Calculated Activation Energy Research Articles

Endoxylanase Immobilized Nanoporous Silica for the Production of Xylooligosaccharides: Equilibrium Kinetics, Thermodynamic Studies, and Enzyme Characteristics

AbstractNanoporous structured silica materials, namely f‐SiO2, SBA‐15, IITM‐41, and MCM‐41 were employed as the matrices for immobilizing endoxylanase by adsorption method. The equilibrium kinetics, activation energy, and thermodynamic parameters associated with endoxylanase adsorption were investigated. Our findings revealed a two‐phase adsorption mechanism: an initial phase featuring rapid adsorption rates, succeeded by a slower phase wherein adsorption gradually progressed until equilibrium was attained. Analysis of the adsorption kinetic data indicated a better fit with the pseudo‐second‐order model, suggesting chemisorption and highlighting its temperature dependency. The calculated activation energy (Ea) values fell within the range of physisorption, indicating the involvement of both types of adsorption processes. Thermodynamic assessments confirmed that the adsorption reactions were spontaneous, feasible, and endothermic. Notably, the immobilization process did not change the optimum pH of the enzyme, while the optimum temperature shifted slightly. Furthermore, immobilized enzymes show a higher reaction rate (Vmax) than the soluble XynC. All immobilized xylanases produced xylobiose (X2) to xylohexose (X6) by hydrolyzing the xylan substrate. Recycling studies showed that up to 80 % of the yield was retained after seven cycles of reuse. Our study demonstrates the potential of nanostructured silica as an effective immobilization matrix for enzymes of industrial significance.

Hydrogen generation via NaBH4 hydrolysis over cobalt-modified niobium oxide catalysts

The increasing concentration of CO₂ in the atmosphere, primarily driven by fossil fuel combustion, is a major contributor to global warming and one of the most pressing environmental challenges of the 21st century. In response, the development of sustainable energy technologies, such as hydrogen (H₂) production, has become crucial in the global transition to a low-carbon economy. In this study, we explored the catalytic activity of cobalt-modified niobium-based catalysts for hydrogen generation through the hydrolysis of NaBH₄. The catalysts were characterized using XRD, FTIR, XPS, SEM-EDX, and N₂ adsorption-desorption. XRD analysis revealed that the synthesized Nb₂O₅ (Nb₂O₅ Synt.) and Nb₂O₅/Co (Nb₂O₅/Co Synt.) exhibited amorphous structures, while the commercial Nb₂O₅ (Nb₂O₅ Com.) and its Co-modified composite displayed orthorhombic phases. The Nb₂O₅/Co Synt. catalyst achieved a surface area of 33.1 m2/g, significantly surpassing that of the commercial Nb₂O₅. The Nb₂O₅/Co Synt. catalyst exhibited superior catalytic activity, yielding 250 mL of hydrogen in 60 min, in contrast to other catalysts that showed no activity under identical conditions. This enhanced activity was attributed to the presence of surface hydroxyl groups and metallic Co nanoparticles, following the Langmuir-Hinshelwood bimolecular mechanism. Temperature was identified as a critical factor in the H₂ production rate, with a calculated activation energy of 11.37 kJ/mol. Moreover, the Nb₂O₅/Co Synt. catalyst demonstrated excellent reusability, maintaining stable performance after multiple reaction cycles, highlighting its potential for sustainable hydrogen production.

Chromium Complex of Macrocyclic Ligands as Precursor for Nitric Oxide Release: A Theoretical Study.

