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Green Micro- and
Nanocomposites
Green Micro- and
Nanocomposites
edited by
Sabu Thomas
Abitha V. K.
Hanna J. Maria
Published by
Jenny Stanford Publishing Pte. Ltd.

101 Thomson Road
#06-01, United Square
Singapore 307591
Email: editorial@jennystanford.com
Web: www.jennystanford.com
British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.
Green Micro- and Nanocomposites
Copyright © 2024 by Jenny Stanford Publishing Pte. Ltd.

All rights reserved. This book, or parts thereof, may not be reproduced in any form
or by any means, electronic or mechanical, including photocopying, recording
or any information storage and retrieval system now known or to be invented,
without written permission from the publisher.
For photocopying of material in this volume, please pay a copying fee through
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USA. In this case permission to photocopy is not required from the publisher.
ISBN 978-981-4968-79-9 (Hardcover)

ISBN 978-1-003-42756-8 (eBook)
Contents
Preface xi
1. Green Micro- and Nanocomposite Materials 1

Abitha V. K., Ajay Vasudeo Rane, Deepti Yadav,
Hanna J. Maria, and Sabu Thomas
2. Biodegradability of Green Composites: Mechanisms

and Evaluation Methods 11
Nikushi S. Yatigala, Dilpreet S. Bajwa,
Sreekala G. Bajwa, and Saptaparni Chanda
2.1 Introduction 12
2.2 Green Polymers 13
2.3 Degradation of Biopolymers 16
2.4 Biodegradation 17
2.4.1 Biodegradation Mechanism Steps 19
2.5 Standard Testing Methods of Biodegradation 23
2.6 Biodegradation Properties of Biopolymers
and Composites 32
2.7 Biodegradation of PLA-Based Composites 40
2.8 Biodegradation of PHB and PHBV-Based
Composites 53
2.9 Biodegradation of Polymers Extracted from
Biomass 59
2.10 Conclusion 61
3. Green Composites Reinforced

with Cellulose 71
L. A. Granda, Q. Tarrés, F. X. Espinach, J. A. Méndez,
and M. Delgado-Aguilar
3.1 Cellulose: From Micro to Nano 72
3.1.1 Cellulose Microfibers 72
3.1.2 Cellulose Nanofibers 73
vi Contents
3.1.2.1 Pretreatments 74
3.1.2.2 Desestructuration 75
3.1.3 Cellulose Nanocrystals 76
3.1.4 Bacterial Cellulose 77
3.2 Introduction to Cellulose Micro- and
Nanocomposites 78
3.3 Thermoplastic Cellulose-Based Micro- and
Nanocomposites 81
3.4 Thermoset Cellulose-Based Micro- and
Nanocomposites 83
3.5 Rubber Cellulose-Based Micro- and
Nanocomposites 86
3.6 Processing of Green Cellulose Composites 88
3.6.1 Composite Production 88
3.6.1.1 Thermoplastic matrix
composites 88
3.6.1.2 Thermoset and rubber
matrix compounding 89
3.6.2 Composite Transformation 89
3.6.2.1 Thermoplastic matrix
composites 89
3.6.2.2 Thermoset matrix
composites 95
3.7 Applications of Cellulose-Based Micro- and
Nanocomposites 98
3.8 Conclusion and Perspectives 100
4. Green Composites Reinforced with Chitin

and Chitosan 113
Sougata Jana, Arijit Gandhi, and Kalyan Kumar Sen
4.1 Introduction 113
4.2 Chitin and Chitosan Chemical Structure and
Characteristics 114
4.3 Preparation of Thermoset-Based Chitin
and Chitosan Composites 115
4.4 Preparation of Thermoplastic-Based
Chitin and Chitosan Composite 116
Contents vii
4.5 Preparation of Rubber-Based Chitin

and Chitosan Composite 116
4.6 Preparation of Micro Chitin and
Chitosan Composites 117
4.7 Preparation of Nano Chitin and
Chitosan Composites 118
4.8 Applications of Chitin/Chitosan-Based
Composites 120
4.8.1 Tissue Engineering 120
4.8.2 Drug Delivery 121
4.8.3 Wound Healing 124
4.8.4 Protein and Gene Delivery 125
4.8.5 Dentistry 127
4.8.6 Food Packaging Applications 129
4.8.7 Textile Industry 130
4.9 Conclusions 131
5. Green Composites Based on Polyhydroxyalkanoates 143

Mufaro Moyo, Ajay Vasudeo Rane, Gbadeyan O. Joseph,
and Krishnan Kanny
5.2 Sources and Classes of Polyhydroxyalkanoate
Composites 144
5.3 Processing of Green PHA Composites 146
5.3.1 PHA-Based Microcomposites 147
5.3.2 PHA-Based Nanocomposites 147
5.4 Properties of PHA Composites 148
5.5 Advantages of PHA Composites 149
5.5.1 Advantages of Green PHA Composites 149
5.5.2 Disadvantages of Green PHA
Composites 152
5.6 Applications of PHA Composites 153
5.6.1 Applications of PHA Microcomposites 153
5.6.2 Applications of PHA Nanocomposites 155
5.7 Recent Developments in Green PHA
Composites 156
5.8 Conclusion and Perspectives 157
viii Contents
6. Green Composites Based on Poly(Lactic Acid) 161

Ajay Vasudeo Rane, Deepti Yadav,
Anupam Glorious Lobo, Sabana Ara Begum,
P. Santhana Gopala Krishnan, Aswathy J. S.,
and Krishnan Kanny
6.1.1 Advantages and Disadvantages
of PLA 162
6.1.2 PLA Composites 163
6.2 Processing 171
6.3 Properties 176
6.4 Applications 176
6.5 Developments 178
6.6 Conclusions 178
7. Green Composites Based on Protein Materials 185

Sabana Ara Begum, Ajay Vasudeo Rane,
Deepti Yadav, P. Santhana Gopala Krishnan,
Treesa Reji, and Krishnan Kanny
7.1 Introduction to Proteins and Protein
Composites 185
7.2 Processing of Protein Composites 190
7.2.1 Wet Process/Solvent Process 190
7.2.2 Dry Process/Thermoplastic
Process 192
7.3 Properties of Protein Composites 192
7.4 Applications of Protein Composites 194
7.5 Selected Works on Protein Composites 194
7.6 Conclusion 210
8. Surface Modification of Biobased

Polysaccharide Nanoparticles via Grafting 219
R. Mincheva, S. Benali, and J.-M. Raquez
8.2 Surface Grafting 221
8.2.1 Grafting From 222
8.2.2 Grafting Onto 226
8.2.3 Grafting Through 226
8.2.4 Supramolecular Grafting 228
Contents ix
8.3 Polysaccharide Nanoparticles 229

8.3.1 Raw Material 229
8.3.2 Preparation 231
8.3.2.1 Nanocellulose 231
8.3.2.2 Nanochitin 233
8.3.2.3 Nanostarch 234
8.3.3 Physicochemical Properties 236
8.3.4 Chemical Properties 237
8.3.5 Surface Modification of Biobased
Polysaccharide Nanoparticles
via Grafting 238
8.3.5.1 The nanocellulose:
nanocrystals and
nanofibers 239
8.3.5.2 Starch nanoparticles 243
8.3.5.3 Chitin nanoparticles 247
8.4 Conclusions 250
Index 267
Preface
In recent years, there has been a growing global concern about

the environmental impact of materials and on the urgent need for
sustainable solutions. In response to this challenge, the field of green
materials has emerged as a promising avenue for developing eco-
friendly alternatives that minimize the ecological footprint while
maintaining or even enhancing performance. One such area of
research is the development of green micro- and nanocomposites,
which combines the principles of green chemistry and advanced
materials science to create sustainable and functional materials.
This book provides a comprehensive overview of the state-
of-the-art advancements in the field of environmentally friendly
micro- and nanocomposite materials. It brings together the
collective knowledge and expertise of researchers and practitioners
from various disciplines, including materials science, chemistry,
engineering, and sustainability.
The objective of this book is to provide a comprehensive
overview of green micro- and nanocomposites, offering a holistic
understanding of their synthesis, properties, and applications. It
encompasses a wide range of aspects, including green synthesis
methods, characterization techniques, mechanical and thermal
properties, electrical conductivity, and barrier performance of
micro- and nanocomposites.
Chapter 1, Green Micro- and Nanocomposites, serves as an
introduction to the subject, discussing the importance of green
composites and their potential to revolutionize various industries. It
sets the stage for the subsequent chapters, which delve deeper into
specific aspects of green composites.
Chapter 2, Biodegradability of Green Composites: Mechanisms
and Evaluation Methods, explores the fascinating world of
biodegradability, examining the mechanisms involved and the
methods used to evaluate the biodegradation potential of these
materials. Understanding the biodegradability of green composites
is crucial for their sustainable use in various applications.
xii Preface
Chapter 3, Green Composites Reinforced with Cellulose, focuses

on the utilization of cellulose, a renewable and abundant resource,
as a reinforcement in green composites. The chapter discusses
the preparation, properties, and applications of cellulose-based
composites, highlighting their unique advantages and challenges.
Chapter 4, Green Composites Reinforced with Chitin and Chitosan,
explores the potential of chitin and chitosan, natural polymers
derived from shellfish, as reinforcements in green composites. The
chapter investigates the properties, processing techniques, and
applications of these composites, shedding light on their immense
potential in various industries.
Chapter 5, Green Composites based on Polyhydroxyalkanoates,
focuses on the applications of polyhydroxyalkanoates (PHAs),
biodegradable and biocompatible polyesters produced by
microorganisms, in green composites. The chapter delves into the
synthesis, properties, and applications of PHA-based composites,
providing insights into their wide-ranging uses.
Chapter 6, Green Composites Based on Poly(Lactic Acid),
explores the utilization of poly(lactic acid) (PLA), a renewable
and biodegradable polymer derived from plant sources, in green
composites. The chapter discusses the processing techniques,
properties, and applications of PLA-based composites, highlighting
their potential to replace conventional petroleum-based materials.
Chapter 7, Green Composites Based on Protein Materials,
examines the use of protein materials, such as soy protein, zein, and
gluten, as reinforcements in green composites. The chapter explores
the preparation methods, properties, and applications of protein-
based composites, emphasizing their biocompatibility and potential
applications in the biomedical field.
Chapter 8, Surface Modification of Biobased Polysaccharide
Nanoparticles via Grafting, focuses on the surface modification
techniques employed to enhance the properties and performance
of biobased polysaccharide nanoparticles. The chapter discusses
various grafting methods and their impact on the composite
materials, paving the way for tailored properties and applications.
This book will be a valuable resource for researchers, scientists,
engineers, and professionals interested in the development and
applications of green micro- and nanocomposites. By providing
a comprehensive understanding of the synthesis, properties,
Preface xiii
and applications of these materials, it aims to inspire further

advancements in the field and contribute to a sustainable future.
We acknowledge the collaborative effort of the authors, editors,
and reviewers who have contributed to this book. Their expertise
and dedication have ensured the quality and relevance of the content
of the book.
Sabu Thomas
Abitha V. K.
Hanna J. Maria
Summer 2023
Chapter 1
Green Micro- and Nanocomposite

Materials
Abitha V. K.,a Ajay Vasudeo Rane,b Deepti Yadav,c

Hanna J. Maria,d and Sabu Thomasa,d,e
aSchool of Chemical Sciences, Mahatma Gandhi University,
Kottayam-686560, Kerala, India

bComposite Research Group, Department of Mechanical Engineering,
Durban University of Technology, Durban-4000, South Africa

cDepartment of Biotechnology and Food Science, Durban University of Technology,
Durban-4000, South Africa

dSchool of Energy Materials, Mahatma Gandhi University,
Kottayam-686560, Kerala, India

eInternational and Inter University Centre for Nanoscience and
Nanotechnology, Mahatma Gandhi University, Kottayam-686560,

