Clay-Containing Polymer Nanocomposites: From Fundamentals to Real Applications

Clay-Containing Polymer Nanocomposites

From Fundamentals to Real Applications

Suprakas Sinha Ray

Council for Scientific and Industrial Research, Pretoria, Gauteng, South Africa

King Abdulaziz University, Jeddah, Kingdom of Saudi Arabia

Table of Contents

Cover image

Title page

Copyright

Dedication

Preface

About the Author

1. An Overview of Pure and Organically Modified Clays

1.1 Introduction

1.2 Structure and Properties of Clays

1.3 Structure and Properties of Organically Modified Clays

1.4 Conclusions

References

2. Thermodynamics, Molecular Modeling, and Kinetics of Nanocomposite Formation

2.1 Introduction

2.2 Types of Nanocomposites

2.3 Preparation Methods

2.4 Conclusions

References

3. Structure and Morphology Characterization Techniques

3.1 Introduction

3.2 X-Ray Diffraction

3.3 Small-Angle X-Ray Scattering

3.4 Transmission Electron Microscopy and Electron Tomography

3.5 Scanning Transmission Electron Microscope

3.6 Scanning Electron Microscopy and Focused-Ion-Beam SEM

3.7 Atomic-Force Microscopy

3.8 Optical Microscopy

3.9 Nuclear Magnetic Resonance

3.10 Infrared Spectroscopy

3.11 Conclusions

References

4. Processing and Characterization

4.1 Introduction

4.2 Processing Techniques and a Morphological Study

4.3 Conclusions

References

5. Mechanical Properties

5.1 Introduction

5.2 Theoretical Aspects

5.3 Tensile Properties

5.4 Dynamic Mechanical Analysis

5.5 Flexural Properties

5.6 Heat-Distortion Temperature

5.7 Conclusions

References

6. Barrier Properties

6.1 Introduction

6.2 Theoretical Aspects

6.3. Overview of Barrier Properties

6.4 Conclusions

References

7. Thermal Stability

7.1 Introduction

7.2 Overview of Thermal Stability

7.3 Conclusions

References

8. Fire-Retardant Properties

8.1 Introduction

8.2 Overview of Flame-Retardant Properties

8.3 Conclusions

References

9. Crystallization Behavior, Morphology, and Kinetics

9.1 Introduction

9.2 Differential Scanning Calorimetry and the Thermodynamics of Melting

9.3 Development of New Crystals or a Change of Crystal Structures

9.4 Crystal Growth and Crystallization Kinetics

9.5 Conclusions

References

10. Melt-State Rheology

10.1 Introduction

10.2 Steady-Shear Rheology

10.3 Dynamic Oscillatory Properties

10.4 Extensional Rheology

10.5 Conclusions

References

11. Foam Processing

11.1 Introduction

11.2 Preparation, Characterization, and Properties of Nanocomposite Foams

11.3 Conclusions

References

12. Real and Potential Applications

References

13. Concluding Remarks and Future Outlook

13.1 Concluding Remarks

13.2 Future Outlook

Index

Copyright

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First edition 2013

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Dedication

Dedicated to my family

Preface

Since the end of the last decade, much research and development effort has emerged in addressing hybrid organic–inorganic systems; particular attention has been given to those systems in which nanofillers are dispersed in polymer matrices. This class of materials called polymer nanocomposites, shows unique value-added properties that are completely absent in neat matrices and conventional composites. Researchers believe that the interaction between the filler and matrix at the nanoscale is the basis for new and unique properties of the nanocomposites, as opposed to conventional composites.

Nanofillers can be made from a wide range of materials, the most common being clays (or layered silicates), carbon nanotubes, polyhedral oligomeric silsesquioxanes, metals, metal-oxide ceramics, and metal-nonoxide ceramics. Recently, other materials have been used for nanofillers, such as polymers and compound semiconductors. However, the former class of materials is used for the majority of polymer nanocomposite applications.

During the past few years, all types of nanofillers have been used for the preparation of composites with almost all types of polymer matrices. However, clay-containing polymer nanocomposites (PNCs) have attracted great interest in today’s materials research, because these substances can significantly enhance nanocomposite properties, especially when compared with those of a neat polymer [1–4]. These improvements may include high moduli; increased strength, flexibility, and heat resistance; decreased gas permeability and flammability; increased rate of crystallization; and enhanced rheological properties.

