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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Tangent gradient concentration material for battery, digital gradient concentration material for battery

The invention provides a cathode active material having a discrete change in concentrations of a first base region and a second pulse region. Also provided is a method for preparing a cathode active material, the method having the steps: supplying chelating agent, aqueous basic solution and a first aqueous metal salt solution to a reactor to create a base region; supplying a second aqueous metal-salt solution to a reactor to form a pulse region, wherein the second aqueous metal-salt solution is intermittently or continuously added during or after the creation of the base region; thermally treating the base region and the pulse region to create active metal precursors; mixing the precursors with lithium salt to produce a mixture; and thermally treating the mixture.

Shin, YoungHo↗

Gravity Induced Formation of Concentration Gradients in Supersaturated Binary Solutions

Experimental and theoretical studies of the formation of solute concentration gradient in supersaturated binary solutions in a gravitational field were carried out. The formation of solute concentration gradient was associated with the gravity induced redistribution of subcritical solute clusters. The birth-death process of the new solute-rich phase domains (subcritical solute clusters) was described in terms of the time-dependent Ginzburg Landau model developed for metastable state relaxation in binary (solute + solvent) non-critical solutions in the presence of a gravitational field. A new mathematical Ansatz was developed for solution of the model equations. This Ansatz has allowed to approach for the first time the following important problems: (1) Microstructure of solute distribution inside of the subcritical solute clusters. The analytical results obtained demonstrate that solute inside of the subcritical solute clusters is heterogeneously distributed with a spatially periodic structure. (2) Macrostructure of the solute subcritical clusters distribution in a gravitational field. The subcritical solute clusters are found to be distributed heterogeneously in a gravitational field. This heterogeneity, which is due to the heterogeneous birth-death process of the subcritical solute clusters in a gravitational field, initiates a noticeable solute concentration gradient in vertical columns of supersaturated binary solutions. An analysis and comparison of theoretical results and experimental data related to the solute concentration gradient formation in a gravitational field are presented. It is also demonstrated that the critical radius of solute clusters (radius of nucleation) and induction time are gravity-dependent.

Izmailov, Alexander F.↗

Influence of Concentration Gradients on Electroconvection at a Cation-Exchange Membrane Surface

Membrane-based systems, such as electrodialysis, play an important role in desalination and industrial separation processes. Electrodialysis uses alternating anion- and cation-exchange membranes with a perpendicular electric field to generate concentrated and diluate streams from a feed solution. It is known that under overlimiting current conditions, reduced charge and mass transfer at the membrane interface leads to regions of high ion depletion generating instability and vortices termed electroconvection. While electroconvective mixing is known to directly impact the separation efficiency of electrodialysis, the influence of ion concentration gradients across the membrane experienced in a functional electrodialysis system is not known. Here, we report the influence of ion concentration gradients across a cation exchange membrane (Nafion) that is both aligned with and opposed to the applied electric field. Experiments were conducted by coflowing NaCl solutions of different concentrations (0.1–100 mM) on each side of the membrane, and electroconvection was visualized with a fluorescence dye (Rhodamine 6G). Here, we obtained concentration profiles from fluorescence image data and systematically measured the thickness of the depletion boundary layer d BL under different conditions. We found smaller d BL values at a higher flow rate both with and without concentration gradients. Our results show that electroconvection is enhanced when the electric field is opposite to the direction of the concentration gradient.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Convective flows in enclosures with vertical temperature or concentration gradients

The transport process in the fluid phase during the growth of a crystal has a profound influence on the structure and quality of the solid phase. In vertical growth techniques the fluid phase is often subjected to vertical temperature and concentration gradients. The main objective is to obtain more experimental data on convective flows in enclosures with vertical temperature or concentration gradients. Among actual crystal systems the parameters vary widely. The parametric ranges studied for mass transfer are mainly dictated by the electrochemical system employed to impose concentration gradients. Temperature or concentration difference are maintained between two horizontal end walls. The other walls are kept insulated. Experimental measurements and observations were made of the heat transfer or mass transfer, flow patterns, and the mean and fluctuating temperature distribution. The method used to visualize the flow pattern in the thermal cases is an electrochemical pH-indicator method. Laser shadowgraphs are employed to visualize flow patterns in the solutal cases.

