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At least 127 records · Page 7

Universal Repulsive Contribution to the Solvent-Induced Interaction Between Sizable, Curved Hydrophobes

In addition to the direct attraction, sizable hydrophobes in water experience an attractive force mediated by interfacial water. Using simple geometric arguments, we identify here the conditions at which the water-induced interaction between curved hydrocarbon surfaces becomes repulsive. The repulsive contribution arises from the thermodynamic penalty due to the emergence of the liquid/vapor boundary created as water gets expelled between curved hydrophobes. By augmenting the mean field approach with atomistic simulations of pristine and alkyl-coated graphitic nanoparticles in three distinct geometries, spherical, cylindrical and planar, immersed in water, we show the macroscopic thermodynamics remarkably works down to the molecular scale. The new insights improve the prediction and control of wetting and dispersion properties for a broad class of nonpolar nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Eruption age of an approximately 100,000-year-old basalt from Ar-40/Ar-39 analysis of partially degassed xenoliths

Eleven samples from five partially degassed Mesozoic granitic xenoliths and two late Pleistocene host basalt samples from Sawmill Canyon in Sierra Nevada, California, have been analyzed using stepwise Ar-40/Ar-39 dating techniques. The petrography and analytic techniques are described and the results are presented. Isotopic compositions of Ar released from the xenoliths in several extraction steps at temperatures below about 900 C were colinear in Ar-36/Ar-40 versus Ar-39/Ar-40 diagrams and defined isochrons, giving a mean age of degassing of 119,000 + or - 7000 yr. Ar-40 extracted at higher temperatures included ancient radiogenic Ar-40 that never diffused from the xenoliths during immersion in the magma. This Ar-40 caused an increase in the apparent age for the high-temperature extractions. The high precision of the eruption age determined by this method is comparable to that obtained elsewhere by conventional K/Ar dating of sanidine.

Gillespie, A. R.↗

Electrochemical aspects of copper atmospheric corrosion in the presence of sodium chloride

Here, this study describes the evolving state of electrolyte and corrosion processes associated with sodium chloride on copper at the initial stage of corrosion and the critical implications of this behavior on controlling kinetics and damage distributions. Sodium chloride droplets were placed on copper in humid conditions and the resulting electrolyte properties, corrosion products and damage were characterized over time using time-lapse imaging, micro Raman spectroscopy, TOF-SIMS and optical profilometry. Within minutes of NaCl droplet placement, NaOH-rich films resultant from oxygen reduction advanced stepwise from the droplets, leaving behind concentric trenching attack patterns suggestive of moving anode-cathode pairs at the alkaline film front. Corrosion attack under these spreading alkaline films was up to 10x greater than under the original NaCl drops. Furthermore, solid Cu 2 Cl(OH) 3 shells formed over the surface of the NaCl drops within hours of exposure. Thermodynamic modeling along with immersed electrochemical experiments in simulated droplet and films electrolytes were used to rationalize this behavior and build a description of the rapidly evolving corroding system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Efficient photon extraction from a quantum dot in a broad-band planar cavity antenna

We analyse the extraction of photons emitted from single InAs quantum dots embedded in planar microcavities. The structures are designed to achieve broad-band operation and high-collection efficiency from a device requiring straightforward fabrication, even with electrical contacts. The designs consist of a quantum dot in a GaAs membrane with asymmetric top and bottom mirrors and a top-side solid immersion lens (SIL). Four separate cases are considered in our design: a GaAs membrane only (case 1), GaAs membrane with a glass SIL on top (case 2), a GaAs membrane with a glass SIL on top and a back mirror consisting of Au (case 3), a GaAs membrane with a glass SIL on top of a distribute Bragg reflector mirror and Au back mirror (case 4). Both finite difference time domain and analytical simulations are used to calculate the electric field, power density, and far-field radiation pattern. For optimized structures (case 4), we obtain significant extraction efficiencies (>50%) with modest Purcell enhancements (∼20%) and a large spectral full-width-half-maximum (>100 nm). The high-extraction efficiency, broad-band operation, and facile fabrication make the proposed structures promising for realistic quantum dot devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Experimental study of the oscillations of a rotating drop

Two- and three-lobed oscillations of a rotating liquid drop immersed in an immiscible fluid of comparable density and the same angular velocity were studied experimentally. Using acoustically suspended drops, it has been found that the relative change in the resonance frequencies of the axisymmetric drop-shape oscillations Delta omega-l/omega-l(0) is proportional to the square of the normalized angular speed (Omega/omega-l/0)-squared when omega-l greater than 2 Omega. This is in agreement with a recent analytical study of the same problem. Some preliminary results regarding the effect of rotation on the free-decay rate of the two-lobed oscillations are also presented.

