Measured Concentration Profiles Research Articles

Concentration Profile Measurements Near the Anode during Lithium Metal Dissolution in Highly Concentrated Electrolyte

In recent years, highly concentrated electrolytes (HCEs) have been attracting attention as electrolytes for next-generation batteries. Lithium metal is used as an anode in next-generation batteries such as lithium-sulfur batteries, and it is important to clarify the deposition and dissolution mechanisms in HCEs. In this study, the concentration profile near the anode and the coordination state surrounding lithium ions were in-situ measured by a laser interferometer and Raman spectroscopy during lithium dissolution in the Sulfolane-based HCE.

Gel network amplifies Nano-Scale adsorption at Solid/Liquid interface to Sub-Millimeter-Scale

HypothesisWe have proposed a spreading-flow model of the solvent movement in a gel, which states that the solvent flows along the gel network segment much easier than in any other direction. An excess amount of the solvent component adsorbed on a flat solid surface in a gel will be transferred over the macroscopic gel network by the spreading-flow. Then, by measuring the concentration distribution of each solvent near the solid surface at the sub-millimeter scale, it should be possible to evaluate adsorption occurring on the nanometer scale. ExperimentsConfocal Raman microscopy was employed to map the concentration distributions of mixed solvents of p-xylene, mesitylene, and octanenitrile gelled by 12-hydroxystearic acid near the atomically flat mica surface. The measured concentration profiles were analyzed by the spreading-flow theory to construct adsorption isotherms. FindingsNearly all isotherms follow power laws with similar exponents, which is consistent with the van der Waals multilayer adsorption with weak adsorbate-adsorbent interactions. The present study demonstrates the concept of gel network amplification and its usefulness for probing nano-phenomena using macro-technology.

Suspended Sediment‐Induced Stratification Inferred From Concentration and Velocity Profile Measurements in the Lower Yellow River, China

AbstractDespite a multitude of models predicting sediment transport dynamics in open‐channel flow, self‐organized vertical density stratification that dampens flow turbulence due to the interaction between fluid and sediment has not been robustly validated with field observations from natural rivers. Turbulence‐suppressing density stratification can develop in channels with low channel‐bed slope and high sediment concentration. As the Yellow River, China, maintains one of the highest sediment loads in the world for a low sloping system, this location is ideal for documenting particle and fluid interactions that give rise to density stratification. Herein, we present analyses from a study conducted over a range of discharge conditions (e.g., low flow, rising limb, and flood peak) from a lower reach of the Yellow River, whereby water samples were collected at targeted depths to measure sediment concentration and, simultaneously, velocity measurements were collected throughout the flow depth. Importantly, sediment concentration varied by an order of magnitude between base and flood flows. By comparing measured concentration and velocity profiles to predictive models, we show that the magnitude of density stratification increases with sediment concentration. Furthermore, a steady‐state calculation of sediment suspension is used to determine that sediment diffusivity increases with grain size. Finally, we calculate concentration and velocity profiles, showing that steady‐state sediment suspensions are reliably predicted over a range of stratification conditions larger than had been previously documented in natural river flows. We determine that the magnitude of density stratification can be predicted by a function considering an entrainment parameter, sediment concentration, and bed slope.

Composition-dependent interdiffusivity matrices of ordered bcc_B2 phase in ternary Ni–Al–Ru system at 1273∼1473 K

Abstract In this paper, 5 Ni–Al–Ru ternary and 2 NiAl/RuAl binary equilibrium alloys were prepared, and their lattice parameters were evaluated by using the X-ray diffraction technique. The relation between the lattice parameters and Ru content satisfies Vegard’s law, confirming that a continuous single bcc_B2 phase exists between NiAl and RuAl in the ternary Ni–Al–Ru system. After that, three diffusion couples located in the bcc_B2 phase region were prepared at 1273, 1373 and 1473 K, respectively. With the presently measured concentration profiles, the composition-dependent interdiffusivity matrices along the entire diffusion paths were efficiently determined by using the High-throughput Determination of Interdiffusion Coefficients (HitDIC) software. The obtained interdiffusivities show a good agreement with the limited experimental data in the literature. Furthermore, the present results show that the addition of Ru to bcc_B2 NiAl alloys can significantly inhibit the interdiffusion rate of Ni, indicating that the bcc_B2 Ru-containing NiAl bond coats can serve as a potential diffusion barrier for Ni-based superalloy substrate.

