Engineering topics
Publications and source records attributed to Kumar, Ashok.
CZFO exhibits low loss tangent, high dielectric constant, large magnetization and magnetodielectric coupling above RT.
The NO x Storage-Reduction (NSR, also known as lean-NO x trap – LNT), is based upon the concept of storing NO x as nitrates over storage components, typically barium species, during a lean-burn operation cycle and then reducing the stored nitrates to N 2 during fuel-rich conditions over a precious metal catalyst [1]. NO x Selective Catalytic Reduction (SCR), on the other hand, is accomplished by deliberately introducing reductant urea into the engine exhaust to reduce NO x with the aid of a Cu(Fe)/zeolite catalyst [2]. These two technologies have been recognized as the most promising approaches for meeting stringent NO x emission standards for diesel vehicles within the Environmental Protection Agency’s (EPA’s) 2007/2010 mandated limits. For NSR, problems arising from either or both thermal and SO 2 deactivation must be addressed to meet durability standards. For SCR, SO 2 deactivation is less of an issue, but hydrothermal deactivation of the zeolite catalysts must be addressed. With continuing R&D efforts in advanced powertrains, highly novel operating modes for internal combustion engines (ICEs) are being researched in order to meet the very stringent new demands for fuel efficiency (e.g., U.S. ‘‘CAFE’’ standards for average miles/gallon are scheduled to increase dramatically over the next 10–15 years). These new ICE engine operation modes, while highly fuel-efficient, result in much lower exhaust temperatures than current engines; temperatures so low that it is hard to imagine how the current catalytic emission control technologies will be able to function. For example, while steady-state operation of the NO x reduction technology at 150 °C may be required, current ‘‘light-off’’ temperatures for CHA-based zeolite catalysts are closer to 200 °C. Therefore, understanding low-temperature limitations in NO x reduction has become one of the most daunting challenges in R&D on new catalyst materials and processes that can effectively eliminate emissions at these quite low exhaust temperatures. This project has two clear focuses: (1) development of potassium-based high-temperature NSR materials, and studying their key causes of deactivation and methods of regeneration. By comparing results obtained on ‘Simple Model’ Pt-K/Al 2 O 3 with ‘Enhanced Model’ Pt-K/ MgAlO x and Pt-K/TiO 2 materials, we have developed an understanding of the role of various additives on the deactivation and regeneration processes. Studies have also been performed on the real commercial samples being used in a Dodge Ram truck with a Cummins diesel emission control system. However, the results about these ‘commercial samples’ will not be covered in this report. Following a brief description of our experimental approach, we will present a few highlights from some of the work performed in this CRADA with more details about these results provided in publications/reports/presentations lists presented at the end of the report. (2) for the Cu and Fe/Chabazite SCR catalysts, since these are so newly developed and references from open literature and industry are nearly absent, our work started from zeolite synthesis and catalyst synthesis methodology development, before research on their low- and high-temperature performance, deactivation, regeneration, etc. was conducted. Again, most work reported here is based on our “model” catalysts synthesized in-house. Work done on the ‘commercial samples’ will not be covered in this report.
The SrZrO{sub 3} is a well known high-k dielectric constant (∼22) and high optical bandgap (∼5.8 eV) material and one of the potential candidates for future generation nanoelectronic logic elements (8 nm node technology) beyond silicon. Its dielectric behavior is fairly robust and frequency independent till 470 K; however, it suffers a strong small-polaron based electronic phase transition (T{sub e}) linking 650 to 750 K. The impedance spectroscopy measurements revealed the presence of conducting grains and grain boundaries at elevated temperature which provide energetic mobile charge carriers with activation energy in the range of 0.7 to 1.2 eV supporting the oxygen ions and proton conduction. X-ray photoemission spectroscopy measurements suggest the presence of weak non-stoichiometric O{sup 2−} anions and hydroxyl species bound to different sites at the surface and bulk. These thermally activated charge carriers at elevated temperature significantly contribute to the polaronic based dielectric anomaly and conductivity. Our dielectric anomaly supports pseudo phase transition due to high degree of change in ZrO{sub 6} octahedral angle in the temperature range of 650–750 K, where electron density and phonon vibration affect the dielectric and conductivity properties.
We report the electronic properties of electrically gated heterostructures of black and blue phosphorene with graphene. The heterostructure of blue phosphorene with graphene is energetically more favorable than black phospherene/graphene. However, both are bonded by weak interlayer interactions. Graphene induces the Dirac cone character in both heterostructure which shows tunabilities with external electric field. It is found that Dirac cone get shifted depending on the polarity of external electric field that results into the so called self induced p-type or n-type doping effect. These features have importance in the fabrication of nano-electronic devices based on the phosphorene/graphene heterostructures.
