• A K Shukla

      Articles written in Bulletin of Materials Science

    • La0.9Sr0.1Ga0.8M0.2O3-δ (M = Mn, Co, Ni, Cu or Zn): Transition metal-substituted derivatives of lanthanum-strontium-galliummagnesium (LSGM) perovskite oxide ion conductor

      Litty Sebastian A K Shukla J Gopalakrishnan

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      Perovskite oxides of the general formula, La0.9Sr0.1Ga0.8M0.2O3-δ for M = Mn, Co, Ni, Cu and Zn, have been prepared and investigated. All the oxides exhibit high electrical conductivities (σ R∼ 10−2 S/cm at 800°C) comparable to that of the best perovskite oxide ion conductor, La0.9Sr0.1Ga0.8Mg0.2O2.85 (LSGM) (σ ∼ 8 × 10−2 S/cm at 800°C). While M = Mn, Co, Ni, Cu members appear to be mixed conductors with a variable electronic contribution to the conductivity, especially at high oxygen partial pressures (pO2 ≥1 atm), arising from mixed-valency of the transition metals, the M = Zn(II) phase is a pure oxide ion conductor exhibiting a conductivity (σ ∼ 1.5 × 10−2 S/cm at 800°C) that is slightly lower than that of LSGM. The lower conductivity of the M = Zn(II) derivative could be due to the preference of Zn(II) for a tetrahedral oxygen coordination.

    • Kinetics of hydrogen evolution reaction on Zr0.5Ti0.5V0.6Cr0.2Ni1.2 alloy in KOH electrolyte

      Shalini Rodrigues N Munichandraiah A K Shukla

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      A hydrogen-storage alloy of the composition Zr0.5Ti0.5V0.6Cr0.2Ni1.2 has been investigated for corrosion resistance and hydrogen-evolution reaction (HER) in KOH electrolyte of varying concentrations. Activation of the electrode by absorption of hydrogen takes place after prolonged cathodic polarization in the potential range of HER. Prior to activation, the open-circuit potential is about −0.4 V vs Hg/HgO, OH, at which the alloy electrode tends to undergo corrosion with oxygen-reduction reaction (ORR) as the conjugate reaction. The corrosion-current density measured from Tafel polarization of ORR is found to be independent of KOH concentration and has an average value of about 30 μA cm−2. Subsequent to activation, the open circuit potential of the electrode is shifted to about −0.93 V vs Hg/HgO, OH, which is equal to the reversible potential of HER. The exchange current density values measured from Tafel polarization of HER are marginally higher in relation to the values obtained before the electrode is activated. Alternating-current impedance spectra in the Nyquist form contain two overlapped semicircles. The high-frequency semicircle is attributed to the electrode geometry, while the low-frequency semicircle is due to the charge-transfer reaction and double-layer capacitance. The impedance data are analyzed by a non-linear least square curve fitting technique and impedance parameters are evaluated.

    • The promise of fuel cell-based automobiles

      A K Shukla C L Jackson K Scott

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      Fuel cell-based automobiles have gained attention in the last few years due to growing public concern about urban air pollution and consequent environmental problems. From an analysis of the power and energy requirements of a modern car, it is estimated that a base sustainable power of $ca$. 50 kW supplemented with short bursts up to 80 kW will suffice in most driving requirements. The energy demand depends greatly on driving characteristics but under normal usage is expected to be 200 Wh/km. The advantages and disadvantages of candidate fuel-cell systems and various fuels are considered together with the issue of whether the fuel should be converted directly in the fuel cell or should be reformed to hydrogen onboard the vehicle. For fuel cell vehicles to compete successfully with conventional internal-combustion engine vehicles, it appears that direct conversion fuel cells using probably hydrogen, but possibly methanol, are the only realistic contenders for road transportation applications. Among the available fuel cell technologies, polymer–electrolyte fuel cells directly fueled with hydrogen appear to be the best option for powering fuel cell vehicles as there is every prospect that these will exceed the performance of the internal-combustion engine vehicles but for their first cost. A target cost of $ 50/kW would be mandatory to make polymer–electrolyte fuel cells competitive with the internal combustion engines and can only be achieved with design changes that would substantially reduce the quantity of materials used. At present, prominent car manufacturers are deploying important research and development efforts to develop fuel cell vehicles and are projecting to start production by 2005.

