Supercritical carbon dioxide Brayton cycle for concentrated solar power

Supercritical carbon dioxide based Brayton cycle for possible concentrated solar power applications is investigated and compared with trans- and sub-critical operations of the same fluid. Thermal efficiency, specific work output and magnitude of irreversibility generation are used as some of the performance indicators. While the thermal efficiency increases almost linearly with low side pressure in the sub- and trans-critical cycles, it attains a maximum in the supercritical regime at 85 bar after which there are diminishing returns on increasing the low side pressure. It is also found that supercritical cycle is capable of producing power with a thermal efficiency of >30% even at a lower source temperature (820K) and accounting for foreseeable non-idealities albeit with a higher turbine inlet pressure (similar to 300 bar) which is not matched by a conventional sub-critical cycle even with a high source temperature of 978K. The reasons for lower efficiency than in an ideal cycle are extracted from an irreversibility analysis of components, namely, compressor, regenerator, turbine and gas cooler. Low sensitivity to the source temperature and extremely small volumetric flow rates in the supercritical cycle could offset the drawback of high pressures through a compact system.

EQCM investigation of electrochemical deposition and stability of Co-Pi oxygen evolution catalyst of solar energy storage

Photoassisted electrolysis of water is considered as an effective way of storing solar energy in the form of hydrogen fuel. This overall reaction involves the oxidation of water to oxygen at the anode and the reduction of protons to hydrogen at the cathode. Cobalt-phosphate-based catalyst (Co-Pi) is a potentially useful material for oxygen evolution reaction. In the present study, electrochemical deposition of Co-Pi catalyst is carried out on Au-coated quartz crystal from 0.1 M phosphate buffer (pH 7) containing 0.5 mM Co2+ ion, along with the simultaneous measurement of mass changes at the electrode surface. Cyclic voltammograms and mass variations are recorded during the course of deposition. A current peak is observed at 0.92 V vs Ag/AgCl, 3 M KCl corresponding to oxidation of Co2+ ion. The mass of the electrode starts increasing at this potential, suggesting the deposition of a Co(III)-based insoluble product on the electrode surface. The stability of the catalyst is also studied at several potentials in both buffered and nonbuffered electrolyte by monitoring the real-time mass variations.

Investigation of phase separation in bulk heterojunction solar cells via supramolecular chemistry

In this work, we have prepared two donor-acceptor-donor (D-A-D) pi-conjugated oligomers to investigate the effect of phase separation on the performance of bulk heterojunction (BHJ) solar cells. These charge transfer low band gap pi-conjugated oligomers (TTB and NMeTTB) were synthesized by Knoevenagel condensation of terthiophenecarbaldehyde and barbiturate appended pyran derivative. The thin film morphology of both the oligomers and along with electron acceptor 6,6]-phenyl-C60-butyric acid methyl ester (PC61BM) was investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The blend of NMeTTB and PC61BM thin film yield highly ordered thin film, whereas there was clear phase separation between TTB and PC61BM in thin film. The BHJ solar cell was fabricated using a blend of NMeTTB and TTB with PC61BM acceptor in 1:1 ratio as active layer, and a power conversion efficiency of 1.8% was obtained. This device characteristic was compared with device having TTB:PC61BM as active layer, and large difference is observed in photocurrents. This poor performance of TTB in BHJ devices was attributed to the difference in the nanoscale morphology of the corresponding derivatives. We rationalize our findings based on the low charge carrier mobility in organic field-effect transistors and miscibility/phase separation parameter of binary components (oligomers and PC61BM) in the active layer of bulk heterojunction solar cells.

Fluctuations in the alpha-effect and grand solar minima

The parameters of a special type of alpha-effect known in dynamo theory as the Babcock-Leighton mechanism are estimated using the data of sunspot catalogs. The estimates support the presence of the Babcock-Leighton alpha-effect on the Sun. Fluctuations of the alpha-effect are also estimated. The fluctuation amplitude appreciably exceeds themean value, and the characteristic time for the fluctuations is comparable to the period of the solar rotation. Fluctuations with the parameters found are included in a numericalmodel for the solar dynamo. Computations show irregular changes in the amplitudes of the magnetic cycles on time scales of centuries and millennia. The calculated statistical characteristics of the grand solar minima and maxima agree with the data on solar activity over the Holocene.

