Probing Photoexcited Carriers in a Few-Layer MoS2 Laminate by Time-Resolved Optical Pump-Terahertz Probe Spectroscopy

We report the dynamics of photoinduced carriers in a free-standing MoS2 laminate consisting of a few layers (1-6 layers) using time-resolved optical pump-terahertz probe spectroscopy. Upon photoexcitation with the 800 nm pump pulse, the terahertz conductivity increases due to absorption by the photoinduced charge carriers. The relaxation of the non-equilibrium carriers shows fast as well as slow decay channels, analyzed using a rate equation model incorporating defect-assisted Auger scattering of photoexcited electrons, holes, and excitons. The fast relaxation time occurs due to the capture of electrons and holes by defects via Auger processes, resulting in nonradiative recombination. The slower relaxation arises since the excitons are bound to the defects, preventing the defect-assisted Auger recombination of the electrons and the holes. Our results provide a comprehensive understanding of the non-equilibrium carrier kinetics in a system of unscreened Coulomb interactions, where defect-assisted Auger processes dominate and should be applicable to other 2D systems.

Rate Model and Mechanism of Liquid-Phase Oxidation of Propionaldehyde

A rate equation is developed for the liquid-phase oxidation of propionaldehyde with oxygen in the presence of manganese propionate catalyst in a sparged reactor. The equation takes into account diffusional limitations based on Brian's solution for mass transfer accompanied by a pseudo m-. nth-order reaction. Sauter-mean bubble diameter, gas holdup, interfacial area, and bubble rise velocity are measured, and rates of mass transfer within the gas phase and across the gas-liquid interface are computed. Statistically designed experiments show the adequacy of the equation. The oxidation reaction is zero order with respect to oxygen concentration, 3/2 order with respect to aldehyde concentration, and order with respect to catalyst concentration. The activation energy is 12.1 kcal/g mole.

A simplified kinetic model for oxidative dehydrogenation of ethylbenzene over Pd-NaBr/Al2O3 catalyst

The oxidative dehydrogenation of ethylbenzene is gaining considerable importance in recent years as a promising alternative for styrene production. This vapour phase reaction has been studied over Pd-NaBr/Al2O3 catalyst in the temperature range 623-793 K in a fixed bed reactor. Kinetic analysis of this reaction has been done using a recursion procedure developed in this work from first principles. The advantage of this method is the absence of any restriction on the conversion level as it uses an integrated rate equation. The rate of styrene formation was found to follow a linear relationship with concentration of ethylbenzene and shows a Langmuir type dependence on the concentration of oxygen.

Mechanism of adsorption effects on electrode kinetics: Part I: Selection rules in the case of low coverage by molecular surfactants

It is shown that the effect of adsorption of inert molecules on electrode reaction rates is completely accounted for, by introducing into the rate equation, adsorption-induced changes in both the effective electrode area as well as in the electrostatic potential at the reaction site with an additional term for the noncoulombic interaction between the reactant and the adsorbate. The electrostatic potential at the reaction site due to the adsorbed layer is calculated using a model of discretely-distributed molecules in parallel orientation when adsorbed on the electrode with an allowance for thermal agitation. The resulting expression, which is valid for the limiting case of low coverages, is used to predict the types of molecular surfactants that are most likely to be useful for acceleration and inhibition of electrode reactions.

Oxidation of acetaldehyde to acetic acid in a sparger reactor

The kinetics of oxidation of acetaldehyde to acetic acid was studied in a sparger reactor using manganese acetate as the catalyst. Data obtained in a stirred tank reactor are used for analyzing the sparger reactor data. The rate of chemical reaction is extremely fast and can be neglected for the rate equation of the sparger reactor. A kinetic model applicable at any temperature and concentration within the range of the variables studied is developed which predicts the performance of the sparger reactor satisfactorily.

