Investigation of Polymer–Plasticizer Blends as SH-SAW Sensor Coatings for Detection of Benzene in Water with High Sensitivity and Long-Term Stability

We report the first-ever direct detection of benzene in water at concentrations below 100 ppb (parts per billion) using acoustic wave (specifically, shear-horizontal surface acoustic wave, SH-SAW) sensors with plasticized polymer coatings. Two polymers and two plasticizers were studied as materials for sensor coatings. For each polymer–plasticizer combination, the influence of the mixing ratio of the blend on the sensitivity to benzene was measured and compared to commercially available polymers that were used for BTEX (benzene, toluene, ethylbenzene, and xylene) detection in previous work. After optimizing the coating parameters, the highest sensitivity and lowest detection limit for benzene were found for a 1.25 μm thick sensor coating of 17.5%-by-weight diisooctyl azelate-polystyrene on the tested acoustic wave device. The calculated detection limit was 45 ppb, with actual sensor responses to concentrations down to 65 ppb measured directly. Among the sensor coatings that showed good sensitivity to benzene, the best long-term stability was found for a 1.0 μm thick coating of 23% diisononyl cyclohexane-1,2-dicarboxylate-polystyrene, which was studied here because it is known to show no detectable leaching in water. The present work demonstrates that, by varying type of plasticizer, mixing ratio, and coating thickness, the mechanical and chemical properties of the coatings can be conveniently tailored to maximize analyte sorption and partial chemical selectivity for a given class of analytes as well as to minimize acoustic-wave attenuation in contact with an aqueous phase at the operating frequency of the sensor device

The Ultimate Fate of Supercooled Liquids

In recent years it has become widely accepted that a dynamical length scale {\xi}_{\alpha} plays an important role in supercooled liquids near the glass transition. We examine the implications of the interplay between the growing {\xi}_{\alpha} and the size of the crystal nucleus, {\xi}_M, which shrinks on cooling. We argue that at low temperatures where {\xi}_{\alpha} > {\xi}_M a new crystallization mechanism emerges enabling rapid development of a large scale web of sparsely connected crystallinity. Though we predict this web percolates the system at too low a temperature to be easily seen in the laboratory, there are noticeable residual effects near the glass transition that can account for several previously observed unexplained phenomena of deeply supercooled liquids including Fischer clusters, and anomalous crystal growth near T_g

Thermal properties, degradation and stability of poly(vinyl chloride) predegraded thermooxidatively in the presence of dioctyl phthalate plasticizer

Thermooxidative degradation of poly(vinyl chloride) (PVC) is inevitable during processing of PVC. Recycling of this polymer requires reprocessing in most of the cases, and due to the low thermal stability of PVC, it is of paramount importance to reveal the effect of thermooxidation on the thermal stability of this commercially important polymer. However, detailed systematic investigations are lacking on this crucial problem. In this study, the thermal behavior of PVCs thermooxidized in dilute dioctyl phthalate (DOP) (di(2-ethylhexyl) phthalate, DEHP) plasticizer was investigated by DSC, thermal gravimetry and isothermal degradation under inert atmosphere. It was found that thermooxidation leads to PVCs with certain extent of internal plasticization by DOP chemically bound to the PVC chains and by the oxidized chain segments as well. Thermogravimetry and isothermal dehydrochlorination under inert atmosphere revealed that even low extent of thermooxidation of PVC (0.4 mol% of HCl loss in 30 minutes at 200 °C) leads to dramatically decreased thermal stability of this polymer with 50-60 oC lower onset decomposition temperature than that of the virgin resin. This unexpected finding means that at least part of the oxidized moieties formed during oxidation of the PVC chains acts as initiators for thermal dehydrochlorination at relatively low temperatures, resulting in significant decrease of the thermal stability of the polymer. These striking results also indicate that the decreased thermal stability caused by thermooxidation in the course of the primary processing of this polymer should be taken into account in order to efficiently stabilize PVC products for reprocessing and recycling

High-performance flexible perovskite solar cells exploiting Zn2SnO4 prepared in solution below 100 degrees C

Fabricating inorganic-organic hybrid perovskite solar cells (PSCs) on plastic substrates broadens their scope for implementation in real systems by imparting portability, conformability and allowing high-throughput production, which is necessary for lowering costs. Here we report a new route to prepare highly dispersed Zn2SnO4 (ZSO) nanoparticles at low-temperature (<100 degrees C) for the development of high-performance flexible PSCs. The introduction of the ZSO film significantly improves transmittance of flexible polyethylene naphthalate/indium-doped tin oxide (PEN/ITO)-coated substrate from similar to 75 to similar to 90% over the entire range of wavelengths. The best performing flexible PSC, based on the ZSO and CH3NH3PbI3 layer, exhibits steady-state power conversion efficiency (PCE) of 14.85% under AM 1.5G 100 mW . cm(-2) illumination. This renders ZSO a promising candidate as electron-conducting electrode for the highly efficient flexible PSC applications.ope

Comparing Laser Diffraction and Optical Microscopy for Characterizing Superabsorbent Polymer Particle Morphology, Size, and Swelling Capacity

