Characteristic Time Research Articles

Performance of V–Fe based catalysts on the oxidation of dibenzothiophenes

To obtain fossil fuels with ultra-low S levels at friendly conditions, different V oxides formulations on alumina modified with Fe were characterized and selected to oxidize dibenzothiophene (DBT), 4-methyl DBT and 4,6-dimethyl DBT prevailing in diesel fuel. V–Fe based catalysts (5 or 10 wt% of V) were obtained by impregnation of ammonium metavanadate solutions on Fe-modified alumina, obtained by impregnation of Mohr salt on pseudoboehmite (2 wt% of Fe). The catalysts were calcined in air atmosphere, and after were partially reduced with H2 flux to obtain a mix of several oxidation states of V and Fe species, to evaluate the interaction of Fe in VOx/Al2O3 catalysts and determine its effect on the oxidation processes. The structural and optical properties, as well as surface species, were determined by SEM-EDS, TPR, XRD, Raman, ATR-FTIR, photoluminescence, UV–Vis diffuse reflectance, and XPS spectroscopy. The catalytic performance was evaluated in oxidative desulfurization (ODS) and photocatalytic ODS (PODS) processes. The experimental results showed the addition of Fe promoted the catalytic activity of both ODS and PODS reactions. ODS activities of V–Fe catalysts increase up to 7.5 times with respect to V catalysts without Fe, and the most active catalyst (V5Fer) presents a characteristic oxidation time of 50 min for 4,6-DMDBT. The PODS activity of V10Fec was like ODS activity, showing it is possible to oxidize the dibenzothiophenes under friendly conditions to obtain lower S levels. The promoting effect of Fe was due to the interaction of Fe2+ and Fe3+ with the catalytic support, favoring the distribution of surface V3+ and V4+ species. Additionally, Fe improved the optical properties of the catalysts since the bandgap energy decrease and low recombination rate of the electron-hole pair were observed. Therefore, V–Fe based catalysts are photocatalytically actives to be used in PODS processes.

Characteristic Vibrational and Rotational Relaxation Times for Air Species from First-Principles Calculations

We present molecular-scale computational rotational-vibrational relaxation studies for N2, O2, and NO. Characteristic relaxation times for diatom-diatom and diatom-atom interactions are calculated using direct molecular simulation (DMS), with ab initio potential energy surfaces (PESs) as the sole model input. Below approximately 8000 K our N2−N2, O2−O2, and O2−N2 vibrational relaxation times agree well with the Millikan–White (M&W) correlation, but gradually diverge at higher temperatures. Park’s high-temperature correction produces a relatively steeper temperature rise compared to our estimates. DMS further shows that, with increasing temperature, the gap between vibrational and rotational relaxation times shrinks for all species. At T>30,000K their magnitudes become comparable and a clear distinction between both energy modes becomes meaningless. For other interactions, our DMS results differ substantially from the M&W correlation, both in magnitude and temperature dependence. Our predicted N2−O2 vibrational relaxation times are noticeably shorter due to vibration-vibration transfer. For O2−O we observe minimal temperature dependence. Our O2−N and N2−N predictions follow the M&W temperature trend at values roughly one order of magnitude smaller. For NO−NO, N2−O, NO−N, and NO−O we generate partial data due to currently incomplete PES sets. These first-principles-derived relaxation times are useful for informing relaxation models in gas-kinetic and fluid-dynamics simulations of high-enthalpy flows.

Cyclic Ion Mobility of Isomeric New Psychoactive Substances Employing Characteristic Arrival Time Distribution Profiles and Adduct Separation.