Kerala, India
abithavk@gmail.com
Environmental issues throughout the world such as rising sea levels,

rising average global temperatures, melting polar ice caps, and
fast depleting petroleum resources have increased the burden on
individuals and industries to find alternative resources to fulfil their

Edited by Sabu Thomas, Abitha V. K., and Hanna J. Maria
Copyright © 2024 Jenny Stanford Publishing Pte. Ltd.
ISBN 978-981-4968-79-9 (Hardcover), 978-1-003-42756-8 (eBook)
www.jennystanford.com
2 Green Micro- and Nanocomposite Materials
demands (Fig. 1.1). Key global challenges include how to respect

the environment and enhance living conditions for the benefit
of all living organisms. These concerns, combined with a growing
understanding of renewable “green” resources, have prompted
several sectors to take steps to reduce their harmful impact on the
environment.
Figure 1.1 Environmental issues throughout the world.
In order to overcome the challenges, there is a demand for

sustainably produced green materials with competitive abilities,
with an emphasis to reduce the harmful impact on the environment.
The global research on composites produced using green materials
makes this area of research more enduring and powerful, with its
contribution to reducing harmful impact on the environment using
a sustainable approach. This chapter discusses the brief on the
chapters, on composites and nanocomposites produced from green
materials. The word “green” here refers to sustainable materials
which are available in abundance and are left untouched as waste.
In recent years, sustainable development has become a major
issue, and the looming depletion of oil-based resources will
necessitate the usage of biomaterials derived from renewable
resources. The widely accepted definition of sustainable development
is “development that meets current demands without jeopardising
future generation’s ability to meet their own needs.” In a broader
sense, sustainable development is made up of three elements:
society, the environment, and the economy. Hence, green composites
are and form an essential part of sustainable development owing to
their applications in different fields.
Biodegradation is the process of converting organic substrates
(polymers) into low molecular weight fragments that may then
Green Micro- and Nanocomposite Materials 3
be degraded to carbon dioxide and water using the activities of

microbial species (Fig. 1.2). Biodegradation is influenced by a
polymer’s physical and chemical characteristics. The biodegradation
mechanism of green composites and its evaluation methods are
discussed in Chapter 2. Different standard testing methods used for
biodegradation such as visual inspection, quantitative estimation of
weight loss of the polymer, changes in properties such as a change in
molecular weight, functional groups, crystallinity, tensile strength,
measurement of CO2 evolution or O2 consumption, radiolabelling,
and clear zone formation are discussed. Furthermore, the authors
have discussed the biodegradation mechanisms of PLA (poly(lactic
acid)), PHB, PHBV, and polymers extracted from biomass-based
compounds [1, 2].
Figure 1.2 Process of biodegradation.
Cellulose is a polysaccharide made up of linear glucan chains

linked by β-1,4 glycosidic bonds with cellobiose residues as the
repeating units at various degrees of polymerization and packed
into microfibrils held together by intramolecular hydrogen bonds
and intermolecular van der Waals forces (Fig. 1.3). Green plants,
algae, and oomycetes all have cellulose as a structural component
of their major cell walls. Some bacteria emit it in order to create
a biofilm. The most common organic polymer on the planet is
cellulose. Cotton fiber has a cellulose percentage of 90%, wood has
a cellulose level of 40–50%, and dry hemp has a cellulose content of
around 57%. Chapter 3 discusses the green composites prepared by
and/or using cellulose. Green composites made from cellulose offer
a unique chance to develop new materials with improved socially
acceptable features. According to the literature, these composites
currently have sufficient characteristics to match glass fiber-based
composites. Herein, the authors have elaborated on the different

types of cellulose reinforcement (in terms of their morphology,
production methods, and properties). In addition, thermoplastic,
thermoset, and rubber-based composites in respect to their potential
use together with micro- and nanostructured cellulosic fibers are
also discussed [3, 4].
Figure 1.3 Cellulose source and chemical structure.
Chitin is a long-chain polymer made up of N-acetyl glucosamine,

a glucose amide derivative. It is a key component of the cell walls of
fungi, the exoskeleton of arthropods such as crustaceans and insects,
and the radulae, cephalopod beaks, and gladii of mollusks and is
the second most prevalent polysaccharide in nature (after only
cellulose) (Fig. 1.4). At least some fish and Lissamphibia synthesize
it as well. Chitin has a structure similar to cellulose, generating
crystalline nanofibers or whiskers. It has a similar function to
the protein keratin. Chitosan is a linear polysaccharide made up
of N-acetyl-D-glucosamine (acetylated unit) and β(1à4)-linked
D-glucosamine (deacetylated unit) that are randomly dispersed.
Chitosan is manufactured by alkaline treatment of shrimp and
other crustaceans’ shells (Fig. 1.4). Chapter 4 discusses the green
composites prepared by and/or using chitin and chitosan. Composites
made by mixing fillers with biopolymers like chitin or chitosan are
very promising materials since they improve characteristics while
retaining biodegradability and non-toxicity. The use of hybrid
polymer matrices comprising chitosan and other biodegradable
polymers has been suggested to improve composite characteristics.
Several research investigations reveal that chitosan may be molded
into a variety of shapes, including hydrogels, films, powders, and
particles, among others. The development of innovative chitosan-
based polymeric materials is a fascinating way to investigate the

applications of chitosan-based composites [5, 6].
Figure 1.4 Chitin, chitosan source, and chemical structure.
Polyhydroxyalkanoates (PHAs) are polyesters created in nature

by a variety of microorganisms, including bacteria that digest
carbohydrates or lipids. They serve as a source of both energy and
carbon storage when created by bacteria. Within this family, more
than 150 distinct monomers can be mixed to create materials with a
wide range of characteristics (Fig. 1.5). These biodegradable plastics
are utilized in the manufacture of bioplastics. Thermoplastic and
elastomeric materials with melting points ranging from 40℃ to 180℃
can be used. Blending, changing the surface, or combining PHAs
with other polymers, enzymes, and inorganic elements can affect
the mechanical properties and biocompatibility of PHAs allowing
for a wider range of uses. Chapter 5 discusses the green composites
prepared using PHAs. PHAs are biodegradable and biocompatible
making them one of a kind composite materials with applications in
biomedical research, packaging film, traditional plastics, membrane
technology, and electronics. Wet and melt processing techniques can
be used to create PHA micro- and nanocomposites. However, their
production costs are now expensive, and their processing has several
technological issues that must be resolved. Continued research into
the issues connected with green composites based on PHAs could

lower production costs and increase output volumes [7, 8].
Figure 1.5 PHA source and chemical structure.
Poly(lactic acid) commonly known as PLA or poly(lactide) is a

thermoplastic polyester made by condensing lactic acid with the
removal of water (Fig. 1.6). Lactide is the cyclic dimer of the basic
repeating unit and can also be produced through ring-opening
polymerization. PLA has grown in popularity as a result of its cost-
effective production from renewable resources. Its widespread use
has been hampered by a number of physical and processing flaws.
In 3D printing, PLA is the most extensively used plastic filament
material. Chapter 6 discusses the green composites prepared using
PLA. PLA is a biocompatible and biodegradable polymer that has
a wide range of applications. PLA’s use in a variety of industrial
applications is predicted to increase dramatically in the next years,
making it a cost-effective commodity plastic with the added virtue of
being environmentally friendly. PLA is considered a “Green” polymer
because it is produced in an environmentally friendly manner and
can be used to replace petrochemical-based polymers [9, 10].
Figure 1.6 PLA source and chemical structure.

Protein-based composites provide a plethora of options for

customizing material qualities by modifying the protein sequences
used to make them or the methods used to make them. Chapter
7 discusses the green composites prepared using proteins. In
this chapter, we look at a variety of different applications using
a variety of proteins available from natural sources (Fig. 1.7).
Proteins have shown promise in terms of intrinsic biodegradability,
biocompatibility, natural abundance, and mechanical and functional
qualities when compared to other natural polymers such as
lignocellulosic components (cellulose, hemicellulose, and lignin) and
starch. To summarize, the use of environmentally benign materials
with improved properties provides a beneficial chance to partially
replace petroleum-based plastics, while increasing the value of the
huge natural macromolecules available [11, 12].
Figure 1.7 Protein sources.
Surface modification is the process of altering the surface of a

material by adding physical, chemical, or biological features that
differ from those found on the surface of the material originally
(Fig. 1.8). Different approaches can be used to alter a wide range
of surface attributes including roughness, hydrophilicity, surface
charge, surface energy, biocompatibility, and reactivity. The current
state of grafting approaches for surface modification of biobased
polysaccharide nanoparticles, such as nanocelluloses, starch, and

chitin nanoparticles, are discussed in Chapter 8 [13, 14].
Figure 1.8 Grafting techniques.
The first section covers the various ways, such as grafting from,
grafting onto, grafting through, and supramolecular grafting. The
current state of the art in polysaccharide particle formation, physical
and chemical properties, and relatively recent trends and methods
are also updated. The final section delves into the most recent
methodologies and successes in surface-modified nanocelluloses,
nanochitin, and nanostarch particles via grafting from, grafting onto,
and, most crucially, supramolecular grafting.
References
1. Wan YZ, Luo H, He F, et al. Mechanical, moisture absorption, and

biodegradation behaviours of bacterial cellulose fibre-reinforced
starch biocomposites. Compos Sci Technol 2009; 69: 1212–1217.
2. Kister G, Cassanas G, Bergounhon M, et al. Structural characterization
and hydrolytic degradation of solid copolymers of D, L-lactide-co-ε-
caprolactone by Raman spectroscopy. Polymer (Guildf) 2000; 41: 925–
932.
3. Iwamoto S, Abe K, Yano H. The effect of hemicelluloses on wood
pulp nanofibrillation and nanofiber network characteristics.
Biomacromolecules 2008; 9: 1022–1026.
4. Alcalá M, González I, Boufi S, et al. All-cellulose composites from
unbleached hardwood kraft pulp reinforced with nanofibrillated
cellulose. Cellulose 2013; 20: 2909–2921.
References 9
5. Busila M, Musat V, Textor T, et al. Synthesis and characterization

of antimicrobial textile finishing based on Ag:ZnO nanoparticles/
chitosan biocomposites. RSC Adv 2015; 5: 21562–21571.
6. Rinaudo M. Chitin and chitosan: Properties and applications. Prog
Polym Sci 2006; 31: 603–632.
7. Ma H, Liu M, Li S, et al. Application of polyhydroxyalkanoate (PHA )
synthesis regulatory protein PhaR as a bio-surfactant and bactericidal
agent. J Biotechnol 2013; 166: 34–41.
8. Barkoula NM, Garkhail SK, Peijs T. Biodegradable composites based on
flax/polyhydroxybutyrate and its copolymer with hydroxyvalerate. J
Ind Crop Prod 2010; 31: 34–42.
9. Rane A V., Kanny K, Mathew A, et al. Comparative analysis of processing
techniques’ effect on the strength of carbon black (N220)-filled poly
(lactic acid) composites. Strength Mater 2019; 51: 476–489.
10. Rarima R, Unnikrishnan G. Poly(lactic acid)/gelatin foams by non-
solvent induced phase separation for biomedical applications. Polym
Degrad Stab 2020; 177: 109187.
11. Tanabe T, Okitsu N, Tachibana A, et al. Preparation and characterization
of keratin-chitosan composite film. Biomaterials 2002; 23: 817–825.
12. Lim SW, Jung IK, Lee KH, et al. Structure and properties of biodegradable
gluten/aliphatic polyester blends. Eur Polym J 1999; 35: 1875–1881.
13. Habibi Y. Key advances in the chemical modification of nanocelluloses.
Chem Soc Rev 2014; 43: 1519–1542.
14. Malmström E, Carlmark A. Controlled grafting of cellulose fibres – an
outlook beyond paper and cardboard. Polym Chem 2012; 3: 1702–
1713.
Chapter 2
Biodegradability of Green Composites:

