Theoretical investigation of intrinsic point defects and the oxygen migration behavior in rare earth hafnates

In this work, the composition-dependent point defect types and formation energies of RE₂Hf₂O₇ (RE = La, Ce, Pr, Nd, Pm, Sm, Eu and Gd) as well as the oxygen diffusion behavior are systematically investigated by first-principles calculations. The possible defect reactions and dominant defect complexes under stoichiometric and non-stoichiometric conditions are revealed. It is found that O Frenkel pairs are the predominant defect in stoichiometric pyrochlore hafnates. Hf-RE cation anti-site defects, accompanied by RE vacancies and/or oxygen interstitials, are stable in the non-stoichiometric case of HfO₂ excess. On the other hand, RE-Hf anti-site defects together with oxygen vacancies and/or RE interstitials are preferable in the case of RE₂O₃ excess. The energy barriers for the migration along the V_O48f - V_O48f pathway of pyrochlore hafnates were calculated to be between 0.81 eV and 0.89 eV. Based on these results, a defect engineering strategy is proposed and the pyrochlore hafnates investigated here are predicted to exhibit potential oxygen ionic conductivity.     

Photophysical investigation of the formation of defect levels in P doped ZnO thin films

Zinc oxide (ZnO) offers a major disadvantage of asymmetry doping in terms of reliability, stability, and reproducibility of p-type doping, which is the main hindrance in realization of optoelectronic devices. The problem is even more complicated due to formation of various native defects in unintentionally doped n-type ZnO. The realization of p-type conductivity in doped ZnO requires an in-depth understanding of the formation of an effective shallow acceptor, as well as donor-acceptor compensation. Photophysical properties such as photoconductivity along with photoluminescence (PL) studies have unprecedentedly and effectively been utilized in this work to monitor the evolution of various in-gap defects. Phosphorus (P) doped ZnO thin films have been grown by RF magnetron sputtering under various Ar to O₂ gas ratios to investigate the effect of O₂ on the donor-acceptor compensation by comprehensive photoconductivity measurements supported by the PL studies. Initial elemental analyses indicate presence of abundant zinc vacancies (V_Zn) in O-rich ambience. The results predict that P sits in the zinc (Zn) site rather than the oxygen (O) site causing the formation of P_Zn–2V_Zn acceptor-like defects, which compensates the donor defects in P doped ZnO films. Photocurrent spectra uniquely reveal presence of more oxygen vacancies (V_O) defects states in lower O₂ flow, which gets compensated with an increase in the O₂ flow. Successive photocurrent transients indicate probable presence of more V_O in the films grown with lower O₂ flow and more V_Zn in higher O₂ flow. Overall the photosensitivity measurements clearly present that O-rich ambience expedites the formation of acceptor defects which are compensated, thereby lowering the dark current and enhancing the ultraviolet photosensitivity.     

Microstructure and coloring mechanism of iron spots on bluish white porcelain from Jingdezhen of the Song Dynasty

Jingdezhen is famous for its bluish white (Qingbai) porcelains of the Song Dynasty, and those decorated with iron spots are distinctive among them. Herein, iron spots on a bluish white porcelain were investigated using a series of microscopic and spectroscopic characterizations. We found the decreasing iron content from more than 8 wt% to about 2 wt% during the glaze color transition from rusty to brown and finally into green, which built a connection on the coloring mechanism of iron-rich crystallized glaze and celadon glaze. We identified the rare ε-Fe₂O₃, a promising magnetic material, in both the dark brown crystals and the triangular crystals in the rusty area, which is its first discovery among bluish white porcelains. Based on these findings, we discussed the coloring mechanism of iron-spot decoration along with the physical form of the iron oxide crystals, indicating the partially reducing atmosphere during firing process.     