In this study, we determined the accuracy and practicality of using optical microscopy (OM) and laser diffraction (LD) to characterize hydrogel particle morphology, size, and swelling capacity (Q). Inverse-suspension-polymerized polyacrylamide particles were used as a model system. OM and LD showed that the average particle diameter varied with the mixing speed during synthesis for the dry (10–120 lm) and hydrated (34–240 lm) particles. The LD volume and number mean diameters showed that a few large particles were responsible for the majority of the water absorption. Excess water present in the gravimetric swelling measurements led to larger Qs (8.2 6 0.37 g/g), whereas the volumetric measurements with OM and LD resulted in reduced capacities (6.5 6 3.8 and 5.7 6 3.9 g/g, respectively). Results from the individual particle swelling measurements with OM (5.2 6 0.66 g/g) statistically confirmed that the volumetric methods resulted in a reduced and more accurate measurement of the Q than the gravimetric method

Predicting the band gap of ternary oxides containing 3d(10) and 3d(0) metals

We present soft x-ray spectroscopy measurements and electronic structure calculations of ZnTiO 3, a ternary oxide that is related to wurtzite ZnO and rutile TiO 2. The electronic structure of ZnTiO 3 was calculated using a variety of exchange-correlation functionals, and we compare the predicted band gaps of this material obtained from each functional with estimates from our experimental data and optical gaps quoted from the literature. We find that the main hybridizations in the electronic structure of ZnTiO 3 can be predicted from the electronic structures of the two binary oxides. We further find that ZnTiO 3 has weaker O 2p-Zn 3d repulsion than in ZnO, resulting in a relatively lower valence band maximum and consequently a larger band gap. Although we find a significant core hole shift in the measured O K XAS of ZnTiO 3, we provide a simple empirical scheme for estimating the band gap that may prove to be applicable for any d10-d0 ternary oxide, and could be useful in finding a ternary oxide with a band gap tailored to a specific energy. © 2012 American Physical Society

Ionic liquids at electrified interfaces

Until recently, “room-temperature” (<100–150 °C) liquid-state electrochemistry was mostly electrochemistry of diluted electrolytes(1)–(4) where dissolved salt ions were surrounded by a considerable amount of solvent molecules. Highly concentrated liquid electrolytes were mostly considered in the narrow (albeit important) niche of high-temperature electrochemistry of molten inorganic salts(5-9) and in the even narrower niche of “first-generation” room temperature ionic liquids, RTILs (such as chloro-aluminates and alkylammonium nitrates).(10-14) The situation has changed dramatically in the 2000s after the discovery of new moisture- and temperature-stable RTILs.(15, 16) These days, the “later generation” RTILs attracted wide attention within the electrochemical community.(17-31) Indeed, RTILs, as a class of compounds, possess a unique combination of properties (high charge density, electrochemical stability, low/negligible volatility, tunable polarity, etc.) that make them very attractive substances from fundamental and application points of view.(32-38) Most importantly, they can mix with each other in “cocktails” of one’s choice to acquire the desired properties (e.g., wider temperature range of the liquid phase(39, 40)) and can serve as almost “universal” solvents.(37, 41, 42) It is worth noting here one of the advantages of RTILs as compared to their high-temperature molten salt (HTMS)(43) “sister-systems”.(44) In RTILs the dissolved molecules are not imbedded in a harsh high temperature environment which could be destructive for many classes of fragile (organic) molecules

STUDI ES ON NATURAL FI BERS OF BRAZI L AND GREEN COM POSI TES

Abstract: Natural resource of any country is one of the contributors for its GDP (gross domestic product). Brazil has a number of such resources, which are abundantly available and being not used to its full potential. Plant fibers belong to this category. This paper presents the data on the availability of some of the resources of such fibers, their production, structure and properties along with their present uses. It also briefly gives perspectives being used for their better utilization while giving a brief overview of the R&amp;D carried out in the country in general and UFPR in particular in the synthesis of composites, to meet the ecological aspects and their increased use

FOXC2 controls adult lymphatic endothelial specialization, function, and gut lymphatic barrier preventing multiorgan failure.

The mechanisms maintaining adult lymphatic vascular specialization throughout life and their role in coordinating inter-organ communication to sustain homeostasis remain elusive. We report that inactivation of the mechanosensitive transcription factor Foxc2 in adult lymphatic endothelium leads to a stepwise intestine-to-lung systemic failure. Foxc2 loss compromised the gut epithelial barrier, promoted dysbiosis and bacterial translocation to peripheral lymph nodes, and increased circulating levels of purine metabolites and angiopoietin-2. Commensal microbiota depletion dampened systemic pro-inflammatory cytokine levels, corrected intestinal lymphatic dysfunction, and improved survival. Foxc2 loss skewed the specialization of lymphatic endothelial subsets, leading to populations with mixed, pro-fibrotic identities and to emergence of lymph node-like endothelial cells. Our study uncovers a cross-talk between lymphatic vascular function and commensal microbiota, provides single-cell atlas of lymphatic endothelial subtypes, and reveals organ-specific and systemic effects of dysfunctional lymphatics. These effects potentially contribute to the pathogenesis of diseases, such as inflammatory bowel disease, cancer, or lymphedema