The most generally used clays for the preparation of PNCs belong to the general family of phyllosilicates, that is, layered or sheetlike structures more commonly referred to as layered silicates. In this subclass, rings of tetrahedrons are linked by shared oxygen atoms to other rings in a two-dimensional plane that produces a sheetlike structure. The best-known member in this family is montmorillonite (MMT), a natural phyllosilicate extracted from bentonite. Therefore, this book focuses on PNCs based on layered-silicate-type clays.

The mixing of clay particles with polymer matrices to form nanocomposites appears to have begun in the late 1940s [5], with a resurgence in the early 1960s with the patent application from Nahim and Backlund [6]. During the same period, the first research articles appeared on this topic [7–9]. In the early 1990s, two major findings stimulated the revival of great interest in these materials: First, a Toyota research group studying Nylon 6–MMT nanocomposites [10, 11] reported that very small amounts (~ 5 vol %) of organically modified MMT loadings resulted in pronounced improvements in mechanical, thermal, and barrier properties; second, Vaia, Ishii, and Giannelis [12] reported that it is possible to melt mix polymers with clay without the use of organic solvents. Today, efforts are being conducted globally, using almost all types of clays and polymer matrices.

One could argue that PNCs are part of a boom that includes other areas of nanoscience and nanotechnology, but there is more work to be conducted [13]. Not every physical mixture of polymer and clay leads to the formation of a PNC. The fundamental understanding of the interfacial interaction between a polymer chain and clay surface at the nanoscale has tremendous implications for the performance and final properties of the obtained nanocomposite material. Therefore, the study of PNCs is not simply about capturing the buzz from nanoscience and nanotechnology; it is about understanding the associated interfacial science and structure–property relationships at the molecular and macromolecular level [13].

During PNC formulation, the nanolevel dispersion of clay particles is the single most important characteristic to achieve to generate a high interfacial or surface area for polymer–clay interactions, improved cooperative phenomena among dispersed particles, and a strong confinement effect. In the case of nonpolar polymer matrices, the primary challenge is to find the right chemistry to provide the best thermodynamic driving force to disperse clay platelets at the nanolevel. To this end, researchers are currently using two approaches. One approach involves the incorporation of functionality into a polymer matrix by grafting, copolymerization, or blending with other polymers. Another approach is the functionalization of clay surfaces to improve compatibility with polymer matrices. Moreover, in the case of nanoclays that have a layered structure, researchers are using ion-exchange chemistry to decrease the inherent van der Waals forces among silicate layers and thereby improve the delamination of silicate platelets in polymer matrices.

Among the preparation methods currently being used, melt blending or melt extrusion is considered a promising approach for the fabrication of PNCs due to its versatility, compatibility with current polymer processing equipment, and environmental friendliness, because no solvents are used. However, to optimize melt-processing conditions, it is essential to have a nanolevel dispersion of clay platelets. Additionally, the processing method and regime should have minimal adverse effects on the polymer matrix or surface-modified clay; that is, the degradation of both components should be avoided.

Furthermore, to establish a structure–property relationship, a certain qualitative measure of the degree of clay platelet dispersion in the polymer matrix is necessary. However, researchers face challenges when analyzing the true dispersion state of clay platelets in PNCs. Therefore, a qualitative understanding of the dispersion state of clay platelets in a PNC is very important.

Recently, the worldwide demand for PNCs has rapidly increased in advanced packaging, automotive, construction, and other industries due to superior barrier, thermal, mechanical, and other properties of PNCs. The development of industries related to PNCs possessing enhanced features and expanding research activities in the development of new PNCs are some of the factors that may drive the PNC market in the coming years (projected growth rate 56%). Currently, the most publicized applications of PNCs are those in the automotive sectors, such as timing belt covers (Toyota Motor Corporation) and exterior step assists (General Motors). Another extensive application of PNCs is in barrier materials. Though a number of PNC-based commercial products are available in the market, many of these have not yet been reported in the literature extensively.

Although structural characterization, physical and mechanical properties, processing, and commercial applications of various types of PNCs are widely published in peer-review journals, patents, conference proceedings, and edited books, to the best of our knowledge, no single book consolidates knowledge on these areas in a concise form. A single book of this nature, covering material from fundamental aspects to real applications, serves as a very useful reference for both undergraduate and postgraduate students, academic researchers, engineers, and other professionals interested in this exciting field of research. This book also helps industrial researchers and R&D managers who want to bring advanced polymer-based products into the market.

