Arrhenius Plot Research Articles

Quaternary functional semiconductor device-based temperature sensors for low and high temperatures (LTs, HTs)

Abstract The Al-(Zn:Cd:Ni:TiO2)-pSi diodes with a ratio of 4;2;2;2 were fabricated and their possible current transport mechanisms (CTMs) were investigated between 80–380 K and ±4.5 V range using current–voltage (IV) measurements. The saturation-current (Is), quality/ideality factor (n), and barrier-height (BH)/(Φ bo) values of the didoes were calculated from the forward-bias ln(IF)-VF curve as function of temperature. While the value of BH is increased with temperature, n value is decreased with increasing temperature. Non-linear behavior was observed in the Arrhenius or Richardson plot (RP) (ln(Io/T2) versus q/kT) at low temperatures (LTs). Also, the Richardson- constant (A*) calculated from the linear part of this plot is quite lesser than its theoretical- value (=32 A.(cm.K)−2 for p-Si), and high values of n at LTs show an evident deviated from thermionic-emission (TE) theory. To explain this case; both the nkT/q-kT/q, Φ bo and n versus q/2kT curves were plotted to determine the other possible-CTMs and they show that both the tunneling and Double Gaussian - distribution (DGD) are more effective rather than TE. The obtained A* value from the modified RP by using the standard deviation from Φ bo-q/2kT plot is closer to its theoretical value. The energy-dependent curve of interface states or traps (Nss) was calculated from the IF-VF characteristics by considering the voltage dependence of the BH and n for the studied temperature range and they generally decline with increase in temperature due to the rearrangement and structure of electrons at traps under the influence of temperature. All these results show that the fabricated The obtained results suggest that the fabricated Al-(ZnCdNiTiO2)-pSi diode can be used as a temperature - sensor in low and high temperature applications.

Synthesis of the cis‐ and trans‐3‐Fluoro Analogues of Febrifugine and Halofuginone

AbstractThe novel synthesis of racemic cis‐ and trans‐3‐fluorofebrifugine and halofuginone is described. This straight‐forward seven‐step process relies on an electrophilic fluorination‐allylation sequence that generates a mixture of N‐Cbz protected, diastereomeric 2‐allyl‐3‐fluoropiperidines. On separation, a Wacker oxidation‐methyl functionalisation sequence enabled introduction of the required quinazolinone portion. Finally, removal of the N‐Cbz protecting group lead to isolation of the 3‐fluorofebrifugine dihydrobromide analogues that are of potentially pharmacological use. Analysis of the NMR spectra for each stereoisomer provides information concerning the preferred conformers of the different diastereomers. Evidence indicates that the cis‐diastereomer favours a conformation where the F‐atom occupies an axial orientation. In contrast, for its trans‐stereoisomeric counterpart, the 2‐substituent overrides any F‐atom effect and it preferentially occupies a conformer where both substituents occupy equatorial positions. Finally, interconversion between the cis‐ and trans‐diastereomers was studied. In DMSO‐d6 and as their free‐bases, isomerisation of each diastereomer gave a common 65 : 35 ratio of trans‐ to cis‐3‐fluorofebrifugine. Determination of the reaction rate constants for the isomerisation process at different temperatures enabled calculation of the activation energy barriers, for each process, using an Arrhenius plot. The activation energy barrier for the isomerisation of the trans‐isomer was 94.3±4.9 kJ mol−1, whereas for the cis‐isomer it was 84.5±3.9 kJ mol−1.

Kinetic Study of Oxidation of Thiophene-2-Carbaldehyde by Imidazolium Dichromate Promoted By 1, 10-Phenanthroline

Kinetic study of oxidation of Thiophene-2-carbaldehyde by Imidazolium dichromate in aqueous acetic acid medium using 1,10-phenanthroline have been studied. In the absence of mineral acids, the oxidation kinetics of Thiophene-2-carbaldehyde acid by Imidazolium dichromate shows a first-order dependence on Imidazolium dichromate and fractional order on Thiophene-2-carbaldehyde. The variation of ionic strength, H+ and reaction product have in significant effect on reaction rate. Activation parameters have been studied for the reaction from the Arrhenius plot by studying the reaction at different temperatures.

