to 360 °C). In DSC experiments,
the glass transition temperature (Tg ) is generally taken as the inflection point of
the specific heat increment at the glass-rubber transition. Incorporation of filler in
thermoplastic starch affects the glass transition temperature (Gironès et al. 2012).
Homogeneous dispersion of flax cellulose nanocrystals within the pea starch matrix
and strong interfacial adherence between matrix and fillers led to an increase of glass

© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2019 19


M. S. Thomas et al., Starch, Chitin and Chitosan Based Composites
and Nanocomposites, Biobased Polymers,
https://doi.org/10.1007/978-3-030-03158-9_3
20 3 Properties of Composites

Fig. 3.1 TG (a) and DTG


(b) curves of PS and
PS/GO-n biocomposite
films). Reprinted with
permission from Li et al.
(2011). Copyright Elsevier

transition temperature ascribed to the starch molecular chains in the starch-rich phase
(Cao et al. 2008).

3.1.2 Thermal Properties of Chitin Based Composites

Thermal properties of materials are of importance for processing issues and practical
applications. The thermal behavior of chitin and chitin/ZnO composite was deter-
mined by thermogravimetry and differential thermal analysis by Wysokowski et al.
(2013a, b). The main thermal degradation of the biopolymer β chitin started at 200 °C
and ended at 550 °C and two steps were strongly exothermic. First exothermic effect
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from early experience be prepared, should the cause arise, to fulfil a
noble destiny, even as he himself, having from his tenth year borne
arms under his father Hamilcar and brother-in-law Hasdrubal, had
been prepared for the mighty role which, with the siege of Saguntum,
he was now commencing to fill in the world’s history.
For the Greek city of Saguntum, on the eastern coast of Spain,
was strictly allied with Rome, and the fact of Hannibal’s attacking it
was, he well knew, equivalent to a commencement of a new war with
mighty Rome herself.
Upon Hannibal’s departure for the siege of Saguntum some eight
months previous, he had taken all the generals and captains in
whom he could put trust and the greater part of the army with him.
Although not styled a king, his power was at that time more than
regal in all the parts of Spain south of the Ebro, and his authority as
regards the care of the City of New Carthage itself he had, on his
departure, delegated under his sign manual and seal absolutely to
his daughter Elissa.
It is, then, no cause for wonder, if her female companions looked
with some degree of awe and respect upon this sixteen-years-old girl
who sat there so pensively dabbling her hands and feet in the marble
basin, while raising her head occasionally to cast a glance through
the embrasures on the battlemented walls surrounding the garden,
upon the gulf below and the blue sea stretching out far beyond.
Elissa had far sight, and it seemed to her once or twice as though
she could make out, shining in the evening sun, far away upon the
horizon, the white sails of ships. But they were no larger than
specks, and soon disappeared altogether; therefore the maiden,
thinking that she had been misled by some sea birds, soon gave up
watching the sea, and returned to the apparent contemplation of the
fishes, but really to the continuation of the reverie upon which she
was engaged.
Meanwhile the ladies under the trees were chatting away merrily.
“Oh! dear me, how hot it is,” exclaimed the rotund little Princess
Cœcilia, fanning herself vigorously with a palm leaf fan. “I am sure
when my poor husband, Hasdrubal, built this city of New Carthage,
he must have selected it purposely as being the warmest site in all
Spain, just to remind him of his native country which he was so fond
of. Or else,” she continued, “it was to try and keep down my
inclination to fat. Oh! dear me!” and she fanned away at herself more
vigorously than ever.
“Don’t call it fat,” interposed Cleandra, a very handsome fair young
woman of about twenty, who was herself by no means inclined to be
thin—“say rather adipose deposit, it is a far more elegant way of
putting it.”
“Or plumpness, Cleandra, that is nicer still,” struck in Melania, a
dark young beauty with vivacious black eyes, who was a year
younger. “I wish I could call myself plump like thee, I am sure I
should not mind the heat,” she added, “instead of being the
scarecrow that I am,” and rising she surveyed with mock ruefulness
her really very graceful figure. She was the tallest of all the young
women there, and was perfectly well aware of the fact that her
comparative slenderness was most becoming to her willowy and
lissome figure.
“A scarecrow, thou a scarecrow,” almost screamed the little
Cœcilia. “Oh! just listen to the conceited thing; why, thou hast a
lovely figure and thou knowest it; there is none in all New Carthage,
save Elissa yonder, who can compare to thee. But then, of course,
no one can compare with her in any way. But what a girl she is! how
can she sit out there in the afternoon sun like that? the worst kind of
sun, my dears, for the complexion, I can assure you. I am sure if I
were to remain like that for only five minutes I should lose my
complexion entirely, yes, become perfectly covered with freckles I
am certain, in even less than five minutes. Now what are you
giggling at, you naughty girls? I declare you are too wicked, both of
you; I shall have to report you to our Queen Regent yonder and ask
her to put you both in the dungeon if you make fun of an old lady like
me. Alas! thirty years of age, don’t you call that old?”
