Tunability of monodispersed intermetallic AuCu nanoparticles through understanding of reaction pathways

Synthesis of size selective monodispersed nanoparticles particularly intermetallic with well-defined compositions represents a challenge. This paper presents a way for the synthesis of intermetallic AuCu nanoparticles as a model system. We show that reduction of Au and Cu precursors is sensitive to the ratio of total molar concentrations of surfactant to metal precursors. A careful design of experiments to understand the kinetics of the reduction process reveals initial formation of seed nanoparticles of pure Au. Reduction of Cu occurs on the surface of the seed followed by diffusion to yield AuCu. This understanding allows us to develop a two step synthesis where the precise size controlled seed of Au nanoparticles produced in the first step is used in the second step reaction mixture as an Au precursor to allow deposition and interdiffusion of Cu that yields size selected AuCu intermetallics of sub 10 nm sizes.

Chemical kinetics and self-ignition in a model supersonic hydrogen-air combustor

Self-ignition tests of a model scramjet combustor were conducted by using parallel sonic injection of gaseous hydrogen from the base of a blade-like strut into a supersonic vitiated airstream. The range of stagnation pressure and temperature studied varied from 1.0 to 4.5 MPa and from 1300 to 2200 K, respectively. Experimental results show that the self-ignition limit, in terms of either global or local quantities of pressure and temperature, exhibits a nonmonotonic behavior resembling the classical homogeneous explosion limit of the hydrogen-oxygen system. Specifically, for a given temperature, increasing pressure from a low value can render a nonignitable mixture to first become ignitable, then nonignitable again, This correspondence shows that, despite the globally supersonic nonpremixed configuration studied herein, ignition is strongly influenced by the intricate chemical reaction mechanism and thereby exhibits the homogeneous explosion character. Consequently, self-ignition criteria based on a global reaction rate approximating the complex chemistry are inadequate. An auxiliary computational study on counterflow ignition was also conducted to systematically investigate the contamination effects of vitiated air. Results indicate that the net contamination effects for the present experimental data are expected to be substantially smaller than contributions from the individual contamination species because of the counterbalancing influences of the H2O-inhibition and NO-promotion reactions in effecting ignition.

Effects of Translational Nonequilibrium on Performance of Flowing Chemical Oxygen-Iodine Laser

The effect of the translational nonequilibrium on performance modeling of flowing chemical oxygen-iodine lasers (COIL) is emphasized in this paper. The spectral line broadening (SLB) model is a basic factor for predicting the performances of flowing COIL. The Voigt profile function is a well-known SLB model and is usually utilized. In the case of gas pressure in laser cavity less than 5 torr, a low pressure limit expression of the Voigt profile function is used. These two SLB models imply that ail lasing particles can interact with monochromatic laser radiation. Basically, the inhomogeneous broadening effects are not considered in these two SLB models and they cannot predict the spectral content. The latter requires consideration of finite translational relaxation rate. Unfortunately, it is rather difficult to solve simultaneously the Navier-Stokes (NS) equations and the conservation equations of the number of lasing particles per unit volume and per unit frequency interval. In the operating condition of flowing COIL, it is possible to obtain a perturbational solution of the conservational equations for lasing particles and deduce a new relation between the gain and the optical intensity, i.e., a new gain-saturation relation. By coupling the gain-saturation relation with other governing equations (such as the NS equations, chemical reaction equations and the optical model of gain-equal-loss), We have numerically calculated the performances of flowing COIL. The present results are compared with those obtained by the common rate-equation (RE) model, in which the Voigt profile function and its low pressure limit expression are used. The difference of different model's results is great. For instance, in the case of lasing frequency coinciding with the central frequency of line profile and very low gas pressure, the gain-saturation relation of the present model is quite different with that of the RE model.

Reconsideration On The Role Of The Specific Heat Ratio In Arrhenius Law Applications

Arrhenius law implicates that only those molecules which possess the internal energy greater than the activation energy E-a can react. However, the internal energy will not be proportional to the gas temperature if the specific heat ratio gamma and the gas constant R vary during chemical reaction processes. The varying gamma may affect significantly the chemical reaction rate calculated with the Arrhenius law under the constant gamma assumption, which has been widely accepted in detonation and combustion simulations for many years. In this paper, the roles of variable gamma and R in Arrhenius law applications are reconsidered, and their effects on the chemical reaction rate are demonstrated by simulating one-dimensional C-J and two-dimensional cellular detonations. A new overall one-step detonation model with variable gamma and R is proposed to improve the Arrhenius law. Numerical experiments demonstrate that this improved Arrhenius law works well in predicting detonation phenomena with the numerical results being in good agreement with experimental data.

