Using low frequency and intensity ultrasound to enhance start-up and operation performance of Anammox process inoculated with the conventional sludge

A lab-scale ultrasound enhancing Anammox reactor (R1) was established and irradiated once a week by ultrasound with the optimal parameter (frequency of 25 kHz, intensity of 0.2 W cm⁻² and exposure time of 3 min) obtained by batch experiments. R1 and the controlled Anammox reactor (R2) without exposure to the ultrasound were operated in parallel. The start-up period of Anammox process (53 days) in R1 was shorter than that (61 days) in R2. The nitrogen loading-enhancing period (day 53-day 135) in R1 was also shorter than that (day 61-day 151) in R2. At the end of the nitrogen loading-enhancing period, NLR (0.76 kg N m⁻³ d⁻¹) and NRR (0.68 kg N m⁻³ d⁻¹) of R1 were both higher than NLR (0.66 kg N m⁻³ d⁻¹) and NRR (0.56 kg N m⁻³ d⁻¹) of R2. Moreover, The stability of Anammox process in R1 was better than that in R2. The results demonstrated that the periodical irradiation of ultrasound enhanced the start-up and operational performance of Anammox reactor. Microbial community analysis indicated that the ultrasound accelerated the microbial succession from some other bacteria to Anammox bacteria so that shorten the start-up period of Anammox process from the conventional activated sludge. It also indicated that the ultrasound strengthened the competitive advantage of Candidatus Kuenenia stuttgartiensis in Anammox bacteria of the mature sludge so as to enhance the nitrogen removal performance of the Anammox reactor under the operation condition of high nitrogen loading.     

Potential-induced sonoelectrochemical graphene nanosheets with vacancies as hydrogen peroxide reduction catalysts and sensors

Defective graphene nanosheets (dGN_4V) with 5-9, 5-8-5, and point defects were synthesised by a sonoelectrochemical method, where a potential of 4 V (vs. Ag/AgCl) was applied to drive the rapid intercalation of phosphate ions between the layers of the graphite foil as a working electrode. In addition to these vacancies, double vacancy defects were also created when the applied potential was increased to 8 V (dGN_8V). The defect density of dGN_8V (2406 μm⁻²) was higher than that of dGN_4V (1786 μm⁻²). Additionally, dGN_8V and dGN_4V were applied as catalysts for the hydrogen peroxide reduction reaction (HPRR). The mass activity of dGN_8V (1.31 × 10⁻² mA·μg⁻¹) was greater than that of dGN_4V (1.17 × 10⁻² mA·μg⁻¹) because of its high electrochemical surface area (ECSA, 1250.89 m²·g⁻¹) and defect density (N_D, 2406 μm⁻²), leading to low charge transfer resistance on the electrocatalytic interface. The ECSA and N_D of dGN_4V were 502.7 m²·g⁻¹ and 1786 μm⁻², respectively. Apart from its remarkable HPRR activity, the cost-effective dGN_8V catalyst also showed potential as an amperometric sensor for the determination of H₂O₂.     

Synergetic effects of ultrasound and sodium alginate coating on mass transfer and qualities of osmotic dehydrated pumpkin

This research studied the effects of combined ultrasound and 3% sodium alginate (SA) coating pretreatment (US + Coat) on mass transfer kinetics, quality aspects, and cell structure of osmotic dehydrated (OD) pumpkin. The results of the pretreatment were compared with the results of control (non-pretreated osmotic dehydration) and other three pretreatment methods, which were 1) ultrasound in distilled water for 10 min (USC), 2) ultrasound in 70% (w/w) sucrose solution (US) for 10, 20 and 30 min, and 3) coating with 1%, 2%, 3% (w/w) SA. The coating pretreatments with SA resulted in a higher water loss (WL) but lower water activity and solid gain (SG) than other treatments. US pretreatments resulted in the highest effective diffusion coefficients of water (D_w) and solid (D_s) but the cell structure of the product was deformed. The 3% SA coating treatment had the highest WL/SG (5.28) but with the longest OD time (12 h). Using the US + Coat pretreatment gave satisfactory high WL/SG (5.18), D_w (1.09 × 10⁻¹⁰ m²s⁻¹) and D_s (5.15 × 10⁻¹¹ m²s⁻¹), reduced the OD time to 9 h, and preserved the cell structure of the product. This research suggests that US + Coat pretreatment can be an effective processing step in the production of OD pumpkin.     

