Desorption Flux Research Articles

Blistering and hydrogen retention in poly- and single- crystals of aluminum by a joint experimental-modeling approach

Abstract Aluminum samples have been exposed to a hydrogen plasma generated by a low-pressure – high-density microwave reactor. Aluminum has been chosen as a surrogate for Beryllium. The fluence was kept below 4 × 1024 ions/m2, in order to study the first steps of nucleation and growth of surface and bulk defects, i.e. blisters and bubbles. Experimental analyzes and macroscopic rate equation (MRE) modeling on poly- and single- crystals were made to investigate the role played by grains boundaries in the hydrogen retention. Temperature programmed desorption (TPD) on Al poly-crystals revealed the production of aluminum hydrides (alanes) as majority species in the desorption flux. Comparison of microscopy observations for three different single-crystal orientations (〈100〉, 〈110〉 and 〈111〉) allowed to determine preferential orientations able to attenuate the formation of blisters.

Spatial and Temporal Variability of the Transformation of Dissolved Matter Runoff in the Mezen River Estuary

Spatial and temporal variability of the transformation of dissolved matter runoff in the Mezen’ River estuary is studied by results of the complex hydrological-hydrochemical researches lead in 2009 and 2015. The conservative behavior of major ions and dissolved forms of Li, Rb, Cs, Sr, B, F, As, Sb, and Mo is demonstrated. The additional input into solution reaching 93 and 32–38% of content in the river water mass is determined for phosphates and silicon. This is caused, apparently, by mobilization of these nutrients from pore waters of regularly tide-stirred bottom sediments and vertical mixing of the water column. The desorption flux of barium and uranium due to long-term interaction of terrigenic material with saline waters exceeded their input with a continental runoff reaching 180–380 and 90–150% of content of these elements in the river waters. Up to 50, 43, 29, 32, 44, 50, and 45% of Fe, Pb, Y, La, Ce, Pr, and Nd supplying with river runoff which are present in the form of strong organic complexes are removed from solution at the beginning of the mixing zone due to coagulation of colloids. It is drawn a conclusion on spatial homogeneity and long-term stability of transformation features of dissolved matter runoff in the Mezen’ River estuary. Peculiar characteristic of migration of dissolved phosphates, silicon, barium, and uranium are caused by hydrological features of the estuary.

Autophoresis of two adsorbing/desorbing particles in an electrolyte solution

Classical diffusiophoresis describes the motion of particles in an electrolyte or non-electrolyte solution with an imposed concentration gradient. We investigate the autophoresis of two particles in an electrolyte solution where the concentration gradient is produced by either adsorption or desorption of ions at the particle surfaces. We find that when the sorption fluxes are large, the ion concentration near the particle surfaces, and consequently the Debye length, is strongly modified, resulting in a nonlinear dependence of the phoretic speed on the sorption flux. In particular, we show that the phoretic velocity saturates at a finite value for large desorption fluxes, but depends superlinearly on the flux for adsorption fluxes, where both conclusions are in contrast with previous results that predict a linear relationship between autophoretic velocity and sorption flux. Our theory can also be applied to precipitation/dissolution and other surface chemical processes.

Fouling formation in membrane contactors for methane recovery from anaerobic effluents

Fouling in membrane contactors for recovery of dissolved methane (CH4) was investigated in this work. Two types of effluents from anaerobic membrane bioreactor (AnMBR) and upflow anaerobic sludge blanket (UASB) were tested under a continuous operational mode. Due to the higher fouling propensity of the UASB effluent, membrane fouling was more drastic, leading to a greater decline in the CH4 desorption flux with respect to the operational time. Also, the flux was observed to be influenced by the gas-liquid contact time and declined more severely with increasing liquid velocity. Membrane characterization revealed cake layer formation as the source of membrane fouling while foulants characterization indicated that the majority of the foulants were protein-like-substances with fluorescence spectra showing signals close to that of extracellular polymeric substances. On this basis, a mass transfer analysis was performed to understand the fouling resistance exerted by the cake layer and identify a parameter which best described the fouling mechanism. It was found that cake thickness can be used to express the change in fouling resistance in the case of the AnMBR effluent, while cake porosity was a better parameter in the case of the UASB effluent.

