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At least 469 records · Page 26

Synchrotron X-ray diffraction of pyrolusite (MnO 2 ) and rutile (TiO 2 ) during heating to ~1000 °C

To compare thermal expansion behaviors in isomorphic structures with different redox behaviors, we separately heated pyrolusite (Mn 4+ O 2 ) and rutile (Ti 4+ O 2 ) powders from 25 to ~1000 °C at a rate of 0.05 °C/s at ambient pressure and analyzed them using synchrotron X-ray diffraction and Rietveld refinement. The pyrolusite exhibited two reduction-induced phase decompositions. Between 531 and 583 °C, pyrolusite decomposed to bixbyite (Mn 3+ 2 O 3 ), and between 972 and 998 °C, bixbyite decomposed to hausmannite (Mn 2+ Mn 3+ 2 O 4 ). The rutile experienced no phase decompositions or transitions over this same temperature interval. The refined bond lengths and angles for pyrolusite showed that the Mn 4+ coordination octahedron became more distorted near the phase decomposition to bixbyite due to the approach of two coordinating oxygen atoms. The 3d electrons of each Mn 4+ ion in pyrolusite make π bonds with the 2p electrons of the surrounding O 2- ions, whereas the Ti 4+ of rutile has no 3d electrons. Thus, π bonding between octahedral Mn 4+ and the surrounding O 2- anions increases the strength of the Mn–O bonds of pyrolusite relative to the Ti–O bonds of rutile. However, we observed a small decrease in O–O distances in pyrolusite before the decomposition, suggesting that at high temperature, increased π bonding between adjacent O anions precedes the release of O 2 and the reduction of Mn 4+ to Mn 3+ . Analogous behavior was observed for bixbyite before its reductive phase decomposition to hausmannite. In contrast, no anomalous changes in the O–O distances occurred for rutile. Our X-ray diffraction analyses provided accurate thermal expansion coefficients for these materials over a broader temperature range than reported in previous studies. The Mn–O bond lengths in pyrolusite were shorter and stronger than the Ti–O bonds of rutile; for example, at 60 °C, bond distances in pyrolusite refined to 1.8854(6) Å whereas the bond lengths of rutile were 1.9575(4) Å. Accordingly, the axial and volumetric thermal expansion coefficients refined for rutile were greater than those for pyrolusite. Further, the axial coefficients of thermal expansion (CTE) for pyrolusite were 96% (a-axis) and 69% (c-axis) of the corresponding values for rutile, and the volumetric CTE for pyrolusite was 85% of that for rutile.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Colossal Strain Tuning of Ferroelectric Transitions in KNbO 3 Thin Films

Strong coupling between polarization ( P ) and strain (ɛ) in ferroelectric complex oxides offers unique opportunities to dramatically tune their properties. Here colossal strain tuning of ferroelectricity in epitaxial KNbO 3 thin films grown by sub‐oxide molecular beam epitaxy is demonstrated. While bulk KNbO 3 exhibits three ferroelectric transitions and a Curie temperature ( T c ) of ≈676 K, phase‐field modeling predicts that a biaxial strain of as little as −0.6% pushes its T c > 975 K, its decomposition temperature in air, and for −1.4% strain, to T c > 1325 K, its melting point. Furthermore, a strain of −1.5% can stabilize a single phase throughout the entire temperature range of its stability. A combination of temperature‐dependent second harmonic generation measurements, synchrotron‐based X‐ray reciprocal space mapping, ferroelectric measurements, and transmission electron microscopy reveal a single tetragonal phase from 10 K to 975 K, an enhancement of ≈46% in the tetragonal phase remanent polarization ( P r ), and a ≈200% enhancement in its optical second harmonic generation coefficients over bulk values. These properties in a lead‐free system, but with properties comparable or superior to lead‐based systems, make it an attractive candidate for applications ranging from high‐temperature ferroelectric memory to cryogenic temperature quantum computing.