We present electronic properties of atomic layer of Au, Au{sub 2}-N, Au{sub 2}-O and Au{sub 2}-F in graphene-like structure within the framework of density functional theory (DFT). The lattice constant of derived monolayers are found to be higher than the pristine Au monolayer. Au monolayer is metallic in nature with quantum ballistic conductance calculated as 4G{sub 0}. Similarly, Au{sub 2}-N and Au{sub 2}-F monolayers show 4G{sub 0} and 2G{sub 0} quantum conductance respectively while semiconducting nature with calculated band gap of 0.28 eV has been observed for Au{sub 2}-O monolayer. Most interestingly, half metalicity has been predicted for Au{sub 2}-N and Au{sub 2}-F monolayers. Our findings may have importance for the application of these monolayers in nanoelectronic and spintronics.
The energetics and electronic properties of different topology of Pt wires including linear, zigzag and ladder structures on MoSe{sub 2} monolayer have been investigated in the framework of density functional theory (DFT). The predicted order of stability of Pt wire on MoSe{sub 2} monolayer is found to be: linear > ladder > zigzag. Pt wires induce states near the Fermi level of MoSe{sub 2} that results into metallic characteristics of Pt-wire/MoSe{sub 2} assembled system. Valence band charge density signifies most of the contribution from Pt atoms near the Fermi energy of assembled wire/MoSe{sub 2} system. These findings are expected to be important for the fabrication of devices based on MoSe{sub 2} layers for flexible nanoelectronics.
We report stability and electronic properties of benzene molecule adsorbed on the Au atomic layer within the framework of density function theory (DFT). Horizontal configuration of benzene on the top site of Au monolayer prefers energetically over other studied configurations. On the adsorption of benzene, the ballistic conductance of Au monolayer is found to decrease from 4G{sub 0} to 2G{sub 0} suggesting its applications for the fabrications of organic sensor devices based on the Au atomic layers.
Choice of proper dopants at A or B-site of ABO{sub 3} perovskite structure can modify the morphotropic phase boundary (MPB), and hence functional properties of polar systems. The chemical nature of donor or acceptor will significantly influence the fundamental properties. Lead-free ferroelectrics have vast potential to replace the lead-based ceramics. The (Na{sub 0.5}Bi{sub 0.5}){sub 1-x}Ba{sub x}TiO{sub 3} (NBT-BT) (at x=0.08) near MPB with small substitution of trivalent cations (Al{sup 3+}) has been synthesized by solid state reaction route. The aim to choose the trivalent cations (Al{sup 3+}) was its relatively smaller radii than that of Bi{sup 3+} cations to develop the antipolar phases in the ferroelectric ceramic. Structural, morphological and elemental compositional analyses were studied by X-ray diffraction (XRD), Secondary electron microscope (SEM) and Energy-dispersive X-ray spectroscopy (EDAX), respectively. Ferroelectric studies were carried out on various compositions of (Na{sub 0.46}Bi{sub 0.46-x}Al{sub x}Ba{sub 0.08})TiO{sub 3} (NBAT-BT) (x=0, 0.05, 0.07, 0.10) electroceramics. It was observed that with increase in concentration of Al the ferroelectricity state changes from soft to hard. Temperature dependent dielectric spectroscopy shows broad dielectric dispersion. The Al doping diminishes the relaxor behavior of NBT-BT ceramics. Impedance spectroscopy shows that electrical resistivity and relaxation frequency decreases with increase in Al-concentration. Modulus spectra indicate that Al significantly change the bulk capacitance of NBT-BT.
We present a first principle study of interaction of toxic gas molecules (NO, NO{sub 2} and SO{sub 2}) with monolayer MoSe{sub 2}. The predicted order of sensitivity of gas molecule is NO{sub 2} > SO{sub 2} > NO. Adsorbed molecules strongly influence the electronic behaviour of monolayer MoSe{sub 2} by inducing impurity levels in the vicinity of Fermi energy. NO and SO{sub 2} is found to induce p-type doping effect while semiconductor to metallic transitions occur on NO{sub 2} adsorption. Our findings may guide the experimentalist for fabricating sensor devices based on MoSe{sub 2} monolayer.
We report electronic behavior of an allotrope of monolayer WS{sub 2} with a square octagon ring structure, refereed to as (so-WS{sub 2}) within state-of-the-art density functional theory (DFT) calculations. The WS{sub 2} monolayer shows semi-metallic characteristics with Dirac-cone like features around Γ. Unlike p-orbital’s Dirac-cone in graphene, the Dirac-cone in the so-WS{sub 2} monolayer originates from the d-electrons of the W atom in the lattice. Most interestingly, the spin-orbit interaction associated with d-electrons induce a finite band-gap that results into the metal-semiconductor transition and topological insulator-like behavior in the so-WS{sub 2} monolayer. These characteristics suggest the so-WS{sub 2} monolayer to be a promising candidate for the next-generation electronic and spintronics devices.
In recent year’s considerable attention has been given to the first principles method for modifying and controlling electronic properties of nano-materials. We performed DFT-based calculations on the electronic properties of zigzag-edged nano-flakes of blue phosphorene with three possible shapes namely rectangular, triangular and hexagonal. We observed that HOMO-LUMO gap of zigzag phosphorene nano-flakes with different shapes is ∼2.9 eV with H-passivations and ∼0.7 – 1.2 eV in pristine cases. Electronic properties of blue phosphorene nano-flakes show the strong dependence on their shape. We observed that distributions of molecular orbitals were strongly affected by the different shapes. Zigzag edged considered nanostructures are non-magnetic and semiconducting in nature. The shape dependent electronic properties may find applications in tunable nano-electronics.
