VOC-Induced Flexing of Single and Multilayer Polyethylene Films As Gas Sensors

The differential swelling and bending of multilayer polymeric films due to the dissimilar uptake of volatile organic compounds (VOCs; <i>n</i>-hexane, limonene) in the different layers was studied. Motions of thin polyethylene films triggered by the penetrant were investigated to learn more about how their deformation is related to VOC absorption. Single layers of metallocene or low-density polyethylene, and multilayers (2–288 layers) of these in alternating positions were considered. Single-, 24-, and 288-layer films displayed no motion when uniformly subjected to VOCs, but they could display simple curving modes when only one side of the film was wetted with a liquid VOC. Two-layer films displayed simple bending when uniformly subjected to VOCs due to the different swelling in the two layers, but when the VOC was applied to only one side of the film, more complex modes of motion as well as dynamic oscillations were observed (e.g., constant amplitude wagging at 2 Hz for ca. 50 s until all the VOC had evaporated). Diffusion modeling was used to study the transport behavior of VOCs inside the films and the different bending modes. Finally a prototype VOC sensor was developed, where the reproducible curving of the two-layer film was calibrated with <i>n</i>-hexane. The sensor is simple, cost-efficient, and nondestructive and requires no electricity

Local Charge Injection and Extraction on Surface-Modified Al₂O₃ Nanoparticles in LDPE

We use a recently developed scanning probe technique to image with high spatial resolution the injection and extraction of charge around individual surface-modified aluminum oxide nanoparticles embedded in a low-density polyethylene (LDPE) matrix. We find that the experimental results are consistent with a simple band structure model where localized electronic states are available in the band gap (trap states) in the vicinity of the nanoparticles. This work offers experimental support to a previously proposed mechanism for enhanced insulating properties of nanocomposite LDPE and provides a powerful experimental tool to further investigate such properties

Aqueous Synthesis of (21̅0) Oxygen-Terminated Defect-Free Hierarchical ZnO Particles and Their Heat Treatment for Enhanced Reactivity

Controlled aqueous growth of 1 μm flower-shaped ZnO particles with a hierarchical subset of exposed nanosheets represented by {21̅0} crystal faces, followed by annealing at temperatures up to 1000 °C, is presented. The flower-shaped particles showed superior photocatalytic performance compared to the crystal faces of 20 nm ZnO nanoparticles. The photocatalytic reaction rate of the flower-shaped particles before annealing was 2.4 times higher per m² compared with that of the nanoparticles with double specific surface area. Crystal surface defects and nanosized pores within the flower-shaped particles were revealed by porosity measurements and electron microscopy. A heat treatment at 400 °C was found to be optimal for removal of nanoporosity/surface defects and impurities while retaining the hierarchical superstructure. The heat treatment resulted in a photodegradation efficiency that increased by an additional 43%, although the specific surface area decreased from 16.7 to 13.0 m²g^–1. The enhanced photocatalytic effect remained intact under both acidic and alkaline environments owing to the {21̅0} crystal surfaces, which were less prone to dissolution than the nanoparticles. The photocatalytic performance relied on primarily three factors: the removal of surface impurities, the oxygen termination of the {21̅0} crystal faces, and the promotion of charge carrier lifetime by removal of lattice defects acting as recombination centers. The synthesis presented is an entirely hydrocarbon- and surfactant-free (“green”) preparation scheme, and the formation of the flower-shaped particles was favored solely by optimization of the reaction temperature after the correct nitrate salt precursor concentrations had been established

Improved Cellulose Nanofibril Dispersion in Melt-Processed Polycaprolactone Nanocomposites by a Latex-Mediated Interphase and Wet Feeding as LDPE Alternative

This work reports the development of a sustainable and green one-step wet-feeding method to prepare tougher and stronger nanocomposites from biodegradable cellulose nanofibrils (CNF)/polycaprolactone (PCL) constituents, compatibilized with reversible addition fragmentation chain transfer-mediated surfactant-free poly­(methyl methacrylate) (PMMA) latex nanoparticles. When a PMMA latex is used, a favorable electrostatic interaction between CNF and the latex is obtained, which facilitates mixing of the constituents and hinders CNF agglomeration. The improved dispersion is manifested in significant improvement of mechanical properties compared with the reference material. The tensile tests show much higher modulus (620 MPa) and strength (23 MPa) at 10 wt % CNF content (compared to the neat PCL reference modulus of 240 and 16 MPa strength), while maintaining high level of work to fracture the matrix (7 times higher than the reference nanocomposite without the latex compatibilizer). Rheological analysis showed a strongly increased viscosity as the PMMA latex was added, that is, from a well-dispersed and strongly interacting CNF network in the PCL