High room-temperature pyroelectric response of MgO-modified Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3 ceramics

The dielectric and pyroelectric responses of MgO-modified Pb_0.99(Zr_0.95Ti_0.05)_0.98Nb_0.02O₃ ceramics were investigated near F_R(LT)–F_R(HT) phase transition. It was found that MgO additive reduced the F_R(LT)–F_R(HT) phase transition temperature from 41 °C to room temperature (24 °C). Superior room-temperature pyroelectric properties were obtained in the composition of 0.10 wt% MgO addition without DC bias. The largest pyroelectric coefficient, 65 × 10⁻⁸ C cm⁻² K⁻¹, was detected. Accordingly, the detectivity figures of merit F_d had maximum values of 20 × 10⁻⁵ Pa^−1/2, and especially the voltage responsivity F_v = 0.91 m²C⁻¹ is the highest value reported so far among all pyroelectric materials. It shows promising potential for application in uncooled pyroelectric infrared detector.     

Noncommutative electromagnetism as a large <Emphasis Type="Italic">N</Emphasis> gauge theory

We map noncommutative (NC) U(1) gauge theory on ℝ _C ^d ×ℝ _NC ²ⁿ to U(N→∞) Yang–Mills theory on ℝ _C ^d , where ℝ _C ^d is a d-dimensional commutative spacetime while ℝ _NC ²ⁿ is a 2n-dimensional NC space. The resulting U(N) Yang–Mills theory on ℝ _C ^d is equivalent to that obtained by the dimensional reduction of (d+2n)-dimensional U(N) Yang–Mills theory onto ℝ _C ^d . We show that the gauge-Higgs system (A _μ ,Φ ^a ) in the U(N→∞) Yang–Mills theory on ℝ _C ^d leads to an emergent geometry in the (d+2n)-dimensional spacetime whose metric was determined by Ward a long time ago. In particular, the 10-dimensional gravity for d=4 and n=3 corresponds to the emergent geometry arising from the 4-dimensional N=4{\mathcal{N}}=4 vector multiplet in the AdS/CFT duality. We further elucidate the emergent gravity by showing that the gauge-Higgs system (A _μ ,Φ ^a ) in half-BPS configurations describes self-dual Einstein gravity.     

Multibubble sonoluminescence as a tool to study the mechanism of formic acid sonolysis

Sonoluminescence spectra collected from 0.1 to 3.0 M aqueous solutions of formic acid sparged with argon show the OH(A²Σ⁺−X²Π_i) and C₂(d³Π_g → a³Π_u) emission bands and a broad continuum typical for multibubble sonoluminescence. The overall intensity of sonoluminescence and the sonochemical yield of HCOOH degradation vary in opposite directions: the sonoluminescence is quenched while the sonochemical yield increases with HCOOH concentration. By contrast, the concentration of formic acid has a relatively small effect on the intensity of C₂ Swan band. It is concluded that C₂ emission originates from CO produced by HCOOH degradation rather than from direct sonochemical degradation of HCOOH. The intensity of C₂ band is much stronger at high ultrasonic frequency compared to 20 kHz ultrasound which is in line with higher yields of CO at high frequency. Another product of HCOOH sonolysis, carbon dioxide, strongly quenches sonoluminescence, most probably via collisional non-radiative mechanism.     

