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Recent Developments in Polymer Macro, Micro and Nano Blends: Preparation and Characterisation
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Comece a lerDuração: 705 páginas
- Editora:
- Elsevier Science
- Lançado em:
- Aug 24, 2016
- ISBN:
- 9780081004272
- Formato:
- Livro
Descrição
Recent Developments in Polymer Macro, Micro and Nano Blends: Preparation and Characterisation discusses the various types of techniques that are currently used for the characterization of polymer-based macro, micro, and nano blends. It summarizes recent technical research accomplishments, emphasizing a broad range of characterization methods.
In addition, the book discusses preparation methods and applications for various types of polymer-based macro, micro, and nano blends. Chapters include thermoplastic-based polymer & nano blends, applications of rubber based and thermoplastic blends, micro/nanostructures polymer blends containing block copolymers, advances in polymer-inorganic hybrids as membrane materials, synthesis of polymer/inorganic hybrids through heterophase polymerizations, nanoporous polymer foams from nanostructured polymer blends, and natural polymeric biodegradable nano blends for protein delivery.
Describes the techniques pertaining to a kind (or small number) of blends, showing specific examples of their applications Covers micro, macro, and nano polymer blends Contains contributions from leading experts in the fieldAções de livro
Comece a lerDados do livro
Recent Developments in Polymer Macro, Micro and Nano Blends: Preparation and Characterisation
Duração: 705 páginas
Descrição
Recent Developments in Polymer Macro, Micro and Nano Blends: Preparation and Characterisation discusses the various types of techniques that are currently used for the characterization of polymer-based macro, micro, and nano blends. It summarizes recent technical research accomplishments, emphasizing a broad range of characterization methods.
In addition, the book discusses preparation methods and applications for various types of polymer-based macro, micro, and nano blends. Chapters include thermoplastic-based polymer & nano blends, applications of rubber based and thermoplastic blends, micro/nanostructures polymer blends containing block copolymers, advances in polymer-inorganic hybrids as membrane materials, synthesis of polymer/inorganic hybrids through heterophase polymerizations, nanoporous polymer foams from nanostructured polymer blends, and natural polymeric biodegradable nano blends for protein delivery.
Describes the techniques pertaining to a kind (or small number) of blends, showing specific examples of their applications Covers micro, macro, and nano polymer blends Contains contributions from leading experts in the field- Editora:
- Elsevier Science
- Lançado em:
- Aug 24, 2016
- ISBN:
- 9780081004272
- Formato:
- Livro
Relacionado a Recent Developments in Polymer Macro, Micro and Nano Blends
Amostra do livro
Recent Developments in Polymer Macro, Micro and Nano Blends
Recent Developments in Polymer Macro, Micro and Nano Blends
Preparation and Characterization
Editors
P.M. Visakh
Gordana Markovic
Daniel Pasquini
Table of Contents
Cover image
Title page
Related titles
Copyright
List of contributors
Editors’ biographies
1. Polymer blends: State of art
1.1. General background on polymer blend/nanofiller composites
1.2. Nanoparticles of the polymer composites
1.3. Functionalized polymer with nanoparticles
1.4. Composite material
1.5. Preparation of polymer blend/nanofiller composites
1.6. Characterization of polymer blend/nanocomposites
1.7. Applications of polymer blend/nanocomposites
2. Thermoplastic-based nanoblends: Preparation and characterizations
2.1. Introduction
2.2. Thermoplastic-based nanoblends
2.3. Characterizations of thermoplastic-based nanoblends
2.4. Interface modification of nanoblends
2.5. Conclusion
3. Hybrid composites using natural polymer blends and carbon nanostructures: Preparation, characterization, and applications
3.1. Introduction
3.2. Formation of conducting nanocomposite films using collagen–chitosan blends and nanocarbons
3.3. Formation of conducting nanocomposite films from collagen and carbon nanotubes
3.4. Conclusions
4. Applications of rubber-based blends
4.1. Introduction
4.2. Conclusion
5. Applications of thermoplastic-based blends
5.1. Introduction
5.2. Conclusion
6. Micro-/nanostructured polymer blends containing block copolymers
6.1. General introduction
6.2. Nanostructured materials from block copolymers
