Theory of membrane capacitive deionization including the effect of the electrode pore space

Membrane capacitive deionization (MCDI) is a technology for water desalination based on applying an electrical field between two oppositely placed porous electrodes. Ions are removed from the water flowing through a channel in between the electrodes and are stored inside the electrodes. Ion-exchange membranes are placed in front of the electrodes allowing for counterion transfer from the channel into the electrode, while retaining the coions inside the electrode structure. We set up an extended theory for MCDI which includes in the description for the porous electrodes not only the electrostatic double layers (EDLs) formed inside the porous (carbon) particles, but also incorporates the role of the transport pathways in the electrode, i.e., the interparticle pore space. Because in MCDI the coions are inhibited from leaving the electrode region, the interparticle porosity becomes available as a reservoir to store salt, thereby increasing the total salt storage capacity of the porous electrode. A second advantage of MCDI is that during ion desorption (ion release) the voltage can be reversed. In that case the interparticle porosity can be depleted of counterions, thereby increasing the salt uptake capacity and rate in the next cycle. In this work, we compare both experimentally and theoretically adsorption/desorption cycles of MCDI for desorption at zero voltage as well as for reversed voltage, and compare with results for CDI. To describe the EDL-structure a novel modified Donnan model is proposed valid for small pores relative to the Debye length

Attractive forces in microporous carbon electrodes for capacitive deionization

The recently developed modified Donnan (mD) model provides a simple and useful description of the electrical double layer in microporous carbon electrodes, suitable for incorporation in porous electrode theory. By postulating an attractive excess chemical potential for each ion in the micropores that is inversely proportional to the total ion concentration, we show that experimental data for capacitive deionization (CDI) can be accurately predicted over a wide range of applied voltages and salt concentrations. Since the ion spacing and Bjerrum length are each comparable to the micropore size (few nm), we postulate that the attraction results from fluctuating bare Coulomb interactions between individual ions and the metallic pore surfaces (image forces) that are not captured by meanfield theories, such as the Poisson-Boltzmann-Stern model or its mathematical limit for overlapping double layers, the Donnan model. Using reasonable estimates of the micropore permittivity and mean size (and no other fitting parameters), we propose a simple theory that predicts the attractive chemical potential inferred from experiments. As additional evidence for attractive forces, we present data for salt adsorption in uncharged microporous carbons, also predicted by the theory.Comment: 19 page

Performance Metrics for the Objective Assessment of Capacitive Deionization Systems

In the growing field of capacitive deionization (CDI), a number of performance metrics have emerged to describe the desalination process. Unfortunately, the separation conditions under which these metrics are measured are often not specified, resulting in optimal performance at minimal removal. Here we outline a system of performance metrics and reporting conditions that resolves this issue. Our proposed system is based on volumetric energy consumption (Wh/m$^3$) and throughput productivity (L/h/m$^2$) reported for a specific average concentration reduction, water recovery, and feed salinity. To facilitate and rationalize comparisons between devices, materials, and operation modes, we propose a nominal standard testing condition of removing 5 mM from a 20 mM NaCl feed solution at 50% water recovery for CDI research. Using this separation, we compare the desalination performance of a flow-through electrode (fte-CDI) cell and a flow between membrane (fb-MCDI) device, showing how significantly different systems can be compared in terms of generally desirable desalination characteristics. In general, we find that performance analysis must be considered carefully so to not allow for ambiguous separation conditions or the maximization of one metric at the expense of another. Additionally, for context we discuss a number of important underlying performance indicators and cell characteristics that are not performance measures in and of themselves but can be examined to better understand differences in performance

Effect of Added Nitrogen on Properties of SiCN Films Prepared by PECVD Using Hexamethyldisilazane

Silicon carbonitride thin films were obtained by plasma-enhanced chemical vapor deposition using native precursor hexamethyldisilazane with a nitrogen addition. Films were investigated by X-ray diffraction spectroscopy, Fourier transform infrared spectroscopy and nanoindentation. It is established that all the films were X-ray amorphous. An increase in nitrogen flow rate leads to increasing the number of Si-N bonds, which, in turn, promotes the rise of nanohardness and elastic modulus up to 20 GPa and 160 GPa, respectively. The optimum deposition parameters were established. The films can be recommended as hard coatings for strengthening cutting tools. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3532

Non-specific abdominal pain and air pollution: a novel association.