Channel II photocurrent quantification in narrow optical gap polymer-fullerene solar cells with complimentary acceptor absorption

Most charge generation studies on organic solar cells focus on the conventional mode of photocurrent generation derived from light absorption in the electron donor component (so called channel I). In contrast, relatively little attention has been paid to the alternate generation pathway: light absorption in the electron acceptor followed by photo-induced hole transfer (channel II). By using the narrow optical gap polymer poly(3,6-dithieno3,2-b] thiophen-2-yl)-2,5-bis(2-octyldodecyl)-pyrrolo- 3,4-c]pyrrole-1,4-dione-5',5 `'-diyl-alt-4,8-bis(dodecyloxy) benzo1,2-b:4,5-b'] dithiophene-2,6-diyl with two complimentary fullerene absorbers; phenyl-C-61-butyric acid methyl ester, and phenyl-C-71-butyric acid methyl ester (70-PCBM), we have been able to quantify the photocurrent generated each of the mechanisms and find a significant fraction (>30%), which is derived in particular from 70-PCBM light absorption.

An experimental set-up for carbon isotopic analysis of atmospheric CO2 and an example of ecosystem response during solar eclipse 2010

We present here, an experimental set-up developed for the first time in India for the determination of mixing ratio and carbon isotopic ratio of air-CO2. The set-up includes traps for collection and extraction of CO2 from air samples using cryogenic procedures, followed by the measurement of CO2 mixing ratio using an MKS Baratron gauge and analysis of isotopic ratios using the dual inlet peripheral of a high sensitivity isotope ratio mass spectrometer (IRMS) MAT 253. The internal reproducibility (precision) for the PC measurement is established based on repeat analyses of CO2 +/- 0.03 parts per thousand. The set-up is calibrated with international carbonate and air-CO2 standards. An in-house air-CO2 mixture, `OASIS AIRMIX' is prepared mixing CO2 from a high purity cylinder with O-2 and N-2 and an aliquot of this mixture is routinely analyzed together with the air samples. The external reproducibility for the measurement of the CO2 mixing ratio and carbon isotopic ratios are +/- 7 (n = 169) mu mol.mol(-1) and +/- 0.05 (n = 169) parts per thousand based on the mean of the difference between two aliquots of reference air mixture analyzed during daily operation carried out during November 2009-December 2011. The correction due to the isobaric interference of N2O on air-CO2 samples is determined separately by analyzing mixture of CO2 (of known isotopic composition) and N2O in varying proportions. A +0.2 parts per thousand correction in the delta C-13 value for a N2O concentration of 329 ppb is determined. As an application, we present results from an experiment conducted during solar eclipse of 2010. The isotopic ratio in CO2 and the carbon dioxide mixing ratio in the air samples collected during the event are different from neighbouring samples, suggesting the role of atmospheric inversion in trapping the emitted CO2 from the urban atmosphere during the eclipse.

FIELD EMISSION EFFICIENCY OF A CARBON NANOTUBE ARRAY UNDER PARASITIC NONLINEARITIES

Carbon Nanotubes (CNTs) grown on substrates are potential electron sources in field emission applications. Several studies have reported the use of CNTs in field emission devices, including field emission displays, X-ray tube, electron microscopes, cathode-ray lamps, etc. Also, in recent years, conventional cold field emission cathodes have been realized in micro-fabricated arrays for medical X-ray imaging. CNTbased field emission cathode devices have potential applications in a variety of industrial and medical applications, including cancer treatment. Field emission performance of a single isolated CNT is found to be remarkable, but the situation becomes complex when an array of CNTs is used. At the same time, use of arrays of CNTs is practical and economical. Indeed, such arrays on cathode substrates can be grown easily and their collective dynamics can be utilized in a statistical sense such that the average emission intensity is high enough and the collective dynamics lead to longer emission life. The authors in their previous publications had proposed a novel approach to obtain stabilized field emission current from a stacked CNT array of pointed height distribution. A mesoscopic modeling technique was employed, which took into account electro-mechanical forces in the CNTs, as well as transport of conduction electron coupled with electron phonon induced heat generation from the CNT tips. The reported analysis of pointed arrangements of the array showed that the current density distribution was greatly localized in the middle of the array, the scatter due to electrodynamic force field was minimized, and the temperature transients were much smaller compared to those in an array with random height distribution. In the present paper we develop a method to compute the emission efficiency of the CNT array in terms of the amount of electrons hitting the anode surface using trajectory calculations. Effects of secondary electron emission and parasitic capacitive nonlinearity on the current-voltage signals are accounted. Field emission efficiency of a stacked CNT array with various pointed height distributions are compared to that of arrays with random and uniform height distributions. Effect of this parasitic nonlinearity on the emission switch-on voltage is estimated by model based simulation and Monte Carlo method.