6.3. Nanostructures in block copolymer blends
6.4. Ordering in block copolymer/block copolymer blends
6.5. Micro- and nanostructured block copolymer blends
6.6. Few selected application of block copolymer-based blends
6.7. Conclusions
7. Advances in polymer-inorganic hybrids as membrane materials
7.1. Introduction
7.2. Preparation of polymer-inorganic hybrid membranes
7.3. Transport mechanisms
7.4. Characterization of polymer-inorganic hybrid membranes
7.5. Applications
7.6. Conclusions and future development
8. Synthesis of polymer/inorganic hybrids through heterophase polymerizations
8.1. General introduction
8.2. Heterophase polymerization processes
8.3. Polymer/magnetic nanoparticle-based nanocomposites
8.4. Polymer/clay-based nanocomposites
8.5. Morphology characterization techniques
8.6. Conclusion
9. Nanoporous polymer foams from nanostructured polymer blends: Preparation, characterization, and properties
9.1. Introduction
9.2. Nanostructured solid polymer blends for the potential production of micro- and nanoporous materials by a foaming process: theoretical features, precursors, and morphologies
9.3. Nano- and microporous structures obtained by gas foaming of nanostructured polymer blends: characterization and evidences of the foaming mechanisms
9.4. Properties and applications of nanoporous foamed materials obtained from nanostructured polymer blends
9.5. Conclusion and perspectives
10. Natural polymeric biodegradable nanoblend for macromolecules delivery
10.1. Introduction
10.2. Nanotechnology
10.3. Natural polymers
10.4. Conclusion
Index
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Copyright
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ISBN: 978-0-08-100408-1 (print)
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List of contributors
L.C. Abdullah, University Putra Malaysia, Serdang, Selangor, Malaysia
P.M. Ajayan, Rice University, Houston, TX, United States
L. Ansaloni, Norwegian University of Science and Technology (NTNU), Trondheim, Norway
A. Anumary
Rice University, Houston, TX, United States
Central Leather Research Institute (Council of Scientific and Industrial Research), Chennai, India
M. Ashokkumar, Rice University, Houston, TX, United States
K.Y. Ching
University of Reading Malaysia, Johor, Malaysia
University of Southampton, Southampton, BJ, United Kingdom
Y.C. Ching, University of Malaya, Kuala Lumpur, Malaysia
C.H. Chuah, University of Malaya, Kuala Lumpur, Malaysia
L. Deng, Norwegian University of Science and Technology (NTNU), Trondheim, Norway
M. Dumon, Université de Bordeaux, Bordeaux, France
G.R. Ferreira, Instituto de Química, Universidade de Brasília, Brasília, DF, Brazil
R. Gambetta, Embrapa Agroenergia, Parque Estação Biológica, Brasília, DF, Brazil
A.F. Glenn, Instituto de Química, Universidade de Brasília, Brasília, DF, Brazil
S.B. Gonçalves, Embrapa Agroenergia, Parque Estação Biológica, Brasília, DF, Brazil
A.M. Grumezescu, Politehnica University of Bucharest, Romania
T.Y. Inan, SAUDI ARAMCO, Research and Development, Dhahran, Saudi Arabaa
Sougata Jana, Gupta College of Technological Sciences, Asansol, West Bengal, India
Subrata Jana, Indira Gandhi National Tribal University, Amarkantak, Madhya Pradesh, India
A.T. Jensen, Instituto de Química, Universidade de Brasília, Brasília, DF, Brazil
F. Machado, Instituto de Química, Universidade de Brasília, Brasília, DF, Brazil
G. Markovic, Technical Rubber Goods, Pirot, Serbia
W.S. Neto, Instituto de Química, Universidade de Brasília, Brasília, DF, Brazil
J. Pinto
Istituto Italiano di Tecnologia (IIT), Genova, Italy
Université de Bordeaux, Bordeaux, France
University of Valladolid, Valladolid, Spain
D. Popescu, University of Craiova, Craiova, Romania
R.C. Popescu
Politehnica University of Bucharest, Romania
Horia Hulubei
National Institute for Physics and Nuclear Engineering (IFIN-HH), Magurele, Romania
A. Rahman, University of Malaya, Kuala Lumpur, Malaysia
J. Rodríguez-Hernández, Institute of Polymer Science and Technology (ICTP-CSIC), Madrid, Spain
M.A. Rodriguez-Perez, University of Valladolid, Valladolid, Spain
P. Thanikaivelan, Central Leather Research Institute (Council of Scientific and Industrial Research), Chennai, India
L.F. Valadares, Embrapa Agroenergia, Parque Estação Biológica, Brasília, DF, Brazil
P.M. Visakh, Tomsk Polytechnic University, Tomsk, Russia
Editors’ biographies
