Effect of engine-based thermal aging on surface morphology and performance of Lean NOx Traps

A small single-cylinder diesel engine is used to thermally age model (Pt + Rh/Ba/γ-Al₂O₃) lean NO_x traps (LNTs) under lean/rich cycling at target temperatures of 600 °C, 700 °C, and 800 °C. During an aging cycle, fuel is injected into the exhaust to achieve reproducible exotherms under lean and rich conditions with the average temperature approximating the target temperature. Aging is performed until the cycle-average NO_x conversion measured at 400 °C is approximately constant. Engine-based NO_x conversion decreased by 42% after 60 cycles at 600 °C, 36% after 76 cycles at 700 °C and 57% after 46 cycles at 800 °C. The catalyst samples were removed and characterized by XRD and using a microreactor that allowed controlled measurements of surface area, precious metal size, NO_x storage, and reaction rates. Three aging mechanisms responsible for the deactivation of LNTs have been identified: (i) loss of dispersion of the precious metals, (ii) phase transitions in the washcoat materials, and (iii) loss of surface area of the storage component and support. These three mechanisms are accelerated when the aging temperature exceeds 850 °C—the γ to δ transition temperature of Al₂O₃. Normalization of rates of NO reacted at 400 °C to total surface area demonstrates the biggest impact on performance stems from surface area losses rather than from precious metal sintering.     

A comparative dielectric relaxation study of PMN–PT and PMN–PZ ceramics using impedance spectroscopy

AC-impedance spectroscopic studies in the temperature range of 30–400 °C are carried out on solid solutions of lead magnesium niobate (PMN) with lead titanate (PT) and lead zirconate (PZ), both of them in the 65/35 atomic ratio. For PMN–PT this corresponds to the morphotropic phase boundary composition (with normal ferroelectric behaviour), and for PMN–PZ it is near the phase boundary between normal ferroelectric and relaxor ferroelectric compositions. The variation of dielectric permittivity with temperature at different frequencies shows normal ferroelectric and relaxor-like dependence for PMN–PT and PMN–PZ, respectively. Temperature-dependent spectroscopic modulus plots reveal a much broader peak for PMN–PZ compared to that for PMN–PT, which is consistent with the dielectric behaviour. PMN–PT shows nearly ideal Debye behaviour below T_m (the temperature of the permittivity maximum) and the behaviour departs from ideality above T_m, whereas non-ideal Debye behaviour is seen both below and above T_m for PMN–PZ. Complex modulus plots fit well with two depressed semicircles and three depressed semicircles, respectively, for PMN–PT and PMN–PZ. The relaxation observed in the spectroscopic plots around 1 MHz for PMN–PT has been assigned to polarisation relaxation expected for normal-sized domains. No such relaxation could be observed for PMN–PZ around 1 MHz because of the mesoscopic domain sizes.     

Feedback based simultaneous correction of imaging artifacts due to geometrical and mechanical cross-talk and tip-sample stick in atomic force microscopy

This paper presents a feedback scheme that simultaneously corrects, in real time, for the imaging artifacts caused by cantilever and photosensor misalignments as well as misinterpretations in relative lateral position of the tip with respect to the sample due to the tip-sample stick in atomic force microscopy (AFM). The optical beam bounce method, typically used in AFM for imaging, is sensitive to inaccuracies of cantilever geometry and the relative misalignment of the laser source, cantilever, and the laser sensitive diode from the intended design. These inaccuracies, which contribute to the geometrical cross-talk between the normal and the lateral signals, become prominent at the atomic and subnanometer scales, and thereby impede high resolution imaging studies. The feedback scheme accounts for these artifacts and makes imaging insensitive to, in fact, practically independent of these inaccuracies. This scheme counteracts the lateral twisting dynamics of the cantilever, and as a result, it avoids the misinterpretation problem of the relative lateral position of the cantilever tip from the sample and thereby avoids the corresponding imaging artifacts that are typically prominent in contact mode friction force microscopy (FFM). The feedback scheme consists of simultaneously regulating the normal as well as the lateral cantilever deflection signal at their respective set points. This not only removes the imaging artifacts due to geometrical misalignments, mechanical cross-talk, and irregular sliding but also the corresponding compensatory control signal gives a more accurate real time measure of the lateral interaction force between the sample and the cantilever as compared to the lateral deflection signal used in FFM. Experimental results show significant improvement, and in some cases, practical elimination of the artifacts. The design and implementation of a split piezoassembly needed for the lateral actuation for the feedback scheme are also presented.     