Rheology and structure of a suspension of deformable particles in plane Poiseuille flow

We present an experimental study of the rheology and structure of a confined suspension of deformable particles flowing in a quasi-two-dimensional Poiseuille flow. Thanks to a precise microfluidic viscosimetry technique combined with measurements of concentration profiles, our study provides the first experimental confirmation with three-dimensional particles of a strong relationship between structuring effects and rheology, previously only reported in numerical simulations of purely two-dimensional systems. In conditions where strong structuring effects take place due to confinement, the evolution of the effective viscosity with particle concentration (here, red blood cells) shows a remarkable succession of ranges of rapid growth and plateaus that are associated with qualitative transitions in the structure of the suspension.

Concentration and temperature measurements by means of Raman spectroscopy in case of condensation with non-condensable gas

Abstract Condensation in presence of non-condensable gas is safety relevant in case of loss-of-coolant accidents in pressurised water reactors. Non-condensable gas reduces the heat and mass transfer in the vapour phase, especially with low steam velocities. Insufficient heated emergency core cooling water can cause thermal shocks at the reactor pressure vessel for example. Within the scope of a research project supported by the Bundesministerium für Wirtschaft (BMWI) experiments have been performed to study the effect of non condensable gases on direct contact condensation at horizontal stratified steam/water flow. The paper presents the laser-optical measurement technique linear Raman spectroscopy for determination of concentration profiles in the vapour phase and temperature profiles in the liquid phase with high local resolution. The film theory, described in this paper, allows the approximation of these measured concentration profiles and therefore the calculation of local heat and mass transfer. If homogenous condensation occurs, the fog density in the vapour phase can also be estimated by means of Raman spectroscopy. Steady state and transient experiments are presented.

Application of tiny-TIM as a mechanistic tool to investigate the in vitro performance of different itraconazole formulations under physiologically relevant conditions

The increasing number of poorly water-soluble compounds in drug development is one of the major challenges in oral drug delivery nowadays. For rational formulation development, biopharmaceutical tools are needed that closely simulate the conditions present within the human gastrointestinal (GI) tract in order to early predict the potential effect of important factors like meal intake or acid-reducing agents on oral bioavailability. The tiny-TIM system equipped with the advanced gastric compartment is one of the most realistic in vitro models for the simulation of the physiological processes occurring in human stomach and small intestine. In the present study, this model was applied to study the in vitro performance of an ASD-based formulation of itraconazole under different clinically relevant conditions. Apart from the assessment of the bioaccessible fraction (i.e., the fraction available for drug absorption), the implementation of two additional sampling ports enabled the measurement of intraluminal concentration profiles. Along with solubility experiments in biorelevant media, deeper mechanistic insights into drug product performance in different prandial states as well as in case of gastric pH modification could be generated. The comparison of the in vitro data with published in vivo data revealed that the model successfully predicted the effect of food intake as well as of modified gastric pH conditions on the bioavailability of itraconazole from this formulation. In contrast, the negative food effect observed for an oral solution formulation could not be predicted. For this cyclodextrin-based formulation, the formulation effect on permeation needs to be considered. Nonetheless, the data presented in this study showed that tiny-TIM is an interesting tool to mechanistically study the impact of different physiological conditions on drug release from oral drug products.

