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At least 145 records · Page 8

Effects of Nonequilibrium Atomic Structure on Ionic Diffusivity in LLZO: A Classical and Machine Learning Molecular Dynamics Study

To improve the performance of electrochemical devices, it is essential to understand the effects of nonequilibrium motifs in solids, such as grain boundaries, amorphous phases, and highly strained regions, on atomic-scale transport and stability. Molecular dynamics simulations are used to explore the combined effect of far-from-equilibrium atomic structures and the choice of interatomic potential on ionic diffusivity predictions for Li 7 La 3 Zr 2 O 12 (LLZO), a promising solid electrolyte for all-solid-state batteries. Amorphization and high strain are considered using both classical Buckingham interatomic potentials and machine learning force fields. Here we find that both crystalline expansion and amorphization tend to slow diffusion, although the different physical encodings in the two potentials impact the properties in different ways. We trace these variations to a combination of structural and transport factors, the contributions of which are deconvoluted computationally. Graph-based analysis reveals that the variations for amorphous LLZO arise from the connectivity of diffusion pathways within the predicted structures, which generally correlates with diffusivity and is notably higher for structures generated by the machine learning force fields. Our study provides additional insight into the relationship between atomic structure and diffusivity in LLZO, while also highlighting the need for care in choosing and validating potentials to simulate far from equilibrium structures.

25 ENERGY STORAGE↗

Structure of deformed silicon and implications for low-cost solar cells

The paper reports on an investigation of the microstructure and minority carrier lifetime of silicon in uniaxially compressed silicon samples, the objective of which was to determine if it is feasible to produce silicon solar cells from sheet formed by high temperature deformation. It is reported that recrystallization was found to be incomplete in both fine and large grained materials, and that the major mode of recrystallization appears to be migration of existing boundaries into the deformed regions. Also, minority carrier diffusion length was found to be drastically reduced after deformation, perhaps due to contamination or cooling rate, and recovered only slightly with annealing. It is concluded that these results suggest that high temperature deformation of silicon for direct production of sheet for high efficiency solar cells is not practical. It is noted that potential may exist for its use as a coarse grained substrate.

Mardesich, N.↗

Modification of Ni-20Cr corrosion dealloying behavior in molten fluorides via cold work induced plastic deformation

The corrosion dealloying behavior of cold-worked (CW) Ni20Cr alloy (wt%) was studied in molten LiF-NaF-KF (or FLiNaK) salts at 600 °C, equal to a homologous temperature (TH) of 0.52. Alloys were cold-rolled to achieve reductions of thickness of 10%, 30%, and 50% introducing plastic deformation and a high density of dislocations. Potentiostatic holds (Eapplied) were applied in two different electrode potential regimes. At 1.75VK+/K$${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$, Cr dealloying to Cr(II) and Cr(III) is predominant, while at 1.90 VK+/K$${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$, both Ni and Cr are oxidized in molten FLiNaK at 600 °C. In these potential regimes, dealloyed Ni20Cr displayed bicontinuous porosity within the grain interior and at grain boundaries, driven by the high driving force for Cr dissolution and sustained by defect mediated outward solid state diffusion of Cr in parallel with surface diffusion of Ni. The bicontinuous porous structure developed was observed to undergo further coarsening and densification of the Ni-rich ligaments at a higher electrode potential. The main effect of CW observed is the introduction of plastic deformation and dislocation substructures that serve as short-circuit paths for Cr solid state diffusion to surfaces exposed to FLiNaK. This modified the evolution of the bicontinuous porous structure which increased with CW substantially. Kinetic analysis reveals that the Cr dealloying at +1.75 VK+/K$${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$ and 1.90 VK+/K$${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$ is initially charge transfer controlled, except for the 50% CW condition at 1.90 VK+/K$${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$, where the process becomes limited by slow Cr defect mediated bulk diffusion. The rate determining factors are explored and compared to experimental results.