Our research on the chromium complex of macrocyclic ligands as a precursor for nitric oxide release makes a significant contribution. We detailed the analysis of nitrito chromium complexes, specifically trans-[M(III)L1-5(ONO)2]+, M=Cr(III) and L1-L5represent different ligands: L1=1,4,8,11-tetraazacyclotetradecane, L2= (5,7-dimethyl-6-benzylcyclam), L3=(5,7-dimethyl-6-anthracylcyclam), L4= (5,7-dimethyl-6-(p-hydroxymethylbenzyl)-1,4, 8,11-cyclam) and L5= (5,7-dimethyl-6-(1¢-methyl-4´-(1"-carboxymethylpyrene) benzyl)-1,4,8,11-tetraazacyclotetradecane). Our objective is to comprehensively understand the mechanism of NO release and identify the key factors influencing NO delivery. The optimized structure of the complexes at spin states S = 1/2 or 3/2 indicates a decrease in the Cr(III)-O bond length (1.669-1.671 Å) along with an increase in the Cr(III)O-NO bond length (2.735 - 2.741 Å), which facilitates the release of NO. Furthermore, there is a significant change in the bond angle (Cr-O-NO), from 120.4° to 116.9°, with respect to S=3/2, thus enlarging theO-NO bond and supporting the β-cleavage of NO from the complex. The calculated activation energy for the complexes reflects the energy difference between the low-spin doublet and high-spin quartet state due to spin crossover (SCO). Moreover, the Natural Transition Orbitals (NTOs) confirm the involvement of a hole-particle in the excitation. Additionally, TD-DFT reveals the pendant chromophore's role in generating NO, as the chromophore antenna effectively enhances light absorption.

Electrokinetics of Nitrite to Ammonia Conversion in the Neutral Medium Over A Platinum Surface.

Polycrystalline Pt electrode was employed to selectively convert nitrite ions ( ) into useful nitrogenous compound through electrochemical reduction reaction in neutral medium. According to adsorptive stripping analysis, the reduction process produced nitric oxide (NO) on the surface of Pt electrode. The spectroscopic test and gas chromatographic studies discovered the presence of ammonia (NH3) in the electrolyzed solution, suggesting the transformation of adsorbed NO into NH3 during the reverse scan. Scan rate dependent investigation was performed to elucidate kinetic information relating to this reaction on Pt surface. From Ep vs scan rate (υ) and jp vs υ (logarithmic plot), it was found that the conversion of ion into NO is an irreversible reaction which relies on the diffusion of ions to electrode surface. The Tafel analysis unveiled that the first electron transfer sets the overall reaction rate, having formal reduction potential, E0'=-0.46 V and standard heterogeneous rate constant, k0= cm s-1. Reductive transfer coefficient (α) is another kinetics parameter, which was found to be approximate 0.77 from the difference between Ep and Ep/2 of the voltammograms obtained over scan rate range 0.005 V s-1 to 0.250 V s-1, indicating a stepwise process. According to temperature-dependent voltammograms, the nitrite reduction reaction on Pt had a calculated activation energy of about 19.8 kJ mol-1 and a pre-exponential factor of about 8.39×103 mA cm-2.

Effect of milling time on structural and electrical properties of thermomechanically synthesized of Ba0.1 (Bi0.45Na0.45)TiO3 nanoceramics for ferroelectric random-access memory device

Lead-free Ba0.1(Bi0.45Na0.45)TiO3 (BBNTO) nanoceramics were synthesized using high-energy ball milling, followed by a solid-state reaction method. XRD analysis of the microstructure indicated the formation of tetragonal symmetry. The crystallite size of the nanoceramic powder decreased from ∼ 28 nm to 10 nm after milling for 0, 30, 60, and 90 hours. The dielectric properties of the nanoceramics showed significant improvement, with a diffuse phase transition occurring around 80 °C). The dielectric constant increased with temperature across various frequencies, reached a maximum value at approximately at temperature ∼ 380 °C. At lower temperatures and higher frequencies, the relative permittivity and tangent loss depend on the crystallite size and milling duration. Impedance spectroscopy data analysis revealed size-dependent impedance characteristics and dielectric relaxation. The ac conductivity plot adhered to the Arrhenius relation, and the calculated activation energy confirmed the negative temperature coefficient of resistance (NTCR) behavior. P-E loops confirmed ferroelectric properties, indicating potential for use in future ferroelectric-based storage devices.