Dielectric and conducting behavior of pyrene functionalized PANI/P(VDF‐co‐HFP) blend

Herein, we present the dielectric and electrical conductivity properties of the partially miscible polymer blend prepared using pyrene functionalized polyaniline (pf‐PANI) and poly(vinylidene fluoride‐co‐hexafluoro propylene) (PVDF‐co‐HFP). The blend mostly retains the fluorescent nature of pf‐PANI as well as can be moldable and possesses good damping property. The dielectric properties have been investigated as a function of temperature at three different frequencies and the plausible origin of polarization responsible for dielectric behavior in this blend has been identified. The experimental results of dielectric measurements are compared with theoretical models and discussed. The surface morphology of the samples has been examined with a scanning electron microscope. The electrical conductivity has also been studied as a function of temperature and explained in terms of hopping of charge carriers/interconnected networks. The combined dielectric and conductivity results together with scanning electron microscope micrographs, reveal that there is hindrance to achieve percolation threshold even after pf‐PANI addition of 57 vol % and subsequent thermal treatment. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44077.     

Flexible and Conductive 3D Printable Polyvinylidene Fluoride and Poly(N,N‐dimethylacrylamide) Based Gel Polymer Electrolytes

In this work, 3D printable gel polymer electrolytes (GPEs) based on N,N‐dimethylacrylamide (DMAAm) and polyvinylidene fluoride (PVDF) in lithium chloride containing ethylene glycol solution are synthesized and their physicochemical properties are investigated. 3D printing is carried out with a customized stereolithography type 3D gel printer named “Soft and Wet Intelligent Matter‐Easy Realizer” and free forming GPE samples having variable shapes and sizes are obtained. Printed PVDF/PDMAAm‐based GPEs exhibit tunable mechanical properties and favorable thermal stability. Electrochemical proprieties of the printed GPEs are carried out via impedance spectroscopy in the temperature range of 25–90 °C by varying PVDF content. Ionic conductivity as high as 6.5 × 10^?4 S cm^?1 is achieved at room temperature for GPE containing low PVDF content (5 wt%) and conductivity of the GPEs is increased as temperature rises.     

Melt‐mixed polypropylene/acrylonitrile‐butadiene‐styrene blends with multiwall carbon nanotubes: Effect of compatibilizer and modifier on morphology and electrical conductivity

Cocontinuous blends of 45/55 polypropylene (PP)/acrylonitrile‐butadiene‐styrene (ABS) with multiwall carbon nanotubes (MWNT) were prepared by melt‐mixing in a conical twin‐screw microcompounder. PP‐grafted‐maleic anhydride (PP‐g‐MA) and styrene MA were used as compatibilizers for PP/ABS blends. Scanning electron microscopic observations showed phase segregation of PP‐g‐MA in the blends. State of dispersion of MWNT in the presence or absence of the compatibilizers was assessed through AC electrical conductivity measurements and crystallization studies of the blends. An improvement in AC electrical conductivity was observed in blends in presence of either styrene MA or dual compatibilizers. The lowest electrical percolation threshold was achieved at 0.1 wt % of MWNT using sodium salt of 6‐amino hexanoic acid‐modified MWNT. Significant increase in crystallization temperature of PP phase of blends with MWNT was observed in the presence of compatibilizers as compared to blends without compatibilizers. An attempt has been made to address the complex issues of phase segregation, compatibilization, and dispersion of MWNT in cocontinuous blends of PP/ABS. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A comparison of two meshing schemes for CFD analysis of the impulse turbine for wave energy applications

