Dependence Of Activation Energy Research Articles

Reliability Study of Metal-Oxide Semiconductors in Integrated Circuits.

This paper is devoted to the study of CMOS IC parameter degradation during reliability testing. The paper presents a review of literature data on the issue of the reliability of semiconductor devices and integrated circuits and the types of failures leading to the degradation of IC parameters. It describes the tests carried out on the reliability of controlled parameters of integrated circuit TPS54332, such as quiescent current, quiescent current in standby mode, resistance of the open key, and instability of the set output voltage in the whole range of input voltages and in the whole range of load currents. The calculated values of activation energies and acceleration coefficients for different test temperature regimes are given. As a result of the work done, sample rejection tests have been carried out on the TPS54332 IC under study. Experimental fail-safe tests were carried out, with subsequent analysis of the chip samples by the controlled parameter quiescent current. On the basis of the obtained experimental values, the values of activation energy and acceleration coefficient at different temperature regimes were calculated. The dependencies of activation energy and acceleration coefficient on temperature were plotted, which show that activation energy linearly increases with increasing temperature, while the acceleration coefficient, on the contrary, decreases. It was also found that the value of the calculated activation energy of the chip is 0.1 eV less than the standard value of the activation energy.

A modification to the Friedman and Ortega isoconversional methods for evaluation of the activation energy as a function of conversion and temperature

The Friedman and Ortega isoconversional methods typically apply linear regression to the isoconversional kinetic data for calculation of activation energy solely as a function of extent of conversion. However, in complex reactions, activation energy depends on both conversion and temperature. Our modification involves quadratic curve fitting instead of linear regression, resulting in the determination of activation energy as a function of conversion and temperature. The new technique enables the calculation of the temperature dependence of activation energy for different heating rates, making it a valuable addition to isoconversional analysis. The conventional and modified approaches were utilized on the isoconversional kinetic data concerning polyethylene thermal degradation. The results provided a more detailed representation of the variations in activation energy when nonlinear regression was used.

Coupling rate of ordering with degree of disorder: Developing a cation pair model for order-disorder in Li2Ti1-xZrxO3 solid solution

The order-disorder phenomenon of the cation sub-lattice is of substantial interests recently. However, randomness of the disordered local atomic structures poses great challenges for the modeling of ordering at larger size/time scales. In this work, a cation-pair model is developed to simulate the order-disorder of layered Li2TiO3. The configurational order of the lattice is simplified by the number of cation pairs at ordered/disordered state. Simulated x-ray diffraction of lattice models is performed to allow comparison with experimental observations. The configuration dependent activation energy is obtained by the simulated evolution of order-disorder based on density functional total energies. The cation-pair simplification enables fast estimation of ordering by tracking the number of pairs with rate theory. The model successfully reproduces the inhibition of ordering from increasing Zr/Ti in the Li2Ti1-xZrxO3 solid solution. Different stages of order-disorder have distinct features of ordering rates, which is explained by the coupling between ordering rates and degree of disorder. In addition, the model predicts stage-specific equilibrium conditions at various Zr/Ti and temperatures.

Hopping nature of the Hall effect in a samarium nickelate film

We analyzed the temperature dependencies of the DC resistivity and Hall coefficient in thin films of samarium nickelate SmNiO3. A dominating hopping conductivity was revealed in the insulating phase below 400 K, which defines an exponential drop in the Hall coefficient with temperature. The estimated dependencies of the hopping activation energy, Hall mobility, and charge carrier density suggest that small polarons are responsible for hopping. The hopping transport explains the observed sign anomaly of the Hall coefficient in rare-earth nickelates.

High-nitrogen azotetrazole based pyrogen gas generating propellants: Aspects on synthesis, characterization, combustion characteristics and kinetics

