Arrhenius Plot Research Articles

Oxidation Mechanism and Surface Characterization of Pyrolytic Graphite in Simulated Air for Pyrochemical Reprocessing Application

Accidental air ingress into the containment chamber of pyrochemical reprocessing of spent nuclear fuels can cause severe oxidation of graphite components. Pyrolytic graphite (PyG) coating on conventional high-density graphite (HDG) is proposed for protection against oxidation, molten salt, and molten metal corrosion. The aim of the present study is to evaluate the thermal stability and kinetic parameters and propose a suitable oxidation mechanism of PyG under simulated air using thermogravimetry analysis (TGA). In dynamic oxidation, a linear increase in the oxidation onset, peak, and burnout temperature is observed for PyG synthesized at increasing pyrolysis temperature from 1200 to 2400°C except for 1400°C. The isothermal oxidation study showed a similar trend i.e., a decrease in the linear oxidation rate constant value for any given isotherm with increasing pyrolysis. The Arrhenius plot showed two-stage oxidation regimes operating between 600 to 1000°C. In regime-I, between 600 to ∼800°C controlled by surface chemical reaction kinetics, the activation energy is measured between 100-200 kJ.mol−1. The graphite-oxygen reaction initiates and propagates preferentially along the prismatic planes at the sample edges, where the dangling bonds of stacked graphite layer structures are exposed. In regime-II operating above ∼800°C, the surface reaction rate is infinitely faster, and the diffusional mass transport becomes a rate-limiting factor. In this regime, the graphite-oxygen initiates by pore formation on defective reactive sites on the bulk surface and propagates by pore-widening and pore-coalescence mechanism. The observed differences in the oxidation rates for different pyrolysis PyG attributed to its intrinsic material properties are investigated. This work provides new insights into the oxidation mechanism of the PyG during accidental air ingress in a pyrochemical reprocessing plant.

Temperature-Dependent Kinetics of the Reactions of the Criegee Intermediate CH2OO with Hydroxyketones.

Though there is a growing body of literature on the kinetics of CIs with simple carbonyls, CI reactions with functionalized carbonyls such as hydroxyketones remain unexplored. In this work, the temperature-dependent kinetics of the reactions of CH2OO with two hydroxyketones, hydroxyacetone (AcOH) and 4-hydroxy-2-butanone (4H2B), have been studied using a laser flash photolysis transient absorption spectroscopy technique and complementary quantum chemistry calculations. Bimolecular rate constants were determined from CH2OO loss rates observed under pseudo-first-order conditions across the temperature range 275-335 K. Arrhenius plots were linear and yielded T-dependent bimolecular rate constants: kAcOH(T) = (4.3 ± 1.7) × 10-15 exp[(1630 ± 120)/T] and k4H2B(T) = (3.5 ± 2.6) × 10-15 exp[(1700 ± 200)/T]. Both reactions show negative temperature dependences and overall very similar rate constants. Stationary points on the reaction energy surfaces were characterized using the composite CBS-QB3 method. Transition states were identified for both 1,3-dipolar cycloaddition reactions across the carbonyl and 1,2-insertion/addition at the hydroxyl group. The free-energy barriers for the latter reaction pathways are higher by ∼4-5 kcal mol-1, and their contributions are presumed to be negligible for both AcOH and 4H2B. The cycloaddition reactions are highly exothermic and form cyclic secondary ozonides that are the typical primary products of Criegee intermediate reactions with carbonyl compounds. The reactivity of the hydroxyketones toward CH2OO appears to be similar to that of acetaldehyde, which can be rationalized by consideration of the energies of the frontier molecular orbitals involved in the cycloaddition. The CH2OO + hydroxyketone reactions are likely too slow to be of significance in the atmosphere, except at very low temperatures.