36 MATERIALS SCIENCE↗

Phase transformations in a Cu−Cr alloy induced by high pressure torsion

Phase transformations induced by high pressure torsion (HPT) at room temperature in two samples of the Cu-0.86 at.% Cr alloy, pre-annealed at 550 °C and 1000 °C, were studied in order to obtain two different initial states for the HPT procedure. Observation of microstructure of the samples before HPT revealed that the sample annealed at 550 °C contained two types of Cr precipitates in the Cu matrix: large particles (size about 500 nm) and small ones (size about 70 nm). The sample annealed at 1000 °C showed only a little fraction of Cr precipitates (size about 2 μm). The subsequent HPT process resulted in the partial dissolution of Cr precipitates in the first sample and dissolution of Cr precipitates with simultaneous decomposition of the supersaturated solid solution in another. However, the resulting microstructure of the samples after HPT was very similar from the standpoint of grain size, phase composition, texture analysis and hardness measurements. - Highlights: • Cu−Cr alloy with two different initial states was deformed by HPT. • Phase transformations in the deformed materials were studied. • SEM, TEM and X-ray diffraction techniques were used for microstructure analysis. • HPT leads to formation the same microstructure independent of the initial state.

36 MATERIALS SCIENCE↗

Direct comparison of Fe-Cr unmixing characterization by atom probe tomography and small angle scattering

The fine microstructure obtained by unmixing of a solid solution either by classical precipitation or spinodal decomposition is often characterized either by small angle scattering or atom probe tomography. This article shows that a common data analysis framework can be used to analyze data obtained from these two techniques. An example of the application of this common analysis is given for characterization of the unmixing of the Fe-Cr matrix of a 15-5 PH stainless steel during long-term ageing at 350 °C and 400 °C. A direct comparison of the Cr composition fluctuations amplitudes and characteristic lengths obtained with both techniques is made showing a quantitative agreement for the fluctuation amplitudes. The origin of the discrepancy remaining for the characteristic lengths is discussed. - Highlights: •Common analysis framework for atom probe tomography and small angle scattering •Comparison of same microstructural characteristics obtained using both techniques •Good correlation of Cr composition fluctuations amplitudes from both techniques •Good correlation of Cr composition fluctuations amplitudes with classic V parameter.

36 MATERIALS SCIENCE↗

A learned closure method applied to phase mixing in a turbulent gradient-driven gyrokinetic system in simple geometry

We present a new method for formulating closures that learn from kinetic simulation data. We apply this method to phase mixing in a simple gyrokinetic turbulent system – temperature-gradient-driven turbulence in an unsheared slab. The closure, called the learned multi-mode (LMM) closure, is constructed by, first, extracting an optimal basis from a nonlinear kinetic simulation using singular value decomposition. Subsequent nonlinear fluid simulations are projected onto this basis and the results are used to formulate the closure. We compare the closure with other closures schemes over a broad range of the relevant two-dimensional parameter space (collisionality and gradient drive). We find that the turbulent kinetic system produces phase-mixing rates much lower than the linear expectations, which the LMM closure is capable of capturing. We also compare radial heat fluxes. A Hammett–Perkins closure, generalized to include collisional effects, is quite successful throughout the parameter space, producing ${\sim }14\,\%$ root-mean-square (r.m.s.) error. The LMM closure is also very effective: when trained at three (two) points (in a 35 point parameter grid), the LMM closure produces $8\,\%$ ( $12\,\%$ ) r.m.s. errors. The LMM procedure can be readily generalized to other closure problems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Molecular Dynamics Study of Combustion Reactions in Supercritical Environment. Part 3: Boxed MD Study of CH 3 + HO 2 → CH 3 O + OH Reaction Kinetics

The kinetics of reaction CH 3 + HO 2 → CH 3 O + OH in supercritical carbon dioxide media at pressures from 0.3 to 1000 atm in the temperature range (600–1600) K was studied using boxed molecular dynamics simulations at QM/MM theory level with periodical boundary conditions. The mechanism of this process includes two consecutive steps: formation and decomposition of CH 3 OOH intermediate. We calculated the activation free energies and rate constants of each step, then used Bodenstein’s quasistationary concentrations approximation to estimate the rate constants of the reaction. On the basis of the temperature dependence of the rate constants, parameters in the extended Arrhenius equation were determined. Furthermore, we found that reaction rate of each step, as well as overall reaction, increases with increasing CO 2 pressure in the system. The most capable zone for the process is T = 1000–1200 K, and the CO 2 pressure is about 100 atm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Restricted Acoustic Modal Analysis Applied to Internal Combustor Spectra and Cross-Spectra Measurements