Regeneration of СO2 Physical Solvents at Elevated Pressures in Gas-Liquid Membrane Contactor

In the present work, a membrane contactor with asymmetric flat-sheet poly(vinyltrimethylsilane) (PVTMS) membranes was proposed for the CO2 desorption process from physical solvents at elevated trans-membrane pressures. Different solvents were studied: water, a mixture of polyethylene glycol dimethyl ethers (Genosorb® tradename, Selexol process) and a number of ionic liquids (ILs). The compatibility of PVTMS with physical solvents was evaluated. Thorough sorption and swelling degree tests, FTIR experiments, and solvent permeation study provided insights into PVTMS-solvent interaction and allowed the selection of water, Genosorb® and 1-ethyl-3-methylimidazolium tetrafluoroborate ([Emim][BF4]) as demo solvents for proof-of-concept. CO2 desorption experiments were successfully realized at elevated trans-membrane pressure (10 bar) and different temperatures (30 and 50oC). Increasing the temperature from 30 tо 50oС allowed obtaining higher CO2 desorption flux for all studied solvents. The combination of such parameters as CO2 flux (up to 4.5 m3 (STP)/(m2.h)) and the pressure difference between gas and liquid phases (up to 10 bar) is the best among the available literature data. The detailed investigation of [Emim][BF4] possessing the highest CO2 flux revealed that an increase of CO2 content in [Emim][BF4] provided by increasing absorption pressure up to 20 bar resulted in a signifcant CO2 desorption flux growth up to 7.5 m3 (STP)/(m2.h). Finally, the SEM and EDXS study of membranes after CO2 desorption tests revealed the deposition of particles containing Na and F elements from ionic liquid [Emim][BF4] on the membrane surface. Nevertheless, the same study proved the stability of the membrane morphology structure at elevated transmembrane pressures even up to 20 bar.

Microstructural evolution of 3C-SiC exposed to simultaneous neutron irradiation and helium implantation

The synergism of transmutant helium and irradiation defects is critically important to understand the performance of SiC when in service in nuclear environments. In this study, we exposed 3C-SiC in contact with a 2 μm Ni foil to neutron irradiation at 500 °C to 29 dpa in the high flux isotope reactor to simulate the simultaneous introduction of helium and irradiation defects into SiC. The combination of TEM observations and thermal desorption measurements helps to elucidate the impact of helium on the microstructural evolution in 3C-SiC. Thermal helium desorption spectra from ion-implanted and neutron-irradiated SiC showed a completely different desorption behavior in terms of the peak position and helium desorption flux. The identification of possible helium trapping sites was attempted by applying the first order dissociation model to the measured thermal helium desorption spectra. TEM observations of the neutron-irradiated samples showed that the presence of helium facilitated the stabilization of the defect clusters and promoted the formation of visible helium bubbles in SiC subject to simultaneous neutron irradiation and in-situ He implantation. Following the subsequent heat treatment during the thermal desorption measurements, large faceted helium bubbles were found along grain boundaries in the neutron-irradiated SiC with in-situ He implantation, while the helium bubbles in the grain interior were relatively smaller than those found in the neutron-irradiated sample without in-situ He implantation due to the reduced mobility of He-defect clusters. The He contents contained in the neutron-irradiated samples were quantified based on the experimental data from TEM and thermal desorption measurements.

CO2 desorption from activated DEA using membrane contactor with vacuum regeneration technology

Carbondioxide (CO2) content in natural gas must be removed because it inhibits liquefication process of natural gas. CO2 gas separation technology using membrane contactor has been developed, however solvent regeneration using membrane contactors are still rare because it requires a larger energy. The regeneration process by using membrane vacuum technology was put forward to reduce the regeneration energy consumption. In this work, arginine, piperazine (PZ), and potassium carbonate (K2CO3) as activators were added into diethanolamine (DEA) solution to form aqueous solutions of activated DEA. The experiment of CO2 desorption from activated DEA was carried out in hollow fibre membrane contactor (HFMC). The solvent with rich CO2 at 30-70°C was flowed in the lumen of the hydrophobic polypropylene HFMC, and the shell side was maintained at a reduced pressure by a vacuum pump at 20 kPa. The effect of solvent temperature and activators were investigated to get CO2 desorption flux and regeneration efficiency. Experimental result shows that increasing of solvent temperature could enhance CO2 desorption flux and regeneration efficiency. Instead of that, the activated DEA also give better result compared with non-activated DEA. Among three activators, K2CO3 give the best result for desorption flux and regeneration efficiency.