Wang, L. W.↗

Convective flows in enclosures with vertical temperature or concentration gradients

The transport process in the fluid phase during the growth of a crystal has a profound influence on the structure and quality of the solid phase. In vertical growth techniques the fluid phase is often subjected to vertical temperature and concentration gradients. The main objective is to obtain more experimental data on convective flows in enclosures with vertical temperature or concentration gradients. Among actual crystal systems the parameters vary widely. The parametric ranges studied for mass transfer are mainly dictated by the electrochemical system employed to impose concentration gradients. Temperature or concentration difference are maintained between two horizontal end walls. The other walls are kept insulated. Experimental measurements and observations were made of the heat transfer or mass transfer, flow patterns, and the mean and fluctuating temperature distribution. The method used to visualize the flow pattern in the thermal cases is an electrochemical pH-indicator method. Laser shadowgraphs are employed to visualize flow patterns in the solutal cases.

Wang, L. W.↗

Magnetic Control of Concentration Gradient in Microgravity

A report describes a technique for rapidly establishing a fluid-concentration gradient that can serve as an initial condition for an experiment on solutal instabilities associated with crystal growth in microgravity. The technique involves exploitation of the slight attractive or repulsive forces exerted on most fluids by a magnetic-field gradient. Although small, these forces can dominate in microgravity and therefore can be used to hold fluids in position in preparation for an experiment. The magnetic field is applied to a test cell, while a fluid mixture containing a concentration gradient is prepared by introducing an undiluted solution into a diluting solution in a mixing chamber. The test cell is then filled with the fluid mixture. Given the magnetic susceptibilities of the undiluted and diluting solutions, the magnetic-field gradient must be large enough that the magnetic force exceeds both (1) forces associated with the flow of the fluid mixture during filling of the test cell and (2) forces imposed by any residual gravitation and fluctuations thereof. Once the test cell has been filled with the fluid mixture, the magnetic field is switched off so that the experiment can proceed, starting from the proper initial conditions.

Leslie, Fred↗

The use of the ion probe mass spectrometer in the measurement of hydrogen concentration gradients in Monel K 500

The ion probe mass spectrometer was used to measure hydrogen concentration gradients in cathodically charged Monel K 500. Initial work with the ion probe involved the calibration of the instrument and the establishment of a suitable experimental procedure for this application. Samples of Monel K 500 were cathodically charged in a weak sulfuric acid solution. By varying the current density, different levels of hydrogen were introduced into the samples. Hydrogen concentration gradients were taken by ion sputtering on the surface of these samples and monitoring the behavior of the hydrogen mass peak as a function of time. An attempt was made to determine the relative amounts of hydrogen in the bulk and grain boundaries by analyzing a fresh fracture surface with a higher proportion of grain boundary area. It was found that substantially more hydrogen was detected in the grain boundaries than in the bulk, confirming the predictions of previous workers. A sputter rate determination was made in order to establish the rate of erosion.

Truhan, J. J., Jr.↗

Effective kinetics driven by dynamic concentration gradients under coupled transport and reaction

Biogeochemical reaction kinetics are generally established from batch reactors where concentrations are uniform. In natural systems, many biogeochemical processes are characterized by spatially and temporally variable concentration gradients that often occur at scales which are not resolved by field measurements or biogeochemical and reactive transport models. Yet, it is not clear how these sub-scale chemical gradients affect reaction kinetics compared to batch kinetics. Here we investigate this question by studying the paradigmatic case of localized pulses of solute reacting with a solid or a dissolved species in excess. Additionally, we consider non-linear biogeochemical reactions, representative of mineral dissolution, adsorption and redox reactions, which we quantify using simplified power-law kinetics. The combined effect of diffusion and reaction leads to effective kinetics that differ quantitatively and qualitatively from the batch kinetics. Depending on the nonlinearity (reaction order) of the local kinetics, these effects lead to either enhancement or decrease of the overall reaction rate, and result in a rich variety of reaction dynamics. We derive analytical results for the effective kinetics, which are validated by comparison to direct numerical simulations for a broad range of Damköhler numbers and reaction order. Our findings provide new insights into the interpretation of imperfectly mixed lab experiments, the effective kinetics of field systems characterized by intermittent reactant release and the integration of sub-scale concentration gradients in reactive transport models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stabilizing Ni-rich layered cathode for high-voltage operation through hierarchically heterogeneous doping with concentration gradient