Experimental investigations on the quinary interdiffusivities in diffusion couples of NiAlCoCr alloy/CoCrFeNi high-entropy alloys

The diffusion couples composed of Ni–Al–Co–Cr alloys and low-entropy (pure Ni, and NiCo, NiCr, and NiCoCr)/medium-entropy (CoCrNi)/high-entropy (CoCrFeNi) alloys were fabricated, and subjected to annealing at 1473 K for 72 h. Their composition profiles were measured by using the electron microprobe analysis technique. By combining the measured concentration profiles and the free-accessible High-throughput Determination of Interdiffusion Coefficients (HitDIC) software, the composition-dependent interdiffusion coefficients in the diffusion couples along the entire diffusion paths were determined in a high-throughput manner. The general relation, D˜CrCrNi>D˜FeFeNi>D˜CoCoNi, exists in most diffusion couples. A comprehensive comparison of the presently interdiffusion coefficients of elements in presently low-, medium- and high-entropy alloys and the available data in the literatures were conducted.

Machine Learning Prediction of the Three Main Input Parameters of a Simplified Physiologically Based Pharmacokinetic Model Subsequently Used to Generate Time-Dependent Plasma Concentration Data in Humans after Oral Doses of 212 Disparate Chemicals.

Physiologically based pharmacokinetic (PBPK) modeling has the potential to play significant roles in estimating internal chemical exposures. The three major PBPK model input parameters (i.e., absorption rate constants, volumes of the systemic circulation, and hepatic intrinsic clearances) were generated in silico for 212 chemicals using machine learning algorithms. These input parameters were calculated based on sets of between 17 and 65 chemical properties that were generated by in silico prediction tools before being processed by machine learning algorithms. The resulting simplified PBPK models were used to estimate plasma concentrations after virtual oral administrations in humans. The estimated absorption rate constants, volumes of the systemic circulation, and hepatic intrinsic clearance values for the 212 test compounds determined traditionally (i.e., based on fitting to measured concentration profiles) and newly estimated had correlation coefficients of 0.65, 0.68, and 0.77 (p < 0.01, n = 212), respectively. When human plasma concentrations were modeled using traditionally determined input parameters and again using in silico estimated input parameters, the two sets of maximum plasma concentrations (r = 0.85, p < 0.01, n = 212) and areas under the curve (r = 0.80, p < 0.01, n = 212) were correlated. Virtual chemical exposure levels in liver and kidney were also estimated using these simplified PBPK models along with human plasma levels. These results indicate that the PBPK model input parameters for humans of a diverse set of compounds can be reliability estimated using chemical descriptors calculated using in silico tools.

Evaporation of Sessile Binary Mixture Droplets: Time Dependence of Droplet Shape and Concentration Profile from One-Dimensional Magnetic Resonance Microscopy.

Many technological applications like inkjet printing, coating, or cooling processes rely on the evaporation of sessile droplets. Regarding liquid mixtures, the understanding of the underlying physics is still incomplete and process optimization requires trial and error. Our main goal is to establish a novel method in this field, one-dimensional magnetic resonance microscopy, to investigate the evaporation of sessile binary mixture droplets in the microliter range. It allows us not only to determine the droplet volume and shape, including contact angle, but also to measure concentration profiles with a spatial resolution of a few micrometers. These capabilities are demonstrated for a mixture of 1-octanol (OCT) and pentadecafluoro-1-octanol (F-OCT) by combining spatially resolved 1H and 19F nuclear magnetic resonance measurements. We clearly observe three evaporation regimes for the OCT/F-OCT mixture. The first and second regimes are characterized by the predominant evaporation of F-OCT and are separated by a depinning event. The third regime starts when no F-OCT is left and, thus, features the evaporation of a pure OCT droplet. During all stages, concentration gradients perpendicular to the substrate are weak in the studied binary droplet.

Numerical Correction of In Situ AFM-SECM Measurements.