Production of biodiesel by using CaO nano-catalyst synthesis from mango leaves extraction

Development and population expansion have the lion's share of driving up the fuel cost. Biodiesel has considerable attention as a renewable, ecologically friendly and alternative fuel source. In this study, CaO nanocatalyst is produced from mango leaves as a catalysis for the transesterification of waste cooking oil (WCO) to biodiesel. The mango tree is a perennial plant, and its fruit holds significant economic worth due to its abundance of vitamins and minerals. This plant has a wide geographical range and its leaves can be utilized without any negative impact on its growth and yield. An analysis was conducted to determine the calcium content in the fallen leaves, revealing a significant quantity of calcium that holds potential for utilization. The catalyst was characterized by different analytic techniques such as XRD, SEM-EDS, FT-IR, and BET analyses. Several parameters impacted on the transesterification process were exploited by conventional transesterification (batch). The result revealed that the optimum reaction was reached at a methanol to oil ratio of 50% w/w, catalyst loading of 3%, temperature of 65℃ and reaction time of 1.5 h with a yield of 93.21%, and the activation energy of the transesterification reaction was found to be 38.906 KJ mol-1. The reaction was verified to be irreversible pseudo-first order based on a linear Arrhenius plot and a high R2 value. The catalyst shows good stability and catalytic activity when it is reused and the yield was found to be 80.293% in the 5th cycle.

Unraveling the Complex Temperature-Dependent Performance and Degradation of Li-Ion Batteries with Silicon-Graphite Composite Anodes

Competing effects of graphite and Si result in a complex temperature dependent performance and degradation of Li-ion batteries with Si-graphite composite anodes. This study examines the influence of varying the Si content (0 to 20.8 wt%) in Si-graphite composite anodes with consistent areal capacity and N/P ratio in full cells containing NMC622 cathodes. One hundred pilot-scale double-layer pouch cells were built and cycle aged in the temperature range from −10 to 55 °C. Electrochemical characterization demonstrated that increasing Si contents enhance capacity and mitigate internal resistance at low temperatures. On the other hand, high Si contents decrease charge-discharge energy efficiency and cycle life, particularly at elevated temperatures. Post-mortem analysis of aged electrodes, including physico-chemical characterization (scanning electron microscopy, energy-dispersive X-ray analysis, thickness measurements) and cell reconstruction revealed significant solid electrolyte interphase growth and increased loss of active material in anodes with high Si content. The optimum temperature for longest cycle life as derived from Arrhenius plots decreased from 30 °C for graphite anodes to 10 °C for cells with moderate Si content up to 5.8 wt%. These findings allow the design of optimized cells by balancing the Si content versus operating temperature in order to achieve lowest cell aging.

The Extraction of the Density of States of Atomic-Layer-Deposited ZnO Transistors by Analyzing Gate-Dependent Field-Effect Mobility

In this study, we investigated the density of states extraction method for atomic-deposited ZnO thin-film transistors (TFTs) by analyzing gate-dependent field-effect mobility. The atomic layer deposition (ALD) method offers ultra-thin and smooth ZnO films, but these films suffer from interface and semiconductor defects, which lead to disordered localized electronic structures. Hence, to investigate the unstable localized structure of ZnO TFTs, we tried to derive the electronic state relationship by assuming field-effect mobility can be expressed as a gate-dependent Arrhenius relation, and the activation energy in the relation is the required energy for hopping. Following this derived relationship, the DOS of the atomic-deposited ZnO transistor was extracted and found to be consistent with those using temperature-dependent measurements. Moreover, to ensure the proposed method is reliable, we applied methods for the extraction of DOSs of doped ZnO transistors, which show enhanced mobilities with shifted threshold voltages, and the results show that the extraction method is reliable. Thus, we can state that the mobility-based DOS extraction method offers practical benefits for estimating the density of states of disordered transistors using a single transfer characteristic of these devices.