This book comprises 13 chapters that highlight recent developments in PNCs and discuss their potential applications and future outlook. Following an overview of pure and organically modified clays (Chapter 1), Chapter 2 discusses the thermodynamics, molecular modeling, and kinetics of PNC formation. Chapter 3 is dedicated to the techniques generally used to characterize the structure and morphology of PNCs and their drawbacks. PNC processing and characterization are described in Chapter 4. Chapters 5 to 8 focus on various properties of PNCs. The effects of the incorporation of clay particles on polymer crystallization behavior and kinetics are summarized in Chapter 9, and Chapter 10 is dedicated to the melt-state rheological behavior of PNCs. A brief summary of the foam processing of PNCs is presented in Chapter 11. Chapters 12 and 13, respectively, summarize the practical uses of PNCs and provide deep insight into the future direction of the field.

I express my sincerest appreciation to all colleagues, postdoctoral fellows, and students for their valuable contributions as well as the reviewers for their critical evaluation of the proposal and manuscripts. I also thank all authors and publishers for their permission to reproduce their published works. My special thanks go to L. Hutchins, K. Marinakis, A. Koch, and R. Mohanapriyan at Elsevier Science for their cooperation, suggestions, and advice during the various phases of preparation, organization, and production of this book. Finally, I thank my wife Dr. Jayita Bandyopadhyay and my son, Shariqsrijon Sinha Ray, for their tireless support and encouragement.

References

1. Sinha Ray S, Okamoto M. Polymer/layered silicate nanocomposites: a review from preparation to processing. Progn Polym Sci. 2003;28:1539–1641.

2. Sinha Ray S, Bousmina M. Biodegradable polymers and their layered silicate nanocomposites: in greening the 21st century materials world. Prog Mater Sci. 2005;50:962–1079.

3. Pavlidou S, Papaspyrides CD. A review on polymer-layered silicate nanocomposites. Prog Polym Sci. 2008;33:1119–1198.

4. Paul DR, Robeson LM. Polymer nanotechnology: nanocomposites. Polym. 2008;49:3187–3204.

5. Carter LW, Bolley DS. Elastomer reinforced with a modified clay. US Patent No. 2531396, 1950.

6. Nahim PG. Light weight rubber composition containing clay. US Patent No. 3084117, 1963.

7. Blumstein A. Étude des polymérisations en couche adsorbée. Bull Soc Chem France. 1961;98:899–906.

8. Dekking HGG. Propagation of vinyl polymers on clay surfaces I Preparation, structure, and decomposition of clay initiators. J Appl Polym Sci. 1965;9:1641–1651.

9. Friedlander HZ, Frink CR. Organized polymerization III Monomers intercalated in montmorillonite. J Polym Sci B Polym Lett. 1964;2:475–479.

10. Okada A, Kawasumi M, Usuki A, Kojima Y, Kurauchi T, Kamigaito O. Nylon 6-clay hybrid. Mater Res Soc Sympo Proc. 1990;171:45–50.

11. Okada A, Usuki A. Twenty years of polymer-clay nanocomposites. Macromol Mater Eng. 2006;291:1449–1476.

12. Vaia RA, Ishii H, Giannelis EP. Synthesis and properties of two-dimensional nanostructures by direct intercalation of polymer melts in layered silicates. Chemf Mater. 1993;5:1694–1696.

13. Morgan AB, Wilkie CA. Flame retardant polymer nanocomposites. Hoboken, NJ: John Wiley & Sons; 2007.

About the Author

Suprakas Sinha Ray is one of the most active and highly cited authors in the field of polymer nanocomposite materials. Recently, was rated one of the top 50 high-impact chemists in the world (February 2011,Thomson Reuter). Professor Sinha Ray is author and coauthor of 10 book chapters and 145 articles in international journals, as well as the holder of several patents.

1

An Overview of Pure and Organically Modified Clays

1.1 Introduction

Clay has been known and used by us for a very long time and recently became an indispensable part of modern living, as used in the form of porcelain, bricks, tiles, and sanitary ware and as an essential constituent of plastics, paints, paper, rubber, cosmetics, and medicine. The term clay is difficult to define exactly. The joint nomenclature committees (JNCs) of the Association Internationale pour l’Etude des Argiles and the Clay Minerals Society jointly define clay as a naturally occurring material composed primarily of fine-grained minerals, which is generally plastic at appropriate water contents and will harden when dried [1]. According to this definition, synthetic clays and claylike materials are not regarded as clay. On the other hand, clay mineral is generally defined as a class of hydrated phyllosilicates making up the fine-grained fraction of rocks, sediments, and soils. According to the JNCs, clay minerals are phyllosilicate minerals which impart plasticity to clay and harden upon drying or firing. Because the origin of the material is not part of the definition, a clay mineral can be synthetic. The distinction between clay and clay mineral can be found in Table 1.1 [1]. In nanocomposite preparation, it is mainly clays that have been used, with few reports on clay mineral–containing polymer nanocomposites. Therefore, the main objective of this chapter is to summarize the structure and properties of pure and organically modified clays.