Graft Copolymerization of Acrylonitrile onto Banana Cellulose Fiber

The graft co-polymerization of acrylonitrile monomer (AN) onto banana cellulose fiber (BCF) was carried out using ceric ammonium nitrate (CAN)/oxalic acid (OA) as redox pair in the aqueous nitric acid medium at 90 ºC. The effect of different reaction conditions on the grafting has been studied by determining the grafting parameters, i.e. concentration of acrylonitrile, ceric ammonium nitrate, oxalic acid, nitric acid, reaction time and temperature were carefully optimized to achieve the highest rate of grafting polymerization (RG), highest percent grafting yield (%GY) and grafting efficiency (%GE). All the reagents enhanced the RG%, GY% and %GE, with an increase of concentration up to a certain extent and then found to decline, except for the concentration of nitric acid. The grafting parameters were also increased with time/duration and temperature. The water retention value (WRV) of the grafted co-polymer was also measured. Activation parameters such as energy of activation (Ea), enthalpy change (ΔH), entropy change (ΔS) and free energy change (ΔG) can also be reported by using the Arrhenius plot. The evidence of grafting can also be predicted by the FTIR spectral analysis, moreover, the organic reaction mechanism has been proposed.

Continuous strain tuning of oxygen evolution catalysts with anisotropic thermal expansion

Compressive strain, downshifting the d-band center of transition metal oxides, is an effective way to accelerate the sluggish kinetics of oxygen evolution reaction (OER) for water electrolysis. Here, we find that anisotropic thermal expansion can produce compressive strains of the IrO6 octahedron in Sr2IrO4 catalyst, thus downshifting its d-band center. Different from the previous strategies to create constant strains in the crystals, the thermal-triggered compressive strains can be real-timely tuned by varying temperature. As a result of the thermal strain accelerating OER kinetics, the Sr2IrO4 exhibits the nonlinear lnjo - T−1 (jo, exchange current density; T, absolute temperature) Arrhenius relationship, resulting from the thermally induced low-barrier electron transfer in the presence of thermal compressive strains. Our results verify that the thermal field can be utilized to manipulate the electronic states of Sr2IrO4 via thermal compressive strains downshifting the d-band center, significantly accelerating the OER kinetics, beyond the traditional thermal diffusion effects.

Electrical properties of strained off-stoichiometric Cu–Cr–O delafossite thin films

Off-stoichiometric Cu–Cr–O delafossite thin films with different thicknesses were grown by metal organic chemical vapor deposition on substrates with different coefficients of thermal expansion. Seebeck thermoelectric coefficient and resistivity measurements were performed on the range of 300–850 K. A qualitative change in the temperature-dependence of the resistivity is observed at the temperature corresponding to the deposition process, where the transition from tensile to compressive strain takes place. Arrhenius plots reveal different slopes in these two thermal ranges. The fact that the shift is more pronounced for the thinner films might indicate the induced strain plays a role in changing electrical behaviour. Furthermore, changes below 0.1% in electrical mobility were measured when the strain is induced by mechanical bending.

Research on the conductivity and self-sensing properties of high strength cement-based material with oriented copper-coated steel fibers

In this paper, a cement-based sensor for monitoring the performance of high-strength concrete was prepared by adding 0.5 vol%, 1.0 vol%, 1.5 vol%, and 2.0 vol% copper-coated steel fibers (CCSF) as conductive fillers. The fresh cement-based mixture was poured into a funnel-type fiber alignment device, which used its fluidity of the mixture to achieve an aligned distribution of shear-induce fiber within the cementitious matrix. The analysis results indicate that the cement-based sensor with fiber oriented distribution exhibits enhanced electrical conductivity and lower percolation threshold. In addition, the aligned CCSF in the cement matrix mitigates the impact of temperature on resistivity. The resistivity and temperature of the copper-coated steel fibers cement-based sensors (CSFCS) between 5 °C and 70 °C conform to the Arrhenius relationship. The specimens with aligned fibers demonstrate greater flexural strength compared to those with randomly distributed fibers. Additionally, they also reflect greater piezoresistive response, including higher sensitivity, better repeatability as well as less hysteresis time. Through the two-dimensional cross-section analysis, the angle between CCSF and the cross-section of the fiber-aligned specimen is significantly reduced, and the fiber orientation factor and fiber orientation coefficient increased considerably. The funnel device for preparing fiber-reinforced cement-based materials can effectively improve fiber orientation.

