Design and synthesis of side-chain optimized poly(2,6-dimethyl-1,4-phenylene oxide)-g-poly(styrene sulfonic acid) as proton exchange membrane for fuel cell applications: Balancing the water-resistance and the sulfonation degree

Side-chain optimized poly (2,6-dimethyl-1,4-phenylene oxide)-g-poly (styrene sulfonic acid) (PPO-g-PSSA) is designed with balanced water-resistance and sulfonation degree. The PPO-g-PSSA is synthesized by controlled atom-transfer radical polymerization (ATRP) from brominated poly (2,6-dimethyl-1,4-phenylene oxide) (PPO-xBr) and ethyl styrene-4-sulfonate and followed by hydrolysis. A series of PPO-g-PSSA are prepared possessing different bromination degree (x) of PPO-xBr and polymerization degree (m) of the side-chains and the water-resistances of the fabricated membranes are investigated. The results show that a PPO-g-PSSA at relatively low x (x < 0.2) and high m (m > 4) exhibits good balance between the water-resistance and the sulfonation degree. Namely, it displays suitable proton conductivity with compromised water-resistance. Moreover, a maximum ion exchange capacity (IEC) of 3.24 mmol g^?1 is reached without the sacrifice of water-resistance. In addition, PPO-g-0.08PSSA-13 and PPO-g-0.14PSSA-4 are chosen characterized by thermogravimetric analysis, proton conductivities and mechanical properties. At 90% RH, the optimized PPO-g-0.08PPSA-13 possesses a proton conductivity of 37.9 mS cm^?1 at 40 °C and 45.5 mS cm^?1 at 95 °C, respectively.     

Chromium evaporation and oxidation characteristics of alumina-forming austenitic stainless steels for balance of plant applications in solid oxide fuel cells

The chromium (Cr) evaporation behavior of several different types of iron (Fe)-based AFA alloys and benchmark Cr₂O₃-forming Fe-based 310 and Ni-based 625 alloys was investigated for 500 h exposures at 800 °C to 900 °C in air with 10% H₂O. The Cr evaporation rates from alumina-forming austenitic (AFA) alloys were ~5 to 35 times lower than that of the Cr₂O₃-forming alloys depending on alloy and temperature. The Cr evaporation behavior was correlated with extensive characterization of the chemistry and microstructure of the oxide scales, which also revealed a degree of quartz tube Si contamination during the test. Long-term oxidation kinetics were also assessed at 800 to 1000 °C for up to 10,000 h in air with 10% H₂O to provide further guidance for SOFC BOP component alloy selection.     

Crystallographic characteristics and microwave dielectric properties of Ni-modified MgTa2O6 ceramics

Ni²⁺ modified MgTa₂O₆ ceramics with a trirutile phase and space group P4₂/mnm were obtained. The correlations between crystallographic characteristics and microwave dielectric performance of MgTa₂O₆ ceramics were systematically studied based on the chemistry bond theory (PVL theory) for the first time. The results indicate that the introduction of Ni²⁺ causes a change in polarizability and the Mg–O bond ionicity, which contributes to the variation of dielectric constant. Moreover, the lattice energy, and packing fraction, full width at half maximum of the Raman peak of Ta–O bond, as the quantitative characterization of crystallographic parameters, regulate the dielectric loss of MgTa₂O₆ ceramics in GHz frequency band. In addition, the study of sintering behavior shows that the densification and micromorphology are the crucial factors affecting the microwave dielectric performance. Typically, Ni²⁺ doping on the A-site of MgTa₂O₆ can effectively promote the Q × f values to 173,000 GHz (at 7.43 GHz), which ensures its applicability in 5G communication technology.     

Investigation of crystal characteristics,Raman spectra,and microwave dielectric properties of Mg1-xZnxTa2O6 ceramics

Mg_(1-x)Zn_xTa₂O₆ (x = 0.00?0.08) dielectric ceramics were synthesized via the traditional solid-state reaction method. We used XRD and Rietveld refinement to demonstrate that a pure Mg_(1-x)Zn_xTa₂O₆ phase with trirutile structure was formed. Zn²⁺ substitution helped to decrease the Raman full width at half width of the A_1g mode at 703 cm^?1, which resulted in an increase in the order and rigidity of the TaO₆ octahedron, this in turn contributed to improving the Q×f values. Additionally, the introduction of Zn²⁺ significantly promoted grain growth and increased the dense, and the molecular polarizability, these factors lead to a higher permittivity. Moreover, enhanced Ta-O bond energy resulted in a more stable TaO₆ octahedron in the Mg_(1?x)Zn_xTa₂O₆ system, which contributed to enhanced τ_f values via substitution of Zn²⁺ doped on the A-site. Correspondingly, the microwave dielectric properties were significantly improved for 0.04-doped samples, obtaining: ε_r = 27, Q × f = 185,000 GHz (at 7.47 GHz), τ_f =32 ppm/°C.     

Structural,optical and electrical properties of indium doped Cu2ZnSn(S,Se)4 thin films synthesized by the DC and RF reactive magnetron cosputtering

Element doping into the Cu₂ZnSn(S,Se)₄ (CZTSSe) absorber is an effective method to optimize the performance of thin film solar cells. In this study, the Cu₂In_xZn_1-xSn(S,Se)₄ (CIZTSSe) precursor film was deposited by magnetron cosputtering technique using indium (In) and quaternary Cu₂ZnSnS₄ (CZTS) as targets. Meanwhile, the In content was controlled using the direct current (DC) power on In target (P_In). A single kesterite CIZTSSe alloy was formed by successfully doping a small number of In³⁺ into the main lattice of CZTSSe. The partial Zn²⁺ cations were substituted by In³⁺ ions, resulting in improving properties of CZTSSe films. Morphological analysis showed that large grain CIZTSSe films could be obtained by doping In. The well-distributed, smooth, and dense film was obtained when the P_In was 30 W. The band gap of CIZTSSe could be continuously adjusted from 1.27 to 1.05 eV as P_In increased from 0 to 40 W. In addition, the CIZTSSe alloy thin film at P_In = 30 W exhibited the best p-type conductivity with Hall mobility of 6.87 cm²V^?1s^?1, which is a potential material as the absorption layer of high-performance solar cells.     

