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Biopolymers-Clay Nanocomposites: Synthesis Pathways, Properties, and Applications

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Fatima Zohra Zeggai, Fouzia Touahra, Radia Labied, Djahida Lerari, Redouane Chebout and Khaldoun Bachari

Submitted: 01 March 2024 Reviewed: 21 March 2024 Published: 22 April 2024

DOI: 10.5772/intechopen.114879

Nanocomposites - Properties, Preparations and Applications IntechOpen
Nanocomposites - Properties, Preparations and Applications Edited by Viorica Parvulescu

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Nanocomposites - Properties, Preparations and Applications [Working Title]

Dr. Viorica Parvulescu and Dr. Elena Maria Maria Anghel

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Abstract

Biopolymer-clay nanocomposites have attracted great attention worldwide from both academic and industrial points of view. This chapter aims to report on very recent developments in types of biopolymer-clay nanocomposites, their constituents, synthetic routes, properties, and their uses in various fields. This new family of composite materials frequently exhibits remarkable improvements in material properties when compared with the matrix biopolymers alone or conventional micro- and macrocomposites. The quality of such materials is a major environmental concern, and the production of nanocomposites may decrease the impact of the problem. Biopolymer reinforced with nanofillers is a potential solution to the issue. Functional nanomaterials can be fabricated by the effective interaction between nanofillers and eco-friendly biopolymers. This interaction also enhances physicochemical features and biological properties. They do not only own exceptional properties but can also be made to display combination of properties for multifunctional applications.

Keywords

  • biopolymer
  • clay
  • nanocomposites
  • nanofillers
  • properties

1. Introduction

A new kind of composite material, nanocomposites, has only recently emerged. According to the literature, nanocomposites are a new type of multifunctional material where at least one component has a nanometre-scale dimension. These composites exhibit novel and, in most cases, enhanced qualities; they are more than just a combination of two elements. The research group at Toyota has modelled the nanocomposites’ intended properties [1, 2, 3, 4], and nanofiller montmorillonite—a naturally occurring clay material—is by far the most popular choice for nanocomposite manufacture [5, 6]. The field of nanocomposite research is expanding at a rapid pace. More and more businesses are pouring resources into nanocomposite R&D, production, and marketing because of the wide variety of possible uses for these materials. Definitions and meanings are subject to much debate, as is the case in every scientific discipline. Although the term “nanocomposites” has not yet been defined in consensus among experts, Most of the time, the different ways of interpreting nanocomposite types come down to the fact that you can tell them apart by looking at the sizes of the nanofillers and the different phases that are in the composite. As an example, a nanocomposite can be described as a material with many phases that contains finely dispersed nanoparticles, where the diameters of all but one of the phases are on the nanometre scale. Typically, this kind of nanocomposite is called a polymer nanocomposite because it has a polymer matrix. However, when we turn the coin upside down, we may make a very durable material out of even something as seemingly weak as concrete by adding a polymer and nanofiller. But there is also the idea that nanocomposites are particulate nanocomposite materials with scattered phases that have at least one particle-like dimension, as in the Bar definition. Before the name “nanofiller” became widespread, there was a kind of composite material known as nano-matrix composites, which describes these particular nanocomposites. They have a long history of usage in construction and automotive materials [7, 8], among others, where very high mechanical qualities [9, 10, 11, 12, 13] are required, and they are often toughened with tough particles. While numerous nanocomposites fail to exhibit the same level of property enhancement as biopolymer-clay nanocomposites, the latter’s biodegradability is an advantageous quality. The application of biodegradable or biopolymer materials represents a significant substitute for polymers derived from petroleum. The incorporation of natural fibres into biopolymer matrices enhances the properties of manufactured plastic products by a substantial amount. Scientists invented biopolymer composites with the intention of producing environmentally sustainable materials [14], consequently leading to a reduction in carbon emissions. By integrating the beneficial characteristics of biopolymers and nanoclays, these materials exhibit enhanced thermal, mechanical, and barrier qualities in comparison to biopolymers in their pure form. In this manuscript, we present the outcomes of the amalgamation of two distinct types of material. Clays are utilised for various purposes in nanocomposites. Clay is suitable for use as reinforcement due to its unique properties. As an illustration, the most prevalent nanofilled material, montmorillonite, possesses an exceptionally high aspect ratio [15].

1.1 Significance of biopolymer/clay nanocomposites

Consequently, there is an increasing need for biodegradable polymers and other eco-friendly products globally. Most of the plastics currently in use are non-biodegradable, which contributes to their durability. This is the reason they are visible in a diverse range of everyday items such as water bottles, cleaning products, packaging, and other items. However, the longevity of plastics is a concern. A key concern is the proper disposal of spent plastics, as global consumption of non-biodegradable plastic reaches 300 million tonnes annually [16]. Research on the characteristics, manufacturing, and possible applications of novel polymer nanocomposites is becoming more crucial. Nanocomposites, a novel class of hybrid materials, have various applications in electronics, biology, medicine, pharmaceuticals, and material sciences. It is measured on the nanoscale scale. This family of materials beats conventional microcomposites in performance due to its greater surface area-to-volume ratio. Nanocomposites can exhibit superior mechanical properties compared to microcomposites when polymers are the predominant component. Nanocomposites display a phenomenon in which nanoparticles are distributed more uniformly throughout the polymer matrix, leading to distinct reinforcing effects compared to microcomposites. Effective dispersion and interfacial contact between nanoparticles and polymers are essential for enhancing the performance of nanocomposites. Biopolymers are derived from renewable sources, biodegradable, and belong to a novel class of polymer materials. Their many applications and small environmental footprint have led to a significant increase in interest in developing polymer nanocomposites with biopolymers as the primary constituent [17]. Research indicates that interfaces have a substantial effect on the overall properties of composites. The potential of nanocomposites is evident, but their ability to be produced on a large scale is influenced by the size, dispersion, and aspect ratio of the nanoparticles. Advancements in performance and cost efficiency in material design have sparked interest and forecasts in this field of research. Currently, there is less knowledge on the scaling issues and maximum limits of nanoparticle reinforcements in nanocomposites. Modelling and simulation are essential components of many research and development projects globally, particularly in the field of material science. These have aided in defining the potential limits of materials within a specific field and their likely practical uses. For instance, the mechanical properties of several nanocomposites can be enhanced by optimising the dispersion and aspect ratio of nanoparticles through models. It is crucial to be cautious while employing this, as the accuracy of these models depends greatly on the efficiency of the dispersion, which has significantly improved in this technologically advanced era.

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2. Synthesis pathways

Research on biopolymer-clay nanocomposite materials started around 20 years ago. Diverse bionanocomposites have been created by incorporating large biopolymers like chitosan, cellulose, starch, alginate, sacran, zein, gelatin, or polylactic acid into clay minerals such as smectites, sepiolite, palygorskite, micas, kaolinites, and synthetic layered double hydroxides. In recent years, this field of study has expanded greatly, leading to the development of novel material systems. Nanocomposites of biopolymers and clay find application in the packaging, automotive, and aerospace industries as coatings, films, and fibres. To lessen their effect on the environment, nanocomposites—also known as “green materials”—can substitute non-degradable polymers. Nanocomposites with clay layers are created by mixing a small amount of clay with a biopolymer matrix. Mechanical, thermal, and barrier qualities are where minimum-filler nanocomposites really shine compared to the old-fashioned microcomposites. The procedures for reinforcing polymer matrixes and controlling their properties have remained a mystery despite 30 years of study. There are a lot of moving parts when producing nanocomposites (Figure 1), including clay exfoliation and matrix dispersion in the biopolymer. Polymer crystallisation procedures, hydrophobic biopolymers, and hydrophilic clay are all examples of immiscible components that must interact and be compatible with one another. Finally, processing methods, clay surface modification, and biopolymer matrix all influence nanocomposite structure and properties. To find structure-property correlations and optimise for applications, all of them necessitate macroscopic and molecular study.

Figure 1.

Illustration of three distinct composite types: (A) traditional composite, (B) nanocomposite with intercalation, and (C) nanocomposite with exfoliation.