Analysis of new psychoactive substances (NPS), which is essential for toxicological and forensic reasons, can be made complicated by the presence of isomers. Ion mobility has been used as a standalone technique or coupled to mass spectrometry to detect and identify NPS. However, isomer separation has so far chiefly relied on chromatography. Here we report on the determination of isomeric ratios using cyclic ion mobility-mass spectrometry without any chromatographic separation. Isomers were distinguished by mobility separation of lithium adducts. Alternatively, we used arrival time distribution (ATD) profiles that were characteristic of individual isomers and were acquired for protonated molecules or fragment ions. Both approaches provided comparable results. Calculations were used to determine the structures and collision cross sections of both protonated and lithiated isomers that accurately characterized their ion mobility properties. The applicability of ATD profiles to isomer differentiation was demonstrated using direct infusion and flow injection analysis with electrospray of solutions, as well as desorption electrospray of solid samples. Data processing was performed by applying multiple linear regression to the ATD profiles. Using the proposed ATD profile-based approach, the relationships between the determined and given content of isomers showed good linearity with coefficients of determination typically greater than 0.99. Flow injection analysis using an autosampler allowed us to rapidly determine isomeric ratios in a sample containing two isomeric pairs with a minor isomer of 10% (determined 9.3% of 3-MMC and 11.0% of 3-FMC in a mixture with buphedrone and 4-FMC). The proposed approach is not only useful for NPS, but also may be applicable to small isomeric molecules analyzed by ion mobility when complete separation of isomers is not achieved.

Effect of dynamic strain ageing on flow stress and critical strain for jerky flow in Al-Mg alloys

A comprehensive approach addressing the flow behavior and the critical strain for the initiation of serrations in Al-Mg alloys is developed in the present work. The basic premise of the approach is that the solute atmosphere influences the friction as well as the strain hardening component of the flow stress. The friction effect of the solute cloud is modeled by considering the interplay between the characteristic solute migration time and the dislocation waiting time according to the cross-core diffusion mechanism. The impact on strain hardening is modeled by considering the apparent strengthening of the forest dislocations because of formation of solute aggregates near the vicinity of dislocation junctions. The apparent forest strengthening effect scales as the square root of the ratio of solute concentration in vicinity of the dislocation junctions and the bulk solute concentration. The modified constitutive model is validated against experimental flow curves obtained for strain rates varying over several orders of magnitude. It was observed that the modified constitutive model outperforms the standard constitutive model (considers only the friction effect of solute atmosphere) in predicting the flow curves in the dynamic strain aging domain. Furthermore, the modified constitutive model also accurately predicts the critical strain for the initiation of the jerky flow in both the normal and inverse regimes of the critical strain versus strain rate curve. Additional validation of the modified constitutive model is provided by dislocation character and density measurements via X-ray diffractograms, dislocation structure investigation via transmission electron microscopy along with fracture surface analysis.

Reprocessable and repairable carbon fiber reinforced vitrimer composites based on thermoreversible dynamic covalent bonding

The emergence of vitrimers breaks through the limitation of traditional carbon fiber reinforced thermoset composites (CFRP) caused by their permanent crosslinking molecular networks. Herein, the dynamic cross-linked network of vitrimer was synthesized from Bisphenol A diglycidyl ether (DGEBA) and glutaric anhydride (GA) under the catalysis of zinc acetylacetonate (Zn(acac)2), and the corresponding carbon fiber reinforced vitrimer composites (CF/Vx) were prepared via an impregnation and hot pressing process. The dynamic covalent adaptable networks (CANs) of vitrimer endow CF/Vx with stress relaxation and creep characteristics. By adjusting the catalyst content, the dynamic performance of CF/V0.05 can be optimized to achieve the highest viscous flow activation energy (60 kJ/mol) and the lowest characteristic relaxation time (1.0 × 10−3 s). The unique dynamic properties enable CF/Vx with reprocessability at high temperature. Typically, the flexural modulus of CF/V0.05 decreased from 87 ± 1.81 GPa at room temperature to 4.62 ± 0.28 GPa at 220 °C, which confirms the feasibility of thermoplastic forming of CF/V0.05 at high temperatures. Based on this, a CF/V0.05-based cap-shaped component was successfully manufactured through a thermoforming process. Additionally, the CF/V0.05 composites also exhibit repairability for interlaminar fractures. The optimal CF/V0.05 can achieve a repair efficiency of 128 % under the hot press conditions of 180 °C, 10 MPa and 1 h. Hence, the reprocessable and repairable CF/Vx composites hold enormous potential in the engineering field.