Propellant formulations containing a novel high nitrogen azotetrazole salt viz., diammonium 5,5′-azotetrazolate (DAAzT) along with two different binders viz., hydroxyl terminated polybutadiene (HTPB) and glycidyl azide polymer (GAP) were realized as potential pyrogen-based gas generators for use in inflatable structures. The DAAzT-GAP and DAAzT-HTPB propellant systems were investigated for their gas generating capabilities and it was found that the GAP based system offers enhanced gas yield of ∼430 mL/g against ∼320 mL/g for the HTPB based propellant at standard operating pressure of 1 bar and temperature of 298 K. Combustion product analyses of the propellant were undertaken by pyro GC–MS and it was found that the combustion products are benign and constitutes 62% and 53% N2 (mass fraction) as major combustion products from GAP and HTPB propellant respectively. A detailed thermal analysis of DAAzT by isoconversional method of Vzayovkin was undertaken and the dependence of activation energy with conversion was evaluated. The activation energy was also determined using a classical Kissinger method. The impact and friction sensitivity of the promising GAP-DAAzT propellant was found to be 3 Nm and 360 N respectively and the auto ignition temperature is 177.0 °C. Functional evaluation and gas generating capability of DAAzT-GAP propellant were successfully demonstrated in a sub-scale inflation test in a stand-alone configuration.

Activation energy and molecular weight dependence of cooperative tracer chains diffusion in highly entangled polymer melts

AbstractThe generalized Langevin equation for cooperative dynamics of Guenza predicts the dynamics of chains in entangled polymers is cooperative with anomalous properties, and at variance with the tube‐reptation model. The center‐of‐mass mean‐square displacements at shorter times are subdiffusive with with β < 1, contradicting the common assumption of reptation within the tube. At some longer time the subdiffusive dynamics exhibits the crossover to free diffusion with . Moreover the subdiffusive dynamics is heterogeneous, non‐Gaussian, and cooperative. These predictions have been confirmed by using neutron spin echo spectroscopy in entangled polyethylene melts [M. Zamponi, et al. J. Phys. Chem. B 2008, 112, 16220], and in tracer diffusion of short polyethylene chains in a highly entangled polyethylene melt [M. Zamponi et al. Phys. Rev. Lett. 2021, 126, 187801]. The latter was confirmed in poly(ethylene oxide) tracer diffusion in highly entangled poly(ethylene oxide) melt [M. Kruteva et al. Macromolecules 2021, 54, 11384]. Notwithstanding, there are other important data sets obtained in the NSE experiments but were left unexplained. One set consists of the activation energies of the Arrhenius temperature dependence of D for each tracer. Another is the molecular weight dependence of D of the tracers determined at the same temperature. In this article the predictions of the Coupling Model are applied to these two sets of data. Good quantitative agreements of the CM predictions with experimental data provide additional support to the cooperativity dynamics of entangled polymers as concluded by others. Additionally, all the properties of cooperative diffusion of entangled polymer chains are shown to be isomorphic to those found in cooperative diffusions in totally different systems. Diffusion in all are governed by interaction between the diffusing units, and from which the universal properties originate.

Thermal decomposition kinetics and mechanism of poly(ethylene 2,5-furan dicarboxylate) Nanocomposites for food packaging applications

Poly(ethylene 2,5-furan dicarboxylate) (PEF) based nanocomposites containing different nanoparticles like Ag, TiO2, ZnO, ZrO2 Ce-Bioglass, have been synthesized via in-situ polymerization techniques targeting food packaging applications. Zeta potential measurements showed an increase in the negative zeta potential value due to an increase in the surface charge density of the nanocomposites. Thermogravimetric analysis results proved that, except PEF-ZnO nanocomposite, all the other nanocomposites exhibited good resistance to thermal degradation without serious mass loss until 330 °C. Thermal decomposition kinetic analysis and the dependence of activation energy on the degree of conversion (α), indicated that the presence of ZnO nanoparticles influences, the degradation mechanism of PEF. In contrast, the presence of Ce-Bioglass nanoparticles leads to a slower degradation process, contributing to the enhanced resistance to thermal degradation of the PEF-Bioglass nanocomposite. The thermal degradation mechanism of PEF nanocomposites analyzed by pyrolysis‒gas chromatography/mass spectrometry (Py-GC/MS) indicated that the primary thermal degradation mechanism for the studied nanocomposites was β-hydrogen bond scission, while to a lesser extent, α-hydrogen bond scission products were noted in PEF-TiO2 and PEF-ZrO2 nanocomposites.