2.1 Solution casting

Clay can expand when mixed with biopolymers in a liquid media, such as water or a solvent that is appropriate for the biopolymer (Figure 2). This process can be accelerated by sonication [18] or agitation. The considerable interlayer swelling of clay minerals makes it an essential material for the intercalation of polar, non-ionic, and cationic polymers from water-based solutions. For biopolymers to be inserted between the silicate layers, the solvents’ properties, particularly the polarity of the medium, are crucial. Hydrogen bonding between hydroxyl groups (e.g., sodium alginate) [19, 20, 21, 22] and nitrogen hetero-atoms (e.g., povidone, also known as polyviylpyrrolidone (PVP) or polyvidone) [23, 24] allows intercalated biopolymers to directly interact with the interlayer siloxane surface of clay, or they can interact indirectly through water molecules coordinated to the interlayer. Cationic polymers cause rapid reaggregation of clay-mineral layers due to strong interactions between the surface and the polymer. Other possible reactants include poly(ethylene oxide) [25, 26, 27] and polylactide [28, 29]. Chitosan forms a monolayer by exchanging cations with the interlayer gap in acidic medium (chitosan is rich in amino-terminated functional group). Interactions between the first polymer layer and the silicate surface, facilitated by hydrogen at high solute concentrations, can intercalate a second layer of chitosan [30, 31, 32, 33]. Some biopolymers use organic solvents to intercalate clay-mineral layers [34, 35, 36, 37]. A dry bionanocomposite material is obtained at the end of this process by evaporation or other methods of removing the solvent.

Figure 2.

Biopolymer/clay prepared by solution casting.

2.2 Melt insertion

Advancements have been made in melt intercalation polymer nanocomposites. The optimal way to make biopolymer-clay nanocomposites is to mix suitable organoclays with biopolymers while they are still molten (without pressing), as shearing forces exfoliate clay particles. This technology is ideal for large-scale processing using twin-screw extruders, twin-roll mills [38, 39], melt blending [40, 41], or injection moulding [42]; it is solvent-free, polymer-specific, easy to use (molten mixing of biopolymer and clay nanoparticles), and environmentally friendly (Figure 3).

Figure 3.

Schematic representation of melt insertion technique (melt blending).

Molten biopolymers can intercalate directly into clay minerals, although most melt intercalation uses montmorillonites that have been organically modified. The clay particles are dispersed in the biopolymer matrix by being processed at high temperatures and shear forces, which makes intercalation easier. The polymeric compatibiliser needs to have a stronger interaction with the oxygen atoms on the clay surface than with the clay surfaces themselves if silicate delamination is to occur [43]. The impact of the compatibiliser molecule is determined by the kind and polarity of the hydrophobic component, as well as the composition and size of the non-polar lipophilic surfactant part. The surfactant capability of the compatibiliser can be anticipated through the assessment of its hydrophilic/lipophilic equilibrium. Polar groups are commonly grafted onto polymers and copolymers in order to serve as compatibilisers. Melt compounds that contain maleic anhydride grafted onto polyethylene (PE-g-MA) [44, 45], polyethylene-1-octene elastomer (POE-g-MA) [46], or polypropylene (PP-g-MA) [47, 48, 49] are commonly used to enhance the dispersion of clay nanoparticles and the compatibility of these compounds with non-polar polymers. When a liquid cools and solidifies, a bionanocomposite is born.

2.3 In situ polymerisation

Throughout the polymerisation of the monomers, the clay nanoparticles are evenly dispersed in the mixture (Figure 4). Choosing monomers that are compatible with the surface of the clay helps ensure that the growing polymer chains and nanofillers form strong contacts. That is why research on fully exfoliated materials has focused on techniques for incorporating biopolymer chains into multilayer silicate minerals. After the monomer or monomer mixture is inflated, polymerisation takes place between the intercalated silicate sheets. An appropriate initiator can be diffused, heat or radiation can be applied, or an organic catalyst or initiator can be embedded through cation exchange within the interlayer. Next, the swelling process can commence. Integrating polymerisation has been effectively utilised with both types of clays, proving to be cost-effective and providing superior exfoliation compared to alternative techniques used for nanocomposite synthesis. Some drawbacks of this method include a modest response amount, dependence on subsequent techniques for silicate sheet exfoliation, and sluggish monomer diffusion in the nanoclay layer.

Figure 4.

Illustration of in situ polymerisation of biopolymer/clay nanocomposites.

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3. Properties of biopolymer/clay nanocomposites

The superiority and competitiveness of biopolymer-clay nanocomposites over traditional microcomposites can be attributed to their mechanical, thermal, gas barrier, antibacterial, optical, and biodegradable properties. These materials possess a clay or organoclay concentration ranging from 1 to 5 weight per cent, rendering them comparable in density to virgin polymers and amenable to processing. The biopolymer, nanoclay, and nanoparticle dispersion in the polymer matrix determines the level of augmentation [50]. Biopolymer-clay nanocomposites are anticipated to experience growth in various sectors, including automotive, packaging, environmental, agricultural, and biomedical applications, owing to the influence of these variables.

3.1 Structure conformation of intercalated/exfoliated bionanocomposites

The type of modified clay and the preparation procedure has a substantial impact on the structure-property links of layered silicate bionanocomposites. Micro, intercalated, or exfoliated biopolymer/layered silicate nanocomposites can be synthesised (Figure 1). The diffraction pattern of microcomposites exhibits no significant alteration in comparison to clays. However, X-ray diffraction (XRD) [51] is frequently employed for the evaluation of their microstructure owing to the influence of intercalated structures, which induce a shift of peaks towards lower values. Exfoliated formations, unlike other structures, are entirely amorphous, indicating the absence of any low-angle diffraction peaks. Subsequently, its structure is identified by X-ray analysis, namely small angle X-ray scattering (SAXS), which includes ultra-small angle X-ray scattering (USAXS) and wide angle X-ray scattering (WAXS), or transmission electron microscopy (TEM), or atomic force microscopy (AFM) [51, 52]. The intercalated-exfoliated intermediate organisation commonly observed during the synthesis of biopolymer/clay nanocomposite has a significant influence on several structures and properties, including mechanical, barrier, flame-retardant, and crystallisation behaviour.

3.2 Mechanical properties

Elongation at break, Young’s modulus, and tensile strength are the mechanical parameters of biopolymer nanocomposites that are often examined the most. The processing methods, additives, and initial materials (like nanoparticles and biopolymer matrices) shape and size, as well as filler content and infiltrating whisker network formation, all have an impact on these mechanical properties [53, 54, 55]. The strong attraction between the nanoclay particles and the biopolymer matrix, together with the nanoclay’s high aspect ratio and stiffness, can increase the mechanical properties of biopolymer nanocomposites [55]. Ramesh et al. [56] Used the twin-screw extruder, two-roll mill, and compression moulding process to create polylactic acid (PLA)-biocomposite and PLA-hybrid biocomposites. The filler used in these composites consisted of 0, 1, 2, and 3 wt% montmorillonite clay. PLA-hybrid biocomposites with 1 wt% montmorillonite (MMT) clay have enhanced tensile, flexural, impact, and abrasion resistance in comparison to other prepared composites.

3.3 Barrier properties

Clay filler not only improves the mechanical properties of nanocomposites but also greatly enhances their barrier qualities. Improved barrier properties have been seen as a result of nanocomposites’ diverse chemical activity [57]. The wide variety of measurement factors and equipment utilised makes it difficult, if not impossible, to compare biopolymers with nanoclays. These variables include temperature, relative humidity, gas pressure, and many more. The gas permeability is greatly affected by the nanocomposite structure, the aspect ratio of clay platelets, the compatibility of the clay with the biopolymer matrix, and the type of clay. Biopolymer nanocomposite gas barrier properties with high aspect ratios and fully exfoliated clay particles are generally better. Because of their intrinsic impermeability, clays create complex routes that make it difficult for gas molecules to pass through barrier biopolymers [58]. So, impermeable nanoparticles in a biopolymer cause impregnating molecules to flow randomly, leading to their dispersion along a complex channel [59]. Improved gas barrier qualities are the main reason why nanocomposite food packaging is so popular.

3.4 Biodegradation properties

To lessen the impact of plastic waste pollution, recent research has focused on using biodegradable polymers in packaging. The process of mineralisation, also known as biodegradation, happens in this specific class of polymers because of chain scission generated by microbes, which is made possible by the enzymatic actions of organisms like fungus, yeasts, and bacteria [60, 61, 62]. Such parameters, including pH, water content, oxygen per cent, and metal concentration, impact this process. Degradation of polymers into their component minerals is known as polymer biodegradation. Rapid deterioration may occur after the disposal of bionanocomposite packaging [63]. Biopolymer films are often made more biodegradable by adding nanoclays to nanocomposites. Chitosan [64, 65, 66], starch [67], polylactic acid [68, 69], and polycaprolactone are biodegradable polymers that are found to be extensively used in packaging.