Mechanisms and Evaluation Methods
Nikushi S. Yatigala,a Dilpreet S. Bajwa,b

Sreekala G. Bajwa,c and Saptaparni Chandab
aAgricultural and Biosystems Engineering, North Dakota State University,
Fargo, ND 58108, USA

bMechanical and Industrial Engineering, Montana State University, Bozeman,
MT 59718, USA
cCollege of Agriculture, Montana State University, Bozeman, MT 59718, USA
dilpreet.bajwa@montana.edu
Petroleum-based plastics cause substantial environmental

problems at disposal because of their slow degradation and
harmful degradation products. Most of the plastic wastes end up in
landfills, creating water and soil pollution. For both water miscible
and immiscible polymers that cannot be recycled nor incinerated,
biodegradation is crucial as these polymers ultimately enter streams,
which cannot be recycled nor incinerated. Biobased biodegradable
polymers and natural fibers have a low environmental impact,
and they are highly sustainable. They reduce waste accumulation,

Edited by Sabu Thomas, Abitha V. K., and Hanna J. Maria
Copyright © 2024 Jenny Stanford Publishing Pte. Ltd.
ISBN 978-981-4968-79-9 (Hardcover), 978-1-003-42756-8 (eBook)
www.jennystanford.com
12 Biodegradability of Green Composites
control carbon dioxide emission, and minimize the dependency on

petroleum-based fuels and products. The incorporation of natural
fibers into biobased polymers causes an increase in specific strength
and degradation rate and cost reduction. During biodegradation,
polymers deteriorate their physical and chemical properties
decreasing their molecular mass and form CO2, H2O, CH4, and
other low molecular weight products. This chapter discusses the
current state of knowledge on the behavior of biobased polymers
and their composites when subjected to accelerated weathering,
ultraviolet, thermal, moisture, water, soil, and aerobic and anaerobic
degradation. A range of biobased polymer composites are presented
in this chapter, focusing on their degradation characteristics and
mechanism, properties, physical and mechanical common standards,
and evaluation methods.
2.1 Introduction
Low degradation rates and harmful degradation products such
as carbon dioxide (CO2) of synthetic polymers create substantial
environmental problems at disposal. These polymers account for
roughly 20% by volume of all wastes generated annually in the
United States and contribute to global warming [1, 2]. Moreover, at
the current rate of consumption, the petroleum that the polymers
are created from can only last for another 50–60 years [3]. Owing
to the negative impacts of petroleum-based plastics on the
environment and ecosystem health, and the uncertain supply of
fossil fuels, there is a great potential for replacing synthetic plastics
with biodegradable alternatives. Not only do green plastics have
a positive impact on the environment, but they also have many
other attractive properties such as biocompatibility, bioactivity,
chemical inertness, high stiffness and strength, good film-forming
properties, and low toxicity [4–6]. For example, PLA, a chemically
synthesized biobased polymer, is similar in mechanical properties
to petrochemical polymers such as polypropylene and polyethylene
[7]. Likewise, PHB, a polymer produced by bacteria, also has similar
mechanical properties to polypropylene and higher moisture
resistance and aroma barrier properties [8]. Similarly, cellulose, a
naturally occurring polymer, is a hard polymer and has a high tensile
Green Polymers 13
strength [9]. When these biodegradable plastics are combined

with biobased fibers and fillers to make green composites, their
biodegradability generally improves.
Although green biodegradable polymers have numerous benefits,
they are restricted in many applications as for their high cost and
some of their undesirable properties such as low biodegradation
rate, higher crystallinity, sensitivity to thermal degradation, and
poor mechanical properties [5, 7, 10–12]. Compared to the waste
accumulation rate, the degradation rate of biobased polymers such
as PLA is still too slow [13]. The majority of biobased plastics tend
to be brittle due to their high crystallinity. As for their thermal
sensitivity, most green plastics are sensitive to thermal degradation
during conventional melt processing. Reduction of molecular
weight occurs as they degrade during thermal processing or under
hydrolytic conditions. Mechanical properties of the processed
biobased materials are likely to be affected by the reduction of
molecular weight [14, 15]. However, mechanical and degradation
properties can be changed while reducing cost by creating green
composites with biobased polymers and other natural polymers or
fillers [7, 12, 16]. Creating polymer blends and composites is a good
cost-effective method to improve the properties such as dimensional
stability, strength, toughness, and environmental degradation
[7, 17]. In addition, mechanical properties of the biopolymer
composites can be enhanced with reactive functional groups such
as compatibilizers and coupling agents since they improve the
adhesion between polymer and the fiber by forming both hydrogen
and covalent bonds with hydroxyl groups of fiber and molecular
entanglement with polymer [10, 16]. This chapter focuses on the
biodegradation properties of biobased composites, how biopolymer
composites containing various fiber and polymers behave, the
different modes of biodegradation, how environmental conditions
affect the biodegradation of these materials, and the standards for
quantifying biodegradation properties.
2.2 Green Polymers

Biobased polymers serve as the matrix or substrate material in
biocomposites, with natural fibers and other biobased materials
serving as the fillers or reinforcement. It is important to understand

the various types of bioplastics and their biodegradation
characteristics in order to understand such properties of composites
containing biopolymer as the substrate.
Polymers can be produced from various renewable and
nonrenewable resources. Green or biobased polymers are the
polymers produced by or from living systems. Some examples of
green polymers from renewable resources are cellulose, starch,
proteins, and DNA. Biodegradable plastics are polymers that will
degrade due to the action of microorganisms, such as bacteria
and fungi. Biodegradable polymers produced from renewable,
biobased resources enjoy a high sustainability score. They reduce
waste accumulation, control CO2 emission, and lessen the need
for petroleum-based fuels and products [18]. Bioplastics can be
classified into biodegradable and nondegradable (Fig. 2.1). For
example, biobased polyethylene is not biodegradable. Also, there
are synthetic polymers (produced from nonrenewable petroleum
resources) that are biodegradable [19]. As Fig. 2.2 illustrates,
biodegradable green polymers from renewable resources can be
divided into three categories: (i) those synthesized from bio-derived
monomers (PLA), (ii) those produced by microorganisms (PHAs,
bacterial cellulose), and (iii) those directly extracted from biomass
with partial modification to meet the requirements [1, 6]. Table 2.1
provides some examples of naturally occurring polymers.
Bioplastics
Biodegradable Biobased
PHA
PBS PCL Starch PE
PLA
PES
NY 11
Figure 2.1 Types of bioplastics (adapted from [1]).

Green Polymers 15
Figure 2.2 Origin of biobased polymers (adapted from [1]).
Table 2.1 Naturally occurring biodegradable polymers (adapted from [4])
Polyesters Polysaccharides (plant/algal)

Polyhydroxyalkanoates Starch (amylose/amylopectin)
Polylactic acid Cellulose
Proteins Agar
Silks Alginate
Collagen/gelatin Carrageenan
Elastin Pectin
Resilin Konjac
Adhesives Various gums (e.g., guar)
Polyamino acids Polysaccharides (animal)
Soy zein, wheat gluten Chitin/chitosan
Casein, serum albumin Hyaluronic acid
Polysaccharides (bacterial) Lipids/surfactants
Xanthan Acetoglycerides, waxes, surfactants
Dextran Emulsan
Gellan Polyphenols
Levan Lignin
(Continued)
Table 2.1 (Continued)

Polyesters Polysaccharides (plant/algal)
Curdlan Tannin
Polygalactosamine Humic acid
Cellulose (bacterial) Specialty polymers
Polysaccharides (fungal) Shellac
Pullulan Poly-gamma-glutamic acid
Elsinan Natural rubber
Yeast glucans Synthetic polymers from natural fats
Nylon from castor oil
2.3 Degradation of Biopolymers

There are many types of polymer degradation mechanisms:
thermal, mechanical, photochemical, radiation chemical, biological,
and chemical degradation [20]. According to ASTM definition,
“degradable plastics are the plastics that are designed to undergo
a significant change in their chemical structure under specific
environmental conditions, resulting in a loss of some properties
that may vary as measured by standard methods appropriate to
the plastic and the application in a period of time that determines
its classification.” This definition can be applied to many polymer
degradation types including photodegradation, thermooxidation,
hydrolysis, and biodegradation. Autooxidation is the cause of
thermooxidative degradation of organic materials without light. In
natural photodegradation, the molecular weight of the polymers
is decreased by sunlight due to photooxidation and direct bond
cleavage [21]. Another mode of degradation is hygrothermal
degradation. Substantial loss of weight and mechanical properties
of a material due to the effects of moisture and temperature is
called hygrothermal degradation [22]. In nature, to decompose
organic matter, biotic and abiotic factors act synergistically. Some
biodegradation studies show that abiotic degradation precedes
microbial assimilation [23–25]. Exposing polymers to naturally
degrading environmental conditions (weather, aging, and burying)
results in different transformations of polymers due to light, thermal,
Biodegradation 17
and chemical agents. These abiotic parameters are useful factors in

initiating the biodegradation process, as these parameters help to
weaken the polymer structures [25, 26]. Some other mechanisms of
polymer degradation include the following:
(i) Chemical degradation: It occurs when the polymers are
brought to contact with chemicals such as acids, bases, and
solvents. Oxygen is the most important as it attacks covalent
bonds creating free radicals [20].
(ii) Thermal degradation: It is the molecular deterioration of
polymer due to heat. For thermoplastics, this occurs at
the melting temperature. The components of the polymer
backbone chain detach (molecular scission) and react with
each other resulting in changed polymer properties.
(iii) Mechanical degradation: Macroscopic changes occur in
polymer material due to compression, tension, and shear
forces. Under shear forces, molecular interaction between
certain molecules at certain sites gets disrupted.
(iv) Photodegradation: In photodegradation, polymers undergo
physical and chemical changes due to ultraviolet light or
visible light, inducing cross-linking/Norrish reactions, or
oxidative processes.
2.4 Biodegradation
During biodegradation, living organisms break down organic
substances, and thus the chemical structure of the material changes
resulting in the production of carbon dioxide, water, and new
microbial cell mass. Only biodegradation or biological degradation
completely removes the polymer or its degradation products from
the environment. It takes about 1–3 years to completely assimilate
and disappear a biodegradable plastic article [21]. Biodegradation
can occur under two different conditions: aerobic and anaerobic.
Polymers can be attacked by living organisms either chemically or
mechanically. Enzymes are involved in the chemical mode while the
mechanical mode refers to the attack by mammals and insects [20].
Enzymes are proteins of complicated chemical structures. Typically,
the catalytic activity of enzymes is related to a special molecular
conformation. Depending on the properties of the biopolymer, the
biodegradation of plastics proceeds under different soil conditions

actively due to ideal growth conditions of microorganisms in the
soil [15].
In biodegradation, microbes such as bacteria and fungi are
engaged in the degradation of both bio- and petroleum-based
plastics. Bacteria involved in the biodegradation process include,
inter alia, Bacillus, Pseudomonas, Klebsiella, Actinomycetes,
Nocardia, Streptomyces, Thermoactinomycetes, Micromonospora,
Mycobacterium, Rhodococcus, Flavobacterium, Comamonas,
Escherichia, Azotobacter, and Alcaligenes (some of them are capable
of consuming polymer about 90% of their dry mass). Fungi active
in the biodegradation process are Sporotrichum, Talaromyces,
Phanerochaete, Ganoderma, Thermoascus, Thielavia, Paecilomyces,
Thermomyces, Geotrichum, Cladosporium, Phlebia, Trametes,
Candida, Penicillium, Chaetomium, and Aerobasidium [27].
Biodegradation depends on many factors such as the type of
organism, pretreatment method, polymer characteristics such as
mobility, molecular weight, crystallinity, and plasticizers or additives
blended with the polymer. For instance, higher molecular weight
lowers the solubility of the polymer, reducing the microbial attack,
and the rate of degradability [15]. The insolubility of polymers
reduces the availability of digestible substrates through bacterial
cellular membrane.
As opposed to degradable/biodegradable synthetic plastics,
biodegradable green polymers/composites generally do not
produce toxic products, or it is much less compared to synthetic
plastics. Biodegradable green composites are not necessarily easy
to decompose, and they require certain environmental conditions.
Even then, they may leave behind toxic residues. There are three
types of degradable plastics:
(1) Degradable: Plastics will undergo a significant change in their
chemical structure under certain environmental conditions
resulting in a loss of some properties.
(2) Biodegradable: Plastics will degrade due to microbial activity
producing CO2, water, and biomass as end products. There
is no requirement for leaving “no toxic residue,” nor for the
time it needs to take to biodegrade. Thus, “biodegradable”
Biodegradation 19
green polymers/composites can leave toxic residues during

biodegradation.
(3) Compostable: According to ASTM, compostable plastic should:
(i) Biodegrade – break down into carbon dioxide, water, and
biomass at the same rate as cellulose.
(ii) Disintegrate – the material is indistinguishable in the
compost.
(iii) Not produce any toxic material and the compost can
support plant growth.
2.4.1 Biodegradation Mechanism Steps

