The present Review addresses current developments related to polymer-derived ceramic nanocomposites (PDC-NCs). Different classes of preceramic polymers are briefly introduced and their conversion into ceramic materials with adjustable phase compositions and microstructures is presented. Emphasis is set on discussing the intimate relationship between the chemistry and structural architecture of the precursor and the structural features and properties of the resulting ceramic nanocomposites. Various structural and functional properties of silicon-containing ceramic nanocomposites as well as different preparative strategies to achieve nano-scaled PDC-NC-based ordered structures are highlighted, based on selected ceramic nanocomposite systems. Furthermore, prospective applications of the PDC-NCs such as high-temperature stable materials for thermal protection systems, membranes for hot gas separation purposes, materials for heterogeneous catalysis, nano-confinement materials for hydrogen storage applications as well as anode materials for secondary ion batteries are introduced and discussed in detail.

https://www.mdpi.com/2079-4991/5/2/468/pdf

Ceramic Nanocomposites from Tailor-Made Preceramic Polymers

A feasible strategy to achieve large-area mechano-, thermo- and solvatochromic hybrid opal (OPC) and inverse opal photonic crystal (IOPC) films based on polymer hydrogels is described. Silica core particles featuring surface-anchored stimuli-responsive polymers are prepared and advantageously used for the melt-shear organization technique. By this approach hybrid OPC films with adjustable periodicities for photonic applications can be prepared. The large-area OPC films can be furthermore converted into IOPC structures simply by etching the silica particles while maintaining the excellent order of the entire opal film. This herein developed new process seems to be universal and is successfully applied to two thermo-responsive polymers, poly(N-isopropylacrylamide) (PNIPAM) and poly(diethylene glycol methylether methacrylate) (PDEGMEMA) as particle shell materials. Besides the remarkable mechanical robustness of the hybrid OPC and IOPC films, optical properties upon changes of temperature, mechanical stress and different solvents as external triggers are successfully confirmed. The herein described novel strategy for the preparation of inorganic/organic OPC and IOPC polymer films is feasible for a wide range of applications in fields of sensing and photonic band gap materials.

/pdf/smart-polymer-inverse-opal-photonic-crystal-films-by-melt-4m3vdhiqvl.pdf

Smart polymer inverse-opal photonic crystal films by melt-shear organization for hybrid core–shell architectures

In this work, the preparation of highly thermoresponsive and fully reversible stretch-tunable elastomeric opal films featuring switchable structural colors is reported. Novel particle architectures based on poly(diethylene glycol methylether methacrylate-co-ethyl acrylate) (PDEGMEMA-co-PEA) as shell polymer are synthesized via seeded and stepwise emulsion polymerization protocols. The use of DEGMEMA as comonomer and herein established synthetic strategies leads to monodisperse soft shell particles, which can be directly processed to opal films by using the feasible melt-shear organization technique. Subsequent UV crosslinking strategies open access to mechanically stable and homogeneous elastomeric opal films. The structural colors of the opal films feature mechano- and thermoresponsiveness, which is found to be fully reversible. Optical characterization shows that the combination of both stimuli provokes a photonic bandgap shift of more than 50 nm from 560 nm in the stretched state to 611 nm in the fully swollen state. In addition, versatile colorful patterns onto the colloidal crystal structure are produced by spatial UV-induced crosslinking by using a photomask. This facile approach enables the generation of spatially cross-linked switchable opal films with fascinating optical properties. Herein described strategies for the preparation of PDEGMEMA-containing colloidal architectures, application of the melt-shear ordering technique, and patterned crosslinking of the final opal films open access to novel stimuli-responsive colloidal crystal films, which are expected to be promising materials in the field of security and sensing applications.