3.5 Thermal stability of biopolymer/clay nanocomposites

Polymeric materials’ thermal stability is typically investigated using thermogravimetric analysis (TGA). Adding inorganic nanofillers to biodegradable polymers has been shown to increase their thermal stability [70, 71]. Modifying clay has also involved the use of a number of organic compounds. An essential first step in developing clay mineral and biopolymer blends is the aforementioned technique. The mineral’s surface composition is changed, making it more organophilic and less hydrophilic [72]. Organic biopolymers improve clay’s compatibility and make it easier for clay particles to exfoliate into the biopolymer matrix [73, 74]. Research on the thermal stability of biopolymer/clay nanocomposites is crucial for determining their operational temperature range and environmental suitability. This is influenced by factors such as thermal decomposition temperature and rate [75]. In a study conducted by Kumar and Babu [76], it was found that the thermal stability of polymeric materials, such as polylactic acid (PLA), can be enhanced through the incorporation of silicate layers, specifically montmorillonite. Improving the ability to withstand tensile and impact stress, while also considering factors such as glass transition temperature (Tg), thermal conductivity (TC), and melting point (Tm).

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4. Biopolymer/clay nanocomposites applications

Biopolymeric/clay composites are favoured because of their enhanced performance and flexibility, which are attributed to the unique features of both biopolymer and clay. The most prevalent categories of packaging materials that are both biocompatible and biodegradable are natural biopolymers, including polysaccharides, polynucleotides, and proteins, as well as synthetic biopolymers such as bio-polyesters, polyvinyl alcohol (PVA), and PLA.

Drug delivery [77, 78, 79], tissue engineering [80, 81, 82, 83, 84, 85, 86], flame-retardant [87, 88, 89, 90, 91, 92], wastewater treatment [93, 94, 95, 96, 97, 98], environment [99, 100], food packaging [101, 102, 103, 104, 105], and antibacterial activity [37, 65, 106, 107] are just a few of the many high-tech sectors that utilise biopolymer/clay composites (Table 1). Moreover, these materials exhibit biodegradability and safety. In recent times, there has been a notable movement in dye research towards the advancement of environmentally friendly nanocomposites. This trend is characterised by a heightened emphasis on the immobilisation of pollutants and the implementation of green chemical techniques.

BiopolymerClayApplicationRef.
ChitosanCo-modified montmorilloniteContaminant uptakes[108]
ChitosanModified montmorilloniteSonocatalysis of dyes[109]
ChitosanNanoclayAdsorbent for Rhodamine 6G[33]
StarchModified montmorilloniteRemoval of Pb(II), Cd(II) and Ni(II) ions[110]
Chitosan-poly(acrylic acid)BentoniteAdsorbent for Cu, Zn, Cd, and Ni[111]
Carboxymethyl chitosan hydrogelsKaoliniteRemoval of Cr(VI) and Pb(II)[112]
ChitosanBentonite; kaoliniteAdsorption of Cu[113]
ChitosanMontmorillonite K10Removal of basic fuchsin[114]
Chitosan/gelatinFe-montmorilloniteRemoval of organic pollutants[115]
Microfibrillated celluloseCloisiteGas barrier[116]
Cellulose acetateMoroccan clayRemoval of cationic dye[117]
ChitosanMontmorillonite nanosheetsRemoval of methylene blue[118]
Biomagnetic chitosan-ethylene glycol diglycidyl etherOrgano-modified clayRemoval of Remazol Brilliant Blue R dye[119]
Magnetic glyoxal-chitosanOrgano-modified montmorilloniteRemoval of reactive blue 19 (RB19)[120]
ChitosanMontmorilloniteRemoval of Basic Green 1 and Reactive Blue 19 Dyes[121]
ChitosanBangladesh clayHeavy metal
Industrial effluent		[96]
Poly-cyclodextrinNa-montmorillonite SWy-2Removal of bisphenol[122]
Poly-cyclodextrinFe-montmorilloniteRecyclable sorbent catalysts[123]
CelluloseKaolin clayRemoval of methylene blue and Congo Red removal dyes[124]
CelluloseBentoniteSolution Cd removal and soil Cd remediation[125]
PVA/alginateDifferent clays; Attapulgite, bentonite, Laponite-RD, and HydroxyapatiteBioremediation hydrocarbons compounds from crude oily wastewater[126]
Calcium alginateMontmorilloniteRemoval of heavy metals[127]
Sodium alginateMoroccan clayAdsorption of metal ions[128]
AlginateMoroccan clayRemoval of H2PO4−, HPO42−, and NO3− ions[129]
Alginate, chitosanBentoniteThe oral delivery of 5-fluorouracil[130]
Poly(ε-caprolactone)Organo-modified Algerian montmorilloniteFood packaging[131]
ChitosanSerbian bentoniteDrug carriers[132]
ChitosanSepiolite, bentonite, and kaoliniteTriboelectric nanogenerator[133]
Starch-microcrystalline celluloseMontmorilloniteFood packaging
Electrical applications		[134]
Cellulose nanofibrilBentoniteFood packaging[135]
Poly(lactic acid)BentoniteFood packaging[136]
Chitosan/polygalacturonic acid (ChiPgA)MontmorilloniteBone tissue engineering[137]
PolycaprolactoneNa-montmorillonite and hydroxyapatite-claysBone tissue engineering[138]
Scaffolds-PCL/chitosanCloisite Na+Bone tissue engineering[139]
ChitosanFe-clayRemoval of arsenic and dye[140]
Polyvinyl alcoholCloisite Na+; Hal Clay MF7High-barrier
Food packaging		[141]
Polyglycerol dimethacrylateBentonite-CTABCationic dye adsorption[142]

Table 1.

Different applications of biopolymer-clay nanocomposites.

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5. Conclusion and future prospects

Research on biopolymers/clay nanocomposites, including their characteristics, production methods, and potential uses, was covered in this chapter. Nanocomposite materials are created through the incorporation of nanofillers, including nanoclays, montmorillonites (MMTs), and plasticisers, into natural polymers. The incorporation of reinforcement serves to mitigate the inherent limitations in the mechanical and barrier properties of the initial polymer. The thermal stability of the composite is enhanced through the incorporation of biopolymers into clay. The presence of a thermal barrier in clay serves to impede the rapid degradation of the polymer upon exposure to heat. Clay enhances the crystallinity of polymer composites, hence improving their thermal degradation. The use of microscopic analysis in various investigations has indicated that composites exhibiting a consistent dispersion of clay inside the biopolymeric matrix possess potential utility across diverse situations. The incorporation of clay into biopolymer composites leads to an enhancement in their tensile strength. The impact strength and rigidity of the polymer matrix are enhanced through the mechanical reinforcement with clay. The utilisation of these materials is expected to witness a growing trend across various domains, including biomedical, tissue engineering, automotive, and food packaging. Research into biopolymer-clay nanocomposite has both potential and obstacles, as is typical of most burgeoning fields. Researchers faced the difficult task of developing a biocompatible polymer clay nanocomposite that exhibited exceptional performance. It is imperative that the substance serves a suitable biological purpose. It is not always the case that biocompatibility in vivo is guaranteed by harmless polymer composite efficacy in vitro. Both in vitro and in vivo success is of the utmost importance when creating clay-reinforced polymer composites for biomedical purposes. In order to manage the structure-property connection in biopolymer-clay nanocomposite, researchers must first understand the interactions between the biopolymer matrix and the inorganic clay filler.

