Calculated Activation Energy Research Articles

Structural Characteristics and Improved Thermal Stability of HDPE/Calcium Pimelate Nanocomposites

In the present research work, calcium pimelate (CaPim) was synthesized and investigated as an additive for high-density polyethylene (HDPE). HDPE/CaPim nanocomposites were prepared by melt-mixing, with CaPim content ranging from 0.1% to 1%, affording white homogeneous materials. The chemical structure of the nanocomposites and the incorporation of CaPim was confirmed by infrared spectroscopy. The surficial morphology and the additive distribution were examined by scanning electron microscopy. Differential scanning calorimetry and X-ray diffraction measurements showed that the thermal transitions and crystal structure of HDPE are not affected by the incorporation of CaPim, while the mechanical properties are retained overall. This study focuses on the thermal degradation of HDPE nanocomposites, investigating the degradation mechanism and kinetic parameters through various analytical methods. Isoconversional techniques, including the Friedman method, Vyazovkin analysis, and Ozawa Flynn Wall analysis, were employed to calculate activation energies (Eα). The degradation mechanism and kinetic triplet were determined based on a multivariate non-linear regression method (model-fitting). Finally, the presence of a CaPim additive was shown to increase the Eα of thermal degradation, consistent with the calculated dependence of Eα on the degree of conversion and the improved thermal stability of the HDPE matrix.

Determining the effective diffusivity coefficient and activation energy in thin-layer drying of Haj Kazemi peach slices and modeling drying kinetics using ANFIS

Abstract This study investigated the moisture changes in Haj Kazemi peach slices during drying in a thin-layer dryer at five temperature levels (40, 50, 60, 70, and 80°C), three levels of inlet air velocity (1, 1.5, and 2 m/s), and three slice thicknesses (2, 4, and 6 mm). The relative moisture content during drying was calculated, and an adaptive neuro fuzzy inference system (ANFIS) was used to predict the drying process of peach slices. The results indicated that slice thickness had a greater impact on drying time than air velocity. Moreover, an almost direct relationship was observed between changes in slice thickness and drying time. The effective moisture diffusivity coefficient in peach slices increased with an increase in slice thickness, temperature, and air velocity and ranged from 9.57 × 10^-10 to 4.33 × 10^-9 m^2/s under different experimental conditions. The calculated activation energy for drying peach slices under experimental conditions ranged from 16.74 to 20.48 kJ/mol. The designed model for simulating the drying conditions was based on an adaptive neuro fuzzy inference system (ANFIS) with input and output membership functions of triangular and linear shapes and a hybrid learning algorithm. The model could simulate the drying process with a correlation coefficient of 0.979.

Purification and partial characterization of a thermostable peroxidase isoenzyme from Bambara groundnut (Vigna subterranea L. Verdc) seedlings

Thermostable isoperoxidases, especially peroxidase A6, have already been found in seedlings of Vigna sp, indicating their potential for biotechnological applications. In this study, peroxidase A6 was purified from the roots of Bambara groundnut (Vigna subterranea L. Verdc) seedlings by a combination of gel filtration on Sephadex G-100, heat treatment, and ion exchange chromatography on CM cellulose and DEAE cellulose. The 41-kDa enzyme shows high catalytic efficiency in the oxidation of O-dianisidine, ABTS, TMB, DAB and OPD at acidic pH optimum and the reduction of H2O2. It has an optimum temperature of activity of 60 °C and a calculated activation energy of 221.5 KJ/mol for its thermal inactivation at pH 8. Mg2+ inhibits the enzyme. Ca2+ strongly increases its thermal stability, while Mn2+ and Zn2+ decrease it. The enzyme is inhibited by sodium azide at concentrations above 1 µM, with an IC50 value of about 10 µM. This inhibition, in addition to the RZ value of 2.4 (A403nm/A280nm), confirms the presence of a haem group in the active site, which is common for class III plant peroxidases. Due to its unique catalytic and thermal properties, peroxidase A6 has the potential to be a valuable tool for various biotechnological applications, especially for enzyme immunoassays and clinical diagnosis.