Estimates of daily oxygen consumption,carbon dioxide and methane emissions,and heat production for beef and dairy cattle using spot gas sampling

A simulation study was conducted to examine accuracy of estimating daily O₂ consumption, CO₂ and CH₄ emissions, and heat production (HP) using a spot sampling technique and to determine optimal spot sampling frequency (FQ). Data were obtained from 3 experiments where daily O₂ consumption, emissions of CO₂ and CH₄, and HP were measured using indirect calorimetry (respiration chamber or headbox system). Experiment 1 used 8 beef heifers (ad libitum feeding; gaseous exchanges measured every 30 min over 3 d in respiration chambers); Experiment 2 used 56 lactating Holstein-Friesian cows (restricted feeding; gaseous exchanges measured every 12 min over 3 d in respiration chambers); Experiment 3 used 12 lactating Jersey cows (ad libitum feeding; gaseous exchanges measured every hour for 1 d using headbox style chambers). Within experiment, averages of all measurements (FQALL) and averages of measurements selected at time points with 12, 8, 6, or 4 spot sampling FQ (i.e., sampling every 2, 3, 4, and 6 h in a 24-h cycle, respectively; FQ12, FQ8, FQ6, and FQ4, respectively) were compared. Within study a mixed model was used to compare gaseous exchanges and HP among FQALL, FQ12, FQ8, FQ6, and FQ4, and an interaction of dietary treatment by FQ was examined. A regression model was used to evaluate accuracy of spot sampling within study [i.e., FQALL (observed) vs. FQ12, FQ8, FQ6, or FQ4 (estimated)]. No interaction of diet by FQ was observed for any variables except for CH₄ production in experiment 1. No FQ effect was observed for gaseous exchanges and HP except in experiment 2 where CO₂ production was less (5,411 vs. 5,563 L/d) for FQ4 compared with FQALL, FQ12, and FQ8. A regression analysis between FQALL and each FQ within study showed that slopes and intercepts became farther from 1 and 0, respectively, for almost all variables as FQ decreased. Most variables for FQ12 and FQ8 had root mean square prediction error (RMSPE) less than 10% of the mean and concordance correlation coefficient (CCC) greater than 0.80, and RMSPE increased and CCC decreased as FQ decreased. When a regression analysis was conducted with combined data from the 3 experiments (mixed model with study as a random effect), results agreed with those from the analysis for the individual studies. Prediction errors increased and CCC decreased as FQ decreased. Generally, all the estimates from FQ12, FQ8, FQ6, and FQ4 had RMSPE less than 10% of the means and CCC greater than 0.90 except for FQ6 and FQ4 for O₂ consumption and CH₄ production. In conclusion, the spot sampling simulation with 3 indirect calorimetry experiments indicated that FQ of at least 8 samples (every 3 h in a 24-h cycle) was required to estimate daily O₂ consumption, CO₂ and CH₄ production, and HP and to detect changes in those in response to dietary treatments. This sampling FQ may be considered when using techniques that measure spot gas exchanges such as the GreenFeed and face mask systems.     

Novel TiC-based composites with enhanced mechanical properties

Novel TiC-based composites were synthesized by reactive hot-pressing at 1800 °C for 1 h with ZrB₂ addition as a sintering aid for the first time. The effects of ZrB₂ contents on the phase composition, microstructure evolution, and mechanical properties were reported. Based on the reaction and solid solution coupling effects between ZrB₂ and TiC, the product ZrC may be partially or completely dissolved into the TiC matrix, and then phase separation within the miscibility gap is observed to form lamellar nanostructured ZrC-rich (Zr, Ti)C. The TiC-10 mol.% ZrB₂ (starting batch composition) exhibits good comprehensive mechanical properties of hardness 27.7 ± 1.3 GPa, flexural strength 659 ± 48 MPa, and fracture toughness of 6.5 ± 0.6 MPa m^1/2, respectively, which reach or exceed most TiC-based composites using ceramics as sintering aids in the previous reports.     

A review on ultrasonic spot welding of copper alloys

As a solid state joining process, ultrasonic spot welding has been proven to be a promising technique for joining copper alloys. However, challenges still remain in employing ultrasonic spot welding to join copper alloys. This article comprehensively reviews the current state of ultrasonic spot welding of copper alloys with a number of critical issues including materials flow, plastic deformation, temperature distribution, vibration, relative motion, vertical displacement, interface friction coefficient, online monitoring technique, coupled with the macrostructure and microstructure, the mechanical properties and electrical conductivity. In addition, the future trends in this field are provided.     

