Microstructural Characterization and Tensile Behavior of Rutile(TiO_2)-Reinforced AA6063 Aluminum Matrix Composites Prepared by Friction Stir Processing

Rutile(TiO_2) particle-reinforced aluminum matrix composites were prepared by friction stir processing. The microstructure was studied using conventional and advanced characterization techniques. TiO_2 particles were found to be dispersed uniformly in the composite. Clusters of TiO_2 particles were observed at a higher particle content of 18 vol%. The interface between the TiO_2 particle and the aluminum matrix was characterized by the absence of pores and reactive layer.Sub-grain boundaries, ultra-fine grains and dislocation density were observed in the composites. TiO_2 particles improved the mechanical properties of the composites. However, a drop in tensile strength was observed at a higher particle content due to cluster formation. All the prepared composites exhibited ductile mode of fracture.     

Effect of W and Ce additions on the electrochemical corrosion behaviour of 444-type ferritic stainless steel

In order to achieve excellent heat resistance and corrosion resistance, high melting-point and rare earth elements were added to ferritic stainless steel. The effect of W and Ce addition in ferritic stainless steel on the corrosion resistance in 0.1?M NaOH solution was studied. Potentiodynamic polarisation curves indicated that W- and Ce-containing samples had lower corrosion rate and lower passive current density. The electrochemical impedance spectroscopy measurements revealed that W–Ce-containing samples had higher polarisation resistance values and thicker passive films. Capacitance analysis indicated that the semiconducting behaviour and the properties of passive film remain unchanged. The addition of W and Ce led to a decrease in donor and acceptor density, which improved the passive film stability.     

Exploiting nanospace for asymmetric catalysis: confinement of immobilized, single-site chiral catalysts enhances enantioselectivity

In the mid-1990s, it became possible to prepare high-area silicas having pore diameters controllably adjustable in the range ca. 20-200 ?. Moreover, the inner walls of these nanoporous solids could be functionalized to yield single-site, chiral, catalytically active organometallic centers, the precise structures of which could be determined using in situ X-ray absorption and FTIR and multinuclear magic angle spinning (MAS) NMR spectroscopy. This approach opened up the prospect of performing heterogeneous enantioselective conversions in a novel manner, under the spatial restrictions imposed by the nanocavities within which the reactions occur. In particular, it suggested an alternative method for preparing pharmaceutically and agrochemically useful asymmetric products by capitalizing on the notion, initially tentatively perceived, that spatial confinement of prochiral reactants (and transition states formed at the chiral active center) would provide an altogether new method of boosting the enantioselectivity of the anchored chiral catalyst. Initially, we anchored chiral single-site heterogeneous catalysts to nanopores covalently via a ligand attached to Pd(II) or Rh(I) centers. Later, we employed a more convenient and cheaper electrostatic method, relying in part on strong hydrogen bonding. This Account provides many examples of these processes, encompassing hydrogenations, oxidations, and aminations. Of particular note is the facile synthesis from methyl benzoylformate of methyl mandelate, which is a precursor in the synthesis of pemoline, a stimulant of the central nervous system; our procedure offers several viable methods for reducing ketocarboxylic acids. In addition to relying on earlier (synchrotron-based) in situ techniques for characterizing catalysts, we have constructed experimental procedures involving robotically controlled catalytic reactors that allow the kinetics of conversion and enantioselectivity to be monitored continually, and we have access to sophisticated, high-sensitivity chiral chromatographic facilities and automated high-throughput combinatorial test rigs so as to optimize the reaction conditions (e.g., H(2) pressure, temperature, time on-stream, pH, and choice of ligand and central metal ion) for high enantioselectivity. This Account reports our discoveries of selective hydrogenations and aminations of synthetic, pharmaceutical, and biological significance, and the findings of other researchers who have achieved similar success in oxidations, dehydrations, cyclopropanations, and hydroformylations. Although the practical advantages and broad general principles governing the enhancement of enantioselectivity through spatial confinement are clear, we require a deeper theoretical understanding of the details pertaining to the phenomenology involved, particularly through molecular dynamics simulations. Ample scope exists for the general exploitation of nanospace in asymmetric hydrogenations with transition metal complexes and for its deployment for the formation of C-N, C-C, C-O, C-S, and other bonds.     

