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SPRINGER BRIEFS IN MOLECULAR SCIENCE
BIOBASED POLYMERS
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.
Laly A. Pothan
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
and
Department of Chemistry
Bishop Moore College
Mavelikara, Kerala, India
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
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
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.
1.1 Starch
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
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
Fig. 1.5 Structure of chitin and chitosan. Reprinted with permission from Jayakumar et al. (2010).
Copyright Elsevier
1.2 Chitosan
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
72:858–863. https://doi.org/10.1016/j.compscitech.2012.02.019
González K, Retegi A, González A, Eceiza A, Gabilondo N (2015) Starch and cellulose nanocrystals
together into thermoplastic starch bionanocomposites. Carbohydr Polym 117:83–90. https://doi.
org/10.1016/j.carbpol.2014.09.055
Ifuku S, Saimoto H (2012) Chitin nanofibers: preparations, modifications, and applications.
Nanoscale 4:3308. https://doi.org/10.1039/c2nr30383c
Jayakumar R, Prabaharan M, Nair SV, Tamura H (2010) Novel chitin and chitosan nanofibers in
biomedical applications. Biotechnol Adv 28(1):142–150. https://doi.org/10.1016/j.biotechadv.
2009.11.001
Kaplan DL (1998) Introduction to biopolymers from renewable resources. Biopolymers from renew-
able resources. Springer, Berlin Heidelberg, pp 1–29
Kaushik A, Singh M, Verma G (2010) Green nanocomposites based on thermoplastic starch and
steam exploded cellulose nanofibrils from wheat straw. Carbohydr Polym 82:337–345. https://
doi.org/10.1016/j.carbpol.2010.04.063
Levengood SL, Zhang M (2014) Chitosan-based scaffolds for bone tissue engineering. J Mater
Chem B 2(21):3161. https://doi.org/10.1039/C4TB00027G
Li M, Li D, Wang L, Adhikari B (2015) Creep behavior of starch-based nanocomposite films with
cellulose nanofibrils. Carbohydr Polym 117:957–963. https://doi.org/10.1016/j.carbpol.2014.10.
023
Lopez O, Garcia M, Villar M, Gentili A, Rodriguez MS, Albertengo L (2014) Thermo-compression
of biodegradable thermoplastic corn starch films containing chitin and chitosan. LWT Food Sci
Technol 57:106–115. https://doi.org/10.1016/j.lwt.2014.01.024
Lu Y, Sun Q, She X, Xia Y, Liu Y, Li J, Yang D (2013) Fabrication and characterisation of α-
chitin nanofibers and highly transparent chitin films by pulsed ultrasonication. Carbohydr Polym
98:1497–1504. https://doi.org/10.1016/j.carbpol.2013.07.038
Mincea M, Negrulescu A, Ostafe V (2012) Preparation, modification, and applications of chitin
nanowhiskers: a review. Rev Adv Mater Sci 30(3):225–42
8 1 Introduction
Muzzarelli RAA (2011) Biomedical exploitation of chitin and chitosan via mechano-chemical
disassembly, electrospinning, dissolution in imidazolium ionic liquids, and supercritical drying.
Marine Drugs 9(9):1510–1533. https://doi.org/10.3390/md9091510
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
Salaberria AM, Diaz RH, Labidi J, Fernandes SCM (2015a) Role of chitin nanocrystals and
nanofibers on physical, mechanical and functional properties in thermoplastic starch films. Food
Hydrocoll 46:93–102. https://doi.org/10.1016/j.foodhyd.2014.12.016
Salaberria AM, Labidi J, Fernandes SCM (2015b) Different routes to turn chitin into stunning
nano-objects. Eur Polym J 68:503–515. https://doi.org/10.1016/j.eurpolymj.2015.03.005
Salehudin MH, Salleh E, Mamat SNH, Muhamad II (2014) Starch based active packaging film
reinforced with empty fruit bunch (EFB) cellulose nanofiber. Procedia Chem 9:23–33. https://
doi.org/10.1016/j.proche.2014.05.004
Tang X, Alavi S (2011) Recent advances in starch, polyvinyl alcohol based polymer blends,
nanocomposites and their biodegradability. Carbohydr Polym 85:7–16. https://doi.org/10.1016/
j.carbpol.2011.01.030
Tzoumaki MV, Moschakis T, Biliaderis CG (2011) Mixed aqueous chitin nanocrystal-whey protein
dispersions: microstructure and rheological behaviour. Food Hydrocoll 25:935–942. https://doi.
org/10.1016/j.foodhyd.2010.09.004
Visakh PM, Thomas S (2010) Preparation of bionanomaterials and their polymer nanocomposites
from waste and biomass. Waste Biomass Valorization 1:121–134. https://doi.org/10.1007/s12649-
010-9009-7
Yu J, Yang J, Liu B, Ma X (2009) Preparation and characterization of glycerol
plasticized-pea starch/ZnO-carboxymethylcellulose sodium nanocomposites. Bioresour Technol
100:2832–2841. https://doi.org/10.1016/j.biortech.2008.12.045
Zia F, Zia KM, Zuber M, Kamal S, Aslam N (2016) Starch based polyurethanes: a critical review
updating recent literature. Carbohydr Polym 134:784–798. https://doi.org/10.1016/j.carbpol.
2015.08.034
Chapter 2
Processing Techniques
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
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
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).
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
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.
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).
The possibility of formation of continuous nanocrystal network and the final prop-
erties of nanocomposite material are governed by the processing method.
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
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
References
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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
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Chapter 3
Properties of Composites
transition temperature ascribed to the starch molecular chains in the starch-rich phase
(Cao et al. 2008).
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.