Warm-white light performance of Dy3+, Eu3+: NaLa(WO4)2 phosphors excited with a 450-nm LED

Dy³⁺, Eu³⁺: NaLa(WO₄)₂ phosphors are successfully synthesized through the solid-state reaction technique. The phase-structure and morphology are measured via X-ray diffraction and energy dispersive spectrometry. The concentrations of Dy³⁺, Eu³⁺, La³⁺, and W⁶⁺ are measured via ICP. The absorption and excited spectra are presented, which indicate that a blue band ranging from 430 to 480 nm is suitable for excitation. Using a commercial blue LED with a wavelength of 450 nm as the excitation light source, emission spectra for samples with varying dopant concentration ratios of Dy³⁺ to Eu³⁺ are obtained, which show good tunable yellow and red emission. For the purpose of investigating white LED performance, CIE spectra and a white light photo are also presented. The results reveal that varying the dopant concentration ratio of Dy³⁺ to Eu³⁺ plays a key role in the warm-white performance. With increasing concentration of Eu³⁺, the correlated color temperature decreases from 4069 to 3172 K, which indicates good warm-white performance.     

Rectangular Section Control Technology for Silicon Steel Rolling

Rectangular section control technology(RSCT)was introduced to achieve high-precision profile control during silicon steel rolling.The RSCT principle and method were designed,and the whole RSCT control strategy was developed.Specifically,RSCT included roll contour design,rolling technology optimization,and control strategy development,aiming at both hot strip mills(HSMs)and cold strip mills(CSMs).Firstly,through the high-performance variable crown(HVC)work roll optimization design in the upper-stream stands and the limited shifting technology for schedule-free rolling in the downstream stands of HSMs,a hot strip with a stable crown and limited wedge,local spot,and single wave was obtained,which was suitable for cold rolling.Secondly,an approximately rectangular section was obtained by edge varying contact(EVC)work roll contour design,edge-drop setting control,and closed loop control in the upper-stream stands of CSMs.Moreover,complex-mode flatness control was realized by coordinating multiple shape-control methods in the downstream stands of CSMs.In addition,the RSCT approach was applied in several silicon-steel production plants,where an outstanding performance and remarkable economic benefits were observed.     

Hot corrosion Type II of FeCr‐based model alloys for boiler and heat exchanger applications

The hot corrosion Type II of the alloys FeCr20, FeCr20Ni10, FeCr20Ni20, and FeCr20Co10 is investigated at 700°C in air + 0.5% SO₂ with deposits consisting of Na₂SO₄ and a eutectic mixture of Na₂SO₄ and MgSO₄ for 24, 100, and 300 h. The alloying elements nickel and cobalt have a positive influence when tests are conducted using a MgSO₄‐Na₂SO₄ deposit. In this case, they reduce the metal loss and increase the time to the propagation stage. In contrast, when the alloys are exposed with a Na₂SO₄ deposit, these alloying elements increase the metal loss and allow for the transition to the propagation stage because they can form molten phases with the Na₂SO₄. During the incubation stage an oxide scale forms on the FeCr20 alloy, which is thicker than the one formed during exposure without a deposit, and iron oxides are observed, which precipitate in the deposit. The propagation stage occurs by a dissolution and precipitation mechanism forming localized pitting attack. Iron is the main species that dissolves and precipitates, while chromium remains mainly as an oxide beneath the initial surface. The additional elements are found in the pit and in the salt deposit.     

Combination of heat treatment and chitosan coating to improve postharvest quality of wolfberry (Lycium barbarum)

The synergistic application of hot water dip at 42 °C for 30 min and 1% chitosan coating on differentiation in postharvest quality traits, microstructure as well as microbiological evolution of wolfberry fruits was investigated. Fresh wolfberry fruits were stored at 2 ± 0.5 °C and 90% relative humidity (RH) for 28 days. Results indicated the combination of prestorage heat treatment and chitosan coating maintained higher levels of ascorbic acid, total phenolic contents and antioxidant capacity as well as lower decay, compared with untreated wolfberry fruits. The possible mechanism was that the heat treatment almost sealed open stomata to limit the sites of pathogen penetration into fruits independently, followed by the biofilm formed by chitosan which controlled secondary infections as well as slowed changes in fruit respiration and metabolic activity in wolfberries. The synergistically treated fruit also exhibited a higher acceptability obtained by sensory analysis after cold storage. In this sense, the integrated application of heat treatment and chitosan coating could be regarded as an effective strategy to extend storage life and maintain the postharvest quality of wolfberry fruits.