Development of the Fray-Farthing-Chen Cambridge Process: Towards the Sustainable Production of Titanium and Its Alloys

The Kroll process has been employed for titanium extraction since the 1950s. It is a labour and energy intensive multi-step semi-batch process. The post-extraction processes for making the raw titanium into alloys and products are also excessive, including multiple remelting steps. Invented in the late 1990s, the Fray-Farthing-Chen (FFC) Cambridge process extracts titanium from solid oxides at lower energy consumption via electrochemical reduction in molten salts. Its ability to produce alloys and powders, while retaining the cathode shape also promises energy and material efficient manufacturing. Focusing on titanium and its alloys, this article reviews the recent development of the FFC-Cambridge process in two aspects, (1) resource and process sustainability and (2) advanced post-extraction processing.     

Co-Extraction of U(VI) and HNO3 Using TBP and its Higher Homologues TiAP and TEHP: Comparison of Equilibria,Kinetics, and Rate of Extraction

In this work, bulk-liquid membrane (BLM) system is used to compare tri-n-butyl phosphate (TBP), tri-isoamyl phosphate (TiAP), and tris(2-ethylhexyl) phosphate (TEHP) for their relative ability to co-extract U(VI) and nitric acid from aqueous nitric acid feed-phase into water strip-phase, through hydrocarbon membrane-phase. The kinetics of extraction is modelled and the model is validated through experiments. The quantity which determines the efficiency of liquid emulsion membrane (LEM) process is the relative rate of extraction of U(VI) to nitric acid. This is in the order TiAP>TEHP>TBP, indicating that TiAP is most suitable for extraction of U(VI) from nitric acid using LEM.     

Affinity Studies of Hemicyanine Derived Water Soluble Colorimetric Probes with Reactive Oxygen/Nitrogen/Sulfur Species

Peroxynitrite (ONOO^-) is an essential endogenous reactive oxygen species (ROS) generated in mitochondria under various pathological and physiological conditions. An increase in its level in mitochondria is related to numerous diseases. Herein, we report a series of hemicyanine-derived water-soluble colorimetric probes ( 1 – 4 ) and the reactivity of which was studied with various reactive oxygen, nitrogen, and sulfur species. Probes 1 – 4 are formed by conjugating 1,2,3,3-tetramethyl-3H-indolium iodide and 4-hydroxybenzaldehyde or its derivatives through an alkene linkage formed by the Knoevenagel reaction. Oxidative cleavage of the electron-rich double bond of the conjugated hemicyanine dye revealed a discerning affinity of probe 3 towards peroxynitrite among all reactive oxygen species. The rapid change in color of 3 provides a sensitive and selective method for detecting peroxynitrite with a low detection limit of 180 nM. Notably, the water solubility of the probe displays excellent performance for the selective detection of peroxynitrite among ROS and reactive nitrogen (RNS)/sulfur species (RSS). UV-vis, ¹H NMR, and ¹³C NMR spectroscopic data and results from theoretical calculations provide further information on the interaction of peroxynitrite with probe 3 .     

Design and Synthesis of Xanthone Analogues Conjugated with Aza-aromatic Substituents as Promising G-Quadruplex Stabilizing Ligands and their Selective Cancer Cell Cytotoxic Action

We have examined the stabilization of higher-order noncanonical G-quadruplex (G4) DNA structures formed by the G-rich sequences in the promoter region of oncogenes such as c-MYC, c-KIT, VEGF and BCl2 by newly synthesized, novel nitrogen-containing aromatics conjugated to xanthone moiety. Compounds with N-heterocyclic substituents such as pyridine (XNiso), benzimidazole (XBIm), quinoxaline (XQX) and fluorophore dansyl (XDan) showed greater effectiveness in stabilizing the G4 DNA as well as selective cytotoxicity for cancer cells (mainly A549) over normal cells both in terms of UV-Vis spectral titrations and cytotoxicity assay. Both fluorescence spectral titrimetric measurements and circular dichroism (CD) melting experiments further substantiated the G4 stabilization phenomenon by these small-molecular ligands. In addition, these compounds could induce the formation of parallel G4 structures in the absence of any added salt condition in Tris ⋅ HCl buffer at 25 °C. In a polymerase stop assay, the formation of stable G4 structures in the promoter of oncogenes and halting of DNA synthesis in the presence of the above-mentioned compounds was demonstrated by using oncogene promoter as the DNA synthesis template. Apoptosis-mediated cell death of the cancer cells was proved by Annexin V-PI dual staining assay and cell-cycle arrest occurred in the S phase of the cell cycles. The plausible mode of binding involves the stacking of the xanthone core on the G4 DNA plane with the possibility of interaction with the 5’-overhang as indicated by molecular dynamics simulation studies.     

