Thermoelectric properties and phase transition of doped single crystals and polycrystals of Bi2Te3

The temperature dependences of the electrical conductivity , Seebeck coefficient , and heat capacity C_p(T) of polycrystalline samples of Bi₂Te₃, Bi₂Te₃+1%CuI, and Bi₂Te₃+1%(CuI+1/2Pb) are investigated in the temperature range below room temperature. Based on the temperature dependences of all investigated physical properties, it is discovered that phase transition occurs at 120–200 K. Investigation of single crystals shows that anomalies in the electrical resistivity occur only across the crystal growth axis (across the well-conducting Bi–Te plane). Investigation of the low-temperature dependence of electrical conductivity shows that all polycrystalline samples exhibit quasi-two-dimensional electron transport. Additionally, quasi-two-dimensional transport is detected in single crystals based on anisotropy analysis (where is the resistivity along the crystal growth axis, and is resistivity across the crystal growth axis) and temperature dependence below 50 K. The Fermi energy is estimated using the temperature dependence of . It is discovered that an increase in at T > 200 K is associated with the phase transition. For single-crystal samples, the maximum thermoelectric figure of merit ZT, as observed along the crystal growth axis, increases with doping. A maximum ZT value of ∼1.1 is observed for the Bi₂Te₃+1%(CuI+1/2Pb) sample at room temperature ().     

Frequency dependence of antiferroelectricferroelectric phase transition of PLZST ceramic

Antiferroelectric (AFE) ceramics are promising for applications in high-power density capacitors, transducers, etc. The forward switching field and backward switching field are critical performance indicators for AFE ceramics, and the coupling between the structure transition and domain orientation makes them different from the coercive field of ferroelectric (FE). Moreover, in practical applications, AFE ceramics are often required to operate at varying frequencies. However, systematic studies regarding the frequency dependence of and are insufficient. In this work, (PLZST) AFE ceramic was fabricated, and two empirical formulas (, ) were proposed to predict the frequency dependence of and . The formulas are based on the electric field–induced phase transition characteristics of AFE and the Kolmogorov–Avrami–Ishibashi domain nucleation-switching model. Furthermore, the dynamic hysteresis loops of PLZST at various frequencies (1–1000 Hz) and temperatures (–) were investigated. The results show that the electric field–induced phase transition of AFE ceramic is dominated by the coupling between the structural transition and domain orientation. The domain orientation hinders the structure transition, leading to an increase in and a decrease in as the frequency of applied electric field increases. Meanwhile, the domain growth process is affected by the structure of AFE, and the value of (domain growth dimensionality) increases with the stability of the AFE structure. For comparison, (PLBZST) relaxor FE ceramic was fabricated. Due to the high mobility of the microdomain, the dynamic hysteresis loop of PLBZST ceramic exhibits excellent frequency stability. The charge–discharge experiment with an ultrahigh equivalent frequency (100 kHz) was performed to investigate the frequency stability of energy release of PLZST and PLBZST. The results may provide guidance for research pertaining to ceramic capacitors with high-power density and high-frequency stability.     

Thermal Degradation of p-Hydroxybenzoic Acid in Macadamia Nut Oil,Olive Oil,and Corn Oil

p-Hydroxybenzoic acid (PHBA) plays a significant role in sustaining the oxidative stability of macadamia nut oil (MNO). However, PHBA undergoes thermal decarboxylation and loses its bioactive antioxidant properties. In this study, we determine PHBA degradation kinetics in oils at various heating temperatures, which provides fundamental understanding of PHBA thermal degradation in oils and oil quality changes during high-temperature processing. PHBA degradation kinetics in MNO, olive oil, and corn oil were evaluated at temperatures typical for cooking and frying. PBHA headspace concentration was measured using selected ion flow tube mass spectrometry. PHBA decarboxylation followed a zero-order reaction, where degradation could be affected by factors such as the type of oil matrix having different FA compositions, antioxidants, and component interactions. PHBA degradation activation energies (E _a) showed that PHBA was more stable against thermal decarboxylation in MNO (85 kJ mol^–1) than in olive oil (40 kJ mol⁻¹) or corn oil (22 kJ mol⁻¹). The higher enthalpy () of decarboxylation in MNO (82 kJ mol⁻¹) indicates that PHBA is more inhibited from decomposition than olive oil (37 kJ mol⁻¹) or corn oil (19 kJ mol⁻¹). Moreover, the negative entropy values () of PHBA degradation from MNO (−192 J mol⁻¹ K⁻¹), olive oil (−277 J mol⁻¹ K⁻¹), and corn oil (−325 J mol⁻¹ K⁻¹) indicates that these oils impart some inhibitory properties against PHBA thermal decarboxylation.     