Table 1.1

Distinction between Clay and Clay Mineral

1.2 Structure and Properties of Clays

Over the last decade, various types of nanofillers have been used for the preparation of composites with almost all types of polymer matrices. However, polymer nanocomposites based on clays attract great interest in today’s materials research because it is possible to achieve impressive property enhancements when compared with neat polymers or conventional filler-filled composites [2]. These improvements may include high moduli, increased strength and heat resistance, decreased gas permeability and flammability, and the increased degradability of biodegradable polymers [2, 3]. In addition, there has been considerable interest in theory and simulations addressing the preparation and properties of these materials, which are also considered to be unique model systems, to study the structure and dynamics of polymer chains in confined environments [4–9]. Moreover, clays are naturally abundant, economical, and more important, benign to the environment [3].

Among all minerals, silicates constitute the largest and most interesting and complex class of minerals available on earth. Approximately 30% of all minerals are silicates, and some geologists estimate that 90% of the earth’s crust is composed of silicates [10]. With oxygen and silicon being the two most abundant elements in the earth’s crust, the abundance of silicates is no real surprise. The basic chemical unit of silicates is SiO4, a tetrahedron-shaped anionic group with a charge of −4. Silicates can be divided into three main categories and many subcategories, Figure 1.1. The central silicon ion has a charge of + 4, while each oxygen has a charge of −2; thus, each silicon-oxygen bond is equal to one half of the total bond energy of oxygen. This condition leaves the oxygen with the option of bonding to another silicon ion and, therefore, linking one SiO4 tetrahedron to another and another and so forth. The complex structures that these silicate tetrahedrons form are truly amazing. They can form single units (known as nesosilicates), double units (known as sorosilicates), chains (known as inosilicates), sheets (known as phyllosilicates), rings (known as cyclosilicates), and framework structures (known as tectosilicates) [10]. The different ways that silicate tetrahedrons combine is what makes the silicate class the largest, most interesting, and most complex class of minerals.

Figure 1.1 Main categories and subcategories of silicates.

Clays are found mixed or associated with other minerals and amorphous materials. The identification of clays in a raw clay or soil always requires a purification step. This is because the presence of carbonates, iron oxides, organic materials, and the like interferes with the identification procedure. Purification is very important for the application of clays in the manufacture of polymer nanocomposites. Purification is also important for studying the properties of clays as well as other applications. A general method for obtaining purified clays is fractionation by sedimentation after the removal of carbonates, hydroxides, and organic materials [1]. However, 100% pure clay may be achieved only at the laboratory scale rather than at an industrial scale. Even then, no more than 90% enrichment is usually achievable.

The most generally used clays for the preparation of polymer nanocomposites belong to the family of phyllosilicates, that is, layered or sheetlike structures more commonly referred to as layered silicates (LSs). In this subclass, rings of tetrahedrons are linked by shared oxygen atoms to other rings on a two-dimensional plane that produces a sheetlike structure (refer to Figure 1.2). The silicon-to-oxygen ratio is generally 1:2.5 (or 2:5) because only one oxygen atom is exclusively bonded to the silicon and the other three are half-shared to other silicon atoms. The symmetry of the members of this group is controlled chiefly by the symmetry of the rings but is usually reduced to a lower symmetry by other ions and other layers. The typical crystal habit of this subclass is, therefore, flat, platy, and booklike and always displays good basal cleavage (refer to Figure 1.3) [11]. Table 1.2 lists some common members of the phyllosilicate class.

Figure 1.2 Structure of phyllosilicates. Source: Adapted from Amethyst Galleries, Inc. web site, accessed on April 18, 2006, with permission [10].

Figure 1.3 Structure of a montmorillonite basic crystal unit and its morphological variations from a perfect hexagonal habit. Source: Reproduced from Yalcin and Cakmak [11] by permission of Elsevier Science Ltd.

