Recent advancements in material technologies have promoted the development of various preparation strategies and applications of novel polymer–nanoclay composites. Innovative synthesis pathways have resulted in novel polymer–nanoclay composites with improved properties, which have been successfully incorporated in diverse fields such as aerospace, automobile, construction, petroleum, biomedical and wastewater treatment. These composites are recognized as promising advanced materials due to their superior properties, such as enhanced density, strength, relatively large surface areas, high elastic modulus, flame retardancy, and thermomechanical /optoelectronic/magnetic properties. The primary focus of this review is to deliver an up-to-date overview of polymer–nanoclay composites along with their synthesis routes and applications. The discussion highlights potential future directions for this emerging field of research.
polymer–nanoclay composites, synthesis, applications
Based on their chemical composition and particle morphology, clays are organized into several classes such as smectite, chlorite, kaolinite, illite, and halloysite  . Due to their wide availability, relatively low cost and relatively low environmental impact, nanoclays have been studied and developed for various applications  . With the rapid growth of nanotechnology, clay minerals are increasingly used as natural nanomaterials  . Nanoclays are nanoparticles of layered mineral silicates with layered structural units that can form complex clay crystallites by stacking these layers  . An individual layer unit is composed of octahedral and/or tetrahedral sheets  . Octahedral sheets consist of aluminum or magnesium in six-fold coordination with oxygen from a tetrahedral sheet and with hydroxyl.
Tetrahedral sheets consist of silicon-oxygen tetrahedra linked to neighboring tetrahedra, sharing three corners while the fourth corner of each tetrahedron sheet is connected to an adjacent octahedral sheet via a covalent bond  , see Figure 1. The arrangements of these sheets impact various defining and distinguishing aspects of nanoclays. Based on their mineralogical composition, there are approximately 30 different types of nanoclays, which depending on their properties are used in different applications  . As shown in Table 1, three major 1:1, 2:1, and 2:1:1 sheet arrangements are observed in common nanoclay materials. In 1:1 structures, each tetrahedral is connected to one octahedral sheet; in 2:1 structures, each octahedral sheet is connected to two tetrahedral sheets (one sheet on each side); and in 2:1:1 structure, each octahedral sheet is adjacent to another octahedral sheet and connected to two tetrahedral sheets [8,9] . For example, Halloysite nanoclay is a naturally occurring aluminosilicate nanotube with the average dimensions of 15 nm × 1000 nm  . Due to the hollow tube structure, halloysite nanoclay (1:1 nanotube) is used for medical applications, food packaging and rheology modification  .
The most common plate-like montmorillonite (MMT) nanoclay (smectite) consists of approximately one nm thick aluminosilicate layers surface-substituted with metal cations and stacked in approximately 10 µm-sized multilayer stacks  . The stacks can be dispersed in a polymer matrix as fillers/additives to form polymer/nanoclay composites, with applications such as mechanical strength enhancement, flame-resistance material, thickening and gelling agents, wastewater treatment and gas permeability modification [12–15] . MMT nanoclay (2:1 layered silicates) with a high cation exchange capacity has cation exchange sites on the siloxane surface which can be combined with dissimilar substances, such as organic or biological molecules  . The MMT nanoclay stacks can be dispersed in a polymer matrix as fillers/additives to form polymer/nanoclay composites, which have been widely studied due to their high cation exchange capacity, swelling behavior, and large surface area [17–19] . Halloysite nanoclays are readily dispersed in various polymers without the need for exfoliation. This is due to there being less abundant hydroxyl groups on the nanoclay surfaces compared to MMTs. Additionally, tubular halloysite nanoclays are excellent nanocontainers for various chemical molecules  . Thus, the functionalized halloysite nanoclays are employed as efficient fillers for polymers to enhance their mechanical and thermal properties. These nanoclays are also used as carriers to achieve a sustained release of active molecules, such as flame-retardants, antioxidants, anticorrosion and antimicrobial agents [21,22] . The research and development of novel polymer/nanoclay materials have been an advancing field in material chemistry in recent years [9,12–15,23–25] . Rigid nanoclay may be used as a filler and is able to reinforce polymer structures and impede the free movement of polymer chains neighboring the filler  . Moreover, it behaves as a load-bearing constituent when the interfacial adhesion between the filler and the chains is fulfilled  .
Two crucial challenges of synthesis are to achieve: (1) chemical compatibility between the polymer matrix and the nanofiller at the nanoscale; and (2) homogeneous dispersion of the nanofiller within the polymer matrix. The interfacial interaction between nanoclay fillers and polymer matrix, as well as the quality of nanoclay dispersion, has a significant influence on the performance of polymer/nanoclay composites  . These intercorrelated features determine the polymer/nanoclay composites’ morphology and, thus, their final bulk properties such as strength, elastic modulus, thermal stability, heat distortion temperature, self-healing, shape memory abilities and gas barrier [28,29] . The surface functionalization of nanoclays is a practical method to enhance the interfacial interactions between nanoclay fillers and polymeric matrix, enabling the transfer of interfacial stress from the polymer to the nanoclays  . For instance, the covalent modification of the outer surfaces of halloysite nanotubes enhances their dispersibility into the polymer matrix, which may improve the thermal stability and tensile properties of the resulting polymer/nanoclay composites  . Synthesis approaches may lead to different combinations of the polymer matrix and nanoclays, such as an immiscible structure, an intercalated structure and an exfoliated structure  .