Mass-transport-limited catalysis and membrane transport can be characterized by concentration profiles surrounding active surfaces. Scanning electrochemical microscopy (SECM) is a tool that has been used to measure concentration profiles; however, the presence and geometry of the tip can distort these profiles due to hindered diffusion, which in turn alters chemical behavior at the catalytic surface. To fully characterize the behavior of surface features such as catalytic sites, it is essential to account for and analytically remove the effect of tip presence. In this work, atomic force microscopy-based SECM (AFM-SECM) measurements over poly(tetrafluoroethylene) (PTFE) and gold electrode surfaces are used to measure negative and positive-feedback approach curves, respectively. By inversely fitting these approach curves with a finite element method (FEM) model, we derive kinetic and geometric tip parameters that characterize the effect of tip presence. Tip effects may be removed in the model to estimate concentration profiles and reaction properties for the case where no tip is present. A maximum 120% increase in the concentration at one tip radii above the surface is observed due to the presence of the tip, where the concentration field is compressed vertically, in proportion to surface feature size and tip separation. Conical AFM-SECM tips, with a higher ratio of tip height to the base size, introduce less concentration distortion than disk-shaped AFM-SECM tips.

Critical Solutal Marangoni Number Correlation for Short-Scale Convective Instabilities in Drying Poly(vinyl acetate)-Methanol Thin Films.

A new empiric correlation for the critical solutal Marangoni number as function of the Péclet and Schmidt numbers is proposed. It is based on previously published experimental flow field data in drying poly(vinyl acetate)-methanol films with an initial thickness in the range of – and an initial solvent load of to , as well as newly derived concentration profile measurements and 1D drying simulations. The analysis accounts for realistic transient material properties and describes the occurrence of short-scale convective Marangoni (in)stabilities during the entire drying process with an accuracy of 9%. In addition, the proposed correlation qualitatively follows trends known from theory. As convective Marangoni instabilities in drying polymer films may induce surface deformations, which persist in the dry film, the correlation may facilitate future process design for either thin films with uniform thickness or deliberate self-assembly.

Formation and growth behavior of intermetallic compound phases in the interfacial reaction of solid Fe / liquid Zn at 450 °C

In the present study, the formation and growth behaviors of intermetallic compound (IMC) layers in the interfacial reaction of solid Fe and molten Zn during hot dipping at 450 °C were investigated. In the early stage of the interfacial reaction, Γ-Fe4Zn9, δ1k-FeZn7, and ζ-FeZn13 phases were formed, among which the growth of the ζ layer was dominant. Columns of the δ1p-Fe13Zn126 phase were formed on the δ1k/ζ interface at approximately 90 s, and the four IMC layers grew simultaneously until 600 s. Subsequently, a layer of the Γ1-Fe21.2Zn80.8 phase was formed along the Γ/δ1k interface and started growing, after which all the equilibrium IMC phases of Γ/Γ1/δ1k/δ1p/ζ grew competitively. The total thickness of the five IMC layers, dtotal, increased proportionally with the square root of the reaction time, t, i.e., dtotal = d0t0.5, which suggested that the growth of the entire IMC layers was controlled by the volume diffusion. However, the values of the time exponent, n, for the individual IMC layers differed depending on their microstructures and chemical concentrations, under equilibrium or nonequilibrium conditions. The formation of the multilayered columnar ζ phase can be attributed to the heterogeneous supersaturation of Fe in the liquid Zn near the columnar ζ / liquid Zn interface during the early stage of the interfacial reaction. The interdiffusion fluxes, J̃ϕ, of Fe and Zn in the ϕ phase (ϕ = Γ, δ1k, and ζ) were estimated from the measured concentration profiles of each phase. This suggested that J̃ϕ caused the growth of each phase as well as the supersaturation of Fe near the interfacial boundaries, thereby resulting in considerable deviations from the equilibrium concentrations. In the later stage of the interfacial reaction, the interfacial concentrations gradually approached the equilibrium concentrations with decreasing J̃ϕ.

A rapid compression machine coupled with time-resolved molecular beam mass spectrometry for gas-phase kinetics studies.

