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      Volume 32, Issue 3

      June 2009,   pages  215-367

    • Foreword

      S B Krupanidhi H L Bhat

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    • Molecule-based magnets

      J V Yakhmi

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      The conventional magnetic materials used in current technology, such as, Fe, Fe2O3, Cr2O3, SmCo5, Nd2Fe14B etc are all atom-based, and their preparation/processing require high temperature routes. Employing self-assembly methods, it is possible to engineer a bulk molecular material with long-range magnetic order, mainly because one can play with the weak intermolecular interactions. Since the first successful synthesis of molecular magnets in 1986, a large variety of them have been synthesized, which can be categorized on the basis of the chemical nature of the magnetic units involved: organic-, metal-based systems, heterobimetallic assemblies, or mixed organic–inorganic systems. The design of molecule-based magnets has also been extended to the design of poly-functional molecular magnets, such as those exhibiting second-order optical nonlinearity, liquid crystallinity, or chirality simultaneously with long-range magnetic order. Solubility, low density and biocompatibility are attractive features of molecular magnets. Being weakly coloured, unlike their opaque classical magnet ‘cousins’ listed above, possibilities of photomagnetic switching exist. Persistent efforts also continue to design the ever-elusive polymer magnets towards applications in industry. While providing a brief overview of the field of molecular magnetism, this article highlights some recent developments in it, with emphasis on a few studies from the author’s own lab.

    • Metal–semiconductor nanojunctions and their rectification characteristics

      Anindita Bose Kuntal Chatterjee Dipankar Chakravorty

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      Junctions of silver–copper oxide and silver–zinc oxide, respectively were prepared within the pores of diameters, 20 nm, in anodic aluminium oxide membranes. Voltage–current characteristics were measured over the temperature range 373–573 K which showed rectification behaviour. Using the standard equation the difference between the work functions of the metal and the semiconductor was calculated. This showed a variation with the temperature of measurement. This is explained as arising due to the effect of pressure generated as a result of thermal expansion of the metallic phases concerned between the electrodes. This is consistent with the theoretical prediction of Fermi level shifting of the semiconductor within the bandgap as a function of pressure.

    • Magnetic and photocatalytic properties of nanocrystalline ZnMn2O4

      Menaka Mohammed Qamar Samuel E Lofland Kandalam V Ramanujachary Ashok K Ganguli

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      The present study describes the synthesis of ZnMn2O4 nanoparticles with the spinel structure. These oxide nanoparticles are obtained from the decomposition of metal oxalate precursors synthesized by

      1. the reverse micellar and
      2. the coprecipitation methods.

      Our studies reveal that the shape, size and morphology of precursors and oxides vary significantly with the method of synthesis. The oxalate precursors prepared from the reverse micellar synthesis method were in the form of rods (micron size), whereas the coprecipitation method led to spherical nanoparticles of size, 40–50 nm. Decomposition of oxalate precursors at low temperature (∼ 450°C) yielded phase pure ZnMn2O4 nanoparticles. The size of the nanoparticles of ZnMn2O4 obtained from reverse micellar method is relatively much smaller (20–30 nm) as compared to those made by the co-precipitation (40–50 nm) method. Magnetic studies of nanocrystalline ZnMn2O4 confirm antiferromagnetic ordering in the broad range of ∼ 150 K. The photocatalytic activity of ZnMn2O4 nanoparticles was evaluated using photo-oxidation of methyl orange dye under UV illumination and compared with nanocrystalline TiO2.