Chan, Ho Lun↗

Grain Boundary-Limited Thermal Transport in Suspended Thin Graphite across an Unexplored Thickness Regime

Here, we present systematic thermal conductivity (κ) measurements of suspended thin graphite ribbons, 234–527 nm thick, using a four-probe 3ω method. Unlike recent reports of phonon hydrodynamics and exceptionally high κ in micrometer-thick graphite ( Science, 2020), we observe significantly lower κ and no signatures of collective phonon flow in this intermediate thickness regime. Instead, our measured κ lies between few-layer graphene and bulk graphite. These results agree with a first-principles-informed Peierls–Boltzmann transport model with spatially resolved Monte Carlo sampling. Additionally, the temperature for the peak κ shifts lower with increasing thickness, due to the interplay of phonon-boundary and phonon-isotope scattering. Incorporating grain boundary scattering into simulations is necessary to replicate the experimental trends. These findings delineate the boundary between ballistic, hydrodynamic, and diffusive transport regimes in graphite and underscore the dominant role of disorder and geometry in phonon transport in quasi-two-dimensional materials, offering insights for nanoscale thermal management.

Boltzmann transport model↗

Mitigation of Cu-Induced Grain Boundary Sensitization in Steel Wire Rods Through a Desensitization Heat Treatment

Steel wire rods are essential for manufacturing high-strength steel tire cords. Yet, the presence of residual copper (Cu) in recycled steel can cause grain-boundary sensitization, embrittlement, and deterioration of the mechanical performance of the final product. This study introduces a desensitization heat treatment step designed to redistribute Cu away from austenite grain boundaries after sensitization occurs. The treatment consists of a 10 min dwell at 1000 °C in a 5%H 2 -Ar reducing atmosphere followed by quench. The temperature and hold time were selected based on diffusion calculations to promote solid-state back diffusion of Cu without altering grain morphology. Experimental validation showed that the dwell step reduced the length of Cu-rich sensitized zones of steel wire rod samples containing 0.21 wt.% Cu by approximately 89% and restored the mechanical properties to nearly 95–98% relative to low-Cu baseline steel (0.01 wt.% Cu). Compared with sensitized and as-obtained samples, these results highlight the effectiveness of the proposed method in improving both the microstructure and tensile performance of recycled steel wire rods, enabling their potential application in tire manufacturing.

copper↗

Onset of Convection in Ice I with Composite Newtonian and Non-Newtonian Rheology: Application to the Icy Galilean Satellites

Ice I exhibits a complex rheology at temperature and pressure conditions appropriate for the interiors of the ice I shells of Europa, Ganymede, and Callisto. We use numerical methods and existing parameterizations of the critical Rayleigh number to determine the conditions required to trigger convection in an ice I shell with the stress-, temperature- and grain size- dependent rheology measured in laboratory experiments by Goldsby and Kohlstedt [2001]. The critical Rayleigh number depends on the ice grain size and the amplitude and wavelength of temperature perturbation issued to an initially conductive ice I shell. If the shells have an assumed uniform grain size less than 0.4 mm, deformation during initial plume growth is accommodated by Newtonian volume diffusion. If the ice grain size is between 0.4 mm and 3 cm, deformation during plume growth is accommodated by weakly non-Newtonian grain boundary sliding, where the critical ice shell thickness for convection depends on the amplitude of temperature perturbation to the _0.5 power. If the ice grain size exceeds 2 cm, convection can not occur in the ice I shells of the Galilean satellites regardless of the amplitude or wavelength of temperature perturbation. If the grain size in a convecting ice I shell evolves to effective values greater than 2 cm, convection will cease. If the ice shell has a grain size large enough to permit flow by dislocation creep, the ice is too stiff to permit convection, even in the thickest possible ice I shell. Consideration of the composite rheology implies that estimates of the grain size in the satellites and knowledge of their initial thermal states are required when judging the convective instability of their ice I shells.