Advanced isoconversional kinetic analysis: Insight in mechanisms and simulations. Successes and future

Various examples of application of advanced isoconversional kinetic analysis are discussed. The paper focuses on polymerization and crystallization mechanisms, protein denaturation and simulations in a model-free way under different temperature programs. It is shown how isoconversional kinetic analysis was developed in the recent years to gain meaningful kinetic information on changes in rate-limiting steps and was applied to multi-step processes. The complementary of the information obtained by estimating pre-exponential factors, rate constants and mathematical function that describes the reaction mechanism, in addition to the usual effective activation energy dependency, is highlighted. In addition, combination of model-free and model-based methods can be used for the elucidation of multi-step kinetics.

Johnson-Mehl-Avrami kinetics as a universal description of crystallization in glasses?

Applicability of the Johnson-Mehl-Avrami (JMA) model beyond the typical range of the negative asymmetries of the crystallization peak was tested by means of theoretical simulations. Using the solid-state kinetic equation with implemented temperature dependences of either activation energy E or pre-exponential factor A, it was shown that the originally monotonically increasing transformation rate constant changes its evolution with temperature to a non-monotonous course, exhibiting a broad maximum. If the crystallization process following the non-isothermal JMA kinetics proceeds near this maximum, the asymmetry of the corresponding kinetic peak can gradually change to significantly positive values. Of particular interest are the cases with the JMA kinetic exponent mJMA ≥ 2, where the asymmetry of the JMA peaks changes with increasing heating rate from the typical negative values to largely positive values – such crystallization behavior was indeed observed for several chemically diverse materials (polymers, small organic molecules, chalcogenide and oxide glasses).

Effect of hyperfine structure on crystallization, microstructure and magnetic properties of amorphous Nd9Fe85B6 alloy

Crystallization of amorphous alloy is a commonly used method to fabricate nanocomposite permanent magnets. However, the effect of the hyperfine structures of amorphous alloy on microstructure evolution and magnetic properties of the obtained nanocomposites is far from understood. Here, amorphous Nd9Fe85B6 alloys with different hyperfine structures, i.e., different short-range orders (Rs = 0.80–0.91 nm), were prepared via melt spinning. The effects of the hyperfine structure on crystallization behavior, microstructure, and magnetic properties of the material upon thermal annealing were investigated in depth. Crystallization kinetics calculations show that a larger Rs leads to a smaller apparent crystallization activation energy, which leads to higher volume fractions of α-Fe and Nd2Fe14B. At the same time, a crystallizaition process dependent stage crystallization activation energy of Nd2Fe14B has been obtained, which is low at nucleation stage and increases with crystallization process, i.e. easy for nucleation but hard for growth, which leads to a smaller grain size of Nd2Fe14B. As a result, optimized magnetic properties were obtained in the sample with Rs = 0.91 nm.

THERMAL DECOMPOSITION OF MONO- AND DIETHANOLAMINEBORATE MODIFIED WOOD IN AIR ATMOSPHERE

"For cellulosic materials used in various branches of the economy, the issue of increasing thermal stability is still relevant today. Especially acute is the problem of fire resistance for wood materials used in building structures. In our work, we investigated the effect of mono- and diethanolamine borates on the thermal decomposition of wood in an air atmosphere. It has been previously found that mono- and diethanolaminoborates, when used as surface modifiers, provide 100% biostability to plant raw materials. In this regard, the purpose of the study was to identify the flame retardant effect of the described modifiers. In the course of the study, it was found that the developed compositions, the main components of which are boron-nitrogen compounds, effectively reduce the combustibility of wood materials, suppress smoldering, and reduce the burning rate of wood. Since it is the smoldering of wood after the liquidation of the fire that is the main cause of structural collapse, which prevents evacuation during the fire, the use of the developed compositions for fire protection of wooden structures is extremely appropriate. A regression model of the dependence of activation energy on conversion has been obtained and substantiated on the basis of correlation and regression analysis. The presented semi-logarithmic model can be further applied to predict the dependence of the activation energy value of the thermal decomposition process of modified wood on the degree of conversion."

Pyrolysis of Pine Wood in the Presence of Boron-Nitrogen Compounds.

