On the redox reactions between allyl radicals and NOx

NO_x mitigation is a central focus of combustion technologies with increasingly stringent emission regulations. NO_x can also enhance the autoignition of hydrocarbon fuels and can promote soot oxidation. The reaction between allyl radical (C₃H₅) and NO_x plays an important role in the oxidation kinetics of propene. In this work, we measured the absolute rate coefficients for the redox reaction between C₃H₅ and NO_x over the temperature range of 1000–1252 K and pressure range of 1.5–5.0 bar using a shock tube and UV laser absorption technique. We produced C₃H₅ by shock heating of C₃H₅I behind reflected shock waves. Using a Ti:Sapphire laser system with frequency quadrupling, we monitored the kinetics of C₃H₅ at 220 nm. Unlike low-temperature chemistry, the two target reactions, C₃H₅ + NO → products (R1) and C₃H₅ + NO₂ → products (R2), exhibited a strong positive temperature dependence for this radical-radical type reaction. However, these reactions did not show any pressure dependence over the pressure range of 1.5–5.0 bar, indicating that the measured rate coefficients are close to the high-pressure limit. The measured values of the rate coefficients resulted in the following Arrhenius expressions (in unit of cm³/molecule/s):$k_1\left({\mathrm{C}}_3{\mathrm{H}}_5+\text{NO}\right)=1.49\times {10}^{?10}\exp \left(?6083.6\frac{\mathrm{K}}{T}\right)\left(1017?1252K\right)$$k_2\left({\mathrm{C}}_3{\mathrm{H}}_5+\mathrm{N}{\mathrm{O}}_2\right)=1.71\times {10}^{?10}\exp \left(?3675.7\frac{\mathrm{K}}{T}\right)\left(1062?1250K\right)$To our knowledge, these are the first high-temperature measurements of allyl + NO_x reactions. The reported data will be highly useful in understanding the interaction of NO_x with resonantly stabilized radicals as well as the mutual sensitization effect of NO_x on hydrocarbon fuels.     

Change of evaporation rate of single monocomponent droplet with temperature using time-resolved phase rainbow refractometry

Droplet evaporation characterization, although of great significance, is still challenging. The recently developed phase rainbow refractometry (PRR) is proposed as an approach to measuring the droplet temperature, size as well as evaporation rate simultaneously, and is applied to a single flowing n-heptane droplet produced by a droplet-on-demand generator. The changes of droplet temperature and evaporation rate after a transient spark heating are reflected in the time-resolved PRR image. Results show that droplet evaporation rate increases with temperature, from ?1.28$\times {10}^{?8}$ m²/s at atmospheric 293 K to a range of (?1.5, ?8)$\times {10}^{?8}$ m²/s when heated to (294, 315) K, agreeing well with the Maxwell and Stefan–Fuchs model predictions. Uncertainty analysis suggests that the main source is the indeterminate gradient inside droplet, resulting in an underestimation of droplet temperature and evaporation rate. With the demonstration on simultaneous measurements of droplet refractive index as well as droplet transient and local evaporation rate in this work, PRR is a promising tool to investigate single droplet evaporation in real engine conditions.     

Synthesis and microwave dielectric properties of an electronic ceramic Y2WO6 for wireless communications

Y₂WO₆ ceramics were fabricated via a solid-state reaction method and investigated structure stability, densification, microstructure, and dielectric properties at microwave frequency range. Y₂WO₆ crystallized in a monoclinic structure and stabilized to 1500 ^∘C, beyond which the decomposition of Y₆WO₁₂ occurred. Y₂WO₆ ceramic could be sintered into a compact bulk at 1450 ^∘C, which was characterized by a high relative density ∼ 97.6% and a dense microstructure. The favorable dielectric performances were achieved at 1450 ^∘C with a relative permittivity ${\epsilon }_r\sim 11.4$, a quality factor $Q\times f\sim 42,380$ GHz ($f=8.6$ GHz), and a temperature coefficient of resonant frequency ${\tau }_f\sim -49.0$ ppm/^∘C. The MW properties of Y₂WO₆ suggest that it could be useful candidate material for low-loss dielectric resonators.     

Exchange bias behavior and magnetocaloric effect in Ni2In-type Mn7Sn4 alloy

In this work, the exchange bias behavior and magnetocaloric effect have been studied in Mn₇Sn₄ alloy. The X-ray powder diffraction pattern recorded at room temperature indicates that the sample crystallizes in a single phase with Ni₂In-type hexagonal structure (space group $P{6}_3/\mathit{mmc}$). The maximum magnetic entropy change value across paramagnetic/ferrimagnetic transition is about 3.3 J kg⁻¹ K⁻¹ under the magnetic field change of ${\mu }_0\mathrm{\Delta }H=0\text{-}5\text{T}$. With further cooling, the reentrant spin-glass-like state is obtained below 150 K, for which the exchange bias effect has been observed. The exchange bias field is ∼7.8 mT and ∼6.7 mT at $T=10\text{K}$ when the cooling field is ${\mu }_0{H}_{\mathrm{CF}}=0.1\text{T}$ and 0.5 T, respectively. The magnetic behavior and the origin of exchange bias in Mn₇Sn₄ are discussed.     