Kinetic characteristics of bornite and chalcopyrite dissolution in nitric acid

The kinetic characteristics of dissolution of copper-bearing sulfides – chalcopyrite (CuFeS₂) and bornite (Cu₅FeS₄) – in nitric acid were studied. The kinetics of the dissolution process was described using a compressible nucleus model. Chalcopyrite of the Vorontsovskoye deposit and bornite of the Karabash deposit were used as research objects. Solution and cake samples were analyzed by optical emission spectrometry and X-ray fluorescence analysis, respectively. The results obtained were processed in the MS Excel software package. The influence of various factors, including temperature, solvent concentration, particle size, and process duration on the dissolution degree of minerals was studied. The process parameters were varied as follows: temperature – from 35 to 95°C; HNO₃ concentration – from 1 to 9 mol/dm³; particle size – from +0.1 to 0.056 mm; duration – from 0 to 60 min. It was established that an increase in temperature and acid concentration leads to a significant increase in the degree of dissolution of both chalcopyrite and bornite. A decrease in particle size also contributes to a more efficient dissolution of both minerals in nitric acid. The calculated activation energy values were 55 kJ/mol for chalcopyrite and 43 kJ/mol for bornite, which is characteristic of the kinetic region of the process. The reaction orders in terms of reactant were determined: 1.62 for chalcopyrite and 1.57 for bornite. In terms of particle size, these were -1.16 for chalcopyrite and -2.53 for bornite. On this basis, generalized equations of dissolution kinetics for both minerals were derived. The results obtained allow an assumption about the kinetic nature of dissolution of chalcopyrite and bornite under the studied conditions.

"Development of a statistical calculation model for the carbon diffusion parameters in metals and alloys"

Carbon diffusion in metals has received a lot of attention and has been the subject of intensive theoretical investigations in recent years. The purpose of this work is development the statistical calculation model (SCM) on the diffusion of carbon in metals and its application for calculating the diffusion coefficients of carbon in alloys. It includes first-principles calculation of the diffusion coefficient according to a statistical model, physicochemical calculation of activation energies for carbon, and linear approximation of carbon diffusion in alloys. The calculated values of the diffusion coefficient for metals are within the range of the experimental values. For low-melting metals, carbon diffusion coefficients are mainly unknown from experiment, but the statistical model allows us to predict their values. The calculations are compared with known experimental data on the diffusion of carbon atoms in some metals Fe, V, Ta and W at high temperatures with fairly good agreement between the results. The SCM-model allows us to determine the influence of the alloying elements Si, Mo and Cr on the diffusion of carbon in the F – C alloy.

KINETIC STUDY OF ESTERIFICATION CATALYZED WITH ALUMINUM SULFATE AIMED AT CONVERTING LEVULINIC ACID INTO METHYL LEVULINATE

Recycling lignocellulosic biomass is a sustainable alternative to the petrochemical industry since it allows the production of valuable, sustainable, and environmentally friendly chemical products, such as levulinic acid (LVA) and levulinate esters. Methyl levulinate (MLV), for example, has been assessed as a fuel additive with low toxicity, high lubricity, and flash point stability. In this respect, the present investigation details a kinetic study of methyl esterification catalyzed with aluminum sulfate aimed at converting levulinic acid into methyl levulinate. The reactions were carried out in a Parr Instruments stainless steel reactor to assess the effect of temperature (120, 140 and 160 °C) and reaction time (30, 60, 120 and 180 min) on LVA conversion into MLV, maintaining a constant LVA:methanol ratio of 1:8 and aluminum sulfate catalyst concentration of 0.04 mol.L-1. The maximum LVA-MLV conversion of 93.04 % was obtained at a temperature of 160 °C and reaction time of 60 minutes. The pseudo first-order kinetic model exhibited the best fit to the experimental data, with correlation coefficients (R²) greater than 0.96, and it was used to calculate activation energy, obtaining a value of 10.19 kcal.mol-1.