Annamalai, P.↗

Local Ultrasonic Resonance Spectroscopy of Lithium Metal Batteries for Aerospace Applications

As next-generation aircraft and vehicles continue to develop, so do their associated energy demands. Lithium metal batteries are a leading candidate to fulfill this energy requirement, but these batteries are prone to internal dendrite defects that can lead to catastrophic thermal runaway events. Current battery management systems are capable of mitigating such risks, but are unable to detect such defects until thermal runaway has already begun. Various nondestructive evaluation (NDE) techniques, particularly ultrasonic NDE, can directly monitor internal battery parameters giving them the potential to detect critical defects prior to catastrophic failure. However, most of the current battery NDE research has focused on improved battery state-of-charge (SOC) and stateof- health (SOH) monitoring with little emphasis on critical defect detection. Thus, a measurement technique sensitive to subtle battery defects is needed. In addition, the complex mechanics of ultrasound in porous, thin, multilayered batteries prompt the use of physics-based simulation to guide inspections. In this work, an ultrasonic NDE technique has been developed utilizing frequency domain analysis of local battery resonances to detect the presence of battery defects. This technique is a practical extension of local ultrasonic resonance spectroscopy (LURS) – which previously required non-contact laser ultrasonics – to measurements with piezoelectric contact and immersion scan transducers. To extend the technique to work with piezoelectric transducers, ultrasonic battery measurements were compared to a sans-battery calibration measurement. Then, a linear systems deconvolution was used to eliminate the transfer functions of extraneous factors such as the transducer and electronics, leaving only the frequency-dependent battery reflection coefficient. The LURS technique was first validated on stainless steel and aluminum plates, producing reflection coefficients in line with analytical and numerical finite element modeling (FEM) results. Functioning Li-metal pouch cells were then seeded with lithium chip defects prior to LURS measurements. The presence of these defects is shown to cause a measurable shift in the battery’s through-thickness local resonances. 2D, frequency-domain poroelastic models of ultrasonic propagation in a single-cell lithium metal pouch battery were created and corroborated these findings. Thus, this work has both extended and proven the feasibility of the LURS technique in the detection of local battery defects.

Ultrasound↗

Hydrodynamic Force on a Cylinder Oscillating at Low Frequency

The hydrodynamic force on a cylinder oscillating transversely to its axis is a nonlinear function of the displacement amplitude x0. We report measurements and numerical calculations of the force at frequencies low enough that delta > R, where delta is the viscous penetration length and R is the cylinder radius. For small amplitudes, the numerically calculated Fourier transform of the force per unit length, F(sub small), agrees with Stokes' analytical calculation. For larger amplitudes, the force per unit length found by both calculation and measurement is F = F(sub small)C (x(sub 0)/delta,R/delta). The complex function C depends only weakly on R/delta, indicating that x0/delta is more appropriate as a scaling variable than the Keulegan-Carpenter number KC = pi*x(sub 0)/R. The measurements used a torsion oscillator driven at frequencies from 1 to 12 Hz while immersed in dense xenon. The oscillator comprised cylinders with an effective radius of R = 13.4 micron and oscillation amplitudes as large as x(sub 0)/delta = 4 (corresponding to KC as large as 71). The calculations used similar conditions except that the amplitudes were as large as x0/delta = 28.