MoS2 nanosheet assisted poly vinyl alcohol cross-linked with carboxylated acryl-amido-2-methyl-1-propanesulfonic acid in medium temperature proton exchange membrane fuel cell application

ABSTRACT Initially, the carboxylated-acryl amido propane sulfonic acid (C-AMPSA) was synthesized through the thiol-ene reaction using 2-acrylamido-2-methylpropane sulfonic acid and 3-mercapto propane sulfonic acid monomers. The C-AMPSA was cross-linked with polyvinyl alcohol to create a non-perfluorinated membranes were of these acid group-containing monomers. Using a cross-linking technique, a poly vinyl alcohol cross-linked C-AMPSA (PVA-C-AMPSA) polymer was prepared. Following that, the MoS2 nanosheets (NSs) were synthesized through the one-pot hydrothermal method, and their phase purity, functionality, and morphology were evaluated by p-XRD, FT-IR, and FE-SEM analyses. These nanosheets were then incorporated into PVA-C-AMPSA polymer nanocomposite membranes at various concentrations (0%, 1%, 2%, 3%, and 5% by weight). In addition, the physicochemical properties of bare and MoS2 nanosheets incorporated PVA-C-AMPSA polymer nanocomposite membranes were assessed, including water uptake, swelling ratio, and ion-exchange capacity. Remarkably, the membrane with 5% of MoS2 NSs in PVA-C-AMPSA displayed an ion-exchange capacity of 1.13 mmol g−1 and a proton conduction of 1.8 × 10−3 S cm−1 at 110°C. The Arrhenius plot indicated that the proton transport was involved in both Grotthuss and vehicular mechanisms. In the fuel cell testing, the PVA-C-AMPSA polymer nanocomposite membrane containing MoS2 NSs demonstrated superior performance, achieving a peak power density (PD) exceeding 0.7 W cm−2 and an open-circuit voltage (OCV) surpassing 0.93 V at 110°C. In contrast, the pure PVA-C-AMPSA membrane exhibited a peak PD of over 0.4 W cm−2 and an OCV of around 0.6 V at the same temperature. Additionally, the 5% of MoS2 NSs incorporated PVA-C-AMPSA polymer nanocomposite membrane exhibited outstanding oxidative stability with 87.7% of degradation when exhibited to a Fenton reagent at 80°C for 8 h.

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.

Determining the constant diffusion coefficient by Fourier series solution of the diffusion equation

The purpose of this study was to obtain the diffusion coefficient by calculating directly from the Fourier series solution of the diffusion equation, which has not been studied so far. The Fourier series solution is the sum of a steady-state solution and a transient solution. The steady-state solution is a linear function of distance. The transient solution is the product of a distance function and a time function. The Fourier sine series solution, a function of distance only, is negative for the steady-state solution. For the sublimation diffusion of disperse dye in paste into polyethylene terephthalate (PET) film using the film-roll method, the constant surface concentration and the diffusion distance were determined from the quadratic regression curve for the concentration distribution at a long time. The concentration distribution of the transient solution is a downwardly convex curve with negative values. The concentration distribution of the Fourier series solution is also a downwardly convex curve. The diffusion coefficient in the exponential term, a function of time only, was determined from the value of the exponential term obtained by the surface concentration and the diffusion distance. The constant diffusion coefficients determined from the Fourier series solution are reliable because they are very similar to those obtained from the error function solution and have excellent linearity of the linear regression lines for their Arrhenius plots.

Comparison of formulas derived from Fourier series solution of diffusion equation

The first Fourier series solution satisfying the boundary condition of zero concentration at the diffusion distance was derived by assuming that the solution consists of a steady-state solution and a transient solution. The first total amount which has passed through the first layer surface was derived from the first Fourier series solution. When the diffusion distance is large, the exponential term in the first total amount cannot be zero. For the sublimation diffusion of disperse dye in paste into polyethylene terephthalate film using the film-roll method, the plot of the first total amount against time was in good agreement with the quadratic regression curve. The second Fourier series solution satisfying the boundary condition of constant concentration at the diffusion distance was derived by assuming that the diffusion distance is the thickness of the first layer. The second total amount which has passed through the second layer surface was derived from the second Fourier series solution and is a linear function of time because the exponential term is zero due to the very small diffusion distance, the thickness of the first layer. The plot of the second total amount against time was in good agreement with the linear regression line. The time-lag formula was derived from the second total amount. The diffusion coefficients determined from the second total amount are much larger than those of the other three types. All four types showed excellent linearity in Arrhenius plot, but the activation energy for the time-lag formula is somewhat greater than the rest.