A treatment of the modal decomposition of the pressure field in a combustor as determined by two Kulite pressure measurements is developed herein. It is applied to a Pratt & Whitney PW4098 engine combustor over a range of operating conditions. For modes other than the plane wave the new part of the treatment is the assumption that there are distinct frequency bands in which the individual modes, including the plane wave mode, overlap such that if circumferential mode m and circumferential mode m-1 are present than circumferential mode m 2 is not. Consequently, in the analysis used herein at frequencies above the first cut-off mode frequency, only pairs of circumferential modes are individually present at each frequency. Consequently, this is a restricted modal analysis. A new result is that the successful use of the same modal span frequencies over a range of operating conditions for this particular engine suggests that the temperature, T, and the velocity, v, of the flow at each operating condition are related by c(sup 2)-v(sup 2) = a constant where c is the speed of sound.

Miles, Jeffrey Hilton↗

A determination of the oxygen non-stoichiometry of the oxygen storage materials LnBaMn{sub 2}O{sub 5+δ} (Ln=Gd, Pr)

The A-site ordered double-perovskite oxides, LnBaMn{sub 2}O{sub 5+δ} (Ln=Gd, Pr), were synthesized and investigated to understand the effect of A site cation substitution on the oxygen storage properties of these materials. The present results are compared with our previous data for YBaMn{sub 2}O{sub 5+δ}. The results clearly reveal that changing the Ln cation strongly influences the oxidation/reduction behavior of LnBaMn{sub 2}O{sub 5+δ}. Based on thermogravimetric analysis data, oxygen uptake begins at lower temperatures in both air and oxygen in compounds with Ln{sup 3+} ions larger than Y{sup 3+}. These oxides exhibit almost complete and reversible oxygen uptake/release between fully-reduced LnBaMn{sub 2}O{sub 5} and fully-oxidized LnBaMn{sub 2}O{sub 6} during changes of the oxygen partial pressure between air and 1.99% H{sub 2}/Ar. In addition, the oxygen non-stoichiometries of GdBaMn{sub 2}O{sub 5+δ} and PrBaMn{sub 2}O{sub 5+δ} were determined as a function of pO{sub 2} at 600, 650, 700 and 750 °C by Coulometric titration at near-equilibrium conditions. The results confirm that these materials have two distinct phases on oxidation/reduction with δ≈0, 0.5 and a third phase with a range of composition with an oxygen content (5+δ) approaching ~6. The stabilities of the LnBaMn{sub 2}O{sub 5+δ} phases extend over a wide range of oxygen partial pressures (∼10{sup −25}≤pO{sub 2} (atm)≤∼1) depending on temperature. Isothermal experiments show that the larger the Ln{sup 3+} cation the lower pO{sub 2} for phase conversion. At some temperatures and pO{sub 2} conditions, the LnBaMn{sub 2}O{sub 5+δ} compounds are unstable with respect to decomposition to BaMnO{sub 3−δ} and LnMnO{sub 3}. This instability is more apparent in Coulometric titration experiments than in thermogravimetric analysis. The Coulometric titration experiments are necessarily slow in order to achieve equilibrium oxygen compositions. - Graphical abstract: Structure of LnBaMn{sub 2}O{sub 5.5} and the variation of stoichiometry of GdBaMn{sub 2}O{sub 5+x} with −log(pO{sub 2}) Display Omitted - Highlights: • Determination of the oxygen non-stoichiometry of GdBaMn{sub 2}O{sub 5+δ} and PrBaMn{sub 2}O{sub 5+δ} as a function of pO{sub 2} and T. • Establishment of pO{sub 2} ranges of stability of O{sub 5} and O{sub 5.5} at 600 °C, 650 °C, 700 °C and 750 °C. • Investigation of the kinetic instability of LnBaMn{sub 2}O{sub 5+δ} (Ln=Gd, Pr) with respect to decomposition to BaMnO{sub 3−x} and LnMnO{sub 3} • Comparison of the thermodynamics of the oxidation of LnBaMnO{sub 5} (Ln=Y, Gd, Pr) as a function of the rare earth cation size.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Conditions for critical effects in the mass action kinetics equations for water radiolysis