Functional differential equations of neutral type with integrable weak singularity: hydrogen thermal desorption model

One of the technological challenges for hydrogen materials science (including the ITER project) is the currently active search for structural materials with various potential applications that will have predetermined limits of hydrogen permeability. One of the experimental methods is thermal desorption spectrometry (TDS). A hydrogen-saturated sample is degassed under vacuum and monotone heating. The desorption flux is measured by mass spectrometer to determine the character of interactions of hydrogen isotopes with the solid. We are interested in such transfer parameters as the coefficients of diffusion, dissolution, desorption. The paper presents a thermal desorption functional differential equations of neutral type with integrable weak singularity and a numerical method for TDS spectrum simulation, where only integration of a nonlinear system of low order ordinary differential equations (ODE) is required. This work is supported by the Russian Foundation for Basic Research (project 15-01-00744).

INVERSE PROBLEM OF IDENTIFICATION OF HYDROGEN THERMODESORPTION SPECTRA

One of the technological challenges for hydrogen materials science (including the ITER project) is the currently active search for structural materials with various potential applications that will have predetermined limits of hydrogen permeability. One of the experimental methods is thermal desorption spectrometry (TDS). A hydrogen-saturated sample is degassed under vacuum and monotone heating. The desorption flux is measured by mass spectrometer to determine the character of interactions of hydrogen isotopes with the solid. The paper presents a distributed boundary-value problem of thermal desorption with dynamical boundary conditions and a numerical method for TDS spectrum simulation, where only integration of a nonlinear system of low order (compared with, e.g., the method of lines) ordinary differential equations (ODE) is required. It has been suggested dissolution and desorption coefficients estimation method in a real dynamic interaction of surface and diffusion processes without the artificial division of studies into diffusion limited regime (DLR) and surface limited regime (SLR). This work is supported by the Russian Foundation for Basic Research (project № 15-01-00744).

Optical control of surface forces and instabilities in foam films using photosurfactants.

Molecular interactions in thin liquid films, such as the disjoining pressure, are involved in interfacial phenomena such as emulsion and foam stabilization. In this article we show that through light stimulation we can control remotely the disjoining pressure in a thin liquid film stabilized by a photosurfactant. We stabilize a horizontal thin liquid film using a cationic photosurfactant, AzoTAB, bearing an azobenzene moiety on the hydrophobic tail which can switch from a trans to a cis conformation upon light stimulation. As the film is illuminated at specific wavelengths the AzoTAB molecules switch continuously their conformation and consequently their interface affinity. The main consequence of stimulating the film with light is increasing the ratio of cis in the film. This provokes a desorption flux, and an increase in the concentration of free surfactants, as the CMC of the cis isomer is higher than that of the trans isomer. Therefore the electrostatic repulsion between the surfactant layers that stabilize the film decreases, inducing an instability in the film thickness. For films with a thickness between 20 nm and 60 nm, we observe the formation of spherical caps up to 100 μm wide, whose shape is controlled by the competition between surface tension and disjoining pressure. The motion of these caps in the film is restrained by the surface viscosity of the surfactant layers. In addition, for thicknesses below 40 nm and depending on light intensity, we can observe flat stratified islands up to 100 μm wide, with thickness steps corresponding to the size of a surfactant micelle. We suggest that this second instability is due to the oscillation of the disjoining pressure isotherm under light.