Characteristic voltages and times from capacitance–voltage analysis of quantum dot light-emitting diodes

The characteristic voltages in the capacitance–voltage (C–V) curve of quantum dot light-emitting diodes (QLEDs) are usually linked to the start of charge injection and recombination in a working device. However, it may lead to a misunderstanding of the carrier process in QLEDs. This is because capacitance change only reflects an electrical response of additional carriers induced by a small signal loaded on an applied DC voltage but does not directly correlate with the total free carrier response governed by the working voltage. In this work, we study the frequency-dependent C–V characteristics of a blue QLED, focusing on the characteristic voltages, characteristic times, and their relationships. First of all, we identify that the charge injection point of QLEDs should be extracted by the current density–voltage–luminance characteristics rather than the C–V curve. As for the characteristic voltages obtained from the C–V curve, they are determined by voltage-dependent characteristic times in different time domains. Furthermore, the C–V characteristic is helpful to evaluate charge accumulation or leakage in blue QLED, serving as an accessible analysis tool in the carrier transport process. Our work provides a definite physical meaning of characteristic voltages in the C–V curve and exhibits the usefulness of C–V characteristics for analyzing the charge dynamics of QLED.

Characteristic times for radiation belt drift phase mixing

Impulsive radial transport events occurring in the radiation belts leave lasting marks in the form of drift echoes, that is, energy-dependent drift phase structures in the radiation belts that evolve at the drift frequency. Drift echoes are known to be transient structures that dissipate due to phase mixing. The objective of this paper is to discuss how much time it takes for drift echoes to dissipate, and what drives this phase-mixing process. While any uncertainty or perturbation in the variables controlling trapped particles’ drift frequency contributes to phase mixing, we highlight two main drivers: the observational uncertainty associated with the finite size of the instrument energy channels, and the natural field fluctuations driving perturbations in trapped particles’ drift frequency. It is the combination of both instrumental and natural sources of phase mixing that determines the observed dissipation and lifetime of drift echoes. This means that the observed magnitude and lifetime of a drift echo are always underestimations of the natural magnitude and lifetime of the structure. This calls into question the applicability of the standard, drift-averaged formulation of radial diffusion. The three key points of the study are the following: First, the time it takes for particles initially localized in local time to phase-mix is measured in hours in the Earth’s radiation belts. Second, phase mixing at the drift scale is primarily due to uncertainties in measured kinetic energy and field perturbations. Third, our analysis can be utilized to set an energy resolution requirement for future particle instruments.

An asymptotic description of a basic FcRn-regulated clearance mechanism and its implications for PBPK modelling of large antibodies.

A basic FcRn-regulated clearance mechanism is investigated using the method of matched asymptotic expansions. The broader aim of the work is to obtain further insight on the mechanism, thereby providing theoretical support for future pharmacologically-based pharmacokinetic modelling efforts. The corresponding governing equations are first non-dimensionalised and the order of magnitudes of the model parameters are assessed based on their values reported in the literature. Under the assumption of high FcRn-binding affinity, analytical approximations are derived that are valid over the characteristic phases of the problem. Additionally, relatively simple equations relating clearance and AUC to physiological model parameters are derived, which are valid over the longest characteristic time scale of the problem. For lower to moderate doses clearance is effectively linear, whereas for higher doses it is nonlinear. It is shown that for all doses sufficiently high the leading-order approximation for the IgG concentration in plasma, over the longest characteristic time scale, is independent of the initial dose. This is because IgG that is in 'excess' of FcRn is eliminated over a time scale much shorter than that of the terminal phase. In conclusion, analytical approximations of the basic FcRn mechanism have been derived using matched asymptotic expansions, leading to a simple equation relating clearance to FcRn binding affinity, the ratio of degradation and FcRn concentration, and the volumes of the system.

Design and study of the flow section of a variable microchannel reformer based on the coupling law of reforming with flow, heat and mass transfer

In the amplification mode, microscale reforming reactions are controlled by the transfer rate. To avoid the amplification effect, the process coupling mechanism in the microchannel reactor must be studied to take full advantage of its precise control. This paper studies the coupling effect between the flow process and the reforming process in the microchannel and constructs a computational model of the flow coupling. A study was conducted on the influence of the coupling effect on the conversion rate, based on a combination of reliability verification and experiments. The following conclusions were obtained: the coupling effect in the reactive flow field was quantified based on the characteristic time of the flow process and the reaction process (Da number), and the microchannel was divided into three parts. The methanol conversion rate of the burst-expansion scheme was increased to more than 6%, and the USAER (unit surface area enhancement rate) reached 7.7. The USAER of the protrusion-expansion scheme can reach 8.342, with a potential for an 10% increase in conversion rate. The distribution of the three-segmented variable cross-section has the most effective regulation effect. The USAER of the protrusion-expansion scheme reaches 9.11, with a conversion rate that can be increased by 7%.