For with a sly glance at each other the two girls had mutually
looked at the lively little princess’s manifestly artificial complexion
which was trickling away in little runnels down her cheeks.
“I wonder what she is thinking about?” she interposed hastily, to
turn away the merry girls’ attention from herself, and glancing across
towards the lady Elissa.
“Who?” said Cleandra.
“Why, Elissa, of course,” replied that lady’s aunt. “Canst thou not
see that she hath been in a brown study for ever so long? She is no
more thinking of the fish than I am; her thoughts are miles and miles
away. But just notice how pretty the ruddy tints are in her dark hair,
lighted up like that by the afternoon sun.”
“Perhaps she is thinking of affairs of State,” answered Cleandra,
“and whether she is to put us in that black hole or no.”
“Or, perhaps,” said Melania with a grain of malice, “and far more
likely, she is thinking of the siege of Saguntum and whether a certain
young officer of cavalry called Maharbal will ever come back from
the war again to do what we girls cannot hope to do, that is cheer
her in her solitude. I really should like to go and disturb her, she
reminds me so of her namesake Dido—Elissa is Hebrew for Dido,
thou knowest, Lady Cœcilia—mourning on the heights of Carthage
for her lost Æneas.”
“I wonder what she sees in that Maharbal,” continued Melania, in a
tone of pique; “a great big mountain of a hobbledehoy, that’s what I
call him, and merely a prefect of the Numidian cavalry, too. Such
assurance on his part to be always making love to her! I wonder that
Hannibal allows it—a mere nobody!”
“A mere nobody! a hobbledehoy! nonsense!” said the princess,
“thou’rt jealous, Melania, because he never looks at thee. Why, he is
own nephew to Syphax, King of Massaesyllia, and cousin to the
powerful Massinissa, King of Massyllia, both great Libyan princes.”
“Mere vassals of Carthage! and the last named not very
trustworthy,” replied the other interrupting.
“Well then,” gabbled on the princess, “look at his strength, a
hobbledehoy indeed; Maharbal is a regular Hercules, and hath a
beautiful face just like the celebrated Hermes of Praxiteles. I think
Elissa will be a very lucky girl if she weds a magnificent fellow like
that; she will be the mother of a race of giants.”
“Shsh! Shsh!” cried both the girls, smiling in spite of themselves.
“Elissa is listening to all we are saying—just look at her.”
“Yes, yes, you wicked people, and she hath been listening for the
last quarter of an hour,” cried Elissa, springing to her feet as red as a
rose. “But really, my aunt is too bad, she maketh me ashamed; say,
what shall we do with her for punishment? put her in the fish pond I
think.” Bounding across the open space, she playfully seized upon
the merry little woman, and aided by the two others, dragged her in
spite of her cries, screams, and vigorous resistance to the very brink
of the marble basin. She struggled violently, and but with difficulty
escaped her fate.
“Oh, dear me! think of my complexion—cold water in the afternoon
is bad for it. Oh! I did not mean a word, dear Elissa. Oh, dear me, I
shall die,” and with a vigorous final effort for freedom, as she was
really a very strong young woman, suddenly she pushed both Elissa
and Melania together over the brink so that they fell with a splash
into the shallow pond. Then being left alone with the plump
Cleandra, who had no strength whatever, she speedily overcame
her, and threw her in after the others, remaining with torn garments
and dishevelled hair, shrieking with laughter, and panting for breath
on the bank.
“Now there is naught for us but to have a bathe,” cried Elissa gaily;
and first drenching the princess with a shower of spray, and then
springing up the marble steps, the three girls quickly threw off their
thin, wet, clinging garments.
Standing there together in a pretty group for a brief minute or two,
poised on the top of the marble steps, with arms raised in graceful
curves while loosening the fillets of silver from the hair that fell in
masses to the hips, they seemed in all their youthful beauty like the
three graces personified.
At that very moment, from behind the trees, the sound was heard
of a horse’s hoofs galloping on the turf, and in a second an armed
warrior, mounted on a black charger covered with foam and utterly
exhausted, appeared upon the scene. At the same time, a great
sound of shouting was heard in the town without the garden walls,
which shouting was taken up again and again, till the clamour
seemed literally to fill the air. The shouting sounded like the cheers
for victory.
The princess was the first to recover her composure.
“Why, it’s Maharbal,” she cried; “jump into the water, girls, instantly.