Mechanistic insight into heat enhanced permeation of diclofenac and piroxicam in combination with chemical penetration enhancers across skin

The topical application of heat offers considerable potential for enhancing the delivery of non-steroidal anti-inflammatory drugs across the skin barrier. A better understanding of the mechanisms underpinning the improved skin permeation and how heat can be best used to work with complementary enhancement strategies would help to realise this potential. In this study the effect of heat on the permeation of diclofenac and piroxicam across different membranes, including human skin was investigated along with use of complementary enhancement strategies including selection of formulation pH, drug salt form and inclusion of chemical penetration enhancers. Heat alone improved drug delivery across human skin for both drugs, with larger increases for piroxicam. This increase was produced by improvements in drug release, molecular diffusivity and partitioning into the stratum corneum. In combination with chemical penetration enhancers, heat synergistically increased the skin permeation of diclofenac and piroxicam up to 13 and 40-fold respectively, with the increase in permeation being ascribed primarily to improvements in drug and enhancer partitioning into the stratum corneum. An Arrhenius plot of diclofenac permeation across skin was linear indicating that the orthorhombic to hexagonal stratum corneum lipid packing transition did not have a significant effect on skin permeation in response to heat.

Investigating the effect of temperature and concentration on the performance of reverse electrodialysis systems

Reverse electrodialysis (RED) is a membrane-based technology proposed for harvesting electricity from a salinity gradient. In this study, a detailed examination of the effect of temperature and concentration on RED membrane properties is undertaken. Modelling of the co-ion concentration as a function of temperature allows the Donnan potential to be estimated, while membrane resistance and ion diffusivity can be modelled by an Arrhenius relationship with temperature. Membrane resistance is best modelled using a reciprocal relationship with concentration, while permeability and diffusivity show a power law dependence upon concentration. Using these results, the effect of increasing the temperature of the entire RED system is compared to the case where only the temperature of the diluate solution is increased. The model is in good agreement with experimental results across temperatures from 10 to 40 °C. It shows that a comparable increase in gross power density can be achieved when only the temperature of the diluate solution is increased, relative to increasing the temperature of the entire system. However, increasing the temperature also reduces the pumping energy required for each stream. In the present case, this reduction in pumping energy with temperature is more significant than the changes within the stack itself. Thus, an increase in temperature of the entire system from 20 to 40 °C results in a 27 % increase in net power density as compared to an increase of the diluate solution alone. It is thus concluded that increasing the temperature of the entire system (rather than just the diluate stream) provides a pathway to increasing the power density of the system if waste heat is available, promoting its adoption for energy harvesting.

Hygrothermal aging and durability prediction of 3D-printed hybrid fiber composites with continuous carbon/Kevlar-fiber and short carbon-fiber

Hybrid Fiber Reinforced Polymers (HFRP) have excellent mechanical properties. However, preparation with 3D-printing technology is prone to hydrothermal aging compared to conventional method. Currently, complex hygrothermal aging and degradation mechanisms of 3D-printed HFRP are still unclear. Thus, hygrothermal aging and durability prediction of 3D-printed HFRP with continuous carbon/Kevlar-fiber and short carbon-fiber are studied, which considers four typical stacking sequences. All experimental samples are manufactured by Fused Deposition Modeling (FDM) 3D-printing. The artificial accelerate aging testing is conducted on samples at different times, and then flexural testing is adopted to evaluate the residual mechanical properties and failure modes. The results show that the stacking sequence significantly influences the moisture absorption behaviors, and [OC4O2K4]S absorbed more moisture than [OK4O2C4]S. During the aging process, the flexural properties of the 3D-printed HFRP first decrease rapidly and then keep stable. Among them, [OK4O2C4]S have the fastest degradation but possessed the highest residual strength. OC8O4K8O possess the slowest degradation but have a lower residual strength. The morphologies and micro failure modes/mechanisms are analyzed to explain the significant mechanical degradation. Finally, the Arrhenius relationship is adopted to accurately predict and analyze the degradation evolution process of specimens. This work offers a novel perspective on the hygrothermal aging and durability of 3D-printed HFRP.

