Solid acid (superacid) catalyzed regioselective adamantylation of substituted benzenes

Adamantylation of substituted benzenes with 1-bromo-adamantane was catalyzed by solid acids including acidic ion exchange and ionomer resins, HY zeolite, sulfated zirconia and supported superacids on HY zeolite and SiO₂. Adamantylation generally takes place in excellent yield giving predominantly para products without formation of byproducts. The reactions did not require the usual workup of Friedel-Crafts reactions as catalysts were simply filtered of. Cross-linked polystyrene resin sulfonic acid (Amberlyst) was found particularly suitable as besides its high catalytic activity, high regioselectivity was observed with almost exclusive formation ofp-adamantylated benzenes. AMI, PM3 and MNDO semiempirical calculations of heats of formation showed that of all regioisomers, the para isomer is the most stable. The temperature dependence of adamantylation was also investigated allowing the optimization ofp-substituted product in high yield and excellent selectivity. Lack of isomerization of 1-p-tolyla-damantane using solid (Amberlyst, Nafion-H) and liquid acids (neat and modified trifluoromethanesulfonic acid) indicates absence of product isomerization, while the intramolecular rearrangement of the intermediate arenium complex is still possible.Catalysis by solid superacids, Part 30. For part 29, see ref.[1A].     

Simulation of population balance model-based particulate processes via parallel and distributed computing

Population Balance Models (PBMs), a class of integro partial differential equations, are utilized for simulating dynamics of numerous particulate systems. PBMs describe the time evolutions and distributions of many particulate processes and their efficient and quick simulation are critical for enhanced process control and optimization, especially for real-time applications. However, their intensive computational resource requirement is largely a prohibitive factor in the utility of PBMs for control and optimization. This paper describes how distributed computing systems may be leveraged to execute PBM-based simulations thus achieving time savings, using MATLAB's Distributed Computing Toolbox. A parallel computing algorithm was developed for a three dimensional and four dimensional population balance model with built-in constructs such as SPMD that ran efficiently on a cluster of two quad-core machines linked via a gigabit ethernet cable. Speedup of 6.2 and 5.7 times were achieved with 8 workers, over an un-parallelized code, for a 3 and 4 dimensional PBM respectively. Evaluations on work efficiency and scalability further affirm the algorithms’ respectable performance on larger clusters despite significant memory transfer overheads.     

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.     

Low-Temperature Sintering of La(Ca)CrO3 Powder Prepared through the Combustion Process

Ultrafine La(Ca)CrO₃ (LCC) powder was prepared through the glycine–nitrate gel combustion process. It was shown for the first time that the use of relatively inexpensive CrO₃ as a starting material for chromium has potential for the bulk preparation of sinter-active LCC powder. As-prepared powder, when calcined at 700°C, resulted in LCC along with a small amount of CaCrO₄. The calcined powder was found to be composed of soft agglomerates with a particle size of ≈70–290 nm. The cold pressing and sintering of the calcined powder at 1200°C resulted in the mono-phasic La_0.7Ca_0.3CrO₃ with density ≈98% of its theoretical value. This is the lowest sintering temperature ever reported for La_0.7Ca_0.3CrO₃. The conductivity of the sintered La_0.7Ca_0.3CrO₃ at 1000°C was found to be ≈57 S/cm in air. The sintering and electrical behavior achieved for La_0.7Ca_0.3CrO₃ may find application as an interconnect material for high-temperature solid oxide fuel cells if problems with chemical expansion and poor conductivity in fuel can be overcome.     