Ultralow dielectric loss in Y-doped SrTiO3 colossal permittivity ceramics via designing defect chemistry

Effects of doping of Y and sintering atmosphere on the dielectric properties of Sr_1-1.5xY_xTiO₃ ceramics (SYT, x = 0-0.014) were systematically investigated. The SYT14 (x = 0.014) ceramic sintered in N₂ attains a colossal permittivity (CP, Ɛ_r = 28 084@ 1kHz, 27 685@ 2MHz) and an ultralow dielectric loss (tanδ = 0.007@ 1kHz, 0.003@ 2MHz) at room temperature. Because of using of the A-site deficient, there are in SYT ceramics. Through the comprehensive analysis of dielectric responses, X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and complex impedance data, it is proved that doping of Y promotes the formation of (Y³⁺ are located at Sr²⁺ site), (Y³⁺ are located at Ti⁴⁺ site), and Ti³⁺, and sintering in reducing atmosphere of N₂ results in more (oxygen vacancy) and (strontium vacancy) generating in SYT ceramics. The defect dipoles, , , , , , and formed by introduced defects make charge carriers localized in SYT ceramics. The combined action of the massive defect dipoles is responsible for the ultralow tanδ and CP in SYT14 ceramics sintered in N₂.     

Dynamics adsorption of the enhanced CH4 recovery by CO2 injection

The dynamic adsorption isotherms of CO₂-EGR were measured by using an Intelligent Gravimetric Analysis system. In the initial CO₂ injecting stage, all the injected CO₂ enters into the adsorbent and the mole fraction of CH₄ in the gas phase () is maintained at 1.0. The CH₄ recovery factor () increases. The duration of this stage (t_CD) depends on the selectivity of CO₂ over CH₄ (). An adsorbent with large has long t_CD. In the second stage, the injected CO₂ competes with CH₄ for adsorption. The cumulative of the second stage is much larger than that of the initial stage. However, decreases sharply. in the whole CO₂ injection is always larger than that before CO₂ injection, suggesting that CH₄ desorption results from the displacement of CO₂ rather than from pressure depletion.     

On the Use of Side-Chain NMR Relaxation Data to Derive Structural and Dynamical Information on Proteins: A Case Study Using Hen Lysozyme

Values of and order parameters derived from NMR relaxation measurements on proteins cannot be used straightforwardly to determine protein structure because they cannot be related to a single protein structure, but are defined in terms of an average over a conformational ensemble. Molecular dynamics simulation can generate a conformational ensemble and thus can be used to restrain and order parameters towards experimentally derived target values (exp) and (exp). Application of and order-parameter restraining MD simulation to bond vectors in 63 side chains of the protein hen egg white lysozyme using 51 (exp) target values and 28 (exp) target values shows that a conformational ensemble compatible with the experimentally derived data can be obtained by using this technique. It is observed that order-parameter restraining of C−H bonds in methyl groups is less reliable than order-parameter restraining because of the possibly less valid assumptions and approximations used to derive experimental (exp) values from NMR relaxation measurements and the necessity to adopt the assumption of uniform rotational motion of methyl C−H bonds around their symmetry axis and of the independence of these motions from each other. The restrained simulations demonstrate that side chains on the protein surface are highly dynamic. Any hydrogen bonds they form and that appear in any of four different crystal structures, are fluctuating with short lifetimes in solution.     