Fancy his coming like that!” Then, rushing in front of the warrior, she
wildly waved her hands at the horse, shouting, “Go back! Maharbal,
go away, thou wicked man, go back. Dost not see that the girls are
bathing?”
At that moment they all plunged into the water once more like
frightened swans.
“In the name of Hannibal!” cried the young warrior, “let me pass. I
must speak to Elissa, and instantly, or my head will fall,” and he held
up Hannibal’s signet ring before the dripping princess’s astonished
gaze.
“Oh!” screamed the princess, falling back affrighted. “Hannibal’s
ring! Yes, of course, Hannibal’s orders are law.”
Maharbal advanced to the edge of the shallow pond. In this the
maidens were now crouching and partially concealing themselves
under some flags, but in spite of all, their heads and shoulders
remained uncovered. Elissa and Cleandra faced Maharbal and
strived to look dignified. Melania, on the other hand, had turned her
back upon him.
Curiosity and anger combined caused her to turn her head, and
she was the first to speak, as Maharbal, his charger beside him,
stood upon the steps. Both she and Cleandra, of noble Iberian
families by birth, were, although treated as of the family, but slave
girls in Hannibal’s household, therefore she had no right to speak in
the tone she now used, except the right of outraged modesty that
every woman possesses.
“Begone! Maharbal, thou insolent wretch, begone instantly, or the
Lady Elissa will have thee scourged and beheaded for thine
impertinence. How darst thou insult us, thou ruffian? I wish that thou
wert dead.”
At this instant, Maharbal’s war-horse, with a mournful kind of half
scream, half sigh, fell upon the ground at the edge of the pond, and
with a quiver of all its limbs expired. The warrior turned to watch it for
a second, then looking back, remarked sadly: “My best charger, and
alas! the third I have killed since yesterday morning. But there is no
time for talk. Lady Elissa, my business is with thee alone, and it
brooks absolutely not a moment’s delay. Wilt thou kindly direct thy
slaves,” and he looked hard at Melania, “to leave the water at once. I
must speak with thee alone. I obey the General’s strict orders.
“Pray be quick,” he added, “for I feel my strength rapidly failing me,
and if I have not fulfilled my duty before, like my horse yonder, I die, I
shall have failed in my vows to my General and to my country.”
He removed his helmet as he spoke, and all the three maidens
noticed not only that the young man was turning deadly pale, but that
a wound on the side of the head, which had been covered with
coagulated blood, had broken out, and was bleeding violently afresh.
But he had yet strength to hand a garment, the first he found to
hand, to Elissa, who, while attiring herself in the water, turned
sharply to her attendants, and addressed them authoritatively.
“Leave the water, maidens, and let no false shame delay ye for a
moment, for I see this is a matter of life or death. Begone at once,
and thou, mine aunt,” she cried.
Like startled deer, the two girls, having recovered some of the
scattered raiment, fled from the pond, and rushed within the palace,
followed by the dishevelled Princess Cœcilia. But whether from
being reminded thus forcibly that she was but a slave, or from a
combination of feelings, no sooner had Melania reached her
apartment than she burst into a flood of violent weeping. The
princess was wringing her hands as she went, and talking aloud.
“Oh, dear me! this is very odd and very dreadful, and most
improper! But poor Maharbal’s horse is dead, and he looks at
death’s door himself. Oh! what hath happened? I hope Hannibal is
not dead as well, or a prisoner, or anything awful. But nay! he hath
sent his seal. But I must prepare a room for poor Maharbal to die in;
where shall I get a bed big enough? what a long body he will be.”
And so chattering to herself, for want of anyone else to talk to, she
left Maharbal, the handsome young warrior, alone with the beautiful
child of sixteen, the Lady Elissa.
CHAPTER II.
MAHARBAL.

The young warrior had sunk down upon the grass, and was leaning
wearily upon his elbow by the time that, having partially robed
herself, Elissa was able to issue from the pond and fly to his side. He
seemed dying. Oblivious of all but the presence of the man whom in
her heart she loved with all the spontaneity of a youthful, ardent
nature, she not only thought of nothing but him, but she shewed it
clearly by the look in her eyes and by her actions.
“Oh, Maharbal! Maharbal! look not thus. Dost thou not know that I
love thee?”
She stooped over, seized his hand and pressed it to her lips, then,
with part of her raiment which was lying at hand, she repeatedly
bathed his brows with the cool water from the pond. But his eyes
closed as though he were in a faint; whereupon she leant over, and
in an agony of fear kissed him madly on the lips, muttering the while
some incoherent loving words, and cooing in his ear. They were the
first kisses that ever she had given to man, the virgin kisses of her
beautiful lips. Her embraces brought him to himself. Despite the
delight that shone in his eyes and the gratitude he felt at the
unlooked-for favour, the wounded warrior had not by any means
forgotten his duty. With returning consciousness he stretched out his
hand and gently pushed her back.
