Formation of Chlorotriophenoxy Radicals from Complete Series Reactions of Chlorotriophenols with H and OH Radicals

The chlorothiophenoxy radicals (CTPRs) are key intermediate species in the formation of polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs). In this work, the formation of CTPRs from the complete series reactions of 19 chlorothiophenol (CTP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution at 600–1200 K. The present study indicates that the structural parameters, thermal data, and rate constants as well as the formation potential of CTPRs from CTPs are strongly dominated by the chlorine substitution at the ortho-position of CTPs. Comparison with the study of formation of chlorophenoxy radicals (CPRs) from chlorophenols (CPs) clearly shows that the thiophenoxyl-hydrogen abstraction from CTPs by H is more efficient than the phenoxyl-hydrogen abstraction from CPs by H, whereas the thiophenoxyl-hydrogen abstraction from CTPs by OH is less impactful than the phenoxyl-hydrogen abstraction from CPs by OH. Reactions of CTPs with H can occur more readily than that of CTPs with OH, which is opposite to the reactivity comparison of CPs with H and OH.     

Technical and economic analysis of solvent-based lithium-ion electrode drying with water and NMP

Processing lithium-ion battery (LIB) electrode dispersions with water as the solvent during primary drying offers many advantages over N-methylpyrrolidone (NMP). An in-depth analysis of the comparative drying costs of LIB electrodes is discussed for both NMP- and water-based dispersion processing in terms of battery pack $/kWh. Electrode coating manufacturing and capital equipment cost savings are compared for water vs. conventional NMP organic solvent processing. A major finding of this work is that the total electrode manufacturing costs, whether water- or NMP-based, contribute about 8–9% of the total pack cost. However, it was found that up to a 2?×?reduction in electrode processing (drying and solvent recovery) cost can be expected along with a $3–6?M savings in associated plant capital equipment (for a plant producing 100,000 10-kWh Plug-in Hybrid Electric Vehicle (PHEV) batteries) using water as the electrode solvent. This paper shows a different perspective in that the most important benefits of aqueous electrode processing actually revolve around capital equipment savings and environmental stewardship and not processing cost savings.     

An approach to measure infill matric suction of irregular infilled rock joints under constant normal stiffness shearing

Rock joints infilled with sediments can strongly influence the strength of rock mass. As infilled joints often exist under unsaturated condition, this study investigated the influence of matric suction of infill on the overall joint shear strength. A novel technique that allows direct measurement of matric suction of infill using high capacity tensiometers (HCTs) during direct shear of infilled joints under constant normal stiffness (CNS) is described. The CNS apparatus was modified to accommodate the HCT and the procedure is explained in detail. Joint specimens were simulated by gypsum plaster using three-dimensional (3D) printed surface moulds, and filled with kaolin and sand mixture prepared at different water contents. Shear behaviours of both planar infilled joints and rough joints having joint roughness coefficients (JRCs) of 8–10 and 18–20 with the ratios of infill thickness to asperity height (t/a) equal to 0.5 were investigated. Matric suction shows predominantly unimodal behaviour during shearing of both planar and rough joints, which is closely associated with the variation of unloading rate and volumetric changes of the infill material. As expected, two-peak behaviour was observed for the rough joints and both peaks increased with the increase of infill matric suction. The results suggest that the contribution of matric suction of infill on the joint peak normalised shear stress is relatively independent of the joint roughness.     

Functional substrates for the gradual release of agents

This work describes the functionalization of a natural and a man-made textile substrate, namely cotton and polyamide 6.6, with inclusion agents, β-cyclodextrins (β-CDs) that are able to release gradually to the user active ingredients. In this study we used aescin (aesculus hippocastanum extract), which is a natural agent with benefits for the treatment of varicose veins.¹H NMR and UV–vis data supported the role of β-CDs as an aescin complexing agent, and the covalent nature of the linkage between β-cyclodextrins and the textile substrates, which showed a wash fastness to more than 45 washing cycles.     

Soret and Dufour effects between two rectangular plane walls with heat source/sink

This study addresses the thermo‐diffusion and the diffusion‐thermo phenomena in a semi‐infinite absorbent channel whose walls are contracting/expanding, with heat source/sink effects. The governing partial differential equations with suitable boundary conditions are transformed to a system of dimensionless ordinary differential equations. An analytic solution of the problem has been found using a technique called homotopy analysis method (HAM). HAM gives consistently valid answers to the problem over an extensive variety of parameters and also provides better accuracy. To validate the analytical results, a comparison has been presented with a numerical solution calculated by using the parallel shooting method. The effects of dimensionless parameters, that is, deformation parameter, Reynolds number, Soret and Dufour numbers, and heat source/sink parameter on the expressions of velocity, temperature, and concentration profiles are analyzed graphically to understand the physics of the deformable channel. It has been noted that the velocity across the channel is higher for the expanding channel, as compared to that for the contracting channel. Also the Soret and Dufour number increases the temperature of the fluid, and decreases the concentration. The temperature profile has an increasing behavior in the case of heat source, and a decreasing behavior in the case of heat sink.     