Dr. Visakh P.M. (MSc, MPhil, PhD) is a prolific editor with more than 16 books already published. Now he is working as Research Associate (Under the Guidance of Prof. Olga B Nazarenko) in Department of Ecology and Basic Safety, Tomsk Polytechnic University (TPU), Tomsk, Russia. He obtained his PhD, MPhil and MSc degreases from School of Chemical Sciences, Mahatma Gandhi University, Kottayam, kerala, India. He edited 16 books from Scrivener (Wiley), Springer, Royal Society of Chemistry, Elsevier and more than 11 books in press. He visited 12 countries; He visited 15 universities in Europe. He published 13 publications, 3 reviews and more than 18 book chapters. He has attended and presented more than 28 conferences. He acts as guest editor for 4 International Journals. His research interests include: polymer nanocomposites, bio-nanocomposites, and rubber based nanocomposites, fire retardant polymers and liquid crystalline polymers and silicon sensors.
Dr. Gordana Markovic (BS, PhD) is working as engineer (Tigar factory Pirot) in Department of quality. She obtained her BS degreases from The faculty of natural science and mathematics (former Yugoslavia), University of Nis, Serbia in 1993; her PhD from Faculty of technology, University of Novi Sad, Serbia in 2004. She edited books from Springer, Royal Society of Chemistry, Elsevier. She published more than 150 publications, manuscripts, reviews and book chapters. She has attended and presented more than 20 conferences. Her research interests include: nanostructured materials, synthesis and characterization of composite materials, composite materials (inorganic filler in polymer matrix), elastomeric materials and rubber blends, effect of gamma irradiation on the thermal behavior of composites.
Dr. Daniel Pasquini (MSc, PhD) graduated in Chemistry from Federal University of Uberlândia (1998), master’s at Chemistry from University of São Paulo (2000) and doctorate at Chemistry from University of São Paulo (2004). Held sandwich-doctorate stage (2003) and Postdoctoral (2005) abroad at the EcoleFrançaise de Papeterieet des Industries Graphiques Grenoble, France. He worked as coordinator of Research and Development in Paints division in Research and Development laboratory in the Company AW Faber-Castell SA from 2004 to 2008. He served as Assistant Researcher at the University of Aveiro, in CICECO - Centre for Research in Ceramics and Composite Materials between 2008 and 2009. He is currently Associate Professor at the Chemistry Institute, Federal University of Uberlândia which is also accredited as a permanent member of the Graduate Program in Biofuels, at master and doctoral degrees. Currently develops projects related to the enhancement of plant macromolecules, chemical modification of these macromolecules, development of new materials derived from waste renewable sources for applications such as polymeric materials for various applications, such as composites, nanocomposites, nanofibers, nanoparticles and spherical membranes. He also works on projects related to the supply chain of Bioethanol and Biodiesel.
1
Polymer blends
State of art
G. Markovic¹, and P.M. Visakh² ¹Technical Rubber Goods, Pirot, Serbia ²Tomsk Polytechnic University, Tomsk, Russia
Abstract
Polymer blends have been intensively studied because of their theoretical and practical importance. A polymer blend/nanocomposite can be defined as a polymer-nanofiller system in which the inorganic filler is on a nanometric scale at least in one dimension and it can be a polymer/nanoparticle blend or a hybrid. Polymer blends are utilized in various applications based on their properties. The most wide-ranging definition of a hybrid is a material that includes two moieties blended on the molecular scale. Commonly the term hybrids is more often used if the inorganic units are formed in situ by the sol–gel process. Meanwhile, use of the word nanocomposites implies that materials consist of various phases with different compositions, and at least one constituent phase (for polymer/silica nanocomposites, that phase is generally silica) has one dimension less than 100 nm. Polymer blend nanocomposite systems can be prepared by various synthesis routes because of their ability to combine in different ways to introduce each phase. The characterization methods used in the analysis of the chemical structure, microstructure, and morphology as well as the physical properties of the nanocomposites are varied Polymer blend nanocomposites received significant attention because of the new and superior properties (eg, electrical, thermal, and mechanical) compared with conventional composites of these materials, and they may be synthesized using surprisingly simple and inexpensive techniques.