    • Performance characteristics of a gelled-electrolyte valve-regulated lead-acid battery

      S K Martha B Hariprakash S A Gaffoor A K Shukla

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      12 V/25 AH gelled-electrolyte valve-regulated lead-acid batteries have been assembled in-house and their performance studied in relation to the absorptive glass-microfibre valve-regulated and flooded-electrolyte counterparts at various discharge rates and temperatures between –40°C and 40°C. Although the performance of the gelled-electrolyte valve-regulated battery is similar to both the absorptive glass-microfibre valve-regulated and flooded-electrolyte lead-acid batteries at temperatures above 0°C, it is superior to both the flooded-electrolyte and absorptive glass-microfibre valve-regulated lead-acid batteries at temperatures between 0°C and -40°C. The latter characteristic is attractive for expanding the application regime of valve-regulated lead-acid batteries. The corrosion rate for the positive grids in the gelled-electrolyte is also lower than both the flooded-electrolyte and absorptive glass-microfibre configurations.

    • Solution-combustion synthesis of Bi1–𝑥Ln𝑥O1.5 (Ln = Y and La–Yb) oxide ion conductors

      Manjunath B Bellakki A S Prakash C Shivakumara M S Hegde A K Shukla

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      Cubic fluorite related Bi1–𝑥Ln𝑥O1.5 (Ln = Y and La–Yb) phases are synthesized by solutioncombustion method using glycine as the fuel. The cubic fluorite phase is stabilized with 25 mole% of rare earth cations. The lattice parameter of cubic phase increases linearly with size of the lanthanide ion. The synthesized powders are nano-metric in size and exhibit excellent compactability and reach 98% densification even on short period of sintering. The oxides with relatively larger cations Nd, Sm, Eu, Pr and Gd with 25 mole% composition transform to rhombohedral structure while others retain cubic upon sintering. All the phases show high oxide–ion conductivity and the values obtained are in good agreement with the reported values.

    • Wavelength dependent laser-induced etching of Cr–O doped GaAs: Morphology studies by SEM and AFM

      B Joshi S S Islam H S Mavi Vinita Kumari T Islam A K Shukla Harsh

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      The laser induced etching of semi-insulating GaAs $\langle$100$\rangle$ is carried out to create porous structure under super- and sub-bandgap photon illumination (ℎν). The etching mechanism is different for these separate illuminations where defect states play the key role in making distinction between these two processes. Separate models are proposed for both the cases to explain the etching efficiency. It is observed that under sub-bandgap photon illumination the etching process starts vigorously through the mediation of intermediate defect states. The defect states initiate the pits formation and subsequently pore propagation occurs due to asymmetric electric field in the pore. Formation of GaAs nanostructures is observed using scanning electron (SEM) and atomic force microscopy (AFM).

    • 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.

    • PEDOT–PSSA as an alternative support for Pt electrodes in PEFCs

      K K Tintula S Pitchumani P Sridhar A K Shukla

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      Poly (3,4-ethylenedioxythiophene) (PEDOT) and poly (styrene sulphonic acid) (PSSA) supported platinum (Pt) electrodes for application in polymer electrolyte fuel cells (PEFCs) are reported. PEDOT–PSSA support helps Pt particles to be uniformly distributed on to the electrodes, and facilitates mixed electronic and ionic (H+-ion) conduction within the catalyst, ameliorating Pt utilization. The inherent proton conductivity of PEDOT–PSSA composite also helps reducing Nafion content in PEFC electrodes. During prolonged operation of PEFCs, Pt electrodes supported onto PEDOT–PSSA composite exhibit lower corrosion in relation to Pt electrodes supported onto commercially available Vulcan XC-72R carbon. Physical properties of PEDOT–PSSA composite have been characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. PEFCs with PEDOT–PSSA-supported Pt catalyst electrodes offer a peak power-density of 810 mW cm-2 at a load current-density of 1800 mA cm-2 with Nafion content as low as 5 wt.% in the catalyst layer. Accordingly, the present study provides a novel alternative support for platinized PEFC electrodes.

    • Temperature dependence of electromechanical properties of PLZT 𝑥/57/43 ceramics

      A K Shukla V K Agrawal I M L Das Janardan Singh S L Srivastava

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      The compositions of lead lanthanum zirconate titanate PLZT [Pb(Zr0.57Ti0.43)O3 + 𝑥 at% of La, where 𝑥 = 3, 5, 6, 10 and 12] have been synthesized using mixed oxide route. The temperature dependent electromechanical parameters have been determined using vector impedance spectroscopy (VIS). The charge constant 𝑑31 and elastic compliance $s^{E}_{11}$ show a peak in all the samples at a temperature 𝑇mt much below the ferroelectric – paraelectric transition temperature, whereas the series resonance frequency 𝑓s shows a dip at these temperatures. The Poisson’s ratio 𝜎𝐸 increases with temperature 𝑇 showing a broad peak at a temperature higher than 𝑇mt. The voltage constant 𝑔31 decreases and the planar coupling coefficient 𝐾p remains constant up to half of the 𝑇mt and then falls sharply with 𝑇. Half of the 𝑇mt can, therefore, be used for specifying the working temperature limit of the piezoceramics for the device applications.