During degradation, polymers initially break down into smaller,
simpler structures such as oligomers and monomers (Fig. 2.3). These
smaller structures of monomers are mineralized to CO2, H2O, or CH4
as end products [15]. Biodegradability is the complete assimilation
of the degraded products as a food source by microorganisms, and it
ensures the effective and safe returning of carbon into the ecosystem.
In addition, at least two categories of cellular enzymes also
participate in the biodegradation process of polymers: extracellular
and intracellular depolymerases. The initial breakdown of the
polymers prompts different kinds of physical forces to occur such
as heating/cooling, freezing/thawing, and wetting/drying, which
result in mechanical damage in the polymer such as cracking [15].
Biodegradation of polymers includes the following steps, and the
process could stop at any stage [25].
Polymer
Enzymes Abiotic degradation Biodeterioration
Oligomers,
dimers, and Depolymerization
monomers
Aerobic Anaerobic
CO2 , H 2O, CO 2, H2O, CH 4, Assimilation
residue, Microbial
residue, and/or
degradation
biomass biomass mineralization
Figure 2.3 General mechanism of polymer biodegradation.

(a) Biodeterioration
Microbial or/and abiotic factors break the biodegradable materials
into small fractions. In thermoplastics, depending on the rate of
chemical diffusion to the materials, and the rate of polymer bond
cleavage, biodeterioration occurs in two ways: bulk and surface
erosion (Fig. 2.4). In bulk erosion (when the chemical diffusion
rate is faster than polymer bond breakage), chemicals or radiation
activity induces bond cleavage resulting in changes in molecular
weight of the polymer matrix. On the other hand, in surface erosion
(when the polymer bond breakage rate is faster than the chemical
diffusion rate), even though the loss of substances occurs, the
molecular weight of the polymer matrix does not change.
Figure 2.4 Bulk and surface erosion mechanisms of PLA.
Microorganisms (bacteria, protozoa, algae, fungi, and lichenaceae

groups) that develop on the surface and/or inside the material act
by physical, enzymatic, and/or chemical means:
Physical – Polymers such as polysaccharides and proteins discharge a
glue textured substance, which is a complex matrix. This slime matrix
changes the size and distribution of pores, and the degree of moisture
and thermal transfers. Also, this substance helps microorganisms
to stick to the material surfaces, protecting microorganisms
against undesirable conditions such as UV radiation. Penetration of
microorganisms into the materials results in increases in the size of
pores and cracks, thus weakening the durability of the material.
Biodegradation 21
Enzymatic – For enzymes to break down specific bonds, the presence

of factors such as cations in the material matrix and coenzymes
synthesized by microorganisms are important.
Chemical – Microbial degradation produces extracellular polymers
that act as surfactants that assist the interactions between hydrophilic
and hydrophobic phases, increasing the microbial penetration
rate. Each of these microorganisms contributes to the chemical
biodeterioration of the material. For instance, chemoorganotrophic
microorganisms use organic substrates as carbon, energy, and
electron sources. They release organic acids, such as oxalic, citric,
gluconic, glutaric, glyoxalic, oxaloacetic, and fumaric acids. Polymers
such as PLA releases succinic acid, adipic acid, lactic acid, and
butanediol due to abiotic and/or biotic hydrolysis. Hydrolysis, which
leads to generating oligomers and monomers, is initiated when
water enters the polymer matrix (Fig. 2.5).
Figure 2.5 PLA hydrolysis in acidic conditions.
(b) Depolymerization
Microorganisms produce catalytic agents (enzymes and free
radicals) that could split polymeric molecules resulting in molecular
weight reduction. This process generates oligomers, dimers,
and monomers, and these are small in size to transfer through
the semipermeable outer bacterial membranes (Fig. 2.6). These
products are then exploited as carbon and energy sources [15]. The
molecules that are recognizable by microbial cell receptors could go
through the plasmic membrane, while the other molecules remain
in the extracellular surroundings. The remaining molecules are
subjected to biotransformation reactions producing assimilable or
unassimilable products.
Polymer scissions are essential to obtain oligomers and/or

monomers. The energy to achieve scissions can be acquired from
different sources: thermal, light, mechanical, chemical, and/or
biological. In biological, microorganisms produce specific enzymes
or free radicals. Enzymes prompt chemical reactions by reducing
the activation energy level of molecules. Discharged enzymes (to the
extracellular environment) can be found as free catalysts or fixed on
particles.
Figure 2.6 Biodegradation of polymers by enzymes.
(c) Assimilation
Transferred molecules integrate the microbial metabolism in
the cytoplasm in order to produce energy, new biomass, storage
vesicles, and many types of metabolites that help in maintaining
cellular activity, structure, and reproduction. Thus, microorganisms
grow while reproducing and consuming nutrient substrate from the
environment. Three different catabolic pathways exist in producing
the energy depending on aerobic or anaerobic conditions: aerobic
respiration, anaerobic respiration, and fermentation.
Aerobic respiration – Microorganisms that can use oxygen as the
final electron acceptor need substrates that are oxidized into the
cell. Initially, basic catabolic pathways such as glycolysis, β-oxidation,
amino acid catabolic reactions, and purine and pyrimidine catabolism
generate a small amount of energy. Oxidative phosphorylation that
is realized by electron transport systems produces more energy
afterward.
Anaerobic respiration – Microorganisms that cannot use oxygen
as the final electron acceptor initiate total oxidation with adapted
Standard Testing Methods of Biodegradation 23
electron transport in membrane systems using NO, SO2, S, CO, Fe3+,

and fumarate as final electron acceptors.
Fermentation – Microorganisms that are unable to use oxygen or
other exogenous mineral molecules as final electron acceptors
produce energy by fermentation. These microbes use self-
synthesized endogenous organic molecules as final electron
acceptors. Mineral and/or organic molecules discharged into the
environment such as CO2, ethanol, lactate, acetate, and butanediol
are the products of fermentation.
(d) Mineralization
At the same time, it is possible for particular metabolites to reach the
extracellular surroundings. Molecules such as CO2, N2, CH4, H2O, and
different salts from intracellular metabolites are released into the
environment. When O2 is available, mostly aerobic microorganisms
destroy the complex materials producing microbial biomass, CO2,
and H2O as final products. Under anoxic conditions, anaerobic
microorganisms deteriorate the polymer. Microbial biomass, CO2,
CH4, and H2O are the end products [15]. Consequently, polymers
biodegrade under two conditions: aerobic (in the presence of
oxygen) and anaerobic (in the absence of oxygen).
2.5 Standard Testing Methods of

Biodegradation
Biodegradability of the polymers is evaluated by measuring the
weight loss of degraded material, reduction in mechanical properties,
change in molecular weight, quantitative estimation of microbial
growth, visual observations, and/or monitoring the amount of the
degradation products that may include the evolution of CO2 and
consumption of O2 [28]. Table 2.2 includes the standards that are
used in evaluating the biodegradability of polymers.
Some of the methods of examining biodegradation are described
below.
1. Visual inspection of mycelium growth on the polymer surface
Visually observable changes are roughening of the surface, holes or
cracks formation, defragmentation, microorganism development on
the surface, and changes in the color of the composites [25]. Crystalline
spherulites can be seen on the surface after initial degradation-
biodeterioration. It is the degradation of amorphous polymer
fraction, scraping the less degradable crystalline parts from the
material. Even though these changes do not prove the biodegradation
of the polymers in terms of metabolism, they indicate the attacks of
microbes [15]. Microscopic techniques such as photonic microscopy,
electronic microscopy, and polarization microscopy are used to
refine the analysis. More detailed observations can be made using
scanning electron microscopy (SEM) and atomic force microscopy
(AFM). Standards such as ASTM G21-70, ASTM G22–76, ISO 846,
NF X41-514, NF X41-513, and ISO 11266 test the biodegradation by
microorganism colonization on Petri dishes.
2. Quantitative estimation of the weight loss of the polymer
Even though this method is commonly used, weight loss of samples
is not a direct proof of a material biodegradability as it can be due
to the disappearance of volatile and soluble impurities, and loss of
material from the sample. However, placing samples in small nets
can facilitate the recovery. Nonetheless, detailed information on
biodegradation can be acquired by structural analysis of both the
material remains and the low molecular weight intermediates [15].
Typical standards used are NF EN ISO 13432, ISO 14852, and ISO
14855.
3. Measurement of changes in polymer properties, such as
changes in molecular weight, functional groups, crystallinity,
tensile strength, or a combination thereof
Changes in mechanical properties do not also provide direct proof
of biodegradation. However, these variations are considered when
changes in the mass of the samples are observed. The tensile strength
of polymers is highly sensitive to the changes in the molar mass of
polymers, which is often taken as a direct indication of degradation
[15]. Determinations of molecular weight (MW) and molecular
weight distribution (MWD) are strong methods of detecting the
degradation of linear soluble polymers. Random main scission,
a chemical reaction in the main chains or at side groups of linear
polymers, results in a change in average MW. MWD is altered upon
main chain rupture and/or cross-linking. MWD can be determined
by gel permeation chromatography (GPC) [20]. Thermal evolution is
studied in many biodegradation studies using a differential scanning

calorimetry (DSC). This provides the glass transition temperature
(Tg), cold crystallization temperature (Tcc), and melting temperature
(Tm). X-ray diffraction (XRD) is used to determine crystallinity
[25]. The formation and disappearance of chromophoric groups
are detected by Fourier transform infrared spectroscopy (FTIR),
while nuclear magnetic resonance spectroscopy (NMR) analyzes
structural changes [20]. There are other techniques that can be
used in assessing biodegradability such as X-ray photoelectron
spectroscopy (XPS), contact angle measurements, and water uptake
[15].
4. Measurement of CO2 evolution/O2 consumption
Measuring the amount of oxygen consumed (respirometric test – ISO
14852) or the amount of CO2 formed (Sturm test) is a more accurate
way of evaluating polymer degradation, as microorganisms utilize
O2 to oxidize carbon and form CO2 under aerobic conditions. There
are a few methods used in detecting O2 and CO2 concentrations
such as trapping of CO2 in Ba(OH)2 solution, monitoring O2 and CO2
concentrations in the air by infrared and paramagnetic O2 detectors,
detecting decreased O2 by the diminution of the pressure, and
utilizing small sealed bottles as degradation reactors in which the
CO2 in the headspace and the drop in dissolved oxygen are dissected
[15]. On the other hand, in anaerobic conditions, augmentation of
the pressure is measured when gases are released. Evolved gasses
are identified by using gas chromatography [25].
CO2 analysis is also used for tests in solid matrices such as in
controlled composting test (ASTM 5338, DIN V 54900, ISO 14855,
JIS K 6953). The only efficient method for analyzing CO2 in a complex
environment is the use of a radiolabeled polymer to perform CO2
respirometry. Unfortunately, in addition to its hazardousness, it is a
time-consuming and expensive test, since it requires a specific lab
room with specific equipment with special training technicians.
5. Radiolabeling
Radiolabeling is a consistent and expensive method of estimating
the evolved amount of 14C carbon dioxide. Using a scintillation
counter, 14C carbon dioxide evolution can be determined by exposing
materials with randomly distributed 14C markers to microbial
environments [15].
6. Clear-zone formation
This method is used to determine the ability of microorganisms to
depolymerize the polymer. Here, the polymer is scattered as fine
particles among the synthetic medium agar, resulting in the agar with
a murky appearance. Following vaccination with microorganisms, if
a clear halo is developed around the settlement, it means that the
microorganisms could depolymerize the polymer. Ordinarily, this
system is used to screen microbes that have the ability to degrade
specific polymer; however, by investigating the development of
clear zones, it can likewise be utilized to acquire semiquantitative
outcomes [15].
Table 2.2 Standards for practicing and testing biodegradability of polymers