Characteristics of Photo Electrodes Based on TiO2 Nanoparticles, Nanotubes and Microspheres for Dye Solar Cell

We have analyzed the characteristics of electrodes made of TiO2 nanotubes, microspheres and commercially available nanoparticles for dye sensitized solar cell. The morphology of the electrodes and the formation of aggregates have been analyzed by scanning electron microscopy and surface profiling technique. The concentration of Ti3+ type impurity state on the surface of these electrodes is quantified by X-ray photoelectron spectroscopy. Micro structural properties have been characterized by Brunauer, Emmett and Teller method The optical properties of the electrodes such as band gap energy, the type of band formation and the diffuse reflectance are evaluated by UV-Visible spectroscopy. The photovoltaic characteristics of dye solar cell made of these electrodes have been evaluated and it is found that the characteristics of the TiO2 film alone can alter the overall conversion efficiency to a great extent. Additional analysis using electrochemical impedance spectroscopy has been carried out to probe the electron transport properties and charge collection efficiency of these electrodes.

Narrowband signal detection techniques in shallow ocean by acoustic vector sensor array

This paper presents the formulation and performance analysis of four techniques for detection of a narrowband acoustic source in a shallow range-independent ocean using an acoustic vector sensor (AVS) array. The array signal vector is not known due to the unknown location of the source. Hence all detectors are based on a generalized likelihood ratio test (GLRT) which involves estimation of the array signal vector. One non-parametric and three parametric (model-based) signal estimators are presented. It is shown that there is a strong correlation between the detector performance and the mean-square signal estimation error. Theoretical expressions for probability of false alarm and probability of detection are derived for all the detectors, and the theoretical predictions are compared with simulation results. It is shown that the detection performance of an AVS array with a certain number of sensors is equal to or slightly better than that of a conventional acoustic pressure sensor array with thrice as many sensors.

Constraints on Be-10 and Ca-41 distribution in the early solar system from Al-26 and Be-10 studies of Efremovka CAIs

Three refractory coarse grained CAIs from the Efremovka CV3 chondrite, one (E65) previously shown to have formed with live Ca-41, were studied by ion microprobe for their Al-26-Mg-26 and Be-10-B-10 systematic in order to better understand the origin of Be-10. The high precision Al-Mg data and the inferred Al-26/Al-27 values attest that the precursors of the three CAIs evolved in the solar nebula over a period of few hundred thousand years before last melting-crystallization events. The initial Be-10/Be-9 ratios and delta B-10 values defined by the Be-10 isochrons for the three Efremovka CAIs are similar within errors. The CAI Be-10 abundance in published data underscores the large range for initial Be-10/Be-9 ratios. This is contrary to the relatively small range of Al-26/Al-27 variations in CAIs around the canonical ratio. Two models that could explain the origin of this large Be-10/Be-9 range are assessed from the collateral variations predicted for the initial delta B-10 values: (i) closed system decay of Be-10 from a ``canonical'' Be-10/Be-9 ratio and (ii) formation of CAIs from a mixture of solid precursors and nebula gas irradiated during up to a few hundred thousand years. The second scenario is shown to be the most consistent with the data. This shows that the major fraction of Be-10 in CAIs was produced by irradiation of refractory grains, while contributions of galactic cosmic rays trapping and early solar wind irradiation are less dominant. The case for Be-10 production by solar cosmic rays irradiation of solid refractory precursors poses a conundrum for Ca-41 because the latter is easily produced by irradiation and should be more abundant than what is observed in CAIs. Be-10 production by irradiation from solar energetic particles requires high Ca-41 abundance in early solar system, however, this is not observed in CAIs. (C) 2013 Elsevier B.V. All rights reserved.