References

  1. 1. Kojima Y, Usuki A, Kawasumi M, Okada A, Fukushima Y, Kurauchi T, et al. Mechanical properties of nylon 6-clay hybrid. Journal of Materials Research. 1993;8:1185-1189. DOI: 10.1557/JMR.1993.1185
  2. 2. Okada A, Kawasumi M, Usuki A, Kojima Y, Kurauchi T, Kamigaito O. Nylon 6–clay hybrid. MRS Online Proceedings Library. 1989;171:45-50. DOI: 10.1557/PROC-171-45
  3. 3. Usuki A, Kojima Y, Kawasumi M, Okada A, Fukushima Y, Kurauchi T, et al. Synthesis of nylon 6-clay hybrid. Journal of Materials Research. 1993;8:1179-1184. DOI: 10.1557/JMR.1993.1179
  4. 4. Usuki A, Koiwai A, Kojima Y, Kawasumi M, Okada A, Kurauchi T, et al. Interaction of nylon 6-clay surface and mechanical properties of nylon 6-clay hybrid. Journal of Applied Polymer Science. 1995;55:119-123. DOI: 10.1002/app.1995.070550113
  5. 5. Kojima Y, Usuki A, Kawasumi M, Okada A, Kurauchi T, Kamigaito O. Synthesis of nylon 6–clay hybrid by montmorillonite intercalated with ϵ-caprolactam. Journal of Polymer Science Part A: Polymer Chemistry. 1993;31:983-986. DOI: 10.1002/pola.1993.080310418
  6. 6. Usuki A, Kawasumi M, Kojima Y, Okada A, Kurauchi T, Kamigaito O. Swelling behavior of montmorillonite cation exchanged for ω-amino acids by ∊-caprolactam. Journal of Materials Research. 1993;8:1174-1178. DOI: 10.1557/JMR.1993.1174
  7. 7. Lu Y, Pilla S. Nanocomposites: Recent development and potential automotive applications (2008-01-1263). In: The Use of Nano Composites in Automotive Applications. United States: SAE International; 2017. pp. 17-26. ISBN 978-0-7680-8284-5
  8. 8. Shah V, Bhaliya J, Patel GM, Deshmukh K. Advances in polymeric nanocomposites for automotive applications: A review. Polymers for Advanced Technologies. 2022;33:3023-3048. DOI: 10.1002/pat.5771
  9. 9. Khan A, Shamsi MH, Choi T-S. Correlating dynamical mechanical properties with temperature and clay composition of polymer-clay nanocomposites. Computational Materials Science. 2009;45:257-265. DOI: 10.1016/j.commatsci.2008.09.027
  10. 10. Luo J-J, Daniel IM. Characterization and modeling of mechanical behavior of polymer/clay nanocomposites. Composites Science and Technology. 2003;63:1607-1616. DOI: 10.1016/S0266-3538(03)00060-5
  11. 11. Tarapow JA, Bernal CR, Alvarez VA. Mechanical properties of polypropylene/clay nanocomposites: Effect of clay content, polymer/clay compatibility, and processing conditions. Journal of Applied Polymer Science. 2009;111:768-778. DOI: 10.1002/app.29066
  12. 12. Champa-Bujaico E, Díez-Pascual AM, Lomas Redondo A, Garcia-Diaz P. Optimization of mechanical properties of multiscale hybrid polymer nanocomposites: A combination of experimental and machine learning techniques. Composites Part B: Engineering. 2024;269:111099. DOI: 10.1016/j.compositesb.2023.111099
  13. 13. Adrar S, Ajji A. Interactions between PLA, organo-montmorillonite and plasticizer: Synergistic effect on the barrier and mechanical properties of PLA nanocomposites blown films. Journal of Applied Polymer Science. 2024;141:e54867. DOI: 10.1002/app.54867
  14. 14. Chivrac F, Kadlecová Z, Pollet E, Avérous L. Aromatic copolyester-based nano-biocomposites: Elaboration, structural characterization and properties. Journal of Polymers and the Environment. 2006;14:393-401. DOI: 10.1007/s10924-006-0033-4
  15. 15. Okada A, Usuki A. Twenty years of polymer-clay nanocomposites. Macromolecular Materials and Engineering. 2006;291:1449-1476. DOI: 10.1002/mame.200600260
  16. 16. Madej-Kiełbik L, Jóźwik-Pruska J, Dziuba R, Gzyra-Jagieła K, Tarzyńska N. The impact of the COVID-19 pandemic on the amount of plastic waste and alternative materials in the context of the circular economy. Sustainability. 2024;16:1555. DOI: 10.3390/su16041555
  17. 17. Mangal M, Rao CV, Banerjee T. Bioplastic: An eco-friendly alternative to non-biodegradable plastic. Polymer International. 2023;72:984-996. DOI: 10.1002/pi.6555
  18. 18. Cherifi Z, Zaoui A, Boukoussa B, Derdar H, El Abed OZ, Zeggai FZ, et al. Ultrasound-promoted preparation of cellulose acetate/organophilic clay bio-nanocomposites films by solvent casting method. Polymer Bulletin. 2023;80:1831-1843. DOI: 10.1007/s00289-022-04129-x
  19. 19. Bakhshizadeh A, Khayat N, Horpibulsuk S. Surface stabilization of clay using sodium alginate. Case Studies in Construction Materials. 2022;16:e01006. DOI: 10.1016/j.cscm.2022.e01006
  20. 20. Wang Y, Wang W, Shi X, Wang A. A superabsorbent nanocomposite based on sodium alginate and illite/smectite mixed-layer clay. Journal of Applied Polymer Science. 2013;130:161-167. DOI: 10.1002/app.39141
  21. 21. Chang P-H, Mukhopadhyay R, Sarkar B, Mei Y-C, Hsu C-H, Tzou Y-M. Insight and mechanisms of tetracycline adsorption on sodium alginate/montmorillonite composite beads. Applied Clay Science. 2023;245:107127. DOI: 10.1016/j.clay.2023.107127
  22. 22. Xu B-T, Jin D, Yu Y, Zhang Q , Weng W, Ren K, et al. Nanoclay-reinforced alginate aerogels: Preparation and properties. RSC Advances. 2024;14:954-962. DOI: 10.1039/D3RA07132D
  23. 23. Krasinskyi V, Malinowski R, Bajer K, Rytlewski P, Miklaszewski A. Study of montmorillonite modification technology using polyvinylpyrrolidone. Arabian Journal of Chemistry. 2023;16:105296. DOI: 10.1016/j.arabjc.2023.105296
  24. 24. Santos VJ, Zafalon AT, Lugao AB, Parra DF. Influence of Dispersion Process on the Characteristics of PVP-CLAY Hydrogel. Brazilian Conference on Composite Materials, Gramado, RS - Brazi 132. CONGRESS PROCEEDINGS - MME SEE 2023. 5th Metallurgical & Materials Engineering Congress of South-East Europe. Belgrade, Serbia. 2017
  25. 25. Ogata N, Kawakage S, Ogihara T. Poly(vinyl alcohol)-clay and poly(ethylene oxide)-clay blends prepared using water as solvent. Journal of Applied Polymer Science. 1997;66:573-581. DOI: 10.1002/(SICI)1097-4628(19971017)66:3<573::AID-APP19>3.0.CO;2-W
  26. 26. Stefanescu EA, Stefanescu C, Negulescu II, Daly WH. Effect of ionic species on the structures and properties of salt-containing PEO/montmorillonite nanocomposites. Macromolecular Chemistry and Physics. 2008;209:2320-2330. DOI: 10.1002/macp.200800371
  27. 27. Ejder-Korucu M, Gürses A, Karaca S. Poly(ethylene oxide)/clay nanaocomposites: Thermal and mechanical properties. Applied Surface Science. 2016;378:1-7. DOI: 10.1016/j.apsusc.2016.03.159
  28. 28. Mansa R, Huang C-T, Quintela A, Rocha F, Detellier C. Preparation and characterization of novel clay/PLA nanocomposites. Applied Clay Science. 2015;115:87-96. DOI: 10.1016/j.clay.2015.07.024
  29. 29. Ogata N, Jimenez G, Kawai H, Ogihara T. Structure and thermal/mechanical properties of poly(l-Lactide)-clay blend. Journal of Polymer Science Part B: Polymer Physics. 1997;35:389-396. DOI: 10.1002/(SICI)1099-0488(19970130)35:2<389::AID-POLB14>3.0.CO;2-E
  30. 30. Bhattacharjee M, Goswami S, Borah P, Saikia M, Barman J, Pramanik NB, et al. Preparation, characterization, and antimicrobial activity of chitosan/kaolin clay biocomposite films. Macromolecular Chemistry and Physics. 2023;224:2300008. DOI: 10.1002/macp.202300008
  31. 31. Majiya H, Clegg F, Sammon C. Bentonite-chitosan composites or beads for lead (Pb) adsorption: Design, preparation, and characterisation. Applied Clay Science. 2023;246:107180. DOI: 10.1016/j.clay.2023.107180