Modulating optical and electrical properties of chemically synthesized ZnMn2O4 nanoparticles through crystallinity: Integrating theoretical and experimental insights

Theoretical and experimental analyses of zinc manganite (ZnMn2O4) nanoparticles were carefully conducted for in-depth exploration of their electronic and optical properties. Nanosized particles, approximately 11–15 nm in size, were synthesized using a post-sintering assisted co-precipitation method. Theoretical calculations using Rietveld refinement were conducted to accurately predict crystal parameters and simulate XRD patterns consistent with experimental XRD observations. UV–visible absorption spectra and Tauc plot analysis indicated a bandgap ranging from 0.65 to 0.79 eV, while photoluminescence spectra revealed the most intense peak at 466 nm, possibly arising from exciton recombination processes or defect-related emissions. Density function theory (DFT) calculations were employed to compute the band structure and density of states of ZnMn2O4, resulting in a calculated bandgap of 0.73 eV, which aligned closely with the experimental findings. Moreover, DFT calculation identified atomic-level transitions responsible for absorption peaks in the material. Comprehensive evaluations of the mechanical and optical properties, integrating theoretical insights with experimental data, provided a holistic understanding of the intricate electronic and optical characteristics of ZnMn2O4. Furthermore, frequency and temperature-dependent dielectric properties demonstrated the MWS-type polarization effect. Besides, the activation energy of 0.582–0.553 eV, calculated using the Arrhenius plot, was good in accordance with our dielectric analysis, solidifying the potential of this nanomaterial for advanced optoelectronic applications.

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.

The effect of ice shelf rheology on shelf edge bending

Abstract. The distribution of pressure on the vertical seaward front of an ice shelf has been shown to cause downward bending of the shelf if the ice is assumed to have vertically uniform viscosity. Satellite lidar observations show that many shelf edges bend upward and that the amplitude of upward deflections depends systematically on ice shelf thickness. A simple analysis is presented showing that upward bending of shelf edges can result from vertical variations in ice viscosity that are consistent with field observations and laboratory measurements. Resultant vertical variations in horizontal stress produce an internal bending moment that can counter the bending moment due to the shelf-front water pressure. Assuming a linear profile of ice temperature with depth and an Arrhenius relation between temperature and strain rate allows derivation of an analytic expression for internal bending moments as a function of shelf surface temperatures, shelf thickness and ice rheologic parameters. The effect of a power-law relation between stress difference and strain rate can also be included analytically. The key ice rheologic parameter affecting shelf edge bending is the ratio of the activation energy, Q, and the power-law exponent, n. For cold ice surface temperatures and large values of Q/n, upward bending is expected, while for warm surface temperatures and small values of Q/n downward bending is expected. The amplitude of bending should scale with the ice shelf thickness to the power 3/2, and this is approximately consistent with a recent analysis of shelf edge deflections for the Ross Ice Shelf. These scaling relations should help guide fully two-dimensional numerical simulations of shelf bending.

Structural, electrical, and transport properties of a PVB: NH4Br complexed solid polymer electrolyte films for electrochemical cell applications

ABSTRACT Polymer electrolytes are a key development in advancing battery technology, enabling more efficient energy storage. This study focused on developing a solid-state polymer electrolyte film by doping NH4Br with Polyvinyl Butyral (PVB) using a solution-cast method. X-ray diffraction (XRD) was employed to evaluate the amorphousness and crystallinity of the films, while Fourier Transform Infrared Spectroscopy (FTIR) confirmed complex formation between the salt and polymer. The glass transition temperature (Tg) of the electrolyte film was estimated using Differential Scanning Calorimetry (DSC). Ionic conductivity was measured through AC impedance spectroscopy, revealing that the PVB-NH4Br electrolyte doped with 30 wt% NH4Br at 30 °C had an ionic conductivity of 1.47 × 10−7 S cm−1. This conductivity followed an Arrhenius relationship, where conductivity increased with temperature. Dielectric studies showed that at low frequencies, the dielectric constant and loss were higher, while both decreased at higher frequencies. DC Wagner’s polarization technique verified that ion transport was the dominant conduction mechanism. Discharge testing of the electrolyte film using a Swagelok cell showed an open-circuit voltage (OCV) of 1.2 V and a short-circuit current (SCC) of 0.42 mA, indicating promising performance for battery applications.