Investigating the thermoelectric properties of Na0.74Co1−xNbxO2 (x = 0.05,0.10) at high temperature region

Here, the thermoelectric (TE) properties of Na_0.74Co${}_{1-x}$Nb_xO₂ ($x=0.05,0.10$) compounds are investigated experimentally and computationally. The experimental measurements are conducted in $300-620$ K. Positive sign of Seebeck coefficient for both the compounds indicates the dominating p-type character. The maximum experimental values of ZT are observed as ∼ 0.12 and ∼ 0.19 at 620 K for $x=0.05$ and $x=0.10$, respectively. The experimental transport properties of these compounds are understood by employing spin-polarized GGA+U (= 4 eV) electronic structure calculations on $x=0.0625$ compound. On the basis of best experimental and computational matching of transport properties, we have estimated ZT till 1200 K computationally. The highest calculated values of ZT are ∼ 1.36 and ∼ 1.22 at 1200 K for $x=0.05$ and $x=0.10$, respectively. The optimum value of efficiency for $x=0.05$ is calculated as ∼ 6.4%, whereas it reaches ∼ 7.5% for $x=0.10$.     

Half-metallicity modulation of zigzag BC2N nanoribbons by transverse electric fields: A first principles study

We performed density functional theory calculations to investigate the electronic and magnetic properties of H-terminated zigzag BC₂N nanoribbons (ZBC₂NNRs) with the atoms arranged as B-C-N-C along zigzag lines. The ribbons can be classified into three groups according to the profiles of band structures and edge atoms: BN-BN, CC-CC and BN-CC. Among them, CC-CC and BN-CC ZBC₂NNRs behave magnetic ground states. The results show that the CC-CC ZBC₂NNR is an antiferromagnetic (AFM) semiconductor. Under the transverse electric field, the half-metallicity of 16-CC-CC ZBC₂NNR can be achieved with electric field in the range of $0.2～0.45$ VÅ^?1. Interestingly, the intrinsic half-metallicity exists in BN-CC ZBC₂NNRs when the ribbon width is smaller than ～29.2 Å. For larger ribbon width (～33.5 Å), the system could be converted from ferromagnetic metal to half-metals at a very low critical field of $E=0.02$ VÅ^?1. Meanwhile, it is also shown that the I–V characteristic of BN-BN ZBC₂NNRs shows a negative differential resistance (NDR) effect. These ample electronic and magnetic properties might open great opportunities for BC₂N materials in spintronics and nanoscale device in the future.     

Structures,mobilities, electronic and optical properties of two-dimensional α-phase group-VI binary compounds: α-Se2Te and α-SeTe2

Based on the first-principles calculations, we confirm the geometry and electronic structures of two binary group-VI compounds: monolayer α-Se₂Te and α-SeTe₂. The stabilities are confirmed by the cohesive energies, phonon dispersions, and elastic constants. The mechanical properties, strain-stress relationships, and strain-dependent variations of band gaps and band structures are investigated detailed. Furthermore, the high carrier mobilities (up to $5.4\times {10}^3$ cm² V⁻¹ s⁻¹) and optical absorption coefficients (several 10⁵ cm⁻¹) are also exhibited, demonstrating the great application potentials in optoelectronics.     

Highly sensitive selectively coated D-shape photonic crystal fibers for surface plasmon resonance sensing

We propose a design for a high sensitivity plasmon resonance (SPR) sensor based on photonic crystal fiber (PCF) and analyze the sensor using finite element software (FEM). By introducing a D-shape hole instead of a circular hole in the first ring of the photonic crystal fiber, which increases the coupling effect and proficient infiltration of the sensing, resulting in enhance the performance of the sensor due to the flat structure of the D-shape hole and the homogeneous metal coating facility. We study the influence of the parameters of the D-shape hole on the sensing performance and analyze the sensor performance based on the wavelength and amplitude sensitivity. The results show that the proposed sensor is capable of detecting analyte refractive index ranging from 1.30 to 1.42, and the maximum sensitivities of 14,600 nm/RIU and 1475 RIU^?1 can be achieved in this sensing range, respectively. The largest sensor resolutions for wavelength and amplitude sensing are $6.84\times {10}^{?6}$ and $6.78\times {10}^{?6}\text{ RIU}$, and the maximum figure of merits (FOM) of the proposed sensor being 618.     

