Small-angle X-ray scattering studies on melting and recrystallization behaviors of poly(oxyethylene) crystallites in poly(d,l-lactide)/poly(oxyethylene) blends

Direct determination of the discrete distribution for crystalline lamellar thickness has been performed for poly(d,l-lactic acid)/poly(oxyethylene) (PDLLA/PEG) blends by conducting small-angle X-ray scattering (SAXS) measurements using synchrotron radiation. The PDLLA used was an random (racemic) copolymer of bio-based poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) with the lactide monomer ratio of l:d = 50:50. It is known that PLA is miscible with PEG in the amorphous state. In the current paper, we report comprehensive results on structural analyses of PDLLA/PEG blends in the course of heating and cooling process using SAXS to elucidate the change in the thickness distribution of the lamellae. As a consequence, it was found that the distribution of the lamellar thickness moves toward the larger value (in other words, lamellar thickening) as temperature approaches the melting point. Typically, the thickness distribution was dispersed in the range of 10–20 nm at room temperature and it changed toward 40 nm in the vicinity of the melting temperature. To the best of our knowledge, this is the first report of direct determination of the discrete distribution for the crystalline lamellar thickness and their in-situ changes in the course of the lamellar thickening process. As a result, the lamellar thickening was found to occur at much lower temperature for the blend samples with 10% and 20% of PDLLA contents as compared to the PEG 100% sample. This phenomenon can be ascribed to the melting point depression owing to the miscibility between PEG and PDLLA. Thereby, thinner lamellae were melted and thicker ones appeared at much lower temperature for the blends than for the PEG 100% sample. As for the average repeating distance (long period) of the lamellar stacks, an abrupt increase similar to the critical divergence was observed (from 25 nm to 50 nm) in the heating process. Not only for the melting behavior but also in the course of recrystallization, change in the lamellar-thickness distribution was uncovered, which shows strong hysteresis depending on what temperature the sample was cooled down from.     

Improvement in thermal endurance of D-mannitol as phase-change material by impregnation into nanosized pores

This paper describes the control of the melting point and improvement of the thermal endurance of D-mannitol (melting point T_m = 440 K) as a phase-change material (PCM) by vacuum impregnation of the PCM into nanosized pores of porous SiO₂ grains. First, we examined the effects of the average pore size (D_P) of porous SiO₂ on T_m and latent heat (L) of PCM/SiO₂ composites. Second, we investigated the thermal endurance of the composites using constant temperature kinetics based on L of the PCM and composites. Third, we performed cyclic tests of melting and freezing on the composite to evaluate leakage of the PCM. Thermophysical properties of the samples were measured by differential scanning calorimetry, and the following results were obtained: (1) The impregnation ratio of the composites was 0.91–0.99; therefore, almost all pores were completely filled with the PCM. (2) T_m shifted to lower temperature with smaller D_P, reaching 413 K in case of the PCM/SiO₂ composite with a D_P of 11.6 nm (3) T_m was derived as a function of D_P from the Gibbs–Thomson equation taking into account the existence of a nonfreezing layer on the surface of the pore wall. (4) The duration of thermal degradation of the PCM/SiO₂ composite with D_P = 11.6 nm was three times longer than that of the pure PCM at a temperature that is 10 K more than each melting point. (5) The PCM/SiO₂ composite with D_P = 11.6 nm can use as a shape-stable PCM composite without leakage of PCM.     

Preparation of Mn2+-Cu+ co-doped P2O5–ZnO–Al2O3 glasses and their red fluorescence properties

To make a Mn²⁺-doped red glass phosphor that can be excited with ultraviolet (UV) light of light-emitting diodes (LEDs), 60P₂O₅-35ZnO-5Al₂O₃-8MnO-xCu₂O glasses (x = 0-1.00) were prepared by a melt-quenching method at 1200-1400°C for 30-180 minutes in atmospheric air, and the redox of Mn and Cu as well as fluorescence properties were investigated. The Mn²⁺ ion was not reduced and oxidized in the melting, quenching, and annealing processes. The valence of Cu in the glasses changed in the order of 0, 1+, and 2+ with the increase in the amount of Cu₂O and in the melting temperature and time. In this study, a 60P₂O₅-35ZnO-5Al₂O₃-8MnO-0.10Cu₂O glass melted at 1250°C for 90 minutes, having the highest Cu⁺ concentration, showed the strongest Mn²⁺ red fluorescence under the UV light at 275 nm. This strong Mn²⁺ red fluorescence has been caused by the energy transfer from excited Cu⁺ ions to Mn²⁺ ions.     

