Simulations of Nanoparticle Synthesis in Laminar Stagnation Flames

A new implementation of a multidimensional solver for studying nanoparticle synthesis in laminar flames is presented. The governing equations are convective-diffusive-reactive partial differential equations that are discretised using the finite volume method. Detailed chemical source terms and transport coefficients are used to close the equations. The implementation of these governing equations is discussed and the numerical algorithm used to solve them is presented. The new solver is verified against analytic solutions and numerical solutions from 1D models for counterflow diffusion flames. The new solver was used to calculate the flame location, shape and temperature of laminar premixed ethylene jet-wall stagnation flames when the equivalence ratio, exit gas velocity and burner-plate separation distance are varied. The simulation results were compared to new experimental 2D measurements of CH* chemiluminescence and temperature. The 2D simulations showed excellent agreement, and correctly predicted the flame shape, location and temperature as the experimental conditions were varied. The new solver was used to study growth of inorganic nanoparticles in premixed, jet-wall stagnation flames. Titanium dioxide, also known as titania and TiO2, is a white powder than has many uses as a pigment, including in paper and cosmetics, and was selected as the system to apply the new solver. TiO2 nanoparticles formed from titanium tetraisopropoxide (TTIP) were simulated using a two step methodology, which enabled insight into the variations of particle properties as a function of the deposition radius. Two different TTIP loadings (280 and 560~ppm) were studied in two flames, a lean flame (equivalence ratio 0.35) and a stoichiometric flame (equivalence ratio 1.0). First, the growth of particles was described with a spherical particle model fully coupled to the conservation equations of chemically reacting flow. Second, particle trajectories were extracted from the 2D simulations and post-processed using a detailed particle model solved with a stochastic numerical method. The simulation produced gas phase predictions of flame location that are in good agreement with available literature. The particle morphologies and size distributions were examined and found to be dependent on the deposition radius. Particles began to have different size distributions at a deposition radius of approximately one and a half times the nozzle radius (1.0 cm), which should be kept in mind when synthesising and modelling nanoparticles for novel applications. This coincided with the growth of total residence time along particle trajectories. It is suggested that experiments critically examine the radially uniformity of deposited particles do not affect the performance for their intended application.Gates Cambridge Foundation, Gates Cambridge Scholarship (OPP1144

An experimental investigation and a simple model of valveless pump

International audienceWe construct a valveless pump consisting of a section of elastic tube and a section of rigid tube connected in a closed loop and filled with water. By periodically squeezing the elastic tube at an asymmetric location, a persistent flow around the tubes is created. This effect, called the Liebau phenomenon or valveless pumping, has been known for some time but is still not completely understood. We study the flow rates for various squeezing locations, frequencies, and elastic tube rigidities. To understand valveless pumping, we formulate a simple model that can be described by ordinary differential equations. The time series of flow velocities generated by the model are qualitatively and quantitatively similar to those seen in the experiment. The model provides a physical explanation of valveless pumping, and it allows us to identify the essential pumping mechanisms

Temperature and CH* measurements and simulations of laminar premixed ethylene jet-wall stagnation flames

New experimental 2D measurements are reported to characterise the flame location, shape and temperature of laminar premixed ethylene jet-wall stagnation flames when the equivalence ratio, exit gas velocity and burner-plate separation distance are varied. Bandpass-filtered optical measurements of the CH* chemiluminescence were used to provide information about the shape and location of the flames. Thin filament pyrometry (TFP) using a 14 um diameter SiC filament was used to make line measurements of the temperature to reconstruct the full 2D temperature field for the first time in premixed, jet-wall stagnation flames. The comparison of CH* measurements with (intrusive) and without (non-intrusive) the presence of the SiC filament showed that the filament resulted in minimal disturbance of the flame when the filament was placed downstream of the flame front. However, the flame was observed to attach to the filament, resulting in more significant disturbance, when the filament was placed upstream of the flame front. The flames were simulated using both 1D and 2D models. The 2D simulations were used to provide estimates of the velocity, kinematic viscosity and thermal conductivity required to obtain the gas temperature from the TFP data. The 1D simulations showed excellent agreement with the experimentally observed centreline quantities, but required the strain boundary condition to be fitted in order to match the experimentally observed flame location. The 2D simulations showed excellent agreement without the need for any fitting, and correctly predicted the flame shape, location and temperature as the experimental conditions were varied. A comparison of the set of simulated temperature-residence time distributions showed relatively uniform distributions within each flame. However, the most uniform set of temperature-residence time distributions did not correlate with the flattest flame

Kinetic Monte Carlo statistics of curvature integration by HACA growth and bay closure reactions for PAH growth in a counterflow diffusion flame