We have performed first principles calculations to find out the effect of mechanical strain on the electronic properties of zig-zag edged nano ribbons of β-phosphorene. It is found that electronic band-gap get opened-up to 2.61 eV by passivation of the edges of ribbons. Similarly, the mechanical strength is found to be increase from 1.75 GPa to 2.65 GPa on going from unpassivated nano ribbons to passivated ones along with the 2% increase in ultimate tensile strain. The band-gap value of passivated ribbon gets decreased to 0.43 eV on applying strain up to which the ribbon does not break. These tunable properties of β-phospherene with passivation with H-atom and applying mechanical strain offer its use in tunable nano electronics.
We report thickness dependent dielectric, ferroelectric, and optical properties of Ni substituted Pb(Zr 0.2 Ti 0.8 )O 3 thin films. The Pb(Zr 0.2 Ti 0.8 ) 0.7 0Ni 0.30 O 3-δ (PZTNi30) thin films for various thicknesses, ranging from 5 nm to 400 nm, were fabricated by pulsed laser deposition technique. Giant dielectric dispersion, low dielectric loss, large dielectric constant ~1000–1500 from 100 Hz to 100 kHz, and diffused dielectric anomaly near 570–630 K were observed in PZTNi30 thin films. These films show well saturated ferroelectric hysteresis, with large remanent polarization. It also illustrated excellent optical transparency which decreased from 82 to 72% with increasing film thickness from 5 nm to 400 nm for the probe wavelengths ranging from 200 to 1100 nm. A decrease in direct bandgap (Eg) values from 4 eV to 3.4 eV and indirect-E g values from 3.5 eV to 2.9 eV were observed for PZTNi30 thin films with increase in film thickness from 5 nm to 400 nm, respectively. The direct and indirect bandgaps were discussed in context of film thickness and grain size effects. Our investigations on optical properties of PZTNi30 thin films suggest that bandgap can be modified as a function of film thickness which may be useful for readers working to develop novel candidates for ferroelectric photovoltaic.
Present work reports the fabrication of a multilayer (5-layer) structure of BiFeO{sub 3}(BFO)/BaTiO{sub 3}(BTO) using spin-coating technique. The crystallographic structure, surface morphology and ferroelectric behavior of multilayer structure in metal-ferroelectric-metal capacitor have been studied. Le-Bail refinement of X-ray diffraction data revealed the formation of polycrystalline pure perovskite phase with induced stress. The values of remnant (P{sub r}) and saturation polarization (P{sub s}) for BFO/BTO multilayer structure are found to be 38.14 μC/cm{sup 2} and 71.54 μC/cm{sup 2} respectively, which are much higher than the corresponding values reported for bare BFO thin film. A large value of dielectric constant of 187 has been obtained for multilayer structure with a low leakage current density of 1.09 × 10{sup −7} A/cm{sup 2} at applied bias of 10 V. The BFO/BTO multilayer structure favors the enhanced energy storage capacity as compared to bare BFO thin film with improved values of energy-density and charge-discharge efficiency as 121 mJ/cm{sup 3} and 59% respectively, suggesting futuristic energy storage applications.
Using a combination of computational simulations, atomic-scale resolution imaging and phenomenological modelling, we examine the underlying mechanism for nanodomain restructuring in lead zirconate titanate nanodisks driven by electron beams. The observed subhertz nanodomain dynamics are identified with relaxation oscillations where the charging/discharging cycle time is determined by saturation of charge traps and nanodomain wall creep. These results are unusual in that they indicate very slow athermal dynamics in nanoscale systems, and possible applications of gated versions are discussed.
This work deals with the synthesis of TiO{sub 2} nanostructures using sol-gel and hydrothermal method for evaluating their photodegradation performance towards decolorization of Rose Bengal (RB). A combination of characterization techniques including X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM) and UV–Vis spectroscopy were utilized to evaluate the structural, morphological and optical properties of the obtained nanostructures. It was observed that the TiO{sub 2} nanoparticles prepared using hydrothermal method were highly crystalline and possess higher band gap value, even when same conditions of temperature, pressure, precursor ratios and solvent amount was kept constant while synthesizing TiO{sub 2} nanostructures via sol-gel method. The obvious effect of porous morphology exhibited by TiO{sub 2} nanoparticles prepared using hydrothermal route is reflected in its decolorization performance whereby 92.5% of the RB dye solution was degraded in 70 min of irradiation time.
We report structural and electronic properties of ZrS{sub 2} monolayer within density functional theory (DFT) by inclusion of Hubbard on-site Coulomb and exchange interactions. The importance of on-site interactions for both ZrS{sub 2} bulk and monolayer has been highlighted that significantly improves the electronic band-gap. It is demonstrated that mechanical strain induces structural phase transition that results in semiconductor-to-metal transition in monolayer ZrS{sub 2}. This phenomenon has important implications in technological applications such as flexible, low power and transparent electronic devices.