Assessment of flow induced vibration in a sodium-sodium heat exchanger

The 500 MWe Prototype Fast Breeder Reactor (PFBR) is under construction at Kalpakkam. It is a liquid metal sodium cooled pool type fast reactor with all primary components located inside a sodium pool. The heat produced due to fission in the core is transported by primary sodium to the secondary sodium in a sodium to sodium Intermediate Heat Exchanger (IHX), which in turn is transferred to water in the steam generator. PFBR IHX is a shell and tube type heat exchanger with primary sodium on shell side and secondary sodium in the tube side. Since IHX is one of the critical components placed inside the radioactive primary sodium, trouble-free operation of the IHX is very much essential for power plant availability. To validate the design and the adequacy of the support system provided for the IHX, flow induced vibration (FIV) experiments were carried out in a water test loop on a 60° sector model. This paper discusses the flow induced vibration measurements carried out in 60° sector model of IHX, the modeling criteria, the results and conclusion.     

Fracture behaviour of fly-ash filled FRP composites

The major objective of this study was to determine the fracture toughness and fracture surface energy of epoxy, epoxy/fly-ash, epoxy/carbon fibre, epoxy/carbon fibre/fly-ash, epoxy/glass fibre and epoxy/glass fibre/fly-ash composites. The quality of composite specimens was evaluated by the ultrasonic method. The results show that a fly-ash particle can arrest the crack path and thus improve the fracture properties of fibre reinforced plastic (FRP) composites. The results of this study have further significance in view of the fact that fly-ash powder is far cheaper than carbon fibre, glass fibre and epoxy resin.     

A figure of merit for evaluating sustainability of renewable energy systems

For grading different types of renewable energy based electricity generation systems, a figure of merit has been proposed and evaluated. The figure of merit has been obtained by analyzing total energy utilization in constructing and installing the systems and by their respective electricity generation. The gross carbon emission has also been estimated for evaluation of figure of merit. This figure of merit clearly indicates that wind power is the most sustainable source for electricity generation, followed by small hydropower and solar photovoltaics.     

Multi-electrode microbial fuel cell (MEMFC): A close analysis towards large scale system architecture

Microbial fuel cells are capable of producing electricity through the treatment of wastewater, however, the low power density poses main hurdles towards their wide application. In present work, microbial fuel cell based on multiple anodes, acting as baffle is constructed for achieving higher performance which can be scaled up for real life application. It is investigated for continuous sixty two days using distillery wastewater (WW) in three batches under ambient condition. During first batch, the WW is maintained under stagnant condition inside the anode chamber where as in the rest of the two batches WW is recirculated in the chamber. A maximum power density 427 mW m⁻², is achieved under stagnant condition which is further enhanced to 597 mW m⁻² under recirculation mode. Recirculation of WW reduces the internal resistance arising from the mass transfer by 50%. Maximum COD removal and Coulombic efficiency obtained is 43% and 23%. Biofouling on the surface of the membrane facing anode chamber is observed.     

Experimental and thermal analysis of energy efficient novel design wet cooling towers

Waste heat is generally dissipated from process water to atmospheric air in cooling towers. In the present study, a novel design is used to extract more amount of heat without any additional energy input by incorporating secondary ambient air in an induced draft wet cooling tower. In addition, more fresh air is induced in the tower from the rain zone, which increases the effectiveness at any value of the water to air flow rate (L/G ratio). Moreover, tower characteristics, range, and evaporation loss were also increased due to the novel design. It is noteworthy that secondary fresh air increases effectiveness, heat rejection, and tower characteristics by 10.12%, 19.65%, and 26.11%, respectively, and decreases approach by 16.32% at 0.55 L/G ratio, 44°C inlet water temperature, 29.7°C dry bulb temperature, and 18.4°C inlet air wet bulb temperature.     

Orientation-Dependent Developments in Misorientation and Residual Stress in Rolled Aluminum: The Defining Role of Dislocation Interactions

Orientation-dependent developments in misorientation and residual stress, in rolled aluminum, were quantified experimentally and simulated numerically. The latter involved analysis using a crystal plasticity finite element model, accounting for anisotropies in slip system hardening but neglecting near-neighbor interactions, and discrete dislocation dynamics of the single crystals. Both were successful in capturing the experimental patterns of orientation dependence. Numerical simulations, without slip transfer across the neighboring grains, thus established the defining role of dislocation interactions in establishing orientation-sensitive microstructural evolution.