Role of methods of blending on polymer–polymer compatibility

The role of methods of blend preparation on polymer-polymer compatibility was investigated. Three different types of methods of blending, such as solution-casting, melt-mixing, and coprecipitation, were applied for three types of blend systems, viz., poly(vinyl chloride-co-vinyl acetate) (VYHH)/polystyrene (PS), VYHH/poly(styrene-co-acrylonitrile) (SAN), and VYHH/poly(methyl methacrylate) (PMMA) by measuring their glass transition temperatures (T_g) by a differential scanning calorimeter (DSC). It has been found that compatibility of the polymers depends on the method of blending and compatibility also varies from one blend system to another. Among the various types of blending methods, the coprecipitation method of blending gives the best compatibility result. © 1996 John Wiley & Sons, Inc.     

Validation of Tuba1a as Appropriate Internal Control for Normalization of Gene Expression Analysis during Mouse Lung Development

The expression ratio between the analysed gene and an internal control gene is the most widely used normalization method for quantitative RT-PCR (qRT-PCR) expression analysis. The ideal reference gene for a specific experiment is the one whose expression is not affected by the different experimental conditions tested. In this study, we validate the applicability of five commonly used reference genes during different stages of mouse lung development. The stability of expression of five different reference genes (Tuba1a, Actb Gapdh, Rn18S and Hist4h4) was calculated within five experimental groups using the statistical algorithm of geNorm software. Overall, Tuba1a showed the least variability in expression among the different stages of lung development, while Hist4h4 and Rn18S showed the maximum variability in their expression. Expression analysis of two lung specific markers, surfactant protein C (SftpC) and Clara cell-specific 10 kDA protein (Scgb1a1), normalized to each of the five reference genes tested here, confirmed our results and showed that incorrect reference gene choice can lead to artefacts. Moreover, a combination of two internal controls for normalization of expression analysis during lung development will increase the accuracy and reliability of results.     

Studies on sulfur vulcanization of natural rubber accelerated combinedly with 2-mercaptobenzothiazole and diphenylguanidine both in presence and absence of dicumyl peroxide

Sulfuration of natural rubber (NR) by the binary accelerator 2-mercaptobenzothiazole (MBT) and diphenylguanidine (DPG) both in presence and in absence of ZnO and stearic acid with or without dicumylperoxide (DCP) was studied in detail. It was observed that the rate of decomposition of DCP in presence of both MBT and DPG is quite similar to that with MBT alone. The reduction of crosslinking depends also on MBT only. Through DPG has no influence on the decomposition rate, it reacts with MBT during the vulcanization process and suppresses the retardation caused by MBT on the DCP vulcanization. In accordance with the initial additiveness of crosslinking in systems containing DCP, the free sulfur decrease, and the rapidity of crosslink formation the vulcanization process of MBT-DPG-S-NR systems was interpreted in terms of a polar mechanism induced by the complex MSH₂NR′R″. In mixtures containing DCP together with sulfur, MBT, DPG, ZnO, and stearic acid, the initial stage of crosslinking is additive as indicated by a mixed reaction as well as by a methyl iodide treatment of the vulcanizates. Comparison with single accelerators shows a pronounced synergistic effect. This is because of the enhanced activity of the MBT-ZnO-stearic acid complex due to DPG which also induces polar sulfuration of NR by forming the active complex MSH₂NR′R″. In presence of ZnO and stearic acid, DCP cannot increase the net crosslink density but suppresses the reversion so much pronounced in its absence.     

Impact of electrically formed interfacial layer and improved memory characteristics of IrOx/high-κx/W structures containing AlOx,GdOx, HfOx,and TaOx switching materials

Improved switching characteristics were obtained from high-κ oxides AlO_x, GdO_x, HfO_x, and TaO_x in IrO_x/high-κ_x/W structures because of a layer that formed at the IrO_x/high-κ_x interface under external positive bias. The surface roughness and morphology of the bottom electrode in these devices were observed by atomic force microscopy. Device size was investigated using high-resolution transmission electron microscopy. More than 100 repeatable consecutive switching cycles were observed for positive-formatted memory devices compared with that of the negative-formatted devices (only five unstable cycles) because it contained an electrically formed interfacial layer that controlled ‘SET/RESET’ current overshoot. This phenomenon was independent of the switching material in the device. The electrically formed oxygen-rich interfacial layer at the IrO_x/high-κ_x interface improved switching in both via-hole and cross-point structures. The switching mechanism was attributed to filamentary conduction and oxygen ion migration. Using the positive-formatted design approach, cross-point memory in an IrO_x/AlO_x/W structure was fabricated. This cross-point memory exhibited forming-free, uniform switching for >1,000 consecutive dc cycles with a small voltage/current operation of ±2 V/200 μA and high yield of >95% switchable with a large resistance ratio of >100. These properties make this cross-point memory particularly promising for high-density applications. Furthermore, this memory device also showed multilevel capability with a switching current as low as 10 μA and a RESET current of 137 μA, good pulse read endurance of each level (>10⁵ cycles), and data retention of >10⁴ s at a low current compliance of 50 μA at 85°C. Our improvement of the switching characteristics of this resistive memory device will aid in the design of memory stacks for practical applications.     