The actuality of this research is determined by the intensification of new ways of processing woody biomass. This requires revealing the impact of various physicochemical factors on the thermal degradation of wood biopolymers. Boron-nitrogen surface modifiers are used for wood antisepsis and we decided to check their effect on flammability. The aim of the research was to evaluate the flame retardant effect of boron-nitrogen surface modifiers of wood in an inert atmosphere (nitrogen was used). The evaluation was carried out by thermal analysis of modified and the control pine wood samples. The thermal analysis included thermogravimetry, differential scanning calorimetry and kinetic parameters of thermal degradation. It was found that the flame retardant effect of boron-nitrogen wood surface modifiers was not significantly pronounced in the nitrogen atmosphere. The mechanism of the flame retardant effect of boron-nitrogen compounds is reduced to "shielding" of the surface and increasing the proportion of carbonized residue. On the basis of correlation-regression analysis of kinetic parameters of wood thermodestruction in a nitrogen atmosphere, mathematical models of activation energy dependence on conversion were obtained and substantiated. The developed models can be further applied to calculate the predicted value of wood activation energy in the nitrogen atmosphere at any conversion value.

Selective Oxidation of Glucose using Hydrogen Peroxide as an Oxidant: On the Structure Sensitivity of the Apparent Activation Energy

AbstractThe selective oxidation of glucose to gluconic acid with hydrogen peroxide was studied using different heterogeneous catalysts with alumina (Al2O3) and titanium silicate (TS‐1, TiMWW) as supports and different noble (Au, Pd) and non‐noble metals (Fe, W) as the catalytically active phases. Supported tungsten oxide catalysts showed a moderate selectivity and activity compared to palladium and iron catalysts. The best performance in the selective oxidation of glucose among the studied catalysts was displayed by gold on alumina. For this kind of catalyst, the structure sensitivity in glucose oxidation was explored, revealing a maximum rate shifted to larger gold particle sizes at higher temperatures in comparison with other studies involving activation of molecular oxygen on gold particles. A significant change in the apparent activation energy was established while changing the particle size of gold. These changes of the activation energy were adequately explained by a theoretical model for the cluster size dependence of the apparent activation energy.

Molecular dynamics simulation unveiling anion charge and lattice volume dependent Li ion diffusion in lithium compounds

To fill knowledge gaps between anion sublattice models and real lithium compounds in terms of the influence of Li-anion interaction on Li ion diffusion, herein, molecular dynamics calculations were applied to systematically study impacts of anion charge and lattice volume on Li ion diffusion in lithium battery materials. Regardless of different Li occupation patterns, Li sublattice type, anion sublattice types and Li ion diffusion channels, there is a universal physical picture of anion charge dependent activation energy (Ea) for Li ion diffusion in lithium compounds, and that is the more negative anion charges increase Ea for Li ion diffusion and then decrease them. While large lattice volumes not always reduce Ea for Li ion migration, and even increase Ea, distinguished from the traditional understandings. These physical pictures of anion charge and lattice volume dependent Ea guide us to apply strains and choose appropriate elements for doping or substituting lithium compounds to reduce Ea for fast Li ion diffusion.

Kinetics of Austenite Decomposition in 54SiCr6 Steel during Continuous Slow Cooling Conditions

In this study, dilatometry and metallography were used to investigate the effect of silicon and copper alloying on the decomposition kinetics of 54SiCr6 steel during continuous slow cooling. It is different from the published literature for using the approach of the local activation energy of the austenite decomposition Ef and the local Avrami exponent n of the volume fraction of the transformed phase f to study the kinetics of austenite-pearlitic transformation in cooled 54SiCr steel at slow cooling rates. The Johnson–Mehl–Avrami equation was used to determine the dependence of the local activation energy for austenite decomposition Ef and the local Avrami exponent n on the volume fraction of the transformed phase f. The mechanism of the austenite decomposition was analysed based on the calculated values of n. Both the local and average activation energies were used to evaluate the alloying effect, and the results were compared with those obtained from other methods. The type of microstructure formed as a result of cooling at rates of 0.5 K/s, 0.3 K/s, 0.1 K/s and 0.05 K/s was determined. The effects of changes in the cooling rate and the content of silicon (1.5–2.5 wt.%) and copper (0.12–1.47 wt.%) on the dimension of nucleation and growth kinetics of the transformed phase were studied. It was revealed that the pearlite microstructure was formed predominantly in 54SiCr6 steel as a result of continuous cooling at slow cooling rates. It was also found that alloying this steel with copper led to a significant decrease in the value of Ef, as well as to a change in the mechanism of the kinetics of the austenite-pearlite transformation, which was realised in predominantly two- and three-dimensional nucleation and growth at a constant nucleation rate. At the same time, alloying this steel with silicon led only to a slight change in Ef. The results of the study of 54SiCr steel presented the dependence of the activation energy of transformation and the local Avrami exponent on the volume fraction of the transformed phase at a given cooling rate at different copper and silicon contents. In addition, the study provides insight into the mechanism of kinetics in cooled 54SiCr steel as a function of the cooling rate.