First-principles study of C3N nanoribbons as anode materials for Li-ion batteries

The potential of C₃N nanoribbons used as anode material for lithium-ion batteries has been systematically investigated through first-principles calculations. The results suggest that C₃N nanoribbons have excellent mechanical properties (stiffness ranging from 286.28 to 412.69 N m⁻¹) and good electronic conductivity (with a bandgap of 0-0.31 eV). Further studies reveal that the H-passivated C₃N nanoribbons have high Li insertion capacity (708.60 mA h g⁻¹) and significantly enhanced Li binding strength (0.21-2.11 eV) without the sacrifice of Li mobility. The high stiffness, superior cycle performance, good electronic conductivity, and excellent Li migration capability indicate the great potential of C₃N nanoribbons to be an anode material. The calculated results provide the valuable insights for the development of high-performance C₃N nanoribbons electrode materials in lithium-ion batteries.     

Isotopieverschiebungskonstanten von Th,U, Pu und Am

The isotope shifts of unperturbed electron configurations have been determined from isotope shift measurements in the spectra of Th, U, Pu, and Am. The screening of the 7s electron charge density at the nucleus by 6d, 7s, and 7p electrons is discussed. It turns out that the same screening factors as for the 6s electron in lighter elements can be used. The screening of the 7s electron charge density at the nucleus by one 5f electron amounts to about 25%: [δT(f ⁿ s)?δT(f ⁿ )]/[δT(f ⁿ }s)?δ(f ^n} )]=0.7₅. The charge density at the nucleus due to the filleds (andp _1/2) shells is considerabely screened by anf electron. The isotope shiftδT(f^n}-1 d ^m +2)?δT(f ⁿ d ^m ) produced by this effect is of the same order of magnitude as the isotope shiftδT(f ⁿ d ^m s)-δT(f ⁿ d ^m ) due to ans electron. The experimental isotope shift constants are found to be:Β C _exp(Th²³⁰–Th²³²)=880±120;Β C _exp(U²³³–U²³⁵)=1000±180;Β C _exp(U²³⁴–U²³⁶)=1070±200;Β C _exp(U²³⁶–U²³⁸)=1080±180;Β C _exp(Pu²³⁸–Pu²⁴⁰)=1200±120;Β C _exp(Pu²³⁹–Pu²⁴¹)=1060±100;Β C _exp(Pu²⁴⁰–Pu242)=900 ±90;Β C _exp(Am²⁴¹–Am²⁴³)=890±50 [10^?3cm^?1]. The ratiosΒ C _exp/C _th are discussed.     

A new way to apply ultrasound in cross-flow ultrafiltration: Application to colloidal suspensions

A new coupling of ultrasound device with membrane process has been developed in order to enhance cross-flow ultrafiltration of colloidal suspensions usually involved in several industrial applications included bio and agro industries, water and sludge treatment. In order to reduce mass transfer resistances induced by fouling and concentration polarization, which both are main limitations in membrane separation process continuous ultrasound is applied with the help of a vibrating blade (20 kHz) located in the feed channel all over the membrane surface (8 mm between membrane surface and the blade). Hydrodynamic aspects were also taking into account by the control of the rectangular geometry of the feed channel.Three colloidal suspensions with different kinds of colloidal interaction (attractive, repulsive) were chosen to evaluate the effect of their physico-chemical properties on the filtration.For a 90 W power (20.5 W cm⁻²) and a continuous flow rate, permeation fluxes are increased for each studied colloidal suspension, without damaging the membrane. The results show that the flux increase depends on the initial structural properties of filtered dispersion in terms of colloidal interaction and spatial organizations.For instance, a Montmorillonite Wyoming–Na clay suspension was filtered at 1.5 × 10⁵ Pa transmembrane pressure. Its permeation flux is increased by a factor 7.1, from 13.6 L m⁻² h⁻¹ without ultrasound to 97 L m⁻² h⁻¹ with ultrasound.     