Poling tuning: A plausible solution for minimizing microphony and secondary pyroelectric coefficient in ferroelectrics

This study proposes the idea of reducing the microphony effect and secondary pyroelectric coefficient in pyroelectric detectors by tuning the poling orientation. Mathematically, it has been shown that piezoelectric strain coefficients get altered by changing the poling direction. Eventually, for a couple of materials it has been demonstrated that microphony and secondary pyroelectric coefficient can be diminished by poling them at a given orientation. The poling angle nullifying secondary pyroelectric coefficient was found to be 58.2°, 47.1°, and 78.9° for (PZN-0.08PT), (PMN-PT), and (BCT-0.48BZT) respectively while no such value existed for (PZT-5A).     

Synchrotron x-ray spectroscopy investigation of the Ca1−xLnxZrTi2−x(Al,Fe)xO7 zirconolite ceramics (Ln = La,Nd, Gd,Ho, Yb)

When incorporating actinides into zirconolite for high-level radioactive waste immobilization, Al³⁺ and Fe³⁺ ions generally act as charge compensators. In this study, we rationally designed a series of (Ln = La, Nd, Gd, Ho, Yb) to unravel the dopant solubility and evolutions of the crystalline phase and local environment of cations through synchrotron X-ray methods. It was found that single zirconolite phase is difficult to obtain and the fraction of perovskite have an increase with x from 0.1 to 0.9 in . Formation of both zirconolite-2M and zirconolite-3O phases was observed in and . Phase transformation from zirconolite-2M to 3O occurs at x = 0.7 for while x = 0.9 for . The solubility of and to form single zirconolite-2M can reach to 0.9 f.u. and 0.7 f.u., respectively. The evolution of lattice parameters of zirconolite in is greatly related to the ionic radii of cations and substitution mechanism among the cations. X-ray absorption near edge spectroscopy revealed that Fe³⁺ ions replace both five- and six-coordinated Ti sites and the ratio of TiO₅ to TiO₆ decreases when increasing dopant concentration in the . For the local environment of Zr⁴⁺, the major form is ZrO₇ with a trace of ZrO₈.     

Application of fracture mechanics for the characterization of poly(vinyl chloride) pipes. II. Evaluation of a ring-type specimen for fracture mechanics testing

An unplasticized poly(vinyl chloride) (U-PVC) pipe sample used in infrastructure applications in Brazil (nominal diameter DN 100, outside diameter 110 mm) was evaluated according to different fracture mechanics methodologies, including essential work of fracture (EWF) and other fracture toughness parameters such as the stress intensity factor and plane strain energy release rate . This pipe sample was also tested for the quality of processing (degree of gelation) via differential scanning calorimetry (DSC) and tensile strength. The comparative evaluation of different specimen configurations—curved specimens in three-point bending (CTPB) and full rings in tension (SNRT), in thicknesses varying from 5 to 30 mm, showed initial evidence of the suitability of ring-type specimens for the evaluation of EWF and . Results also indicate that the full ring geometry, at least in the present experimental setup, presents some drawbacks probably due to the storage of large amounts of elastic energy throughout the test. This fact leads to relevant deviations in both load–displacement behavior and results for strain energy release rate (), and the results found here will guide future research using full and split rings in different loading modes and improved experimental setups. It was also confirmed that the value of , determined by a modified Charpy test, is independent of the type of specimen tested, as long as the test mode and specimen width are the same. Both the experimental value of and the estimated value for the plane strain stress intensity factor () showed excellent agreement with values reported for other U-PVC compositions.     