    • Resorcinol–formaldehyde based carbon nanospheres by electrospraying

      Chandra S Sharma Sandip Patil Suman Saurabh Ashutosh Sharma R Venkataraghavan

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      Carbon nanospheres were synthesized using sol–gel processing of organic and aqueous resorcinol formaldehyde (RF) sols combined with electrospraying technique. RF sol was electrosprayed to form nanodroplets which were collected on a Si wafer. After oven drying at 60°C for 12 h, RF nano-droplets were pyrolyzed at 900°C in an inert atmosphere to yield the carbon nanospheres. This study reports the optimization of various process parameters including needle diameter, applied electric potential and liquid flow rate in order to get spherical, mono-disperse particles. For the organic RF sol, the optimized parameters, needle diameter 0.241 mm, electric potential, 1.5 kV/cm and a flow rate of 0.8 ml/h, enabled the synthesis of nearly monodispersed carbon nano-spheres with diameter of 30.2 ± 7.1 nm. With the same conditions, aqueous RF sol produced irregularly shaped nanoparticles with a smaller mean diameter and much higher variance (17.4 ± 8.0 nm). The surface properties were significantly influenced by the surface morphologies as demonstrated by the water contact angle (WCA) studies. The surface covered with the RF derived carbon nano-spheres was extremely hydrophilic (WCA 10.1°) as compared to a much weaker hydrophilicity of the RF derived carbon films (WCA 83.3°). The hydrophilic carbon nanospheres reported here may have potential applications as adsorbents and in controlled drug delivery, biosensors and carbon-based microelectromechanical systems (C-MEMS) including bio-MEMS.

    • Studies on nonvolatile resistance memory switching in ZnO thin films

      L M Kukreja A K Das P Misra

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      Six decades of research on ZnO has recently sprouted a new branch in the domain of resistive random access memories. Highly resistive and c-axis oriented ZnO thin films were grown by us using d.c. discharge assisted pulsed laser deposition on Pt/Ti/SiO2/Si substrates at room temperature. The resistive switching characteristics of these films were studied in the top-bottom configuration using current–voltage measurements at room temperature. Reliable and repeated switching of the resistance of ZnO thin films was obtained between two well defined states of high and low resistance with a narrow dispersion and small switching voltages. Resistance ratios of the high resistance state to low resistance state were found to be in the range of 2–5 orders of magnitude up to 20 test cycles. The conduction mechanism was found to be dominated by the Ohmic behaviour in low resistance states, while Poole–Frenkel emission was found to dominate in high resistance state. The achieved characteristics of the resistive switching in ZnO thin films seem to be promising for nonvolatile memory applications.

    • ZnO(101) films by pulsed reactive crossed-beam laser ablation

      S Angappane N R Selvi G U Kulkarni

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      We have employed pulsed reactive crossed-beam laser ablation (PRCLA) to deposit a (101) oriented ZnO film. In this method, a supersonic jet of oxygen pulse is made to cross the laser plume from a zinc metal target while being carried to the Si(111) substrate. The obtained deposit was nanocrystalline ZnO as confirmed by a host of characterization techniques. When the substrate was held at varying temperatures, from room temperature to 900°C, the crystallinity of the obtained films increased as expected, but importantly, the crystallographic orientation of the films was varied. High substrate temperatures produced the usual (001) oriented films, while lower substrate temperatures gave rise to increasingly (101) oriented films. The substrate held at room temperature contained only the (101) orientation. The film morphology also varied with the substrate temperature, from being nanoparticulate to rod-like deposits for higher deposition temperatures. Surprisingly, the (101) orientation showed reactivity with acetone forming carbonaceous nanostructures on the surface.

    • Electrocaloric effect of PMN–PT thin films near morphotropic phase boundary

      D Saranya Ayan Roy Chaudhuri Jayanta Parui S B Krupanidhi

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      The electrocaloric effect is calculated for PMN–PT relaxor ferroelectric thin film near morphotropic phase boundary composition. Thin film of thickness, ∼ 240 nm, has been deposited using pulsed laser deposition technique on a highly (111) oriented platinized silicon substrate at 700°C and at 100 mtorr oxygen partial pressure. Prior to the deposition of PMN–PT, a template layer of LSCO of thickness, ∼ 60 nm, is deposited on the platinized silicon substrate to hinder the pyrochlore phase formation. The temperature dependent P–E loops were measured at 200 Hz triangular wave operating at the virtual ground mode. Maximum reversible adiabatic temperature change, 𝛥 𝑇 = 31 K, was calculated at 140°C for an external applied voltage of 18 V.