Barr, A. C.↗

Techniques Optimized for Reducing Instabilities in Advanced Nickel-Base Superalloys for Turbine Blades

The High-Speed Research (HSR) Airfoil Alloy program developed fourth-generation single-crystal superalloys with up to an 85 F increase in creep rupture capability over current production airfoil alloys. Recent results have been generated at the NASA Glenn Research Center on these fourth-generation alloys, but in coated form, for subsonic turbine blade applications under NASA's Ultra-Efficient Engine Technology (UEET) Program. One goal for UEET is to optimize the airfoil alloy/thermal barrier coating system for 3100 F turbine inlet temperatures. The state-of-the art turbine blade airfoil system consists of a superalloy single crystal that provides the basic mechanical performance of the airfoil. A thermal barrier coating is used to reduce the temperature of the base superalloy, and a bondcoat is deposited between the base material and the thermal barrier coating. The bondcoat improves the oxidation and corrosion resistance of the base superalloy and improves the spallation resistance of the thermal barrier coating. A commercial platinum aluminide bondcoat was applied to the HSR-developed alloys, and a diffusion zone developed as a result of interaction between the bondcoat and the superalloy. Optimized strength is obtained for superalloys when the refractory element content is high and the limits of microstructural stability are approached or exceeded slightly. For fourthgeneration alloys, instability leads to the formation of topologically close packed (TCP) phases, which form internally in the superalloy, and a secondary reaction zone (SRZ), which forms under the diffusion zone. There was a concern that excessive quantities of either TCP or SRZ might decrease the mechanical properties of the superalloy, with SRZ thought to be particularly detrimental and its formation unpredictable. Thus, an SRZreduction effort was initiated in the NASA UEET Program so that methods developed during the HSR project could be optimized further to reduce or eliminate the SRZ. An SRZ is a three-phase constituent composed of TCP and stringers of gamma phase in a matrix of gamma prime. An incoherent grain boundary separates the SRZ from the gammagamma prime microstructure of the superalloy. The SRZ is believed to form as a result of local chemistry changes in the superalloy due to the application of the diffusion aluminide bondcoat. Locally high surface stresses also appear to promote the formation of the SRZ. Thus, techniques that change the local alloy chemistry or reduce surface stresses have been examined for their effectiveness in reducing SRZ. These SRZ-reduction steps are performed on the test specimen or the turbine blade before the bondcoat is applied. Stressrelief heat treatments developed at NASA Glenn have been demonstrated to reduce significantly the amount of SRZ that develops during subsequent high-temperature exposures. Stress-relief heat treatments reduce surface stresses by recrystallizing a thin surface layer of the superalloy. However, in alloys with very high propensities to form SRZ, stress relief heat treatments alone do not eliminate SRZ entirely. Thus, techniques that modify the local chemistry under the bondcoat have been emphasized and optimized successfully at Glenn. One such technique is carburization, which changes the local chemistry by forming submicron carbides near the surface of the superalloy. Detailed characterizations have demonstrated that the depth and uniform distribution of these carbides are enhanced when a stress relief treatment and an appropriate surface preparation are employed in advance of the carburization treatment. Even in alloys that have the propensity to develop a continuous SRZ layer beneath the diffusion zone, the SRZ has been completely eliminated or reduced to low, manageable levels when this combination of techniques is utilized. Now that the techniques to mitigate SRZ have been established at Glenn, TCP phase formation is being emphasized in ongoing work under the UEET Program. The limitsf stability of the fourth-generation alloys with respect to TCP phase formation are currently being defined along with high-temperature creep rupture properties. In addition, a regression model is being developed at Glenn for the prediction of the presence of TCP phase in the microstructure and SRZ under the diffusion zone. The model is based on a design-of-experiments methodology with emphasis on the potential synergistic effects of alloying elements.

MacKay, Rebecca A.↗

A compartmentalized model of multiphase chemical kinetics

There are significant challenges in predicting multiphase chemical kinetics due to the complex coupling of reaction and mass transport across a phase boundary (i.e., interface). Here, we describe a framework for predicting multiphase kinetics that embeds the elementary kinetic steps of reaction, solvation, and diffusion into a coarse grain spatial description of two phases. The model is constructed to bridge the short-timescale interfacial dynamics observed in molecular simulations with the longer timescales observed in kinetic experiments. A simple set of governing differential equations is derived, which, when solved numerically or analytically, yield accurate predictions of multiphase kinetics in microdroplets. Although the equations are formulated for gas-liquid reactions, the underlying conceptual framework is general and can be applied to transformations in other two-phase systems (solid-liquid, liquid-liquid, etc.).