Thermal degradation evaluation of polyethylene terephthalate microplastics: Insights from kinetics and machine learning algorithms using non-isoconversional TGA data

The thermal stability of polyethylene terephthalate (PET) microplastics (MPs) is crucial in diverse applications, necessitating a comprehensive understanding of their behavior under high temperatures. This study explores the impact of chemical modifications and aging on the thermal degradation of different PET MPs, including pristine (Pr-PET), acid-modified (Mod-PET), and oxidatively aged (Ag-PET), using kinetics, thermodynamics, and machine learning algorithms using non-isoconversional thermogravimetric analysis (TGA) data. The calculated activation energy (E) and pre-exponential factor (A) for Coats-Redfern model showed Pr-PET with highest E value of 21.09 and 15.24 kJ/mol for zero-order and first order kinetic model, indicating its increased energy requirement for chemical reactions, while Mod-PET and Ag-PET demonstrated improved thermal resistance with lower E values. Thermodynamic data from kinetic parameters showed positive values of Gibbs free energy (ΔG°), enthalpy (ΔH°) and negative values of entropy (ΔS°) (−0.17. kJ/mol·K to −0.20 kJ/mol·K) indicated non-spontaneous degradation process, necessitated energy input, and reduced disorder with decreased reactivity. For accurate predictions of thermal behavior, various machine learning algorithms, including Support Vector Machine (SVM), Decision Tree Regressor (DTM), Random Forest Regressor (RFM), and Artificial Neural Network (ANN), were utilized. The RFM consistently outperformed other models, exhibiting the lowest error metrics and providing reliable predictions of weight loss and derivative thermogravimetric (DTG) for different PET MPs with a predicted-R2 of 0.999. This study sheds light on the thermal stability of PET MPs, considering chemical modifications and aging. The integration of these methods offers a powerful approach to understanding and predicting PET MPs under thermal conditions.

Thermal, Morphological, and mineralogical characterization of ancient potsherds: Insights from activation energy and degradation profiles

The six representative potsherds sourced from the excavated Buddhist site of Udayagiri, Odisha, in eastern India, were studied using analytical characterization techniques of X-ray diffractometry (XRD), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS), thermogravimetry (TG-DTG), and a porosity study. The analysis has unveiled the clay composition, firing temperatures, and environment along with internal morphology of these potsherds after firing process. The thermal behavior of the pottery samples was meticulously examined and degradation profiles depicted through TG-DTG curve. The activation energy of potsherds was calculated using the Horowitz and Metzger equation, shedding light on the various stages of degradation. Notably, the calculated activation energies for the first stage of degradation ranged from 5.78 to 16.64 kJ/Mole, while for the 2nd/3rd stage degradation, the range was between 2.59 KJ/Mole to 8.38 KJ/Mole, underlining the intricate firing processes involved. This research has successfully estimated firing temperatures across different environmental conditions, spanning from 450 to 900 °C. The pottery fragments were categorized into two distinct varieties following a comprehensive analysis of firing temperature, inclusions, morphological characteristics, firing conditions, and degradation profiles. The multifaceted approach employed in this study has contributed significantly to our understanding of these potsherds' composition and their firing profile.

Performance of novel Ca-biocomposites produced from banana peel and eggshell for highly efficient removal and recovery of phosphate from domestic wastewater