We report on a subtle global feature of the mass action kinetics equations for water radiolysis that results in predictions of a critical behavior in H2O2 and associated radical concentrations. While radiolysis kinetics has been studied extensively in the past, it is only in recent years that high speed computing has allowed the rapid exploration of the solution over widely varying dose and compositional conditions. We explore the radiolytic production of H2O2 under various externally fixed conditions of molecular H2 and O2 that have been regarded as problematic in the literature – specifically, “jumps” in predicted concentrations, and inconsistencies between predictions and experiments have been reported for alpha radiolysis. We computationally map-out a critical concentration behavior for alpha radiolysis kinetics using a comprehensive set of reactions. We then show that all features of interest are accurately reproduced with 15 reactions. An analytical solution for steady-state concentrations of the 15 reactions reveals regions in [H2] and [O2] where the H2O2 concentration is not unique – both stable and unstable concentrations exist. The boundary of this region can be characterized analytically as a function of G-values and rate constants independent of dose rate. Physically, the boundary can be understood as separating a region where a steady-state H2O2 concentration exists, from one where it does not exist without a direct decomposition reaction. We show that this behavior is consistent with reported alpha radiolysis data and that no such behavior should occur for gamma radiolysis. We suggest experiments that could verify or discredit a critical concentration behavior for alpha radiolysis and could place more restrictive ranges on G-values from derived relationships between them.

Wittman, Richard S.↗

Reliable and Efficient Parallel Processing Algorithms and Architectures for Modern Signal Processing

Least-squares (LS) estimations and spectral decomposition algorithms constitute the heart of modern signal processing and communication problems. Implementations of recursive LS and spectral decomposition algorithms onto parallel processing architectures such as systolic arrays with efficient fault-tolerant schemes are the major concerns of this dissertation. There are four major results in this dissertation. First, we propose the systolic block Householder transformation with application to the recursive least-squares minimization. It is successfully implemented on a systolic array with a two-level pipelined implementation at the vector level as well as at the word level. Second, a real-time algorithm-based concurrent error detection scheme based on the residual method is proposed for the QRD RLS systolic array. The fault diagnosis, order degraded reconfiguration, and performance analysis are also considered. Third, the dynamic range, stability, error detection capability under finite-precision implementation, order degraded performance, and residual estimation under faulty situations for the QRD RLS systolic array are studied in details. Finally, we propose the use of multi-phase systolic algorithms for spectral decomposition based on the QR algorithm. Two systolic architectures, one based on triangular array and another based on rectangular array, are presented for the multiphase operations with fault-tolerant considerations. Eigenvectors and singular vectors can be easily obtained by using the multi-pase operations. Performance issues are also considered.

Liu, Kuojuey Ray↗

Process R&D for Particle Size Control of Molybdenum Oxide

The primary goal of this study was to produce MoO 3 powder with a particle size range of 50 to 200 μm for use in targets for production of the medical isotope 99 Mo. Molybdenum metal powder is commercially produced by thermal reduction of oxides in a hydrogen atmosphere. The most common source material is MoO 3 , which is derived by the thermal decomposition of ammonium heptamolybdate (AHM). However, the particle size of the currently produced MoO 3 is too small, resulting in Mo powder that is too fine to properly sinter and press into the desired target. In this study, effects of heating rate, heating temperature, gas type, gas flow rate, and isothermal heating were investigated for the decomposition of AHM. The main conclusions were as follows: lower heating rate (2-10°C/min) minimizes breakdown of aggregates, recrystallized samples with millimeter-sized aggregates are resistant to various heat treatments, extended isothermal heating at >600°C leads to significant sintering, and inert gas and high gas flow rate (up to 2000 ml/min) did not significantly affect particle size distribution or composition. In addition, attempts to recover AHM from an aqueous solution by several methods (spray drying, precipitation, and low temperature crystallization) failed to achieve the desired particle size range of 50 to 200 μm. Further studies are planned.