Rapid preparation of high electrochemical performance LiFePO4/C composite cathode material with an ultrasonic-intensified micro-impinging jetting reactor

A joint chemical reactor system referred to as an ultrasonic-intensified micro-impinging jetting reactor (UIJR), which possesses the feature of fast micro-mixing, was proposed and has been employed for rapid preparation of FePO₄ particles that are amalgamated by nanoscale primary crystals. As one of the important precursors for the fabrication of lithium iron phosphate cathode, the properties of FePO₄ nano particles significantly affect the performance of the lithium iron phosphate cathode. Thus, the effects of joint use of impinging stream and ultrasonic irradiation on the formation of mesoporous structure of FePO₄ nano precursor particles and the electrochemical properties of amalgamated LiFePO₄/C have been investigated. Additionally, the effects of the reactant concentration (C = 0.5, 1.0 and 1.5 mol L⁻¹), and volumetric flow rate (V = 17.15, 51.44, and 85.74 mL min⁻¹) on synthesis of FePO₄·2H₂O nucleus have been studied when the impinging jetting reactor (IJR) and UIJR are to operate in nonsubmerged mode. It was affirmed from the experiments that the FePO₄ nano precursor particles prepared using UIJR have well-formed mesoporous structures with the primary crystal size of 44.6 nm, an average pore size of 15.2 nm, and a specific surface area of 134.54 m² g⁻¹ when the reactant concentration and volumetric flow rate are 1.0 mol L⁻¹ and 85.74 mL min⁻¹ respectively. The amalgamated LiFePO₄/C composites can deliver good electrochemical performance with discharge capacities of 156.7 mA h g⁻¹ at 0.1 C, and exhibit 138.0 mA h g⁻¹ after 100 cycles at 0.5 C, which is 95.3% of the initial discharge capacity.     

Single-pulse shock-tube study on the pyrolysis of small esters (ethyl and propyl propanoate,isopropyl acetate) and methyl isopropyl carbonate

Single-pulse shock-tube experiments were used to study the thermal decomposition of selected oxygenated hydrocarbons: Ethyl propanoate (C₂H₅OC(O)C₂H₅; EP), propyl propanoate (C₃H₇OC(O)C₂H₅; PP), isopropyl acetate ((CH₃)₂HCOC(O)CH₃; IPA), and methyl isopropyl carbonate ((CH₃)₂HCOC(O)OCH₃; MIC) The consumption of reactants and the formation of stable products such as C₂H₄ and C₃H₆ were measured with gas chromatography/mass spectrometry (GC/MS). Depending on the considered reactant, the temperatures range from 716–1102 K at pressures between 1.5 and 2.0 bar. Rate-coefficient data were obtained from first-order analysis. All reactants primarily decompose by six-center eliminations: EP → C₂H₄ + C₂H₅COOH (propionic acid); PP → C₃H₆ + C₂H₅COOH; IPA → C₃H₆ + CH₃COOH (acetic acid); MIC → C₃H₆ + CH₃OC(O)OH (methoxy formic acid). Experimental rate-coefficient data can be well represented by the following Arrhenius expressions: k(EP → products) = 10^13.49±0.16 exp(−214.95±3.25 kJ/mol/RT) s⁻¹; k(PP → products) = 10^12.21±0.16 exp(–191.21±2.79 kJ/mol/RT) s⁻¹; k(IPA → products) = 10^13.10±0.31 exp(–186.38±5.10 kJ/mol/RT) s⁻¹; k(MIC → products) = 10^12.43±0.29 exp(–165.25±4.46 kJ/mol/RT) s⁻¹. The determination of rate coefficients was based on the amount of C₂H₄ or C₃H₆ formed. The potential energy surface (PES) of the thermal decomposition of these four reactants was determined with the G4 composite method. A master-equation analysis was conducted based on energies and molecular properties from the G4 computations. The results indicate that the length of a linear alkyl substituent does not significantly influence the rate of six-center eliminations, whereas the change from a linear to a branched alkyl substituent results in a significant reactivity increase. The comparison between rate-coefficient data also shows that alkyl carbonates have higher reactivity towards decomposition by six-center elimination than esters. The results are discussed in in the context of reactivity patterns of carbonyl compounds.     