  32. 32. Azzam EMS, Eshaq G, Rabie AM, Bakr AA, Abd-Elaal AA, El Metwally AE, et al. Preparation and characterization of chitosan-clay nanocomposites for the removal of Cu(II) from aqueous solution. International Journal of Biological Macromolecules. 2016;89:507-517. DOI: 10.1016/j.ijbiomac.2016.05.004
  33. 33. Vanamudan A, Pamidimukkala P. Chitosan, nanoclay and chitosan– nanoclay composite as adsorbents for Rhodamine-6G and the resulting optical properties. International Journal of Biological Macromolecules. 2015;74:127-135. DOI: 10.1016/j.ijbiomac.2014.11.009
  34. 34. Hachemaoui A, Yahiaoui A, Belbachir M. Synthesis and characterization of water soluble poly(N-acetyl)iminoethylene and poly(ethyleneimine) by ion-exchanged clay montmorillonite. Journal of Applied Polymer Science. 2006;102:3741-3750. DOI: 10.1002/app.24660
  35. 35. Nath AK, Sharma B, Borah BJ, Deka N, Hazarika J. Structural and electrochemical properties of montmorillonite-poly(ethylene oxide) intercalated nanocomposites for lithium-ion batteries. International Journal of Polymer Analysis and Characterization. 2023;28:279-291. DOI: 10.1080/1023666X.2023.2207867
  36. 36. Güney BC, Arslan Y. Removal of Cu(II) by biopolymer-clay nanocomposite adsorbent. Reaction Kinetics Mechanisms and Catalysis. 2023;136:433-448. DOI: 10.1007/s11144-022-02340-5
  37. 37. Abayt FM, Yalcinkaya EE. Poly (Ɛ-caprolactone)-CTAB montmorillonite-silver nanoparticles: A hybrid electrospun nanofibers for in vitro antibacterial activity. Journal of Materials Research. 2024;39:1-19. DOI: 10.1557/s43578-024-01287-8
  38. 38. Lu H, Hu Y, Li M, Song L. Effects of charring agents on the thermal and flammability properties of intumescent flame-retardant HDPE-based clay nanocomposites. Polymer-Plastics Technology and Engineering. 2008;47:152-156. DOI: 10.1080/03602550701816001
  39. 39. Koshy RR, PothAn LA, Thomas S. Starch-based bionanocomposite: Processing techniques. In: Biopolymer Nanocomposites. New York, United-States: John Wiley & Sons, Ltd; 2013. pp. 203-226. ISBN 978-1-118-60995-8
  40. 40. Rhim J-W, Ng PKW. Natural biopolymer-based nanocomposite films for packaging applications. Critical Reviews in Food Science and Nutrition. 2007;47:411-433. DOI: 10.1080/10408390600846366
  41. 41. Siddiqui MN, Redhwi HH, Belioka MP, Achilias DS. Effect of nanoclay on the thermal degradation kinetics of recycled biodegradable/non-biodegradable polymer blends using the random chain-scission model. Journal of Analytical and Applied Pyrolysis. 2024;177:106291. DOI: 10.1016/j.jaap.2023.106291
  42. 42. Harnkarnsujarit N, Wongphan P, Chatkitanan T, Laorenza Y, Srisa A. Chapter 7—Bioplastic for sustainable food packaging. In: Galanakis CM, editor. Sustainable Food Processing and Engineering Challenges. Academic Press; 2021. pp. 203-277. ISBN 978-0-12-822714-5
  43. 43. Chrissopoulou K, Anastasiadis SH. Polyolefin/layered silicate nanocomposites with functional compatibilizers. European Polymer Journal. 2011;47:600-613. DOI: 10.1016/j.eurpolymj.2010.09.028
  44. 44. Hammache Y, Serier A, Chaoui S. The effect of thermoplastic starch on the properties of polypropylene/high density polyethylene blend reinforced by nano-clay. Materials Research Express. 2020;7:025308. DOI: 10.1088/2053-1591/ab7270
  45. 45. Chen RS, Ahmad S. Tensile, water absorption and thermal properties of recycled polyethylene/nanoclay. AIP Conference Proceedings. 2023;2544:060001. DOI: 10.1063/5.0116429
  46. 46. Kazemi A, Nouri Khorasani S, Dinari M, Khalili S. Mechanical and barrier properties of LLDPE/TPS/OMMT packaging film in the presence of POE-g-IA or POE-g-MA. Journal of Polymer Research. 2021;28:133. DOI: 10.1007/s10965-021-02465-6
  47. 47. Tang Y, Hu Y, Wang S, Gui Z, Chen Z. Preparation of poly(propylene)/clay layered nanocomposites by melt intercalation from pristine montmorillonite (MMT). Polymers for Advanced Technologies. 2003;14:733-737. DOI: 10.1002/pat.420
  48. 48. Abdel Aziz ME, Saad GR, Abou El-khair MT. Preparation of polypropylene organically modified clay nanocomposites with enhanced physico-chemical properties. Macromolecular Research. 2022;30:900-908. DOI: 10.1007/s13233-022-0099-4
  49. 49. Arbelaiz A, Fernández G, Orue A. The effect of montmorillonite modification and the use of coupling agent on mechanical properties of polypropylene–clay nanocomposites. Polymers and Polymer Composites. 2021;29:660-671. DOI: 10.1177/0967391120930613
  50. 50. Šupová M, Martynková GS, Barabaszová K. Effect of nanofillers dispersion in polymer matrices: A review. Science of Advanced Materials. 2011;3:1-25. DOI: 10.1166/sam.2011.1136
  51. 51. Bee S-L, Abdullah MAA, Mamat M, Bee S-T, Sin LT, Hui D, et al. Characterization of silylated modified clay nanoparticles and its functionality in PMMA. Composites Part B: Engineering. 2017;110:83-95. DOI: 10.1016/j.compositesb.2016.10.084
  52. 52. Alexandre M, Dubois P. Polymer-layered silicate nanocomposites: Preparation, properties and uses of a new class of materials. Materials Science and Engineering: R: Reports. 2000;28:1-63. DOI: 10.1016/S0927-796X(00)00012-7
  53. 53. Wang L, Wang A. Adsorption characteristics of Congo Red onto the chitosan/montmorillonite nanocomposite. Journal of Hazardous Materials. 2007;147:979-985. DOI: 10.1016/j.jhazmat.2007.01.145
  54. 54. Kim SW, Cha S-H. Thermal, mechanical, and gas barrier properties of ethylene–vinyl alcohol copolymer-based nanocomposites for food packaging films: Effects of nanoclay loading. Journal of Applied Polymer Science. 2014;131:40289. DOI: 10.1002/app.40289
  55. 55. Sadasivuni KK, Saha P, Adhikari J, Deshmukh K, Ahamed MB, Cabibihan J-J. Recent advances in mechanical properties of biopolymer composites: A review. Polymer Composites. 2020;41:32-59. DOI: 10.1002/pc.25356
  56. 56. Ramesh P, Prasad BD, Narayana KL. Influence of montmorillonite clay content on thermal, mechanical, water absorption and biodegradability properties of treated kenaf fiber/PLA-hybrid biocomposites. Silicon. 2021;13:109-118. DOI: 10.1007/s12633-020-00401-9
  57. 57. Jafarzadeh S, Ariffin F, Mahmud S, Alias AK, Hosseini SF, Ahmad M. Improving the physical and protective functions of semolina films by embedding a blend nanofillers (ZnO-Nr and nano-kaolin). Food Packaging and Shelf Life. 2017;12:66-75. DOI: 10.1016/j.fpsl.2017.03.001
  58. 58. Singha S, Hedenqvist MS. A review on barrier properties of poly(lactic acid)/clay nanocomposites. Polymers. 2020;12:1095. DOI: 10.3390/polym12051095
  59. 59. Müller K, Bugnicourt E, Latorre M, Jorda M, Echegoyen Sanz Y, Lagaron JM, et al. Review on the processing and properties of polymer nanocomposites and nanocoatings and their applications in the packaging, automotive and solar energy fields. Nanomaterials. 2017;7:74. DOI: 10.3390/nano7040074
  60. 60. Ip M, Lui SL, Poon VKM, Lung I, Burd A. Antimicrobial activities of silver dressings: An in vitro comparison. Journal of Medical Microbiology. 2006;55:59-63. DOI: 10.1099/jmm.0.46124-0
  61. 61. Rhim J-W, Hong S-I, Park H-M, Ng PKW. Preparation and characterization of chitosan-based nanocomposite films with antimicrobial activity. Journal of Agricultural and Food Chemistry. 2006;54:5814-5822. DOI: 10.1021/jf060658h
  62. 62. Travan A, Marsich E, Donati I, Benincasa M, Giazzon M, Felisari L, et al. Silver–polysaccharide nanocomposite antimicrobial coatings for methacrylic thermosets. Acta Biomaterialia. 2011;7:337-346. DOI: 10.1016/j.actbio.2010.07.024