Impact of Stone-Wales and lattice vacancy defects on the electro-thermal transport of the free standing structure of metallic ZGNR

We report the effect of topological as well as lattice vacancy defects on the electro-thermal transport properties of the metallic zigzag graphene nano ribbons at their ballistic limit. We employ the density function theory–Non equilibrium green’s function combination to calculate the transmission details. We then present an elaborated study considering the variation in the electrical current and the heat current transport with the change in temperature as well as the voltage gradient across the nano ribbons. The comparative analysis shows, that in the case of topological defects, such as the Stone-Wales defect, the electrical current transport is minimum. Besides, for the voltage gradient of 0.5 Volt and the temperature gradient of 300 K, the heat current transport reduces by \({\sim }62\,\%\) and \({\sim }50\,\%\) for the cases of Stones-Wales defect and lattice vacancy defect respectively, compared to that of the perfect one.     

Skin permeation of buflomedil form adhesive matrix patches

The main objective of this research work was to fabricate and evaluate adhesive matrix-type transdermal patches of buflomedil hydrochloride, employing different ratios of pressure sensitive adhesives (PSAs) by solvent casting technique. The adhesive matrix-type transdermal patches were evaluated by their in vitro physicochemical properties such as thickness, moisture content, weight variation, drug content uniformity, etc. The effects of PSAs ratio, drug loading, and concentration of permeation enhancer were evaluated thoroughly. Ex vivo skin permeation studies with kinetic modeling of adhesive matrix patches were systematically evaluated. Based on the above observations, the best optimized buflomedil hydrochloride-loaded adhesive matrix-type transdermal patch was further characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction study, and differential scanning calorimetry analyses. Drug containing adhesive matrix patches showed sustained release property without showing any incompatibility in adhesive matrix system. Hence, adhesive matrix-type transdermal patches of buflomedil hydrochloride can be used as a potential carrier for sustained transdermal delivery of hydrophilic drugs like buflomedil hydrochloride.     

Electric power distribution system design and planning in a deregulated environment

This study presents a hierarchical dynamic optimisation model to address the design, planning and energy scheduling problem in power distribution systems. In addition to planner controlled investments, uncoordinated investor distributed generation investments are also respected, for which recommendations given policies can be made. Beyond planning, this model's usefulness also extends into predicting the impact of different energy policies on system operation and economics.     

Failure Analysis of a Cylindrical Roller Bearing from a Rolling Mill

Premature failure of a cylindrical roller bearing of a gear box input shaft from a hot strip mill has been investigated. The pins of the cylindrical rollers of the bearing broke from the welded joints at their ends on the cage ring. Investigations were carried out on the failed roller pin and the welded joint. The investigation consists of visual observation, chemical analysis, characterization of macro- and microstructures, measurement of hardness profile, fractography, and energy dispersive spectroscopy (EDS). The fracture surface of the roller pins exhibits beach marks. Scanning electron microscopy (SEM) of the fracture surfaces reveals striations suggesting fatigue failure. The measured hardness profile along the welded joint shows very high hardness due to the presence of untempered martensite at the fusion boundary as revealed by the microstructural examination. Analyses of the results infer that the roller pins failed by the initiation of fatigue cracks from the welded joint because of the presence of untempered martensite originated due to improper welding process.