Using biowaste-based adsorbents to remove phosphorus (P) from wastewater offers significant benefits concerning eutrophication mitigation and addressing waste management challenges. In this work, Ca-biocomposites were prepared by pyrolysis (700 °C) of a mixture of banana peel (BP) and eggshell (ES). The mass ratio of BP to ES was varied in 2:1, 1:1, and 1:2 ratios. Among the tested mixtures, the BPES-1:2 sample exhibited excellent P removal performance, reaching a maximum P adsorption capacity (Qmax) of 214 ± 5 mg P/g. The adsorption process fitted well with the Avrami order kinetic model (R2 > 0.996) and the Liu isotherms model (R2 > 0.997). The excellent fit of the experimental data to the Avrami model suggests that chemisorption is the dominant interaction mechanism, leading to precipitation through the formation of calcium phosphates. Additionally, the Liu model anticipates that the energetic characteristics of the adsorbent's active sites cannot be identical. This is in agreement with the presence of Ca(OH)2 and CaCO3 in the adsorbent material, where the Ca(OH)2 active sites are preferred by the adsorbate molecules (PO43−) for occupation. Furthermore, thermodynamic analysis revealed that P adsorption is a spontaneous process of exothermic nature (ΔH° < 0). The calculated activation energy for the process (72.81 kJ/mol) suggests the P adsorption mechanism involves strong chemical bonding between the adsorbent and P species. In addition, precipitation of apatite (Ca5(PO4)3OH), a vital component in fertilizer production, was observed during the adsorption process. In tertiary treated wastewater applications, the BPES-1:2 biocomposite demonstrated a P removal efficiency of 90%. The solubility of P in a 2% formic acid solution was 100%, while the water-soluble P content was measured at 5.6%. These findings highlight the product's sustainable and environmentally beneficial nature by demonstrating its potential as a slow-release fertilizer, contributing to the application of the 3R slogan: Reduce, Reuse, Recycle. This value-added product is promising in supplying nutrients to plants over an extended period while minimizing the risk of nutrients leaching into the environment.

Improving the proton conductivity of MOF materials by regulating the pore space

The construction of metal-organic frameworks (MOFs) with structural tunability, designability, and high stability is crucial in proton conduction studies. In this paper, MOF-801 and UiO-66 were used as precursors. A solvothermal synthesis method was employed to modulate the pore space of composite MOFs. The hydrogen-bonding network and structure within the pore cavities are adjusted by varying the molar ratios of fumaric acid and terephthalic acid to improve the proton transfer rate and proton conductivity of the materials. A total of 14 materials, MOF/MOG-801&UiO-66-X (X is the molar ratio of fumaric acid and terephthalic acid) were synthesised, the variation of proton conductivity with temperature of which was investigated at different tempertures and humidities. The results shows that MOG-801&UiO-66–1:1 has the best proton conductivity with 0.12 S cm−1 at 353 K and 100 % RH, which is 5 times higher than that of MOF-801&UiO-66–1:3 (2.54 × 10−2 S cm−1), 11 times higher than that of MOF-801 and 22 times higher than that of UiO-66. Based on the calculated activation energy and structural characterisation, the proton conduction mechanism of the composite was investigated. This work opens up novel research fields for the design of new proton-conducting MOF materials.

Degradation of NTO induced by superoxide and hydroperoxyl radicals: a comprehensive DFT study.

Reactive oxygen species, produced in the aquatic environment under sunlight irradiation, actively take part in degradation of environmental pollutants. NTO (5-nitro-1,2,4-triazol-3-one), being a primary ingredient in a suite of insensitive munitions formulations, may be released into training range soils after incomplete detonations and dissolved in surface water and groundwater due to good water solubility. A detailed investigation of a possible mechanism for NTO decomposition in water induced by superoxide and hydroperoxyl radicals as one of the pathways for NTO environmental degradation was performed with a computational study at the PCM(Pauling)/M06-2X/6-311++G(d,p) level. Superoxide causes rapid deprotonation of NTO. Decomposition of NTO induced by hydroperoxyl radicals was found to be a multistep process leading to mineralization of the nitrocompound. The reaction process may begin with hydroperoxyl radical attachment to carbon atom of the CN double bond of NTO, then proceeds through rupture of C-N bonds and addition of water molecules leading to the formation of nitrous acid, ammonia, nitrogen gas, hydrazine, and carbon(IV) oxide. The obtained results indicate that the anionic form of NTO shows a higher reactivity towards hydroperoxyl radicals than its neutral form. Excitation of NTO by sunlight enables complete mineralization of NTO induced by superoxide. The calculated activation energies and exergonicity of the studied processes support the contribution of hydroperoxyl radicals and superoxide to the degradation of NTO in the environment into low-weight inorganic compounds.