Chemical kinetics and dynamics↗

Defect Production and Microstructural Feature Impact for Radiation Damage in Additively Manufactured 316 Stainless Steel

This milestone presents multi-scale modeling research results for additively manufactured 316 stainless steel. A combination of phase field, cluster dynamics, molecular dynamics, and density functional theory with machine learning is used, allowing for predictions of radiation-driven microstructural evolution in additively manufactured 316 stainless steel over a range of temperatures, damage rates, neutron spectra, and microstructures, and supporting the development of combined ion and neutron irradiation for material qualification. Informed by ion irradiation and neutron irradiation results across the Advanced Materials and Manufacturing Technologies program, we investigate the unique aspects of radiation-driven microstructure evolution in additively manufactured 316 stainless steel. In particular, we focus on understanding the impact of carbon concentration (varying, for example, between the 316L and 316H standards) on void formation; radiation-induced segregation at dislocation cells and grain boundaries; and the evolution of dislocation loops and network dislocation populations. We find that the unique characteristics of the additively manufactured microstructures must be accounted for in understanding the evolution of dislocation populations under thermal and irradiation conditions, such as the variation in sink strengths arising due to the variation in dislocation density. We also find that the radiation-induced segregation of Cr and Ni to grain boundaries and cell walls differs due to the differences in their defect sink biases. We also find that increasing the Ni content can slow vacancy diffusion, which may provide a mechanism for the observed reduction in transient swelling rate for austenitic Fe-Cr-Ni alloys with increasing Ni content. In addition, ion irradiations have shown that increasing carbon content in 316 SS results in a larger population of smaller voids, suggesting reduced vacancy diffusion. Our results show that the carbon content of additively manufactured 316 SS has a significant impact on the migration rate of defect clusters. The presence of carbon atoms results in carbon-vacancy trapping, significantly reducing the diffusion rate of vacancies. Carbon atoms may also be trapped near the surface of a void, which may reduce void growth by trapping vacancies that diffuse toward the void.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Structural defects in crystalline silicon

The basic photovoltaic properties of a given crystalline silicon specimen seem to be governed by density and nature of two to three dimensional lattice defects. These are mainly generated by primary growth conditions as grain boundaries of more or less intrinsic character or second phase precipitates from supersaturated solutions of carbon or oxygen. Considerably high values of both solubility and diffusivity in connection with their abundance in common refractory material systems account for the predominance of the two particular elements. Unsaturated dislocations of different types very often can be seen as a consequence of the existence of more dimensional defects as described initially. The final performance of a solar cell is dependent of the concentration and distribution of recombination active centers in the different regions of this device. Typical representatives are fast diffusing transition metals in form of either single atoms or simple complexes. Their avoidance, annihilation, or removal is of great concern in different fields of electronic materials development.

Sirtl, E.↗

Tambo Quemado: Extraordinary concentrations of REE and refractory trace elements caused by artificial heating

Buchwald examined samples of the IIIB iron Tambo Quemado (TAMQ) cut from the 130 kg main mass. He determined it had been artificially heated, at some time prior to being reported, in an attempt to obtain metal from it. Although the Widmanstatten structure appears relatively unaffected under macroscopic examination, microscopic study of etched sections reveals the effect of the heating. Taenite and plessite area boundaries are indistinct due to high temperature diffusion. Schreibersite, once present in significant amounts, has been melted. Schreibersites in the interior have resolidified in fine-grained eutectic textures surrounded by dark-etching metal rims supersaturated with phosphorus. Buchwald states that phosphate minerals were probably present originally, because graftonite, and its polymorph sarcopside (both essentially Fe3(PO4)2), are common in irons of the IIIB groups. Based on his metallographic study Buchwald estimates TAMQ was heated to 1000 C for about one hour. An interior sample from TAMQ was examined in order to determine what effect this unintended heating 'experiment' had upon the phosphate phases.