Geo- and Hydro-Mechanical Evaluation of Slope Failure Induced by Torrential Rains in Northern-Kyushu Area,July 2009

Torrential rainfall in mid-July 2009 triggered numerous geodisasters such as slope failure and debris flow in Chugoku and Northern Kyushu areas of Japan. A number of slope failures and debris flows occurred in Yamaguchi and Fukuoka prefectures resulting in extensive damage to human life and infrastructure. One of the most serious geodisasters included a slope failure followed by debris flow at Sasaguri-machi and Fukuchi-machi, Fukuoka prefecture, Japan. This paper summarizes the results of geotechnical investigations on the geodisaster sites in Fukuoka prefecture. The geotechnical investigation included determining a series of grain size distributions, consistency limits and conducting direct box shear tests for collapsed soils collected at six disaster sites. The generation mechanisms of slope failure followed by debris flow were also investigated by analyzing the precipitation, topography, geology, and strength properties of the collapsed soils. Moreover, slope deformation and stability analyses were coupled with an unsaturated-saturated seepage analysis to investigate the slope failure mechanism. The main findings from the study are summarized as: The physical properties, such as the grain size distribution, the plastic limit and liquid limit of collapsed soils, are summarized and compared with the results of other failure slopes in the literature. The collapsed soil was characterized as being a well grained soil (the uniformity coefficient >50) and highly weathered (the ignition loss >5%), however, with regard to the liquid limit and plastic index, there were no remarkable findings. The original shear strength for collapsed soils with natural water content is relatively large and slope failure doesn't occur because the cohesion in the shear strength is induced by a suction force between the soil particles under unsaturated condition. However, water seepage into the soil induces a drastic decrease in the shear strength, which is mainly caused by a decrease in cohesion (losing suction) resulting from soil saturation. In addition, the drained/undrained condition in the shear process is also sensitive to shear strength. For example, both water seepage and the shear process with constant volume cause an approximate 30% reduction in shear strength for Fukuchi-machi and Sasaguri-machi soil samples. Therefore, the reduction of cohesive strength due to water seepage and the low permeability of the slope are the parameters which trigger geodisaster. Based on the results of slope deformation and a stability analyses which took the change in water pressure and cohesive strength into account, the geodisaster at Fukuchi-machi was simulated, it is reasonable to assume that the shallow failure near the top of slope occurred due to torrential precipitation of about 100 mm per hour which triggered a debris flow.     

Origin of electron mobility enhancement in (1 1 1)-oriented InGaAs channel metal-insulator-semiconductor field-effect-transistors

Electrical and physical characteristics of the Al₂O₃/InGaAs interfaces with (1 1 1)A and (1 0 0) orientations were investigated in an attempt to understand the origin of electron mobility enhancement in the (1 1 1)A-channel metal-insulator-semiconductor field-effect-transistor. The (1 1 1)A interface has less As atoms of high oxidation states as probed by X-ray photoelectron spectroscopy. The electrical measurements showed that energy distribution of the interface traps for the (1 1 1)A interface is shifted toward the conduction band as compared to that for the (1 0 0) interface. Laterally-compressed cross-section transmission electron microscopy images showed that the characteristic lengths of the interface roughness are different between the (1 1 1)A and (1 0 0) interfaces. The contributions of the Coulomb and roughness scattering mechanisms are discussed based on the experimental results.     

新型吸附床的研究进展

吸附床是吸附式制冷装置的核心部件,其性能的优劣直接关系到吸附式制冷装置的制冷效果.通过吸附床的热阻分析,得出强化吸附床传热的措施.文中重点介绍了提高吸附剂与换热壁面的换热系数和吸附剂间的导热系数来强化吸附床传热的方法,详细介绍了填充式吸附床、涂抹式吸附床以及固化式吸附床的结构特点,比较分析3种吸附床的传热传质特点,并阐...     

Styrene–butadiene rubber/cellulose II/clay nanocomposites prepared by cocoagulation—mechanical properties

In this work, nanocomposites of styrene butadiene rubber (SBR), cellulose II, and clay were prepared by cocoagulation of SBR latex, cellulose xanthate, and clay aqueous suspension mixtures. The incorporated amount of cellulose II was 15 phr, and the clay varied from 0 to 7 phr. The influence of cellulose II and clay was investigated by rheometric, mechanical, physicochemical, and morphological properties. From the analysis of transmission electron microscopy (TEM), dispersion in nanometric scale (below 100nm) of the cellulosic and mineral components throughout the elastomeric matrix was observed. XRD analysis suggested that fully exfoliated structure could be obtained by this method when low loading of silicate layers (up to 5 phr) is used. The results from mechanical tests showed that the nanocomposites presented better mechanical properties than SBR gum vulcanizate. Furthermore, 5 phr of clay is enough to achieve the best tensile properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011