Keywords
Coefficient of thermal expansion; Differential scanning calorimetry; Dynamic light scattering; Organic light-emitting devices; Poly(vinyl alcohol); Poly(methyl methacrylate); Proton exchange membrane; Transmission electron microscopy
1.1. General background on polymer blend/nanofiller composites
Organic/inorganic composite materials have been extensively studied for a long time. When inorganic phases in organic/inorganic composites become nanosized, they are called nanocomposites. Organic/inorganic nanocomposites are generally organic polymer composites with inorganic nanoscale building blocks. They combine the advantages of the inorganic material (eg, rigidity, thermal stability) and the organic polymer (eg, flexibility, dielectric, ductility, and processability). Moreover, they usually also contain special properties of nanofillers leading to materials with improved properties. A defining feature of polymer nanocomposites is that the small size of the fillers leads to a dramatic increase in interfacial area as compared with traditional composites. This interfacial area creates a significant volume fraction of interfacial polymer with properties different from the bulk polymer even at low loadings [1].
A polymer blend is a mixture of two or more polymers that have been blended together to create a new material with different physical properties. Polymer blending has attracted much attention as an easy and cost-effective method of developing polymeric materials that have versatility for commercial applications. In other words, the properties of the blends can be manipulated according to their end use by correct selection of the component polymers [2].
Polymer blends have been intensively studied because of their theoretical and practical importance. In general, polymer blends are classified into either homogeneous (miscible on a molecular level) or heterogeneous (immiscible) blends. For example, poly(styrene) (PS)–poly(phenylene oxide) and poly(styrene-acrylonitrile)–poly(methyl methacrylate) (PMMA) are miscible blends, whereas poly(propylene) (PP)–PS and PP–poly(ethylene) (PE) are immiscible blends. Miscible (single-phase) blends are usually optically transparent and are homogeneous to the polymer segmental level. Single-phase blends also undergo phase separation that is usually brought about by variations in temperature, pressure, or in the composition of the mixture.
Fillers are typically used to enhance specific properties of polymers, and the polymer/nanocomposites based on nanoclays have gained attention because of their ability to improve the mechanical, thermal, barrier, and fire-retardant properties of polymers [3]. Nanosized fillers have been introduced in a wide spectrum of applications ranging from providing photocatalyst activation and conductivity to improve melting processability and moisture barrier properties. The special properties of nanoparticles are due to their size and high relative surface area-to-volume ratio. The optical clarity of a spherical nanosize particle is better than that of its equivalent conventional-size filler because the diameter is smaller than the wavelengths of light. Because a nanosize filler particle has a larger specific surface area than its analogous traditional-size filler particle, it interacts more with its surroundings [4].
Polymer blend/nanocomposites have been shown at lower or equal loadings to have properties that are equal or better than those of polymer composites with conventional filler. Inorganic nanoscale building blocks include nanotubes, layered silicates (eg, montmorillonite, saponite), nanoparticles of metals (eg, Au, Ag), metal oxides (eg, TiO2, Al2O3), semiconductors (eg, PbS, CdS), and so forth, among which SiO2 is viewed as being very important. The nanofillers featuring antibacterial properties, such as nanoscale titanium- and silver-based particles, could be applicable in filtration, hygiene, and hospital disposables applications or in consumer products. Thermodynamic stability of the polymer blend nanocomposite, which is due to the large interfacial phase between the matrix and the nanoparticle, yields the physical properties of the composite [5].
A polymer blend/nanocomposite can be defined as a polymer-nanofiller system in which the inorganic filler is on a nanometric scale at least in one dimension and it can be a polymer/nanoparticle blend or a hybrid. The composite interconnection can be based on a secondary force or physical entanglement [6]. In turn, the polymer/nanofiller hybrid is formed when the polymer and the nanoparticle are covalently bonded. The covalent bond can be formed during the in situ polymerization (the monomer or the growing polymer chain can react with the filler particle) or during the composite processing.