High-nickel LiNi x Mn y Co 1-x-y O 2 (NMC) cathodes have demonstrated superior energy density, yet their stability is compromised under high voltage conditions. To address this, here we propose a strategy of heterogeneous doping with a concentration gradient, specifically through Sr–Zr co-modification. We synthesized Ni-rich NMC particles featuring several micron-sized secondary particles composed of micron-sized primary grains. This design aims to harness the structural robustness of single-crystalline grains and the favorable diffusion kinetics of polycrystalline secondary particles. Systematic characterization using a combination of electrochemical measurements and synchrotron analytics reveals an intriguing pattern of hierarchically heterogeneous Sr–Zr co-doping. It demonstrates a depth-dependent concentration gradient at the secondary particle level and competing dopant segregation over the buried grain boundaries. This unique characteristic creates opportunities for enhancing battery performance, particularly by optimizing precursors and implementing advanced modulation techniques. We also investigate the dissolution and precipitation of the cathode's transition metal cations upon high-voltage cycling. These insights suggest that a tailored compositional variation can be a viable approach to effectively design the next-generation high-Ni NMC cathode materials for high-voltage lithium batteries.

36 MATERIALS SCIENCE↗

Rational design of mechanically robust Ni-rich cathode materials via concentration gradient strategy

Mechanical integrity issues such as particle cracking are considered one of the leading causes of structural deterioration and limited long-term cycle stability for Ni-rich cathode materials of Li-ion batteries. Indeed, the detrimental effects generated from the crack formation are not yet entirely addressed. Here, applying physicochemical and electrochemical ex situ and in situ characterizations, the effect of Co and Mn on the mechanical properties of the Ni-rich material are thoroughly investigated. As a result, we successfully mitigate the particle cracking issue in Ni-rich cathodes via rational concentration gradient design without sacrificing the electrode capacity. Our result reveals that the Co-enriched surface design in Ni-rich particles benefits from its low stiffness, which can effectively suppress the formation of particle cracking. Meanwhile, the Mn-enriched core limits internal expansion and improve structural integrity. The concentration gradient design also promotes morphological stability and cycling performances in Li metal coin cell configuration.

36 MATERIALS SCIENCE↗

A Technique for Rapidly Deploying a Concentration Gradient with Applications to Microgravity

The latter half of the last century has seen rapid advancements in semiconductor crystal growth powered by the demand for high performance electronics in myriad applications. The reduced gravity environment of space has also been used for crystal growth tests, especially in instances where terrestrial growth has largely been unsuccessful. While reduced gravity crystal growth affords some control of the gravity parameter, many crystals grown in space, to date, have structural flaws believed to result from convective motions during the growth phase. The character of these instabilities is not well understood but is associated with thermal and solutal density variations near the solidification interface in the presence of residual gravity and g-jitter. In order to study these instabilities in a separate, controlled space experiment, a concentration gradient would first have to be artificially established in a timely manner as an initial condition. This is generally difficult to accomplish in a microgravity environment because the momentum of the fluid injected into a test cell tends to swirl around and mix in the absence of a restoring force. The use of magnetic fields to control the motion and position of liquids has received growing interest in recent times. The possibility of using the force exerted by a non-uniform magnetic field on a ferrofluid to not only achieve fluid manipulation but also to actively control fluid motion makes it an attractive candidate for space applications. This paper describes a technique for quickly establishing a linear or exponential fluid concentration gradient using a magnetic field in place of gravity to stabilize the deployment. Also discussed is a photometric technique for measuring the concentration profile using light attenuation. Results of the ground-based experiments indicate that the concentration distribution is within 3% of the predicted value. Although any range of concentations can be realized, photometric constraints are discussed which impose some limitations on measurements.

Leslie, Fred↗

High-Nickel Cathodes with Mechanical and Interfacial Robustness via Tailored Concentration Gradients for Stable Li-Ion Batteries

Here, we have developed a versatile mathematical framework integrated with an automated reactor system to design and reify highly customizable full concentration gradient (FCG) in high-nickel cathodes for advanced Li-ion batteries. This method provides precise and independent control of the average composition, slope, and curvature of FCGs, enabling the optimization of structural and mechanical properties of the cathode materials. We have showcased this method with Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 precursors of controlled FCGs, which unlocked an optimized cathode with excellent cycling stability without crack formation after repeated cycles. This work opens up new possibilities for the design and manufacturing of advanced cathode materials, enabling safer, high-performance batteries.

25 ENERGY STORAGE↗

Fugacity and concentration gradients in a gravity field

Equations are reviewed which show that at equilibrium fugacity and concentration gradients can exist in gravitational fields. At equilibrium, the logarithm of the ratio of the fugacities of a species at two different locations in a gravitational field is proportional to the difference in the heights of the two locations and the molecular weight of the species. An analogous relation holds for the concentration ratios in a multicomponent system. The ratio is calculated for a variety of examples. The kinetics for the general process are derived, and the time required to approach equilibrium is calculated for several systems. The following special topics are discussed: ionic solutions, polymers, multiphase systems, hydrostatic pressure, osmotic pressure, and solubility gradients in a gravity field.