The influence of hydrogen and oxygen vacancy concentrations on diffusion coefficients of oxide and hydride ions in reduced barium titanate oxyhydride using molecular dynamics simulation

A molecular dynamics method with a reax force field has been employed to investigate the effect of hydrogen and oxygen vacancy concentrations on the diffusion of oxygen and hydrogen atoms in BaTiO3−xHy□(x-y). The result shows that by using this force field, the BaTiO3−xHy□(x-y) samples are stable under the condition of x < 0.18. Therefore, the samples have been simulated under conditions of (x-y) <0.15, y < 0.18 and x < 0.18. The results reveal that the dominant diffusion dynamics of hydrogen atoms is the motion between next-nearest neighboring oxygen vacancies in the form of hydride. The diffusion coefficients and activation energies are evaluated using mean square displacements and Arrhenius plots. The results show that the activation energies of oxide and hydride ions are close together and are in the range of 0.03–0.9 eV and they both decrease by increasing y. The results also show that the pre-exponential factors of hydrogen and oxygen diffusion are in the range of 10−6 to 0.0045 cm2s-1 and 1.7710−6 to 0.0017 respectively.

Constructing supercapacitors with biopolymer bearing zwitterion as hydrogel electrolyte and binder for superior performance at −40 °C

This study demonstrates how to construct supercapacitors with biopolymer bearing zwitterion as hydrogel electrolyte and binder for superior performance at the temperature of −40 °C. Carboxylated chitosan (CCS) and carboxymethyl cellulose (CMC) are used as hydrogel electrolyte and binder respectively, as well as, subject to oxa-Mickael addition with sulfobetaine methacrylate (SBMA) to obtain CCS-SBMA and CMC-SBMA. For electrolytes, CCS and CCS-SBMA hydrogel electrolytes are prepared by different concentrations of NaClO4 intake at swelling ratio of 8.5. Among all electrolytes, there exist the highest ionic conductivities 9 mS cm−1 and 25 mS cm−1 in CCS and CCS-SBMA with 10 m and 12 m NaClO4 respectively. Accordingly, CCS-10 and CCS-SBMA-12 are used for Arrhenius plot from 25 °C to −40 °C. Surprisingly, the ionic conductivity in CCS-SBMA-12 at −40 °C (9.48 mS cm−1) is still higher than one in CCS-10 at 25 °C (8.23 mS cm−1). CCS-SBMA-12 is used for supercapacitors with CMC and CMC-SBMA as binders, respectively as SCs-CMC and SCs-CMC-SBMA. SCs-CMC shows poor performance below −0 °C due to the crystallization of CMC, corroborated by Differential scanning calorimetry. In contrast, SCs-CMC-SBMA still possesses 33 F∙g−1 at −40 °C. This study gives some light on the superior performance of supercapacitor with hydrogel electrolyte at −40 °C.

Prediction of shelf life and sensory qualities of beef meatball with biodegradable taro starch-duck bone gelatin packaging at different storage temperatures

Biodegradable packaging from taro starch-duck bone gelatin is environmentally friendly packaging made from natural materials and has not been widely applied to beef meatball storage. This study applied the Accereleted Shelf Life Testing (ASLT) method to the Arrhenius kinetic model of chemical quality with three different storage temperatures and calculates the effect of temperature by analyzing its kinetic parameters. The temperature variations used were 4, 10, and 29°C. Parameters of changes in chemical quality during storage suitable for Arrhenius plots (R2>0.93). The critical parameter for determining the shelf life of biodegradable beef meatball packaging from taro starch-duck bone gelatin was pH with an activation energy value (Ea) of 16,878.81 cal/mol. The calculation of the shelf life obtained was at 29°C for 1.01 days, 10°C for 6.68 days, and 4°C for 12.81 days. The Q10 method can be used to determine the expiration time of beef meatballs at various storage temperatures. The increase in temperature caused an increase in the rate of deterioration kinetics and a decrease in shelf life. Differences in temperature and length of storage time cause a decrease in the sensory quality of beef meatballs. The use of biodegradable taro starch-duck bone gelatin packaging is suitable for use as packaging at a storage temperature of 29℃. Biodegradable taro starch-duck bone gelatin can be used to extend the shelf life of beef meatballs using the Arrhenius kinetic model.

Extended theoretical modeling of reverse intersystem crossing for thermally activated delayed fluorescence materials.