(adapted from [29–31])
Standard Composting
ASTM D5209 Standard Test Method for Determining the Aerobic
Biodegradation of Plastic Materials in the Presence
of Municipal Sewage Sludge
Biodegradation of Plastic Materials Under Controlled
Composting Conditions
ASTM D5509 Standard Practice for Exposing Plastics to a
Simulated Compost Environment
Simulated Compost Environment Using an Externally
Heated Reactor
ASTM D6003 Standard Test Method for Determining Weight
Loss from Plastic Materials Exposed to a Simulated
Municipal Solid Waste (MSW) Aerobic Compost
Environment
Biodegradation in Soil of Plastic Materials or
Residual Plastic Materials After Composting
ASTM D6002 Guide to Assess the Compostability of
Environmentally Degradable Plastics – ISR Program
Standard Composting
ASTM D6340 Standard Test for Determining Aerobic
Biodegradation of Radiolabeled Plastic Materials in
Compost Environment – ISR Program
ASTM D6400 Specifications for Compostable Plastics – ISR
Program
ASTM D5951 Standard Practice for Preparing Residual Solids
Obtained After Biodegradability Standard Methods
for Toxicity and Compost Quality Testing –
Fate & Effect Testing
ASTM D5152 Standard Practice for Water Extraction of Residual
Solids from Degraded Plastics for Toxicity Testing –
Fate & Effect Testing
ASTM D6868 Standard Specification for Biodegradable Plastics
Used as Coatings on Paper and Other Compostable
Substrates
ASTM G160 Standard Practice for Evaluating Microbial
Susceptibility of Nonmetallic Materials by
Laboratory Soil Burial
ASTM D6954 Standard Guide for Exposing and Testing Plastics
That Degrade in the Environment by a Combination
of Oxidation and Biodegradation
ASTM G29 Standard Practice for Determining Algal Resistance
of Plastic Films
EN ISO 846 Plastics – Evaluation of the action of microorganisms
ISO 846 Plastics: Determination of behavior under the
action of fungi and bacteria. Evaluation by visual
examination or measurement of changes in mass or
physical properties
OECD 304 A Inherent Biodegradability in Soil
Anaerobic digestion/processes
Biodegradation of Plastic Materials or Residual
Plastic Materials After Composting in Contact with
Soil
(Continued)
Standard Anaerobic digestion/processes

ASTM D5271 Standard Test Method for Assessing the Aerobic
Biodegradation of Plastic Materials in an Activated-
Sludge-Wastewater-Treatment System
ASTM D5210 Standard Test Method for Determining the Anaerobic
ASTM D5511 Standard Test Method for Determining Anaerobic
Biodegradation of Plastic Materials Under High-
Solids Anaerobic Digestion Conditions
ASTM D5526 Standard Test Method for Determining Anaerobic
Biodegradation of Plastic Materials Under
Accelerated Landfill Conditions
Simulated Landfill Environment
Others
ASTM D5437 Standard Practice for Weathering of Plastics Under
Marine Floating Exposure
ASTM D5510 Standard Practice for Heat Aging of Oxidatively
Degradable Plastics
ASTM D6118 Standard Test Method for Determining Hydrolytic
Degradation of Plastic Materials in an Aqueous
Solution
ASTM D1435 Standard Practice for Outdoor Weathering of Plastics
ASTM D4364 Standard Practice for Performing Outdoor
Accelerated Weathering Tests of Plastics Using
Concentrated Sunlight
OECD 306 Biodegradability in Seawater
Biodegradability of Degradable Plastics by Specific
Microorganisms
OECD 303 A Aerobic Sewage Treatment: Activated Sludge Units
Standard Others
ASTM D5071 Practice for Operating Xenon Arc-Type
Exposure Apparatus with Water for Exposure of
Photodegradable Plastics
ASTM D5208 Practice for Operating Fluorescent UV and
Condensation Apparatus for Exposure of
ASTM D5272 Standard Practice for Outdoor Exposure Testing of
Evaluation by the content of carbon, oxygen, CO2,
biogas, etc.
OECD 301 A DOC Die-Away Test
OECD 301 B CO2 Evolution Test
OECD 301 C Modified MITI Test
OECD 301 D Closed Bottle Test
OECD 301 E Modified OECD Screening Test
OECD 301 F Manometric Respirometry Test
OECD 302 A Modified SCAS Test
OECD 302 B Zahn-Wellens Test
OECD 302 C Modified MITI Test
ISO 7827 Water quality – Evaluation in an aqueous medium
of the “ultimate” aerobic biodegradability of organic
compounds – Method by analysis of dissolved
organic carbon (DOC)
compounds – Method by analysis of released carbon
dioxide
compounds – Method by determining the oxygen
demand in a closed respirometer
ISO 9887 Water quality – Evaluation of the aerobic
biodegradability of organic compounds in an
aqueous medium – Semi-continuous activated sludge
method (SCAS)
(Continued)

Standard biogas, etc
ISO 9888 B Water quality – Evaluation of the aerobic
aqueous medium – Static test (Zahn-Wellens
method)
ISO 10634 Water quality – Guidance for the preparation
and treatment of poorly water-soluble organic
compounds for the subsequent evaluation of their
biodegradability in an aqueous medium
of the ultimate aerobic biodegradability of organic
compounds – Method by analysis of biochemical
oxygen demand (closed bottle test)
of the ultimate aerobic biodegradability of
organic compounds – Method by determining the
biochemical oxygen demand in a two-phase closed
bottle test
ISO 11733 Water quality – Evaluation of the elimination and
the biodegradability of organic compounds in an
aqueous medium. Activated sludge simulation test
ISO 11734 Water quality – Evaluation of the ultimate anaerobic
biodegradability of organic compounds in digested
sludge. Method by measurement of the biogas
production
ISO/FDIS 14592-1 Water quality – Evaluation of the aerobic
biodegradability of organic compounds at low
concentrations – Part 1: Shake-flask batch test with
surface water or surface water/sediment suspension
ISO/DIS 14592-2 Water quality – Evaluation of the aerobic
biodegradability of organic compounds at low
concentrations – Part 2: Continuous flow river model
with attached biomass
ISO 14593 Water quality – Evaluation of ultimate aerobic
biodegradability of organic compounds in aqueous
medium – Method by analysis of inorganic carbon in
sealed vessels (CO2 headspace test)
ISO/TR 15462 Water quality – Selection of tests for biodegradability

ISO 16221 B Water quality – Guidance for determination of
biodegradability in the marine environment
EN ISO 7827 Water quality – Evaluation in an aqueous medium
compounds – Method by analysis of dissolved
organic carbon (DOC)
EN ISO 9439 Water quality – Evaluation of ultimate aerobic
medium – Carbon dioxide evolution test
medium by determination of oxygen demand in a
closed respirometer
EN ISO 9887 Water quality – Evaluation of the aerobic
aqueous medium – Semi-continuous activated sludge
method (SCAS)
medium – Static test (Zahn-Wellens method)
EN ISO 10634 Water quality – Guidance for the preparation
and treatment of poorly water-soluble organic
compounds for the subsequent evaluation of their
biodegradability in an aqueous medium
EN ISO 10707 Water quality – Evaluation in an aqueous medium
compounds – Method by analysis of biochemical
oxygen demand (closed bottle test)
EN ISO 11733 Water quality – Evaluation of the elimination
and biodegradability of organic compounds in an
aqueous medium – Activated sludge simulation test
EN ISO 11734 Water quality – Evaluation of the “ultimate”;
anaerobic biodegradability of organic compounds
in digested sludge – Method by measurement of the
biogas production
ISO 8192 B Water quality – Test for inhibition of oxygen
consumption by activated sludge
(Continued)

ISO 9509 B Water quality – Method for assessing the inhibition
of nitrification of activated sludge microorganisms
by chemicals and waste waters
ISO 10712 B Water quality – Pseudomonas putida growth
inhibition test (Pseudomonas cell multiplication
inhibition test)
ISO 11348 Water quality – Determination of the inhibitory
Part 1, 2, 3 effect of water samples and the light emission of
Vibrio fischeri (Luminescent bacteria test)
EN ISO 8192 Water quality – Test for inhibition of oxygen
consumption by activated sludge
EN ISO 9509 Water quality – Method for assessing the inhibition
of nitrification of activated sludge microorganisms
by chemicals and waste waters
EN ISO 10712 Water quality – Pseudomonas putida growth
inhibition test (Pseudomonas cell multiplication
inhibition test)
EN ISO 11348 Water quality – Determination of the inhibitory
Teil 1, 2, 3 effect of water samples on the light emission of
Vibrio fischeri (Luminescent bacteria test)
2.6 Biodegradation Properties of Biopolymers

and Composites
Polymer composites can be formulated to have specific mechanical
and physical properties that do not exist in nature, and this increases
the range of applications that these biomaterials can be used
[18]. Polymer composites can be designed for specific mechanical
performance through a selection of the polymer and natural fibers,
their formulation, and processing methods [9, 32]. Polymers such as
PLA, PHA, and starch are blended with other natural polymers and
fibers to increase and control biodegradation [9, 12, 33]. In order
to use these biodegradable composites for outdoor and indoor
applications, it is important to understand the degradation behavior
of the composites.
Biodegradation Properties of Biopolymers and Composites 33
Natural fibers used in biodegradable composites are obtained