Methodology for optimization of pouring variables using bottom pour for low masses of SS304 (<300 kg) in investment casting process (case study)

Bottom pour ladles with stopper rod systems are commonly used in the metal casting industry. However, stopper rod bottom-pouring systems have not yet been developed for the lower thermal masses of alloys typically used in the investment casting industry. Large thermal masses used with bottom pour systems are typically limited for ladles larger than 700 kg and to certain alloys with higher fluidity and longer solidification time like cast iron, aluminum alloys etc. In this study, bottom pour ladle designs and low thermal mass refractory systems have been developed and evaluated in production investment foundry trials with 300 kg pouring ladle. The ladles system and pouring practices used will be described along with the results from the pouring trials for SS304 that represents typical alloys used in Investment casting industries. Optimization of the variables used in an experimentation using Genetic algorithm is also explained.     

Development of mobile miniature natural gas liquefiers

With increasing consumption of natural gas (NG), small NG reservoirs, such as coalbed methane and oil field associated gas, have recently drawn significant attention. Owing to their special characteristics (e.g., scattered distribution and small output), small-scale NG liquefiers are highly required. Similarly, the mixed refrigerant cycle (MRC) is suitable for small-scale liquefaction systems due to its moderate complexity and power consumption. In consideration of the above, this paper reviews the development of mobile miniature NG liquefiers in Technical Institute of Physics and Chemistry (TIPC), China. To effectively liquefy the scattered NG and overcome the drawbacks of existing technologies, three main improvements, i.e., low-pressure MRC process driven by oil-lubricated screw compressor, compact cold box with the new designed heat exchangers, and standardized equipment manufacturing and integrated process technology have been made. The development pattern of “rapid cluster application and flexible liquefaction center” has been eventually proposed. The small-scale NG liquefier developed by TIPC has reached a minimum liquefaction power consumption of about 0.35 kW·h/Nm³. It is suitable to exploit small remote gas reserves which can also be used in boil-off gas reliquefaction and distributed peak-shaving of pipe networks.     

Efficiency and effectiveness enhancement of an intercooler of two‐stage air compressor by low‐cost Al2O3/water nanofluids

The present study was aimed to utilize low‐cost alumina (Al₂O₃) nanoparticles for improving the heat transfer behavior in an intercooler of two‐stage air compressor. Experimental investigation was carried out with three different volume concentrations of 0.5%, 0.75%, and 1.0% Al₂O₃/water nanofluids to assess the performance of the intercooler, that is, counterflow heat exchanger at different loads. Thermal properties such as thermal conductivity and overall heat transfer coefficient of nanofluid increased substantially with increasing concentration of Al₂O₃ nanoparticles. Specific heat capacity of nanofluids were lower than base water. The intercooler performance parameters such as effectiveness and efficiency improved appreciably with the employment of nanofluid. The efficiency increased by about 6.1% with maximum concentration of nanofluid, that is, 1% at 3‐bar compressor load. It is concluded from the study that high concentration of Al₂O₃ nanoparticles dispersion in water would offer better heat transfer performance of the intercooler.     

Tribological behaviour of a 3Y-TZP/Ta ceramic-metal biocomposite against ultrahigh molecular weight polyethylene (UHMWPE)

This study aims to evaluate the tribological behaviour of 3Y-TZP/Ta (20 vol%) ceramic-metal composites and 3Y-TZP monolithic ceramic prepared by spark plasma sintering (SPS) against ultrahigh molecular weight polyethylene (UHMWPE). According to the results of pin (UHMWPE)-on-flat wear test under dry conditions, the UHMWPE – 3Y-TZP/Ta system exhibited lower volume loss and friction coefficient than the UHMWPE – monolithic ceramic combination due to the presence of an autolubricating layer that provides sufficient lubrication for reducing the friction. Owing to the lubrication of the liquid media, under wet conditions obtained using simulated body fluid (SBF), similar behaviour is observed in both cases. Additionally, the ceramic and biocomposite materials were subjected to a low temperature degradation (LTD) process (often referred to as “ageing”) to evaluate the changes in the tribological behaviour after this treatment. In this particular case, the wear properties of the UHMWPE-biocomposite system were found to be less influenced by ageing in contrast to the case of the UHMWPE-zirconia monolithic material. In addition to their exceptional mechanical performance, 3Y-TZP/Ta composites also showed high resistance to low temperature degradation and good tribological properties, making them promising candidates for biomedical applications, especially for orthopaedic implants.