Effect of solvent and temperature on the micellization and thermophysical properties of cetyltrimethylammonium bromide

The Micellization is the fundamental phenomenon in colloid and surface chemistry which plays a pivotal role in a multitude of industrial processes, biological systems, and everyday applications. In this study, we investigate the micellization behavior of the cationic surfactant, cetyltrimethylammonium bromide (CTAB) within aqueous and ethanol–water mixtures across a temperature range. The electrical conductivity measurements unveil insights into the critical micelle concentration (CMC) and the degree of counterion dissociation (β) at each temperature. Notably, as ethanol content increases in the solvent, both CMC and β values exhibit a corresponding uptick. These findings enable the assessment of standard Gibbs free energy (ΔGmic0). Furthermore, our investigation extends to find out the thermophysical properties (viz., density, dynamic viscosity, and kinematic viscosity) assessments across varying ethanol compositions and temperatures. These metrics facilitate the calculation of activation energy for mixed systems. The implications of these results (data) could be useful for both the fundamental as well applied research, and promise valuable insights for future endeavors.

Trapping and diffusion in high-pressure hydrogen charged CoCrFeMnNi high entropy alloy compared to austenitic steel 316L

High entropy alloys (HEAs) have attracted considerable research attention as potential substitute materials for austenitic steels in high-pressure hydrogen environments. The corresponding hydrogen absorption, diffusion and trapping has received less scientific attention. Therefore, the CoCrFeMnNi-HEA was investigated and compared to an austenitic steel AISI 316L. Both were subjected to high-pressure hydrogen charging at 200 bar and 1000 bar. Thermal Desorption Analysis (TDA) was used to clarify the specific desorption behavior and hydrogen trapping. For this purpose, the underlying TDA spectra were analyzed in terms of a reasonable peak deconvolution into a defined number of peaks and the activation energies for the respective and predominant hydrogen trapping sites were then calculated. Both materials show comparable hydrogen diffusivity. However, there were significant differences in the absorbed hydrogen concentrations at both charging pressures. The calculated activation energies suggest strong hydrogen trapping in the CoCrFeMnNi-HEA.

Lannea microcarpa Leaves Extract as Corrosion Inhibitor for Aluminium Metal in Acid Medium

Techniques for weight loss, electrochemistry, scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR) were used to investigate the inhibitory impact of Lannea microcarpa leaves extract. The weight loss data showed that the plant extract's ability to suppress corrosion increased with higher concentrations and decreased with higher temperatures and HCl acid concentrations. According to the electrochemical data, the plant extract uses a mixed type mechanism to limit both cathodic and anodic reaction rates. Calculated activation energies were found to be higher in inhibited systems than in uninhibited systems, indicating physisorption, while negative values of ∆G point to a process that is both possible and spontaneous. The inhibitory mechanism was demonstrated by FTIR spectra to be an adsorption process through the functional groups present in the phytochemicals of the plant extract onto the surface of Al metal. SEM surface morphology study demonstrated the protection that the extract provided on the metal surface. Compared to other isotherm models that were examined, the adsorption data were found to be more reliable and suited the Langmuir isotherm well.

PRODUCTION AND CHARACTERIZATION OF CELLULASES FROM ASPERGILLUS NIGER UNDER STATIC FERMENTATION

The ever-increasing uses of cellulase in various industries have made it popular among researchers. Annually, a large amount of fruit wastes go into vain, which is a great source of cellulases. The objective of this study is to use grape wastes as substrate for production of cellulases from Aspergillus niger using static fermentation. CMCase and FPase assays were performed to characterize the cellulases. The cellulases’ CMCase and FPase activities and stabilities were analyzed for optimum temperature and pH. The effect of substrate concentration and kinetic constants Km and Vmax, along with thermodynamic analysis, were determined. The effects of several metals on the activity of the enzyme were observed. The optimal temperatures were found as 40 °C and 50 °C for CMCase and FPase activity, respectively. CMCase activity shows stability at 20 °C-60 °C, FPase shows low thermal stability as its activity starts to decrease after 50 °C. CMCase and FPase both show maximum activity at pH 6, and maintain their stability at pH 6-7. The values of Km and Vmax obtained from Lineweaver and Burk plot for CMCase are 0.648 mM and 12.953 mM/min, and for FPase are 0.975 mM and 41.493 mM/min. The Arrhenius plot was used to calculate activation energy (Ea) as -19 kJ/mol, and enthalpy of reaction (ΔH) as 16.4 kJ/mol, while entropy ΔS -16.4 kJ/mol was obtained from the plot of ln(Vmax/T) versus the inverse of temperature (1/T). Most metals induce enzyme activities, whereas EDTA inhibits enzyme activities. The findings suggest A. niger has remarkable cellulase production potential from grape wastes in static fermentation, at optimum temperature and pH levels for achieving enzyme activity and stability.