    • Effect of microstructural evolution on magnetic properties of Ni thin films

      Prashant Kumar M Ghanashyam Krishna A K Bhattacharya

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      The magnetic properties of Ni thin films, in the range 20–500 nm, at the crystalline–nanocrystalline interface are reported. The effect of thickness, substrate and substrate temperature has been studied. For the films deposited at ambient temperatures on borosilicate glass substrates, the crystallite size, coercive field and magnetization energy density first increase and achieve a maximum at a critical value of thickness and decrease thereafter. At a thickness of 50 nm, the films deposited at ambient temperature onto borosilicate glass, MgO and silicon do not exhibit long-range order but are magnetic as is evident from the non-zero coercive field and magnetization energy. Phase contrast microscopy revealed that the grain sizes increase from a value of 30–50 nm at ambient temperature to 120–150 nm at 503 K and remain approximately constant in this range up to 593 K. The existence of grain boundary walls of width 30–50 nm is demonstrated using phase contrast images. The grain boundary area also stagnates at higher substrate temperature. There is pronounced shape anisotropy as evidenced by the increased aspect ratio of the grains as a function of substrate temperature. Nickel thin films of 50 nm show the absence of long-range crystalline order at ambient temperature growth conditions and a preferred [111] orientation at higher substrate temperatures. Thin films are found to be thermally relaxed at elevated deposition temperature and having large compressive strain at ambient temperature. This transition from nanocrystalline to crystalline order causes a peak in the coercive field in the region of transition as a function of thickness and substrate temperature. The saturation magnetization on the other hand increases with increase in substrate temperature.

    • Materials science research for sodium cooled fast reactors

      Baldev Raj

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      The paper gives an insight into basic as well as applied research being carried out at the Indira Gandhi Centre for Atomic Research for the development of advanced materials for sodium cooled fast reactors towards extending the life of reactors to nearly 100 years and the burnup of fuel to 2,00,000 MWd/t with an objective of providing fast reactor electricity at an affordable and competitive price.

    • Nafion and modified-Nafion membranes for polymer electrolyte fuel cells: An overview

      A K Sahu S Pitchumani P Sridhar A K Shukla

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      Polymer electrolyte fuel cells (PEFCs) employ membrane electrolytes for proton transport during the cell reaction. The membrane forms a key component of the PEFC and its performance is controlled by several physical parameters, viz. water up-take, ion-exchange capacity, proton conductivity and humidity. The article presents an overview on Nafion membranes highlighting their merits and demerits with efforts on modified-Nafion membranes.

    • Li-storage and cycling properties of spinel, CdFe2O4, as an anode for lithium ion batteries

      Yogesh Sharma N Sharma G V Subba Rao B V R Chowdari

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      Cadmium ferrite, CdFe2O4, is synthesized by urea combustion method followed by calcination at 900°C and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR–TEM) and selected area electron diffraction (SAED) techniques. The Li-storage and cycling behaviour are examined by galvanostatic cycling, cyclic voltammetry (CV) and impedance spectroscopy in the voltage range, 0.005–3.0 V vs Li at room temperature. CdFe2O4 shows a first cycle reversible capacity of 870 (± 10) mAhg-1 at 0.07C-rate, but the capacity degrades at 4 mAhg-1 per cycle and retains only 680 (± 10) mAhg-1 after 50 cycles. Heat-treated electrode of CdFe2O4 (300°C; 12 h, Ar) shows a significantly improved cycling performance under the above cycling conditions and a stable capacity of 810 (± 10) mAhg-1 corresponding to 8.7 moles of Li per mole of CdFe2O4 (vs theoretical, 9.0 moles of Li) is maintained up to 60 cycles, with a coulombic efficiency, 96–98%. Rate capability of heat-treated CdFe2O4 is also good: reversible capacities of 650 (± 10) and 450 (± 10) mAhg-1 at 0.5 C and 1.4 C (1 C = 840 mAg-1) are observed, respectively. The reasons for the improved cycling performance are discussed. From the CV data in 2–15 cycles, the average discharge potential is measured to be ∼ 0.9 V, whereas the charge potential is ∼2.1 V. Based on the galvanostatic and CV data, ex situ-XRD, -TEM and -SAED studies, a reaction mechanism is proposed. The impedance parameters as a function of voltage during the 1st cycle have been evaluated and interpreted.