Inorganic polymer phosphazene disulfide as cathode material for rechargeable lithium batteries

Novel inorganic network polymer phosphazene disulfide [(NPS₂)₃]_n was synthesized by a solution cross-link method. IR and element content analysis confirmed the polymer's molecular structure. The polymer has an average particle size of d_0.5 = 7.7 μm and the specific surface area is 57.4 m² g^− 1. TG/DTA analysis showed that [(NPS₂)₃]_n underwent a decomposition reaction from 200 to 300 °C. When used as cathode material in lithium batteries, its initial discharge capacity was 459.1 mAh g^− 1, which is almost 93.5% of theoretical specific capacity (490.9 mAh g^− 1). After 30 charge–discharge cycles, the discharge capacity of [(NPS₂)₃]_n stabilized at approximately 400.1 mAh g^− 1 which revealed an excellent cyclic ability. Therefore [(NPS₂)₃]_n is of great potential as cathode material for secondary lithium batteries.     

Sonochemical nitrogen fixation for the generation of NO2− and NO3− ions under high-powered ultrasound in aqueous medium

Sonochemical species such as nitrite (NO₂⁻) and nitrate (NO₃⁻) were detected in ultrapure aqueous medium with 28 kHz low frequency ultrasound (US) in the range of 200–1200 W output power. The concentration of their anionic ions monitored with a high-performance liquid chromatography increased with increasing US power especially under air atmosphere. When the generation of NO₂⁻ and NO₃⁻ ions under US exposure was investigated for N₂, O₂ and Ar-bubbled solutions, no trace of NO₂⁻ was observed while NO₃⁻ was slightly generated. Under air atmosphere, the concentration of dissolved oxygen in the aqueous medium increased especially when 1200 W power was used. In addition, the bulk pH shifted towards the acidic side with an increase in exposure time, which indicated that NO₂⁻ was formed. The formation of oxidizing species under 28 kHz low frequency ultrasonic treatment was confirmed with an absorption spectrum which was dominated by two maxima peaks at 288 nm and 352 nm representing triiodide I₃⁻ anion.     

The effects of power ultrasound (24 kHz) on the electrochemical reduction of CO2 on polycrystalline copper electrodes

The electrochemical CO₂ reduction reaction (CO2RR) on polycrystalline copper (Cu) electrode was performed in a CO₂-saturated 0.10 M Na₂CO₃ aqueous solution at 278 K in the absence and presence of low-frequency high-power ultrasound (f = 24 kHz, P_T ~ 1.23 kW/dm³) in a specially and well-characterized sonoelectrochemical reactor. It was found that in the presence of ultrasound, the cathodic current (I_c) for CO₂ reduction increased significantly when compared to that in the absence of ultrasound (silent conditions). It was observed that ultrasound increased the faradaic efficiency of carbon monoxide (CO), methane (CH₄) and ethylene (C₂H₄) formation and decreased the faradaic efficiency of molecular hydrogen (H₂). Under ultrasonication, a ca. 40% increase in faradaic efficiency was obtained for methane formation through the CO2RR. In addition, and interestingly, water-soluble CO₂ reduction products such as formic acid and ethanol were found under ultrasonic conditions whereas under silent conditions, these expected electrochemical CO2RR products were absent. It was also found that power ultrasound increases the formation of smaller hydrocarbons through the CO2RR and may initiate new chemical reaction pathways through the sonolytic di-hydrogen splitting yielding other products, and simultaneously reducing the overall molecular hydrogen gas formation.     

The effect of gamma irradiation on electrical and dielectric properties of Al-TiW-Pd2Si/n-Si Schottky diode at room temperature

The effects of ⁶⁰Co (γ-ray) irradiation on the electrical and dielectric properties of Al-TiW-Pd₂Si/n-Si Schottky diodes (SDs) have been investigated by using capacitance-voltage (C-V) and conductance-voltage (G/ω-V) measurements at room temperature and 500 KHz. The corrected capacitance and conductance values were obtained by eliminating the effect of series resistance (R_s) on the measured capacitance (C_m) and conductance (G_m) values. The high-low frequency capacitance (CHF-CLF) method given in [12] as N_ss = (1/qA) [((1/C_LF) − (1/C_ox))⁻¹ −  ((1/C_HF) − (1/C_ox))⁻¹] was successfully adapted to the before-after irradiation capacitance given in this report as N_ss = (1/qA) [((1/C_bef) − (1/C_ox))⁻¹ − ((1/C_after) − (1/C_ox))⁻¹] for the analyzing the density of interface states. The N_ss-V plots give a distinct peak corresponding to localized interface states regions at metal and semiconductor interface. The experimental values of the ac electrical conductivity (σ_ac), the real (M′) and imaginary (M″) parts of the electrical modulus were found to be strong functions of radiation and applied bias voltage, especially in the depletion and accumulation regions. The changes in the dielectric properties in the depletion and accumulation regions stem especially from the restructuring and reordering of the charges at interface states and surface polarization whereas those in the accumulation region are caused by series resistance effect.     