36 MATERIALS SCIENCE↗

Data-scarce surrogate modeling of shock-induced pore collapse process

Understanding the mechanisms of shock-induced pore collapse is of great interest in various disciplines in sciences and engineering, including materials science, biological sciences, and geophysics. However, numerical modeling of the complex pore collapse processes can be costly. To this end, a strong need exists to develop surrogate models for generating economic predictions of pore collapse processes. Here, in this work, we study the use of a data-driven reduced-order model, namely dynamic mode decomposition, and a deep generative model, namely conditional generative adversarial networks, to resemble the numerical simulations of the pore collapse process at representative training shock pressures. Since the simulations are expensive, the training data are scarce, which makes training an accurate surrogate model challenging. To overcome the difficulties posed by the complex physics phenomena, we make several crucial treatments to the plain original form of the methods to increase the capability of approximating and predicting the dynamics. In particular, physics information is used as indicators or conditional inputs to guide the prediction. In realizing these methods, the training of each dynamic mode composition model takes only around 30 s on CPU. In contrast, training a generative adversarial network model takes 8 h on GPU. Moreover, using dynamic mode decomposition, the final-time relative error is around 0.3% in the reproductive cases. We also demonstrate the predictive power of the methods at unseen testing shock pressures, where the error ranges from 1.3 to 5% in the interpolatory cases and 8 to 9% in extrapolatory cases.

97 MATHEMATICS AND COMPUTING↗

21 cm Power Spectrum Analysis of North Celestial Pole Observations with the Tianlai Dish Pathfinder Array

The Tianlai Dish Pathfinder Array (TDPA) is a radio interferometer designed to test techniques for 21 cm intensity mapping in the post-reionization Universe as a means of measuring large-scale cosmic structure. Using nine nights of observations targeting the North Celestial Pole field, totaling approximately 107 hr of integration time, we analyze data in the frequency range 700–800 MHz (corresponding to redshift z ∼ 0.9). We do the data format conversion, radio frequency interference flagging, calibration, imaging and point source subtraction, and foreground removal via Singular Value Decomposition. The spherically averaged power spectrum Δ 2 (k) is obtained. Furthermore, this work successfully establishes and validates a comprehensive data analysis framework for the TDPA. We identify key improvements including sky model refinement, increased integration time, and pipeline optimization that will enable future detection of the 21 cm signal through auto-correlation and cross-correlation with optical galaxy surveys.

cosmology: large-scale structure of universe↗

Tensor Toolbox for MATLAB v. 3.0

Tensors (also known as multidimensional arrays or N-way arrays) are used in a variety of applications ranging from chemometrics to network analysis. The Tensor Toolbox provides classes for manipulating dense, sparse, and structured tensors using MATLAB's object-oriented features. It also provides algorithms for tensor decomposition and factorization, algorithms for computing tensor eigenvalues, and methods for visualization of results.

Kolda, Tamara↗

Ice in the lunar polar regions

The idea that ice and other trapped volatiles exist in permanently shadowed regions near the lunar poles was proposed by Watson, Murray, and Brown (1961). It is reexamined in the present paper, in the light of the vast increase of lunar knowledge. The stability of the traps and the trapping mechanism are verified. Four potential sources of lunar H2O, namely (1) solar wind reduction of Fe in the regolith, (2) H2O-containing meteoroids, (3) cometary impact, and (4) (the least certain) degassing of the interior, can supply amounts of trapped H2O estimated in the range of 10 to the 16th to 10 to the 17th g. Two important destructive mechanisms have been identified: photodissociation of H2O molecules adsorbed on the sunlit surface and sputtering or decomposition of trapped H2O by solar wind particles. The effect of impact gardening is mainly protective. The question of the presence of H2O in the traps remains open; it can be settled by experiment.

