Spatial confinement of exciton transfer and the role of conformational order in organic nanoparticles

Organic nanoparticles consisting of single conjugated polymer chains were investigated as a function of degree of conjugation by means of single-molecule spectroscopy. The degree of conjugation was synthetically controlled. For highly conjugated chains, singlet excitons are efficiently funneled over nanometer distances to a small number of sites. In contrast, chains with less conjugation and a high number of saturated bonds do not exhibit energy funneling due to a highly disordered conformation.

Measurement of Heat Transfer Rate on Backward-Facing Steps at Hypersonic Mach Number

Two backward-facing models with step heights of 2 and 3 mm are used to measure the convective surface heat transfer rates by using platinum thin-film gauges, deposited on Macor inserts. Heat transfer rates have been theoretically calculated along the flat plate portion of a model using the Eckert reference temperature method. The experimentally determined surface heat transfer rate distributions are compared with theoretical and numerical estimations. Experimental heat flux distribution over a flat plate model showed good agreement with the reference temperature method at stagnation enthalpy range of 0.8-2 MJ/kg. Theoretical analysis has been used for downstream of a backward-facing step using Gai's nondimensional analysis. It has been found from the present study that approximately 10 and 8 step heights are required for the flow to reattach for 2 and 3 mm step height backward-facing step models, respectively, at a nominal Mach number of 7.6.

Electric Field Directed Growth of Molecular Wires of Charge Transfer Molecules on Prefabricated Metal Electrodes

Molecular wires of charge transfer molecules were formed by co-evaporating the 7 7 8 8-Tetracyanoquinodimethane [TCNQ] (acceptor) and Tetrathiafulvalene [TTF] (donor) molecules across prefabricated metal electrodes. Molecular wires of TTF TCNQ were also formed by evaporating single complex of TTF:TCNQ across prefabricated metal electrodes The prefabricated metal electrodes were made using electron beam lithography on SiO2 and glass cover slip substrates. Even though TTF: TCNQ wires grown from both co-evaporation and evaporation techniques show semiconductor like behavior in temperature dependence of resistance they show different activation energies due the difference in stoichiometry of TTF and TCNQ.

Numerical Study Of Heat Transfer From Pin Fin Heat Sink Using Steady And Pulsated Impinging Jets

The work reported in this thesis is an attempt to enhance heat transfer in electronic devices with the use of impinging air jets on pin-finned heat sinks. The cooling per-formance of electronic devices has attracted increased attention owing to the demand of compact size, higher power densities and demands on system performance and re-liability. Although the technology of cooling has greatly advanced, the main cause of malfunction of the electronic devices remains overheating. The problem arises due to restriction of space and also due to high heat dissipation rates, which have increased from a fraction of a W/cm2to 100s of W /cm2. Although several researchers have at-tempted to address this at the design stage, unfortunately the speed of invention of cooling mechanism has not kept pace with the ever-increasing requirement of heat re- moval from electronic chips. As a result, efficient cooling of electronic chip remains a challenge in thermal engineering. Heat transfer can be enhanced by several ways like air cooling, liquid cooling, phase change cooling etc. However, in certain applications due to limitations on cost and weight, eg. air borne application, air cooling is imperative. The heat transfer can be increased by two ways. First, increasing the heat transfer coefficient (forced convec- tion), and second, increasing the surface area of heat transfer (finned heat sinks). From previous literature it was established that for a given volumetric air flow rate, jet im-pingement is the best option for enhancing heat transfer coefficient and for a given volume of heat sink material pin-finned heat sinks are the best option because of their high surface area to volume ratio. There are certain applications where very high jet velocities cannot be used because of limitations of noise and presence of delicate components. This process can further be improved by pulsating the jet. A steady jet often stabilizes the boundary layer on the surface to be cooled. Enhancement in the convective heat transfer can be achieved if the boundary layer is broken. Disruptions in the boundary layer can be caused by pulsating the impinging jet, i.e., making the jet unsteady. Besides, the pulsations lead to chaotic mixing, i.e., the fluid particles no more follow well defined streamlines but move unpredictably through the stagnation region. Thus the flow mimics turbulence at low Reynolds number. The pulsation should be done in such a way that the boundary layer can be disturbed periodically and yet adequate coolant is made available. So, that there is not much variation in temperature during one pulse cycle. From previous literature it was found that square waveform is most effective in enhancing heat transfer. In the present study the combined effect of pin-finned heat sink and impinging slot jet, both steady and unsteady, has been investigated for both laminar and turbulent flows. The effect of fin height and height of impingement has been studied. The jets have been pulsated in square waveform to study the effect of frequency and duty cycle. This thesis attempts to increase our understanding of the slot jet impingement on pin-finned heat sinks through numerical investigations. A systematic study is carried out using the finite-volume code FLUENT (Version 6.2) to solve the thermal and flow fields. The standard k-ε model for turbulence equations and two layer zonal model in wall function are used in the problem Pressure-velocity coupling is handled using the SIMPLE algorithm with a staggered grid. The parameters that affect the heat transfer coefficient are: height of the fins, total height of impingement, jet exit Reynolds number, frequency of the jet and duty cycle (percentage time the jet is flowing during one complete cycle of the pulse). From the studies carried out it was found that: a) beyond a certain height of the fin the rate of enhancement of heat transfer becomes very low with further increase in height, b) the heat transfer enhancement is much more sensitive to any changes at low Reynolds number than compared to high Reynolds number, c) for a given total height of impingement the use of fins and pulsated jet, increases the effective heat transfer coefficient by almost 200% for the same average Reynolds number, d) for all the cases it was observed that the optimum frequency of impingement is around 50 − 100 Hz and optimum duty cycle around 25-33.33%, e) in the case of turbulent jets the enhancement in heat transfer due to pulsations is very less compared to the enhancement in case of laminar jets.