Surface modification and deuterium retention in reduced-activation steels under low-energy deuterium plasma exposure. Part I: undamaged steels

In this paper, reduced-activation ferritic/martensitic (RAFM) steels including Eurofer (9Cr) and oxide dispersion strengthening (ODS) steels by the addition of Y2O3 particles with different amounts of Cr, namely, (9-16)Cr were exposed to low energy deuterium (D) plasma (~20–200 eV per D) up to a fluence of 2.9 × 1025 D m−2 in the temperature range from 290 K to 700 K. The depth profile of D in steels was measured up to 8 µm depth by nuclear reaction analysis (NRA) and the total retained amount of D in those materials was determined by thermal desorption spectroscopy (TDS). It was found that the D retention in ODS steels is higher compared to Eurofer due to the much higher density of fine dispersoids and finer grain size. This work shows that in addition to the sintering temperature and time, the type, size and concentration of the doping particles have an enormous effect on the increase in the D retention. The D retention in undamaged ODS steels strongly depends on the Cr content: ODS with 12Cr has a minimum and the D retention in the case of ODS with (14-16)Cr is higher compared to (9-12)Cr. The replacing of Ti by Al in ODS-14Cr steels reduces the D retention. The formation of nano-structure surface roughness enriched in W or Ta due to combination of preferential sputtering of light elements and radiation-induced segregation was observed at incident D ion energy of 200 eV for both Eurofer and ODS steels. Both the surface roughness and the eroded layer enhance with increasing the temperature. The surface modifications result in a reduction of the D retention near the surface due to increasing the desorption flux and can reduce the overall D retention.

Computer simulation of hydrogen thermal desorption by ODE-approximation

One of the technological challenges for hydrogen materials science (including ITER project) is the currently active search for structural materials with various potential applications that will have predetermined limits of hydrogen permeability. One of the experimental methods is thermal desorption spectrometry (TDS). A hydrogen-saturated sample is degassed under vacuum and monotone heating. The desorption flux is measured by mass spectrometer to determine the character of interactions of hydrogen isotopes with the solid. We are interested in such transfer parameters as the coefficients of diffusion, dissolution, desorption. The paper presents a distributed boundary value problem of thermal desorption and a numerical method for TDS-spectrum simulation, where only integration of a non-linear system of low order (compared with, e.g., the method of lines) ordinary differential equations (ODE) is required. The results of computer simulation are presented.

Modelling of hydrogen thermal desorption spectrum in nonlinear dynamical boundary-value problem

One of the technological challenges for hydrogen materials science (including the ITER project) is the currently active search for structural materials with various potential applications that will have predetermined limits of hydrogen permeability. One of the experimental methods is thermal desorption spectrometry (TDS). A hydrogen-saturated sample is degassed under vacuum and monotone heating. The desorption flux is measured by mass spectrometer to determine the character of interactions of hydrogen isotopes with the solid. We are interested in such transfer parameters as the coefficients of diffusion, dissolution, desorption. The paper presents a distributed boundary-value problem of thermal desorption and a numerical method for TDS spectrum simulation, where only integration of a nonlinear system of low order (compared with, e.g., the method of lines) ordinary differential equations (ODE) is required. This work is supported by the Russian Foundation for Basic Research (project 15-01-00744).

Approximation of the boundary-value problem of hydrogen thermal desorption by ODE system: convergence acceleration

One of the technological challenges for hydrogen materials science (including ITER project) is the currently active search for structural materials with various potential applications that will have predetermined limits of hydrogen permeability. One of~the experimental methods is thermodesorption spectrometry (TDS). A hydrogen-saturated sample is degassed under vacuum and monotone heating. The desorption flux is measured by mass spectrometer to determine the character of interactions of~hydrogen isotopes with the solid. We are interested in such transfer parameters as the coefficients of diffusion, dissolution, desorption. The paper presents a distributed boundary value problem of thermal desorption and a numerical method for TDS-spectrum simulation, where only integration of a non-linear system of low order ordinary differential equations (ODE) is required. The method of convergence acceleration based on the allocation of integrable weak singularity is explained. This work is supported by the Russian Foundation for Basic Research (project 15-01-00744).

Numerical analysis of TDS spectra under high and low flux plasma exposure conditions

A recently developed numerical model, based on the dislocation-driven nucleation of gas bubbles, is used to analyse experimental results on deuterium retention in tungsten under ITER relevant plasma exposure conditions. Focus is placed on understanding the relation between exposure temperature and flux on primary features of thermal desorption spectra: peak positions and intensities of the desorption flux. The model allows one to relate the peak positions with the size of plasma induced deuterium bubbles and envisage exposure conditions (temperature and flux) for their formation. Based on the performed analysis, dedicated experimental conditions to validate the model are proposed.