Arnold, J. R.↗

Equivalent Dipole Vector Analysis for Detecting Pulmonary Hypertension

Various 12-lead ECG criteria have been established to detect right ventricular hypertrophy as a marker of pulmonary hypertension (PH). While some criteria offer good specificity they lack sensitivity because of a low prevalence of positive findings in the PH population. We hypothesized that three-dimensional equivalent dipole (ED) model could serve as a better detection tool of PH. We enrolled: 1) 17 patients (12 female, 5 male, mean age 57 years, range 19-79 years) with echocardiographically detected PH (systolic pulmonary arterial pressure greater than 35 mmHg) and no significant left ventricular disease; and 2) 19 healthy controls (7 female, 12 male, mean age 44, range 31-53 years) with no known heart disease. In each subject we recorded a 5-minute high-resolution 12-lead conventional ECG and constructed principal signals using singular value decomposition. Assuming a standard thorax dimension of an adult person with homogenous and isotropic distribution of thorax conductance, we determined moving equivalent dipoles (ED), characterized by the 3D location in the thorax, dipolar strength and the spatial orientation, in time intervals of 5 ms. We used the sum of all ED vectors in the second half of the QRS complex to derive the amplitude of the right-sided ED vector (RV), if the orientation of ED was to the right side of the thorax, and in the first half the QRS to derive the amplitude of the left-sided vector (LV), if the orientation was leftward. Finally, the parameter RV/LV ratio was determined over an average of 256 complexes. The groups differed in age and gender to some extent. There was a non-significant trend toward higher RV in patients with PH (438 units 284) than in controls (280 plus or minus 140) (p = 0.066) but the overlap was such that RV alone was not a good predictor of PH. On the other hand, the RV/LV ratio was a better predictor of PH, with 11/17 (64.7%) of PH patients but only in 1/19 (5.3%) control subjects having RV/LV ratio greater than or equal to 0.70 (p less than 0.001). The use of ED for evaluating PH shows good specificity at a reasonable sensitivity. The results are limited due to the small study groups and differences in age and gender, but further investigations are warranted, including of ED's diagnostic accuracy for PH versus that of other proposed ECG and VCG criteria.

Harlander, Matevz↗

Ionic Liquids to Replace Hydrazine

A method for developing safe, easy-to-handle propellants has been developed based upon ionic liquids (ILs) or their eutectic mixtures. An IL is a binary combination of a typically organic cation and anion, which generally produces an ionic salt with a melting point below 100 deg C. Many ILs have melting points near, or even below, room temperature (room temperature ionic liquids, RTILs). More importantly, a number of ILs have a positive enthalpy of formation. This means the thermal energy released during decomposition reactions makes energetic ILs ideal for use as propellants. In this specific work, to date, a baseline set of energetic ILs has been identified, synthesized, and characterized. Many of the ILs in this set have excellent performance potential in their own right. In all, ten ILs were characterized for their enthalpy of formation, density, melting point, glass transition point (if applicable), and decomposition temperature. Enthalpy of formation was measured using a microcalorimeter designed specifically to test milligram amounts of energetic materials. Of the ten ILs characterized, five offer higher Isp performance than hydrazine, ranging between 10 and 113 seconds higher than the state-of-the-art propellant. To achieve this level of performance, the energetic cations 4- amino-l,2,4-triazolium and 3-amino-1,2,4-triazolium were paired with various anions in the nitrate, dicyanamide, chloride, and 3-nitro-l,2,4-triazole families. Protonation, alkylation, and butylation synthesis routes were used for creation of the different salts.

Koelfgen, Syri↗

Three-dimensional indium distribution in electron-beam irradiated multiple quantum wells of blue-emitting InGaN/GaN devices

The compositional distribution of In atoms in InGaN/GaN multiple quantum wells is considered as one of the candidates for carrier localization center, which enhances the efficiency of the light-emitting diodes. However, two challenging issues exist in this research area. First, an inhomogeneous In distribution is initially formed by spinodal decomposition during device fabrication as revealed by transmission electron microscopy. Second, electron-beam irradiation during microscopy causes the compositional inhomogeneity of In to appear as a damage contrast. Here, a systematic approach was proposed in this study: Electron-beam with current density ranging from 0 to 20.9 A/cm{sup 2} was initially exposed to the surface regions during microscopy. Then, the electron-beam irradiated regions at the tip surface were further removed, and finally, atom probe tomography was performed to run the samples without beam-induced damage and to evaluate the existence of local inhomegenity of In atoms. We proved that after eliminating the electron-beam induced damage regions, no evidence of In clustering was observed in the blue-emitting InGaN/GaN devices. In addition, it is concluded that the electron-beam induced localization of In atoms is a surface-related phenomenon, and hence spinodal decomposition, which is typically responsible for such In clustering, is negligible for biaxially strained blue-emitting InGaN/GaN devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