Study of haze emission efficiency based on new co-opetition data envelopment analysis

As haze intensifies in China, controlling haze emission has become the country's top priority for environmental protection. Because haze moves across different regions, it is necessary to develop a data envelopment analysis (DEA) model underpinned by both competition and cooperation to evaluate the haze emission efficiency in different provinces. This study innovatively adopts the spatial econometrics to construct the co-opetition matrices of Chinese provinces, then builds the co-opetition DEA model to evaluate the haze emission efficiency of them, and finally uses the haze data of 2015 as an example to assess the applicability of the model. The results of the study include the following: First, compared with the traditional CCR (A. Charnes & W. W. Cooper & E. Rhodes) model, this study constructs the co-opetition DEA cross-efficiency model that integrates haze's feature of cross-border moving; thus, it is more in line with the reality of haze emission and movement. Second, compared with the efficiency value gained from the CCR model, the haze emission efficiency values for Tianjin and Guangdong, two decision-making units, register greater variance when using the DEA model. The reason might lie in that they have a different spatial transportation relationship with their surrounding provinces. Third, the haze emission efficiency of provinces, according to the evaluation based on the co-opetition DEA method, varies greatly: Those with high efficiency are mostly inland provinces with slow economic growth and adverse climatic conditions, whereas many of the provinces with low efficiency are located in the relatively prosperous East China. The specific co-opetition DEA model constructed in this study enriches the research on the DEA model, which can be applied to the emission efficiency evaluation of similar pollutants around the world and can contribute empirical support to the haze reducing efforts of the government with its empirical results.     

Preparation and electrochromism of pyrochlore-type tungsten oxide film

Pyrochlore-type WO_3 powder was synthesized via hydrothermal method using aqueous sodium tungstate solution and oxalic acid as raw materials. The as-prepared powder was made into a soliquoid,from which films were made by dip coating process with indium-tin oxide(ITO).The obtained films were characterized by thermogravimetric and differential thermal analysis(TG-DTA), X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM), cyclic voltammetry(CV), chronoamperometry(CA) and ultravioletvisible(UV-Vis) absorption. Results show that the crystal of the pyrochlore-type WO_3 powder is perfect. When the calcination temperature rises from room temperature to500 ℃,the pyrochlore-type structure first becomes deformed, then it is destroyed and turns into amorphous phase,finally it will completely convert to WO_3 with a monoclinic structure. Electrochemical and optical tests demonstrate that the film calcined at 300 ℃ exhibits the best electrochromic performance and has a coloration efficiency of up to 68.5 cm~2 C~(-1) at 884 nm.     

Ferroelastic domain structure and phase transition in single-crystalline [PbZn1/3Nb2/3O3]1-x[PbTiO3]x observed via in situ x-ray microbeam

(1-x)Pb(Zn_1/3Nb_2/3)O₃-xPbTiO₃ ((1-x)PZN-xPT in short) is one of the most important piezoelectric materials. In this work, we extensively investigated (1-x)PZN-xPT (x = 0.07–0.11) ferroelectric single crystals using in-situ synchrotron μXRD, complemented by TEM and PFM, to correlate microstructures with phase transitions. The results reveal that (i) at 25 °C, the equilibrium state of (1-x)PZN-xPT is a metastable orthorhombic phase for x = 0.07 and 0.08, while it shows coexistence of orthorhombic and tetragonal phases for x = 0.09 and x = 0.11, with all ferroelectric phases accompanied by ferroelastic domains; (ii) upon heating, the phase transformation in x = 0.07 is Orthorhombic → Monoclinic → Tetragonal → Cubic. The coexistence of ferroelectric tetragonal and paraelectric cubic phases was in-situ observed in x = 0.08 above Curie temperature (T_C), and (iii) phase transition can be explained by the evolution of the ferroelectric and ferroelastic domains. These results disclose that (1-x)PZN-xPT are in an unstable regime, which is possible factor for its anomalous dielectric response and high piezoelectric coefficient.     

Stabilizing temperature-capacitance dependence of (Sr,Pb, Bi)TiO3-Bi4Ti3O12 solutions for energy storage

(1-x)Sr_0.7Pb_0.15Bi_0.1TiO₃-xBi₄Ti₃O₁₂ ((1-x)SPBT-xBIT, x = 0-0.125) bulk ceramics were developed and calcined via the solid-state method, aimed at the application of pulsed power capacitors. The phase structures, temperature stability, hysteresis loop, and discharge properties were systematically investigated. Considering both the temperature stability and dielectric properties, 0.925SPBT-0.075BIT bulk ceramics with a capacitance variation satisfying the X7R specification were developed for pulsed power capacitors. The energy storage density was 0.252 J/cm³, and the ceramics showed high temperature stability at 80 kV/cm. The discharge current waveforms of the 0.925SPBT-0.075BIT ceramics were recorded. A high discharge power density of approximately 1.01 × 10⁸ W/kg with an 8 Ω load resistor and short discharge period of 84 ns were achieved at 50 kV/cm. The good temperature stability properties and high power density show that the 0.925SPBT-0.075BIT ceramics are well suited for pulsed power capacitors with a wide temperature range.