Uniform filler distribution in the polymer blend matrix is desired. It can be a challenge to create a favorable interaction between the polymer and the nanofiller, and thus avoid phase separation and agglomeration of the filler particles. An example is the natural layered clay; it delaminates completely in water and in some polar polymer melts or solutions such as in polyamide, but it does not spontaneously disperse in nonpolar polyolefin melts such as PP melt. Two possible options for improving the compatibility of the components will be examined here: chemically modifying one or more of the components or introducing a suitable compatibilizer.
1.2. Nanoparticles of the polymer composites
Nanoparticles exist in spherical, tube and whisker, and plate-like shapes and at least one of the three dimensions is required to be on a nanometric scale. Nanostructures of layered clays are further categorized as intercalated, in which the polymer chains have penetrated between the clay layers in a well-ordered multilayer morphology, and exfoliated, in which the clay layers have dispersed along the matrix and have no organized structure [7]. Carbon nanotubes also exhibit two nanostructures: single-walled nanotube and multiwalled nanotube, which is composed of several tubes within each other.
Similar to the conventional filler particles, nanoparticles can be prepared by breaking up a large particle (nanoclays and other minerals) or by building them from the bottom up (carbon nanotubes and metal oxides). Regardless of the preparation method, it is important to inhibit agglomeration of the nanoparticles and ensure good adhesion to the matrix. It is possible to coat or surface treat the nanosize particles [8] as done with microsize particles. A wide spectrum of polar agents (such as silanes and polyalcohols) and nonpolar agents (such as stearic acid and fatty acids) are commercially available coating agents for inorganic particles [9]. In contrast, layered nanoclays [10] and carbon nanotubes are surface treated.
Surface treatment of nanoclays, which typically involves cation exchange, promotes delamination of the clay sheets in the matrix. The cation, or alternatively the intercalated media between the clay layers, determines the interlayer space, the gallery, and the cation exchange capacity [11].
1.3. Functionalized polymer with nanoparticles
Polymer blends are utilized in various applications based on their properties. PP is used for its mechanical strength in consumer packages; poly(vinyl alcohol) is widely used for its water solubility and transparency in film applications on various paper and textile surfaces; and polyamide, in turn, is used for its good dimensional stability and chemical resistance in yarn applications [12].
Changes in a polymer’s structure can have a dramatic effect on its behavior, which is not always desired. Structure–property relationships can be illustrated by the following two examples: the solubility of poly(vinyl alcohol) is influenced by the degree of hydrolysis [13], and the moisture resistance of polyamide is dependent on the number of carbon atoms of the monomer used. The structure of a polymer can be modified by introducing functional groups to the polymer backbone and/or to the side chains [14] in various ways such as grafting [15] and using various different monomers in the polymerization reaction [16]. However, unwanted cross-linking and polymer degradation reactions can also be observed when postmodifying by melt-free radical grafting, which could be avoided by using polymerization techniques such as atomic transfer radical polymerization [17] and reversible-addition fragmentation chain transfer. For example, these offer intriguing new possibilities to produce the polymers and thereby polymer nanocomposites, such as initiating polymerization on the hydroxyl groups on the surface of a clay sheet. The monomers could be styrene, methyl methacrylate, or vinyl acetate [18]. In addition, developments in catalyst technology such as metallocene polyolefin polymerizations enable production of an excellent controlled comonomer distribution and stereospecificity along the polymer backbone or chain end [19].
If chemical treatment of the matrix polymer blend or the filler needs to be avoided or the interaction between the components is insufficient, then a third component, such as a polymer compatibilizer [20], can be added to the composite. Compatibilizers are added especially to polyolefin/nanoclay composites prepared by melt blending because the organo modification of the clay is seldom sufficient to create a favorable interaction between polymer chains and the clay sheets [21]. The interfacial adhesion between the compatibilizer and clay galleries is influenced by the functionality and its concentration, molecular weight and molecular weight distribution of the compatibilizer, and the mass ratio of the compatibilizer to the clay [22].