In the immiscible structure, the nanoclay dispersion aggregates within the polymer matrix, and the polymers are separated from the clay layers  . The polymer chains form an intercalated structure between the clay layers, altering the geometry of the clay layers. This alternation includes variation in the stacking mode of the layers, modification in interlayer spacing, and diminishing the electrostatic forces between the clay layers, which lead to greater enhancement of the mechanical and thermal properties of the composites [34–36] . Nanoclay stacks are fully separated by polymer chains in the exfoliated structure, providing superior mechanical properties and polymer processability  . There are three major synthesis procedures for polymer/nanoclay composites including the melt-blending method, solution-blending method, an in-situ polymerization method  . Heretofore, the most widely applied synthesis method was the in-situ polymerization method, where the grafted amounts of organics were adjusted and the clay interlayer spacing was controlled by changing the polymerization conditions  . The combination of in-situ polymerization with efficient coupling methods, including click chemistry  , radical-mediated polymerization [40,41] , tandem preparation  , photopolymerization  and miniemulsion  , has enabled effective dispersion of nanoclays in the form of individual platelets in the polymer matrix, which is a significant challenge inherent to the synthesis of polymer/nanoclay composites. All these methods have been successfully implemented for the chemical modification of clay surfaces with low molecular or polymeric grafts.
Polymer/nanoclay composites have been expanded to several hybrids, innovative materials including nanoclay/conductive polymer (polypyrrole (PPy), polyaniline (PANI), polythiophene (PT), and poly(3,4-ethylene dioxythiophene) (PEDOT), biocomposites and organoclay hybrid films with properties superior to conventional composite materials  . These novel composites are attained with a lower modified nanoclay filler content in comparison to conventionally filled systems and are, as a result, lighter in weight  . Due to their unique properties, polymer/nanoclay composites have been used in a number of industrial applications, such as construction (building sections and structural panels), automotive (gas tanks, bumpers, interior and exterior panels), chemical processes (catalysts), pharmaceutical (as carriers of drugs and penetrants), aerospace (flame retardant panels and high-performance components), food packaging and textiles  . Limitations in fossil resources and an urgent need to protect the environment have led to new generations and applications of polymer/nanoclay composites. Innovative bioinspired polymer/nanoclay composite materials are expected to find applications in various scientific and technological fields  . This article presents a review of recent advances in the synthesis and novel applications of polymer/nanoclay composites. It provides an up-to-date summary of synthesis methods and applications with a focus on the surface-modified nanoclay fillers, and the potential future scope for composite materials.
Conclusions and Prospects
The development of innovative polymer–nanoclay composites has resulted in novel materials with specialized properties, which are mainly dependent on the type of modified nanoclay and synthesis approach. In general, melt blending is considered to be an industrially viable, as well as an eco-friendly synthesis approach. The in-situ polymerization technique delivers more control of the synthesis process in terms of the grafted amounts of organics, the clay interlayer spacing, and the dispersion of nanoclays in the polymer matrix. Three different synthesis methods and their impact on the structure and properties of polymer–nanoclay composites were discussed in this review. Applications of polymer–nanoclay composites have gained momentum and these composites show promise in a wide range of innovative applications. This paper presents recent developments in novel polymer–nanoclay composites with potential applications in various industries, such as petroleum, food packaging, biomedical, and wastewater treatment. Some composites exhibit excellent reinforcement characteristics for the physicochemical properties of materials. The process of selecting combinations of polymer and nanoclay to design and synthesize composites appears to be without a well-established scientific principle. Thus, the theory and modeling related to the design of polymer–nanoclay composites may require additional focus to provide a better understanding of high-performance composites. The Freedonia Group  estimates that by 2020, the demand for novel composite materials is likely to increase to about 3.2 million tons and at a cost of US$ 15 billion per year. Major areas of application for future novel polymer–nanoclay composites are likely to include health (biomedical applications), safety (food packaging) and the environment (biodegradable materials).
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FULL Paper PDF file:A Review of the Synthesis and Applications of Polymer–Nanoclay Composites
Feng Guo 1 , Saman Aryana 1,* , Yinghui Han 2,* and Yunpeng Jiao 2
1 Department of Chemical Engineering, University of Wyoming, Laramie, WY 82072, USA; firstname.lastname@example.org
2 Department of Mathematics and Physics, North China Electric Power University, Baoding 071003, China; email@example.com
A Review of the Synthesis and Applications of Polymer–Nanoclay Composites
Appl. Sci, Nanoclays for Technological Applications