  63. 63. Dallas P, Kelarakis A, Giannelis EP. Nanostructured materials for environmentally conscious applications. In: Sustainable Nanotechnology and the Environment: Advances and Achievements, ACS Symposium Series. Vol. 1124. Washington: American Chemical Society; 2013. pp. 59-72. ISBN 978-0-8412-2784-2
  64. 64. Qu B, Luo Y. A review on the preparation and characterization of chitosan-clay nanocomposite films and coatings for food packaging applications. Carbohydrate Polymer Technologies and Applications. 2021;2:100102. DOI: 10.1016/j.carpta.2021.100102
  65. 65. Bhattacharjee M, Goswami S, Pramanik NB, Barman J, Saikia M, Swami Hulle NR, et al. Chitosan/clay biocomposite films with enhanced physico-chemical, mechanical and antimicrobial properties. Analytical Chemistry Letters. 2023;13:609-625. DOI: 10.1080/22297928.2023.2293812
  66. 66. Laaraibi A, Moughaoui F, Damiri F, Ouakit A, Charhouf I, Hamdouch S, et al. Chitosan-clay based (CS-NaBNT) biodegradable nanocomposite films for potential utility in food and environment. In: Chitin-Chitosan—Myriad Functionalities in Science and Technology. London, UK, London, UK: IntechOpen; 2018. ISBN 978-1-78923-407-7
  67. 67. Mohan T, Devchand K, Kanny K. Barrier and biodegradable properties of corn starch-derived biopolymer film filled with nanoclay fillers. Journal of Plastic Film & Sheeting. 2017;33:309-336. DOI: 10.1177/8756087916682553
  68. 68. Bezerra Lima EM, Middea A, Marconcini JM, Corrêa AC, Fernandes Pereira J, Vieira Guimarães A, et al. Biodegradable PLA based nanocomposites for packaging applications: The effects of organo-modified bentonite concentration. Journal of Applied Polymer Science. 2021;138:50907. DOI: 10.1002/app.50907
  69. 69. Radoor S, Karayil J, Jayakumar A, Parameswaranpillai J, Siengchin S. 7—PLA based bionanocomposites for food packaging applications. In: Ahmed S, editor. Bionanocomposites for Food Packaging Applications, Woodhead Publishing Series in Composites Science and Engineering. Amsterdam, Netherlands: Woodhead Publishing; 2022. pp. 115-133. ISBN 978-0-323-88528-7
  70. 70. Cherifi BI, Belbachir M, Rahmouni A, Derail C, Hannaoui F, Zeggai FZ, et al. Improvement of the viscoelastic and thermal properties of polyvinyl acetate reinforced with organophilic clay (Algerian MMT). Journal of Molecular Structure. 2022;1252:132100. DOI: 10.1016/j.molstruc.2021.132100
  71. 71. Lerari D, Benaboura A. Preparation method effect on thermal properties of PMMA/clay nanocomposite. Moroccan Journal of Chemistry. 2015;3(2):202-211. DOI: 10.48317/IMIST.PRSM/morjchem-v3i2.2487
  72. 72. Liu L, Pu X, Tao H, Chen K, Guo W, Luo D, et al. Pickering emulsion stabilized by organoclay and intermediately hydrophobic nanosilica for high-temperature conditions. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2021;610:125694. DOI: 10.1016/j.colsurfa.2020.125694
  73. 73. Massinga PH, Focke WW, de Vaal PL, Atanasova M. Alkyl ammonium intercalation of Mozambican bentonite. Applied Clay Science. 2010;49:142-148. DOI: 10.1016/j.clay.2010.04.017
  74. 74. Paul M-A, Alexandre M, Degée P, Henrist C, Rulmont A, Dubois P. New nanocomposite materials based on plasticized poly(l-lactide) and organo-modified montmorillonites: Thermal and morphological study. Polymer. 2003;44:443-450. DOI: 10.1016/S0032-3861(02)00778-4
  75. 75. Bikiaris D. Can nanoparticles really enhance thermal stability of polymers? Part II: An overview on thermal decomposition of polycondensation polymers. Thermochimica Acta. 2011;523:25-45. DOI: 10.1016/j.tca.2011.06.012
  76. 76. Nirmal Kumar K, Dinesh Babu P. Experimental study of mechanical, morphological and thermal performance of bamboo-reinforced polylactic acid-based montmorillonite clay hybrid composite. Industrial Crops and Products. 2024;209:117950. DOI: 10.1016/j.indcrop.2023.117950
  77. 77. Surya R, Mullassery MD, Fernandez NB, Thomas D. Exfoliated clay-polymer nanocomposite as a promising delivery system for bovine serum albumin. Indian Chemical Engineer. 2023;66:1-14. DOI: 10.1080/00194506.2023.2280651
  78. 78. Tran VA, Vo T-TT, Dang VQ , Vo GNL. Clay-based composites and nanocomposites for drug delivery. In: Hasnain MS, Nayak AK, Alkahtani S, editors. Carbon Nanostructures in Biomedical Applications, Advances in Material Research and Technology. Cham: Springer International Publishing; 2023. pp. 343-361. ISBN 978-3-031-28263-8
  79. 79. Cardoso HP, Bacalhau Rodrigues JF, Nunes da Silva H, Galdino TP, Luna CBB, Fook MVL, et al. Chitosan/montmorillonite nanocomposite film as anticancer drug carrier: A promising biomaterial to treat skin cancers. Ceramics International. 2024. DOI: 10.1016/j.ceramint.2024.02.337
  80. 80. Dawson JI, Oreffo ROC. Clay: New opportunities for tissue regeneration and biomaterial design. Advanced Materials. 2013;25:4069-4086. DOI: 10.1002/adma.201301034
  81. 81. Mikofsky RA, Armistead SJ, Srubar WV. On the bonding characteristics of clays and biopolymers for sustainable Earthen construction. In: Amziane S, Merta I, Page J, editors. Proceedings of the Bio-Based Building Materials. Cham: Springer Nature Switzerland; 2023. pp. 280-292
  82. 82. Xiang C, Zhang Q , Guo Z, Wang Z, Chen W, Li X, et al. Facile preparation and properties of porous poly(vinyl alcohol)/trehalose/nano-clay hydrogels with high mechanical strength for potential application in bone tissue engineering. European Polymer Journal. 2023;197:112336. DOI: 10.1016/j.eurpolymj.2023.112336
  83. 83. Bharadwaz A, Jayasuriya AC. Recent trends in the application of widely used natural and synthetic polymer nanocomposites in bone tissue regeneration. Materials Science and Engineering: C. 2020;110:110698. DOI: 10.1016/j.msec.2020.110698
  84. 84. Zhai X, Ma Y, Hou C, Gao F, Zhang Y, Ruan C, et al. 3D-printed high strength bioactive supramolecular polymer/clay nanocomposite hydrogel scaffold for bone regeneration. ACS Biomaterials Science & Engineering. 2017;3:1109-1118. DOI: 10.1021/acsbiomaterials.7b00224
  85. 85. Niu X, Wang L, Xu M, Qin M, Zhao L, Wei Y, et al. Electrospun polyamide-6/chitosan nanofibers reinforced nano-hydroxyapatite/polyamide-6 composite bilayered membranes for guided bone regeneration. Carbohydrate Polymers. 2021;260:117769. DOI: 10.1016/j.carbpol.2021.117769
  86. 86. Zhai X, Ruan C, Shen J, Zheng C, Zhao X, Pan H, et al. Clay-based nanocomposite hydrogel with attractive mechanical properties and sustained bioactive ion release for bone defect repair. Journal of Materials Chemistry B. 2021;9:2394-2406. DOI: 10.1039/D1TB00184A
  87. 87. Nguyen Thanh TT, Szolnoki B, Vadas D, Nacsa M, Marosi G, Bocz K. Effect of clay minerals on the flame retardancy of polylactic acid/ammonium polyphosphate system. Journal of Thermal Analysis and Calorimetry. 2023;148:293-304. DOI: 10.1007/s10973-022-11712-x
  88. 88. Olonisakin K, Li R, He S, Aishi W, Lifei F, Mengting C, et al. Flame rating of nano clay/MCC/PLA composites with both reinforced strength and toughness. Journal of Polymer Research. 2022;29:502. DOI: 10.1007/s10965-022-03351-5
  89. 89. Bee S-T, Hassan A, Ratnam CT, Tee T-T, Sin LT, Hui D. Dispersion and roles of montmorillonite on structural, flammability, thermal and mechanical behaviours of electron beam irradiated flame retarded nanocomposite. Composites Part B: Engineering. 2014;61:41-48. DOI: 10.1016/j.compositesb.2014.01.035