1.4. Composite material
It is necessary to make clear the terms hybrids and nanocomposites before the discussion of the nanocomposites because it is somewhat ambiguous to identify whether materials fall into nanocomposites or not. The most wide-ranging definition of a hybrid is a material that includes two moieties blended on the molecular scale. Commonly the term hybrids is more often used if the inorganic units are formed in situ by the sol–gel process. Meanwhile, use of the word nanocomposites implies that materials consist of various phases with different compositions, and at least one constituent phase (for polymer/silica nanocomposites, that phase is generally silica) has one dimension less than 100 nm. A gradual transition is implied by the fact that there is no clear borderline between hybrids and nanocomposites. Expressions of nanocomposites seem to be very trendy, and although the size of silica particles is greater than 100 nm, the composites are often called nanocomposites in some literature. Composites can be classified as particle-reinforced composites, in which particles are used as the reinforced phase, and fiber-reinforced composites, in which the reinforcing phase is in the form of fiber (Fig. 1.1). Fig. 1.1 illustrates the correlation among particle diameter, distance, and volume content.
The particle-reinforced composites can be further classified into large-particle composites and dispersion-strengthened composites on the basis of particle size [23].
In polymer blend matrix composites, the matrix phase is polymer blend and the reinforcing phase can be metals, fibers, or ceramic particles. They are being used in various medical applications and sensing applications.
The polymer blend composites can be classified into three categories:
1. Macrocomposites (10−² m): Polymer macrocomposites are heterogeneous composites of polymers and macrosized fillers. The macroscopic characteristics of the composite often reflect its own microstructure.
2. Microcomposites (10−⁶ m): Composites using micron size fibers with high aspect ratio or fine hollow spheres or fibers as reinforcement are called microcomposites. The matrix can be any polymer. The reinforcing phase will be a continuous fiber or short fiber or micron sized fillers such as metal particles. The main advantage of using fibers is to improve strength, stiffness, and thermal stability of composites.
3. Nanocomposites (10−⁹ m): Polymer nanocomposites usually comprise the composites of polymers with dispersed inorganic nanofillers. The nanofiller can be an insulator, a semiconductor, or a metal, and it can have spherical, cylindrical, or flake shapes. The polymer (matrix) can be conductive or nonconductive in nature.
Figure 1.1 Length scales involved in multiscale modeling.
The macroscopic characteristics of the composite often reflect its own microstructure. The properties of composites depend on the unique filler properties and on the morphology and interface features of the composite [24]. Such composites will exhibit interesting electric, optical, and magnetic properties. The characteristics of these systems depend on the compatibility of the constituents and the sizes of their contact surfaces. One of the challenges in preparing nanocomposite materials is to mix compatible and homogeneous nanofillers in a polymer matrix, guaranteeing or improving the matrix performance. With respect to manufacturing of polymeric nanocomposites, direct incorporation of inorganic nanoscale building blocks into polymers represents a typical way. However, because of the strong tendency of nanoparticles to agglomerate, nanosize fillers are hard to be uniformly dispersed in polymers by conventional techniques. The most important issue for producing nanocomposites lies in surface modification of the nanofillers. An ideal measure should be able to increase the hydrophobicity of the fillers, enhance the interfacial adhesion via physical interaction or chemical bonding, and eliminate the loose structure of filler agglomerates. In addition, the fragile nanoparticle agglomerates become stronger because they turn into a nanocomposite microstructure comprising the nanoparticles and the grafted and ungrafted (homopolymerized) polymer (Fig. 1.2).
A series of works has been done in this field of growing interest for the purposes of improving the dispersibility of nanoparticles in solvents and their compatibility in polymers [25]. Mostly, the graft polymerization is conducted via two routes: (1) monomers are polymerized from active compounds (initiators or comonomers). PMMA is a commonly used thermoplastic matrix for fibers, sheets, and particles. There have been several studies on PMMA-fiber composites prepared by in situ polymerization [26], solution mixing [27], or melt blending [28]. The last one is already an industrial process for fabricating carbon fiber-reinforced thermoplastic composites.
A combination of solvent casting and melt mixing allowed building composites with enhanced mechanical and electrical properties and exceptional fiber alignment [29]. Platelets and sheets also influence the composite’s thermal and mechanical properties in relation to the material’s composition and dispersion state within the matrix [30]. Musbah et al. [31] discovered that nanopowders of phosphors Y2O3 (Eu³+) embedded in a PMMA matrix, prepared using a laboratory mixing molder, influence almost linearly the optical and dynamic mechanical properties of the nanocomposites.