Utilizing Stretch‐Tunable Thermochromic Elastomeric Opal Films as Novel Reversible Switchable Photonic Materials

SiO2@Co3O4 core–shell nanorattles with different Co3O4 shell thicknesses have been successfully synthesized by the calcination of SiO2@α-Co(OH)2 at 500 °C. The synthetic approach is facile, economical, and requires no surface modification. The synthesized materials were thoroughly characterized using powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA), Brunauer–Emmett–Teller (BET) analysis, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and diffuse reflectance spectroscopy (DRS). SEM analysis indicates a hierarchical core–shell morphology for SiO2@Co3O4 and the TEM results indicate the core–shell nanorattle morphology. Diffuse reflectance spectroscopy studies indicate that the SiO2@Co3O4 core–shell nanorattles show two absorption bands in the range 420–450 nm and 700–750 nm related to ligand to metal charge transfer transitions (O2− → Co2+ and O2− → Co3+). The SiO2@Co3O4 core–shell nanorattles act as an artificial peroxidase enzyme mimic with enhanced intrinsic peroxidase-like activity compared to pure Co3O4 nanoparticles and horseradish peroxidase (HRP), a natural enzyme. The SiO2@Co3O4 core–shell nanorattles show higher kcat and kcat/Km values compared to pure Co3O4 and HRP indicating their applicability as an artificial enzyme mimic in biomedicine and bio-sensing.

A facile synthetic approach for SiO2@Co3O4 core–shell nanorattles with enhanced peroxidase-like activity

Diverse innovative fabrics with specific functionalities have been developed for requirements such as self-decontamination of chemical/biological pollutants and toxic nerve agents. In this work, Zr(OH)4 -coated nylon-6,6 nanofiber mats were fabricated for the decontamination of nerve agents. Nylon-6,6 fabric was prepared via the electrospinning process, followed by coating with Zr(OH)4 , which was obtained by the hydrolysis of Zr(OBu)4 by a sol-gel reaction on nanofiber surfaces. The reaction conditions were optimized by varying the amounts of Zr(OBu)4 ,the reaction time, and the temperature of the sol-gel reaction. The composite nanofibers show high decontamination efficiency against diisopropylfluorophosphate, which is a nerve agent analogue, due to its high nucleophilicity that aids in the catalysis of the hydrolysis of the phosphonate ester bonds. Composite nanofiber mats have a large potential and can be applied in specific fields such as military and medical markets.

Zirconium Hydroxide-coated Nanofiber Mats for Nerve Agent Decontamination.

The control over structure and function in hierarchically multidimensional materials based on hollow spheres, nanowires, nanorods, nanotubes, fibres, membranes or inverse opals with adjustable dimensions has gained considerable attention due to their tremendous potential for a wide variety of applications. Herein we describe convenient and efficient synthetic concepts for synthesis and processing of well-defined polymer-templated inorganic materials with 0D, 1D, 2D and 3D nano- and microstructures. In the first step, we describe universal methodologies for the controlled build-up of polymer-templated non-functional inorganic structures by taking advantage of lower dimensional structures such as core–shell particles or fibres. With this approach it is possible to obtain more sophisticated architectures such as 3D ordered macroporous (3DOM) materials after applying different procedures for organization, e.g. the powerful melt shear technique as well as novel double-templating strategies towards multidimensional carbon architectures. To prove the feasibility of our protocols established herein we have exemplarily applied these methods to the formation of functional inorganic high-temperature materials, such as silicon carbide (β-SiC) and yttria-stabilized zirconia (YSZ). The general pathways for the controlled build-up of nano- and micro-scaled structures based on polymer templates may thus provide a facile and versatile route to an even wider variety of organic/inorganic composite materials offering a wider range of future applications in the fields of catalysis, separation, sensors, optics, and biomedicine. Herein we show first examples of selected new material morphologies towards energy related issues, namely Li-ion battery applications and heterogeneous catalysis (selective ethanol oxidation).

/pdf/a-polymer-based-and-template-directed-approach-towards-23aja89ya0.pdf

A polymer based and template-directed approach towards functional multidimensional micro-structured organic/inorganic hybrid materials

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A polymer based and template-directed approach towards functional multidimensional micro-structured organic/inorganic hybrid materials