Potentiodynamic deposition of poly (o-anisidine-co-metanilic acid) on mild steel and its application as corrosion inhibitor

For the first time, poly (o-anisidine-co-metanilic acid) (PASM) was deposited on mild steel substrate by electrochemical polymerization of o-anisidine and metanilic acid monomers in aqueous solution of 0.1 M H₂SO₄. The electrochemical polymerization of o-anisidine takes place in the presence of metanilic acid monomer and uniform, strongly adherent coating was obtained on the substrate. The electroactivity of copolymer was studied by cyclic voltammetry and AC impedance techniques. There is an increasing anodic current due to oxidation of metanilic acid monomer at the surface of the electrode when the applied potential is cycled from −0.2 V to 0.8 V. These deposits were characterized by Fourier transform infrared (FTIR) spectroscopy, UV-vis and TG/DTA techniques. The effect of various concentrations of PASM copolymer solution in acid rain corrosive media has been studied through potentiodynamic polarization, AC impedance and I-E curve methods. The soluble form of polymeric solution provided better anti-corrosive behavior in artificial acid rain solution.     

Anomalous mechanical behavior upon recycling of poly(phenylene‐ether)‐based thermoplastic elastomer

Recycling of thermoplastic elastomers based on poly (phenylene ether) (PPE) was studied in detail. The quaternary blend comprising of styrene–ethylene–butylene–styrene (SEBS)/ethylene vinyl acetate (EVA)/PPE‐PS (polystyrene) showed improvement in mechanical properties upon recycling, which was correlated with the formation of crosslinked network in the system. Presence of crosslinked network was confirmed by the gel content analysis. The blend components involved in the crosslinking were evaluated by gel morphology analysis. Fourier transform infrared spectroscopy revealed the chemical composition of the crosslinked gel. Crosslinking mechanism was established based on the reactivity of allylic EVA radical during recycling. Rheological study supported the notion of crosslinking upon recycling that resulted in higher storage modulus (G′) as a manifestation of restrained flow by network formation. On the basis of the earlier data, a reaction mechanism for crosslinking was proposed. Finally, structure–property correlation was developed through morphological, chemical, and rheological analysis to understand the anomalous enhancement in mechanical properties upon recycling. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Redox solid catalysts for the selective oxidation of cyclohexane in air

The selective oxidation of cyclohexane to cyclohexanol, cyclohexanone and adipic acid using molecular oxygen as the oxidant and at moderate temperatures (403 K) has been investigated over four different cobalt‐containing aluminophosphate (AlPO) molecular sieves. There is a correlation between catalytic activity and the fraction of (framework) Co(II) ions that is first oxidised to Co(III) in air. CoAlPO‐36 (pore aperture 6.5 x 7.5 Å) exhibits significant activity for the oxidation of cyclohexane in contrast to CoAlPO‐18, which, although it has the highest fraction of oxidisable cobalt, does not show any activity chiefly because of its smaller pores.     

Responses of bimetallic Ag/ZnO alloy nanoparticles and urea on morphological and physiological attributes of wheat

Wheat (Triticum aestivum L.) is the most important staple food crop globally. According to economic survey 2018‐19, agriculture sector of Pakistan grew by 0.85%, with wheat accounting for 8.9% of agriculture and 1.6% of GDP, and its production fell short of the target by 4.9%. Wheat requires beneficial ties to improve its efficiency with the help of modern technology. Nanotechnology modifies conventional agricultural practices as these are stimulating agents for plant growth. Green bimetallic Ag/ZnO alloy nanoparticles (NPs) synthesised from salts reduced by Moringa oleifera and characterised by UV‐visible spectroscopy, scanning electron microscopy, and energy‐dispersive X‐ray spectroscopy are studied herein. Different concentrations of urea and Ag/ZnO alloy NPs were applied exogenously to wheat plants (Pakistan‐13 and Galaxy13). A significant effect of 100 mg/L urea and 75 ppm Ag/ZnO alloy NPs was observed on the morphology of wheat, with a maximum increase of 58% plant length, 85% leaf area, 89% plant fresh weight and 76% plant dried weight. In physiological parameters, relative water content and membrane stability index have shown maximum increases of 39% and 77%, while chlorophyll a, b, and total chlorophyll content (TCC) showed maximum increases of 92%, 71%, and 84% respectively. Evidence of the morpho‐physiological responses of urea and green synthesised alloy NPs on wheat varieties are reported on.     