Ab initio insight into furan conversion to levulinate ester in reaction with methylal and methanol

Ab initio calculations of reaction energies and activation energies for furan conversion into methyl levulinate in reaction with methylal and methanol were performed with consideration of methanol solvent effect eight explicitly or implicitly.

Effect of a mesoporous NiCo2O4 urchin-like structure catalyzed with a surface oxidized LiBH4 system for reversible hydrogen storage applications.

A mesoporous NiCo2O4 urchin-like structure was synthesized by applying a facile hydrothermal method. Different concentrations of NiCo2O4 urchin-like structures were mixed with a surface oxidized LiBH4 system using a wet-impregnation method, followed by heat treatment. The hydrogen storage capacity of LiBH4 + 25% NiCo2O4, LiBH4 + 50% NiCo2O4 and LiBH4 + 75% NiCo2O4 systems was investigated. Typically, hydrogenated LiBH4 + 25% NiCo2O4, LiBH4 + 50% NiCo2O4 and LiBH4 + 75% NiCo2O4 systems desorbed 2.85 wt%, 3.78 wt% and 3.91 wt% of hydrogen, respectively, at the dehydrogenation temperature ranging from room temperature (RT) to 275 °C. Further, the LiBH4 + 75% NiCo2O4 system exhibited better kinetics than other systems and released ∼5.8 wt% of hydrogen at a isothermal dehydrogenation temperature of 250 °C in 60 minutes. Hydrogen binding energies were calculated as 0.28 eV, 0.27 eV and 0.26 eV for LiBH4 + 25% NiCo2O4, LiBH4 + 50% NiCo2O4 and LiBH4 + 75% NiCo2O4 systems, respectively. Moreover, the calculated activation energies of LiBH4 + 25% NiCo2O4, LiBH4 + 50% NiCo2O4 and LiBH4 + 75% NiCo2O4 systems are 17.99 kJ mol-1, 17.03 kJ mol-1 and 16.92 kJ mol-1, respectively. The calculated BET (Brunauer-Emmett-Teller) surface area of NiCo2O4 and LiBH4 + 75% NiCo2O4 systems is 124.05 and 136.62 m2 g-1, respectively. These results showed that hydrogen sorption and desorption properties are significantly increased by the influence of mesoporous structure, lower binding energy and activation energy of LiBH4 + 75% NiCo2O4 system.

DLPNO-CCSD(T) and DFT study of the acetate-assisted C-H activation of benzaldimine at [RuCl2(p-cymene)]2: the relevance of ligand exchange processes at ruthenium(II) complexes in polar protic media.

To gain mechanistic insights into the acetate-assisted cyclometallations of arylimines promoted by [RuCl2(p-cymene)]2 in polar protic media, DFT geometry optimizations (with M06 and ωB97X-D3 functionals and the cc-pVDZ-PP[Ru] basis set) followed by DLPNO-CCSD(T)/CBS energy evaluations were performed using benzaldimine as a model substrate and methanol as the solvent (with CPCM or SMD models). The calculation results show that coordination of the imine to an acetate ruthenium precursor is followed by anion (chloride or acetate) dissociation as the rate-determining step of the process. H-Bonding of two explicit MeOH to the anion reduces the calculated activation energy to ca. 23 kcal mol-1, in good agreement with the experimental half-life at room temperature. Subsequent AMLA/CMD C-H activation of the intermediate cationic complexes is a faster, reversible process. Alternative reaction pathways involving neutral diacetate ruthenium complexes offer AMLA/CMD transition state structures of lower energy but are precluded due to higher energy barriers for the initial ligand exchange processes at ruthenium. Solvent assistance accelerates the final chloride/acetate exchange processes on the cycloruthenate intermediates, particularly when compression in the condensed phase is taken into consideration. The performance of six DFT functionals (with the aug-pVTZ-PP[Ru] basis set) was assessed using the DLPNO-CCSD(T)/CBS reference energies. Neutral diacetate ruthenium complexes were incorrectly predicted as being kinetically relevant when using hybrid DFT methods (PBE0-D3(BJ), M06-2X or ωB97M-V). Good agreement between the calculated barrier heights and our benchmark energy results was obtained by using double-hybrid DFT methods. PWPB95 with D3(BJ) or D4 dispersion energy corrections was found to be the most accurate (ΔG≠ MUE of ca. 1 kcal mol-1). This study may aid our understanding of and help with further experimental investigations of synthetically useful carboxylate-assisted C-H bond functionalizations involving (N,C)-cyclometallated (p-cymene)Ru(II) intermediate complexes in sustainable polar protic solvents.