Design of a defect-induced orange persistent luminescence phosphor BaZnGeO4:Bi3+

We report a novel bright orange persistent luminescence (PersL) phosphor BaZnGeO₄:Bi³⁺ with broad emission and PersL spectra. Its crystal structure, photoluminescence (PL) spectra, thermoluminescence (TL) spectra and PersL spectra were investigated in detail. The two emission bands at 440 nm and 595 nm originate from Bi³⁺ ions in normal Ba²⁺ sites (Bi1) and Ba²⁺ sites close to vacancy defects (Bi2), respectively. The introduction of and defects improves the emission intensity of Bi2 more than that of Bi1, demonstrating that Bi2 is related to the vacancy defects. The orange emission and PersL properties of BZGO:Bi³⁺ can be improved when a little and defects are introduced, because the introduction of and defects makes it easier for Bi³⁺ to enter in Ba²⁺ sites; and for PersL, and defects can perform as the effective trap centers to capture more charges, which is beneficial for PersL. BZGO:Bi³⁺ has quite good thermal stability, and the bright orange PersL can be observed by the naked eye for 1 h. Finally, a feasible PersL mechanism of BZGO:Bi³⁺ was proposed to clarify the PersL-generation process.     

Fabrication and characterization of tetragonal yttria-stabilized zirconia single-crystalline thin film

Tetragonal yttria-stabilized zirconia thin film was successfully fabricated by a pulsed laser deposition method. The thin film grew heteroepitaxially with the orientation relationship of ZrO₂‖Al₂O₃. Energy dispersive X-ray spectroscopy mapping revealed that Y³⁺ ions were distributed homogeneously without local segregations. X-ray and electron-diffraction analysis confirmed a single crystalline structural feature of the film. On the other hand, high-resolution scanning transmission electron microscopy observations show that this film contains small-angle tilt grain boundaries, which is composed of the periodic array of dislocations with the Burgers vector .     

Investigation of the effect of surface phosphate ester dispersant on viscosity by coarse-grain modeling of BaTiO slurry

To understand the role of phosphate ester dispersant, we investigated the rheology of a BaTiO slurry. For the model case, a coarse-grain molecular dynamics (CGMD) simulation was performed with the butyral polymer didodecyl hydrogen phosphate (DHP) in the toluene/ethanol solvent. By systematically analyzing the effect of DHP from an atomic-scale first principle and from all-atom MD to microscale CGMD simulation, we investigated how the adsorption of a DHP dispersant on a BaTiO surface affects the microstructure rheology of a BaTiO slurry. The first-principle and all-atom MD simulation suggests that DHP molecules prefer to locate near the BaTiO surface. CGMD simulation shows a reduction in viscosity with an increase in dispersants, suggesting that the dispersant population near the BaTiO surface plays a key role in controlling the rheology of the BaTiO slurry. In this study, we propose an approach for understanding the BaTiO slurry with molecular-level simulations, which would be a useful tool for efficient optimization of slurry preparation.     

Influence of water activity on belite (β-C2S) hydration

The hydration of the two most reactive phases of ordinary Portland cement (OPC), tricalcium silicate (C₃S), and tricalcium aluminate (C₃A) is successfully halted when the activity of water () falls below critical thresholds of 0.70 and 0.45, respectively. It has been established that the reduction in relative humidity (RH) and  suppresses the hydration of all anhydrous phases in OPC, including less explored phases like dicalcium silicate, that is, belite (β-C₂S). However, the degree of suppression, that is, the critical threshold, for β-C₂S, standalone has yet to be established. This study utilizes isothermal microcalorimetry and X-ray diffraction techniques to elucidate the influence of on the hydration of -C₂S suspensions via incremental replacements of water with isopropanol (IPA). Experimentally, this study shows that with increasing IPA replacements, hydration is increasingly suppressed until eventually brought to a halt at a critical threshold of approximately 27.7% IPA on a weight basis (wt.%_IPA). From thermodynamic estimations, the exact critical threshold and solubility product constant of -C₂S () are established as 0.913 and 10^−12.68, respectively. This study enables enhanced understanding of β-C₂S reactivity and provides thermodynamic parameters during the hydration of β-C₂S-containing cementitious systems such as OPC-based and calcium aluminate-based systems.     

