Table Of ContentSpringer Series in Materials Science 278
Editor
Suprakas Sinha Ray
Processing of
Polymer-based
Nanocomposites
Processing-structure-property-
performance relationships
Springer Series in Materials Science
Volume 278
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Suprakas Sinha Ray
Editor
Processing of Polymer-based
Nanocomposites
Processing-structure-property-performance
relationships
123
Editor
Suprakas SinhaRay
DST-CSIRNational Centrefor
NanostructuredMaterials
Council for ScientificandIndustrial
Research
Pretoria, SouthAfrica
and
Department ofApplied Chemistry
University of Johannesburg
Johannesburg, SouthAfrica
ISSN 0933-033X ISSN 2196-2812 (electronic)
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ISBN978-3-319-97791-1 ISBN978-3-319-97792-8 (eBook)
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Preface
Over the last few years, “nanomaterial” and “nanotechnology” have become
well-known terms, not only among scientists, engineers, fashion designers, and
architects,butalsothegeneralpublic.Owingtotheirextraordinaryandunexpected
behavior, nanomaterials have gained tremendous attention in fields such as auto-
motive, electronics, aerospace, health care, and biomedical and have significant
potentialformanymodernadvancedtechnologicalapplications.Inthisdirection,a
great deal of research and development effort has emerged around the hybrid
organic–inorganic systems, and, in particular, attention has been given to those in
which nanofillers (or nanoparticles, NPs) are dispersed in a polymer matrix. This
class of materials is called polymer nanocomposites (PNCs) and shows unique
value-addedpropertiesthatarecompletelyabsentinneatmatricesandconventional
composites.
NPs can be made from a wide range of materials, the most common being
layered silicates, carbon nanotubes, graphene or graphite oxide, and metal oxides.
Overthelasttwodecades,varioustypesofNPshavebeenusedforthepreparation
of PNCs with almost all types of polymers and polymer blends. However, layered
silicates,carbonnanotubes,andgraphene-containingPNCshaveattractedincurrent
advanced materials research, because these NPs can remarkably enhance the
inherent properties of neat polymers after PNCs formation.
Control of the dispersion of NPs in polymer matrices and the interactions
between NPs and macromolecular chains is necessary to explore PNCs full
potential for a wide range of applications. This can be achieved by proper surface
functionalizationandmodificationoftheNPs,whichenhancetheirinteractionwith
matrix. Functionalization of NPs consequently influences the colloidal stability,
dispersion, and controlled assembly of NPs.
The performance of a PNC is dictated by three main factors: (i) the inherent
properties of the components; (ii) interfacial interactions; and (iii) structure of the
PNCs. The structure of a PNC depends on the dispersion and distribution of the
NPs in the polymer matrix. However, improving the dispersion by mechanical
means or via chemical bonding can influence the properties of the obtained PNCs.
v
vi Preface
Therefore, elucidating the dispersion and distribution characteristics and the asso-
ciated mechanisms is important and can allow prediction of the final properties.
Over the past few years, great deals of advancements have been made in PNCs
research and development, and the dispersion of the NPs in the polymer matrix
remainsakeychallengetotheirwidespreadapplication.Undoubtedly,tomaximize
the interfacial area in the PNCs, the dispersion should be on the scale of the
individual NPs; otherwise, aggregation resultsina lower specific surfacearea, and
microcompositesareultimatelyformed.Alargeportionofthisbookisdedicatedto
reviewing methods for manipulating the interface, as well as the kinetic aspects
of the dispersion of nanoparticles in polymer matrices, for example, controlling
extrusion parameters during melt processing.
AnotherpressingmatteristhecontrolofthestructuralmorphologyofthePNCs
to achieve time-independent equilibrium. Often, further processing, for example
extrusion and then injection molding, results in a different dynamic equilibrium,
which makes it difficult to tune the emergent properties. A similar complex chal-
lenge involves scaling-up preparationofthePNCs toindustrially viablequantities,
especially for solvent-based systems. To secure economic and other societal
impacts, sufficient volumes of NPs and PNCs need to be manufactured in order to
be transformed into market-ready products. Most research and development labo-
ratories around the world focus on processes with tightly controlled laboratory
environmentswhicharenotnecessarilyappropriateforsafe,reliable,effective,and
affordable large-scale production. Funding to address these challenges is still
required. In addition, as with other new technologies, societal aspects need to be
considered in parallel with the development of the technology. Consumer percep-
tionsregardingtherisksofcertainnanoparticles,whetherprovenornot,needtobe
addressed to ensure a smoother uptake of the technology.
Insummary,thefieldofPNCshasshowndisparateresults,successesaswellas
challenges. Much work remains to be done in fundamental research to achieve
better control of the desired properties, for example, processing PNCs to achieve
thedesired level ofdispersion oftheNPs. Thisbookfocusses theeffectofprocess
variables on the structural evolution of polymer composites and the production of
eithermicro-ornanocomposites,aswellastheeffectofthedispersionstateonthe
final properties at a fundamental level.