Markovian noise-induced delta synchronization approach for Hindmarsh–Rose model

The paper explores noise-induced synchronization in uncoupled Hindmarsh–Rose neurons, introducing two distinctive elements: the application of Markovian noise and an analysis of synchronization via unpredictability. The noise is defined as an unpredictable and continuous process with characteristics proper for stochasticity. While identical synchronization is also investigated, the primary focus is to reveal synchronization in noise intensity domains that elude conventional detection methods, through delta synchronization within the neural system. Furthermore, a stronger form of synchronization, namely complete synchronization of unpredictability, is found to emerge in the domain with identical synchronization. The research findings are substantiated by numerical outcomes assessing unpredictability and synchronization, alongside comprehensive tables displaying characteristic time sequences for synchronization.

Evidence for double resonant Raman decay from a Ag surface

We have investigated the electron pair emission from a Ag(100) surface upon photon absorption which leads to the emission of a 4p photoelectron. The subsequent Auger decay proceeds in a single-step process as shown previously. Key finding was the emergence of a diagonal intensity feature in a two-dimensional kinetic energy distribution of the electron pair whose width reveals a characteristic time of 30 as for the dynamics of the core-hole decay process. We utilize this observation as a tool to identify an unexpected pathway of electron pair emission. Once the photon energy is at the threshold of a double 4p core hole creation we notice a sizeable broadening of the energy sharing distribution. We associate this process to the excitation of two 4p electrons between the Fermi and vacuum level followed by radiation less double electron excitation. This feature is characterized by an energy sum of the pair which disperses linearly with the photon energy. Therefore, we regard it as a double resonant Raman decay. Published by the American Physical Society 2024

Exciton migration in two-dimensional materials

Excitons play an essential role in the optical response of two-dimensional materials. These are bound states showing up in the band gaps of many-body systems and are conceived as quasiparticles formed by an electron and a hole. By performing real-time simulations in hBN, we show that an ultrashort (few-fs) UV pulse can produce a coherent superposition of excitonic states that induces an oscillatory motion of electrons and holes between different valleys in reciprocal space, leading to a sizeable exciton migration in real space. We also show that an ultrafast spectroscopy scheme based on the absorption of an attosecond pulse in combination with the UV pulse can be used to read out the laser-induced coherences, hence to extract the characteristic time for exciton migration. This work opens the door towards ultrafast electronics and valleytronics adding time as a control knob and exploiting electron coherence at the early times of excitation.

Research on features and localization of AE signals from the mechanical body of industrial robots based on WD-EMD

Abstract In order to reveal the propagation characteristics of acoustic emission (AE) signals in the body of industrial machinery, the characteristic frequencies and wave speeds of AE signals propagated on the interior and exterior surfaces (IS and ES) of the body were extracted. Subsequently, an algorithm utilizing characteristic frequency and time difference of arrival (TDOA) is proposed for the identification and localization of AE sources. Initially, an AE source is induced on the IS and ES of the body using the pencil-lead break method in accordance to ASTM standards, and the AE signal is captured by two piezoelectric sensors at a sampling frequency of 3 MHz. Then, to avoid the limitations of wavelet decomposition using self-selected wavelet scale and the problem that a single indicator cannot properly evaluate the correlation between independent mode functions (IMFs) with the original signal, this paper will conduct 4-layer wavelet decomposition of the original signal according to the response frequency range of the sensor, and select the wavelet details within the stable range of the response frequency of the sensor for preliminary reconstruction,and then the empirical mode decomposition (EMD) method is used to decompose the de-noised AE signal into 7 IMFs, and the AE waveform is reconstructed by the combined information of correlation coefficient and variance accounted for. Secondly, the reconstruction method combined with EMD analysis and a single index is compared with the proposed method in this paper to verify the reliability of the proposed method. In addition, the frequency domain characteristics of AE signal propagation process on the IS and ES of the body are extracted. Finally, based on the TDOA principle, the propagation speed of AE signal on the IS and ES of the body is calculated. Based on the geometric relationship between the AE source and two sensors, an algorithm for the location of the AE source is proposed. The results show that the proposed signal reconstruction method can effectively extract the features of AE signals, and the average positioning accuracy of the localization algorithm based on characteristic frequency and TDOA reaches 0.86%.