Figure 1.2 Schematic drawing of the structural change of nanoparticle agglomerates before and after graft polymerization treatment.
In fact, transmission electron microscopy (TEM) observation showed that the size of the dispersed phases increases with increasing filler content in the nanocomposites (Fig. 1.3). It should be noted here that the dispersed phases in the nanocomposites illustrated in Fig. 1.3(b)–(e) are clearly smaller than the untreated SiO2 (Fig. 1.3(a)), but they are still much larger than the size of the primary nano-SiO2 particles (7 nm). Therefore these dispersed phases are actually microcomposite agglomerates consisting of primary particles, grafting polymer, homopolymer, and a certain amount of matrix.
These results contribute to a further understanding of the modified nanoparticles and their role in the composites.
Figure 1.3 Transmission electron micrographs of poly(propylene)-based nanocomposites (MFI = 6.7g/10 mm) filled with (a) SiO 2 as received (content of SiO 2 = 1.96 vol%), (b) SiO 2 -g-poly(styrene) (PS; content of SiO 2 = 1.96 vol%), (e) SiO 2 -g-PS (content of SiO 2 = 6.38 vol%), (d) SiO 2 -g-poly(methyl methacrylate) (content of SiO 2 = 1.96 vol%), and (e) (content of SiO 2 = 6.38 vol%). Magnification = 2 × 104 [31] .
Scheme 1.1 Three general approaches to prepare polymer/silica nanocomposites.
1.5. Preparation of polymer blend/nanofiller composites
As pointed out by Hajji et al. [32], polymer blend nanocomposite systems can be prepared by various synthesis routes because of their ability to combine in different ways to introduce each phase. The organic component can be introduced as (1) a precursor, which can be a monomer or an oligomer; (2) a preformed linear polymer (in molten, solution, or emulsion states); or (3) a polymer network, physically (eg, semicrystalline linear polymer) or chemically (eg, thermosets, elastomers) cross-linked. The mineral part can be introduced as (1) a precursor (eg, tetraethyl orthosilicate) or (2) preformed nanoparticles. Organic or inorganic polymerization generally becomes necessary if at least one of the starting moieties is a precursor.
Regardless of the preparation method of the polymer nanocomposite, a good compatibility between the components is essential to produce a homogenous polymer nanocomposite [33]. Compatibility can be improved by selecting suitable external blending conditions, such as by adjusting the temperature and the mixing intensity [34] or by chemical modifications of the filler and/or the polymer, as mentioned earlier. For example, Scheme 1.1 shows the three general preparative methods of polymer/silica nanocomposites.
1.6. Characterization of polymer blend/nanocomposites
The characterization methods used in the analysis of the chemical structure, microstructure, and morphology as well as the physical properties of the nanocomposites are varied. Many of these techniques are specific for characterization of particular properties of nanocomposites, and the properties of nanocomposites are also correspondingly discussed. To fully understand the structure–property relationships, several characterization techniques are often used. The properties of the polymer blend nanocomposites strongly depend on their composition, size of the particles, interfacial interaction, etc [35].
Chemical structure: The chemical structure of polymer/filler nanocomposites is generally identified by Fourier transform infrared and solid-state spectroscopy [36].
Microstructure and morphology: Crystallization behaviors of the polymer nanoparticle-filled composites are usually studied by differential scanning calorimetry (DSC).
Mechanical properties: Because one of the primary reasons for adding inorganic fillers to polymers is to improve their mechanical performance, the mechanical properties of polymer nanocomposites are most concerned [37].
It is well known that one of the major requirements of polymer nanocomposites is to optimize the balance between the strength/stiffness and the toughness as much as possible. Therefore it is usually necessary to characterize the mechanical properties of nanocomposites from different viewpoints. Several criteria, including tensile strength, impact strength, flexural strength, hardness, fracture toughness, and so forth, have been used to evaluate the nanocomposites.
Tensile, impact, and flexural properties: Tensile test is the most widely used method to evaluate the mechanical properties of the resultant nanocomposites, accordingly. Young’s modulus, tensile strength, and elongation at break are the three main parameters obtained. These vary with the silica content, but the variation trends are different. Furthermore, the impact test is also widely used for mechanical property characterization.