Table 1.2

Some Common Members of the Phyllosilicates

The thickness of each layer or sheet is around 1 nanometer, and the lateral dimensions of these layers may vary from 30 nanometers to several microns or larger, depending on the particular layered silicate. The stacking of these layers leads to a regular van der Waals gap between the layers, called the interlayer or gallery. The layer surface has 0.25 to 0.9 negative charges per unit cell and various types of exchangeable cations within the interlayer galleries. Isomorphic substitution within the layers, for example, the replacement of Al+ 3 by Mg+ 2 or Fe+ 2 or the replacement of Mg+ 2 by Li+ 1, generates negative charges that are counterbalanced by alkali and alkaline earth cations situated inside the galleries. This type of layered silicate is characterized by a moderate surface charge known as the cation exchange capacity (CEC) and is generally expressed as mequiv/100 gm. This charge is not locally constant but varies from layer to layer and must be considered as an average value over the whole crystal.

Layered silicates have two types of structures: tetrahedrally substituted and octahedrally substituted. In the case of tetrahedrally substituted layered silicates, the negative charge is located on the surface of the silicate layers, and hence, the polymer matrices can react–interact more readily with those than with octahedrally substituted material. Most layered silicates are chemically and structurally analogous to each other but contain varying amounts of water and allow for a greater degree of substitution of their cations [10].

Clays are the most important minerals within the layered silicate or phyllosilicate family and generally contain huge percentages of trapped water molecules inside their silicate galleries [10]. Most of them are chemically and structurally analogous to each other but contain varying amounts of water and allow for a greater degree of substitution of their cations [10]. Generally, clay minerals are divided into three major groups:

1. Kaolinite group. Kaolinite, dickite, and nacrite are the main members of this group. The general chemical formula of these members is Al2Si2O5(OH)4. All members have the same chemistry but differ in structure. This property is generally known as polymorphism. The general structure of this group is composed of silicate sheets bonded to aluminum oxide–hydroxide layers called gibbsite layers [10].

2. Smectite group. This group consists of several layered silicate minerals, the most important of which are vermiculate, saponite, hectorite, montmorillonite, talc, sauconite, and nontronite. The general formula of these members is (Ca, Na, H)(Al, Mg, Fe, Zn)2(Si, Al)4O10(OH)2-xH2O, where x represents the variable amount of water that members of this group contain. In this group, the gibbsite layers of the kaolinite group are replaced by a similar layer, known as oxide brucite, Mg2(OH)4. The structure of this group is composed of silicate layers with a brucite layer sandwiched in between, and water molecules are present between the sandwich layers [10].

3. Illite or mica–clay group. Minerals in this group are basically hydrated microscopic muscovites. Muscovite is a common rock-forming mineral found in igneous, metamorphic, and detrital sedimentary rocks. The general formula of this mineral is (K, H)Al2(Si, Al)4O10(OH)2-xH2O, where x represents the variable amount of water that members of this group contain, and the structure of this group is similar to that of the smectite group [10].

Among the three major groups, smectite types, or more precisely montmorillonite, saponite, and hectorite, are the most commonly used clays in the field of polymer nanocomposites. Their chemical formula and characteristic parameters are summarized in Table 1.3. Again, among montmorillonite, saponite, and hectorite, montmorillonite (MMT) is the most commonly used layered silicate for the fabrication of nanocomposites, because it is highly abundant and inexpensive. MMT is the name given to the layered silicate found near Montmorillon in France, where MMT was first identified by Knight in 1847 [10].

Table 1.3

Chemical Formula and Characteristic Parameters of the Most Commonly Used Clays

M, monovalent cation; x, degree of isomorphous substitution (between 0.5 and 1.3).

The specific surface area of MMT is equal to 750–800 m²/g, and the modulus of each MMT sheet is approximately 178 − 220 GPa [12]. The interlayer thickness of hydrated MMT is equal to 1.45 nm, and its average density is ρ = 2.385 g/ml. Drying MMT at 150°C reduces the gallery height to 0.28 nm, which corresponds to a water monolayer; hence, the interlayer spacing decreases to 0.94 nm and the average density increases to 3.138 g/ml. Various properties of MMT are tabulated in Table 1.4 and the unit structure is presented in Figure 1.4.

Table 1.4

Physical Characteristics of Montmorillonite Clay

Source: This table has been prepared on the basis of information found in the Amethyst Galleries, Inc. website [10].

Figure 1.4 Unit crystal structure of montmorillonite. Source: Reproduced from Yalcin and Cakmak [11] by permission of Elsevier Science Ltd.