Surface‐modified nanosilica–chitinase (SiNp‐Chs)‐doped nano enzyme conjugate and its synergistic pesticidal activity with plant extracts against armyworm Spodoptera litura (Fab.) (Lepidoptera: Noctuidae)

A laboratory experiment was conducted to evaluate enhanced pesticidal activity of silica nanoparticles‐doped chitinase nano enzyme conjugate against an economically important insect pest Spodoptera litura (Fab.) (Lepidoptera; Noctuidae). Silica nanoparticles were synthesized by hydrolysis and condensation of precursor tetraethylorthosilicate (TEOS) followed by functionalization with functioning agent 3‐aminopropyltriethoxysilane. Functionalized silica nanoparticles thus acquired were doped with chitinase enzyme produced by Serratia marcescens SU05. Doped nanosilica–chitinase nano enzyme conjugate was loaded with pesticidal plant extracts to study the improved pesticidal activity. Synthesized nano enzyme conjugate revealed high stable, monodisperse spherical nanoparticles and exhibited effective loading with respective plant extracts. Nano enzyme conjugates and plant extracts loaded with nano enzyme conjugate recorded high rate of mortality against the larval instars and brought about a distinct effect on the life stage parameters of S.litura. Non‐target toxic effect of nano enzyme conjugate was carried out by determination of lethality and changes in protein profiling against brine shrimp (Artemia salina) that shows less lethality and no distinct changes in protein profiling which suggest the effective utilization of silica nanoparticles doped chitinase as an insecticidal agent against economically important insect pests associated with various crops.     

Study of the structure and corrosion behavior of PEO coatings on AM50 magnesium alloy by electrochemical impedance spectroscopy

In this work coatings were developed on the surface of AM50 magnesium alloy using four different electrolytes containing 10 wt.% each of K₃PO₄ and Na₃PO₄ in combination with either potassium or sodium hydroxides. Electrolyte conductivity and breakdown voltage were measured in order to correlate the property of the coating to the nature of electrolyte. Further, the coatings were examined using scanning electron microscopy for surface morphology and cross sectional investigation, X-ray diffraction for phase determination, and electrochemical impedance spectroscopy for corrosion resistance evaluation. The effect of employing different ions in the electrolytes results in different surface morphologies, chemical phases and, consequently, the corrosion resistance of the coatings. The EIS results indicate the presence of porous and compact layers in the structure of the PEO coatings, whilst the overall coating resistance mainly results from the compact layer, the role of the porous layer as a barrier against corrosion is negligible. Finally, a correlation between the passive current density of the bare alloy and the corrosion resistance of the PEO coating is proposed.     

Optimisation of metal sputtered and electroplated substrates for solar selective coatings

This study describes the performance of selective coatings to have maximum solar absorptance and minimum thermal emittance, in relation to substrate preparation. Aluminium and copper substrates, covered with sputtered or electroplated metal base layer, have been used to see the influence of different types of substrates for solar selective coatings. The effect of the base layer material, thickness, deposition process and deposition condition, on the optical performance of selective coatings has been analysed. Nickel was electroplated and nickel and vanadium were sputtered as a base layer on the Al and Cu substrates. A comparison of plated and sputtered nickel substrates for Ni:SiO₂ and V:Al₂O₃ composite solar selective coatings is presented. Theoretical results using computer simulation for solar selective composites on various substrates, and the effect of the base layer thickness on these substrates are compared with experimental results. The effects of the base layer thickness for cobalt and tungsten are also included. The sputtered base layers selective coatings produced higher absorptance along with higher emittance and electroplated base layer coatings resulted in comparatively lower absorptance and lower emittance. Hundred nanometre metal sputtered base layer is optimised for solar selective coatings.