Non-linear dynamical analyses of transient surface temperature fluctuations during subcooled pool boiling on a horizontal disk

The class of dynamics in pool boiling on a large-size heater is assessed under subcooled pool boiling conditions. Transient surface temperature measurements are obtained using surface micro-machined K-type thin film thermocouples (TFT) in 10 °C subcooled pool boiling experiments on a 62.23 mm diameter silicon wafer using PF-5060 as the test liquid. Surface temperature data is obtained at each steady state condition to generate the boiling curve. The fraction of false-nearest neighbors, recurrence plots and space–time separation plots are obtained using the TISEAN package. The correlation dimension is then estimated from the re-constructed phase space data using a naïve algorithm. The correlation dimension varies from ～11.2 to 11.5 near onset of nucleate boiling (ONB), to ～7–10 in fully developed nucleate boiling (FDNB) ～7–9 near critical heat flux (CHF) condition, and from ～6.6 to 7.7 in film boiling. False-nearest neighbor estimates and recurrence plots show that nucleate boiling may be dominated by statistical processes near ONB and in partial nucleate boiling (PNB). In contrast, FDNB, CHF and film boiling seem chaotic and governed by deterministic processes.     

Evaluation of Enhanced Heat Transfer Within a Four Row Finned Tube Array of an Air Cooled Steam Condenser

Air cooled steam condensers (ACSC) consist of finned-tube arrays bundled in an A-frame structure. Inefficient performance under extreme temperature operating conditions is a common problem in ACSCs. The purpose of this study was to improve the heat transfer characteristics of an annular finned-tube system for better performance in extreme climatic conditions. Perforations were created on the surface of the annular fins to increase heat transfer coefficient (h). Mesh generation and finite volume analyses were performed using Gambit 2.4.6 and Fluent 6.3 with an RNG k–? turbulent model to calculate pressure drop (ΔP), heat flux (q), and heat transfer coefficient (h). Solid (no perforations) finned-tubes were simulated with free stream velocity ranging between 1 m/s–5 m/s and validated with the published data. Computations were performed for perforations at 30° interval starting at ±60°, ±90°, ±120°, ±150°, and ±180° from the stagnation point. Five cases with single perforation and three cases with multiple perforations were evaluated for determining the maximum q and h, as well as minimum ΔP. For the perforated case (perforations starting from 60° at interval of 30°), the fin q and h performance ratios increased by 5.96% and 7.07%, respectively. Consequently, the fin ΔP performance ratio increased by 11.87%. Thus, increased q and h is accompanied with a penalty of higher ΔP. In contrast, a single perforation location at 120° provided favorable results with a 1.70% and 2.23% increase in q and h performance ratios, respectively, while there was a relatively smaller increase (only 1.39%) of ΔP performance ratio. Perforations in the downstream region at ±120°, ±150°, and ±180° also resulted in a similar favorable outcome. Furthermore, the spacing of the fins along the arms of an A-frame ACSC was altered to decrease ΔP across the finned-tube array. Fin spacing in the A-frame structure with sparsely spaced fins in the center resulted in a 1.80% reduction in ΔP. Thus, penalty in ΔP for a perforated fin can possibly be offset by changing the fin spacing along the arms of an A-frame structure.     

Ionic liquid-based deep eutectic solvents as novel solvent-cum-catalyst media for thermal dehydrogenation of chemical hydrides

The current work explores the usage of novel synthesized Deep Eutectic Solvent (DES) as a catalyst cum solvent media for the thermal dehydrogenation of chemical hydrides, namely Ammonia Borane (AB) and Ethylene diamine bisborane (EDAB). In the first instance, the quantum chemistry based COSMO-SAC (COnductor like Screening MOdel Segment Activity Coefficient) model was used for the selection of the pertinent solvent. 1-Butyl-3-methylimidazolium methanesulfonate: Imidazole ([BMIM][MeSO₃]:[Im]) turned out to be an ideal eutectic mixture with the highest predicted solubility with amine boranes. The DES was synthesized by combining the Hydrogen Bond Acceptor (HBA), namely 1-Butyl-3-methylimidazolium methanesulfonate and Imidazole as Hydrogen Bond Donor (HBD) at a molar ratio of 1:2 and T = 70 °C. The formation of DES was confirmed by recording the NMR spectra. Further, the thermal dehydrogenation study was performed at a vacuum of 4 × 10^?2 mbar (gauge pressure) of AB/DES and EDAB/DES systems at 105 °C, where a hydrogen equivalent of 1.40 and 2.55 was produced, respectively. The residual samples were further analyzed through ¹H NMR analysis for the reaction mechanism and to confirm the role of Ionic Liquid-based DES as catalyst cum solvent media.     