Rapid compression machines (RCMs) are used to simulate a single stroke of an internal combustion engine. After a high-speed compression process, a high-pressure and low-to-intermediate temperature condition can be obtained, under which ignition processes are usually studied. With the help of different diagnostic methods, the detailed speciation information of the ignition process can be quantified. In this study, the molecular beam mass spectrometry (MBMS) diagnostic method was applied on an RCM to realize time-resolved concentration profile measurements. To realize the combination between RCM and MBMS, particle dampers were adopted to suppress the vibrations of the RCM, and a novel flexible interface was designed to maintain a high vacuum, which ensured the safe and effective operation of a high-repetition-rate time-of-flight mass spectrometer (HRR-TOF-MS). The detailed configuration of this diagnostic method is presented, and the data acquisition system and data analysis method are described. The arrangement was validated through the investigation of the well-studied decomposition of 1,3,5-trioxane at temperatures between 697 and 777K at 10 bars. The measured concentration profiles of 1,3,5-trioxane and formaldehyde were in good agreement with previous experimental and theoretical calculation results. The experimental results showed that the newly developed RCM coupled with the HRR-TOF-MS has advantages in time-resolved speciation measurements at low-to-intermediate temperatures and high pressures, and it can be applied in low-temperature combustion chemical kinetics studies.

Separation of multicomponent aromatic/aliphatic mixtures by simulated moving bed adsorption: Modeling and experiments

AbstractSimulated moving bed (SMB) adsorption has potential for efficient separation of many valuable chemical mixtures, but considerably less attention has been devoted to multicomponent feeds relative to binary mixtures. We take a rigorous experimental and modeling approach to study multicomponent separation of aromatics and aliphatics with a mesoporous silica adsorbent, which is relevant in many petrochemical applications such as separation of reformate and distillate streams. Our approach involves refining multicomponent adsorption, mass transfer, and SMB process parameters based upon detailed experimental inputs, with progressive addition of components. We develop a robust model that quantitatively predicts the influence of key operating parameters such as stream flow rates, desorbent/feed ratio, and switch time on the separation results and concentration profiles. The model is validated as a function of feed complexity by SMB experiments and column concentration profile measurements in a 16‐column mini‐plant. Furthermore, conditions for clear separation of each mixture are developed.

Anomalous bulk diffusion of methylene diphenyl diisocyanate in silicone elastomer

In this study, we investigate the anomalous diffusion of methylene diphenylmethane-4,4′-diisocyanate (MDI) into fumed silica filled poly(dimethylsiloxane) (PDMS) elastomer, which occurs in the industrial application of polyurethane vacuum casting. The absorbed MDI polymerizes with moisture to polyurea within the silicone medium, forming a sequential semi interpenetrating polymer network. This results in the formation of polyurea clusters near the exposed surface. Here we focus on the spatially resolved chemical characterization on the micrometer scale utilizing time-of-flight secondary ion mass spectrometry (ToF-SIMS), transmission electron microscopy (TEM), helium ion microscopy (HIM), atomic force microscopy (AFM), thermo-gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) as well as nuclear magnetic resonance spectroscopy (NMR). The concentration profile was determined experimentally using a customized method based on TGA. It was shown that the polyurea reaction of the MDI causes a time-dependency of both the surface concentration and the diffusion coefficient. Six analytical solutions to the diffusion equation obeying different time-dependent boundary conditions with different physical implications are proposed and used to model the measured concentration profiles. The parameterized models showed good predictive power for the measured absorption data and thus substantiated the conjectured molecular phenomena.