THERMAL DEGRADATION OF POLY(VINYL CHLORIDE)/POLYSTYRENE BLENDS IN THE PRESENCE OF DERIVATIVES OF Hura crepitans SEED OIl.

Poly(vinyl chloride) (PVC) is a versatile polymer that has found applications in various sphere of our daily life. However, it is intrinsically unstable at elevated temperatures usually employed in processing it into useful articles. The thermal stability of poly(vinyl chloride) (PVC) has been reported to improve in a blend with polystyrene (PS) and compatibility of the polymers was a factor which influenced the stabilization process. There has been no report of thermal stability of PVC/PS blends in the presence metal soap of seed oil. In this study, the thermal degradation of poly(vinyl chloride)/polystyrene (PVC/PS) blends in the absence and presence of metal soaps of Hura crepitans seed oil (HCSO) has been investigated in air and under nitrogen atmosphere. Metal soaps of Hura crepitans seed oil; Al, Ba, Ca, Mg and Zn were prepared by precipitation method involving metathesis in alcohol. Kinetics of thermal degradation of PVC and the blends were carried out titrimetrically in the temperature range 170-190 oC under nitrogen atmosphere. The interaction of the additives with PVC was studied with FTIR spectrophotometer while the melt properties of PVC and the blends were determined using differential scanning calorimeter. The thermal stability study of the polymer and the blends was carried with thermogravimetric analyzer under nitrogen and air atmospheres. In the absence of metal soaps, the kinetics of thermal degradation of PVC in PVC/PS blends, 95/5, and 90/10 ratios, measured titrimetrically under nitrogen atmosphere in the temperature range 170- 190 oC, was determined by the rates of dehydrochlorination of the polymer. The rates of dehydrochlorination were of the order, 10-2 %min-1 and showed stabilization of PVC by PS in the blends. Specifically, at 190 oC, the rates of dehydrochlorination of PVC under nitrogen atmosphere were reduced by 23.7 and 11.2% for the 95/5 and 90/10 blends respectively with calculated activation energy of 50.7kJ mol-1for the process. In the presence of HCSO soaps of Al, Ba, Ca, Mg and Zn, there were marked reductions in stabilization of PVC by PS and were associated with increased polarity of the blends. Miscibility of the blends was enhanced by the soaps, as was evident from FTIR and DSC analyses, showing from the latter, single Tgs of 98.2 and 96.2 oC for 95/5 and 90/10 blends respectively. The enhanced stability of PVC in the blends by PS and reduced stability of the polymer in the presence of metal soaps were confirmed by thermogravimetry. PS enhanced thermal stability of PVC in PVC/PS blends while the presence of metal soaps of Hura crepitans seed oil in PVC/PS blends is antithetical to thermal stability of PVC.

Физико-химические свойства суспензий на основе оксида алюминия и перспективы их применения