Thermally activated delayed fluorescence (TADF) materials and multi-resonant (MR) variants are promising organic emitters that can achieve an internal electroluminescence quantum efficiency of ~100%. The reverse intersystem crossing (RISC) is key for harnessing triplet energies for fluorescence. Theoretical modeling is thus crucial to estimate its rate constant (kRISC) for material development. Here, we present a comprehensive assessment of the theory for simulating the RISC of MR-TADF molecules within a perturbative excited-state dynamics framework. Our extended rate formula reveals the importance of the concerted effects of nonadiabatic spin-vibronic coupling and vibrationally induced spin-orbital couplings in reliably determining kRISC of MR-TADF molecules. The excited singlet-triplet energy gap is another factor influencing kRISC. We present a scheme for gap estimation using experimental Arrhenius plots of kRISC. Erroneous behavior caused by approximations in Marcus theory is elucidated by testing 121 MR-TADF molecules. Our extended modeling offers in-depth descriptions of kRISC.

Uncertainly Analysis of Prior Distribution in Accelerated Degradation Testing Bayesian Evaluation Method Based on Deviance Information Criterion

The accelerated degradation testing (ADT) Bayesian evaluation method comprehensively utilizes product degradation data under accelerated stress levels collected over a short period of time and multiple sources of prior information, such as historical information, similar product information, simulation information, etc., to conduct life and reliability evaluation. Through the prior distribution, prior information affects the ADT Bayesian evaluation results ultimately. However, different evaluators may obtain different prior distributions based on the same prior information due to varying experiences or rules, which may lead to differences in the ADT Bayesian evaluation results. Therefore, it is necessary to analyze and study the impact of prior distribution uncertainty on the ADT Bayesian evaluation results while also finding criteria to judge the quality of prior distributions. This paper focuses on the ADT Bayesian evaluation method based on the Wiener process and the Arrhenius relation, studying the influence of different prior distributions on the robustness of ADT Bayesian evaluation results. Additionally, based on the deviance information criterion (DIC), a criterion for selecting prior distributions in the ADT Bayesian evaluation method is proposed. Through carrying out uncertainty analysis of prior distribution in the ADT Bayesian evaluation method, a theoretical system and framework for analyzing prior uncertainty in ADT Bayesian evaluation based on DIC are established, providing a better foundation for the practical application of the ADT Bayesian evaluation method in engineering.

Synthesis and electrical characterization of Sb modified lithium bismuth titanate

Sb-modified lithium bismuth titanate Li0.5Bi0.3Sb0.2TiO3 is prepared following the mixed oxide method. The development of a new compound with a single-phase orthorhombic crystal structure is approved from the XRD analysis at environmental temperature. The electrical behavior like dielectric and electrical conductivity are analyzed in a wide temperature as well as frequency range by the impedance analyzer, which exhibits that these properties effectively depend on frequency and temperature. The ac conductivity versus temperatures plots obeys the Arrhenius relation and confirm the presence of the mixed type of conductivity process like space charge conductivity created from oxygen ion vacancies, ionic-polaronic conductivity, and so on, in the sample. Ac conductivity versus frequency spectra is as per Jonscher’s Universal Power law.

Controlled Assembly of a Dawson-like Antimoniotungstate-Supported Trefoil-type Trimer with Good Proton Conductivity Performance.

With the excellent properties of POM in the field of proton conductivity, the preparation of POM-based proton-conductive materials has burst into life. Herein, an unprecedented Sb-templated all-inorganic trimer Na8H18.64[(SbW14O52)3(Sb2W6.12Ru5.88O18)]·85H2O (1), which is based on tetravacant Dawson-like [SbW14O52]17- blocks and exhibits a trefoil type with D3 symmetry, has been successfully designed and synthesized by the assembly of simple materials with a one-pot hydrothermal method under acidic conditions. Also, compound 1 is systematically characterized by single-crystal X-ray diffraction, PXRD, ESI-MS, IR spectroscopy, UV-vis, elemental analysis, and TGA. Crystal structure data analysis demonstrates that compound 1 is constructed by a hexagonal prismatic heterometallic {Sb2W6.12Ru5.88O18} core and three equivalent {SbW14} units bridged through μ2-O atoms in periphery. Subsequently, further property experiments show that compound 1 exhibits high proton conductivity with a conductivity value (σ) of 3.07 × 10-2 S cm-1 at 75 °C and 80% relative humidity (RH). The activation energy of compound 1 evaluated by the Arrhenius plots is 0.22 eV, which indicates that the Grotthuss mechanism is dominant during the process of proton transfer.