Berg, Robert F.↗

Acceleration of Solvation Free Energy Calculation via Thermodynamic Integration Coupled with Gaussian Process Regression and Improved Gelman–Rubin Convergence Diagnostics

The determination of the solvation free energy of ions and molecules holds profound importance across a spectrum of applications spanning chemistry, biology, energy storage, and the environment. Molecular dynamics simulations are powerful tools for computing this critical parameter. Nevertheless, the accurate and efficient calculation of the solvation free energy becomes a formidable endeavor when dealing with complex systems characterized by potent Coulombic interactions and sluggish ion dynamics and, consequently, slow transition across various metastable states. Here, in the present study, we expose limitations stemming from the conventional calculation of the statistical inefficiency g in the thermodynamic integration method, a factor that can hinder the determination of convergence of the solvation free energy and its associated uncertainty. Instead, we propose a robust scheme based on Gelman–Rubin convergence diagnostics. We leverage this improved estimation of uncertainties to introduce an innovative accelerated thermodynamic integration method based on the Gaussian Process regression. This methodology is applied to the calculation of the solvation free energy of trivalent rare-earth elements immersed in ionic liquids, a scenario in which the aforementioned challenges render standard approaches ineffective. The proposed method proves to be effective in computing solvation free energy in situations where traditional thermodynamic integration methods fall short.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Resonance scattering and radiation force calculations for an elastic cylinder using the translational addition theorem for cylindrical wave functions

The standard Resonance Scattering Theory (RST) of plane waves is extended for the case of any two-dimensional (2D) arbitrarily-shaped monochromatic beam incident upon an elastic cylinder with arbitrary location using an exact methodology based on Graf’s translational addition theorem for the cylindrical wave functions. The analysis is exact as it does not require numerical integration procedures. The formulation is valid for any cylinder of finite size and material that is immersed in a nonviscous fluid. Partial-wave series expansions (PWSEs) for the incident, internal and scattered linear pressure fields are derived, and the analysis is further extended to obtain generalized expressions for the on-axis and off-axis acoustic radiation force components. The wave-fields are expressed using generalized PWSEs involving the beam-shape coefficients (BSCs) and the scattering coefficients of the cylinder. The off-axial BSCs are expressed analytically in terms of an infinite PWSE with emphasis on the translational offset distance d. Numerical computations are considered for a zeroth-order quasi-Gaussian beam chosen as an example to illustrate the analysis. Acoustic resonance scattering directivity diagrams are calculated by subtracting an appropriate background from the expression of the scattered pressure field. In addition, computations for the radiation force exerted on an elastic cylinder centered on the axis of wave propagation of the beam, and shifted off-axially are analyzed and discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Protocol for Screening Water Oxidation or Reduction Electrocatalyst Activity in a Three-Electrode Cell for Alkaline Exchange Membrane Electrolysis

Accurate and reproducible screening of the electrocatalytic activity of novel materials for Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER) requires establishing an easily adoptable harmonized testing protocol. Herein, we describe a robust, instrumentation-independent testing technique utilizing a three-electrode cell with a fully immersed working electrode. Compared to rotating disk electrode (RDE) techniques, this protocol produces current densities close to those obtained in real electrolyzers and eliminates the usage of the expensive RDE apparatus.

08 HYDROGEN↗

Sample Size Effects on Petrophysical Characterization and Fluid-to-Pore Accessibility of Natural Rocks

Laboratory-scale analysis of natural rocks provides petrophysical properties such as density, porosity, pore diameter/pore-throat diameter distribution, and fluid accessibility, in addition to the size and shape of framework grains and their contact relationship with the rock matrix. Different types of laboratory approaches for petrophysical characterization involve the use of a range of sample sizes. While the sample sizes selected should aim to be representative of the rock body, there are inherent limitations imposed by the analytical principles and holding capacities of the different experimental apparatuses, with many instruments only able to accept samples at the μm–mm scale. Therefore, a total of nine (three limestones, three shales, two sandstones, and one dolomite) samples were collected from Texas to fill the knowledge gap of the sample size effect on the resultant petrophysical characteristics. The sample sizes ranged from 3 cm cubes to <75 μm particles. Using a combination of petrographic microscopy, helium expansion pycnometry, water immersion porosimetry, mercury intrusion porosimetry, and (ultra-) small-angle X-ray scattering, the impact of sample size on the petrophysical properties of these samples was systematically investigated here. The results suggest that the sample size effect is influenced by both pore structure changes during crushing and sample size-dependent fluid-to-pore connectivity.