A new approach to the kinetics of size reduction in ball milling

The rate of breakage of feed in ball milling is usually represented in the form of a first-order rate equation. The equation was developed by treating a simple batch test mill as a well mixed reactor. Several case of deviation from the rule have been reported in the literature. This is attributed to the fact that accumulated fines interfere with the feed material and breaking events are masked by these fines. In the present paper, a new rate equation is proposed which takes into account the retarding effect of fines during milling. For this purpose the analogy of diffusion of ions through permeable membranes is adopted, with suitable modifications. The validity of the model is cross checked with the data obtained in batch grinding of ?850/+600 ?m size quartz. The proposed equation enables calculation of the rate of breakage of the feed at any instant of time.

Influence of temperature and strain rate on the flow stress of an FeAl alloy

The deformation behavior of an FeAl alloy processed by hot extrusion of water atomized powder has been investigated. Compression tests are performed in the temperature range 1073–1423 K and in the strain rate range 0.001–100 s−1 up to a true plastic strain of 0.5. The flow stress has been found to be strongly dependent on temperature as well as strain rate. The stress exponent in the power law rate equation is estimated to be in the range 7.0–4.0, decreasing with temperature. The activation energy for plastic flow in the range 1073–1373 K varies from 430 kJ mol−1 at low stresses to 340 kJ mol−1 at high stresses. However, it is fairly independent of strain rate and strain. The activation area has similarly shown a stress dependence and lies in the range 160–45b2. At 1423 K and at strain rates lower than 0.1 s−1 a strain rate sensitivity of 0.3 is observed with an associated activation energy of 375 kJ mol−1. The plastic flow in the entire range of temperature and strain rate investigated appears to be controlled by a diffusion mechanism. The results have revealed that it is possible to process the alloy by superplastic forming in the range 1373–1423 K at strain rates lower than 0.1 s−1.

On the Presumed Kinetic Consequences of Pre-equilibrium. Implications for the Michaelis-Menten Equation

The overall rate equation for a reaction sequence consisting of a pre-equilibrium and rate-determining steps should not be derived on the basis of the concentration of the intermediate product (X). This is apparently indicated by transition state theory (as the path followed to reach the highest energy transition state is irrelevant), but also proved by a straight-forward mathematical approach. The thesis is further supported by the equations of concurrent reactions as applied to the partitioning of X between the two competing routes (reversal of the pre-equilibrium and formation of product). The rate equation may only be derived rigorously on the basis of the law of mass action. It is proposed that the reactants acquire the overall activation energy prior to the pre-equilibrium, thus forming X in a high-energy state en route to the rate-determining transition state. (It is argued that conventional energy profile diagrams are misleading and need to be reinterpreted.) Also, these arguments invalidate the Michaelis-Menten equation of enzyme kinetics, and necessitate a fundamental revision of our present understanding of enzyme catalysis. (The observed ``saturation kinetics'' possibly arises from weak binding of a second molecule of substrate at the active site; analogous conclusions apply to reactions at surfaces).

Heat and mass transfer and chemical transformation in a cerium nitrate droplet

This paper deals with the thermo-physical changes that a droplet undergoes when it is radiatively heated in a levitated environment. The heat and mass transport model has been developed along with chemical kinetics within a cerium nitrate droplet. The chemical transformation of cerium nitrate to ceria during the process is predicted using Kramers' reaction mechanism which justifies the formation of ceria at a very low temperature as observed in experiments. The rate equation modeled by Kramers is modified suitably to be applicable within the framework of a droplet, and predicts experimental results well in both bulk form of cerium nitrate and in aqueous cerium nitrate droplet. The dependence of dissociation reaction rate on droplet size is determined and the transient mass concentration of unreacted cerium nitrate is reported. The model is validated with experiments both for liquid phase vaporization and chemical reaction. Vaporization and chemical conversion are simulated for different ambient conditions. The competitive effects of sensible heating rate and the rate of vaporization with diffusion of cerium nitrate is seen to play a key role in determining the mass fraction of ceria formed within the droplet. Spatially resolved modeling of the droplet enables the understanding of the conversion of chemical species in more detail.