Using Temperature-Programmed Photoelectron Emission (TPPE) to Analyze Electron Transfer on Metallic Copper and Its Relation to the Essential Role of the Surface Hydroxyl Radical

Surface processes such as coatings, corrosion, photocatalysis, and tribology are greatly diversified by acid–base interactions at the surface overlayer. This study focuses on the action of a metallic copper surface as an electron donor/acceptor related to the inactivation of viruses. It was found that regarding Cu2O or Cu materials, electrostatic interaction plays a major role in virus inactivation. We applied the TPPE method to clarify the mechanism of electron transfer (ET) occurring at light-irradiated copper surfaces. The TPPE characteristics were strongly influenced by the environments, which correspond to the temperature and environment dependence of the total count of emitted electrons in the incident light wavelength scan (PE total count, NT), the photothreshold, and further the activation energy (ΔE) analyzed from the Arrhenius plot of NT values obtained in the temperature increase and subsequent temperature decrease processes. In this study, we re-examined the dependence of the TPPE data from two types of Cu metal surfaces: sample A, which was mechanically abraded in alcohols, water, and air, and sample C, which was only ultrasonically cleaned in these liquids. The NT for both samples slowly increased with increasing temperature, reached a maximum (NTmax) at 250 °C (maximum temperature, Tmax), and after that, decreased. For sample A, the NTmax value decreased in the order H2O &gt; CH3OH &gt; C2H5OH &gt; (CH3)2CHOH &gt; C3H7OH, although the last alcohol gave Tmax = 100 °C, while with sample C, the NTmax value decreased in the order C3H7OH &gt; (CH3)2CHOH &gt; C2H5OH &gt; CH3OH &gt; H2O. Interestingly, both orders of the liquids were completely opposite; this means that a Cu surface can possess a two-way character. The NT intensity was found to be strongly associated with the change from the hydroxyl group (–Cu–OH) to the oxide oxygen (O2−) in the O1s spectra in the XPS measurement. The difference between the above orders was explained by the acid–base interaction mode of the –Cu–OH group with the adsorbed molecule on the surfaces. The H2O adsorbed on sample A produces the electric dipole –CuOδ−Hδ+ ⋅⋅⋅ :OH2 (⋅⋅⋅ hydrogen bond), while the C3H7OH and (CH3)2CHOH adsorbed on sample C produce RO−δHδ+ ⋅⋅⋅ :O(H)–Cu− (R = alkyl groups). Gutmann’s acceptor number (AN) representing the basicity of the liquid molecules was found to be related to the TPPE characteristics: (CH3)2CHOH (33.5), C2H5OH (37.1), CH3OH (41.3), and H2O (54.8) (the AN of C3H7OH could not be confirmed). With sample A, the values of NTmaxa and ΔEaUp1 both increased with increasing AN (Up1 means the first temperature increase process). On the other hand, with sample C, the values of NTmaxc and ΔEcUp1 both decreased with increasing AN. These findings suggest that sample A acts as an acid, while sample C functions as a base. However, in the case of both types of samples, A and C, the NTmax values were found to increase with increasing ΔEUp1. It was explained that the ΔEUp1 values, depending on the liquids, originate from the difference in the energy level of the hydroxyl group radical at the surface denoted. This is able to attract electrons in the neighborhood of the Fermi level of the base metal through tunnelling. After that, Auger emission electrons are released, contributing to the ET in the overlayer. These electrons are considered to have a strong ability of reducibility.