“This is no time for kisses, Elissa; there is other work to be done.
The State, thy father’s life, and thine own are to be considered; help
me to sit up and to rest against my poor dead charger. There, that
will do; now I feel better.”
For with all the might of her weak arms she had managed to drag
rather than help him into a sitting posture, and place him with his
back against the dead horse.
“Now sit by me and listen, and read what I have brought thee.
First, take this seal from my finger; it is a duplicate of Hannibal’s
signet ring. Here within my doublet I have a letter; canst thou get it? I
have no strength left.”
Elissa felt for some time beneath the doublet with trembling
fingers, but could not find the letter.
“Hold my hand and guide it,” he said, smiling faintly. Thus aided,
he produced a sealed letter from under his leather jerkin. “Take my
dagger and cut it open,” he said authoritatively.
She obeyed, trembling like the child she really was.
“Now read aloud, that I may know thou hast the meaning. But stay;
first bathe my face once more, for I must keep my senses about me.”
Once more she plunged her garment into the cool water, and for a
few minutes bathed his head and face. The young colossus gave a
sigh, then seemed restored: the colour partly came back to his
cheek.
“Now read!” he said; “read.”
But Elissa’s eyes were filled with tears, so that she could not read
the triangular Punic characters.
“Read it to me thyself, Maharbal,” she answered at length, “for I
cannot. There! I will hold it for thee; will that do?”
So he began:

“In the name of the Great God Melcareth, the Invisible God,
the God of Tyre, of Sidon, the God of Carthage, Greeting.
From Hannibal, the son of Hamilcar, Commander-in-Chief of
the Carthaginian troops and Governor-General of Iberia, to his
daughter Elissa, Regent and Governor of New Carthage.
“My daughter, these words are written by the hand of my
scribe and friend, Silenus, but they will be sealed with my
signet, which thou knowest, and thou canst verify the seal if
so be they arrive in thy hands.
“They are sent by the hand of Maharbal, whose fidelity to
me is assured. He also hath some liking for thee if I be not
mistaken. Maharbal was wounded in yesterday’s action, but
he is young, of great strength, and of a great courage; he may
succeed in accomplishing the journey. No other but Maharbal
in mine army could ride 2,000 stades without rest. Should he
not succeed, the gods will not have willed it.
“Yesterday, oh, my daughter, after a siege of over eight
months’ duration, we stormed and took the town and suburbs
of Saguntum. The enemy fought to the last with the greatest
courage, and our losses are very great.
“Several of my generals, including Hanno, who was the
Commander of the Numidian Cavalry—he was killed in the
pursuit of the fugitives—are dead. Most of the tribunes are
dead or disabled, and, in short, there is scarce an officer of
either cavalry or infantry who is not either dead or wounded. I
myself am seriously wounded, but not dangerously. Maharbal
was, by the favour of Melcareth, the means of preserving my
life. He will now succeed Hanno as Commander of the
Numidian Cavalry.
“Every male Greek in the city of Saguntum, no matter of
what age, we have put to the sword. All the older women, that
is all women over thirty, I have ordered to be sent out into the
country to be an incumbrance to the tribes of their Iberian
allies. All young matrons up to about the age of thirty, and all
girls under that age, I have handed over to my troops to do
with as they will. They will probably soon wish to sell them as
slaves for the Carthaginian market. This refers to the Greek
and also Roman women of all classes, from the wives and
daughters of the generals and rich citizens down to the
women of the lowest orders. For all are captives, and all are
slaves in the hands of my officers and men. Every Iberian
woman hath been allowed to go free. Every Iberian man hath
likewise been granted his liberty. This clemency on my part
will gain us many allies among the Celtiberians north of the
river Iberus, whence most of these people came.
“Our spoils of war are enormous, although the citizens
foolishly attempted to burn themselves with their goods in the
marketplace, which folly was prevented by our rapid advance
when the breaches were stormed. In saying burn themselves,
I intended to convey that the male inhabitants, being Greeks,
tried to burn their women and save themselves; this is the
usual Greek custom. But the women were saved, and are
now being consoled by my army. It is the men who sought to
burn them by fire because they could not carry them away
with them who are dead. This is all the news.
“Now, my daughter, I cease to write to thee as thy father,
but as thy General I command thee. It is the Commander-in-
chief writing to the Regent and Governor of New Carthage.
“Maharbal is charged to deliver unto thee this letter if he be
alive, and if thou be alive. He is to find thee, and not to quit
thee until thou readest this letter in his presence. Should he
fail in this duty of his own fault, he will lose his head.