May, C. E.↗

Fourier transform infrared and Raman spectroscopic characterization of homogeneous solution concentration gradients near a container wall at different temperatures

Fourier transform infrared (FTIR) and Raman spectroscopic techniques were used to study the solution concentration gradient in succino nitrile-rich and water-rich homogeneous solutions. The spectroscopic data shows significant concentration dependency. Although FTIR-attenuated total reflectance could not yield surface spectra since the evanescent infrared wave penetrated deep into the bulk solution, it showed that water-rich clusters were decreased at higher temperatures. This result is consistent with the calorimetric results reported earlier.

Loo, B. H.↗

Decay of the zincate concentration gradient at an alkaline zinc cathode after charging

The study was carried out by observing the decay of the zincate concentration gradient at a horizontal zinc cathode after charging. This decay was found to approximate first order kinetics as expected from a proposed boundary layer model. The decay half life was shown to be a linear function of the thickness of porous zinc deposit on the cathode indicating a very rapid transport of zincate through porous zinc metal. The rapid transport is attributed to an electrochemical mechanism. The data also indicated a relatively sharp transition between the diffusion and convection transport regions. The diffusion of zincate ion through asbestos submerged in alkaline electrolyte was shown to be comparable with that predicted from the bulk diffusion coefficient of the zincate ion in alkali.

Kautz, H. E.↗

Decay of the zincate concentration gradient at an alkaline zinc cathode after charging

The transport of the zincate ion to the alkaline zinc cathode was studied by observing the decay of the zincate concentration gradient at a horizontal zinc cathode after charging. This decay was found to approximate first order kinetics as expected from a proposed boundary layer model. The concentrations were calculated from polarization voltages. The decay half life was shown to be a linear function of the thickness of porous zinc deposit on the cathode indicating a very rapid transport of zincate through porous zinc metal. The rapid transport is attributed to an electrochemical mechanism. From the linear dependence of the half life on the thickness the boundary layer thickness was found to be about 0.010 cm when the cathode was at the bottom of the cell. No significant dependence of the boundary layer thickness on the viscosity of electrolyte was observed. The data also indicated a relatively sharp transition between the diffusion and convection transport regions. When the cathode was at the top of the cell, the boundary layer thickness was found to be roughly 0.080 cm. The diffusion of zincate ion through asbestos submerged in alkaline electrolyte was shown to be comparable with that predicted from the bulk diffusion coefficient of the zincate ion in alkali.

Kautz, H. E.↗

The development of concentration gradients in a suspension of chemotactic bacteria

When a suspension of bacterial cells of the species Bacillus subtilis is placed in a chamber with its upper surface open to the atmosphere complex bioconvection patterns are observed. These arise because the cells: (1) are denser than water; and (2) usually swim upwards, so that the density of an initially uniform suspension becomes greater at the top than the bottom. When the vertical density gradient becomes large enough, an overturning instability occurs which ultimately evolves into the observed patterns. The reason that the cells swim upwards is that they are aerotactic, i.e., they swim up gradients of oxygen, and they consume oxygen. These properties are incorporated in conservation equations for the cell (N) and oxygen (C) concentrations, and these are solved in the pre-instability phase of development when N and C depend only on the vertical coordinate and time. Numerical results are obtained for both shallow- and deep-layer chambers, which are intrinsically different and require different mathematical and numerical treatments. It is found that, for both shallow and deep chambers, a thin boundary layer, densely packed with cells, forms near the surface. Beneath this layer the suspension becomes severely depleted of cells. Furthermore, in the deep chamber cases, a discontinuity in the cell concentration arises between this cell-depleted region and a cell-rich region further below, where no significant oxygen concentration gradients develop before the oxygen is fully consumed. The results obtained from the model are in good qualitative agreement with the experimental observations.

NASA Discipline Cell Biology↗

Concentration gradients and growth/decay characteristics of the seasonal sea ice cover

The characteristics of sea ice cover in both hemispheres are analyzed and compared. The areal sea ice cover in the entire polar regions and in various geographical sectors is quantified for various concentration intervals and is analyzed in a consistent manner. Radial profiles of brightness temperatures from the poles across the marginal zone are also evaluated at different transects along regular longitudinal intervals during different times of the year. These radial profiles provide statistical information about the ice concentration gradients and the rates at which the ice edge advances or retreats during a complete annual cycle.

Comiso, J. C.↗