Experimental investigation on the cavity-based scramjet model

The present work focused on improving the engine performance with different fuel equivalence ratios and fuel injections. A scramjet model with strut/cavity integrated configurations was tested under Mach 5.8 flows. The results showed that the strut may sreve as an effective tool in a kerosene-fueled scramjet. The integration of strut/cavities also had great effect on stablizing the combustion in a wide range of fuel equivalence ratio. The one-sdimensional analysis method was used to analyze the main characteristics of the model. The two-stage fuel injection should have better performance in increasing the chemical reaction rate in the first cavity region.

Semi-gas kinetics model for performance modeling of flowing chemical oxygen-iodine lasers (COIL)

A semi-gas kinetics (SGK) model for performance analyses of flowing chemical oxygen-iodine laser (COIL) is presented. In this model, the oxygen-iodine reaction gas flow is treated as a continuous medium, and the effect of thermal motions of particles of different laser energy levels on the performances of the COIL is included and the velocity distribution function equations are solved by using the double-parameter perturbational method. For a premixed flow, effects of different chemical reaction systems, different gain saturation models and temperature, pressure, yield of excited oxygen, iodine concentration and frequency-shift on the performances of the COIL are computed, and the calculated output power agrees well with the experimental data. The results indicate that the power extraction of the SGK model considering 21 reactions is close to those when only the reversible pumping reaction is considered, while different gain saturation models and adjustable parameters greatly affect the output power, the optimal threshold gain range, and the length of power extraction.

An Improved CE/SE Scheme for Numerical Simulation of Gaseous and Two-Phase Detonations

A new structure of solution elements and conservation elements based on rectangular mesh was pro- posed and an improved space-time conservation element and solution element (CE/SE) scheme with sec- ond-order accuracy was constructed. Furthermore, the application of improved CE/SE scheme was extended to detonation simulation. Three models were used for chemical reaction in gaseous detonation. And a two-fluid model was used for two-phase (gas–droplet) detonation. Shock reflections were simu- lated by the improved CE/SE scheme and the numerical results were compared with those obtained by other different numerical schemes. Gaseous and gas–droplet planar detonations were simulated and the numerical results were carefully compared with the experimental data and theoretical results based on C–J theory. Mach reflection of a cellular detonation was also simulated, and the numerical cellular pat- terns were compared with experimental ones. Comparisons show that the improved CE/SE scheme is clear in physical concept, easy to be implemented and high accurate for above-mentioned problems.

Differentiated adipose-derived stem cells act synergistically with RGD-modified surfaces to improve neurite outgrowth in a co-culture model.

Peripheral nerve damage is a problem encountered after trauma and during surgery and the development of synthetic polymer conduits may offer a promising alternative to autografts. In order to improve the performance of the polymer to be used for nerve conduits, poly-ε-caprolactone (PCL) films were chemically functionalized with RGD moieties, using a chemical reaction previously developed. In vitro cultures of dissociated dorsal root ganglion (DRG) neurons provide a valid model to study different factors affecting axonal growth. In this work, DRG neurons were cultured on RGD-functionalized PCL films. Adult adipose-derived stem cells differentiated to Schwann cells (dASCs) were initially cultured on the functionalized PCL films, resulting in improved attachment and proliferation. dASCs were also co-cultured with DRG neurons on treated and untreated PCL to assess stimulation by dASCs on neurite outgrowth. Neuron response was generally poor on untreated PCL films, but long neurites were observed in the presence of dASCs or RGD moieties. A combination of the two factors enhanced even further neurite outgrowth, acting synergistically. Finally, in order to better understand the extracellular matrix (ECM)-cell interaction, a β1 integrin blocking experiment was carried out. Neurite outgrowth was not affected by the specific antibody blocking, showing that β1 integrin function can be compensated by other molecules present on the cell membrane. Copyright © 2013 John Wiley & Sons, Ltd.

Controlled amine functionality in self-assembled monolayers via the hidden amine route: chemical and electronic tunability.