Synthesis and aldehyde absorption properties of aspartate-octacalcium phosphate inclusion compound

Double salt of octacalcium phosphate (Ca₈(HPO₄)₂(PO₄)₄·5H₂O; OCP) and aspartate (⁻OOCCH₂CH(NH₂)COO⁻; Asp) was synthesized by hydrolysis of α-tricalcium phosphate (α-Ca₃(PO₄)₂; α-TCP) in the presence of sodium aspartate. The compositional formula of the obtained inclusion compound (Asp-OCP inclusion compound) was Ca₈(HPO₄)_1.28(C₄H₅NO₄)_0.72(PO₄)₄·6.3H₂O, which included higher content of aspartate than that in our precedent paper. Asp-OCP inclusion compound reacted with aldehdyes in the interlayer. In the absorption experiments using formaldehyde gas, the amounts of absorption for Asp-OCP inclusion compound was approximately twice as that for activated charcoal (for Asp-OCP inclusion compound: 3.1×10⁻³ mol/g, activated charcoal: 1.6×10⁻³ mol/g), in spite that the BET specific surface area of Asp-OCP inclusion compound was approximately one-thirtieth part of that of activated charcoal (Asp-OCP inclusion compound: 43 m²/g, activated charcoal: 1225 m²/g). When the gas absorption experiments using acetaldehyde and leaf aldehyde under higher concentrations were carried out, the imine formation in the interlayer were observed in FT-IR and solid state ¹³C-NMR spectra.     

Cellulose-based carbon—A potential anode material for lithium-ion battery

A series of hard carbons was produced by the carbonization of microcrystalline cellulose powder in the temperature range of 950–1100 °C. The properties of the carbons were characterized using elemental analysis, X-ray diffraction and N₂ and CO₂ adsorption. The effect of heat-treatment temperature (HTT), pyrolytic carbon (PC) coating and discharging mode on the lithium insertion/deinsertion behavior of the carbons was assessed in a coin-type half-cell with metal lithium cathode. Increasing cellulose HTT modifies mostly carbon porosity, the surface area (S_DFT) decreases from about 500 to 167 m² g⁻¹. It is associated with lowering the reversible C_rev and irreversible C_irr capacities, but without improving relatively low (0.72) 1st cycle coulombic efficiency. Applying constant current (CC)+constant voltage (CV) discharging mode instead of conventional CC enhances the reversible capacity by 15–18%. PC coating is effective in reducing C_irr by ∼20% with a little change of C_rev. The best capacity parameters, C_rev of 458 mA h g⁻¹ and C_irr of 139 mA h g⁻¹, were measured for PC coated 1000 °C carbon. The prolonged cycling of full-cell assembled with anode of the carbon and commercial cathode revealed that after initial 20 cycles the capacity decay (0.029 mA h/cycle) is comparable to that of commercial cell with graphite-based anode.     