In-situ determination of strain during transient burst testing and the temperature dependence of Zircaloy-4 claddings

Understanding fuel system behavior during postulated loss-of-coolant accidents is pertinent for continued safe and efficient operation of light water reactors, particularly as higher burnups are being pursued and safety margins re-evaluated. Conventional mechanical models for the incumbent Zr alloys typically rely on the assumption that steady-state creep is the dominant fuel cladding response during transient accident conditions. To investigate this assumption, simulated accident burst testing was performed on Zircaloy-4 claddings with balloon behavior measured in-situ. Two distinct loading conditions were utilized during burst testing: (1) constant-gas-inventory where pressure was allowed to increase with temperature and (2) constant pressure. In-situ strains and strain rates were measured via 2-dimensional digital image correlation techniques and synchronized with temperature to determine deformation dependencies. The temperature dependence of strain rate was characterized by a two segment Arrhenius relationship, with a distinct transition between the high and low temperature/strain regimes. The average activation energy of the lower temperature/strain regime was 328 ± 25 kJ/mol, in agreement with the ∼320 kJ/mol used for conventional LOCA models. However, the higher temperature/strain segment, which encompassed most of ballooning, showed increased activation energies as well as a dependence on whether the burst region was in view. For tests that burst away from the camera view, the average high temperature/strain segment activation energy was 635 ± 150 kJ/mol. For samples where the rupture opening formed in view, the average activation energy was 1015 ± 179 kJ/mol. This observed shift in temperature dependence indicates a transition in deformation mechanism at the end of life, possibly to time independent failure mechanisms, which has not yet been visualized in the literature for Zr alloys. Parameters at the transition points were analyzed to determine thresholds for this change in behavior, which occurred at an average hoop strain of 6.9 ± 2.1 %.

Biochemical and thermodynamic properties of de novo synthesized urease from Vicia sativa seeds with enhanced industrial applications

Urease is one of the most significant enzymes in the industry. The objective of this research was to isolate and partially purify urease from Vicia sativa seeds with urease characterization. With a 6.4 % yield, the purification fold was 9.0. By using chromatography, it was determined that the isolated urease had a molecular weight of 55 kDa. The maximum urease activity was found following a 60-s incubation period at 40 °C and pH 8. The activity of urease was significantly boosted by a mean of calcium, barium, DL-dithiothreitol, Na2EDTA, and citrate (16.9, 26.6, 18.6, 13.6, and 31 %), respectively. But nickel and mercury caused inhibitory effects and completely inhibited urease activity, indicating the presence of a thiol (-SH) group in the enzyme active site. The Arrhenius plot was used to analyze the thermodynamic constants of activation, Ea, ΔH*, ΔG*, and ΔS*. The results showed that the values were 30 kJ/mol, 93.14 kJ/mol, 107.17 kJ/mol/K, and −40.80 J/mol/K, respectively. The significance of urease extraction from various sources may contribute to our understanding of the metabolism of urea in plants. The current report has novelty as it explained for the first time the kinetics and thermodynamics of hydrolysis of urea and inactivation of urease from V. sativa seeds.

Structural and electrical characteristics of manganese modified BaTiO3 ceramic

The material Ba(Ti0.5Mn0.5)O3 synthesized through the conventional solid-state reaction method has hexagonal structure free from any impurity phase. The complex dielectric dispersion, temperature and frequency-dependent dielectric, impedance, AC conductivity, and leakage behavior of the sample are studied. The impedance study of the material encloses non-Debye type relaxation, negative temperature coefficient of resistance nature and the grain and grain boundary effects. The ferroelectric to paraelectric phase transition occurs at T C ∼ 270 °C. The dielectric constant and loss-tangent values are found to be less as compared to that of the parent barium titanate sample. R g < R gb, that is, grain boundary has greater opposition than the grain region. The material follows correlated barrier hopping model. The carrier transport process through AC conductivity study obeys the Jonscher’s power law and the Arrhenius relation while varying with the frequency and temperature.

Self-assembly of water-filled molecular saddles to generate diverse morphologies and high proton conductivity.

The design of single-component organic compounds acting as efficient solid-state proton conduction (SSPC) materials has been gaining significant traction in recent times. Molecular design and controlled self-assembly are critical components in achieving highly efficient SSPC. In this work, we report the design, synthesis, and self-assembly of an organic macrocyclic aza-crown-type compound, P2Mac, which complements synthetic ease with efficient SSPC. P2Mac is derived from the pyridine-2,6-dicarboxamide (PDC) framework and contains polar amide and amine residues in its inner region, while aromatic residues occupy the periphery of the macrocycle. The crystal structure analysis revealed that P2Mac adopts a saddle-shaped geometry. Each P2Mac molecule interacts with one water molecule that is present in its central polar cavity, stabilized by a network of five hydrogen bonds. We could self-assemble P2Mac in a variety of unique, aesthetically pleasing morphologies such as micron-sized octahedra, hexapods, as well as hollow nanoparticles, and microrods. The water-filled polar channels formed through the stacking of P2Mac allow attaining a high proton conductivity value of 21.1 mS cm-1 at 27 °C under a relative humidity (RH) of 95% in the single crystals of P2Mac, while the as-prepared P2Mac pellet sample exhibited about three-orders of magnitude lower conduction under these conditions. The low activation energy of 0.39 eV, calculated from the Arrhenius plot, indicates the presence of the Grotthus proton hopping mechanism in the transport process. This report highlights the pivotal role of molecular design and self-assembly in creating high-performance SSPC organic materials.

