Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications, and Applications

Polymer/layered silicate nanocomposites: a review from preparation to processing

This review aims at reporting on very recent developments in syntheses, properties and (future) applications of polymer-layered silicate nanocomposites. This new type of materials, based on smectite clays usually rendered hydrophobic through ionic exchange of the sodium interlayer cation with an onium cation, may be prepared via various synthetic routes comprising exfoliation adsorption, in situ intercalative polymerization and melt intercalation. The whole range of polymer matrices is covered, i.e. thermoplastics, thermosets and elastomers. Two types of structure may be obtained, namely intercalated nanocomposites where the polymer chains are sandwiched in between silicate layers and exfoliated nanocomposites where the separated, individual silicate layers are more or less uniformly dispersed in the polymer matrix. This new family of materials exhibits enhanced properties at very low filler level, usually inferior to 5 wt.%, such as increased Young’s modulus and storage modulus, increase in thermal stability and gas barrier properties and good flame retardancy.

Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials

Polymer nanocomposites with layered silicates as the inorganic phase (reinforcement) are discussed. The materials design and synthesis rely on the ability of layered silicates to intercalate in the galleries between their layers a wide range of monomers and polymers. Special emphasis is placed on a new, versatile and environmentally benign synthesis approach by polymer melt intercalation. In contrast to in-situ polymerization and solution intercalation, melt intercalation involves mixing the layered silicate with the polymer and heating the mixture above the softening point of the polymer. Compatibility with various polymers is accomplished by derivatizing the silicates with alkyl ammonium cations via an ion exchange reaction. By fine-tuning the surface characteristics nanodispersion (i. e. intercalation or delamination) can be accomplished. The resulting polymer layered silicate (PLS) nanocomposites exhibit properties dramatically different from their more conventional counterparts. For example, PLS nanocomposites can attain a particular degree of stiffness, strength and barrier properties with far less inorganic content than comparable glass- or mineral reinforced polymers and, therefore, they are far lighter in weight. In addition, PLS nanocomposites exhibit significant increase in thermal stability as well as self-extinguishing characteristics. The combination of improved properties, convenient processing and low cost has already led to a few commercial applications with more currently under development.

Polymer Layered Silicate Nanocomposites

Background Since at least 400 C.E., when the Mayans first used layered clays to make dyes, people have been harnessing the properties of layered materials. This gradually developed into scientific research, leading to the elucidation of the laminar structure of layered materials, detailed understanding of their properties, and eventually experiments to exfoliate or delaminate them into individual, atomically thin nanosheets. This culminated in the discovery of graphene, resulting in a new explosion of interest in two-dimensional materials. Layered materials consist of two-dimensional platelets weakly stacked to form three-dimensional structures. The archetypal example is graphite, which consists of stacked graphene monolayers. However, there are many others: from MoS 2 and layered clays to more exotic examples such as MoO 3 , GaTe, and Bi 2 Se 3 . These materials display a wide range of electronic, optical, mechanical, and electrochemical properties. Over the past decade, a number of methods have been developed to exfoliate layered materials in order to produce monolayer nanosheets. Such exfoliation creates extremely high-aspect-ratio nanosheets with enormous surface area, which are ideal for applications that require surface activity. More importantly, however, the two-dimensional confinement of electrons upon exfoliation leads to unprecedented optical and electrical properties. Liquid exfoliation of layered crystals allows the production of suspensions of two-dimensional nanosheets, which can be formed into a range of structures. (A) MoS 2 powder. (B) WS 2 dispersed in surfactant solution. (C) An exfoliated MoS 2 nanosheet. (D) A hybrid material consisting of WS 2 nanosheets embedded in a network of carbon nanotubes. Advances An important advance has been the discovery that layered crystals can be exfoliated in liquids. There are a number of methods to do this that involve oxidation, ion intercalation/exchange, or surface passivation by solvents. However, all result in liquid dispersions containing large quantities of nanosheets. This brings considerable advantages: Liquid exfoliation allows the formation of thin films and composites, is potentially scaleable, and may facilitate processing by using standard technologies such as reel-to-reel manufacturing. Although much work has focused on liquid exfoliation of graphene, such processes have also been demonstrated for a host of other materials, including MoS 2 and related structures, layered oxides, and clays. The resultant liquid dispersions have been formed into films, hybrids, and composites for a range of applications. Outlook There is little doubt that the main advances are in the future. Multifunctional composites based on metal and polymer matrices will be developed that will result in enhanced mechanical, electrical, and barrier properties. Applications in energy generation and storage will abound, with layered materials appearing as electrodes or active elements in devices such as displays, solar cells, and batteries. Particularly important will be the use of MoS 2 for water splitting and metal oxides as hydrogen evolution catalysts. In addition, two-dimensional materials will find important roles in printed electronics as dielectrics, optoelectronic devices, and transistors. To achieve this, much needs to be done. Production rates need to be increased dramatically, the degree of exfoliation improved, and methods to control nanosheet properties developed. The range of layered materials that can be exfoliated must be expanded, even as methods for chemical modification must be developed. Success in these areas will lead to a family of materials that will dominate nanomaterials science in the 21st century.