Although MMT is highly abundant and inexpensive, it is a mineral with variable composition, which makes it impossible to purify MMT completely. For this reason, there is a growing interest to use fully or semi-synthetic layered silicates for the preparation of nanocomposites; they have well-controlled physical and chemical properties. One of the most commonly used synthetic layered silicates in polymer nanocomposite (PNC) technology is synthetic fluorine hectorite (SFH). SFH is generally synthesized by heating a mixture of talc and Na2SiF6 in an electric furnace for several hours. Like MMT, SFH belongs to the same general family of 2:1 layered or phyllosilicates. The only difference between MMT and SFH is that SFH (NaMg2.5(Si4O10)F2) contains F groups on its surface. SEM and TEM (transmission electron microscope) images of pure MMT and SFM are presented in Figure 1.5.

Figure 1.5 Scanning and transmission electron microscopy images of pure montmorillonite (MMT) and synthetic fluorine mica (SFM).

Two particular characteristics of clays are generally considered for the preparation of PNCs. The first is the ability of the silicate particles to disperse into individual layers. The second characteristic is the ability to fine-tune their surface chemistry through ion-exchange reactions with organic and inorganic cations. These two characteristics are interrelated, of course, because the degree of dispersion of layered silicates in a particular polymer matrix depends on the interlayer cation.

The physical mixture of a polymer and clay may not always form a nanocomposite. This situation is analogous to that of immiscible polymer blends, and in most cases, separation into discrete phases takes place. In immiscible systems, which typically correspond to more conventionally filled polymers, the poor physical interaction between the organic and the inorganic components leads to poor mechanical and thermal properties. In contrast, strong interactions between the polymer and the clay in PNCs lead to the organic and inorganic phases being dispersed at the nanometer level. As a result, nanocomposites exhibit unique properties not shared by their micro counterparts or conventionally filled polymers [2].

1.3 Structure and Properties of Organically Modified Clays

Purified pristine layered silicates usually contain hydrated Na+ or K+ ions [13]. Obviously, in this pristine state, layered silicates are miscible only with hydrophilic polymers, such as poly(ethylene oxide) (PEO) [14] or poly(vinyl alcohol) (PVA) [15]. To render silicate particles miscible with other polymer matrices, one must convert the normally hydrophilic silicate surface to an organophilic one, making the intercalation of many engineering polymers possible. Generally, this can be performed by ion-exchange reactions with cationic surfactants including primary, secondary, tertiary, and quaternary alkyl ammonium or alkylphosphonium cations. MMT containing Na+ or K+ is dispersed in water; its silicate layers swell uniformly, and the extent of the swelling is approximately 30%. Now, if an alkyl-ammonium or –phosphonium salt is added to that aqueous dispersion, the surfactant ions are exchanged with the intergallery cations. This ion-exchange reaction leads to the formation of an organophilic clay, where alkyl-ammonium or –phosphonium cations are intercalated between the layers and the intergallery height increases [16]. By changing the length or type of alkyl chain or adding some polar groups, the hydrophilicity–hydrophobicity and other characteristics of the clay can be adjusted such that the modification of the clay surface is possible.

A representative commercial method for the preparation of organophilic MMT (CEC = 110 meq/100 g; OMMT) by using octadecyl ammonium chloride is described here. The alkyl ammonium cation (it may be primary, secondary, quaternary, or tertiary) is dissolved in a 50:50 mixture of ethanol and deionized water at 50 to 70°C. In the case of primary amines, an equivalent amount of HCl is generally added to the solution. A 1 wt % aqueous suspension of the MMT is added to the alkylammonium solution, and the mixture is stirred for 5–6 h at 70°C. The cation-exchanged silicates are collected by filtration and subsequently washed with a mixture of hot ethanol and deionized water until a silver nitrate test indicates the absence of halide anions. The filter cake is dried at room temperature, ground, and further dried at 70–80°C under vacuum for at least 24 h [17]. Table 1.5 summarizes various types of commercially available OMMTs generally used for the preparation of PNCs. Table 1.6 lists the chemical structure and abbreviations of the most commonly used surfactants.

Table 1.5

Physical Properties of Commercially Available Organically Modified Layered Silicates

CEC = cation-exchange capacity.