Autocombustion Route Derived Zinc Ferrite Nanoparticles as Chemiresistive Sensor for Detection of Alcohol Vapors.

Prolonged exposure to alcohol vapors can have detrimental effects on human health, potentially leading to eye irritation, dizziness, and in some cases, damage to the nervous system. The present article aims to provide a comprehensive understanding on the synthesis and characterization of zinc ferrite (ZnFe2O4) nanoparticles, as well as their interactions with a range of alcohol vapors, including methanol, ethanol, n-propanol, and isopropanol. These alcohols differ in their molecular weight, boiling points, diffusivity, and other properties. The study reveals the semiconducting ZnFe2O4 nanoparticulate sensor's capability for reversible, repeatable, and sensitive detection of alcohol vapors. The sensor exhibits the highest response to ethanol within operating temperature range (225-300 °C). An attempt is made to establish a correlation between the properties of the target analytes and the observed sensing signals. Additionally, the response conductance transients of ZnFe2O4 under the exposure to the studied alcohol vapors are modeled based on the Langmuir-Hinshelwood adsorption mechanism. The characteristic time constants obtained from this modeling are justified with respect to the properties of the analytes.

Miniaturizable Chemiluminescence System for ATP Detection in Water.

We present the design, fabrication, and testing of a low-cost, miniaturized detection system that utilizes chemiluminescence to measure the presence of adenosine triphosphate (ATP), the energy unit in biological systems, in water samples. The ATP-luciferin chemiluminescent solution was faced to a silicon photomultiplier (SiPM) for highly sensitive real-time detection. This system can detect ATP concentrations as low as 0.2 nM, with a sensitivity of 79.5 A/M. Additionally, it offers rapid response times and can measure the characteristic time required for reactant diffusion and mixing within the reaction volume, determined to be 0.3 ± 0.1 s. This corresponds to a diffusion velocity of approximately 44 ± 14 mm2/s.

Rheological behaviors of the multi-wall carbon nanotubes/polyethylene composites prepared by a master batch method

In this work, the rheological properties of four multi-wall carbon nanotubes (MWCNTs)/polyethylene (PE) composites containing 1 wt.% (mPEC1), 3 wt.% (mPEC3), 5 wt.% (mPEC5), and 10 wt.% (mPEC10) MWCNTs prepared by the masterbatch method were investigated and compared with those of the pure PE. The rheological investigation includes strain sweeping, frequency sweeping, stress relaxation behavior, yield stress, characteristic relaxation time, temperature effect on linear viscoelastic behavior, and gel behavior. It is mainly found that (1) the MWCNTs-MWCNTs interaction resulting in MWCNTs network structure in the PE matrix and the MWCNTs-PE interfacial interaction increase the storage and loss moduli of the MWCNTs/PE composite in comparison with those of pure PE; (2) the time-temperature equivalence principle is applicable only for pure PE and mPEC1; (3) for gel behavior of MWCNTs/PE composite at 160–180 °C, the φ g value decreases with the increase of temperature and the highest S g value is obtained at 170 °C.

Scaling Properties of Gelling Systems in Nonlinear Shear Experiments.

We study model near-critical polymer gelling systems made of gluten protein dispersions stabilized at different distances from the gel point. We impose different shear rates and follow the time evolution of the stress. For sufficiently large shear rates, an intermediate stress overshoot is measured before reaching the steady state. We evidence self-similarity of the stress overshoot as a function of the applied shear rate for samples with various distances from the gel point, which is related to the elastic energy stored by the samples, as for dense systems close to the jamming transition. In concordance with the findings for glassy and jammed systems, we also measure that the stress after flow cessation decreases as a power law with time, with a characteristic relaxation time that depends on the shear rate previously imposed. These features revealed in nonlinear rheology could be the signature of a mesoscopic dynamics, which would depend on the extent of gelation.