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Liquid Exfoliation of Layered Materials

Bionanocomposites represent an emerging group of nanostructured hybrid materials. They are formed by the combination of natural polymers and inorganic solids and show at least one dimension on the nanometer scale. Similar to conventional nanocomposites, which involve synthetic polymers, these biohybrid materials also exhibit improved structural and functional properties of great interest for different applications. The properties inherent to the biopolymers, that is, biocompatibility and biodegradability, open new prospects for these hybrid materials with special incidence in regenerative medicine and in environmentally friendly materials (green nanocomposites). Research on bionanocomposites can be regarded as a new interdisciplinary field closely related to significant topics such as biomineralization processes, bioinspired materials, and biomimetic systems. The upcoming development of novel bionanocomposites introducing multifunctionality represents a promising research topic that takes advantage of the synergistic assembling of biopolymers with inorganic nanometer-sized solids.

Bionanocomposites: A New Concept of Ecological, Bioinspired, and Functional Hybrid Materials

Poly(ethylene oxide)-silicate intercalation materials

Nanostructured hybrids derived from clays are materials of increasing interest based on both structural characteristics and functional applications, including environmental and biomedical uses. This review introduces some recent examples of nanostructured clay derivatives (organoclays) useful as adsorbents or photocatalysts for environmental applications such as the removal of pollutants or development of environmentally oriented pesticide formulations. The second group of nanostructured materials considered here are related to the so-called bio-nanohybrids, formed by combination of an inorganic solid (clay mineral) with organic entities from biological origin at the nanometric scale. Bionanocomposites are an emerging group of nanomaterials resulting from the assembly of different clay minerals and biopolymers. Among the proposed applications, the development of novel hybrid materials for scaffolds and regenerative medicine, as well as new substrates to immobilize biological species from enzymes to viruses, is notable. Hybrid materials based on layered double hydroxides are receiving special attention in view of the possible applications as drug delivery systems.

https://www.researchgate.net/profile/Giora_Rytwo/publication/233733191_ChemInform_Abstract_Hybrid_Materials_Based_on_Clays_for_Environmental_and_Biomedical_Applications/links/53d34a6e0cf228d363e97449.pdf

Hybrid materials based on clays for environmental and biomedical applications

The rapid increase of interest in the field of biohybrid and biomimetic materials that exhibit improved structural and functional properties is attracting more and more researchers from life science, materials science, and nanoscience. Concomitant results offer valuable opportunities for applications that involve disciplines dealing with engineering, biotechnology, medicine and pharmacy, agriculture, nanotechnology, and others. In the current contribution we collect recent illustrative examples of assemblies between materials of biological origin and inorganic solids of different characteristics (texture, structure, and particle size). We introduce here a general overview on strategies for the preparation and conformation of biohybrids, the synergistic effects that determine the final properties of these materials, and their diverse applications, which cover areas as different as tissue engineering, drug delivery systems, biosensing devices, biocatalysis, green nanocomposites, etc.

Advances in Biomimetic and Nanostructured Biohybrid Materials

A new family of functional hybrid nanocomposites based on the intercalation of naturally occurring anionic biopolymers including alginic acid, pectin, κ-carrageenan, ι-carrageenan, and xanthan gum in [Zn2Al(OH)6]Cl·nH2O layered double hydroxide (LDH), have been synthesized. The “coprecipitation” or “co-organized assembly” method has been successfully employed for the intercalation of such polysaccharides within the [Zn2Al] LDH. However, the “reconstruction” procedure from the calcined LDH in the presence of the anionic polysaccharides only resulted in a partial intercalation of the organic guest. Particular effort was devoted to the study of ι-carrageenan−[Zn2Al] systems. An essential feature of the prepared biopolymer−[Zn2Al] nanocomposites is that the anionic exchange capacity of the pristine LDH is turned into a cationic exchange capacity due to negatively charged groups in the polysaccharide structure that do not interact with the positively charged LDH layers. In agreement with the fact that most of ...

Pilar Aranda

Papers

Bionanocomposites: A New Concept of Ecological, Bioinspired, and Functional Hybrid Materials

Poly(ethylene oxide)-silicate intercalation materials

Hybrid materials based on clays for environmental and biomedical applications

Advances in Biomimetic and Nanostructured Biohybrid Materials

Bio-Nanocomposites Based on Layered Double Hydroxides