Suboptimal light curing and direct exposure to water of two contemporary composites: degree of conversion, sorption, solubility, and Knoop hardness.

The water sorption and solubility of two polymer resin-based dental composite materials were assessed in order to evaluate the effects of immediate post-cure water exposure on the water sensitivity of the composites. Each material was tested with two different light curing setups. The radiant exposure of the two curing setups differed by a factor of 5. After exposure to water and subsequent drying, the Knoop surface hardness was measured. The change in the degree of conversion in both water and air storage medium within the first 24 h after curing was monitored by Raman spectroscopy. No significant differences in the degree of conversion were detected 24 h after curing. Samples exposed to the lower irradiation dose showed higher solubility and a lower surface hardness than the samples exposed to the higher irradiation dose. Early exposure to water did not cause detectable differences in the ongoing polymerization process. Increase in radiant exposure reduced the fraction of unbound constituents and increased the crosslink density, thereby reducing the plasticity of the material.

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.

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 (21Ì 0) 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.

Antibacterial properties of tough and strong electrospun PMMA/PEO fiber mats filled with Lanasol--a naturally occurring brominated substance.

A new type of antimicrobial, biocompatible and toughness enhanced ultra-thin fiber mats for biomedical applications is presented. The tough and porous fiber mats were obtained by electrospinning solution-blended poly (methyl methacrylate) (PMMA) and polyethylene oxide (PEO), filled with up to 25 wt % of Lanasol--a naturally occurring brominated cyclic compound that can be extracted from red sea algae. Antibacterial effectiveness was tested following the industrial Standard JIS L 1902 and under agitated medium (ASTM E2149). Even at the lowest concentrations of Lanasol, 4 wt %, a significant bactericidal effect was seen with a 4-log (99.99%) reduction in bacterial viability against S. aureus, which is one of the leading causes of hospital-acquired (nosocomial) infections in the world. The mechanical fiber toughness was insignificantly altered up to the maximum Lanasol concentration tested, and was for all fiber mats orders of magnitudes higher than electrospun fibers based on solely PMMA. This antimicrobial fiber system, relying on a dissolved antimicrobial agent (demonstrated by X-ray diffraction and Infrared (IR)-spectroscopy) rather than a dispersed and "mixed-in" solid antibacterial particle phase, presents a new concept which opens the door to tougher, stronger and more ductile antimicrobial fibers.

Validation of a 3D CT method for measurement of linear wear of acetabular cups.

BACKGROUND: We evaluated the accuracy and repeatability of a 3D method for polyethylene acetabular cup wear measurements using computed tomography (CT). We propose that the method be used for clinical in vivo assessment of wear in acetabular cups. MATERIAL AND METHODS: Ultra-high molecular weight polyethylene cups with a titanium mesh molded on the outside were subjected to wear using a hip simulator. Before and after wear, they were (1) imaged with a CT scanner using a phantom model device, (2) measured using a coordinate measurement machine (CMM), and (3) weighed. CMM was used as the reference method for measurement of femoral head penetration into the cup and for comparison with CT, and gravimetric measurements were used as a reference for both CT and CMM. Femoral head penetration and wear vector angle were studied. The head diameters were also measured with both CMM and CT. The repeatability of the method proposed was evaluated with two repeated measurements using different positions of the phantom in the CT scanner. RESULTS: The accuracy of the 3D CT method for evaluation of linear wear was 0.51 mm and the repeatability was 0.39 mm. Repeatability for wear vector angle was 17°. INTERPRETATION: This study of metal-meshed hip-simulated acetabular cups shows that CT has the capacity for reliable measurement of linear wear of acetabular cups at a clinically relevant level of accuracy.

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; n-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 n-hexane. The sensor is simple, cost-efficient, and nondestructive and requires no electricity.

Hydrophobic matrix-free graphene-oxide composites with isotropic and nematic states.

We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been immobilised on anionic GO and subsequently grafted with hydrophobic polymer grafts. Dense grafts of PBA, PBMA and PMMA with a wide range of average graft lengths (MW: 1-440 kDa) were polymerised by surface-initiated controlled radical precipitation polymerisation from the statistical MI. The surface modification is designed similarly to bimodal graft systems, where the cationic MI generates nanoparticle repulsion, similar to dense short grafts, while the long grafts offer miscibility in non-polar environments and cohesion. The state-of-the-art dispersions of grafted GO were in the isotropic state. Transparent and translucent matrix-free GO-composites could be melt-processed directly using only grafted GO. After processing, birefringence due to nematic alignment of grafted GO was observed as a single giant Maltese cross, 3.4 cm across. Permeability models for composites containing aligned 2D-fillers were developed, which were compared with the experimental oxygen permeability data and found to be consistent with isotropic or nematic states. The storage modulus of the matrix-free GO-composites increased with GO content (50% increase at 0.67 wt%), while the significant increases in the thermal stability (up to 130 °C) and the glass transition temperature (up to 17 °C) were dependent on graft length. The tuneable matrix-free GO-composites with rapid thermo-responsive shape-memory effects are promising candidates for a vast range of applications, especially selective membranes and sensors.