  90. 90. Ryu H-J, Lee J-H, Choi JY, Choi G, Rejinold NS, Choy J-H. Composite nanoarchitectonics with ionic clay nanofillers-embedded polypropylene for efficient flame retardance. Applied Clay Science. 2023;246:107181. DOI: 10.1016/j.clay.2023.107181
  91. 91. Szustakiewicz K, Cichy B, Gazińska M, Pigłowski J. Comparative study on flame, thermal, and mechanical properties of HDPE/clay nanocomposites with MPP or APP. Journal of Reinforced Plastics and Composites. 2013;32:1005-1017. DOI: 10.1177/0731684413481508
  92. 92. García-Muñoz MA, Valera- Zaragoza M, Aguirre-Cruz A, Carmona-García R, Ramírez-Hernández A, Ramírez-Vargas E, et al. Influence of compatibility in the EVA/starch/organoclay biodegradable nanocomposite on thermal properties and flame self-extinguishing behavior. Polymer-Plastics Technology and Materials. 2023;62:2318-2333. DOI: 10.1080/25740881.2023.2258396
  93. 93. Kolya H, Kang C-W. Next-generation water treatment: Exploring the potential of biopolymer-based nanocomposites in adsorption and membrane filtration. Polymers. 2023;15:3421. DOI: 10.3390/polym15163421
  94. 94. Barakan S, Aghazadeh V. The advantages of clay mineral modification methods for enhancing adsorption efficiency in wastewater treatment: A review. Environmental Science and Pollution Research. 2021;28:2572-2599. DOI: 10.1007/s11356-020-10985-9
  95. 95. Biswas S, Fatema J, Debnath T, Rashid TU. Chitosan–clay composites for wastewater treatment: A state-of-the-art review. ACS ES&T Water. 2021;1:1055-1085. DOI: 10.1021/acsestwater.0c00207
  96. 96. Biswas S, Rashid TU, Debnath T, Haque P, Rahman MM. Application of chitosan-clay biocomposite beads for removal of heavy metal and dye from industrial effluent. Journal Of Composites Science. 2020;4:16. DOI: 10.3390/jcs4010016
  97. 97. Das NC, Rahman MM, Kabir SF. Preparation of novel clay/chitosan/ZnO bio-composite as an efficient adsorbent for tannery wastewater treatment. International Journal of Biological Macromolecules. 2023;249:126136. DOI: 10.1016/j.ijbiomac.2023.126136
  98. 98. Momina, Ahmad K, Rafatullah M. Chapter 15—Applications of biodegradable polymer nanocomposites in water and wastewater treatment. In: Deshmukh K, Pandey M, editors. Biodegradable and Biocompatible Polymer Nanocomposites. Amsterdam, Netherlands: Elsevier; 2023. pp. 515-553. ISBN 978-0-323-91696-7
  99. 99. Moola AK, Prabhakar MR, Dey B, Paramasivan B, Vangala SM, Jakkampudi R, et al. Biopolymeric composite materials for environmental applications. Physical Sciences Reviews. 2023. DOI: 10.1515/psr-2022-0223
  100. 100. Palanisamy SB. Biopolymers as a versatile tool with special emphasis on environmental application. Physical Sciences Reviews. 2023. DOI: 10.1515/psr-2022-0218
  101. 101. Pinto L, Bonifacio MA, De Giglio E, Santovito E, Cometa S, Bevilacqua A, et al. Biopolymer hybrid materials: Development, characterization, and food packaging applications. Food Packaging and Shelf Life. 2021;28:100676. DOI: 10.1016/j.fpsl.2021.100676
  102. 102. El Mouzahim M, Eddarai EM, Eladaoui S, Guenbour A, Bellaouchou A, Zarrouk A, et al. Food packaging composite film based on chitosan, natural kaolinite clay, and ficus. Carica leaves extract for fresh-cut apple slices preservation. International Journal of Biological Macromolecules. 2023;233:123430. DOI: 10.1016/j.ijbiomac.2023.123430
  103. 103. Cheikh D, Majdoub H, Darder M. An overview of clay-polymer nanocomposites containing bioactive compounds for food packaging applications. Applied Clay Science. 2022;216:106335. DOI: 10.1016/j.clay.2021.106335
  104. 104. Alexandre EMC, Lourenço RV, Bittante AMQB, Moraes ICF, Sobral PJDA. Gelatin-based films reinforced with montmorillonite and activated with nanoemulsion of ginger essential oil for food packaging applications. Food Packaging and Shelf Life. 2016;10:87-96. DOI: 10.1016/j.fpsl.2016.10.004
  105. 105. Youssef AM, El-Sayed SM. Bionanocomposites materials for food packaging applications: Concepts and future outlook. Carbohydrate Polymers. 2018;193:19-27. DOI: 10.1016/j.carbpol.2018.03.088
  106. 106. Alboofetileh M, Rezaei M, Hosseini H, Abdollahi M. Morphological, physico-mechanical, and antimicrobial properties of sodium alginate-montmorillonite nanocomposite films incorporated with marjoram essential oil. Journal of Food Processing and Preservation. 2018;42:e13596. DOI: 10.1111/jfpp.13596
  107. 107. Holesova S, Barabaszova KC, Hundakova M, Kratosova G, Joszko K. In: Poothanari MA, Leterrier Y. Editors.Advanced Antimicrobial PCL/Clay Nanocomposite Films: Preparation, Characterization, Properties and Degradation in Simulated Body Fluid. 2023:116. Available from: https://www.researchsquare.com [Accessed: 1 March 2024]
  108. 108. Zhu L, Wang L, Xu Y. Chitosan and surfactant co-modified montmorillonite: A multifunctional adsorbent for contaminant removal. Applied Clay Science. 2017;146:35-42. DOI: 10.1016/j.clay.2017.05.027
  109. 109. Karaca S, Önal EÇ, Açışlı Ö, Khataee A. Preparation of chitosan modified montmorillonite biocomposite for sonocatalysis of dyes: Parameters and degradation mechanism. Materials Chemistry and Physics. 2021;260:124125. DOI: 10.1016/j.matchemphys.2020.124125
  110. 110. Nguyen Van H, Chu Van H, Luu Hoang T, Vo Nguyen DK, Ha Thuc CN. The starch modified montmorillonite for the removal of Pb(II), Cd(II) and Ni(II) ions from aqueous solutions. Arabian Journal of Chemistry. 2020;13:7212-7223. DOI: 10.1016/j.arabjc.2020.08.003
  111. 111. Kumararaja P, Manjaiah KM, Datta SC, Ahammed Shabeer TP, Sarkar B. Chitosan-g-poly(acrylic acid)-bentonite composite: A potential immobilizing agent of heavy metals in soil. Cellulose. 2018;25:3985-3999. DOI: 10.1007/s10570-018-1828-x
  112. 112. El-Sayed Abdel-Raouf M, Kamal RS, Hegazy DE, Sayed A. Gamma irradiation synthesis of carboxymethyl chitosan-nanoclay hydrogel for the removal of Cr(VI) and Pb(II) from aqueous media. Journal of Inorganic and Organometallic Polymers. 2023;33:895-913. DOI: 10.1007/s10904-023-02543-w
  113. 113. Futalan CM, Yang J-H, Phatai P, Chen I-P, Wan M-W. Fixed-bed adsorption of copper from aqueous media using chitosan-coated bentonite, chitosan-coated sand, and chitosan-coated kaolinite. Environmental Science and Pollution Research. 2020;27:24659-24670. DOI: 10.1007/s11356-019-06083-0
  114. 114. El-Shafie AS, El-Azazy M. Crosslinked chitosan–montmorillonite composite and its magnetized counterpart for the removal of basic fuchsin from wastewater: Parametric optimization using Box-Behnken design. International Journal of Biological Macromolecules. 2024;263:130224. DOI: 10.1016/j.ijbiomac.2024.130224
  115. 115. Yao A, Wang Y, Yu J, Tian S, Zhan Y, Liao H, et al. Fe-pillared montmorillonite functionalized chitosan/gelatin foams for efficient removal of organic pollutants by integration of adsorption and Fenton degradation. Carbohydrate Polymers. 2023;321:121265. DOI: 10.1016/j.carbpol.2023.121265
  116. 116. Superhydrophobic and Fluorine-Free Microfibrillated Cellulose-Clay Composite Films for Gas Barrier Applications. Available from: https://www.researchsquare.com [Accessed: 13 March 2024]
  117. 117. Kouda I, Ben Seddik N, Laaziz A, Hadri M, Draoui K, Elmidaoui A. Efficient removal of cationic dye from wastewater using novel low-cost adsorbent, cellulose-clay composite: Insights from isotherm, kinetic, thermodynamic, and molecular dynamics simulation studies. Journal of Molecular Structure. 2023;1291:135865. DOI: 10.1016/j.molstruc.2023.135865