A synthetic strategy for fabricating a dense amine functionalized self-assembled monolayer (SAM) on hydroxylated surfaces is presented. The assembly steps are monitored by X-ray photoelectron spectroscopy, Fourier transform infrared- attenuated total reflection, atomic force microscopy, variable angle spectroscopic ellipsometry, UV-vis surface spectroscopy, contact angle wettability, and contact potential difference measurements. The method applies alkylbromide-trichlorosilane for the fabrication of the SAM followed by surface transformation of the bromine moiety to amine by a two-step procedure: S(N)2 reaction that introduces the hidden amine, phthalimide, followed by the removal of the protecting group and exposing the free amine. The use of phthalimide moiety in the process enabled monitoring the substitution reaction rate on the surface (by absorption spectroscopy) and showed first-order kinetics. The simplicity of the process, nonharsh reagents, and short reaction time allow the use of such SAMs in molecular nanoelectronics applications, where complete control of the used SAM is needed. The different molecular dipole of each step of the process, which is verified by DFT calculations, supports the use of these SAMs as means to tune the electronic properties of semiconductors and for better synergism between SAMs and standard microelectronics processes and devices.

Initial stages of GaN/GaAs (100) growth by metalorganic chemical vapor deposition

We have investigated the growth of GaN buffers by metalorganic chemical vapor deposition (MOCVD) on GaAs (100) substrates. Atomic force microscope (AFM) and reflection high-energy electron diffraction (RHEED) were employed to study the dependence of the nucleation on the growth temperature, growth rate, annealing effect, and growth time. A two-step growth sequence must be used to optimize and control the nucleation and the subsequent growth independently. The size and distribution of islands and the thickness of buffer layers have a crucial role on the quality of GaN layers. Based on the experimental results, a model was given to interpret the formation of hexagonal-phase GaN in the cubic-phase GaN layers. Using an optimum buffer layer, the strong near-band emission of cubic GaN with full-width at half maximum (FWHM) value as small as 5.6 nm was observed at room temperature. The background carrier concentration was estimated to be in the range of 10(13) similar to 10(14) cm(-3).

Effects of annealing treatment on the formation of CO2 in ZnO thin films grown by metal-organic chemical vapor deposition

Post-growth annealing was carried out on ZnO thin films grown by metal-organic chemical vapor deposition (MOCVD). The grain size of ZnO thin film increases monotonically with annealing temperature. The ZnO thin films were preferential to c-axis oriented after annealing as confirmed by Xray diffraction (XRD) measurements. Fourier transformation infrared transmission measurements showed that ZnO films grown at low temperature contains CO2 molecules after post-growth annealing. A two-step reaction process has been proposed to explain the formation mechanism of CO2, which indicates the possible chemical reaction processes during the metal-organic chemical vapor deposition of ZnO films.

Simulação de um processo de pirólise rápida de biomassa

Mestrado em Engenharia Química - Ramo Optimização Energética na Indústria Química

NOx and O3 above a tropical rainforest: an analysis with a global and box model

A cross-platform field campaign, OP3, was conducted in the state of Sabah in Malaysian Borneo between April and July of 2008. Among the suite of observations recorded, the campaign included measurements of NOx and O3 – crucial outputs of any model chemistry mechanism. We describe the measurements of these species made from both the ground site and aircraft. We then use the output from two resolutions of the chemistry transport model p-TOMCAT to illustrate the ability of a global model chemical mechanism to capture the chemistry at the rainforest site. The basic model performance is good for NOx and poor for ozone. A box model containing the same chemical mechanism is used to explore the results of the global model in more depth and make comparisons between the two. Without some parameterization of the nighttime boundary layer – free troposphere mixing (i.e. the use of a dilution parameter), the box model does not reproduce the observations, pointing to the importance of adequately representing physical processes for comparisons with surface measurements. We conclude with a discussion of box model budget calculations of chemical reaction fluxes, deposition and mixing, and compare these results to output from p-TOMCAT. These show the same chemical mechanism behaves similarly in both models, but that emissions and advection play particularly strong roles in influencing the comparison to surface measurements.

Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water

We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KM-GAP) that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KM-GAP is based on the PRA model framework (Pöschl-Rudich-Ammann, 2007), and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modelled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmo- spheric aerosols and clouds. In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at 270 K is close to unity. Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for eðcient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the formation and evaporation of volatile reaction products like nonanal can cause a decrease in the size of oleic acid particles exposed to ozone.