Fouling mitigation in crossflow filtration using chaotic advection: A numerical study

Fouling mitigation in a crossflow filtration system using chaotic advection is numerically studied. A barrier-embedded partitioned pipe mixer (BPPM) is selected as a static mixer, creating chaotic advection in a laminar flow regime. Mixing characteristics are controlled via two design parameters, the mixing protocol and the dimensionless barrier height (β). The average dimensionless concentration boundary layer thickness () and the surface-averaged dimensionless wall concentration () dramatically decrease with the introduction of the BPPM, incorporating a chaotic flow system. and decrease as β increases, and the largest reduction of is observed in the counter-rotational protocol. A semi-ring configuration is revealed to be the most appropriate configuration to characterize mixing near the membrane surface. It is found that a filtration system with a globally chaotic flow shows the best mixing performance and the largest reduction of fouling.     

The axial dispersion of liquid solutions and solid suspensions in planar oscillatory flow crystallizers

The planar oscillatory flow crystallizer (planar-OFC) was designed with a rectangular cross-section to improve the flow and suspension of solids of conventional OFCs. Residence time distribution experiments with liquid and solid tracers were performed to assess the effect of the net flow rate, Q , the frequency, f , and the amplitude of oscillation, x₀ , on the axial dispersion of liquids, , and solids, , in three planar-OFCs with different geometries. It was found that Q and f have in general positive effects on and , and x₀ has negative effects. Furthermore, identical values of and were obtained in each crystallizer. It was also found that the interaction between Q and x₀ is the most significant one in all systems. These results show that the three crystallizers have similar axial dispersion performances with liquids and solids. This is of paramount importance for multiphase systems such as crystallization.     

Role of oxygen-vacancy in piezoelectric properties and fatigue behavior of (Bi0.5Na0.5)0.93Ba0.07Ti1+xO3 ceramics

In this reported study, (Bi_0.5Na_0.5)_0.93Ba_0.07Ti_1+xO₃ (abbreviated as BNBT_1+x) ceramics, containing Ti-nonstoichiometry that ranged from a 2% deficiency to a 1% excess, were designed and systematically characterized. The results of the X-ray diffraction Rietveld refinement and X-ray photoelectron spectroscopy analysis of these materials revealed that the amount of Ti in the BNBT_1+x ceramics significantly affected the degree of coexistent rhombohedral/tetragonal phases and also affected the content of singly/doubly charged oxygen-vacancy (/) in the ceramics. After poling and 10⁵ fatigue cycles, the variation in Raman resonance line-width of the Ti–O bond in the BNBT_1+x ceramics was found to be strongly dependent on the amount of Ti in the ceramic. The → transformation and clustering of the defects under electrical loading were considered to be a critical factor in electric field-induced structural transition and fatigue properties of the material.     

Sintering-driven effects on the band gap of (Pb,La)(Ti,Ni)O3 photovoltaic ceramics

In this work, the influence of the sintering temperature on the physical properties of (Pb_0.8La_0.2)(Ti_0.9Ni_0.1)O₃ (PLT-Ni) ceramics is reported. The experimental data revealed that the energy band gap of PLT-Ni ceramics could be tailored from approximately 2.7 to 2.0 eV by changing the sintering temperature from 1100°C to 1250°C. It is demonstrated that the simple substitution of Ti⁴⁺ by Ni²⁺ cations is effective to decrease the intrinsic band gap while increasing the tetragonality factor and the spontaneous polarization. However, the additional red-shift observed in the absorption edge of the PLT-Ni with increasing the sintering temperature was associated with a continuous increase in the oxygen vacancies () amount. It is believed that the impact of the creation of these thermally induced is manifold. The presence of and Ni²⁺ ions generate the Ni²⁺- defect-pairs that promoted both a decrease in the intrinsic band gap and an additional increase of the tetragonality factor, consequently, increasing the spontaneous polarization. The creation of Ni²⁺- defects also changed the local symmetry of Ni²⁺ ions from octahedral to a square pyramid, thus lifting the degeneracy of the Ni²⁺ 3d orbitals. With the increase in the sintering temperature, lower-energy absorbing intraband states were also formed due to an excess of , being responsible for an add-on shoulder in the absorption edge, extending the light absorption curve to longer wavelengths and leading to an additional absorption in “all investigated” spectrum as well.     

