Spatial distribution of silica fillers in phase-separated rubber blends investigated by three-dimensional elemental mapping

The distribution of nano-sized silica in binary rubber blends is characterized by scanning transmission electron microscopy (STEM) tomography combined with energy dispersive X-ray spectrometry (EDX). 3D distribution of silica is visualized by STEM-EDX tomography with the tilt-series of silicon elemental maps, while the phase-separated morphologies of polyisoprene rubber (IR) and styrene-butadiene rubber (SBR) are visualized by STEM-tomography in high-angle-annular-dark field (HAADF) mode. The combination of STEM-EDX and STEM-HAADF tomography enables us to determine the distribution of silica between the two rubber phases quantitatively even with high contents of silica up to 70 phr (weight parts per hundred rubber). It is found that silica is preferentially distributed in the SBR phase, but it is also distributed in the IR phase when the IR fraction in the total rubber components is higher than 40 wt%. The preferential distribution of silica in the SBR phase improves the dispersion of the IR domains. This is the first use of this technique for a multicomponent polymer system, showing the advantage to characterize the complicated multicomponent polymer composite morphologies.     

Shrinkable Nanotubes for Duplex Formation of Short Nucleotides

Molecular monolayer nanotubes produced by self‐assembly of an amphiphile modified with a 2‐nitrobenzyl group as a photoresponsive unit are able to encapsulate dinucleotides via electrostatic attraction. Upon photoirradiation, the 18 nm inner diameter of the nanotubes shrinks to less than 2 nm as a result of photochemical cleavage of the 2‐nitrobenzyl group in the amphiphile. This shrinking of the nanotube channels leads to a propulsive release of the dinucleotides into the bulk solution and simultaneously accelerates formation of the dinucleotide duplexes. The larger nanotube channels without photoirradiation merely release each dinucleotide into the bulk solution, indicating that the squeezing via transportation in the narrow nanotube channels is necessary for duplex formation. In addition to the size effect, water with a lower polarity confined within the narrow nanotube channels helps to stabilize the energetically unfavorable hydrogen‐bonded base pair between the dinucleotides. This system should enable researchers to perform biological reactions that occur only in specific environments and conditions in living organisms.     

Boroxine Nanotubes: Moisture‐Sensitive Morphological Transformation and Guest Release

Boroxines, (R‐BO)₃, which can be easily synthesized via a dehydration reaction of boronic acids, R–B(OH)₂, selectively self‐assemble in toluene into nanofibers, nanorods, nanotapes, and nanotubes, depending on the aromatic substituent (R). Spectroscopic measurements show that the nanotube consists of a J‐aggregate of the boroxine. Humidification converts the morphology from the nanotube to a sheet as a result of the hydrolysis of the boroxine components and subsequent molecular‐packing rearrangement from the J‐aggregate to an H‐aggregate. Such a transformation leads to the compulsive release of guest molecules encapsulated in the hollow cylinder of the nanotube. The hydrolysis and the molecular‐packing rearrangement described above are suppressed by coordination of pyridine to the boron atom, with the resulting moiety acting as a Lewis acid of the boroxine component. The pyridine‐coordinated nanotube is transformed into a helical coil by humidification. Guest release during the nanotube‐to‐helical‐coil transformation is much slower than during the nanotube‐to‐sheet transformation, but faster than from a nanotube that did not undergo morphological transformation. The storage and release of guest molecules from the boroxine nanotubes can be precisely controlled by adjusting the moisture level and the concentration of Lewis bases, such as amines.     

Simple Method for Measuring the Peroxide Value in a Colored Lipid

We developed a simple method for quantification of the peroxide value (PV) in colored lipids on the basis of the reaction between triphenylphosphine (TPP) and oxidized oil to afford triphenylphosphineoxide (TPPO). Diphenylphosphineoxide (DPPO) was employed as internal standard. The formed TPPO was analyzed by high-pressure liquid chromatography–UV spectroscopy with absorption at 260 nm. The conditions that gave the highest correlative calibration curve between the peak area on the chromatogram and peroxide value were identified: the optimum TPP–oxidized oil mix ratio, reaction temperature, and reaction time were found to be 2:1, 40 °C, and 30 min, respectively. Linear calibration curves, passing through the origin, were obtained for PV versus TPPO and TPPO versus DPPO. The quantification limit for this method was 2.01 pmol hydroperoxyl group, which corresponds to a PV value of 0.2 meq/kg in a 10-mg oil sample. This method was used to measure the PV in colored fats and oils or lipids extracted from dark meat and processed food containing a coloring agent. Though the official method could not measure the PVs in the colored lipids, the method proposed here, which uses an inexpensive chemical reagent and machine, could. The developed method could play an important role for food quality control.     