36 MATERIALS SCIENCE↗

Hydrodynamics of suspensions of passive and active rigid particles: a rigid multiblob approach

We develop a rigid multiblob method for numerically solving the mobility problem for suspensions of passive and active rigid particles of complex shape in Stokes flow in unconfined, partially confined, and fully confined geometries. As in a number of existing methods, we discretize rigid bodies using a collection of minimally resolved spherical blobs constrained to move as a rigid body, to arrive at a potentially large linear system of equations for the unknown Lagrange multipliers and rigid-body motions. Here we develop a block-diagonal preconditioner for this linear system and show that a standard Krylov solver converges in a modest number of iterations that is essentially independent of the number of particles. Key to the efficiency of the method is a technique for fast computation of the product of the blob-blob mobility matrix and a vector. For unbounded suspensions, we rely on existing analytical expressions for the Rotne-Prager-Yamakawa tensor combined with a fast multipole method (FMM) to obtain linear scaling in the number of particles. For suspensions sedimented against a single no-slip boundary, we use a direct summation on a graphical processing unit (GPU), which gives quadratic asymptotic scaling with the number of particles. For fully confined domains, such as periodic suspensions or suspensions confined in slit and square channels, we extend a recently developed rigid-body immersed boundary method by B. Kallemov, A. P. S. Bhalla, B. E. Griffith, and A. Donev (Commun. Appl. Math. Comput. Sci. 11 (2016), no. 1, 79-141) to suspensions of freely moving passive or active rigid particles at zero Reynolds number. We demonstrate that the iterative solver for the coupled fluid and rigid-body equations converges in a bounded number of iterations regardless of the system size. In our approach, each iteration only requires a few cycles of a geometric multigrid solver for the Poisson equation, and an application of the block-diagonal preconditioner, leading to linear scaling with the number of particles. We optimize a number of parameters in the iterative solvers and apply our method to a variety of benchmark problems to carefully assess the accuracy of the rigid multiblob approach as a function of the resolution. We also model the dynamics of colloidal particles studied in recent experiments, such as passive boomerangs in a slit channel, as well as a pair of non-Brownian active nanorods sedimented against a wall.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Optimal control of open quantum systems: A combined surrogate Hamiltonian optimal control theory approach applied to photochemistry on surfaces

In this paper, control of open quantum systems with emphasis on the control of surface photochemical reactions is presented. A quantum system in a condensed phase undergoes strong dissipative processes. From a theoretical viewpoint, it is important to model such processes in a rigorous way. In this work, the description of open quantum systems is realized within the surrogate Hamiltonian approach [R. Baer and R. Kosloff, J. Chem. Phys. 106, 8862 (1997)]. An efficient and accurate method to find control fields is optimal control theory (OCT) [W. Zhu, J. Botina, and H. Rabitz, J. Chem. Phys. 108, 1953 (1998); Y. Ohtsuki, G. Turinici, and H. Rabitz, J. Chem. Phys. 120, 5509 (2004)]. To gain control of open quantum systems, the surrogate Hamiltonian approach and OCT, with time-dependent targets, are combined. Three open quantum systems are investigated by the combined method, a harmonic oscillator immersed in an ohmic bath, CO adsorbed on a platinum surface, and NO adsorbed on a nickel oxide surface. Throughout this paper, atomic units, i.e., ({Dirac_h}/2{pi})=m{sub e}=e=a{sub 0}= 1, have been used unless otherwise stated.