Numerical Investigation of Heat Transfer from a Two-Dimensional Sudden Expansion Flow Using Nanofluids

Laminar forced convection heat transfer from two-dimensional sudden expansion flow of different nanofluids is studied numerically. The governing equations are solved using the unsteady stream function-vorticity method. The effect of volume fraction of the nanoparticles and type of nanoparticles on heat transfer is examined and found to have a significant impact. Local and average Nusselt numbers are reported in connection with various nanoparticle, volume fraction, and Reynolds number for expansion ratio 2. The Nusselt number reaches peak values near the reattachment point and reaches asymptotic value in the downstream. Bottom wall eddy and volume fraction shows a significant impact on the average Nusselt number.

A computational study of heat transfer, soot production and transport in an acetylene-air laminar diffusion flame in the field of a line vortex

The present work involves a computational study of soot formation and transport in case of a laminar acetylene diffusion flame perturbed by a co nvecting line vortex. The topology of the soot contours (as in an earlier experimental work [4]) have been investigated. More soot was produced when vortex was introduced from the air si de in comparison to a fuel side vortex. Also the soot topography was more diffused in case of the air side vortex. The computational model was found to be in good agreement with the ex perimental work [4]. The computational simulation enabled a study of the various parameters affecting soot transport. Temperatures were found to be higher in case of air side vortex as compared to a fuel side vortex. In case of the fuel side vortex, abundance of fuel in the vort ex core resulted in stoichiometrically rich combustion in the vortex core, and more discrete so ot topography. Overall soot production too was low. In case of the air side vortex abundan ce of air in the core resulted in higher temperatures and more soot yield. Statistical techniques like probability density fun ction, correlation coefficient and conditional probability function were introduced to explain the transient dependence of soot yield and transport on various parameters like temperature, a cetylene concentration.

On the Mechanism of Phase Transfer Catalysis in Brust-Schiffrin Synthesis of Metal Nanoparticles

The two-phase Brust-Schiffrin method (BSM) is used to synthesize highly stable nanoparticles of noble metals. A phase transfer catalyst (PTC) is used to bring in aqueous phase soluble precursors into the organic phase to enable particle synthesis there. Two different mechanisms for phase transfer are advanced in the literature. The first mechanism considers PTC to bring in an aqueous phase soluble precursor by complexing with it. The second mechanism considers the ionic species to be contained in inverse micelles of PTC, with a water core inside. A comprehensive experimental study involving measurement of interfacial tension, viscosity, water content by Karl-Fischer titration, static light scattering, H-1 NMR, and small-angle X-ray scattering is reported in this work to establish that the phase transfer catalyst tetraoctylammonium bromide transfers ions by complexing with them, instead of encapsulating them in inverse micelles. The findings have implications for particle synthesis in two-phase methods such as BSM and their modification to produce more monodispersed particles.

NH3 adsorption on PtM (Fe, Co, Ni) surfaces: Cooperating effects of charge transfer, magnetic ordering and lattice strain

Adsorption of a molecule or group with an atom which is less electronegative than oxygen (0) and directly interacting with the surface is very relevant to development of PtM (M = 3d-transition metal) catalysts with high activity. Here, we present theoretical analysis of the adsorption of NH3 molecule (N being less electronegative than 0) on (111) surfaces of PtM (Fe, Co, Ni) alloys using the first principles density functional approach. We find that, while NH3-Pt interaction is stronger than that of NH3 with the elemental M-surfaces, it is weaker than the strength of interaction of NH3 with M-site on the surface of PtM alloy. (C) 2016 Published by Elsevier B.V.

Visualisation of charge-transfer excitations in donor-acceptor molecules using the particle-hole map: a case study

Charge-transfer (CT) excitations are essential for photovoltaic phenomena in organic solar cells. Owing to the complexity of molecular geometries and orbital coupling, a detailed analysis and spatial visualisation of CT processes can be challenging. In this paper, a new detail-oriented visualisation scheme, the particle-hole map (PHM), is applied and explained for the purpose of spatial analysis of excitations in organic molecules. The PHM can be obtained from the output of a time-dependent density-functional theory calculation with negligible additional computational cost, and provides a useful physical picture for understanding the origins and destinations of electrons and holes during an excitation process. As an example, we consider intramolecular CT excitations in Diketopyrrolopyrrole-based molecules, and relate our findings to experimental results.

Determination of Proper Processing Conditions of Material Surface Heat Treatment Through Finite Element Method

A two-dimensional model has been developed based on the experimental results of stainless steel remelting with the laminar plasma technology to investigate the transient thermo-physical characteristics of the melt pool liquids. The influence of the temperature field, temperature gradient, solidification rate and cooling rate on the processing conditions has been investigated numerically. Not only have the appropriate processing conditions been determined according to the calculations, but also they have been predicted with a criterion established based on the concept of equivalent temperature area density (ETAD) that is actually a function of the processing parameters and material properties. The comparison between the resulting conditions shows that the ETAD method can better predict the optimum condition.

Micro- and macroscopic characterizations of the viscoelastic fracture of resin-based fibre composites

Micro- and macroscopic characterizations of the viscoelastic fracture of a unidirectional carbon-fibre-reinforced epoxy composite are presented. First, the micro-cracking behavior of the material is studied by the use of scanning electron microscopy; the in situ creep cracking process is observed and the crack propagation is measured. In order to obtain insight into the mechanisms of the observed creep cracking, macroscopic investigations were also carried out. Finite-element method simulations were carried out to calculate the stress distribution and the variation of stresses with time. A theoretical analysis of the orthotropy of viscoelastic fracture behavior of the material is also conducted.