Shouldest thou cause him to fail by thine own neglect of duty,
thine own life will be at stake. For as Regent and Governor of
New Carthage thou hast many lives in thine hands, and thou
art answerable for all to me, thy commanding officer, and
through me to the State.
“Now, know this, I have learned only this very day from
some Roman emissaries captured by me, and since
executed, that there is a plot against me in Carthage. Upon
learning that I had attacked the city of Saguntum, contrary, it
must be owned, to the treaty signed, from sheer inability to
resist, after my father Hamilcar’s death, by my brother-in-law,
thy late uncle Hasdrubal, the Roman Senate decided to send
an embassy to Carthage to demand my surrender to Rome.
That embassy departed quite recently, comparatively
speaking, but found the party of Hanno, the late Suffete of
Carthage, who was, in his lifetime, the enemy of Hamilcar, in
the ascendant. Adherbal, the deceased Hanno’s eldest son, is
now the head of that party. He entertained the Roman envoys
handsomely, and, without any authority from the State, but
merely in his private capacity as a citizen, promised them,
when drunk, both the loss of my head, and the loss of thy
virtue. He is a mere boaster, as was his father, who sought to
have me sacrificed at the age of nine years to Moloch, and
who, but for my own childish words, which saved him, would
himself have been sacrificed instead. Yet, nevertheless,
boasters sometimes succeed. For having boasted, they seek
to make good their words, and the greatest success is often to
those who attempt much. I am not, remember, writing now,
oh! Elissa, as a father, but as thy Commander-in-chief,
therefore hearken unto my words.
“Should the sacrifice of my head benefit my country, the
enemy or the country are welcome to my head.
“Again! Should the sacrifice of thy virtue benefit thy country,
the enemy or the country must be welcome to thy virtue. But
here there is no sacrifice necessary. I therefore do not intend
to lose my head, nor do I suggest unto thee that thou shouldst
sacrifice thy virtue. Yet there is a deep-laid plot, and Melcareth
alone, the great, the invisible God, knoweth whether Maharbal
will reach thee in time to stay it.
“Being a man of war myself, and accustomed to open
warfare from my very earliest youth, I love not the torture. Yet
for once I praise the rack, since by it I have gained the secrets
of this plot.
“Know then this. Without waiting for the decision in council
of the Hundred, the party of Hanno are about to send, or have
already despatched Adherbal, with a fleet strongly armed with
rowers and many marines who are desperate, mere
mercenaries drawn from the disbanded armies in Greece and
Sicily, all ruffians of the very worst description. His intention is
to obtain by fraud or force both possession of New Carthage
and of thine own person, knowing me to be away at
Saguntum. After that, through thee, he hopes to obtain
possession of me also. I cannot tell if these words will reach
thee in time or no, but thou art now, if they do reach thee in
time, forewarned. Pay no attention to the false letters that
Adherbal may bring thee; they are but a snare; he and all his
accursed faction are but scheming against the State. In no
case let him in mine absence, thou living, obtain possession
of New Carthage or of thyself.
“As for Hannibal, thy father and thy commander, fear not for
him. Do but thy duty in this crisis, oh, my daughter and my
delegate!
“(Sealed) Hannibal.”
As Maharbal read the last lines of this letter, he pushed it back
towards Elissa, who held it.
“Go!” he said, “go at once, heed not me. I saw the sails of
Adherbal’s fleet as I rode up. Leave me instantly.”
“I saw them too!” cried the girl, “but I knew not what they were. Oh,
beloved Maharbal! what if thou shouldst not survive? How can I
leave thee thus?”
“Go! go at once,” replied Maharbal feebly, “send someone to me if
thou choosest, but it is immaterial; go thou at once, do thy duty. Art
thou not Regent and Governor of Carthage? Stay, kiss me once, an’
thou wilt, for indeed ’tis sweet, Elissa, my beloved, thus for once to
feel thy kiss. Ah! now I can die in peace, but go, go! thine own
honour, thy country, and the safety of Hannibal are all at stake.”
Leaving the imprint of her fervent kisses on his lips, she hastily
departed.
The instant she had left him, Maharbal, the self-reliant young
giant, who had hitherto kept himself up by mere force of will, went off
into a dead swoon. For the blood had been continually oozing from
the wound above his temple while he had been reading Hannibal’s
letter, and moreover, he had not been out of the saddle or tasted
food for forty-eight hours.
Thus it came to pass that when, shortly after, the lively little
princess came out again, accompanied by Melania, they found the
beautiful young man lying all alone, quite inert and apparently dead,
by the side of his horse. And under his head was a large pool of
blood. They had brought wine with them, and sought to force it
between his lips, but the attempt was useless. They then strove to
move him from where he was lying, but in vain. No assistance could
be obtained from any of the men, for Elissa had issued orders to
double all the guards, and placed every available man on duty on the
ramparts or the quays. And so poor Maharbal lay bleeding and
unconscious.