Interface-Engineered Organic Near-Infrared Photodetector for Imaging Applications.

We report a high-speed low dark current near-infrared (NIR) organic photodetector (OPD) on a silicon substrate with amorphous indium gallium zinc oxide (a-IGZO) as the electron transport layer (ETL). In-depth understanding of the origin of dark current is obtained using an elaborate set of characterization techniques, including temperature-dependent current-voltage measurements, current-based deep-level transient spectroscopy (Q-DLTS), and transient photovoltage decay measurements. These characterization results are complemented by energy band structures deduced from ultraviolet photoelectron spectroscopy. The presence of trap states and a strong dependency of activation energy on the applied reverse bias voltage point to a dark current mechanism based on trap-assisted field-enhanced thermal emission (Poole-Frenkel emission). We significantly reduce this emission by introducing a thin interfacial layer between the donor: acceptor blend and the a-IGZO ETL and obtain a dark current as low as 125 pA/cm2 at an applied reverse bias of -1 V. Thanks to the use of high-mobility metal-oxide transport layers, a fast photo response time of 639 ns (rise) and 1497 ns (fall) is achieved, which, to the best of our knowledge, is among the fastest reported for NIR OPDs. Finally, we present an imager integrating the NIR OPD on a complementary metal oxide semiconductor read-out circuit, demonstrating the significance of the improved dark current characteristics in capturing high-quality sample images with this technology.

Oxidation thermolysis kinetics of asphaltenes with various chemical prehistory

In this research, six various asphaltenes extracted from crude oil mixtures of three Russian refinery plants and some heavy residues of these plants were studied with applying thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques. The kinetic experiments were performed at four various heating rates (5, 10, 15, 20 °C/min), all under air static atmosphere. The TGA data were transformed to conversions and first analyzed with the approved methods of Friedman, Ozawa-Flynn-Wall (OFW) and Kissinger-Akahira-Sunose (KAS). The results indicated of the complexity of decomposition-thermolysis process and a complicated and non-uniform dependency of the effective activation energy as a function of conversion, unique for each asphaltene studied. A kinetic model of two independent N-order reactions was proposed to make corresponding kinetic descriptions of complicated thermolysis reactions under non-isothermal conditions. The developed model was proved to be valid, and kinetic descriptions were obtained that fitted the experimental data. Activation energies for the first reaction and the second reaction were found to be in the interval 24–48 kJ/mol and 110–125 kJ/mol respectively (asphaltenes (1–3) extracted from the initial crude oil mixtures and pyrolysis resin). Activation energies for secondary asphaltenes (4–6) extracted from heavy refinery residues - 115–155 kJ/mol (1-st reaction) – 110–148 kJ/mol (2-nd reaction).

The role of Zn and Ru substitution on the structural, magnetic and dielectric properties of ferrite cuprospinels