Discrete-Rate Adaptation and Selection in Energy Harvesting Wireless Systems

In a system with energy harvesting (EH) nodes, the design focus shifts from minimizing energy consumption by infrequently transmitting less information to making the best use of available energy to efficiently deliver data while adhering to the fundamental energy neutrality constraint. We address the problem of maximizing the throughput of a system consisting of rate-adaptive EH nodes that transmit to a destination. Unlike related literature, we focus on the practically important discrete-rate adaptation model. First, for a single EH node, we propose a discrete-rate adaptation rule and prove its optimality for a general class of stationary and ergodic EH and fading processes. We then study a general system with multiple EH nodes in which one is opportunistically selected to transmit. We first derive a novel and throughput-optimal joint selection and rate adaptation rule (TOJSRA) when the nodes are subject to a weaker average power constraint. We then propose a novel rule for a multi-EH node system that is based on TOJSRA, and we prove its optimality for stationary and ergodic EH and fading processes. We also model the various energy overheads of the EH nodes and characterize their effect on the adaptation policy and the system throughput.

Crystallization kinetics of poly(l-lactic acid)

The morphology and crystal growth of poly(l-lactic acid), PLLA have been studied from the melt as a function of undercooling and molecular weight using hot stage microscopy. Attention has been given to the application of growth rate equation on the growth rate data of PLLA and thus various nucleation parameters have been calculated. The criteria of Regime I and Regime II types of crystallization has been applied for the evaluation of substrate lengths.

Effect of Pressure on Polymer Ignition

Auto-ignition temperature of polystyrene, poly(vinyl chloride) and carboxy terminated polybutadiene has been measured at various oxygen pressures (1-28 atm) in a high pressure differential thermal analysis assembly at a heating rate of 10°C/min. The exothermic peak appears between 250-350°C in polystyrene and poly(vinyl chloride) and between 150-200°C for carboxy terminated polybutadiene. Ignition appears to be controlled by in situ forma tion and degradation of polymeric peroxides. Inverse dependence of ignition temperature on oxygen pressure is explained by the rate equation which con siders that ignition of a particular sample, of a fixed geometry, occurs when gasification rate reaches a unique critical value.

Nucleation parameters for polymer crystallization from non-isothermal thermal analysis

Differential scanning calorimetry (DSC) has been used to obtain kinetic and nucleation parameters for polymer crystallization under a non-isothermal mode of operation. The available isothermal nucleation growth-rate equation has been modified for non-isothermal kinetic analysis. The values of the nucleation constant (K g ) and surface free energies (sgr, sgr e ) have been obtained for i-polybutene-1, i-polypropylene, poly(L-lactic acid), and polyoxymethylene and are compared with those obtained from isothermal kinetic analysis; a good agreement in both is seen.

Kinetics of vapour phase oxidation of furfural on vanadium catalyst

Vapour phase oxidation of furfural over vanadium pentoxide catalyst was studied using an isothermal flow reactor in the temperature range of 220–280°C. Maleic anhydride and carbon dioxide are found to be formed from furfural by a parallel reaction scheme. The following rate equation based on the two-stage redox mechanism—the substance to be oxidized reduces the catalyst which in turn is reoxidized by oxygen from the feed—is found to explain the data satisfactorily.The reoxidation of the reduced catalyst was found to be the rate controlling step.

Regularized numerical integration of multibody dynamics with the generalized alpha method*

This paper discusses the consistent regularization property of the generalized α method when applied as an integrator to an initial value high index and singular differential-algebraic equation model of a multibody system. The regularization comes from within the discretization itself and the discretization remains consistent over the range of values the regularization parameter may take. The regularization involves increase of the smallest singular values of the ill-conditioned Jacobian of the discretization and is different from Baumgarte and similar techniques which tend to be inconsistent for poor choice of regularization parameter. This regularization also helps where pre-conditioning the Jacobian by scaling is of limited effect, for example, when the scleronomic constraints contain multiple closed loops or singular configuration or when high index path constraints are present. The feed-forward control in Kane's equation models is additionally considered in the numerical examples to illustrate the effect of regularization. The discretization presented in this work is adopted to the first order DAE system (unlike the original method which is intended for second order systems) for its A-stability and same order of accuracy for positions and velocities.