Hardness: Hardness refers to the properties of a material resistant to various kinds of shape changes when force is applied. It is fundamental for many applications and is an important mechanical parameter of materials. There are three principal types of hardness: scratch hardness (resistance to fracture or plastic deformation due to friction from a sharp object), indentation hardness (resistance to plastic deformation due to impact from a sharp object), and rebound hardness (height of the bounce of an object dropped on the material). There are several different definitions of hardness, including Brinell hardness, Knoop hardness, Vickers hardness, Shore hardness, etc.
Fracture toughness: Fracture toughness is a property that describes the ability of a material containing a crack to resist fracture. It is also one of the most important properties of materials. A parameter called stress intensity factor is used to determine the fracture toughness of most materials. As the stress intensity factor reaches a critical value (KIc), unstable fracture occurs. This critical value of the stress intensity factor is known as the fracture toughness of the material. Fracture toughness can be measured by different methods, such as single-edge notch bend and indentation fracture toughness.
Friction and wear properties: Both friction and wear belong to the discipline of tribology. Friction is the force of two surfaces in contact or the force of a medium acting on a moving object, and wear is the erosion of material from a solid surface by the action of another solid. Factors that exert influence on friction and wear characteristics of polymer composites are the particle size, morphology, and concentration of the filler [38].
Thermal properties: Thermal properties are the properties of materials that change with temperature. They are studied by thermal analysis techniques, which include DSC, thermogravimetric analysis (TGA), differential thermal analysis (DTA), thermomechanical analysis (TMA), dynamic mechanical analysis (DMA)/dynamic mechanical thermal analysis (DMTA), dielectric thermal analysis, etc. As is well known, TGA/DTA and DSC are the two most widely used methods to determine the thermal properties of polymer nanocomposites. TGA can demonstrate the thermal stability, the onset of degradation, and the percentage of silica incorporated in the polymer matrix. DSC can be efficiently used to determine the thermal transition behavior of polymer/silica nanocomposites. Furthermore, the coefficient of thermal expansion (CTE), which is the criterion for the dimensional stability of materials, can be measured with TMA. In addition, thermal mechanical properties measured by DMA/DMTA are very important to understand the viscoelastic behavior of the nanocomposites. The storage modulus (G′), loss modulus (G″), and tan δ (G″/G′) are three important parameters of dynamic mechanical properties that can be used to determine the occurrence of molecular mobility transitions, such as the Tg. Dielectric thermal analysis is also useful to understand the viscoelastic behavior of the nanocomposites. In general, the incorporation of nanometer-sized inorganic particles into the polymer matrix can enhance the thermal stability by acting as a superior insulator and mass transport barrier to the volatile products generated during decomposition [39]. Meanwhile, the incorporation of nanometer-sized inorganic particles such as silica is very effective in decreasing the CTE of the polymer matrix.
Flame-retardant properties: A fire retardant is used to make materials harder to ignite by slowing decomposition and increasing the ignition temperature. It functions by various methods such as absorbing energy away from the fire or preventing oxygen from reaching the fuel. Polymer nanocomposites for flame-retardant applications are attractive, and the nanoscale silica particle is a new type of nanoparticle for flame-retardant nanocomposites [40].
The flammability behavior of polymer is defined on the basis of several processes or parameters, such as burning rates, spread rates, ignition characteristics, etc. Meanwhile, the flame-retardant characteristics of the nanocomposites are generally studied by measuring their limiting oxygen index (LOI). The LOI is defined as the minimum fraction of O2 in a mixture of O2 and N2 that will just support flaming combustion. Furthermore, the UL-94 test (Underwriter’s Laboratory Test #94) is conducted to quantify and rank the flame retardance of the materials. The UL-94 covers two types of testing: vertical burn and horizontal burn. The vertical burning test uses a Bunsen burner as the ignition source, and specimens are classified according to their burning times as V0 (best), V1, V2, or nonclassifiable (fail).
The horizontal burning test is less severe, and specimens are classified as HB or fail accordingly. The horizontal burning test is also used to evaluate the fire-spread rate of materials by giving fire travel information on the horizontal surface, including fire-spread rate, burning behavior, and ease of extinction if the material burns
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