either from plants or animals. Compared to commonly used glass fiber
that is not biodegradable, the mechanical properties of natural fibers
are inferior. However, natural fibers have low density and, therefore,
have a high strength-to-density ratio and stiffness [19, 34]. Fibers
are commonly used as reinforcement or fillers in biocomposites for
many advantages such as their low cost, low density, high specific
strength, low health hazards during processing and utilization;
good thermal, electric, and acoustic insulation properties; and less
abrasiveness to processing equipment as compared to conventional
inorganic fillers [35]. Even though natural fibers offer many benefits,
there are some factors that should be taken into consideration.
Poor adhesion between the fiber and the matrix, poor moisture
resistance, flame-retardant properties, homogenization of the
fiber’s properties, degree of polymerization and crystallization,
aggregation during processing, and lower durability are some of the
challenges [14]. The mechanical properties of composites strongly
depend on the quality of the fiber-matrix interface [35]. The main
reason for poor interfacial adhesion between the matrix and fibers
is the hydroxyl and other polar groups of natural fibers which make
them hydrophilic [36]. Hemicelluloses and lignin in natural fiber are
amorphous with a high affinity for water. The hydrophilic fractions
of the fibers with their free hydroxyl group make it incompatible
with the hydrophobic polymer matrix [14]. This leads to the poor
mechanical performance of the composites [15, 37]. However,
interfacial treatments can improve the bonding between the fiber
and the polymer. Many studies have reported the changes exhibited
by green composites and explained their degradation characteristics
and changes in mechanical properties. A summary of degradation
studies conducted on biobased polymers is given in Table 2.3.
Many biobased composites use nanosized mineral fillers
such as clay. Recent studies indicate that layered silicate-filled
polymer composites exhibit improved mechanical, thermal, and
physicochemical properties at low filler concentrations, primarily
due to the nano-level interactions with the polymer matrix.
Montmorillonite (MMT), hectorite, and saponite are the commonly
used clays for polymer composites [38]. Quaternary alkylammonium
salt is a commonly used biodegradable (under certain waste
treatment conditions) organic modifier with nanoclays [38].
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INTESTINAL INVAGINATION IN DOGS AND
CATS.
Anatomical conditions favor. Causes: as in other animals, common in icterus,
and surgical operations from deranged peristalsis. Lesions: most common in small
intestines, congestion, inflammation, necrosis, sloughing. Symptoms: may be colic,
but not always, dullness, anorexia, vomiting, constipation, palpation, swelling
firmer than from impacted twine. Treatment: shot, castor oil and exercise on hind
legs. Demulcents. Laparotomy.
The intestines of the carnivora are more open to invagination than
in other domestic animals for even the colon is free enough
throughout its course to allow of one part sliding into another. The
causes to which it is attributed are in kind the same as in other
domestic animals. The swallowing of ice cold water in excess when
heated, diarrhœa, superpurgation, intestinal worms, the active
peristalsis of early life, and jaundice have been especially blamed.
Reynal found intussusception twenty times in forty cases of icterus
and Rancilla four times in five cases. It has been frequently seen after
severe surgical operations, and it is surmised that in both cases alike
the deranged peristalsis attendant on severe suffering was the cause
of the accident.
Seat and Lesions. The most common seat of invagination is in the
small intestines, and less so in the cæcum and colon, or rectum. The
lesions are as in the other animals, congestion, infiltration, adhesion,
necrosis, gangrene and sloughing.
Symptoms. There may be colics as in the larger animals, but in
some instances there are simply prostration, dullness, inappetence,
vomiting, constipation, or the passage of a little liquid and fœtid
excrement. Palpation of the abdomen detects a firm, cylindroid and
very tender swelling on the line of the softer intestine which taken
with the other symptoms is nearly pathognomonic. If situated in the
small intestine and disconnected from the rectum and pelvis the
diagnosis is more satisfactory. Impaction is most commonly in the
rectum and floating colon and can be traced into the pelvis and even
felt by the finger introduced into the anus. It might be confounded
with obstruction of the intestine by the ingestion of twine, but the
swelling is usually firmer and the cylindroid outline more uniform in
intussusception.
Treatment. The measures recommended for the larger animals are
applicable to the dog. Cadeac has had four recoveries in seven cases
after the use of leaden shot and castor oil. Three balls of No. 16
calibre are dipped in castor oil and given to the dog. This is followed
by ½ oz. of castor oil slightly heated, and walking or running
exercise, or take the dog by his fore limbs and walk him around on
his hind. No drink is allowed for 24 hours, and a quart of decoction
of flax seed on the day following.
Should these measures fail, laparotomy is available, yet it is more
promising in proportion as it is resorted to early, before ulceration,
or gangrene has set in. The manipulations are practically the same as
in the ox and the outcome is even more promising. The diet should
be restricted to milk or mucilaginous gruels for a week after the
operation.
VOLVULUS (TWISTING) OF THE INTESTINE
IN SOLIPEDS.
Definition: rolling of a loop on its mesenteric axis, bending in a vicious direction,

rolling of one loop round another. Causes: laxity of mesentery in hernia, relaxation
or rupture of linea alba, pot belly in old breeding mares, sudden movements in
falls, leaps, draught, galop, slipping, mounting, warm weather, casting, rolling,
rising, sudden filling of a loop, heavy feeding and fermentescible food, cold drinks,
chills. Lesions, most in double colon, next in jejunum, cæcum wrapped in small
intestine, floating colon, tympany and pallor of obstructed loops, later congestion,
infiltration, extravasation, adhesions, necrosis, sloughs, infective peritonitis.
Symptoms: sudden severe attack, violent, reckless colicy movements, pain
constant with exacerbations, fever, prostration, collapse. Diagnosis: only by rectal
exploration and exceptionally. Treatment: by rectal manipulation, eserine, castor
oil, laparotomy.
Strictly speaking this lesion consists in the twisting of a loop of

intestine upon its mesenteric axis, so that the portion which is drawn
spirally over the mesentery of the other is more or less completely
obstructed. The term has, however, been applied as well to the
turning of a viscus at a sharp angle from its normal direction so as to
interfere more or less with the passage of its contents and with its
circulation. This has been especially seen in a vicious direction given
to the cæcum, but also at times to the double colon. The simple
twisting on the mesenteric axis is common to the floating portion of
the small intestines, the double colon, floating colon and rectum. A
third form of twisting which is, however, rather a strangulation,
consists in the rolling of one loop of intestine round the loop of
another, the mesentery of which has become unduly long.
Causes. The predisposing cause is a certain laxity or undue
lengthening of the mesenteric attachment of the intestine. This is
sometimes formed in connection with the existence of hernia, into
which the bowel protrudes, or short of this a relaxation or rupture of
the linea alba so that the whole of the intestinal mass hangs down
unduly, or finally in unthrifty pot-bellied animals and in breeding
mares in which the abdomen is unduly pendent.
Next comes the question of sudden movement as in falls, in
leaping, in violent exertions of draught, or galop, in sudden slipping
upon wet or icy ground, and of stallions in mounting mares. In the
Omnibus Company’s (Paris) horses Palat found 35 cases in entire
horses, 23 in mares, and 11 in geldings. The stallions in the stables
were fewer than the mares and geldings put together, but it does not
appear that the difference was sufficient to make the above figures
very significant. These stallions it should be added, are not used for
breeding, so that the statistics have no bearing on the effect of
mounting.
Palat’s figures show a greater number of cases in summer, than in
winter. There were 58 cases from April to October and but 21 from
November to March. It would seem as if the relaxation of the system
and mesentery in summer more than counterbalanced the combined
effect of slipping on ice and sudden chills.
A large proportion of the cases have been found in horses that
have died of colic, or which have been cast for operation, and the
recent character of the lesions has often shown that we must look
upon them as the result of the tumultuous peristalsis, and the lying,
rolling, sitting and other sudden and unwonted movements
performed. A heavily loaded portion of bowel, occupying a position
slightly lower than a lighter portion or parallel to it, suddenly moves
by gravitation when their relative positions are altered as in rolling,
decubitus, or rising, and it thereby becomes twisted upon itself. Or a
portion of intestine filled with liquid or gaseous contents is suddenly
emptied by the passage of these onward into another and the latter
portion of intestine or some other lodged alongside it, in moving to
fill the place, rotates upon itself and establishes a volvulus.
Hard worked horses which are subjected to stimulating feeding are
much more frequently attacked than those which have light work
and feeding. In the same way newly harvested hay or oats, spoiled or
otherwise indigestible food have apparently been productive causes.
Cold drinks, and exposure to cold draughts have been similarly
charged. Indeed any cause of indigestion and colic may be held to
predispose to volvulus.
Lesions. Seat. Twisting of the small intestine is impossible in the
duodenum, and for the floating portion it is far more common in the
ileum and terminal portion of the jejunum where the mesentery is
long than in the anterior jejunum where it is short.
The double colon from the sternal portion to the pelvic flexure
being free from any restraint by omental or mesenteric bands is
especially liable to torsion. Palat found four cases of torsion of the
colon to one of the small intestine, and Schutze gives the ratio as 56
of the first to 13 of the second.
The cæcum has been frequently found twisted upon itself with a
portion of the small intestine rolled round it.
The floating colon like the small intestine is rolled around its
mesenteric axis, but cases are much more rare than in the case of the
small intestine.
In a recent and complete twisting with obstruction of the bowel,
the loop of intestine is distended with gas the result of fermentation
of its contents, and its walls may be thin and pale. Much more
commonly and when the lesion is of longer standing there is
hyperæmia, and infiltration and thickening with inflammatory
products, and blood extravasations. At the seat of torsion the
compressed intestine is congested, covered with petechiæ, and its
peritoneal surface with fibrinous exudate tending to bind the parts
together. Later there may be seen spots of necrosis and perforating
sores and semi-detached sloughs, or the whole mass of twisted bowel
may be gangrenous. The patient usually dies before this last stage
has been reached. If the animal survives long enough the lesions of
infective peritonitis are constantly present.
Symptoms. The disease usually sets in suddenly with intense
severity. In exceptional cases there is an insidious onset, the twist
being at first but partial and gradually increasing and for a time the
contents pass on in a restricted but still physiological manner. Colics
at first slight become by degrees more and more intense until all the
symptoms of obstruction and acute inflammation are developed.
More commonly symptoms of extreme gravity appear at once, the
patient stops, paws, kicks at his belly, tries to lie down, strains to
defecate or urinate, lies down, rolls, sits, gets up and moves round
uneasily trying to lie down again. He looks at the flank with anxious
eye and countenance and has all indications of the most violent colic.
Pain is constant, but worse at one time than another, the pulse is
from 50 to 90 and becomes weak and even imperceptible as the case
advances, and hyperthermia, at first slight or absent rises with the
onset of inflammation. Finally great prostration, depression and
stupor, sunken, glazed eye with dilated pupil, and cold sweats and
extremities bespeak collapse or general infection.
Diagnosis is rarely certain. The sudden onset, extreme violence of
the symptoms, and rapidly fatal progress are significant and in
exceptional cases rectal exploration will detect obstruction in the
rectum or floating colon, or a tympanitic condition of the pelvic
flexure.
Treatment. A rational treatment is only possible in those rare
cases in which the diagnosis is certain. When the lesion can be
reached in the rectum or adjacent part of the floating colon, the oiled
hand may be made to drag on the interior of the viscus so as to
restore it to its normal position.
Cadiot has had recoveries from supposed volvulus by the use of
eserine hypodermically, and Trasbot by the use of castor oil and it is
just possible that active peristalsis, and plenitude of the bowel
running into the volvulus, may serve to unwind slight cases. When
the diagnosis is certain and the case, as usual, intractable the resort
of laparotomy and the attempt at untwisting is fully warranted. The
case is a fatal one if unrelieved.
VOLVULUS IN RUMINANTS.
This condition is almost unknown in ruminants, Reichert
recording a single case of volvulus of the ileum involving 8 inches of
the gut. The reason for the habitual immunity is to be found in the
arrangement of the small intestine at the end of a mesentery which is
strengthened and stiffened by the winding folds of the colon until
twisting is practically impossible. There remains, therefore, only the
floating colon and rectum at all exposed to the lesion. The isolated
case of Reichert only proves the rule.
VOLVULUS IN DOGS.
Rare. Short mesentery hinders. Occurs with hernia. Symptoms: obstruction,

prostration, colic, tense, painful abdomen, retching, anorexia, exhaustion.
Treatment: laparotomy.
The carnivora seem to be protected against volvulus by the

shortness of their mesentery, the comparative lightness of the
intestinal contents, and the restricted area of the abdominal cavity.
Cadiot, Müller, and Friedberger and Fröhner agree in ignoring the
subject as a canine disease, while Cadeac mentions only such cases as
are complicated by mesenteric hernia, the protruding loop becoming
twisted in the wound through which it has protruded.
“The symptoms are those of invagination or intestinal obstruction;
sometimes the animal is dull, anxious, resting almost constantly
down on his belly, and this prostration dominates the table of
symptoms; sometimes, on the contrary, the subject manifests signs
of excitement and intestinal pain; it trembles, lies down, glances at
its flanks; sometimes it even lets itself fall abruptly, straightens out
stiffly its limbs and head, clenches its jaws and rolls its eyes.”
“In all cases the belly is hard, drawn up, painful to pressure or
palpation; but these means of exploration are insufficient to feel the
intestinal knot.”
“Constipation is persistent, obstinate, and efforts at vomiting
continuous; anorexia is incomplete, or the animal rejects the solid
and liquid aliments immediately after their ingestion. Vomited
matters, when they exist, become glairy, bilious toward the end of the
attack; but sometimes the animal becomes exhausted in his fruitless
efforts; one is rendered uncertain and hesitates to confirm his
diagnosis by laparotomy.”
The only treatment advised is by laparotomy.
INTESTINAL STRANGULATIONS BY
ADVENTITIOUS BANDS.
Result of circumscribed peritonitis. Extends from one part of abdominal wall to