A Mathematical Model for Estimating Molecular Compressibility of Fatty-Acid Methyl Ester and Biodiesel

In this study, the molecular compressibility (k_m) of a fatty-acid methyl ester (FAME) or a biodiesel is correlated with ΔG, , via the Gibbs energy additivity method, where MW is the molecular weight of the FAME or the average MW of the biodiesel. The Gibbs energy associated with molecular compressibility () is further correlated with the structure of FAME. Thus, the relationship between the structure (of a FAME or a biodiesel) and the physical property (k_m) is established. Thus, k_m of a FAME at different temperatures can be easily estimated from the carbon numbers of fatty acid (z) and the number of double bonds (n_d) with good accuracy. For biodiesel, k_m is calculated from the same equation with the average z (z_(ave)) and average n_d (n_d(ave)). k_m is not temperature independent and a slight change in k_m depends on the structure of the FAME and biodiesel. For FAME having 14 carbon atoms or less in the fatty acid, k_m decreases as temperature is increased. On the other hand, for FAME with a longer chain length (16 or higher), k_m increases as temperature is increased. Similarly, a double bond in the long-chain FAME is more sensitive to temperature than the saturated FAME.     

Influence of Different Additives on the Interaction of Quinolone Antibiotic Drug with Surfactant: Conductivity and Cloud Point Measurement Study

Conductometric and cloud point (CP) measurement studies have been performed to investigate the interaction of tetradecyltrimethylammonium bromide (TTAB) and Triton® X-100 (TX-100) with ciprofloxacin hydrochloride (CFH) in different solvents over the temperature range of 295.15–315.15 K. CFH is used for the treatment of various bacterial infections. The observed critical micelle concentration (CMC) values of TTAB were found to be reduced in the presence of electrolytes (Na₂SO₄/Na₃PO₄), and this reduction proceeds with the elevation of salt concentration. The order of the CMC of TTAB follows the trend: > >. The observed CMC values of TTAB were found to increase with increasing temperature and decrease with increasing concentration of CFH in aqueous medium. The values of Gibbs free energy of micellization () for the TTAB/TTAB + CFH mixture were found to be negative, implying spontaneous micellization. The estimated CP of TX-100 decreases with increasing concentration of TX-100 in aqueous medium. The CP values first decrease with increasing concentration of CFH and then increase at higher concentration of CFH almost in all cases investigated. The values of free energy of clouding were found to be positive in all cases studied implying that phase separation of TX-100 was nonspontaneous. The other thermodynamic parameters associated with the micellization of TTAB and the phase separation of TX-100 were estimated and explained.     

Regeneration and utilization of waste phenolic formaldehyde resin: A performance investigation

Recycled thermosetting phenolic formaldehyde (RPF) resins were pulverized to micron-sized powders and successfully reused as an effective component by reactive-injecting with neat phenolic formaldehyde (PF) and/or trioxymethylene (TOX) to prepare regenerated phenolic formaldehyde (i.e., and ). Tensile strength (σ_f), impact strength (I_s), and density (ρ) of and specimens were reduced as RPF concentrations or average particle sizes increased. It is worth emphasizing that σ_f, I_s, and ρ of each reaction-injected series having a fixed RPF concentration and average particle size improved to a maximum value, as TOX concentrations reached a corresponding optimal value. This is the first investigation to report that σ_f and I_s of proper regenerated PF/RPF/TOX specimens using ≦20 wt % RPF waste were ≥ 95% of those of the virgin reaction-injected PF. Possible reasons accounting for these improved mechanical properties were proposed based on results from their Fourier transform infrared analysis (FTIR). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47445.