Correction: Hydrophobic matrix-free graphene-oxide composites with isotropic and nematic states.

Correction for 'Hydrophobic matrix-free graphene-oxide composites with isotropic and nematic states' by Martin Wåhlander, et al., Nanoscale, 2016, DOI: 10.1039/c6nr01502f.

Charge Transport in LDPE Nanocomposites Part I-Experimental Approach.

This work presents results of bulk conductivity and surface potential decay measurements on low-density polyethylene and its nanocomposites filled with uncoated MgO and Al2O3, with the aim to highlight the effect of the nanofillers on charge transport processes. Material samples at various filler contents, up to 9 wt %, were prepared in the form of thin films. The performed measurements show a significant impact of the nanofillers on reduction of material's direct current (dc) conductivity. The investigations thus focused on the nanocomposites having the lowest dc conductivity. Various mechanisms of charge generation and transport in solids, including space charge limited current, Poole-Frenkel effect and Schottky injection, were utilized for examining the experimental results. The mobilities of charge carriers were deduced from the measured surface potential decay characteristics and were found to be at least two times lower for the nanocomposites. The temperature dependencies of the mobilities were compared for different materials.

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.

Highly Efficient Interfaces in Nanocomposites Based on Polyethylene and ZnO Nano/Hierarchical Particles: A Novel Approach toward Ultralow Electrical Conductivity Insulations.

Polyethylene nanocomposites based on functionalized ZnO nano/hierarchical particles with highly effective interfacial surface area are presented, for the next generation of ultralow transmission-loss high-voltage DC insulating materials.

Unusual effects of monocarboxylic acids on the structure and on the transport and mechanical properties of chitosan films.

The purpose of this study was to study the transport of monocarboxylic acids in chitosan films, since this is important for understanding and predicting the drying kinetics of chitosan from aqueous solutions. Despite the wealth of data on chitosan films prepared from aqueous monocarboxylic acid solutions, this transport has not been reported. Chitosan films were exposed to formic, acetic, propionic and butyric acid vapours, it was found that the rate of uptake decreased with increasing molecular size. The equilibration time was unexpectedly long, especially for propionic and butyric acid, nine months. A clear two-stage uptake curve was observed for propionic acid. Evidently, the rate of uptake was determined by acid-induced changes in the material. X-ray diffraction and infrared spectroscopy indicated that the structure of the chitosan acetate and buffered chitosan films changed during exposure to acid and during the subsequent drying. The dried films previously exposed to the acid showed less crystalline features than the original material and a novel repeating structure possibly involving acid molecules. The molar mass of the chitosan decreased on exposure to acid but tensile tests revealed that the films were always ductile. The films exposed to acid vapour (propionic and butyric acid) for the longest period of time were insoluble in the size-exclusion chromatography eluent, and they were also the most ductile/extensible of all samples studied.

Micromechanics of ultra-toughened electrospun PMMA/PEO fibres as revealed by in-situ tensile testing in an electron microscope.

A missing cornerstone in the development of tough micro/nano fibre systems is an understanding of the fibre failure mechanisms, which stems from the limitation in observing the fracture of objects with dimensions one hundredth of the width of a hair strand. Tensile testing in the electron microscope is herein adopted to reveal the fracture behaviour of a novel type of toughened electrospun poly(methyl methacrylate)/poly(ethylene oxide) fibre mats for biomedical applications. These fibres showed a toughness more than two orders of magnitude greater than that of pristine PMMA fibres. The in-situ microscopy revealed that the toughness were not only dependent on the initial molecular alignment after spinning, but also on the polymer formulation that could promote further molecular orientation during the formation of micro/nano-necking. The true fibre strength was greater than 150 MPa, which was considerably higher than that of the unmodified PMMA (17 MPa). This necking phenomenon was prohibited by high aspect ratio cellulose nanocrystal fillers in the ultra-tough fibres, leading to a decrease in toughness by more than one order of magnitude. The reported necking mechanism may have broad implications also within more traditional melt-spinning research.