Table 1.6

Chemical Structure of the Most Commonly Used Surfactants for the Modification of Layered Silicates

Alkylammonium or alkylphosphonium cations (refer to Table 1.6) in the organosilicates lower the surface energy of the inorganic host, improve the wetting characteristics of the polymer matrix, and result in a larger interlayer spacing. Additionally, the alkylammonium or alkylphosphonium cations can provide functional groups that can react with the polymer matrix or, in some cases, initiate the polymerization of monomers to improve the strength of the interface between the inorganic and the polymer matrix.

Traditional structural characterization to determine the orientation and arrangement of the alkyl chain was performed by Lagaly in 1986 using X-ray diffraction (XRD) [18]. Depending on the packing density, temperature, and alkyl chain length, the chains were thought to lay either parallel to the silicate layers, forming mono- or bilayers, or radiate away from the silicate layer’s forming mono- or bimolecular arrangements, as described in Figure 1.6 [19–21]. Such idealized structures, based almost exclusively on all-trans segments, are potentially misleading, because they fail to convey the most significant structural characteristics of aliphatic chains—the capacity to assume an enormous array of configurations because of the relatively small energy difference between trans and gauche conformers (0.6 kcal/mol, 2.5 kJ/mol) [22]. Vaia and Giannelis [17] proposed an alternative arrangement, based on a disordered chain configuration containing numerous gauche conformers, which is consistent with the observed gallery height, Figure 1.7. These arrangements, however, indistinguishable by XRD, lead to a very different interlayer structures and molecular environments.

Figure 1.6 Alkyl chain aggregation in mica-type silicates: (a) lateral monolayer; (b) lateral bilayer; (c) paraffin-type monolayer; (d) paraffin-type bilayer. Source: Reproduced from Vaia and Giannelis [17] by permission of the American Chemical Society.

Figure 1.7 Different chain arrangements leading to the same gallery height: (a) tilted, all-trans chains and (b) chains with numerous gauch conformers.

Open circles (ο) represent CH segments, while cationic head groups are represented by filled circles (•). Source: Reproduced from Vaia anhd Giannelis [17] by permission of the American Chemical Society.

According to the Jordan [21], when the area that would be occupied by the amphiphilic ion lying flat on a surface is less than the area per unit negative charge on the surface, the amphiphilic ions are adsorbed in a monolayer, with the molecules lying approximately parallel to the platelet surface. As the charge on the silicate surface increases, the amphiphilic cations first form a flat bilayer, then become increasingly tilted. Bilayer complexes for a given clay and a homologous series of N-alkylammonium cations show a regular increase in the spacing per carbon atom, with differences sometimes, but not always, occurring between even- and odd-numbered carbon chains [22].

To understand the layering behavior and structure of confined quaternary alkylammoniums in the two-dimensional layered silicate galleries, Zeng et al. [23] performed isothermal–isobaric molecular dynamics simulations. Their work was focused on systems consisting of two silicate layers and a number of alkylammoniums and involved the use of a modified Dreiding force field. The results clearly demonstrate the layering behavior of the surfactant chains within the interlayer space of the MMT. A pseudo-quadrilayer structure is observed, and the alkyl chains in each layer adopt an orientation in which their longest axis is approximately parallel to the MMT surface. The positive-charge head groups of surfactant chains are found close to the MMT layers. The methyl carbon atoms observed in the middle layers are mainly attributed to the tail methyls in the long alkyl chains. Their simulated results show that an all-trans conformation is difficult to realize. Therefore, idealized structural models, such as pseudo-trilayers and paraffin-type monolayers and bilayers, do not directly reveal the significant structural characteristics of alkyl chains.

These simulated results, however, are consistent with a study by Vaia et al. [17] performed using Fourier-transform infrared (FTIR) spectroscopic techniques. They showed that alkyl chains can vary from being liquidlike to solidlike, with the liquidlike structure dominating as the interlayer density or chain length decreases or as the temperature increases. This occurs because of the relatively small energy differences between the trans and gauche conformers; the idealized models described earlier assume all-trans conformations. A schematic drawing of these conformations is shown in Figure 1.8. In addition, for longer-chain-length surfactants, the surfactants in the layered silicate can show a thermal transition akin to melting or liquid-crystalline to liquidlike transitions on heating. In addition, an NMR (nuclear magnetic resonance) study reported by Wang et al. indicated the coexistence of ordered trans and disordered gauche conformations [24].

Figure 1.8 Alkyl chain aggregation models for FH-C.