another, around or between intestines, on omentum, or adhesion of omentum to
inguinal ring. In cattle tubercular products strangulate bowels. Symptoms: the
colic of obstruction, rectal exploration. Treatment: laparotomy, removal of
constricting band.
Adventitious fibrous bands in the abdomen are the result of a pre-

existing peritonitis of a circumscribed area. The fibrinous exudate
thrown out on the parietal peritoneum is detached in its median part
but remains adherent at the ends, and when organized into tense
resistant white fibrous tissue remains as a trap to entangle and
strangulate the intestinal folds. In other cases they form on or
between intestines or other viscera which are for the moment torpid
and inactive, and contracting as they become organized, they bind
these together and hamper their movements, and endanger the
integrity of all movable viscera in the vicinity. Again they form on the
omentum and threaten the integrity of the bowels by strangulation.
The omentum protruding at castration becomes adherent to the
inguinal ring and forms a dangerous band.
In cattle the growth of peritoneal tubercle often binds the small
intestines together in an inextricable tangle leading to considerable
compression, and obstruction without a complete stenosis.
Symptoms. These vary with the organ constricted, but they are
usually those of a more or less perfect obstruction of some portion of
the intestine small or large, which has passed over or under the
constricting band and fails to return, often undergoing a torsion
which renders its imprisonment still more secure. The author has
found the double colon fatally constricted in this way, and Leblanc
furnishes a similar case. Cases are on record of the binding of the
duodenum to the right lobe of the liver by a strong fibrous band, of
the binding of the double colon to the right flank and in another case
to the floor of the abdomen, and of the ileum to the meso-rectum and
in another case to the left flank. These give rise sooner or later to
obstruction of these viscera or, to incarceration of adjacent ones so
that the animal dies of intestinal obstruction with its attendant
symptoms.
Treatment. If the true nature of the case can be made out by rectal
exploration the appropriate treatment is by laparotomy and the
removal of the constricting band.
PELVIC HERNIA IN THE OX. GUT TIE.
Cause: laceration of parietal peritoneum by tearing through the spermatic artery,
a loop of intestine is strangulated in the resulting pouch. Diagnosis: patient is a
steer castrated by the method named, rectal exploration confirms. Treatment: turn
on back, jump from a height, trot down hill, dislodge incarcerated mass by hand in
rectum, pass cannula through rectum, introduce probpointed bistoury and cut
through the band, or laparotomy. Second Form: adhesion of stump of spermatic
cord to intestine, or abdominal wall or formation of a pediculated tumor, and
resulting strangulation of intestine. Third Form: weight of testicles tears the
peritoneum from the abdominal wall forming pouch. Treatment: laparotomy.
Causes. This is a peculiar affection said to be connected with a
faulty mode of castration in calves. When the testicle has been
exposed, the spermatic cord is torn through by sheer force, or the
posterior portion having been cut across the anterior division is
dragged upon violently until torn apart. The gelders usually estimate
the quality of the operation by the length of the artery which can be
torn out. The artery which is the most resistant portion of the cord
and the last to give way takes its origin from the posterior aorta
opposite the posterior mesenteric artery, extends outward by a
curvilinear course just in front of the brim of the pelvis, and when
stretched violently it is straightened out and carries with it the
peritoneum, tearing it from the portion immediately in front and
forming a sac, or tearing it completely apart from the abdominal wall
in its median part and leaving it attached above and below. Into this
sac, or above this band, which is just below the sacral transverse
processes, a loop of intestine may pass, and becoming strangled
there, produces all the symptoms of intestinal obstruction.
Diagnosis is helped by the fact that the animal is a steer, and in a
locality where the above-named mode of castration is in vogue. It is
completed by feeling the imprisoned intestine and the constricting
cord just under the right or left transverse processes of the sacrum.
Treatment. The gut will sometimes escape from the sac if the
animal is turned quickly on its back. Another method is to invoke the
influence of gravitation by jumping the animal from a high step
down to a lower level, or by trotting him down a steep incline. A still
more effective method is to introduce the hand into the rectum and
press the palm upward and forward against the soft mass of the
imprisoned intestine. In this way the gaseous, liquid and solid
contents are passed over into the portion of the gut in front of the
constriction, and by continuing the process the intestine itself can
usually be pressed out and the suffering relieved. It is further
suggested to press the thumb or the whole hand forward against the
constricting band and tear it in two. A certain amount of to and fro
movement is usually required and in exceptional cases the cord is so
strong that the measure has to be abandoned.
Another resort is to pass a cannula and trochar through the
adjacent part of the rectum, and withdrawing the trochar, to pass a
probpointed bistoury through the cannula, and beneath the cord and
cut it in two.
These measures failing an incision must be made in the right flank,
following the line of the fibres of the external oblique, and the hand
being introduced and passed round the posterior border of the
omentum the seat of the disease is found and the constricting cord is
cut with a probpointed bistoury or a bistouri caché. The wound is
then sutured, disinfected and covered with antiseptic gauze or cotton
and bandage. The sounds of peristalsis are resumed and in five or six
hours defecation is restored.
2nd Form. Another alleged condition vouched for by English and
continental veterinarians depends on drawing down the spermatic
cord as far as possible, cutting it off and allowing it to be retracted
into the abdomen. Having been detached by the traction from the
abdominal wall it is alleged to float free, sometimes establishing an
adhesion to one of the intestines of which it later limits the
movements; sometimes forming a connection with the abdominal
wall and forming a sling in which the intestines may be snared, and
sometimes swelling at its free end to form a pedunculated tumor,
and winding around a loop of intestine so as to strangle it. For these
conditions incision of the abdominal wall and section of the
offending cord are recommended.
3rd Form. Lobbe tells us that the disease is common in bulls as
well as oxen in mountainous regions, being determined by violent
exertions, or by the struggle to rise, when the animal has accidently
fallen. In this alleged form there is the suggestion of the heavy
pendent testicles as factors in detaching the cord with its vessels and
nerves from the abdominal wall, so as to form a loop or snare for the
intestine.
DIAPHRAGMATOCELE. DIAPHRAGMATIC
HERNIA. PHRENIC HERNIA.
Definition. Susceptibility by genera, horse, dog, ox. Enterocele, epiplocele,
gastrocele, hepatocele. Congenital, arrest of development and of closure of
foramen or elsewhere, diaphragm absent. Traumatic, blows on false ribs by pole,
shaft, buffer, gate, bars, beams, kicks, blows with horns, tusks, clubs, fractured rib
perforating diaphragm, falls on projecting bodies, muscular strains in draught,
plunging, falling, slipping, casting, parturition; trotting or galloping down hill,
jumping to lower level, slipping to knees, dystokia, colic, tympany. Symptoms:
extreme dyspnœa and asphyxia; or difficult breathing slowly increasing, colics,
dilated nostrils, retracted angle of mouth, projecting eyeballs, shallow, rapid
catching respirations, gurgling in chest, drumlike percussion sounds, with perhaps
flat areas; in slight cases, listlessness, colics, double lift of flank, tender
intercostals; in chronic cases, short wind on exertion, sluggishness, colics after
meals. Hernia through intercostal space. Lesions: unduly large foramen sinistrum
or dextrum, lacerations of all forms and sizes, edges ragged, thickened, bloody,
broken rib, inflated stomach causes shreddy tear; post mortem lacerations show no
inflammatory products; chronic cases have edges devoid of inflammation and
often smooth, serosæ usually perforated, nature of hernial mass, omentum,
intestine, colon, cæcum, stomach, spleen, liver, congestion of viscera involved.
Prognosis: slight cases may survive, to be fattened or to breed, but are useless for
work. Treatment: quiet, sedatives, antiferments, cathartic, concentrated food, lift
by fore limbs, incline stall backward and downward, laparotomy in cattle, dogs,
and swine.
As this lesion is shown by symptoms referable to internal organs
only, and as it is considered irremediable by surgical measures, it
may be properly considered in the class of medical affections.
Definition. A displacement of one or more of the abdominal organs
into the cavity of the thorax.
Frequency in different animals. It has been found most frequently
in the horse, and less so in the dog and ox. Severe exertions conduce
to it in horse and dog, while in the ruminant the great bulk of the
gastric cavities, covering the whole posterior surface of the
diaphragm, tends to prevent protrusion even if a slight rupture has
taken place. On the other hand, the weight of the gastric cavities in
the ox and the tension upon the œsophagus, when the animals ride
each other, sometimes cause laceration of the foramen sinistrum and
hernia of the reticulum.
Hernial mass in different animals. In the horse the protruding
organ is most commonly the small intestine (enterocele), omentum
(epiplocele), colon, or less frequently the cæcum, stomach
(gastrocele), or liver (hepatocele). In the ox the reticulum most
commonly protrudes, and after that the liver, abomasum, the
omentum or the small intestine. In the dog the mass is usually
formed by the stomach or liver, or less frequently by the small
intestine or omentum.
Causes and mode of formation. The hernia is either congenital or
acquired after birth. Again, it may result from imperfect
development or from a trauma. Congenital cases usually depend on
an arrest of development, the foramen sinistrum fails to close and
the abdominal organ passes through by the side of the œsophagus
into the chest; or the diaphragm is left imperfect at some other point,
and the two cavities, abdominal and thoracic, communicate. In some
instances there is left not a distinct opening but a mere relaxation of
the parts and under traction, as, for example, by the gullet, an orifice
is torn and a hernia protrudes. Such cases are very rare. Other
lacerations may be almost all referred to external injuries on the
posterior ribs, violent muscular exertions, sudden shocks in
connection with falls, or throwing for operations, and overdistension
of the abdominal viscera.
1st. External Violence. In the larger animals this may come
from blows on the last ribs, by poles or shafts of carriages, the buffers
of cars, the end of a gate and the gatepost, projecting ends of bars or
beams against which they run, kicks by horse or ox, blows by the
horns of cattle or tusks of boars. In the smaller animals in addition to
the above, blows with heavy clubs and kicks with heavy boots. In all
such cases there is usually a fracture of one or more ribs, the sharp
broken ends of which are forced into the diaphragm, which they tear
when they again spring outward. The same occurs as the result of
falls on hard projecting bodies of any kind.
2nd. Muscular Strain. In heavy draught the fixing of the glottis,
ribs and diaphragm and the extreme contraction of the abdominal
muscles often lead to extraordinary tension of the muscular septum
by the mere violence of which, or when there is superadded a sudden
shock, (in plunging in harness, or displacement of the feet or slipping
and falling,) the diaphragm is torn, usually in its tendinous portion,
and the abdominal viscus protrudes into the chest. If the diaphragm
is momentarily relaxed the lesion may take place in the peripheral
muscular portion. In still other cases the lesion is at one of the
natural openings. The same accident occurs in animals thrown for
operation, the abdominal viscera being full, the hind limbs drawn
forward so as to further compress the belly, and the muscles being
subjected to violent contraction in the efforts to get loose. Violent
straining in dystokia is another cause which, however, usually
partakes of a sudden shock on the diaphragm when a violent pain
sets in.
3rd. Sudden Shocks on the diaphragm, and pressure by
the abdominal organs. In the horse especially the weight of the
abdominal viscera is very great and the floor of the abdomen inclines
downward and forward so that the whole mass presses with great
force against the concave diaphragm. In cattle the great weight of the
stomach and liver is especially important and in dog and pig of the
liver mainly. In trotting or galloping down hill or jumping from a
higher to a lower level, or in slipping back on the fore feet so that the
horse falls on the knees or shoulders, this pressure is suddenly
greatly enhanced and the tense diaphragm may give way in its
tendinous portion or the relaxed organ through its muscular tissue. A
similar danger attends on the violent straining which attends on
difficult cases of parturition, and even in cases of overloaded
stomach and tympany and especially when the tortured animal
throws itself suddenly and recklessly on the ground. In cattle and
sheep this is usually the result of tympany of the rumen, and in
solipeds of stomach and intestines.
Rupture by simple overloading or overdistention is, however, a
rare occurrence, and many cases attributed to this are in reality
instances of post mortem lesions, to be identified by the seat of the
laceration in the muscular portion, and by the absence of blood clots,
exudate, thickening or other sign of inflammation on the torn border.
Symptoms. These bear a direct relation to the size of the laceration
and the mass of abdominal organs that protrude into the chest.
In very grave, recent cases, with a great phrenic rupture and a
most extensive protrusion of abdominal organs into the chest, there
may be simply the indications of extreme dyspnœa, nostrils and
chest widely and persistently distended, nasal mucosa darkly
congested, countenance pinched, eyes protruding and fixed, pupils
dilated, breathing rapid, shallow and oppressed, and in a few
minutes the animal staggers and falls in the death agony.
In cases which are less rapidly fatal, the patient lasting for hours
or even days, there occurs, after the accident, deep, difficult and
oppressed breathing, but not so violent as to threaten instant
suffocation, or more commonly, these symptoms increase slowly as
more and more of the hernial mass protrudes through the narrow
opening into the chest. This form is usually seen only in animals of a
specially quiet disposition, and which have not been subjected to
active exertion or excitement after the accident and the hernia has
increased by slow degrees only. The patient becomes listless, or very
restless, paws, looks at his flanks, shifts from one hind foot to the
other or even kicks at the abdomen, lies down carefully, rolls, sits on
his haunches (though no more than in other forms of colic), and
manifests the anxious, pinched, colic-countenance. The advance of
the pain is constant but slow, and usually it is not characterized by
that intensity which drives the animal to throw himself down
recklessly and to roll and kick with violence. There is also usually an
absence of the weak running down pulse of hemorrhagic congestion
(thrombosis) and of the pallor of the surface mucosæ which usually
attend on the extensive blood extravasations of that disease. An
exception may be made in those cases in which the hernial mass is
strangulated, as these may closely resemble spasmodic colic or
hemorrhagic congestion.
The respiration furnishes more distinctive symptoms. The
breathing which may be hurried and almost panting in colic and
acute congestion, is changed in this lesion to a condition of extreme
oppression, the nostrils remain widely dilated in expiration as well as
inspiration, the angle of the mouth is retracted so as to show the
teeth and gums, all the facial muscles stand out, the eyes are
protruding and fixed, with dilated pupils, the head is held extended
on the neck, and the ribs are not allowed to fall in freely, as after
ordinary inspiration, but like the nostrils they remain permanently
drawn out. The efforts at inspiration are violent though shallow and
marked by lifting of the flanks. There are usually one or two nervous
catches in each expiration and sometimes in inspiration as well. This
is partly due to the impotence of the deeply lacerated diaphragm as
an organ of respiration, but also to the pressure of the displaced and
overdistended abdominal organs on the lungs, and to the profound
nervous shock. The whole work has been suddenly thrown on the
costal muscles, and the depressed nervous system proves unequal to
sustaining them in the unwonted toil.
Still clearer indications may be obtained from auscultation and
percussion. These are gurgling, rumbling and clucking, or a coarse
mucous râle which seem abnormally close to the ear, and a drumlike
resonance, much greater than that of emphysematous lung and
enormously in excess of what is given out by the sound lung tissue.
These may be heard at points where only pulmonary murmurs
naturally occur or where abdominal sounds, if heard at all, are
distant in health. There may also be areas of abnormal flatness on
percussion by reason of the protrusion of a solid viscus like the liver
or spleen or one with solid contents. These symptoms are only clear
when there is a large intrusion of abdominal organs into the thorax,
and they increase rapidly until asphyxia supervenes.
In cases which do not immediately threaten life the extent of the
phrenic laceration is usually small and the orifice may be blocked by
a bulky organ like the rumen, double colon, stomach or liver, so that
any protrusion takes place only to a limited amount and the function
of the diaphragm can still be carried on to a reasonable extent. In
these cases there may be no very marked symptom at the outset,
though the animal is dull, listless and without appetite, or, if he eats
or drinks, it is liable to be followed by slight colics and a double
action of the flank in expiration as in pulmonary emphysema
(heaves). Pressure or percussion in the posterior intercostal spaces is
painful. Cough when roused by pinching the larynx is broken and
abortive. These symptoms are not distinctive, however, and unless
there is a protrusion of a loop of small intestine, to give gurgling and
drumlike sounds the diagnosis of the case is liable to fail. The fact of
a recent injury may however assist in the recognition of the lesion.
The chronic cases are even more difficult to recognize as there is
no record of recent injury and no fever. There may be short wind, the
animal breathing hurriedly on slight exertion, and showing a double
lift of the flank in expiration (Girard). In place, however, of the
tympanitic bowels and frequent passage of flatus which characterize
heaves, there is a tendency to colic, especially after meals, and in a
certain number of cases there are all the symptoms of fatal
strangulation, due to the contraction of the diaphragmatic wound.
When the hernia is made by a loop of intestine there are the
characteristic symptoms of thoracic gurgling and drumlike
resonance.
Cases are on record in which the intestine protrudes through one
of the last intercostal spaces or between the ends of the broken rib as
a hernia and diagnosis becomes easy by auscultation, palpation and
percussion. But in a large proportion of cases the lesion escapes
recognition and is only found on post mortem examination.
Lesions. The lacerated orifice in the diaphragm varies much as
regards situation, extent, form and the nature of its border. In
congenital cases due to an imperfect closure of the natural openings
there may be simply a round or ovoid opening, too spacious to be
filled by the gullet, vena cava or aorta as the case may be, and
capable in the different cases, of containing an organ of any size from
the omentum to the liver or stomach. Its margins may be perfectly
smooth and even, without any thickening, irregularity, fringe, clot or
exudate. In traumatic cases on the other hand the orifice may be of
almost any form, size or situation. It may be round, elliptical,
triangular, or irregular in many ways. It may be so small as to admit
nothing more than a small fold of the omentum, or it may be large
enough to open the two cavities, thoracic and abdominal into one
common space, and to practically abolish the function of the
diaphragm. If the lesion is a recent one the torn margin is irregularly
indented or fimbriated and marked by small black blood clots, and
somewhat later by exudate and irregular thickening or swelling.
When due to a broken rib, the existence of the fracture is patent and
the laceration extends along two lines often radiating from point of
perforation by the rib. When the laceration has resulted from
tympany of the stomach or intestines or from other overdistension of
the abdominal organs, the general and comparatively equable
pressure has determined the independent laceration of numerous
tendinous or muscular bundles all over the diaphragm, so that the
divided ends stand out at intervals each bearing its little clot of dark
blood, but without actual perforation. The actual orifice in such cases
is confined to one point where the tension has been greater or the
resistance less. Post mortem lacerations, from tympany or other
cause, are easily distinguished from those occurring during life, in
that the edges of the wound are pale and bloodless, without clot or
exudate.
When the hernia is chronic there is an absence of exposed fringes,
and of indications of inflammation, the margins of the orifice being
in some cases smooth, even and fibrous, and in others irregularly
notched or indented with nodular, fibroid swellings of various sizes
at intervals. In such cases the orifice is always relatively small and
the hernial mass inconsiderable.
As a rule the peritoneum and pleura, being firmly adherent to the
diaphragm, are involved in the laceration so that the hernial mass is
not retained in a special sac, but simply protrudes into the pleural
cavity, after the manner of an eventration. In exceptional cases they
become detached from the muscle, and becoming distended,
envelope the hernial mass in a distinct sac.
In hernia with a very small orifice the omentum alone may pass
through, even the small intestine proving too large for admission. In
such cases it is usual to find the band of omentum adherent to the
callus formed by the repair of a fractured rib. When the orifice is
somewhat larger a portion of small intestine or of the double colon or
cæcum may be engaged, while with a still larger opening the
stomach, spleen, or liver may form the hernia. In cattle the reticulum
is most likely to be the hernial mass, as noted in an article below. In
rare cases the small intestines, omentum or liver protrude (Youatt,
Lafosse). The protruding organ is liable to be constricted and
strangulated sooner or later by increase in its bulk in connection with
its vermicular movements, the accumulation of its contents or the
extrication of gas in its lumen, or by the gradual contraction of the
orifice in process of healing. Then there may be dark red venous
congestion, blood extravasation and effusion, friability and even
rupture of the intestinal walls, and adhesions to the wound or the
lungs. Once started this congestion and extravasation may extend
backward into the abdominal cavity involving a great part of the
contiguous intestinal canal.
Prognosis. The worst cases are promptly fatal, while others
destroy life in one or two days and such are always to be recognized

