Diffusion-limited Mode Research Articles

Mass transport at gas-evolving electrodes

Direct numerical simulations are utilised to investigate mass-transfer processes at gas-evolving electrodes that experience successive formation and detachment of bubbles. The gas–liquid interface is modelled employing an immersed boundary method. We simulate the growth phase of the bubbles followed by their departure from the electrode surface in order to study the mixing induced by these processes. We find that the growth of the bubbles switches from a diffusion-limited mode at low to moderate fractional bubble coverages of the electrode to a reaction-limited growth dynamics at high coverages. Furthermore, our results indicate that the net transport within the system is governed by the effective buoyancy driving induced by the rising bubbles and that mechanisms commonly subsumed under the term ‘microconvection’ do not significantly affect the mass transport. Consequently, the resulting gas transport for different bubble sizes, current densities and electrode coverages can be collapsed onto one single curve and only depends on an effective Grashof number. The same holds for the mixing of the electrolyte when additionally taking the effect of surface blockage by attached bubbles into account. For the gas transport to the bubble, we find that the relevant Sherwood numbers also collapse onto a single curve when accounting for the driving force of bubble growth, incorporated in an effective Jakob number. Finally, linking the hydrogen transfer rates at the electrode and the bubble interface, an approximate correlation for the gas-evolution efficiency has been established. Taken together, these findings enable us to deduce parametrisations for all response parameters of the systems.

Hexagonal Boron Nitride Growth on Cu-Si Alloy: Morphologies and Large Domains.

Controllable synthesis of high-quality hexagonal boron nitride (h-BN) is desired toward the industrial application of 2D devices based on van der Waals heterostructures. Substantial efforts are devoted to synthesize h-BN on copper through chemical vapor deposition, which has been successfully applied to grow graphene. However, the progress in synthesizing h-BN has been significantly retarded, and it is still challenging to realize millimeter-scale domains and control their morphologies reliably. Here, the nucleation density of h-BN on Cu is successfully reduced by over two orders of magnitude by simply introducing a small amount of silicon, giving rise to large triangular domains with maximum 0.25 mm lateral size. Moreover, the domain morphologies can be modified from needles, tree patterns, and leaf darts to triangles through controlling the growth temperature. The presence of silicon alters the growth mechanism from attachment-limited mode to diffusion-limited mode, leading to dendrite domains that are rarely observed on pure Cu. A phase-field model is utilized to reveal the growing dynamics regarding B-N diffusion, desorption, flux, and reactivity variables, and explain the morphology evolution. The work sheds lights on the h-BN growth toward large single crystals and morphology probabilities.

Shaping particles by chemical diffusion and reaction

Here, we report a general role of chemical diffusion and reaction in shaping particles. It is supposed that chemical diffusion and reaction play a role in shaping particles by changing the chemical distribution around the growth front of particles. Based on this understanding, three growth modes of particles are proposed in this paper, namely, reaction-limited mode, diffusion-limited mode, and reaction–diffusion balance mode. Silver particles are synthesized in different growth modes by various methods. No matter which method is employed, silver particles synthesized in the same mode have similar morphologies. To further generalize diffusion and reaction effects, copper and gold particles are synthesized. The morphological evolution of these two types of particles is similar to that of silver. These results indicate the general role of chemical diffusion and reaction in shaping particles, promising that a regulation on these two kinetic factors is a green and powerful technique for rational synthesis of materials.

Chemical kinetics parameters and model validation for the gasification of PCEA nuclear graphite

A series of gasification experiments, using two right cylinder specimens (∼12.7×25.4mm and 25.4×25.4mm) of PCEA nuclear graphite in ambient airflow, measured the total gasification flux at weight losses up to 41.5% and temperatures (893–1015K) characteristics of those for in-pores gasification Mode (a) and in-pores diffusion-limited Mode (b). The chemical kinetics parameters for the gasification of PCEA graphite are determined using a multi-parameters optimization algorithm from the measurements of the total gasification rate and transient weight loss in experiments. These parameters are: (i) the pre-exponential rate coefficients and the Gaussian distributions and values of specific activation energies for adsorption of oxygen and desorption of CO gas; (ii) the specific activation energy and pre-exponential rate coefficient for the breakup of stable un-dissociated C(O2) oxygen radicals to form stable (CO) complexes; (iii) the specific activation energy and pre-exponential coefficient for desorption of CO2 gas and; (iv) the initial surface area of reactive free sites per unit mass. This area is consistently 13.5% higher than that for nuclear graphite grades of NBG-25 and IG-110 and decreases inversely proportional with the square root of the initial mass of the graphite specimens in the experiments. Experimental measurements successfully validate the chemical-reactions kinetics model that calculates continuous Arrhenius curves of the total gasification flux and the production rates of CO and CO2 gases. The model results at different total weight losses agree well with measurements and expand beyond the temperatures in the experiments to the diffusion-limited mode of gasification. Also calculated are the production rates of CO and CO2 gases and their relative contributions to the total gasification rate in the experiments as functions of temperature, for total weight losses of 5% and 10%.

Catalytic enhancement of SnO2 gas sensors as seen by the moving gas outlet method

Abstract The moving gas outlet technique was employed to determine the transient and steady-state response behaviour of nano-crystalline SnO2 gas sensors. We find that the temperature dependence of the response and recovery time constants to reactive gases follow an Arrhenius-type behaviour of the form τ(T) = τ0 exp(Ea/kBT) with the activation energies Ea being lowered by catalytic activation. We further find that the catalyst-induced lowering of Ea is partly compensated by an increase in the prefactor τ0. Using the moving gas outlet technique in a stationary mode we further find that in the normal diffusion-limited mode of sensor operation the gas sensitivity of metal oxide gas sensors is not solely determined by the speed of the detection reactions at the sensor surface but also by the diffusive transport of gas species through a thin stagnant layer of air that forms at the sensor surface as a result of the sensor heating.

Investigation of Evaporation and Diffusion Phenomena in Porous Media

Many industrial and biological phenomena involve the evaporation of liquids in porous media. In drying processes the evaporation of a liquid meniscus from the solid is the key mechanism in the process and its efficiency. After a first steady stage of evaporation the meniscus becomes unsteady and recedes inside the pore. Diffusion of vapour becomes the controlling mechanism for evaporation in a later stage. In this work an experimental investigation is undertaken to study the various stages of evaporation of different liquids in capillary tubes (pores) of various sizes. The analysis of the data obtained from this investigation reveals some interesting behaviours and emphasizes the role played by vapour diffusion in the case of unsteady interface. The preliminary transient regime allowing the thermal field establishment, is followed by the first stage of evaporation is found to be dominated by thermocapillary effects associated with non-uniform evaporation and temperature gradients. The laste stage is a molecular diffusion-limited mode. The liquid volatility and the effect of the size of the tube (ranging from 200 to 900 μm) are also analysed to show the interaction between the various effects at different scales.

Surface structures on titanium dioxide electrodes after electrochemical silver deposition

Selective silver deposition on the surface of titanium dioxide electrodes provides the possibility to create various structures due to the adjustment of deposition conditions: type of TiO 2 film, current density, external UV-irradiation or modification by the predeposition of silver particles. We observed the formation of ultrafine Ag under small current and fractal deposits under the diffusion-limited mode. Features of the Ag state on the electrodes are studied by TEM, STM, and XPS. The selectivity effect of the deposition is explained by the formation of a specific AgTiO 2 structure with strong metal-support interaction.