As the number of carbon atoms increases, the chains adopt n more ordered structure. For the shortest lengths (a), the molecules are effectively isolated from each other. At intermediate lengths (b), quasidiscrete layers form with various degrees of inplane disorder and interdigitation between the layers. For longer lengths (c), interlayer order increases leading to a LC environment. Open circles (ο) represent CH2 segments, while cationic head groups are represented by filled circles (•). The top silicate layer has been left transparent to improve the perspective of the interlayer. Source: Reproduced from Vaia and Giannelis [17] by permission of the American Chemical Society.

In the same vein, Williams-Daryn and Thomas [22] studied the dimensions of the interlamellar space following the intercalation of a range of cationic surfactants and monitored the subsequent swelling of the organoclay compounds with several organic solvents. They used Eucatex vermiculite, which has a much lower cation-exchange capacity than MMT. To test the effect of surfactant charge on the intercalation process, they used Gemini surfactants, which comprise two N-alkyldimethylammonium bromide groups joined together by an alkyl spacer and with the general formula (CnN(CH3)2Br)2X (CnCmCn), where n = number of carbons in the free N-alkyl chain and X is the bridging alkyl group containing m carbon atoms. The important difference between Gemini surfactants and the other surfactant series described previously is that the Geminis carry a double charge and provide the opportunity to test the effect of surfactant charge on the intercalation process. The bridging groups in the authors’ study were N-alkylene chains of varying lengths (C3–C12) as well as the rigid xylyl group. The X-ray diffraction patterns of various samples are presented in Figure 1.9. The C12C4C12 and C12C6C12 samples in particular have very sharp diffraction patterns, while the C12(xylyl)C12, with its rigid spacer, appears to be the least ordered.

Figure 1.9 X-ray diffraction patterns of oriented crystals of complexes of Gemini surfactants with Eucatex vermiculite at 25° C: (a) C12xylylC12 and (b) C12C6C12. Source: Reproduced from Williams-Daryn and Thomas [22] by permission of Elsevier Science Ltd.

Based on the XRD results, three possible conformations are sketched in idealized form in Figure 1.10. These assume that the N-alkyl chains and spacer adopt the all-trans conformation. In reality, gauche defects will most likely intervene to create a less rigid and ordered structure and, hence, to optimize the packing. The key point about the structures shown is that, because of the presence of two cationic entities on each surfactant, the surfactants have some freedom in how they interact with the clay surface. They can attach to either one or two negative surface charges along the same surface; they can also act as a bridge between two surfaces (model (c)), or as in model (b), only one of the two charges need be directly attached to the clay with the other existing as an ion pair.

Figure 1.10 Three possible arrangements of Gemini surfactant chains in the interlamellar space of complexes of Geminis with Eucatex vermiculite.

In (a), the spacer lies flat on the surface to optimize the contact between the two head groups and the surface; in (b), one head group is left floating in the interlamellar space; and in (c), the spacer is long enough to bridge the gap between the platelets. Source: Reproduced from Williams-Daryn and Thomas [22] by permission of Elsevier Science Ltd.

The average charge separation on the clay surface is 9.4 Å, and the standard values for the fully extended spacer lengths indicate that, in C12C3C12, C12C4C12, and C12(xylene)C12, they are too short to adopt the structure shown in model (a), Figure 1.10 [22]. However, a less homogeneous distribution of surface charge might allow for this structure to be formed, as would the formation of an ion pair by one of the charged head groups. If each molecule carried one ion pair, the fractional filling by charge-neutralizing species would be 0.5, and the value for C12C3C12 is not much higher than this. This is the most probable structure for the short-spacer Geminis. It is worth noting that, when Geminis are adsorbed at the air–water interface, there are indications that they are often bound to one Br anion; that is, on average, they consist of one unpaired head group and one ion pair [25]. The fractional filling indicates that only an insignificant number of ion pairs occur in the structure for the C12C6C12 and C12C12C12 complexes, and these could adopt either structure (a) or (c). Because the fractional filling in these two compounds approaches 1, it is likely that there are a much higher proportion of gauche defects than in the simpler single chain complexes, enabling the chains to adopt conformations that maximize the space filling. This may explain the remarkably small basal spacing observed for the compound with the C6 spacer [22].

Li and Ishida documented the detailed structure of a surfactant inside silicate galleries. They studied the intercalation of hexadecylamine into bentonite clay and the fine structure of surfactants in nanoconfined space using a differential scanning calorimeter (DSC) [26]. Strong layering behavior with an ordered amine arrangement was observed. Less than 35% of the confined amines form ordered structures within the silicate galleries and exhibit much