Olsen, E.↗

Morphologies of dealloying corrosion attack at grain boundaries

Dealloying corrosion at grain boundaries severely compromises the performance of polycrystalline materials across a wide variety of technological applications. The impact of this phenomenon depends upon the morphology and rate of intergranular dealloying, which can range from planar to wormhole-like patterns that rapidly advance into the alloy. Using 2D and 3D multi-phase field simulations, we reveal how diverse microstructures result from a fundamental interplay between alloy composition and a grain boundary migration mechanism that alters diffusional pathways of dealloying. Inside intergranular dealloying channels, corrosion product buildup can spawn new channels that branch into grain interiors, such that alloys can be degraded from the inside out. These processes further lead to an atypical coarsening mode assisted by diffusion in the dealloying agent. We summarize a unifying explanation for dealloying morphology selection in polycrystalline alloys, which provides an important step towards their optimization for dealloying corrosion environments.

Corrosion↗

Molecular dynamics study of grain boundaries as defect sinks under irradiation in LiAlO 2 and LiAl 5 O 8

Lithium aluminate ceramics, LiAlO 2 and LiAl 5 O 8 , show promise in nuclear environments due to their excellent radiation tolerance. Molecular dynamics simulations investigate grain boundaries (GB) and their role in defect evolution. Results reveal that GBs act as efficient defect sinks, with Li and Al atoms exhibiting distinct behaviors during displacement cascades. Tritium migration in LiAlO 2 is also studied, showing rapid diffusion and stable configurations with oxygen, corroborated by ab initio simulations from the literature. The calculated tritium diffusion coefficient of 1.33 × 10 - ¹⁴ m²/s aligns with the literature, validating the model. LiAl 5 O 8 demonstrates superior defect healing compared to LiAlO 2 , attributed to enhanced atomic transfer between grains and GBs. These findings reveal key insights into defect dynamics, providing essential insights for their application in tritium-producing burnable absorber rods (TPBARs).

36 MATERIALS SCIENCE↗

Electro-carburization of mild steel through two-step reaction in molten-salt electrolyte

The rapid carburization of mild steel is demonstrated via the electrochemical deposition of solid carbon, followed by thermochemical iron-carbon (Fe-C) reaction using a molten lithium-potassium carbonate (LiKCO 3 ) salt electrolyte and carbon dioxide as the carbon source. Depth-dependent microstructural and compositional changes in the steel are shown to be controlled by the applied cell voltage and reaction temperatures. Reaction temperatures above the Fe-C eutectoid temperature promote faster carburization due to carbon dissolution into austenite. The carbon deposition rate is regulated by the applied cell voltage: At - 2.4 V, carbon deposition occurs much faster than its diffusion into the steel, resulting in the accumulation of a carbon-rich layer exceeding 1 mm, which does not diffuse into the steel. In contrast, at - 1.8 V, all deposited carbon effectively diffuses into the steel, leaving a minimal external deposit. In both cases, carbon ingress forms a carbide-rich surface layer and precipitates additional carbides along the grain boundaries within the steel electrode. This method offers a potential approach to increase the carbon content of mild or low-carbon steel feedstocks, such as scrap or direct reduced iron, for industrial applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chromium-doped uranium dioxide fuels: A review

UO 2 doped with parts per million CR 2 O 3 powder is considered a potential near term accident tolerant fuel candidate. Here, the results of decades of industry and academic research into Cr-doped UO 2 are analyzed and their shortcomings are critiqued. Focusing on the incorporation mechanisms of Cr into the fuel matrix, we explore a mechanistic understanding of the characteristic properties of Cr-doped UO 2 , notably, enhanced fission gas retention attributed to enlarged grain sizes following sintering, along with marginal improvements in the thermophysical properties. The findings of recent X-ray Adsorption Near Edge Spectroscopy studies were compared and put into conversation with historic data regarding the incorporation of Cr in UO 2 . On the basis of defect mechanisms, the case is made for the substitutional incorporation of Cr governing the lattice solubility but not the enhanced U diffusivity. Instead, Cr/CR 2 O 3 redox chemistry in a well-defined oxygen potential explains the differences in the U diffusivity and O/M ratio. The primary mechanism of doping enhanced grain growth is found to be liquid assisted sintering due to a CRO (1) eutectic phase at the grain boundaries. The role of inhomogeneities in Cr concentration in UO 2 at various length scales across the materials microstructure is highlighted and connected to promising experimental and modeling work to fill in the gaps in the current understanding of Cr-doped UO 2 . The review considers both the open scientific questions and engineering applications to illustrate the deep connections between the practice and theory in the design of accident tolerant nuclear fuels. In conclusion, the review ends with an outline of future works that combine meticulous irradiation studies and high resolution experiments with next generation modeling and simulations techniques empowered by machine learning advances to accelerate the fabrication and adoption of Cr-doped UO 2 light water reactors.