Study of rectifying properties and true Ohmic contact on Sn doped V2O5 thin films deposited by spray pyrolysis method

In this paper, V2O5 thin-films were deposited on glass substrates by using the ultrasonically nebulized spray pyrolysis technique. Doping concentration of 1 %, 2 %, and 7 % of Sn, in V2O5 thin-films is studied by using metal–semiconductor-metal (MSM) based device structure. X-ray diffractometer (XRD) and field emission scanning electron microscope (FESEM) were used to analyze the surface morphology of the thin films. The XRD spectroscopic analysis shows the crystal size of above-mentioned samples, to be respectively 39 nm, 58 nm, 60 nm and 72 nm. The FESEM images showed the enhancement of crystal size with increase in Sn doping concentration. The optical properties of Sn doping on V2O5 thin film were studied by using UV–Vis spectrometer. The UV–Vis spectroscopic analysis shows that the absorption coefficient values decrease with increase in concentration of Sn metal doping in V2O5 thin film. The activation energies of all thin-film samples were calculated from Arrhenius plots and were found to be 0.938 eV, 1.101 eV, 1.11 eV and 1.169 eV, respectively, for all the thin-film samples mentioned above. The MSM based structure was fabricated by using a shadow mask and thermal evaporation. Later, the I-V characteristics of all the thin films were obtained by using semiconductor parameter analyzed at a biased voltage between −50 V and + 50 V with a step size of 1 V. Rectification ratio of the V2O5 films is significantly enhanced as the doping concentration increases. It was found that the rectification ratio of undoped V2O5 thin films increased linearly from 1.018 to 1.059 with an increase in temperature from room temperature to 130 °C. Similar trend was followed for 1 % (from 1.079 to 1.198), 2 % (from 1.081 to 1.224) and 7 % (from 1.095 to 1.311) Sn doped films. These results show the potential application of V2O5 thin films in the field of optoelectronics and thin film gas sensors.

High-temperature sensitivity complex dielectric/electric modulus, loss tangent, and AC conductivity in Au/(S:DLC)/p-Si (MIS) structures

Complex dielectric (ε* = ε′ − jε″)/electric modulus (M* = M′ + jM″), loss tangent (tanδ), and ac conductivity (σac) properties of Au/(S-DLC)/p-Si structures were investigated by utilizing admittance/impedance measurements between 80 and 440 K at 0.1 and 0.5 MHz. Sulfur-doped diamond-like carbon (S:DLC) was used an interlayer at Au/p-Si interface utilizing electrodeposition method. The capacitance/conductance (C/G) or (ε' ~ C) and (ε″ ~ G) values found to be highly dependent on both frequency and temperature. The increase of them with temperatures was attributed to the thermal-activated electronic charges localized at interface states (Nss) and decrease in bandgap energy of semiconductor. The observed high ε′ and ε″ values at 0.1 MHz is the result of the space/dipole polarization and Nss. Because the charges are at low frequencies, dipoles have sufficient time to rotation yourself in the direction of electric field and Nss can easily follow the ac signal. Arrhenius plot (ln(σac) vs 1/T) shows two distinctive linear parts and activation energy (Ea) value was found as 5.78 and 189.41 from the slope; this plot at 0.5 MHz is corresponding to low temperature (80–230 K) and high temperature (260–440 K), respectively. The observed higher Ea and ε′ (~ 14 even at 100 kHz) show that hopping of electronic charges from traps to others is predominant charge transport mechanism and the prepared Au/(S:DLC)/p-Si structure can be used to store more energy.