    • Dielectric response of PLZT ceramics 𝑥/57/43 across ferroelectric– paraelectric phase transition

      A K Shukla V K Agrawal I M L Das Janardan Singh S L Srivastava

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      The dielectric properties of lead lanthanum zirconate titanate (PLZT) ceramics [Pb(Zr0.57Ti0.43)O3 +𝑥 at% of La, 𝑥 = 3, 5, 6, 10 and 12] have been measured in the frequency range 1 Hz–1 MHz using the vector impedance spectroscopy (VIS) at different temperatures. All the compositions show both non-dispersive and dispersive dielectric responses in different temperature regions. The non-dispersive region obeys the universal dielectric response. A low frequency (< 1 kHz) relaxation phenomenon with a high value of distribution parameter `ℎ’ (∼0.4 to 0.6) has been observed in all the compositions around the temperature corresponding to themaximum dielectric constant (𝑇m). The activation energies as calculated from the relaxation and d.c. conduction processes are comparable. The ferroelectric phase transition is diffuse in nature and broadening of the peak increases with La content.

    • Synthesis of new (Bi, La)3MSb2O11 phases (M = Cr, Mn, Fe) with KSbO3-type structure and their magnetic and photocatalytic properties

      K Ramesha A S Prakash M Sathiya Giridhar Madras A K Shukla

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      Synthesis and structure of new (Bi, La)3MSb2O11 phases (M = Cr, Mn, Fe) are reported in conjunction with their magnetic and photocatalytic properties. XRD refinements reflect that Bi3CrSb2O11, Bi2LaCrSb2O11, Bi2LaMnSb2O11 and Bi2LaFeSb2O11 adopt KSbO3-type structure (space group, 𝑃𝑛$\bar{3}$). The structure can be described through three interpenetrating networks where the first is the (M/Sb)O6 octahedral network and other two are the identical networks having Bi6O4 composition. The magnetic measurements on Bi2LaCrSb2O11 and Bi2LaMnSb2O11 show paramagnetic behaviour with magnetic moments close to the expected spin only magnetic moments of Cr+3 and Mn+3. The UV-Visible diffuse reflectance spectra are broad and indicate that these materials possess a bandgap of ∼ 2 eV. The photocatalytic activity of these materials has been investigated by degrading Malachite Green (MG) under exposure to UV light.

    • Pt–Au/C cathode with enhanced oxygen-reduction activity in PEFCs

      G Selvarani S Vinod Selvaganesh P Sridhar S Pitchumani A K Shukla

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      Carbon-supported Pt–Au (Pt–Au/C) catalyst is prepared separately by impregnation, colloidal and micro-emulsion methods, and characterized by physical and electrochemical methods. Highest catalytic activity towards oxygen-reduction reaction (ORR) is exhibited by Pt–Au/C catalyst prepared by colloidal method. The optimum atomic ratio of Pt to Au in Pt–Au/C catalyst prepared by colloidal method is determined using linear-sweep and cyclic voltammetry in conjunction with cell-polarization studies. Among 3:1, 2:1 and 1:1 Pt–Au/C catalysts, (3:1) Pt–Au/C exhibits maximum electrochemical activity towards ORR. Powder X-ray diffraction pattern and transmission electron micrograph suggest Pt–Au alloy nanoparticles to be well dispersed onto the carbon-support. Energy dispersive X-ray analysis and inductively coupled plasma-optical emission spectroscopy data suggest that the atomic ratios of the alloying elements match well with the expected values. A polymer electrolyte fuel cell (PEFC) operating at 0.6 V with (3:1) Pt–Au/C cathode delivers a maximum power-density of 0.65 W/cm2 in relation to 0.53 W/cm2 delivered by the PEFC with pristine carbon-supported Pt cathode.

    • Nitrates–melt synthesized LiNi0.8Co0.2O2 and its performance as cathode in Li-ion cells

      M Sathiya K Hemalatha K Ramesha A K Shukla A S Prakash

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      Layered LiNi0.8Co0.2O2 crystallizing in 𝑅$\bar{3}$𝑚 space group is synthesized by decomposing the constituent metal–nitrate precursors. Oxidizing nature of metal nitrates stabilizes nickel in +3 oxidation state, enabling a high degree of cation ordering in the layered LiNi0.8Co0.2O2. The powder sample characterized by XRD Rietveld refinement reveals < 2% Li–Ni site exchange in the layers. Scanning electron microscopic studies on the as-synthesized LiNi0.8Co0.2O2 sample reflect well defined particles of cubic morphology with particle size ranging between 200 and 250 nm. Cyclic voltammograms suggest that LiNi0.8Co0.2O2 undergoes phase transformation on first charge with resultant phase being completely reversible in subsequent cycles. The first-charge-cycle phase transition is further supported by impedance spectroscopy that shows substantial reduction in resistance during initial de-intercalation. Galvanostatic charge–discharge cycles reflect a firstdischarge capacity of 184 mAh g-1 which is stabilized at 170 mAh g-1 over 50 cycles.

