Mechanical Behavior of Hybrid Thin Films Fabricated by Sequential Infiltration Synthesis in Water-Rich Environment.

Sequential infiltration synthesis (SIS) is an emerging technique for fabricating hybrid organic-inorganic materials with nanoscale precision and controlled properties. Central to SIS implementation in applications such as membranes, sensors, and functional coatings is the mechanical properties of hybrid materials in water-rich environments. This work studies the nanocomposite morphology and its effect on the mechanical behavior of SIS-based hybrid thin films of AlOx-PMMA under aqueous environments. Water-supported tensile measurements reveal an unfamiliar behavior dependent on the AlOx content, where the modulus decreases after a single SIS cycle and increases with additional cycles. In contrast, the yield stress constantly decreases as the AlOx content increases. A comparison between water uptake measurements indicates that AlOx induces water uptake from the aqueous environment, implying a "nanoeffect" stemming from AlOx-water interactions. We discuss the two mechanisms that govern the modulus of the hybrid films: softening due to increased water absorption and stiffening as the AlOx volume fraction increases. The decrease in the yield stress with SIS cycles is associated with the limited mobility and extensibility of polymer chains caused by the growth of AlOx clusters. Our study highlights the significance of developing hybrid materials to withstand aqueous or humid conditions which are crucial to their performance and durability.

Facile and Novel Eco-Friendly Poly(Vinyl Alcohol) Nanofilters Using the Photocatalytic Property of Titanium Dioxide.

This study aimed to develop a highly efficient nanofilter for capturing fine particles using electrostatic forces. Poly(vinyl alcohol) (PVA), a water-soluble synthetic polymer, was selected as the main component of the filter because it can be easily fabricated by electrospinning. Titanium dioxide (TiO2) nanopowder with an anatase structure was applied to the nanofilters as it has the highest photocatalytic activity among the existing photocatalysts. PVA nanofilters fabricated by electrospinning could still be dissolved in water by hydrolysis. Therefore, heat treatment was performed to make the nanofilters stable, thereby forming C=O bonds by keto-enol tautomerization. Structural changes in the PVA nanofilter before and after heat treatment were investigated by X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) analysis. As the TiO2 concentration increased, the fiber diameter of the PVA nanofilter decreased and a homogeneous fiber was obtained. The filtration efficiency and pressure drop also improved significantly, compared to those of the PVA-only nanofilter. Moreover, we observed eco-friendly decomposition of the PVA/TiO2 nanofilter into water and carbon dioxide by a photocatalytic reaction under UV irradiation.

Preparation and Characterization of Superabsorbent Polymers Based on Starch Aldehydes and Carboxymethyl Cellulose.

Superabsorbent polymers (SAPs) are crosslinked hydrophilic polymers that are capable of absorbing large amounts of water. Commercial SAPs are mostly produced with acrylic acid that cannot be easily biodegraded. Therefore, in this study, polysaccharide-based SAPs using carboxymethyl cellulose as a major component were prepared. Starch aldehydes and citric acid were selected due to their environment-friendly, non-toxic, and biodegradable properties compared to conventional crosslinking agents. Starch aldehydes were prepared by periodate oxidation, which forms aldehyde groups by taking the places of C⁻OH groups at C-2 and C-3. Furthermore, starch aldehydes were analyzed through the change in FT-IR spectra, the aldehyde quantitation, and the morphology in FE-SEM images. In the crosslinking of polysaccharide-based SAPs, the acetal bridges from starch aldehydes led to a large amount of water entering the network structure of the SAPs. However, the ester bridges from citric acid interfered with the water penetration. In addition, the swelling behavior of the SAPs was analyzed by the Fickian diffusion model and the Schott's pseudo second order kinetics model. The relationship between swelling behavior and morphology of the SAPs was analyzed by FE-SEM images. In conclusion, polysaccharide-based SAPs were well prepared and the highest equilibrium swelling ratio was 87.0 g/g.

Covalent Functionalization of Multi-Walled Carbon Nanotubes Surface via Chemical Treatment.