A comprehensive study on the structural, magnetic and dielectric behavior of ferrite cuprospinels with site specific substitution of non-magnetic Zn and weakly magnetic Ru ions has been presented. Such substitution leads to two classes of stable crystal symmetries, (i) tetragonal (I41/amd): CuFe1.95Ru0.05O4 and Cu0.95Zn0.05Fe1.95Ru0.05O4 and (ii) cubic (Fd-3m):Cu0.60Zn0.40Fe1.95Ru0.05O4 and Cu0.05Zn0.95Fe1.95Ru0.05O4 bulk polycrystals. The former set of compounds undergo significant Jahn-Teller (JT) distortion due to high Cu content and such distortion gets lifted with the substitution of non-magnetic Zn ions. Ferrimagnetic (FiM) behavior is predominant in all these compounds except the highest Zn (95 at.%) content cubic system with diluted substitution of Ru (2.5 at.%) which exhibits antiferromagnetic ordering below the Néel temperature (T N ∼ 10.9 K). We employed Néel’s expression for FiM systems applicable for the two sublattice model to extract the dominant exchange interactions (J AA , J AB and J BB ) between the A-site and B-site cations. Subsequently the high temperature (300 K T 900 K) inverse paramagnetic susceptibility data has been fitted to the above expression which yields dominant ∼ 391 K with very high asymptotic Curie temperature for the tetragonally distorted dilute Zn substituted cuprospinel, while the Zn-rich cubic system exhibits ∼ 300 K. On the other hand, the tetragonally distorted spinel devoid of Zn exhibits dominant ∼ 229 K with negligible and moderate (65 K) signifying that the JT active ions cause the onset of magnetic frustration and enhanced ordering temperatures. All the investigated systems exhibit significant magneto-crystalline anisotropy with a maximum anisotropy field H K ∼ 6 kOe and maximum anisotropy constant (K 1 ∼ 10.88×105 erg cm−3). The broadband dielectric spectroscopy studies reveal significant enhancement of mid-frequency dielectric constant ε R (f, T) with plateau-like feature over a wide temperature and frequency window, together with low-loss as a result of the incorporation of Ru ions into the tetragonally distorted spinel lattice. The ac resistivity ρ(f, T) studies reveal that the mode of conduction follows Mott’s variable-range hopping (VRH) model with a linear logarithmic variation of ρ ac versus T −0.25. The temperature dependence of the VRH activation energy of charge carriers follows a linear behavior which indicates the presence of localized polaron in all the investigated systems.

Insights into co-pyrolysis of polyethylene terephthalate and polyamide 6 mixture through experiments, kinetic modeling and machine learning

The non-isothermal pyrolysis of polyethylene terephthalate (PET), polyamide 6 (PA6), and their mixtures was studied in a thermogravimetric analyzer at different heating rates. Temperature of maximum decomposition (Tmax) decreased by 25–45 °C and 35–55 °C for the PET:PA6 mixtures (3:1, 1:1, 1:3) compared to PET and PA6, respectively. The kinetic analysis was initially carried out using isoconversional method. However, the dependency of activation energy on conversion was observed for the co-pyrolysis of PET and PA6 that suggested the occurrence of multi-step reactions in the mixtures. Distributed activation energy model (DAEM) was used in this study to describe the multistep reactions occurring during pyrolysis of PET:PA6 mixtures. In this work, a four-parallel reaction DAEM was developed to describe the pyrolysis kinetics of PET:PA6 mixtures. The apparent mean activation energies (Eo) for PET, PA6, and mixtures varied in the range of 244–255, 140–215, and 138–255 kJ mol−1, respectively. The mass loss profiles of PET and PA6 mixtures were also modeled using artificial neural network (ANN). Out of 155 ANN models, the best prediction was made by ANN511 with R2 greater than 0.997 for both test and unseen data. The interaction effects observed through TGA experiments and subsequent kinetic analysis were further assessed in terms of product composition using analytical pyrolysis coupled with gas chromatograph/mass spectrometer (Py-GC/MS). Co-pyrolysis of PET and PA6 resulted in the formation of new aromatic compounds with nitrogen-containing functional groups, which were not detected when PET or PA6 were pyrolyzed individually.

Nonisothermal Crystallization Kinetics by DSC: Practical Overview

Providing a minimum of theory, this review focuses on practical aspects of analyzing the kinetics of nonisothermal crystallization as measured with differential scanning calorimetry (DSC). It is noted that kinetic analysis is dominated by approaches based on the Avrami and Arrhenius equations. Crystallization kinetics should not be considered synonymous with the Avrami model, whose nonisothermal applications are subject to very restrictive assumptions. The Arrhenius equation can serve only as a narrow temperature range approximation of the actual bell-shaped temperature dependence of the crystallization rate. Tests of the applicability of both equations are discussed. Most traditional kinetic methods tend to offer very unsophisticated treatments, limited only to either glass or melt crystallization. Differential or flexible integral isoconversional methods are applicable to both glass and melt crystallization because they can accurately approximate the temperature dependence of the crystallization rate with a series of the Arrhenius equations, each of which corresponds to its own narrow temperature interval. The resulting temperature dependence of the isoconversional activation energy can be parameterized in terms of the Turnbull–Fisher or Hoffman–Lauritzen theories, and the parameters obtained can be meaningfully interpreted and used for kinetic simulations.