Hydration kinetics of C3A: effect of lithium, copper and sulfur-based mineralizers

AbstractCalcium aluminate phases have a particular effect on the early heat release during setting initiation and have a substantial influence on the further workability of ordinary Portland cement. The nature of the calcium aluminate hydration products and its kinetics strongly depends on sulfate content and humidity. The effect of mineralisers on melt formation and viscosity is well described for calcium silicate systems, but information is still lacking for calcium aluminates. Therefore, the synergistic effect on the crystal structure and hydration mechanism of the tricalcium aluminate phase of the addition of mineralizers, i.e. Li2O, CuO, SO3 to the raw meal is here investigated. Co-doped calcium aluminate structures were formed during high-temperature treatment. Thermal analysis (TG–DTA and heating microscopy) was used to describe the ongoing high-temperature reaction. Resulting phase composition was dependent on the concentration of the mineralizer. While phase pure system was prepared with low mineralizer concentrations, with increasing mineralizer content the secondary phases were formed. Raman spectroscopy and XPS analysis were used to investigate the cation substitution and to help describe the cations bonding in co-doped calcium aluminate system. Prepared powders have been hydrated in a controlled manner at different temperatures (288, 298, 308 K). The resulting calorimetric data have been used to investigate the hydration kinetics and determine the rate constant of hydration reaction. First-order reaction (FOR) model was here applied for the activation energy and frequency factor calculations. The metastable and stable calcium aluminate hydrates were formed according to initial phase composition. In phase pure systems with low S content, the formation of stable and metastable hydrates was depended on the reaction temperature. Conversely, in systems with secondary phases and higher S content, the hydration mechanism resembled that which appears in calcium sulfoaluminates.

The Dependence of NiMo/Cu Catalyst Composition on Its Catalytic Activity in Sodium Borohydride Hydrolysis Reactions.

The production of high-purity hydrogen from hydrogen storage materials with further direct use of generated hydrogen in fuel cells is still a relevant research field. For this purpose, nickel-molybdenum-plated copper catalysts (NiMo/Cu), comprising between 1 and 20 wt.% molybdenum, as catalytic materials for hydrogen generation, were prepared using a low-cost, straightforward electroless metal deposition method by using citrate plating baths containing Ni2+-Mo6+ ions as a metal source and morpholine borane as a reducing agent. The catalytic activity of the prepared NiMo/Cu catalysts toward alkaline sodium borohydride (NaBH4) hydrolysis increased with the increase in the content of molybdenum present in the catalysts. The hydrogen generation rate of 6.48 L min-1 gcat-1 was achieved by employing NiMo/Cu comprising 20 wt.% at a temperature of 343 K and a calculated activation energy of 60.49 kJ mol-1 with remarkable stability, retaining 94% of its initial catalytic activity for NaBH4 hydrolysis following the completion of the fifth cycle. The synergetic effect between nickel and molybdenum, in addition to the formation of solid-state solutions between metals, promoted the hydrogen generation reaction.

Effect of nano-scaled Al2O3 particles on dynamic recrystallization behavior and microstructure evolution of pure copper in hot deformation

The unusual dynamic recrystallization (DRX) behavior and microstructure evolution during compression deformation at 400–800 °C of a Cu–Al2O3 alloy were investigated herein. The calculation of activation energy (Q) and critical strain for DRX (εc), as well as the prediction of the volume fraction of DRX, are achieved through the construction of constitutive equations and a kinetic model of DRX. The nano-scaled Al2O3 particles are found to exert a significant pinning effect on dislocations and grain boundaries, significantly increasing the dislocation density. The Cu–Al2O3 exhibits a higher work hardening rate and stress compared to pure Cu under the same deformation conditions. The peak stresses of Cu–Al2O3 at 400 °C and 800 °C are 319.7 MPa and 155.4 MPa, respectively, 80.4 % and 243.1 % higher than those of pure Cu. The addition of nano-scaled Al2O3 particles reduces Q and εc of DRX, promoting the transition from low-angle to high-angle grain boundaries during high-temperature deformation. Additionally, distortion zones induced by Al2O3 particles as potential nucleation sites for DRX. While the addition of these particles promotes DRX of pure Cu, the initial DRX rate of Cu–Al2O3 is suppressed by the strong pinning effect of Al2O3 particles.