We studied whether short-term exposure to air pollution was associated with non-specific abdominal pain in epidemiologic and animal studies. Patients visiting the emergency department with non-specific abdominal pain were identified in Edmonton (1992 to 2002, n = 95,173) and Montreal (1997 to 2002, n = 25,852). We calculated the daily concentrations for ozone (O(3)), nitrogen dioxide (NO(2)), sulfur dioxide (SO(2)), carbon monoxide (CO), and particles <10 (PM(10)) or <2.5 (PM(2.5)) µm. A case crossover study design was used to estimate the odds ratio (OR) and 95% confidence interval (CI) associated with an increase in the interquartile range of the air pollutants. We investigated differential effects by age and sex. Mice were gavaged with urban particle extracts. In animal models, colonic motility was tested, and visceral abdominal pain was measured using a writhing test, and behavioral response to oil of mustard and neostigmine. Motility and pain was measured acutely (1.5 hours after gavage) and chronically (7-days and 21-days after gavage). Emergency department visits for non-specific abdominal pain were primarily by women between the ages of 15-24 years. Individuals aged 15 to 24 years were at increased risk of non-specific abdominal pain in Edmonton (same day CO: OR = 1.04, 95% CI = 1.02-1.06; and NO(2): OR = 1.06, 95% CI = 1.03-1.09). The risk of air pollution among 15-24 year olds in Montreal was significantly positive (same day CO: OR = 1.11, 95% CI = 1.05-1.17; NO(2): OR = 1.09, 95% CI = 1.01-1.16; SO(2): OR = 1.17, 95% CI = 1.10-1.25; PM(2.5): OR = 1.09, 95% CI = 1.04-1.15). Abdominal pain was increased by an acute gavage of pollution extract but not to chronic exposure to pollutants. Colonic transit was delayed following chronic but not acute exposure with the pollutants. Epidemiological and animal data suggest that short-term exposure to air pollution may trigger non-specific abdominal pain in young individuals

On the potential vegetation feedbacks that enhance phosphorus availability &ndash; insights from a process-based model linking geological and ecological timescales

In old and heavily weathered soils, the availability of P might be so small that the primary production of plants is limited. However, plants have evolved several mechanisms to actively take up P from the soil or mine it to overcome this limitation. These mechanisms involve the active uptake of P mediated by mycorrhiza, biotic de-occlusion through root clusters, and the biotic enhancement of weathering through root exudation. The objective of this paper is to investigate how and where these processes contribute to alleviate P limitation on primary productivity. To do so, we propose a process-based model accounting for the major processes of the carbon, water, and P cycles including chemical weathering at the global scale. Implementing P limitation on biomass synthesis allows the assessment of the efficiencies of biomass production across different ecosystems. We use simulation experiments to assess the relative importance of the different uptake mechanisms to alleviate P limitation on biomass production. We find that active P uptake is an essential mechanism for sustaining P availability on long timescales, whereas biotic de-occlusion might serve as a buffer on timescales shorter than 10 000 yr. Although active P uptake is essential for reducing P losses by leaching, humid lowland soils reach P limitation after around 100 000 yr of soil evolution. Given the generalized modelling framework, our model results compare reasonably with observed or independently estimated patterns and ranges of P concentrations in soils and vegetation. Furthermore, our simulations suggest that P limitation might be an important driver of biomass production efficiency (the fraction of the gross primary productivity used for biomass growth), and that vegetation on old soils has a smaller biomass production rate when P becomes limiting. With this study, we provide a theoretical basis for investigating the responses of terrestrial ecosystems to P availability linking geological and ecological timescales under different environmental settings