Meanwhile two bodies of men had been hastily employed in
placing booms across the entrances to the harbour; other armed
forces were drawn up in detachments upon the island and wharves,
and on all sides of the entrances to the harbour, and a large fleet of
vessels, flying the Carthaginian flag of a white horse on a purple
ground, and consisting of fifty-two stately quinquiremes and twenty-
two splendid hexiremes, all crowded with armed marines, in addition
to the full crews averaging three hundred rowers apiece, being
disappointed at finding the entrance to the harbour closed, was just
heaving to, and casting its anchors in the open sea.
CHAPTER III.
FOREWARNED.

The City of New Carthage, built by Hasdrubal, the son-in-law of


Hamilcar, with whose second wife and now disconsolate widow we
have just made acquaintance, was most excellently situated,
whether from an æsthetic or a strategic point of view.
It was built upon a hilly promontory jutting out into a gulf which lay
towards the south-west. The two entrances to this gulf, which were
separated by an island, were at a distance of about two thousand
yards from the walls of the town, and were narrow enough to be
easily commanded by a small body of defenders. The whole of the
interior of the gulf formed a magnificent harbour.
At the back of the city, on the north-western or land side, there
was situated a long lagoon. This had formerly been separated from
the sea by a narrow isthmus, but Hasdrubal, who had, before his
assassination, been aiming at royal power, had determined to make
New Carthage his royal city, and in consequence as nearly
impregnable as possible.
He had therefore cut a channel through this narrow isthmus, thus
allowing the sea and the lagoon to join. And then he had bridged the
channel with a wide and excellent bridge. This bridge was a short
way from the gates of the city, and was the sole means of land
communication with the rest of Spain. The gates were strongly
fortified, and inside and near the walls were erected commodious
barracks for the troops; a little beyond these barracks rose, on an
eminence, a well-designed and formidable-looking citadel, above
which proudly floated the Carthaginian ensign.
The town, as has been said, was hilly, and its designer had taken
advantage of the natural features by making it as beautiful as
possible. On every hill top stood a magnificent marble temple. On
the most commanding hill of all, that which was due east, was reared
the glorious temple to Æsculapius, while those to Moloch and Tanais
or Tanith occupied other prominent sites. In every square and at
every street corner were placed the most exquisite and costly
statues, some of the purest of Parian marbles, and others of solid
silver. Some of the richest silver mines in the then-known world lay
close to Carthagena. The supply of the metal was apparently
inexhaustible and unbounded. For there were not only no such
sailors, but no such skilful miners in those days as the Phœnicians,
who had, like the Greeks, formed peaceful settlements in Spain long
before the first of the Punic wars.
By means of pipes coming under the lagoon from various high hills
on the mainland, the supply of water in the town was abundant, and
tinkling fountains, shaded by splendid plane trees, formed on every
side picturesque rendezvous for the gossips of the town. In addition
there were many excellent wells on the island itself which never ran
dry.
For the situation of his own palace and court, in whose gardens
we made the acquaintance of Hannibal’s daughter Elissa,
Hasdrubal, who was eminently a man of genius, had selected the
most advantageous site on the island, by taking in the whole of a
flat-topped hill on the western side which overlooked the sea and
country and all the city, except the temple to Æsculapius. Here he
had reared the most beautiful and luxuriously-furnished edifice of
which the architects of those days were capable; and from what
Carthage was, and what Syracuse was, we know that their abilities
were great. Graceful colonnades, wonderful mosaic-paved corridors
and walls were everywhere; gorgeous saloons, filled with pictures
and statues, formed banqueting halls or audience chambers; while
the richly-furnished sleeping apartments had been designed with a
view to comfort and æstheticism combined.
In one of these, in front of an open window facing south, the
carved lattice fretwork of which was made of the sweet-scented
cedar of Lebanon, and out of which she cast many anxious glances,
stood Elissa, attiring herself as gorgeously as possible with the
assistance of Cleandra, an old white-headed warrior in armour being
also in attendance. The door of the apartment was closed and
barred, and in addition heavy curtains were drawn across it, so that
there could be no chance of a word that was said within the room
being heard outside.
“And so, my good Gisco,” said Elissa, while putting on a
magnificent chain of gold and emeralds, “thou dost estimate the
numbers of the fighting men, leaving the rowers on one side, at
about eight thousand, dost thou not? I should have thought there
had been more. Why, just see how their spears glisten in the sun
where they are crowded together on the decks.”