Cordierite blocks of a honeycomb structure with square cross-section channels are used as ceramic carriers for three-route automotive catalysts. Catalytically active layers are applied from suspensions based on γ-Al2O3, which is introduced into the internal volume of the carrier. The preparation of suspensions included impregnation of Al2O3 powder with solutions of Pt, Eu precursors, dilution with water, grinding to particles with an average size of 4 microns, setting acidity in the required range. The study of the physicochemical properties (point of zero charge, specific surface area, particle size, pore volume, average pore diameter) of a suspension prepared on the basis of aluminium oxide and modified with europium and platinum ions is relevant due to the possibility of using three-path catalysts in technology. The surface and porosity parameters were determined by low-temperature nitrogen adsorption/desorption. pHzcp values were determined by gravimetric titration, the pH of the points were in the range of 6.01-7.1, therefore, the specified acidity range should not be beyond these limits. The processes of thermal destruction of suspensions during heating were studied by thermal analysis. During the heating process from -100 to 250°C, a weight loss was observed throughout the heating process. Endothermic effects were discovered, corresponding to the melting of ice, evaporation of moisture, and decomposition of nitrogen-containing compounds. The greatest weight loss was observed in an aluminium oxide sample modified with europium and platinum ions (Eu,Pt/γ-Al2O3). Quantitative assessment of the forms of moisture bonds in the suspension was carried out using experimental dependences on weight changes of the TG sample and the rate of change in the DTG weight in the temperature range of 270-380 K. Based on the activation energy values, it was established that the mechanism of moisture release from the Eu,Pt/γ-Al2O3 differs from others. The calculated activation energies for the release of moisture was high (41-92 kJ/mol), which indicates the bound state of water in the structure of the solid phase. The suspension was applied to a ceramic catalyst base and annealed at 500 °C, information about the mechanism of moisture release during heating of the suspension will help to avoid a decrease in the specific surface area.

Taguchi method for optimizing the cation exchange resin catalyzed esterification of oleic acid with ethanol and adsorption kinetics study

In this study, solid acid catalysts (cation exchange resins) were used to catalyze the esterification reaction of acidified oil and ethanol for the preparation of biodiesel. The catalyst was characterized by SEM, BET, XRD, and FTIR. The esterification reaction was studied under various conditions using one-way analysis. Process optimization was performed by the Taguchi method, revealing that the optimal conditions for maximum oleic acid conversion (91.63%) were a catalyst dosage of 20 wt%, ethanol/oleic acid molar ratio of 9:1, reaction time of 5 h, and reaction temperature of 80 ℃. In addition, the adsorption behavior of cation exchange resin (S-CER) on oleic acid and ethanol during the esterification process was investigated. The Freundlich and Langmuir adsorption kinetic models of the resin were also established. This study focused on the dynamic equilibrium of oleic acid and ethanol adsorption on the S-CER catalyst surface. The adsorption process was found to align better with the Freundlich isotherm equation. According to this equation, oleic acid's maximum adsorption capacity was found to be 371.24 mg/g. Lastly, a pseudo-primary kinetic equation for the esterification reaction was formulated, and the calculated activation energy for the reaction was 35.59 kJ/mol.

(Invited) Computational Predictions of Site-Dependent Reactivities for Complex Reactions in Confinement

It is well known that the relatively high overpotentials for oxygen evolution reactions arise from similar binding energies for HO* and HOO* intermediates that tend to move in lockstep on different catalysts. A strategy to break this scaling limitation is through differential stabilization of the two intermediates by engineering the reaction environment. Nanoporous materials such as zeolites and metal-organic frameworks provide such a possibility through their well-defined pore space that presents microscopically tunable reaction environments. Yet the predictive understanding of catalytic actions in these heterogeneous catalysts requires the ability to describe not only the electronic structure at the active site, but also how the extended environment interacts with the reacting species through individually weak yet collectively significant non-covalent interactions. In this talk, we present a new computational procedure that couples quantum-chemical methods and forcefield-based sampling to enable a consistent calculation of local activation energies for articulated reactants. As a first application, we studied hydrocarbon reactions in four different zeolites and showed how the method allows for the estimation of transition-state entropy and for the systematic calculation of site-dependent activation energies. The latter can be used to derive rigorous ensemble-averaged barriers for comparison with experiments, as well as guiding future strategies for controlling Al distributions during zeolite synthesis.