Equal heartbeat intervals and their effects on the nonlinearity of permutation-based time irreversibility in heart rate

The association of equal heartbeat intervals with cardiac conditions and the effect of the equality on permutation-based time irreversibility are investigated in this paper. We measure the distributions of equal heartbeat intervals under three conditions, namely congestive heart failure (CHF), healthy young and elderly, whose time irreversibility is detected by measuring the probabilistic difference between permutations instead of raw vectors. We demonstrate that heartbeats contain high rates of equal states, particularly the CHF with around 20% equalities, and the distributions of equal values discriminate the heartbeats at very short data length. The CHF have more equal values than the healthy young (p $<1.47?{10}^{?15}$) and elderly (p $<2.48?{10}^{?11}$), and the healthy young have less equalities than the elderly (p $<3.16?{10}^{?4}$). Time irreversibility considering equal values is promising to extract nonlinear behaviors of heartbeats, confirming the decreased nonlinear complexity of the diseased and aging heart rates, while that involving no equality leads to erroneous nonlinearity detection. In our contribution, we highlight the pathological or physiological information contained by the distribution of equal heartbeat intervals that might contribute to develop relevant biomarkers in the area of heart analysis, and demonstrate the effectiveness of equality-based time irreversibility in the nonlinearity detection of heartbeats.     

Application of a multiple mapping conditioning mixing model to ECN Spray A

The engine combustion network (ECN) Spray A is modelled using the Reynolds-averaged Navier–Stokes-transported probability density function (RANS-TPDF) approach to validate the application of a new multiple mapping conditioning (MMC) mixing model to multiphase reactive flows. The composition TPDF equations are solved using a Lagrangian stochastic approach and the spray is modelled with a discrete particle approach. The model is first validated under non-reacting conditions (at 900 K) using experimental mixture-fraction data. Reactive simulations are then performed for three different ambient temperatures (800, 900, 1100 K) and oxygen concentrations (13, 15, 21%) at an ambient density of 22.8 kg/m³. The MMC mixing model is compared with the interaction by exchange with the mean (IEM) mixing model. The ignition delay predictions are not sensitive to the mixing model and are predicted well by both the mixing models under all the tested ambient conditions. The IEM model overpredicts the flame lift-off length (FLOL) at high temperature and high oxygen conditions with a mixing constant $C_{?}=2$. The MMC model with $C_{?}=2$ and a target correlation coefficient $r_t=0.935$ between the mixture fraction and a reference variable used to condition mixing predicts good FLOL under all the conditions except 800 K. It is demonstrated that the lift-off length is controllable by changing the target correlation coefficient, while C_? and therefore the mixing fields are held fixed. In comparison to the MMC model, the IEM model predicts a higher variance of temperature conditioned on mixture fraction near the flame base owing to its lacking the property of localness. The mixing distance between the notional TPDF particles in the composition space is also higher with the IEM model and it is demonstrated that by changing r_t, different levels of mixing locality can be achieved.     

Theoretical study on UH4, UH8 and UH10 at high pressure

Stable structures of uranium hydrides at 0–550 GPa were studied using genetic algorithm (GA) combined with density functional theory calculations. We investigated two stoichiometries of U–H system, UH₄ and UH₁₀ at high pressure, and properties of UH₄, UH₈ and UH₁₀. The study found that UH₈ is the most stable phase at 100–550 GPa, UH₄ is a stable phase at 100–550 GPa, and UH₁₀ could become stable over 450 GPa. For UH₁₀, the most phase is $Fm\stackrel{￣}{3}m$, which was found to be a superconductor with the transition temperature $T_c=51,21,12,10$ and 15 K at 100, 200, 300, 400 and 550 GPa, respectively.     

High-pressure disproportionation phases of CO2 and CO

First-principles enthalpy minimization simulations with target pressures suggest that dense-packed disproportionation phases of CO₂ and CO can be transformed from selected molecular precursors under hydrostatic compression. In transformations, electrons are pushed from oxygen to carbon atoms to form electronic disproportionation phases with their chemical formulas of C^?2O${}_2^{+}$ and C^?O⁺. Simulations indicate that the space packing properties of reactive groups in a molecular crystal precursor, including the orientation and the number of bonding partners of each reactive group, mainly control transformation bonding pathways. Phonon dispersion spectra and molecular dynamic simulations confirm the metastability of both electronic disproportionation phases under high pressures.     

Multiferroic behaviors of Co-doped Bi4NdTi3FeO15 ceramics

By using a multicalcination procedure, Co-doped Bi₄NdTi₃Fe${}_{1?x}$Co_xO₁₅ ($x=0.1,0.3,0.5\text{ and }0.7$) (Co_x) ceramics were synthesized. The samples showed a single-phase (SP) Aurivillius structure containing four perovskite layers. Plate-like morphology of the grains which is related to the layered perovskite structure of the samples was clearly observed by SEM. The multiferroic properties of the samples at room temperature (RT) were demonstrated by dielectric, ferroelectric and magnetic measurements. With x ranging from 0.1 to 0.7, all the samples show RT multiferroic properties although there is no obvious regularity between the Co content and the multiferroic property. Very interestingly, Co_0.3 sample exhibits the optimum RT magnetic property, which can be attributed to the inclination of occupying the inner octahedra center for doped Co ions and the nearly 1:1 ratio of Fe and Co ions in the inner octahedra. The present work offers new insight into the compositional design of promising lead-free RT multiferroic materials.