Real-time monitoring and hydrodynamic scaling of shear exfoliated graphene

Shear-assisted liquid exfoliation is a primary candidate for producing defect-free two-dimensional (2D) materials. A range of approaches that delaminate nanosheets from layered precursors in solution have emerged in recent years. Diverse hydrodynamic conditions exist across these methods, and combined with low-throughput, high-cost characterization techniques, strongly contribute to the wide variability in performance and material quality. Nanosheet concentration and production rate are usually correlated against operating parameters unique to each production method, making it difficult to compare, optimize and predict scale-up performance. Here, we reveal the shear exfoliation mechanism from precursor to 2D material and extract the derived hydrodynamic parameters and scaling relationship that are key to nanomaterial output and common to all shear exfoliation processes. Our investigations use conditions created from two different hydrodynamic instabilities—Taylor vortices and interfacial waves—and combine materials characterization, fluid dynamics experiments and numerical simulations. Using graphene as the prototypical 2D material, we find that scaling of concentration of few-layer nanosheets depends on local strain rate distribution, relationship to the critical exfoliation criterion, and precursor residence time. We report a transmission-reflectance method to measure concentration profiles in real-time, using low-cost optoelectronics and without the need to remove the layered precursor material from the dispersion. We show that our high-throughput, in situ approach has broad uses by controlling the number of atomic layers on-the-fly, rapidly optimizing green solvent design to maximize yield, and viewing live production rates. Combining the findings on the hydrodynamics of exfoliation with this monitoring technique, we unlock targeted process intensification, quality control, batch traceability and individually customizable 2D materials on-demand.

Interdiffusion and impurity diffusion behavior in polycrystalline Mg-Y binary system

The diffusion behavior in binary Mg-Y system was investigated using polycrystalline Mg/Y diffusion couples at temperatures ranging from 573 to 823 K. For all diffusion couples, electron microprobe analysis was utilized for the measurement of concentration profiles. The interdiffusion coefficients in Mg solid solution and intermetallic phases were determined via the Boltzmann-Matano and Heumann-Matano method, respectively. In addition, the Hall method was employed to extrapolate the impurity diffusion coefficients of Y in pure polycrystalline Mg and Mg in pure polycrystalline Y. The results showed that the interdiffusion coefficient in Mg solid solution increased with an increase of Y concentration, and the corresponding pre-exponential factor and activation energy both increased nearly linearly. The pre-exponential factor and activation energy for Y impurity diffusion in Mg were determined to be 2.36×10−8 (±9.0×10−9) m2/s and 85.61 (±2.0) kJ/mol, while those for Mg impurity diffusion in Y were determined to be 3.47×10−7 (±7.6×10−7) m2/s and 95.90 (±6.7) kJ/mol. Simultaneously, the pre-exponential factor and activation energy for interdiffusion in intermetallic phase Mg24Y5 were determined to be 9.96×10−9 (±2.9×10−9) m2/s and 68.98 (±2.0) kJ/mol；while those for Mg2Y were determined to be 1.18×10−9 (±9.0×10−10) m2/s and 64.54 (±3.2) kJ/mol. Additionally, the vacancy diffusion was dominant mechanism above 723 K, while the grain boundary diffusion mechanism dominated below 723 K in polycrystalline Mg-Y binary system.

Improving CO₂ Concentration Profile Measurements From a Ground-Based CO₂-DIAL Through Conditional Adjustment

Improving CO₂ Concentration Profile Measurements From a Ground-Based CO₂-DIAL Through Conditional Adjustment

Measurement of velocity and concentration profiles of pneumatically conveyed particles in a square-shaped pipe using electrostatic sensor arrays

Cross-sectional measurement of particle velocity and concentration in a pneumatic conveying pipe is desirable for the characterisation of particle flow dynamics and determination of particle mass flow rate. In this study, an inner-inserted electrostatic sensor array consisting of nine pairs of electrodes is implemented to measure the cross-sectional velocity and concentration profiling of particles over the whole cross section in a square-shaped pipe. Experimental tests were conducted on both vertical and horizontal pipe sections on a test rig under dilute conditions with different air velocities and particle mass flow rates. Test results show that the slope-shaped particle concentration profile changes to an arch-shaped one when the particles flow from a horizontal pipe to a vertical one. The particle velocity profile is arch-shaped in both vertical and horizontal pipes. A comparative study of cross-sectional mean particle velocity and concentration measured by the developed electrostatic sensor arrays is conducted.