Local atomic configuration and dynamic properties of liquid Ag-Si eutectic alloy by ab initio molecular dynamics

The structural evolution and dynamic properties of liquid Ag89Si11 eutectic alloy during rapid cooling were explored by ab initio molecular dynamics. The calculated pair distribution functions and structure factors at 1173 K agree well with the experimental reference data. The comprehensive analyses including Honeycutt-Andersen index, Voronoi tessellation, and atomistic cluster alignment reveal a gradual enhancement of chemical short-range order with the decreasing temperature and a dominant structural shifting towards perfect and distorted icosahedra. Additionally, the dynamic properties of liquid Ag89Si11 eutectic alloy were obtained and the diffusion coefficients follow Arrhenius relationship.

Molecular dynamics simulation of the diffusion behaviour in Ti–Ag using diffusion couple method

The diffusion behaviour of the Ti–Ag system was investigated using classical molecular dynamics by simulating a diffusion couple at various temperatures. One bulk of the diffusion couple consisted of titanium atoms arranged in a hexagonal close-packed (hcp) structure, i.e., α-Ti, and the other consisted of silver atoms arranged in a face-centred cubic (fcc) structure. The modern second nearest-neighbour modified embedded-atom method (2NN-MEAM) interatomic potential was used. The mean square displacement (MSD) of Ti atoms diffusing into Ag and Ag atoms into α-Ti was recorded during the simulation. Diffusion coefficients were determined from the slopes of lines fit to linear regions of MSD dependence on time. The Arrhenius relation was used to determine the activation energy and the frequency of attempts. The activation energy of Ti was 0.61eV and frequency of attempts 1.90⋅10−8m2s−1. The determined activation energy of Ag and frequency of attempts were not considered reliable because the Ag diffusion coefficient did not grow exponentially with temperature. Ti atoms penetrated deeper and greater amounts into Ag than Ag into α-Ti and also had a greater diffusion coefficient at all temperatures. The results were compared with the available experimental data, and for these purposes, self-diffusion in α-Ti and Ag was further investigated. Finally, it was determined that Ag diffuses in α-Ti by hopping over interstitial positions and Ti in Ag via vacancies.

Structure-Glass Transition Relationships in Non-Isocyanate Polyhydroxyurethanes.

The molecular dynamics, with an emphasis on the calorimetric and dynamic glass transitions, of non-isocyanate polyhydroxyurethanes (PHUs) produced by the equimolar polyaddition of polyether-based dicyclic carbonates (P-CCs) and various short diamines was studied. The diamine component consisted of a short aliphatic diamine (1,4-diaminobutane, DAB) and a more complex 'characteristic' diamine. The study was conducted to investigate (i) the chemical structure of the characteristic amine, (ii) its molar ratio, and (iii) the structure and molar mass of the P-CC. Infrared spectroscopy, differential scanning calorimetry, and broadband dielectric spectroscopy were employed. The P-CC, constituting the bulk of the systems, was the most crucial component for the glass transition. The characteristic amine influenced the glass transition as a result of its bulky structure, but also presumably as a result of the introduction of free volume and the formation of hydrogen bonds. The dynamic glass transition (α relaxation) trace in the Arrhenius plots showed a subtle change at a certain temperature that merits further study in the future. The charge mobility was fully coupled with the molecular mobility, as evidenced by dc conductivity being directly proportional to the characteristic frequency of α relaxation. The fluctuation in carbonyl units (β relaxation) was mildly affected by changes in their immediate environment.