Due to the strong hydrophobic and van der Waals interactions between individual carbon nanotubes (CNTs), these particles easily aggregate with themselves. When CNTs were introduced into a polymer matrix as a filler, aggregations formed that can adversely affect the mechanical and thermal properties of polymer/CNTs composites. To prevent aggregation, covalent functionalizations via chemical treatments using H2SO4/HNO3, H2O2/H2O and a silane coupling agent(STX)-glycidoxypropyltrimethoxysilane, GPTMS) on the CNTs were chosen in this study. Moreover, the effect of the functional groups on the solubility of CNTs in tetrahydrofuran (THF) was investigated. The surface-modified multi-walled carbon nanotubes (MWCNTs) were also characterized and compared with pristine MWCNTs using several techniques. Morphology changes in surfacemodified MWCNTs were observed by Raman spectroscopy and Field-Emission Scanning Electron Microscopy (FE-SEM) images. Qualitative analyses of the functional groups on the surface-modified MWCNTs were performed by Fourier Transform Infrared Spectroscopy (FT-IR). Additionally, quantitative analyses were performed by X-Ray Photoelectron Spectroscopy (XPS), Energy Dispersive Spectroscopy (EDS), a titration method and Thermogravimetric analysis (TGA).

Effect of the Grafting Reaction of Aluminum Nitride on the Multi-Walled Carbon Nanotubes on the Thermal Properties of the Poly(phenylene sulfide) Composites.

In this study, the PPS/MWCNTs/AlN composite was prepared with poly(phenylene sulfide) (PPS), covalent functionalized multi-walled carbon nanotubes (fMWCNTs), and aluminum nitride (AlN) via melt-blending techniques. The AlN is a fascinating non-oxidizing ceramic material having the highest thermal conductivity among the ceramic materials. In order to introduce the functional groups on the surface of the AlN particles, a silane coupling agent was used as it is able to graft with the functional groups on the covalent functionalized MWCNTs. The silanization reaction of the AlN was confirmed qualitatively and quantitatively by FT-IR (Fourier Transform Infrared Spectroscopy), and XPS (X-ray Photoelectron Spectroscopy). The grafting reaction of the AlN particles on the MWCNTs was confirmed using UV⁻Vis (Ultraviolet-Visible Spectroscopy), FE-SEM (Field-Emission Scanning Electron Microscopy) and FE-TEM (Field-Emission Transmission Electron Microscopy) images. The grafting reaction was accomplished by observing the change of the transmittance, the morphology of the AlN particle bonded to the MWCNTs. For the morphological changes of the fractured surface of the PPS/MWCNTs/AlN composites by FE-SEM, the hybrid filler was homogeneously dispersed on the PPS matrix when the AlN particle was grafted on the MWCNTs. The homogeneous distribution of the hybrid filler acts as a heat transfer path, which led the higher thermal properties, such as thermal conductivity, thermal resistance, and melting temperature than those of not grafted MWCNTs.

Effects of Covalent Functionalization of MWCNTs on the Thermal Properties and Non-Isothermal Crystallization Behaviors of PPS Composites.

In this study, a PPS/MWCNTs composite was prepared with poly(phenylene sulfide) (PPS), as well as pristine and covalent functionalized multi-walled carbon nanotubes (MWCNTs) via melt-blending techniques. Moreover, the dispersion of the MWCNTs on the PPS matrix was improved by covalent functionalization as can be seen from a Field-Emission Scanning Electron Microscope (FE-SEM) images. The thermal properties of the PPS/MWCNTs composites were characterized using a thermal conductivity analyzer, and a differential scanning calorimeter (DSC). To analyze the crystallization behavior of polymers under conditions similar with those in industry, the non-isothermal crystallization behaviors of the PPS/MWCNTs composites were confirmed using various kinetic equations, such as the modified Avrami equation and Avrami-Ozawa combined equation. The crystallization rate of PPS/1 wt % pristine MWCNTs composite (PPSP1) was faster because of the intrinsic nucleation effect of the MWCNTs. However, the crystallization rates of the composites containing covalently-functionalized MWCNTs were slower than PPSP1 because of the destruction of the MWCNTs graphitic structure via covalent functionalization. Furthermore, the activation energies calculated by Kissinger's method were consistently decreased by covalent functionalization.