Gold recovery from chloride leach solution of TCCA using D301 anion exchange resin and elution with thiourea

Trichloroisocyanuric acid (TCCA), which is used for gold leaching, is an alternative to cyanidation due to its lower toxicity and higher efficiency. This study investigated the gold recovery procedures from highly effective chloride leaching solution using the D301 resin. This approach prevented the inhibition of gold adsorption when using activated carbon. Herein, the optimal conditions for gold adsorption were discussed, including establishing adsorption kinetics and isotherms, and calculating adsorption activation energy. Additionally, SEM (Scanning Electron Microscope), FTIR (Fourier Transform Infrared Spectroscopy), and XPS (X-ray Photoelectron Spectroscopy) techniques were used to reveal the mechanism of gold adsorption using D301 resin. Under optimal conditions (pH 4.0, temperature 25 °C, time 120 min), an average adsorption percentage of 99.2% was achieved. Analysis of the adsorption data confirmed that gold adsorption followed the pseudo-second-order kinetic model and Freundlich adsorption isotherm. The calculated activation energy was 9.69 kJ mol−1, indicating a predominance of physical adsorption involving ion exchange reactions with protonated tertiary amine groups in the D301 resin beads. Furthermore, among various eluents tested in desorption experiments, a solution containing a mixture of thiourea and hydrochloric acid with 0.4 mol L−1 and 0.8 mol L−1, respectively, demonstrated superior efficiency, achieving a successful desorption percentage reaching 95.7 ± 0.3% within 80 min. After three cycles of resin regeneration, the regeneration efficiency reached 91.2% while maintaining an average adsorption percentage of 95.3%.

Developing High-Purity Sodium Oxychloride Solid-State Electrolyte for Sodium-Ion Batteries

Sodium-ion batteries have attracted significant attention as an alternative energy source to lithium-ion batteries. Solid-state sodium oxyhalides (Na3OX, X = Cl, Br, I) have the advantages of easy synthesis from cheap raw materials. In this study, sodium oxychloride (Na3OCl) antiperovskite was synthesized using a microwave furnace, the first instance in currently available literature. Using the microwave furnace also significantly decreased the reaction time when compared to other published procedures. The ionic conductivity of Na3OCl pellets was determined using electrochemical impedance spectroscopy (EIS). Na3OCl was hot pressed between sodiated hard carbon in a PEEK lined split cell with stainless steel current collectors. The symmetric cell was tested at room temperature with varying external pressures (1 MPa to 12 MPa). Symmetric cells were also tested at constant external pressure (6 MPa) from room temperature to 80˚C.Arrhenius plots demonstrated linear behavior in the whole temperature range with a calculated activation energy of 0.98 eV. The melting and crystallization temperatures were determined using differential scanning calorimetry (DSC). The purity of as-synthesized Na3OCl was evaluated using x-ray diffraction (XRD). The results on chemical composition and crystal-to-glass phase transformations were produced from in-situ X-ray diffraction (XRD) spectroscopy in the temperature range from 25˚C up to the melting point of Na3OCl. Cross-sectional SEM images of the Na3OCl pellets showed regions that were dense, but also regions with many pores (≤ 5 μm). SEM also showed microcracks that ranged from 1-5 μm. Future work will investigate methods of minimizing pores and microcracks during the cell manufacturing process as these surface features can impede efficient ionic movement.