ProcessingthesePNCsusuallyrequiresspecialattentionastheresultantstructures
onthemicro-andnanolevelaredirectlyinfluencedbythepolymer/NPchemistryand
processing strategy, among others. The structure then affects the properties of the
resultant composite materials. This book is structured into two volumes. The first
volumeintroducesreaderstonanomaterialsandPNCsprocessing.AfterdefiningNPs
and PNCs and discussing environmental aspects, Chap. 2 focuses on the synthesis
andfunctionalizationofnanomaterialswithapplicationsinPNCtechnology.Abrief
overview on nanoclay and nanoclay-containing PNC formation is provided in
Chap. 3. Chapter 4 provides an overview of the PNCs structural elucidation tech-
niques, such as X-ray diffraction and scattering, microscopy and spectroscopy,
nuclearmagneticresonance,Fouriertransforminfraredspectroscopyandmicroscopy,
andrheology.Thelastchapterprovidesanoverviewonhowmelt-processingstrategy
Preface vii
impacts structure and mechanical properties of polymer nanocomposites by taking
layered silicate-containing polypropylene nanocomposite as a model system.
The second volume focuses heavily on the processing technologies and strate-
gies and extensively addresses the processing–structure–property–performance
relationships in a wide range of polymer nanocomposites, such as commodity
polymers (Chap. 1), engineering polymers (Chap. 2), elastomers (Chap. 3), ther-
mosets (Chap. 4), biopolymers (Chap. 5), polymer blends (Chap. 6), and electro-
spun polymer (Chap. 7). The important role played by NPs in polymer blends
structures in particular is illustrated.
This two-volume book is useful to undergraduate and postgraduate students
(polymer engineering, materials science and engineering, chemical and process
engineering), as well as research and development personnel, engineers, and
material scientists.
Finally, I express my sincerest appreciation to all authors for their valuable
contributions as well as reviewers for their critical evaluation of the proposal and
manuscripts. I also thank all authors and publishers for their permission to repro-
duce their published works. My special thanks go to Kirsten Theunissen, Aldo
Rampioni,editor,andproductionmanageratSpringerNaturefortheirsuggestions,
cooperation, and advice during the various stages of manuscripts preparation,
organization, and production of this book. The financial support from the Council
for Scientific and Industrial Research, the Department of Science and Technology,
and the University of Johannesburg is highly appreciated. Last but not least, I
would like to thank my wife Prof. Jayita Bandyopadhyay and my son Master
Shariqsrijon Sinha Ray, for their tireless support and encouragement.
Pretoria/Johannesburg, South Africa Suprakas Sinha Ray
Contents
1 Processing Nanocomposites Based on Commodity Polymers. . . . . . . 1
Prasanna Kumar S. Mural and Suprakas Sinha Ray
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Processing of Commodity PNCs . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2.1 Melt Mixing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2.2 In Situ Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2.3 Solution Mixing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.3 Methods for Functionalizing Polymers for PNC Preparation . . . . 6
1.3.1 Modification of NPs. . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.2 Modification of Polymers. . . . . . . . . . . . . . . . . . . . . . . . 10
1.4 Structure–Property Relationships in PNC . . . . . . . . . . . . . . . . . . 11
1.4.1 Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.4.2 Effect on Glass Transition Temperature. . . . . . . . . . . . . . 12
1.4.3 Thermal Stability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.4.4 Thermal Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.4.5 Electrical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.4.6 Fire Retardancy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.4.7 Membrane Separation and Barrier Properties . . . . . . . . . . 17
1.5 Performance and Applications . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.5.1 Automotive Parts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1.5.2 Packaging Applications . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.5.3 Flammability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.5.4 Other Applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.6 Challenges, Opportunities, and Future Trends. . . . . . . . . . . . . . . 20
1.6.1 Challenges and Opportunities . . . . . . . . . . . . . . . . . . . . . 20
1.6.2 Future Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.7 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
ix
x Contents
2 Processing Nanocomposites Based on Engineering Polymers:
Polyamides and Polyimides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Vincent Ojijo and Suprakas Sinha Ray
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.1.1 PA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.1.2 PIs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.1.3 Overview of Engineering Polymer-Based
Nanocomposites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.2 Processing Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.2.1 In Situ Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.2.2 Solution Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.2.3 Melt Compounding . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.2.4 Electrospinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.2.5 3D Printing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.3 Polyamide Nanocomposites. . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.3.1 Processing, Structure and Properties of PA/Clay
Nanocomposites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.3.2 Processing, Structure, and Properties of
PA/CNT PNCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.3.3 Processing, Structure, and Properties of PA/Graphene/
Graphene Derivative PNCs. . . . . . . . . . . . . . . . . . . . . . . 52
2.4 PI Nanocomposites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
2.4.1 In Situ Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . 54
2.4.2 Additive Manufacturing . . . . . . . . . . . . . . . . . . . . . . . . . 56
2.4.3 Electrospinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
2.5 Conclusions and Future Outlook . . . . . . . . . . . . . . . . . . . . . . . . 59
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3 Rubber Nanocomposites: Processing, Structure–Property
Relationships, Applications, Challenges, and Future Trends. . . . . . . 75
Reza Salehiyan and Suprakas Sinha Ray
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.2 Rubber Fabrication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.3 Rubber Nanocomposite Manufacturing. . . . . . . . . . . . . . . . . . . . 77
3.3.1 Melt Compounding . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.3.2 Solution Mixing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.3.3 In Situ Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . 78
3.3.4 Latex Compounding. . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
3.4 Vulcanization Characteristics. . . . . . . . . . . . . . . . . . . . . . . . . . . 79
3.5 Dynamic Properties of Filled Rubbers . . . . . . . . . . . . . . . . . . . . 81
3.6 Rubber/Clay Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.6.1 Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.6.2 Barrier Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