Highly Absorbing Antimicrobial Biofoams Based on Wheat Gluten and Its Biohybrids

This paper presents the absorption, mechanical, and antimicrobial properties of novel types of biofoams based on wheat-gluten (WG) and its biohybrids with silica. The hybrid WG foams were in situ polymerized with silica using two different silanes. When immersed in water, the 90–95% porous WG and silica-modified hybrid WG foams showed a maximum water uptake between 32 and 11 times the original sample weight. The maximum uptake was only between 4.3 and 6.7 times the initial weight in limonene (a nonpolar liquid) but showed reversible absorption/desorption and that the foams could be dried into their original shape. The different foams had a cell size of 2–400 μm, a density of 60–163 kg/m³, and a compression modulus of 1–9 MPa. The integrity of the foams during swelling in water was improved by cross-linking with glutaraldehyde (GA) or by a thermal treatment at 130 °C, which polymerized the proteins. In the never-dried state, the foam acted as a sponge, and it was possible to squeeze out water and soak it repeatedly. If the foam was dried to its glassy state, then the cells collapsed and did not open again even if the solid foam was reimmersed in water, saving as a sensor mechanism that can be used to reveal unintended exposure to polar liquids such as water under a product’s service life. Small-angle X-ray scattering revealed that the gliadin-correlated structure expanded and then disappeared in the presence of water. The foam was made antimicrobial by impregnation with a Lanasol solution (a bromophenol existing in algae). It was also shown that the foam can act as a transfer/storage medium for liquids such as natural oils (rapeseed oil) and as a slow-release matrix for surfactant chemicals

Polyethylene Nanocomposites for the Next Generation of Ultralow-Transmission-Loss HVDC Cables: Insulation Containing Moisture-Resistant MgO Nanoparticles

The use of MgO nanoparticles in polyethylene for cable insulation has attracted considerable interest, although in humid media the surface regions of the nanoparticles undergo a conversion to a hydroxide phase. A facile method to obtain MgO nanoparticles with a large surface area and remarkable inertness to humidity is presented. The method involves (a) low temperature (400 °C) thermal decomposition of Mg­(OH)₂, (b) a silicone oxide coating to conceal the nanoparticles and prevent interparticle sintering upon exposure to high temperatures, and (c) heat treatment at 1000 °C. The formation of the hydroxide phase on these silicone oxide-coated MgO nanoparticles after extended exposure to humid air was assessed by thermogravimetry, infrared spectroscopy, and X-ray diffraction. The nanoparticles showed essentially no sign of any hydroxide phase compared to particles prepared by the conventional single-step thermal decomposition of Mg­(OH)₂. The moisture-resistant MgO nanoparticles showed improved dispersion and interfacial adhesion in the LDPE matrix with smaller nanosized particle clusters compared with conventionally prepared MgO. The addition of 1 wt % moisture-resistant MgO nanoparticles was sufficient to decrease the conductivity of polyethylene 30 times. The reduction in conductivity is discussed in terms of defect concentration on the surface of the moisture-resistant MgO nanoparticles at the polymer/nanoparticle interface

Three-Dimensional Nanometer Features of Direct Current Electrical Trees in Low-Density Polyethylene

Electrical trees are one reason for the breakdown of insulating materials in electrical power systems. An understanding of the growth of electrical trees plays a crucial role in the development of reliable high voltage direct current (HVDC) power grid systems with transmission voltages up to 1 MV. A section that contained an electrical tree in low-density polyethylene (LDPE) has been visualized in three dimensions (3D) with a resolution of 92 nm by X-ray ptychographic tomography. The 3D imaging revealed prechannel-formations with a lower density with the width of a couple of hundred nanometers formed around the main branch of the electrical tree. The prechannel structures were partially connected with the main tree via paths through material with a lower density, proving that the tree had grown in a step-by-step manner via the prestep structures formed in front of the main channels. All the prechannel structures had a size well below the limit of the Paschen law and were thus not formed by partial discharges. Instead, it is suggested that the prechannel structures were formed by electro-mechanical stress and impact ionization, where the former was confirmed by simulations to be a potential explanation with electro-mechanical stress tensors being almost of the same order of magnitude as the short-term modulus of low-density polyethylene