CO<sub>2</sub> Desorption by Hydrophilic PTFE Hollow Fiber Membranes via a Membrane Flash Process

In this study, hydrophilic PTFE hollow fiber membranes were prepared and applied for CO2 desorption via a membrane flash process, which is a new CO2 desorption process by utilizing waste thermal energy. The methyldiethanolamine was selected as the absorbent. Effects of the flashing temperature, flashing pressure, rich solution flow rate and MDEA concentration on CO2 release ratio and CO2 desorption flux were deeply investigated. The results show that flashing temperature is positive to the CO2 release ratio and CO2 desorption flux. However, the flashing pressure, rich solution flow rate and MDEA concentration are negative to the CO2 release ratio and CO2 desorption flux.

Catastrophe in diffusion-controlled annihilation dynamics: general scaling properties

We present a systematic analytical and numerical study of the annihilation catastrophe phenomenon which develops in an open system, where species A and B diffuse from the bulk of restricted medium and die on its surface (desorb) by the reaction A + B → 0. This phenomenon arises in the diffusion-controlled limit as a result of self-organizing explosive growth (drop) of the surface concentrations of, respectively, slow and fast particles (concentration explosion) and manifests itself in the form of an abrupt singular jump of the desorption flux relaxation rate. In the recent work [B.M. Shipilevsky, Phys. Rev. E 76, 031126 (2007)] a closed scaling theory of catastrophe development has been given for the asymptotic limit when the characteristic time scale of explosion becomes much less than the characteristic time scales of diffusion of slow and fast particles at an arbitrary ratio of their diffusivities 0 < p < 1. In this paper we consider the behavior of the system at strong difference of species diffusivities p ≪ 1 and reveal a rich general pattern of catastrophe development for an arbitrary ratio of the characteristic time scales of explosion and fast particle diffusion. As striking results we find remarkable scaling properties of catastrophe evolution at the crossover between two limiting regimes with radically different dynamics.

Approximation of the boundary-value problem of hydrogen thermal desorption by ODE system

One of the technological challenges for hydrogen materials science (including ITER project) is the currently active search for structural materials with various potential applications that will have predetermined limits of hydrogen permeability. One of the experimental methods is thermodesorption spectrometry (TDS). A hydrogensaturated sample is degassed under vacuum and monotone heating. The desorption flux is measured by mass spectrometer to determine the character of interactions of hydrogen isotopes with the solid. We are interested in such transfer parameters as the coefficients of diffusion, dissolution, desorption. The paper presents a distributed boundary value problem of thermal desorption and a numerical method for TDSspectrum simulation, where only integration of a non-linear system of low order (compared with, e. g., the method of lines) ordinary differential equations (ODE) is required. This work is supported by the Russian Foundation for Basic Research (project N15-01-00744).

Longitudinal estimates of sediment-water diffusive flux of PCB congeners in the Houston Ship Channel

Sediment-water diffusive exchange fluxes were estimated for PCB congeners between 2002 and 2012 for the Houston Ship Channel in Texas. These estimations were determined for four different sampling periods representing a unique effort to quantify fluxes, their magnitudes and variability, over a longer time period than similar studies. Total PCB fluxes, on the order of 0.10–250 μg/m2-yr, were most dependent on bulk sediment and total water concentrations and the partitioning models used. Diffusive flux directions were highly variable on a single-PCB analyte basis though they were generally sediment-to-water or indeterminate. Sediment concentrations from after Hurricane Ike (September 2008) were highly elevated (median increase 360%) from immediately before the event leading to much higher diffusive flux estimates. Lastly, sediment-water diffusive flux was 2–3 orders of magnitude less than net deposition and associated desorption fluxes leading to the possibility that burial would eventually lower the sediment impact to the estuary. This is, however, uncertain because depositing sediment still had elevated PCB concentrations.

Thermal desorption spectroscopy from the surfaces of metal-oxide-semiconductor nanostructures.

An experimental setup, which combines direct heating and temperature measurement of metal nanofilms allowing temperature programmed desorption experiments is described. This setup enables the simultaneous monitoring of the thermal desorption flux from the surface of chemi-electric devices and detection of chemically induced hot charge carriers under UHV conditions. This method is demonstrated for the case of water desorption from a Pt/SiO2-n-Si metal-oxide-semiconductor nanostructure.