Transition from decaying to decayless kink oscillations of solar coronal loops

ABSTRACT The transition of an impulsively excited kink oscillation of a solar coronal loop to an oscillation with a stationary amplitude, i.e. the damping pattern, is determined using the low-dimensional self-oscillation model. In the model, the decayless kink oscillations are sustained by the interaction of the oscillating loop with an external quasi-steady flow. The analytical solution is based on the assumption that the combined effect of the effective dissipation, for example, by resonant absorption, and interaction with an external flow, is weak. The effect is characterized by a dimensionless coupling parameter. The damping pattern is found to depend upon the initial amplitude and the coupling parameter. The approximate expression shows a good agreement with a numerical solution of the self-oscillation equation. The plausibility of the established damping pattern is demonstrated by an observational example. Notably, the damping pattern is not exponential, and the characteristic decay time is different from the time determined by the traditionally used exponential damping fit. Implications of this finding for seismology of the solar coronal plasmas are discussed. In particular, it is suggested that a very rapid, in less than the oscillation period, decay of the oscillation to the stationary level, achieved for larger values of the coupling parameter, can explain the relative rareness of the kink oscillation events.

Optimized α/β pulse shape discrimination in Borexino

Borexino could efficiently distinguish between α and β radiation in its liquid scintillator by the characteristic time profile of its scintillation pulse. This α/β discrimination, first demonstrated on the ton scale in the counting test facility prototype, was used throughout the lifetime of the experiment between 2007 and 2021. With this method, the α events are identified and subtracted from the solar neutrino events similar to β. This is particularly important in liquid scintillators, as the α scintillation is strongly quenched. In Borexino, the prominent Po210 decay peak was a background in the energy range of electrons scattered from Be7 solar neutrinos. Optimal α/β discrimination was achieved with a , with a higher ability to leverage the timing information of the scintillation photons detected by the photomultiplier tubes. An event-by-event, high efficiency, stable, and uniform pulse shape discrimination was essential in characterizing the spatial distribution of background in the detector. This benefited most Borexino measurements, including solar neutrinos in the pp chain and the first direct observation of the CNO cycle in the Sun. This paper presents key milestones in α/β discrimination in Borexino as a term of comparison for current and future large liquid scintillator detectors. Published by the American Physical Society 2024

Polarity-Induced Reactive Wetting: Spreading and Retracting Sessile Water Drops.

Wetting is typically defined by the relative liquid to solid surface tension/energy, which are composed of polar and nonpolar subcontributions. Current studies often assume that they remain invariant, that is, surfaces are wetting-inert. Complex wetting scenarios, such as adaptive or reactive wetting processes, may involve time-dependent variations in interfacial energies. To maximize differences in energetic states, we employ low-energy perfluoroalkyls integrated with high-energy silica-based polar moieties grown on low-energy polydimethylsiloxane. To this end, we tune the hydrophilic-like wettability on these perfluoroalkyl-silica-polydimethylsiloxane surfaces. Drop contact behaviors range from invariantly hydrophobic at ca. 110° to rapidly spreading at ca. 0° within 5 s. Unintuitively, these vapor-grown surfaces transit toward greater hydrophilicity with increasing perfluoroalkyl deposition. Notably, this occurs as sequential silica-and-perfluoroalkyl deposition also leaves behind embedded polar moieties. We highlight how surfaces having such chemical heterogeneity are inherently wetting-reactive. By creating an abrupt wetting transition composed of reactive and inert domains, we introduce spatial dependency. Drops contacting the transition spread before retracting, occurring over the time scale of a few seconds. This phenomenon contradicts current understanding, exhibiting a uniquely (1) decreasing advancing contact angle and (2) increasing receding contact angle. To explain the behavior, we model such time- and space- dependent reactive wetting using first order kinetics. In doing so, we explore how reactive and recovery mechanisms govern the characteristic time scales of spreading and retracting sessile drops.