36 MATERIALS SCIENCE↗

Silica Surface States and their Wetting Characteristics

The wetting characteristics of silica (SiO 2 ) surfaces can be described by molecular dynamics (MD) and ab initio simulations, including comparison of silica surfaces (talc (001), siloxanated quartz, tridymite (001) and quartz (001)), some of which have not been considered previously in the literature. Classic MD and ab initio simulation methods have been used to determine the contact angle, interfacial water structure, hydroxylation reaction and hydration energy, the results of which are compared with experimental results reported in the literature. Additionally, wetting of silica surfaces depends on surface polarity and extent of hydroxylation. The non-polar siloxane surfaces are characterized by a contact angle of about 80°, an MD ‘water exclusion zone’ of about 3 Å, a relaxed interfacial water orientation, inertness to hydroxylation and minimal hydration energy. The polar silica surfaces can be wetted by water and have a more ordered interfacial water structure. Silanol groups form at the polar silica surface during hydroxylation reactions, and the calculated hydration energy of -1·2 and -1·6 eV matches the experimental heat of immersion measurements reported in the literature, which correspond to hydrogen (H) bonding with interfacial water. In conclusion, fundamental understanding of silica surfaces is important for understanding flotation phenomena and fluid flow in silica nanopores.

36 MATERIALS SCIENCE↗

The equilibrium and stability of the gaseous component of the galaxy, 3

The stability of a self-gravitating, nonrotating, isothermal gas layer threaded by a one-dimensional equipartition magnetic field, immersed in a rigid isothermal layer of stars, is considered with respect to waves with motions in and perpendicular to the X plane, where X is the equilibrium magnetic and gravitational field vectors. When motions are perpendicular to the X plane, the magnetic field hinders gravitational instability, increasing the minimum length necessary to produce instability by the factor (1 + alpha) to the 1/2 power, where alpha is the ratio of magnetic pressure to gas pressure. When motions are in the plane, no such simple analytical solution is found. However, the resulting system of equations reduces to a single fourth order differential equation in the perturbed gas potential that defines an eigenvalue problem for the marginally unstable state when the four appropriate boundary conditions are considered.

Kellman, S. A.↗

Evaluation of Changes to the MTR Fuel Dissolution Flowsheet to Increase the Number of L-Bundles Charged to a Dissolver

Material Test Reactor (MTR) fuels are dissolved in the H-Canyon facility using a Hg-catalyzed, HNO₃ dissolution flowsheet. The flowsheet is based on experimental work in which laboratory-scale experiments were used to provide bounding values for both offgas and H₂ generation rates. The generation of H₂ gas, primarily from the dissolution of Al, is controlled by limiting the surface area exposed to the solution. The number of L-Bundles charged and their submergence level defines the exposed surface area which is directly proportional to the H₂ generation rate. For the MTR fuel dissolution flowsheet, the maximum number of L-Bundles which can be charged to a dissolver was specified as a function of the Al concentration in the solution and the submergence level of the bundle. The MTR fuels are currently dissolved in the 6.1D dissolver. To reach the desired terminal Al concentration, a total of 12 L-Bundles of fuel are dissolved per batch. Depending on the submergence level being used in the dissolver, the 12 bundles are dissolved in three charges of four bundles per charge or in a sequence of three, four, and five bundles. However, if six L-Bundles could be dissolved in the initial charge, a dissolver batch could be completed in two dissolutions instead of three. To assess the feasibility of dissolving six bundles in the first charge, the Savannah River National Laboratory evaluated changes to the MTR flowsheet which increase the number of bundles which can be charged to a dissolver. Since the development of the existing MTR fuel dissolution flowsheet, improved offgas measurement methods have been developed to more accurately calculate the offgas composition and generation rate during laboratory-scale dissolutions. In the first part of this study, improvements in the calibration model for the Raman spectrometer (used for offgas characterization) and a more effective data smoothing routine were applied to existing data. The uncertainty in the offgas composition data used to define the MTR fuel dissolution flowsheet were subsequently re-evaluated which resulted in an approximate 50% reduction in the uncertainty of the H₂ gas concentration measurements. The reduced uncertainty was used in new calculations to define the maximum number of L-Bundles which can be charged to either the 6.1D or 6.4D dissolver as a function of the Al concentration. With the reduced uncertainty in the H₂ concentration measurements, a flowsheet was defined which supported initially charging 6 bundles to a dissolver. This flowsheet is based on the use of 0.002 M Hg, an L-Bundle immersion depth of 54 in., an air sparge/purge flowrate of 40 scfm, an iodine reactor operating temperature of 200 °C, and not exceeding 60% of the H₂ LFL in the dissolver offgas. In the second phase of this study, calculations were performed to assess the impact of changing various operating parameters to increase the number of L-Bundles charged to an H-Canyon dissolver. Applying the improved offgas measurement techniques including the reduced uncertainty in the H₂ concentration measurements to the existing data, the number of bundles of MTR fuel which can be charged to either the 6.1D or 6.4D dissolver were calculated based on varying the bundle immersion depth (44-60 in.), air sparge/purge flowrate (40-60 scfm), iodine reactor operating temperature (150-200 °C), and the percentage of the H₂ LFL which must not be exceeded (60-76%). Qualitatively, the percentage of the LFL had the largest influence on the maximum number of bundles which can be charged to a dissolver followed by the air sparge/purge flowrate, L-Bundle immersion depth, and the iodine reactor operating temperature. During the evaluation of each variable, the other variables were held at the baseline flowsheet conditions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Evaluation of Radiolysis Data for Hydrogen Gas Generation During Gamma Irradiation of Pre-Corroded and Pristine Aluminum Samples - An Aluminum SNF Dry Storage Study Interim Report