Synthesis, structure, characterization and photocatalytic activity of Bi2Zr2O7 under solar radiation

Bi2Zr2O7 was synthesized via a facile solution combustion method. Two different fuels, urea and tartaric acid were used in the synthesis, which resulted in Bi2Zr2O7 crystals with different band gaps and surface areas. The structure has been determined by Rietveld refinement followed by the difference Fourier technique. The compound crystallizes in the space group Fm (3) over barm. The photocatalytic degradation of two dyes was carried out under solar radiation. Bi2Zr2O7 prepared using urea as the fuel exhibits a higher photocatalytic activity than the compound prepared using tartaric acid and comparable activity to that of commercial Evonik P-25 TiO2. It is suggested that this is due to the oxygen vacancies occurring in the two cases, the urea based compound has an occupancy of 0.216, whereas the tartaric acid based synthesis shows disorder in the oxygen position amounting to a small number of oxygen vacancies.

Studies of grand minima in sunspot cycles by using a flux transport solar dynamo model

We propose that grand minima in solar activity are caused by simultaneous fluctuations in the meridional circulation and the Babcock-Leighton mechanism for the poloidal field generation in the flux transport dynamo model. We present the following results: (a) fluctuations in the meridional circulation are more effective in producing grand minima; (b) both sudden and gradual initiations of grand minima are possible; (c) distributions of durations and waiting times between grand minima seem to be exponential; (d) the coherence time of the meridional circulation has an effect on the number and the average duration of grand minima, with a coherence time of about 30 yr being consistent with observational data. We also study the occurrence of grand maxima and find that the distributions of durations and waiting times between grand maxima are also exponential, like the grand minima. Finally we address the question of whether the Babcock-Leighton mechanism can be operative during grand minima when there are no sunspots. We show that an alpha-effect restricted to the upper portions of the convection zone can pull the dynamo out of the grand minima and can match various observational requirements if the amplitude of this alpha-effect is suitably fine-tuned.

Diketopyrrolopyrrole-Based Conjugated Polymers and Small Molecules for Organic Ambipolar Transistors and Solar Cells

The present highlight discusses major work in the synthesis of low bandgap diketopyrrolopyrrole (DPP)-based polymers with donor-acceptor-donor (D-A-D) approach and their application in organic electronics. It examines the past and recent significant advances which have led to development of low bandgap DPP-based materials with phenyl and thiophene as donors. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4241-4260

Polymer solar cells: design of materials by donor-acceptor approach

A brief overview of our group research activities is given and the concept of donor acceptor is described for the development of conjugated polymers for optoelectronic devices. In particular, a new family of conjugated polymers based on dithienopyrrole has been synthesized to demonstrate the concept of donor-acceptor. The dithienopyrrole was coupled to benzodithiophene via Stille coupling to obtain two low band gap polymers P5a and P5b having -C18H37 and -2-ethylhexyl alkyl chain respectively. Both the polymers exhibit absorption within the solar spectrum with an optical band gap below 2 eV. Atomic force microscopy revealed that both the polymers form smooth film with roughness of 2.4 nm and photoluminescence measurement of polymer/fullerene derivative blend film suggests effective dissociation of exciton.

Morphology and electrochemical performance of graphene nanosheet array for Li-ion thin film battery

Highly branched and porous graphene nanosheet synthesized over different substrates as anode for Lithium ion thin film battery. These films synthesized by microwave plasma enhanced chemical vapor deposition at temperature 700 degrees C. Scanning electron microscopy and X-ray photo electron spectroscopy are used to characterize the film surface. It is found that the graphene sheets possess a curled and flower like morphology. Electrochemical performances were evaluated in swezelock type cells versus metallic lithium. A reversible capacity of 520 mAh/g, 450 mAh/g and 637 mAh/g was obtained after 50 cycles when current rate at 23 mu A cm(2) for CuGNS, NiGNS and PtGNS electrodes, respectively. Electrochemical properties of thin film anode were measured at different current rate and gave better cycle life and rate capability. These results indicate that the prepared high quality graphene sheets possess excellent electrochemical performances for lithium storage. (C) 2013 Elsevier Ltd. All rights reserved.