Catalytic properties of dispersed iron oxides Fe2O3/MO2 (M = Zr,Ce, Ti and Si) for sulfuric acid decomposition reaction: Role of support

Supported iron oxides have been established as an important class of catalyst for high temperature sulfuric acid decomposition. With an objective to elucidate the role of support in modifying the overall catalytic properties of dispersed iron oxide catalysts, a series of supported iron oxide based catalysts, Fe₂O₃ (15 wt%)/MO₂ (M = Zr, Ce, Ti and Si), synthesized by adsorption-equilibrium method, is investigated for sulfuric acid decomposition reaction. The structure of dispersed iron oxide phases largely depended on the nature of the support oxide as revealed by the XRD and Mössbauer studies. α-Fe₂O₃ is found to be present as a major phase on ZrO₂ and CeO₂ support while ε-Fe₂O₃ was the major phase on silica supported iron oxide. On the other hand, presence of mixed oxide Fe₂TiO₅ was revealed over TiO₂ support. Strong dispersed metal oxide-support interactions inhibited the total reduction of the dispersed phase on SiO₂ and TiO₂ as compared to complete reduction of dispersed iron oxide on CeO₂ and ZrO₂ supports during temperature programmed reduction upto 1000 °C. The order of catalytic activity at a temperature of ～750 °C is observed as Fe₂O₃/SiO₂ > Fe₂TiO₅/TiO₂ > Fe₂O₃/ZrO₂ > Fe₂O₃/CeO₂, while at higher temperatures of ～900 °C the SO₂ yield is found to be comparable for all catalysts. A relationship between the rate of sulfate decomposition and catalytic activity is established through detailed TG-DTA investigations of sulfated catalyst and support. Considerable influence of the support oxide on the composition, structure, redox properties, morphology and catalytic activities of the active iron oxide dispersed phase has been observed. Thus, the support oxides operate as a critical component in the complex supported metal oxide catalysts and these findings might influence the design and development of future high temperature sulfuric acid decomposition catalysts.     

Lab scale optimization of various factors for photocatalytic hydrogen generation over low cost Cu0.02Ti0.98O2-δ photocatalyst under UV/Visible irradiation and sunlight

We have demonstrated earlier that maximum H₂ generated @ 1.167 l/h/m² over Cu_0.02Ti_0.98O_2-δ photocatalyst with apparent quantum efficiency, AQE of 7.5% and solar fuel efficiency, SFE of 3.9% under sunlight. With an aim to scale-up the solar photocatalytic hydrogen process to pilot plant, optimization studies at lab scale as well as in upscaled photoreactors were performed over Cu_0.02Ti_0.98O_2-δ, photocatalyst under UV/visible and sunlight. Cu_0.02Ti_0.98O_2-δ was synthesized by facile sol-gel route and characterized by relevant techniques. Several operational parameters were investigated in order to finalize the conditions which are most favourable for photocatalytic hydrogen yield. Factors such as photocatalyst loadings, v/v concentration of sacrificial reagent, replacement of methanol by industrial waste glycerol, role of different configuration of light source with reactor, effect of stirring during the photocatalytic reaction, effect of fluctuations of solar flux at hourly basis, illumination area on hydrogen yield were studied. Contribution of each factor in determining the hydrogen yield was quantified. Relative standard deviation in hydrogen yield as a function of each factor was estimated. Our findings suggest that in addition to catalyst loadings and sacrificial reagent, improved dispersion of photocatalyst obtained by stirring the reaction mixture in horizontal geometry resulted in enhanced H₂ yield. Hydrogen yield obtained at lab scale can be appropriately extrapolated with respect to illumination area instead of weight of photocatalyst. A relative standard deviation (RSD) of ± 3.82% and ± 4.53% in H₂ yield was calculated for sunny and cloudy days in time zone of 10.30–16.30 h IST. Deviation of H₂ yield was more on cloudy days and beyond 16:30 h. These studies have provided a daily window of 11:00–15:00 h to be utilized throughout the year for a commercial scaled up process, prohibiting the illumination during less productive hours of the day for shaping the improved economics of solar hydrogen generation. Our results obtained at lab scale would be useful to perform sunlight driven scaled –up photocatalytic process using low cost visible light efficient photocatalyst, Cu_0.02Ti_0.98O_2-δ.