    • Ordered oxygen deficient ‘112’ perovskites, LnBaCo2O5.50+𝛿: complex magnetism and transport properties

      B Raveau Md Motin Seikh V Pralong V Caignaert

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      The ordered oxygen deficient `112’ perovskites, LnBaCo2O5.50+𝛿 (Ln = lanthanide or Y), exhibit a very flexible structure which can either uptake (𝛿 > 0) or release oxygen (𝛿 < 0) depending on the experimental conditions of synthesis and on the size of the lanthanide. These compounds exhibit remarkably complex magnetic transitions, metal–insulator transition and exceptionally high magnetoresistance. We show herein that their physics is mainly dominated by three different ferromagnetic states, depending on the cobalt valency: FM1 for 𝛿 = 0 (Co3+), FM2 for 𝛿 < 0 (Co2+/Co3+) and FM3 for 𝛿 > 0 (Co3+/Co4+). The competition between ferromagnetism and antiferromagnetism in these phases and the various transitions are discussed taking into consideration the spin state of cobalt, the issue of phase separation and the effect of cobalt coordination and disproportionation.

    • Compatibility of RuO2 electrodes with PZT ceramics

      K T Jacob G Rajitha V S Saji

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      Because of its high electrical conductivity and good diffusion barrier properties ruthenium dioxide (RuO2) is a good electrode material for use with ferroelectric lead zirconate–titanate (PZT) solid solutions. Under certain conditions, RuO2 can react with PZT to form lead ruthenate (Pb2Ru2O6.5) during processing at elevated temperatures resulting in lead depletion from PZT. The standard Gibbs energies of formation of RuO2 and Pb2Ru2O6.5 and activities of components of the PZT solid solution have been determined recently. Using this data along with older thermodynamic information on PbZrO3 and PbTiO3, the stability domain of Pb2Ru2O6.5 is computed as a function of PZT composition, temperature and oxygen partial pressure in the gas phase. The results show PbZrO3-rich compositions are more prone to react with RuO2 at all temperatures. Increasing temperature and decreasing oxygen partial pressure suppress the reaction. Graphically displayed are the reaction zones as a function of oxygen partial pressure and PZT composition at temperatures 973, 1173 and 1373 K.

    • Structural variations in layered alkaline earth metal cyclohexyl phosphonates

      Ramaswamy Murugavel Nayanmoni Gogoi

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      Two series of alkaline earth metal cyclohexyl phosphonates, M(C6H11PO3H)2(H2O) (M = Ca, Sr and Ba) (1–3) and M(C6H11PO3)(H2O) (M = Mg, Ca, Sr, and Ba) (4–7) have been synthesized under mild reaction conditions. All new compounds have been characterized using elemental analysis, IR, TGA and powder X-ray diffraction techniques. The molecular structure of compound 2 determined using single crystal X-ray diffraction technique reveals a layered polymeric structure.

    • Surface degradation behaviour of sodium borophosphate glass in aqueous media: Some studies

      K V Shah M Goswami S Manikandan V K Shrikhande G P Kothiyal

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      The degradation behaviour of phosphate glass with nominal composition, 40Na2O–10BaO–𝑥B2O3–(50–𝑥)P2O5, where 0 ≤ 𝑥 ≤ 20 mol%, was studied in water, HCl and NaOH solutions at room temperature to 60°C for different periods extending up to 300 h. These glasses were synthesized by conventional melt-quench technique. Dissolution rates were found to increase with B2O3 content in the glass. The dissolution rates for the glass having 10 mol% B2O3 were found to be 0.002 g/cm2 and 0.015 g/cm2 in distilled water and 5% NaOH solution, respectively, at room temperature after 225 h of total immersion period, whereas it increased considerably to 0.32 g/cm2 in 5% NaOH at 60°C after 225 h. However, glass samples with 𝑥 = 15 and 20 mol% B2O3 were dissolved in 5% HCl solution after 5 h immersion. The degradation behaviour has been correlated with the structural features present in the glass. The optical microscopy of the corroded surface revealed that the corrosion mechanism were different in acid and alkali media.