Effect of ultrasound and chlorine dioxide on Salmonella Typhimurium and Escherichia coli inactivation in poultry chiller tank water

This study evaluated the application of ultrasound alone or combined with chlorine dioxide (ClO₂) for Salmonella Typhimurium and Escherichia coli inactivation in poultry processing chiller tank water. A Full Factorial Design (FFD) 2² was conducted for each microorganism to evaluate the effect of ultrasound exposure time (x₁: 1 to 9 min; fixed: 37 kHz; 330 W; 25 °C) using a bath, and ClO₂ concentration (x₂: 1 to 17 mg L⁻¹) on microorganism count expressed in log CFU mL⁻¹ in distilled water. Variable x₂ had a negative effect on Salmonella Typhimurium (-5.09) and Escherichia coli (-2.00) count, improving the inactivation; while a x₁ increase present no inactivation improvement, explaining the use of x₁ lower level (1 min) and x₂ higher level (17 mg L⁻¹). The best condition for microorganism inactivation based on FFD was evaluated in chiller tank water (with organic matter) at 25, 16, and 4 °C; x₁ was kept (1 min), however x₂ was adjusted to obtain the same residual free chlorine (2.38 mg L⁻¹) considering the ClO₂ consumption by organic matter, achieving the value of 30 mg L⁻¹. An inactivation of 49% and 31% were observed for Salmonella Typhimurium and Escherichia coli. When ultrasound was replaced by a simple agitation in the presence of ClO₂, there was no inactivation for both microorganisms. Moreover, at poultry carcass pre-chilling (16 °C) and chilling (4 °C) conditions, the synergism of ultrasound combined with ClO₂ was more pronounced, with microorganisms’ reductions up to 100%.     

First-principles study of the electronic structure and magnetism of SrFe0.5Ru0.5O2

We study the electronic structures and magnetism of SrFe_0.5Ru_0.5O₂ by first-principles calculations in the framework of density functional theory (DFT) with generalized gradient approximation plus on site repulsion (GGA+U). The DFT calculations were carried out with ten kinds of Fe-site doping form. Calculations show that the d-orbital electronic configurations of Fe²⁺ and Ru²⁺ ions are (d_z²)²(d_yzd_xz)²(d_xy)²(d_x²_−y²)¹ and (d_z²)²(d_yzd_xz)³(d_xy)¹(d_x²_−y²) , respectively, which are independent of the doping form. The degenerated (d_xzd_yz) orbitals of Ru²⁺ ions are occupied by three electrons, so it gives rise to the Jahn–Teller distortion. The calculated magnetic moments of Fe²⁺ and Ru²⁺ ions are 3.7 μ_B and 1.6 μ_B, respectively. The exchange parameters including nearest neighbor (NN) ions and next nearest neighbor (NNN) ions are calculated by using Heisenberg model and the magnetic frustration in the ordered structure is explained by the competition of the exchange parameters. We also study the external pressure effect on the compound. A pressure-induced orthorhombic to tetragonal structure transition accompanied by an insulator to half-metal transition and an antiferromagnetic (or spin glass) to ferromagnetic state transition is observed.     

Enhancing electrical properties of high-Curie temperature piezoelectric ceramics BNT-PZT and their mechanism

Due to the urgent demands for high-Curie temperature (T_C/T_m) piezoelectric materials in geothermal exploration, aerospace and related fields, high-T_C/T_m ferroelectrics have attracted booming research attention. The high-T_m 0.25Bi(Ni_1/2Ti_1/2)O₃-0.75 Pb(Zr_1/2Ti_1/2)O₃ (0.25BNT-0.75PZT) ceramics were prepared by solid-state sintering method and via partial oxalate route, where the 0.25BNT-0.75PZT ceramics prepared via the partial oxalate route exhibit better electrical properties (T_m = 232 °C (10 kHz), ε_m = 10963, P_r = 26.14 μC/cm², E_c = 15.61 kV/cm, d₃₃ = 521 pC/N, d₃₃* = 553.3 pm/V, K_p = 47.1%, and Q_m = 21.6). The nano-scale domain configuration of the ceramics was revealed by piezoelectric force microscopy (PFM), and the relationship between the micro-structure and macro-electrical properties was analyzed. The ferroelectric phase transition mechanism was studied by temperature dependent Raman spectroscopy. The reduction of energy barrier of lattice distortion and polarization deflection is caused by nanometer-sized domain structure, low symmetric polar nano-regions and/or coexistence of multi-ferroelectric phases, contributing to the excellent electrical properties of the 0.25BNT-0.75PZT ceramics prepared via the partial oxalate route.