Application of Near-Infrared Spectroscopy for Evaluation of Drying Stress on Lumber Surface: A Comparison of Artificial Neural Networks and Partial Least Squares Regression

This study aimed to examine the feasibility of evaluating the stress level at the surface of lumber during drying using near-infrared (NIR) spectroscopy combined with artificial neural networks (ANNs). Sugi (Cryptomeria japonica D. Don) lumber with an initial moisture content ranging from 41.1 to 85.8% was dried using a commercial drying schedule. An ANN model for predicting surface-released strain (SRS) was developed based on NIR spectra collected from the lumber during drying. The predictive ability of the ANN model was compared with a partial least squares (PLS) regression model.

The ANN model showed good correlation between laboratory-measured SRS and predicted SRS with an R ² of 0.79, a root mean square error of prediction (RMSEP) of 0.0009, and a ratio of performance to deviation (RPD) of 1.81. The PLS regression model gave a lower R ² of 0.69, a higher RMSEP of 0.0010, and a lower RPD of 1.38 than the ANN model, suggesting that the predictive performance of the ANN model was superior to the PLS regression model. The SRS evolution during drying as predicted by the models showed a similar trend to the laboratory-measured one. The predicted elapsed times to reach maximum tensile SRS and stress reversal roughly coincided with the laboratory-measured times. These results suggest that NIR spectroscopy combined with multivariate analysis has the potential to predict the drying stress level on the lumber surface and the critical periods during drying, such as the points of maximum tensile stress and stress reversal.     

Optical Properties of Dysprosium-Doped Low-Phonon-Energy Glasses for a Potential 1.3 μm Optical Amplifier

Dysprosium-doped glasses were prepared in the system of gallium-based sulfide, tellurite, zirconium-baed and indium-based fluorides and their optical properties were studied. From the absorption cross sections of five f-f bands, three Judd-Ofelt parameters, ω _t ( t = 2, 4, 6), of Dy³⁺ ion were determined. The compositional variaton of the ω₂value showed the order sulfide > tellurite > fluorozirconate > fluoroindate, whereas the ω₆ value showed the opposite tendency. Compositional variaton of the fluorescence intensity ratio of the (⁴F_9/2⁶H_13/2)/(⁴F_9/2)→⁶H_15/2) is explained by the ratio of ω₂/ω₆ of doped Dy³⁺. The emission probabilities A and the branching ratio β from ⁶H_9/2 and ⁶F_11/2 levels, which are the doublet initial level of the 1.3 μm luminescence, were calculated for the glasses, and it was found that both values showed a tendency similar to that of ω₂ against the glass composition. In the sulfide glass, A was 2.6 × 10³S^-1 and β was 93%, both the highest in all of the glasses investigated. By 1.06 μm pumping of a Nd: YAG laser, the sulfide glass showed strong 1.3 μm emission and the lifetime was 25 μs, resulting in a quantum efficiency of 7%. This value is higher than that of the Pr³⁺:¹G₄ level in ZBLAN glass with β= 60%.     

Impedance Spectroscopy of Undoped BaTiO3 Ceramics

The electrical properties of ceramic BaTiO₃ were investigated by ac impedance spectroscopy over the ranges 25°-330°C and 0.03 Hz-1 MHz. Results are compared with those obtained from fixed-frequency measurements, at 1 kHz and 100 kHz. Fixed-frequency Curie-Weiss plots show deviations from linearity at temperatures well above t _c. The ac measurements show that grain boundary impedances influence Curie-Weiss plots in two ways: at high temperatures, they increasingly dominate the fixed-frequency permittivities; at lower temperatures, closer to T ^c, the high-frequency permittivity contains a contribution from grain boundary effects. Methods for extraction of bulk and grain boundary capacitances from permittivity and electric modulus complex plane plots are discussed. The importance of selecting the appropriate equivalent circuit to model the impedance response is stressed. A constriction impedance model for the grain boundary in BaTiO₃ ceramics is proposed: the grain boundary capacitance is neither temperature-independent, nor shows Curie-Weiss behavior. The grain boundary is ferroelectric, similar to the grains, but its impedance is modified by either air gaps or high-impedance electrical inhomogeneity in the region of the necks between grains; the activation energy of the constriction grain boundary impedance differs from that of the bulk, suggesting differences in defect states or impurity levels.