Computationally Predicted New Solid-State Electrolyte (Li5+x PS4+x Cl2-x : 0 ≤ x ≤ 2) and Poly Sulfide Cathodes (Li3+y PS9 or Li5+y PS9Cl2: 0 ≤ y ≤ 9) for High Performance Li Metal Anode Batteries

We used Molecular Dynamics (MD) simulations to study the structures and conductivity of sulfide-based ceramics from the superionic conductor argyrodite family for applications as solid-state electrolyte and cathode materials. These studies combined quantum mechanics (QM) and ReaxFF reactive force field based MD, where the ReaxFF parameters were developed from QM MD.[1]Currently Li10GeP2S12 (LGPS) demonstrates one of the highest Li-ion conductivity for solid state electrolyte, 12 mS/cm at 300K, but it is highly reactive with the Li-metal anode, and it is expensive due to the presence of Ge. We studied the Li ion diffusion mechanism and ionic conductivity of the promising Li6(PS4)SCl solid state electrolyte, predicted to have a conductivity of s = 6 mS/cm, close to experiment (4 mS/cm). We find that Li migration in this electrolyte occurs via conjugated substitutional type diffusion involving rearrangements of three (or more) Li-ions and ~ 3 vacant sites in a 3D matrix of anions that are essentially stationary at 298K (over 20 ns of simulation). We carried out 10 ns of MD simulation to predict a Li-ion conductivity for a single phase Li6(PS4)SCl of 5.9 mS/cm in agreement with solid state NMR measurements of 3.9 mS/cm. Our calculated activation energy of 0.24 eV is within experimentally reported range.[2]We report here the computationally predicted structure of Li5PS4Cl2, a new sulfide Li-superionic conductor with the highest Li-ion conductivity at solid state, which we predict to have Li-ion conductivity of 20 mS/cm at 298 K. We also predicted the directional ionic conductivity and Li-migration barrier in it. This Li5PS4Cl2 has not yet been synthesized and studied experimentally.We also report our results on QM and ReaxFF MD for new polysulfide cathodes, Li3+y PS4+n and Li5+y PS4+nCl2 , both based on Li3PS4. Here, n is the number of excess sulfur atoms in the fully charged polysulfide cathode per formula unit with y=0 and y is the excess Li added to the cathode during discharge processes. We evaluated the performance of these cathode electrolyte systems in terms of interfacial stability and discharge voltages.Li3PS4+5 is a potential cathode for lithium-sulfur batteries. We predicted the structures of Li3PS4+5 finding extra S3 and S7 chains attached to one S atom of each PS4 group. This leads to a density of 2.2 g/cm3. As the cathode is discharged, the lithium atoms fill up all the gaps between S atoms, leading to Li3+9 PS4+5, with 1.7 g/cm3. We studied the dynamics of the discharge as lithium ions from the metal move into the material and react with the S-S bonds to make Li2S. Our predicted discharge curve agrees well with the experimental data (Figure 1).[3]We extended these studies to design a new polysulfide cathode Li5PS4+5Cl2 to be used with our newly predicted Li-superionic conductor electrolytes. The interfacial stability of the Solid electrolyte with S-based cathode and with Li-anode were studied (Figure 2).Our work presents a new strategy for designing materials and processes for solid-state batteries using computational screening and chemical substitution. This demonstrates the potential of using lithium PS4 based superionic conductors with PS4 based cathodes for applications in solid-state batteries. We also addresses some of the key challenges in accelerating solid-state battery development, such as phase stability, transport properties, electrode compatibility etc. This work demonstrates how computational studies can guide new avenues for experimental developments to advance of solid-state battery technology for applications ranging from grid storage to electric vehicles.Acknowledgements:We acknowledge the support from Hong Kong Quantum AI Lab, AIR@InnoHK of Hong Kong Government.

Formation of (Aza)fulvenallene, Cyanocyclopentadiene, and (Aza)fluorenes in the Thermal Rearrangements of Indazoles, Azaindazoles, and Homoquinolinic Anhydride.