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Green Micro and Nanocomposites

Ten Years Later S. E. Green

Nickel-Titanium Smart Hybrid Materials: From Micro- to

Nano-Optics: Fundamentals, Experimental Methods, and

Handbook of Chitin and Chitosan: Volume 2: Composites

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Spectroscopic Methods for Nanomaterials

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Biomass, Biofuels, Biochemicals: Green-Economy: Systems

Jenny Stanford Publishing Pte. Ltd.

British Library Cataloguing-in-Publication Data

Green Micro- and Nanocomposites

Copyright © 2024 by Jenny Stanford Publishing Pte. Ltd.

ISBN 978-981-4968-79-9 (Hardcover)

1. Green Micro- and Nanocomposite Materials 1

2. Biodegradability of Green Composites: Mechanisms

3. Green Composites Reinforced

4. Green Composites Reinforced with Chitin

4.5 Preparation of Rubber-Based Chitin

5. Green Composites Based on Polyhydroxyalkanoates 143

6. Green Composites Based on Poly(Lactic Acid) 161

7. Green Composites Based on Protein Materials 185

8. Surface Modification of Biobased

8.3 Polysaccharide Nanoparticles 229

In recent years, there has been a growing global concern about

Chapter 3, Green Composites Reinforced with Cellulose, focuses

and applications of these materials, it aims to inspire further

Green Micro- and Nanocomposite

Abitha V. K.,a Ajay Vasudeo Rane,b Deepti Yadav,c

Kottayam-686560, Kerala, India

Durban University of Technology, Durban-4000, South Africa

Durban-4000, South Africa

Kottayam-686560, Kerala, India

Nanotechnology, Mahatma Gandhi University, Kottayam-686560,

Environmental issues throughout the world such as rising sea levels,

Green Micro- and Nanocomposites

demands (Fig. 1.1). Key global challenges include how to respect

Figure 1.1 Environmental issues throughout the world.

In order to overcome the challenges, there is a demand for

be degraded to carbon dioxide and water using the activities of

Figure 1.2 Process of biodegradation.

Cellulose is a polysaccharide made up of linear glucan chains

composites. Herein, the authors have elaborated on the different

Figure 1.3 Cellulose source and chemical structure.

Chitin is a long-chain polymer made up of N-acetyl glucosamine,

based polymeric materials is a fascinating way to investigate the

Figure 1.4 Chitin, chitosan source, and chemical structure.

Polyhydroxyalkanoates (PHAs) are polyesters created in nature

the issues connected with green composites based on PHAs could

Figure 1.5 PHA source and chemical structure.

Poly(lactic acid) commonly known as PLA or poly(lactide) is a

Figure 1.6 PLA source and chemical structure.

Protein-based composites provide a plethora of options for

Figure 1.7 Protein sources.

Surface modification is the process of altering the surface of a

polysaccharide nanoparticles, such as nanocelluloses, starch, and

Figure 1.8 Grafting techniques.

1. Wan YZ, Luo H, He F, et al. Mechanical, moisture absorption, and

5. Busila M, Musat V, Textor T, et al. Synthesis and characterization

Biodegradability of Green Composites:

Nikushi S. Yatigala,a Dilpreet S. Bajwa,b

Fargo, ND 58108, USA

Petroleum-based plastics cause substantial environmental