Mechanism and stereoselectivity of epoxidation reaction of a β-himachalene derivative: Insights from DFT, molecular docking, ADMET, and molecular dynamics investigations

Epoxidation of a β-himachalene derivative (A) can be carried out using meta-chloroperoxybenzoic acid (m-CPBA). An oxygen atom is added to the double bond C9C10, during the process, producing the epoxides P1 and P2. DFT calculations at the B3LYP/6-31G(d) level were used to study, Theoretically, the mechanism and stereoselectivity of the epoxidation reaction of compound A with m-CPBA. The calculation of activation energies associated with both possible reaction pathways, indicated that this epoxidation reaction is exothermic and highly stereoselective, favoring the formation of product P1 which is in agreement with the experimental results. Additionally, the IRC calculation shows that this reaction occurs via a one-step mechanism. The products P1, P2, and the starting compound A were evaluated for their antidiabetic activity and their potential to inhibit alpha-amylase and alpha-glucosidase through molecular docking, molecular dynamics, and ADMET studies. The evaluation of these three compounds aimed to study the effect of epoxidation and stereoselectivity on their inhibitory activity against the two enzymes.

5-Amino-1,2,4-triazol-3-one Degradation by Indirect Photolysis: A Density Functional Theory Study.

Sunlight irradiation induces formation of reactive oxygen species (superoxide, hydroperoxyl radical, singlet oxygen, etc.), which readily take part in degradation of environmental pollutants. Being a primary ingredient in a suite of insensitive munition formulations, NTO (5-nitro-1,2,4-triazol-3-one) can be released onto training range soils and reduced to ATO (5-amino-1,2,4-triazol-3-one) by soil bacteria or iron-contained minerals. ATO can be dissolved in surface water and groundwater due to its good water solubility and then undergo further decomposition. A detailed investigation of possible mechanisms for ATO decomposition in water induced by superoxide, hydroperoxyl radical, and singlet oxygen as pathways for ATO environmental degradation was performed by computational study at the PCM(Pauling)/M06-2X/6-311++G(d,p) level. Hydrolysis and degradation of ATO induced by superoxide are unlikely to occur due to the high activation energy or endergonicity of the processes. The hydroperoxyl radical causes rapid and reversible hydrogen transfer from ATO, while an attachment of the hydroperoxyl radical to ATO can induce decomposition of ATO, leading to its mineralization. Singlet oxygen shows a higher reactivity toward ATO than the hydroperoxyl radical. Decomposition of ATO was found to be a multistep process that begins with singlet oxygen attachment to the carbon atom of the C═N double bond. The intermediate that is formed undergoes recyclization, cycle opening, and sequential elimination of nitrogen gas, ammonia, and carbon(IV) oxide. Isocyanic acid, which arises intermediately, hydrolyzes into ammonia and carbon(IV) oxide. Calculated activation energies and high exergonicity of the studied processes support the contribution of singlet oxygen and the hydroperoxyl radical to ATO degradation into low-weight inorganic compounds in the environment.

Excellent magnetic properties obtained in planar flow casting Fe-6.5 %Si steel via low strain cold-rolling and annealing

Planar flow casting (PFC) has been applied to prepare Fe-6.5wt. %Si ultra-thin ribbons with a strong 〈001〉 fiber texture. However, critical issues such as fine grain size and large surface roughness are vital to overcome. In this study, low strain cold-rolling and subsequent annealing are applied to planar flow casting Fe-6.5 %Si ribbons. Cold-rolling reduces surface roughness and introduces heterogeneous deformation in the ribbons. Recrystallization occurs preferentially in high deformed areas during annealing. Recrystallizing grains grow significantly by consuming neighboring deformed grains with fine size and 〈001〉 orientation, leading to greatly reduced iron loss. Thus, the ribbon annealed at 1000 ℃ exhibits the best combination of magnetic properties with B8 of 1.29 T and P2/5000 of 6.95 W/kg. The kinetics of recrystallization and grain growth are described along with the calculations of activation energies, which suggests the cold-rolled ribbon has a faster growth rate than the undeformed one. Two mechanisms, namely strain-induced boundary migration (SIBM) and thermo-induced boundary migration (TIBM), are used to explain the grain growth. SIBM is dominant at low temperatures while TIBM is dominant at high temperatures. This work presents a strategy to tailor the microstructures and properties of PFC-prepared alloys with fine grain.