Flash vacuum pyrolysis (FVP) of pyrazoles and indazoles constitutes a valuable route to carbenes and nitrenes. In this study, we employed M062X and CCSD(T) calculations to provide a mechanistic rationale for the formation of fulvenallene and fluorenes from indazoles and the corresponding formation of azafulvenallene 15, cyanocyclopentadiene 19, and azafluorenes, e.g. 45, from azaindazoles, e.g. 12, and from homoquinolinic anhydride. The results reveal the importance of initial tautomerization in the pyrazole moiety of 7-azaindazole 12, which drives the mechanism toward 2-diazo-3-methylene-2,3-dihydropyridine 29 and hence 3-methylene-2,3-dihydropyridin-2-ylidene 26, followed by Wolff-type ring contraction to 1-azafulvenallene 15. This path has a calculated activation energy ∼10 kcal/mol lower than that for an alternate route involving ring opening to 3-diazomethylpyridine, dediazotization, and rearrangement of 3-pyridylcarbene to azacycloheptatetraene and phenylnitrene 24. FVP of 2,5-diphenyltetrazoles and phenyl(pyridyl)tetrazoles leads to nitrile imines, which cyclize to 3-phenylindazoles and -azaindazoles. Nitrogen elimination from these (aza) indazoles results in the formation of (aza) fluorenes, for which two alternate mechanisms are described: route A by rearrangement of (aza) indazoles to diazo(aza)cyclohexadienes and (aza)cyclohexadienylidenes and route B by rearrangement to diaryldiazomethanes and diarylcarbenes. Both paths are energetically feasible, but path A is preferred and corresponds to the azafluorenes obtained experimentally.

Rational design of methane dissociation catalyst based on first principles

Based on the first principle, this paper uses the generalised gradient approximation density functional theory and slab model to investigate the dissociation of methane (CH4→CH3 + H) on the surfaces of Co group (Co, Rh, Ir) and Ni group (Ni, Pd, Pt), and investigate the influence of PtIr(100), PdRh(100) and PtPd(100) on methane decomposition. From the calculated activation energies of methane dissociation on single metal surfaces and alloy surfaces,we find that Pt and Ir are better catalysts for methane dissociation in the single metals studied. In addition, methane dissociation (CH4→CH3 + H) on PtIr(100) and PdRh(100) surfaces are easier than that on single metal surfaces(Co, Rh, Ir, Ni, Pd, Pt).

Characterization and transport properties of ceramic filler incorporated natural rubber composites

AbstractCrystalline glass–ceramic fillers were prepared from calcium carbonate, silica, alumina, and calcium fluoride by heating and subsequent quenching in cold water. The fillers were incorporated into natural rubber (1,4‐cis‐polyisoprene) and the filled rubber composites were crosslinked with sulfur in the presence of different rubber additives. The unfilled and filled rubber composites were characterized. The transport properties of benzene, toluene, and p‐xylene (BTX) through the rubber composites were studied in terms of sorption, diffusion, permeation, and mass transfer coefficients. The effect of the ceramic fillers on the mechanical, thermal and transport properties were studied. The sorption data at different temperatures were used for calculating activation energy of diffusion, permeation, free energy, and enthalpy of sorption. The BTX remained in the liquid state within the composite matrix as evident from negative ΔS. The diffusion coefficient (D) and mass transfer coefficient (kmtc) of BTX decreased with the increase in filler loading. Accordingly, for the transport of BTX the unfilled rubber showed a D (D × 107 cm2/s) and mass transfer coefficient (kmtc × 104 cm/s) of 5.67/3.97/2.96 and 7.71/7.08/7.04, respectively which decreased to 5.06/2.95/2.57 and 7.53/6.95/6.90, respectively for the composite containing 50 wt.% ceramic filler.

Anisotropy of flow behavior and microstructure evolution of selective laser melted 718 alloy during high temperature deformation

The uniaxial hot compression tests of selective laser melted (SLM) 718 alloy with different orientations were carried out by thermal simulation tester, and the microstructure of the as-built and deformed samples was analyzed by scanning electron microscope (SEM) and electron backscattered diffraction (EBSD) technologies. The results indicate that the orientation of the sample has little effect on the variation of flow stress, but it has a certain impact on the value of the peak stress. The constitutive equation could accurately predict the flow behavior of two orientations samples, and the calculated activation energies (Q) values of the H-orientation samples is 517.07 kJ/mol, which is slightly lower than 543.77 kJ/mol of V-orientation samples. The analysis of microstructure shows that the dynamic recrystallization (DRX) process in the H-orientation samples is more likely to occur than that in V-orientation samples under the same deformation conditions, which is caused by the difference in the evolution of initial deformed grains of the two orientations samples during deformation.