    • Synthesis, structure and photocatalytic properties of 𝛽-ZrMo2O8

      Prangya Parimita Sahoo S Sumithra Giridhar Madras T N Guru Row

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      Monoclinic ZrMo2O8 was synthesized via solid state method and single crystals of the title compound have been grown by the hydrothermal method. The crystals belong to monoclinic crystal system with space group 𝐶2/c (No. 15) with 𝑎 = 11.4243(19) Å, 𝑏 = 7.9297(6) Å, 𝑐 = 7.4610(14) Å and 𝛽 = 122.15(2)°, 𝑍 = 4. The bandgap of the compound was 2.57 eV. Unlike the other polymorphs of ZrMo2O8, the monoclinic form has unique crystallographic features with ZrO8 and Mo2O8 polyhedra. The photocatalytic activity of this compound has been investigated for the first time for the degradation of various dyes under UV irradiation and has been compared with the photoactivity of the trigonal form of ZrMo2O8. It has been observed that this compound exhibits specificity towards the degradation of cationic dyes.

    • On stability of NiTi wire during thermo-mechanical cycling

      C N Saikrishna K V Ramaiah S Allam Prabhu S K Bhaumik

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      The use of NiTi wire as thermal actuator involves repeated thermal cycling through the transformation range under a constant or fluctuating load. The stability of the material under such conditions has been a concern for the past many years. Experimental results show that for a given alloy composition, the repetitive functional behaviour of NiTi wire is largely dependent on the processing schedule/parameters and the stress–strain regime of thermo-mechanical cycling (TMC). Among the various processing parameters, retained cold work in the material and the shape memory annealing temperature/time have significant influence. It has been shown in the present study that for a stable functional behaviour, the material needs to be tailored through judicious selection of these parameters. Study also shows that, after processing, the material requires an additional stabilization treatment for ensuring minimal variation in the repetitive functional response upon TMC.

    • 3𝑑 Transition metal decorated B–C–N composite nanostructures for efficient hydrogen storage: A first-principles study

      S Bhattacharya C Majumder G P Das

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      Ti decorated BC_4N nanotube has been studied using first-principles density functional approach, to explore the storage of molecular hydrogen. It combines the advantages of carbon nanotube, together with the thermal stability of BN nanotube. The local structural unit of BN3 and NB3 linked with B–N bonds are responsible for the extra stability of BC_4N nanotube as compared with CNT. While the host carbon nanotube is metallic, the substitutional doping of B and N with a large enough concentration (33%) turns it to semiconducting. Endohedral decoration, although energetically favourable, encounters a rather high barrier height of ∼4 eV, as obtained from our nudge elastic band calculation of the minimum energy path. Exohedral Ti@BC4N can bind up to four H2 molecules. For full Ti coverage, the system can absorb up to 5.6 wt% of hydrogen. Ab initio molecular dynamics simulation reveals that at 500 K hydrogen gets released in molecular form. We believe that this novel composite nanotube, functionalized by Ti atoms from outside, serves as a promising system for hydrogen storage.

    • Structure, synthesis and multiferroic nature of BiFeO3 and 0.9BiFeO3–0.1BaTiO3: An overview

      Dhananjai Pandey Anar Singh

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      A brief review of the crystal structure and multiferroic nature of pure BiFeO3 and 0.9BiFeO3–0.1BaTiO3 (BF–0.1BT) is presented. An atomic level evidence for magnetoelectric coupling of intrinsic multiferroic origin in BF–0.1BT is presented.

© 2017 Indian Academy of Sciences, Bengaluru.