“I did not say they had only eight thousand men, Lady Elissa,”
answered the old Prefect Gisco, a faithful and rugged old retainer of
Hamilcar and Hannibal, who had risen from the ranks and was now
the captain of the garrison of Carthagena. “They must, calculating a
hundred and twenty-five marines to each ship, have at least
considerably over nine thousand fighting men with them; but, as they
would leave at least a thousand on board as a guard to the ships,
they would, if they strove to make a landing, disembark, say, about
eight thousand. But they will not seek to land this evening by force
without a parley first, and even if they should do so, we could defend
the two entrances to the harbour to the last. They could never get in
to-night without fighting at a disadvantage. We have, after all, got six
hundred well seasoned soldiers, who will take a lot of killing; and
then we have three hundred more of the wounded and
convalescents, who came down two months ago from Saguntum.
They can bear a hand, and a very useful one too, as many of them
are Balearic slingers, who will prove most deadly to men in boats.”
“And what about to-morrow, oh, most sapient Gisco, when all our
men are dead?” asked Elissa, smiling the while, and examining her
pearly teeth in the mirror of polished and burnished gold, which
Cleandra was holding up before her. “But I agree with thee; I do not
think this Adherbal will dare to attack Carthaginians without a parley.
He will first try to obtain possession of myself and New Carthage in
some other way. No,” she continued, “we must have no fighting. We
can do better than that, I think, and yet save the situation both for
Hannibal and for the country’s welfare. It will be far better than
Carthaginians fighting against Carthaginians. I have, too, other and
better use to which to place those mercenaries in the ships with
Adherbal.”
The old soldier looked at the young Regent with a puzzled
expression, and waited for an explanation. Elissa smiled
enigmatically.
“Listen carefully now, oh! Gisco,” she added, while putting up each
of her little feet in turn upon an ivory and ebony stool for Cleandra to
fasten her jewelled sandals. “Listen, and I will disclose to thee the
details of my plot, by which I believe that we shall avoid any fighting,
for I think by this time to-morrow it will be a case of the biter bit. But
before I tell thee my plans, inform me, my good Gisco, how much
time we have before it will be possible for Adherbal to land?”
Gisco looked out of the window over the gulf to the sea.
“The current that sets this evening out of the lagoon and the gulf is
just now flowing out to sea with its greatest force, the ships are
anchored at a considerable distance from the shore, and the breeze
is blowing strong off the land. Even if he were to attempt to row
ashore now, Adherbal could not reach the booms under an hour. He
is evidently aware of that fact, and is waiting for the slack tide, for I
see a large galley, with a flag in the stern, lying alongside the largest
of the ships.”
“Then we have plenty of time,” said Elissa, and rapidly she
disclosed her plans to Gisco. Then she sent him off to convey the
necessary instructions to the officers, who were waiting for him
outside, bidding him return instantly and have a herald waiting for
her with a State barge and a crew of swift rowers at the steps below
the palace.
Meanwhile, she dictated a letter to Cleandra, which she sealed
with Hannibal’s signet-ring, given to her by Maharbal. Another letter
she wrote herself, and signed with her own seal of office as Regent
and Governor of New Carthage.
By the time these two letters were ready, old Gisco had returned to
inform her that the State galley was waiting at the steps.
“And further,” he added with a smile, “all the preparations for the
fulfilment of thy clever plans are ready, oh! Lady Elissa. Ah, me! to
think of the cunning contained in that little woman’s head of thine!”
And he looked admiringly at her, while the young girl flushed with
pleasure at the compliment.
“Come, Cleandra,” she called, “we must go. But first let us see
what they have done for poor Maharbal.”
Maharbal had been carried in by Gisco’s orders, and was now
lying on a couch in a comfortable apartment, attended by Melania
and the Princess Cœcilia. A learned leech was feeling his pulse, but
they saw that he was still quite unconscious.
Elissa heaved a sigh, then beckoning to her aunt to follow, left the
room.
“My aunt,” she said, changing from the soft Punic tongue, in which
she had been conversing with the old Prefect Gisco, to the Iberian or
Spanish dialect, which the ladies of the household, being all either
half or wholly Iberians, used habitually among themselves; “my aunt,
grave tidings are to hand, or, rather, both grave and good tidings.
Saguntum has fallen, and Hannibal is wounded. The shouting we
heard in the town, as we were surprised by Maharbal, was doubtless
caused by his informing the guards as he passed the city gates of
the fall of that city. It is uncertain”—here she was purposely
deceiving her aunt, whose tongue she feared—“exactly how long it is
since the town of Saguntum fell; but about a week more or less, so I
judge from a letter I have received from my father Hannibal. Further,
we may expect to see some of his advanced guard of returning
troops almost at once; perchance indeed this very day some of them
may arrive. But that is not the grave part of my news—a large fleet
hath arrived from Carthage, and is now lying anchored without the
Gulf. It is under the command of Adherbal, the son of Hanno, one of
a family that never bore good will to my father or my uncle, thy
husband’s house. I fear they come with no good design.