  118. 118. Wang W, Zhang C, He J, Peng W, Cao Y, Liu J, et al. Chitosan-induced self-assembly of montmorillonite nanosheets along the end-face for methylene blue removal from water. International Journal of Biological Macromolecules. 2023;227:952-961. DOI: 10.1016/j.ijbiomac.2022.12.206
  119. 119. Abdulhameed AS, Hapiz A, Musa SA, ALOthman ZA, Wilson LD, Jawad AH. Biomagnetic chitosan-ethylene glycol diglycidyl ether/organo-nanoclay nanocomposite for azo dye removal: A statistical modeling by response surface methodology. International Journal of Biological Macromolecules. 2024;255:128075. DOI: 10.1016/j.ijbiomac.2023.128075
  120. 120. Abdulhameed AS, Hapiz A, Musa SA, Kashi E, Wu R, ALOthman ZA, et al. Organically modified montmorillonite composited with magnetic glyoxal-chitosan schiff base for reactive blue 19 dye removal: Process optimization and adsorptive mechanism. International Journal of Biological Macromolecules. 2024;256:128463. DOI: 10.1016/j.ijbiomac.2023.128463
  121. 121. Rosli K, Abdulhameed AS, Surip SN, ALOthman ZA, Jawad AH. An eco-friendly adsorbent of chitosan/montmorillonite/algae for removal of basic green 1 and reactive blue 19 dyes: Box-Behnken design optimization mechanistic study. Journal of Polymers and the Environment. 2023;31:3907-3924. DOI: 10.1007/s10924-023-02869-z
  122. 122. Shabtai IA, Mishael YG. Polycyclodextrin–clay composites: Regenerable dual-site sorbents for bisphenol A removal from treated wastewater. ACS Applied Materials & Interfaces. 2018;10:27088-27097. DOI: 10.1021/acsami.8b09715
  123. 123. Kundu S, Korin Manor N, Radian A. Iron–montmorillonite–cyclodextrin composites as recyclable sorbent catalysts for the adsorption and surface oxidation of organic pollutants. ACS Applied Materials & Interfaces. 2020;12:52873-52887. DOI: 10.1021/acsami.0c17510
  124. 124. Reghioua A, Atia D, Hamidi A, Jawad AH, Abdulhameed AS, Mbuvi HM. Production of eco-friendly adsorbent of kaolin clay and cellulose extracted from peanut shells for removal of methylene blue and Congo Red removal dyes. International Journal of Biological Macromolecules. 2024;263:130304. DOI: 10.1016/j.ijbiomac.2024.130304
  125. 125. Li X, Zhang G, Jin Y, Gu X, Xie G, Li Y, et al. Removal of Cd from solution and in-situ remediation of Cd-contaminated soil by a mercapto-modified cellulose/bentonite intercalated nanocomposite. Environmental Research. 2024;251(2):118303. DOI: 10.1016/j.envres.2024.118303
  126. 126. Farid E, Kamoun EA, Taha TH, El-Dissouky A, Khalil TE. Eco-friendly biodegradation of hydrocarbons compounds from crude oily wastewater using PVA/alginate/clay composite hydrogels. Journal of Polymers and the Environment. 2024;32:225-245. DOI: 10.1007/s10924-023-02991-y
  127. 127. Santoso SP, Kurniawan A, Angkawijaya AE, Shuwanto H, Warmadewanthi IDAA, Hsieh C-W, et al. Removal of heavy metals from water by macro-mesoporous calcium alginate–exfoliated clay composite sponges. Chemical Engineering Journal. 2023;452:139261. DOI: 10.1016/j.cej.2022.139261
  128. 128. Aziam R, Stefan DS, Nouaa S, Chiban M, Boșomoiu M. Adsorption of metal ions from single and binary aqueous systems on bio-nanocomposite, alginate-clay. Nanomaterials. 2024;14:362. DOI: 10.3390/nano14040362
  129. 129. Aziam R, Stefan DS, Aboussabek A, Chiban M, Croitoru A-M. Alginate–moroccan clay, new bio-nanocomposite for removal of H2PO4−, HPO42−, and NO3− ions from aqueous solutions. Polymers. 2023;15:4666. DOI: 10.3390/polym15244666
  130. 130. Surya R, Mullassery MD, Fernandez NB, Thomas D. Alginate-bentonite composite decorated by chitosan-folate conjugate for the oral delivery of 5-fluorouracil. Analytical Chemistry Letters. 2023;13:461-474. DOI: 10.1080/22297928.2023.2263018
  131. 131. Yahiaoui F, Benhacine F, Ferfera-Harrar H, Habi A, Hadj-Hamou AS, Grohens Y. Development of antimicrobial PCL/nanoclay nanocomposite films with enhanced mechanical and water vapor barrier properties for packaging applications. Polymer Bulletin. 2015;72:235-254. DOI: 10.1007/s00289-014-1269-0
  132. 132. Krajišnik D, Uskoković-Marković S, Daković A, Smiljanić D, Kozarski M, Lazić V. Preparation and characterization of chitosan–clay composites as potential drug carriers. In: 5th Metallurgical & Materials Engineering Congress of South-East Europe. 2023. pp. 123-127
  133. 133. Yar A, Okbaz A, Parlayıcı Ş. A biocompatible, eco-friendly, and high-performance triboelectric nanogenerator based on sepiolite, bentonite, and kaolin decorated chitosan composite film. Nano Energy. 2023;110:108354. DOI: 10.1016/j.nanoen.2023.108354
  134. 134. Gürler N, Torğut G. Physicomechanical, thermal and dielectric properties of eco-friendly starch-microcrystalline cellulose-clay nanocomposite films for food packaging and electrical applications. Packaging Technology and Science. 2022;35:473-483. DOI: 10.1002/pts.2643
  135. 135. Zheng M, Tajvidi M, Tayeb AH, Stark NM. Effects of bentonite on physical, mechanical and barrier properties of cellulose nanofibril hybrid films for packaging applications. Cellulose. 2019;26:5363-5379. DOI: 10.1007/s10570-019-02473-2
  136. 136. Oliver-Ortega H, Vandemoortele V, Bala A, Julian F, Méndez JA, Espinach FX. Nanoclay effect into the biodegradation and processability of poly(lactic acid) nanocomposites for food packaging. Polymers. 2021;13:2741. DOI: 10.3390/polym13162741
  137. 137. Ambre AH, Katti KS, Katti DR. Nanoclay based composite scaffolds for bone tissue engineering applications. Journal of Nanotechnology in Engineering and Medicine. 2010;1:031013. DOI: 10.1115/1.4002149
  138. 138. Kundu K, Afshar A, Katti DR, Edirisinghe M, Katti KS. Composite nanoclay-hydroxyapatite-polymer fiber scaffolds for bone tissue engineering manufactured using pressurized gyration. Composites Science and Technology. 2021;202:108598. DOI: 10.1016/j.compscitech.2020.108598
  139. 139. Chen M, Le DQ , Hein S, Li P, Nygaard JV, Kassem M, et al. Fabrication and characterization of a rapid prototyped tissue engineering scaffold with embedded multicomponent matrix for controlled drug release. International Journal of Nanomedicine. 2012;7:4285-4297. DOI: 10.2147/IJN.S33083
  140. 140. Noormohammadi M, Zabihi M, Faghihi M. Novel chitosan–clay–iron nanocomposites supported on anodic aluminum as an efficient plate-shaped adsorbent for the removal of arsenic and dye from aqueous solutions. Journal of Physics and Chemistry of Solids. 2024;187:111874. DOI: 10.1016/j.jpcs.2024.111874
  141. 141. Schiessl S, Kucukpinar E, Cros S, Miesbauer O, Langowski H-C, Eisner P. Nanocomposite coatings based on polyvinyl alcohol and montmorillonite for high-barrier food packaging. Frontiers in Nutrition. 2022;9: 790157. DOI: 10.3389/fnut.2022.790157
  142. 142. Cherifi Z, Boukoussa B, Mokhtar A, Hachemaoui M, Zeggai FZ, Zaoui A, et al. Preparation of new nanocomposite poly(GDMA)/mesoporous silica and its adsorption behavior towards cationic dye. Reactive and Functional Polymers. 2020;153:104611. DOI: 10.1016/j.reactfunctpolym.2020.104611

Written By

Fatima Zohra Zeggai, Fouzia Touahra, Radia Labied, Djahida Lerari, Redouane Chebout and Khaldoun Bachari

Submitted: 01 March 2024 Reviewed: 21 March 2024 Published: 22 April 2024

© 2024 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution 3.0 License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.