    • A soluble-lead redox flow battery with corrugated graphite sheet and reticulated vitreous carbon as positive and negative current collectors

      A Banerjee D Saha T N Guru Row A K Shukla

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      A soluble-lead redox flow battery with corrugated-graphite sheet and reticulated-vitreous carbon as positive and negative current collectors is assembled and performance tested. In the cell, electrolyte comprising of 1.5M lead (II) methanesulfonate and 0.9 M methanesulfonic acid with sodium salt of lignosulfonic acid as additive is circulated through the reaction chamber at a flow rate of 50 ml min-1. During the charge cycle, pure lead (Pb) and lead dioxide (PbO2) from the soluble lead (II) species are electrodeposited onto the surface of the negative and positive current collectors, respectively. Both the electrodeposited materials are characterized by XRD, XPS and SEM. Phase purity of synthesized lead (II) methanesulfonate is unequivocally established by single crystal X-ray diffraction followed by profile refinements using high resolution powder data. During the discharge cycle, electrodeposited Pb and PbO2 are dissolved back into the electrolyte. Since lead ions are produced during oxidation and reduction at the negative and positive plates, respectively there is no risk of crossover during discharge cycle, preventing the possibility of lowering the overall efficiency of the cell. As the cell employs a common electrolyte, the need of employing a membrane is averted. It has been possible to achieve a capacity value of 114 mAh g−1 at a load current-density of 20 mA cm-2 with the cell at a faradaic efficiency of 95%. The cell is tested for 200 cycles with little loss in its capacity and efficiency.

    • Pt–Ru decorated self-assembled TiO2–carbon hybrid nanostructure for enhanced methanol electrooxidation

      K G Nishanth P Sridhar S Pitchumani A K Shukla

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      Porous titanium oxide–carbon hybrid nanostructure (TiO2–C) with a specific surface area of 350 m2/g and an average pore-radius of 21.8 Å is synthesized via supramolecular self-assembly with an in situ crystallization process. Subsequently, TiO2–C supported Pt–Ru electro-catalyst (Pt–Ru/TiO2–C) is obtained and investigated as an anode catalyst for direct methanol fuel cells (DMFCs). X-ray diffraction, Raman spectroscopy and transmission electron microscopy (TEM) have been employed to evaluate the crystalline nature and the structural properties of TiO2–C. TEM images reveal uniform distribution of Pt–Ru nanoparticles (𝑑Pt−Ru = 1.5–3.5 nm) on TiO2–C. Methanol oxidation and accelerated durability studies on Pt–Ru/TiO2–C exhibit enhanced catalytic activity and durability compared to carbon-supported Pt–Ru. DMFC employing Pt–Ru/TiO2–C as an anode catalyst delivers a peak-power density of 91 mW/cm2 at 65 °C as compared to the peak-power density of 60 mW/cm2 obtained for the DMFC with carbon-supported Pt–Ru anode catalyst operating under similar conditions.

    • Iron–carbon hybrid capacitor: A proof-of-concept study

      V R Chari S R Aravamuthan A K Shukla

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      In the present study, cost-intensive Ni electrode is replaced by high surface-area activated carbon (AC) cathode and the possibility of the Fe anode, used in Ni–Fe battery, to function as Fe–C hybrid capacitor has been examined. The electrochemical properties of Fe–C hybrid capacitor assembly are studied using cyclic voltammetry (CV) and galvanostatic charge–discharge cycles. Over 100 galvanostatic charge–discharge cycles for Fe–C hybrid capacitor are carried out and a maximum capacitance of 24 F g-1 is observed.

    • Series-connected substrate-integrated lead-carbon hybrid ultracapacitors with voltage-management circuit

      A Banerjee R Srinivasan A K Shukla

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      Cell voltage for a fully charged-substrate-integrated lead-carbon hybrid ultracapacitor is about 2.3 V. Therefore, for applications requiring higher DC voltage, several of these ultracapacitors need to be connected in series. However, voltage distribution across each series-connected ultracapacitor tends to be uneven due to tolerance in capacitance and parasitic parallel-resistance values. Accordingly, voltage-management circuit is required to protect constituent ultracapacitors from exceeding their rated voltage. In this study, the design and characterization of the substrate-integrated lead-carbon hybrid ultracapacitor with co-located terminals is discussed. Voltage-management circuit for the ultracapacitor is presented, and its effectiveness is validated experimentally.

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