Cleveland, Mack Wesley [Massachusetts Inst. of Tec↗

Effect of Long-Term 1093 K Exposure to Air or Vacuum on the Structure of Several Wrought Superalloys

Long-term 1093 K heat treatments of three commercial superalloy sheet materials were undertaken in air -IAI and vacuum. With either exposure, significant precipitation of second phases occurred in the Co-base Haynes(R) Alloy 188 (HA 188) and the Ni-base Haynes(R) Alloy 230 (HA 230); however, much less precipitation was found in the exposed Ni-base alloy Inconel(R) 617 (IN 617). Although some grain growth occurred in HA 198, no changes in the grain size of either HA 230 or IN 617 were observed after 22,500 h at temperature. Oxidation during air heat treatments led to weight gain due to the formation of chromia + spinel scales and surface-connected grain boundary pits/oxides in all three superalloys. Both the weight gain and depth of intergranular attack were dependent on the square root of time, which is indicative of diffusion-controlled phenomena. Because many alloy samples had neighbors in close proximity, most vacuum heat treated specimens did not suffer significant loss of volatile elements. However, some exposed samples were subjected to unrestricted vacuum heat treatments, allowing estimates of volatilization to be made. Based on the data for HA 188, the weight loss during 1093 K vacuum exposure was diffusion controlled once the inhibiting effects of surface films on the as-received alloys were broken down.

J.D. Whittenberger↗

Exploring Local Ionic Motion in Perovskite Solar Cells at Nanoscale through Scanning Thermo-Ionic Microscopy

We investigate the local ionic motion in the absorber layer of perovskite solar cells using scanning thermo-ionic microscopy (STIM). STIM images of perovskite films show higher STIM amplitude at most of the grain boundaries due to higher ionic motion at those regions. The perovskite absorber layer of devices aged under blue (450 nm) light soaking shows higher amplitude in STIM signal compared to controls kept in dark storage. Such enhancement of STIM amplitude upon aging under light implies an increased concentration or diffusivity (or both) of mobile ionic species in stressed devices. Our results demonstrate the utilization of the STIM technique to assess and understand the intrinsic local ionic motion in perovskite absorbers for further advancement in device stability and functionality.

aging↗

Flux Synthesis of A-site Disordered Perovskite La 0.5 M 0.5 TiO 3 (M$=$Li, Na, K) Nanorods Tailored for Solid Composite Electrolytes

Inorganic fillers play an important role in improving the ionic conductivity of solid composite electrolytes (SCEs) for Li-ion batteries. Among inorganic fillers, perovskite-type lithium lanthanum titanate (LLTO) stands out for its high bulk Li + conductivity on the order of 10 -3 S cm -1 at room temperature. According to a literature survey, the optimal LLTO filler should possess the following characteristics: i) a single-crystal structure to minimize grain boundaries; ii) a small particle size to increase the filler/polymer interface area; iii) a 1D morphology for efficient interface channels; and iv) cubic symmetry to facilitate rapid bulk Li + diffusion within the filler. However, the synthesis of single crystal, 1D LLTO nanomaterials with cubic symmetry is challenging. Herein, a flux strategy is developed to synthesize La 0.5 M 0.5 TiO 3 (LMTO, M$=$Li, Na, and K) single-crystal nanorods with an A-site-disordered, cubic perovskite phase. The flux media promotes the oriented growth of nanorods, prevents nanorods from sintering, and provides multiple alkali metal ion doping at M sites to stabilize the cubic phase. SCEs compositing the Li + -conducting LMTO nanorods as fillers and poly[vinylene carbonate- co -lithium sulfonyl(trifluoromethane sulfonyl)imide methacrylate] matrix exhibit more than twice the conductivity of the neat polymer electrolyte (30.6 vs 14.0 µS cm -1 at 303 K).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