This paper uses a Kinetic Monte Carlo model that includes processes to integrate curvature due to the formation of five- and seven-member rings to simulate polycyclic aromatic hydrocarbons (PAHs) growing in lightly sooting ethylene and acetylene counterflow diffusion flames. The model includes new processes to form seven-member rings via hydrogen-a bstraction-acetylene-addition and bay closure reactions on sites containing partially embedded five-member rings. The model additionally includes bay closure and HACA bay capping reactions for the integration of five-member rings. The mass spectra of PAHs predicted by the model are assessed against experimental data, and the distribution of embedded five-member rings and seven-member rings is studied as a function of spatial location, molecule size and frequency of events sampled in the simulation. The simulations show that the formation of seven-member rings and the embedding of five-member rings is a competitive process. Both types of rings are observed more frequently as the simulation proceeds from the fuel outlet towards the stagnation plane. Approximately 15% of the events that integrate curvature resulted in the formation of a seven-member ring coupled to an embedded five-member ring, and the remaining 85% of events embedded five-member rings via the formation of six-member rings. The proportion of PAHs containing embedded five-member rings and/or seven-member rings is observed to be a function of PAH size, passing through a maximum for PAHs containing 15–20 six-member rings. However, the proportion of PAHs containing both types of ring increases with PAH size, where upwards of 10% of PAHs containing at least one five-member ring and 15 or more six-member rings also contain a seven-member ring.CONACYT Cambridge Commonwealth Trust National Research Foundation (NRF), Prime Minister’s Office, Singapore under its CREATE programme Johnson Matthey Gates Cambridge Scholarshi

Bis(2,5-dimethyl­anilinium) tetra­chlorido­zincate(II)

In the title compound, (C8H12N)2[ZnCl4], the Zn2+ ion adopts a distorted tetra­hedral coordination geometry. In the crystal, the cations and anions are linked by N—H⋯Cl hydrogen bonds, leading to ribbons propagating parallel to the a axis

Phase control of La2CuO4 in thin-film synthesis

The lanthanum copper oxide, La2CuO4, which is an end member of the prototype high-Tc superconductors (La,Sr)2CuO4 and (La,Ba)2CuO4, crystallizes in the "K2NiF4" structure in high-temperature bulk synthesis. The crystal chemistry, however, predicts that La2CuO4 is at the borderline of the K2NiF4 stability and that it can crystallize in the Nd2CuO4 structure at low synthesis temperatures. In this article we demonstrate that low-temperature thin-film synthesis actually crystallizes La2CuO4 in the Nd2CuO4 structure. We also show that the phase control of "K2NiF4"-type La2CuO4 versus "Nd2CuO4"-type La2CuO4 can be achieved by varying the synthesis temperature and using different substrates.Comment: 4 pages, 5 figures, submitted to PRB, revte

Bis(2-amino-1,3-benzothia­zol-3-ium) tetra­chloridozincate(II)

The asymmetric unit of the title compound, (C7H7N2S)2[ZnCl4], contains a network of 2-amino­benzothia­zolium cations and tetra­hedral [ZnCl4]2− anions. The crystal packing is influenced by cation-to-anion N—H⋯Cl and C—H⋯Cl hydrogen bonds. The [ZnCl4]2− anions have a distorded tetra­hedral geometry. Inter­molecular π–π stacking inter­actions are present between neighboring benzene rings, thia­zole and benzene rings and neighboring thia­zole rings [centroid–centroid distances = 3.711 (2), 3.554 (1), 3.536 (2) and 3.572 (1) Å]

4-(3-Ammonio­prop­yl)morpholin-4-ium tetra­chloridozincate(II)

In the title compound, (C7H18N2O)[ZnCl4], the ZnII ion is coordinated by four Cl atoms in a close to tetra­hedral geometry. The crystal packing exhibits C—H⋯Cl, N—H⋯Cl and N—H⋯O hydrogen bonds

Polymorphism of nanocrystalline TiO2 prepared in a stagnation flame: formation of the TiO2-II phase.

A metastable "high-pressure" phase known as α-PbO2-type TiO2 or TiO2-II is prepared via a single-step synthesis using a laminar premixed stagnation flame. Three other TiO2 polymorphs, namely anatase, rutile and TiO2-B phases, can also be obtained by tuning the oxygen/fuel ratio. TiO2-II is observed as a mixture with rutile under oxygen-lean flame conditions. To the best of our knowledge, this is the first time that this phase has been identified in flame-synthesised TiO2. The formation of TiO2-II in an atmospheric pressure flame cannot be explained thermodynamically and is hypothesised to be kinetically driven through the oxidation and solid-state transformation of a sub-oxide TiO2-x intermediate. In this scenario, rutile is nucleated from the metastable TiO2-II phase instead of directly from a molten/amorphous state. Mixtures containing three-phase heterojunctions of anatase, rutile, and TiO2-II nanoparticles as prepared here in slightly oxygen-lean flames might be important in photocatalysis due to enhanced electron-hole separation