Nevertheless, we must make a show of entertaining the General
Adherbal and his principal followers as well; and I am about to invite
them to come here and to pass the night. Therefore, while I am
away, I pray thee make suitable preparations for a becoming repast,
and see ye that chambers are prepared. As the evenings are now
long, and it is, moreover, fresher without than within, I pray thee also
to be kind enough to have the repast spread upon the western
balcony beneath the colonnade.”
The foolish little princess, in a flutter of excitement, was about to
ask a thousand questions; but Elissa, giving her no time to talk,
merely waved her hand and departed, accompanied by Cleandra
and the Prefect Gisco.
Passing through a postern gate in the wall of the palace, they
descended by a wide flight of marble stairs to a landing-stage at the
foot, where was lying moored a magnificent, gilded barge, the prow
of which was shaped like the head and wings of a swan. By the side
of this a gorgeously-clad herald awaited them. He bowed low as the
party approached, and the youthful Regent and Governor of New
Carthage beckoned him to join them, out of earshot of the sailors
who formed the crew.
“Sir Herald,” she said, delivering to him the two letters, “thou wilt
accompany us to the steps at the mouth of the harbour where we
shall land. Thou wilt then proceed to the ship of the Admiral of the
fleet which is lying without the harbour, and deliver to him these two
letters with my greetings. In reply to all questions make only one
answer, namely, that tidings have come that the city of Saguntum fell
over a week ago—fell more than a week ago, dost understand? With
reference to everything else, plead ignorance.”
Entering the barge, followed by Cleandra and Gisco, who gave a
short word of command to the crew, they were, a moment later,
being borne swiftly down the waters of the gulf, and very soon
arrived at the disembarking steps on the south side of the entrance
to the harbour, where a large body of spearmen, who had been
standing about on the quay, fell into rank as they saw the State
barge approaching. As the young girl disembarked, they received
her with the same salute as they would have given to their
Commander-in-Chief Hannibal himself.
The young girl acknowledged the salute by a bow, and never,
perhaps, had she looked so noble and dignified. Her dress was
calculated to enhance her beauty and dignity. She was attired in a
chiton of purple silk, with a broad hem at the bottom, which, as well
as a band at the edge of the loose-hanging sleeves, was of white
silk, trimmed with rich, golden braid. On her dark tresses was now
poised a small diadem of gold, inlaid with rubies and pearls. Two
large drops of single pearls were in her ears, while on her arms, both
above and below the elbow, were clasped costly bands of purest
gold. On her slender fingers she wore many beautiful rings, while
round her neck hung the long chain of emeralds, which has been
already mentioned. Cleandra also was upon this occasion very richly
attired in white and silver, which suited well her fair complexion. Her
jewels and ornaments were likewise costly and becoming; for
although by the fortune of war she had become a slave, she was
ever allowed by Elissa, who loved her, to dress in a style befitting the
princely Iberian family from which she had sprung.
After acknowledging the salute, Elissa walked along the ranks of
the soldiers, addressing a word here and there, complimenting one
upon his soldierly appearance, and another on the brilliancy of his
arms and accoutrements. By this tact, and the gentle ways which
she had always displayed in her dealings with the soldiery left under
her command, she had long ago won the heart of every man among
the troops, and there was not that day an officer or man present who
would not have willingly fought for her to the death.
When she had concluded her inspection, she caused Gisco to
form up the troops close round her in a circle. Owing to their
numbers, this circle was many files in depth; but the young Regent
wished all to hear what she had to say.
A bundle of merchandise which was lying on the quay she caused
to be placed in the middle of the circle of warriors, and, mounting
thereon, she addressed the men:
“Soldiers of Carthage, I have glorious news to announce to you.
Maharbal, the Prefect of the Numidian Horse, hath ridden through
with tidings from our General and Commander-in-chief, my father
Hannibal, that he hath captured Saguntum; and not only hath he put
all the garrison to the sword, but seized an enormous booty in
treasures and slaves, of which booty, no doubt, you, my faithful
garrison, will receive your portion. The number of female Greek
slaves captured is, so Hannibal writes, almost unlimited.”
Upon hearing these words, the assembled troops broke into such
a burst of cheering that the crews on the ships lying out in the roads
wondered exceedingly at the cause. But Elissa had purposely
appealed to the baser feelings of her audience. Having allowed a
few minutes for the natural ebullition of feeling, the fair young orator
raised her hand as a sign, and instantly silence was restored.
“I grieve,” she continued, “to say that our losses have been heavy,
and that Hannibal is sorely, although not dangerously, wounded. But,
soldiers of Carthage, a worse danger threatens Hannibal; a worse

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