Information and data from radiolysis testing to measure hydrogen (H₂) generated from hydrated oxides on aluminum exposed to ⁶⁰Co radiation were reviewed to evaluate hydrogen generation with radiation dose. Hydrogen generation rate is a primary input to the coupled thermal-chemical system model of the performance of aluminum-clad spent nuclear fuel in a dry storage canister (ASNF-in-canister) over its storage life. Hydrogen generation data and hydrogen generation rate (hydrogen generated per absorbed radiation dose, $\Delta$(H₂)/$\Delta$(dose)) were reported in two reports for radiolysis testing [1, 2]. The testing involved first-time data¹ for radiolytic yield of hydrogen from hydrated-oxides-on-aluminum substrates, and from pristine (non-corroded) aluminum substrates. The laboratory-grown hydrated-oxides-on-aluminum substrates contained a ~ 5 μm film consisting of the trihydroxide bayerite (Al(OH)₃) with amounts of the oxyhydroxide boehmite (AlOOH). These specimens were assumed to also contain physisorbed water (unquantified). The pristine substrates were flat coupons of aluminum that were ground to a 600-grit finish but were not immersed in water to grow a hydrated oxide. The pristine substrates were tested as companion specimens to provide information on hydrogen generation from material without chemisorbed water and were assumed to contain physisorbed water (unquantified).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Virtual Flow Simulator

Virtual Flow Simulator (VFS) is a state-of-the-art computational fluid mechanics (CFD) package that is capable of simulating multi-physics/multi-phase flows with the most advanced turbulence models (RANS, LES) over complex terrains. The flow solver is based on the Curvilinear Immersed Boundary (CURVIB) method to handle geometrically complex and moving domains. Different modules of the VFS package can provide different simulation capabilities for specific applications ranging from the fluid-structure interaction (FSI) of solid and deformable bodies, the two-phase free surface flow solver based on the level set method for ocean waves, sediment transport models in rivers and the large-scale models of wind farms based on actuator lines and surfaces. All numerical features of VFS package have been validated with known analytical and experimental data as reported in the related journal articles. VFS package is suitable for a broad range of engineering applications within different industries. VFS has been used in different projects with applications in wind and hydrokinetic energy, offshore and near-shore ocean studies, cardiovascular and biological flows, and natural streams and river morphodynamics. Over the last decade, the development of VFS has been supported and assisted with the help of various United States companies and federal agencies that are listed in the sponsor lists. In this version, VFS-Wind contains all the necessary modeling tools for wind energy applications, including land-based and offshore wind farms. VFS is highly scalable to run on either desktop computers or high performance clusters (up to 16,000 CPUs). This released version comes with a detailed user’s manual and a set of case studies designed to facilitate the learning of the various aspects of the code in a comprehensive manner. The included documentation and support material has been elaborated in a collaboration effort with Sandia National Labs under the contract DE-EE0005482. The VFS-Wind source code is distributed under the GNU General Public License (GPL 2.0), offering to the community the flexibility to use and expand the capabilities of the package. We note that future publications including academic journals that result from the use of VFS must be cited appropriately under the GPL v.2 license agreement.

Yang, Xiaolei↗