This paper presents the comparison of a three-dimensional Computational Fluid Dynamics (CFD) analysis with empirical performance data of a 0.6 m Impulse Turbine with Fixed Guide Vanes used for wave energy power conversion. Pro-Engineer, Gambit and Fluent 6 were used to create a 3-D model of the turbine. A hybrid meshing scheme was used with hexahedral cells in the near blade region and tetrahedral and pyramid cells in the rest of the domain. The turbine has a hub-to-tip ratio of 0.6 and results were obtained over a wide range of flow coefficients. Satisfactory agreement was obtained with experimental results. The model yielded a maximum efficiency of approximately 54% as compared to a maximum efficiency of around 49% from experiment. A degree of insight into flow behaviour, not possible with experiment, was obtained. Sizeable areas of separation on the pressure side of the rotor blade were identified toward the tip. The aim of the work is to benchmark the CFD results with experimental data and to investigate the performance of the turbine using CFD and to with a view to integrating CFD into the design process.     

Radiation-curable carbon fiber prepreg composites

Radiation processing is the utilization of ionizing radiation, usually photons or electron beams, to produce useful physical and chemical changes in a material. A potential application for electron beam processing for composite manufacturing is for curing carbon fiber prepregs. These prepregs, carbon fibers or fabrics preimpregnated with liquid polymer resin, are commonly used in the aircraft industry. Their use, however, can be time consuming and labor intensive. The advantages of radiation curing over thermal or chemical curing methods include improved rate control, reduced curing times, and curing at ambient temperature. There is no need for chemical initiators. A radiation-curable prepreg has been designed to meet the mechanical and physical property specifications of a leading aircraft manufacturing company. The resin is a mixture of an expoxy diacrylate, polybutadiene diacrylate, and a multifunctional monomer. This resin was used to impregnate a plain weave carbon fabric, at a loading of 35 percent (by mass), using a solvent process. Preliminary characterization studies show that the cured polymer produced by irradiation in air to a dose of 40 kGy is amorphous with a maximum gel fraction of 85 percent. The softening point of the polymer varied from 228°C (30-kGy sample) to 237°C (50-kGy sample). The linear thermal expansion coefficient of the polymer was 1.7 × 10⁻⁴ m/m°C from 25°C to 150°C and was unaffected by varying the applied dose from 30 to 50 kGy.     

Development and Validation of HPTLC Method for Estimation of Tacrolimus in Formulations

A new, simple, and rapid high-performance thin-layer chromatographic method with a derivatization procedure was developed and validated for quantitative determination of tacrolimus. Tacrolimus was chromatographed on silica gel 60 F₂₅₄ TLC plate using toluene–acetonitrile–glacial acetic acid (6:4:0.1, by volume) as mobile phase. Tacrolimus was visualized using a derivatization reagent containing anisaldehyde–sulfuric acid in absolute alcohol and quantified by densitometric analysis in the reflectance mode at 675 nm. The method was found to give compact spots for the drug (R_f?=?0.40?±?0.03). The linear regression analysis data for the calibration plots showed good linear relationship with r²?=?.9989 in the concentration range 100–800 ng/spot. The method was validated for precision, recovery, repeatability, and robustness as per the International Conference on Harmonization guidelines. The minimum detectable amount was found to be 28.90 ng, whereas the limit of quantitation was found to be 97.04 ng. Statistical analysis of the data showed that the method is precise, accurate, reproducible, and selective for the analysis of tacrolimus. The method was successfully employed for the estimation of equilibrium solubility and quantification of tacrolimus as a bulk drug and in commercially available capsules and in-house developed self-microemulsifying formulations.